Design of a peptide linker group to increase the surface enhanced Raman spectroscopy signal intensity of a rhodamine-nanoparticle system

The surface enhanced resonance Raman spectra of three modified carboxy-x-rhodamine dyes were recorded using Au nanoparticles and an excitation laser operating at 670 nm. The dyes were modified with a linker group designed both to increase the surface enhanced Raman spectroscopy signal and to couple the dye to the Au nanoparticles surface. The maximum signal intensity was recorded for a Cys-Gly linker with Cys thiol group acting as the coupling point to the Au surface and Gly-NH₂ group used to attach the carboxy-x-rhodamine dye. This gave a signal intensity in the 1503 cm⁻¹ Raman peak that was more than 20 times greater than for the unmodified dye. The Au nanoparticles used had a diameter of 49.8 ± 1.2 nm and were synthesised by the citrate reduction method.     

Photoreduction kinetics of sodium tetrachloroaurate under synchrotron soft X-ray exposure

We report on the time evolution of the sodium tetrachloroaurate (NaAuCl(4)) chemical properties as a function of soft X-ray exposure in a dried sample on a silicon surface using X-ray photoelectron spectroscopy (XPS). Our investigations provide mechanistic insight into the photoreduction kinetics from Au(III) to Au(I) and then Au(I) to Au(0). We unambiguously show that XPS photoreduction occurs in stepwise fashion via the Au(I) state. Both photoreduction steps undergo first-order kinetics.     

Binary Au/MWCNT and Ternary Au/ZnO/MWCNT Nanocomposites: Synthesis,Characterisation and Catalytic Performance

Gold nanoparticles of 10–24 and 5–8 nm in size were obtained by chemical citrate reduction and UV photoreduction, respectively, on acid‐treated multiwalled carbon nanotubes (MWCNTs) and on ZnO/MWCNT composites. The shape and size of the deposited Au nanoparticles were found to be dependent upon the synthetic method used. Single‐crystalline, hexagonal gold particles were produced in the case of UV photoreduction on ZnO/MWCNT, whereas spherical Au particles were deposited on MWCNT when the chemical citrate reduction method was used. In the UV photoreduction route, n‐doped ZnO serves as the e^? donor, whereas the solvent is the hole trap. All materials were fully characterised by UV/Vis spectroscopy, scanning electron microscopy, transmission electron microscopy, X‐ray photoelectron spectroscopy, Raman spectroscopy and BET surface analysis. The catalytic activity of the composites was studied for the selective hydrogenation of α,β‐unsaturated carbonyl compound 3,7‐dimethyl‐2,6‐octadienal (citral). The Au/ZnO/MWCNT composite favours the formation of unsaturated alcohols (selectivity=50 % at a citral conversion of 20 %) due to the presence of single‐crystalline, hexagonal gold particles, whereas saturated aldehyde formation is favoured in the case of the Au/MWCNT nanocomposite that contains spherical gold particles.     

Laser-assisted synthesis of Au-Ag alloy nanoparticles in solution

By using laser-induced heating, we prepared Au-Ag nanoalloys via three different procedures: (i) mixture of Au nanoparticles and Ag(+) ions irradiated by a 532 nm laser, (ii) mixture of Au and Ag nanoparticles irradiated by a 532 nm laser, and (iii) mixture of Au and Ag nanoparticles irradiated by a 355 nm laser. Procedure i is advantageous for the production of spherical alloy nanoparticles; in procedures ii and iii, nanoalloys with a sintered structure have been obtained. The morphology of the obtained nanoalloys depends not only on the laser wavelength but also on the concentration of nanoparticles in the initial mixture. When the total concentration of Ag and Au nanoparticles in the mixture is increased, large-scale interlinked networks have been observed upon laser irradiation. It is expected that this selective heating strategy can be extended to prepare other bi- or multi-metallic nanoalloys.     

金负载氧化石墨烯/PDPB复合材料用于同步去除六价铬离子和苯酚

近年来,电镀和染料行业工业废水中排放的有机污染物和重金属离子严重危害着环境.构建无机-有机新型纳米材料用于光催化去除重金属离子和有机污染物受到了广泛的关注.共轭聚合物因其低廉的制造成本,快速的电子传送能力,优秀的电化学性能和高的机械性能,它们作为一类新能源材料已经快速发展起来.Remita等使用软模板方法制备的一种共轭聚合物聚1,4-二苯基丁二炔(PDPB)在可见光下对苯酚表现出较好的去除率.然而,聚合物PDPB的一些缺陷限制了其应用,比如高的疏水特性和快速的光生电子-空穴复合.因此,我们引入氧化石墨烯(GO)和金纳米粒子来提高PDPB的光催化活性.通过简单的机械搅拌和光还原方法制备了Au-GO/PDPB复合材料.通过TEM,XRD,XPS,固体紫外和光电流测试等技术对催化剂进行了一系列表征,结果发现氧化石墨烯作为优秀的电子传送基地,金纳米粒子作为电子捕获剂,在空间上实现了电子空穴的空间隔离,从而大大提高了Au-GO/PDPB复合材料对于六价铬离子和苯酚的同步光去除的光催化活性.XPS表征和TEM图像表明了GO和Au纳米粒子的存在.其PDPB有着纳米纤维的结构,宽度在20 nm左右,长度在几个微米.当复合了氧化石墨烯后,可以明显看出氧化石墨烯的形态,进一步光还原负载金纳米粒子,同样可以在TEM图中观察到金纳米粒子的存在,其直径在10 nm左右.之后通过光催化同步去除六价铬离子和苯酚来探究Au-GO/PDPB复合材料的活性,结果表明所制备的Au-GO/PDPB比纯的PDPB有着增强的光催化活性在同步光去除六价铬离子(Cr(VI))和苯酚中.更进一步地是,我们同样确定了GO和Au纳米离子的最佳负载量,结果发现,Au1-GO2/PDPB复合材料(金的负载量为1 wt%,氧化石墨烯的负载量为2 wt%)在所有催化剂中有着最好的光催化活性,其在4 h内对苯酚的去除率达到49.4%,相应的对于六价铬离子的还原率达到了77.4%.我们的研究提供了一种构建有机-无机杂化复合材料的方法,其在太阳光下对于有机污染物和重金属离子的同步去除有着高的光催化活性.     

Intermediate phase upon alloying Au–Ag nanoparticles under laser exposure of the mixture of individual colloids

The dynamics of Au–Ag alloy formation under laser irradiation of a mixture of the monometallic colloidal solutions are experimentally investigated and the factors influencing the alloy genesis are determined. Ag or Au nanoparticles are obtained by laser ablation of the corresponding metals in water or ethanol. Evidence is presented for the formation of an intermediate Au–Ag phase characterized by a transient red-shifted absorption peak. The changes in absorption spectrum and morphology of the colloidal particles are studied as a function of exposure time to laser radiation. It is found that the rate of alloying depends on both the concentration of nanoparticles and the presence of surface-active substances.     

Surface-enhanced Raman scattering of p-aminothiophenol on a Au(core)/Cu(shell) nanoparticle assembly.

Surface-enhanced Raman scattering (SERS) of p-aminothiophenol (PATP) molecules adsorbed onto assemblies of Au(core)/Cu(shell) nanoparticles is reported. We compare it with the SERS spectrum of PATP adsorbed onto gold nanoparticles: both the absolute and relative scattered intensities of various bands in the two spectra are very different. The difference in relative intensity can be ascribed to chemical effects; the chemical enhancement ratio of the two substrates is approximately 3-5. A theoretical analysis based on a charge-transfer model is carried out, which yields a consistent result and shows that the difference in chemical enhancement is mainly due to the state densities and Fermi levels of the substrates. The difference in absolute intensity originates from electromagnetic (EM) enhancement. EM enhancement of Au(core)/Cu(shell) nanoparticles is unlike that of single-component gold or copper SERS-active substrates. The core/shell particle size for optimal enhancement is about 20 nm in the case of a 632.8 nm incident laser (the size ratio of the core and shell layers is about 0.6).     

Space-Selective Precipitation of Au Nanoparticles Inside Silica Gel

Au colloids were prepared by irradiation with a Nd:YAG laser. Au nanoparticles were characterized by absorption spectra, transmission electron microscopy (TEM) and X-ray diffraction (XRD) analysis. It is found that the wavelength of the laser has no effect on the size but the number of the Au nanoparticles. By irradiating a transparent silica gel doped with gold ions with the focused laser in the gel and subsequent exposing in air, a space-selective pattern of letter “P” consisting of Au nanoparticles was observed inside the silica gel.     

表面增强拉曼散射强度与金纳米粒子粒径关系

表面增强拉曼散射（SurfaceenhancedRamanscattering,简称SERS）的增强机理主要分为两类’‘－‘’：电磁增强和化学增强．通常SERS活性表面的获得需要粗糙化．MOSkovitS最先提出,可将粗糙化的SERS活性表面模型化为平整金属基底上排列的金属胶体粒子“’．这样的模型与实际体系比较符合,同时给理论处理提供了便利．在这一模型基础之上,人们提出了一系列SERS电磁增强的理论计算方法’‘－“．在这些理论计算中,大多包含有SERS强度与粒径关系的结果．粒径对SERS强度的影响体现在两方面：1）SERS与粗糙度有关,粒径可视为粗…     

Mechanism of laser-induced size-reduction of gold nanoparticles as studied by nanosecond transient absorption spectroscopy

Gold nanoparticles with an average diameter of approximately 8 nm (Au approximately 15,000) were irradiated with a tightly focused pulse laser at 355 nm in an aqueous solution of sodium dodecyl sulfate (SDS). Transient absorption spectra of the solution were measured at 25-100 ns after the laser irradiation. The observed transient absorption around 720 nm is assignable to the 2p <-- 1s transition of solvated electrons produced via multiple ionization of the gold nanoparticles. The nascent charge state of the gold nanoparticles was estimated from the transient absorbance. The dependence of the charge state on the SDS concentration shows a gradual increase from approximately +60 to approximately +70 in the 2 x 10(-4) to 3 x 10(-4) M range and an abrupt increase up to approximately +710 at the critical micelle concentration (CMC) of SDS, 8 x 10(-3) M. TEM measurements after laser irradiation reveal that the gold nanoparticles fragment into Au(approximately 1000) at a SDS concentration of 3 x 10(-4) M, whereas they are significantly dissociated into Au(approximately 100) above the CMC. The observed correlation between the nascent charge states and the extent of size reduction of the gold nanoparticles after the laser treatment indicates that the size reduction is caused by the Coulomb explosion of the highly charged gold nanoparticles. The mechanism of laser-induced size reduction is quantitatively discussed based on the liquid drop model.     

Photoinduced electron transfer between chlorophyll a and gold nanoparticles

Excited-state interactions between chlorophyll a (Chla) and gold nanoparticles have been studied. The emission intensity of Chla is quenched by gold nanoparticles. The dominant process for this quenching has been attributed to the process of photoinduced electron transfer from excited Chla to gold nanoparticles, although because of a small overlap between fluorescence of Chla and absorption of gold nanoparticles, the energy-transfer process cannot be ruled out. Photoinduced electron-transfer mechanism is supported by the electrochemical modulation of fluorescence of Chla. In absence of an applied bias, Chla cast on gold film, as a result of electron transfer, exhibits a very weak fluorescence. However, upon negatively charging the gold nanocore by external bias, an increase in fluorescence intensity is observed. The negatively charged gold nanoparticles create a barrier and suppress the electron-transfer process from excited Chla to gold nanoparticles, resulting in an increase in radiative process. Nanosecond laser flash experiments of Chla in the presence of gold nanoparticles and fullerene (C60) have demonstrated that Au nanoparticles, besides accepting electrons, can also mediate or shuttle electrons to another acceptor. Taking advantage of these properties of gold nanoparticles, a photoelectrochemical cell based on Chla and gold nanoparticles is constructed. A superior performance of this cell compared to that without the gold film is due to the beneficial role of gold nanoparticles in accepting and shuttling the photogenerated electrons in Chla to the collecting electrode, leading to an enhancement in charge separation efficiency.     

Morphology and optical properties of thin silica films containing bimetallic Ag/Au nanoparticles

We have studied the optical spectra in the UV and visible regions, the morphology by scanning electron microscopy (SEM), and the X-ray photoelectron spectra (XPS) of bimetallic Ag/Au nanoparticles incorporated into transparent silicate films in the sol-gel transition stage. The bimetallic nanoparticles, obtained by a combination of photoreduction and thermal reduction, form structures of the alloy or core-shell type. Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 44, No. 6, pp. 348–353, November–December, 2008.     

Nanoparticle MALDI-TOF mass spectrometry without fragmentation: Au25(SCH2CH2Ph)18 and mixed monolayer Au25(SCH2CH2Ph)(18-x)(L)(x)

Intact molecular ions of the organothiolate-protected nanoparticle Au25(SCH2CH2Ph)18, including their isotopic resolution, can be observed at 7391 Da as 1- and 1+ ions in negative and positive mode, respectively, by MALDI-TOF mass spectrometry when using a tactic of threshold laser pulse intensities and trans-2-[3-(4-tert-butylphenyl)-2-methyl-2-propenylidene]malononitrile (DCTB) as matrix. Previous MALDI-TOF studies of Au nanoparticles using other matrices have encountered extensive fragmentation of nanoparticle as well as thiolate ligands. Absence of fragmentation enables precise determination of the distribution of mixed monolayer compositions on nanoparticles prepared by ligand exchange reactions and by synthesis using thiol mixtures. Reaction conditions producing mixed monolayers containing only one or a small number of usefully functional ligands can be readily identified. At increased laser pulse intensity, the first fragmentation step(s) for the Au25(SCH 2CH2Ph)18 nanoparticle results in losses of AuL units and, in particular, loss of Au4(SCH2CH2Ph)4.     

Ag_核Au_壳金属复合纳米粒子的制备及表面增强拉曼光谱研究

在已制备好的Ag纳米粒子表面,通过化学还原的方法沉积生长Au包裹层,制备了粒子尺寸为50-70nm的Ag核Au壳复合纳米粒子.通过改变AuCl₄^-量,使Ag_100-xAu_x中Au的含量由x=0变为x=30.用UV-Vis吸收光谱和透射电子显微镜(TEM)对该结构纳米粒子进行了表征,并以对巯基苯胺(PATP)为探针分子进行表面增强拉曼光谱(SERS)研究.表面拉曼光谱表明,该结构的纳米粒子具有比Ag更强的SERS活性,随着Au:Ag比例的逐渐增加,其活性呈现先增大后减小的趋势,其最大增强约为Ag纳米粒子的10倍.     

水溶液中碳纳米管的表面增强拉曼光谱研究

合成了碳纳米管和金纳米颗粒的复合物, 测量了水溶液相中复合物的表面增强拉曼光谱, 结果表明, 碳纳米管的巯基化修饰可以提高碳纳米管与金纳米颗粒复合的效率, 随着金纳米颗粒负载量的增加, 碳纳米管的拉曼信号逐渐增强. 加入己二胺分子可以减小金纳米颗粒之间的距离使表面增强效应更显著, 碳纳米管的拉曼光谱得到进一步的增强. 还可进一步在复合体系中加入对巯基苯胺和罗丹明B等小分子拉曼探针, 利用金纳米颗粒的表面增强效应, 这种多元复合体系有望作为多通道拉曼成像探针材料.     

ZnO纳米粒子的表面光电压谱和光催化性能

采用焙烧前驱物碱式碳酸锌的方法制备了不同粒径的ZnO纳米粒子，而用粒径 最小的作为光催化剂，通过光还原过程分别得了贵金属质量分数为0.5%和0.75%的 Pd/ZnO或Ag/ZnO复合纳米粒子。利用XRD，TEM，XPS，SPS和EFISPS等测试技术对样 品进行了表征，并通过光催化氧化气相正庚烷评估了样品的光催化活性，考察了微 晶尺寸和贵金属Pd或Ag的沉积对ZnO纳米粒子表面光电压信号以及光催化活性的影 响，探讨了样品表面光电压谱与其光催化活性的关系，说明了可以通过表面光电压 谱的测试来初步地评估纳米粒子的光催化活性。结果表明：随着ZnO纳米微晶尺寸 的减小，其SPS信号强度逐渐变弱，而光催化活性逐渐升高；沉积适量的贵金属Pd 或Ag后，ZnO纳米粒子的SPS信号强度明显下降，而其光催化活性却有所升高。此外 ，对ZnO纳米粒子光催化剂的失活机理进行了分析。     

半导体纳米粒子与金纳米粒子间荧光共振能量转移研究

采用水相法合成的CdTe半导体纳米粒子作为能量给体, 通过Schiff碱反应将单链DNA连接到表面. 采用柠檬酸钠还原氯金酸法制取的Au纳米粒子作为能量受体, 通过Au—S键将单链DNA连接到表面. 通过DNA链间的杂交, 构建了荧光共振能量转移体系(FRET). 测定了CdTe-DNA、 探针体系和探针体系+目标DNA的荧光强度. 结果表明, 探针体系的荧光强度最弱, 加入目标DNA后, 体系荧光增强, 表明该体系的构建是成功的.     

Laser-assisted synthesis of superparamagnetic Fe@Au core-shell nanoparticles

A novel method combining wet chemistry for synthesis of an Fe core, 532 nm laser irradiation of Fe nanoparticles and Au powder in liquid medium for deposition of an Au shell, and sequential magnetic extraction/acid washing for purification has been developed to fabricate oxidation-resistant Fe@Au magnetic core-shell nanoparticles. The nanoparticles have been extensively characterized at various stages during and up to several months after completion of the synthesis by a suite of electron microscopy techniques (HRTEM, HAADF STEM, EDX), X-ray diffraction (XRD), UV-vis spectroscopy, inductively coupled plasma atomic emission spectroscopy, and magnetometry. The surface plasmon resonance of the Fe@Au nanoparticles is red shifted and much broadened as compared with that of pure colloidal nano-gold, which is explained to be predominantly a shell-thickness effect. The Au shell consists of partially fused approximately 3-nm-diameter fcc Au nanoparticles (lattice interplanar distance, d = 2.36 A). The 18-nm-diameter magnetic core is bcc Fe single domain (d = 2.03 A). The nanoparticles are superparamagnetic at room temperature (300 K) with a blocking temperature, T(b), of approximately 170 K. After 4 months of shelf storage in normal laboratory conditions, their mass magnetization per Fe content was measured to be 210 emu/g, approximately 96% of the Fe bulk value.     

Au nanoparticle monolayers covered with sol-gel oxide thin films: optical and morphological study

In this work, we provide a detailed study of the influence of thermal annealing on submonolayer Au nanoparticle deposited on functionalized surfaces as standalone films and those that are coated with sol-gel NiO and TiO(2) thin films. The systems are characterized through the use of UV-vis absorption, X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), and spectroscopic ellipsometry. The surface plasmon resonance peak of the Au nanoparticles was found to red-shift and increase in intensity with increasing surface coverage, an observation that is directly correlated to the complex refractive index properties of Au nanoparticle layers. The standalone Au nanoparticles sinter at 200 °C, and a relationship between the optical properties and the annealing temperature is presented. When overcoated with sol-gel metal oxide films (NiO, TiO(2)), the optical properties of the Au nanoparticles are strongly affected by the metal oxide, resulting in an intense red shift and broadening of the plasmon band; moreover, the temperature-driven sintering is strongly limited by the metal oxide layer. Optical sensing tests for ethanol vapor are presented as one possible application, showing reversible sensing dynamics and confirming the effect of Au nanoparticles in increasing the sensitivity and in providing a wavelength dependent response, thus confirming the potential use of such materials as optical probes.