Sensors & Actuators: B.

Chemical 350 (2022) 130848

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Sensors and Actuators: B. Chemical

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Aligned TiO2 nanorod arrays decorated with closely interconnected Au/Ag

nanoparticles: Near-infrared SERS active sensor for monitoring of antibiotic
molecules in water
Anxin Jiao a, Qingqiang Cui a, Shuang Li b, Hengshuai Li c, Linlin Xu a, Yue Tian a, Hui Ma a,
Mengya Zhang a, Xiangdong Liu a, Ming Chen a, *
a
School of Physics, Shandong University, Jinan 250100, Shandong, PR China
b
School of Science, Shandong Jianzhu University, Jinan 250101, Shandong, PR China
c
Shandong Key Laboratory of Optical Communication Science and Technology, School of Mechanical&Automotive Engineering, Liaocheng University, Liaocheng
252000, Shandong, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: Near-infrared (NIR) excited surface-enhanced Raman scattering (SERS) spectroscopy is expected to have more
Near-infrared (NIR) appealing multiple-features than that of traditional ultraviolet (UV) or visible light excitation. Herein, we
Surface-enhanced Raman scattering (SERS) demonstrate an interesting and highly active hybrid semiconductor-based NIR-SERS sensor via well-aligned TiO2
Bimetallic Au/Ag nanoparticles (NPs)-TiO2
nanorod arrays (NRAs) decorated with bimetallic Au/Ag nanoparticles (NPs). The obtained Au/Ag NPs-TiO2
nanorod arrays (NRAs)
Antibiotics
NRAs with a stronger absorption capacity in 400–1300 nm region exhibit a remarkable higher NIR-SERS activity
Photocatalytic degradation than that of monometallic Au or Ag loaded on TiO2 NRAs. Then, the established NIR-SERS sensor can provide
ultrasensitive 785 nm laser excited-SERS detection of antibiotic ciprofloxacin and chloramphenicol in real-world
water samples with detection limits as low as 10–9 M and 10–8 M, respectively. Interestingly, superior to the
present bare metallic nanosubstrates, the Au/Ag NPs-TiO2 NRAs with unique heterostructures can also be served
as reusable NIR-SERS sensor due to its excellent photocatalytic degradation ability, and ~84.2% residual SERS
activity can be maintained after 5 recycling tests. Therefore, it is believed that the established multifunctional
NIR-SERS sensor holds greater potential for ultrasensitive monitoring of diverse biomolecules in many specific
applications.

1. Introduction the bare metallic nanomaterials (NMs), the semiconductor-based SERS

substrates with unique pronounced photocatalytic degradation proper­
Nowadays, surface-enhanced Raman scattering (SERS) spectroscopy ties possess excellent SERS reusability under repeated applications.
has been regarded as a well-known powerful and promising spectro­ Moreover, the SERS activity of hybrid NMs can be significantly
scopic analysis method, which is characterized by unique fingerprint improved by the double contributions of the excellent electromagnetic
recognition ability, non-destructive characteristics, single-molecule enhancement (EM) originated from plasmonic nanoparticles (NPs)
sensing capability, high accuracy and sensitivity [1–3]. Initially, plas­ coupled with an additional chemical enhancement (CM) derived from
monic metallic nanostructures including gold (Au), silver (Ag) and the effective charge transfer (CT) between band-gap semiconductor
copper (Cu) were frequently used as excellent SERS substrates due to supports and adsorbed molecules [6]. Especially, titanium dioxide
strong SERS enhancements derived from their unique local surface (TiO2) is served as a representative semiconductor for construction of
plasmonic resonance (LSPR) properties. In recent years, hybrid efficient hybrid SERS nanosubstrates, due to its excellent chemical sta­
nano-heterostructures composed of semiconductor and plasmonic metal bility, non-toxicity, low cost, high photosensitivity, self-cleaning func­
have attracted more attention since the ability to integrate multiple tion and bio-compatibility [4,6]. Additionally, well-aligned TiO2
functions into a composite nanostructure to meet application re­ nanorod arrays (NRAs) grafted with Au or Ag NPs possess excellent
quirements of low cost, high stability, reproducibility [4,5]. Superior to multiple light-scattering effect in three-dimensional (3D) arrays that

* Corresponding author.
E-mail address: chenming@[Link] (M. Chen).

[Link]
Received 28 June 2021; Received in revised form 27 August 2021; Accepted 25 September 2021
Available online 30 September 2021
0925-4005/© 2021 Elsevier B.V. All rights reserved.
A. Jiao et al. Sensors and Actuators: B. Chemical 350 (2022) 130848

allows photons to have a longer optical path and longer time to interact 785 nm NIR-SERS performances in this work. Furthermore, the estab­
with plasmonic NMs and also improve the CT efficiency by increasing lished NIR-SERS sensor provides ultrasensitive detection of antibiotic
the concentration of photo-generated electron-hole pairs [7]. Therefore, ciprofloxacin and chloramphenicol in real-world water samples with
the optimal design of TiO2 NRAs-based heterostructures is very impor­ detection limits as low as 10–9 M and 10–8 M, respectively. Moreover,
tant to provide high-performance SERS for diverse special applications. based on the excellent photocatalytic degradation ability of Au/Ag
On the other hand, as for the present semiconductor-based SERS, NPs-TiO2 NRAs, the antibiotic residues could be almost completely
there is still a huge barrier that should be considered in practical ap­ removed under UV irradiation, and ~ 84.2% NIR-SERS activity can be
plications. Generally, most of previous researches have mainly relied on maintained after 5 cycles. Superior to the present bare metallic sub­
the use of short-wavelength ultraviolet (UV) or visible light as excitation strates, the established Au/Ag NPs-TiO2 NRAs can be served as an
light sources [1,4,7–10]. The main reason is that the band-gap structure excellent reusable NIR-SERS active sensor toward widespread
of semiconductor coupled with visible LSPR property of isolated applications.
monometallic Au or Ag NPs can be merely excited by UV or visible light
(<700 nm) with high photon energy. Compared with traditional UV or 2. Experimental
visible light irradiation, near-infrared (NIR) excited SERS indeed pos­
sesses more appealing multiple-advantages: (1) NIR-SERS with low 2.1. Preparation of TiO2 NRAs
photo-damage to biological samples can truly reflect the actual response
of molecular structures in photo-thermal therapy or bioimaging in living The preparation method of TiO2 NRAs was supplied in the Supple­
biosystems [11,12]. In vivo SERS imaging application, the endogenous mentary materials.
tissue absorption coefficients of NIR (700–900 nm) are more than two
orders of magnitude lower than that of UV or visible light [13,14], and 2.2. Preparation of Au NPs-TiO2 NRAs and Ag NPs-TiO2 NRAs
then the specific biological molecules can be well maintained under NIR
irradiation. In contrast, the short-wavelength UV or visible light with The overgrowth of Au NPs on TiO2 NRAs was simply achieved via
high photon energy is extensively used as bactericidal agents, which can laser irradiation of TiO2 NRAs in Au3+ solution. Typically, 25 μL HAuCl4
easily result in obvious destructive effect to biomolecules. (2) The (0.05 M) and 1 mL ethanol were added into 5 mL deionized (DI) water
band-gap semiconductor-based NIR-SERS is more beneficial to obtain by 10 min ultrasonic vibration, then, the FTO covered with TiO2 NRAs
ultrasensitive SERS information. It has the ability to significantly reduce was immersed into the Au3+ precursor and irradiated by a continuous
and weaken the fluorescence background, which will remove unwanted 375 nm UV laser beam with power of ~400 mW for different time
interference noise from Raman spectra. The photo-induced fluorescence (10–25 min) to achieve Au NPs-TiO2 NRAs. Finally, the sample was
is mainly originated from the band-gap transition of taken out, washed with DI water and dried naturally. The reduction of
semiconductor-hybrid substrates excited by short-wavelength light with Ag+ ions on TiO2 NRAs was similar to the growth of Au on TiO2 NRAs.
high photon energy. Additionally, the use of UV or visible laser irradi­ Briefly, 1 mL ethanol and 0.01 M of 200 μL AgNO3 were added into 5 mL
ation could cause photobleaching and plasma heating, which will result DI water containing TiO2 NRAs. The Ag NPs-TiO2 NRAs were obtained
in a loss of SERS signals and also reduce the SERS performance [15]. (3) via laser irradiation for different time (5–20 min) at a wavelength of 375
As an optical biological window (700–900 nm), NIR light source can nm with power of ~400 mW.
provide high penetrating capability of optical signals in the case of live
animal deep tissues, as compared to that of UV or visible light excitation. 2.3. Synthesis of bimetallic Au/Ag NPs-TiO2 NRAs
Taken together, compared to short-wavelength laser excitation, the
semiconductor-based NIR-SERS sensor with multiple pronounced merits The bimetallic Au/Ag NPs-TiO2 NRAs were obtained by two-step
has greater potential ability for ultrasensitive monitoring biomolecules. procedure, as shown in Fig. S1. Firstly, TiO2 NRAs was immersed in
As for the emerging NIR-SERS sensor, most of present works remain the precursor solution containing 25 μL/0.05 M HAuCl4, 1 mL ethanol
restricted solely to anisotropic growth of bare metallic Au/Ag hollow- and 5 mL DI water, the mixed solutions were irradiated by 375 nm UV
shell assemblies [13], Au nanorods [14], star-shaped Au/Ag NPs [16], laser beam for 15 min. Then, the FTO sample was thoroughly washed
Au nanocapsules [17], bumpy Ag nanoshells [18], or 3D cloud-like with DI water for the subsequent growth of Ag. As for the overgrowth of
aluminum hierarchical NPs [19], etc. However, the development of Ag NPs, 100 μL AgNO3 (0.01 M) and 1 mL ethanol were added into 5 mL
semiconductor-based NIR-SERS active sensor is severely hampered, due DI water containing the as-prepared sample. The Au/Ag NPs-TiO2 NRAs
to the low/insufficient efficiency of photon absorption-conversion at were obtained via UV (375 nm) laser beam irradiation for different time
longer wavelength region. In fact, these previous semiconductor-based (5–20 min).
SERS substrates were simply constructed by loading isolated mono­
metallic Ag or Au NPs, resulting in a low sensitivity response in NIR 2.4. SERS measurements and materials characterization
region. Compared with monometallic isolated NPs, bimetallic NPs with
unique intermetallic synergy among different metals can provide SERS measurements and materials characterization were supplied in
tunable enhanced LSPR under NIR excitation. In this way, the expected the Supplementary materials.
good NIR light response of bimetallic NPs-semiconductor nano-­
heterostructures is suitable for extending SERS from conventional UV or 3. Results and discussion
visible region to NIR excitation region, promoting the subsequent
NIR-SERS activity. Initially, the original TiO2 NRAs (Fig. S2) exhibit a neatly arranged
Herein, we propose an ingenious facile strategy to develop a high array structure that is composed of well-aligned uniform nanorods with
active semiconductor-based NIR-SERS sensor that is composed of TiO2 average diameter of ~100 nm. After overgrowth of Au NPs
NRAs decorated with bimetallic Au/Ag NPs. Different from traditional (Figs. S3–S4), numerous interconnected bumpy nanostructures are
deposition of monometallic Au or Ag NPs via ordinary sol-hydrothermal supported on the top surface and some isolated disperse Au NPs can be
methods [1,5] or plasma sputtering technique [4,20], the overgrowth of found at the side region. As for the loading of Ag (Figs. S5–S6), large-
closely interconnected Au/Ag NPs on TiO2 NRAs can be performed by a sized Ag NPs with average diameter of ~80 nm are mainly formed on
two-step 375 nm laser-induced photochemical reactions. The nano­ the top of TiO2 NRAs, while few NPs can be found on the side walls. To
products with pronounced intermetallic synergy exhibit a stronger ab­ further synthesis bimetallic Au/Ag NPs-TiO2 NRAs, the as-prepared Au
sorption capacity in the range of 400–1300 nm than the deposition of NPs-TiO2 NRAs were then immersed in AgNO3 solution by 375 nm laser
monometallic Au or Ag NPs on TiO2 NRAs, giving rise to the excellent irradiation for 15 min. As shown in Fig. 1, bimetallic NPs are fully

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A. Jiao et al. Sensors and Actuators: B. Chemical 350 (2022) 130848

Fig. 1. (a) Cross-sectional and (b–d) top SEM images of Au/Ag NPs-TiO2 NRAs. The inset is the corresponding EDS pattern.

deposited on the top region of the NRAs and further accumulated and NIR light response capacity in comparison with that of loading mono­
interconnected with each other, giving rise to the overgrowth of metallic Au or Ag on TiO2 NRAs.
popcorn-like wrinkled structures on TiO2 NRAs. In addition, the EDS Furthermore, the elemental compositions and chemical states of as-
pattern shows the chemical composition of Au/Ag NPs-TiO2 NRAs, prepared Au/Ag NPs-TiO2 NRAs and other three reference samples
confirming the existence of Ti, O, Au, and Ag elements. Based on the EDS were examined by X-ray photoelectron spectroscopy (XPS). The survey
results, the relative atomic ratios of Ti, O, Au and Ag elements in the spectra of these four samples (Fig. S9) illustrate that the XPS peaks of Ti
nanoproducts are 32.6%, 59.4%, 3.1% and 4.9%, respectively. and O originated from TiO2 supports can be well maintained after
Moreover, the closely interconnected bimetallic Au/Ag NPs formed overgrowth of metallic NPs. Generally, the peak of C1s at 284.8 eV is
on TiO2 NRAs were further illustrated by TEM measurements (Fig. 2(a)– used to calibrate the binding energy to reduce the charge effect of the
2(c)). The enlarged TEM image in Fig. 2(b) illustrates that the bumpy sample in XPS tests [21,22]. The high-resolution XPS spectra (Fig. 3(a))
and wrinkled metallic NPs are indeed inserted on TiO2 NRAs instead of reveal that the double peaks of Ti2p originated from pristine TiO2 at
simple physical mixture of different NMs, owing to the obvious inter­ 458.3 eV and 464.2 eV are attributed to Ti2p3/2 and Ti2p1/2, corre­
connected structure formed at boundary region. The HRTEM image in sponding the values of Ti4+ [23,24]. Compared to the original TiO2, the
Fig. 2(c) reveals that the measured lattice-spacing distance of 0.237 nm XPS peak positions of Ti2p3/2 and Ti2p1/2 gradually shift to higher
is located between the theoretical values of (111) lattice plane of Au values after decorated with metallic NPs, which is attributed to the
(0.235 nm) and Ag (0.238 nm), which could be well-indexed to (111) electron transfer via the interaction between metallic NPs and TiO2. The
plane of miscible Au/Ag face centered cubic (fcc) crystal structure. XPS pattern of O1s (Fig. 3(b)) can be de-convoluted into three couples of
Additionally, the lattice fringe of 0.320 nm is related to the (110) plane peaks: peak 1 (529.9 eV), peak 2 (531.5 eV) and peak 3 (532.6 eV) are
of TiO2, implying that the well crystalline of pristine TiO2 can be kept assigned to the Ti-O of TiO2, surface hydroxyl oxygen and absorbed O2
during the overgrowth process. The selective area electron diffraction [25], respectively. Moreover, the typical XPS of Au4f (Fig. 3(c)) show
(SAED) pattern in Fig. 2(d) shows many diffraction dots/spots constitute the double peaks of pure Au NPs at 84.0 and 87.7 eV, respectively.
a ring-like diffraction pattern, confirming the existence of poly­ Evidently, the double peaks derived from Au NPs-TiO2 NRAs have a
crystalline properties in this hybrid nanostructures. Furthermore, the negative shift of 0.54 eV compared to the bare Au NPs, indicating the
element mapping images of an individual sample are performed in Fig. 2 formation of negative charge of Au NPs because of the electrons transfer
(e)–2(i). It reveals that the nanoproducts are indeed composed of Ti and from TiO2 to Au. The formation of negative charge of Au NPs should be
O elements in the inside regions, as well as Au and Ag species on the attributed to the large difference in work function between Au and TiO2
surface of Supporting materials. In addition, X-ray diffraction (XRD) that promotes the transfer of electrons from TiO2 to Au, confirming the
pattern (Fig. S7) shows the crystallographic structures of the obtained electronic interaction between metallic NPs and semiconductor TiO2
Au/Ag NPs-TiO2 NRAs and other reference samples, supporting the [26,27]. The negative shift of Au4f peaks originated from bimetallic
successful overgrowth of bimetallic nanocrystals on TiO2 NRAs. The Au/Ag NPs-TiO2 NRAs become more obvious than that of Au NPs-TiO2
UV–Vis–NIR absorption spectra (Fig. S8) illustrate that the inter­ NRAs, owing to the stronger interaction between Au and Ag in hybrid
connected bumpy bimetallic Au/Ag NPs-TiO2 NRAs with intermetallic Au/Ag NPs-TiO2 NRAs. As for bare Ag NPs, the double peaks of Ag3d5/2
synergy enable the absorption spectra to be obviously enhanced in and Ag3d3/2 are located at 367.50 eV and 373.50 eV (Fig. 3(d)).
visible-NIR region (400–1300 nm). It is beneficial for providing higher Compared with bare Ag NPs and Ag NPs-TiO2 NRAs, the pronounced

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A. Jiao et al. Sensors and Actuators: B. Chemical 350 (2022) 130848

Fig. 2. . (a–c) The typical low-magnification TEM and HRTEM images of Au/Ag NPs-TiO2 NRAs. (d) The SAED pattern. (e–i) The HAADF-STEM image of a typical
Au/Ag NPs-TiO2 nanorod and the corresponding elemental mapping images.

blue-shift of double Ag3d peaks derived from bimetallic Au/Ag reduces the number of hot spots. Meanwhile, the optimal SERS activity
NPs-TiO2 NRAs also implies the formation of enhanced synergistic of Au NPs-TiO2 NRAs and Ag NPs-TiO2 NRAs can be obtained at the
coupling effect. Taken together, compared to the overgrowth of mono­ irradiation time of ~20 min and ~15 min, respectively (Fig. S10(b)–
metallic Au or Ag NPs, the obtained Au/Ag NPs-TiO2 NRAs with (c)). The Au/Ag NPs-TiO2 NRAs with appropriate bimetallic composi­
wrinkle-like and bumpy bimetallic surfaces are characterized by strong tion obtained by 15 min overgrowth of Au NPs and then 15 min over­
synergistic effects between bimetallic Au/Ag and semiconductor TiO2 growth of Ag NPs can provide an obviously higher SERS activity than
supports. It is beneficial to boost the transmission of photon-excited hot other reference samples. It should be related to strong EM via the syn­
carriers on this hybrid interfaces, giving rise to a high NIR light con­ ergistic coupling effect between bimetal Au and Ag in Au/Ag as well as
version efficiency for promoting NIR-SERS activity. additional high CM contribution offered by effective electron transfer
Then, the NIR-SERS spectra of 10–8 M CV molecules adsorbed on among substrate and probe molecules. Superior to monometallic iso­
bimetallic Au/Ag NPs-TiO2 NRAs, monometallic Au NPs- and Ag NPs- lated Au or Ag NPs, the obtained bimetallic Au/Ag with unique inter­
TiO2 NRAs were separately performed by using 785 nm laser excitation, connected structures on TiO2 NRAs will be more suitable for improving
as shown in Fig. 4(a). The NIR-SERS signals originated from the obtained EM effect due to the stronger NIR absorption and conversion. The CM
Au/Ag NPs-TiO2 NRAs are much higher than that of monometallic Au or originated from the CT mechanism between TiO2 NRAs and probe
Ag loaded on TiO2. For instance, the Raman intensity at 1175 cm–1 is molecules was also verified (Fig. S11). In addition, the photo­
~11970 a.u for Au/Ag NPs-TiO2 NRAs, which is about 2.9 and 7.2 times luminescence (PL) emission spectra illustrate the lower PL intensity of
higher than that of Ag NPs-TiO2 NRAs and Au NPs-TiO2 NRAs, respec­ Au/Ag NPs-TiO2 NRAs (Fig. S12) and support a higher transmission of
tively. Then, the effect of bimetallic composition in Au/Ag NPs-TiO2 photo-induced electrons from TiO2 to bimetallic NPs, giving rise to a
NRAs on SERS activity was investigated by changing the overgrowth better CT effect for enhancing SERS activity. The limit of detection
time of Ag species on Au NPs-TiO2 NRAs precursor, since the optimal (LOD) of this optimal Au/Ag NPs-TiO2 NRAs can reach at picomole (pM,
SERS is related to the metallic composition in nanocomposites [28,29]. 10− 12 M) level (Fig. S13(a)), which is even better than that of Au
The initial increase of Ag species by an increase of reaction time NPs-TiO2 or Ag NPs-TiO2 NRAs (Fig. S13(b)–(c)) as well as many pre­
(5–15 min) results in the steady increase of SERS intensity (Fig. S10(a)). vious reports, such as metallic nanotube arrays [30], monometallic
Further increasing the reaction time to 20 min will lead to gradual Au@H-C3N4 [31] or Ni@Mil-100(Fe)@Ag nanowires [32]. On the other
decrease of SERS signal, due to the excessive aggregations of NPs that hand, based on the SERS signal of CV molecules at 1175 cm− 1, the

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Fig. 3. XPS spectra of original TiO2 NRAs, Au NPs-TiO2 NRAs, Ag NPs-TiO2 NRAs and bimetallic Au/Ag NPs-TiO2 NRAs, respectively. (a) Ti2p, (b) O1s, (c) Au4f and
(d) Ag3d.

Fig. 4. (a) SERS spectra of 10–8 M CV molecules adsorbed on bimetallic Au/Ag NPs-TiO2 NRAs, and monometallic Au NPs- and Ag NPs-TiO2 NRAs, separately. (b–d)
SERS spectra of CV (10–8 M) and antibiotic molecules (10–6 M ciprofloxacin, 10–6 M chloramphenicol) adsorbed on Au/Ag NPs-TiO2 NRAs, respectively, measured
with laser excitation wavelengths of 532, 633, and 785 nm at the same power level.

enhancement factor (EF) value of Au/Ag NPs-TiO2 NRAs is estimated to NRAs (4.21 × 109) as well as many previous reports [30,31,33]. Besides
be about 3.44 × 1010 in Supplementary materials, which is higher than the excellent NIR-SERS activity, the good uniformity, reproducibility,
that of monometallic Au NPs-TiO2 NRAs (6.03 × 107) and Ag NPs-TiO2 long-term stability and chemical stability of Au/Ag NPs-TiO2 NRAs are

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also illustrated in Fig. S14, enabling them to have the required features monitoring of antibiotic molecules in diverse complicated practical
of an excellent NIR-SERS sensor for practical applications. Moreover, the scenes.
obvious advantage of Au/Ag NPs-TiO2 NRAs-based NIR-SERS sensor In order to verify the practical applicability of the established NIR-
was then evaluated by using specific antibiotic molecules that will be SERS sensor in the actual water environment, the ultrasensitive assess­
easily interfered by fluorescence background via shorter wavelength ments of antibiotic ciprofloxacin and chloramphenicol in different water
laser excitation (Fig. 4(b)–(d)). As for common stable CV dye molecules, samples (DI water, mineral water, tap water, Black Tiger Springs water
both visible (532 and 633 nm) and NIR (785 nm) laser wavelengths are and Daming Lake water) were performed in this work. Ciprofloxacin, as
appropriate as excitation light sources for SERS analyses. However, the representative fluoroquinolone antibiotics, has been widely used in the
visible light excitations are no longer suitable for SERS monitoring of treatment of human and domestic animal infections. At present, the
antibiotic ciprofloxacin and chloramphenicol molecules adsorbed on abuse of fluoroquinolones is very harmful, and their extensive use may
Au/Ag NPs-TiO2 NRAs, due to strong fluorescence background noises induce drug-resistant bacteria, posing potential threats to human health
originated from short-wavelength laser excitation of the band-gap and ecological environment [34]. Chloramphenicol is a typical amide
semiconductor TiO2. Under the excitation of 785 nm NIR laser, the alcohol antibiotic that is associated with serious toxic effects in some
fluorescence interference is significantly reduced, and more plentiful susceptible people, including bone marrow suppression, especially fatal
characteristic bands of antibiotics with well-defined Raman spectral aplastic anemia [35,36]. Therefore, ultrasensitive monitoring of these
lines could be clearly identified in NIR-SERS spectra. Due to the unique antibiotics is very necessary for biological systems. As shown in Fig. 5
fingerprint recognition characteristics of NIR-SERS system, the obtained (a), it reveals that there is no SERS signal can be detected in any water
Au/Ag NPs-TiO2 NRAs will be suitable for ultrasensitive and reliable sample, supporting that the pure water without antibiotic ciprofloxacin

Fig. 5. (a) SERS spectra of five different water samples in the presence of Au/Ag NPs-TiO2 NRAs. (b–e) SERS spectra of antibiotic ciprofloxacin (10–5–10–9 M) and
chloramphenicol (10–5–10–8 M) adsorbed on Au/Ag NPs-TiO2 NRAs from Black Tiger Springs water, and the variations of SERS intensities versus the negative
logarithm of antibiotics molecules, respectively.

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or chloramphenicol residues indeed exist in our surrounding environ­ Table 1

ment. In order to verify the sensitivity of this NIR-SERS sensor toward Determination of antibiotic residues in Black Tiger Springs water by NIR-SERS
the detection of antibiotics in these pure water samples, we have arti­ method.
ficially added 10–5 M ciprofloxacin and chloramphenicol molecules in Analyte Added Measured Fitting Relative
these different real-world liquids. Compared with the negligible Raman concentration intensity concentration Error (RE)
signals in Fig. 5(a), the obvious SERS spectra of ciprofloxacin and Ciprofloxacin 5 × 10− 6
M 22475 4.83 × 10− 6
M 3.4%
chloramphenicol molecules can be easily detected in the mentioned five Ciprofloxacin 5 × 10− 7
M 16924 5.24 × 10− 7
M 4.8%
6 6
water samples (Fig. S15), and band assignments are presented in Chloramphenicol 5 × 10−
7
M 7742 5.22 × 10−
7
M 4.4%
Chloramphenicol 5 × 10− M 4931 4.80 × 10− M 4.0%
Tables S1 and S2, respectively. Therefore, if the real-world water sample
was polluted by antibiotic ciprofloxacin or chloramphenicol molecules,
these contaminates can be surely monitored by this NIR-SERS sensor. In molecules will be sharply decreased after UV light irradiation of 60 min,
order to further evaluate the corresponding NIR-SERS sensitivity, one implying the complete elimination of residual antibiotic molecules from
real water sample (Black Tiger Springs water) was then selected for this sensor via the effective photocatalytic degradation. It can be found
subsequent experiments. The SERS analyses of 10–5–10–9 M ciprofloxa­ that the as-prepared NIR-SERS sensor possesses an excellent reusability
cin and 10–5–10–8 M chloramphenicol were separately performed in this under repeated tests, since 84.2% residual SERS activity can be well
work. As shown in Fig. 5(b)–(e), the LOD values of ciprofloxacin and maintained after 5 recyclable runs. Moreover, it is clear that the
chloramphenicol can be achieved at 10–9 M and 10–8 M, respectively. NIR-SERS sensor still maintains the identical morphology with
The ultralow LOD values of ciprofloxacin and chloramphenicol adsorbed wrinkle-like Au/Ag NPs loaded on well-aligned TiO2 NRAs (Fig. S19).
on Au/Ag NPs-TiO2 NRAs is also superior to many previous works Taken together, the appealing reusable NIR-SERS active sensor possesses
(Table S3), exceeding the maximum of residue limit (3.01 × 10–7 M) multiple fascinating features in comparison with bare plasmonic NMs,
stipulated by the European Union. Moreover, the excellent holding greater potential for ultrasensitive and accurate monitoring of
anti-interference capability and selectivity of the established NIR-SERS special biomolecules.
active sensor are also verified in this paper (Fig. S16). In addition, the
variations of SERS intensities of ciprofloxacin and chloramphenicol as a 4. Conclusion
function of different concentrations are shown in Fig. 5(c) and (e),
respectively. It can be found that the established excellent linear re­ In summary, the well-aligned TiO2 NRAs grafted with closely inter­
lationships can sensitively response to the slight variation of concen­ connected Au/Ag NPs have been successfully constructed by a facile UV
tration. Therefore, the obtained Au/Ag NPs-TiO2 NRAs could be applied laser-induced photochemical overgrowth strategy. The obtained Au/Ag
for the ultra-trace and sensitive detection of antibiotic residue in real NPs-TiO2 NRAs exhibit an obviously higher NIR-SERS activity than that
environment. of monometallic Au or Ag NPs modified TiO2 NRAs, due to the stronger
In addition, in order to verify the accuracy of the proposed sensor by intermetallic synergistic effect among nano-heterostructures. The pro­
adopting the NIR-SERS toward real water sample (Black Tiger Springs posed NIR-SERS sensor enables the LOD values of ciprofloxacin and
water), five reproducible tests of ciprofloxacin and chloramphenicol chloramphenicol to be achieved at 10–9 M and 10–8 M, respectively.
with two settled different concentrations (5 × 10–6 and 5 × 10–7 M) More importantly, taking advantage of effective photocatalytic degra­
were performed in this paper. As shown in Table 1, the Raman charac­ dation, the NIR-SERS sensor could be reused by UV irradiation for
teristic peaks of ciprofloxacin and chloramphenicol at 1386 and 60 min, and ~84.2% residual SERS activity can be maintained after 5
1346 cm–1 were separately used to quantitative analysis the corre­ cycles. Superior to previous bare plasmonic NMs-based NIR-SERS, the
sponding antibiotic concentrations, based on the established linear re­ novel Au/Ag NPs-TiO2 NRAs possess both conventional excellent SERS
lationships in Fig. 5(c) and (e). As presented in Table 1, the estimated features and unique pronounced reusability in repeated tests, which is
value of relative error (RE) can be calculated < 4.8% for two antibiotic particular suitable for NIR-SERS monitoring of diverse biomolecules in
molecules, indicating that this NIR-SERS active sensor has a good ac­ the near future.
curacy to quantitative analysis ciprofloxacin and chloramphenicol in
real-world scenarios. On the other hand, as an excellent NIR-SERS sensor CRediT authorship contribution statement
in real-life applications, it should also possess high spectroscopic
distinguishability for simultaneous SERS detection of multiple probe Anxin Jiao: Conceptualization, Methodology, Writing – original
molecules in mixed condition. The NIR-SERS analyses of the mixed draft, writing – review & editing. Qingqiang Cui: Investigation, Re­
antibiotic sample (ciprofloxacin (10− 5 M) and chloramphenicol (10− 5 sources, Data curation, Writing – review & editing. Shuang Li： ：Inves­
M)) were carried out in this work, in order to verify independent trace tigation, Resources, Data curation, Writing – review & editing, Funding
detection on the same substrate using one light source in complex so­ acquization. Hengshuai Li: Investigation, Resources, Data curation,
lution system. The results (Fig. S17) show that the characteristic bands Writing – review & editing, Funding acquization. Linlin Xu: Investiga­
located at 1108, 1346 and 1602 cm–1 can be attributed to chloram­ tion, Writing – review & editing. Yue Tian: Investigation, Writing –
phenicol molecules; the Raman peaks at 1386, 1485, 1554 and review & editing. Hui Ma: Investigation, Writing – review & editing.
1628 cm–1 should be belonged to ciprofloxacin molecules. It is clearly Mengya Zhang: Investigation, Writing – review & editing. Xiangdong
suggested that the proposed 785 nm NIR-SERS sensor has a high reso­ Liu: Resources, Data curation, Validation, Writing – review & editing,
lution and accuracy in the detection of multiple antibiotic residues. Funding acquization. Ming Chen: Conceptualization, Data curation,
The excellent reusability of NIR-SERS sensor is also another impor­ Supervision, Funding acquization.
tant criterion for promoting practical applications, which is seldom
achieved by using bare plasmonic nanosubstrates in previous studies. It Declaration of Competing Interest
is well known that semiconductor materials (TiO2, ZnO) can be used as
the reusable SERS substrates due to their unique photocatalytic degra­ The authors declare that they have no known competing financial
dation properties [37–39]. Therefore, the Au/Ag NPs-TiO2 NRAs is ex­ interests or personal relationships that could have appeared to influence
pected to provide an effective photocatalytic degradation performance the work reported in this paper.
for removing antibiotic residues. To verify it, the corresponding
reversible NIR-SERS processes before and after UV light assisted
self-cleaning procedures were performed in this work (Fig. S18). During
one recycling experiment, the strong Raman bands of two antibiotic

7
A. Jiao et al. Sensors and Actuators: B. Chemical 350 (2022) 130848

Acknowledgements [19] N. Zhao, H. Li, Z. Yang, C. Tian, Y. Xie, Z. Feng, Z. Wang, X. Yan, W. Wang, H. Yu,
Wafer-scale 3D cloud-like aluminum hierarchical nanostructure for NIR SERS, Opt.
Mater. Express 9 (2019) 3546–3556.
This work was supported by National Natural Science Foundation of [20] N.T. Nguyen, M. Altomare, J. Yoo, P. Schmuki, Efficient photocatalytic H2
China (Grant nos. 11905115, 11575102, 12175126, 11775134 and evolution: controlled dewetting-dealloying to fabricate site-selective high-activity
11375108), Shandong Jianzhu University XNBS Foundation (Grant no. nanoporous Au particles on highly ordered TiO2 nanotube arrays, Adv. Mater. 27
(2015) 3208–3215.
1608), Fundamental Research Fund of Shandong University (Grant no. [21] L. Zhou, M. Zhou, C. Zhang, Y. Jiang, Z. Bi, J. Yang, Electro-Fenton degradation of
2018JC022), and Key Research and Development Project of Shandong p-nitrophenol using the anodized graphite felts, Chem. Eng. J. 233 (2013)
Province (Public Welfare Science and Technology Research) (Grant no. 185–192.
[22] J. Wang, C. Luo, T. Gao, A. Langrock, A.C. Mignerey, C. Wang, An advanced MoS2/
2019GGX103010). The authors would like to thank [Link] for carbon anode for high-performance sodium-ion batteries, Small 11 (2015)
support of XPS analysis. 473–481.
[23] X. Zhang, L. Wang, C. Liu, Y. Ding, S. Zhang, Y. Zeng, Y. Liu, S. Luo, A bamboo-
inspired hierarchical nanoarchitecture of Ag/CuO/TiO2 nanotube array for highly
Appendix A. Supporting information photocatalytic degradation of 2,4-dinitrophenol, J. Hazard. Mater. 313 (2016)
244–252.
Supplementary data associated with this article can be found in the [24] N. Khaliq, M.A. Rasheed, G. Cha, M. Khan, S. Karim, P. Schmuki, G. Ali,
Development of non-enzymatic cholesterol bio-sensor based on TiO2 nanotubes
online version at doi:10.1016/[Link].2021.130848. decorated with Cu2O nanoparticles, Sens. Actuators B: Chem. 302 (2020), 127200.
[25] P. Ramasamy, D.M. Seo, S.H. Kim, J. Kim, Effects of TiO2 shells on optical and
References thermal properties of silver nanowires, J. Mater. Chem. 22 (2012) 11651–11657.
[26] B. Tian, J. Zhang, T. Tong, F. Chen, Preparation of Au/TiO2 catalysts from Au(I)–
thiosulfate complex and study of their photocatalytic activity for the degradation of
[1] W. Wang, Q. Sang, M. Yang, J. Du, L. Yang, X. Jiang, X. Han, B. Zhao, Detection of
methyl orange, Appl. Catal. B: Environ. 79 (2008) 394–401.
several quinolone antibiotic residues in water based on Ag-TiO2 SERS strategy, Sci.
[27] K. Yang, K. Huang, Z. He, X. Chen, X. Fu, W. Dai, Promoted effect of PANI as
Total Environ. 702 (2020) 134956–134963.
electron transfer promoter on CO oxidation over Au/TiO2, Appl. Catal. B: Environ.
[2] J. Chen, M. Huang, L. Kong, Flexible Ag/nanocellulose fibers SERS substrate and its
158–159 (2014) 250–257.
applications for in-situ hazardous residues detection on food, Appl. Surf. Sci. 533
[28] J. Huang, Y. Zhu, C. Liu, Y. Zhao, Z. Liu, M.N. Hedhili, A. Fratalocchi, Y. Han,
(2020), 147454.
Fabricating a homogeneously alloyed AuAg shell on Au nanorods to achieve strong,
[3] L. Yang, P. Li, H. Liu, X. Tang, J. Liu, A dynamic surface enhanced Raman
stable, and tunable surface plasmon resonances, Small 11 (2015) 5214–5221.
spectroscopy method for ultra-sensitive detection: from the wet state to the dry
[29] X. Wang, G. Ma, A. Li, J. Yu, Z. Yang, J. Lin, A. Li, X. Han, L. Guo, Composition-
state, Chem. Soc. Rev. 44 (2015) 2837–2848.
adjustable Ag-Au substitutional alloy microcages enabling tunable plasmon
[4] Y. Ling, Y. Zhuo, L. Huang, D. Mao, Using Ag-embedded TiO2 nanotubes array as
resonance for ultrasensitive SERS, Chem. Sci. 9 (2018) 4009–4015.
recyclable SERS substrate, Appl. Surf. Sci. 388 (2016) 169–173.
[30] Y. Lu, W.H. Chiang, C. Liu, J.P. Chu, H.C. Ho, C.H. Hsueh, Wafer-scale SERS
[5] X. Li, G. Chen, L. Yang, Z. Jin, J. Liu, Multifunctional Au-coated TiO2 nanotube
metallic nanotube arrays with highly ordered periodicity, Sens. Actuators B: Chem.
arrays as recyclable SERS substrates for multifold organic pollutants detection,
329 (2021), 129132.
Adv. Funct. Mater. 20 (2010) 2815–2824.
[31] W. Tang, Y. An, K.H. Row, Fabrication of Au nanoparticles embedded holey g-C3N4
[6] Y. Wang, M. Zhang, H. Yu, Y. Zuo, J. Gao, G. He, Z. Sun, Facile fabrication of Ag/
as SERS substrates for sensitive and reliable detection, Chem. Eng. J. 402 (2020),
graphene oxide/TiO2 nanorod array as a powerful substrate for photocatalytic
126194.
degradation and surface-enhanced Raman scattering detection, Appl. Catal. B:
[32] G. Jiang, Z. Wang, S. Zong, K. Yang, K. Zhu, Y. Cui, Peroxidase-like recyclable SERS
Environ. 252 (2019) 174–186.
probe for the detection and elimination of cationic dyes in pond water, J. Hazard.
[7] N. Filippin, J. Castillo-Seoane, M.C. López-Santos, C.T. Rojas, K. Ostrikov,
Mater. 408 (2021), 124426.
A. Barranco, J.R. Sánchez-Valencia, A. Borrás, Plasma-enabled amorphous TiO2
[33] G. Shi, M. Wang, Y. Zhu, Y. Wang, H. Xu, A novel natural SERS system for crystal
nanotubes as hydrophobic support for molecular sensing by SERS, ACS Appl.
violet detection based on graphene oxide wrapped Ag micro-islands substrate
Mater. Interfaces 12 (2020) 50721–50733.
fabricated from Lotus leaf as a template, Appl. Surf. Sci. 459 (2018) 802–811.
[8] B. Samransuksamer, M. Horprathum, T. Jutarosaga, A. Kopwitthaya,
[34] G. Zhu, G. Cheng, P. Wang, W. Li, Y. Wang, J. Fan, Water compatible imprinted
S. Limwichean, N. Nuntawong, C. Chananonnawathorn, V. Patthanasettakul,
polymer prepared in water for selective solid phase extraction and determination
P. Muthitamongkol, A. Treetong, A. Klamchuen, A. Leelapojanaporn,
of ciprofloxacin in real samples, Talanta 200 (2019) 307–315.
C. Thanachayanont, P. Eiamchai, Facile method for decorations of Au
[35] K. Yang, Y. Hu, N. Dong, A novel biosensor based on competitive SERS
nanoparticles on TiO2 nanorod arrays toward high-performance recyclable SERS
immunoassay and magnetic separation for accurate and sensitive detection of
substrates, Sens. Actuator B Chem. 277 (2018) 102–113.
chloramphenicol, Biosens. Bioelectron. 80 (2016) 373–377.
[9] Z.C. Hong, E. Perevedentseva, S. Treschev, J.B. Wang, C.L. Cheng, Surface
[36] A. Chatzitakis, C. Berberidou, I. Paspaltsis, G. Kyriakou, T. Sklaviadis, I. Poulios,
enhanced Raman scattering of nanodiamond using visible-light-activated TiO2 as a
Photocatalytic degradation and drug activity reduction of chloramphenicol, Water
catalyst to photo-reduce nano-structured silver from AgNO3 as SERS-active
Res. 42 (2008) 386–394.
substrate, J. Raman Spectrosc. 40 (2009) 1016–1022.
[37] L. Xu, H. Zhang, Y. Tian, A. Jiao, F. Chen, M. Chen, Photochemical synthesis of
[10] A. Jiao, H. Zhang, L. Xu, Y. Tian, X. Liu, M. Chen, F. Chen, Core-shell Au@Ag
ZnO@Au nanorods as an advanced reusable SERS substrate for ultrasensitive
nanodendrites supported on TiO2 nanowires for blue laser beam-excited SERS-
detection of light-resistant organic pollutant in wastewater, Talanta 194 (2019)
based pH sensing, Opt. Express 27 (2019) 23981–23995.
680–688.
[11] N. Vermeulen, W.J. Keeler, K. Nandakumar, K.T. Leung, The bactericidal effect of
[38] A.K. Pal, S. Pagal, K. Prashanth, G.K. Chandra, S. Umapathy, D.B. Mohan, Ag/ZnO/
ultraviolet and visible light on Escherichia coli, Biotechnol. Bioeng. 99 (2008)
Au 3D hybrid structured reusable SERS substrate as highly sensitive platform for
550–556.
DNA detection, Sens. Actuator B Chem. 279 (2019) 157–169.
[12] A. Gupta, P. Avci, T. Dai, Y. Huang, M.R. Hamblin, Ultraviolet radiation in wound
[39] X. Li, H. Hu, D. Li, Z. Shen, Q. Xiong, S. Li, H. Fan, Ordered array of gold semishells
care: sterilization and stimulation, Adv. Wound Care 2 (2013) 422–437.
on TiO2 spheres: an ultrasensitive and recyclable SERS substrate, ACS Appl. Mater.
[13] H. Kang, S. Jeong, Y. Park, J. Yim, B.H. Jun, S. Kyeong, J.K. Yang, G. Kim, S. Hong,
Interfaces 4 (2012) 2180–2185.
L.P. Lee, J.H. Kim, H.Y. Lee, D.H. Jeong, Y.S. Lee, Near-infrared SERS nanoprobes
with plasmonic Au/Ag hollow-shell assemblies for in vivo multiplex detection,
Adv. Funct. Mater. 23 (2013) 3719–3727. Anxin Jiao is currently pursuing Doctor degree in Shandong University, Jinan, China. Her
[14] G. von Maltzahn, A. Centrone, J.H. Park, R. Ramanathan, M.J. Sailor, T.A. Hatton, research interests are mainly focused on chemical sensor and SERS-based sensor.
S.N. Bhatia, SERS-coded gold nanorods as a multifunctional platform for densely
multiplexed near-infrared imaging and photothermal heating, Adv. Mater. 21
Qingqiang Cui is an engineer in Shandong University, Jinan, China. His research interests
(2009) 3175–3180.
are nanomaterial-based sensors.
[15] N.G. Greeneltch, A.S. Davis, N.A. Valley, F. Casadio, G.C. Schatz, R.P. Van Duyne,
N.C. Shah, Near-infrared surface-enhanced Raman spectroscopy (NIR-SERS) for the
identification of eosin Y: theoretical calculations and evaluation of two different Shuang Li is an associate professor in Shandong Jianzhu University, Jinan, China. Her
nanoplasmonic substrates, J. Phys. Chem. A 116 (2012) 11863–11869. research interests are nanomaterials and optoelectronic devices.
[16] C.H. Lai, G.A. Wang, T.K. Ling, T.J. Wang, P.K. Chiu, Y.F. Chou Chau, C.C. Huang,
H.P. Chiang, Near infrared surface-enhanced Raman scattering based on star- Hengshuai Li is an associate professor in Liaocheng University, Liaocheng, China. His
shaped gold/silver nanoparticles and hyperbolic metamaterial, Sci. Rep. 7 (2017) research interests are physical properties of nanomaterials, new energy materials (pho­
5446. tocatalysis, new energy batteries).
[17] P. Singh, T.A.F. Konig, A. Jaiswal, NIR-active plasmonic gold nanocapsules
synthesized using thermally induced seed twinning for surface-enhanced Raman
scattering applications, ACS Appl. Mater. Interfaces 10 (2018) 39380–39390. Linlin Xu is currently pursuing Doctor degree in Shandong University, Jinan, China. Her
[18] H. Kang, J.K. Yang, M.S. Noh, A. Jo, S. Jeong, M. Lee, S. Lee, H. Chang, H. Lee, S. research interests are mainly focused on the study of photoelectric catalysis properties of
J. Jeon, H.I. Kim, M.H. Cho, H.Y. Lee, J.H. Kim, D.H. Jeong, Y.S. Lee, One-step nanomaterials.
synthesis of silver nanoshells with bumps for highly sensitive near-IR SERS
nanoprobes, J. Mater. Chem. B 2 (2014) 4415–4421.

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A. Jiao et al. Sensors and Actuators: B. Chemical 350 (2022) 130848

Yue Tian is currently pursuing Doctor degree in Shandong University, Jinan, China. Her Xiangdong Liu is a professor in Shandong University, Jinan, China. His research interests
research interests are mainly focused on SERS-based sensor. are ion beam, laser beam and matter interaction and material microcosmic design.

Hui Ma is currently pursuing Doctor degree in Shandong University, Jinan, China. Her Ming Chen is a researcher in Shandong University, Jinan, China. His research interests are
research interests are mainly focused on SERS-based sensor. nanomaterial-based sensors.

Mengya Zhang is currently pursuing Master degree in Shandong University, Jinan, China.
Her research interests are mainly focused on SERS-based sensor.