低头-头链含量的聚偏氟乙烯合成

研究了偏氟乙烯的聚合条件与其聚合物的头-头链含量的关系。实验表明聚合物的头-头链的含量与聚合温度有关,而与引发剂的种类无关。因而,可以在较低的聚合温度下聚合制得带有低的头-头结构(约3％)的聚偏氟乙烯。将聚合物链的A结构含量对其熔点作图,得一直线,可表示为方程式A=24.8+0.362T_m(％)。     

General calculation of 4f-5d transition rates for rare-earth ions using many-body perturbation theory

The 4f-5d transition rates for rare-earth ions in crystals can be calculated with an effective transition operator acting between model 4f(N) and 4f(N-1)5d states calculated with effective Hamiltonian, such as semiempirical crystal Hamiltonian. The difference of the effective transition operator from the original transition operator is the corrections due to mixing in transition initial and final states of excited configurations from both the center ion and the ligand ions. These corrections are calculated using many-body perturbation theory. For free ions, there are important one-body and two-body corrections. The one-body correction is proportional to the original electric dipole operator with magnitude of approximately 40% of the uncorrected electric dipole moment. Its effect is equivalent to scaling down the radial integral (5d/r/4f) to about 60% of the uncorrected HF value. The two-body correction has magnitude of approximately 25% relative to the uncorrected electric dipole moment. For ions in crystals, there is an additional one-body correction due to ligand polarization, whose magnitude is shown to be about 10% of the uncorrected electric dipole moment.     

Preparation and characterization of trans-RhCl(CO)(TPPTS)2-intercalated layered double hydroxides

trans-RhCl(CO)(TPPTS)₂ (TPPTS=tris(m-sulfonatophenyl)phosphine) has been intercalated into Zn-Al layered double hydroxides (LDHs) by the method of ion exchange. The structure, composition and thermal stability of the composite material have been characterized by powder X-ray diffraction, Fourier transform infrared and ³¹P solid-state magic-angle spinning nuclear magnetic resonance spectroscopy, elemental analysis, thermogravimetry, and differential thermal analysis. The geometry of trans-RhCl(CO)(TPPTS)₂ was fully optimized using the PM3 semiempirical molecular orbital method, and a schematic model for the intercalated species has been proposed. The thermal stability of trans-RhCl(CO)(TPPTS)₂ is significantly enhanced by intercalation, which suggests that such materials may have prospective application as the basis of a supported catalyst system for the hydroformylation of higher olefins.     

Study on the Phase Diagram of CsCl-CeCl3-HCl(11%)-H2O System and the Properties of the Compounds

The equilibrium solubility of CsCl-CeCl3-HCl(11%)-H2O qua-ternary system at 25℃ has been determined by the physicchemical analysis method ,and the phase diagram was plotted, Two new double salts 3CsCl.CeCl3.3H2O and CsCl.CeCl3.4H2O obtained from the complicated system were identified and characterized by XRD,TG-DTA ,DSC,UV and fluorescence spectroscopy, Studies on the fluorescence excitation and emission show that 3CsCl.CeCl3.3H2O and CsCl.CeCl3.4H2O have upconversion luminescence of infrared-visible range,and the upconversion emission intensity increases with the increase of ratio of CeCl3 in CsCl.     

Self-assembling of helical poly(phenylacetylene) carrying L-valine pendants in solution, on mica substrate, and on water surface

In the present work, we investigated self-assembling of a poly(phenylacetylene) carrying L-valine pendants (PPA-Val) in a water/methanol solution, upon evaporation of the solution on mica, and on the water surface. With intercalation of a fluorescence probe of Ru(phen)2(dppx)2+ (phen = 1,10-phenanthroline, dppx=7,8-dimethyldipyridophenazine) into the hydrophobic cavities associated by the PPA-Val chains, their helical structures were directly detected in solution with an in situ fluorescence microscope. Helical aggregates were observed with AFM upon evaporation of the solvents, suggesting that the helical structures in the solution are the building blocks of the helical aggregates. Self-assembling structures of PPA-Val on the water surface were, however, very different from that formed upon evaporation of its THF solution on the mica surface. The polymer chains associated into a monolayer of extended fibers on the water surface, whereas superhelical fibers formed on the mica surface. Water molecules play a critical role in inducing the polymer to form diverse morphological structures in its bulk solution and on its surface. In solution, the isotropic hydrophobic effect drove the polymer chains to form superhelical aggregates, while on the water surface, the hydrophobic effect concentrated mainly on the lateral part of the polymer, thus giving a monolayer of extended fibers.     

离子交换色谱法检测离子液体中阴离子

建立了用阴离子交换分离柱、化学抑制模式、电导检测测定系列离子液体中BF-4阴离子及其他杂阴离子(F-、Cl-、Br-)含量的方法,并用于在线监控离子液体合成工艺中阴离子杂质含量.确定淋洗液组成为1.6 mmol/L Na2CO3+3.9 mmol/L NaHCO3,流速为0.6 mL/min.本方法对所测阴离子检出限分别为50 μg/L(F-、Br-)和80 μg/L(BF-4);线性范围在3个数量级以上;r＞0.999;回收率在98%～102%之间.方法用于对离子液体小试工艺样品分析及过程监控时,结果满意,样品的RSD小于2.6%(n＝6).     

Cyclodextrin Solubilization of the Antibacterial Agents Triclosan and Triclocarban: Effect of Ionization and Polymers

The natural β-cyclodextrin (βCD) and its complexes have limited solubility in aqueous solutions. This low aqueous solubility, as well as low aqueous solubility of the guest molecule (i.e. triclosan or triclocarban (TCC)), can result in low complexation efficiency (CE). The purpose of this study was to enhance the apparent intrinsic solubility (S ₀) of the guest molecule and its βCD complexes through ionization and addition of auxiliary compounds such as polymers, amino acids and metal ions. Both triclosan (pK _a 7.9) and TCC (pK _a 12.7) are weak acids. Addition of ethanol to the complexation medium enhanced S ₀ of both triclosan and TCC but at the same time ethanol lowered the stability constant (K _c ) of their βCD complexes resulting in overall lowering of CE. Addition of small amount of water-soluble polymers enhanced the βCD solubilization of both guests, and addition lysine enhanced the solubilization of TCC. Ionization of triclosan resulted in significant enhancement of CE and enhanced triclosan release from tablets containing triclosan/βCD complex. The effect of ionization was not as pronounced in the case of TCC.This revised version was published online in July 2005 with a corrected issue number.     

A modified internal lock-mass method for calibration of the product ions derived from sustained off-resonance irradiation collision-induced dissociation using a Fourier transform mass spectrometer

A modified internal lock-mass calibration method is introduced for improving the mass measurement accuracy of the product ion spectra derived from sustained off-resonance irradiation collision-induced dissociation (SORI-CID) Fourier transform ion cyclotron resonance (FTICR) mass spectrometry. This method involves an initial external calibration of the Fourier transform mass spectrometer to obtain the initial A- and B-terms for the equation (f(i) = A/(m/z)(i) + B). The A-term is adjusted by using an empirical relationship between the up-shift of the A-term and the pulse-gas duration, whereas the B-term is adjusted by using the mass of the unfragmented precursor ion from the SORI-CID mass spectrum of the unknown sample as internal lock-mass. These adjusted A- and B-terms are then used to provide exact mass SORI-CID calibration for the unknown sample. The modified internal lock-mass method achieved average mass measurement accuracy of approximately 3 ppm which is significantly better than that of the conventional internal lock-mass calibration ( approximately 9 ppm) and is approaching that of the internal calibration ( approximately 2 ppm) and requires no addition of internal calibrant or instrumental modifications.     

Novel hydrogen-bonded three-dimensional network complexes containing cobalt-pyridine-2,6-dicarboxylic acid

The novel complex, Co(H₂O)₅[Co(2,6-pydc)₂] (1) has been prepared in aqueous solution and characterized by single-crystal X-ray diffraction, elemental analyses and i.r. spectra. X-ray structural analysis revealed that three novel compounds each possess both – stacking and hydrogen-bonding interaction three-dimensional (3-D) networks.     

熔融碳酸盐燃料电池阳极材料表面改性

选择铌作为合金化元素，通过氟化物熔盐电化学表面合金化的方法对熔融碳酸盐燃料电池阳极材料镍进行表面改性，改性后的阳极材料的耐蚀性能与电催化性能均得到明显的改善。