单分子层表面修饰铜纳米颗粒的制备方法

在乙醇-水体系中,以N,N'-二丁基二硫代氨基甲酸烷基酯为修饰剂,在NaOH和十六烷基三甲基溴化铵(CTAB)存在下,用硼氢化钠还原硫酸铜,制备了粒径、形貌可控的单分子层表面修饰铜纳米颗粒.利用FT-IR、TEM、XPS、UV-Vis等手段对铜纳米颗粒进行了表征.结果表明:修饰剂对铜纳米颗粒的粒径大小、分布、形貌有一定影响,N,N'-二丁基二硫代氨基甲酸烷基酯能在铜纳米颗粒表面形成较紧密的吸附层,有效提高了铜纳米颗粒的稳定性和分散性,并且随着修饰剂烷基链的增长,铜纳米颗粒的粒径略有增大.     

Tribological properties of OTS self-assembled monolayers

Octadecyltrichlorosilane (OTS) self-assembled monolayers (SAMs) were prepared on the substrates of silicon and glass. The tribological properties were tested with a self-made point-contact pure sliding micro tribometer. The effect of humidity on the tribological properties of both OTS SAMs and the naked substrates were studied. When the substrate is covered by OTS monolayer, the friction coefficient is reduced from 0.5 to 0.1 and the stick-slip phenomenon is weakened. OTS monolayer can keep its friction coefficient steady in a wide range of humidity, because it is highly hy-drophobic and thus not sensitive to humidity. In addition, the OTS monolayer has a considerable anti-wear ability.     

铁表面植酸钠自组装层缓蚀性能的电化学研究

将环境友好缓蚀剂植酸钠组装到铁基电极表面,运用电化学极化曲线方法,考察了不同组装液浓度、组装时间及次数形成的植酸钠层对铁基电极表面缓蚀性能的影响.实验结果表明:铁电极在10-2 mol.L-1和10-3 mol.L-1植酸钠溶液中分别组装数分钟,再经10-6mol.L-1植酸钠溶液组装7 h,获得的植酸钠层对铁的缓蚀性能最佳.利用交流阻抗技术探究了最佳组装条件下形成的植酸钠层对铁电极表面的缓蚀机理,等效电路为R(QR)(QR).同时借鉴拉曼光谱进一步解释其缓蚀机理和组装方式.     

Helical self-assembled polymers from cooperative stacking of hydrogen-bonded pairs

The double helix of DNA epitomizes this molecule's ability to self-assemble in aqueous solutions into a complex chiral structure using hydrogen bonding and hydrophobic interactions. Non-covalently interacting molecules in organic solvents are used to design systems that similarly form controlled architectures. Peripheral chiral centres in assemblies and chiral side chains attached to a polymer backbone, have been shown to induce chirality at the supramolecular level, and highly ordered structures stable in water are also known. However, it remains difficult to rationally exploit non-covalent interactions for the formation of chiral assemblies that are stable in water, where solvent molecules can compete effectively for hydrogen bonds. Here we describe a general strategy for the design of functionalized monomer units and their association in either water or alkanes into non-covalently linked polymeric structures with controlled helicity and chain length. The monomers consist of bifunctionalized ureidotriazine units connected by a spacer and carrying solubilizing chains at the periphery. This design allows for dimerization through self-complementary quadruple hydrogen bonding between the units and solvophobically induced stacking of the dimers into columnar polymeric architectures, whose structure and helicity can be adjusted by tuning the nature of the solubilizing side chains.     

自组装单分子膜的缺陷及修饰研究现状

综述了自组装单分子膜的结构及组装方法,缺陷产生的机理、表征方法,以及对自组装单分子膜缺陷的修饰方法．自组装单分子膜可分为单层膜和多层膜．单层膜主要指以共价键和离子键为驱动力形成的,多层膜的组装方法主要是分子沉积(MD)技术和基于化学吸附的自组装单分子膜技术．自组装膜的缺陷对其具有的特殊性能有影响,分子的倒伏造成了膜的缺陷,其影响因素很多,其中基片表面的化学组成与化学性质和成膜分子自身性质起决定作用;优化成膜反应条件,可有效地控制膜的增长．     

Atomic stick-slip friction between commensurate self-assembled monolayers

The classical molecular dynamics simulations have been used to examine the compression and friction between commensurate self-assembled monolayers (SAMs) on Au (111). The friction force changes in a period corresponding to the geometric structure of sliding surfaces. The simulations reveal an ordered atomic stick-slip motion and discontinuous movements of diverse monomers, mainly head and tail groups. All of the head groups of the static film have 2～3 metastable positions (MPs). They oscillate around one of the MPs in stick phases and jump simultaneously to a new MP in slip phases. The tail groups of the sliding film are pulled forward together with opposite ones while sticking and jump forward half of the lattice constant relative to opposite ones while slipping. A complete vision of the motion of SAM chains is thereby built up and compared with the molecule behavior predicted by the Tomlinson model.     

硅烷自组装单分子层生长条件的优化

对长碳链硅烷在玻璃片表面自组装形成单分子层膜进行研究。以甲苯为溶剂,使辛烷基三乙氧基硅烷(OTES)、十二烷基三甲氧基硅烷(DTMS)、3-胺丙基三乙氧基硅烷(APTES)和十八烷基三氯硅烷(OTS)在玻璃表面进行生长,考察反应时间、反应浓度和可水解基团对自组装单分子层膜的影响。用接触角仪和全反射红外光谱仪(FT-IR)对单分子膜进行表征。结果表明:带有—Cl水解基团的OTS最易生长,而带有乙氧基离去基团的OTES比带有甲氧基的DTMS容易反应。在24℃时,1 mmol/L OTES反应20 min自组装单分子层膜生长很好,并且表面比较规整均一。     

氨基硅烷自组装分子膜的制备与摩擦特性

采用原子力显微镜对3-氨基丙基-三乙氧基硅烷自组装分子膜成膜过程进行了表征,其成膜过程包括两个阶段,第一阶段为APS水解产物与基体表面发生聚合反应,表现为"岛"式结构数量增多.第二阶段为APS分子之间发生聚合反应,表现为"岛"式结构长大.在微摩擦磨损试验机对氨基硅烷摩擦特性的研究表明,在载荷为50 mN时,钢球与APS自组装分子膜间的摩擦系数随滑动速度的增加而减小.在滑动速度为0.33×10-4 m/s时,钢球与APS自组装分子膜间的摩擦系数随着载荷的增大逐渐减小,但变化幅度不大.     

自组装OTS分子膜的成膜过程与形貌特征

采用自组装技术制备了三氯十八硅烷分子膜，并通过原子力显微镜对自组装三氯十八硅烷分子膜的形貌进行了表征和分析结果表明，自组装三氯十八硅烷分子膜的形貌是成膜时间的函数，随着成膜时间的增加，分子膜的形貌趋于稳定，同时分子膜的形貌还与成膜溶液的组成相关。     

Preparation and characterization of 3-mercaptopropyl trimethoxysilane self-assembled monolayers

Silane coupling regent (3-mercaptopropyl trimethoxysilane (MPTS)) was prepared on the single-crystal silicon substrate to form 2-dimensional self-assembled monolayers (SAMs). The growth behavior of SAMs formed from 3-MPTS was investigated using atomic force microscopy (AFM), contact angle measurements, ellipsometry, and X-ray photoelectron spectroscopy (XPS). The formation behavior of MPTS SAMs was investigated by a series of AFM images and the roughness of MPTS SAMs on silicon substrates with the assembling time from 1 min to 24 h. The water contact angle measurements indicated the growth behavior of MPTS that correlated with the AFM measurements at different immersion times, too. The chemical states of the typical elements in the MPTS SAMs were analyzed using X-ray photoelectron spectroscopy. The results show that MPTS is self-assembled on the substrate.     

Patterned deposition of multi-walled carbon nanotubes on self-assembled monolayers

The excellent electro-mechanical properties and chemical stability of CNTs promise a prospective ap- plications in nanotechnology. For electronic applica- tions, CNTs have been proved successful in practice in producing components such as a junction and f…     

巯基丙酸自组装单分子膜电化学交流阻抗表征方法的研究

自组装技术(SA)提供了在分子水平上构造化学界面的简便手段,在生物传感器、润滑、金属防腐、催化、刻蚀、分子器件、非线形光学等诸多领域具有广泛的应用前景,已成为近20年来界面化学与材料化学领域研究的热点.自组装单分子膜(SAMs)的表征是SA研究的重要内容,电化学交流阻抗技术(EIS)是表征SAMs的有效手段.但是,关于在水溶液中制备羧基硫醇SAMs以及EIS测试条件的系统研究鲜有报道.以KCl为支持电解质,以[Fe(CN)6]3-/4为探针离子,在优化实验条件下,对磷酸盐缓冲溶液(PBS,pH 7.0)中制备的巯基丙酸SAMs修饰金电极(MPA SAMs/Au)进行了EIS表征,探讨了溶剂以及浸泡时间对MPA SAMs的影响,研究结果对SAMs的制备与应用具有一定参考价值.     

一类巯基衍生卟啉的合成及其电化学性质研究

以香草醛、苯甲醛和吡咯为起始原料合成了3种新型尾式巯基卟啉和相应的钴卟啉,用IR、UV-Vis和1HNMR进行了表征.将巯基衍生卟啉自组装在金电极表面,用电化学方法研究了自由碱卟啉和金属卟啉自组膜性质的差异.     

基于巯基自组装膜的乙肝电化学免疫传感器

研制了以乙肝表面抗原(HBsAg)为检测对象的电化学免疫传感器.在金电极表面自组装半胱胺,戊二醛进行醛基化,最后通过竞争组装在自组装膜上同时固定乙肝表面抗体和硫堇,在PBS底液中以硫堇和辣根过氧化物酶(HRP)的还原峰电流的下降[△/p(%)]对乙肝表面抗原进行定性和定量的检测.结果表明,传感器具有良好的选择性,丙肝阳性对照血清对其无干扰△/p随HBsAg的质量浓度(P)的增加而增大.HBsAg的质量浓度在0.85×10~(-2)～5.12×10~(-2)μg/mL时,线性方程为△/p=5.19+1.56×ρ,相关系数为0.981 5;HBsAg的质量浓度在0.32～1.28μg/mL时,线性方程为△/p=17.05+0.075×ρ,相关系数为0.990 6.并取临床血清进行检测,探索该传感器应用于临床检验的可行性.     

磁头表面氟代硅烷自组装膜的制备和表征

采用分子自组装成膜技术,在磁头表面制备了1H,1H,2H,2H-全氟癸烷基三乙氧基硅烷(FTE)自组装膜。使用时间飞行二次离子质谱仪(TOF-S IM S)、X射线光电子能谱仪(XPS)、原子力显微镜(AFM)和接触角测量仪对FTE自组装膜进行了表征。XPS测得的FTE自组装膜C 1s谱图中有分谱出现在287.905 eV位置,这证明FTE分子以C—O—S i键与磁头表面结合。通过分析TOF-S IM S测量的不同反应时间的膜厚和其对应的AFM表面形貌图发现,FTE自组装膜形成过程分为表面亚单层膜低覆盖、表面亚单层膜中等覆盖、团聚和聚结4个阶段。实验结果表明,控制反应时间可以在磁头表面制备超薄平整的FTE自组装膜,膜厚为(1.20±0.01)nm,表面粗糙度小于0.2 nm。该层超薄膜使磁头对水的接触角增加到110.5°±0.1,°令磁头的疏水性能得到很大提高,进而较大幅度地提高了磁头表面的抗污染能力。     

铝金属薄膜上制备OTS自组装分子膜的摩擦学特性

为研究铝金属薄膜上三氯十八硅烷(OTS)自组装分子膜的摩擦学特性,采用自组装的方法在铝金属薄膜上制备OTS自组装分子膜,分析了纳米尺度和毫牛尺度下载荷、滑动速度以及紫外照射对薄膜摩擦学特性的影响.结果表明:制备的OTS自组装分子膜具有疏水特性和良好的润滑性能.紫外照射5 min后,自组装分子膜摩擦力降低;紫外照射15 min时,自组装分子膜的网状结构受到破坏,减弱了润滑效果.在纳米尺度和毫牛尺度下,摩擦力随载荷和滑动速度的增大而增大;铝金属薄膜摩擦系数降低时,自组装分子膜磨损显著降低,摩擦副的耐久性略有提高.     

Electrochemical behavior of a series of azobenzene self-assembled monolayers on gold

Conclusion This work shows that the structures of C_n AzoC₂ (n = 1, 2, 3, 4) SAMs are significantly different and influence the observed electrochemical behavior of these novel azobenzene systems. The sluggish electron-transfer kinetics of azobenzene SAMs were explained by the alkyl spacer between azobenzene and electrode, the spatial inhibition for structural change in the redox process of azobenzene, as well as the ion-transportation barriers. For decrease of the apparent electrontransfer rate constants with increasing the length of end-groups, and the electrochemical inaccessibility of C₄AzoC₂ SAMs, the spatial inhibition for structure conformational change and ion-transportation was considered as the predominant factor.     

Surface Dissociation Properties of Short Chain Carboxyl Mercaptan Self-Assembled Monolayers by Impedance Titration

Impedance titration was used to determine the surface dissociation characteristics of short-chain carboxyl mercaptan self-assembled monolayers （SAMs）. Based on the change of the cyclic voltammetric peak current and the charge-transfer resistance, which was related to pH value of the solution, the surface pKa of mercaptoacetic acid（MA）, 3-mercaptopropionic acid（MPA） and ω-mercaptohexanic acid（MHA） self-assembled membranes, with ionic strength being 0.1 mol/L, were determined to be 5.20, 4.80, 7.40, respectively. In addition, factors such as time needed for assembling, structure of monolayers and ionic strength, which effected the surface pKa, were studied as well. Such surface pKa shifts were sufficiently explained by interactions between interfacial molecules and hydrophobicity.     

电化学联用技术差分法研究二茂铁硫醇自组装膜氧化构型变化机制

采用电化学-表面等离子体激元共振技术和电化学-石英晶体微天平联用技术结合差分方法,研究11-二茂铁基十一烷基-1-硫醇自组装膜在氧化过程中的构型变化机制.研究结果表明:二茂铁硫醇自组装膜在氧化过程中同时发生了2种结构变化, 一是烷基链远离电极表面,即烷基链与电极表面的夹角增大;二是二茂铁上的2个平行的戊基环绕着二茂铁-碳轴发生旋转.伴随着结构变化,二茂铁硫醇自组装膜还发生2种溶剂化过程,一是氧化的二茂铁与溶液中的阴离子产生静电吸引而形成“离子对”;二是溶剂分子进入膜内形成水化膜.二茂铁硫醇氧化时烷基链的偏移和膜的溶剂化都是快速步骤,而戊基环的翻转是唯一的慢速步骤.     

2-巯基苯并噻唑衍生物自组装分子膜对45#钢的缓蚀性能

合成了2-辛巯基苯并噻唑化合物,运用IR、MS和元素分析等方法对其结构进行了表征。通过自组装技术在钢片表面制备有机分子膜;采用静态失重法和电化学测试技术研究了自组装膜在1mol/LHCl中对钢片的缓蚀性能。结果表明,2-巯基苯并噻唑衍生物缓蚀剂自组装膜对钢片有良好的缓蚀能力。