笼形聚羧酸钒(Ⅳ)—硫脲体系引发丙烯腈聚合动力学

研究了笼形聚羧酸钒(PV)-硫脲(TU)体系在硝酸溶液中引发丙烯腈(AN)聚合动力学。表观聚合速度(R_p)是 R_p=9.7×10~5e~(-10500)/RT[AN]~1.0[PV]~0.50[TU]~0.76[HNO_3]~1.5聚合诱导期(τ)随反应条件而变化,聚合温度越高,引发种浓度越大,聚合诱导期越短,但与单体浓度的变化无关。 1/τ=4.6×10~(12)e~(-13500)/RT[AN]~0[PV][TU]~(-3/2)[HNO_3]~3=K_τ·R_i聚合物分子量随单体浓度增大而提高,但随聚合温度及引发种浓度增大而下降,即 笼形聚羧酸钒—硫脲体系引发丙烯腈聚合的动力学参数和引发机理与杨梅型聚羧酸钒—硫脲体系在相同的条件下引发聚合的行为有明显的区别,认为是和两种树脂大分子链的空间结构所引起的传质阻力有关。     

聚丙烯基聚偕氨肟—硫脲络合物引发丙烯腈聚合动力学及机理

研究了硝酸溶液中聚丙烯基聚偕氨肟(PPAO)—硫脲(TU)络合物引发丙烯腈(AN)聚合动力学。在[TU]/[PPAO]<0.5摩尔比的条件下,表观聚合速度(R_p)是R_p=9.1×10~4e~(-45.2k J/RT)[AN]~(2.0)[HNO_3]~(1.5)[TU]~(1.0)聚合物分子量随聚合温度升高而下降,并与硝酸浓度的1.5次方和硫脲浓度的1.0次方成反比,与丙烯腈浓度和 PPAO 浓度无关。可表示为_m=K·1/T·(1/[HNO_3]~(1.5)[TU]~(1.0))=K_M·1/T·(R_p/R_t)根据实验结果,提出了“络合—质子转移”引发机理。     

杨梅形聚肟偕亚氨二乙酸钒(Ⅳ)—硫脲体系引发丙烯腈聚合的研究

研究了杨梅形聚肟偕亚氨二乙酸树脂负载VO~(2+)(PV)与疏脲(TU)组合在硝酸溶液中引发丙烯腈(AN)的聚合反应。在实验条件下,表观聚全速度可表示为 R_p=1.91×10~5e~(-45.0/RT)c~(1.9)(AN)c~(1.0)(HNO_3)c~(0.60)(PV)c~(1.50)(TU) 聚合诱导期(τ)与反应物浓度和聚合温度关系是 1/τ=8.27×10~7e~(-38.3/RT)c~(1.9)(HNO_3)c~(0.60)(PV)C~(1.50)(TU)=K_τ;·R_i/R_p 在酸性介质中,氨羧基的协同作用促使键合的VO~(2+)氧化为VO_2~+,随后硫脲配位并通过氢桥缔合,后者分解生成初级自由基,引发丙烯腈的聚合反应。     

笼形聚肟偕亚氨二乙酸钒(Ⅳ)-硫脲体系引发丙烯腈聚合的研究

 研究了笼形聚肟偕亚氨二乙酸钒(CPV)-硫脲(TU)体系在硝酸溶液中引发丙烯腈(AN)聚合反应.表观聚合速度(R_P)是 R_P=1.0×10⁸e(-10.500/RT)[AN]^1.0[CPV]^1.0[TU]^1.5[HNO₃]^3.0 聚合诱导期(τ)随反应温度和物料浓度发生变化,可表示为 1/τ=5.2×10⁹e^-12.800/RT[AN]^1.0[CPV]^1.0[TU]^1.5[HNO₃]^3.0实验结果表明,聚合反应以单基终止为特征,可能是和高分子载体较大的空间位阻有关.     

丙烯腈在金属镁引发下的聚合动力学

研究了金属镁在硝酸溶液中引发丙烯腈的聚合反应。实验结果表明,聚合速度与金属镁的用量无关,并且当[HNO_3]>[AN]时服从下列关系式: R_p=1.91×10~5e~(-15000/RT)[Mg]~0[AN]~(2.2)[HNO_3]~(0.45) 丙烯腈-丙烯酸甲酯的共聚试验证明,聚合反应是按自由基机理进行。     

钒(V)—硫脲氧化还原体系引发丙烯腈聚合的研究 Ⅰ.聚合动力学

研究了钒(V)—硫脲氧化还原体系在硝酸溶液中引发丙烯腈的聚合反应.表观聚合速度是:R_p=2.80×10~5e~(-14000/RJ)[AN]~(2.2)[HNO_3]~(0102)[V~(5+)~(0～1/3)[TU]~(0～4/3),实验结果表明钒(V)和硫脲产生引发种是一个相当复杂的过程。     

STUDIES ON THE POLYMERIZATION OF ACRYLONITRILE INITIATED BY METAVANADATE-CONTAININ G ANION EXCHANGER-THIOUREA REDOX SYSTEM

The polymerization of acrylonitrile (AN) in aqueous nitric acid initiated by metavanadate-containing anion exchange resin (PV)-thiourea (TU) redox system at 20—40℃. has been investigated. The overall rate of polymerization (R_p) is given byR_p=1.92×10~4e~(-6.860/RT) [AN]~(1.2) [PV]~(0.44) [TU]~(1.0)[HNO_3]~(1.0)The kinetic parameters differed from those of V~(5+)-TU system indicated that the generation of the primary radicals is mainly a difffusion-controlled reaction. The effect of macromolecular field arisen from the polymer matrix exerts a great influence on the polymerization process.     

Cu~(2+)—Na_2SO_3体系引发甲基丙烯酸甲酯聚合动力学

研究了Cu~(2+)—Na_2SO_3氧化还原体系在静置的密闭空气气氛下引发甲基丙烯酸甲酯水溶液聚合。表现聚合速度(R_P)是 R_=1.86×10~(15)e~(-101.6k/RT)[MMA]~(1.0)[Cu~(2+)]~0[Na_2SO_3]~(0.50) 复盖气氛对聚合有显著影响。氧抑制聚合反应,但可使Cu~(2+)离子氧化再生,表现为低的表观聚合速度和高的碰撞频率因子与表观聚合活化能。本文讨论了引发聚合机理。     

杨梅型聚丙烯基亚氨二乙酸钒(Ⅳ)—硫脲体系引发丙烯腈聚合的研究

研究了杨梅型聚丙烯基亚氨二乙酸钒(PIDA/VO)—硫脲(TU)体系在硫酸溶液中引发丙烯腈聚合动力学。表观聚合速度(Rp)和聚合物分子量(Mn)可分别表示为: Rp=2.2×10~5e~(-0860)/RT[AN]~1.0[PV]~0.50[TU]~1.5[H_2SO_4]~2.0 Mn=K·1/T·[AN]/[PV]~0.50[TU]~1.5[H_2SO_4]~2.0其中([PV]~0.05[TU]~1.5[H_2SO_4]~2.0)~2是正比于引发种浓度。由此可见,链自由基是以双基反应终止,伯基终止及链转移终止的可能性较少。和聚羧酸钒(Ⅳ)—硫脲体系引发丙烯腈聚合的机理相同,杨梅型聚丙烯基亚氨二乙酸钒(Ⅳ)也表现出强烈的羧基间协同作用和大分子场效应。     

STUDY ON THE POLYMERIZATION OF ACRYLONITRILE INITIATED BY POLYPROPYLENE-BASED VANADYL POLYIMIDODIACETATE——THIOUREA REDOX SYSTEM

The present paper deals with the kinetics of polymerization of acrylonitrile (AN) initialed by the redox system of polypropylene-based vanadyi polyimidodiacetate (PV)-thiourea (TU)in aqueous sulfuric acid in the temperature range from 25 to 40℃. The polymerization rate was measured by varying the concentrations of monomer, vanadyl polyimidodiacetate, thiourea and sulfuric acid. The overall rate of polymerization was summarized asRp=2.2×10~5e~(-6.560/RT) [AN]~(1.0)[PV]~(0.50)[TU]~(1.5)[H_2SO_4]~(2.0)The molecular weight of polyacrylonitrile based on the experimental data was:(?)=k 1/T [pv]~(0.50)[TU]~(1.5)[H_2SO_4]~(2.0)These results indicated that the chain radicals are terminated by combination and/or disproportionation rather than chain transfer. The cooperation effect of carboxylic groups and the macromolecular field effect of polymer supporter are the characters of vanadyl polyimidodiacetate such as the case reported in early paper.     

"True" iron(V) and iron(VI) porphyrins: a first theoretical exploration

We present here a first theoretical characterization of iron(V) (S = (3)/(2)) and iron(VI) (S = 0) porphyrin intermediates. The Fe(V) calculations exhibit exceptionally narrow convergence radii and we believe that for this reason they have long eluded researchers working on high-valent iron intermediates. The Fe(V)-N(nitrido) bond distance in the DFT(PW91/TZP) optimized geometry of Fe(V)(P)(N) is 1.722 A, comparable to and slightly longer than the Fe(IV)-O bond distance of 1.684 A in Fe(IV)(P)(O) and the Fe(IV)-N(imido) bond distance of 1.698 A in Fe(IV)(P)(NH). In contrast, the Fe(VI)-N(nitrido) bond distances in [Fe(VI)(P)(N)](+) (S = 0) and Fe(VI)(P)(N)(F) (S = 0) are dramatically shorter, 1.508 and 1.533 A, respectively, consistent with the formal triple bond character of the Fe(VI)-N(nitrido) bond. The nitrido ligand appears to be uniquely capable of stabilizing a "true" Fe(V) center, in the sense defined in the paper. All three unpaired electrons in Fe(V)(P)(N) are completely localized on the Fe(V)-N(nitrido) axis, with the Fe and N gross atomic spin populations being 1.579 and 1.550, respectively. In contrast, an axial ligand set consisting of an oxide and a fluoride do not stabilize an Fe(V) ground state but favor an electronic structure best described as an Fe(IV)-oxo porphyrin pi-cation radical.     

Syntheses and crystal structures of "unligated" copper(I) and copper(II) trifluoroacetates

Two extremely unstable copper trifluoroacetates with no exogenous ligands, namely, Cu(O2CCF3) (1) and Cu(O2CCF3)2 (2), are prepared for the first time and obtained in crystalline form by deposition from the vapor phase. Their structures are determined by X-ray crystallography. The crystallographic parameters are as follows: for 1, monoclinic space group P2(1)/c, with a = 9.7937(6) A, b = 15.322(1) A, c = 12.002(1) A, beta = 106.493(9) degrees, and Z = 4; for 2, orthorhombic space group Pcca, with a = 16.911(1) A, b = 10.5063(9) A, c = 9.0357(6) A, and Z = 4. Both structures are unique among other CuI and CuII carboxylates, as well as among metal carboxylates in general. Compound 1 consists of a planar rhombus of four copper atoms with sides of 2.719(1)-2.833(1) A and trifluoroacetate ligands bridging the pairs of adjacent metal atoms alternately above and below the plane. The tetrameric units are further aggregated in a polymeric zigzag ribbon [Cu4(O2CCF3)4]infinity by virtue of intermolecular Cu...O contacts. The structure of 2 is built on cis bis-bridged dimers in which every metal atom is also connected with two copper atoms of the neighboring units. The stacking planes in this extended chain are almost perpendicular to one another. The Cu...Cu distance inside the dimer is 3.086(2) A, indicating a nonbonding interaction.     

Electrochemical "switching" of Si(100) modular assemblies

We report on a modular approach for producing well-defined and electrochemically switchable surfaces on Si(100). The switching of these surfaces is shown to change a Si(100) surface from resistant to cell adsorption to promoting cell adhesion. The electrochemical conversion of the modified electrode surface is demonstrated by X-ray photoelectron spectroscopy, X-ray reflectometry, contact angle and cell adhesion studies.     

"Inject-mix-react-separate-and-quantitate" (IMReSQ) method for screening enzyme inhibitors

Many regulatory enzymes are considered attractive therapeutic targets, and their inhibitors are potential drug candidates. Screening combinatorial libraries for enzyme inhibitors is pivotal to identifying hit compounds for the development of drugs targeting regulatory enzymes. Here, we introduce the first inhibitor screening method that consumes only nanoliters of the reactant solutions and is applicable to regulatory enzymes. The method is termed inject-mix-react-separate-and-quantitate (IMReSQ) and includes five steps. First, nanoliter volumes of substrate, candidate inhibitor, and enzyme solutions are injected by pressure into a capillary as separate plugs. Second, the plugs are mixed inside this capillary microreactor by transverse diffusion of laminar flow profiles. Third, the reaction mixture is incubated to form the enzymatic product. Fourth, the product is separated from the substrate inside the capillary by electrophoresis. Fifth, the amounts of the product and substrate are quantitated. In this proof-of-principle work, we applied IMReSQ to study inhibition of recently cloned protein farnesyltransferase from parasite Entamoeba histolytica. This enzyme is a potential therapeutic target for antiparasitic drugs. We identified three previously unknown inhibitors of this enzyme and proved that IMReSQ could be used for quantitatively ranking the potencies of inhibitors.     

A high-nuclearity, beyond "fully reduced" polyoxo(alkoxo)vanadium(III/IV) cage

The solvothermal synthesis, crystal structure and preliminary magnetic studies are reported of the first high nuclearity V(III)-based polyoxo(alkoxo)vanadium cage, a V(III)16V(IV)2 complex.     

"Click"-modification of a functionalized poly(3,4-ethylenedioxythiophene) (PEDOT) soluble in organic solvents

A PEDOT-based conductive copolymer soluble in organic solvents was synthesized electrochemically using dihexyl-EDOT and azidomethyl-EDOT as monomers and was successfully post-functionalized by "click"-cycloaddition reaction with a functionalized terminal alkyne under mild heterogeneous conditions.     

Unexpected thermal decomposition of the "Alder carbene" (iPr(2)N)(2)C

The "Alder carbene" (iPr(2)N)(2)C undergoes a β-fragmentation in solution already at room temperature, affording propene and N,N,N'-triisopropylformamidine. This stands in sharp contrast to the indefinite stability previously claimed for this iconic compound.