Surface Modification of PTMS Particles with Organosilanes: TEOS-, VTMS-, and MTMS-Modified Particles

The surface modification of phenyltrimethoxysilane (PTMS) particles was performed in an alcoholic solution with tetraethyl orthosilicate (TEOS) and in an aqueous solution with other organoalkoxysilane monomers such as vinyltrimethoxysilane (VTMS) and methyltrimethoxysilane (MTMS). The surface modification with organoalkoxysilane monomers could lead to the improvement in functionality of PTMS particles. In addition, the surface-modified PTMS particles could be made the channeled hollow particles by core dissolution in organic solvents instead of by chemical etching. This resulted from that PTMS particles serving as cores have the selective solubility in organic solvents.     

木材表面改性的XPS分析

利用微波等离子体对木材表面进行处理，并诱导引发接枝甲基丙烯酸甲酯；达到表面改性的效果以提高木质材料的性能，利用X射线光电子能谱(XPS)对木材表面改性前后的表面化学结构进行分析；结果表明：木材经微波等离子体处理，表面氧与碳的原子浓度比(no／nc)增加，产生大量的含氧官能团或过氧化物，从而引发木材与甲基丙烯甲酯单体产生接枝共聚反应。     

Reversible Immobilization of Peptides: Surface Modification and In Situ Detection by Attenuated Total Reflection FTIR Spectroscopy

A generic method is described for the reversible immobilization of polyhistidine‐bearing polypeptides and proteins on attenuated total reflecting (ATR) sensor surfaces for the detection of biomolecular interactions by FTIR spectroscopy. Nitrilotriacetic acid (NTA) groups are covalently attached to self‐assembled monolayers of either thioalkanes on gold films or mercaptosilanes on silicon dioxide films deposited on germanium internal reflection elements. Complex formation between Ni²⁺ ions and NTA groups activates the ATR sensor surface for the selective binding of polyhistidine sequences. This approach not only allows a stable and reversible immobilization of histidine‐tagged peptides (His–peptides) but also simultaneously allows the direct in situ quantification of surface‐adsorbed molecules from their specific FTIR spectral bands. The surface concentrations of both NTA and His–peptide on silanized surfaces were determined to be 1.1 and 0.4 molecules nm^?2, respectively, which means that the surface is densely covered. A comparison of experimental FTIR spectra with simulated spectra reveals a surface‐enhancement effect of one order of magnitude for the gold surfaces. With the presented sensor surfaces, new ways are opened up to investigate, in situ and with high sensitivity and reproducibility, protein–ligand, protein–protein, protein–DNA interactions, and DNA hybridization by ATR–FTIR spectroscopy.     

表面增强拉曼光谱研究吸附态的变化

测量了吡啶分子在电化学处理的银表面和亚甲基蓝分子在硝酸刻蚀银表面的表面增强拉曼光谱（ＳＥＲＳ）．对ＳＥＲＳ谱线的分析结果表明，吡啶分子在较低的表面吸附分子密度时倾向于平躺方式；而在较高的表面分子密度时，则倾向于向垂直吸附态转化．亚甲基蓝分子在较低浓度时主要是平躺吸附，随Ｃｌ－浓度的增加，亚甲基蓝从“平躺”吸附态转向“站立”吸附态．     

Interfacial Behavior of beta-Lactoglobulin at a Stainless Steel Surface: An Electrochemical Impedance Spectroscopy Study

The electrochemical impedance spectroscopy technique was used to investigate the interfacial behavior of beta-lactoglobulin at an austenitic stainless steel surface over the temperature range 299 to 343 K at an open circuit potential. The electrode/electrolyte interface and corresponding surface processes were successfully modeled by applying an equivalent-electrical-circuit approach. A charge-transfer resistance value was found to be very sensitive to the amount of adsorbed protein (surface concentration), thus indicating that the adsorption of the protein (i) was accompanied by the transfer of the charge, via chemisorption, and (ii) influenced the mechanism and kinetics of the corrosion reaction. This was also apparent from the large decrease in the corrosion activation energy (16 kJ mol(-1)) caused by the adsorption of the protein. Adsorption of beta-lactoglobulin onto the stainless steel surface at an open circuit potential resulted in a unimodal isotherm at all the temperatures studied and the adsorption process was described with a Langmuir adsorption isotherm. From the calculated Gibbs free energies of adsorption it was confirmed that beta-lactoglobulin molecules adsorb strongly onto the stainless steel surface. The enthalpy and entropy values indicated that the molecule partially unfolds at the surface upon adsorption. The adsorption process was found to be entirely governed by the change in entropy. Copyright 2000 Academic Press.     

氧化乐果的振动光谱及其表面增强拉曼散射研究

采用ATR-FTIR、FT-拉曼表征了氧化乐果在酸、碱、中性条件下的振动光谱,获得了氧化乐果分子较为全面的结构振动信息;以金/银核-壳粒子为基底,获得了不同浓度及其酸碱条件下氧化乐果的表面增强拉曼散射(SERS)光谱,考察了其分子在该基底表面的吸附状态及其酸碱影响,推测了氧化乐果的SERS机理;结果表明:νas(NH),νas(CH3),Amide Ⅰ,ν( POC ),ν( PO ),ν(C-S)为氧化乐果分子特征振动;中性条件下,氧化乐果浓度低于2.0×10-2 mol/L已无明显SERS,酸、碱条件下,在2.0×10-10 mol/L氧化乐果分子与基底的作用仍显著,尤其酸性的SERS更强;氧化乐果主要以磷酸酯结构与基底表面作用,探讨了酸碱条件下的不同水解历程对该作用的影响,为研究有机磷农药的形态变化提供了参考.     

Activation of Water in Titanium Dioxide Photocatalysis by Formation of Surface Hydrogen Bonds: An In Situ IR Spectroscopy Study

The hole‐driving oxidation of titanium‐coordinated water molecules on the surface of TiO₂ is both thermodynamically and kinetically unfavorable. By avoiding the direct coordinative adsorption of water molecules to the surface Ti sites, the water can be activated to realize its oxidation. When TiO₂ surface is covered by the H‐bonding acceptor F, the first‐layer water adsorption mode is switched from Ti coordination to a dual H‐bonding adsorption on adjacent surface F sites. Detailed in situ IR spectroscopy and isotope‐labeling studies reveal that the adsorbed water molecules by dual H‐bonding can be oxidized to O₂ even in the absence of any electron scavengers. Combined with theoretical calculations, it is proposed that the formation of the dual H‐bonding structure can not only enable the hole transfer to the water molecules thermodynamically, but also facilitate kinetically the cleavage of O? H bonds by proton‐coupled electron transfer process during water oxidation.     

血液相容性及表面改性的研究

血液相容性是生物材料的必要条件 ,本文结合血栓形成的机理 ,综述了改善生物材料血液相容性的主要的几种表面改性方法     

碳氟等离子体改性PET表面的反应机制的研究

利用CF₄与cH₄/CF₄等离子体来处理涤沦膜(PET),讨论了不同摩尔比的碳氟等离子体改性PET表面的作用机制.利用变角x光电子能谱(XPS)和接触角测试技术研究了改性后PET表面的结构和性质.结果表明,碳氟等离子体的处理可以显著地改善PET表面的憎水性.不同摩尔比的碳氟混合气体的作用机制不同,其中碳氟混合气体等离子体以聚合为主,在PET表面形成均匀的改性层;而纯CF₄气体则以刻蚀为主,含氟基团主要分布在PET表面.     

Surface Layers on Chromium in Sulfuric Acid Solutions of Organic Substances: An X-ray Photoelectron Spectroscopy Study

Surface layers formed at a contact of chromium with sulfuric acid solutions containing some organic substances (sodium oxalate, dimethylformamide, methanol) are analyzed by the X-ray photoelectron spectroscopy method. The layers are shown to contain products of deep destruction of organic molecules, i.e. carbon species and those containing functional groups. The data obtained point to the electrocatalytic activity of chromium in cathodic processes. The results of this study may provide a deeper insight into the mechanism of carbon incorporation (in the form of carbide compounds as well) into amorphous chromium deposits formed in sulfuric acid baths containing some organic substances.     

Surface Modification of Montmorillonites by Chlorosilanes

Montmorillonite was modified by chlorosilane derivatives (trimethylchlorosilane and tert-butyldimethylchlorosilane)based on the reaction between OH group and chlorosilane,Fourier-transformed infrared spectra(FTIR)confirmed that chlorosilanes did react with the OH groups of montmorillonite.The effect of reaction time and dispersing agents on the intercalation was studied by wide angle X-ray diffraction(WAXD) method.Further experiments proved that there is no reactive OH group on the surface of layers in the interlayer galleries of montmorillonite.The cation exchange capacity(CEC) of montmorillonites was measured.showing that after modification by chlorosilane derivatives,CEC values drastically decreased.The dispersibility measurements of montmorillonites were conducted.which showed that the dispersibility of modified montmorillonites both in H2O and toluene wer improved due to the decrease of attractions of particles and layers.     

血红蛋白在银溶胶上的表面增强喇曼光谱研究

表面增强喇曼光谱已广泛应用于物质分子在金属表面吸附的研究.人们发现,不仅无机物和有机小分子能产生SERS,而且生物分子,如核酸、色蛋白以及蛋白质均能产生SERS效应,并以此来研究生物分子-蛋白质的变性问题.     

微波等离子体对聚乙烯材料的表面改性

对高分子材料进行表面修饰,可以赋予材料表面新的物理和化学性能,提高材料的亲水性、粘结性、电镀和生物匹配性等．在表面改性方法中,新近发展的等离子体改性技术由于具有操作简单,工艺干法化,不影响材料本体结构和性能等优点而日益受到人们的重视［１,２］．微波等...     

聚对苯二甲酸乙二酯的等离子体表面改性研究

阐述了等离子体原理,综述了等离子体对聚对苯二甲酸乙二酯表面改性的研究工作,大量的实验数据表明了这种方法可以成功改善各种性能。等离子体处理后PET材料表面粗糙度增加,并产生化学基团,因此可改善以下各种性能:润湿性、粘接性、染色性、抗静电性,对人体的生物相容性,添加TiO2的杀菌性,PET表面化学镀金属的性能。PET表面的刻蚀作用,导致其重量的减轻,可替代部分碱减量处理。     

Catalytic ipso-Nitration of Organosilanes Enabled by Electrophilic N-Nitrosaccharin Reagent

Nitroaromatic compounds represent one of the essential classes of molecules that are widely used as feedstock for the synthesis of intermediates, the preparation of nitro-derived pharmaceuticals, agrochemicals, and materials on both laboratory and industrial scales. We herein disclose the efficient, mild, and catalytic ipso-nitration of organotrimethylsilanes, enabled by an electrophilic N-nitrosaccharin reagent and allows chemoselective nitration under mild reaction conditions, while exhibiting remarkable substrate generality and functional group compatibility. Additionally, the reaction conditions proved to be orthogonal to other common functionalities, allowing programming of molecular complexity via successive transformations or late-stage nitration. Detailed mechanistic investigation by experimental and computational approaches strongly supported a classical electrophilic aromatic substitution (S_EAr) mechanism, which was found to proceed through a highly ordered transition state.     

表面增强拉曼光谱检测联苯胺

采用柠檬酸钠还原法制备了具有表面增强拉曼散射(SERS)活性的银纳米溶胶, 利用透射电子显微镜、 扫描电子显微镜和紫外-可见光谱仪对银纳米溶胶进行了表征. 对水相的联苯胺进行了SERS研究, 并对联苯胺的拉曼谱带进行了归属. 考察了团聚剂氯化镁的浓度对检测的影响, 发现随着氯化镁浓度的变大, SERS信号呈现出先增大后减弱的趋势, 即氯化镁的浓度存在一个最佳值, 此时联苯胺的检测限可达到10^-8 mol/L.     

Plasma Surface Modification of Fluoropolymers Studied by ToF-SIMS

Surface modification by plasma treatment is an efficient way of improving metal adhesion to polymers. Here, Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) is used to characterize the surfaces of Teflon PFA and Teflon AF1600 films, following plasma treatments in H₂, O₂ and N₂ gases. This work is complementary to our previous study using XPS, and is particularly directed toward the identification of incorporated hydrocarbons which could seriously affect metal adhesion. Plasma treatments strongly modify the surfaces of fluoropolymers, causing the ablation of a part of the fluorocarbon structure, with H₂ being the most effective gas. The hydrocarbon content of such surfaces is not negligible, and a comparison with hydrocarbon levels on untreated surfaces suggests that a substantial fraction of this material was incorporated on plasma treatment; this is particularly so in the case of H₂ plasma treatment. Due to expected strong matrix effects caused by significant changes in surface chemistry and structure following the various plasma treatments, the use of SIMS absolute intensity values is discussed in terms of data treatment artifacts. Moreover, due to the differences in secondary ion yields between characteristic hydrocarbon and fluorocarbon SIMS peaks, the use of peaks normalized to the total intensity is also impractical. Here, positive mode absolute intensities and negative mode peak intensity values, when normalized to I_tot - I(H^–) - I(F^–), give valuable information, as in the comparison of hydrocarbon and N incorporations.     

Modification of Nano-alumina Surface by Michael Addition Reaction

With recent interest in polymer-based nanocomposites, nano-alumina has receivedconsiderable attention because of their high hardness, high strength and good wearresistance. Improvements in mechanical, tribological, conductive and barrier propertiesof some…     

Modification of Surface Forces by Metal Ion Adsorption

Abstract

Sorption of ions may lead to variations in interparticle forces and, thus, changes in the stability of colloidal particles. Chemical interactions between metal ions and colloidal particles modify the molecular structure of the surface, the surface charge, and the electrical potential between colloidal particles. These modifications to the surface and to the electrical double layer due to metal ion sorption are reflected in the interaction force between a particle and another surface, which is measured in this study by atomic force microscopy (AFM). Specifically, AFM is used to investigate the sorption of copper ions from aqueous solutions by silica particles. The influence of metal ion concentration and solution ionic strength on surface forces is studied under transient conditions. Results show that as the metal ion concentration is decreased, charge reversal occurs and a longer period of time is required for the system to reach equilibrium. The ionic strength has no significant effect on sorption kinetics. Furthermore, neither metal concentration nor ionic strength exhibits any effect on sorption equilibria, indicating that for the experimental conditions used in this study, the surface sites of the silica particle are fully occupied by copper ions.