The Electronic Structure of Phenylene and Naphthylene Bicyclobutanes. Photoelectron spectroscopy and model calculations

The photoelectron (PE.) spectra of 1,2,3-methenoindane ( 2 ), 1,2,3-metheno-2,3-dihydro-1H-cyclopenta [b]naphthalene ( 3 ) and 1,2,3-metheno-2,3-dihydro-1H-phenalene ( 4 ) are investigated. The PE. spectrum of 1,3-methano-2,3-dihydrophenalene ( 7 ) is reported and compared with that of 4 . The experimental results are analyzed in terms of empirical correlation diagrams and the results of semiempirical MINDO/3 and CNDO/S calculations. The analysis indicates that the strong impact of the bicyclobutylene group on the spectroscopic properties of the aromatic π-systems in 2 , 3 and 4 is due to hyperconjugative interactions involving bicyclobutane Walsh orbitals.     

The Electronic Structure of Carcinogenic Dibenzopyrenes: Linear Dichroism, Fluorescence Polarization Spectroscopy and Quantum Mechanical Calculations

Abstract— In studies of polycyclic aromatic hydrocarbon carcinogenicity three dibenzopyrenes have been named as the strongest mutagens together with the frequently studied benzo[a]pyrene. A detailed study of the electronic structure of one of the three compounds, dibenzo [ a, i ] pyrene, was performed several years ago. Here we present a similar study of the two remaining compounds, dibenzo [ a, h ] pyrene and dibenzo [ a, e ] pyrene. The studies include electronic linear dichroism spectra, fluorescence polarization spectra and quantum mechanical calculations for both molecules, as well as vibrational linear dichroism spectra for the former of the two.     

Magnetic Circular Dichroism and Electronic Spectra of Tropothione

The magnetic circular dichroism (MCD) and electronic absorption spectra of tropothione have been measured. The circular-dichroism (CD) spectrum of the β-cyclodextrin complex with tropothione is also reported. The absorption bands of tropothione are assigned.     

基于噻吩和亚苯基合成的新物质的结构和电子性质

Theoretical study on the geometries and electronic properties of new conjugated compounds based on thiophene and phenylene was carried out. The theoretical ground-state geometries and electronic structures of the studied molecules were obtained using the density functional theory (DFT) method at B3LYP level with 6-31G(d) basis set. The electronic properties were determined by ZINDO/s, CIS/3-21G(d), and TD//B3LYP/3-21G(d) calculations performed on the B3LYP/6-31(d) optimized geometries. The effects of the ring structure and the substituents on the geometries and electronic properties of these materials were discussed. The results of this study indicate how the electronic properties can be tuned by the backbone ring or side group and suggest these compounds as good candidates for opro-electronic applications.     

Structural and Electronic Properties of New Materials Based on Thiophene and Phenylene

Theoretical study on the geometries and electronic properties of new conjugated compounds based on thiophene and phenylene was carried out. The theoretical ground-state geometries and electronic structures of the studied molecules were obtained using the density functional theory (DFT) method at B3LYP level with 6-31G(d) basis set. The electronic properties were determined by ZINDO/s, CIS/3-21G(d), and TD//B3LYP/3-21G(d) calculations performed on the B3LYP/6-31(d) optimized geometries. The effects of the ring structure and the substituents on the geometries and electronic properties of these materials were discussed. The results of this study indicate how the electronic properties can be tuned by the backbone ring or side group and suggest these compounds as good candidates for opto-electronic applications.     

The Glass Transition of Linear Polyethylene

The assignment of the glass transition temperature of polyethylene has been a matter of heightened controversy in recent years, and has formed the basis of several reviews [la-Id] as well as numerous original contributions. The controversy in polyethylene has also focused attention on other issues: analogous questions of T_g's of other highly crystalline'polymers, a renewed interest in the molecular mechanism of frictional loss and mechanical relaxations in polymers and their relation to thermodynamic measurements, and in the origin of differences in the properties of branched and linear polyethylene and, by implication, other polymers with similar structural variations. The purpose of this paper is twofold: a) to undertake a limited discussion of some of the wider issues listed above, and b) to present the results of new heat capacity measurements for polyethylene that have bearing on the T_g controversy.     

Electronic Circular Dichroism Spectra of DNA Quadruple Helices Studied by Molecular Dynamics Simulations and Excitonic Calculations including Charge Transfer States

We here investigate the Electronic Circular Dichroism (ECD) Spectra of two representative Guanine-rich sequences folded in a Quadruple helix (GQ), by using a recently developed fragment diabatisation based excitonic model (FrDEx). FrDEx can include charge transfer (CT) excited states and consider the effect of the surrounding monomers on the local excitations (LEs). When applied to different structures generated by molecular dynamics simulations on a fragment of the human telomeric sequence (Tel21/22), FrDEx provides spectra fully consistent with the experimental one and in good agreement with that provided by quantum mechanical (QM) method used for its parametrization, i.e., TD-M05-2X. We show that the ECD spectrum is moderately sensitive to the conformation adopted by the bases of the loops and more significantly to the thermal fluctuations of the Guanine tetrads. In particular, we show how changes in the overlap of the tetrads modulate the intensity of the ECD signal. We illustrate how this correlates with changes in the character of the excitonic states at the bottom of the La and Lb bands, with larger LE and CT involvement of bases that are more closely stacked. As an additional test, we utilised FrDEx to compute the ECD spectrum of the monomeric and dimeric forms of a GQ forming sequence {"type":"entrez-nucleotide","attrs":{"text":"T30695","term_id":"612793"}}T30695 (5′TGGGTGGGTGGGTGGG3′), i.e., a system containing up to 24 Guanine bases, and demonstrated the satisfactory reproduction of the experimental and QM reference results. This study provides new insights on the effects modulating the ECD spectra of GQs and, more generally, further validates FrDEx as an effective tool to predict and assign the spectra of closely stacked multichromophore systems.     

傅立叶红外光谱法对LDPE和LLDPE的快速鉴定

低密度聚乙烯(low density polyethylene, LDPE)具有良好的柔软性、延伸性、透明性,有优良的加工性,化学稳定性、透气性能好,电绝缘性能优异,但其机械强度、耐环境老化性能较差.LDPE的用途十分广泛,可用于各种薄膜和注塑、吹塑制品.线型低密度聚乙烯(linear low density polyethylene, LLDPE)是乙烯和а-烯烃的共聚物,其热变形温度高,具有较高的耐热性和耐低温性、优良的弯曲强度和电绝缘性能,还具有很好的柔软性,是一种耐热、耐穿刺、耐撕裂和阻隔性较好的理想包装薄膜材料[1].LDPE和LLDPE用途广泛,我国对LDPE和LLDPE树脂的进口量较大,海关通常要对其进行抽验.LDPE树脂的海关商品编号为3901.1000,LLDPE树脂的海关商品编号为3901.9020[2].确定样品的品名对于商品的归类关系重大,商品归类的不同,那么商品的海关监管条件和进口税率相应会有所变化.因此,建立一种快速鉴定LDPE和LLDPE的方法,对加快海关的通关放行,避免客户的损失具有较大的意义.实验室应用傅立叶红外光谱法经过反复的检测分析,找出LDPE和LLDPE的红外特征性,建立了快速鉴定LDPE和LLDPE的方法,方法快速、安全、简便.     

Gaussian 09软件在电子圆二色谱教学中的应用

利用Gaussian 09软件优化并计算了手性农药R-丁烯氟虫腈和S-丁烯氟虫腈的电子圆二色谱,讨论了其在立体化学(电子圆二色谱)教学中的具体应用,帮助学生对手性分子的三维空间结构、电子圆二色谱的理解及归属等方面有更加感性的认识,使教学内容形象生动,提高了学生的学习兴趣及积极性。     

LLDPE／LDPE共混体系的相容性与性能

ＬＬＤＰＥ／ＬＤＰＥ共混体系的相容性与性能杨毓华，花荣，白春霞，于旻李三喜，葛铁军（中国科学院长春应用化学研究所长春１３００２２）（沈阳化工学院高分子系沈阳）关键词ＤＳＣ，ＷＡＸＤ，力学性能，ＬＬＤＰＥ，ＬＤＰＥ，共混，相容性非晶－非晶－结晶共混体系...     

Excited Biradicals in Thermal Dimerization and Polymerization of Bicyclobutanes

The structure and electronic parameters of 1-cyanobicyclobutane and 1-cyano-3-vinylbicyclo-butane were determined by RHF, ROHF, and GVB (TCSCF)/6-31G* quantum-chemical calculations.     

Supercritical CO_2 Assisted Preparation of Open-cell Foams of Linear Low-density Polyethylene and Linear Low-density Polyethylene/Carbon Nanotube Composites

The open-cell structure foams of linear low-density polyethylene(LLDPE) and linear low-density polyethylene(LLDPE)/multi-wall carbon nanotubes(MWCNTs) composites are prepared by using supercritical carbon dioxide(sc-CO_2)as a foaming agent. The effects of processing parameters(foaming temperature, saturation pressure, and depressurization rate) and the addition of MWCNTs on the evolution of cell opening are studied systematically. For LLDPE foaming, the foaming temperature and saturation pressure are two key factors for preparing open-cell foams. An increase in temperature and pressure promotes both the cell wall thinning and cell rupture, because a high temperature results in a decrease in the viscosity of the polymer, and a high pressure leads to a larger amount of cell nucleation. Moreover, for the given temperature and pressure, the high pressurization rate results in a high pressure gradient, favoring cell rupture. For LLDPE/MWCNTs foaming, the addition of MWCNTs not only promotes the cell heterogeneous nucleation, but also prevents the cell collapse during cell opening, which is critical to achieve the open-cell structures with small cell size and high cell density.     

Processability and Application of Metallocene Linear Low Density Polyethylene

1. The structure and feature ofm-LLDPE Due to having a kind of active site in metallocene catalyst, the rate of polymerization and insertion of comonomer are very uniform. Compared with conventional LLDPE, the structure of m-LLDPE has such features: (1) a narrow molecular weight distribution, about 2.0-2.5. The conventional LLDPE, however, has a wide molecular weight distribution, about 4.0-8.0, (2) the distribution of comonomer between different m-LLDPE molecular chain is very uniform, (3) the distribution of comonomer intermolecular-chain is very uniform.     

Novel Generation of Liquid Crystalline Photo‐Actuators Based on Stretched Porous Polyethylene Films

The preparation of photo‐actuators based on stretched porous polyethylene and an azobenzene‐containing liquid crystalline polymer network is reported for the first time. It is revealed that this kind of photo‐actuator possesses the following advantages: the lack of a need for using aligning coatings and cells preparation, high deformation of the actuator and its complete reversibility, good mechanical properties, and relatively low cost of fabrication. In addition some kinetic and thermodynamic features of the bending and unbending processes have been studied.     

Resolving Electronic Transitions in Synthetic Fluorescent Protein Chromophores by Magnetic Circular Dichroism

The detailed electronic structures of fluorescent chromophores are important for their use in imaging of living cells. A series of green fluorescent protein chromophore derivatives is examined by magnetic circular dichroism (MCD) spectroscopy, which allows the resolution of more bands than plain absorption and fluorescence. Observed spectral patterns are rationalized with the aid of time‐dependent density functional theory (TDDFT) computations and the sum‐over‐state (SOS) formalism, which also reveals a significant dependence of MCD intensities on chromophore conformation. The combination of organic and theoretical chemistry with spectroscopic techniques also appears useful in the rational design of fluorescence labels and understanding of the chromophore's properties. For example, the absorption threshold can be heavily affected by substitution on the phenyl ring but not much on the five‐member ring, and methoxy groups can be used to further tune the electronic levels.     

Limitations of Linear Dichroism Spectroscopy for Elucidating Structural Issues of Light-Harvesting Aggregates in Chlorosomes

Linear dichroism (LD) spectroscopy is a widely used technique for studying the mutual orientation of the transition-dipole moments of the electronically excited states of molecular aggregates. Often the method is applied to aggregates where detailed information about the geometrical arrangement of the monomers is lacking. However, for complex molecular assemblies where the monomers are assembled hierarchically in tiers of supramolecular structural elements, the method cannot extract well-founded information about the monomer arrangement. Here we discuss this difficulty on the example of chlorosomes, which are the light-harvesting aggregates of photosynthetic green-(non) sulfur bacteria. Chlorosomes consist of hundreds of thousands of bacteriochlorophyll molecules that self-assemble into secondary structural elements of curved lamellar or cylindrical morphology. We exploit data from polarization-resolved fluorescence-excitation spectroscopy performed on single chlorosomes for reconstructing the corresponding LD spectra. This reveals that LD spectroscopy is not suited for benchmarking structural models in particular for complex hierarchically organized molecular supramolecular assemblies.     

线性低密度聚乙烯合成研究进展

共单体效应;原位共聚;后过渡金属催化剂;综述     

Linear Viscoelasticity of Concentrated Polyethylene Glycol tert-Octylphenyl Ether Solutions

Linear viscoelastic studies were carried out on concentrated polyethylene glycol tert-octylphenyl ether solutions over a range of temperatures and concentrations comprising the lamellar and hexagonal liquid-crystalline phases and the isotropic surfactant-rich phase. The generalized or a simple Maxwell model fits the frequency dependence of the dynamic functions for the hexagonal and isotropic surfactant-rich phases, respectively. The combined influence of temperature and concentration on both the zero-shear rate-limiting viscosity and the relaxation time for isotropic samples follows an exponential dependence. The results are discussed according to the phase behaviour of these systems.     

Circular and Linear Dichroism of Aggregates of Chlorophyll a and Chlorophyll b in 3-Methylpentane and Paraffin Oil

A circular (CD) and linear dichroism (LD) study of the water adducts of the green plant chlorophylls a (Chl a) and b (Chl b) in hydrocarbon solvents 3-methylpentane and paraffin oil is presented. A strong red shift of the Q_y-absorption band from 663 to 746 nm (1678 cm^?1) is observed as the water adduct of Chl a is formed. The Chl a-water adduct shows a strong, nonconservative CD signal, which is characterized by a positive peak at 748 nm and two negative peaks at 720 and 771 nm. The maximum CD (A_L - A_R) is only one order of magnitude smaller than the isotropic absorption maximum. We propose that this exceptionally strong signal is the so-called psi-type CD. The LD spectrum was measured in a flow of paraffin oil. The isotropic absorption maximum peaks at 742 nm in paraffin oil, whereas the maximum of the LD signal is at 743 nm. The LD signal is positive over the whole water-adduct absorption band indicating that the transition dipole of the 742 nm transition is preferentially oriented along the long axis of the aggregate. The structure of the Chl b-water adduct is less well defined. The preparations of the Chl b-water adduct are unstable. The Chl b-water adduct absorption band maximum is at 683 nm. The CD signal of the Chl a-water adduct is about 200-fold the CD of the Chl b-water adduct. We could not orient the Chl b-water adducts by flow, which suggests that the adducts are small or disordered.     

Pulsed Electric Linear Dichroism of Triphenylmethane Dyes Adsorbed on Montmorillonite K10 in Aqueous Media

Electric linear dichroism (ELD) spectra of two cationic triphenylmethane dyes, crystal violet (CV) and malachite green (MG), bound to sodium montmorillonite K10 (MK-10) were studied at 20 degrees C in aqueous media at two mixing ratios, D/S, of 0.10 and 0.24 in the 700- to 400-nm wavelength region and in the applied electric field strength range between 0 and 3 kV/cm. The specific parallel and perpendicular dichroism (Delta A( ||)/A and Delta A( perpendicular)/A) spectra of dye-adsorbed MK-10 suspension were measured at a fixed field strength with an apparatus equipped with a 512-channel photodiode array detector. By changing the field strength over a wide range, a series of the reduced dichroism values of the bound dyes were measured at a fixed wavelength. By fitting these dichroism values to theoretical orientation functions, the intrinsic reduced dichroism (Delta A/A)(int) spectra at the limiting high fields (ELD spectrum) were determined for CV and MG bound to MK-10. No appreciable difference was observed at the two D/S values. The ELD spectra of these bound dyes are undulatory but never constant, throughout their absorption region; thus, the dye plane does not lie flatly either on the surface or between layers of MK-10 particle. The isotropic absorption spectra, A, of bound CV and MG were each deconvoluted to eight partial absorption bands, which were grouped into three differently polarized transitions, i.e., one out-of-plane and two mutually perpendicular in-plane. The optical transition dipole moment direction of each group was found to make a considerable angle with respect to the symmetry axis of the disklike MK-10 particle, whose plane (or surface) tends to orient toward the applied electric field at the limiting high fields. By simulating the observed ELD spectra of bound CV and MG with those deconvoluted bands, the roll, tilt, and inclination angles of both dyes were evaluated quantitatively with a new analytical method. The average angles (+/-θ(R), +/- θ(T), |θ(N)|) are -(34-47) degrees, 34 degrees, and 51 degrees for bound CV and -44 degrees, 32 degrees, and 53 degrees for bound MG at two D/S values; thus, the triangular plane of each dye is rolled as well as tilted with a large inclination angle. Copyright 2000 Academic Press.