The surface-enhanced Raman scattering(SERS) optical fiber probes were successfully prepared by self-assembling on polyelectrolyte multilayers. Gold nanorods(Au NRs) were used as SERS enhancement material to give excel...The surface-enhanced Raman scattering(SERS) optical fiber probes were successfully prepared by self-assembling on polyelectrolyte multilayers. Gold nanorods(Au NRs) were used as SERS enhancement material to give excellent biological affinity and stability to the SERS optical fiber probes. Au NRs were synthesized by seed growth method. The synergistic effect between AgNO_(3) and surfactant was investigated, and the highest yield was found when AgNO_(3) was 500 uL. Meanwhile, different SERS optical fiber probes were obtained by selecting silane coupling agent, polyelectrolyte multilayer and graphene oxide(GO) to treat quartz fiber. It was found that the SERS optical fiber probes obtained by the self-assembled on polyelectrolyte multilayers method performed better than those by other methods. In addition, Mapping was combined with finite element simulation to analyze the electromagnetic field distribution at the fiber end face.The electromagnetic field distribution of Au NRs was investigated, the difference of electromagnetic field intensity around the Au NRs with different arrangements was compared, the strongest signal was obtained when the Au NRs were head-to-head. Finally, sensitivity of the optimized SERS optical fiber probes could reach 10^(-9)mol/L, with excellent stability and repeatability.展开更多
We report the synthesis of gold nanorods （NRs） by seed-mediated growth method. A small amount of different shapes such as triangles, hexagons and a large amount of rods are obtained by varying the proportion of seed...We report the synthesis of gold nanorods （NRs） by seed-mediated growth method. A small amount of different shapes such as triangles, hexagons and a large amount of rods are obtained by varying the proportion of seed to metal salt, adding NaOH to growth solution as well as using the seed solution of CTAB-capped agent. The gold nanorod （NR） formation yield is improved. Meanwhile, the growth mechanism of high yield gold NRs is discussed. The high quality single size NRs can be separated from polydisperse samples using surfactant-assisted nanorod self-assembly. The gold NRs synthesized were characterized by transmission electron microscopy （TEM） and UV-vis spectroscopy.展开更多
We developed a general and effective strategy to afford rod-like [Au25(SPh)5(PPh3)10X2]X2 (X = Cl/Br) nanoclusters, capped by conjugated delocalized pπ electron mediated ligands. The detailed atomic structure of thes...We developed a general and effective strategy to afford rod-like [Au25(SPh)5(PPh3)10X2]X2 (X = Cl/Br) nanoclusters, capped by conjugated delocalized pπ electron mediated ligands. The detailed atomic structure of these materials was resolved by synchrotron radiation X-ray diffraction (SRXRD) combined with electrospray ionization mass spectrometry (ESI-MS) and UV–vis analyses. The Au17(SR)3(PPh3)6X2minimum asymmetric unit, with exposed Au atoms at the center, can serve as an important model to understand the transformation of homogold nanoclusters into alloy nanoclusters. The conjugated delocalized pπ electrons of the thiolate ligands can effectively tune the electronic properties of the Au25 kernel, as qualitatively evidenced by the energy gaps measured by UV–vis experiments and density functional theory (DFT) calculations. The delocalized electrons distinctly flow to the orbitals of the Au25 kernel via the S atoms of the aromatic thiolates. The ESI-MS analysis indicates that Au3 clusters are formed during the etching reactions, which provide an opportunity to gain insight into the intriguing conversion pathway of the Aun(PPh3)mXy precursor to the final Au25 nanorods. Finally, the thiophenol-protected Au25 nanorods, immobilized on activated carbon, show good catalytic activity in the aerobic oxidation of glucose to gluconic acid (74% glucose conversion and 100% selectivity for gluconic acid), much higher than that of the aliphatic Au25 analogue. The Au25(SPh)5(PPh3)10X2 catalyst yields a turnover frequency (TOF) of 13.5 s^–1, higher than that of commercial catalysts such as Pd/activated carbon (AC) and Pd-Bi/AC. The insight obtained from this study will support the development and design of efficient nanogold catalysts for special oxidation reactions.展开更多
Accurate researches on the surface plasmon resonance(SPR)-based applications of chiral plasmonic metal nanoparticles(NPs)still remain a great challenge.Herein,a series of chiral plasmonic metal NPs,e.g.,chiral Au nano...Accurate researches on the surface plasmon resonance(SPR)-based applications of chiral plasmonic metal nanoparticles(NPs)still remain a great challenge.Herein,a series of chiral plasmonic metal NPs,e.g.,chiral Au nanorods(c-Au NRs),c-Au@Ag core–shell,and c-Au@TiO_(2) core–shell NRs,with different chiroptical activities have been produced.Plasmonic circular dichroism(PCD)bands of c-Au NRs can be precisely tailored by tuning the longitudinal SPR(LSPR)and amount of Au NRs as seeds.Besides,a shift of PCD bands within ultraviolet–visible–near infrared ray(UV–vis–NIR)region can also be achieved through the functionalization of a shell of another metal or semiconductor.Interestingly,chirality transfer from c-Au core to Ag shell leads to new PCD bands at the near-UV region.The tuning of PCD bands and chirality transfer are confirmed by our developed theoretical model.Developing chiral Au NRs-based chiral plasmonic nanomaterials with tunable chiroptical activities will be helpful to understand the structure-direct PCD and to extend circularly polarized-based applications.展开更多
在金纳米棒(AuNRs)-Ag^+-甲醛(HCHO)体系中,HCHO快速将Ag^+还原为Ag,Ag包裹在AuNRs表面形成Au@AgNRs,改变了AuNRs周围的电介质环境,导致纵向最大吸收波长(LPAB)红移,同时伴随着溶液的颜色发生显著的变化。据此,发展了一种测定HCHO的快...在金纳米棒(AuNRs)-Ag^+-甲醛(HCHO)体系中,HCHO快速将Ag^+还原为Ag,Ag包裹在AuNRs表面形成Au@AgNRs,改变了AuNRs周围的电介质环境,导致纵向最大吸收波长(LPAB)红移,同时伴随着溶液的颜色发生显著的变化。据此,发展了一种测定HCHO的快响应、简便、灵敏、选择性的AuNRs比色传感器。该比色传感器的检出限为6.3×10^(-11)(g m L^(-1)),比表面增强拉曼光谱法低,显示很高的灵敏度;尤其是本比色传感器用于水样品中HCHO的测定,结果与固体基质室温磷光法相吻合,展示较高的实用性。此外,探讨了测定HCHO的机理。展开更多
基金Funded by National Natural Science Foundation of China (Nos.51372179, 51772224)the Open Projects Foundation of Yangtze Optical Fiber and Cable Joint Stock Limited Company (YOFC)(No.SKLD1705)。
文摘The surface-enhanced Raman scattering(SERS) optical fiber probes were successfully prepared by self-assembling on polyelectrolyte multilayers. Gold nanorods(Au NRs) were used as SERS enhancement material to give excellent biological affinity and stability to the SERS optical fiber probes. Au NRs were synthesized by seed growth method. The synergistic effect between AgNO_(3) and surfactant was investigated, and the highest yield was found when AgNO_(3) was 500 uL. Meanwhile, different SERS optical fiber probes were obtained by selecting silane coupling agent, polyelectrolyte multilayer and graphene oxide(GO) to treat quartz fiber. It was found that the SERS optical fiber probes obtained by the self-assembled on polyelectrolyte multilayers method performed better than those by other methods. In addition, Mapping was combined with finite element simulation to analyze the electromagnetic field distribution at the fiber end face.The electromagnetic field distribution of Au NRs was investigated, the difference of electromagnetic field intensity around the Au NRs with different arrangements was compared, the strongest signal was obtained when the Au NRs were head-to-head. Finally, sensitivity of the optimized SERS optical fiber probes could reach 10^(-9)mol/L, with excellent stability and repeatability.
基金Funded by the Swiss National Science Foundation (No.pp002-68678)the China Scholarship Council Program (No.2006180267)
文摘We report the synthesis of gold nanorods （NRs） by seed-mediated growth method. A small amount of different shapes such as triangles, hexagons and a large amount of rods are obtained by varying the proportion of seed to metal salt, adding NaOH to growth solution as well as using the seed solution of CTAB-capped agent. The gold nanorod （NR） formation yield is improved. Meanwhile, the growth mechanism of high yield gold NRs is discussed. The high quality single size NRs can be separated from polydisperse samples using surfactant-assisted nanorod self-assembly. The gold NRs synthesized were characterized by transmission electron microscopy （TEM） and UV-vis spectroscopy.
基金We thank the financial support by the National Natural Science Foundation of China (No. 21701168), Liaoning Natural Science Foundation (No. 20170540897),open project Foundation of State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University (No. 201709)Shanxi Province Hundred Talent ProjectBL14B and BL17B beamline of National Facility for Protein Science in Shanghai, Shanghai Synchrotron Radiation Facility for providing the beam time.
文摘We developed a general and effective strategy to afford rod-like [Au25(SPh)5(PPh3)10X2]X2 (X = Cl/Br) nanoclusters, capped by conjugated delocalized pπ electron mediated ligands. The detailed atomic structure of these materials was resolved by synchrotron radiation X-ray diffraction (SRXRD) combined with electrospray ionization mass spectrometry (ESI-MS) and UV–vis analyses. The Au17(SR)3(PPh3)6X2minimum asymmetric unit, with exposed Au atoms at the center, can serve as an important model to understand the transformation of homogold nanoclusters into alloy nanoclusters. The conjugated delocalized pπ electrons of the thiolate ligands can effectively tune the electronic properties of the Au25 kernel, as qualitatively evidenced by the energy gaps measured by UV–vis experiments and density functional theory (DFT) calculations. The delocalized electrons distinctly flow to the orbitals of the Au25 kernel via the S atoms of the aromatic thiolates. The ESI-MS analysis indicates that Au3 clusters are formed during the etching reactions, which provide an opportunity to gain insight into the intriguing conversion pathway of the Aun(PPh3)mXy precursor to the final Au25 nanorods. Finally, the thiophenol-protected Au25 nanorods, immobilized on activated carbon, show good catalytic activity in the aerobic oxidation of glucose to gluconic acid (74% glucose conversion and 100% selectivity for gluconic acid), much higher than that of the aliphatic Au25 analogue. The Au25(SPh)5(PPh3)10X2 catalyst yields a turnover frequency (TOF) of 13.5 s^–1, higher than that of commercial catalysts such as Pd/activated carbon (AC) and Pd-Bi/AC. The insight obtained from this study will support the development and design of efficient nanogold catalysts for special oxidation reactions.
基金supported by the National Natural Science Foundation of China(Nos.21902148,11774036,12174032,and 22071172)the National Key Research and Development Program of China(No.2017YFA0303400)+1 种基金the National Natural Science Foundation of China-Research Grant Council(No.11861161002)K.Y.W.acknowledges the support by the Patrick S.C.Poon endowed professorship.
文摘Accurate researches on the surface plasmon resonance(SPR)-based applications of chiral plasmonic metal nanoparticles(NPs)still remain a great challenge.Herein,a series of chiral plasmonic metal NPs,e.g.,chiral Au nanorods(c-Au NRs),c-Au@Ag core–shell,and c-Au@TiO_(2) core–shell NRs,with different chiroptical activities have been produced.Plasmonic circular dichroism(PCD)bands of c-Au NRs can be precisely tailored by tuning the longitudinal SPR(LSPR)and amount of Au NRs as seeds.Besides,a shift of PCD bands within ultraviolet–visible–near infrared ray(UV–vis–NIR)region can also be achieved through the functionalization of a shell of another metal or semiconductor.Interestingly,chirality transfer from c-Au core to Ag shell leads to new PCD bands at the near-UV region.The tuning of PCD bands and chirality transfer are confirmed by our developed theoretical model.Developing chiral Au NRs-based chiral plasmonic nanomaterials with tunable chiroptical activities will be helpful to understand the structure-direct PCD and to extend circularly polarized-based applications.
文摘在金纳米棒(AuNRs)-Ag^+-甲醛(HCHO)体系中,HCHO快速将Ag^+还原为Ag,Ag包裹在AuNRs表面形成Au@AgNRs,改变了AuNRs周围的电介质环境,导致纵向最大吸收波长(LPAB)红移,同时伴随着溶液的颜色发生显著的变化。据此,发展了一种测定HCHO的快响应、简便、灵敏、选择性的AuNRs比色传感器。该比色传感器的检出限为6.3×10^(-11)(g m L^(-1)),比表面增强拉曼光谱法低,显示很高的灵敏度;尤其是本比色传感器用于水样品中HCHO的测定,结果与固体基质室温磷光法相吻合,展示较高的实用性。此外,探讨了测定HCHO的机理。
