Adsorption of purpald SAMs on silver and gold electrodes: a Raman mapping study

The adsorption modes of 4‐amino‐3‐hydrazino‐5‐mercapto‐1,2,4‐trizole (purpald) self‐assembled monolayers (SAMs) formed on SERS‐active silver and gold electrodes were comparatively studied using surface‐enhanced Raman scattering (SERS), and the self‐assembling procedures were investigated by the Raman mapping technique. Purpald SAMs adopted a titled orientation with S, N2 atoms anchoring to the silver electrode and the  N7H₂ close to the surface, whereas purpald stood up on the gold electrode through S, N5 atoms and with  N8H₂ adjacent to the surface. The density functional theory (DFT) at the level of B3LYP was performed to help explain their different adsorption behaviors on the silver and gold electrodes. Copyright © 2006 John Wiley & Sons, Ltd.     

导线非共线的分子器件输运性质的第一性原理研究

分子器件是电子器件向小体积化发展的极限,分子器件中的电子在输运过程中体现出明显的量子效应,分子导线与分子接触的位置和导线间的角度等器件结构因素都会对分子器件的输运性质产生较大的影响.迄今为止,尚未见利用第一性原理量子输运计算方法研究导线非共线的分子器件输运性质的报道.本文以金-苯(硫醇)-金结构的分子器件为例,利用基于非平衡格林函数理论和密度泛函理论的第一性原理量子输运计算方法对其输运性质进行了系统研究,特别注重于研究随着非共线导线间导线夹角角度的变化及导线和苯(硫醇)分子接触位置的不同对器件输运性质的影响.计算表明,金导线与苯(硫醇)的接触位置及导线的夹角等器件结构细节不仅能够定量地影响金-苯(硫醇)-金分子器件的电流大小,还能够定性地改变器件的输运性质,使得部分器件结构出现负微分电阻效应.研究结果对全面理解分子器件的输运性质具有一定的指导意义.     

一种多组电极的高功率多脉冲气体开关

 设计了一个有3组电极的开关，给出了开关的结构，分析了多组电极共存的可行性和开关内的电场，利用通用电路模拟软件对通过开关的电流进行了计算。此开关在单组电极导通时，耐电压约为50kV，电流100kA以上，电流脉宽约20μs；在间隔1ms，脉宽为μs级的预触发脉冲触发下，开关能在电感负载中产生间隔为1ms的3个电脉冲，实验测得平均峰值电压约38kV，电流约100kA，脉宽约20μs。     

碳纳米管熔接金电极的分子动力学模拟

利用分子动力学模拟方法,研究了单壁碳纳米管与Au电极的高温熔接. 模拟结果表明,用端口吸附了Au团簇的碳纳米管在高温下能很好地与Au电极熔接. 首先将Au团簇放置于碳纳米管开口处进行高温退火,退火温度在1100 K左右,Au团簇部分Au原子进入碳纳米管管内,吸入碳纳米管中的Au原子形成壳层螺旋结构的Au纳米线,管外Au团簇呈无定形结构. 然后将吸附了Au团簇的碳纳米管与Au电极进行熔接,高温退火后,碳纳米管与Au电极表面之间形成了稳固的熔接,熔接最佳温度在800 K左右. 关键词： 碳纳米管 金电极 分子动力学模拟     

Modified titanium surface with gelatin nano gold composite increases osteoblast cell biocompatibility

This study examined the gelatin nano gold (GnG) composite for surface modification of titanium in addition to insure biocompatibility on dental implants or biomaterials. The GnG composite was constructed by gelatin and hydrogen tetrachloroaurate in presence of reducing agent, sodium borohydrate (NabH₄). The GnG composite was confirmed by UV-VIS spectroscopy and transmission electron microscopy (TEM). A dipping method was used to modify the titanium surface by GnG composite. Surface was characterized by scanning electron microscopy (SEM) and energy dispersive X-ray (EDX). The MC-3T3 E1 cell viability was assessed by trypan blue and the expression of proteins to biocompatibility were analyzed by Western blotting. The GnG composite showed well dispersed character, the strong absorption at 530 nm, roughness, regular crystal and clear C, Na, Cl, P, and Au signals onto titanium. Further, this composite allowed MC-3T3 E1 growth and viability compared to gelatin and pure titanium. It induced ERK activation and the expression of cell adherent molecules, FAK and SPARC, and growth factor, VEGF. However, GnG decreased the level of SAPK/JNK. This shows that GnG composite coated titanium surfaces have a good biocompatibility for osteoblast growth and attachment than in intact by simple and versatile dipping method. Furthermore, it offers good communication between cell and implant surfaces by regulating cell signaling and adherent molecules, which are useful to enhance the biocompatibility of titanium surfaces.     

Potential dependent thiocyanate adsorption on gold electrodes: a comparison study between SERS and SHINERS

Potential dependent adsorption of target molecules on electrode surface has long been analyzed by several analytical techniques at the electrochemical interfaces. Here, the adsorption of thiocyanate (SCN⁻) on gold electrodes [Au (111) and Au (poly)] is investigated by electrochemical shell isolated nanoparticle‐enhanced Raman spectroscopy (EC‐SHINERS) and surface‐enhanced Raman spectroscopy. Based on the experimental observation, C − N stretching mode of N‐bound SCN⁻ can be observed around 2080 cm⁻¹ throughout the whole potential range. The band corresponding to ν_C−N of S‐bound SCN⁻ appears as a shoulder at more negative potentials, and as a well‐defined band are more positive potentials. However, the overlapped bands provoke a negative shift in the frequency of S‐bound thiocyanate. Therefore, a change in the calculated Stark slope is observed. Interestingly, SHINERS has been employed to demonstrate the thiocyanate orientation and its effect on Raman spectra. Our results widen the opportunities of SHINERS to unravel the potential‐dependent adsorption behavior of target molecules on single‐crystal electrode surfaces. Copyright © 2016 John Wiley & Sons, Ltd.     

Transport in solid oxide porous electrodes: Effect of gas diffusion

We extend our previous treatment of a mixed ionic electronic conductor membrane, consisting of a porous cathode and anode separated by a thin non-porous layer, to the case where mass transport of molecules in the porous electrodes can be the rate-limiting step. The linearized transport equations for the ion-hole pairs in the solid and of the gas molecules in the pores are characterized by the length scales L_P = √L_d(1 − φ)/Sτ_s and L_g = 2L_p√[τ_sφ/τ(1 − φ)][D_gc_g/D_IEc_i] respectively, where L_d = D_IE/K is the length scale that determines the transition from diffusion limited to surface exchange limited transport in the non-porous electrodes, K is the surface exchange coefficient, D_IE and D_g are the diffusion coefficients of the ion-hole pairs and of the molecules, c_i and c_g are the concentrations of the ions and molecules, S is the pore surface area per unit volume, φ the porosity and τ_s and τ the tortuosities of the solid and pore phases respectively. When L_g L_p, which is the case treated previously, the rate-limiting step in the transport is ionic diffusion and surface exchange. Enhancements in oxygen ion current of two orders in magnitude, over non-porous electrodes, are in principle achievable with porous perovskite MIEC having surface area s = 10⁶ cm⁻¹. When L_g L_p the rate-limiting step is mass transport in the pores and the enhancement in ion current is substantially reduced.     

A practical comparison of surface resistance test electrodes

Four surface resistance test electrodes are compared using a selection of materials under similar test conditions. The results vary considerably with some materials due to variation in surface resistivity. Using a relatively uniform material two concentric ring electrodes compliant with the same standard differed in results by a factor of 1.8. Silver stripe and copper tape electrodes gave results a factor 0.4 and 0.7 compared to the reference electrode. A 2-pin electrode gave results a factor 4.7 greater. The 2 pin probe cannot be expected to give similar results to the other electrodes for materials that have variable resistivity.     

Effects of contact oxidization on the transport properties of Au/ZGNR junctions

The transport properties of the junction assembled by zigzag graphene nanoribbons (ZGNRs) and Au electrode (Au/ZGNR) are investigated using first‐principles calculations. It is found that the Au/ZGNR junction behaves as a typical diode with Schottky barrier at the contact. Our results indicate that although the oxidization at the contact slightly influences the Schottky barrier, the I –V characteristic is effectively modulated. Such effect derives from the impact of the oxidization on the coupling between the ZGNRs and Au electrode.

     

A high figure of merit localized surface plasmon sensor based on a gold nanograting on the top of a gold planar film

We investigate the sensitivity and figure of merit （FOM） of a localized surface plasmon （LSP） sensor with gold nanograting on the top of planar metallic film. The sensitivity of the localized surface plasmon sensor is 317 nm/RIU, and the FOM is predicted to be above 8, which is very high for a localized surface plasmon sensor. By employing the rigorous coupled-wave analysis （RCWA） method, we analyze the distribution of the magnetic field and find that the sensing property of our proposed system is attributed to the interactions between the localized surface plasmon around the gold nanostrips and the surface plasmon polarition on the surface of the gold planar metallic film. These findings are important for developing high FOM localized surface plasmon sensors.     

Optical and electrochemical properties of ordered macroporous gold array on the ITO surface

The electrochemical and optical properties of transparent, two-dimensional macroporous gold film were investigated. Colloidal crystal templates were assembled onto indium-doped tin oxide (ITO) glass surface through vertical depositing method. Following gold electrodeposition, they were removed by dissolution with tetrahydrofuran (THF). The highly ordered macroporous gold array was achieved. It was characterized by scanning electron microscope (SEM) and ultraviolet visible (UV-vis) spectrophotometry. The optical transparency of the gold film was near 25% and fairly constant between 300 and 900 nm. The macroporous gold film electrode was mounted into a thin-layer transmission cell. The electrochemical response was evaluated by thin-layer cyclic voltammograms (CV) of the Fe (CN)₆³⁻/Fe (CN)₆⁴⁻ couple. Thin-layer cell exhibits good shape of waves and nearly symmetric cathodic and anodic waves. E⁰′ value and n of TMPD⁺/TMPD (TMPD is acronyms for N,N,N′,N′-tetramethyl-p-phenylenediamine, and TMPD⁺ is its mono-cation radical) couple were determined. Furthermore, results demonstrated electrolytic equilibrium was faster reached in macroporous gold film than ITO electrode.     

密度泛函理论研究Hg与Auqn(n=1—6, q=0,+1,-1) 团簇的相互作用

采用密度泛函理论中的广义梯度近似对Hg与小团簇Au ^q_n (n=1—6, q=0, +1, -1)的相互作用进行了系统研究. 结果表明,除Au₅^+,-团簇外,前线分子轨道理论可以成功预测大部分Au _n Hg ^q 复合物的最低能量结构. Au_n团簇对Hg的吸附受团簇尺寸大小和团簇所携带电荷的影 关键词： 密度泛函理论 汞 金团簇 吸附能     

Spin-polarizing properties of heterostructures with magnetic nano elements

The problem of electron resonant and non-resonant scatterings on two magnetized barriers is studied in the one-dimension. The transfer-matrix is built up to exactly calculate the coefficient of the electron transmittance through the system of two magnetic barriers with non-collinear magnetizations. The polarization of the transmitted electron wave for resonance and non-resonance transmittances is calculated. The transmittance coefficient and spin polarization can be drastically enhanced and controlled by the angle between the barrier magnetizations.     

A theoretical study of a plasmonic sensor comprising a gold nano-disk array on gold film with a SiO_2 spacer

A plasmonic refractive index(RI) sensor with high RI sensitivity based on a gold composite structure is proposed.This composite structure is constructed from a perfect gold nano-disk square array on a gold film, with a SiO_2 spacer. The reflection spectra of the composite structure, with analyte RI in the range of 1.30 to 1.40, are theoretically studied using the finite-difference time-domain method. The incident light beam is partly coupled to the localized surface plasmons(LSP) of the single nano-disks and partly transferred to the propagating surface plasmons(PSP) by grating coupling. The reflectivity is nearly zero at the valley of the reflection spectrum because of the strong coupling between LSP and PSP. Also, the full width at half maximum(FWHM) of one of the surface plasmon polaritons(SPPs) modes is very narrow, which is helpful for RI sensing. An RI sensitivity as high as 853 nm/RIU is obtained. The influence of the structure parameters on the RI sensitivity and the sensor figure of merit(FOM) are investigated in detail. We find that the sensor maintains high RI sensitivity over a large range of periods and nano-disk diameters. Results of the theoretical simulation of the composite structure as a plasmonic sensor are promising. Thus, this composite structure could be extensively applied in the fields of biology and chemistry.     

A comparative study of electron transport in benzene molecule covalently bonded to gold and silicon electrodes for pioneering the electron transport properties of silicon quantum dot-molecule hybrid polymers

In order to pioneer the electron transport properties of silicon (Si) quantum dot-molecule hybrid polymers, we investigate the electron transport properties of the benzene molecule in silicon (Si) semiconductor electrodes, based on nonequilibrium Green's function (NEGF) method coupled with density functional theory (DFT), in comparison with conventional gold (Au) metal electrodes, with three different anchoring linker groups: thiol for dithiol-benzene (DTB), methylene for dimethyl-benzene (DMB), and direct bonding for benzene (Ph). It is interestingly found that, due to band gap nature of the Si semiconductor electrodes, the molecular junctions with the Si electrodes show no current up to the bias voltage of around 0.8 V. In addition, the DTB molecular junctions in the Si semiconductor electrodes connected with Si–S bond show higher conducting properties than other DMB and Ph molecular junctions directly coupled to the electrodes with the Si–C bonds (DMB < Ph < DTB). The electron transport properties of the molecules in the two different electrodes are analyzed on the basis of the understanding transmission spectra, projected density of states (PDOS), and molecular orbitals. We believe that the use of thiol linker may open new possibility in the molecular electronics with the Si semiconductor electrodes and the Si QD-molecule hybrid polymers concept.     

Performances of RETGEM with resistive electrodes made of kapton foils

THGEM with resistive Kapton electrodes (RETGEM) has been developed to make the THGEM more tolerant to discharges. At higher gains with resistive electrodes, serious discharges may travel to the streamer mode, in contrast to violent sparks in conventional GEMs. These streamers are mild and less dangerous to the detector and the front-end electronics. RETGEM looks very promising, and its basic properties are being studied. Recently we developed and tested the THGEM with electrodes using 20 um thick resistive kapton foils. The new RETGEM performs at a lower discharge current, has a lower discharge probability, and has a good energy resolution of 27% and a high effective gas gain and long-term stability.     

Investigating the impact of internal standard heterogeneity on gold quantification with total reflection X-ray fluorescence: A simulation study

Total reflection X-ray Fluorescence (TXRF) is a powerful analytical tool with high detection sensitivity that has been applied to a variety of biological samples. While its ability to quantify gold nanoparticles (AuNPs) in cancer cells has been demonstrated, the extension to tissue slices would be of interest. To that end, the preservation of the underlying tissue microstructure requires samples to be measured as microtome slices. In this form, internal standard spiking is warranted. Thus, it is important to examine the impact of sample heterogeneity on the TXRF's quantification accuracy. To address these questions, a TXRF spectrometer along with 5 μm thin heterogeneous and homogeneous samples were modeled using TOPAS. The simulation model generated TXRF spectra which were then analyzed to obtain recovery rates of Au in both sample types. The results showed near 100% recovery regardless of the elemental spatial distribution in the samples. This provides insights into the quantification potential for AuNPs inside tumors that are histologically processed into thin tissue slices. In addition, this simulation toolkit provides the first practical means of modeling TXRF spectroscopy which will hopefully be of use to the TXRF community.     

表面等离激元探针的高介电灵敏度与液体折射率测定

利用金纳米棒在光照射下激发表面等离激元的性质,实验研究了其在不同介电环境下的吸收光谱.通过分析纵向等离子体共振吸收峰峰位随介质折射率的变化,获得了金纳米棒表面等离激元探针测量介质折射率的经验公式为n=(385.59)-1(λ/nm-290.56).利用金纳米棒表面等离激元探针的高介电灵敏度,测试了一些未知液体的折射率,并与阿贝折射仪测量法的结果相比较.结果与分析表明,本方法较之阿贝折射仪测量介质折射率的方法具有更高的精密度.因此,表面等离探针可用于拓展大学物理实验中的介质折射率测量实验.     

The effect of semi-infinite crystalline electrodes on transmission of gold atomic wires using DFT

First principle calculations of the conductance of gold atomic wires containing chain of 3–8 atoms each with 2.39 Å bond lengths are presented using density functional theory. Three different configurations of wire/electrodes were used. For zigzag wire with semi-infinite crystalline electrodes, even–odd oscillation is observed which is consistent with the previously reported results. A lower conductance is observed for the chain in semi-infinite crystalline electrodes compared to the chains suspended in wire-like electrode. The calculated transmission spectrum for the straight and zig-zag wires suspended between semi-infinite crystalline electrodes showed suppression of transmission channels due to electron scattering occurring at the electrode-wire interface.     

聚甲基丙烯酸甲酯间隔的金纳米立方体与金膜复合结构的表面增强拉曼散射研究

金属纳米颗粒与金属薄膜的复合结构由于其局域表面等离子体和传播表面等离子体间的强共振耦合作用,可作为表面增强拉曼散射(SERS)基底,显著增强吸附分子的拉曼信号.本文提出了一种聚甲基丙烯酸甲酯(PMMA)间隔的90 nm金纳米立方体与50 nm金膜复合结构的SERS基底,通过有限元方法数值模拟,得到PMMA的最优化厚度为15 nm.实验制备了PMMA间隔层厚度为14 nm的复合结构,利用罗丹明6G (R6G)为拉曼探针分子, 633 nm的氦氖激光器作为激发光源,研究了复合结构和单一金纳米立方体的SERS效应,发现复合结构可以使探针分子产生比单一结构更强的拉曼信号.在此基础上,研究了不同浓度金纳米立方体水溶液条件下复合结构中R6G的拉曼光谱.结果表明,当金纳米立方体水溶液浓度为5.625μg/mL的条件下复合结构中R6G的拉曼信号最强,且可测量R6G的最低浓度达10~(–11) mol/L.