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1.
《中国化学会会志》2017,64(11):1308-1315
In this study, the galvanic displacement reaction between silver and AuCl4 was carried out to synthesize a series of silver nanowire (Ag NW) @ gold nanoparticle (Au NP) hybrid nanowires. The influence of Ag NW @ Au NP hybrid nanowires on the fluorescence properties of the poly (3‐hexylthiophene) (P3HT) was investigated. The particle sizes of Au NPs on the hybrid nanowires could be adjusted by varying the reaction time and the concentration of the HAuCl4 solution. Furthermore, steady‐state fluorescence measurements showed that the fluorescence intensity of the P3HT films was higher on various Ag NW @ Au NP hybrid nanowires compared to that on a bare silicon substrate. This was due to the increase in the intensity of electromagnetic field by the localized surface plasmon resonances of Au NPs and surface plasmon polaritons of Ag NWs from the hybrid nanowires. The results were further confirmed by the Raman spectra of the P3HT films on different substrates.  相似文献   

2.
A key to realizing the sustainable society is to develop highly active photocatalysts for selective organic synthesis effectively using sunlight as the energy source. Recently, metal‐oxide‐supported gold nanoparticles (NPs) have emerged as a new type of visible‐light photocatalysts driven by the excitation of localized surface plasmon resonance of Au NPs. Here we show that visible‐light irradiation (λ>430 nm) of TiO2‐supported Au NPs with a bimodal size distribution (BM‐Au/TiO2) gives rise to the long‐range (>40 nm) electron transport from about 14 small (ca. 2 nm) Au NPs to one large (ca. 9 nm) Au NP through the conduction band of TiO2. As a result of the enhancement of charge separation, BM‐Au/TiO2 exhibits a high level of visible‐light activity for the one‐step synthesis of azobenzenes from nitrobenzenes at 25 °C with a yield greater than 95 % and a selectivity greater than 99 %, whereas unimodal Au/TiO2 (UM‐Au/TiO2) is photocatalytically inactive.  相似文献   

3.
ZHENG  Pengcheng  HU  Juan  SHEN  Guoli  JIANG  Jianhui  YU  Ruqin  LIU  Guokun 《中国化学》2009,27(11):2137-2144
By simply adding ascorbic acid in advance of AgNO3, the size and shape controllable Au/Ag bimetallic nanoparticles (NP) were prepared in the traditional Au growth solution free of seed at room temperature. The size distribution of NP is well uniform with ca. 10%–15% standard deviation in diameter. By changing CTAB concentration, the size and shape of NPs are tunable. After researching the surface‐enhanced Raman spectroscopy (SERS) behavior of the prepared NPs, an enhancement factor varied from 4.3×104 to 1.1×105 was obtained for the NP centered at ca. (64±8) nm. Electrochemical cyclic voltammetric results revealed that the so formed nanoparticles were Au riched Au/Ag bimetallic NP, and this formation might be due to the disproportionation reaction of Au+ prompted by Ag+ and the under potential deposition process of Ag+ on Au.  相似文献   

4.
Purified recombinant green fluorescent protein (GFP) expressed in E. coli was used for single-step synthesis of gold nanoparticles (Au NPs) with extraordinary size specificity in aqueous medium. The fluorescence of GFP offered a probe for concomitant changes in the protein during the course of synthesis, in addition to the monitoring of the time-dependent formation of Au NPs by the surface plasmon resonance. Reaction of AuCl4 with the protein produced spherical Au NPs having diameters ranging from 5–70 nm. Remarkably, addition of 1.0×10−5 M AgNO3 in the medium produced uniform spherical Au NPs with particle diameter of 2.2±0.5 nm. Fluorescence spectroscopic measurements suggest that during synthesis of Au NPs in absence of AgNO3, partial denaturation of the protein occurred resulting in the lowering of fluorescence intensity. On the other hand, when the NPs were synthesized in the presence of AgNO3 complete denaturation of the protein with complete loss of fluorescence could be observed, which was further confirmed by native and sodium dodecyl sulfate (SDS) polyacrylamide gel electrophoresis (PAGE). However, use of AgNO3 only resulted neither in the formation of NPs nor had any significant effect on the fluorescence of GFP.  相似文献   

5.
使用L-半胱氨酸作为连接剂, 利用硼氢化钠原位还原预先吸附在介孔氧化亚铜表面的氯金酸根离子,得到了Au/Cu2O异质结构. 应用X射线粉末衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、X射线光电子能谱(XPS)、紫外-可见(UV-Vis)光谱和N2物理吸附等手段对催化剂进行表征, 并以λ>400 nm的可见光作为光源, 评价了该催化剂光催化降解亚甲基蓝(MB)的活性. 实验结果表明, 直径为4 nm的金颗粒完好地负载在介孔氧化亚铜的表面, 并且介孔氧化亚铜的细微结构与孔径均未发生变化. 研究表明, 以乙醇作为反应溶剂有效抑制了AuCl4-与Cu2O之间的氧化还原反应, 从而有利于氧化亚铜介孔结构的保持及金颗粒的原位还原. 光催化降解亚甲基蓝的结果表明, Au/Cu2O异质结构的光催化活性比纯氧化亚铜光催化活性有明显提高. 推测其光催化性能提高的主要原因如下: 一方面, 金颗粒良好的导电性有利于氧化亚铜表面电子的快速转移, 实现电子-空穴分离; 另一方面, 金颗粒可能存在的表面等离子共振现象加速了光生电子的产生.  相似文献   

6.
Yu-Lun Hung  Yi-You Chen 《Talanta》2010,82(2):516-405
We have developed a simple, colorimetric and label-free gold nanoparticle (Au NP)-based probe for the detection of Pb2+ ions in aqueous solution, operating on the principle that Pb2+ ions change the ligand shell of thiosulfate (S2O32−)-passivated Au NPs. Au NPs reacted with S2O32− ions in solution to form Au+·S2O32− ligand shells on the Au NP surfaces, thereby inhibiting the access of 4-mercaptobutanol (4-MB). Surface-assisted laser desorption/ionization time-of-flight ionization mass spectrometry (SALDI-TOF MS) and inductively coupled plasma mass spectrometry (ICP-MS) measurements revealed that PbAu alloys formed on the surfaces of the Au NPs in the presence of Pb2+ ions; these alloys weakened the stability of the Au+·S2O32− ligand shells, enhancing the access of 4-MB to the Au NP surfaces and, therefore, inducing their aggregation. As a result, the surface plasmon resonance (SPR) absorption of the Au NPs red-shifted and broadened, allowing quantitation of the Pb2+ ions in the aqueous solution. This 4-MB/S2O32−-Au NP probe is highly sensitive (linear detection range: 0.5-10 nM) and selective (by at least 100-fold over other metal ions) toward Pb2+ ions. This cost-effective sensing system allows the rapid and simple determination of the concentrations of Pb2+ ions in real samples (in this case, river water, Montana soil and urine samples).  相似文献   

7.
Silica nanoparticles (NPs) dispersed in an aerated aqueous solution containing Ag+ were irradiated to a dose of 10 kGy using 60Co γ-rays. The typical surface plasmon band of Ag NPs was observed around 400 nm, indicating that even in the presence of dissolved oxygen the reduction of Ag+ occurred by silica NPs. Transmission electron microscopy images indicated that Ag NPs formed on the surface of the silica NPs. The subtraction spectra showed broad absorption around 500 nm with the absorbance depending on the dose. The electrons generated by charge separation from silica NPs with a size of about 12 nm reduce Ag+ to Ag0 and form (Ag0) n species on the silica NPs, and the type of (Ag0) n species formed depended on the silica NP, and Ag+ contents, and the dose. In the co-presence of organic molecules on the silica NP such as rhodamine, the absorbance of the surface plasmon band of both Ag NPs and rhodamine decreased, indicating the electrons to participate in the reductive decomposition of rhodamine molecules adsorbed on the silica NP. Furthermore, in the case when the silica NPs contained fluorescein molecules, the fluorescein molecules were also decomposed, indicating that the fluorescein molecules adsorbed on the inner surface of the silica NPs. The addition of I2 as an oxidative reagent prevented the decomposition of the fluorescein molecules, indicating that electrons are the main species emitted from irradiated silica NPs.  相似文献   

8.
Xiao Wei Shen 《Talanta》2007,72(4):1432-1437
In this paper, the formation of gold nanoparticles (Au NPs) as a result of the thermo-active redox reaction of chlorauric acid (HAuCl4) and glucose in alkaline medium was identified by measuring the plasmon resonance absorption, localized surface plasmon resonance (LSPR), and transmission electron microscopy (TEM) images, for the formation of Au NPs displays characteristic plasmon resonance absorption bands and corresponding LSPR signals. It was found that the resulted LSPR signals could be easily detected with a common spectrofluorometer. With increasing glucose concentration, the LSPR intensity displays linear response with the glucose content over the range from 2.0 to 250.0 μmol l−1. Thus, a novel assay of glucose was established with the limits of determination (3σ) being 0.21 μmol l−1, and the detection of glucose could be made easily in the serum samples of diabetes sufferers. Mechanism investigations showed that the activation energy and molar ratio of the reaction were 34.8 kJ mol−1 and 3:2, respectively.  相似文献   

9.
We presented a novel electrogenerated chemiluminescence (ECL) biosensor for monitoring the activity and inhibition of protein kinases based on signal amplification using enzyme-functionalized Au NPs nanoprobe. In this design, the biotin-DNA labeled glucose oxidase/Au NPs (GOx/Au NPs/DNA-biotin) nanoprobes, prepared by conjugating Au NPs with biotin-DNA and GOx, were bound to the biotinylated anti-phosphoserine labeled phosphorylated peptide modified electrode surface through a biotin−avidin interaction. The GOx assembled on the nanoprobe can catalyze glucose to generate H2O2 in the presence of O2 while the ECL reaction occurred in the luminol ECL biosensor. At a higher concentration of kinase, there are more nanoprobes on the electrode, which gives a higher amount of GOx at the electrode interface and thus higher electrocatalytic efficiency to the luminol ECL reaction. Therefore, the activity of protein kinases can be monitored by ECL with high sensitivity. Protein kinase A (PKA), an important enzyme in regulation of glycogen, sugar, and lipid metabolism in the human body, was used as a model to confirm the present proof-of-concept strategy. The as-proposed biosensor presents high sensitivity, low detection limit of 0.013 U mL−1, wide linear range (from 0.02 to 40 U mL−1), and excellent stability. Moreover, this biosensor can also be used for quantitative analysis of kinase inhibition. On the basis of the inhibitor concentration dependent ECL signal, the half-maximal inhibition value IC50 of ellagic acid, a typical PKA inhibitor, was estimated, which is in agreement with those obtained using the conventional kinase assay. The simple and sensitive biosensor is promising in developing a high-through assay of in vitro kinase activity and inhibitor screening for clinic diagnostic and drug development.  相似文献   

10.
A simple spectrophotocolorimetric method devoted to the measurement of gold content in nanoparticles (NPs) was developed. It includes two steps: (i) metal gold NPs (Au NPs) are oxidized into the AuCl4 anion using a 5 × 10−2 M HCl-1.5 × 10−2 M NaCl-7 × 10−4 M Br2 solution, next (ii) AuCl4 concentration is measured using a spectrophotometric assay based on the reaction of AuCl4 with the cationic form of Rhodamine B to give a violet ion pair complex. This latter is extracted with diisopropyl ether and the absorbance of the organic complex is measured at 565 nm. The method is linear in the range 6-29 μM of AuCl4 with a limit of detection of 4.5 μM.The analytical method was optimized with respect of bromine excess to obtain complete Au NPs oxidation. The method was applied to two types of Au NPs currently under investigation: citrate-stabilized Au NPs and Au NPs capped with dihydrolipoic acid (Au@DHLA). Both the gold content of Au NPs and the concentration of NPs (using NP diameter measured by transmission electron microscopy) have been calculated.  相似文献   

11.
In this work, a novel multiplex electrochemiluminescence (ECL) DNA sensor has been developed for determination of hepatitis B virus (HBV) and hepatitis C virus (HCV) based on multicolor CdTe quantum dots (CdTe QDs) and Au nanoparticles (Au NPs). The electrochemically synthesized graphene nanosheets (GNs) were selected as conducting bridge to anchor CdTe QDs551-capture DNAHBV and CdTe QDs607-capture DNAHCV on the glassy carbon electrode (GCE). Then, different concentrations of target DNAHBV and target DNAHCV were introduced to hybrid with complementary CdTe QDs-capture DNA. Au NPs-probe DNAHBV and Au NPs-probe DNAHCV were modified to the above composite film via hybrid with the unreacted complementary CdTe QDs-capture DNA. Au NPs could quench the electrochemiluminescence (ECL) intensity of CdTe QDs due to the inner filter effect. Therefore, the determination of target DNAHBV and target DNAHCV could be achieved by monitoring the ECL DNA sensor based on Au NPs-probe DNA/target DNA/CdTe QDs-capture DNA/GNs/GCE composite film. Under the optimum conditions, the ECL intensity of CdTe QDs551 and CdTe QDs607 and the concentration of target DNAHBV and target DNAHCV have good linear relationship in the range of 0.0005–0.5 nmol L−1 and 0.001–1.0 nmol L−1 respectively, and the limit of detection were 0.082 pmol L−1 and 0.34 pmol L−1 respectively (S/N = 3). The DNA sensor showed good sensitivity, selectivity, reproducibility and acceptable stability. The proposed DNA sensor has been employed for the determination of target DNAHBV and target DNAHCV in human serum samples with satisfactory results.  相似文献   

12.
通过一定体积比的CdS和普鲁士蓝(PB)胶体纳米溶液的简单混合,制备了PB/CdS纳米复合物。在共反应剂存在条件下,PB纳米粒子含量较低时,在ITO电极上CdS纳晶的电致化学发光(ECL)强度可以增强3倍左右。PB纳米粒子含量较高时,CdS纳晶的ECL强度则显著降低。详细讨论了PB纳米粒子对CdS纳晶ECL影响的机理。PB纳米粒子对CdS纳晶的ECL增强可用于H2O2传感。该传感器对H2O2响应的线性范围为3.3×10-8~6.5×10-3 mol.L-1(R=0.999 2),检测限为12 nmol.L-1(S/N=3),传感器具有良好的稳定性和重现性。  相似文献   

13.
The NAD(P)H-mediated growth of Au nanoparticles (NPs) in the presence of ascorbic acid, AuCl4-, and cetyltrimethylammonium bromide leads to the formation of shaped NP structures consisting of dipods, tripods, and tetrapods. The shaped particles exhibit a red-shifted plasmon absorbance at lambda = 680 nm, consistent with the existence of a longitudinal plasmon exciton. High-resolution transmission electron microscopy analysis of the tripod and tetrapod structures reveals directional growth along the <211> and <010> directions, respectively. The shaped Au NPs could be generated by a biocatalytic process using alcohol dehydrogenase, NAD+, and ethanol, and the resulting blue color provides a colorimetric test for ethanol.  相似文献   

14.
In this study, we developed a fluorescence assay for the highly sensitive and selective detection of Hg2+ and Pb2+ ions using a gold nanoparticle (Au NP)-based probe. The Hg–Au and Pb–Au alloys that formed on the Au NP surfaces allowed the Au NPs to exhibit peroxidase-mimicking catalytic activity in the H2O2-mediated oxidation of Amplex UltraRed (AUR). The fluorescence of the AUR oxidation product increased upon increasing the concentration of either Hg2+ or Pb2+ ions. By controlling the pH values of 5 mM tris–acetate buffers at 7.0 and 9.0, this H2O2–AUR–Au NP probe detected Hg2+ and Pb2+ ions, respectively, both with limits of detection (signal-to-noise ratio: 3) of 4.0 nM. The fluorescence intensity of the AUR oxidation product was proportional to the concentrations of Hg2+ and Pb2+ ions over ranges 0.05–1 μM (R2 = 0.993) and 0.05–5 μM (R2 = 0.996), respectively. The H2O2–AUR–Au NP probe was highly selective for Hg2+ (>100-fold) and Pb2+ (>300-fold) ions in the presence of other tested metal ions. We validated the practicality of this simple, selective, and sensitive H2O2–AUR–Au NP probe through determination of the concentrations of Hg2+ and Pb2+ ions in a lake water sample and of Pb2+ ions in a blood sample. To the best of our knowledge, this system is the first example of Au NPs being used as enzyme-mimics for the fluorescence detection of Hg2+ and Pb2+ ions.  相似文献   

15.
Plasmonic superstructures (PS) based on Au/SiO2 were prepared for Shell-Isolated Nanoparticle-Enhanced Raman Spectroscopy (SHINERS) in liquid phase applications. These superstructures are composed of functionalized SiO2 spheres with plasmonic Au nanoparticles (NPs) on their surface. Functionalization was performed with (3-aminopropyl)trimethoxysilane, (3-mercaptopropyl)trimethoxysilane and poly(ethylene-imine) (PEI). Of these three, PEI-functionalized spheres showed the highest adsorption density of Au NPs in TEM, UV/Vis and dynamic light scattering (DLS) experiments. Upon decreasing the Au NP/SiO2 sphere size ratio, an increase in adsorption density was also observed. To optimize plasmonic activity, 61 nm Au NPs were adsorbed onto 900 nm SiO2-PEI spheres and these PS were coated with an ultrathin layer (1–2 nm) of SiO2 to obtain Shell-Isolated Plasmonic Superstructures (SHIPS), preventing direct contact between Au NPs and the liquid medium. Zeta potential measurements, TEM and SHINERS showed that SiO2 coating was successful. The detection limit for SHINERS using SHIPS and a 638 nm laser was around 10−12 m of Rhodamine (10−15 m for uncoated PS), all with acquisition settings suitable for catalysis applications.  相似文献   

16.
Azafullerene (C59N) was functionalized using a Mannich‐type reaction and then subsequently condensed with lipoic acid to yield dithiolane‐modified C59N. In the following step, the extended dithiolane moiety from the C59N core was utilized to decorate the azafullerene sphere with gold nanoparticles (Au NPs). The latter were initially stabilized with dodecanothiol (DT ? Au) and then integrated on azafullerene through a ligand exchange reaction with the dithiolane‐functionalized C59N to produce the C59N/DT ? Au nanohybrid. The nanohybrid was fully characterized by spectroscopy and microscopy, revealing the formation of spherical nanoparticles with a diameter in the range of 2–5 nm, as imaged by HR‐TEM. In the electronic absorption spectrum of C59N/DT ? Au nanohybrid, the characteristic surface plasmon band (SPB) of Au NPs was observed, however, it was redshifted compared with that of DT ? Au. The redshift of the SPB is indicative of closer interparticle proximity of Au NPs, in accordance with the formation of aggregated NPs as observed by TEM, in C59N/DT ? Au nanohybrid. Excited‐state interactions in C59N/DT ? Au were probed by photoluminescence assays. It was found that the weak emission of C59N at 819 nm was blueshifted by 14 nm in C59N/DT ? Au, but was stronger in intensity, thus suggesting energy transfer to C59N, within the organic–inorganic C59N/DT ? Au nanohybrid. Finally, with the aid of pump–probe measurements and transient absorption spectroscopy, the formation of the singlet excited state of C59N was identified.  相似文献   

17.
Composite materials of polydopamine (PDA) and gold nanoparticles on glass substrates (Au/PDA@slide) were obtained via a simple chemical process. First, PDA films (PDA@slide) were formed by immersing slides in 20 mg ml−1 dopamine aqueous solution at pH = 8.5 for 1 h. Then, PDA@slide was dipped in 0.02 M chloroauric acid (HAuCl4) aqueous solution for a certain time, Au/PDA@slide being formed. Gold nanoparticles were obtained by the reductive properties of PDA. The morphology and chemical composition of the composite material were characterized using scanning electron microscopy, X‐ray diffraction and X‐ray photoelectron spectroscopy. The catalytic properties of Au/PDA@slide were evaluated using the reduction of 4‐nitrophenol (4‐NP) in the presence of sodium borohydride (NaBH4) aqueous solution at room temperature. The catalytic activity of the optimal Au/PDA@slide was so satisfactory that the reduction of 4‐NP was completed within 10 min. Moreover, the Au/PDA@slide composite material was stable up to five cycles without significant loss of its catalytic activity. In addition, Au/PDA@slide also exhibited photocatalytic ability, photodegrading 2.5 ml of 17.5 mg l−1 methyl orange in 100 min. By measuring the UV–visible absorption bands of Au/PDA@slide, it was proved that the condition of the strongest surface plasmon resonance of Au/PDA@slide was the optimal condition for catalytic reduction of 4‐NP.  相似文献   

18.
We demonstrate the multiple plasmonic effect on the photocurrent properties of photoanodes containing Ag or Au nanoparticles (NPs) loaded onto titanium dioxide film (Ag–TiO2 or Au–TiO2) on Au grating surfaces. Ag–TiO2 or Au–TiO2 nanocomposite particles are prepared by a flame spray pyrolysis route. The structures and morphologies of the prepared products are characterized by high‐resolution transmission electron microscopy. The Ag–TiO2 or Au–TiO2 composite NPs are deposited by spin coating onto the Au grating surfaces. The photoanode electrode is a layered structure of blu‐ray disc‐recordable grating substrate/Au/Ag (or Au)–TiO2/dye/electrolyte/indium‐tin oxide. The plasmonic effect is induced when Ag or Au NPs are located within the propagating surface plasmon (SP) field on the Au grating surface. The short‐circuit photocurrent is increased by exciting the grating‐coupled propagating SP on the Au gratings and is further enhanced by positioning the Ag or Au NPs within the grating‐coupled SP field. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

19.
In this study, we used size-exclusion chromatography (SEC) to evaluate the sizes of Au and Au/Pd core/shell nanoparticles (NPs) that had been subjected to thermal treatment, with the eluted NPs monitored through diode array detection (DAD) of the surface plasmon (SP) absorption of the NPs. In the absence of an adequate stabilizer, thermal treatment resulted in longer retention times for the Au NPs and shorter retention times for the Au/Pd core/shell NPs in the SEC chromatograms. Thus, thermal treatment influenced the sizes of these Au and Au/Pd core/shell NPs, through digestive ripening and Ostwald-type growth, respectively. In addition, the trends in the SP absorption phenomena of the NPs in the eluted samples, as measured using DAD, were consistent with the trends of their size variations, as measured from their elution profiles. In the presence of 3A-amino-3A-deoxy-(2AS,3AS)-??-cyclodextrin (H2N-??-CD) as a stabilizer, the retention times and SP absorptions of the eluted Au and Au/Pd NP samples remained constant. Thus, H2N-??-CD is a good stabilizer against size variation duration the thermal treatment of Au and Au/Pd core/shell NPs. A good correlation existed between the sizes obtained using SEC and those provided by transmission electron microscopy. Therefore, this SEC strategy is an effective means of further searching for suitable stabilizers for NPs, especially those exposed to harsh reaction conditions (e.g., in catalytic reactions).  相似文献   

20.
局域表面等离激元共振(LSPR)显微探针的检测灵敏性主要取决于针尖上修饰的纳米粒子的LSPR性质.本文采用阴离子辅助法,在水溶液中通过调节Au核与Ag+的物质的量之比,实现Au核上不同厚度的Ag壳层包覆,可控地一步合成均一性好、银壳层较厚(≥10 nm)的核壳比不同的球形Au@Ag纳米粒子.通过扫描电镜(SEM)、透射电镜(TEM)及扫描透射电子显微镜X射线能谱(STM-EDS)线扫描分析对不同核壳比的Au@Ag纳米粒子进行形貌组成表征,证实了所合成核壳结构的可控性.将不同核壳比的Au@Ag纳米粒子置于不同折射率溶液中进行纳米粒子介电敏感性的研究,表明7.5 nm Au@28 nm Ag的纳米结构具有最高的品质因子.同时将不同核壳比的Au@Ag纳米粒子置于不同折射率的非导电性基底上进行单颗纳米粒子散射性质的研究,结果表明7.5 nm Au@28 nm Ag纳米粒子适合作为LSPR显微探针的高检测灵敏性纳米结构之一.  相似文献   

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