银纳米棱镜的形成及其光学性能研究

以有机溶剂作为反应介质,聚合物为稳定剂,通过微波辅助溶液法成功地制备了具有特殊光学性能的银纳米棱镜.利用X射线衍射、透射电子显微镜和紫外-可见光谱等手段跟踪反应过程.结果显示,随着反应的进行,银纳米粒子由10nm左右的球形颗粒逐渐转变为具有规则三角形(或缺角的三角形)形貌的纳米棱镜;同时,紫外-可见吸收峰不但显示出明显的量子尺寸效应,而且吸收峰也由单一的等离子共振吸收峰变为多重的多极吸收峰共同存在,胶体溶液也随之显示出不同的颜色.改变反应物的配比、体系的浓度及无机前驱物都会得到位置和峰形各不相同的吸收曲线,从而得到多彩的纳米银胶体溶液.     

Time‐Dependent Surface Plasmon Resonance Spectroscopy of Silver Nanoprisms in the Presence of Halide Ions

Herein, we find that the surface plasmon resonance (SPR) spectra of silver nanoprisms in the presence of halide ions change gradually with reaction time. The changes in the spectra correspond to the shape transformation of silver nanoprisms. There are threshold concentrations of halide ions that initiate the shape‐transformation reaction. The threshold concentrations for Cl^?, Br^?, and I^? are about 3×10^?4 M , 1×10^?6 M , and 1.5×10^?6 M , respectively. Any concentrations of the added halide ions above these thresholds can eventually etch the silver nanoprisms into nanodisks if the reaction time is long enough. The higher the concentration of the halide ions, the higher the etching rate will be. The kinetics of the shape transformation of the silver nanoprisms can be studied by recording their time‐dependent surface plasmon resonance (SPR) spectra on a commercial UV/Vis–NIR spectrometer. The peak positions of in‐plane dipole SPR bands of silver colloids in the presence of chloride and bromide ions can be fitted very well with the biexponential functions. We propose that the fast components of the biexponential behaviors should correlate to the truncating effect on the corners of silver nanoprisms, and the slow component should correlate to the redeposition of the truncated residues onto the basal plane of the nanoplates.     

Spectroscopy vs. Electrochemistry: Catalyst Layer Thickness Effects on Operando/In Situ Measurements

In recent years, operando/in situ X-ray absorption spectroscopy (XAS) has become an important tool in the electrocatalysis community. However, the high catalyst loadings often required to acquire XA-spectra with a satisfactory signal-to-noise ratio frequently imply the use of thick catalyst layers (CLs) with large ion- and mass-transport limitations. To shed light on the impact of this variable on the spectro-electrochemical results, in this study we investigate Pd-hydride formation in carbon-supported Pd-nanoparticles (Pd/C) and an unsupported Pd-aerogel with similar Pd surface areas but drastically different morphologies and electrode packing densities. Our in situ XAS and rotating disk electrode (RDE) measurements with different loadings unveil that the CL-thickness largely determines the hydride formation trends inferred from spectro-electrochemical experiments, therewith calling for the minimization of the CL-thickness in such experiments and the use of complementary thin-film control measurements.     

Single‐Molecule Spectroscopy on a Ladder‐Type Conjugated Polymer: Electron–Phonon Coupling and Spectral Diffusion

We employ low‐temperature single‐molecule spectroscopy combined with pattern recognition techniques for data analysis on a methyl‐substituted ladder‐type poly(para‐phenylene) (MeLPPP) to investigate the electron–phonon coupling to low‐energy vibrational modes as well as the origin of the strong spectral diffusion processes observed for this conjugated polymer. The results indicate weak electron–phonon coupling to low‐frequency vibrations of the surrounding matrix of the chromophores, and that low‐energy intrachain vibrations of the conjugated backbone do not couple to the electronic transitions of MeLPPP at low temperatures. Furthermore, these findings suggest that the main line‐broadening mechanism of the zero‐phonon lines of MeLPPP is fast, unresolved spectral diffusion, which arises from conformational fluctuations of the side groups attached to the MeLPPP backbone as well as of the surrounding host material.     

XPS法测量铝箔表面氧化铝的厚度

介绍了一种无需溅射、无需变角，只需一次简单的ＸＰＳ（Ｘ射线光电子能谱）窄扫描，即可根据谱图中氧化态和金属态的相对强度算出铝金属表面氧化铝的厚度。用该法测量了一系列不同方法处理的铝表面氧比铝厚度，并与椭偏法及ＮＲＡ法（核反应分析法）测定结果进行了对比，结果表明，该法是一种简便准确的膜厚测量法。     

Effect of Strain on the Electronic Structure and Phonon Stability of SrBaSn Half Heusler Alloy

This paper presents the strain effects on the structural, electronic and phonon properties of a newly proposed SrBaSn half Heusler compound. Since it is stable considering chemical thermodynamics, we tested its strength against uniform strain w.r.t phonon spectrum and it produces a direct bandgap of 0.7 eV. The direct bandgap reduces to 0.19 eV at −12% strain beyond which the structure is unstable. However, an indirect gap of 0.63 eV to 0.39 eV is observed in the range of +5% to +8% strain and afterwards the strain application destabilizes the structure. From elastic parameters, the ductile nature of this material is observed.     

基板受限条件下聚合物薄膜厚度对结晶的影响研究

通过溶液铸膜方法,用匀胶机(spin-coater)在铝箔基板上制备出一系列具有不同厚度的结晶聚合物聚羟基丁酸酯(PHB)和聚ε-己内酯(PCL)超薄膜.经退火处理后,用差热扫描量热仪(DSC)测试了薄膜厚度对其结晶熔点T_m和结晶温度T_c的影响.结果表明,结晶熔点T_m随超薄膜厚度的减小逐渐减小;在减至一定的厚度时,熔点有突升,至极大值后,随膜厚继续减小熔点又会骤降.而结晶温度T_c则一直随膜厚的减小而逐渐降低.可以认为,结晶聚合物的分子在基板受限作用下,主要是熔融熵的变化导致了熔点的上述变化,而受限条件下的扩散控制结晶使结晶温度降低.     

Ultrafast Spectroscopy of Hydroxy‐Substituted Azobenzenes in Water

Ultrafast UV/Vis pump/probe experiments on ortho‐, meta‐ and para‐hydroxy‐substituted azobenzenes (HO‐ABs), as well as for sulfasalazine, an AB‐based drug, were performed in aqueous solution. For meta‐HO‐AB, AB‐like isomerisation behaviour can be observed, whereas, for ortho‐HO‐AB, fast proton transfer occurs, resulting in an excited keto species. For para‐HO‐AB, considerable keto/enol tautomerism proceeds in the ground state, so after excitation the trans‐keto species isomerises into the cis form. Aided by TD‐DFT calculations, insight is provided into different deactivation pathways for HO‐AB, and reveals the role of hydroxy groups in the photochemistry of ABs, as well as their acetylation regarding sulfasalazine. Hydroxy groups are position‐specific substituents for AB, which allow tuning of the timescale of thermal relaxation, as well as the amount and contribution of the keto species to photochemical processes.     

Ultraviolet-visible and Surface-enhanced Raman Scattering Spectroscopy Studies on Ruthenium Phthalocyanine Monolayer Films Formed on Terephthalonitrile-modified Silver Substrates

A self-assembled monolayer film(SAM) of ruthenium phthalocyanine (RuPe) fabricated on a silver sub-strate premodified with an SAM of terephthalonitrile (TPN) was studied by means of surface-enhanced Ra-man seattering(SERS) and ultraviolet-visible (UV-Vis) speetroseopies. TPN was used as a ligand to linkRuPe since it can not only modify the silver suhstrate but also deliver the nitrile groups protruding from thesilver surface. Therefore, we can explore the relationship between the structure and the orientation of RuPeand the TPN-modified substrate. The UV-Vis spectra indicate a strong interaction between RuPe and TPN inthe composite film. The result is further confirmed by the SERS spectra of RuPe-TPN SAM, in which the vi-brational bands arising from both the RuPe and TPN moieties appear clearly, indicating that the RuPe is suc-cessfully assembled on the TPN film.     

半花菁染料LB膜的铁电性与厚度关系

报道了半花菁染料LB膜铁电性与膜厚度的依赖性.根据所测得的电滞回线发现,矫顽电场(Ec)随薄膜厚度(以薄膜的层数N表示)的增加而减少,在薄膜厚度为30～200 nm的范围内,它们之间的关系可用幂指数公式表示为Ec∝N－4/3,这种关系与其它传统的无机铁电材料完全相同.通过样品介电和铁电性能的测量,以存贮元件的物理参量－优值(Ps/εrEc)作为参比标准,可得铁电半花菁染料LB膜的最佳厚度为60 nm,且其优值的数值与偏氟乙烯-三氟乙烯共聚物P(VdF-TrFE) (n :n=70:30)的优值数值处在同一数量级上.     

Colorimetric Determination Of Hydrogen Peroxide Based on Localized Surface Plasmon Resonance of Silver Nanoprisms Using a Microchannel Chip

Silver nanoprisms (AgNPrs) have unique optical phenomena due to their localized surface plasmon resonance that results in the extinction of light from the visible to the near-infrared spectral region. In this study, we propose the colorimetric determination of silver nanoprisms in microchannels using a smartphone camera. Image acquisition was performed by capturing an image of the colloidal solution of the silver nanoprisms in the microchannel using the transmitted light. Red, green, and blue chromaticity levels were extracted from the recorded images for further quantification of the silver nanoprisms. This technique was employed for the detection and colorimetric determination of hydrogen peroxide (H₂O₂). Good linearity between the change in the green chromaticity level and concentration of hydrogen peroxide was observed for values from 10 to 300?μM with an R² value of 0.9670. We anticipate that the developed methodology for the quantification of silver nanoprisms and hydrogen peroxide by monitoring the change in color in the images of transmitted light will enhance the development of simple, rapid, and reliable detection systems for quality control in the production of silver nanoprisms as well as in chemical sensor applications.     

Characterization of Locally Excited and Charge-Transfer States of the Anticancer Drug Lapatinib by Ultrafast Spectroscopy and Computational Studies

Lapatinib (LAP) is an anticancer drug, which is metabolized to the N- and O-dealkylated products (N-LAP and O-LAP, respectively). In view of the photosensitizing potential of related drugs, a complete experimental and theoretical study has been performed on LAP, N-LAP and O-LAP, both in solution and upon complexation with human serum albumin (HSA). In organic solvents, coplanar locally excited (LE) emissive states are generated; they rapidly evolve towards twisted intramolecular charge-transfer (ICT) states. By contrast, within HSA only LE states are detected. Accordingly, femtosecond transient absorption reveals a very fast switching (ca. 2 ps) from LE (λ_max=550 nm) to ICT states (λ_max=480 nm) in solution, whereas within HSA the LE species become stabilized and live much longer (up to the ns scale). Interestingly, molecular dynamics simulation studies confirm that the coplanar orientation is preferred for LAP (or to a lesser extent N-LAP) within HSA, explaining the experimental results.     

纳米银对表面吸附甲基橙分子的光谱学性质的影响

甲基橙溶液中引入纳米银胶,甲基橙分子的π-π*和n-π*电子跃迁吸收蓝移。随着纳米银胶浓度增加,S2-S0跃迁荧光发射强度不断下降,发射峰红移,而S1-S0跃迁荧光发射强度不断增加。纳米银对pH=2.1的甲基橙溶液的S1-S0跃迁荧光发射强度增强高于pH=6的甲基橙溶液。采用透射电子显微镜、紫外-可见吸收分光光度计和荧光分光光度计等手段从局域场增强、分子间的相互作用和能量传输等方面初步探讨了纳米银胶对表面吸附甲基橙分子光谱学性质影响机制。     

用XPS法精确测量硅片上超薄氧化硅的厚度

简单介绍了硅片表面超薄(0.3～8nm)氧化硅厚度的XPS测量方法。方法根据XPS测得的元素硅和氧化硅的Si2p谱线强度,使用较简单的厚度分析公式计算。本文还介绍了厚度分析公式中两个关键参数(光电子衰减长度LSiO2和氧化硅纯硅体材料的Si2p电子强度比R0)的理论计算和实验测量方法。此外,文中还介绍了用XPS测量厚度的实验步骤,包括样品方位角和光电子发射角的选择以及XPS数据处理方法。使用上述XPS测量方法,目前对于超薄SiO2的厚度测量不确定度已可达到1%。     

Probing Effect of Solvation on Photoexcited Quadrupolar Donor-Acceptor-Donor Molecule via Ultrafast Raman Spectroscopy

The symmetric and quadrupolar donor-acceptordonor (D-A-D) molecules usually exhibit excitedstate charge redistribution process from delocalized intramolecular charge transfer (ICT) state to localized ICT state. Direct observation of such charge redistribution process in real-time has been intensively studied via various ultrafast time-resolved spectroscopies. Femtosecond stimulated Raman spectroscopy (FSRS) is one of the powerful methods which can be used to determine the excited state dynamics by tracking vibrational mode evolution of the specific chemical bonds within molecules. Herein, a molecule, 4, 4′-(buta-1, 3-diyne-1, 4-diyl)bis(N, N-bis(4-methoxyphenyl)aniline), that consists of two central adjacent alkyne (-C≡C-) groups as electron-acceptors and two separated, symmetric N, N-bis(4-methoxyphenyl)aniline at both branches as electron-donors, is chosen to investigate the excited-state photophysical properties. It is shown that the solvation induced excited-state charge redistribution in polar solvents can be probed by using femtosecond stimulated Raman spectroscopy. The results provide a fundamental understanding of photoexcitation induced charge delocalization/localization properties of the symmetric quadrupolar molecules with adjacent vibrational markers located at central position.

     

粗糙化银电极上氰基钴胺素的电化学行为

比较研究氰基钴胺素在光滑和粗糙化银电极上的电化学行为，发现在光滑银电极上氰基钴胺素的还原为一个二电子过程，而在粗糙化银电极上则为两个一电子过程，其原因是由于粗糙化银电极对氰根的强吸附作用。     

银岛膜中银颗粒间表面电磁波的耦合

自从Hartstcil。等人用衰减全反射技术（AT则得到覆盖在银岛膜上的有机超薄膜的表面增强红外吸收光谱以来山，对其增强机理及应用的研究一直是人们关注的热点．人们不论是从实验上还是从理论上都通过种种努力来探索表面增强红外光谱的机理，但仍然没有给出一个清晰的图象．一般     

左心室厚度的声学超声造影评估效果分析

本文探究了声学超声造影评估左心室厚度的效果,旨在提高临床测量室壁厚度的准确度。选取2018年1月~2019年5月我院心内科患者94例为研究对象,按照随机数表法将患者分为两组,对照组47例,接受二维超声心动图检测,观察组47例,接受左心声学造影检测。将左心室室壁划分为18节段,比较两组患者检测结果的准确度差异。比较两组患者心尖两腔(A2CH)切面舒张期全部阶段以及收缩期3、6、15、18阶段室壁厚度,差异具有统计学意义(P<0.05);两组患者心尖三腔(A3CH)切面舒张期4、10、13、16阶段以及收缩期4、10、16阶段室壁厚度比较,差异具有统计学意义(P<0.05);两组患者心尖四腔切面(A4CH)切面舒张期5、14、17阶段以及收缩期5、17阶段室壁厚度比较,差异具有统计学意义(P<0.05)。二维超声心动图检测在舒张期1、2、7、8、11节段以及收缩期1、2、7、8、9、11、12、13、14节段的测量结果准确可靠,而左心声学造影检测能提供更为准确的左心室厚度指标,对提高临床对左心室室壁厚度检测的准确度具有重要意义。     

火焰原子荧光光谱法测定矿石样品中的银

为满足矿产资源领域地质找矿的检测工作需要,寻找一种操作便捷、重现性好、检出限低的检测方法,进行银元素的定量分析测试。通过对样品取样重量、复溶盐酸用量等参数进行条件优化试验,选出最优前期处理条件;对火焰原子荧光光谱仪进行条件试验,针对灯电流、燃气气流量等关键参数进行单一变量试验,最终确立了仪器最佳测试条件;测试方法精密度为精密度为1.80%～4.52%,准确度为0.46%～1.82%,检出限为0.4g/t。本方法具有稳定性好,灵敏度高,分析效率快等特点,适合在样品量多、精度要求高的实验室间推广。