SPR effect of Au nanoparticles on the visible photocatalytic RhB degradation and NO oxidation over TiO2 hollow nanoboxes

Three-dimensional (3D) TiO₂ hollow structures have attracted much attention due to their unique properties. However, the large bandgap of (3.2 eV) results in the fact that anatase TiO₂ photocatalyst can only be excited by UV light, which only accounts for 3–5% of the solar energy. On considering that nobel metallatic nanomaterials can harvest visible light due to surface plasmon resonance (SPR) effect, in this paper, three kinds of Au nanoparticles with different morphologies, namely Au nanospheres (Au-NSs), Au nanorods (Au-NRs) and Au nanopentogons (Au-NPs) were prepared and used as photosensitizers to modified TiO₂ hollow nanoboxes (TiO₂-HNBs), aiming to explore high efficient visible-light-responsive photocatalyst. The photoreacitivty of Au/TiO₂-HNBs was evaluated by photoctalytic oxidation of Rhodamine B (RhB) and NO under visible irradiation (λ > 420 nm). It was found that the visible photoreactivity of TiO₂-HNBs was greatly enhanced after modified with Au nanoparticles, and TiO₂-HNBs loaded with Au-NRs exhibit the highest visible photocatalytic activity towards both RhB degradation and NO oxidation. Upon visible irradiation, SPR effect induces the production of hot electrons from the Au nanoparticles, which can further transfer to the conduction band of TiO₂-HNBs to produce superoxide radicals (O₂⁻), resulting in an efficient separation of photo-generated electron-hole pairs. The photoreactivity of Au-NRs/TiO₂-HNBs towards RhB degradation almost keeps unchanged even after recycling used for 5 times, indicating that it is promising to be use in practical applications.     

Surface plasmon resonance biosensor based on water-soluble ZnO-Au nanocomposites

A wavelength modulation surface plasmon resonance biosensor based on ZnO-Au nanocomposites for the detection of human IgM was developed. Self-assembly technique has the advantages of flexibility, simplicity and the precise control of film component and was applied to the building of the sensor. The ZnO-Au nanocomposites are in a dumbbell-like shape and can be immobilized on the Au film through 1,6-hexanedithiol by covalent attachment. Meanwhile the activated ZnO nanocrystals can be used to connect protein. The biosensor based on ZnO-Au nanocomposites was used to detect human IgM. Some experimental conditions were examined and optimized. In the selected conditions, the modified biosensor exhibits a satisfactory response for human IgM in the concentration range of 0.30-20.00 μg mL⁻¹. However, the biosensor without ZnO-Au nanocomposites shows a response for human IgM in the concentration range of 1.25-20.00 μg mL⁻¹. Compared with the biosensor based on Au film, when the biosensor based on the ZnO-Au nanocomposites was applied, the sensitivity for determination of human IgM is significantly enhanced.     

Bioinspired synthesis of multifunctional silver nanoparticles for enhanced antimicrobial and catalytic applications with tailored SPR properties

In the developing nanotechnology world, numerous attempts have been made to prepare the nobel metallic nanoparticles (NPs), which can improve their applicability in diverse fields. In the present work, the biosynthesis of silver (Ag) NPs has been successfully achieved through the medicinal plant extract (PE) of G. resinifera and effectively used for the catalytic and antibacterial applications. The size dependant tuneable surface plasmon resonance (SPR) properties attained through altering precursor concentrations. The X-ray and selected area diffraction pattern for Ag NPs revealed the high crystalline nature of pure Ag NPs with dominant (111) phase. The high-resolution TEM images show the non-spherical shape of NPs shifting from spherical, hexagonal to triangular, with wide particle size distribution ranging from 13 to 44 nm. Accordingly, the dual-band SPR spectrum is situated in the UV–Vis spectra validating the non-spherical shape of Ag NPs. The functional group present on the Ag NPs surface was analysed by FT-IR confirms the capping and reducing ability of methanolic PE G. resinifera. Further, the mechanism of antimicrobial activity studied using electron microscope showed the morphological changes with destructed cell walls of E. coli NCIM 2931 and S. aureus NCIM 5021 cells, when they treated with Ag NPs. The Ag NPs were more effective against S. aureus and E. coli with MIC 128 μg/ml as compared to P. aeruginosa NCIM 5029 with MIC 256 μg/ml. Apart from this, the reduction of toxic organic pollutant 4-NP to 4-AP within 20 min reveals the excellent catalytic activity of Ag NPs with rate constant k = 15.69 s^?1.     

Au/Ag复合纳米笼在表面增强拉曼光谱中的应用

表面增强拉曼光谱（SERS）技术是一种基于贵金属纳米结构基底对被检测物进行高灵敏度检测的一种方法.具有特殊纳米结构的贵金属表面受到激光的照射时，金属表面的自由电子会受到极大的振荡，当入射光频率与振荡频率相近时，则会发生表面等离子体共振现象（SPR），使金属表面的局域电场强度极大增强，入射光强度和散射光强度都得到成倍的放大，从而使吸附在贵金属纳米结构表面的分子的拉曼散射信号得到有效的增强.使用NaBH₄还原-酸刻蚀模板法，制备了八面体Au/Ag复合纳米笼，其形貌规整，尺寸均匀约为600 nm，无Cu₂O模板的残留，Au元素均匀负载在Ag纳米笼上，质量分数约为16.8%；Au/Ag复合纳米笼的紫外可见吸收峰相对于Ag纳米笼发生了红移，更重要的是，Au和Ag元素协同赋予了复合纳米笼超高的SERS灵敏度和重复性，Au/Ag复合纳米笼实现了对罗丹明6G的痕量检测（5×10^-14 mol/L），通过时域有限差分法（FDTD）模拟证实：这主要归因于等离子共振作用产生的高电磁场强度；此外，Au元素的加入使Au/Ag复合纳米笼具有优异的抗氧化性和化学稳定性，即使在1%的H₂O₂溶液中浸泡3 h，仍然能够保持优异的SERS性能.八面体Au/Ag复合纳米笼有望成为一种具有应用前景的高灵敏度、高稳定性的SERS基底.     

有序Au/Ag纳米碗阵列的简易制备及其表面增强拉曼散射性能

通过湿法化学合成基于SiO₂胶体晶体的大面积有序Au/Ag纳米碗(Au/AgNB)阵列。首先,在玻璃基板上组装3D SiO₂胶体晶体作为模板。然后,以Au纳米颗粒(AuNP)为种子,通过原位生长法在SiO₂模板上沉积一层Au纳米壳(AuNS)。再通过HCHO还原Ag⁺成Ag⁰,进一步在AuNS表面沉积Ag纳米壳,形成Ag/Au双纳米壳(Ag/AuNS)阵列。最后通过丙烯酸酯改性双向取向聚丙烯(BOPP)膜方便地获得了单层有序反转Ag/AuNB阵列。这种有序Au/AgNB阵列具有更佳的表面增强拉曼散射(SERS)活性,其SERS分析增强因子(AEF)可达2.23×10⁷。     

有序Au/Ag纳米碗阵列的简易制备及其表面增强拉曼散射性能

通过湿法化学合成基于SiO₂胶体晶体的大面积有序Au/Ag纳米碗(Au/AgNB)阵列。首先,在玻璃基板上以3D SiO₂胶体晶体作为模板。然后,在Au纳米颗粒(AuNP)种子的帮助下,通过原位生长方法在模板上沉积一层Au纳米壳(AuNS)。再通过HCHO还原Ag⁺使AuNS表面进一步沉积Ag纳米壳,形成Ag/Au双纳米壳(Ag/AuNS)阵列。通过丙烯酸酯改性双向取向聚丙烯(BOPP)方便地获得了单层有序反转Ag/AuNB阵列。这种有序Au/AgNB阵列具有更佳的表面增强拉曼散射(SERS)活性,其SERS分析增强因子(AEF)可达2.23×10⁷。     

A rapid and simple chemical method for the preparation of Ag colloids for surface-enhanced Raman spectroscopy using the Ag mirror reaction

Colloidal silver (Ag) nanoparticles (AgNP) have been widely used for surface-enhanced Raman spectroscopy (SERS) applications. We report a simple, rapid and effective method to prepare AgNP colloids for SERS using the classic organic chemistry Ag mirror reaction with Tollens’ reagent. The AgNP colloid prepared with this process was characterized using SEM, and the reaction conditions further optimized using SERS measurements. It was found that Ag mirror reaction conditions that included 20 mM AgNO₃, 5 min reaction time, and 0.5 M glucose produced AgNP colloids with an average size of 319.1 nm (s.d ± 128.1). These AgNP colloids exhibited a significant SERS response when adenine was used as the reporter molecule. The usefulness of these new AgNP colloids was demonstrated by detecting the nucleotides adenosine 5′-mono-phosphate (AMP), guanosine 5′-monophosphate (GMP), cytidine 5′-monophosphate (CMP), and uridine 5′-monophosphate (UMP). A detection limit of 500 nM for AMP was achieved with the as-prepared AgNP colloid. The bacterium Mycoplasma pneumoniae was also easily detected in laboratory culture with these SERS substrates. These findings attest to the applicability of this AgNP colloid for the sensitive and specific detection of both small biomolecules and microorganisms.     

亮氨酸与异亮氨酸在金/银核-壳复合纳米粒子上的吸附状态

The Raman spectra and Surface enhanced Raman spectra (SERS) of leucine and isoleucine adsorbed on core-shell Au/Ag nanoparticles were obtained and assigned, and the different Raman peaks resulting from different vibrational models of the isomers忆groups were analysed. In Raman spectra, the leucine’s (ω(CH3)) is at 962, 945, 924 cm-1, (δas(CH3)) at 1408, 1454 cm-1; corresponding values for isoleucine are, 922 cm-1 and 1448, 1420, 1394 cm-1, respectwely. The difference in the peak positions of corresponding groups between leucine and isoleucine is more apparent in the SERS at acidic and basic conditions. The relationship between leucine and isoleucine’s concentration and SERS was interpreted preliminarily and the adsorption model on the core-shell Au/Ag nanoparticle surface was speculated.     

银金硫三元团簇的形成与光过程的硫金敏化

采用激光烧蚀银金硫混合物样品产生团簇离子,用飞行时间质谱仪检测的方法研究了银金硫三元团簇离子的形成。研究表明,银硫二元团簇、金硫二元团簇和银金硫三元团簇同时生成,主要系列有(Ag~2~n~+~1S~n~-~1)^+、(Ag~2~n~-~1S~n)^-、(Ag~2~nAuS~n)^+和(Ag~2~nAuS~n~+~1)^-。将其与感光乳剂中的金硫敏化中心相关联,指出正离子团簇和负离子团簇分别在曝光过程中起着光电子陷阱和正空穴陷阱的作用。     

波长型SPR检测仪的灵敏度探讨

利用自行设计构建的可变入射角的波长型表面等离子体共振(SPR)检测仪, 在不同浓度的蔗糖溶液中测定了不同入射角度(80°~66°)的共振曲线, 经过处理得到共振峰位、半高宽及灵敏度随入射角和样品折射率变化的三维图像. 在此基础上探讨了波长型SPR检测仪的主要参数对仪器性能的影响, 从理论和实验上证明了影响灵敏度的主要因素为共振波长, 并且随着共振波长的增大, 检测灵敏度迅速提高.     

具有SPR效应的Ag/Ag2MoO4材料在可见光区的光催化性能研究

作为一类新兴的光催化材料,钼酸盐纳米材料具有高表面能、多活性位点和高选择性等优点,在可见光催化降解污染物方面有着重要应用,近年来受到广泛关注.作为钼酸盐家族重要的一员,钼酸银在杀菌、表面增强拉曼光谱、气敏材料等方面均有重要应用,但其光催化性能却鲜见报道.这是由于它的光谱响应范围窄和广生载流子分离效率低所致.虽然近来有少量基于钼酸银的复合材料的光催化研究,但催化效果不佳.众所周知,作为自由电子体系,诸多金属纳米粒子,如贵金属、碱金属等,存在表面等离子体共振效应(SPR),使得贵金属,特别是Ag,Au等纳米粒子在可见区域有较强的吸收.利用这一特性,Awazu等将Ag纳米颗粒沉积在TiO2表面,创造性地将SPR应用于光催化反应,开发出在可见光谱区具有宽光谱吸收特征的Ag/TiO2.随后陆续合成出基于SPR效应的Ag@AgCl,Ag/Ag3PO4材料均具有良好的光催化性能.基于此,本文在十二烷基硫酸钠(SDS)的存在下,采用水热法一步合成了具有SPR效应的Ag/Ag2MoO4可见光催化材料,并利用X射线粉末衍射(XRD)、紫外可见漫反射(DRS)、X射线光电子能谱(XPS)和扫描电子显微镜(SEM)等技术对材料进行了表征.系统地探讨了体系pH值、反应时间、表面活性剂用量对产物的晶相和微观形貌等的影响.此外,还利用罗丹明B降解实验考察了上述合成条件对材料可见光催化活性的影响,并通过捕获剂实验深入地研究了起催化作用的活性物种.XRD结果表明,体系的pH值对材料的晶型有极大影响,随着pH由酸性变至中性、碱性,最终得到的钼酸银也由Ag2Mo2O7过渡到Ag2MoO4.SEM图显示在最优条件(pH为7,加入0.5 g SDS,160oC下水热14 h)下制得的钼酸银为八面体的Ag2MoO4,且其表面均匀地分布着Ag纳米颗粒,与XPS图谱结果一致.另外表面活性剂SDS的用量对所合成材料的形貌影响很大.本文可一步得到以八面体Ag2MoO4为主的Ag/Ag2MoO4复合材料,是因为SDS的疏水长链可以诱导Ag2MoO4的各向异性生长.DRS结果表明,Ag2MoO4八面体上Ag颗粒的引入使其在可见光区的吸收明显加强,因而它在可见光下催化降解罗丹明B降解反应活性增加.捕获剂实验结果表明,起决定性作用的活性物种是光生空穴,另外?OH也起了一定作用.     

Studies on surface plasmon resonance and photoluminescence of silver nanoparticles

Silver nanoparticles of different sizes were prepared by citrate reduction and characterized by UV-vis absorbance spectra, TEM images and photoluminescence spectra. The morphology of the colloids obtained consists of a mixture of nanorods and spheres. The surface plasmon resonance (SPR) and photoemission properties of Ag nanoparticles are found to be sensitive to citrate concentration. A blue shift in SPR and an enhancement in photoluminescence intensity are observed with increase in citrate concentration. Effect of addition of KCl and variation of pH in photoluminescence was also studied.     

QCM and EC-SPR Studies of Cytochrome cSelf-assembled on Au Electrode and Enhancement of SPR Signal by Au Nanoparticles

Quartz crystal microbalance(QCM) and cyclic voltammetry(CV) were used to characterize the monolayer of cytochrome c(Cyt c), which was adsorbed on gold film modified with alkanethiol mixed monolayer. A direct comparison of protein surface coverages calculated from QCM and cyclic voltammetric measurements illustrates that the ratio of the electroactive Cyt c to the total surface-confined Cyt cis 34%, which suggests that the orientation is a main factor affecting the electroactivity of Cyt c. Moreover, surface plasmon resonance(SPR) measurement combined with CV “in situ” was used to investigate the conformational change of Cyt c in the redox process. Besides, Au nanoparticles(Au NPs) were adsorbed on the surface of Cyt c. The result indicates that Au NPs promote electron transfer between Cyt c and the gold electrode, and SPR result suggests Au NPs enhance SPR signal.     

AuAg bimetallic nanoparticles film fabricated based on H2O2-mediated silver reduction and its application

A method to fabricate AuAg bimetallic nanoparticles film by H₂O₂-mediated reduction of silver was reported. Gold nanoparticles (Au NPs) were first adsorbed onto the surface of a self-assembled 2-aminoethanethiol monolayer-modified gold film or 3-aminopropyltriethoxysilane (APTES) monolayer-modified quartz slide. Upon further treatment of this modified film with the solution containing silver nitrate (AgNO₃) and H₂O₂, silver was deposited on the surface of Au NPs. The size of the AuAg bimetallic particles could be readily tuned by manipulating the concentration of H₂O₂. Surface plasmon resonance (SPR) was used to investigate the process, the deposition of silver on Au NPs modified gold film resulted in an obvious decrease of depth in the SPR reflectance intensity and minimum angle curves (SPR R-θ curves), which may be utilized for the quantitative SPR detection of the analyte, H₂O₂. Combination of the biocatalytic reaction that could yield H₂O₂ by using the enzyme, glucose oxidase, with the deposition of silver may enable the design of a glucose biosensor by SPR technique. Furthermore, we evaluated the AuAg bimetallic nanoparticles film for their ability to be an effective substrate for surface-enhanced Raman scattering (SERS).     

Spectrophotometric and physicochemical investigations of Congo,alizarin red dyes and BSA interactions with Au,Ag and Au/Ag mix nanoparticles,and their antimicrobial activities

Individual and mix metal nanoparticles of Ag and Au have been prepared by the reducing method where citrate was used as reducing/stabilizing agent. The prepared NPs were characterized with UV/Visible and transmission electron microscopic (TEM) tools. The characteristic peak in UV/Visible at 525, 444 and 531 nm for Au, Ag and Ag/Au mix NPs respectively, gave primary confirmation of prepared NPs. TEM analysis showed the size of nanoparticles as 44.04, 19.78 and 30.93 nm for Ag, Au and Ag/Au mix NPs respectively. Congo and alizarin red dye interactions studies have been performed with prepared NPs to see the removal of the pollutants from water. Congo dye has shown weaker interaction as compared to alizarin due to structural symmetry. Amongst all, the AgNPs have shown maximum 67% and 75% interactions with Congo red and alizarin respectively due to high negative charges on the surface. The Au, Ag and Au/Ag mix NPs have shown stronger interaction with bovine serum albumin (BSA) protein up to 51, 59, 55% respectively, estimated through UV/Vis and physicochemical analysis. The biological evaluations of the prepared NPs have shown their antibacterial activity against Gram + ve and –ve species showing up to 9 cm zone of inhibition. The BSA interaction and antibacterial activity of NPs reveal the importance of NPs in medicinal field.     

纳米金增强SPR检测产毒赭曲霉中PKS基因的特异性碱基

基于双通道表面等离子体子共振(surface plasmon resonance,SPR)传感器,分别采用直接法和金纳米粒子作为传感层的方法,通过检测赭曲霉毒素A(ochratoxin A,OTA)合成初期阶段表达的聚酮合成酶(polyketide synthase,PKS)基因的25个特异性碱基的寡核苷酸链,建立了一种高灵敏、间接检测OTA的新方法.同时考察了6-巯基己醇(6-mercapto-1-hexanol,MCH)作为封闭液对SPR响应信号的影响.结果表明,直接法的检测限为12.5 nmol/L,MCH的加入可使响应信号有所增强,使用金纳米粒子作为传感层的检测下限为0.25 nmol/L,与直接法相比较灵敏度提高了50倍,与以往使用金纳米粒子标记抗体或抗原相比,其作为传感层也能大大提高SPR检测灵敏度,且操作简单易行.     

Chemisorption assembly of Au nanorods on mercaptosilanized glass substrate for label-free nanoplasmon biochip

The fabrication of a localized surface plasmon resonance nanosensor in a chip based format that utilizes Au nanorods (GNRs) as the optical transducer were systematically studied. (3-mercaptopropyl)trimethoxysilane (MPTMS) modified glass substrate offers GNR deposition with maximal sensitivity to local refractive index changes, which subsequently results in better optical recognition of receptor–analyte binding. Kinetics governing the mass transport and chemisorption of nanorods from bulk to solid surface can be dynamically controlled in a predictable fashion. We demonstrate that slight aggregation induced by a low ionic strength (5 mM NaCl) can facilitate the nanorod assembly to result in a dense, well-distributed surface monolayer. In high ionic media (e.g. 40–80 mM), anions present electrostatically bind with the positively charged cetyltrimethylammonium bromide (CTAB) surrounding nanorod surfaces, thereby leading to instability with heavy aggregation in solution. However, once chemically bound on silanized substrates, the nanorods exhibit excellent stability in physiological buffer where high amount of ionic species are present. The fundamental study is followed by demonstration of a practical application of the fabricated biochip in label-free detection based on GNR wavelength shift of the longitudinal palsmon maxima as the optical signature of human IgG model detection.     

Composite Assembly of Silver Nanoparticles with Avidin and Biotinylated AChE on Gold for the Pesticidal Electrochemical Sensing

An amperometric pesticide biosensor has been devised by the composite assembly of silver nanoparticles with avidin and biotinylated acetylcholinesterase (AChE) on gold electrodes modified with a biotin‐terminated self assembly monolayer (SAM). This composite assembly strategy takes use of the biospecific recognition avidin with the biotin from the SAM‐terminals and biotinylated AChE, as well as the electrostatic interaction between silver nanoparticles with negatively charged citrate shell and avidin with encounter charge at pH 7.2. The construction process of the composite interface on gold was monitored by surface plasmon resonance (SPR), and its structure was characterized by attenuated total reflection Fourier‐transform infrared spectra, atomic force microscopy and UV‐vis spectra. The composite interface shows excellent electron transfer ability, as characterized by cyclic voltammetry and electrochemical impedance spectroscopy. Under the optimum conditions a quantitative measurement of organophosphate pesticide dimethoate was achieved with the linear range of 0.05 μM to10 μM and the detection limit 0.01 μM, taken as the concentration equivalent to a 10% decrease in signal. Silver nanoparticles conjugated biotin‐avidin system represents a simple and functional approach to the integration of electrode sensing interface with improved biocompatibility and electron transfer ability, which may provide an analytical access to a large group of enzymes for bioelectrochemical application.     

Partial stripping of Ag atoms from silver bilayer on a Au(111) surface accompanied with the reductive desorption of hexanethiol SAM

The interfacial structures of Ag bilayer prepared by underpotential deposition on Au(111) (Ag(2ML)/Au(111)) were determined by ex situ scanning tunneling microscopy and in situ surface X-ray scattering measurements before and after oxidative adsorption and after reductive desorption of a self-assembled monolayer (SAM) of hexanethiol (C₆SH) in alkaline ethanol solution. While no structural change was observed after oxidative formation of C₆SH SAM on the Ag(2ML)/Au(111) in an ethanol solution containing 20 mM KOH and 0.1 mM C₆SH, some of the Ag atoms in the bilayer were stripped when the SAM was reductively desorbed. Dedicated to Professor J. O’M. Bockris on the occasion of his 85th birthday.     

金纳米棒的表面改性及与H_2O_2的作用

通过调控过氧化氢与金纳米棒相互作用时溶液的H~+和Br~-浓度,考察了过氧化氢刻蚀金纳米棒的条件.通过静电相互作用将聚苯乙烯磺酸钠修饰到带正电的金纳米棒表面,并探讨了表面配体变化对过氧化氢与金纳米棒相互作用的影响,比较了聚苯乙烯磺酸钠浓度改变对过氧化氢刻蚀金纳米棒所引起的等离子体吸收峰的变化.结果表明,过氧化氢与金纳米棒作用过程中,H~+浓度增加可以加快刻蚀反应速率,Br~-起到稳定金离子的作用.采用聚苯乙烯磺酸钠修饰抑制了过氧化氢对金纳米棒的刻蚀,当聚苯乙烯磺酸钠与金纳米棒表面的CTAB完全作用后,复合材料电位接近零,金纳米棒的稳定性降低,继续增加聚苯乙烯磺酸钠的量至电位为负,复合材料稳定性增加.