Spec SciX Ebook Sept2020

SEPTEMBER 2020
Spectroscopy: Introduction to the

Techniques and Recent Advances
The SciX 2020 Preview and Companion Guide
Presented in partnership with An e-book from

Spectroscopy:
Introduction to the
Techniques and
Recent Advances
The SciX 2020 Preview and
Companion Guide
SEPTEMBER 2020
tomertu/stock.adobe.com
Introduction Raman Spectroscopy

Laura Bush Xiaoyun (Shawn) Chen
SERS and TERS Infrared Spectroscopy

Zachary D. Schultz André J. Sommer
Inductively Coupled
Plasma–Based Techniques Laser-Induced
(ICP-OES and ICP-MS) Breakdown Spectroscopy
Derrick Quarles Jr. and Matthieu Baudelet
Benjamin T. Manard
Charles Mann Award RSC Award: the Sir George

Biomedical Applications of Stokes Prize Spectroscopy for
Raman Spectroscopy Medicine: From SERS, Laser-In-
Over Several Decades duced Fluorescence, and Biosen-
An Interview with sors to Analytical Nanotools
Yukihiro Ozaki An Interview with Tuan Vo-Dinh
SAS Strock Award

Craver Award: Micro-Spatially Advancing Trace Elemental
Offset Raman Spectroscopy and Speciation Analysis with
(Micro-SORS) for Research in the a Focus on Metrology
Conservation of Cultural Heritage
An Interview with
An Interview with Claudia Conti Heidi Goenaga-Infante
The 2020 Emerging Leader

SAS Meggers Award in Molecular Spectroscopy:
Analyzing Soil and Meat with Advancing Spectroscopy, Bio-
Shifted Excitation Raman technology, and Nanotechnology
Difference Spectroscopy
An Interview with
An Interview with Kay Sowoidnich Markita Landry
ADVANCES IN SPECTROSCOPY
THE SCIX 2020 PREVIEW AND COMPANION GUIDE
The 2020 SciX conference—October 12–15, with pre-event activities already under way—will be held virtually this year.
Not only is the virtual format safer for everyone during the current pandemic, but it also presents a particular opportunity
for those who don’t normally get to travel to the event. Right from your desk, you can listen to scientific talks from top
speakers, both live and on-demand; check out posters and hear the presenters’ mini-orals; and participate in meaningful
networking conversations.
This e-book, prepared in collaboration with the SciX conference organization, is meant to serve both as a preview of
the conference and as a companion guide during and after the event. It offers two sets of articles, for readers with
different interests and needs.
The first section offers introductions to five core spectroscopy techniques:
• Raman spectroscopy
• surface enhanced Raman scattering (SERS) and tip-enhanced Raman scattering (TERS)
• Infrared spectroscopy
• Inductively coupled plasma–based techniques (ICP-OES and ICP-MS), and
• laser-induced breakdown spectroscopy (LIBS).
The second section presents the work of six spectroscopists who have won prestigious awards and will give talks at
the virtual event. These articles are part of an annual series of interviews with the winners of these awards, and include:
• Prof. Yuki Ozaki of Kwansei Gakuin University in Japan, the winner of the Charles Mann Award for Applied Raman
Spectroscopy, who discusses biomedical applications of Raman spectroscopy
• Prof. Tuan Vo-Dinh of Duke University, the winner of the Royal Society of Chemistry (RSC) Sir George Stokes
Award, who is using a range of analytical techniques in medicine, from SERS, laser-induced fluorescence, and
biosensors, to analytical nanotools
• Claudia Conti, of the Institute of Heritage Science of the Italian National Research Council (CNR), the winner of
the Coblentz Society’s Clara Craver Award, who is conducting research in cultural heritage conservation using
micro-spatially offset Raman spectroscopy (micro-SORS)
• Heidi Goenaga-Infante of LGC, the winner of the Lester W. Strock Award from the Society for Applied
Spectroscopy (SAS) and the SAS New England Regional Section, who is advancing the analysis of trace metals in
biological samples, with an emphasis on metrology and validated reference methodologies
• Kay Sowoidnich of the Ferdinand Braun Institute of the Leibniz Institute for High Frequency Technology, one of the
winners of the SAS William F. Meggers Award, who is developing the use of shifted-excitation Raman difference
spectroscopy (SERDS) as an efficient tool for the analysis of soil nutrients and for rapid screening of meat
samples along the supply chain, and
• Markita Landry of the University of California, Berkeley, the 2020 Emerging Leader in Molecular Spectroscopy,
presented by Spectroscopy, who is combining single-molecule biophysics and nanomaterial-polymer science to
develop new tools for understanding biological systems.
These interviews provide an excellent sampling of the fascinating information that will be presented this October during
the SciX conference. The technique introductions, in turn, will provide a handy reference—for you, your colleagues, your
students, or anyone who wants a brief tutorial.
We hope to “see” you online at the conference!
Laura Bush Editorial Director, Spectroscopy

Emerging Leader in
Charles Mann Sir George Stokes Craver Award: Lester W. Strock Award: William F. Meggers
Molcular Spectroscopy
Award: Raman Award: Spectroscopy Raman in Trace Elemental Award: Raman
Award: Advancing
Spectroscopy in Medicine Cultural Heritage Analysis Difference Spectroscopy
Spectroscopy
Raman
Raman Introduction to Infrared ICP-OES and ICP- LIBS
Applications SERS and TERS Spectroscopy MS Techniques Analysis Applications
Raman
Spectroscopy
Xiaoyun (Shawn) Chen
tomertu/stock.adobe.com
H
ave you used Raman onto a charge-coupled device (CCD) camera
spectroscopy? If not, you’re to generate Raman spectra. Such vibrational
really missing out, and now spectra contain information similar and
is a great time to try. Raman complementary to that provided by infrared
spectroscopy has come a long way since spectroscopy. The sampling mode in Raman
its discovery in the 1920s. Named after spectroscopy is highly versatile, and can
the Indian scientist C. V. Raman, who won be achieved using microscopes or probes
the 1930 Nobel Prize in physics, Raman in both contact and non-contact fashion,
spectroscopy had remained for a long time and even in a remote-sensing setup. The
mostly a specialized tool only accessible to development of these versatile sampling
trained scientists. Since the early 2000s, capabilities has enabled users to carry out
however, advances in laser technology, fiber many unique types of analysis not previously
optics, and grating technology have come possible, such as the non-invasive analysis of
together to break down technology barriers historical paintings or archaeological artifacts.
and revolutionized and democratized Raman Advances in chemometrics, big data, and
spectroscopy technology. artificial intelligence are now enabling
Most modern Raman spectroscopy maximum extraction of the rich information
instruments focus a laser beam to a tight embedded in Raman spectra. Compared to
focal point where Raman signals are separations-based analytical technologies
generated. The back-scattered signals are such as gas chromatography (GC) and liquid
then collected and dispersed using a grating chromatography (LC), chemical resolution
4 SEP T E MB E R 2 0 2 0 | S P E CT ROS COP Y

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Raman
Figure 1: Raman spectroscopy has found its use in numerous fields

(left column) and offers a wealth of analytical information (right col-
umn). The basic Raman measurement configuration is illustrated.
Laser excitation
Art
Agricultural Focusing optic
Archaeological Unknown identification
Biological
Chemical Compositions and concentrations
Food & Beverage Quality control
Forensic
Material Crystallinity and polymorphism
Pharmaceutical Microscopy and chemical imaging
Planetary Exploration
Polymer Big data analytics
by Raman spectroscopy is achieved instruments enable users to deploy Raman

through analyte spectral separation, spectroscopy not only in everyday life, such
rather than through physical separation as for the analysis of microplastics and
of analytes via the use of separation the identification of unknown substances
columns. Analysis of convoluted spectra by law enforcement, but also in remote
has often been a bottleneck in Raman reaches of science, such as deployment on
spectroscopy, but this challenge is the Mars rover to study the geology of the
being addressed through the use of the red planet.
abovementioned computational tools. Numerous commercial options for portable
Raman spectroscopy has found its and handheld Raman spectrometers are
way into numerous application fields, available. This range of options makes it a
a number of them shown in Figure 1. “buyers” market for users interested in
The reason behind such a wide range exploring Raman spectroscopy for their
of successful applications stems from own unique applications, but may also
the robustness and versatility of modern make it a daunting task to select the right
Raman spectrometers, as well as the tool. Interested readers are recommended
rich information available from the Raman to find expert opinions on such topics from
spectra. Robust and miniaturized Raman professional organizations such as the

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Raman
Society for Applied Spectroscopy (https:// the diffraction limit and offers chemical
www.s-a-s.org/index.html) and the Coblentz information with a spatial resolution on
Society (http://www.coblentz.org/). the order of tens of nanometers. From the
Raman spectroscopy is a maturing nano-scale to microscopy to applications
technology, and there are many areas under of handheld and portable instruments to
active academic and industrial investigation. analyzing industrial-scale reactions, Raman
For example, surface enhanced Raman spectroscopy is a widely used and valuable
spectroscopy (SERS) enables orders-of- analytical technique.
magnitude improvements in detection Xiaoyun (Shawn) Chen
limits. Spatially offset Raman scattering is with The Dow Chemical
(SORS) allows chemical analysis of objects Company in Midland,
beneath opaque packages. Tip-enhanced Michigan.
Raman spectroscopy (TERS) overcomes
Next generation Raman imaging
High performance Raman systems for a range of applications

Raman spectroscopy produces chemical and structural images to help you understand more about the
material being analyzed. Renishaw has decades of experience developing flexible Raman systems that
give reliable results, for even the most challenging measurements. With Renishaw’s suite of Raman
systems, you can see the small things, the large things and things you didn’t even know were there.
Visit www.renishaw.com/raman
Renishaw, Inc. 1001 Wesemann Drive, West Dundee, Illinois, 60118, United States
T +1 847 286 9953 F +1 847 286 9974 E raman@renishaw.com
www.renishaw.com
AD216(EN)-01-A (For inc).indd 1 12/20/2019 9:36:12 AM

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Raman Introduction to Infrared ICP-OES and ICP- LIBS SERS and TERS
Applications SERS and TERS Spectroscopy MS Techniques Analysis
SERS and TERS

Zachary D. Schultz
Alena/stock.adobe.com
S
urface enhanced Raman scattering rise to unique combinations of bands in the
(SERS), and the high resolution Raman spectrum, which is often considered
imaging analog tip-enhanced Raman a molecular fingerprint for identification.
scattering (TERS), have emerged as The challenge with Raman spectroscopy is
ultrasensitive methods of chemical analysis that the probability of a photon inelastically
(1). SERS derives from Raman scattering, scattering is very low (about a billion times
and is a nondestructive, label-free, chemical- less than that of a photon fluorescing).
specific method. In Raman spectroscopy, Fortunately, in the presence of silver and
laser radiation incident on a molecule is gold nanostructures, SERS can enhance
inelastically scattered at frequencies that can Raman scattering signals by as much as
be correlated to the vibrational modes of the 1011, such that single molecules can be
molecule (2). These vibrational modes are investigated (3).
similar to the energy levels probed in infrared The general phenomenon responsible for
spectroscopy, and arise from how elements SERS is shown in Figure 1, and arises from
are connected within a molecule. The an intense localized electromagnetic field on
energy of each vibrational mode is sensitive the nanostructures when the laser excites
to interactions with other molecules, a localized surface plasmon resonance
temperature, and other conditions, providing (LSPR) (4). The LSPR is the collective
insight into physical properties. Additionally, oscillation of electrons in the conduction
the unique organization and combination band of the metal nanoparticle. Silver and
of elements that compose a molecule give gold nanoparticles are most commonly

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used because their LSPR is found in the more sensitive than fluorescence (12,13).
visible region of the electromagnetic At this point, it is well understood the
spectrum, where most Raman spectroscopy physical interactions that generate a large
experiments are performed. Other materials SERS enhancement; however, controlling
can also generate SERS; for example, the interactions for quantitative analysis
aluminum nanoparticles exhibit a LSPR at has been more challenging. The observed
ultraviolet wavelengths and can generate Raman intensity arises from the organization
SERS (5). When excited, the oscillation of the of the nanoparticles and the location of
electrons concentrates the laser radiation the analyte molecule interacting with the
into intense local electromagenetic fields nanoparticles. Although nanoparticles are
at the nanostructure surface. Molecules often modeled as spheres, small features
in close proximity (generally <5 nm) to on the surface can modulate the enhanced
the nanostructure surface experience fields. Additionally, the spacing between
this field and generate increased Raman particles affects the resulting fields, and
scattering. The Raman scattering occurs at forming reproducible aggregates can be
a wavelength similar to the LSPR, causing challenging and affect the observed signals.
the nanoparticle to further re-radiate the Because only molecules near the surface
increased Raman scattering from nearby can be detected, the signal saturates at
molecules. In essence, the nanoparticle acts higher concentrations.
as an antenna to amplify the Raman signal
from molecules (6–8). TERS
The electric field in the junction between The plasmonic effects that give rise to
two plasmonic nanoparticles is significantly SERS can also be localized at the apex of a
larger than on the surface of a single scanning probe microscope tip to perform
particle, and gives rise to very large Raman TERS (14,15). This approach has been
enhancements. Similarly, asymmetric demonstrated using both atomic force
nanoparticles, such as nanorods and microscopy (AFM) and scanning tunneling
nanostars (9,10), have higher enhancements microscopy (STM) to control the position of
at points and vertices. Highly enhancing the tip. The advantage of AFM-based TERS is
locations are often called “hotspots” and it can be done on almost any sample, while
have been shown to dominate the SERS STM–TERS requires a conductive sample.
signal (11). Plasmon-enhanced scattering In either approach, a plasmonic metal
has enabled Raman detection of single nanoparticle (or sharp metal point) is located
molecules and, in some applications, is at the very apex of the tip to generate
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Figure 1: The images illustrate a laser interacting with a thiophenol

molecule to scatter light by spontaneous Raman scattering as well as
a laser interacting with thiophenol on plasmonic nanoparticles to gen-
erate surface enhanced Raman scattering (SERS). The SERS spectra
from thiophenol on silver nanostructures and the spontaneous Raman
spectrum from pure thiophenol are shown. The enhanced electric field
on the nanoparticle surface enhances the observed Raman signal in
the SERS experiment. The SERS spectrum arises from ~10,000x few-
er molecules, is obtained at lower incident power, and requires shorter
acquistion times, demonstrating the signal enhancement.
Spontaneous Raman Surface enhanced Raman
(SERS)
hνlaser
hνRaman hνlaser
hνSERS
SERS
Raman
500 1000 1500 2000 2500
Raman shift (cm-1)
the Raman signal enhancement from demonstrated. Under ambient conditions,

molecules beneath the tip. By controlling the TERS experiments are capable of imaging
location and configuration of the enhancing with a spatial resolution of 1 to 2 nm (17–19).
nanostructure, high sensitivity spectroscopy
can be obtained from precise locations on Applications of SERS and TERS
a sample (16). Figure 2 illustrates how, by A number of applications of SERS and
scanning the sample under the TERS tip TERS have been reported in the literature.
in the laser focus, high spatial-resolution Many SERS applications use the enhanced
images of samples can be obtained. In signal for trace detection. A large number
ultrahigh-vacuum (UHV) experiments, of papers have been published describing
where molecular motion can be minimized, many ways to generate a SERS substrate,
TERS imaging within a molecule has been and commercial solutions are available.

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One common use is to create “SERS allow multiple different tags to be detected
tags,” where a reporter molecule with a and unmixed simultaneously (22). Other
strong Raman response is attached to recent work has investigated novel ways
the surface of the nanoparticle along with to utilize the molecular enhancements for
some kind of recognition agent (such as an chemical sensing, such as SERS pipettes
antibody or nucleic acid sequence) (20,21). for optophysiology (23) and online detection
The unique SERS signal from the reporter with chromatographic separations (24). In
molecule is used to quantify, and image, addition to analytical experiments, new
the detected analyte. Although this is physical understanding is being uncovered
similar to fluorescence, SERS tags do not at length scales suggesting picoscience
photobleach, and the narrow Raman bands (25). As SERS and TERS continue to mature,
Figure 2: Tip enhanced Raman scattering (TERS) is performed by

positioning a metallic nanoparticle, or sharp metallic point, at the
apex of a scanning probe microscope tip. The TERS tip amplifies
Raman signal from the molecules immediately beneath it, increasing
the observed signal relative to the spontaneous Raman signal with-
out enhancement. By moving the sample with respect to the tip and
analyzing the recorded spectra, chemical images, such as the map of
multilayer graphene shown, can be obtained. In the TERS map, the
red, green, and blue colors correspond to different multilayer thick-
nesses of the graphene as determined from the TERS spectra.
hνlaser TERS
hνTERS
Raman
!!"" 1200 1300 1400 1500 1600 !(""
Raman shift (cm-1)
1 µm

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one can expect to see these techniques 12. D. Graham, R. Stevenson, D.G. Thompson, L. Barrett,
C. Dalton, and K. Faulds, Faraday Discuss. 149,
enabling new physical insights and methods 291–299 (2011).
of chemical analysis. 13. I. A. Larmour, K. Faulds, and D. Graham, Chem. Sci. 1,
151–160 (2010).
References 14. R.M. Stockle, Y.D. Suh, V. Deckert, and R. Zenobi,
Chem. Phys. Lett. 318, 131–136 (2000).
1. J. Langer, D. Jimenez de Aberasturi, J. Aizpurua,
R.A. Alvarez-Puebla, B. Auguié, J.J. Baumberg, G.C. 15. N. Hayazawa, Y. Inouye, Z. Sekkat, and S. Kawata,
Bazan, S.E.J. Bell, A. Boisen, A.G. Brolo, J. Choo, D. Opt. Commun.183, 333–336 (2000).
Cialla-May, V. Deckert, L. Fabris, K. Faulds, F.J. García
16. R. Zhang, Y. Zhang, Z.C. Dong, S. Jiang, C. Zhang,
de Abajo, R. Goodacre, D. Graham, A.J. Haes, C.L.
L.G. Chen, L. Zhang, Y. Liao, J. Aizpurua, Y. Luo, J.L.
Haynes, C. Huck, T. Itoh, M. Käll, J. Kneipp, N.A. Kotov,
Yang, and J.G. Hou, Nature 498, 82–86 (2013).
H. Kuang, E.C. Le Ru, H.K. Lee, J.-F. Li, X.Y. Ling, S.
Maier, T. Mayerhoefer, M. Moskovits, K. Murakoshi, J.- 17. P.Z. El-Khoury and E. Aprà, J. Physical Chemistry C
M. Nam, S. Nie, Y. Ozaki, I. Pastoriza-Santos, J. Perez- 124, 17211–17217 (2020).
Juste, J. Popp, A. Pucci, S. Reich, B. Ren, G.C. Schatz,
18. Z. He, Z. Han, M. Kizer, R.J. Linhardt, X. Wang, AM.
T. Shegai, S. Schlücker, T. Li-Lin, K.G. Thomas, Z.-Q.
Sinyukov, J. Wang, V. Deckert, A.V. Sokolov, J. Hu, and
Tian, R.P. Van Duyne, T. Vo-Dinh, Y. Wang, K.A. Willets,
M.O. Scully, J. Am. Chem. Soc. 141, 753–757 (2019).
C. Xu, H. Xu, Y. Xu, Y.S. Yamamoto, B. Zhao, and L.M.
Liz-Marzán, ACS Nano. 14, 28–117 (2019) 19. T. Deckert-Gaudig, E. Kaemmer, and V. Deckert, J.
Biophotonics 5, 215–219 (2012).
2. E. Smith and G. Dent, Modern Raman Spectroscopy:
A Practical Approach (John Wiley & Sons, Hoboken, 20. D. Graham, B.J. Mallinder and W.E. Smith,
New Jersey, 2005). Angewandte Chemie Intl. Ed. 39, 1061-1063 (2000).
3. M. Moskovits, J. Raman Spectrosc. 36, 485–496 21. T. Vo-Dinh, K. Houck, and D. L. Stokes, Anal. Chem.
(2005). 66, 3379–3383 (1994).
4. P.L. Stiles, J.A. Dieringer, N.C. Shah, and R.R. Van 22. S. Laing, K. Gracie, and K. Faulds, Chem Soc. Rev. 45,
Duyne, Annu. Rev. Anal. Chem. 1, 601–626 (2008). 1901–1918 (2016).
5. S. Tian, O. Neumann, M.J. McClain, X. Yang, L. Zhou, 23. F. Lussier, D. Missirlis, J. P. Spatz, and J. F. Masson,
C. Zhang, P. Nordlander, and N.J. Halas, Nano. Lett. 17, ACS Nano. 13, 1403–1411 (2019).
5071–5077 (2017).
24. L. Xiao, C. Wang, C. Dai, L.E. Littlepage, J. Li, and Z.D.
6. K. Yoshida, T. Itoh, H. Tamaru, V. Biju, M. Ishikawa and Schultz, Angewandte Chemie 59, 3439–3443 (2020).
Y. Ozaki, Phys. Rev. B 8, 9 (2010).
25. J. Lee, K.T. Crampton, N. Tallarida, and V.A. Apkarian,
7. P. Bharadwaj, R. Beams, and L. Novotny, Chem. Sci. Nature 568, 78–82 (2019).
2, 136–140 (2011).
8. L. Novotny and S.J. Stranick, Annu Rev. Phys. Chem.
57, 303–331 (2006). Zachary D. Schultz is
9. B. Nikoobakht, Z.L. Wang, and M.A. El-Sayed, J. Phys. with the Department
Chem. B 104, 8635–8640 (2000).
of Chemistry and
10. C.G. Khoury and T. Vo-Dinh, J. Phys. Chem. C 112,
18849–18859 (2008).
Biochemistry at The
11. Y. Fang, N.-H. Seong, and D.D. Dlott, Science 321,
Ohio State University, in
388–392 (2008). Columbus, Ohio.

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Infrared
Applications SERS and TERS Spectroscopy MS Techniques Analysis Spectroscopy
Infrared
Spectroscopy
André J. Sommer
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I
nfrared (IR) spectroscopy had formed to educate early practitioners
its beginning in the early 1900s, in the art. The IR method was used
when William Weber Coblentz widely, but experienced a significant
demonstrated that chemical resurgence in the sciences with the
functional groups exhibited specific advent of Fourier transform IR (FT-IR)
and characteristic IR absorptions. In instruments in the late 1960s and early
this early work, Coblentz collected the 1970s. These instruments could collect
IR spectra of ~135 compounds with spectra in a matter of seconds, and, by
an accuracy that still stands the test signal averaging, spectra of very high
of time some 60 years later. Interest quality could be measured. Although
in the method grew during World War instruments of that era were very large
II, when a method for characterizing and bulky, current instruments are
synthetic rubber formulations was approaching the size of a cell phone.
needed for the war effort. The early to Today, the method is widely used in
mid 1940s saw the first commercial fields as diverse as planetary modeling,
instruments come on the market from chemical characterization, climate
both Beckman and Perkin Elmer. In monitoring, chemical threat detection,
1957, Perkin Elmer introduced the first forensics, and disease detection, to
low-cost IR spectrophotometer, the name a few.
Model 137, priced at just $3800. Several The mid-IR spectrum ranges
years later, the Coblentz Society was in wavelengths from 2.5 to 50

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Infrared
micrometers. To correlate these sensitive to molecules possessing

wavelengths with bond energies, the hetero-nuclear bonds and molecular
wavenumber (cm-1) is used, which is vibrations that are asymmetric. For
simply the number of wavelengths example, the features near 1751 and
contained in one centimeter. The 1683 cm-1 arise as a result of the C=O
corresponding wavenumbers relating stretch of the ester and acid carbonyl
to the above wavelength range is groups, respectively. In contrast, the
4000 to 200 cm-1, respectively. For Raman method is sensitive to homo-
qualitative work, a transmission nuclear bonds and molecular vibrations
spectrum is collected by passing that are symmetric. Thus, the C=C
these wavelengths through a very thin stretch located near 1600 cm-1 is the
sample (~10 micrometers thick), and most intense transition in the Raman
recording how much light is absorbed spectrum. Both IR and Raman spectra
by the sample. Figure 1 illustrates are unique for a given compound, and
the IR and Raman spectra of acetyl are considered fingerprints for that
salicylic acid (aspirin). Both spectra compound. Indeed, in 1962, Ellis R.
are rich in information, but to contrast Lippincott testified before the United
the two methods, the IR method is States Congress that an IR spectrum is
Figure 1: Infrared and Raman spectra of acetyl salicylic acid (aspirin).

Transmittance
Infrared
O OH
O
O
Intensity (a.u.)
Raman
4000 3500 3000 2500 2000 1750 1500 1250 1000 750 500
Wavenumber (cm-1)

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Infrared
a unique fingerprint that could be used sample preparation or specialized

in patent litigation. accessories. Using the ATR method, the
sample is brought into intimate contact
In the late 1980s, two more with an internal reflection element
significant developments took place: (IRE). Figure 2 illustrates a typical
the development of novel sampling ATR accessory. Contact between the
accessories, most notably attenuated sample and the IRE is achieved using
total internal reflection (ATR) sampling a pressure applicator. Although several
accessories, and the development of IR IREs are available, the most common
microscopes. ATR accessories allowed ones are made of synthetic diamond.
any sample to be measured on a routine Diamond is both chemically inert and
basis. Previously, the samples had to IR-transparent, but is also hard, and, as
be in a specific form (a thin film less a result, can withstand high pressures.
than 10 micrometers thick) to obtain a At the diamond–sample interface, the
suitable transmission spectrum. This IR light penetrates into the sample
requirement involved considerable only a few micrometers. As a result,
Figure 2: A Typical ATR Accessory (diagram provided by RedWave

Technology).
Pressure
Applicator
Diamond Internal
Reflection Element
Miniature IR
Interferometer Sample
Infrared
Beam
Detector

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Infrared
highly absorbing samples like aqueous had the advantage of increasing the
solutions can be easily studied without spatial resolution of the measurement
significant sample preparation. Today, by changing the refractive index of the
the vast majority of IR spectra are IRE employed.
collected using ATR accessories. Recently, IR spectroscopy has been
Although the first IR microscope coupled with atomic force microscopy
(the Perkin Elmer 85) was introduced (AFM), and a new generation of IR
in the 1950s, its use was limited microscopes has been outfitted with
because it was interfaced to a prism or tunable IR lasers. AFM-coupled IR
grating spectrometer. The limited light microscopes allow one to collect
throughput associated with micrometer- spectra on spatial domains much
sized samples and the serial data smaller than the wavelength of light.
collection of the spectrophotometer However, these microscopes have a
translated into long scan times by high price tag, and are not considered
today’s standards. In the mid 1980s, routine analytical instruments.
these microscopes were interfaced Similar to the AFM–IR microscopes,
to FT-IR instruments. The reduced IR microscopes outfitted with solid-
collection times, along with computer state lasers are expensive, and not
averaging, made it possible to analyze considered routine. In addition, the
samples whose size approached the spectral range of these systems is
wavelengths of IR light. limited to ~1800–900 cm-1.
In the late 1990s and early 2000s, the It remains to be seen where the
IR microscopes began to be outfitted technology will take IR analysis in the
with both linear and two-dimensional future, but the method is one of the
array detectors, along with motorized most important tools in the arsenal of
stages. These detectors allowed one many scientists throughout the world.
to obtain IR maps and images from
micrometer-sized spatial domains
over large areas. In addition, the IR André J. Sommer the
microscope could be used in a variety Director of the Molecular
of different modes which included Microspectroscopy
transmission, reflection, and ATR Laboratory at Miami
microspectroscopy. This latter method University in Oxford, Ohio.

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Inductively Coupled
Raman Introduction to Infrared ICP-OES and ICP- LIBS Plasma–Based Techniques
(ICP-OES and ICP-MS)
Inductively
Coupled Plasma–
Based Techniques
(ICP-OES and
ICP-MS)
Derrick Quarles Jr. and
Benjamin T. Manard
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T
he “Atomic Spectroscopy” emission spectroscopy (OES) or
section of the SciX program mass spectrometry (MS) detection
focuses on many areas of platform (1). The ICP, initially employed
research that include low as an excitation source for OES
pressure glow discharge, atmospheric detection, was first implemented
pressure glow discharge, inductively by Fassel and colleagues (2,3), later
coupled plasma, and laser ablation. by Greenfield and coworkers (4),
This article provides an educational and subsequentially realized as an
summary on inductively coupled ionization source for MS detection (5).
plasma–based instrument platforms. The ICP is formed when the energy
There is an imminent need for of a radio frequency (RF) generator
routine trace element and isotopic interacts with a tangential flow of
analysis, expanding across many argon gas (~15 L/min) in a quartz tube
fields including, but not limited to, often referred to as the plasma torch.
geological, industrial, nuclear, health, This process subsequentially ionizes
and environmental analysis. Arguably, the gas forming a high-temperature
the gold-standard technique for the plasma, in which photons and ions can
majority of these measurements be generated.
is through an inductively coupled Sample Introduction
plasma (ICP) excitation–ionization Sample introduction schemes in ICP-
source coupled to an optical OES and ICP-MS are dominated by

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Inductively Coupled
solution-based analysis. Ultimately, an ICP-OES instrument. Techniques

an aerosol must be generated such as laser ablation have become
before the sample enters the ICP, popular because of the reduction
because of the plasma’s inefficiency in sample preparation (little to no
at dissociating bulk solution (large sample preparation is required), and
droplets). Traditionally, a solution is the ability to obtain spatial (lateral or
carried into a concentric nebulizer, depth) elemental information, rather
where a Venturi effect is achieved than the bulk analysis that is more
via argon gas and low pressure typical of solution-based ICP analysis.
to generate a fine aerosol. Next, The combination of laser ablation
the aerosolized sample is further with ICP-MS is not the only
separated such that the larger hyphenated configuration that
droplets dissipate (becoming solution is employed; the coupling of
waste), and the fine droplets exit liquid chromatography or ion
the spray chamber and are directed chromatography are extremely useful
into the torch. Many advances sample introduction techniques
over the years have been focused for ICP-MS. These techniques offer
on improving nebulizers, spray the ability to separate compounds,
chambers, and membrane desolvation isotopes, proteins, or elemental
to improve sensitivity and precision species based on column chemistry
for elemental and isotopic analysis. prior to introducing into the ICP-MS
Another means of sample instrument, which ultimately acts as
introduction for ICP-based analysis an element-specific detector.
is laser ablation sampling. With this Detecion Platforms
approach, a pulsed laser ablates a The detection platforms for ICP
sample surface within an ablation instrumentation consist of OES
cell, and the subsequently formed and MS instrumentation. For OES
nanoparticles are carried into detection, the photons emitted from
the ICP via a carrier gas (such as the ICP are commonly collected
helium) (6,7). Most commonly, laser via radial or axial viewing, each
ablation is combined with an ICP-MS with their respective advantages
instrument; however, it is not out of and disadvantages. Axial viewing,
the realm to utilize laser ablation with collecting photons down the

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Inductively Coupled
longitudinal axis of the plasma, platform is ultimately the workhorse

is often preferred for enhanced ICP-MS system for routine trace
sensitivity, because more photons elemental analysis. This approach has
are collected; however, more photons been enhanced with the introduction
could be detrimental if there are of collision–reaction cells that
large amounts of total dissolved facilitate the reduction or elimination
solids (TDS). Radial viewing, of polyatomic interferences caused
collecting photons perpendicular by sample matrix or plasma gas
of the plasma, is less sensitive and (8). More recently, the focus has
less hindered by interferences from been on the introduction of triple-
background and complex matrices. quadrupole ICP-MS systems, utilizing
Spectrometers employed with OES the first quadrupole as a mass filter,
detection can primarily be found followed by collision or reaction gas
in two configurations: scanning- in the second; the third quadrupole
based Czerny-Turner spectrometers, acts as a pass-through or mass
or simultaneous-based echelle filter, depending on application
spectrometers. The Czerny-Turner needs (9). Sector-based platforms
design allows for higher resolution, are often sought out for enhanced
which can be favorable for complex capabilities when performing isotope
samples; however, it is accompanied ratio analysis, particularly if multiple
by longer analysis time, particularly detectors are employed such as in
if many elements are of interest. multi-collector (MC) ICP-MS. Sector-
Echelle spectrometers allow for based platforms can also offer higher
the simultaneous measurement mass resolution for separating
of many wavelengths in a timely polyatomic or isobaric interferences.
manner, but often lack spectral Finally, time-of-flight–based ICP-MS
resolution compared to Czerny-Turner instruments offer the ability to collect
spectrometers. every mass simultaneously rather
than sequentially, as is done in the
For ICP-MS detection platforms, aforementioned quadrupole-based
commercially available options platforms. Time-of-flight instruments
primarily consist of quadrupole, time- have become increasingly popular
of-flight, and magnetic sector-based for single particle and laser ablation
mass analyzers. The quadrupole imaging applications.

Emerging Leader in
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Inductively Coupled
References Acta 835, 1–18 (2014).

8. D.W. Koppenaal, G.C. Eiden, and C.J. Barinaga,
1. R. Thomas, Practical Guide to ICP-MS–A J. Anal. At. Spectrom. 19, 561–570 (2004).
Tutorial for Beginners (CRC Press, Boca
Raton, Florida, 3rd Ed., 2013. 9. L. Balcaen, E. Bolea-Fernandez, M. Resano,
and F. Vanhaecke, Anal. Chim. Acta 894, 7-19
2. R.H. Wendt and V.A. Fassel, Anal. Chem. (2015).
37(7), 920–922 (1965).
3. V.A. Fassel and R.N. Kniseley, Anal. Chem.
46(13), 1110a–1120a (1974). C. Derrick Quarles Jr. (l)
4. S. Greenfield, I.L. Jones, and C. Berry, and Benjamin T. Manard
Analyst 89(1064), 713–720 (1964).
(r) are co-chairs of the
5. R.S. Houk, V.A. Fassel, G.D. Flesch, H.J. Svec, Atomic Section. Quarles
A.L. Gray, and C.E. Taylor, Anal. Chem. 52(14),
2283–2289 (1980). is with Elemental
6. R.E. Russo, X. Mao, H. Liu, J. Gonzalez, and Scientific, Inc., in Omaha, Nebraska.
S.S. Mao, Talanta 57(3), 425–451 (2002). Manard is with Oak Ridge National
7. J.S.Becker, A. Matusch, And B. Wu, Anal. Chim. Laboratory, in Oak Ridge, Tennessee.
Figure 1: Common sample introduction techniques and detection op-

tions for the inductively coupled plasma (ICP) excitation–ionization
source.
Optical emission
spectroscopy
Quadrupole–
Laser ablation
triple quadrupole
-
Traditional solution-based
Liquid chromatography,
Ion chromatography Time-of-flight
Magnetic sector

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Laser-Induced
Applications SERS and TERS Spectroscopy MS Techniques Analysis Breakdown Spectroscopy
Laser-Induced
Breakdown
Spectroscopy
Matthieu Baudelet
Sono Creative/stock.adobe.com
L
aser-induced breakdown the excitation medium is a plasma,
Spectroscopy (LIBS) is it can be controlled (although non-
principally an elemental necessarily) by the background gas and
analytical approach. It relies the ablation chamber. Finally, the OES
on the sampling and excitation of from such a short-lived plasma does
the material by a laser pulse. The not suffer from as much interference
excitation is sustained by the laser- from atmospheric dimers as a signal
induced plasma, and the emission of from a torch plasma would. OES also
each element provides the spectral allows much more freedom in the
fingerprint we rely on to identify and choice of the analyte signal than a
quantify it. mass spectrum would, circumventing
interferences with ease.
LIBS benefits from the unique
features of laser ablation (LA) and LIBS has increasingly been used
the accessibility of optical emission in many fields for imaging or for
spectroscopy (OES). Given that field applications when elemental
sampling is controlled by the laser– information is required. Its main
matter interaction, sampling can advantages result from the fact that
be designed to attain micrometer the sampling is done by laser ablation,
resolution, and still obtain an analytical allowing both elemental analysis
signal from the plasma. Given that and chemical mapping, as well as

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Laser-Induced
emission spectroscopy, making it rubber is highly susceptible to

possible to exploit the technological melting, it is usually hard to ablate it
miniaturization of spectrometers. efficiently and get a good elemental
signature from it. But LIBS offers
LIBS provides important chemical a unique approach to perform
information in quasi-real time, and is elemental analysis of the overall
very versatile, capable of detecting organic matrix of rubber, as well
both major and minor elements in the as the vulcanization agents it may
sample. New approaches using LIBS contain, such as sulfur and various
provide protocols for the analysis metals. This capability enables the
of halogens via molecular emission analysis of few micrograms of tire
in the plasma that are easier to skid mark material and a search for
accomplish than mass spectrometry its provenance. We have shown that,
methods for such analyses.
by conducting elemental analysis
with LIBS, it is possible to classify
I have explored and contributed to the
development of LIBS for 15 years, ever tire chemistry and origin; we now are
since I used LIBS for microbiological expanding our research to describe
applications during my MS internship. a full analytical approach from
After having explored many applications crime scene collection to statistical
throughout these years, I have settled decision making.
on two main areas of focus for my
forensic research portfolio: the forensic Forensic anthropology has typically
analysis of rubber (tire forensics), relied on X-ray fluorescence (XRF)
and the development of matrix- for elemental analysis in the field
matched standards for the analysis as well as in the laboratory. LIBS,
of hard biological materials (forensic however, can provide so much
anthropology). This focus is motivated more, thanks to its efficiency. For
both by the needs in forensic analysis example, it can provide information
but also by the interesting challenges about low-Z elements beyond C, N,
these two applications pose. and O; hydrogen, lithium, and boron
can now be easily detected. But
Rubber is a very tricky material for elemental trace analysis requires
analytical laser ablation. Because reliable standards. And, just as XRF

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is matrix-sensitive, LIBS analysis of knowledge I could find from physics,

bones, hair, and teeth cannot rely on chemistry, optics, engineering, data
compressed standard powders. This science, material development, and
is why my research group is working more. It is this sense of connection
to develop such standards for hard and the “multilingual” blend of all this
biological materials. Our research knowledge that keeps me excited
has succeeded in the creation of and passionate about LIBS. Laser
elemental standards for the analysis technology keeps providing better
of hair, teeth, and fingernails. We are tools for us as LIBS spectrometers
also now exploring new approaches become more popular, and better
for more reliable standards and a optics get integrated into instruments.
wider breadth of applications such as Data analysis becomes more
medical analysis and bio-archaeology. and more powerful, and can take
into account the highly non-linear
The LIBS community has known me aspects of LIBS. Now, discovering
with multiple hats: from an impulsive the potential of material science
graduate student working on bacteria for quantitative analysis, I feel like
analysis and polymer laser ablation in a DJ in a record store: Every single
a physics department, to a research track, whatever the genre, can have
scientist then faculty member a jewel sample, and we have the
focusing on defense applications potential to put these pieces together
of LIBS within the UCF College of to form a masterpiece. This is what
Optics, to a cheerful member of the makes me passionate about LIBS—
chemistry faculty establishing his the opportunity to put many pieces
own research in the National Center together to solve analytical problems.
for Forensic Science at UCF. Every
time, I have found challenges and
Matthieu Baudelet is an
motivation to develop new approaches
associate professor at
for the main goal of what LIBS is for:
the National Center for
quantitative analytical science. Forensic Science and the
Dedicating my research to analytical Chemistry Department,
spectroscopy and its applications, I at University of Central Florida, in
have always mixed all the evolving Orlando, Florida.

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Biomedical Applications of
Raman Introduction to ICP-OES and ICP- LIBS
Applications SERS and TERS Spectroscopy MS Techniques Analysis Raman Spectroscopy
Charles Mann Award

Biomedical Applications
of Raman Spectroscopy
Over Several Decades
An Interview with Yukihiro Ozaki
CK/stock.adobe.com
O
verall, the application the use of Raman spectroscopy for
of Raman spectroscopy biomedical applications requiring in
has yielded a greater situ measurements where no sample
understanding of multiple preparation or manipulated pathlength
biomedical problems. We interviewed of samples is permitted. Raman
Yukihiro Ozaki, professor emeritus and spectroscopy is being used for tissue
a university fellow at Kwansei Gakuin examination, for discovering disease
University in Japan, about his work in mechanisms and etiology, and for
this field. Ozaki is the winner of the 2020 determining the detailed spatial chemical
Charles Mann Award for Applied Raman composition of tissue structures for
Spectroscopy, to be given at the 2020 diseased and normal tissues. In biology,
SciX conference, for his Raman work in Raman spectroscopy has been used to
biomedical applications. This interview nondestructively measure component
is part of a series of interviews with changes in proteins and other
winners of awards presented at SciX.
Raman spectroscopy has become Yukihiro Ozaki, PhD
Professor emeritus, guest fellow, guest
an important analytical technique for professor, guest principal researcher
exploration of organic and inorganic Kwansei Gakuin University, Toyota
RIKEN, Peking University, Kobe
compounds for applications from University, and Fukui University, RIKEN
astrobiology to zoology. Since the 1980s,
there has been an interest in exploring

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metabolites affected by variations in of this paper is to describe protein-

environmental conditions, genetics, and mediated SERS-active substrates
metabolic activity. The enhancement of for application as both label-free
Raman signals by the use of surface- and Raman dye-labeled protein
enhanced Raman spectroscopy (SERS) detection methods These methods
and resonance Raman spectroscopy
provide tools for the study of
has led to an improved understanding
protein-controlled processes within
of their mechanisms and also to the
development of bioassays, such as
living cells. How did you become
enzyme immunoassays and quantitative
interested in this subject?
analysis of double-stranded DNA, When I was a PhD student at Osaka
amplified by polymerase chain reaction University, I investigated resonance
(PCR). Overall, the application of Raman Raman spectroscopy of hemeproteins
spectroscopy has yielded greater at the Institute for Protein Research of
understanding of multiple biomedical Osaka University. After I got my PhD,
problems. We interviewed Professor I became a research associate at the
Yukihiro Ozaki, professor emeritus and National Research Council of Canada,
a university fellow at Kwansei Gakuin where I was involved in enzyme research
University in Japan, about his work in using a resonance Raman label method.
this field. Ozaki is the winner of the Therefore, I have strong background
2020 Charles Mann Award for Applied for both Raman spectroscopy and
Raman Spectroscopy to be given protein research since the 1970s. When
at the 2020 SciX conference for his I encountered SERS, I just thought of
Raman work in biomedical applications. highly sensitive detection of proteins by
This interview is part of a series of SERS. Then, I started studies on protein-
interviews with winners of awards mediated SERS-active substrates for
presented at SciX. application as both label-free and Raman
dye-labeled protein detection methods
with Dr. Xiaoxia Han, who was a postdoc
One of your most cited papers in our group.
to date on the subject of Raman
spectroscopy (1) reviews the In your work, you have described
development of SERS-based both resonance Raman and
methods for proteins. The emphasis SERS spectroscopy. Why are
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Infrared
these techniques important How is the Raman spectroscopy

and what are the differences work you have done different from
between resonance Raman what others have done previously?
spectroscopy and SERS for In my opinion, among various optical
biomedical applications, in terms molecular spectroscopy techniques,
of sensitivity and specificity? Raman, near-infrared (NIR), and
For biomedical applications, normal fluorescence spectroscopy are the most
Raman, resonance Raman, and SERS important for biomedical applications.
are all very important. The sensitivity Fluorescence spectroscopy has very
and specificity are low for normal high sensitivity, and, thus, it is very
Raman, but normal Raman will detect suitable to detect a tiny number of
most biomolecules nonspecifically, biological components. Fluorescent
such as proteins, lipids, nucleic acids, spectroscopic imaging is also a
and so forth. It can detect everything powerful technique for biomedical
in tissues and cells. Resonance applications. A disadvantage of
Raman spectroscopy has much higher fluorescence spectroscopy is that one
sensitivity and specificity than normal cannot explore structural changes of
Raman, but resonance Raman cannot biological molecules such as proteins.
detect lipids and proteins, except The advantage of NIR spectroscopy is
for those such as hemeproteins and that it has very high permeability. NIR
metalloproteins, unless one uses enables us to probe whole biomedical
UV-resonance Raman spectroscopy. materials or whole living bodies in situ;
However, resonance Raman is useful one can examine even their internal
for highly sensitive and selective structures nondestructively. There is
detection of biological pigments now a big research filed named fNIR
such as carotenoids. SERS has the (functional NIR) spectroscopy. The
highest sensitivity and selectivity, disadvantages of NIR spectroscopy
but SERS always requires silver or are that sensitivity and specificity are
gold nanoparticles, which are not relatively low. Spectral analysis is also
always biocompatible. Therefore, not straightforward for NIR. Compared
it is important to use these three with fluorescence spectroscopy and NIR
methods properly, depending on the spectroscopy, Raman spectroscopy can
research purpose. detect proteins, lipids, and nucleic acids

Emerging Leader in
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separately and one can disclose their SERS imaging, and TERS imaging. So,
structural changes. However, sensitivity Raman imaging offers a very wide set of
for normal Raman spectroscopy is imaging capabilities. The existing issues
rather low. of spectroscopic imaging are the speed
of the imaging measurement, the ability
to image materials with roughness,
You have edited a text on the and the analysis of depth direction.
analytical methods of Raman, Raman spectroscopy imaging has strong
infrared (IR), and NIR chemical potential for solving these issues.
imaging (2). You are one of the
few researchers who has made
major contributions using all three In an earlier article, you wrote about
spectral measurement regions. the use of Raman spectroscopic
From your perspective, what are the imaging with an emphasis on
applications of Raman imaging that the chemometrics used for data
highlight its advantages over IR and processing (3). What did you learn
NIR imaging? regarding the unique properties
of Raman spectra and how
One of my strong points is I have
been involved in all three spectral
chemometrics can best be applied
measurement regions: Raman, IR, to Raman data?
and NIR spectroscopy. So, I can Chemometrics was used first for NIR
evaluate fairly these spectroscopies. spectroscopy, because NIR spectra often
The advantage of Raman imaging over have high multicollinearity. Nowadays,
IR and NIR imaging is its high special chemometrics is powerful for all kinds of
resolution. Even without using tip- spectroscopy. For Raman spectroscopy,
enhanced Raman spectroscopy (TERS), from time to time chemometrics
one can obtain a spatial resolution of is highly useful (3), but sometimes
300 nm by using Raman. If one uses Raman does not require chemometrics
SERS imaging, one can expect higher because Raman bands are sharp
sensitivity and selectivity over IR and compared with NIR bands. Generally
NIR imaging. In Raman imaging, it is speaking, chemometrics is useful for
possible to properly use normal Raman the discrimination of Raman spectra and
imaging, resonance Raman imaging, qualitative analysis of Raman spectra,

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but not always suitable for quantitative and a SERS measurement system
analysis of Raman spectroscopy, for the same single nanoparticle.
particularly when Raman spectral We measured SERS and plasmon
intensity is fluctuating. resonance spectra, and EM images,
and based on this information we
calculated the SERS spectra. By
You have made significant comparing the experimental SERS
contributions to the biomedical spectra with the calculated ones, we
applications of SERS. Your succeeded in quantitative verification
contributions include the of the electromagnetic enhancement
elucidation of the SERS effect. A group at Jilin University in
electromagnetic mechanism (4), as China and our group also contributed
well as discovery research related to the studies of chemical effects
to the chemical mechanism of SERS and semiconductor-enhanced Raman
(5,6). Would you summarize for our scattering (5). Our recent study on
the Mie resonance scattered near-
readers what your main discoveries
field effect provided a coherence
were in this work?
framework for modeling the
The SERS mechanism had been electromagnetic mechanism of SERS
investigated by an ensemble on semiconductors (6).
nanoparticle system, where the
cause of the enhancement (plasmon
resonance) was averaged, and,
What were some of the key
thus, it was difficult to elucidate
challenges you encountered
directly the relation between the
cause and the result (SERS). Dr.
during your career of teaching and
Tamitake Itoh, who was a postdoc in
research?
my group, thought of using a single The key challenges I encountered
nanoparticle system to solve this during my career of teaching and
problem (4). We developed a new research were finding my academic
experimental setup for studying the position; recruiting students,
SERS mechanism consisting of an postdocs, and collaborators; and
electron microscope (EM), a plasmon getting funding. Here, I would like
resonance measurement system, to mention something about the

Emerging Leader in
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Infrared
second point. For recruiting, I placed disease by Raman spectroscopy (7).

an emphasis on collecting people The second is the establishment of
who have different backgrounds. I application of NIR spectroscopy to
belonged to a chemistry department, physical chemistry (8). The third is the
so I had enough chemists. But in proposal of ATR-far-ultraviolet (FUV)
my group, I always included a few spectroscopy (9)
people who had a strong background
in physics. This has been quite
successful. I also accepted people Would you share with our
from bioscience, pharmaceutical readers your philosophy for work
science, agricultural science, and so and success in an academic
on. As a result, our group was always research career?
full of new ideas. Moreover, our The group motto of our research
group was always quite international group is “top among the top” and our
and big, and, thus again, I have been mission is “promoting science and
surrounded by new ideas and high application of molecular spectroscopy
energy. From our group, about 50 throughout the world.” The most
people have obtained their PhD. Also, important things in my philosophy
about 50 people have joined our for work and success are to have
group as postdoctoral fellows and ambition and consider working on
assistant professors. About half of significant contributions that benefit
them were foreigners; we were able the world.
to establish quite an international
group. Currently, many of them References
are very active in academia and 1. X.X. Han, B. Zhao, and Y. Ozaki, Anal. Bioanal.
Chem. 394(7), 1719–1727 (2009).
industries.
2. S. Sasic, and Y. Ozaki, eds., Raman, Infrared,
and Near-Infrared Chemical Imaging (John
What would you consider Wiley & Sons, Hoboken, New Jersey, 2011).
to be the most meaningful 3. H. Shinzawa, K. Awa, W. Kanematsu, and Y. Ozaki,
contributions of your work? J. Raman Spectrosc. 40(12), 1720–1725 (2009).
4. T. Itoh, Y.S. Yamamoto, and Y. Ozaki, Chem.
I have three most meaningful Soc. Rev. 46(13), 3904–3921 (2017).
contributions. The first is the first
5. X.X. Han, W. Ji, B. Zhao, and Y. Ozaki, Nanoscale
trial of the studies of mechanism of 9(15), 4847-4861 (2017).

Emerging Leader in
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Infrared
6. W. Ji, L. Li, W. Song, X. Wang, B. Zhao, and Y. Ozaki is a professor emeritus and
Ozaki, Angew. Chem. Int. Ed. 58, 14452 (2019).
a university fellow at the Kwansei
7. Y. Ozaki, Appl. Spectrosc. Rev., 24, 259–312
(1988).
Gakuin University, a guest fellow of
Toyota RIKEN, a guest professor of
8. M. A. Czarnecki, Y. Morisawa, Y. Futami, and
Y. Ozaki; Advances in Molecular Structure Peking University, Kobe University,
and Interaction Studies Using Near-Infrared and Fukui University, and a guest
Spectroscopy, Chem. Rev., 115, 9707–9744
(2015). principal researcher of RIKEN. Ozaki
9. Y. Ozaki, Y. Morisawa, A. Ikehata, and N. has been internationally known in the
Higashi; Far-Ultraviolet Spectroscopy in the research and education of physical
Solid and Liquid States: A Review, Appl.
Spectrosc., 66, 1 (2012).
chemistry, analytical chemistry,
and spectroscopy for the past four
decades. He was a senior research
Yukihiro Ozaki fellow of the Chemistry Department
Yukihiro Ozaki graduated from of Princeton University in 1993. He
Osaka University in 1973 with a BS is a fellow of the Society for Applied
degree in chemistry and MS (1975) Spectroscopy (since 2010), the Royal
and PhD (1978) degrees in physical Society of Chemistry (since 2015),
chemistry from the same university. The Chemical Society of Japan
After he had spent for two and a half (since 2016), and the International
years as a research associate at the Council of Near-infrared Spectroscopy
National Research Council, Canada, (since 2017). Ozaki was also given
he joined the Jikei University School a Doctorate Honoris Causa from
of Medicine in Tokyo as an assistant Jagiellonian University, Poland (2016)
professor in 1981. In 1989, he moved and from the University of Wroclaw,
to Kwansei Gakuin University, Hyogo, Poland (2019). He has received
Japan as an associate professor in multiple international awards, such
the Chemistry Department. Since as the Bomem Michaelson Award
1993, he has been a professor in the and Pittsburgh Spectroscopy Award.
Department of Chemistry, School Ozaki has published six textbooks
of Science and Technology, Kwansei and approximately 1000 papers with
Gakuin University. He was a Vice an H-index of 72. The number of
Rector of Kwansei Gakuin University citations of his papers is more than
from 2013 to 2018. Currently, 24500.

Emerging Leader in
Award: Advancing
Spectroscopy
SERS, Laser-Induced
Raman Introduction to Infrared ICP-OES and ICP- LIBS Fluorescence, Biosensors,
and Analytical Nanotools
RSC Award: the Sir George

Stokes Prize
Spectroscopy for Medicine:
From SERS, Laser-Induced
Fluorescence, and
Biosensors to Analytical
Nanotools
An Interview with Tuan Vo-Dinh
Helen Davies/stock.adobe.com
W
orking at the frontiers of of Duke University has developed
biotechnology, fiberoptics, multiple sensor technologies useful for
lasers technique, and medical research and diagnostics. His
molecular spectroscopy, contributions include the first antibody-
Tuan Vo-Dinh of Duke University has based fiberoptics fluoroimmunosensor
developed multiple sensor technologies (FIS), the first antibody-based nanoprobe
useful for medical research and for monitoring biochemical species
diagnostics. In this interview, he talks in a single living human cell, the first
about his work in spectroscopy and paper on the analytical use of surface-
photonics. Vo-Dinh is the winner of the enhanced Raman spectroscopy (SERS)
2019 Royal Society of Chemistry (UK) Sir for chemical analysis, the development
George Stokes Award and is scheduled of a laser-induced fluorescence (LIF)
to give a plenary lecture at the 2020 technique for non-invasive optical biopsy,
SciX conference, This interview is part and plasmonic nanoprobe assays for
of an ongoing series with the winners of
awards that are presented at SciX. Tuan Vo-Dinh
Duke University
Working at the frontiers of biotechnology,

fiberoptics, lasers technique, and
molecular spectroscopy, Tuan Vo-Dinh

Emerging Leader in
Award: Advancing
Spectroscopy
SERS, Laser-Induced
early cancer diagnostics. Throughout this disciplines. I strongly believe that the
work, Vo-Dinh and his research colleagues integration of different areas of science
have brought spectroscopy to biomedical and technology is needed to provide
applications. In this interview, Vo-Dinh solutions to complex problems of global
talks about his work in spectroscopy and importance. More than three decades
photonics. Vo-Dinh is the winner of the ago, I collaborated with a team of
2019 Royal Society of Chemistry (UK) Sir chemists, spectroscopists, and biologists
George Stokes Award and is scheduled from Oak Ridge National Laboratory
to give a plenary lecture at the 2020 SciX (ORNL) and the University of Tennessee
conference, which takes place October to integrate molecular spectroscopy,
11–16 in Sparks, Nevada. This interview is fiberoptics technology, laser techniques,
part of an ongoing series with the winners and molecular biology; together, we
of awards that are presented at SciX. developed the first antibody-based
fiberoptics fluoroimmunosensor (FIS)
device. The FIS is a fiberoptics biosensing
For many years, you have worked device that combines antibodies designed
in the development of analytical to recognize and trap target molecules
capabilities for antibody-based of interest, laser excitation to induce
fiberoptics biosensor probes using the fluorescence emission from the targets,
concept of the fluoroimmuno-sensor and ultrasensitive optical detection. The
FIS concept was quite a “novelty item”
(FIS) (1). In early work on FIS, you had
at that time. This technology has now
proposed that these sensing probes
opened new possibilities for a wide
would prove useful in detection of
spectrum of chemical, environmental,
various analytes for cancer research, and biomedical clinical applications, such
environmental monitoring, and other as the assessment of an individual’s
health applications. How did you exposure to chemical carcinogens,
become interested in this specific monitoring response to drug therapy,
analytical approach, and how have and identification of toxic substances
these tools proved effective or useful in the environment. For instance, we
in clinical applications? demonstrated that the FIS is capable
Throughout my research career, I have of detecting DNA-adduct biomarkers of
always been interested in working at human exposure to carcinogens in human
the intersection of multiple scientific clinical samples. The FIS technology

Emerging Leader in
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SERS, Laser-Induced
opened new horizons for a fundamental different from the traditional biopsy
technology of the “smart catheter/sensor” procedures currently used for
for in vivo biomedical analysis. Today, the cancer diagnostics? Would you
usefulness of fluoroimmuno-biosensors discuss this technology and its
as powerful bioanalytical tools is well potential applications?
recognized worldwide.
In situ, rapid, and minimally invasive
In the 1990s, we expanded the procedures for tissue diagnosis are
biosensing concept in a single-fiber important for early detection and timely
approach to a multisensing platform, the treatment of cancer. Traditionally,
multifunctional biochip by combining endoscopy is used to detect abnormal
microelectronics, molecular biology, tissues in the esophagus. Once an
and biotechnology. The device was abnormality is found, biopsies are taken
one of the first chip-based 2D array for determination of histopathology.
biosensor systems combining molecular The laboratory results are generally not
bioreceptors with CMOS phototransistors available for several days. There was
integrated circuits. It was capable of an urgent need for a more practical
performing simultaneous detection of technique that would allow real-time
multiple disease end-points on a single in vivo classification of the tissue
platform by using different bioreceptors type, and provide a less invasive tool
such as antibody and gene probes. The for cancer diagnosis at lower cost. In
biochip could be used to diagnose genetic this clinical work, I collaborated with
susceptibility and diseases, monitor clinical colleagues at the Thompson
exposure to bioactive environmental Cancer Survival Center, in Knoxville,
samples, and provide an important tool Tennessee, to develop a laser-induced
for medical diagnostics at the point-of- fluorescence (LIF) technique that
care and homeland defense applications. rapidly provided effective indices to
diagnose cancer in the esophagus. LIF
measurements were conducted during
You have been involved in a clinical routine gastrointestinal endoscopic
study with the development of a examinations of patients using a
laser-induced fluorescence (LIF) fiberoptic probe inserted into the
technique for non-invasive optical biopsy channel of an endoscope. This
biopsy (2). How is this approach LIF diagnostic information could be

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available in real time without the need The SERS effect was discovered in 1977
of surgical biopsy. The LIF measurement by R. Van Duyne, J.A. Creighton, and
was completed in approximately 0.6 coworkers, who reported an enormous
seconds for each tissue site. The results intensity enhancement of Raman
of this optical approach were compared signals for some chemicals adsorbed on
with histopathology results of the roughened electrode surfaces. In 1984,
biopsy samples, and indicated excellent my team reported the first demonstration
agreement in the classification of normal of the analytical potential of the SERS
tissue and malignant tumors. The LIF effect. Until our work, the reproducibility
method was successfully tested with and quantification of SERS-active media
over 100 patients, with nearly 100% (mainly electrodes, silver sols) had been
accuracy. The LIF method could lead to a major difficulty for SERS to be used in
the development of a rapid, minimally chemical analysis. An additional limitation
invasive, and cost effective technique in the early development of SERS was
for cancer diagnosis. Such a technique that the Raman enhancement had been
that is minimally invasive, requires observed for only a few highly polarizable
no physical biopsy, and provides small molecules, such as pyridine, benzoic
instantaneous results could revolutionize acid, and their derivatives. Even the
cancer diagnostics as we know it. general applicability of the SERS effect
was still questioned in the early 1980s.
Our work on SERS analysis of several
You have also worked for many years polycyclic compounds contributed to
on the development and improvement firmly establish the general applicability of
the SERS phenomenon. We introduced a
of SERS (3,4). What were some of
new type of SERS-active substrate based
the most valuable or surprising
on a silver metal film on arrays of 30-nm
discoveries that you encountered nanoparticles. In a sense, more than three
during your research in SERS? Has decades ago and long before the hype
this technique proven to be a useful about nanotechnology, we were already
tool for trace organic analysis and adopting “nano” when nano wasn’t “cool.”
other applications? What comments The kind of SERS-active substrates we
would you have regarding the developed, also referred to as nanowaves
analytical figures of merit and or metal film on nanoparticles (MFON),
limitations of the SERS technique? has led to substantially improved

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reproducibility and quantification. Since based technology, northern blotting,

then, they have been widely adopted and sequencing, and quantitative real
used by other research groups. time polymerase chain reaction (qRT-
My lab has also developed a wide PCR) analyses are often employed,
variety of other types of SERS-active but these lab-based techniques
platforms, such as nanorods, nanodots, involve elaborate, time-consuming,
nanowires, nanostars, and nanorattles. and expensive equipment. Our team
Our SERS nanoplatforms have multiple demonstrated successful detection of
applications in environmental sensing, microRNA biomarkers for esophageal
bioenergy research, biomedical adenocarcinoma within patient tissue
diagnostics, and molecular imaging. samples without requiring sample
In 1994, we introduced a novel type amplification (no PCR needed). Our
of nonradioactive SERS-based DNA studies have demonstrated the potential
probe that could be used for genomic of the SERS-based nanoprobes for the
analysis, biomedical diagnostics, and detection of cancers (gastrointestinal
pathogen detection. A decade later, we cancer, and head and neck cancer)
developed a novel type of SERS-based and infectious diseases (HIV, dengue,
nanoprobe, referred to as molecular malaria). Our SERS nanoprobe approach
sentinels (MS) and inverse molecular could lead to an accessible strategy
sentinels (iMS), that can be used for for early diagnosis, which is a major
the detection of early biomarkers of unmet need in screening, and will
diseases. The iMS homogeneous assay have transformative potential for
format requires no washing steps and medical research as well as diagnostic
no sample amplification, due to the applications at the point of care.
intense signal amplification of SERS. We
used the iMS assay to monitor a class of I am also fascinated by the contribution
molecular targets known as microRNAs. of science and technology to the
MicroRNAs have demonstrated great sustainability of our world. In this line
promise as important biomarkers for of research, I worked with a team of
early detection of various cancers, bioengineers and plant biologists at
yet these small molecules have not Duke and physicists at Argonne National
been adopted into early diagnostics for Laboratory to further develop the SERS
clinical practice because of challenging iMS biosensing technology for renewable
analytical aspects in the lab. Microarray- bioenergy research. Knowing when and

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which genes turn on inside a plant would changes in their geometry. Incident light
be enormously useful to scientists, (for example, a laser beam) irradiating
because they could potentially select metallic nanoparticles or nanostructures
plants with preferred growth patterns or induces oscillations in the metal
control plant growth for optimizing biofuel conduction electrons. These oscillating
production. We used our technology for electrons, which are called surface
sensing and imaging specific microRNAs plasmons—hence the term “plasmonic
that regulate flowering and vegetative nanoparticles”— produce secondary
growth in plants. We demonstrated the intense electric fields concentrated at
possibility to detect and image genomic high curvature points on nanoparticles.
biomarkers in living plant leaves under The multiple sharp branches of GNS are
ambient conditions without requiring ideal structures to create the so-called
sample extraction and lab-based analysis. “lightning rod” effect that enhances the
This research sets the basis for functional local electromagnetic field dramatically,
in vivo imaging of genomic biomarkers in thus producing intense SERS signals from
plants, a much needed tool for in vivo plant molecules that are on or near the branch
biology research and biofuel development. tips, in very good agreement with our
theoretical calculations. Recognizing this
unique property, my lab first proposed
GNS as a platform for SERS sensing.
In your work you have synthesized
gold nanostars for use in SERS (5). With the goal of developing biocompatible
Are you able to tune these nanostars nanoparticles for in vivo biomedical
for specific applications? What is applications, we first introduced a
the theory and modeling approach new surfactant-free synthesis of GNS
that can be used to tune these? For that does not require toxic surfactant
chemicals often used in nanoparticle
example, you have reported that
synthesis. We demonstrated that GNS
variations in star size resulted in
optical properties could be engineered by
observed shifts of the long plasmon making subtle changes in their synthesis
band in the near-infrared (NIR) region. chemistry that resulted in geometry
Among various kinds of metallic changes. For biomedical applications
nanoparticles, gold nanostars (GNS) involving in vivo excitation in deep tissue,
are of particular interest, as they offer we demonstrated that an increase in the
optical tunability by engineering subtle branch number of GNS can shift their peak
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absorption band into the near-infrared

(NIR) region (700–1200 nm). This spectral
“It’s critical to build evidence
range is very important for in vivo medical during the clinical trial that
applications, and is often called the “tissue a differentiated outcome is
optical window,” where photons are less possible, whether it’s versus
absorbed by tissue, and can travel further
in tissue for sensing and therapy.
existing treatments, a tablet
We can also control the size of GNS such
form, or a less optimal form
that they can passively accumulate in of the same treatment.”
tumors selectively by taking advantage of heating around the tumor region, but
the enhanced permeability and retention cannot target or ablate cancer cells at
(EPR) effect of tumor vasculature for the microprecision scale. GNS, which
cancer therapy. The EPR effect is a result accumulate preferentially in and around
of the inherent leakiness of the tumor cancer cells, can be triggered with light to
vasculature, which allows nanoparticles rapidly achieve high ablative intratumoral
having certain sizes to escape the temperatures, and can also induce milder
circulation and accumulate passively fever-range hyperthermia in the tumor
in tumors. In addition, retention of microenvironment. We demonstrated
nanoparticles in the tumor is enhanced by that GNS-mediated treatment with a
the lack of an efficient lymphatic system near-infrared laser provides a controllable
that would normally carry extravasated method to photothermally treat sarcoma
fluid back to the circulatory system. in the murine tumor model. We also
For light-induced photothermal therapy showed that, in a brain cancer mouse
applications, we showed that GNS are model, it was possible to achieve selective
excellent nano-sources for heating tumor accumulation of GNS within target brain
cells ”from the inside.” In hyperthermia tumors but not in adjacent normal brain
treatment of tumors, elevating the tissue, demonstrating spatial specificity in
temperature to more than 42 °C, focal disruption of brain tumor vasculature
malignant cells are killed through apoptosis and the blood-brain barrier for potential
or necrosis. Traditional hyperthermia drug delivery applications. The combination
modalities, such as microwave, or of the EPR effect and the capacity for
radiofrequency, and focused ultrasound, efficient photon to heat conversion make
have been used to control macroscopic GNS an ideal photothermal transducer

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for selective cancer therapy at the to probe individual chemical species in

cellular level. specific locations throughout a cell. The
fiberoptics nanoprobes were covalently
Your research in 2000 described an bound with antibodies designed to target
antibody-based nanoprobe for in situ benzopyrene tetrol (BPT), a biomarker of
measurements of a single cell (6). DNA-adducts of the carcinogen benzo[a]
The nanoprobe you selected used pyrene (BaP). DNA adduct formation
involves the binding of a compound
antibody-based receptors targeted to
to DNA, a process that could damage
a fluorescent analyte, benzopyrene
DNA, resulting in abnormal replication
tetrol (BPT). You had hoped that the and, without proper DNA repair, could
detection of this BPT nanoprobe could lead to a cancerous cell. Monitoring DNA
be used as a biomarker for monitoring adducts is a strategy that could be used
DNA damage due to exposure to the to monitor the extent of environmental
carcinogen benzo[a]pyrene (BaP), and exposure and health effects on people
that this may result in a technique for before occurrence of cancer. Such a
possible precancer diagnosis. Would precancer diagnosis approach could lead
you tell our readers how these types of to appropriate pretreatment or early
probes have been applied, and what prevention actions. We focused on the
clinical applications or additional detection of BPT because it is a biomarker
research has resulted from this work? of human exposure to BaP, a byproduct of
combustion processes and a compound
Two decades ago, we developed the
of great environmental and toxicological
first antibody-based nanosensor capable
interest, due to its mutagenic and
of monitoring chemicals in a single
carcinogenic properties and its ubiquitous
living cell. The nanosensors had tiny
presence in the environment.
probes fabricated with optical fibers
pulled down to tips with distal ends of We also used nanobiosensors to
approximately 30 nm. The nano-scale monitor a molecular signaling process,
size of this new class of sensors allows apoptosis, in a single living cell that
for measurements in the smallest of was treated with a photodynamic drug
environments. One such environment for cancer. Apoptosis or programmed
that has evoked a great deal of interest is cell death is a process by which cells
that of individual living cells. Using these degenerate during normal development,
nano-biosensors, it has become possible aging, or disease. When the process

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of apoptosis malfunctions, it can lead However, many tumors have acquired the
to clinical problems such as cancer and ability to manipulate these checkpoints
neurodegenerative disease. Drugs are and to block the action of the immune
often designed to provoke apoptosis system. Drugs designed to counter-
selectively in cancer cells. Unlike block immune checkpoints have recently
traditional bioanalytical techniques, the shown efficacy in the treatment of
nanobiosensor technology could probe certain cancers. In this interdisciplinary
the cell machinery, elucidating life-and- study, I collaborated with a group of
death processes such as apoptosis. bioengineers, medical researchers, and
This will help us better understand and clinicians throughout the Duke campus
cure disease occurring at the cellular and the Duke medical school. Our team
and molecular level that were heretofore demonstrated that the use of GNS in
invisible to human inquiry. combination with a checkpoint blockade
immunotherapy drug (antiPD-L1)—a
In your research you have introduced treatment we referred to as synergistic
the concept of synergistic immune immuno photothermal nanotherapy
photothermal nanotherapy (SYMPHONY)—can dramatically enhance
(SYMPHONY) for potential cancer the efficacy of immunotherapy. Our
treatment of inoperable cancer sites studies indicated it is possible to achieve
(7). Would you explain this approach complete eradication of primary treated
and any further results or insights that tumors as well as distant untreated
tumors in mice implanted with a bladder
have been gained from this work?
cancer cell line. GNS were designed to
How does your approach differ from
efficiently absorb laser light for conversion
other forms of photodynamic therapy? into heat and to accumulate preferentially
From disease diagnostics, my research within a tumor due to the EPR effect.
interests also expanded to the treatment We now have the combined ability to
of illnesses such as cancer. We have use laser light in order to selectively and
recently seen an increasing interest in effectively treat tumor areas where GNS
immunotherapy. Molecular processes, are located while keeping surrounding
called immune checkpoints, are normally healthy tissues at significantly lower
safeguards used by the body to prevent and safer temperatures. This GNS-
inappropriate processes or control mediated photothermal treatment
overactivation of the immune response. strategy offers significant advantages

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over other traditional thermal therapies new tumor formation, indicating that the
such as ultrasound, microwaves, and combined treatment induced effective
radiofrequency, which can control long-lasting immunity that could provide
macroscopic heating around the tumor protection against tumor recurrence long
region, but cannot target or ablate cancer after treatment of the initial tumors, like
cells at microprecision scale, and cannot an “anticancer vaccine” effect. We are
differentiate tumor cells from healthy in the initial stage of this SYMPHONY
cells. Our studies showed that the project and more studies involving
effectiveness of the combination therapy larger cohorts of laboratory animals and
was synergistic and not just additive. different types of cancer cell lines are
Remarkably, we found that SYMPHONY being performed. Further fundamental
not only eradicated primary tumors studies are also being conducted by our
treated by the laser, but also induced team to obtain better understanding of
immune-mediated destruction of distant the mechanisms underlying these novel
metastatic tumors that were untreated synergistic treatment modalities, in
by the laser. The approach could provide order to help us enhance and broaden
an effective treatment when aggressive the effect of immune-checkpoint
tumors that spread throughout the body inhibitors for successful eradication of
cannot be surgically removed. It is our metastatic cancer.
hope that the SYMPHONY strategy
could lead to an entirely new treatment
paradigm that challenges traditional What were some of the key
surgical resection approaches for many challenges you have encountered
cancers and metastases. during your career of laboratory
Of great interest was our observation that research and teaching?
the SYMPHONY approach was capable Life presents plenty of challenges to
of inducing long-term immunological us, and challenges often create new
memory that can provide protection opportunities. There are important
against future tumor recurrence. In our challenges facing scientists today. With
studies involving two murine models our planet’s limited resources, we are
of bladder cancer and brain tumor now witnessing a paradigm shift from
(glioblastoma), delayed rechallenge with a development-driven society (20th
repeated tumor injections did not lead to century) to a sustainability-driven society

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(21st century). Scientists and engineers in this and coming decades will evolve
in photonics, like me, all have many into a framework to fit the new reality of
opportunities to use our knowledge, learn our world, a world that will be faced with
new skills, and apply our innovativeness and embrace cross-disciplinary, systems
to address the global sustainability and level, and global challenges. It is important
environmental challenges, and ultimately for us to educate our students, the next
contribute to a sustainable future as best generation of innovators and leaders,
as we can. not only to solve scientific and technical
problems, but also to understand societal
Another great challenge of our time is the
connections between various human
exponential increase in the complexity
activities, and create bridges between
of knowledge. In my teaching classes,
elements spanning multiple disciplines
I try to instill in my students a certain
in order to ultimately build a better
sense of scientific humility by telling
interconnected world.
them that no single discipline can solve
big problems. I hope this statement
will encourage my students to pursue
teamwork and establish cross-disciplinary What would you consider to be the
collaborations in their future careers. We most meaningful contributions of your
are now entering a new phase where the work, including patents?
knowledge of individual elements is no An invention or new technique is, in an
longer sufficient but should be combined intellectual sense, like a child that you have
and integrated in order to attain knowledge created and nurtured throughout your
at the next level; that is at the multi-scale work and scientific career. Each has its
systems level, where the information own unique features and values. Therefore,
on organization, activity and function I have no favorite invention or contribution;
requires a much higher level of complexity I cherish all of them. They all have a favorite
and sophistication. This transition from a place in my heart. I feel very fortunate to
knowledge base of individual elements have the opportunity to contribute in the
to a systems level is one of the major important field of photonics. I believe that
paradigm shifts of the 21st century, photonics is one of the ultimate enabling
and can be achieved only by integrating technologies that has played a crucial
multiple disciplines and different domains role by contributing key revolutionary and
of knowledge. Education and research disruptive advances, and will open new

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avenues and new possibilities that will professional duties. However, if you have
define the next century. Light influences a great passion for what you are doing,
our lives today in new ways that we could this is a small price to pay for a very
never have imagined just a decade ago. intellectually rewarding life experience.
As we enter a new decade, light will play Stimulating collaborative work, learning
an even more significant role, further new knowledge, and exchanges of
empowering the information revolution new ideas with colleagues from other
in global communications, creating new disciplines are added benefits that I truly
nanotools to unveil the inner world of cherish. I have had the opportunity to
matter, uncover medical cures to save work with many talented coworkers,
us from emerging global health threats, postdocs, and students; they all share
inventing new renewable energy sources, with me, as a team, all the recognitions
and galvanizing human exploration to the and honors that I have received
frontiers of the universe. throughout my career.
Would you share with our readers to What words of wisdom do you have
describe your work ethic, philosophy, for any young people interested in a
and how you plan your daily or scientific research career?
weekly work schedule? This is a most important and exciting
The career of a scientist requires a time in science. Dream out of the box.
passion to learn and discover new things Think long-term. Be patient.
with the hope that the fruit of his or her
efforts can contribute, even a very small
part, to society. I would also say that it References
involves tremendous efforts in innovative 1. T. Vo-Dinh, B.J. Tromberg, G.D. Griffin, K.R.
thinking and intellectual pursuits. It Ambrose, M.J. Sepaniak, and E.M. Gardenhire,
Appl. Spectrosc. 41(5), 735–738 (1987).
also requires large amounts of energy
2. T. Vo-Dinh, M. Panjehpour and B.F. Overholt,
for the long working hours required for Laser-Induced Differential Normalized
inventing new ideas, designing new Fluorescence Method for Cancer Diagnosis,”
US Patent 5,579,773 (1996).
devices, planning new experiments,
3. T. Vo-Dinh, M.Y.K. Hiromoto, G.M. Begun, and
writing reports, publications, and R.L. Moody, Anal. Chem. 56(9), 1667–1670
research grants, as well as many other (1984).

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4. T. Vo-Dinh, Anal. Chem. 17(8-9), 557–582 spectroscopy, molecular biology

(1998).
and nanotechnology for biomedical
5. C.G. Khoury and T. Vo-Dinh, J. Phys. Chem.
112(48), 18849–18859 (2008).
diagnostics, photoimmunotherapy,
precision medicine, and global health.
6. T. Vo-Dinh, J.P. Alarie, B.M. Cullum, and G.D.
Griffin, Nat. Biotechnol. 18(7), 764–767 (2000). Dr. Vo-Dinh has received seven
7. Y. Liu, P. Maccarini, G.M. Palmer, W. Etienne, Y. R&D 100 Awards for Most
Zhao, C.T. Lee, X. Ma, B.A. Inman, and T. Vo-
Dinh, Sci. Rep. 7(1), 1–6 (2017). Significant Advance in Research
and Development; the Gold
Medal Award, Society for Applied
Spectroscopy (1988); the Languedoc-
Tuan Vo-Dinh Roussillon Award (France) (1989);
Dr. Vo-Dinh is R. Eugene and Susie the Scientist of the Year Award,
E. Goodson Distinguished Professor ORNL (1992); the Thomas Jefferson
of Biomedical Engineering, Professor Award, Martin Marietta Corporation
of Chemistry, and Director of the (1992); two Awards for Excellence
Fitzpatrick Institute for Photonics at in Technology Transfer, Federal
Duke University. After high school Laboratory Consortium (1995, 1986);
in Vietnam, he pursued studies in the Lockheed Martin Technology
Europe, receiving a BS in physics Commercialization Award (1998); the
at EPFL-Lausanne (1970) and a PhD Distinguished Inventors Award, UT-
in physical chemistry at ETH-Zurich Battelle (2003); the Distinguished
(1975). Before joining Duke University Scientist of the Year Award, ORNL
in 2006, he was Director of the (2003); the Exceptional Services
Center for Advanced Biomedical Award, U.S. Department of Energy
Photonics and a Corporate Fellow, (1997); the Award for Spectrochemical
one of the highest honors for Analysis, American Chemical Society
distinguished scientists at Oak Ridge (ACS) Division of Analytical Chemistry
National Laboratory (ORNL). His (2011); and the Sir George Stokes
main research goal is focused on Award, Royal Society of Chemistry
developing advanced technologies to (United Kingdom (2019). He has
protect the environment and human authored over 500 publications,
health. His research has centered is a Fellow of the U.S. National
on the development, integration and Academy of Inventors and holds over
application of biophotonics, molecular 50 patents.

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Micro-SORS for Research

Raman Introduction to Infrared ICP-OES and ICP- LIBS in the Conservation of
Cultural Heritage
Craver Award:
Micro-Spatially Offset
Raman Spectroscopy
(Micro-SORS) for Research
in the Conservation of
Cultural Heritage
An Interview with Claudia Conti
khamkula/stock.adobe.com
I
n this interview, Dr. Claudia using an invasive and destructive
Conti, a senior researcher cross section approach, which for
at the Institute of Heritage obvious reasons is completely
Science (ISPC) of the Italian unsatisfactory. The use of micro-
National Research Council (CNR), SORS provides a breakthrough in
talks about her work in micro- noninvasive and nondestructive
spacially offset Raman spectroscopy analysis of the subsurface layers of
(micro-SORS). Micro-SORS is a new artworks and is a key development
method for the chemical analysis, in the understanding of conservation
identification, and assessment of science for cultural heritage objects.
decay of cultural heritage objects. Conti is the winner of the 2020
The ability to measure the chemistry Craver Award presented by the
of multilayered, micrometer-scale Coblentz Society, to be given at the
structures is providing the answers 2020 SciX conference for her Raman
and knowledge base from which
to catalog and construct artwork Claudia Conti
histories and the decay processes of Senior Researcher
Institute of Heritage Science (ISPC) of
priceless cultural treasures. Before the Italian National Research Council
the development of micro-SORS, (CNR)
subsurface molecular analysis of
valuable objects was performed

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Cultural Heritage
research. This interview is part of a Zerbi, suggested that I attend the

series of interviews with winners of ICORS conference in Boston (2010),
awards presented at SciX. where I became aware of a novel
tool developed by Professor Pavel
Matousek that enables Raman
sensing deep inside turbid media
You have worked with
on a macro-scale. Right from the
SORS related research for
beginning, I realized the strong
several years and were able impact that this method could
to demonstrate its utility have in conservation sciences,
for analysis paintings (1). permitting the noninvasive molecular
Specifically, you were able to identification of pigments and decay
penetrate the topmost highly and conservation products through
turbid layers of paintings to the stratigraphy volume of paintings,
measure and analyze the pure frescoes, painted sculptures, and
Raman spectra of paint sublayers so forth. In fact, the knowledge
completely obscured by the of the subsurface composition of
paint overlayers. What prompted artifacts is critically important in
you to explore this approach to conservation sciences: Beyond
surface layer analysis? Since the surface there are a number
this work, do think that SORS has of hidden compounds, selected
by the artist or formed during the
lived up to your expectations, or
decay processes or applied over the
from your perspective are there
centuries for conservation purposes.
still further instrumentation
Scientists are required to provide the
or method developments that conservators and art historians with
are required to make this an the elucidation of these puzzles to
optimized analysis method? facilitate comprehensive knowledge
After my PhD in Materials of these objects to enable proper
Engineering at Milan Polytechnic planning of the conservation actions;
(2010), I searched for new innovative to reach this goal we need to develop
solutions to face critical needs in noninvasive methods, one of the
conservation of cultural heritage. most vital research activities of the
My supervisor, Professor Giuseppe last decades in our field.

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Cultural Heritage
At the beginning of the collaboration micro-SORS measurements in situ

with Professor Matousek, macro- with portable devices.
scale SORS did not live up our
expectations because it did not
work with our samples. Then we What are the real advantages
tried to find an alternative way of using micro-SORS for
to discriminate between painted
probing through thin painted
layers, extending SORS to the micro-
layers compared to other
scale by combining SORS with
microscopy. In fact, conventional
analytical methods, including
SORS is only applicable to relatively
confocal Raman microscopy
thick layers (on the order of and conventional Raman
millimeters or greater), whereas the spectroscopy?
thickness of typical overlayers of the In-depth probing using conventional
concealed substances in artworks is backscattering confocal Raman
an order of magnitude or two lower. microscopy is applicable only to
After almost six years of micro- semi-transparent materials, since
SORS research, I would say that this in turbid media the diffusion of
method exceeded my expectations the light in the sample leads to
because we have found a wide subsurface Raman signal being
range of successful applications often overwhelmed and obscured by
both within as well as outside the surface Raman signals and the deep
field of cultural heritage. Based photons cannot be discriminated by
on these promising achievements, conventional confocal optics. These
and also taking into consideration deeper generated Raman photons
existing limitations, we are now are subject to a large number of
focusing on further technical and scattering events and consequently
methodological developments to end up spread further apart from
extend the noninvasive molecular each other as they reach the surface.
subsurface investigations to more Cultural heritage materials are
complex situations, for example, mainly turbid; transparent varnishes
the detection of the diffusion are an exception to this, and these
of conservation treatments into can be scanned with conventional
decayed substrates and also the confocal z-scanning. Pigments, decay

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Cultural Heritage
products, and other turbid compounds, compounds, not fully accomplished

as well as tissues and powders, need by these alternative techniques.
to be scanned with micro-SORS, which
is able to acquire and discriminate
the contribution of the sublayer from
that of the top layer, even when You have applied micro-SORS to
dealing with highly diffusive materials. artifacts of historical significance
This is achieved by enlarging the originating from Italy and dating
illumination and collection areas or from the medieval to contemporary
by collecting the Raman signal from periods (2,3). What discoveries
an area which is spatially offset from you have made on rare artifacts
the laser illumination point. So, in using this Raman technique?
other words, before the development First of all, I would highlight that our
of micro-SORS the only feasible way research produced a methodological
to study the stratigraphy of cultural discovery, going beyond the specific
heritage objects with Raman involved results achieved on the analyzed
destructive cross-sectional analysis, artworks. We were able to “see”
which should be avoided in this through the surface in a non-invasive
context. way, and get information about the
presence of hidden pigments, decay
Other analytical methods have products, and preparation layers spread
been developed for the knowledge over different substrates such as paper,
of the subsurface of cultural plaster, and stone. To name just a few
heritage materials by non-invasive examples of discoveries in artworks, we
means, such as multispectral, have analyzed prestigious Renaissance
hyperspectral and Terahertz imaging, terracotta sculpture of the “Sacred
X-ray radiography and infrared Mounts” (UNESCO World Heritage
reflectography, scanning macro sites),which have been repainted several
and confocal X-ray fluorescence, times over the centuries, thus exhibiting
and optical coherence tomography. a complex stratigraphy made of a number
The specificity of micro-SORS is of superimposed micrometric layers.
the direct retrieval of the molecular
composition of organic, inorganic, Conventional confocal Raman
crystalline and amorphous microscopy on the intact fragments

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Cultural Heritage
identified only the pigments on the lead, which was not visible to the
sample surface, and was prevented naked eye because it is covered by
by the interfering surface signal from the external pigments, emerged
seeing the composition of individual from the subsurface. This outcome
layers below the surface; in contrast, indicates the presence of a layer,
a micro-SORS analysis on the same on top of the card paper and below
intact fragment allowed the presence the external layer, applied for the
of pigments as separate (deeper) preparation of the painting. Moreover,
layers to be ascertained. It is also in a red part of the card, above the
important to be aware of the method most internal white lead layer and
limitations highlighted by the parallel below the external red layer made of
cross-sectional analysis carried cinnabar, we observed the presence
out to validate the micro-SORS of another, intermediate layer made
results: A number of compounds of Prussian blue. This is important
may not be “visible” due to their information for the understanding
weak scattering cross section or of artist’s technique and for
fluorescence, or due to their depth conservation purposes and we
being deeper than the accessible achieved this in a noninvasive way.
depth of the technique. However,
micro-SORS has demonstrated the
possibility of recovering the pigment
information from below the surface You were able to expand the
in a non-destructive way and thus use of micro-SORS from cultural
reconstructing, even partially, the heritage objects to a variety
sample stratigraphy. of other sample types where
A second example concerns a
detailed non-invasive analysis
publicity card from the 19th century of diffusely scattering turbid
that we placed directly under the layers were involved, including
Raman microscope objective without polymers, seeds, and paper (4).
any sampling. We performed mapping What was most surprising to you
of selected areas of the card, and, in relating to technique or sampling
all the micro-SORS sequences, the requirements as you moved from
Raman signal of a pigment, white cultural heritage objects to other

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Award: Advancing
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Cultural Heritage
materials? Are you able to image prepared by painting the letter “F”
or create images of surfaces using using phthalocyanine blue over a
micro-SORS? whitewashed background; two pieces
of paper colored with pink ink were
One of the most exciting experiments
used as the top layer. Conventional
outside cultural heritage was the
mapping showed only the Raman
investigation by micro-SORS of the
signal distribution of the pink ink,
structure of the wheat seed, research
whereas, with the chemical image
carried out in collaboration with the
obtained with micro-SORS mapping,
Norwegian Institute of Food. The
we were able to “read” through this
identification of diseases at an early
turbid overlayer and reconstruct the
stage is very important for the grain
graphic symbol of the letter “F.”
producers, therefore the use of
rapid and non-destructive methods
for characterization of inner grain
components is essential. The seed
has an external micrometric envelope In one research application
made of ferulic acid and an internal of micro-SORS, you analyzed
kernel containing starch. Micro-SORS medieval polychrome sculptures
experiments made it possible to from the Parma baptistery and
unequivocally discriminate the Raman Ferrara cathedral (5). What
spectrum of the envelope from that of specifically was learned from
the starch, without touching the seed.
these objects?
As for the second question, we carried In a sculpture of the Ferrara cathedral
out an exciting experiment concerned portal, painted with a red hue, we
the reconstruction of images hidden discovered that, under the external
by a turbid overlayer. We simulated red layer made of cinnabar, a second
in a laboratory environment real hidden red layer is present and made
situations encountered in cultural of minium (a bright orange red pigment
heritage that deal, for example, with made of red lead), indicating that
hidden paintings vandalized with the external cinnabar layer is most
graffiti or covered by superimposed likely a repainting. In fact, it is well
painted layers or whitewash. One known that the portals of European
of the mock-up specimens was cathedrals could have been subject

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Cultural Heritage
to more than one decorative phase, between laser illumination and Raman
probably whenever the color started collection areas. We realized that a
to look shabby due to the outdoor more sophisticated variant could be
environment and natural degradation, necessary to investigate complex
and with micro-SORS we had direct and heterogeneous materials as
analytical evidence of this historical encountered in cultural heritage. With
information. Moreover, in the same limited funds, we focused our research
sample we have found the presence of for more than one year on searching
two salts, related to decay processes; for the best technical solution; these
micro-SORS sequences and the related research efforts ultimately led to
spectral subtractions allowed us to the successful modification of a
ascertain that they are mainly diffused conventional micro-Raman, able to
on the surface and within the cinnabar separate the laser and Raman paths. In
layer. This is an outstanding outcome, this way, we fully extended the macro-
since it informs us about the migration SORS to the microscale.
and the re-crystallization processes of
soluble salts within the layers, with a One of the major obstacle in Raman
consequent effect on the mechanical spectroscopy is the fluorescence
stress of the entire system. emission from the sample, especially
when dealing with cultural heritage
materials. We have faced a critical
situation when the top layer is
fluorescent and we needed to
What were some of the key recover chemical information from the
challenges you encountered subsurface. It was tricky because it is
during your research? How did you well known that fluorescence signal
overcome them? can be much more intense than Raman,
The first major challenge emerged after and, furthermore, in our case the target
the development of the first micro- compound was covered by a turbid
SORS setup, called defocusing. This is overlayer. The challenge was very high
the most basic and easily deployable but we applied the analytical capability
micro-SORS variant, but it is not as of micro-SORS in the most advanced
effective as a full micro-SORS setup variant and it worked; at the imaged
because there is not a real separation position the Raman spectrum was

Emerging Leader in
Award: Advancing
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Cultural Heritage
overwhelmed by the fluorescence of the multianalytical approach, essential

top layer, whereas at a certain value of when dealing with complex materials
spatial offset the signal of the subsurface as encountered in the cultural
kept increasing, emerging clearly from heritage field. Portable micro-SORS
the fluorescence background. could be relevant also outside the art
field, as in forensic science and solar
cells analysis. Further optimizations
of our current portable device are
What would you consider to be still required to improve its stability
and the sensitivity; this work is in
the most meaningful contributions
progress.
of your research work? What
discovery has most impressed you?
Recently, we obtained an outstanding
result: We analyzed with micro-SORS
two 16th century panel paintings by
Would you share with our readers
Marco d’Oggiono, using a modified your philosophy of how to work in
portable instrument directly in situ. a research environment?
This is one of key goals of our From my experience, I learned that
research since the beginning, namely curiosity triggers the research. This
the development of a portable device may seem trivial, but, in practical
able to carry out micro-SORS without terms, I noticed that it is not easy to
any restrictions on the dimensions keep our minds open to new inputs,
of the artwork or its location. In fact, accepting the risk of going beyond
cultural heritage objects cannot be our comfort zone and far from what
easily moved and transferred to our we already know. Making curiosity
laboratory for analytical purposes; we prevail over habit is one of the
have to find a way to analyze them most prolific exercises we have to
where they are (museum, churches, perform every day; how does it help
historical buildings, and so forth). In me? To find researchers with whom
this context portable micro-SORS to share passion for knowledge
can be considered a very important and innovation, someone to learn
development, providing a further step from, and create a research team
toward establishing a more powerful available to overcome limitations

Emerging Leader in
Award: Advancing
Spectroscopy

Cultural Heritage
and barriers. I will never forget Claudia Conti

when my PhD supervisor, Professor
Claudia Conti is a permanent
Zerbi, pushed me to broaden my
researcher at CNR-ISPC (Institute
horizons presenting my analytical
of Heritage Science), unit of Milan.
results at one of the most important
Conti obtained a degree in geological
spectroscopy conferences in the
sciences at the University of Perugia
United States when I still was a
in the field of archaeometric problems,
PhD student. I felt inadequate for
and a PhD in materials engineering at
that, but I went to the conference,
the Politecnico di Milano working on
and I discovered that curiosity and
the analysis of chemical stability of
boldness were an integral part of
calcium oxalate in conservation and in
my work. The power of our micro-
historical films. Conti has established
SORS research is the fruitful and
expertise in the area of advanced
unceasing collaboration between
applications of vibrational spectroscopy
CNR Italian and UK teams, providing
to material analysis, particularly in the
the necessary incentive to face the
field of cultural heritage. In 2012, she
numerous challenges of the research.
established a major collaboration with
the Rutherford Appleton Laboratory
(UK) to explore a novel tool, Spatially
References Offset Raman Spectroscopy (SORS)
1. C. Conti, C. Colombo, M. Realini, G. Zerbi, that enables Raman sensing deep
and P. Matousek, Appl. Spectrosc. 68(6),
inside turbid media on macro-
686–691 (2014).
scale. This collaboration lead to the
2. C. Conti, C. Colombo, M. Realini, and P.
Matousek, J. Raman Spectrosc. 46(5), successful transformation of macro-
476–482 (2015). SORS conceptually to the area of
3. A. Botteon, C. Colombo, M. Realini, S. cultural heritage and the demonstration
Bracci, D. Magrini, P. Matousek, and C. Conti,
J. Raman Spectrosc. 49(10), 1652–1659
of a new SORS variant, micro-SORS,
(2018). capable of resolving micrometer
4. C. Conti, M. Realini, C. Colombo, K. thick layers of paint for the first time.
Sowoidnich, N.K. Afseth, M. Bertasa, Anal. Outside cultural heritage, the most
Chem., 87(11), 5810–5815 (2015).
relevant impact of her research on
5. C. Conti, A. Botteon, C. Colombo, D. Pinna,
M. Realini, and P. Matousek, J. Cultural micro-SORS concerns the biomedical
Heritage 43, 319–328 (2020) area, polymer, paper, and food fields.

Emerging Leader in
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Trace Elemental and

Raman Introduction to Infrared ICP-OES and ICP- LIBS Speciation Analysis
in Metrology
SAS Strock Award

Advancing Trace Elemental
and Speciation Analysis
with a Focus on Metrology
An Interview with Heidi Goenaga-Infante
Crystal light/stock.adobe.com
F
or more than 20 years, Heidi with the winners of awards that are
Goenaga-Infante, a science presented at the SciX conference.
fellow and the leader of the
inorganic analysis team at LGC What led you to study trace elemental
Ltd., has been working on elemental and and speciation analysis?
speciation analysis. Two recent areas My PhD supervisor, Professor Alfredo
of investigation include the analysis of Sanz-Medel at the University of Oviedo,
trace metals in biological samples and inspired me with a fascinating lecture
the study of nanomaterials. In these on the speciation work by his group in
studies, Goenaga-Infante puts particular the 1990s. This was at the very early
emphasis on metrology—advancing this stages of my university journey, and
work by developing validated reference my heart and head fell in love with the
methodologies. Goenaga-Infante is topic. Professor Sanz-Medel supervised
the 2020 recipient of the Lester W. my PhD on the “Speciation Analysis of
Strock Award from Society of Applied
Spectroscopy (SAS) and the SAS New Heidi Goenaga-Infante
England Regional Section in recognition of Science fellow and the leader of the
inorganic analysis team
her contributions to the field of analytical LGC Ltd.
atomic spectrometry, and she recently
spoke to us about her work. This interview
is part of an ongoing series of interviews

Emerging Leader in
Award: Advancing
Spectroscopy
Trace Elemental and

in Metrology
Cadmium in Biological Samples,” and this invaluable in identifying emerging areas

was followed by postdoctoral research on of high impact in which metrological
trace elemental and speciation analysis principles can play an important role to
at the University of Antwerp under improve the quality of measurements.
the supervision of Professor C. Freddy Moreover, within the organization as a
Adams. I was then fortunate to be offered whole there are many opportunities to
a permanent position at LGC Ltd. in work with different disciplines that benefit
Teddington, UK, and asked to lead a small the output of our work. One important
group developing metrological applications thing to highlight is the importance of
of speciation analysis. recruiting high-caliber scientists and having
access to state-of-the art instrumentation.
Without that, we would not be able to
Your research covers a range of deliver high-quality science in such a
areas-from metallomics research to broad portfolio of measurement areas.
the characterization of nanoparticles. My biggest overall challenge has been
How do you choose your projects, and coaching emerging scientists to deliver
what are your biggest challenges in first-class measurement solutions to key
problems as well as helping develop them
these areas?
to develop their careers within LGC.
The UK National Measurement Laboratory
(NML) at LGC is one of the top three
institutes worldwide for chemical and
You coauthored a study on quantitated
bioanalytical measurements. Our world-
iron spatial distribution in biological
leading science and method development
tissues using online double isotope
helps solve measurement challenges
dilution analysis with laser ablation–
across areas such as healthcare and food
safety, both in the United Kingdom and
inductively coupled plasma–mass
globally. As such, our project areas are
spectrometry (LA-ICP-MS) (1). Can
underpinned by a range of stakeholder and you explain the significance of this
customer needs, prioritized and reviewed work and how it can advance disease
by an expert group involving academia, model development and detection of
industry, clinical experts, and government neurodegenerative diseases?
representatives. LGC’s presence in the I wish I could say that our work directly
atomic spectrometry community is impacts the treatment and cure of

Emerging Leader in
Award: Advancing
Spectroscopy
Trace Elemental and

in Metrology
these chronic diseases affecting many is invaluable to validate existing

of our friends and families, but our higher throughput methods used for
contribution is rather modest, although medical research as carried out by our
important. The role of metals, including collaborators and stakeholders across the
iron (Fe) in the diagnosis or treatment of United Kingdom.
neurodegenerative diseases, has been
studied by many groups. Having reliable
methods to image key disease biomarkers You developed a systematic
and monitor targeted treatments or approach to accurately quantitate
drugs is essential to the development plasma selenoprotein P (SEPP1)—a
of improved therapies. LA-ICP-MS is biomarker for human nutrition and
a powerful tool for determining the disease—at clinical levels using
spatial distribution of elements, both
species-specific double isotope
endogenous and externally tagged to
dilution MS (2). What is the impact of
biological samples, such as preclinical
this work?
or post-mortem brain tissue. However,
the relationship between the intensity The output of this work was a validated
of the element and the concentration reference methodology for SEPP1. This
at which it is present is often biased is the major selenoprotein in plasma
by matrix effects. Therefore, absolute responsible for transport and distribution
concentrations obtained by reliable of selenium (Se), which is a key essential
calibration strategies in the absence of element to human health. SEPP1 has
reference materials are urgently needed been associated with neurodegenerative
to help validate measurements by non- diseases, such as Alzheimer’s disease and
destructive techniques. With this in mind, type 2 diabetes. Considering that SEPP1
our work has described a reference is a biological active form of selenium and
methodology based on the use of LA- most of the plasma selenium is associated
ICP-MS with isotope dilution analysis for with is this protein, it represents one
the accurate quantification of the spatial of the most accurate selenium-status
distribution of iron in a model-tissue biomarkers for human nutrition. For
sample. A comprehensive estimation of clinical purposes, SEPP1 has usually
the associated measurement uncertainty been characterized and quantified using
for the analyte spatial distribution was antibody-based enzyme immunoassays
also achieved. Our high-level approach such as ELISA. However, those assays

Emerging Leader in
Award: Advancing
Spectroscopy
Trace Elemental and

in Metrology
often suffer from a lack in selectivity, and enhanced, unique properties of great
results are usually associated with high commercial and societal value. Measuring
standard deviation values. Hence, there the number concentration of nanoparticles
are some inconsistencies and lack of in colloidal suspension is a major
data comparability in the results obtained interest for a large range of industries,
for SEPP1 in humans. Since developed, including the pharmaceutical, personal
our methodology has been actively used care, cosmetics, and food packaging
to estimate the bias of ELISA results industries. Such methods are invaluable
for SEPP1 in clinical research led by to underpin industry measurements. They
collaborators from hospitals in the United also help industry to ensure the quality
Kingdom and from overseas. It is planned and efficacy of products and compliance
to use such a valuable measurement with legislation. A number of methods
tool for the production of new speciated capable of measuring particle number
reference materials that the community concentration in colloidal suspensions
can use to validate their measurements have been proposed, but neither SI-
and also to provide reference values to traceable approaches nor reference
clinical trials involving selenium and its materials certified for nanoparticle number
species as mediating agents. concentration were available when we
did the work. Therefore, in our role as a
National Measurement Laboratory, we
In a recent study, you developed undertook the challenge of developing and
and validated a methodology for validating a methodology traceable to the
the accurate determination of SI, enabling the determination of analyte
number concentration of inorganic transport efficiency (TE) on the basis
nanoparticles using single-particle of weight measurements, only without
the need for a reference material for
ICP-MS (spICP-MS) without a
calibration. Because the approach is based
nanoparticle reference material
on direct and continuous measurements
(3). Why did you undertake this
of the weight of sample uptake and the
project? What challenges did you weight of sample reaching the plasma
face in this work? online over time (sample mass flow) while
Nanomaterials are increasingly being the ICP-MS system is in equilibrium,
used in innovative products manufactured we named it the “dynamic mass flow”
by advanced industries and provide method. We faced great challenge; in

Emerging Leader in
Award: Advancing
Spectroscopy
Trace Elemental and

in Metrology
particular, elucidating whether there Receiving such a prestigious award made

was agreement between the mass- me feel very honored, and to be honest,
based TE of the sample solution and it took me by surprise. It increases my
the nanoparticle-based TE was the most motivation to achieve my best, and to
critical. It is important to note that in this keep seeking new opportunities. I wish to
work, a conventional nebulizer with a express my thanks those that have helped
cooled spray chamber (2 °C) was used. me and mentored me during my career,
This helped reduce the amount of water to my wonderful team at LGC, and last
vapor (produced from evaporation of water but not least, to those who nominated
from the aerosol in the spray chamber) me, and to the Society for Applied
entering the plasma, thus minimizing Spectroscopy (SAS) for the award.
the contribution of this source of error
to the uncertainty of the mass-based TE.
Therefore, investigation of the feasibility of Where is the future of your work
the dynamic mass flow (DMF) approach headed?
to obtain accurate nanoparticle number
Our mission is to maintain our capability
concentration data when using interfaces
on core areas of metrology (high accuracy
operated at ambient temperature or
elemental, isotope ratio, and speciation
other types of nebulizers (such as high
and metallomic analysis), as well as
transport efficiency nebulizers) is still
continue bringing our metrology impact
ongoing. Having said that, the DMF
to emerging areas of research such as
method shows promise for the validation
the characterization of nanomaterials. This
of other laboratory techniques for particle
work will focus on application areas driven
number concentration. It has also been
by legislation and with a keen interest in
demonstrated to be useful for the
nanomedicine. Also, more effort will be
characterization of quality control nano-
put into establishing a multidisciplinary
objects (such as LGCQC5050) that can be
platform for biomarker quantification and
used with the particle frequency or size
imaging of tissue down to single cells.
methods in a more targeted manner for a
This work will support medical research
range of applications.
into the diagnosis and treatment of chronic
diseases like cancer, neurogenerative
diseases, and Wilson’s disease. A
What does the Lester W. Strock significant amount of our time and effort
award mean to you? will continue to be dedicated to providing
Emerging Leader in
Award: Advancing
Spectroscopy
Trace Elemental and

in Metrology
calibration services for reference material quantitative elemental bio-imaging,

certification and for proficiency testing and and the characterization of “speciated”
clinical trials. reference materials and standards.
Goenaga-Infante is the UK
References
representative at the Inorganic Analysis
1. D.N. Douglas, J. O’Reilly, C. O’Connor, B.L. Sharp,
and H. Goenaga-Infante, J. Anal. At. Spectrom. 31, Working Group of the international
270–279 (2016). DOI: 10.1039/c5ja00351b. Consultative Committee for Metrology
2. (2) C.L. Deitrich, S. Cuello-Nuñez, D. Kmiotek, F.A. in Chemistry (CCQM). She is also a
Torma, M.-E. Del Castillo Busto, P. Fisicaro, and H.
Goenaga-Infante, Anal Chem. 88(12), 6357–6365
member of the international advisory
(2016). boards of Analytical and Bioanalytical
3. (3) S. Cuello-Nuñez, I. Abad-Alvaro, D. Bartczak, Chemistry and the RSC journal
M.E. del Castillo Busto, D.A. Ramsay, F. Pellegrino, Metallomics and of the Editorial Board
and H. Goenaga-Infante, J. Anal. At. Spectrom.
Advance Article (2020). DOI: 10.1039/c9ja00415g. of the Journal of Analytical Atomic
Spectrometry, and a member of IUPAC.
She is the Government Chemist
representative on the Nanomaterials
Heidi Goenaga-Infante Environment and Health Government
Heidi Goenaga-Infante has more than Group chaired by the UK Department
20 years of experience in elemental of Environment, Food, and Rural Affairs
and speciation analysis, starting with (DEFRA) and the LGC representative
her PhD at Oviedo University, Spain. to ISO TC 24 (Particle characterization).
She joined LGC in 2003 as a senior She is the EURAMET representative
researcher in speciation analysis, and for inorganic analysis at the CCQM
is currently a science fellow. She is Key Comparison Working Group. She
also the principal scientist and team has acted as the coordinator of the
leader of the Inorganic Analysis team, EU EUROPEAN Metrology Research
leading 14 PhD and postgraduate Proposal (EMRP) NanoChop “Chemical,
scientists. Her group currently Optical and Biological characterisation
focuses on trace element speciation of Nanomaterials in Biological
analysis, metallomics research, the Samples.” She is the lead author of
characterization of nanomaterials, more than 106 scientific research
high-accuracy isotope ratio analysis, papers and five book chapters.

Emerging Leader in
Award: Advancing
Spectroscopy
Shifted Excitation Raman

Raman Introduction to Infrared ICP-OES and ICP- LIBS Difference Spectroscopy for
Analyzing Soil and Meat
SAS Meggers Award

with Shifted Excitation
Raman Difference
Spectroscopy
An Interview with Kay Sowoidnich
Helen Davies/stock.adobe.com
K
ay Sowoidnich, PhD, is a research limitations, and his work using spatially
associate with Laser Sensors offset Raman spectroscopy (SORS) to
Lab at the Ferdinand-Braun- diagnosis skeletal disorders.
Institut, Leibniz-Institut für
Höchstfrequenztechnik, and one of the
2020 winners of the Society for Applied You’ve been applying SERDS for
Spectroscopy William F. Meggers Award. the analysis of soil, food, and other
His group have been able to demonstrate constituents for several years (1, 2).
the potential of shifted-excitation Raman How has this analytical technique
difference spectroscopy (SERDS) as an proven to be advantageous for soil
efficient tool for soil nutrient analysis.
and food analysis? What type of
Additionally, his previous research impact could it have on precision
work applied SERDS for the analysis agriculture and for food supplies?
of meat could enable rapid screening
of large numbers of meat samples for
authentication and quality monitoring Kay Sowoidnich, PhD
research associate with Laser
purposes at different points along Sensors Lab
the distribution chain from the Ferdinand-Braun-Institut
slaughterhouse to the supermarket.
We spoke with Sowoidnich about his
work applying SERDS, its impact and

Emerging Leader in
Award: Advancing
Spectroscopy

Conventional Raman spectroscopy allows developed and realized at Ferdinand-

obtaining chemically specific information Braun-Institut, Leibniz-Institut für
from numerous samples, and is a powerful Höchstfrequenztechnik (FBH). Heinz-
tool for qualitative and quantitative Detlef Kronfeldt’s laser spectroscopy
analysis. As Raman scattering is usually group at Technical University Berlin
a weak effect, interfering contributions had established a fruitful collaboration
can easily mask the characteristic with Dr. Bernd Sumpf and Dr. Martin
Raman signals,and thus complicate or Maiwald from FBH, and we were
prevent meaningful sample investigation. able to use unique diode lasers for
Prominent examples of such interferences our Raman and SERDS experiments.
are laser-induced fluorescence and, Within a collaborative research project,
driven by improvements in the sensitivity SERDS has successfully been applied
of portable Raman instrumentation, for the noninvasive optical discrimination
various types of ambient light. Among between meat of selected animal
other techniques, SERDS is a powerful species, exemplarily demonstrated
instrumental approach to address this for beef, pork, chicken, and turkey.
issue by separating Raman signals from Furthermore, Raman investigations could
unwanted light contributions using a dual- demonstrate the noninvasive quantitative
wavelength excitation light source. If two detection of meat spoilage with respect
slightly shifted excitation wavelengths are to legal limits. In the future, this could
used to record two Raman spectra, then enable rapid screening of large numbers
the Raman signal positions will follow that of meat samples for authentication,
shift in wavelength, while fluorescence and quality monitoring purposes at
and other quasistatic contributions will different points along the distribution
remain virtually unchanged. Subtracting chain from the slaughterhouse to the
the two recorded Raman spectra supermarket. The nondestructive Raman
can thus effectively retain the Raman technique could become a valuable asset
spectroscopic information while removing for food inspectors, enabling analysis
the unwanted interferences. of large production batches rather
Diode lasers are well-suited as than relying on random sampling and
excitation light source for SERDS, as cumbersome laboratory analysis. The
they offer compact size, low-power topic of Raman spectroscopy for food
consumption, and high efficiency. Such analysis has further been developed by
innovative and customized lasers are my former colleague Dr. Heinar Schmidt

Emerging Leader in
Award: Advancing
Spectroscopy

at University of Bayreuth. His group What types of limitations does SERDS

conducted successful Raman trials for present when, for example, using it to
meat inspection in a slaughterhouse as investigate fluorescent heterogenous
well for on-site inspection of Australian samples (3, 4)? How do you overcome
lamb meat using a portable device at these limitations or challenges?
671 nm excitation.
SERDS is based on the alternate and
During my current role within the Laser subsequent recording of Raman spectra
Sensors Lab at FBH, our group was able excited at two slightly shifted wavelengths.
to demonstrate the potential of SERDS as Using a conventional charge-coupled
an efficient tool for soil nutrient analysis. device (CCD) detector, one SERDS cycle
Currently, soil investigations require would then comprise the following steps:
sample collection followed by complex 1) exposure at first wavelength, 2) read-
and time-consuming laboratory analysis. out of Raman spectrum recorded at
Optical methods could be very beneficial first wavelength, 3) exposure at second
in this instance, as they enable rapid wavelength, and 4) read-out of Raman
analysis without prior sample collection. spectrum recorded at second wavelength.
Conventional Raman spectroscopy If, during that period of time ,unwanted
can provide information on the present background interferences are not
molecular species, but suffers from constant, residual artifacts could remain
fluorescence from soil organic matter. after subtraction of the two spectra,
Here, SERDS could enable in situ soil and this would compromise qualitative
investigations at a large number of spots and quantitative analysis. Potential
across the whole field, thus allowing examples are fluorescence quenching,
mapping the distribution of relevant sample or instrument movement in
soil components, including nutrients. case of heterogeneous specimens, and
This could be a major advantage, as varying ambient light intensities. Faster,
the needs-based precision fertilization ideally quasi-simultaneous, acquisition of
is already possible with state-of-the-art SERDS spectra would therefore be highly
farming equipment. But to fully exploit beneficial to address this issue. On the
this benefit, it would require knowledge excitation side, this will require a dual-
of spatially-resolved information about the wavelength light source with reproducible
actual soil status that is not yet available and fast-shifting capabilities between
from current analytical methods. the two emission lines. Such lasers have

Emerging Leader in
Award: Advancing
Spectroscopy

readily been demonstrated, for example, are generated by Raman scattered light
by FBH with rapid modulation up to the excited at the first excitation wavelength.
kilohertz range. The limitation rather lies This alternate shifting procedure is
on the detection side, where one could repeated until sufficient charge in the two
reduce the individual exposure times. distinct areas on the CCD, corresponding
However, there is a fundamental physical to charges generated by Raman scattered
limit to the time required to read out the light at the two excitation wavelengths,
charges from the CCD in conventional is accumulated. Finally, only one read-out
operation mode. step at the very end is performed.
During my time at the United Kingdom’s Through a prolific cooperation between
Science and Technology Facilities Council STFC and FBH, which developed a
(STFC), I was working in the Central custom 830 nm diode laser with tailored
Laser Facility (CLF) under the supervision electro-optical properties, putting special
of Professor Pavel Matousek, who is emphasis on fast wavelength switching,
a brilliant scientist full of exciting new the charge-shifting SERDS approach
ideas. He came up with a neat solution by has been realized experimentally. Using
combining the advantages of SERDS with a stock CCD that has been modified
the benefits of a charge-shifting approach. according to our requirements, we
The basic concept of charge-shifting CCD could successfully demonstrate
operation was proposed in 1990, while a alternate recording of Raman spectra
pilot study in 2008 by others has shown at frequencies of 1000 Hz, and that is
its suitability for conventional Raman about two orders of magnitude faster
spectroscopy. The major advantage here than speeds achievable in conventional
is that the read-out steps after each single CCD read-out mode. The reproducibility
exposure are omitted. Instead, the charges of SERDS spectra recorded on
generated by Raman scattered light exemplarily chosen heterogeneous
excited at the first excitation wavelength rock samples in charge-shifting mode
are electronically shifted towards a non- was superior to spectra recorded in
illuminated area on the CCD before conventional CCD operation. This led to
charges are generated by Raman scattered improved classification accuracy for the
light excited at the second excitation discrimination between rock species. We
wavelength. These charges, in turn, are also applied the charge-shifting concept
then shifted to another unilluminated to suppress rapidly varying ambient
area on the CCD when additional charges light interference (5) and successfully

Emerging Leader in
Award: Advancing
Spectroscopy

translated it toward sub-surface SORS works in such a way that the point
analysis using spatially offset Raman of laser illumination on the surface is
spectroscopy (SORS). set at a certain spatial distance from
the point where the Raman-scattered
photons are collected, thus probing
Through your work using SORS to subsurface layers within the sample. For
diagnosis skeletal disorders as well the development of SORS as medical
as other medical conditions, what diagnostic technique it is essential to
did you learn about the technique (6)? know from what depth the detected
How is it advantageous as a medical Raman spectroscopic information is
actually emerging for a chosen spatial
diagnostic technique? Is it currently
offset. Our photon migration study was
used clinically or are there plans for
addressing this important point, using
clinical deployment?
typical long bone tissue, as well as antler
The current gold standard for the diagnosis and bulla, to include two types of bone
of bone conditions are X-ray-based exhibiting among the lowest and highest
methods. Despite being able to assess mineralization levels found in nature.
the mineral phase of the bone very well, Results indicated that photons can more
this kind of technique is unfortunately easily migrate inside less mineralized
insensitive to collagen, the second bone tissue and that porosity can play
important component of the composite an important role as well. We were
material bone. Raman spectroscopy, in also able to estimate the approximate
contrast, is able to retrieve chemically depth from which the major Raman
specific information from both phases, signal contribution is collected for a
for example, mineral and collagen, thus given spatial offset within exposed bone
giving a more complete picture of the during SORS investigations. Under safe
overall bone status. As conventional laser illumination conditions compatible
Raman spectroscopy is restricted to the with in vivo applications even in highly
investigation of surface-near layers, we mineralized bulla depths of up to 3.8 mm
applied SORS for efficient subsurface are still accessible using large spatial
analysis. This enables us to measure the offsets in the range of 9 to10 mm.
bone composition, noninvasively, through The findings of our study significantly
the skin at selected anatomical locations, increased our understanding of SORS
such as at lower legs and fingers. analysis through bones of different

Emerging Leader in
Award: Advancing
Spectroscopy

composition, thus providing vital What would you consider to be the

information to assess the potential of most meaningful contributions of your
SORS for medical diagnostics. work?
We are aiming to develop SORS as In my opinion, the charge-shifting SERDS
a valuable tool for the noninvasive approach has made a significant impact,
in vivo diagnosis of bone disorders as it has overcome existing fundamental
and diseases. In close collaboration limitations of conventional CCD operation.
with the Royal National Orthopaedic The potential applications are numerous,
Hospital in London, we were running and the examples described in our
a preclinical SORS trial with a custom corresponding publications only cover a
instrument to apply the technique in fraction of what will actually be possible.
a clinical environment. More than 150 The underlying technology has already
patients were recruited to date, either been implemented into a novel CCD
having one of the diagnosed bone camera of one of the world’s leading
conditions—osteoporosis, osteoarthritis, companies for spectroscopic equipment.
or osteogenesis imperfecta (also known The future will show what exciting new
as brittle bone disease)—or belonging research fields can be explored by the
to a matched healthy control group enabling capabilities of the charge-shifting
without any bone condition. Within the technique. This is actually a hot topic, as in
frame of this SORS trial, for the first parallel to our study, similar research has
time, the in vivo bone disease detection been undertaken independently by Leibniz-
in case of osteogenesis imperfecta Institut für Astrophysik Potsdam (Germany)
was demonstrated. For the other bone and University of Tokyo (Japan).
conditions, particularly for less severe
cases, our results indicate a difference
between healthy and diseased bone, but Besides doing cutting-edge research, it
the differentiation is not yet statistically is equally important to communicate the
significant. We are, however, confident findings not only to scientific experts
that improvements in instrument but also addressing the layman. Another
hardware and data analysis will pave important contribution is therefore related
the way for SORS to become a routine to public outreach activities. During my
analytical technique for bone quality time at STFC’s Rutherford Appleton
assessment, complementing or even Laboratory, our group has developed a
partially replacing existing methods. SORS demonstration setup within the
Emerging Leader in
Award: Advancing
Spectroscopy

frame of the International Year of Light significant contributions to application-

2015. The instrument was basically a oriented research aiming to address
simplified version of the commercial current as well as upcoming societal
SORS devices used at airports to scan needs and global challenges. FBH’s big
liquids inside containers. During numerous advantage is that the whole value chain is
exhibitions, the SORS demo setup was located in-house, with expertise reaching
one of the most popular and most reliable from the design and manufacture of novel
exhibits highlighting an important part diode lasers with unique properties to
of STFC’s science to the public. The the application of these laser sources
instrument has been also presented to as part of customized portable SERDS
key stakeholders and decision-makers, instruments for in situ field experiments.
including the UK science minister. Due to As the area of photonic technologies
its tremendous success, a second device in general and optical spectroscopy in
was realized that is now permanently particular is a very dynamic field, I am
installed in the CLF visitor’s centers at keen to see what opportunities and
STFC’s Rutherford Appleton Laboratory. scientific challenges I will come across in
the future.
What are your plans for the future,

your next steps? References
1. FBH research, April 16, 2020. https://www.fbh-
My immediate next steps are further berlin.de/forschung/forschungsnews/detail/raman-
research efforts to establish SERDS as spectroscopic-investigations-on-soil-using-a-785-
a valuable tool for the analysis of soil, nm-dual-wavelength-diode-laser.
paving the way for efficient nutrient 2. K. Sowoidnich and H.D. Kronfeldt, Encyclopedia of
Analytical Chemistry, Wiley Online Library (2015).
management in the frame of precision https://doi.org/10.1002/9780470027318.a9510.
agriculture (the consortium Intelligence 3. K. Sowoidnich, M. Towrie, M. Maiwald, B. Sumpf,
for Soil (I4S) in funding measure Soil and P. Matousek, Appl. Spectrosc. 73, 1265–1276
(2019).
as a Sustainable Resource for the
Bioeconomy (BonaRes) by Federal 4. K. Sowoidnich, M. Maiwald, B. Sumpf, M. Towrie,
and P. Matousek, Proc. SPIE11236, 112360K (2020).
Ministry of Education and Research).
5. K. Sowoidnich, M. Towrie, and P. Matousek, J.
On a long-term scale, at FBH the Laser Raman Spectrosc. 50, 983–995 (2019).
Sensors Lab provides excellent working 6. K. Sowoidnich, J.H. Churchwell, K. Buckley, et al.,
conditions for me to make further Analyst. 142, 3219–3226 (2017).

Emerging Leader in
Award: Advancing
Spectroscopy
Advances in Spectroscopy,
Raman Introduction to Infrared ICP-OES and ICP- LIBS Biotechnology,
and Nanotechnology
The 2020 Emerging Leader

in Molecular Spectroscopy:
Advancing Spectroscopy,
Biotechnology, and
Nanotechnology
An Interview with Markita Landry
agsandrew/stock.adobe.com
B
y combining single- position at the University of California,
molecule biophysics and Berkeley. She is also currently a
nanomaterial-polymer faculty scientist with Lawrence
science, Markita Landry Berkeley National Laboratory, an
of the University of California, investigator at the Chan-Zuckerberg
Berkeley has developed new tools Biohub in San Francisco, and an
for understanding biological systems. investigator with the Innovative
Using a combination of nanoparticles, Genomics Institute in Berkeley.
imaging, and spectroscopy, her work Landry’s research focuses on the
has led to the discovery of aspects of intersection of single-molecule
neuromodulation in the brain and for biophysics and nanomaterial-polymer
the delivery of genetic materials into science to develop new tools to
plants for crop biotechnology. She is the probe and characterize biological
2020 winner of the Emerging Leader systems. Her research has generated
in Molecular Spectroscopy Award,
presented by Spectroscopy magazine. Markita Landry, PhD
Faculty scientist, investigator
Landry received her PhD from the University of California,
University of Illinois at Urbana- Lawrence Berkeley National
Laboratory, Chan-Zuckerberg Biohub,
Champaign in 2012. She then Innovative Genomics Institute in
completed a postdoctoral fellowship Berkeley
at MIT before taking her current

Emerging Leader in
Award: Advancing
Spectroscopy
and Nanotechnology
nanoparticle-polymer conjugates for work. My goal as a postdoc was

imaging and spectroscopic detection to leverage my expertise in single-
of neuromodulation in the brain, molecule biophysics to design
and for the delivery of genetic molecular recognition tools, during
materials into plants for crop which time I developed a generic
biotechnology applications. platform to create synthetic near-
infrared nanosensors (2,3), enabling
the detection of any molecule with
In recognition of her work, Landry purely synthetic molecular recognition
was scheduled to be presented the elements. When I started my lab
2020 Emerging Leader in Molecular at UC Berkeley in 2016, I grew
Spectroscopy Award at the SciX 2020 increasingly interested in developing
conference in October, where she was tools to study biological systems:
to give a plenary lecture and be honored As a scientist, I find the complexity
in an award symposium, but the in- of thought and intricacy of the brain
person conference has been cancelled fascinating. As a friend of several
because of the COVID-19 pandemic. individuals suffering from mental
This interview with Landry describes health illnesses, I find it astounding
her early and most recent research. that the status quo for diagnosing
and treating psychiatric disorders
remains qualitative. Understanding
Please tell us about some of how our brain cells communicate
(and miscommunicate) needs
your earliest research interests.
to be addressed by a collective
How did you become interested
and interdisciplinary approach to
in science? What has kept you overcome the many limitations
motivated? What are the most currently rendering this information
exciting aspects of your work inaccessible. Motivated by this,
each day? one of my lab’s research directions
I am a physicist by training, having is in developing optical probes
developed several instruments to image brain chemistry—the
capable of measuring piconewton- neurotransmitters in the brain that
scale forces and imaging at the support healthy brain function
nanometer-scale (1) for my doctoral but can also lead to psychiatric or

Emerging Leader in
Award: Advancing
Spectroscopy
and Nanotechnology
near-infrared (NIR) fluorescence

neurodegenerative disease when their
signaling is disrupted. monitoring of nitric oxide both ex
vivo and in vivo,demonstrating
that a plant can be altered to
What have been the most difficult function as a photonic chemical
aspects of your research to sensor. How did you conceive this
date? How have you worked to idea and what has been learned
overcome these challenges? from this work?
Research is inherently challenging In this work, we hypothesized that
because we initiate projects with the broad absorption spectrum of
big goals and don’t usually have a nanomaterials such as single walled
clear path to achieve those goals. carbon nanotubes, which extends well
For every successful dopamine into the near infrared and past the
imaging experiment my lab performs absorption spectrum of chlorophyll
today, there are dozens of failed pigments, could capture a broader
experiments that have led up to it. range of photons from broad-spectrum
The students and postdocs in my sunlight. This work demonstrated that
lab are the reason for the success these nanotubes could internalize into
of our lab’s research: Their tenacity, chloroplasts and could increase their
intelligence, and clever approaches photosynthetic activity as assessed by
to their research projects are what in vitro assays. This paper opens the
enable our science to progress. opportunity for the incorporation of
nanomaterials into plants for energy-
harvesting purposes and for detection
In your postdoctoral work, you of chemicals in the environment to
and your colleagues created which plants may be exposed.
single-walled carbon nanotubes
(SWNTs) that were inserted into
the lipid envelope of extracted Also as a postdoctoral
plant chloroplasts to promote researcher, you used corona
higher photosynthetic activity phase molecular recognition
and maximum electron transport (CoPhMoRe) to identify adsorbed
rates (4). SWNTs have allowed polymer phases on fluorescent
Emerging Leader in
Award: Advancing
Spectroscopy
and Nanotechnology
single-walled carbon nanotubes The work you have done on

(SWCNTs) for the selective carbon nanomaterials has been
detection of neurotransmitters, highly cited and has been shown
such as dopamine (5). This to be useful in biomedicine for
research suggested that polymer– imaging, sensing, targeting,
SWCNT constructs may be useful delivery, therapeutics, catalysis,
as fluorescent neurotransmitter and energy harvesting (6). Are
sensors, potentially within living these materials and techniques
tissue. Is this work continuing restricted to research and
to show promise? And what has discovery use or do you think
been unique about this approach? this technology will lead to
This is an exciting body of work, a clinically viable tool for
showing that molecular recognition can measurements on patients? Are
be conferred synthetically. Normally, to there any plans for creating a
detect biomolecules, natural molecular diagnostic method for physicians
recognition elements such as antibodies using carbon nanomaterials?
are used to detect the target molecule For the foreseeable future, the tools
over all other molecules that can be developed with nanomaterials in
found in a biological system—for my lab are intended for research
example, detecting dopamine over purposes. Until the nascent field of
other neurotransmitters. With this nanotechnology achieves consensus
approach, we show that synthetic on the toxicity and environmental
polymers can be adsorbed to the impacts of nanomaterials, their
surface of carbon nanotubes, and while restricted use in a research setting
most polymers will take on random is best. However, one advantage of
conformations, every once in a while abiotic (nonbiologically based) tools
a polymer will take on a conformation in neuroscience is that they can be
that can selectively bind the target deployed in nonmodel organisms.
molecule, such as dopamine. In this This feature of our neurotransmitter
manner, we can screen for polymer– imaging technologies could be
nanotube conjugates that can in turn incorporated into form factors
serve as synthetic probes to image enabling their use in humans, for
biomolecules. instance, using our dopamine probes

Emerging Leader in
Award: Advancing
Spectroscopy
and Nanotechnology
to measure changes in brain dopamine model dicot plant); Triticum aestivum

in organisms other than those (wheat, non-model monocot plant),
traditionally used for neuroscience and Gossypium hirsutum (cotton, non-
research, such as mice. model dicot plant). Wheat and cotton
are cash crops; cotton, in particular,
is challenging to genetically transform
with current technologies. We further
Of all your research papers so demonstrate with single-molecule
far, what are the most meaningful imaging that the process of grafting
papers you would like to highlight DNA on nanoparticles prevents
for our readers that describe your DNA degradation by nucleases,
current research interests? providing a complete picture of how
Our most meaningful work at this nanotechnology both promotes
this point involves both genetic delivery of functional biomolecules to
engineering and spectroscopy as plants, and also protects cargo from
separate, but related, pursuits. enzymatic degradation en route to its
intracellular function.
In our genetic engineering related
work, my lab demonstrates the use In our spectroscopy-related work, my
of various nanomaterials and their lab has developed a tool that newly
associated surface chemistries to enables imaging of the chemical
controllably graft and quickly deliver communication between neurons in
functional biomolecular cargoes such the brain at the spatial (micrometer)
as whole DNA plasmids to various and temporal (millisecond) scales
agriculturally relevant plants (7, 8). We the brain uses to communicate
accomplish nanoparticle-mediated (9). In particular, chemicals known
heterologous and transient expression as neuromodulators tune neuronal
of a protein in plants, and show that networks that control a wide variety of
there is no transgenic DNA integration brain function, including motor control,
into the host plant genome. We learning, and attention. Aberrations
demonstrate gene expression in both in the chemistry of neuromodulators
model and non-model plant species lies at the core of many psychiatric
of agricultural relevance: Nicotiana and neurological disorders such as
benthamiana (tobacco, model dicot schizophrenia, Parkinson’s disease,
plant), Eruca sativa (arugula, non- addiction, depression, and anxiety. Yet,

Emerging Leader in
Award: Advancing
Spectroscopy
and Nanotechnology
the inability to measure the dynamics antidepressants and antipsychotics

of neuromodulation at high spatial that are used to treat psychiatric
and temporal resolution has hindered and neurodegenerative disease.
fundamental neuroscience research Owing to its synthetic nature, our
and the validation of neuropsychiatric probe is remarkably flexible in
drugs. Thus, a technology that enables implementation, requiring no reliance
neuromodulator visualization could on genetic engineering techniques
be influential for our understanding that protein-based optical probes
of basic neurobiology and for the typically demand. This latter point
treatment of our psychiatric and is important because nIRCats are
neurodegenerative disorders. based on a purely synthetic molecular
We have developed a near-infrared recognition element for dopamine.
nanoscale catecholamine probe This last feature has enabled us,
(nIRCat) that can be used to image for example, to optically record
the neuromodulator dopamine in previously undetected heterogeneity
the brain, and is validated against in D2 dopamine autoreceptor
“gold standard” techniques modulation of presynaptic dopamine
in neuroscience, including release upon exposure to various
electrophysiology and optogenetics. drugs with micrometer spatial
This work elucidates the core resolution. This result is important
of what neuroscientists can use because most psychiatric drugs
to implement this technology to target dopamine receptors, thus it is
image the dynamics of dopamine imperative to know where receptors
neuromodulation at the spatial and are expressed within neurons—pre-
temporal scales that have eluded vs. post-synaptically—and whether
existing methods of inquiry. To our they respond to drugs similarly or
knowledge, this is the only optical heterogeneously. The non-genetically
probe for dopamine that enables encoded nature of the probe has
dopamine imaging in the presence also enabled us to newly measure
of dopamine receptor agonists dopamine modulation in bats,
and antagonists, and thus the only a largely genetically intractable
probe that can be implemented species. This method should
to study how dopamine dynamics therefore uniquely support similar
gets modulated by full-panel explorations of the effects of other

Emerging Leader in
Award: Advancing
Spectroscopy
and Nanotechnology
dopaminergic drugs at the level of chemical, or environmental

individual synapses, experiments that problems?
are currently unachievable.
The goal of our lab is to develop
What is the most difficult or tools that can be as broadly useful
as possible. The tools we develop
challenging aspect of your
for neuroscience and for plant
current research? How do you
biomolecule delivery are meant to fill
manage a research group, while
voids in the toolkits available to study
at the same time mentoring and the brain and to genetically modify
directing students? plants, respectively. Therefore, the
Research is inherently hard. By directions that my lab takes seek
far the best part of my job is to avoid redundancy in the tools we
mentoring and directing students and develop with preexisting tools, and
postdocs—working with talented lab developing technologies that uniquely
members to come up with ideas and enable studies that would not be
research directions together. Of my possible without our developments.
tasks as a professor, meetings with
students and postdocs to discuss
research are the highlights of my
day. And of the “outputs” of my What areas would you like to
work, more so than papers, awards, see this research expand into
or grants, what I am most proud when looking toward the future?
of are the scientists that emerge Do you plan to stay your current
from the lab, and the careers they work with carbon nanomaterials
subsequently build for themselves. or are there another analytical
techniques or areas of research
that look promising?
How were you able to direct In the future, I am excited to take
your research toward discovery the tools my lab has developed
of important biomedical and and to use them to learn more
agricultural challenges? What about biological systems. This
made you choose the path of will require parallel developments
your research versus industrial, in nanotechnology, and also in

Emerging Leader in
Award: Advancing
Spectroscopy
and Nanotechnology
near-infrared spectroscopy and and participating in extracurricular

microscopy that are necessary to activities in STEM.
complete our studies. While carbon
nanotubes in particular, and their
unique spectroscopic properties, References
have been very useful as the basis 1. M.P. Landry, X. Zou, L. Wang, W.M. Huang,
of our research thus far, we are also K. Schulten, and Y.R. Chemla, Nucleic acids
research. 41(4), 2416–2427 (2013).
exploring other nanomaterials such
2. J. Zhang, M.P. Landry, P.W. Barone, J.H.
as graphene quantum dots and Kim, S. Lin, Z.W. Ulissi, D. Lin, B. Mu, A.A.
gold nanoparticles. Boghossian, A.J. Hilmer, and A. Rwei, Nature
nanotechnology. 8(12), 959–968 (2013).
3. M.P. Landry, H. Ando, A.Y. Chen, J. Cao, V.I.
Kottadiel, L. Chio, D. Yang, J. Dong, T.K. Lu,
and M.S. Strano, Nature nanotechnology.
What would you tell young people 12(4), 368–377 (2013).
interested in science about 4. J.P. Giraldo, M.P. Landry, S.M. Faltermeier,
T.P. McNicholas, N.M. Iverson, A.A
how to prepare for a career in Boghossian, N.F. Reuel, A.J. Hilmer, F. Sen,
research? J.A. Brew, and M.S. Strano, Nat. Mater.
13(4), 400-408 (2014).
It is never too late to get involved
5. S. Kruss, M.P. Landry, E. Vander Ende, B.M.
in science and in research. Before Lima, N.F. Reuel, J. Zhang, J. Nelson, B. Mu,
starting as a professor at UC A. Hilmer, and M. Strano, J. Am. Chem. Soc.
136(2), 713–724 (2014).
Berkeley, I had never been involved
6. S.F. Oliveira, G. Bisker, N.A. Bakh, S.L. Gibbs,
in research with living systems. M.P. Landry, M.S. Strano, Carbon 95. 767–
This transition from physics to the 779 (2015).
research areas my lab works on 7. G.S. Demirer, H. Zhang, J. Matos, N. Goh,
today was not an easy change, and F.J. Cunningham, Y. Sung, R. Chang, A.J.
Aditham, L. Chio, M.-J. Cho, B. Staskawicz,
required a lot of time spent with M.P. Landry, NaturevNanotechnology. 14,
introductory level textbooks to get 456–464 (2019).
up to speed on this new field of 8. H. Zhang, G.S. Demirer, H. Zhang, T. Ye, N.S.
Goh, A.J Aditham, F.J. Cunningham, C. Fan,
research. Just to say, if I can learn M.P. Landry, Proc. Natl. Acad. Sci. U.S.A.
new areas of science and research 116(15), 7543–7548 (2019). DOI: 10.1073/
this late in my career, aspiring young pnas.1818290116.
scientists should feel empowered 9. A.G. Beyene, K. Delevich, J.T.D.B. ODonnell,

D.J. Piekarski, W.C. Lin, A.W. Thomas, S.J.
to get involved by volunteering in Yang, P. Kosillo, D. Yang, L. Wilbrecht, M.P.
research labs, taking science classes, Landry, Sci. Adv. 5(7),1–11 (2019).

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SEPTEMBER 2020

Spectroscopy: Introduction to the

Presented in partnership with An e-book from

Introduction Raman Spectroscopy

SERS and TERS Infrared Spectroscopy

Charles Mann Award RSC Award: the Sir George

SAS Strock Award

The 2020 Emerging Leader

Laura Bush Editorial Director, Spectroscopy

4 SEP T E MB E R 2 0 2 0 | S P E CT ROS COP Y

Figure 1: Raman spectroscopy has found its use in numerous fields

by Raman spectroscopy is achieved instruments enable users to deploy Raman

5 SEP T E MB E R 2 0 2 0 | S P E CT ROS COP Y

Next generation Raman imaging

High performance Raman systems for a range of applications

AD216(EN)-01-A (For inc).indd 1 12/20/2019 9:36:12 AM

SERS and TERS

7 SEP T E MB E R 2 0 2 0 | S P E CT ROS COP Y

Figure 1: The images illustrate a laser interacting with a thiophenol

the Raman signal enhancement from demonstrated. Under ambient conditions,

9 SEP T E MB E R 2 0 2 0 | S P E CT ROS COP Y

Figure 2: Tip enhanced Raman scattering (TERS) is performed by

Raman shift (cm-1)

10 SEP T E MB E R 2 0 2 0 | S P E CT ROS COP Y

11 SEP T E MB E R 2 0 2 0 | S P E CT ROS COP Y

12 SEP T E MB E R 2 0 2 0 | S P E CT ROS COP Y

micrometers. To correlate these sensitive to molecules possessing

Figure 1: Infrared and Raman spectra of acetyl salicylic acid (aspirin).

13 SEP T E MB E R 2 0 2 0 | S P E CT ROS COP Y

a unique fingerprint that could be used sample preparation or specialized

Figure 2: A Typical ATR Accessory (diagram provided by RedWave

14 SEP T E MB E R 2 0 2 0 | S P E CT ROS COP Y

15 SEP T E MB E R 2 0 2 0 | S P E CT ROS COP Y

16 SEP T E MB E R 2 0 2 0 | S P E CT ROS COP Y

solution-based analysis. Ultimately, an ICP-OES instrument. Techniques

17 SEP T E MB E R 2 0 2 0 | S P E CT ROS COP Y

longitudinal axis of the plasma, platform is ultimately the workhorse

18 SEP T E MB E R 2 0 2 0 | S P E CT ROS COP Y

References Acta 835, 1–18 (2014).

Figure 1: Common sample introduction techniques and detection op-

19 SEP T E MB E R 2 0 2 0 | S P E CT ROS COP Y

20 SEP T E MB E R 2 0 2 0 | S P E CT ROS COP Y

emission spectroscopy, making it rubber is highly susceptible to

21 SEP T E MB E R 2 0 2 0 | S P E CT ROS COP Y

is matrix-sensitive, LIBS analysis of knowledge I could find from physics,

22 SEP T E MB E R 2 0 2 0 | S P E CT ROS COP Y

Charles Mann Award

23 SEP T E MB E R 2 0 2 0 | S P E CT ROS COP Y

metabolites affected by variations in of this paper is to describe protein-

these techniques important How is the Raman spectroscopy

25 SEP T E MB E R 2 0 2 0 | S P E CT ROS COP Y

26 SEP T E MB E R 2 0 2 0 | S P E CT ROS COP Y

27 SEP T E MB E R 2 0 2 0 | S P E CT ROS COP Y

second point. For recruiting, I placed disease by Raman spectroscopy (7).

28 SEP T E MB E R 2 0 2 0 | S P E CT ROS COP Y

29 SEP T E MB E R 2 0 2 0 | S P E CT ROS COP Y

RSC Award: the Sir George