含非线性光学单元侧链液晶共聚物的合成及极化膜的紫外研究

通过自由基共聚合合成了含有高二阶非线性光学活性偶氮单元的侧链液晶共聚物。共聚物的液晶转变温度为ＤＳＣ测定，实验证明当偶氮单元含量超过４０ｍｏｌ％时，共聚物的液晶性消失。通过高压电场对该聚合物膜进行针尖电晕极化取向，并由紫外测试给出了聚合物膜的取向参数及其稳定性，对液晶聚合物的非线性光学性质进行了初步的研究。     

CnB-的激光等离子体产生与质谱分析

Time-of-flight mass spectrum of C_nB~- has been recorded on a selfbuilt instrument with laser vaporization of tetraphenylboron sodium. By analysis of the com-position of the anions, it is found that number of the boron atoms in any of these ions equals to the number of the charges carried by the anion, and the sum of the numbers of the carbon and boron atoms in these species are always the odd numbers. The experimental results show that boron atom has a strong tendency to attract an electron so that those C_nB~- will have similar electronic structures as C_n, and carbon clusters with odd members are always more stable than their even neighbors.     

PIXE法分析共聚物中痕量氯

四氟乙烯和全氟4-甲基-3,6-二氧杂-△~7辛基磺酰氟在溶剂氟里昂-113(F-113)中进行自由基引发聚合反应时,共聚物(T-O)是否有链转移,可以通过测定所得共聚物中的含氯量来得以证实。我们首次应用质子X萤光分析法(PIXE)进行分析。结果表明,共聚物中含氯量小于1ppm,F-113溶剂并未发生链转移。同时,我们测定了已证明有F-113参与链转移反应的F_(40)试样,含氯量高达700ppm。     

Melt‐state polymer chain dimensions as a function of temperature

The unperturbed chain dimensions (〈R²〉_o/M) of cis/trans‐1,4‐polyisoprene, a near‐atactic poly(methyl methacrylate), and atactic polyolefins were measured as a function of temperature in the melt state via small‐angle neutron scattering (SANS). The polyolefinic materials were derived from polydienes or polystyrene via hydrogenation or deuteration and represent structures not encountered commercially. The parent polymers were prepared via lithium‐based anionic polymerizations in cyclohexane with, in some cases, a polymer microstructure modifier present. The polyolefins retained the near‐monodisperse molecular weight distributions exhibited by the precursor materials. The melt SANS‐based chain dimension data allowed the evaluation of the temperature coefficients [dln 〈R²〉_o/dT(κ)] for these polymers. The evaluated polymers obeyed the packing length (p)‐based expressions of the plateau modulus, G = kT/np³ (MPa), and the entanglement molecular weight, M_e = ρN_anp³ (g mol^?1), where n_t denotes the number (～21) of entanglement strands in a cube with the dimensions of the reptation tube diameter (d_t) and ρ is the chain density. The product np³ is the displaced volume (V_e) of an entanglement that is also expressible as pd or kT/G. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1768–1776, 2002     

Synthesis of substituted polymethylenes by radical polymerization of N,N,N′,N′-tetraalkylfumaramides and their characterization

Radical polymerization of N,N,N′,N′-tetraalkylfumaramides (TRFAm) bearing methyl, ethyl, n-propyl, isopropyl, and isobutyl groups as N-substituents (TMFAm, TEFAm, TnPFAm, TIPFAm, and TIBFAm, respectively) was investigated. In the polymerization of TEFAm initiated with 1,1′-azobiscyclohexane-1-carbonitrile (ACN) in benzene, the polymerization rate (R_p) was expressed as follows: R_p = k [ACN]^0.28 [TEFAm]^1.26, and the overall activation energy was 102.1 kJ/mol. The introduction of a bulky alkyl group into N-substituent of TRFAm decreased the R_p in the following order: TMFAm > TEFAm > TnPFAm > TIBFAm > TIPFAm ～ 0. The relative reactivities of these monomers were also investigated in radical copolymerization with styrene (St) and methyl methacrylate (MMA). In copolymerization of TRFAm (M₂) with St (M₁), monomer reactivity ratios were determined to be r₁ = 1.07 and r₂ = 0.20 for St–TMFAm, and r₁ = 1.88 and r₂ = 0.11 for St–TEFAm, from which Q₂ and e₂ values were estimated to be 0.35 and 0.44 for TMFAm, and 0.19 and 0.47 for TEFAm, respectively. The other TRFAm were also copolymerized with St, but copolymerization with MMA gave polymers containing a small amount of TRFAm units. The polymer from TRFAm consists of a less-flexible poly(N,N-dialkylaminocarbonylmethylene) structure. The solubility and thermal property of the polymers were also investigated.     

The length of the polymethine chain and the spectral-luminescent properties of symmetrical cyanine dyes

The general characteristics that relate the length of the polymethine chain of symmetrical cyanine dyes to their spectral-luminescent properties depending on the electron-donor character of the heterocycles and the nature of the solvent are formulated. For various types of symmetrical cyanines, the Stokes shifts decrease with the elongation of the polymethine chain due to weakening of the vibronic interactions. The vinylene shifts of the band maxima are essentially constant and fall within the range 100 to 130 nm depending on the nature of the heterocycles and the solvent. When the polymethine chain elongates the fluorescence quantum yields first increase and then decrease. The greater the effective length of the heterocycle the stronger the decrease. The fluorescence decay occurring when the polymethine chain gets longer is associated with intensification of the internal conversion. For symmetrical cyanines, the changes in the shapes of the electronic bands (their width, asymmetry, excess, and fine structure) as the chain elongates are governed by the competing effects of the vibronic and intermolecular interactions. The former decrease as the chain lengthens, causing the narrowing of the absorption bands for the lower vinylogs. On the other hand, the latter increase as chain lengthens, which leads to broadening of the bands for the higher vinylogs. The higher the solvent nucleophilicity and the greater the deviation of the electron-donor ability of the heterocycle from the average value the greater the broadening. Any elongation of the polymethine chain of symmetrical cyanines causes only narrowing of the bands and an increase in the asymmetry, excess, and structuring in the fluorescence spectra, which, unlike the absorption spectra, is independent of the electron-donor character of the heterocycles and the nature of the solvent. These effects are caused by the fact that, in contrast to absorption, changes in the shape of emission bands with increasing chain length are governed predominantly by vibronic rather than by intermolecular interactions.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1227–1239, July, 1994.     

Surface plasmon resonance biosensor for genetically modified organisms detection

The development of a surface plasmon resonance (SPR) affinity biosensor based on DNA hybridisation is described. This biosensor has been applied to genetically modified organisms (GMOs) detection. Single stranded DNA (ssDNA) probes were immobilised on the sensor chip of an SPR device and the hybridisation between the immobilised probe and the complementary sequence (target) was monitored. The probe sequences were internal to the sequence of 35S promoter and NOS terminator which are inserted sequences in the genome of GMO regulating the transgene expression. The system has been optimised using synthetic oligonucleotides, then applied to real samples analysis. Samples, containing the transgenic target sequences, were amplified by polymerase chain reaction (PCR) and then detected with the SPR biosensor.     

Effect of disorder on relaxation in the one-dimensional Glauber model

We study the long-time relaxation of magnetization in a disordered linear chain of Ising spins from an initially aligned state. The coupling constants are ferromagnetic and nearest-neighbor only, taking valuesJ ₀ andJ ₁ with probabilitiesp and 1–p, respectively. The time evolution of the system is governed by the Glauber master equation. It is shown that for large timest, the magnetizationM(t) varies as [exp(–₀ t](t), where ₀ is a function of the stronger bond strengthJ ₀ only, and (t) decreases slower than an exponential. For very long times, we find that ln (t) varies as –t ^1/3. For low enough temperatures, there is an intermediate time regime when ln (t) varies as –t ^1/2. The results can be extended to more general probability distributions of ferromagnetic coupling constants, assuming thatM(t) can only increase if any bond in the chain is strengthened. If the coupling constants have a continuous distribution in which the probability density varies as a power law near some maximum valueJ ₀, we find that ln (t) varies as –t ^1/3(lnt)^2/3 for large times.     

甾醇边链的化学修饰

本文对近年来甾醇边链结构改造的新方法和新动向--Barton 的Gif系统氧化反应及Breslow的远程功能化反应进行了综述。     

STATISTICS OF A NOVEL CLASS OF LIQUID CRYSTAL POLYMERS

A novel class of the liquid crystal polymers with mesogens laterally attached to flexible main chain backbones has been synthesized recently by us. While the flexible backbones tend to take configuration of maximum entropy the mesogenic side groups tend to orientate because of the anisotropie soft dispersion forces. A mean field theory is presented to describe the competition between these two trends which makes it possible for this class of polymers to show anisotropic (liquid crystal) phase within certain temperature range where the polymer main chains and the side chain mesogens will take approximately parallel arrangement, which is different from the normal side chain liquid crystal polymers. The temperature range of the liquid crystal phase, its ordering and phase transition all depend on the flexibility of the backbone, the strengthof the anisotropic forces of the side groups and the hinge elasticity. The results show that the liquid crystalisotropic phase transition is of the first order. The phase diagram, i. e. the dependence of the transition temperature on the structure of the polymers is also given.