液晶的激光拉曼光谱研究——Ⅰ.十九种液晶的固相激光拉曼光谱

本文报道联苯、联苯酯、单酯、双酯、Schiff碱和氧化偶氮苯型十九种液晶化合物的固相激光拉曼光谱,讨论了2300～400 cm~(-1)范围内基团的特征谱带归属以及光谱与结构之间的关系.     

RE2CuO4的热力学稳定性（RE=La,Nd,Sm,Eu）

构筑了ＭｇＯ部分稳定的ＺｒＯ２基固体电解质电化学电池测量ＥＡＦ的实验装置，测定了Ｓｍ２ＣｕＯ４的标准Ｇｉｂｂｓ生成自由能。结果表明化合物ＲＥ２ＣｕＯ２３（ＲＥ＝Ｌａ，Ｎｄ，Ｓｍ，Ｅｕ）随着镧系元素离子半径减小，热力学稳定性下降，并用晶体场理论解释了这一规律。     

螯合型二甘醇钛酸酯的合成及其催化性能研究

报导了两种新的螯合型二甘醇钛酸酯的合成方法，进行了ＩＲ和ＵＶ鉴定，并作为酯化反应催化剂催化合成了邻苯二甲酸二辛酯。研究了酯化反应转化率与反应时间、反应温度及催化剂用量的关系，探讨了催化剂结构与催化性能的关系。     

Single-photon vacuum-ultraviolet laser-pulsed-field ionization-photoelectron studies of trans- and cis-1-bromopropenes

The vacuum-ultraviolet (VUV) pulsed-field ionization-photoelectron (VUV-PFI-PE) spectra of trans-1-bromopropene (trans-CH(3)CH[Double Bond]CHBr) and cis-1-bromopropene (cis-CH(3)CH[Double Bond]CHBr) have been measured in the energy region of 74 720-76 840 cm(-1). The simulation of fine structures observed in the origin VUV-PFI-PE vibrational bands of these molecules has provided the ionization energies (IEs) of trans-1-bromopropene and cis-1-bromopropene to be 74 779.3+/-2.0 cm(-1) (9.2715+/-0.0002 eV) and 75 140.2+/-2.0 cm(-1) (9.3162+/-0.0002 eV), respectively. The vibrational bands resolved in these VUV-PFI-PE spectra at energies 0-1700 cm(-1) above the IEs of trans-1-bromopropene and cis-1-bromopropene have been assigned based on theoretical vibrational frequencies and calculated Franck-Condon factors for the ionization transitions.     

含氰基侧基聚芳醚砜的合成与表征

汉２，６－二卤苯甲腈、４，４′－二氯二苯砜、４，４′－二羟基二苯砜、间苯二酚、对苯二酚、酚酞及双酚Ａ为主要原料，合成了含不同结构单元和不同氰基含量的含氰基侧基的聚芳醚砜，并采用ＩＲ、＾１３ＣＮＭＲ等分析手段对其结构进行了表征，同时研究了结构单元和氰基含量对聚芳醚砜性能的影响。     

A Kinetic Evidence for the Nitroxyl Radicals Recycling Mechanism in the Photostabilizing Process of HALS

The photoinduced bulk polymerization of a reactive-hindered amine fight stabilizers(r-HALS), 4-acryloyl-2, 2, 6, 6-tetramethylpiperidinyl (ATMP), was performed at 80℃ by using a DPC technique. An unique periodic exponential attenuation-type oscillating curve was found when the polymerization was carried out in air, but this phenomenon was not found in nitrogen.It is supposed that this unique kinetic performance may be attributed to nitroxyl radicals that are produced in situ from the oxidation of ATMP. ATMP polymer with narrow polydispersity (d =1.03) can be obtained by photoinduced solution polymerization of ATMP. The signal detected in ESR may be assigned to the nitroxyl radicals in the matrix of ATMP polymer. Since this kind of recycling of nitroxyl radicals is well documented for the photostabilizing mechanism of HALS, the present results may serve as a kinetic evidence for this mechanism.     

可逆与不可逆吸附氢在合成甲醇反应中的作用

在自行设计和建立的加压动态分析装置上研究了合成甲醇催化剂上氢的吸附和反应行为。结果表明:在反应条件下催化剂上吸附的氢可分为可逆吸附氢和不可逆吸附氢;不可逆吸附氢又可分为能被CO顶替出来的和不能被CO顶替出来的两部分;能被CO顶替出来的不可逆吸附氢对CO的吸附起促进作用,不能被CO顶替出来的不可逆吸附氢是合成甲醇催化剂必不可少的“组分”或称“促进剂”;同时甲醇的生成是可逆吸附氢与一氧化碳作用的结果。     

Synthesis of Thiourea Derivatives on Soluble Polymeric Support

A modified poly(ethylene glycol) (PEG) has been developed as the soluble polymeric supports for liquid phase synthesis of novel thiourea derivatives.In each step of the sequence,the PEG-bound products were precipitated in cold Et2O and the unreacted materials and by-products were removed by simple filtration.The progress of reaction,purity of the isolation and the structure of the PEG-bound products were easily monitored by TLC,IR and ^1H NMR spectra.Representative thiourea derivatives were obtained in moderate yields with excellent purity from this modified PEG-bound product by the cleavage with 50% TFA/H2O.     

两亲性丙烯酸酯共聚物的聚合研究

利用过氧化苯甲酰为引发剂探讨了甲基丙烯酸β－羟乙酯和丙烯酸长链烷基酯的自由基共聚合。重点讨论了合成条件如溶剂、沉淀剂、引发剂用量、单体配比、反应时间等对共聚反应的影响以及各种聚合条件对该共聚物的组成、结构和性能的影响。并用ＩＲ，ＧＰＣ，＾１３ＣＮＭＲ等手段对共聚物进行了表征。     

ROOM-TEMPERATURE FLUORESCENCE PROPERTIES OF THE POLYNUCLEOTIDE POLYdA POLYdT

The room-temperature fluorescence spectrum of the non-alternating polynucleotide polydA.polydT is found to have its maximum at about 325 nm and, when exciting in the spectral region where both adenine (A) and thymine (T) absorb, to coincide with that obtained for excitation at 293 nm where thymine is selectively excited. The fluorescence anisotropy is found to be equal to 0.18 and independent of the excitation and emission wavelengths. These observations are consistent with: (i) emission stemming from T; and (ii) transfer of electronic energy from A to T being not efficient. These inferences are also supported by the observed dependence of the fluorescence quantum yield on the excitation wavelength.