The sensitive and on-site detection of inorganic explosives has raised serious concerns regarding public safety. However, high stability and non-volatility features currently limit their rapid on-site detection. Surfa...The sensitive and on-site detection of inorganic explosives has raised serious concerns regarding public safety. However, high stability and non-volatility features currently limit their rapid on-site detection. Surface-enhanced Raman spectroscopy （SERS） is emerging as a powerful technique for the trace-level detection of different molecules. Plasmonic Ag nanowires were produced by a hydrothermal synthesis method using polyvinylpyrrolidone （PVP） as a negatively charged stabilizer. Here, we report a rapid detection method for inorganic explosives based on a simple surface swab with a positively charged diethyldithiocarbamate-modified Ag nanowire membrane coupled with SERS. This membrane, serving as an excellent SERS substrate with high uniformity, stability, and reusability, can capture both typical oxidizers in inorganic explosives and organic nitro-explosives, via electrostatic interaction. The detection level of perchlorates （ClO4-）, chlorates （ClO3-）, nitrates （NO3）-, picric acid, and 2,4- dinitrophenol is as high as 2.0, 1.7, 0.1, 45.8, and 36.6 ng, respectively. In addition, simulated typical inorganic explosives such as black powders, firecrackers, and match heads could also be detected. We believe that this membrane represents an attractive alternative for rapid on-site detection of inorganic explosives with high efficiency.展开更多
Uniform silver-containing metal nanostructures with well-defined nanogaps hold great promise for ultrasensitive surface-enhanced Raman scattering （SERS） analyses. Nevertheless, the direct synthesis of such nanostruc...Uniform silver-containing metal nanostructures with well-defined nanogaps hold great promise for ultrasensitive surface-enhanced Raman scattering （SERS） analyses. Nevertheless, the direct synthesis of such nanostructures with strong and stable SERS signals remains extremely challenging. Here, we report a DNA-mediated approach for the direct synthesis of gold-silver nano-mushrooms with interior nanogaps. The SERS intensities of these nano-mushrooms were critically dependent on the area of the nanogap between the gold head and the silver cap. We found that the formation of nanogaps was finely tunable by controlling the surface density of 6-carboxy-X-rhodamine （ROX） labeled single-stranded DNA （ssDNA） on the gold nanoparticles. We obtained nano-mushrooms in high yield with a high SERS signal enhancement factor of -1.0×109, much higher than that for Au-Ag nanostructures without nanogaps. Measurements for single nano- mushrooms show that these structures have both sensitive and reproducible SERS signals.展开更多
This study reports the controllable surface roughening of Au-Ag alloy nanoplates via the galvanic replacement reaction between single-crystalline triangular Ag nanoplates and HAuC14 in an aqueous medium. With a combin...This study reports the controllable surface roughening of Au-Ag alloy nanoplates via the galvanic replacement reaction between single-crystalline triangular Ag nanoplates and HAuC14 in an aqueous medium. With a combination of experimental evidence and finite element method （FEM） simulations, improved electromagnetic field （E-field） enhancement around the surface-roughened Au- Ag nanoplates and tunable light absorption in the near-infrared （NIR） region （-800-1,400 nm） are achieved by the synergistic effects of the localized surface plasmon resonance （LSPR） from the maintained triangular shape, the controllable Au-Ag alloy composition, and the increased surface roughness. The NIR light extinction enables an active photothermal effect as well as a high photothermal conversion efficiency （78.5%）. The well-maintained triangular shape, surface- roughened evolutions of both micro- and nanostructures, and tunable NIR surface plasmon resonance effect enable potential applications of the Au-Ag alloy nanoplates in surface-enhanced Raman spectroscopic detection of biomolecules through 785-nm laser excitation.展开更多
We report the first attempt of using molecularly imprinted polymers （MIPs） in the shape of nanoparticles that were doped with gold nanoparticles （AuNPs） for surface enhanced Raman scattering （SERS）-based sensing...We report the first attempt of using molecularly imprinted polymers （MIPs） in the shape of nanoparticles that were doped with gold nanoparticles （AuNPs） for surface enhanced Raman scattering （SERS）-based sensing of molecular spedes. Specifically, AuNPs doped molecularly imprinted nano-spheres （AuNPs@nanoMIPs） were synthesized by one-pot precipitation polymerization using Sudan IV as the template for the SERS sensing. The AuNPs@nanoMIPs were characterized by various modes of scanning transmission electron microscopy （STEM） that showed the exact location of the AuNPs inside the MIP particles. The effects of Au concentration and solution stirring on the shape and the polydispersity of the particles were studied. Significant enhancement of the Raman signals was observed only when the MIP particles were doped with the AuNPs. The SERS signal improved significantly with increase in the Au concentration inside the AuNPs@nanoMIPs. Selectivity measurements of the Sudan IV imprinted AuNPs@nanoMIPs carried out with different Sudan derivatives showed high selectivity of the AuNPs-doped MIP particles.展开更多
The design and synthesis of plasmonic nanoparticles with Raman-active molecules embedded inside them are of significant interest for sensing and imaging applications. However, direct synthesis of such nanostructures w...The design and synthesis of plasmonic nanoparticles with Raman-active molecules embedded inside them are of significant interest for sensing and imaging applications. However, direct synthesis of such nanostructures with controllable shape, size, and plasmonic properties remains extremely challenging. Here we report on the preparation of uniform Au@Ag core/sheU nanorods with controllable Ag shells of 1 to 25 nm in thickness. 1,4-Aminothiophenol （4-ATP） molecules, used as the Raman reporters, were located between the Au core and the Ag shell. Successful embedding of reporter molecules inside the core/shell nanoparticles was confirmed by the absence of selective oxidation of the amino groups, as measured by Raman spectroscopy. The dependence of Raman intensity on the location of the reporter molecules in the inside and outside of the nanorods was studied. The molecules in the interior showed strong and uniform Raman intensity, at least an order of magnitude higher than that of the molecules on the nanoparticle surface. In contrast to the usual surface-functionalized Raman tags, aggregation and clustering of nanoparticles with embedded molecules decreased the surface-enhanced Raman scattering （SERS） signal. The findings from this study provide the basis for a novel detection technique of low analyte concentration utilizing the high SERS response of molecules inside the core/shell metal nanostructures. As an example, we show robust SERS detection of thiram fungicide as low as 10-9 M in solutions.展开更多
Actinide elements encaged in a superatomic cluster can exhibit unique properties due to their hyperactive valence electrons. Herein, the electronic and spectroscopic properties of Th@Au14 are predicted and compared wi...Actinide elements encaged in a superatomic cluster can exhibit unique properties due to their hyperactive valence electrons. Herein, the electronic and spectroscopic properties of Th@Au14 are predicted and compared with that of the isoelectronic entities [Ac@Au14]- and [Pa@Au14]＋ using density functional theory. The calculation results indicate that these clusters all adopt a closed- shell superatomic 18-electron configuration of the 1S21p61D10 Jellium state. The absorption spectrum of Th@Au14 can be interpreted by the Jelliumatic orbital model. In addition, calculated spectra of pyridine-Th@Au14 complexes in the blue laser band exhibit strong peaks attributable to charge transfer （CT） from the metal to the pyridine molecule. These charge-transfer bands lead to a resonant surface-enhanced Raman scattering （SERS） enhancement of -104. This work suggests a basis for designing and synthesizing SERS substrate materials based on actinide-embedded gold superatom models.展开更多
Facile synthesis of multi-branched gold nanostructures by using the tetrabutyl ammonium bromide （TBAB） as a capping agent is described. The reaction is carried out in a one-step process at mild temperature. Gold nan...Facile synthesis of multi-branched gold nanostructures by using the tetrabutyl ammonium bromide （TBAB） as a capping agent is described. The reaction is carried out in a one-step process at mild temperature. Gold nanostructures with more than six sharp branches ranging from 70 to 130 nm in length are synthesized in high yield. It is proposed that the relative weak adsorption capacity of TBAB leads to the incompletely covered gold surface and the growth of nanoparticles occurs on the uncovered gold surface, and therefore short branches appear consequently. Then positively charged TBAB layers on the gold surfaces prevent the branches from aggregating with each other which stimulates the branch growth. The prepared branched gold nanoparticles show efficient surface-enhanced Raman scattering （SERS） properties. Low temperature （4 ℃） is unfavorable to the formation of multi-branched gold nanostructures, and only thin small irregular plate-like nanoparticles are produced. The addition of SDS in TBAB aqueous solution results in forming SDS micelles at much lower concentration of SDS （0.4 mmol/L） as compared to that in pure water, and short branched gold nanoparticles are obtained in the SDS-TBAB system.展开更多
A major challenge with studying plasmon-mediated emission events is the small size of plasmonic nanoparticles relative to the wavelength of light. Objects smaller than roughly half the wavelength of light will appear ...A major challenge with studying plasmon-mediated emission events is the small size of plasmonic nanoparticles relative to the wavelength of light. Objects smaller than roughly half the wavelength of light will appear as diffraction-limited spots in far-field optical images, presenting a significant experimental challenge for studying plasmonic processes on the nanoscale. Super-resolution imaging has recently been applied to plasmonic nanosystems and allows plasmon-mediated emission to be resolved on the order of ~5 nm. In super-resolution imaging, a diffraction-limited spot is fit to some model function in order to calculate the position of the emission centroid, which represents the loca- tion of the emitter. However, the accuracy of the centroid position strongly depends on how well the fitting function describes the data. This Perspective discusses the commonly used two-dimensional Gaussian fitting function applied to super-resolution imaging of plasmon-mediated emission, then introduces an alternative model based on dipole point spread flmctions. The two fitting models are compared and contrasted for super-resolution imaging of nanoparticle scattering/luminescence, surface-enhanced Raman scattering, and surface-enhanced fluorescence.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
Although nanotechnology has led to important advances in in vitro diagnostics, the development of nanosensors for in vivo detection remains very challenging. Here, we demonstrated the proof-of-principle of in vivo det...Although nanotechnology has led to important advances in in vitro diagnostics, the development of nanosensors for in vivo detection remains very challenging. Here, we demonstrated the proof-of-principle of in vivo detection of nudeic acid targets using a promising type of surface-enhanced Raman scattering （SERS） nanosensor implanted in the skin of a large animal model （pig）. The in vivo nanosensor used in this study involves the ＂inverse molecular sentinel＂ detection scheme using plasmonics-active nanostars, which have tunable absorption bands in the near infrared region of the ＂tissue optical window＂, rendering them efficient as an optical sensing platform for in vivo optical detection. Ex vivo measurements were also performed using human skin grafts to demonstrate the detection of SERS nanosensors through tissue. In this stud, a new core--shell nanorattle probe with Raman reporters trapped between the core and shell was utilized as an internal standard system for self-calibration. These results illustrate the usefulness and translational potential of the SERS nanosensor for in vivo biosensing.展开更多
The size and density of Ag nanoparticles on n-layer MoS2 exhibit thickness- dependent behavior. The size and density of these particles increased and decreased, respectively, with increasing layer number （n） of n-la...The size and density of Ag nanoparticles on n-layer MoS2 exhibit thickness- dependent behavior. The size and density of these particles increased and decreased, respectively, with increasing layer number （n） of n-layer MoS2. Furthermore, the surface-enhanced Raman scattering （SERS） of Ag on this substrate was observed. The enhancement factor of this scattering varied with the thickness of MoS2. The mechanisms governing the aforementioned thickness dependences are proposed and discussed.展开更多
基金We thank the financial support from the National Basic Research Program of China （973 Program, No. 2013CB934301）, the National Natural Science Foundation of China （NSFC, Nos. 21377068 and 21575077）.
文摘The sensitive and on-site detection of inorganic explosives has raised serious concerns regarding public safety. However, high stability and non-volatility features currently limit their rapid on-site detection. Surface-enhanced Raman spectroscopy （SERS） is emerging as a powerful technique for the trace-level detection of different molecules. Plasmonic Ag nanowires were produced by a hydrothermal synthesis method using polyvinylpyrrolidone （PVP） as a negatively charged stabilizer. Here, we report a rapid detection method for inorganic explosives based on a simple surface swab with a positively charged diethyldithiocarbamate-modified Ag nanowire membrane coupled with SERS. This membrane, serving as an excellent SERS substrate with high uniformity, stability, and reusability, can capture both typical oxidizers in inorganic explosives and organic nitro-explosives, via electrostatic interaction. The detection level of perchlorates （ClO4-）, chlorates （ClO3-）, nitrates （NO3）-, picric acid, and 2,4- dinitrophenol is as high as 2.0, 1.7, 0.1, 45.8, and 36.6 ng, respectively. In addition, simulated typical inorganic explosives such as black powders, firecrackers, and match heads could also be detected. We believe that this membrane represents an attractive alternative for rapid on-site detection of inorganic explosives with high efficiency.
基金We thank the National Basic Research Program of China （973 program） （Nos. 2013CB932802 and 2012CB932600）,Alexander von Humboldt Foundation, and the National Natural Science Foundation of China （Nos. 91127037 and 91123037） for financial support.
文摘Uniform silver-containing metal nanostructures with well-defined nanogaps hold great promise for ultrasensitive surface-enhanced Raman scattering （SERS） analyses. Nevertheless, the direct synthesis of such nanostructures with strong and stable SERS signals remains extremely challenging. Here, we report a DNA-mediated approach for the direct synthesis of gold-silver nano-mushrooms with interior nanogaps. The SERS intensities of these nano-mushrooms were critically dependent on the area of the nanogap between the gold head and the silver cap. We found that the formation of nanogaps was finely tunable by controlling the surface density of 6-carboxy-X-rhodamine （ROX） labeled single-stranded DNA （ssDNA） on the gold nanoparticles. We obtained nano-mushrooms in high yield with a high SERS signal enhancement factor of -1.0×109, much higher than that for Au-Ag nanostructures without nanogaps. Measurements for single nano- mushrooms show that these structures have both sensitive and reproducible SERS signals.
基金This work was supported by the National Natural Science Foundation of China （Nos. 91323301, 21322105, and 51372025）, the Research Fund for the Doctoral Program of Higher Education of China （No. 2011101120016） and Program for New Century Excellent Talents in University （No. NCET-11-0793）. The authors would like to thank Prof. Chen Wang and Prof. Yanjun Guo of National Center for Nanoscience and Technology, China for AFM and SERS measure- ments and helpful discussions, respectively Dr. Haiwei Li for help on BET tests and helpful discussions.
文摘This study reports the controllable surface roughening of Au-Ag alloy nanoplates via the galvanic replacement reaction between single-crystalline triangular Ag nanoplates and HAuC14 in an aqueous medium. With a combination of experimental evidence and finite element method （FEM） simulations, improved electromagnetic field （E-field） enhancement around the surface-roughened Au- Ag nanoplates and tunable light absorption in the near-infrared （NIR） region （-800-1,400 nm） are achieved by the synergistic effects of the localized surface plasmon resonance （LSPR） from the maintained triangular shape, the controllable Au-Ag alloy composition, and the increased surface roughness. The NIR light extinction enables an active photothermal effect as well as a high photothermal conversion efficiency （78.5%）. The well-maintained triangular shape, surface- roughened evolutions of both micro- and nanostructures, and tunable NIR surface plasmon resonance effect enable potential applications of the Au-Ag alloy nanoplates in surface-enhanced Raman spectroscopic detection of biomolecules through 785-nm laser excitation.
文摘We report the first attempt of using molecularly imprinted polymers （MIPs） in the shape of nanoparticles that were doped with gold nanoparticles （AuNPs） for surface enhanced Raman scattering （SERS）-based sensing of molecular spedes. Specifically, AuNPs doped molecularly imprinted nano-spheres （AuNPs@nanoMIPs） were synthesized by one-pot precipitation polymerization using Sudan IV as the template for the SERS sensing. The AuNPs@nanoMIPs were characterized by various modes of scanning transmission electron microscopy （STEM） that showed the exact location of the AuNPs inside the MIP particles. The effects of Au concentration and solution stirring on the shape and the polydispersity of the particles were studied. Significant enhancement of the Raman signals was observed only when the MIP particles were doped with the AuNPs. The SERS signal improved significantly with increase in the Au concentration inside the AuNPs@nanoMIPs. Selectivity measurements of the Sudan IV imprinted AuNPs@nanoMIPs carried out with different Sudan derivatives showed high selectivity of the AuNPs-doped MIP particles.
文摘The design and synthesis of plasmonic nanoparticles with Raman-active molecules embedded inside them are of significant interest for sensing and imaging applications. However, direct synthesis of such nanostructures with controllable shape, size, and plasmonic properties remains extremely challenging. Here we report on the preparation of uniform Au@Ag core/sheU nanorods with controllable Ag shells of 1 to 25 nm in thickness. 1,4-Aminothiophenol （4-ATP） molecules, used as the Raman reporters, were located between the Au core and the Ag shell. Successful embedding of reporter molecules inside the core/shell nanoparticles was confirmed by the absence of selective oxidation of the amino groups, as measured by Raman spectroscopy. The dependence of Raman intensity on the location of the reporter molecules in the inside and outside of the nanorods was studied. The molecules in the interior showed strong and uniform Raman intensity, at least an order of magnitude higher than that of the molecules on the nanoparticle surface. In contrast to the usual surface-functionalized Raman tags, aggregation and clustering of nanoparticles with embedded molecules decreased the surface-enhanced Raman scattering （SERS） signal. The findings from this study provide the basis for a novel detection technique of low analyte concentration utilizing the high SERS response of molecules inside the core/shell metal nanostructures. As an example, we show robust SERS detection of thiram fungicide as low as 10-9 M in solutions.
基金Acknowledgements We would like to thank Drs. Jun Liu and Lei Chen for the stimulating discussions. We would also like to acknowledge the support of the National Natural Science Foundation of China （No. 11374004） and the Science and Technology Development Program of Jilin Province of China （No. 20150519021JH）. Z. W. also acknowledges the Fok Ying Tung Education Foundation （No. 142001） and High Performance Computing Center of Jilin University.
文摘Actinide elements encaged in a superatomic cluster can exhibit unique properties due to their hyperactive valence electrons. Herein, the electronic and spectroscopic properties of Th@Au14 are predicted and compared with that of the isoelectronic entities [Ac@Au14]- and [Pa@Au14]＋ using density functional theory. The calculation results indicate that these clusters all adopt a closed- shell superatomic 18-electron configuration of the 1S21p61D10 Jellium state. The absorption spectrum of Th@Au14 can be interpreted by the Jelliumatic orbital model. In addition, calculated spectra of pyridine-Th@Au14 complexes in the blue laser band exhibit strong peaks attributable to charge transfer （CT） from the metal to the pyridine molecule. These charge-transfer bands lead to a resonant surface-enhanced Raman scattering （SERS） enhancement of -104. This work suggests a basis for designing and synthesizing SERS substrate materials based on actinide-embedded gold superatom models.
基金Project supported by the National Natural Science Foundation of China （Nos. 50872042, 51003040）, Open Research Project （No. KF0802） from State Key Laboratory of Crystal Material （Shandong University） and the Special Fund for Postdoctoral Innovation Program of Shandong Province （No. 200703075）.
文摘Facile synthesis of multi-branched gold nanostructures by using the tetrabutyl ammonium bromide （TBAB） as a capping agent is described. The reaction is carried out in a one-step process at mild temperature. Gold nanostructures with more than six sharp branches ranging from 70 to 130 nm in length are synthesized in high yield. It is proposed that the relative weak adsorption capacity of TBAB leads to the incompletely covered gold surface and the growth of nanoparticles occurs on the uncovered gold surface, and therefore short branches appear consequently. Then positively charged TBAB layers on the gold surfaces prevent the branches from aggregating with each other which stimulates the branch growth. The prepared branched gold nanoparticles show efficient surface-enhanced Raman scattering （SERS） properties. Low temperature （4 ℃） is unfavorable to the formation of multi-branched gold nanostructures, and only thin small irregular plate-like nanoparticles are produced. The addition of SDS in TBAB aqueous solution results in forming SDS micelles at much lower concentration of SDS （0.4 mmol/L） as compared to that in pure water, and short branched gold nanoparticles are obtained in the SDS-TBAB system.
文摘A major challenge with studying plasmon-mediated emission events is the small size of plasmonic nanoparticles relative to the wavelength of light. Objects smaller than roughly half the wavelength of light will appear as diffraction-limited spots in far-field optical images, presenting a significant experimental challenge for studying plasmonic processes on the nanoscale. Super-resolution imaging has recently been applied to plasmonic nanosystems and allows plasmon-mediated emission to be resolved on the order of ~5 nm. In super-resolution imaging, a diffraction-limited spot is fit to some model function in order to calculate the position of the emission centroid, which represents the loca- tion of the emitter. However, the accuracy of the centroid position strongly depends on how well the fitting function describes the data. This Perspective discusses the commonly used two-dimensional Gaussian fitting function applied to super-resolution imaging of plasmon-mediated emission, then introduces an alternative model based on dipole point spread flmctions. The two fitting models are compared and contrasted for super-resolution imaging of nanoparticle scattering/luminescence, surface-enhanced Raman scattering, and surface-enhanced fluorescence.
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.
文摘Although nanotechnology has led to important advances in in vitro diagnostics, the development of nanosensors for in vivo detection remains very challenging. Here, we demonstrated the proof-of-principle of in vivo detection of nudeic acid targets using a promising type of surface-enhanced Raman scattering （SERS） nanosensor implanted in the skin of a large animal model （pig）. The in vivo nanosensor used in this study involves the ＂inverse molecular sentinel＂ detection scheme using plasmonics-active nanostars, which have tunable absorption bands in the near infrared region of the ＂tissue optical window＂, rendering them efficient as an optical sensing platform for in vivo optical detection. Ex vivo measurements were also performed using human skin grafts to demonstrate the detection of SERS nanosensors through tissue. In this stud, a new core--shell nanorattle probe with Raman reporters trapped between the core and shell was utilized as an internal standard system for self-calibration. These results illustrate the usefulness and translational potential of the SERS nanosensor for in vivo biosensing.
文摘The size and density of Ag nanoparticles on n-layer MoS2 exhibit thickness- dependent behavior. The size and density of these particles increased and decreased, respectively, with increasing layer number （n） of n-layer MoS2. Furthermore, the surface-enhanced Raman scattering （SERS） of Ag on this substrate was observed. The enhancement factor of this scattering varied with the thickness of MoS2. The mechanisms governing the aforementioned thickness dependences are proposed and discussed.
