Surface-enhanced Raman scattering(SERS)is a powerful technology for obtaining vibrational information from molecules that present in different chemical or biological environments.This paper presents a 3D SERS substrat...Surface-enhanced Raman scattering(SERS)is a powerful technology for obtaining vibrational information from molecules that present in different chemical or biological environments.This paper presents a 3D SERS substrate based on nanocone forests.The substrates are prepared by using plasma treatment technique,which is a simple,fast and high-throughput approach.The SERS substrate based on nanocone forests exhibits high sensitivity.In the experiment,miRNA with a concentration as low as 10-10 M can be achieved.Meanwhile,the proposed SERS substrate shows a high uniformity over a large area.These experimental results demonstrate great potential of the 3D SERS substrate in wide applications.展开更多
Although surface-enhanced Raman spectroscopy(SERS)has been applied for gathering fingerprint information,even in single molecule analysis,the decayed Raman signals in aqueous solutions largely obstruct the on-site ins...Although surface-enhanced Raman spectroscopy(SERS)has been applied for gathering fingerprint information,even in single molecule analysis,the decayed Raman signals in aqueous solutions largely obstruct the on-site insight reaction process.In this study,large-scaled semiconductor films with multi-walled(TiO_(2)/WO_(3)/TiO_(2))nanopore distribution are fabricated by combining electrochemical anodization and sputtering technique,and then employed as the SERS substrates for detection of molecules at the solid/liquid interfaces.Given the remarkably improved electrochromic property of the multi-walled film,such SERS substrates were endowed with tunable oxygen vacancy(VO)density and distribution via simply applying electrochemical bias voltage,which enabled one to achieve an enhanced charge transfer efficiency and thus a remarkably increased Raman signal even in solution.The VO-rich SERS substrate is highly repeatable,thus providing a reliable platform for in-situ monitoring of the target molecules or intermediates at the solid/liquid interfaces.展开更多
To develop a smart free-standing surface enhanced Raman scattering(SERS) substrate,silver nanoparticles(AgNPs) embedded temperature-sensitive nanofibrous membrane was fabricated by electrospinning their aqueous soluti...To develop a smart free-standing surface enhanced Raman scattering(SERS) substrate,silver nanoparticles(AgNPs) embedded temperature-sensitive nanofibrous membrane was fabricated by electrospinning their aqueous solution containing the copolymer poly(N-isopropylacrylamide-co-Nhydroxymethylacrylamide),followed by heat treatment to form crosslinking structure within its constituent nanofibers.To avoid negative effect of the additive like stabilizer and the reactant like reductant on their SERS efficiency,the AgNPs were in-situ synthesized through reducing Ag^+ions dissolved in the polymer solution by ultraviolet irradiation.The prepared hybrid nanofibrous membrane with high stability in aqueous medium can reach its swelling or deswelling equilibrium state within 15 seconds with the medium temperature changing between 25℃and 50℃alternately.When it was used as a free-standing SERS substrate,10^-12 mol/L of 4-nitrothiophenol in aqueous solution can be detected at room temperature,and elevating detection temperature can further lower its low detection limit.Since its generated SERS signal has desirable reproducibility,it can be used as SERS substrate for quantitative analysis.Moreover,the hybrid membrane as SERS substrate is capable of real-time monitoring the reduction of 4-nitrothiophenol into 4-aminothiophenol catalyzed by its embedded AgNPs,and the detected intermediate indicates that the reaction proceeds via a condensation route.展开更多
In the pursuit of advancing molecular sensing through surface-enhanced Raman spectroscopy(SERS),the combination of plasmonic nanoparticles and metal-organic frameworks(MOFs)has emerged as a highly effective approach t...In the pursuit of advancing molecular sensing through surface-enhanced Raman spectroscopy(SERS),the combination of plasmonic nanoparticles and metal-organic frameworks(MOFs)has emerged as a highly effective approach to enhance the sensitivity and selectivity of SERS substrates.However,most prior investigations have predominantly focused on MOF-coated plasmonic nanoparticles in core@shell or layer-by-layer configurations,leaving a notable knowledge gap in exploring alternative configurations.Herein we present a facile method to construct a particle-on-mirror architecture by selectively coating a MOF,zeolitic imidazolate framework-8(ZIF-8),onto the tips of Au nanostars and subsequently depositing the resultant nanoparticles onto a Au film.This design integrates the electric field enhancement at the sharp tips and nanogaps,along with the molecular enrichment function within the porous MOF immobilized at the tips and nanogaps,leading to a substantial boost in the SERS signal intensity.Such a unique SERS platform enables consistent and outstanding SERS performance for analytes of different sizes.This work opens up a promising strategy for constructing multifunctional nanostructures for sensitive SERS detection in real-life scenarios.展开更多
Early or very early detection of hepatocellular carcinoma(HCC)is an effective means to resolve the low cure rates,but there currently lacks a method that fulfills clinical requirements.One of the most prospective appr...Early or very early detection of hepatocellular carcinoma(HCC)is an effective means to resolve the low cure rates,but there currently lacks a method that fulfills clinical requirements.One of the most prospective approaches to detecting early-stage HCC is directly testing a compendium of disease-relevant biomolecules contained within human serum through surface-enhanced Raman scattering(SERS)nanobiosensing and recognizing the biomolecular patterns.We report a novel Si-based bimetallic nanoensembles-functionalized SERS substrate(its analytical enhancement factor reaches 1.47×10^(12))and introduce an ultrasensitive nanobiosensing for capturing the subtle characteristic changes in SERS spectra caused by HCC,hepatitis B,or cirrhosis.Toward early diagnosis,we created an intelligent serological test with this nanobiosensing and the deep learning algorithm to gain key biomolecular phenotypes of early-stage HCC.Using clinical samples from four target populations(normal,HCC,cirrhosis,and hepatitis B),the proof-of-principle result indicates that the test yielded a predictive accuracy of 98.75%on a held-out dataset(randomly drew 4 out of 28 samples per population).On the same held-out dataset,the sensitivity and specificity of the test were both 100%for distinguishing HCC.Such a new-concept liquid biopsy could provide an opportunity for early diagnosis of HCC.展开更多
Plasmonic surface of flexible multilayered nanofibers possesses special superiority for the surface-enhanced Raman scattering(SERS)sensing of molecules and microbial cells.However,the fabrication of flexible plasmonic...Plasmonic surface of flexible multilayered nanofibers possesses special superiority for the surface-enhanced Raman scattering(SERS)sensing of molecules and microbial cells.However,the fabrication of flexible plasmonic nanofibers with high sensitivity and reproducibility is difficult.Herein,we report a smart strategy for fabricating flexible plasmonic fibers,in which compact and homogeneous gold nanoparticles(Au NPs)are in-situ grown on the high-curvature surface of multilayered fibers of electrospun polyvinylidene fluoride(PVDF).Firstly,the surface of PVDF fibers is changed electrically,and Au seeds are deposited on the surface of PVDF fibers using electrostatic driving force.Secondly,a stable AuI_(4)−complex is formed employing coordination between I−and AuCl4−ions,which could decrease the reduction potential of AuCl4−and restrain the self-nucleation,and then the reduction reaction of AuI4−is initiated by introducing PVDF@Au seeds to pull down the barrier of potential energy.Finally,in-situ growth of AuNPs is generated on the high-curvature surface of PVDF nanofibers,and large-scale hotspots are generated by adjacent AuNPs coupling in the three-dimensional(3D)space of multilayered fibers.Membrane of PVDF@Au nanofibers also realizes the sensitive detection of thiram molecules(low limit of detection of 0.1 nM)and good reproducibility(relative standard deviation of 10.6%).Meanwhile,due to the multilayered construction of PVDF@Au nanofibers,a valid SERS signal on 3D surface of bacteria could be generated.3D distribution of hotspots on multilayered PVDF@Au nanofibers gives a clear advantage for SERS sensing of organic molecules and microbial cells.展开更多
Development of cost-effective, highly reproducible non-conventional fabrication techniques for anisotropic metal nanostructures is essential to realizing potential applications of plasmonic devices, photonic devices, ...Development of cost-effective, highly reproducible non-conventional fabrication techniques for anisotropic metal nanostructures is essential to realizing potential applications of plasmonic devices, photonic devices, and surface enhanced Raman scattering （SERS） phenomenon based sensors. This report highlights the fabrication of nanotriangle arrays via nanoimprinting to overcome difficulties in creating large-area SERS active substrates with uniform, reproducible Raman signals. Electron beam lithography of anisotropic nanostructures, formation of arrays of nanotriangles in silicon and the transfer of triangular shapes to polymethylmethacrylate （PMMA） sheets via nanoimprinting have not been reported elsewhere. The reuse of silicon masters offers potential for production of low cost SERS substrates. The SERS activity and reproducibility of nanotriangles are illustrated and a consistent average enhancement factor of up to -2.9 × 1011, which is the highest value reported for a patterned SERS substrate, is achieved.展开更多
Concerns over exposure to mercury have motivated the exploration of cost-effective,rapid,and reliable method for monitoring Hg^2＋ in the environment.Recently,surface-enhanced Raman scattering（SERS） has become a pro...Concerns over exposure to mercury have motivated the exploration of cost-effective,rapid,and reliable method for monitoring Hg^2＋ in the environment.Recently,surface-enhanced Raman scattering（SERS） has become a promising alternative method for Hg^2＋ analysis.SERS is a spectroscopic technique which combines modern laser spectroscopy with the optical properties of nano-sized noble metal structures,resulting in substantially increased Raman signals.When Hg^2＋ is in a close contact with metallic nanostructures,the SERS effect provides unique structural information together with ultrasensitive detection limits.This review introduces the principles and contemporary approaches of SERS-based Hg^2＋detection.In addition,the perspective and challenges are briefly discussed.展开更多
Plasmon coupling is an essential strategy to realize strong local electromagnetic(EM)field which is crucial for high-performance plasmonic devices.In this work,multiple plasmon couplings are demonstrated in three-dime...Plasmon coupling is an essential strategy to realize strong local electromagnetic(EM)field which is crucial for high-performance plasmonic devices.In this work,multiple plasmon couplings are demonstrated in three-dimensional(3D)hybrid plasmonic systems composed of polydimethylsiloxane-supported ordered silver nanocone(AgNC)arrays decorated with high-density gold nanoparticles(AuNPs)which are fabricated by a template-assisted physical vapor deposition process.Strong interparticle coupling,particle-film coupling,inter-cone coupling,and particle-cone coupling are revealed by numerical simulations in such composite nanostructures,which produce intense and high-density EM hot spots,boosting highly sensitive and reproducible surface enhanced Raman scattering(SERS)detection with an enhancement factor of-1.74×10^(8).Furthermore,a linear correlation between logarithmic Raman intensity and logarithmic concentration of probe molecules is observed in a large concentration range.These results offer new ideas to develop novel plasmonic devices,and provide alternative strategy to realize flexible and high-performance SERS sensors for trace molecule detection and quantitative analysis.展开更多
文摘Surface-enhanced Raman scattering(SERS)is a powerful technology for obtaining vibrational information from molecules that present in different chemical or biological environments.This paper presents a 3D SERS substrate based on nanocone forests.The substrates are prepared by using plasma treatment technique,which is a simple,fast and high-throughput approach.The SERS substrate based on nanocone forests exhibits high sensitivity.In the experiment,miRNA with a concentration as low as 10-10 M can be achieved.Meanwhile,the proposed SERS substrate shows a high uniformity over a large area.These experimental results demonstrate great potential of the 3D SERS substrate in wide applications.
基金supported by National Natural Science Foundation of China(Nos.21874013,22074013 and 22073030)the Fundamental Research Funds for the Central Universities(Nos.N2105018 and N2005027)+1 种基金the China Postdoctoral Science Foundation(No.2019M661109)supported by the Supercomputer Centre of East China Normal University(ECNU Public Platform for Innovation No.001).
文摘Although surface-enhanced Raman spectroscopy(SERS)has been applied for gathering fingerprint information,even in single molecule analysis,the decayed Raman signals in aqueous solutions largely obstruct the on-site insight reaction process.In this study,large-scaled semiconductor films with multi-walled(TiO_(2)/WO_(3)/TiO_(2))nanopore distribution are fabricated by combining electrochemical anodization and sputtering technique,and then employed as the SERS substrates for detection of molecules at the solid/liquid interfaces.Given the remarkably improved electrochromic property of the multi-walled film,such SERS substrates were endowed with tunable oxygen vacancy(VO)density and distribution via simply applying electrochemical bias voltage,which enabled one to achieve an enhanced charge transfer efficiency and thus a remarkably increased Raman signal even in solution.The VO-rich SERS substrate is highly repeatable,thus providing a reliable platform for in-situ monitoring of the target molecules or intermediates at the solid/liquid interfaces.
基金the National Natural Science Foundation of China(Nos.51503033,51373030)
文摘To develop a smart free-standing surface enhanced Raman scattering(SERS) substrate,silver nanoparticles(AgNPs) embedded temperature-sensitive nanofibrous membrane was fabricated by electrospinning their aqueous solution containing the copolymer poly(N-isopropylacrylamide-co-Nhydroxymethylacrylamide),followed by heat treatment to form crosslinking structure within its constituent nanofibers.To avoid negative effect of the additive like stabilizer and the reactant like reductant on their SERS efficiency,the AgNPs were in-situ synthesized through reducing Ag^+ions dissolved in the polymer solution by ultraviolet irradiation.The prepared hybrid nanofibrous membrane with high stability in aqueous medium can reach its swelling or deswelling equilibrium state within 15 seconds with the medium temperature changing between 25℃and 50℃alternately.When it was used as a free-standing SERS substrate,10^-12 mol/L of 4-nitrothiophenol in aqueous solution can be detected at room temperature,and elevating detection temperature can further lower its low detection limit.Since its generated SERS signal has desirable reproducibility,it can be used as SERS substrate for quantitative analysis.Moreover,the hybrid membrane as SERS substrate is capable of real-time monitoring the reduction of 4-nitrothiophenol into 4-aminothiophenol catalyzed by its embedded AgNPs,and the detected intermediate indicates that the reaction proceeds via a condensation route.
基金supported by Hong Kong Innovation and Technology Commission(Innovation and Technology Support Programme(Seed),No.ITS/176/22)Shenzhen Science and Technology Innovation Commission(No.JSGGKQTD20221101115701006)+1 种基金the University Development Fund(No.UDF01002665)the Program of Guangdong Introducing Innovative and Entrepreneurial Teams(No.2019ZT08L101).
文摘In the pursuit of advancing molecular sensing through surface-enhanced Raman spectroscopy(SERS),the combination of plasmonic nanoparticles and metal-organic frameworks(MOFs)has emerged as a highly effective approach to enhance the sensitivity and selectivity of SERS substrates.However,most prior investigations have predominantly focused on MOF-coated plasmonic nanoparticles in core@shell or layer-by-layer configurations,leaving a notable knowledge gap in exploring alternative configurations.Herein we present a facile method to construct a particle-on-mirror architecture by selectively coating a MOF,zeolitic imidazolate framework-8(ZIF-8),onto the tips of Au nanostars and subsequently depositing the resultant nanoparticles onto a Au film.This design integrates the electric field enhancement at the sharp tips and nanogaps,along with the molecular enrichment function within the porous MOF immobilized at the tips and nanogaps,leading to a substantial boost in the SERS signal intensity.Such a unique SERS platform enables consistent and outstanding SERS performance for analytes of different sizes.This work opens up a promising strategy for constructing multifunctional nanostructures for sensitive SERS detection in real-life scenarios.
基金supported by the National Natural Science Foundation of China(No.81988101)。
文摘Early or very early detection of hepatocellular carcinoma(HCC)is an effective means to resolve the low cure rates,but there currently lacks a method that fulfills clinical requirements.One of the most prospective approaches to detecting early-stage HCC is directly testing a compendium of disease-relevant biomolecules contained within human serum through surface-enhanced Raman scattering(SERS)nanobiosensing and recognizing the biomolecular patterns.We report a novel Si-based bimetallic nanoensembles-functionalized SERS substrate(its analytical enhancement factor reaches 1.47×10^(12))and introduce an ultrasensitive nanobiosensing for capturing the subtle characteristic changes in SERS spectra caused by HCC,hepatitis B,or cirrhosis.Toward early diagnosis,we created an intelligent serological test with this nanobiosensing and the deep learning algorithm to gain key biomolecular phenotypes of early-stage HCC.Using clinical samples from four target populations(normal,HCC,cirrhosis,and hepatitis B),the proof-of-principle result indicates that the test yielded a predictive accuracy of 98.75%on a held-out dataset(randomly drew 4 out of 28 samples per population).On the same held-out dataset,the sensitivity and specificity of the test were both 100%for distinguishing HCC.Such a new-concept liquid biopsy could provide an opportunity for early diagnosis of HCC.
基金This work is supported by the National Natural Science Foundation of China(No.81801122)Natural Science Basic Research Program of Shaanxi(No.2020JQ-529)+4 种基金Scientific Research Program Funded by Shaanxi Provincial Education Department(No.20JK0658)The industry-University-Research collaborative innovation project of Keqiao Textile Industry Innovation Institute of Xi’an Polytechnic University(No.19KQZD01)Xi’an Science and Technology Project(GXYD7.3)Key R&D projects of Shaanxi(No.2020GY-273)Project of China National Textile Industry Association(No.2020047)。
文摘Plasmonic surface of flexible multilayered nanofibers possesses special superiority for the surface-enhanced Raman scattering(SERS)sensing of molecules and microbial cells.However,the fabrication of flexible plasmonic nanofibers with high sensitivity and reproducibility is difficult.Herein,we report a smart strategy for fabricating flexible plasmonic fibers,in which compact and homogeneous gold nanoparticles(Au NPs)are in-situ grown on the high-curvature surface of multilayered fibers of electrospun polyvinylidene fluoride(PVDF).Firstly,the surface of PVDF fibers is changed electrically,and Au seeds are deposited on the surface of PVDF fibers using electrostatic driving force.Secondly,a stable AuI_(4)−complex is formed employing coordination between I−and AuCl4−ions,which could decrease the reduction potential of AuCl4−and restrain the self-nucleation,and then the reduction reaction of AuI4−is initiated by introducing PVDF@Au seeds to pull down the barrier of potential energy.Finally,in-situ growth of AuNPs is generated on the high-curvature surface of PVDF nanofibers,and large-scale hotspots are generated by adjacent AuNPs coupling in the three-dimensional(3D)space of multilayered fibers.Membrane of PVDF@Au nanofibers also realizes the sensitive detection of thiram molecules(low limit of detection of 0.1 nM)and good reproducibility(relative standard deviation of 10.6%).Meanwhile,due to the multilayered construction of PVDF@Au nanofibers,a valid SERS signal on 3D surface of bacteria could be generated.3D distribution of hotspots on multilayered PVDF@Au nanofibers gives a clear advantage for SERS sensing of organic molecules and microbial cells.
文摘Development of cost-effective, highly reproducible non-conventional fabrication techniques for anisotropic metal nanostructures is essential to realizing potential applications of plasmonic devices, photonic devices, and surface enhanced Raman scattering （SERS） phenomenon based sensors. This report highlights the fabrication of nanotriangle arrays via nanoimprinting to overcome difficulties in creating large-area SERS active substrates with uniform, reproducible Raman signals. Electron beam lithography of anisotropic nanostructures, formation of arrays of nanotriangles in silicon and the transfer of triangular shapes to polymethylmethacrylate （PMMA） sheets via nanoimprinting have not been reported elsewhere. The reuse of silicon masters offers potential for production of low cost SERS substrates. The SERS activity and reproducibility of nanotriangles are illustrated and a consistent average enhancement factor of up to -2.9 × 1011, which is the highest value reported for a patterned SERS substrate, is achieved.
基金supported by the Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDB14020201)the National Natural Science Foundation of China (Nos. 21337004, 21321004)
文摘Concerns over exposure to mercury have motivated the exploration of cost-effective,rapid,and reliable method for monitoring Hg^2＋ in the environment.Recently,surface-enhanced Raman scattering（SERS） has become a promising alternative method for Hg^2＋ analysis.SERS is a spectroscopic technique which combines modern laser spectroscopy with the optical properties of nano-sized noble metal structures,resulting in substantially increased Raman signals.When Hg^2＋ is in a close contact with metallic nanostructures,the SERS effect provides unique structural information together with ultrasensitive detection limits.This review introduces the principles and contemporary approaches of SERS-based Hg^2＋detection.In addition,the perspective and challenges are briefly discussed.
基金supported by the National Natural Science Foundation of China(No.51871003).
文摘Plasmon coupling is an essential strategy to realize strong local electromagnetic(EM)field which is crucial for high-performance plasmonic devices.In this work,multiple plasmon couplings are demonstrated in three-dimensional(3D)hybrid plasmonic systems composed of polydimethylsiloxane-supported ordered silver nanocone(AgNC)arrays decorated with high-density gold nanoparticles(AuNPs)which are fabricated by a template-assisted physical vapor deposition process.Strong interparticle coupling,particle-film coupling,inter-cone coupling,and particle-cone coupling are revealed by numerical simulations in such composite nanostructures,which produce intense and high-density EM hot spots,boosting highly sensitive and reproducible surface enhanced Raman scattering(SERS)detection with an enhancement factor of-1.74×10^(8).Furthermore,a linear correlation between logarithmic Raman intensity and logarithmic concentration of probe molecules is observed in a large concentration range.These results offer new ideas to develop novel plasmonic devices,and provide alternative strategy to realize flexible and high-performance SERS sensors for trace molecule detection and quantitative analysis.
