Thermal analysis and X-ray studies of chiral ferroelectric liquid crystalline materials and their binary mixtures

Summary Thermal properties of a homologous series of ferroelectric liquid crystals S-(-)-[4-(2-n-alkoxy-propionyloxy)]biphenyl-4'-[n-alkoxy-(3,5-dimethyl)]benzoate have been investigated by polarizing optical microscopy and differential scanning calorimetry. The mesophases were identified and confirmed by X-ray too. Three binary mixtures were prepared from the individual homologues. In one of the mixtures (Mix1), the ferroelectric SmC* phase has broadened and became enantiotropic. This mesophase remained monotropic in the other two mixtures (Mix2, Mix3). The chiral nematic N* phase did not appear in Mix1, but remained monotropic for the other two mixtures. Two molecular parameters, the layer spacing and the average intermolecular distance have been calculated from the X-ray results for the homologues and their mixtures. An intercalated tail-to-tail packing of molecules was found both in the single compounds and their mixtures resulting in the layer spacing about half of the molecular length of the single compounds.     

Properties of the skeleton of aggregates grown on a Cayley tree

We discuss and analyze a family of trees grown on a Cayley tree, that allows for a variable exponent in the expression for the mass as a function of chemical distance, M(l)l ^dl . For the suggested model, the corresponding exponent for the mass of the skeleton,d _l ^s , can be expressed in terms ofd _l asd _l ^s = 1,d _l d _l ^c = 2;d _l ^s = d _l –1,d ₁ d _l ^c = 2, which implies that the tree is finitely ramified ford _l 2 and infinitely ramified whend _l 2. Our results are derived using a recursion relation that takes advantage of the one-dimensional nature of the problem. We also present results for the diffusion exponents and probability of return to the origin of a random walk on these trees.     

三级相互作用对聚亚甲基链末端距四次矩的影响

本文用三级相互作用近似理论导出了高分子链末端距的四次矩的计算公式。计算聚亚甲基链的末端距四次矩,并同二级相互作用的结果进行了比较。对于聚亚甲基链,三级相互作用近似的四次矩小于二级相互作用近似的四次矩。     

QSAR Studies on the COX-2 Inhibition by 3,4-Diarylcycloxazolones Based on MEDV Descriptor

Selective inhibition of cyclooxygenase-2 (COX-2) might avoid the side effects of current available nonsteroidal antiinflammatory drugs while retaining their therapeutic efficacy. A novel variable selection and modeling method based on prediction is developed to construct the quantitative structure-activity relationships (QSAR) between the molecular electronegativity distance vector (MEDV) based on 13 atomic types and the biological activities of a set of selective cyclooxygenase-2 inhibitory molecules, 3,4-diarylcycloxazolones (DAA) plus indomethacin,naproxen, and celecoxib. Using multiple linear regression, a 5-variable linear model is developed with the calibrated correlation coefficient of 0.9271 and root mean square error of 0.17 in modeling stage and the validated correlation coefficient of 0.9030 and root mean square error of 0.20 in leave-one-out validation step, respectively. To further test the predictive ability of the model, 20 DAA compounds are picked up to construct a training set which is used to build a QSAR model and then the model is employed to predict the biological activities of the balance compounds. The predicted correlation coefficient and root mean square error are 0.9332 and 0.19, respectively.     

ELASTIC BEHAVIOR OF PROTEIN-LIKE SINGLE CHAIN

The conformational properties and elastic behaviors of protein-like single chains in the process of tensile elongation were investigated by means of Monte Carlo method. The sequences of protein-like single chains contain two types of residues: hydrophobic (H) and hydrophilic (P). The average conformations and thermodynamics statistical properties of protein-like single chains with various elongation ratio λ were calculated. It was found that the mean-square end-to-end distance r increases with elongation ratio,λ. The tensor eigenvalues ratio of : decreases with elongation ratio λ for short (HP)x protein-like polymers, however, the ratio of : increases with elongation ratioλ,especially for long (H)x sequence. Average energy per bond increases with elongation ratioλ, especially for(H)x protein-like single chains. Helmholtz free energy per bond also increases with elongation ratioλ. Elastic force (f), energy contribution to force (fU) and entropy contribution to force (fs) for different protein-like single chains were also calculated.These investigations may provide some insights into elastic behaviors of proteins.     

离子簇合物HeN_2~+的电子光谱的从头算研究

本文报道了离子簇合物HeN2＋的电子光谱的从头算结果。在MCSCF／6－31G（d，p）水平上，对其基态进行了几何优化，用该构型．在SDC1／6－31（d，p）水平上计算了基态的总能量。用SDCI方法计算得到HeN2＋从基态到选择激发态的垂直跃迁能、振子强度、跃迁频率、辐射寿命以及Einstain系数。该结果可以较好的验证maier的实验。     

聚合物异核交叉弛豫及二维NOE谱

The heteronuclear cross-relaxation rates in polymers were determined by selective and conventional ~(13)C spin-lattice relaxation experiments, the proton-carbon distances were calculated by the theoretical formula, and two-dimensional NOE spectra of the polymers were also measured. The results showed that (1) the measured proton-carbon distances coincide with the distances from molecular models, (2) there is the observable dipolar cross-relaxation effect between the quaternary carbons and their neighboring protons, and (3) the optimum mixing times depend on the relaxation properties of the proton and carbon.     

Application of the iterative difference-dedicated configuration interaction method to the determination of excitation energies in some benchmark systems: Be, CH+, BH and CH2

The iterative difference-dedicated CI method (IDDCI) has been applied to determine excitation energies in small systems for which benchmark FCI and other high-level calculations exist. Transitions to excited singlet and triplet states in Be and vertical transitions in CH⁺, BH and CH₂ are reported. The deviations from FCI results are lower than 0.1 eV and compare advantageously with SDCI including size-consistency corrections, (SC)²SDCI, and with coupled cluster calculations including the effect of triples, especially for the states which have a predominant double excitation character. The IDDCI procedure has been speeded up by using smaller subspaces for optimizing the molecular orbitals. Received: 17 January 1997 / Accepted: 31 July 1997     

Influence of development distance on resolution in thin-layer chromatography

Theoretical equations are given to relate resolution with development distance. Comparative experiments undertaken with quaternary ammonium compounds as test substances and using a selection of basic drugs are presented. As expected, resolution decreases with shorter development distance. However, this effect is less pronounced for compounds with small R_f values and when the spot size at the starting point is kept small. It was also shown that, for correctly assessing resolution in relation to development distance, the amounts of material spotted have to be decreased for shorter development distances.     

A solvent-free lift-off method for realizing vertical organic transistors with low leakage current and high ON/OFF ratio

A solvent-free lift-off method has been introduced to fabricate the aluminum nano-hole array with diameter down to 80 nm as the base electrode for a vertical organic transistor. The imprinted vertical organic transistor exhibited base leakage current density as low as 5 × 10⁻⁵ mA/cm² and high ON/OFF current ratio as high as 10⁵.