pubs.acs.

org/journal/abseba Article

Facile Bacterial Cellulose Nanofibrillation for the Development of a

Plasmonic Paper Sensor
Agnes Purwidyantri,* Myrtha Karina, Chih-Hsien Hsu, Yoice Srikandace, Briliant Adhi Prabowo,
and Chao-Sung Lai
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ABSTRACT: In this present work, a plasmonic sensor is developed through an

extremely cheap cellulose-based source, widely known as a food product, nata de coco
(NDC). Capturing its interesting features, such as innate surface roughness from
Downloaded via UNIV OF EXETER on July 17, 2020 at 10:12:02 (UTC).

naturally grown cellulose during its fermentation period, the engineering and
modulation of NDC fibril size and properties were attempted through a high-pressure
homogenization (HPH) treatment to obtain highly dense nanofibrils. After the
transformation into a thin, paper-sheet form through a casting process, the homogenized
bacterial cellulose (HBC) resulting from HPH was compared with the normally agitated
bacterial cellulose (BC) pulp and decorated with silver nanoparticles (AgNPs) to
produce plasmonic papers, for further application as surface-enhanced Raman scattering
(SERS) substrate. As demonstrated in the measurement of Rhodamine 6G (R6G)
molecule, the plasmonic HBC paper sheet provided more prominent SERS signals than
the plasmonic BC due to its high surface roughness and improved textural properties
from the nanofibrillation process favoring better adsorption of AgNPs and effective
SERS hotspots generation. The plasmonic HBC obtained a 2 order higher estimated SERS enhancement factor over the plasmonic
BC with a limit of detection of approximately 92 fM. Results denote that the proposed approach provides a new, green-synthesis
route toward the exploration of biodegradable sources integrated into an inexpensive and simple nanostructuring process for the
production of flexible, paper-based, plasmonic sensors.
KEYWORDS: nata de coco, nanofibrillation, bacterial cellulose, plasmonic paper, SERS sensor

1. INTRODUCTION reproducibility of the SERS signal intensity. Nevertheless,

The surface-enhanced Raman scattering (SERS) effect has nanopatterning and nanolithography are followed by laborious
been a revolutionary discovery where intensive electromagnetic and pricey fabrication under cleanroom conditions, as well as
complex and non-ecofriendly chemical processes mainly
field confinement and scattering phenomena known as the
conducted via wet-bench work. In fact, there is an ever-
plasmonic effects are generated in nanoscale-roughened noble
increasing demand also for a simple and handy SERS substrate
metallic nanoparticles (NPs).1,2 Since its first discovery in
that is cost-effective for use as a portable and disposable
1974,3 strategies toward creation of SERS substrates have been
screening substrate.
widely expanding, not only using conventional lithography but
Among SERS-active substrate materials, polymeric bioma-
also metallic electrodes roughening,4 nanopatterning through a
terials, such as bacterial cellulose (BC)-based material, have
chemical strategy such as by surface oxidation,5 surface
been a captivating alternative for nanopatterning to produce a
manipulation with polymer nanotemplate,6 and development
substrate from BC nanofibrils for the production of a low-cost
of biodegradable plasmonic substrates.7 The varied fabrication
biodegradable paper-based sensor, such as in the form of a
methods have been directed toward optimizing SERS substrate
transparent substrate.9−11 In building up effective SERS
properties, such as higher roughness for spot-to-spot and
hotspots, BC is more beneficial over plant cellulose for high
structure reproducibility, high enhancement factor, durable
entrapment, density, and dispersion of noble metal nano-
shelf-life, and resistance to laser excitation and mechanical
stress. The key for effective SERS signal enhancement is the
nanogap interspacing arrangement within the metallic nano- Received: December 11, 2019
particles’ position to produce localized surface plasmon Accepted: April 16, 2020
resonance (LSPR) coinciding with the excitation wavelength, Published: April 16, 2020
which must be as small as 2−20 nm, called “hotspots”.8 Hence,
there is an urgent need to obtain highly ordered arrays of
metallic nanostructures with a high aspect ratio for excellent

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ACS Biomaterials Science & Engineering
particles due to its native fibrils with a width of less than 100
nm, which concomitantly provide large surface area and
outstanding wicking ability with great compatibility with other
printing-based methods.12,13 BC is also noted as a remarkable
nanoparticle matrix due to its high purity and strong
mechanical properties, such as its high tensile strength,
which lowers the NPs aggregation, and the presence of its
active hydroxyl-rich surface for its ease of surface engineering
and modifications.14 The pulp of the cellulose fibers can be
modified through a nanofibrillation process using a high-speed
blender, ultrasonic irradiation,15 a high-shear homogenizer,16
or microfluidization17 with a variety of pretreatments, such as
to flexibilize the fibers to reduce the energy consumption.18
Among the fibrillation treatments, high-pressure homogeniza-
tion (HPH) has been noted as an efficient technique in
biomass refinery, since it is simple and highly efficient with
minimum use of organic solvents.19 The principle of HPH
covers mainly the fall off of the pressure gradient, by
combination of high turbulence and shearing force under
depressurization, of highly compressed aqueous suspensions.20
This technique opens a way for modification of the
morphology, topology, and rheology of the paper substrate,
as well as nanofibrillation; therefore, entrapment of NPs onto
the substrate could be tuned as well for maximum optical
properties. A variety of NPs have been incorporated with BC-
nanofiber-based organic/inorganic hybrid nanocomposites
through different of processes. Almasi et al. reported a CuO-
impregnated BC structure created by in situ synthesis methods
including sonochemical and precipitation methods.21 With the
assistance of amidoxime groups, Au nanoparticles were
successfully in situ hydrothermally grown on BC nanofibers
by Chen et al. for catalyst production.22 A novel avenue can be
built through nanofibrillation methods and optimized NPs
immobilization for effective SERS hotspots creation.23,24
One potentially exploited biodegradable BC-based material
is nata de coco (NDC), a very popular food product, typically
prepared in the form of a thick jelly, simply prepared by the
fermentation of coconut juice, mostly using Acetobacter
xylinum.25,26 In tropical countries like Indonesia, the
Philippines, Vietnam, and other Southeast Asian countries,
NDC is widely produced not only by high-scale industries but
in home industry and is marketed with a considerably cheap
price; therefore, it can be potentially exploited as a new
generation of green-synthesized thin-film material. NDC has a
highly regarded potential due to its favorable functionalities in
many applications, such as in the production of optical and
transparent substrates, food packaging, tissue scaffolds, smart
textiles, or substrate coating, since it has a smaller diameter of
nanofibers (less than 100 nm)27 in comparison with most plant
fibers with microscale diameter and it is capable of absorbing
water to about 200 times higher than its initial mass.28 These
properties can be prospectively incorporated with NP
entrapment for SERS-active substrate architecture. From the
noble nanoparticle class, silver nanoparticles (AgNPs) have
been greatly noticed as a robust material to prepare SERS
substrate because of their high plasmon oscillation damping
due to an interband transition in the visible light generating
highly energetic hot electrons with low energy, the so-called
localized surface plasmon resonance (LSPR).29 In addition,
AgNPs’ attractive properties are reflected by their unique size-
and shape-dependent electrical, chemical, biological, magnetic,
and optical properties for a wide range of applications.30 The
embedment of AgNPs in nanopaper transparent substrates can
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be straightforwardly achieved through many methods, such as
via immersion or mixing of both organic/inorganic hybrids
prior to the paper-casting process without the need for linking
molecules or reducing agents.
In this study, we are the first to report the production of nata
de coco nanopaper with different mechanical fibrillation
methods to embed AgNPs to create a hybrid SERS-active
substrate. The plasmonic paper sheet prepared from smaller
sized fibers through disintegration and high-pressure homog-
enization processes, later called a plasmonic homogenized
bacterial cellulose (plasmonic HBC) paper sheet, showed more
prominent SERS character than the plasmonic bacterial
cellulose (plasmonic BC) paper sheet prepared by normal
agitation with high-speed blending. This is due to more
effective entrapment of AgNPs as a result of HBC paper having
a rougher structure and tinier fibrils, leading to hotspot
formation and a higher enhancement factor in the detection of
Rhodamine 6G (R6G) molecules. The proposed hybrid
material had been demonstrated to offer the realization of
green technology for cost-effective and simple fabrication of
SERS-active substrate, providing an alternate to the conven-
tional chemical route, nanostructuring, and nanolithography
involving harsh chemicals, tedious processing, and expensive
instrumentation. Moreover, the plasmonic paper provides the
means toward easy-to-use, portable, flexible (for roll-to-roll or
swabbing samples), and disposable sensing substrate.
2. MATERIALS AND METHODS
2.1. Materials. NDC gel blocks were purchased from Cianjur
City, Indonesia. Ascorbic acid, trisodium citrate dihydrate, NaOH
solution, and AgNO3 were purchased from Merck. Rhodamine 6G
(R6G) was purchased from Sigma-Aldrich. The deionized water used
in the entire experiment (resistivity at 25 °C = 18.2 MΩ·cm) was
provided by a Milli-Q system.
2.2. Apparatus. The crushing of NDC gels was conducted using a
kitchen blender (Philips), and the casting processes of BC and HBC
paper sheets were done using an oven from Binder. In HBC paper-
sheet preparation, the disintegrator machine was from Psychotron and
the homogenizer was model HJP 25001 from Sugino. The particle
size analyzer (PSA) was a Zetasizer Nano ZS from Malvern. The
ultraviolet (UV) absorption study was conducted using a V-670 UV−
vis spectrometer from JASCO. A field emission scanning electron
microscope (FE-SEM) (HITACHI S-4700) was utilized to capture
the morphological characteristics of the NDC-based papers. Infrared
(IR) absorption was analyzed by a Nicolet iS 5 Fourier-transform
infrared (FTIR) spectrometer (Thermo Scientific). Crystallinity
analysis was performed by X-ray diffraction (XRD) with a D8
Advance with LYNXEYE XE-T detector from Bruker. Surface
roughness analysis was done with an Innova atomic force microscope
(AFM) from Bruker. SERS analysis was conducted using a RAMaker
system from Protrustech. Co, Ltd., equipped with a charge-coupled
device (CCD) camera monitoring set coupled with an Olympus
microscope body and using Andor Solis software from Oxford
Instruments (UK) for imaging.
2.3. Methods. 2.3.1. Silver Nanoparticles (AgNPs) Synthesis.
The AgNPs were prepared through a reduction and stabilization
process using ascorbic and citric acids. First, a mixture of 8 mL of 0.6
mM ascorbic acid in aqueous phase and 3 mM trisodium citrate
dihydrate was fixed to pH 6.0 by the addition of 0.2 mol/L citric acid
or 0.1 mol/L NaOH solution. Once the pH fixation was
accomplished, the solution was stirred at a velocity of 900 rpm in a
30 °C temperature setup followed by the addition of 0.08 mL of 0.1
M AgNO3 solution until the color of the solution gradually changed
from transparent to yellow and finally to turbid grayish color. The
concentration of the AgNPs was fixed to 200 ppm by homogeneously
mixing with deionized water at room temperature for 10 min. The
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Figure 1. (a) Process flow of nata de coco (NDC) paper-sheet fabrication and (b) plasmonic paper-sheet production for SERS substrate.
reaction was stably prolonged for about 15 min. The prepared liquid
was ready to be used for the entire experimental stages.
2.3.2. NDC-Based Paper Production. For BC paper-sheet
production, blocks of NDC gel prepared from coconut juice
fermentation with A. xylinum were exposed to running water to
achieve pH neutrality. The gel blocks were then brought to boiling
temperature with 1% w/v NaOH in order to complete the removal of
noncellulosic components and the reduction of bacterial cells. In the
next stage, the gels were washed again to remove the remaining alkali
compounds until pH 7 was obtained. The gels were transformed into
the form of a slurry by an hour-long crushing process using a
mechanical blender and subsequently stored in a 4 °C refrigerator.
For HBC paper-sheet preparation, a 2% w/w suspension of NDC was
homogenized using a laboratory disintegrator at a rotational speed of
1550 rpm for 30 s. The fragmented NDC was then homogenized
using a high-pressure homogenizer at 20 MPa for 15 cycles, and the
slurry was then ready for paper-casting. Finally, for both BC and HBC
paper-sheet production, 200 mL of the slurry (BC or HBC) was
degassed using a bell jar in vacuo and casted on a Teflon-based
templating tray at 45 °C overnight. The thin, paperlike substrates
were subsequently peeled off and ready for the next steps.
The particle size distribution after 60 min of ultrasonication was
tested with the Malvern Zetasizer Nano ZS instrument (Malvern
Instruments Ltd.). Samples of nanocellulose suspended in water were
diluted and analyzed with a particle size analyzer using dynamic light
scattering (DLS). The noninvasive back-scattering technique was
used with a 173° detector angle using a HeNe 4 mW laser (633 nm).
Measurements were repeated three times for each sample
2.3.3. SERS-Active Substrates Preparation. The preparation of the
SERS-active substrate was done via AgNPs spotting onto both BC
and HBC paper sheets through drop and dry methods. A 10 μL
droplet of AgNPs solution was dropped onto the NDC-based papers
with an approximate perpendicular distance between the pipet tip and
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the paper-sheet surface of about 50 mm and allowed to dry for about
60 min at 25 °C in a defined humidity chamber. Furthermore, for
SERS measurement, 15 μL of R6G was dropped right onto the AgNPs
spot to allow an even dispersion and uniform adsorption. The process
flow of SERS substrate preparation is illustrated in Figure 1.
2.3.4. Characterization of Surface Morphology, Topology,
Absorption, and SERS. To understand the morphology of the
NDC-based SERS papers, the surface observation was completed
using FE-SEM with an operation system set at 10.000 V accelerating
voltage. The topology of the modified substrate was examined using
an AFM in tapping mode with a scanning area of 1 × 5 μm2. The UV
absorption properties were studied using UV−vis spectrometry with a
wavelength ranging from 200 to 600 nm, while the IR absorption
spectra of the fabricated plasmonic paper sheets was acquired using a
Fourier-transform infrared (FTIR) spectrometer over wavenumbers
from 4000 to 500 cm−1. The crystallinity observation was carried out
using XRD with Cu Kα = 1.54 Å, 0.020° steps, and 164 time
collections of 60 s per step.
The prepared substrates were used to measure the SERS intensity
of the R6G Raman probe in a series of concentrations ranging from
100 pM to 1 μM. A 20 μL aliquot of the R6G was placed and air-dried
onto the fabricated plasmonic paper sheets. SERS analysis was
conducted using an excitation wavelength of 473 nm with the
excitation and light collection performed with a 100× objective lens
(NA 0.5), 100 mW laser power, 2 s exposure time, scan coverage of
100 × 100 μm area with 10 μm laser spot size, and 3 accumulations
for 10 different locations. The data acquisition and extraction of the
baselines were performed using Raman software (Andor Solis for
Imaging, Oxford Instruments). The finite-difference time domain
(FDTD) simulation for AgNPs over the BC sheets was performed
with the 3D configuration setup by Lumerical software. The AgNP
spheres were simulated with a diameter of 50 nm, and the optical
constant properties were obtained from Sultanova et al.31 The field
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Figure 2. (a) Particle size distribution and three-dimensional structure showing the surface roughness properties of (b) BC and (c) HBC paper
sheets.
Figure 3. FE-SEM photographs of as prepared (a) BC and (b) HBC paper sheets and (c) BC and (d) HBC paper sheets after decoration with
AgNPs (plasmonic papers).
source for the excitation was simulated using a Gaussian model with a
wavelength range from 400 to 700 nm in the full width half-maximum
(fwhm). The mesh configuration was fixed with a huge density mesh
with space less than 1 nm, particularly in the boundary region, to
obtain an accurate profile of the plasmonic field in the interface of
nanoparticles. Finally, 2D monitoring was shown for the sake of
determining a simple mapping field of the simulated structures.
3. RESULTS AND DISCUSSION
The study was initially conducted to produce particle size
analysis using dynamic light scattering technology. Quantified
in 1 wt % (volume fraction) of the aqueous NDC pulp, the
HBC produced through the HPH fibrillation technique had
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approximately 50% smaller particle size than the BC prepared
via conventional grinding methods. The details can be seen in
Figure 2a displaying a histogram of the particle size
distribution of the aqueous BC particles at 1194 nm, while
the distribution of HBC is at around 617.4 nm. The particle
sizes denote the hydrodynamic diameters of equivalent
spheres, and therefore, they are not a representation of the
actual physical dimension of the cellulose particles; however,
they are valid for comparison purposes.32 In addition to
smaller size, the HBC prepared by the HPH system yielded a
relatively narrower particle size distribution than the BC,
reflecting a more homogeneous nanosized cellulose production
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Figure 4. UV−vis absorption spectra of (a) as prepared BC and HBC paper sheets and (b) AgNPs-decorated BC and HBC paper sheets
(plasmonic papers).
in the HPH system. Figure 2b,c displays the morphological
properties of the BC and HBC nanosheets. Aiming for the
effective creation of SERS hotspots, the nanofibrillation
successfully generated higher surface roughness, as presented
by the higher Rq value of the HBC paper sheet, with values
almost twice those of the BC paper sheet. During the HPH,
the HBC sheets formed smaller fibrils with more aggregate
bundles as a consequence of the large number of surface
hydroxyl groups, which strongly interact and result in the
agglomeration that ultimately contoured the surface. This
contour is beneficial for liquid absorption during nanoparticles’
modification, since the higher roughness observed in the HBC
sheet provides more porosity, which consequently increases
the surface hydrophilicity. In Figure S1 (Supporting
Information, SI), the effect of HPH on the surface hydro-
philicity of the HBC paper sheet is demonstrated in a water
contact angle (WCA) measurement resulting in a value of
31.1°, while the BC showed a larger WCA of 77.8°.
The SEM photographs in Figure 3 show that mechanical
fibrillation of a NDC slurry influences the topology of the
produced paper sheets. In Figure 3a, the sheet structure of BC
produced by high-speed blending agitation demonstrates
considerably larger and longer fibril networks with the
tendency to generate much bigger holes on the surface. In a
lower resolution observation, the fibrils clumped and generated
a thicker rootlike structure with a width of 300−500 nm. In
contrast, with mechanical fibrillation using a disintegrator and
high-pressure homogenizer, as in Figure 3b, the sheet structure
of the HBC shows a lot of small pores on the surface with
mostly smaller tangled cellulose ribbons with widths of
approximately <100 nm per single fiber. The finding is in a
good agreement with the results of Lee et al., who reported
that the HPH of microcrystalline cellulose (MCC) resulted in
a diameter of cellulose fibrils mostly ranging from 28 to 100
nm.33 The pressure and cycles applied in HPH were known to
be the major factor for optimum crushing of the fibrils as a
result of coalescence and recoalescence of the cellulose
aqueous droplets,34 as it was found in the literature that
increasing both factors proportionally lowered the fibril size
and restructured the fibrous structure in the homogeneous
cellulose system.35 Subsequently, in the plasmonic paper
development, the drop-casting of AgNPs (particle size of
∼50 nm) successfully immobilized the NPs within the
fibrillated paper sheets. This is proven in our SEM observation
taken from different sites on the samples (Figure S2, SI), where
we could observe a high dispersion and uniformity of the
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AgNPs’ coverage, which should fit the requirements of SERS
measurement. It is also a good proof of a successful
homogenization engineering from an economic source like
nata de coco to optimize the AgNPs’ impregnation onto the
substrate. In this setup, HBC showed mostly full and even
coverage of the AgNPs, which confirms the optimized
conditions after HPH treatment. In a higher magnification, it
is seen that in the BC paper sheet, the AgNPs could not cover
the whole substrate well, along with the appearance of
aggregated NPs, as shown in Figure 3c. However, with HBC
paper-sheet structure, the high dispersion of AgNPs could be
achieved, leading to uniform coverage on the substrate (Figure
3d), indicating that smaller fibrils facilitate more effective
molecular entrapment. These findings are plausibly due to the
higher surface area, where nanofibrillated cellulose may
typically exhibit an order of 50−70 m2/g area,36 along with
the higher number of available surface hydroxyl groups to bind
the Ag+ ion through chemical bonding, which also serve as the
seeding material for the Ag reduction phenomenon.14
Figure 4a shows the UV−visible spectra of the BC and HBC.
The as prepared paper sheets display relatively similar
absorbance peaks at around 255−260 nm, which is in a
good agreement with the findings of Cazon et al., who reported
a typically low UV-C transmittance peak for the pure BC
fiber.37 However, the HPH process produced a higher
transparency of the paper sheet, which in turn lowered the
absorbance peak of the bacterial cellulose. This can be
elucidated by the emergence of tinier fiber bundles separated
from bigger fibrils, triggering a higher aspect ratio of fiber
bundles in a thinner fabricated sheet as more homogenization
cycles were applied.33 Furthermore, the less pronounced
absorbance peak of the HBC paper sheet can be explained
by the shear-thinning impact through HPH, implying the
dispersal of large floccules and agglomerates by the shear
forces,38 which finally resulted in a more transparent substrate
than the BC paper sheet. A similar finding was observed in the
form of a photograph showing the physical appearance of the
paper sheets in Figure S3 (SI) in which the nanofibrillation in
HBC clearly produced a much more transparent substrate than
the BC paper sheet, as well as more even dispersion of AgNPs
after drying that resulted from more hydrophilicity due to
higher surface roughness, as observed in the AFM and WCA
tests mentioned above. Accordingly, in Figure 4b, after
modification, the characteristic peak of AgNPs was successfully
recorded at around 420 nm, confirming the embedment of the
nanoparticles onto the paper sheets. A more uniform coverage
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Figure 5. (a) IR spectra and (b) X-ray diffraction pattern of as prepared and plasmonic BC and HBC paper sheets.
and higher density of AgNPs trapped in the HBC fibril
network was validated by about a 4 times higher absorbance
percentage than the AgNPs-decorated BC paper sheet. The
entanglement of finer and thinner fibrils from mechanical HPH
treatment in HBC paper-sheet preparation triggers more
effective penetration and diffusion of AgNPs due to 3D porous
fibril interspacing on the sheet surface.
The incorporation of the AgNPs onto the NDC-based sheet
evaluated by FTIR spectroscopy analysis is displayed in Figure
5a, where in all modification approaches, the most dominant,
conspicuously observed bacterial cellulose absorbance peaks
appear at around 3342 and 2895 cm−1, assigned to the OH
stretch of cellulose type I and CH stretching of CH2 groups,
respectively. Additionally, some other typically ascribed
bacterial cellulose peaks were visibly recorded at 1648, 1366,
and 1163 and 1061 cm−1, assigned to −CH−, C−O
asymmetric stretching vibrations and pyranose ring skeleton
vibrations, respectively.39−41 This indicates that the backbone
structure of the cellulose remained even after the NPs’
incorporation. In contrast, with immobilized AgNPs, the most
dominant peaks show noticeable decrement of infrared
absorbance, indicating the AgNPs’ physical adsorption onto
hydroxyl groups over both paper sheets.40,42 In Figure 5b,
under all conditions, the XRD pattern of the typical cellulose
persistently appears as broad diffraction peaks at 14.8° (110)
and 23.5° (200), assigned to the cellulose Iα and Iβ
allomorphs, respectively.43 This represents that the HPH did
not alter the native cellulose type I, with its native interplanar
spacing, to other types of cellulose and, thus, may facilitate well
the entrapment of AgNPs, especially in HBC, as displayed by
the intense Ag peaks at around the 37° (111), 44.8° (200),
64.7° (220), and 77° (311) reflections of the face-centered
cubic metallic silver (JCPDS #76-1393), respectively. The
degree of crystallinity of all samples was calculated by Seagal’s
formula
CrI = 100% × [(I002 − Iam)/I002] (1)
where I002 is the major diffraction peak at 2θ = 22.6° and Iam is
the intensity of the amorphous counterpart measured at 2θ =
18°. Moreover, the average crystallite size of the nanocrystal-
line cellulose was estimated according to Scherrer’s method as
follows
L002 = kλ /β cos θ (2)
where L002 is the average crystallite size, k is the shape factor
(0.9), λ is the X-ray wavelength, β is the fwhm from the XRD
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peak in radians, and θ is the Bragg angle corresponding to the
intense (002) diffraction peak. The calculated values of the
crystallinity index, fwhm, and the average crystallite size of all
samples are presented in Table 1. Even though the HPH did
Table 1. XRD Physical Properties of the Fabricated Paper
Sheet SERS Substrates
sample CrI (%) fwhm ⟨Dav⟩ (nm)
BC 71.31 1.38 5.73(200)
HBC 43.32 1.43 5.87(200)
BC+AgNPs (plasmonic BC) 62.17 1.20 6.40(200)
HBC+AgNPs (plasmonic HBC) 33.41 1.46 5.46(200)
not change the conformation of the cellulosic phase, this
mechanical process was found to decrease the crystallinity
index of the cellulose, as seen in the HBC paper sheet before
and after the modification with AgNPs in comparison with that
in BC paper-sheet group. The shearing and agitation during
nanofibrillation with the HPH process had caused crushing
effects on the native cellulose crystals.
Both plasmonic paper sheets were then applied in SERS
detection of a series of R6G concentrations due to its strong
Raman resonance at the molecular level when excited into its
matching absorption band. Figure 6 represents the better
sensitivity of R6G molecule detection using the plasmonic
HBC than the plasmonic BC. Principal peaks of R6G
molecules were seen clearly at ca. 1330 and 1574 cm−1,
assigned as the in-plane vibration of C−H bonds. Other small
peaks at below 1300 cm−1 are attributed to the typical BC
peaks.44 The plasmonic HBC paper sheet generated through
HPH treatment clearly resulted in stronger SERS hotspots
with nanogaps of about 10 nm (Figure 3d), resulting from the
high aspect ratio and high density of the tiny fiber bundles
capturing more AgNPs and reinforcing localized surface
plasmon resonance (LSPR) effects.45 In such a configuration
of hotspots, with regard to the photonics particles size and
interstitial distance, the intraband transition occurred more
easily when Ag is exposed to photons, yielding holes and super-
energetic hot electrons that can cross the Schottky energy
barrier.46
Additionally, the HPH process was noticed to maintain the
textural properties of the HBC, where the firmness (in relation
with the water absorbance capacity) of the fibrils was not
impacted by the high pressure in the present setup, which is in
good agreement with the report of Lin et al. on the evaluation
of the BC aqueous suspension.35 Hence, the immobilization of
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Figure 6. SERS spectra and calibration curves for the dynamic range detection of a R6G series on plasmonic (a and c) BC and (b and d) HBC
paper sheets and the intensity distribution of the 1576 cm−1 peak from 1 μM R6G molecules on plasmonic (e) BC and (f) HBC paper sheets.
AgNPs and, ultimately, the penetration of R6G molecules onto
the plasmonic HBC paper sheet could be facilely performed. In
the R6G series screening, a typical Raman band at 1576 cm−1
attributed to a strong aromatic carbon bond was the most
conspicuous peak and was plotted in calibration curves where
10 different point positions were taken to ascertain the uniform
distribution of the AgNPs on both plasmonic BC and HBC
paper sheets, as well as the low-deviation signals presented in
Figure 6c,d. The uniform SERS intensity is well-represented in
waterfall graphs in Figure 6e,f for the detection of 1 μM R6G
molecules on plasmonic BC and HBC paper sheets. With the
dynamic range of 100 pM to 1 μM R6G, the HBC sheet with
its high SERS hotspots has exhibited more than 50% higher
sensitivity than the BC sheet and with a limit of detection
(LoD) of 92 fM, as calculated on the basis of the lowest
concentration of the R6G producing an alteration in the
Raman intensity signal equal to 3 times the average
background signals without the presence of R6G. The higher
transparency of the HBC could also contribute to the
increment of the light absorption from the outer toward the
inner side of the cellulose triggering the AgNPs for plasmonic
oscillation.47 A preliminary study to explore the wide-range
potency of the plasmonic paper sheets was performed via
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detection of Methylene Blue (MB) (Figure S4, SI), a
compound well-known as a typical counterpart of Rhodamine
B and a highly toxic pollutant in water pertaining to its use as a
dye in textile industries.48,49
The intensity of the strongest R6G Raman peak at 1576
cm−1 was later applied in the calculation of the SERS
enhancement factor (EFSERS) with the formula below
ISERS/NSERS
EFSERS =
IR6G norm /NR6G norm (3)
where ISERS and IR6Gnorm refer to the SERS and normal Raman
intensities of R6G molecules, while NSERS and NR6Gnorm are the
average number of R6G molecules in the scattering volume
(V) giving out both normal and Raman intensities.44,50 In
Figure 7a,b, effective SERS hotspots from AgNPs entrapment
within the cellulose fibrils were apparent in comparison with
the as prepared BC and HBC paper sheets with an optimum
spike in the plasmonic HBC, which reflects the favorable
effects of HPH for molecular capture. In our calculation using
the depth of field approach (Table S1, SI), the EFSERS of the
plasmonic HBC paper sheet was 1.23 × 105. This value
showed effective enhancement by 2 orders as compared to the
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ACS Biomater. Sci. Eng. 2020, 6, 3122−3131
ACS Biomaterials Science & Engineering
Figure 7. SERS signal comparison of (a) BC and (b) HBC paper sheets with and without AgNPs decoration for 1 μM R6G measurement, with the
respective normal Raman spectrum of 1 μM R6G depicted in each inset, and two-dimensional FDTD simulation of the EM field distribution on
plasmonic (c) BC and (d) HBC paper sheets.
EFSERS of the BC paper sheet. This is in line with the findings
of the morphological structure and SERS intensity as a
consequence of the robust hotspots in the plasmonic HBC
paper sheet that resulted from HPH. To comprehend the
impact of nanofibrillation in the construction of SERS-active
hotspots inducing electromagnetic (EM) field enhancement,
we performed a FDTD simulation as displayed in Figure 7c,d.
The EM distribution of 50 nm AgNPs used in this study was
simulated on a sparse mesh density and highly dense mesh
mimicking the textural properties of the plasmonic BC and
HBC paper sheets, respectively. The closer interparticle
distance arranged on the HBC, being nearly 10 nm, exhibits
greater EM field localization, amplifying the oscillation of the
electron clouds surrounding the AgNPs for optimum SERS
enhancement factor compared with the BC sheet with sparser
particle-to-particle distance. It was observed that the field
enhancement amplitude exponentially decreased as the
nanogap is increased. Additionally, it can be assumed that
the EM distribution of each single AgNP was contributed by
AgNPs’ interfaces with cellulose and air with regard to the
normal photon direction to the AgNPs/nanosheet interfacial
layer. The density of the particles was taken into an important
account, where in our setup approximately >100 particles were
confined in a single laser spot of 78.5 μm2; thus, the average
signals produced from the nanogaps could be confirmed as a
uniform Raman signal from the nanosheet substrate. This
simulation result is indicative of the potential niche and fitness
of nanostructuring green-synthesized materials as an alternative
for rigid solid-state inorganic materials, such as silicon or glass,
for use as an excellent SERS paper substrate.
4. CONCLUSION
A simple and low-cost nanostructuring of a natural and
abundant polymer was realized to build up an enticing
alternative SERS paper substrate. Nanofibrillation involving
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high-pressure homogenization of ubiquitous cellulose-based
food products, such as nata de coco, yielding HBC paper
sheets effectively reinforced the SERS hotspots creation after
the integration of AgNPs due to morphological, textural, and
crystallinity alteration of the cellulose. Immense reinforcement
of the SERS signal studied by detection of R6G molecules
mainly resulted from the high surface roughness from dense
and tangled nanocellulose ribbons caused by the mechanical
pressure and cycles throughout the nanofibrillation process,
which left the fibril stiffness unchanged. The alterations
ultimately provided more surface hydroxyl groups and a larger
surface anchoring site for AgNPs. As compared to the naturally
grown bacterial cellulose, the HBC sheet effectively generated
subnanometer interparticle spacing for a strong electro-
magnetic field localization, favoring SERS enhancement, as
proven by the more than 50% sensitivity enhancement in the
screening of R6G, as well as the 2 order higher enhancement
factor. In addition, the HBC sheet SERS paper sensor has
paved a novel path toward simple in situ nanostructuring,
which can be combined with a variety of techniques, including
dip-coating, spraying, and electrospinning, toward the goal of
highly ordered nanoparticles for more intense SERS enhance-
ment.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsbiomaterials.9b01890.
Water contact angle measurement of the NDC-based
paper sheets, FE-SEM photographs the plasmonic paper
sheets, photographs of the paper sheets, SERS measure-
ment of Methylene Blue on plasmonic paper sheets for a
preliminary study of other compound detection, and
https://dx.doi.org/10.1021/acsbiomaterials.9b01890
ACS Biomater. Sci. Eng. 2020, 6, 3122−3131
ACS Biomaterials Science & Engineering
variability of parameters for the EFSERS calculation
(PDF)
■
AUTHOR INFORMATION
Corresponding Author
Agnes Purwidyantri − Research Unit for Clean Technology,
Indonesian Institute of Sciences, Bandung 40135, Indonesia;
International Iberian Nanotechnology Laboratory, 4715-330
Braga, Portugal; Biosensor Group, Chang Gung University,
Taoyuan 33302, Taiwan; orcid.org/0000-0002-4457-
2778; Email: agnes.purwidyantri@lipi.go.id
Authors
Myrtha Karina − Research Unit for Clean Technology,
Indonesian Institute of Sciences, Bandung 40135, Indonesia
Chih-Hsien Hsu − Department of Electronic Engineering,
Chang Gung University, Taoyuan 33302, Taiwan
Yoice Srikandace − Research Unit for Clean Technology,
Indonesian Institute of Sciences, Bandung 40135, Indonesia
Briliant Adhi Prabowo − Research Center for Electronics and
Telecommunications, Indonesian Institute of Sciences, Bandung
40135, Indonesia; International Iberian Nanotechnology
Laboratory, 4715-330 Braga, Portugal; Biosensor Group,
Chang Gung University, Taoyuan 33302, Taiwan;
orcid.org/0000-0002-7543-5143
Chao-Sung Lai − Department of Electronic Engineering and
Biosensor Group, Chang Gung University, Taoyuan 33302,
Taiwan; Department of Nephrology, Chang Gung Memorial
Hospital, Taoyuan 33305, Taiwan; Department of Materials
Engineering, Ming-Chi University of Technology, 24301,
Taiwan; orcid.org/0000-0002-2069-7533
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsbiomaterials.9b01890
Author Contributions
General concept and experiments were designed by A.P, M.K,
C.-H.H, and C.-S.L. Morphological and textural analysis of the
NDC-based paper sensor was performed by A.P, C.-H.H, and
Y.S. Graphical abstract, illustration design, and simulation work
were performed by B.A.P. The first draft, submitted manu-
script, and the revision were prepared by A.P and B.A.P. All
aspect of this work was supervised by A.P. All authors have
given approval to the final version of the manuscript.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
A.P. is wholeheartedly thankful for the Mandiri 2019 Grant
from the Research Unit for Clean Technology (LPTB),
Indonesian Institute of Sciences (LIPI) under the letter no. B-
227/IPT.7/KP/I/2019. Y.S. is grateful for the Insinas (Insentif
Riset Sistem Inovasi Nasional) Grant from the Indonesian
Ministry of Research and Technology/National Agency for
Research and Innovation (RISTEK-BRIN) under the contract
number 048/P/RPL-LIPI/Insinas-1/II/2019. B.A.P. thanks
the Chang Gung University, Taiwan, for the Visiting Scholar
Invitation under grant number BMRP741. C-S.L. thanks the
Ministry of Science and Technology (MOST), Taiwan, R.O.C.
project with contract no. MOST 108-2218-E-182-002 and
Chang Gung Memorial Hospital (CGMH) project with
contract nos. CMRPD2K0051 and CORPD2J0071.
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ABBREVIATIONS USED
NDC, nata de coco; HPH, high-pressure homogenization;
HBC, homogenized bacterial cellulose; BC, bacterial cellulose;
AgNPs, Ag nanoparticles; R6G, Rhodamine 6G; SERS,
surface-enhanced Raman scattering; XRD, X-ray diffraction;
FTIR, Fourier-transform infrared; AFM, atomic force micro-
scope; PSA, particle size analyzer; FE-SEM, field emission
scanning electron microscope; CCD, charge-coupled device;
FDTD, finite-difference time domain
■
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