J Mater Sci (2018) 53:8677–8698

Review
REVIEW

A review of the preparation and application of magnetic

nanoparticles for surface-enhanced Raman scattering
Huasheng Lai1 , Fugang Xu1,* , and Li Wang1

1
College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang 330022, People’s Republic of China

Received: 11 September 2017 ABSTRACT

Accepted: 31 January 2018
Published online:
6 February 2018
Ó Springer Science+Business
Media, LLC, part of Springer
Nature 2018
In recent years, the unique properties of magnetic functional nanomaterials have
received considerable attentions and show promising applications in separation,
detection, diagnosis, catalysis, environment remediation and so on. Specifically,
introducing magnetic nanomaterials (MNPs) into traditional sensing techniques
greatly simplifies detection operation and improves sensing performances,
which makes magnetic nanomaterial-based sensing techniques become a hot
research topic. Compared with other sensing techniques such as chromatogra-
phy, fluorescence, mass spectrum and electrochemistry, surface-enhanced
Raman scattering (SERS) displays unique properties of high-sensitivity, finger-
print specificity and nondestructive detection. The introduction of MNPs in
SERS has proven to be an efficient way to resolve several critical challenges in
practical SERS analysis leading to highly efficient target separation and
enrichment, high-sensitive detection and precise outcomes analysis. This makes
the MNPs involved SERS analysis a powerful technique with very appealing
and promising application in various branches of analytical science. In this
review, we first briefly introduced the preparation, encapsulation and surface
modification of magnetic nanoparticles, assembly of magnetic nanoparticle–
plasmonic substrates and then discussed their applications in SERS analysis,
including biomedical application, environmental analysis, food safety and
chemical reaction monitoring. Finally, we presented some outlooks on further
developments of magnetic nanoparticles in SERS applications.

Introduction analytical methods, but also accelerate the birth of

The past few decades have witnessed the rapid
development of analytical science, and there is no
doubt that nanomaterials play a vital role in this
process. Functional nanomaterials not only greatly
improve the sensing performance of traditional
some new analytical techniques. Among various
nanomaterials, magnetic nanoparticles (MNPs) with
unique magnetism and excellent physicochemical
properties have attracted much attention recently [1]
and have shown great potential in catalysts [2], sen-
sors [3], adsorbents [4], wastewater treatments [5],

Address correspondence to E-mail: fgxu@jxnu.edu.cn

https://doi.org/10.1007/s10853-018-2095-9
8678
semiconductors [6], pigments, magnetic data storage
devices [7], magnetic resonance imaging (MRI) [8],
bio-separations [9] and medicines [10]. Specifically,
the superior adsorption capacity, magnetic separa-
tion/concentration ability and magnetic resonance
imaging utility of MNPs arouse intensive interests for
researchers in various branches of analytical science
[11–13]. As the properties and application of MNPs
are closely related to the size, shape and surface
ligand of MNPs, thus manipulating the size, shape,
component, surface ligand of MNPs is greatly
desired, and much effort has been devoted to the
controllable preparation of MNPs in the past decades,
and several reviews are available on this issue
[14–18]. However, the direct application of bare or
single-component MNPs is limited due to their
shortcomings including poor stability/dispersity,
relative inertness and poor surface functionality.
Hence, in most cases, the modified MNPs or MNP-
based composite structure was employed. The MNP-
based composites not only overcome the shortcoming
of bare single MNPs, but also incorporate new
properties of the second material in catalysis, optical,
spectroscopy, electrochemistry and so on, which
greatly extended the application area of magnetic
particle-based hybrid. The successful preparation of
modified MNPs or MNP-based hybrid also promotes
the application of MNPs in other analytical tech-
niques in addition to separation and MRI. Consider-
ing this, efficiently coupling these materials to
various analytical techniques such as electroanalyti-
cal chemistry, chromatography and spectroscopy is
vital to take full advantages of the unique properties
of MNPs for advanced sensing performance.
As a powerful analytical technique [19], surface-
enhanced Raman scattering (SERS) has been widely
employed for molecule sensing (environmental pol-
lutants [20], biomarkers [21], pesticides [22], explo-
sives [23] and drugs [24, 25]), bio-imaging [26],
diagnostic [27], reaction monitoring [28] and so on
due to its incomparable superiority of the unique
fingerprint spectroscopy, nondestructive data acqui-
sition [29] and single-molecule sensitivity (single-
molecule SERS has been reported with enhancement
factor up to 1014–1015 in total [30]). Even so, the
application of SERS in practical analysis still
encounters several critical challenges, such as (1) the
interferences from complex matrix of real sample; (2)
the high cost of SERS analysis due to the utilization of
noble metal as substrate and its low recyclability; (3)
J Mater Sci (2018) 53:8677–8698
the limited concentration/enrichment effect of the
substrate for target; (4) and the complex or sophisti-
cated procedure for fabricating enhancement hot
spots. Fortunately, the unique properties of MNPs
may provide efficient solutions to these challenges.
By simply manipulating magnetic force, we can
easily achieve: (1) facilely and fast separate analyte
from sample matrix to reduce the interference; (2)
recycling utilization of magnetic substrate; (3) effec-
tive and simultaneous separation and enrich-
ment/concentration ability, which is beneficial to
detect low-abundance analyte; and (4) ordered
arrangement or controllable aggregation of substrates
under magnetic attraction, which can generate a
favorable density of ‘‘hot spots’’ for subsequent SERS
enhancements. Therefore, rational designed MNP–
plasmonic nanostructures and efficiently coupling
MNPs with SERS could greatly improve the sensing
ability of SERS and extended their application fields.
Given that many solutions have been given in the
fabrication of MNPs–Au, MNPs–Ag and multifunc-
tional MNPs–Au/Ag-based hybrid in the past dec-
ades, it is also convenient to introduce MNPs in SERS
analysis.
Though much of work has been done to prepare
various MNPs and huge progresses have been made
to apply MNPs in SERS, the research on MNPs
preparation and its application in various fields
including SERS still continue with full passion and
tempting potential and a large space is still available
to explore the application of MNPs in SERS analysis.
Considering this, it is quite necessary to summarize
the recent advances of MNPs in SERS analysis. Pre-
viously, lots of review articles on preparation and
applications of MNPs have been published; however,
most of these reviews focus on biomedical related
application [31, 32] (including diagnosis, drug deliv-
ery) and pollutant treatment [33]. Reviews on
preparation and application of MNP biosensors are
also reported, while most presented the general
introduction of MNPs in sample pretreatment and
application in specific analyte detection [34, 35] using
different sensing techniques (typically electrochemi-
cal methods, MRI, SPR), in which SERS is seldom
involved. Very recently, reviews focus on application
of MNPs in fluorescence detection [36] and electro-
chemical sensing [37] are also available. Nevertheless,
reviews on application of MNPs in SERS, an impor-
tant, powerful analytical technique with high sensi-
tivity and promising application, have not been
J Mater Sci (2018) 53:8677–8698
reported despite the fact that many good original
works have been published. On the other hand,
reviews about SERS and its application were also
widely reported, which often pay attention to the
plasmonic substrate fabrication and their application
in specific molecule sensing [38] or biomedical diag-
nosis, while few special focus on MNPs. Some com-
prehensive reviews on biosensing may involve MNPs
and SERS [11, 39, 40], but with quite limited, frag-
mented space, and they did not clearly correlate
MNPs with SERS. To grasp the whole picture of
MNPs in SERS, the reader needs lots of time and
great effort to search among volume reviews on
MNPs and SERS. Therefore, there is a large space and
great necessity to summarize the progress on appli-
cation of MNPs in SERS. The introduction and dis-
cussion of these achievements will provide the
appropriate background for developing novel mate-
rials and analysis methods for the detection of
diverse analytes in real sample with SERS and MNPs.
To better understand the research progress in this
area and shed a light on future research road, a crit-
ical review is present here. First, recent progress on
preparation methods of MNPs including the prepa-
ration, encapsulation and surface modification of
MNPs is briefly reviewed. Then, assembly of MNP–
plasmonic substrates for efficient SERS is introduced.
After that, application of MNPs in SERS analysis is
intensively discussed. Finally, the outlook about the
MNPs and their application in SERS is presented.
Preparation of magnetic nanoparticles
Preparation method
Synthesis of MNPs with desirable properties and
high potential applications are greatly demanded. Up
to now, there are several typical and newly emerging
methods to prepare MNPs with various morpholo-
gies and properties. These preparation methods
include co-precipitation, thermal decomposition,
hydrothermal, sol–gel, microemulsion, flow injection
technique, aerosol/vapor, sonochemical technique
and electrochemical methods [14–18, 41–48]. The
characters of these methods are listed in Table 1.
Seeing the above preparation methods, co-precipi-
tation is the most facile and convenient wet chemical
method to prepare MNPs with reproducible quality
once the reaction conditions are well controlled, but
8679
the size and shape control are not so good. Thermal
decomposition is the most well-known technique to
prepare uniform-sized superparamagnetic MNPs by
heating iron precursors in solvents (or aqueous
solution) at high temperature under autogenous
pressure. Sol–gel method can obtain pure amorphous
phases MNPs with good monodispersity and con-
trolled microstructure. Microemulsion route can be
used to prepare the size- and shape-controlled MNPs,
yet the presence of surfactants in the reaction may
cause the aggregation of prepared MNPs which need
additional washing progress and stabilization treat-
ment. Flow injection technique is a novel strategy
with several superiorities to fabricate small-sized
MNPs, such as high mixing homogeneity, high
reproducibility and precise control of reaction con-
ditions. Sonochemical technique has been widely
employed to synthesis highly monodispersive
nanoparticles with different morphologies, but has
some limitations in the size control and large-scale
production. Electrochemical method is a cost-effec-
tive and easily available way, which does not need
high temperature to fabricate MNPs; however, as-
prepared MNPs are often poorly ordered, and the
electrodeposition is only available to execute on
conducting substrates. Generally speaking, the cho-
sen of proper method depends on the desire prop-
erties what we need, so the advantages and
shortcomings of each method should be balanced. All
in all, there is still a great need to develop a cost-
effective, convenient and efficient approach to pro-
duce monodispersed MNPs with uniform size and
controllable shape and surface properties for differ-
ent applications.
Encapsulation and surface modification
Although MNPs have many unique properties, bare
MNPs are easily oxidized, eroded by acids or bases,
and they have fewer active groups, and thus, it is
hard to keep their stability without aggregation or
precipitation for a long time [49]. These issues have
severely restricted the practical applications of MNPs
in many fields. Consequently, encapsulation and
surface modification of bare MNPs with appropriate
materials is necessary to resolve these issues.
 8680

Table 1 Summary comparison of the synthetic methods

Method Synthesis Reaction Reaction Solvent Size- Shape Yield Reference

temperature (°C) period distribution Control

Co-precipitation Very simple, ambient conditions 20–90 Minutes Water Relatively Not good High/ [43]
method narrow scalable
Sol–gel method Simple, ambient conditions \ 1000 Days–weeks Organic compound Narrow Very High/ [18, 42]
good scalable
Hydrothermal Simple, high pressure 220 Hours–days Water–ethanol Very Very Medium [18, 42, 43]
method narrow good
Microemulsion Complicated, ambient conditions 20–50 Hours Organic compound Relatively Good Low [16, 42]
method narrow
Thermal Complicated, inert atmosphere 100–320 Hours–days Organic compound Very Very High/ [16, 41, 43–46]
decomposition narrow good scalable
method
Flow injection Complicated, pressure, current —— 10-8–10-5 s Organic compound Very Good High/ [16, 18]
technique velocity, temperature etc. narrow scalable
Aerosol/vapor Complicated, high pressure – Minutes– Ethanol/organic Narrow Not good High/ [47]
method hours compound scalable
Sonochemical Very simple, ambient conditions – Seconds– Organic compound Narrow Good High/ [16]
technique minutes scalable
Electrochemical Simple, ambient conditions Room temp. Milliseconds– Water–ethanol/water/ Quite Not good Low [17]
method minutes organic compound narrow
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J Mater Sci (2018) 53:8677–8698
Organic polymer materials
To avoid agglomeration, endowing the bare magnetic
particles with new properties, organic polymers are
often employed to encapsulate MNPs. Polymer as
coating will prevent nanoparticles from oxidation,
enhance compatibility and reduce susceptibility to
leach [15]. As a result, encapsulated MNPs display
improved monodispersity, enhanced chemical sta-
bility and reduced toxicity [50]. In general, polymers
can be self-polymerized to form a shell on the surface
of MNPs, either chemically anchored or physically
adsorbed, which could create repulsive forces to
balance the van der Waals attractive forces and the
magnetic [51].
Usually, three typical polymerizations methods are
employed to prepare polymer-coated MNPs: seed
precipitation polymerization [52], cross-linking of
polymers [53–55] and inverse emulsion polymeriza-
tion [56]. The thickness of stable polymeric shells
created by these strategies around the nanoparticles
can be turned by changing the monomer concentra-
tion, polymerization temperature, polymerization
time and water/surfactant ratio.
Organic polymers as coating shell endow the
MNPs’ surface with functional groups, such as car-
boxyl (–COOH), amino (–NH2), hydroxy (–OH) and
sulfhydryl (–SH). The most frequently used polymers
include noncytotoxic folic acid [57, 58], poly(acrylic
acid) (PAA) [59], multifunctional poly(styrene-alt-
maleic acid) (PSMA) [60], poly(methacrylic acid)
(PMAA) [61], thermosensitive poly(N-isopropy-
lacrylamide) (PNIPAM) [62, 63], poly(ethylenimine)
(PEI) [64–66] and conductive and electromagnetic
wave absorptive polyaniline (PANI) [67]. Moreover,
poly(pyrrole) (PPy) [68], poly(ethylene glycol) (PEG)
[69], polyesters and their copolymers are also
involved. The introduced functional groups can
easily bond biomolecules or substances with opposite
charge, and it is a quite effective way to bond elec-
tronegative noble metallic nanoparticles on shell
surface to generate hot spots for Raman signals
enhancement.
However, the introduction of organic polymers
may cause additional Raman peaks or signal back-
ground in the Raman spectrogram, which would
have a large impact on the analysis of unknown
samples. Moreover, inherent shortcomings of organic
polymers would also accompany by the introduction.
And additional washing progresses and further
8681
treatments are necessary to remove excess polymers.
Consequently, these vital influences should take into
consideration in the modification step as well as take
effective treatments before the polymer-modified
MNPs was used for SERS analysis.
Inorganic materials
Inorganic matrixes have early been explored to wrap
MNPs to improve their performances. These inor-
ganic material modifications could shield the
nanoparticles, avoid oxidation and aggregation,
enhance compatibility and obtain new functional
groups [70]. Ordinarily, porous natural matrixes
(silica and carbon [71–73]), noble metal nanoparticles
(antibacterial silver [74], biocompatible gold [75]),
photocatalytic metal-oxide semiconductor (ZnO [76]
and TiO2 [77]) and graphene are used to wrap MNPs.
These inorganic shells employed for the encapsula-
tion of bare MNPs show incomparable advantages
like economical, green environmental, nontoxic.
Furthermore, new functions introduced by inorganic
modification, such as porous silica and carbon, are
physicochemical stable interlayers to further grow
SERS-active nanoparticles, and carbon has strong
adsorption capacity; roughed Ag and Au can gener-
ate tremendous enhancement effects; ZnO and TiO2
are photocatalytic interlayers to adsorb and degrade
organic pollutions in wastewater; graphene with
large surface area could increase the adsorption
ability and generate chemical enhancement effect for
SERS signals. Nevertheless, these inorganic coatings
still have some problems: Au and Ag nanoparticles
are prone to agglomerate, and Ag is easily oxidized;
graphene materials are usually overlapped and can-
not coat the MNPs uniformly and so on. These issues
should be solved to better shield the core and
improve their applications in various fields like
flexible SERS substrates. Specifically, silica is an
effective and widely used material to coat MNPs due
to its high chemical and thermal stability, good
compatibility and non-toxicity property [70]. The
Stöber process is a typical method for wrapping
MNPs with SiO2, which have been reported in the
extensive literature [78]. In this approach, the thick-
ness of coated SiO2 shell could be changed by
adjusting the reaction time, the concentration of
ammonia catalyst, TEOS precursor, etc. There are still
some other methods to challenge for the preparation
of uniform silica shells with controlled thickness,
8682
such as microemulsion method [79], aerosol pyrolysis
[80] and sonochemical deposition [81]. The silica-
coated MNPs can be easily modified by silanization
reagent to endow it with functional group such as –
SH or –NH2, which facilitates loading SERS-active Au
or Ag nanoparticles on the MNPs surface. It should
be mentioned that it is far from enough to purely use
inorganic nanomaterials wrapped MNPs for SERS
application. Hence, further modification steps are
also demanded to enable the MNPs to bond various
Au or Ag nanoparticles in a narrow distribution.
As both organic polymer and inorganic coating
have their advantages, the choice of the modified
material really depends on the specific application. In
many cases, the combination usage of inorganic and
organic polymeric materials would realize better
performance in application, such as biocompatibility,
stability and monodispersity of MNPs, and uniform
distribution of Au or Ag nanoparticles on the surface.
Whatever the capping layer is, the main object is to
protect MNPs from oxidation and aggregation and
facilitate its surface functionalization. But, the poly-
mer or inorganic material coating process may com-
plicate the preparation and degrade the crystal
quality of MNPs, and importantly, thick coating will
greatly influence the magnetic susceptibility of
MNPs.
Assembly of MNP–plasmonic substrates
Based on the effective modification methods to
overcome several limitations of bare MNPs, fabri-
cating of assembly of MNP–plasmonic SERS sub-
strates with intrinsic hot spots would be much easy
and controllable. Combining the magnetic-induced
aggregation, multidimensional hot spots can be gen-
erated. This will greatly improve the performance of
MNP–plasmonic SERS substrates, including sensi-
tivity and reproductivity. Normally, in situ growth
and ex situ assembly are widely used to prepare the
multicomponent substrates, and the example of the
preparation of Fe3O4/Au substrates is shown in
Fig. 1a [82].
The in situ method means directly growing plas-
monic nanoparticles onto the surface of modified
MNPs. The most well-known way is reducing
metallic irons into nanoparticles in the presence of
reducing agents, which can directly deposit onto
MNPs. Choi et al. [83] used butylamine to reduce
AgNO3 in ethanol to directly deposit Ag onto the
J Mater Sci (2018) 53:8677–8698
Figure 1 a Three different techniques for the synthesis of c
Fe3O4@Au core–shell nanoparticles. Adapted from Ref. [75].
Copyright: 2015 American Scientific Publishers. Used with
permission. b Plasmonic hot spots formed on Fe3O4@Au
(a) and calculated electric field intensity distribution (b–e).
Adapted from Ref. [82]. Copyright: 2016 Elsevier B.V. Used
with permission. c Synthesis and functionalization of star-shaped
Fe3O4@Au NPs. Adapted from Ref. [87]. Copyright: 2013 Royal
Society of Chemistry. Used with permission. d The synthesis
procedure of Fe3O4@Ag/PEI/Au@Ag core–shell–satellite micro-
spheres. Adapted from Ref. [89]. Copyright: 2015 Royal Society
of Chemistry. Used with permission.
Fe3O4@SiO2 particles. Du et al. [84] developed a one-
pot solvothermal route to synthesis Ag/Au/Fe3O4
composite in the presence of PVP and trisodium
citrate. Physical deposition is also a widely accept
approach, and Gao et al. [85] fabricated flowerlike
Fe3O4/Ag via magnetron sputtering Ag nanoparti-
cles onto immobilized Fe3O4 microflowers. Further-
more, photochemical deposition is a possible way to
deposit silver nanostructures on ZnO/Fe3O4 com-
posite under UV light irradiation [76]. The in situ
approach has the advantages of inexpensive and
convenient, but the disadvantages are also obvious:
the shape, size and distribution of plasmonic
nanoparticles on MNPs are hard to control. For
example, the morphology of MNPs–Au composite is
often limited in sphere.
In ex situ method, pre-synthesized MNPs and
plasmonic nanoparticles are assembled to construct
multicomponent MNP-based substrates. In this
approach, the surface properties of the capping
materials of MNPs are crucial to the bonding of
nanoparticles. For example, negatively charged
PMAA or positively charged branched PEI is often
used to increase the negative or positive charge of the
surface of MNPs through layer-by-layer assembly
technique. Then, opposite charged noble metal par-
ticles can be easily and stably anchored onto the
modified MNPs as efficient SERS substrates [86]. The
ex situ strategy is effective to produce high-perfor-
mance MNP–plasmonic SERS substrates, while the
size, shape and attachment density of plasmonic
particles–MNPs can be flexibly tuned. However,
sometimes, ingenious design and sophisticated skill
is need to control the interaction between MNPs and
plasmonic particles to form highly efficient SERS
substrate.
J Mater Sci (2018) 53:8677–8698 8683
8684
Additionally, the morphology and structure of
SERS substrates is closely related to the enhancement
effect; hence, it is important to fabricate MNP-based
SERS substrates with various and multidimensional
hot spots (Fig. 1b). Plasmonic structures with sharp
protrusions or tips in all directions would also pro-
duce multiple intrinsic hot spots. And seed-mediated
growth method plays an important role in producing
desired substrates with large enhancement effects.
For example, star-shaped MNP–Au nanoparticles
could be formed by the growth of Au seeds in the
presence of HAuCl4, PVP and DMF (Fig. 1c) [87, 88].
Besides, layer-by-layer assembly technique is a good
approach to form multidimensional hotspots. Wang
et al. [89] presented a core–shell–satellite 3D Fe3-
O4@Ag/Au@Ag substrate by the growth of Au seeds
to form Ag shell and then attach Au@Ag (Fig. 1d).
Polymer PEI was used between each step to attach
Au and Au@Ag nanoparticles.
By rational designing the arrangement of MNPs
and plasmonic particles, the efficient coupling
between plasmonic particles could generate high
enhancement effect, together with the facile separa-
tion, effective enrichment, concentration effect, the
MNPs–Au/Ag hybrid could greatly promote the
sensing performance of SERS. For practical analysis,
it is still needed to fabricate novel MNPs–plasmonic
particle hybrid with high enhancement ability, good
stability and multiple functionality.
Applications in SERS
MNPs have been widely used in SERS research due
to its incomparable superiorities: (1) unique size
offered bio-imaging function, drug deliver capacity,
stability and reproducibility; (2) the magnetic prop-
erties improve the efficiency of sample pretreatment
and enrichment and achieve the control of targeting
movement; (3) diverse morphologies facilitate the
formation of abundant hot spots to improve SERS
sensitivity; and (4) intrinsic excellent properties of
surface functionalized MNPs possess. MNP-based
SERS substrates with outstanding characteristics can
achieve high-sensitivity recognition and rapid
detection. And this is a rapid growing and very
promising research branch in analytical science.
Here, the application of MNPs in SERS analysis for
biomedicine, food safety, environment, reaction
monitoring is briefly introduced.
J Mater Sci (2018) 53:8677–8698
Biomedical application
MNPs have been widely used in biomedical field.
SERS also exhibits good biomedical application val-
ues as a high-sensitive and nondestructive single
molecular detection technique. A hybrid of MNPs–
plasmonic particle may hold the function of diagno-
sis, drug delivery and treatment in one solid, which is
not only beneficial for precise early diagnosis of dis-
eases [90–92], but also make it easier to monitor the
drug fate and evaluate treatment effect [93]. Gener-
ally, the labeled MNPs are used for cancer diagnostic
and target detection (e.g., for nucleic acid (DNA/
RNA) [59, 94–97], protein [64, 66, 98–102] and even
bacteria [96, 103–106]).
As an example of MNPs application in cancer
diagnostic study, Rong et al. [107] designed a sand-
wich magnetic immune complexes sensor to detect
cancer biomarkers. In this work, capture antibody-
coated Ag decorated Fe3O4 MNPs were employed as
the carcinoembryonic antigen (CEA) concentration
platform and the signal magnification substrate.
Meanwhile, the SERS tags and Ag-coated Au nanor-
ods were decorated with testing antibody. Because
the plasmon peak of resonant Raman dye diethylth-
iatricarbocyanineiodide (DTTC) is near to the excita-
tion wavelength, the Raman signals were greatly
enhanced. Moreover, the high-sensitive sensors can
detect CEA with a low LOD of 4.75 fg/mL (Fig. 2a)
and a well-defined dynamic linear range between
10 fg/mL and 100 ng/mL (Fig. 2b). Similarly,
through changing antigens and corresponding anti-
bodies in the sandwich magnetic core–shell-based
immune complexes, Lin et al. [108] tested CEA in
human serum and Qiu et al. [61] detected CEA-ex-
pressed A549 cells at a very low abundance (* 10
cells/mL). Ge et al. [109] determined human epi-
didymis protein 4 (HE4) of ovarian cancer. Interest-
ingly, Yang et al. [110] developed a label-free Fe3O4/
Au/Ag nanocomposite for the detection of lung
cancer biomarker (adenosine) in urine samples and
achieved on-site screen adenosine by magnetically
assisted SERS protocol (Fig. 2c). The substrate shows
a good stability, excellent reproducibility, time effi-
ciency (within 20 min to test one sample), high sen-
sitivity with a LOD down to 10-10 M and a good
linear range from 5 mM to 0.5 nM (Fig. 2d–f).
For the DNA/RNA detection, Wu et al. [96]
achieved Bacillus thuringiensis special gene fragment
detection by Fe3O4 magnetic beads and Au/Ag core–
J Mater Sci (2018) 53:8677–8698
Figure 2 a SERS spectra of CEA at various concentrations under
785 nm excitation. b Plot of the Raman intensity at 1238 cm-1
versus the logarithmic concentration of CEA. Adapted from Ref.
[107]. Copyright: 2016 Elsevier B.V. Used with permission.
c Schematic illustration of array setup and procedures in the
detection of adenosine by Fe3O4/Au/Ag nanocomposites with a
portable Raman. SERS spectra of aqueous adenosine recorded
shell nanorods based on the biotin–streptavidin-
specific interaction with a good linear responsive
range of 0.1 pM to 1 nM and a LOD of 0.14 pM. Pang
et al. [95] reported that miRNA let-7b can be specif-
ically captured by MNPs within a PE tube without
8685
after mixing with Fe3O4/Au/Ag nanocomposites d using confocal
Raman (excitation laser at 633 nm) and e using a portable stabi-
lized R. laser analyzer (excitation laser at 785 nm, 300 mW).
f Linear correlation of Raman intensities (at 730 cm-1) with the
logarithm of adenosine concentrations from 0.5 nM to 5 mM.
Adapted from Ref. [110]. Copyright: 2014 American Chemical
Society. Used with permission.
any PCR pre-amplification treatment and quantita-
tive detection of miRNA from 1 fM to 1 nM with a
LOD as low as 0.3 fM (15 zeptomole, 50 lL) (Fig. 3a,
b). Li et al. [59] demonstrated the sensitive detection
of a specific single-stranded DNA (ssDNA) sequence
8686
Figure 3 a SERS intensities (1586 cm-1) versus let-7b concen-
trations. Inset: SERS spectra and linear relationship between the
SERS intensity and the miRNA concentration. b Specificity of
miRNA assay. Adapted from Ref. [95]. Copyright: 2015 Elsevier
B.V. Used with permission. SERS spectra of d MGITC detecting
on the basis of the SERS liquid chip. In their work, the
corresponding probe DNA was grafted to the poly
(styrene-co-acrylic acid)/Ag/SiO2 composite SERS
tags, and the capture DNA was attached to the
Fe3O4/PAA core–shell nanospheres. Quantitative
detection of target ssDNA was achieved based on the
well-defined linear correlation between the SERS
J Mater Sci (2018) 53:8677–8698
E. coli, e DACITC detecting S. typh and f PPY detecting MRSA
with the concentration range 104 to 101 CFU/mL, and correspond-
ing histogram of the intensity of the characteristic peak. Adapted
from Ref. [103]. Copyright: 2017 American Chemical Society.
Used with permission.
signal intensity and the target ssDNA quantity in the
range of 10 nM to 10 pM, and the LOD was
approximately 10 pM.
Protein detection is one of the earliest works in the
development of MNPs application in biomedicine.
Wang et al. [66] employed Fe3O4@PEI@Ag versatile
SERS substrate to detect adsorbed p-ATP molecules
J Mater Sci (2018) 53:8677–8698
and human immunoglobulin (lgG) with a LOD as
low as 10-11 M and 10-14 g/mL, respectively.
Besides, the model of Raman intensities with the
logarithmic concentrations has good curve fitting
characteristics, and corresponding coefficient of
determinations is R2 = 0.995 of p-ATP and
R2 = 0.992 of lgG. Balzerova et al. [100] presented the
determination of IgG in blood. Alula et al. [76] pre-
pared Ag@ZnO/Fe3O4 composites to determine cre-
atinine in urine sample and quantitative analyses in
aqueous solution. Yang et al. [101] presented an
aptamer-modified MNPs–AuNPs satellite to detect
prostate specific antigen (PSA) assay based on highly
specific biorecognition, which possesses high sensi-
tivity of LOD as low as 5 pg/mL and good repeata-
bility with the recoveries between 97.63% and
103.84%.
Immobilized MNPs as high-performance SERS
substrates can also be employed for the detection and
identification of bacteria. Zhang et al. [105] utilized
the SERS peak of mercaptobenzoic acid (MBA) at
1582 cm-1 or 5,50 -dithiobis (2-nitrobenzoic acid)
(DNTB) at 1333 cm-1 to measure S. typhimurium or
S. aureus in the range from 102 CFU/mL to 107 CFU/
mL, respectively. The LOD of S. aureus is 35 CFU/
mL, and S. typhimurium is 15 CFU/mL. Similarly,
Kearns et al. [103] achieved simultaneous detection of
multiple pathogens by combining lectin (Con A)-
functionalized Ag@MNPs extraction with the unique
Raman reporters of biorecognition antibody-func-
tionalized AgNPs. In detail, malachite green isothio-
cyanate (MGITC), 7-dimethylamino-4-
methylcoumarin-3-isothiocyanate (DACITC) and
4-(1H-pyrazol-4-yl)-pyridine (PPY) as Raman repor-
ters were used to detect Escherichia coli, Salmonella
typhimurium and methicillin-resistant Staphylococ-
cus aureus, respectively. And LODs of single com-
ponent are 101 CFU/mL (Fig. 3d, e), but quantitative
analysis is not clarified.
To summary, MNP-based SERS substrates have
realized accurate, fast and highly sensitive detection
of biomarkers on the basis of specific biorecognition.
However, most of current investigations are limited
in the detection of target molecules in simple
matrixes, and most of the cells, aptamers or bacteria
pathogens are obtained in special artificial cultures.
That means much of work need to be done on the real
practice in complex matrixes, where detected sub-
stances are extracted from natural environment or
cells, tissues and organs of living animals. Moreover,
8687
some limitations of MNP-based SERS substrates
should be mentioned that the real-time vivo detec-
tions are restricted in the penetration ability of
Raman laser and signal receiver. Additionally,
antifouling ability, stability, biocompatibility and
multiplex sensing ability of MNP-based SERS sub-
strates still need to be improved in practice biomed-
ical analysis.
Food safety
SERS analytical techniques have been proven to be
an applicable approach for scrutinizing food safety
[111], especially for the detection of bacterial patho-
gens [112–114], antibiotics [57, 115], pesticide resi-
dues [65, 89, 116–122] and banned food additives
[123–125].
Sun et al. [123] designed a versatile core–satellite
Fe3O4@SiO2/Au 3D magnetic microsphere (the Au
nanoparticle gap was sub-10 nm) for charge selective
detection of food dye molecules. This is one of the
earliest reports on magnetic-based SERS-active
hybrid for simultaneous selective enrichment, mag-
netic separation and SERS-based detection of multi-
ple food dyes.
Much of work has been done for the detection of
pesticide residues, commonly thiram, one of the
typical dithiocarbamate fungicides. Yang et al. [117]
directly grafted Au nanoparticles onto the magnetic
network nanostructure surface with the assistance of
inositol hexakisphosphate (IP 6), which exhibited
sufficient adsorption, enrichment, separation and
Raman enhancement for the on-site detection of trace
thiram in multiple vegetable peels as low as 10-15 M
by a portable Raman spectrometer, and a good linear
relationship in the range of 500 nM to 50 fM (Fig. 4a–
c). Liu et al. [116] introduced multifunctional Fe3-
O4@GO@Ag ternary complex to detect pesticide
residues on the fruit peels based on a surface mag-
netic solid-phase extraction (SMSPE) method. SMSPE
exhibits great advantage in simple pretreatment. The
combined method displays fast detection (within
20 min), high efficiency and a high-sensitivity detec-
tion with LOD of 0.48 and 40 ng/cm2 for thiram and
thiabendazole, respectively. The two LODs are much
lower than the prescribed standards of the US Envi-
ronmental Protection Agency (USEPA).
Bacterial pathogens are great threats to food safety.
Wang et al. [112] used a magnetic SERS immunoas-
say, pathogens modified MNPs@SiO2 and
8688
Figure 4 a SERS spectra of thiram with Au dotted magnetic
network nanostructure (Au-MNN). b SERS spectra of cabbage
peel spiked with thiram by the enhancement of Au-MNN. c The
linear correlation of Raman intensities (at 1373 cm-1) with thiram
concentrations from 50 fM to 500 nM in ethanol. Adapted from
Ref. [116]. Copyright: 2013 Wiley–VCH Verlag GmbH & Co.
KGaA, Weinheim. Used with permission. d Raman spectra for
corresponding antibodies functionalized Au
nanoparticles, to detect various pathogens in selected
food matrices. The LOD of both Staphylococcus
aureus and Salmonella entericaserovar Typhimurium
can reach 103 CFU/mL in spinach wash, and the LOD
was also successfully achieved in peanut butter.
Najafi et al. [114] applied Fe3O4/Au nanoclusters for
the detection of Escherichia coli O157 in apple juice
J Mater Sci (2018) 53:8677–8698
E. coli O157:H7 capture in apple juice using MNP. e Stacked
spectra showing E. coli O157:H7 concentration-dependent Raman
shift signature of the MGITC reporter at vibrational frequency
zones of 1180, 1370 and 1620 cm-1. f Plot representing SERS
intensity at 1620 cm-1 vs. Log CFU/mL of target E. coli
O157:H7. Adapted from Ref. [114]. Copyright: 2014 Elsevier
B.V. Used with permission.
with a LOD down to 102 CFU/mL less than an hour
(Fig. 4d–f). What is more, the capture efficiency for
E. coli O157 using MNPs was approximately 84–94%
in liquid food matrix.
Chen et al. [126] first achieved the highly sensitive
and selective SERS detection of NO2- in pond, urine
and pickles. In their experiment, Fe3O4@SiO2/Au
MNPs was modified by 4-aminothiophenol (4-ATP),
J Mater Sci (2018) 53:8677–8698
which was used to react with NO2- to form a com-
plex containing diazonium salt and azo bonds. Sub-
sequently, three SERS peaks of the complex were
used to analyze the concentration of nitrite ions. The
corresponding LODs of NO2- were 15.63, 13.69 and
17.77 lM. These LODs are much lower than the
standard (\1.0 mg/L (71.4 lM) in drinking water) of
USEPA.
MNP-based SERS techniques have greatly
improved the efficiency of food safety analysis, which
used to be tedious, complex and time-consuming.
Even so, novel structured MNPs–plasmonic substrate
is still in great demand to achieve sensitive detection
of low-abundance analyte and reduce the back-
ground from complicated food matrix. Besides, the
design of substrate and the explanation of the results
should consider the fact that the analyte might
metabolize to new chemical substances during food
processing, which is largely neglected in the past.
Finally, quantitative reproducibility of SERS analysis
is also needed to be improved.
Figure 5 a Schematic of the transition of the iron oxide shell from
the magnetite (Fe3O4) phase to the hematite (a-Fe2O3) phase under
the irradiation of different laser intensities. b Phase transition
properties of the Fe3O4-decorated AuNPs revealed by SERS
8689
Reaction monitoring
SERS is a real-time detection and characterization
technique. The unique advantage to provide the fin-
gerprint of molecule structure makes SERS a
promising tool to monitor some important course of
chemical reactions, including discriminating inter-
mediate product of organic reaction, monitoring
oxidation–reduction reaction, in situ characterizing
catalytic reaction [76, 127–132].
Mezni et al. [127] studied an interesting phase
transition of iron oxide shell (Fig. 3a). The phase of
iron oxide (lepidocrocite (c-FeOOH), magnetite
(Fe3O4), maghemite (c-Fe2O3) or hematite (a-Fe2O3),
(Fig. 5a, b) can be discriminated by monitoring the
formation of diiron-oxo bonds during the phase
transition through the strong SERS effect of Au/
Fe3O4 substrate, in which the gold cores also play a
role as plasmonic nanoheaters to induce the thermal
phase transition.
Additionally, by introducing porous carbon [128]
and catalytic semiconductor titania [77, 129, 130]
shield MNPs as SERS substrates, other multifunc-
tional applications including catalysis, adsorption
and degeneration process can also be monitored by
spectra excited at 638 nm with laser intensity ranging from 0.1 to
100%. Adapted from Ref. [127]. Copyright: 2013 American
Chemical Society. Used with permission.
8690
SERS. For example, Lv et al. [129] developed core–
satellite Fe3O4/Au@TiO2 substrate to monitor pho-
toreduction in Cr(VI), and this platform with selec-
tivity can quantitatively determinate Cr(VI) with
evident sensitivity lasting one month. Cai et al. [128]
employed Fe3O4/C/Au nanoparticles for in situ
SERS monitoring the catalytic reaction of p-nitroth-
iophenol (p-NTP) to p-aminothiophenol (p-ATP),
and the experiment found that the catalytic rate could
be turned by the external magnetic field either pre-
sent or absent. Shen et al. [77] synthesized Fe3O4@-
TiO2@Ag/Au microsphere substrate for in situ SERS
monitoring of catalytic reduction of 4-nitrophenol.
The excellent SERS-active substrate not only shows
efficient catalytic performances, but also exhibits
recyclability to self-cleaning for photocatalytical
activity of TiO2, and the magnetism of Fe3O4 endows
the substrates convenient separation and concentra-
tion ability.
It can be seen that MNP-based SERS substrates
could be used to monitor surface plasmon-driven
catalytic reaction and Raman laser-induced photo-
catalytic reaction. And real-time monitoring course of
reaction would provide a perfect opportunity to
better understand the process and mechanism of
chemical reactions, which has a great impact on
electrochemistry, pharmaceutical production and
environmental remediation. Additionally, the cat-
alytic property endows the substrates with recycla-
bility to self-cleaning.
Environmental analysis
Environment pollution has become a worldwide
problem, which has caused great threaten to public
health. Considering this issue, accurate and fast
detection methods for various pollutants are of great
importance for environment monitoring and reme-
diation. SERS-based techniques have received con-
siderable attentions in this area due to its high
sensitivity, nondestructive detection, ability to pro-
vide plenty of molecule structure information and
in situ detection ability. The magnetic nanomaterials
usually have high adsorption toward pollutant
materials, and they are easily separated from the
samples by magnetic forces. The combination of
MNPs with SERS has shown powerful capacity for
environment monitoring. The representative MNP-
based SERS substrates applied in the field are noble
metal nanoparticles decorated magnetic particles
J Mater Sci (2018) 53:8677–8698
with strong adsorption capacity or abundant hot-
spots, such as nanotube-like [67], nanoclusters [133],
3D flowerlike [134], Fe3O4 nanostructured hollow
microspheres, GO [135, 136] and rGO [137]. The tar-
get molecules analyzed by SERS included explosives
[23, 138], pesticides [58, 138–141], heavy metal ions
(e.g., Hg2?, Cr6? and As3?) [142–144], organic dyes
and persistent organic pollutants [72, 145–154], and
pathogenic bacteria and pathogens [155].
Complex unknown sample together with the inef-
ficient use of hot spots makes SERS discriminating
and detecting target species in real environmental
samples still a great challenge [155]. Undeniably,
typical solid MNP-based substrates cover over-
whelming majority for real environmental monitor-
ing. But several of interesting structures obtained by
immobilized MNPs are quite amazing to practice. A
removable 3D macroscale superlattice array of Au
nanorods doped with MNPs is obtained by evapo-
rative self-assembly. The superlattice arrays not only
possess fast separation and enrichment ability, but
also achieve excellent sensitivity for SERS detection
of thiram, diquat and polycyclic aromatic hydrocar-
bons with LOD down to * nM [20]. Poly(N-iso-
propylacrylamide) (pNIPAM), thermoresponsive
glue, encapsulated Ag NPs and MNPs into a colloidal
substrate could adsorb analytes in solution when it is
swelled (low temperature) and reversibly generate
hot spots upon collapse (high temperature or drying).
While the substrate concentrated into small space
region, it could detect PCP with a LOD as low as
10-12 M [62] (Fig. 6). In addition, Wang et al. [63]
used multifunctional pNIPAM-co-acrylamide net
incorporated with Au and MNPs to fabricate a com-
posite substrate with magnetism, themosensitivity,
SERS effect and drug delivery ability. This multi-
functional composite substrate provides a new syn-
thetic strategy to fabricate substrates combined with
probing and label-free detection functions together.
What is more, burgeoning magnetic platform with
selective adsorption, catalysis and detection in the
field is worth expected.
In short, MNP-based SERS substrates provide the
rapid extraction capacity for environmental pollu-
tants detection with high sensitivity. But the coexis-
tence of various pollutants with unrecognizable
Raman signals would seriously interfere the selective
detection. Moreover, not all of the pollutants have
distinguished Raman signals; hence, proper desig-
nation of MNP-based substrates and effective
J Mater Sci (2018) 53:8677–8698 8691

Figure 6 Representative
TEM images of a the
encapsulated magnetic
nanoparticles after pNIPAM
polymerization, b the
magnetite@pNIPAM
nanohybrid materials
containing silver seeds and
c the final magnetite–
Ag@pNIPAM composite
microgels. d SERS spectra of
1NAT in magnetite–
Ag@pNIPAM in the swollen
(4 °C, blue) and collapsed
(60 °C, red) states, for
different excitation laser lines
(532, 633 and 785 nm).
e Comparison of intensities of
the band at 1368 cm-1 at low
(blue) and high (red)
temperature (average intensity
and standard deviation for five
measurements, green bars).
f Optical image of the
magnetite–Ag@pNIPAM
microgels before and after
exposure to a permanent
magnet. g Detection limits for
1NAT in dilute dispersions of
magnetite–Ag@pNIPAM after
concentration of the material
using a permanent magnet.
Adapted from Ref. [62].
Copyright: 2011 American
Chemical Society. Used with
permission.

modification of probe molecule are necessary to solve significant efforts are still required to further develop
the problem. Furthermore, poor reproducibility and more sensitive, stable and specific SERS substrates for
stability also restricted the application of MNP-based these types of pollutants.
SERS substrates in environmental analysis. Therefore,
8692
Conclusion and outlooks
Applications of functionalized MNPs have been
introduced to many fields over the past decades.
Taking its SERS application as an example, MNPs
could facilely separate SERS substrate from matrix to
reduce background response and meanwhile achieve
the capture and enrich target, manipulate hot spots
simultaneously, which greatly improve the sensing
performance of SERS with LOD down to femto-mole
level. This makes the MNPs involved SERS analysis a
powerful technique for real sample analysis. The
introduction and discussion of these achievements
will provide the appropriate background for devel-
oping novel materials and analysis methods for the
detection of diverse analytes in real sample with
SERS.
Although great achievement has been done on
MNPs involved SERS analysis, several issues should
be considered in future research. (1) It is still neces-
sary to develop a robust synthesis and modification
system to prepare stable, well-dispersed, highly
uniformed MNPs with desired properties in a simple
and low-cost way for its further application. (2)
Rational design and fabrication of highly active,
multifunctional MNPs–Au/Ag substrate is in great
demand as certain analytes at trace concentration are
still difficult to detect, and the reliable analysis of real
samples still poses challenges. (3) Most MNP–Au/Ag
substrates are prepared in laboratory with low yield
and complex process. To extend the application of
MNPs involved SERS in laboratory and in field, a
low-cost, high-yield batch fabrication approach for
MNPs–Au/Ag substrate should be developed. (4)
For real sample practice, the requirements on sensi-
tivity, reproducibility, specificity, stability should
always be kept in mind, while the portable detection
system should also be considered. So far, it remains a
great challenge to realize discriminating and quanti-
tative detecting target species in complex real sample
in various phases. Although a long way to go, it is
believed that combination of MNPs with SERS and
other advanced material or technique will have a
bright future.
Acknowledgements
This work is financially supported by the National
Natural Science Foundation of China (21665011 and
J Mater Sci (2018) 53:8677–8698
21705063) and Natural Science Foundation of Jiangxi
Province (20161BAB203088).
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