盐类对4-氯-4′-羟基二苯砜钾盐真空熔融聚合的影响

聚苯砜醚是一种综合性能比较好、可在180℃长期使用的热塑性工程塑料,在国内外受到一定的重视。我们与武汉化工原料厂协作,对4-氯-4′-羟基二苯砜钾盐真空熔融缩聚合成聚苯砜醚的途径进行过一些探索,得到了较好的结果。但是,在实践中发现,由于这一反应速度快,放出的热量大而集中,在真空中聚合热不易导出,随着单体用量     

Aging of poly(2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene)/toluene solutions and subsequent effects on luminescence behavior of cast films

Morphological effects in luminescence properties of a representative semiconducting polymer, poly(2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV), has recently attracted much attention. Previous studies indicated that short-term heat treatment of solution-cast MEH-PPV films may result in the formation of mesomorphic order that is responsible for the "red" emission around 640 nm, in contrast to the single-chromophore "yellow" emission near 590 nm from the disordered matrix. On the basis of microscopic and spectroscopic evidence for films cast from freshly prepared and aged solutions, here we show that prolonged storage of MEHyellowPPV solutions at room temperature or lower may result in retardation of the thermally induced mesophase formation in the subsequently cast films. According to small-angle neutron scattering and differential scanning calorimetric observations over aged MEH-PPV/toluene solutions, we propose that the suppressed transformation into mesomorphic order is due to further development of nanocrystalline aggregates that serve as physical cross-links among MEH-PPV chains in the solution state upon long-term storage. These solvent-induced nanocrystalline aggregates, however, do not exhibit new spectroscopic features beyond the suppression of "red" emission at 640 nm from the mesomorphic phase.     

An immune algorithm for resolution of multicomponent overlapping chromatograms

A novel immune algorithm for resolution and quantitative determination of the components in overlapping chromatograms was proposed by imitating biological immune systems. The algorithm takes an overlapping chromatogram as its input and subtracts the chromatograms of standard samples from the input by iteration of a network. When the residual does not change, the network will converge and chromatographic information of the components in overlapping chromatogram will be obtained. Both simulated and experimental data sets were investigated by the method. Results showed that both resolved results and recoveries of quantitative determination are satisfactory. Comparing with conventional least-square method, the immune algorithm is fast in calculation.     

Synthesis and optical resolution of a series of inherently chiral calix[4]crowns with cone and partial cone conformations

A series of inherently chiral calix[4]arenes with cone and partial cone conformations and with crown ether moieties of variable size have been readily synthesized. By taking advantage of the carboxy appendage on the lower rim, these were condensed with the chiral auxiliary (S)-BINOL to form diastereomers which, in most cases, could be separated by preparative TLC, or more desirably, by column chromatography on silica gel (diastereomeric excess >99 % based on HPLC analysis). Seven enantiopure antipodes of inherently chiral calix[4]crowns were obtained after hydrolysis. It has been found that both the size of the crown moiety and alkylation of the last phenolic hydroxy group (accompanied with or without a change in the conformation) affect the separation of the diastereomers.     

Adsorption energy distribution model for VOCs onto activated carbons

An adsorption isotherm model was proposed for two types of volatile organic compounds (VOCs) on a heterogeneous carbon surface. The Langmuir isotherm was used as a local isotherm for describing heterogeneous surfaces to obtain the adsorption energy distribution. The adsorption temperature studied ranged from 30 to 50 degrees C, and the pressure of VOCs varied from 0 to 0.35 atm. The present model differed from previous studies in assuming that the pre-exponential factor was not to be a constant. The pre-exponential factors were determined directly from the experimental data, and the result empirically showed that the pre-exponential factor was correlated with the adsorption energy by a simple exponential function. We found that both adsorption energy distributions of two VOCs were essentially step functions over the restricted pressure range, indicating adsorbates on the carbon surface with its own uniform distribution. By incorporation of the energy distribution and the relationship between the pre-exponential factor and the adsorption energy, the adsorption isotherms for the two VOCs on the carbons can be well predicted.     

DOPING LEVEL INCREASE OF POLY(3-METHYLTHIOPHENE)FILM DURING ELECTROCHEMICAL POLYMERIZATION PROCESS

The Raman spectra of poly(3-methylthiophene) (PMeT) films with different thicknesses, which have beenelectrochemically deposited on a flat stainless steel electrode surface by direct oxidation of 3-methylthiophene in borontrifluoride diethyl etherate (BFEE) at a constant applied potential of 1.38 V (versus SCE), have been investigated byexcitation with a 633-nm laser beam. The spectroscopic results demonstrated that the doping level of PMeT film wasincreasing during film growth. This finding was also confirmed by electrochemical examination. Moreover, the Raman bandsassigned to radical cations and dications in doped PMeT films were found approximately at 1420 and 1400 cm~(-1),respectively. Radical cations and dications coexist on the backbone of PMeT as conductive species and their concentrationsincrease with the increase of doping level. Successive cyclic voltammetry was proved to be an effective approach toimproving the doping level of as-grown thin compact PMeT film.     

STABILITY OF POLY（N,N＇-METHYLENEBISACRYLAMIDE-co-4-VINYLPYRIDINE） MICROGEL DISPERSION AND ADJUSTMENT OF THE HYDROPHOBICITY IN THE MICROGELS

In the UV-Vis spectra of pure light-scattering systems, there is an exponential relationship between absorbance and wavelength （A = Kλ^-n）. Here, the exponent n is named as flocculation-coagulation parameter. In the present paper, the effects of different additives on the stability of poly（N,N＇-methylenebisacrylamide-co-4-vinylpyridine） （poly（Bis-co-4-VP）） microgel dispersion were studied in detail via this parameter. The results showed that the stability of the dispersion mainly comes from the ionization of pyridine groups, making the microgel positively charged on its surface. This was confirmed by the measurement of Zeta potential and the result of conductometric titration. The result of fluorescence analysis indicated that the hydrophobicity in the microgels is enhanced with the increase in total 4-VP unit content.     

Electron Paramagnetic Resonance Study of Radical Pairs and Isolated Radicals Trapped in Irradiated Long-Chain Hydrocarbons at Low Temperatures

The intrinsic characteristics of radical pairs produced in squalane and in cetane receiving high gamma-dose are extensively studied with the EPR technique at temperatures from 77°K up to 150°K. The spectra of the paired radicals occur at g=4 with a very low transition probability in contrast to that of isolated radicals which appear at g=2 A well-resolved hyperfine spectrum corresponding to the species (CH₃CH₂.CH₂CH₃) is observed in cetane. The isothermal decay rates of radical pairs in cetane below 100°K are significantly slow; however, the decay kinetics at 150°K is first order with rate constant=1.86 min^?1. A relatively slower decay rate is obtained for isolated radicals suggesting that the decay mechanism of paired radicals is through geminate recombination. The relative inter-radical distance in radical pairs is known from a decay curve as a function of temperature. The yields of radical pairs are low in both matrices, only few percents of those of isolated radicals. The formation mechanisms of paired radicals with direct radiolytic bond scission process are discussed in connection with the experimental observations.     

Characterization of highly sulfated cyclodextrins

A class of highly sulfated cyclodextrins (HS-CDs) was developed for enantiomeric separation of chiral compounds by capillary electrophoresis (CE). The HS-CDs were produced by a facile single-step direct sulfation of cyclodextrin using sulfur trioxide-trimethylamine complex in dimethylformamide. Characterization of the HS-CDs by electrospray ionization mass spectrometry and by CE using a well-established indirect detection method indicated the species have very narrow heterogeneity in terms of degree of sulfation. Elemental analysis of the HS-alpha-, beta- and gamma-CDs showed that the average sulfate contents were 11, 12, and 13 per CD molecule, respectively. The 13C NMR of HS-CDs is consistent with the structural assignment of nearly complete sulfation at C-6 primary hydroxyl groups and partial sulfation at the C-2 secondary hydroxyls (>70%), while the C-3 hydroxyls remain unsubstituted. Enantiomeric separation by CE using the HS-CDs as chiral selectors showed that HS-alpha-, beta- and gamma-CDs complement each other by exhibiting different chiral selectivities, resulting in resolution of many chiral neutral, acidic and basic compounds of greatly varying structural features. The part of HS-CD that interacts with the guest molecule during complexation and, therefore, the receiving end of the cyclodextrin hydrophobic bucket was surrounded with largely regiospecifically substituted C-2 sulfates and intact C-3 hydroxyls, both at the equatorial positions. Such global regiospecific structural arrangement in HS-CDs provides differential diasteroisomeric complexation is proposed to be the principal contributing factor in the resolving racemates.     

Effect of some factors on the energy band structure of proteins

The effects of four factors (different side chains, side-chain disorder, conformational change, and ions and water) on the energy band structures of proteins have been investigated with the aid of the CNDO/2 crystal orbital method. The results indicate that these factors are very important. The consequences of these effects on the semiconductive properties of proteins are discussed.