纳秒强激光场中苯电离产生高价离子的研究

用25 ns脉冲Nd-YAG 532 nm的激光，在1010～1011 W•cm－2的光场强度下，利用飞行时间质谱对He、 N2、Ar载气条件下苯的激光电离过程进行了研究.发现当利用氩作为载气时，除观察到C2＋、C2H2+、C3H3+、C6H6+离子外，还观察到很强的Cq＋(q=1～3)高价离子.这些离子都有很高的平动能， C2＋的最可几平动能为12.9 eV， C3＋为37.5 eV.通过改变载气种类和压力及在不同光场强度条件下的实验，可以认为这些高价离子来源于含苯团簇的库仑爆炸过程.     

铁硅酸盐分子筛乙苯氧化脱氢催化性能研究Ⅱ．FeZSM－5的酸碱性质和积炭对反应活性的影响

本文应用碱性气体吸附的红外光谱和ＴＰＤ技术研究了ＦｅＺＳＭ－５（Ｆ＿４）的酸性，酸性顺序为：Ｈ－Ｆ＿４＞Ｆｅ＿２Ｏ＿３／Ｆ＿４＞Ｆ＿４原粉＞水热处理的Ｋ－Ｆ＿４＞Ｌｉ－Ｆ＿４＞ＮａＦ＿４＞Ｋ－Ｆ＿４＞ＮａＯＨ／Ｆ＿４，比较了酸强度和积炭对乙苯氧化脱氢性能的影响，以及催化剂酸碱性质与积炭的关系．结果表明，乙苯氧化脱氢反应是在酸碱协同作用下进行的，积炭也参与了氧化脱氢反应，催化剂表面上Ｌ酸中心产生的具有一定Ｃ、Ｈ、Ｏ比的积炭具有高的氧化脱氢活性．碱金属阳离子改性的具有Ｌ酸中心的ＦｅＺＳＭ－５是乙苯氧化脱氢的高活性催化剂。     

Application of Phosphorus-31 Nuclear Magnetic Resonance Spectrosocopy for the Study of Human Diabetic Cataractogenesis

Intact human Senses incubated at 5.5 mM (normal) and 35.5 mM glucose were examined by phosphorus-31 nuclear magnetic resonance (31P NMR) spectroscopy. Lense in 35.5 mM glucose showed an altered metabolic steady-state characterized by a lowered adenosine triphosphate/inorganic orthophosphate ratio. ³¹P NMR spectroscopy can be used to measure metabolic changes in the lens. This model offers an important means to study dynamic metabolism in the human lens in the setting of diabetic cataractogenesis.     

Identification of low molecular weight proteins isolated by 2-D liquid separations

Proteins with molecular mass (M(r)) <20 kDa are often poorly separated in 2-D sodium dodecyl sulfate polyacrylamide gel electrophoresis. In addition, low-M(r) proteins may not be readily identified using peptide mass fingerprinting (PMF) owing to the small number of peptides generated in tryptic digestion. In this work, we used a 2-D liquid separation method based on chromatofocusing and non-porous silica reversed-phase high-performance liquid chromatography to purify proteins for matrix-assisted laser desorption/ionization time-of-flight mass spectrometric (MALDI-TOFMS) analysis and protein identification. Several proteins were identified using the PMF method where the result was supported using an accurate M(r) value obtained from electrospray ionization TOFMS. However, many proteins were not identified owing to an insufficient number of peptides observed in the MALDI-TOF experiments. The small number of peptides detected in MALDI-TOFMS can result from internal fragmentation, the few arginines in its sequence and incomplete tryptic digestion. MALDI-QTOFMS/MS can be used to identify many of these proteins. The accurate experimental M(r) and pI confirm identification and aid in identifying post-translational modifications such as truncations and acetylations. In some cases, high-quality MS/MS data obtained from the MALDI-QTOF spectrometer overcome preferential cleavages and result in protein identification.     

Theoretical studies on vibrational spectra of some halides of Group IIB elements

The vibrational spectra of Group IIB elements halides MX2 and their dimers M2X4 (M=Zn(II), Cd(II) and Hg(II); X=F, Cl, Br and I) have been systematically investigated by ab initio RHF and B3LYP methods with LanL2MB, LanL2DZ and SDD basis sets. The optimized geometries, calculated vibrational frequencies are evaluated via comparison with the experimental data. The vibrational frequencies, calculated by these methods with different basis sets, are compared to each other too. The best results can be obtained by RHF/SDD method, with this method, the deviations for MX2 and Hg2X4 are <7%. Some vibrational frequencies of M2X4 that have not been experimentally reported are also predicted.     

Electronic structure and molecular orbital study of the first excited state of the high‐efficiency blue OLED material bis(2‐methyl‐8‐quinolinolato)aluminum(III) hydroxide complex from ab initio and TD‐B3LYP

Bis(2‐methyl‐8‐quinolinolato)aluminum(III) hydroxide complex (AlMq₂OH) is used in organic light‐emitting diodes (OLEDs) as an electron transport material and emitting layer. By means of ab initio Hartree–Fock (HF) and density functional theory (DFT) B3LYP methods, the structure of AlMq₂OH was optimized. The frontier molecular orbital characteristics and energy levels of AlMq₂OH have been analyzed systematically to study the electronic transition mechanism in AlMq₂OH. For comparison and calibration, bis(8‐quinolinolato)aluminum(III) hydroxide complex (Alq₂OH) has also been examined with these methods using the same basis sets. The lowest singlet excited state (S₁) of AlMq₂OH has been studied by the singles configuration interaction (CIS) method and time‐dependent DFT (TD‐DFT) using a hybrid functional, B3‐LYP, and the 6‐31G* basis set. The lowest singlet electronic transition (S₀ → S₁) of AlMq₂OH is π → π* electronic transitions and primarily localized on the different quinolate ligands. The emission of AlMq₂OH is due to the electron transitions from a phenoxide donor to a pyridyl acceptor from another quinolate ligand including C → C and O → N transference. Two possible electron transfer pathways are presented, one by carbon, oxygen, and nitrogen atoms and the other via metal cation Al³⁺. The comparison between the CIS‐optimized excited‐state structure with the HF ground‐state structure indicates that the geometric shift is mainly confined to the one quinolate and these changes can be easily understood in terms of the nodal patterns of the highest occupied and lowest unoccupied molecular orbitals. On the basis of the CIS‐optimized structure of the excited state, TD‐B3‐LYP calculations predict an emission wavelength of 499.78 nm. An absorption wavelength at 380.79 nm on the optimized structure of B3LYP/6‐31G* was predicted. They are comparable to AlMq2OH 485 and 390 nm observed experimentally for photoluminescence and UV‐vis absorption spectra of AlMq₂OH solid thin film on quartz, respectively. Lending theoretical corroboration to recent experimental observations and supposition, the reasons for the blue‐shift of AlMq2OH were revealed. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2004     

Design and Synthesis of 3‐Aryl‐5‐Alicylic‐[1,2,4]‐oxadiazoles as Novel Platelet Aggregation Inhibitors

A series of 4‐[2‐(alicyclic‐[1,2,4]oxadiazol‐3‐yl)phenoxy]‐butyric acids were synthesized from N‐hydroxy‐2‐isopropoxy benzamidine in 4 steps with good yields. These [1,2,4]oxadiazoles are novel platelet aggregation inhibitors preventing human platelet aggregation induced by thromboxane derivative U44,619 and adenosine diphosphate. A structure‐activity‐relationship study revealed that the potency for these 5‐oxadiazoles increases with the increase in the ring size of the alicylic rings. Derivative 8f may be useful as a template for the design of more potent anti‐platelet agents.     

Ti-ZSM-11的红外光谱研究

随着杂原子分子筛研究领域的开拓与发展，近年来，对钛硅沸石的研究逐渐增多．Ti－ZSM－11（TS－2）型分子筛是由Reddy，Ratanasarny等[1]首先合成的．钛硅沸石的表征与其它杂原子分子筛相比较为复杂，对杂原子Ti是否进入了骨架还没有一个直接的证据，且争议较多．在红外光谱的研究中，对960cm－1－980cm－1区间的特征吸收的归属也存在着很大的分歧[2－4]．钛硅沸石在H2O2对有机化合物的选择氧化领域有极其优良的催化性能[1]，因此，对它的开发有广泛的应用前景．本文以动态和静态相结合的水热晶化法合成了Ti－ZSM－11型分子筛．IR光…     

Room-temperature multiferroic properties of Co-doped KNbO3 ceramics

KNb_0.95Co_0.05O₃ (KN–Co) ceramic was prepared via a solid-state reaction method, and the effect of cobalt dopant on the structural, electric, and magnetic properties was studied. The KN–Co ceramic with polycrystalline perovskite structure exhibited ferromagnetic and ferroelectric properties simultaneously at room temperature, and the coupling of them was confirmed by a large magnetocapacitance effect (about 13%) near the Curie temperature. The possible causes for the magnetism and magnetoelectric properties are discussed.     

Synthesis and mesomorphic properties of 4-[(4-n-polyfluoroalkoxy-2,3,5,6-tetrafluorophenyl)ethynyl]phenyl fluoro-substituted benzoates

A series of 4-[(4-n-polyfluoroalkoxy-2,3,5,6-tetrafluorophenyl)ethynyl]phenyl fluoro-substituted benzoate liquid crystals have been synthesized. Their phase transition temperatures have been measured by optical polarizing microscopy and confirmed by DSC. The results show that a highly fluorinated terminal chain impairs mesomorphic properties.