Structure of solid monolayers and multilayers of n -hexane on graphite

We present all-atom molecular dynamics simulations ofn-hexane on the basal plane of graphite at monolayer and multilayer coverages. In keeping with experimental data, we find the presence of ordered adsorbed layers both at single monolayer coverage and when the adsorbed layer coexists with excess liquid adsorbate. Using a simulation method that does not impose any particular periodicity on the adsorbed layer, we quantitatively compare our results to the results of neutron diffraction experiments and find a structural transition from a uniaxially incommensurate lattice to a fully commensurate structure on increasing the coverage from a monolayer to a multilayer. The zig-zag backbone planes of all the alkane molecules lie parallel to the graphite surface at the multilayer coverage, while a few molecules are observed to attain the perpendicular orientation at monolayer coverage. Dedicated to Professor C N R Rao on his 70th birthday     

Photochemical attachment of polymers on planar surfaces with a covalently anchored monolayer of a novel naphthyl ketone photochemical radical generator

A monolayer of covalently anchored, novel, binaphthyl ketone is used as a surface‐confined photochemical radical generator (PRG) for anchoring a variety of polymers to silicon surfaces. The precursor PRG is synthesized by the application of a facile and novel method for the oxidation of sterically hindered benzylic hydrocarbons to carbonyl compounds. Oxidation was carried out with a stoichiometric amount of potassium peroxydisulfate, in the presence of a catalytic amount of copper sulfate in an acetonitrile/water mixture. The PRG synthesized is characterized by ¹H NMR, UV, and Fourier transform infrared (FTIR). The covalently attached monolayers are characterized by X‐ray photoelectron spectroscopy, ellipsometry, and water contact angle measurements. The method developed is applicable to the preparation of a monolayer of a variety of polymers on a wide range of substrates carrying surface hydroxyl groups. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5413–5423, 2004     

Tetrafunctional initiators for cationic polymerization of olefins

3,3′,5,5′‐Tetrakis(2‐chloro‐2‐propyl)biphenyl (biphenyl tetracumyl chloride, BPTCC) and 1,3‐bis[3,5‐bis(2‐chloro‐2‐propyl)phenoxy]propane (diphenoxypropane tetracumyl chloride, DPPTCC) were synthesized as initiators for quasiliving cationic polymerization of isobutylene (IB). In the synthesis of BPTCC, tetrafunctionality was achieved via the coupling of dimethyl 5‐bromoisophthalate (DMBI) using nickel dibromide bis(triphenylphosphine) and zinc in the presence of a base; in the synthesis of DPPTCC, two equivalents of dimethyl 5‐hydroxyisophthalate were linked via reaction with 1,3‐dibromopropane in the presence of potassium carbonate. Both initiators were used to initiate the polymerization of IB under quasiliving cationic polymerization conditions. PIB initiated from BPTCC revealed a chain end/molecule value (as determined by ¹H‐NMR) of 3.85, verifying the nearly exclusive production of 4‐arm polyisobutylene (PIB). GPC analysis revealed a narrow peak representing the target four‐arm PIB, with a slight shoulder at high elution volumes (low molecular weights). GPC analysis of the PIB initiated by DPPTCC revealed multimodal distributions, suggesting the formation of two‐, three‐, and four‐arm star polymers during the polymerization. This behavior was attributed to Friedel–Crafts alkylation of the initiator core after the addition of one IB unit, which was activated by the electron‐donating oxytrimethyleneoxy linking moiety. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5942–5953, 2004     

Synthesis of A2B star block copolymers from a heterotrifunctional initiator

We described the obtention of A₂B star block copolymers through the use of a new heterotrifunctional initiator. That way, well‐defined (PCL)₂‐arm‐PtBuMA and (PCL)₂‐arm‐PS star block copolymers have been synthesized from a heterotrifunctional initiator bearing two hydroxyl groups able to initiate ROP of CL (with AlEt₃ or Sn(Oct)₂ as coinitiator) and a bromide function able to initiate ATRP of tBuMA or styrene. Firstly, we have proceeded using a sequential process (two‐steps), leading to an intermediate macroinitiator. Secondly, attempt to polymerize these two monomers in a simultaneous process (one‐step), that is directly from the mixture of monomers, initiator, coinitiators, and solvent, has been realized and has shown that some interferences between the two polymerizations occurred, leading to an inhibition of ATRP when Sn(Oct)₂ was used and an unexpected increase in control when AlEt₃ was used as catalyst for the ROP (obtention of well‐defined (PCL)₂‐arm‐PtBuMA with pdi of 1.18). © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1796–1806, 2006     

六甲氧基甲基三聚氰胺-多元醇-丙烯酸酯混杂聚合体系的研究

六甲氧基甲基三聚氰胺 (HMMM) 多元醇 丙烯酸酯 酸催化剂混杂聚合体系在高温下同时进行缩聚和自由基聚合并表现出协同效应 .体系中的活泼亚甲基在HMMM的催化下被空气氧化成过氧化氢物 ;过氧化氢物在酸催化下分解成自由基进而引发自由基聚合反应 .研究结果表明 ,体系中存在固化加速的协同效应 ;同时体系中还存在热互补效应 ,丙烯酸酯的自由基聚合反应放出的热可以传递给缩聚反应 ,满足缩聚反应吸热的要求 .混杂聚合得到的高分子合金膜具有优良的机械性能和耐溶剂性能 ,这是由于在混杂聚合过程中形成了互穿聚合物网络 (IPN)结构 .使用潜酸催化剂作为酸的来源 ,可以提高体系的储存稳定性 ;交联 引发剂的使用可以拓宽它的使用范围 ;对超枝化聚合物在混杂体系中的应用也进行了初步研究     

偏氟乙烯的聚合反应

本文研究了用有机引发剂引发偏氟乙烯的水相聚合,并对制得的聚偏氟乙烯的性质进行了研究。有机引发剂引发聚合的聚偏氟乙烯的热稳定性、强度、结晶度和熔点均比用过硫酸盐引发聚合的聚偏氟乙烯高。     

Detection of metal ions using ion-channel sensor based on self-assembled monolayer of thioctic acid

Gold electrodes were chemically modified with thioctic acid monolayer designed to mimic biological ion-channel membranes. The technique was then used in the determination of alkali, alkaline earth, thallium(I), and lanthanum metal cations as analytes. Cyclic voltammograms (CV) of [Fe(CN)6]³⁻ an electroactive marker, were measured in the presence of the various types of analyte cations. In the absence of the analyte cation, electrostatic repulsion between the marker anions and the carboxylate groups of the receptor monolayer hindered the approach of the marker anion to the electrode surface and hence hindered its reduction. The modified electrodes responded well to the metal cations except the alkali metal cations. The sensors could detect the trivalent cation La³⁺ at concentrations as low as 10⁻⁸ M. The response of the sensor to the metal cations increase in the order alkali metal3+ can be discriminated in the ratio 1:100. This makes it possible to determine the trivalent ion in a sample matrix containing monovalent and divalent cations. Thallium(I) ion showed marked deviation in its response as compared to monovalent ions of the alkali metals. The ion-channel sensor based on self-assembled monolayer of thioctic acid therefore offers a potential alternative technique for the selective determination of metal ions.     

VINYL MONOMERS BEARING CHROMOPHORE MOIETIES AND THEIR POLYMERS——Ⅹ.INITIATION AND PHOTOCHEMICAL PROPERTIES OF p-(N,N-DIMETHYLAMINO)STYRENE AND ITS POLYMERS*

A vinyl monomer having an electron-donating moiety, p-(N,N-dimethylamino)styrenc (DMAS),was synthesized. It was combined with benzoyl peroxide (BPO) to form a redox initiation system to initiatethe polymerization of methyl methacrylate (MMA). UV spectra measurements show that DMAS enters thePMMA chain as well. Both DMAS and its polymer P(DMAS) display strong fluorescence, and thefluorescence can be quenched by electron-deficient compounds such as methacrylonitrile, fumaronitrile andmethyl methacrylate etc. Moreover, DMAS can also form charge transfer complex (CTC) with strongelectron acceptors such as tetracyanoethylene (TCNE). The difference between the photochemical propertiesof DMAS and P(DMAS) were explained in terms of molecular structure change and polymer conformationeffect in solution. In addition, the CTC and exciplex formation of DMAS or P(DMAS) with C_(60) were alsostudied.     

Electrochemical Behavior of Diphenyl Disulfide and Thiophenol on Glassy Carbon and Gold Electrodes in Aprotic Media

The investigation of the electrochemical reduction processes of C₆H₅SSC₆H₅ and C₆H₅SH in CH₃CN using cyclic voltammetry indicates a different behavior on GC and Au electrodes. On GC surface adsorption phenomena are absent, the electrochemical reduction process is irreversible and diffusion controlled. For both the starting molecules the same species, C₆H₅S^?, is formed upon reduction. The E° values of the reduction processes were determined by convolution method and the standard free energy of the S? S bond of C₆H₅SSC₆H₅ estimated. On Au surface instead, a self‐assembled monolayer of C₆H₅SAu_ads originated after the S? S or S? H bond breaking can be observed by simply dipping the electrode in solution of C₆H₅SSC₆H₅ and C₆H₅SH, respectively. The properties of the SAM were investigated by electrochemical reduction of the adsorbed thiolates. On Au electrode the reduction processes involve C₆H₅SAu_ads and give rise to desorbed C₆H₅S^?. A neutral radical is obtained by electrochemical oxidation of thiolate anion. It reacts rapidly with the electrode surface to give the S‐Au bond again.     

Spreading of dipalmitoyl phosphatidylcholine on the surface of sodium deoxycholate aqueous solution

The surface pressure vs. mokcular surface area relations for dipalmitoyl phosphatidylcholine (DPPC) insoluble monolayer and sodium deoxycholate (SDC) adsorbed monolayer,L and D1, respectively, were obtained from the analyses of surface tensions measured by the Wilhelmy glass plate. Also, D1 was obtained by a drop-weight method. Next, the surface pressure time course,(t), of the SDC aq. was measured by the Wilhelmy plate before and after DPPC was spread on the liquid surface. At DPPC spreading,(t) jumped to a maximum,, and decreased along an exponential curve. The values of with various surface amounts of DPPC and bulk concentrations of SDC were analyzed using a dual surface-region model. The model enabled the estimation of. For better fitting, modified relations were constructed in place of D1. The exponential decrease of(t) was also observed on the SDC adsorbed monolayer which was rapidly compressed by a moving barrier. The(t) relaxation rate constants of the SDC monolayers which were compressed by DPPC spreading and the moving barrier agreed with each other, suggesting a desorption of SDC from the surface.