Co-reporter:Binbin Zhou;Shaofei Li;Xianghu Tang;Pan Li;Xiaomin Cao;Borong Yu;Jinhuai Liu
Nanoscale (2009-Present) 2017 vol. 9(Issue 34) pp:12307-12310
Publication Date(Web):2017/08/31
DOI:10.1039/C7NR04050D
Intramolecular proton transfer of hypoxanthine, induced by application of a laser on the surface of a bare noble nanomaterial, was monitored in real time using surface-enhanced Raman spectroscopy (SERS). This monitoring demonstrated the dependence of the reaction on the identity of the nanomaterial and on the laser power density. The results pave the way for monitoring the proton transfer reaction in various relevant fields. In addition, we observed the presence of the proton transfer phenomenon of hypoxanthine in serum, providing a way to avoid the effect of proton transfer and hence achieve more reliable spectra of sera for clinical diagnosis.
Co-reporter:Binbin Zhou, Xiaoyun Li, Xianghu Tang, Pan Li, Liangbao Yang, and Jinhuai Liu
ACS Applied Materials & Interfaces 2017 Volume 9(Issue 8) pp:
Publication Date(Web):February 8, 2017
DOI:10.1021/acsami.6b15205
Target analyte detection in complex systems with high selectivity and repeatability is crucial to analytical technology and science. Here we present a two-dimensional (2D) surface-enhanced resonance Raman scattering (SERRS) platform, which takes advantages of the high selectivity of the SERRS sensor as well as the sensitivity and reproducibility of the interfacial SERS platform, for detecting trace epinephrine (EP) in the serum. To realize sensitive and selective detection of EP in a complex system, Au NPs are modified with α,β-nitriloacetic acid and Fe(NO3)3 to form the Au NP-(Fe-NTA) sensor, and as a consequence, EP can be rapidly captured by the sensor on the surface of Au NPs and then delivered at the cyclohexane/water interface. More importantly, we synthesized the extremely stable Au NPs (PVP-stabilized Au NPs), where the presence of PVP prevents aggregation of Au NPs during the self-assembly process and then makes a more uniform distribution of Au NPs with analytes at the cyclohexane/water interface, approximately 2 nm interparticle distance between the Au NPs, which has been proved by synchrotron radiation grazing incidence small-angle X-ray scattering (SR-GISAXS) experiments. The self-assembly method not only effectively avoids the aggregation of Au NPs and decreases the influence of the background signal but also can capture and enrich EP molecules in the cyclohexane/water interface, realizing the sensitive and selective detection of EP in complex serum sample. This strategy overcomes the difficulty of bringing nanostructures together to form efficient interparticle distance with simple fabrication and maximum uniformity and also provides a powerful nanosensor for tracing amounts of analyte molecules in a complex system with the advantages of capturing and enriching of target molecules in the liquid/liquid interface during the self-assembly process. Our SERRS platform opens vast possibilities for repeatability, sensitivity, and selectivity detection of targets in various complex fields.Keywords: epinephrine; interface; self-assemble; SERRS; serum;
Co-reporter:Pan Li;Xiunan Yan;Fei Zhou;Xianghu Tang;Jinhuai Liu
Journal of Materials Chemistry C 2017 vol. 5(Issue 13) pp:3229-3237
Publication Date(Web):2017/03/30
DOI:10.1039/C7TC00150A
Designing plasmonic hot spots within an active platform that has well-defined and highly reproducible features is one of the most critical issues in obtaining ultrasensitive detection and credible signals for surface-enhanced Raman spectroscopy (SERS). Hot spots between two or more nanostructures can amplify Raman signals for single-molecule-level detection. Here, we report a SERS-active platform by using spontaneous capillary imbibition to assemble a single Au nanoparticle (NP) onto the surface of a single Ag nanowire (NW). Optical excitation of this coupled nanostructure provides a SERS hot spot at the gap between the single NP and NW. This platform can be easily fabricated, and the position of the single hot spot can be conveniently located during SERS measurements. Moreover, the single Au NP coupled to the Ag NW acts as an optical antenna for localizing and enhancing the electromagnetic field (E-field). Most importantly, the single hot spot platform can provide a “nano-channel” for trapping molecules because of the presence of capillary imbibition. We show that high quality SERS spectra of various molecules with different natures can be generated on a single hot spot structure with reliable reproducibility and excellent sensitivity. Our approach not only overcomes the difficulty of bringing two nanostructures together to form an efficient junction with simple fabrication and maximum uniformity, but also provides a SERS-active platform with a narrow enhancement factor (EF) distribution.
Co-reporter:Yongmei Ma, Honglin Liu, Mei Mao, Juan Meng, Liangbao Yang, and Jinhuai Liu
Analytical Chemistry 2016 Volume 88(Issue 16) pp:8145
Publication Date(Web):July 12, 2016
DOI:10.1021/acs.analchem.6b01884
The design and application of liquid interfacial plasmonic platform is still in its infancy but is an exciting topic in tunable optical devices, sensors, and catalysis. Here, we developed an interfacial surface-enhanced Raman scattering (SERS) platform through the large-scale self-assembly of gold nanoparticle (GNP) arrays at the cyclohexane (CYH)/water interface for detecting trace drug molecules in the urine of humans. The molecules extracted by the CYH phase from a urine sample were directly localized into the self-organized plasmonic hotspots, yielded excellent Raman enhancement, and realized the substrate-free interfacial SERS detection. Synchrotron radiation small-angle X-ray scattering (SR-SAXS) experiments reveals a good uniformity of approximately 2–3 nm interparticle distance in the GNP arrays. SERS colocalization experiments demonstrated that amphetamine molecules of different concentration levels could be loaded into the interfacial GNP arrays and realized the coassembly together with nanoparticles at the liquid/liquid interface. Interfacial GNP arrays with dynamic nanogaps in liquid interfacial structure can make surrounding molecules easily diffuse into the nanogaps. In contrast, the fixed GNP arrays on Si wafer were more irregular, such as multilayer stack, random aggregates, and voids, during the drying process. When the drugs directly participate in the self-assembly process, it becomes easier for analytes diffusing into the nanogaps of GNP arrays, produces a concentration effect, and amplified the SERS sensitivity. This feature also enables molecules to be adsorbed evenly in the arrays and makes a more uniform distribution of both the analytes and GNPs in the liquid interface and realizes the significant increase in signal reproducibility. Interfacial SERS produced a standard deviation of 12.5% at 1001 cm–1 peak of methamphetamine (MAMP) molecules under the concentration of 1 ppm, implying a good reproducibility. Moreover, dual-analyte detection at organic and aqueous phases was also realized and confirmed a good capability for analytes detection by liquid interfacial SERS platform, which promises nonengineering detection of analytes dissolved in often-inaccessible environments.
Co-reporter:Xiunan Yan, Pan Li, Liangbao Yang and Jinhuai Liu
Analyst 2016 vol. 141(Issue 17) pp:5189-5194
Publication Date(Web):27 Apr 2016
DOI:10.1039/C6AN00771F
Based on the bianalyte method, time-dependent surface-enhanced Raman spectrosopy (SERS) spectra were applied to observe and study the competitive adsorption of bipyridine isomerides 2,2′-bpy and 4,4′-bpy. These time-dependent SERS spectra offer a significant advantage for observing the continuous SERS spectra of analyte with 2 s resolution, letting one monitor real-time competitive adsorption and corresponding SERS signal intensity for mixed or pure analyte type events under different concentrations. In this study, we report experimental evidence of competitive adsorption of two bipyridine isomerides using SERS mapping and independent spectra in chronological order. On the one hand, the time-dependent SERS spectra of 2,2′-bpy were prior dominated in the early stage either in high concentration or in low concentration. On the other hand, pure type 2,2′-bpy or 4,4′-bpy events only occurred for strong intensity, whereas weak intensity events exhibited more mixed analytes in low concentration, showing a great difference from those at the higher concentration. In addition, we believe that these results and this evidence can motivate the use of time-dependent SERS spectra for distinguishing the fingerprint information of several molecules from similar isomeride molecules in chemical and biological systems.
Co-reporter:Juan Meng, Suhua Qin, Li Zhang, Liangbao Yang
Applied Surface Science 2016 Volume 366() pp:181-186
Publication Date(Web):15 March 2016
DOI:10.1016/j.apsusc.2016.01.078
Highlights
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Gold nanodumbbells as SERS substrates represent robust, highly sensitive, excellent and reproducible SERS performance.
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Economic and on-site detection of prohibited colorants in two kinds of sweet drinks have been realized using a portable Raman device.
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These analyses are rapid and direct, without the need for any pretreatment of the samples.
Co-reporter:Suhua Qin, Juan Meng, Xianghu Tang, Liangbao Yang
Talanta 2016 Volume 146() pp:452-456
Publication Date(Web):1 January 2016
DOI:10.1016/j.talanta.2015.09.011
•The SERS substrates of the silver nanoparticle assemblies based on capillaries were conveniently prepared without complicated instruments.•The SERS substrates based on capillaries exhibited remarkable sensitivity and reproducibility.•The inorganic chemical reaction of Fe3+ converted to Fe2+ was monitored indirectly.•The kinetics of catalyzed reaction can be real-time monitored by in situ using the SERS technique on a single constructed capillary.Monitoring the process of organic chemical reactions to study the kinetics by surface-enhanced Raman spectroscopy (SERS) is currently of immense interest. However, monitoring the inorganic chemical reaction is still an extremely difficulty for researchers. This study exactly focused on the monitor of inorganic chemical reaction. Capillary coated with silver nanoparticles was introduced, which was an efficient platform for monitoring reactions with SERS due to the advantages of sensitivity and excellent reproducibility. The photoreduction of [Fe(phen)3]3+ to [Fe(phen)3]2+ was used as model reaction to demonstrated the feasibility of SERS monitoring inorganic chemical reaction by involving in metal–organic complexes. Moreover, the preliminary implementation demonstrated that the kinetics of photoreduction can be real-time monitored by in situ using the SERS technique on a single constructed capillary, which may be useful for the practical application of SERS technique.
Co-reporter:Liangbao Yang, Pan Li, Honglin Liu, Xianghu Tang and Jinhuai Liu
Chemical Society Reviews 2015 vol. 44(Issue 10) pp:2837-2848
Publication Date(Web):12 Mar 2015
DOI:10.1039/C4CS00509K
Surface-enhanced Raman spectroscopy (SERS) has been demonstrated to be an excellent analytical tool for a wide range of research and practical applications owing to its ability to achieve highly sensitive detection and provide fingerprint information for analytes. Improving the sensitivity of SERS is beneficial for the rapid analysis of target molecules in various systems, where the ultimate goal is to obtain quantitative analysis and detection. Considerable efforts have been made to develop new methods for SERS detection that improve upon its high sensitivity and reproducibility. In this tutorial review, we first introduce the traditional methods for SERS detection and then report in detail on the features of a new strategy for implementing SERS. This new method, namely, a dynamic surface-enhanced Raman spectroscopy method proposed by our group, is based on state translation nanoparticle-enhanced Raman spectroscopy (STNERS) from the wet state to the dry state. Notably, during this process, a three-dimensional (3D) hotspot matrix that can hold hotspots between every two adjacent particles in 3D space, with minimal polydispersity of the particle size and maximal uniformity of the interparticle distance, can be simply achieved. Experiments and applications using STNERS are reviewed starting with an investigation of STNERS mechanisms and a discussion of sample preparation. Next, evidence of the advantages of STNERS and practical applications are discussed. Finally, the future outlook for STNERS and the development of STNERS as an ultra-sensitive detection method are also discussed.
Co-reporter:Yongmei Ma, Honglin Liu, Zhenzhen Han, Liangbao Yang and Jinhuai Liu
Journal of Materials Chemistry A 2015 vol. 3(Issue 28) pp:14642-14650
Publication Date(Web):08 Jun 2015
DOI:10.1039/C5TA03143E
An effective near-infrared (NIR) active photocatalyst, NaYF4:Yb,Tm@TiO2/Ag (UC@TiO2/Ag) core@comby shell composite, was synthesized by a simple three-step hydrothermal process. Under the full-spectrum light of a Xe lamp in UV-Vis absorbance experiments, about 96% of R6G dyes in solution were degraded by UC@TiO2/Ag in 120 minutes, while only about 64% of the dyes were degraded by pure TiO2 under the same conditions. Under a UV-filtered Xe lamp, about 35% of the dyes were degraded by UC@TiO2/Ag in 120 minutes; interestingly, only about 8% of the dyes were degraded by pure TiO2. Under irradiation by a 785 nm laser in surface enhanced Raman scattering (SERS) experiments, the photodegradation rate constants were 0.02612 s−1 for UC@TiO2/Ag and 0.00046 s−1 for TiO2/Ag, indicating a nearly 58 fold improvement. After deducting the photobleaching effect, the photodegradation rate constants for UC@TiO2/Ag under 633 and 532 nm lasers were 0.00715 s−1 and 0.00565 s−1, respectively, revealing a sharp decrease under irradiation at shorter wavelengths. Electron spin resonance (ESR) analysis revealed that the presence of UC in this photocatalytic system certainly induced the increase of ˙OH free radicals with NIR irradiation, i.e. the UC core converts NIR light into ultraviolet (UV) light and initiates excellent photocatalytic activity of the TiO2/Ag comby shell. Furthermore, the decorating of Ag nanoparticles not only enhances the photocatalytic ability, but also provides a structural basis for monitoring the photocatalytic kinetics by the SERS technique. By virtue of monochrome laser lines, SERS analysis provides direct evidence to prove the capability of UC-initiated non-UV photocatalysis and the improvement of the utilization of non-UV lights on TiO2. The results revealed that this new photocatalytic platform can efficiently utilize different bands of the solar spectrum and also find new applications in SERS fields.
Co-reporter:Pan Li, Bingbing Ma, Liangbao Yang and Jinhuai Liu
Chemical Communications 2015 vol. 51(Issue 57) pp:11394-11397
Publication Date(Web):09 Jun 2015
DOI:10.1039/C5CC03792A
A hybrid single nanoreactor composed of small Au nanoparticles (NPs) and a long Ag nanowire (NW) with a length of 10 μm can be conveniently located by optical microscopy, allowing us to monitor by in situ surface enhanced Raman spectroscopy (SERS) the plasmon-driven and small Au NPs catalyzed reactions with high sensitivity and reproducibility.
Co-reporter:Ronglu Dong, Shizhuang Weng, Liangbao Yang, and Jinhuai Liu
Analytical Chemistry 2015 Volume 87(Issue 5) pp:2937
Publication Date(Web):January 29, 2015
DOI:10.1021/acs.analchem.5b00137
A new, novel, rapid method to detect and direct readout of drugs in human urine has been developed using dynamic surface-enhanced Raman spectroscopy (D-SERS) with portable Raman spectrometer on gold nanorods (GNRs) and a classification algorithm called support vector machines (SVM). The high-performance GNRs can generate gigantic enhancement and the SERS signals obtained using D-SERS on it have high reproducibility. On the basis of this feature of D-SERS, we have obtained SERS spectra of urine and urine containing methamphetamine (MAMP). SVM model was built using these data for fast identified and visual results. This general method was successfully applied to the detection of 3, 4-methylenedioxy methamphetamine (MDMA) in human urine. To verify the accuracy of the model, drug addicts’ urine containing MAMP were detected and identified correctly and rapidly with accuracy more than 90%. The detection results were displayed directly without analysis of their SERS spectra manually. Compared with the conventional method in lab, the method only needs a 2 μL sample volume and takes no more than 2 min on the portable Raman spectrometer. It is anticipated that this method will enable rapid, convenient detection of drugs on site for the police.
Co-reporter:Zhenzhen Han, Honglin Liu, Juan Meng, Liangbao Yang, Jing Liu, and Jinhuai Liu
Analytical Chemistry 2015 Volume 87(Issue 18) pp:9500
Publication Date(Web):August 25, 2015
DOI:10.1021/acs.analchem.5b02899
A portable kit was demonstrated for rapid and reliable surface-enhanced Raman scattering (SERS) detection of drugs in human urine. This kit contains two sealed reagent tubes, a packet of standardized SERS substrates, and a mini Raman device. A 3 min pretreatment for separating amphetamines from human urine was developed with an extraction rate of >80% examined by ultraperformance liquid chromatography (UPLC). Simultaneously, highly reproducible two-dimensional (2D) gold nanorod (GNR) arrays were assembled by the use of methoxymercaptopoly(ethylene glycol) (mPEG-SH) capping. Thirty batches of GNR arrays produced the 1001 cm–1 intensity of methamphetamine (MA) molecules with a relative standard deviation (RSD) of 7.9%, and a 21 × 21 μm2 area mapping on a 2D GNR array produced a statistical RSD of <10%, implying an excellent reproducibility and uniformity. The detection limit of amphetamines in human urine was at least 0.1 ppm. Moreover, the portable kit was successfully used for detecting MA, 3,4-methylenedioxymethamphetamine (MDMA), and methcathinone (MC) in 30 volunteers’ urine samples with various clinical natures, and the dual-analyte detection of MA and MDMA implied a good capability of multiplex analysis. UPLC examination and the SERS recovery test clearly indicated that our pretreatment procedure was sufficient to lower the high background signals caused by complex components in urine and demonstrated the practicability and the resistance to false positives, which is a vital problem for law enforcement applications. The excellent performance of our portable kit promises a great prospective toward a rapid, reliable, and on-spot analyzer, especially for public safety and healthcare.
Co-reporter:Zhenzhen Han, Honglin Liu, Bin Wang, Shizhuang Weng, Liangbao Yang, and Jinhuai Liu
Analytical Chemistry 2015 Volume 87(Issue 9) pp:4821
Publication Date(Web):April 8, 2015
DOI:10.1021/acs.analchem.5b00176
Rapid component separation and robust surface-enhanced Raman scattering (SERS) identification of drugs in real human urine remain an attractive challenge because of the sample complexity, low molecular affinity for metal surface, and inefficient use of hotspots in one- or two-dimensional (2D) geometries. Here, we developed a 5 min strategy of cyclohexane (CYH) extraction for separating amphetamines from human urine. Simultaneously, an oil-in-water emulsion method is used to assemble monodisperse Ag nanoparticles in the CYH phase into spherical colloidal superstructures in the aqueous phase. These superstructures create three-dimensional (3D) SERS hotspots which exist between every two adjacent particles in 3D space, break the traditional 2D limitation, and extend the hotspots into the third dimension along the z-axis. In this platform, a conservative estimate of Raman enhancement factor is larger than 107, and the same CYH extraction processing results in a high acceptability and enrichment of drug molecules in 3D hotspots which demonstrates excellent stability and reproducibility and is suitable for the quantitative examination of amphetamines in both aqueous and organic phases. Parallel ultraperformance liquid chromatography (UPLC) examinations corroborate an excellent performance of our SERS platform for the quantitative analysis of methamphetamine (MA) in both aqueous solution and real human urine, of which the detection limits reach 1 and 10 ppb, respectively, with tolerable signal-to-noise ratios. Moreover, SERS examinations on different proportions of MA and 3,4-methylenedioxymethamphetamine (MDMA) in human urine demonstrate an excellent capability of multiplex quantification of ultratrace analytes. By virtue of a spectral classification algorithm, we realize the rapid and accurate recognition of weak Raman signals of amphetamines at trace levels and also clearly distinguish various proportions of multiplex components. Our platform for detecting drugs promises to be a great prospect for a rapid, reliable, and on-spot analyzer.
Co-reporter:Yongmei Ma, Honglin Liu, Zhenzhen Han, Liangbao Yang and Jinhuai Liu
Analyst 2015 vol. 140(Issue 15) pp:5268-5275
Publication Date(Web):01 Jun 2015
DOI:10.1039/C5AN00441A
This study reported the significantly improved Raman enhancement ability of silver nanoparticles (Ag NPs) by decorating them on single NaYF4:Yb,Er@SiO2 core–shell particles (UC@SiO2@Ag) under a 785 nm excitation. The optimal thickness of the silica shell can be easily obtained by adjusting the amounts of TEOS, which is the crucial element to balance the upconversion and the formation of a hot spot by Ag NP aggregation. This substrate revealed highly reproducible properties, which is crucial to the practical application of SERS technology. This substrate exhibited an excellent sensitivity for methylamphetamine detection under near-infrared excitation. The advantages of NIR excitation in our SERS sensing open up a new application field of UC-noble metal composites, and also promise a new research direction for the synthesis and applications of SERS-active nanostructures.
Co-reporter:Bingbing Ma, Pan Li, Liangbao Yang, Jinhuai Liu
Talanta 2015 Volume 141() pp:1-7
Publication Date(Web):15 August 2015
DOI:10.1016/j.talanta.2015.03.053
•The T-SERS mapping exhibits remarkable sensitivity in comparison with that of traditional method.•T-SERS strategy is beneficial to generate reproducible SERS signal.•T-SERS strategy is easy operation without complicated sample preparation.•Hydrophobic surfaces dramatically reduce the contact area between droplet and Si wafer.For the sensitive and convenient detection of pesticides, several sensing methods and materials have been widely explored. However, it is still a challenge to obtain sensitive, simple detection techniques for pesticides. Here, the simple and sensitive Time-resolved SERS mapping (T-SERS) and Spatial-resolved SERS mapping (S-SERS) are presented for detection of pesticides by using Au@Ag NPs as SERS substrate. The Time-resolved SERS mapping (T-SERS) is based on state translation nanoparticles from the wet state to the dry state to realize SERS measurements. During the SERS measurement, adhesive force drives the particles closer together and then average interparticle gap becomes smaller. Following, air then begins to intersperse into the liquid network and the particles are held together by adhesive forces at the solid-liquid-air interface. In the late stage of water evaporation, all particles are uniformly distributed. Thus, so called hotspots matrix that can hold hotspots between every two adjacent particles in efficient space with minimal polydispersity of particle size are achieved, accompanying the red-shift of surface plasmon peak and appearance of an optimal SPR resonated sharply with excitation wavelength. Here, we found that the T-SERS method exhibits the detection limits of 1–2 orders of magnitude higher than that of S-SERS. On the other hand, the T-SERS is very simple method with high detection sensitivity, better reproducibility (RSD=10.8%) and is beneficial to construction of a calibration curve in comparison with that of Spatial-resolved SERS mapping (S-SERS). Most importantly, as a result of its remarkable sensitivity, T-SERS mapping strategies have been applied to detection of several pesticides and the detect limit can down to 1 nM for paraoxon, 0.5 nM for sumithion. In short, T-SERS mapping measurement promises to open a market for SERS practical detection with prominent advantages.
Co-reporter:Honglin Liu ; Zhilin Yang ; Lingyan Meng ; Yudie Sun ; Jie Wang ; Liangbao Yang ; Jinhuai Liu ;Zhongqun Tian
Journal of the American Chemical Society 2014 Volume 136(Issue 14) pp:5332-5341
Publication Date(Web):March 18, 2014
DOI:10.1021/ja501951v
The “fixed” or “flexible” design of plasmonic hotspots is a frontier area of research in the field of surface-enhanced Raman scattering (SERS). Most reported SERS hotspots have been shown to exist in zero-dimensional point-like, one-dimensional linear, or two-dimensional planar geometries. Here, we demonstrate a novel three-dimensional (3D) hotspot matrix that can hold hotspots between every two adjacent particles in 3D space, simply achieved by evaporating a droplet of citrate-Ag sols on a fluorosilylated silicon wafer. In situ synchrotron-radiation small-angle X-ray scattering (SR-SAXS), combined with dark-field microscopy and in situ micro-UV, was employed to explore the evolution of the 3D geometry and plasmonic properties of Ag nanoparticles in a single droplet. In such a droplet, there is a distinct 3D geometry with minimal polydispersity of particle size and maximal uniformity of interparticle distance, significantly different from the dry state. According to theoretical simulations, the liquid adhesive force promotes a closely packed assembly of particles, and the interparticle distance is not fixed but can be balanced in a small range by the interplay of the van der Waals attraction and electrostatic repulsion experienced by a particle. The “trapping well” for immobilizing particles in 3D space can result in a large number of hotspots in a 3D geometry. Both theoretical and experimental results demonstrate that the 3D hotspots are predictable and time-ordered in the absence of any sample manipulation. Use of the matrix not only produces giant Raman enhancement at least 2 orders of magnitude larger than that of dried substrates, but also provides the structural basis for trapping molecules. Even a single molecule of resonant dye can generate a large SERS signal. With a portable Raman spectrometer, the detection capability is also greatly improved for various analytes with different natures, including pesticides and drugs. This 3D hotspot matrix overcomes the long-standing limitations of SERS for the ultrasensitive characterization of various substrates and analytes and promises to transform SERS into a practical analytical technique.
Co-reporter:Xianghu Tang, Wenya Cai, Liangbao Yang and Jinhuai Liu
Nanoscale 2014 vol. 6(Issue 15) pp:8612-8616
Publication Date(Web):03 Jun 2014
DOI:10.1039/C4NR01939C
Investigating the kinetics of catalytic reactions with surface-enhanced Raman scattering (SERS) on a single particle remains a significant challenge. In this study, the single particle of the constructed hierarchical peony-like silver microflowers (SMFs) with highly roughened surface led to the coupling of high catalytic activity with a strong SERS effect, which acts as an excellent bifunctional platform for in situ monitoring of surface catalytic reactions. The kinetics of the reaction of 4-nitrothiophenol (4-NTP) dimerizing into 4,4′-dimercaptoazobenzene (DMAB) was investigated and comparatively studied by using the SERS technique on a single particle of different morphologies of SMFs. The results indicate that a fully developed nanostructure of a hierarchical SMF has both larger SERS enhancement and apparent reaction rate constant k, which may be useful for monitoring and understanding the mechanism of plasmon-driven surface catalyzed reactions.
Co-reporter:Wenya Cai, Xianghu Tang, Bai Sun and Liangbao Yang
Nanoscale 2014 vol. 6(Issue 14) pp:7954-7958
Publication Date(Web):12 May 2014
DOI:10.1039/C4NR01147C
In this study, multifunctional Fe3O4/C/Au nanoparticles (NPs), which catalytically integrated active small Au NPs with surface-enhanced Raman scattering (SERS) active large Au NPs, were fabricated via a facile method and employed for the in situ SERS monitoring of a catalytic reaction of p-nitrothiophenol (p-NTP) to p-aminothiophenol (p-ATP). In addition, the effect of magnet power was tested and it was demonstrated that the SERS intensity of the reaction system was stronger, and the reaction proceeded more smoothly because more hot spots existed and remained the same in the magnetic field; hence, the catalytic rate could be determined.
Co-reporter:Ying Zhou, Xuanhua Li, Xingang Ren, Liangbao Yang and Jinhuai Liu
Analyst 2014 vol. 139(Issue 19) pp:4799-4805
Publication Date(Web):15 May 2014
DOI:10.1039/C4AN00540F
Recently, nanoparticle–film coupling systems in which metal nanoparticles (supported localized surface plasmons, LSPs) are separated from a flat metal film (supported surface plasmon polaritons, SPPs) by a spacer have been widely reported due to its strong local enhancement field. However, there is are limited studies, which employ the design of combing metal grating into the nanoparticle–film gap system. Here, we propose and fabricate a novel double-resonance SERS system by strategically assembling Au NPs separated by a MoO3 nanospacer from an Ag grating film. The Ag grating with clear SPP effect is used for the first time in a double-resonance system, and the monolayer Au NPs array is well assembled onto the top of the Ag grating with a compact and uniform distribution (inter-particles gap of about 5 nm). As a result, we experimentally and theoretically demonstrate a significant near-field enhancement. The very strong near-field produced in the proposed SERS substrates is due to multiple couplings, including the Au NPs–Ag grating film coupling and Au NPs–Au NPs coupling. In addition, the as-proposed SERS substrates show good reproducibility of SERS, which have potential applications in plasmonic sensing and analytical science.
Co-reporter:Yongmei Ma, Honglin Liu, Zhenzhen Han, Liangbao Yang, Bai Sun and Jinhuai Liu
Analyst 2014 vol. 139(Issue 22) pp:5983-5988
Publication Date(Web):10 Sep 2014
DOI:10.1039/C4AN01202J
This study has investigated the plasmonic photocatalytic ability of silver nanoparticles (Ag NPs) and the significantly improved Raman achieved by decorating them on a single NaYF4:Yb,Er upconversion (UC) microcrystal under near-infrared excitation. This points to new applications for UC-noble metal composites and promises a novel method for constructing SERS-active nanostructures.
Co-reporter:Liangbao Yang, Pan Li and Jinhuai Liu
RSC Advances 2014 vol. 4(Issue 91) pp:49635-49646
Publication Date(Web):22 Sep 2014
DOI:10.1039/C4RA09231G
In recent years, surface-enhanced Raman scattering (SERS) has attracted tremendous attention and has been widely used as a powerful analytical tool. Simultaneously, a variety of SERS substrates also have been explored in order to obtain sensitive and reproducible detection. Though researchers have designed and fabricated several SERS-active substrates by employing new technological methods, these substrates have not gotten rid of disadvantages of single-use or single function compared with multifunctional substrates. These limit the development of SERS substrates and promote researchers to prepare new-type multifunctional SERS substrates that not only provide real-time representation of information by monitoring and tracing detection but also have a high sensitivity and reproducibility. This review first reports the applications of multifunctional materials as SERS substrates, which involve a wider range of use in nontraditional but important degradation of organic contaminants, enrichment of target analytes, assembly of nano-materials and imaging of living cells/organisms. We expect this review to be of interest to researchers who could benefit from multifunctional SERS substrates on the basis of the native advantages of unprecedented sensitivity and non-destructive signals of this type of spectroscopy.
Co-reporter:Pan Li, Ronglu Dong, Yiping Wu, Honglin Liu, Lingtao Kong, Liangbao Yang
Talanta 2014 Volume 127() pp:269-275
Publication Date(Web):1 September 2014
DOI:10.1016/j.talanta.2014.03.075
•The method enhances 1–2 orders of magnitude the signals of analyte in comparison to the traditional method.•All of the successive spectra can reflect the dynamics process of this dynamic-SERS method.•The method shows much better correlations between concentration and intensity.•The natural samples tests show that this dynamic-SERS method is capable of quantitative analysis.We report the use of Polystyrene/Ag (PS/Ag) nanoparticles as dynamic surface-enhanced Raman spectroscopy (dynamic-SERS) substrates for sensitive detection of low levels of organophosphorus pesticides. The PS particles clearly observed using Raman microscopy provide the masterplate for in situ growth of Ag NPs, leading to multiple active sites for SERS measurements. Besides obtaining the fingerprints of target molecules and recording time-resolved Raman spectra, this dynamic-SERS method can be used as an ultra-sensitive analytical technique which can enhance 1–2 orders of magnitude the signals of analytes in comparison to that of the traditional methods. On the other hand, importantly, it shows much better correlations between concentration and intensity than does the conventional SERS technique so that it can build the foundation for quantitative analysis of analytes. The as-prepared individual PS/Ag nanoparticle has been demonstrated for the sensitive detection of organophosphorus paraoxon and sumithion. SERS spectra are acquired at different concentrations of each pesticide and linear calibration curves are obtained by monitoring the strongest intensity value of bands arising from stronger stretching mode as a function of analyte concentration. The limits of detection and limits of quantitation are reported for two pesticides. The limit of detection for paraoxon is 96 nM (0.026 ppm) and for sumithion is 34 nM (0.011 ppm). The limits of quantitation are 152 nM (0.042 ppm) and 57 nM (0.016 ppm) for paraoxon and sumithion, respectively. It can be seen that these two organophosphorus pesticides can be detected in the low nM range based on this dynamic-SERS analytical method. Also, in the real sample experiments of paraoxon and sumithion, the results confirm that this dynamic-SERS technique would have potential applicability for quantitative analysis with slight interference.
Co-reporter:Yudie Sun, Honglin Liu, Liangbao Yang, Bai Sun, Jinhuai Liu
Materials Research Bulletin 2014 53() pp: 89-95
Publication Date(Web):
DOI:10.1016/j.materresbull.2014.01.044
Co-reporter:Yudie Sun;Dr. Honglin Liu;Dr. Fei Zhou;Dr. Shengnan He;Bai Sun;Jinhuai Liu
Chemistry - A European Journal 2014 Volume 20( Issue 33) pp:10414-10424
Publication Date(Web):
DOI:10.1002/chem.201402424
Abstract
Anisotropic noble-metal structures are attracting increasing attention because of interesting size- and shape-dependent properties and have emerging applications in the fields of optics and catalysis. However, it remains a significant challenge to overcome chemical contributions and acquire molecular insight into the relationship between Raman enhancement and photocatalytic activity. This study gives visualized experimental evidence of the anisotropic spatial distribution of Raman signals and photocatalytic activity at the level of single nanometer-thin Au microtriangles and microhexagons. Theoretical simulations indicate an anisotropic spatial distribution and sharpness-dependent strength of the electric-field enhancement. Analysis by using statistical surface-enhanced Raman scattering (SERS) supports this view, that is, Raman enhancement is on the order of corner>edge>face for a single microplate, but SERS measurements at different depths of focus also imply a concentration-dependent feature of SERS signals, especially at the corners and edges. Similarly, the SERS signals of product molecules in plasmonic photocatalysis also exhibit asymmetrical strengths at different corners of the same microplate. However, by examining the variations in the relative intensities of the SERS peaks, the difference in the photocatalytic activities at the corners, edges, and faces has been successfully calculated and is highly consistent with electric-field simulations, thus indicating that an increased number of molecules adsorbed at specific sites does not necessarily lead to a higher conversion ratio in noble-metal photocatalysis. Our strategy weakens the assumed impact of plasmonic local heating and, to a certain extent, excludes the influence of concentration effects and chemical contributions in noble-metal photocatalysis, thus clearly profiling plasmon-related characteristics. This study also promises a new research direction to understand the enhancement mechanism of SERS-active structures.
Co-reporter:Yiqun Zhu, Minqiang Li, Daoyang Yu, Liangbao Yang
Talanta 2014 Volume 128() pp:117-124
Publication Date(Web):1 October 2014
DOI:10.1016/j.talanta.2014.04.066
•Eeconomical, flexible and practical SERS substrate based on deposition of silver nanoparticles (Ag NPs) on commercially available low-cost filter paper is prepared by simple silver mirror reaction without complex reaction process.•‘D-SERS’ technique owns high sensitivity and has protective effects on paper substrate.•High sensitivity and reproducibility and stability can be obtained by paper substrate with ‘D-SERS’ method in the practical applications.•Paper substrate can act as a rag to collect samples in real world just by swabbing across surface.•Paper substrate with ‘D-SERS’ method can realize trace detection of the real-world sample.Many important considerations in the design of practical Surface enhanced Raman spectroscopy (SERS) substrates are necessary, such as the low cost, simple preparation, mass production and high efficiency of sample collection, which the conventional rigid substrates are lack of. In this work, practical SERS substrates based on deposition of silver nanoparticles (Ag NPs) on commercially available low-cost filter paper were prepared by simple silver mirror reaction in a large scale, and utilized for rapid, portable and accurate identification and detection of pesticide residues at various peels. Compared with conventional substrates, this novel SERS substrate dramatically enhanced the sample collection efficiency by simply swabbing paper-based device across different surfaces without destroying the sample, meanwhile avoiding the substrate signal of real-world samples. Considering their low cost, portability, simplicity and high sample collection efficiency, Ag NP-decorated filter paper, as practical SERS substrate, are used in solving critical problems for detection of pesticide residues at various peels. SERS experiments were carried out on Ag NP-decorated filter paper combined with ‘dynamic SERS’ (D-SERS) due to its high detection sensitivity. The excellent detection performance of the Ag NP-based filter paper was demonstrated by detection thiram and paraoxon residues at various peels. Besides, the stability and reproducibility of the practical substrates were also involved.
Co-reporter:Honglin Liu, Yudie Sun, Zhen Jin, Liangbao Yang and Jinhuai Liu
Chemical Science 2013 vol. 4(Issue 9) pp:3490-3496
Publication Date(Web):19 Jun 2013
DOI:10.1039/C3SC51231B
SERS hot spots with outstanding enhancement ability can spontaneously form in a reversible and reproducible way by the self-approach of flexible silver nanorods driven by the capillary force of solvent evaporation, and at the same time the target analytes can be trapped in the top-closed silver nanorods in the solvent evaporation process. The Raman intensity of the top-closed vs. top-opened nanorod arrays was a factor of 100–1000 higher for SERS reporters such as p-aminothiophenol or crystal violet. Furthermore, triplicate measurements on long nanorod arrays at the same position show a variation of the Raman intensity <10%, demonstrating a good reproducibility of the enhancement. Moreover, we found that the self-approach is highly dependent on the nanorod length and the molecules with different adsorptivity have different SERS performance in the solvent evaporation process. This solvent evaporation-controlled self-approach is an extremely simple and efficient strategy for the spontaneous formation of Raman hot spots with outstanding enhancement ability. These characteristics promise a generic platform for molecule trapping and SERS sensing with high sensitivity and reproducibility, which can help to transform SERS into a practical analytical technique.
Co-reporter:Xianghu Tang, Wenya Cai, Liangbao Yang and Jinhuai Liu
Nanoscale 2013 vol. 5(Issue 22) pp:11193-11199
Publication Date(Web):05 Sep 2013
DOI:10.1039/C3NR03671E
Here, Au nanoparticles (NPs) grafted on dendritic α-Fe2O3 (NPGDF) are designed as a highly uniform surface-enhanced Raman scattering (SERS) substrate with a feature of optical visualization by an optical microscope (OM) system and used for in situ detection of pesticide residues that are annually used in agriculture. With this strategy, the dendritic α-Fe2O3 has been synthesized by a hydrothermal method and significantly functionalized by an inductively coupled plasma (ICP) apparatus and then Au NPs were grafted on it densely and uniformly. In addition, the profile of NPGDF can be clearly observed using an OM platform of a Raman spectrometer, and the profile of SERS spectral mapping with NPGDF as substrate almost exactly coincides with the OM image, the electron microscope (EM) image and the elemental mapping of NPGDF, which indicates remarkable uniformity of the NPGDF as SERS substrate, thus ensuring the laser beam focuses on the efficient sites of the substrate under the OM platform. Moreover, NPGDF can be dispersed in the liquor and the NPGDF microparticles can be adsorbed on the target surface. Therefore, it can be used for in situ detection of pesticide residues on tea leaves, fruits etc., with high sensitivity and reproducibility.
Co-reporter:Yingjie Ye, Jin Chen, Qianqian Ding, Dongyue Lin, Ronglu Dong, Liangbao Yang and Jinhuai Liu
Nanoscale 2013 vol. 5(Issue 13) pp:5887-5895
Publication Date(Web):23 Apr 2013
DOI:10.1039/C3NR01273E
Ag-coated sea-urchin-like Fe3O4@C core–shell particles can be synthesized by a facile one-step solvothermal method, followed by deposition of high-density Ag nanoparticles onto the carbon surface through an in situ growth process, respectively. The as-synthesized Ag-coated Fe3O4@C particles can be used as a surface-enhanced Raman scattering (SERS) substrate holding reproducible properties under an external magnetic force. The magnetic function of the particles allows concentrating the composite particles into small spatial regions, which can be exploited to decrease the amount of material per analysis while improving its SERS detection limit. In contrast to the traditional SERS substrates, the present Fe3O4@C@Ag particles hold the advantages of enrichment of organic pollutants for improving SERS detection limit and recycled utilization.
Co-reporter:Yiping Wu, Fei Zhou, Liangbao Yang and Jinhuai Liu
Chemical Communications 2013 vol. 49(Issue 44) pp:5025-5027
Publication Date(Web):09 Apr 2013
DOI:10.1039/C3CC40875B
This study reports a strategy that allows one to finely tune the distance between Ag nanoparticles decorated on thermoresponsive microgels to create vast ‘hot spots’ for electromagnetic enhancement. The dynamic gap (i.e. the interparticle distance) can be tuned easily because the microgel template undergoes a phase transition upon changing the temperature. This change could increase the SERS intensity for three orders of magnitude.
Co-reporter:Xia Zhou, Honglin Liu, Liangbao Yang and Jinhuai Liu
Analyst 2013 vol. 138(Issue 6) pp:1858-1864
Publication Date(Web):08 Jan 2013
DOI:10.1039/C3AN36683A
A gold monolayer film and cysteine layer-by-layer self-assemble onto modified glasses, and through the use of optical waveguide spectroscopy (OWGS) and a dynamic SERS technique for the first time to study the dynamic generation process of the Meisenheimer complex between TNT and cysteine. This strategy can detect TNT down to 1 nM with high sensitivity and selectivity.
Co-reporter:Xia Zhou, Fei Zhou, Honglin Liu, Liangbao Yang and Jinhuai Liu
Analyst 2013 vol. 138(Issue 19) pp:5832-5838
Publication Date(Web):17 Jul 2013
DOI:10.1039/C3AN00914A
A very simple and versatile polymer assembly approach was developed. We use methoxy-mercapto-poly(ethylene glycol) (mPEG-SH) to conjugate multiple Au shapes to form dense Au monolayer films (MLFs) with 5 nm gaps and generate gigantic enhancement. The results of the discrete dipole approximation (DDA) method to calculate the local electric field distribution of the nanoparticle dimer are in agreement with the experimental data of sensitivity of multiple Au MLFs. 3D Raman spectra, relative standard deviation (RSD) calculation and Raman mapping were used to study the high-reproducibility of the assembled substrate, which is sufficient for trace pesticide residue detection.
Co-reporter:Yongmei Ma, Qianqian Ding, Liangbao Yang, Li Zhang, Yuhua Shen
Applied Surface Science 2013 Volume 265() pp:346-351
Publication Date(Web):15 January 2013
DOI:10.1016/j.apsusc.2012.11.010
Abstract
Ag NPs were obtained by isopropyl alcohol restore silver nitrate with silicotungstic acid as a stabilizer under the condition of UV irradiation. From changing the amount of isopropyl alcohol and silver nitrate, we obtained Ag NPs of which plasmon peak was similar to the excitation wavelength, and the enhancement effect will be greatly improved. Enriching, degrading, and detecting dye molecular can be achieved by the simple SERS substrate, and the photo-degradation process was monitored by SERS successfully for the first time, and the sensitivity was improved compare to traditional detection by UV–vis spectroscopy.
Co-reporter:Pan Li, Honglin Liu, Liangbao Yang, Jinhuai Liu
Talanta 2013 Volume 106() pp:381-387
Publication Date(Web):15 March 2013
DOI:10.1016/j.talanta.2013.01.013
A sensitive surface–enhanced Raman scattering (SERS) probe for selective detection of Hg(II) was designed and prepared by incorporating the well-known Rhodamine 6G and ethylenediamine into one molecule which is a aminated ring-close structure of Rhodamine 6G (R-NH2). Due to the presence of oxygen and nitrogen functional groups of R-NH2, Hg(II) would combined with two R-NH2 molecules. The probe molecule R-NH2 displays a highly selectively response of SERS enhancement towards 1 nM Hg(II) and featured SERS response with a broad pH span. The results establish the well-fitted linearity function of the SERS intensity with the concentration of Hg(II) in aqueous solution, suggesting the possibility for real-time detection of Hg(II) and the convenience for potential application.Highlights► The aminated structure of R6G indicates different colors and structures under different pH. ► R6G derivatives firstly as SERS probe enables to be selectively detection of Hg(II). ► The close-ring structure of R6G would trap the Hg(II). ► CT and EM should make contribution to this experimental process. ► The probe shows the potential application in detection of other metalions.
Co-reporter:Pan Li, Honglin Liu, Liangbao Yang, Jinhuai Liu
Talanta 2013 Volume 117() pp:39-44
Publication Date(Web):15 December 2013
DOI:10.1016/j.talanta.2013.08.050
•The time-resolved spectroscopic technique offers the fingerprints information of target molecules with high sensitivity.•The adsorptive structure of this pesticide thiram upon different concentrations is different.•CT and EM should make contribution to this experimental process.•Thiram could interact with Au NPs with different structures: mono-ligand and bi-ligand groups.•The Raman intensities of b2 and a1 modes of thiram related to the standard band appear different regulars.Time-resolved dynamic-SERS (D-SERS) can observe the process of chemical reaction between target and substrate and changes of adsorptive forms for analytes. In this paper, the vibrational spectra of pesticide thiram adsorbed on Au nanoparticles and intensity alternation of SERS spectra depended on different laser powers have been systematically investigated using the method of D-SERS. The Raman intensities of b2 and a1 modes of thiram related to the standard band appear different regulars with the extending time. Meanwhile, due to SERS vibrational spectra of pesticide thiram at different concentrations exhibit different SERS signals, the results of time-resolve D-SERS demonstrate the breakdown of band and different adsorptive forms of molecule on Au substrate. The continuous time-resolved the spectroscopic method offers the fingerprints of target molecules and provides great practical potentials for the continuous assessment and identification of pesticide or other probe molecules.
Co-reporter:Dr. Honglin Liu;Dongyue Lin;Yudie Sun;Dr. Liangbao Yang; Jinhuai Liu
Chemistry - A European Journal 2013 Volume 19( Issue 27) pp:
Publication Date(Web):
DOI:10.1002/chem.201390097
Co-reporter:Dr. Honglin Liu;Dongyue Lin;Yudie Sun;Dr. Liangbao Yang; Jinhuai Liu
Chemistry - A European Journal 2013 Volume 19( Issue 27) pp:8789-8796
Publication Date(Web):
DOI:10.1002/chem.201300815
Abstract
Surface-enhanced resonance Raman scattering (SERRS) is not realized for most molecules of interest. Here, we developed a new SERRS platform for the fast and sensitive detection of 2,4,6-trinitrotoluene (TNT), a molecule with low Raman cross section. A cationic surfactant, cetylpyridinium chloride (CPC) was modified on the surface of silver sols (CP-capped Ag). CPC not only acts as the surface-seeking species to trap sulfite-sulfonated TNT, but also undergoes complexation with it, resulting in the presence of two charge-transfer bands at 467 and 530 nm, respectively. This chromophore absorbs the visible light that matches with the incident laser and plasmon resonance of Ag sols by the use of a 532.06 nm laser, and offered large resonance Raman enhancement. This SERRS platform evidenced a fast and accurate detection of TNT with a detection limit of 5×10−11 M under a low laser power (200 μW) and a short integration time (3 s). The CP-capped Ag also provides remarkable sensitivity and reliable repeatability. This study provides a facile and reliable method for TNT detection and a viable idea for the SERS detection of various non-resonant molecules.
Co-reporter:Yingjie Ye, Honglin Liu, Liangbao Yang and Jinhuai Liu
Nanoscale 2012 vol. 4(Issue 20) pp:6442-6448
Publication Date(Web):16 Aug 2012
DOI:10.1039/C2NR31985C
In this article, we have demonstrated a sensitive and selective surface enhanced Raman spectroscopy (SERS) probe, based on citrate-capped gold nanoparticles (AuNPs), for trivalent chromium (Cr3+) detection. After introducing Tween 20 to a solution of citrate-capped AuNPs, the as-prepared Tween 20/citrate–AuNP probe could recognize Cr3+ at a 50 × 10−9 M level in an aqueous medium at a pH of 6.0. Tween 20 can stabilize the citrate-capped AuNPs against conditions of high ionic strength. Due to the chelation between Cr3+ and citrate ions, AuNPs undergo aggregation. As a result, it formed several hot spots and provided a significant enhancement of the Raman signal intensity through electromagnetic (EM) field enhancements. A detailed mechanism for tremendous SERS intensity change had been discussed. The selectivity of this system toward Cr3+ was 400-fold, remarkably greater than other metal ions.
Co-reporter:Qianqian Ding, Honglin Liu, Liangbao Yang and Jinhuai Liu
Journal of Materials Chemistry A 2012 vol. 22(Issue 37) pp:19932-19939
Publication Date(Web):08 Aug 2012
DOI:10.1039/C2JM33200K
Ni nanowires with high purity were synthesized by a wet chemical reduction method in an external magnetic field without any assistance from surfactants and templates. Different morphologies of these nanostructures were obtained through changing the experimental conditions. Ni nanowires acted as templates for the deposition of metallic silver over the nanowire. The Ni/Ag nanocomposites were fabricated in situ by a simple and rapid redox-transmetalation reaction. The as-synthesized Ni/Ag nanocomposites were reproducible and stable for use as a surface-enhanced Raman scattering (SERS) substrate. The reproducible and stable properties will promote practical application of these substrates in the SERS field. The SERS effect of the nanocomposites were evaluated by the use of R6G and 4-ATP as the Raman probes and the results demonstrate that these nanocomposites exhibited strong SERS effects and could be reused.
Co-reporter:Kai Qian, Honglin Liu, Liangbao Yang and Jinhuai Liu
Nanoscale 2012 vol. 4(Issue 20) pp:6449-6454
Publication Date(Web):20 Aug 2012
DOI:10.1039/C2NR31339A
In general, the procedures for producing a high density hot spots structure should be stable, inexpensive, and easy to make. It still remains a grand challenge to assemble silver or gold nanoparticles (Au NPs) with well-defined hot spots for SERS detection. In this study, we present a very simple method for designing and fabricating a surface-enhanced Raman scattering (SERS) substrate with high density hot spots, using large area positively charged polyaniline (PANI) nanofibers as template to assemble negatively charged Au NPs. In order to obtain the optimized SERS-active substrates, different experiments to synthesize diverse Au/PANI with different sizes of Au NPs from about 50, 30 to 15 nm were carried out. The results revealed that the PANI nanofibers were fully coated by the ∼15 nm Au NPs, forming a high density Au/PANI SERS substrate. The results evidence that we can obtain stable and sensitive SERS measurements.
Co-reporter:Honglin Liu, Liangbao Yang, Li Yu, Fanli Meng, Xinyao Yu and Jinhuai Liu
Journal of Materials Chemistry A 2012 vol. 22(Issue 13) pp:6139-6147
Publication Date(Web):17 Feb 2012
DOI:10.1039/C2JM14635E
A novel strategy is proposed to facilely hybridize the single-walled carbon nanotubes (SWCNTs) and gold nanoparticles (Au NPs) with the assistance of a mild O2-plasma process and annealing at 500 °C in air. An immunosensor was constructed by the SWCNT-Au network bridging an interdigital electrode. The O2-plasma-oxidized SWCNTs can easily assemble positively charged Au NPs with a high-density and uniform morphology. The annealing leads to surface melting and aggregation of the Au NPs and makes the survival of the SWCNTs much less likely, moreover, it helps to remove any impurities adsorbed on the SWCNT-Au and to form a good contact between the network and the electrode. The annealing-induced alterations result in an interesting power-law current–voltage behavior because of the Au NPs cotunneling effects and its energy-band modulation of the SWCNTs, and greatly amplify the sensitivity on antibody-antigen interactions. The sensor realized high-sensitive, rapid, and selective detections of Salmonella enteritidis flagellin (SEF) and Staphylococcus aureus enterotoxins A (SEA), which was functionalized with the SEF antibody (anti-SEF) and the SEA antibody (anti-SEA), respectively. The results demonstrate a detection limit of at least 2 ng mL−1 in 5 min incubation for the antibody–antigen reaction. The proposed strategy represents a novel, robust, and simple way to establish immunosensor chips.
Co-reporter:Dongyue Lin, Honglin Liu, Kai Qian, Xia Zhou, Liangbao Yang, Jinhuai Liu
Analytica Chimica Acta 2012 Volume 744() pp:92-98
Publication Date(Web):26 September 2012
DOI:10.1016/j.aca.2012.07.029
This study found that 1,2-ethylenediamine (EDA) as a primary amine could be modified onto the surface of citrate-stabilized gold nanoparticles (Au NPs), and the EDA-capped Au NPs were successfully used as an ultrasensitive optical probe for TNT detection. The strong donor–acceptor (D–A) interactions between EDA and trinitrotoluene (TNT) at the Au NP/solution interface induced significant aggregation of the EDA-capped Au NPs, and enabled to easily realize the direct colorimetric detection of ultratrace TNT. The results showed that such a color change was readily seen by the naked eye, and the colorimetric detection could be down to 400 pM level of TNT with excellent discrimination against other nitro compounds. UV–vis absorption spectroscopy was used to examine the TNT-induced changes in local surface plasmon resonance (LSPR) of EDA-capped Au NPs, and a new LSPR band at ca. 630 nm arose along with the addition of TNT, which produced a detection limit of TNT down to ca. 40 pM. Furthermore, dynamic light scattering measurements evidenced the ultratrace TNT-induced small changes in the size of the EDA-capped Au NPs, and realized the quick and accurate detection of TNT in 0.4 pM level. These results demonstrated the ultrahigh sensitivity of this optical probe for TNT detection. Moreover, this optical probe is sample, stable, low-cost, and these excellent properties make it quite promising for infield and rapid detection of TNT.Graphical abstractHighlights► EDA can interact with the citrate-stabilized Au NPs through electrostatic attraction. ► EDA-capped Au NPs can be used as an ultrasensitive optical probe for TNT detection. ► Direct colorimetric assays for TNT have a detection limit of 400 pM. ► DLS assays evidenced the aggregation of the probe induced by TNT in 0.4 pM level. ► The probe has an excellent discrimination against other nitro compounds.
Co-reporter:Liangbao Yang, Honglin Liu, Yongmei Ma and Jinhuai Liu
Analyst 2012 vol. 137(Issue 7) pp:1547-1549
Publication Date(Web):20 Jan 2012
DOI:10.1039/C2AN16240G
An extremely simple and sensitive approach using solvent-induced hot spot switch on silver nanorod enhanced Raman spectroscopy has been found and experimentally demonstrated, which can be used for detection and identification analyte molecules.
Co-reporter:Kai Qian, Honglin Liu, Liangbao Yang and Jinhuai Liu
Analyst 2012 vol. 137(Issue 20) pp:4644-4646
Publication Date(Web):09 Aug 2012
DOI:10.1039/C2AN35947B
Shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS), which acts as the next generation of advanced spectroscopy, expands the versatility of surface-enhanced Raman spectroscopy (SERS). Here we present a facile one-step method to prepare functionalized core–shell nanoparticles for selective detection of trinitrotoluene (TNT) through the formation of Meisenheimer complexes. A well-designed type of tunable poly(2-aminothiophenol) (PAT) shells on gold nanoparticles was prepared for the first time and the shell thickness of 2 nm could be controlled by only adjusting the molar ratio of sodium dodecylsulfate (SDS) to 2-aminothiophenol. The polymer shells shows prominent advantages, including uniformity, better chemical stability, being free of pin-holes and amino-functionalized.
Co-reporter:Ying Zhou;Jin Chen;Li Zhang
European Journal of Inorganic Chemistry 2012 Volume 2012( Issue 19) pp:3176-3182
Publication Date(Web):
DOI:10.1002/ejic.201200009
Abstract
A novel method to prepare TiO2-coated Ag nanowire arrays for use as multifunctional surface enhanced Raman scattering (SERS) active substrates is introduced. Such an array is made by the synthesis of an Ag nanowire array utilizing an anodic aluminum oxide (AAO) template, followed by coating of the Ag wires with a layer of titania that is several nanometers thick. Employing these TiO2-coated Ag nanowire substrates in the detection of organic contaminants allows high SERS enhancement to be achieved. Moreover, owing to the high photocatalytic activity of titania, the substrate can degrade target molecules into small inorganic molecules under UV irradiation, and in this manner the arrays are able to self-clean. The unique properties of this integrated substrate enable it to exhibit its feasibility as an analytical tool for the assessment of environmental pollution and thus to assist in the detection and disposal of contaminants.
Co-reporter:Dr. Honglin Liu;Yingjie Ye;Jin Chen;Dongyue Lin;Dr. Zheng Jiang;Dr. Zhijun Liu;Dr. Bai Sun;Dr. Liangbao Yang; Jinhuai Liu
Chemistry - A European Journal 2012 Volume 18( Issue 26) pp:8037-8041
Publication Date(Web):
DOI:10.1002/chem.201200397
Co-reporter:Liangbao Yang, Honglin Liu, Jin Wang, Fei Zhou, Zhongqun Tian and Jinhuai Liu
Chemical Communications 2011 vol. 47(Issue 12) pp:3583-3585
Publication Date(Web):15 Feb 2011
DOI:10.1039/C1CC10228A
Metastable state silver nanoparticle surface-enhanced Raman scattering has been experimentally and theoretically demonstrated; the signal is two to three orders of magnitude higher than that for the traditional method. Ultrasensitive surface-enhanced Raman scattering signals of illicit drug cocaine and organophosphate pesticide methyl-parathion were observed.
Co-reporter:Xuanhua Li;Guangyu Chen;Zhen Jin;Jinhuai Liu
Advanced Functional Materials 2010 Volume 20( Issue 17) pp:2815-2824
Publication Date(Web):
DOI:10.1002/adfm.201000792
Abstract
A multifunctional Au-coated TiO2 nanotube array is made via synthesis of a TiO2 nanotube array through a ZnO template, followed by deposition of Au particles onto the TiO2 surface using photocatalytic deposition and a hydrothermal method, respectively. Such arrays exhibit superior detection sensitivity with high reproducibility and stability. In addition, due to possessing stable catalytic properties, the arrays can clean themselves by photocatalytic degradation of target molecules adsorbed to the substrate under irradiation with UV light into inorganic small molecules using surface-enhanced Raman spectroscopy (SERS) detection, so that recycling can be achieved. Finally, by detection of Rhodamine 6G (R6G) dye, herbicide 4-chlorophenol (4-CP), persistent organic pollutant (POP) dichlorophenoxyacetic acid (2,4-D), and organophosphate pesticide methyl-parathion (MP), the unique recyclable properties indicate a new route in eliminating the single-use problem of traditional SERS substrates and show promising applications for detecting other organic pollutants.
Co-reporter:Tingting Wang, Liangbao Yang, Buchang Zhang, Jinhuai Liu
Colloids and Surfaces B: Biointerfaces 2010 Volume 80(Issue 1) pp:94-102
Publication Date(Web):1 October 2010
DOI:10.1016/j.colsurfb.2010.05.041
We reported a very simple, reliable, clean, nontoxic and eco-friendly biological method for the synthesis of semiconductor monoclinic Se nanoparticles by the Bacillus subtilis. The as-synthesized Se nanoparticles were spherical shaped with diameters ranging from 50 to 400 nm. These spherical monoclinic Se nanoparticles can be transformed into highly anisotropic, one-dimensional (1D) trigonal structure after one day at the room temperature and grown from aqueous solutions. Furthermore, the obtained two kinds of Se nanomaterial crystals with high surface-to-volume ratio, good adhesive ability and biocompatibility have been employed as enhancing and settled materials for H2O2 biosensor. The results show that the H2O2 biosensor has high sensitivity and affinity for H2O2. The detection limit for H2O2 was found to be 8 × 10−8 M. Different crystals of Se nanomaterials have no significant difference in electrochemical application.
Co-reporter:Jingjing Lu, Liangbao Yang, Anjian Xie, Yuhua Shen
Biophysical Chemistry 2009 Volume 145(2–3) pp:91-97
Publication Date(Web):December 2009
DOI:10.1016/j.bpc.2009.09.005
A very simple and novel approach of fabricating Ag–DNA network is herein reported. The Ag–DNA network can be formed from reduction of silver ion absorbed on DNA template by sunlight. Mesh size of the Ag–DNA network and the diameter of the Ag–DNA nanowire can be controlled by adjusting the concentration of DNA and irradiation time, respectively. Furthermore, the Ag–DNA network placed onto comb-like gold electrodes can be utilized as a sensor for humidity, which presents a good response to the detection of relative humidity (RH).
Co-reporter:Li Zhang
Crystal Research and Technology 2008 Volume 43( Issue 10) pp:1022-1025
Publication Date(Web):
DOI:10.1002/crat.200800092
Abstract
ZnS microspheres have been synthesized in large scale by a hydrothermal route. The influence of reaction time on the phase constitution is studied. The evolution process from cubic phase to hexagonal phase is showed with prolonging reaction time. It is observed that the luminescence intensity of the same sample decreases dramatically with increasing the temperature. At the same time, the Luminescence intensity of ZnS particles increases with prolonging the reaction time. The luminescence intensity of the particles is affected by the reaction time and temperature. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)
Co-reporter:Li Zhang
Crystal Research and Technology 2008 Volume 43( Issue 10) pp:1026-1029
Publication Date(Web):
DOI:10.1002/crat.200811159
Abstract
PbS microspheres have been synthesized in large scale by a hydrothermal route, in which tungstosilicate acid (TSA) is used. The obtained PbS microspheres have been characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), Scanning electron microscopy (SEM) and X-ray photoemission spectroscopy (XPS). Experiments show that Tungstosilicate acid plays an important role for the control of the morphology of PbS microstructures. An evolution process is described based on experimental facts. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)
Co-reporter:Juan Meng, Xianghu Tang, Binbin Zhou, Qiwen Xie, Liangbao Yang
Talanta (1 March 2017) Volume 164() pp:
Publication Date(Web):1 March 2017
DOI:10.1016/j.talanta.2016.10.101
•A rapid and efficient pretreatment strategy for separation and purification of cocaine in human urine within 3 min has been developed, which can efficiently lower the interference of complex biological components in urine of SERS platform.•Quasi-spherical, uniform GNPs have been functionalized with CTAB to form orderly close-packed GNPs film, which has high sensitivity, uniformity, and reproducibility.•The purification and detection progress only needs 5 min, which makes it highly practical applications on spot detection.A novel and rapid method to detect cocaine in human urine has been developed by using self-assembly ordered two dimensional (2D) gold nanoparticles (GNPs) film as surface-enhanced Raman spectroscopy (SERS) substrates. In order to obtain high sensitivity, uniformity, and reproducibility of SERS platform, quasi-spherical, uniform GNPs were firstly synthesis using seed growth method, in which the GNPs have been functionalized with CTAB to form orderly close-packed GNPs film as SERS substrate. Importantly, the high-performance GNPs on solid substrates can produce a high yield of sub-10-nm gaps which can generate gigantic signals enhancement for analytes adsorbed GNPs surface. In view of the complex component of human urine, we develop a rapid and efficient pretreatment strategy for separation and purification of cocaine by using hexane extraction in real human urine samples within 3 min. With the advantages of better extraction rates (>75%) examined by ultraperformance liquid chromatography (UPLC) and the excellent signal-to-noise ratio detected by SERS, our pretreatment procedure can efficiently lower the interference of complex biological components in urine. To reach on-spot analyzer, a handheld Raman spectrometer was used for feasible SERS detection of cocaine in real human urine. The favorable results demonstrated our pretreatment strategy combined with SERS platform will be a great prospective method toward rapid, reliable, and on-spot cocaine detection for public safety.
Co-reporter:Pan Li, Xiunan Yan, Fei Zhou, Xianghu Tang, Liangbao Yang and Jinhuai Liu
Journal of Materials Chemistry A 2017 - vol. 5(Issue 13) pp:NaN3237-3237
Publication Date(Web):2017/02/09
DOI:10.1039/C7TC00150A
Designing plasmonic hot spots within an active platform that has well-defined and highly reproducible features is one of the most critical issues in obtaining ultrasensitive detection and credible signals for surface-enhanced Raman spectroscopy (SERS). Hot spots between two or more nanostructures can amplify Raman signals for single-molecule-level detection. Here, we report a SERS-active platform by using spontaneous capillary imbibition to assemble a single Au nanoparticle (NP) onto the surface of a single Ag nanowire (NW). Optical excitation of this coupled nanostructure provides a SERS hot spot at the gap between the single NP and NW. This platform can be easily fabricated, and the position of the single hot spot can be conveniently located during SERS measurements. Moreover, the single Au NP coupled to the Ag NW acts as an optical antenna for localizing and enhancing the electromagnetic field (E-field). Most importantly, the single hot spot platform can provide a “nano-channel” for trapping molecules because of the presence of capillary imbibition. We show that high quality SERS spectra of various molecules with different natures can be generated on a single hot spot structure with reliable reproducibility and excellent sensitivity. Our approach not only overcomes the difficulty of bringing two nanostructures together to form an efficient junction with simple fabrication and maximum uniformity, but also provides a SERS-active platform with a narrow enhancement factor (EF) distribution.
Co-reporter:Liangbao Yang, Pan Li, Honglin Liu, Xianghu Tang and Jinhuai Liu
Chemical Society Reviews 2015 - vol. 44(Issue 10) pp:NaN2848-2848
Publication Date(Web):2015/03/12
DOI:10.1039/C4CS00509K
Surface-enhanced Raman spectroscopy (SERS) has been demonstrated to be an excellent analytical tool for a wide range of research and practical applications owing to its ability to achieve highly sensitive detection and provide fingerprint information for analytes. Improving the sensitivity of SERS is beneficial for the rapid analysis of target molecules in various systems, where the ultimate goal is to obtain quantitative analysis and detection. Considerable efforts have been made to develop new methods for SERS detection that improve upon its high sensitivity and reproducibility. In this tutorial review, we first introduce the traditional methods for SERS detection and then report in detail on the features of a new strategy for implementing SERS. This new method, namely, a dynamic surface-enhanced Raman spectroscopy method proposed by our group, is based on state translation nanoparticle-enhanced Raman spectroscopy (STNERS) from the wet state to the dry state. Notably, during this process, a three-dimensional (3D) hotspot matrix that can hold hotspots between every two adjacent particles in 3D space, with minimal polydispersity of the particle size and maximal uniformity of the interparticle distance, can be simply achieved. Experiments and applications using STNERS are reviewed starting with an investigation of STNERS mechanisms and a discussion of sample preparation. Next, evidence of the advantages of STNERS and practical applications are discussed. Finally, the future outlook for STNERS and the development of STNERS as an ultra-sensitive detection method are also discussed.
Co-reporter:Honglin Liu, Liangbao Yang, Li Yu, Fanli Meng, Xinyao Yu and Jinhuai Liu
Journal of Materials Chemistry A 2012 - vol. 22(Issue 13) pp:NaN6147-6147
Publication Date(Web):2012/02/17
DOI:10.1039/C2JM14635E
A novel strategy is proposed to facilely hybridize the single-walled carbon nanotubes (SWCNTs) and gold nanoparticles (Au NPs) with the assistance of a mild O2-plasma process and annealing at 500 °C in air. An immunosensor was constructed by the SWCNT-Au network bridging an interdigital electrode. The O2-plasma-oxidized SWCNTs can easily assemble positively charged Au NPs with a high-density and uniform morphology. The annealing leads to surface melting and aggregation of the Au NPs and makes the survival of the SWCNTs much less likely, moreover, it helps to remove any impurities adsorbed on the SWCNT-Au and to form a good contact between the network and the electrode. The annealing-induced alterations result in an interesting power-law current–voltage behavior because of the Au NPs cotunneling effects and its energy-band modulation of the SWCNTs, and greatly amplify the sensitivity on antibody-antigen interactions. The sensor realized high-sensitive, rapid, and selective detections of Salmonella enteritidis flagellin (SEF) and Staphylococcus aureus enterotoxins A (SEA), which was functionalized with the SEF antibody (anti-SEF) and the SEA antibody (anti-SEA), respectively. The results demonstrate a detection limit of at least 2 ng mL−1 in 5 min incubation for the antibody–antigen reaction. The proposed strategy represents a novel, robust, and simple way to establish immunosensor chips.
Co-reporter:Yongmei Ma, Honglin Liu, Zhenzhen Han, Liangbao Yang and Jinhuai Liu
Journal of Materials Chemistry A 2015 - vol. 3(Issue 28) pp:NaN14650-14650
Publication Date(Web):2015/06/08
DOI:10.1039/C5TA03143E
An effective near-infrared (NIR) active photocatalyst, NaYF4:Yb,Tm@TiO2/Ag (UC@TiO2/Ag) core@comby shell composite, was synthesized by a simple three-step hydrothermal process. Under the full-spectrum light of a Xe lamp in UV-Vis absorbance experiments, about 96% of R6G dyes in solution were degraded by UC@TiO2/Ag in 120 minutes, while only about 64% of the dyes were degraded by pure TiO2 under the same conditions. Under a UV-filtered Xe lamp, about 35% of the dyes were degraded by UC@TiO2/Ag in 120 minutes; interestingly, only about 8% of the dyes were degraded by pure TiO2. Under irradiation by a 785 nm laser in surface enhanced Raman scattering (SERS) experiments, the photodegradation rate constants were 0.02612 s−1 for UC@TiO2/Ag and 0.00046 s−1 for TiO2/Ag, indicating a nearly 58 fold improvement. After deducting the photobleaching effect, the photodegradation rate constants for UC@TiO2/Ag under 633 and 532 nm lasers were 0.00715 s−1 and 0.00565 s−1, respectively, revealing a sharp decrease under irradiation at shorter wavelengths. Electron spin resonance (ESR) analysis revealed that the presence of UC in this photocatalytic system certainly induced the increase of ˙OH free radicals with NIR irradiation, i.e. the UC core converts NIR light into ultraviolet (UV) light and initiates excellent photocatalytic activity of the TiO2/Ag comby shell. Furthermore, the decorating of Ag nanoparticles not only enhances the photocatalytic ability, but also provides a structural basis for monitoring the photocatalytic kinetics by the SERS technique. By virtue of monochrome laser lines, SERS analysis provides direct evidence to prove the capability of UC-initiated non-UV photocatalysis and the improvement of the utilization of non-UV lights on TiO2. The results revealed that this new photocatalytic platform can efficiently utilize different bands of the solar spectrum and also find new applications in SERS fields.
Co-reporter:Qianqian Ding, Honglin Liu, Liangbao Yang and Jinhuai Liu
Journal of Materials Chemistry A 2012 - vol. 22(Issue 37) pp:NaN19939-19939
Publication Date(Web):2012/08/08
DOI:10.1039/C2JM33200K
Ni nanowires with high purity were synthesized by a wet chemical reduction method in an external magnetic field without any assistance from surfactants and templates. Different morphologies of these nanostructures were obtained through changing the experimental conditions. Ni nanowires acted as templates for the deposition of metallic silver over the nanowire. The Ni/Ag nanocomposites were fabricated in situ by a simple and rapid redox-transmetalation reaction. The as-synthesized Ni/Ag nanocomposites were reproducible and stable for use as a surface-enhanced Raman scattering (SERS) substrate. The reproducible and stable properties will promote practical application of these substrates in the SERS field. The SERS effect of the nanocomposites were evaluated by the use of R6G and 4-ATP as the Raman probes and the results demonstrate that these nanocomposites exhibited strong SERS effects and could be reused.
Co-reporter:Yiping Wu, Fei Zhou, Liangbao Yang and Jinhuai Liu
Chemical Communications 2013 - vol. 49(Issue 44) pp:NaN5027-5027
Publication Date(Web):2013/04/09
DOI:10.1039/C3CC40875B
This study reports a strategy that allows one to finely tune the distance between Ag nanoparticles decorated on thermoresponsive microgels to create vast ‘hot spots’ for electromagnetic enhancement. The dynamic gap (i.e. the interparticle distance) can be tuned easily because the microgel template undergoes a phase transition upon changing the temperature. This change could increase the SERS intensity for three orders of magnitude.
Co-reporter:Pan Li, Bingbing Ma, Liangbao Yang and Jinhuai Liu
Chemical Communications 2015 - vol. 51(Issue 57) pp:NaN11397-11397
Publication Date(Web):2015/06/09
DOI:10.1039/C5CC03792A
A hybrid single nanoreactor composed of small Au nanoparticles (NPs) and a long Ag nanowire (NW) with a length of 10 μm can be conveniently located by optical microscopy, allowing us to monitor by in situ surface enhanced Raman spectroscopy (SERS) the plasmon-driven and small Au NPs catalyzed reactions with high sensitivity and reproducibility.
Co-reporter:Liangbao Yang, Honglin Liu, Jin Wang, Fei Zhou, Zhongqun Tian and Jinhuai Liu
Chemical Communications 2011 - vol. 47(Issue 12) pp:NaN3585-3585
Publication Date(Web):2011/02/15
DOI:10.1039/C1CC10228A
Metastable state silver nanoparticle surface-enhanced Raman scattering has been experimentally and theoretically demonstrated; the signal is two to three orders of magnitude higher than that for the traditional method. Ultrasensitive surface-enhanced Raman scattering signals of illicit drug cocaine and organophosphate pesticide methyl-parathion were observed.
Co-reporter:Honglin Liu, Yudie Sun, Zhen Jin, Liangbao Yang and Jinhuai Liu
Chemical Science (2010-Present) 2013 - vol. 4(Issue 9) pp:NaN3496-3496
Publication Date(Web):2013/06/19
DOI:10.1039/C3SC51231B
SERS hot spots with outstanding enhancement ability can spontaneously form in a reversible and reproducible way by the self-approach of flexible silver nanorods driven by the capillary force of solvent evaporation, and at the same time the target analytes can be trapped in the top-closed silver nanorods in the solvent evaporation process. The Raman intensity of the top-closed vs. top-opened nanorod arrays was a factor of 100–1000 higher for SERS reporters such as p-aminothiophenol or crystal violet. Furthermore, triplicate measurements on long nanorod arrays at the same position show a variation of the Raman intensity <10%, demonstrating a good reproducibility of the enhancement. Moreover, we found that the self-approach is highly dependent on the nanorod length and the molecules with different adsorptivity have different SERS performance in the solvent evaporation process. This solvent evaporation-controlled self-approach is an extremely simple and efficient strategy for the spontaneous formation of Raman hot spots with outstanding enhancement ability. These characteristics promise a generic platform for molecule trapping and SERS sensing with high sensitivity and reproducibility, which can help to transform SERS into a practical analytical technique.