Y-Al双金属稀土配合物的合成和晶体结构

稀土化合物和烷基铝反应的研究,不仅对揭示f轨道的本质且对阐明稀土配位催化聚合烯烃的催化剂结构都有重要意义。Grcco等曾报道C_8H_8Ce(μ-O-i-C_3H_7)_2Al(C_2H_5)_2配合物,但尚未见晶体结构数据。 本文介绍了一种新的Y-Al双金属配合物的合成和培养晶体的方法。用四圆衍射仪确定了它的晶体结构,并用~1H NMR、ESCA等方法研究了配合物中钇的价态。

Methane dehydro-aromatization over a Mo/phosphoric rare earth-containing penta-sil type zeolite in the absence of oxygen

The dehydro-aromatization of methane over a Mo-modified penta-sil type high-silica zeolite containing phosphoric and rare earth oxide (abbreviated as Mo/HZRP-1) was investigated. As a modification of HZSM-5, HZRP-1 is also a good support for the preparation of Mo-based zeolite catalysts, and is active for methane dehydro-aromatization. Mo/HZRP-1 catalysts are more active at high Mo loadings compared with Mo/HZSM-5 catalysts. Al-27 MAS NMR spectra of Mo/HZRP-1 reveal that there are two kinds of framework Al in HZRP-1. It is suggested that only the tetrahedral coordinated Al atoms in the form of Al-O-Si species in the zeolite, in the proton forms, are responsible for the formation of aromatics.

Ultrasonic synthesis of silica-alumina nanomaterials with controlled mesopore distribution without using surfactants

A novel sol-gel process has been developed for the synthesis of amorphous silica-aluminas with controlled mesopore distribution without the use of organic templating agents, e.g., surfactant molecules. Ultrasonic treatment during the synthesis enables production of precursor sols with narrow particle size distribution. Atomic force microscopy analysis shows that these sol particles are spherical in shape with a narrow size distribution (i.e., 13-25 nm) and their aggregation during the gelation creates clusters containing similar sized interparticle mesopores. A nitrogen physiadsorption study indicates that the mesoporous materials containing different Si/Al ratios prepared by the new synthesis method has a large specific surface area (i.e., 587-692 m(2)/g) and similar pore sizes of 2-11 nm. Solid-state Al-27 magic angle spinning (MAS) NMR shows that most of the aluminum is located in the tetrahedral position. A transmission electron microscopy (TEM) image shows that the mesoporous silica-alumina consists of 12-25 nm spheres. Additionally, high-resolution TEM and electron diffraction indicate that some nanoparticles are characteristic of a crystal, although X-ray diffraction and Si-29 MAS NMR analysis show an amorphous material.

Structure and base properties of calcined hydrotalcites

Five hydrotalcites with Mg/Al molar ratio range of 3-15 were prepared. The structure and basicity of Mg-Al mixed oxides (Mg(Al)O) transformed from hydrotalcites were investigated by TPD, XPS, XRD, FT-IR and NMR techniques. The results of elemental analysis and XPS indicate that Al is enriched in the surface regions of Mg(Al)O, and its amount increases with the Mg/Al molar ratio and, the calcination temperature. Al-27-MAS-NMR results show that Al exists in two chemical environments: tetrahedral aluminium (Al(t)) and octahedral aluminium (Al(o)) in Mg(AI)O. The amount of Al(t) increases with the Mg/Al molar ratio and the calcination temperature. It is assumed that Al(t) may be mainly from the surface Al. Temperature-programmed desorption (TPD) of CO2 shows that the number of basic sites of Mg(Al)O samples increases with the Mg/Al molar ratio, and the maximum number of basic sites is obtained for hydrotalcite calcined at 773 K. Infrared spectra of adsorbed CO2 and B(OCH3)(3) reveal that there are two kinds of basic sites: weak basic OH- sites and strong basic O2- sites on the Mg(AI)O samples, the base strength depends on the Mg/Al molar ratio and calcination temperature.

Xenon probe for detecting the microporous structure of nanosized HZSM-5 zeolite

The secondary pores in the nanosized HZSM-5 zeolite have been observed for the first time via Xe-129 NMR spectroscopy using xenon as a probe; the location of non-framework Al can also be identified.

Studies on the phase diagram of the surfactant/1-pentanol water ternary system II: The liquid crystalline phase

The phase behavior of liquid crystalline in the ternary system of dodecyl dimethyl ammonium hydroxyl propyl sulfonate(DDAHPS)/1-pentanol(C5H11OH)/water deuteron (D2O) has been investigated by polarizing optical microscopy, H-2 NMR spectroscopy methods. The results indicate that two kinds of liquid crystals (the lamellar, and the hexagonal) exist in the liquid crystalline phase region. In this paper, we also use the polarized Raman spectroscopy method to measure the values of the order/disorder parameters and the values of the environment polarity parameters for the samples selected from the liquid crystalline phase region, and compare these two parameters of the samples with those of solid state DDAHPS and liquid state pentan-1-ol.

Studies on the phase behavior of lyotropic liquid crystal in DAD/C4OH/n-C8H18/D2O system

The lytropic liquid crystals in dodecanic acid diethanolamine (DAD)/n-butanol (C4OH)/octane (n-C8H18)/deuteron (D2O) system were studied to determine the phase regions and were investigated by H-2-NMR spectroscopy,optical polarizing microscope and small-angle X-ray diffraction (SAXD) methods. The results indicate that the lamellar, hexagonal and cubic liquid crystals all exist in the above system. Keeping the weight ratio of DAD and C4OH constant,the microphase structure, H-2 quadruple splitting and the interlayer spacing are all changed with the addition of deuteron.

Anti-HIV-1 Activity of Lignans from the Fruits of Schisandra rubriflora

This study investigated the 70% aqueous acetone extract of the fruits of Schisandra rubriflora which led to the isolation of eight lignans, including a new isolate, rubrisandrin C (1), and seven known lignans (2-8). The structure of 1 was established by extensive 1D and 2D NMR spectroscopy and its absolute stereochemistry was determined by CD spectrum. Compounds 1-5 and 7-8 were evaluated for their anti-HIV-1 activity that showed inhibitory activity on HIV-1(IIIB) induced syncytium formation with EC50 values in the range of 2.26 similar to 20.4 mu g/mL. Compounds 1 and 7 exerted their obvious protection of HIV-1(IIIB) inducted MT-4 host cells lytic effects with a selectivity index of 15.4 and 24.6, respectively.

Hyperfine quenching of the 3s3p P-3(0) level in Mg-like ions

Hyperfine quenching rates of the 3s3p P-3(0) level in Mg-like ions were calculated using the GRASP2K package based on the multi-configuration Dirac-Hartree-Fock method. Valence and core-valence correlation effects were accounted for in a systematic way. Breit interactions and QED effects were included in the subsequent relativistic CI calculations. Calculated rates were compared with other theoretical values and with experiment, and a good agreement with the latest experimental value for the Al-27(+) ion (Rosenband et al 2007 Phys. Rev. Lett. 98 220801) was found. Furthermore, we showed in detail the contributions from Breit interaction and QED effects to concerned physical properties. Finally, electronic data were presented in terms of a general scaling law in Z that, given isotopic nuclear spin and magnetic moment, allows hyperfine-induced decay rates to be estimated for any isotope along the isoelectronic sequence.

Identification of a new band and its signature inversion in Re-174

High spin states in Re-174 are investigated via the Sm-152(Al-27, 5n gamma)Re-174 reaction and gamma-gamma coincidence relationships are analysed carefully. A new band is identified due to its spectroscopic connection with the known pi 1/2(-)[541] circle times nu 1/2(-)[521] band. This band is proposed to be the ground-state band built on the pi 1/2(-)[541] circle times nu 5/2(-)[512] configuration in view of the low-lying intrinsic states in the neighbouring odd-mass nuclei. It is of particular interesting that the new band exhibits a phenomenon of low-spin signature inversion, providing a new situation for theoretical investigations.

Dipole bands in nucleus Pm-139

High-spin states in nucleus Pm-139 have been studied using the reaction Cd-116(Al-27, 4n)Pm-139. Two dipole cascades have been found. Spin and parity assignments were based on the Directional Correlation of Oriented Nuclei (DCO) ratios and systematic behavior in neighboring odd-proton nuclei. The level structures of Pm-139 are compared with those of the N = 78 isotone Eu-141 in which two dipole bands have been confirmed as magnetic rotational bands. The close similarity between them suggests that the dipole bands in Pm-139 may be magnetic rotational bands.

耗散反应激发函数中能量结构现象的机制研究

耗散反应激发函数中涨落的研究，是分析耗散反应系统时间演化和耗散过程的一个有效手段。本论文报道了114-120MeV~(27)Al+~(27)Al和102-108MeV~(19)F+~(93)Nb耗散反应激发函数的实验结果，通过关联函数分析关结合有关理论模型探讨了耗散反应截面特征涨落现象的物理根源。实验采用△E-E粒子鉴别方法和位置灵敏探测器对114-120MeV~(27)Al+~(27)Al和102-108MeV~(19)F+~(93)Nb反应产物进行电荷鉴别和角度分辩。各个出射道的激发函数中都观测到了涨落结构，运用涨落关联的统计理论方法对激发函数进行了系统地研究和分析，揭示出~(27)Al+~(27)Al和 ~(19)F+~(93)Nb耗散反应截面涨落区别于复合核截面涨落的一系列特征性质，如强烈的出射道关联、长程的能量关联和长程的角度关联。通过提取各不同出射道的能量相干宽度Γ，研究Γ与出射道的电荷数Z、出射角度θ的依赖关系，结果表明出射产物与入射弹核的差别越大所需的反应时间越长，质心系出射角度越大反应时间越长，表现出强烈的耗散系统随时间的弛豫特征。通过经典理论的计算和对激发函数的能量关联性质分析，研究了耗散碰撞过程中形成的中间双核系统随时间的演化过程。从实验的能量自关联函数中提取了中间双核系统的平均寿命(～10~(-21)s)和平均转动角速度(～10~(21)s~(-1))等物理信息，结果的比较还表明耗散反应的中间双核系统存在较大的角动量耗散和形状的改变。中间双核系统的转动对于不同出射道产物的寿命存在很大的影响，也是影响出射道之间关联、不同出射击角度之间关联的主要原因。通过基于“核分子”共振图象的能级部分重叠模型的分析，部分能级重叠和窄的角动量范围内的角动量相干是耗散反应截面中存在涨落的必要条件，进一步讨论并模拟了激发函数的涨落性质与上述两个因素之间的关系。通过驱动势分析了入射道对耗散反应激发函数中涨落结构的影响，在较轻的反应系统中，在很大的入射能范围内其激以函数中存在涨落现象，对于A > 120的重系统，则难于观测到反应截面中的涨落结构。

中能核反应中的统计发射过程及核温度参量

在过去的几年里，利用兰州重离子加速器（HIRFL）提供的束流，以及在OUVERTURE合作研究中，利用意大利国家核物理研究院南方实验室（INFN-LNS）超导回旋提供的束流，进行了多次中能区重离子核反应实验研究工作。如，最初的46.7MeV/u ~(12)C+~(58)Ni，~(115)In，~(197)Au的实验及30MeV/u ~(40)Ar+~(58)Ni，~(64)Ni~(115)In和30MeV/u Ni轰击Ni，Au，Al在MULTICS+MEDEA：4π装置上进行的实验工作。此外，本人还从事过一些理论研究工作，包括多粒子散射形式理论和相关数学物理问题研究，量子分子动力学和量子统计模型计算。本文是从事这些核物理研究工作的积累，主要侧重于实验结果的物理内容分析，而不强调实验技术，数据处理的技巧。主要的物理内容有以下几个方面：1.对于利用双同位素产额比提取同位素核温度的方法进行研究推广，使得对于实验中碰到的仅有部分能谱可以实现很好同位素分辩的情况，即使不能得到总的同位素产额，仅仅通过一段能区的同位素产额也可提取核温度。用于具体的实验研究工作中后，对于46.7MeV/u ~(12)C+~(58)Ni，~(115)In，~(197)Au核反应过程，同一体系利用这种方法得到的同位素核温度和利用粒子非稳态布居提取的核温度一致。2.围绕核反应过程中核温度的参量的提取，对于双同位素产额比与核温度的刻度关系进行了分析研究，通过计算考虑中等质量碎片（IMF）内部激发能后的内部配分函数表明，中等质量碎片的内部激发对刻度关系有重要影响。零阶近似下区域密度近似的结果和Gemini模拟计算的结果反映了相同的情况。3.研究核反应机制，多个粒子散射的形式理论的必需的，对于两体散射，其形式理论已经比较成熟，但是对于多个粒子散射问题出现的严重的困难是多体Lippmann-Schwinger方程无唯一收敛的解。作为一种探索性的研究工作，开展了多体散射理论研究工作，发展了一些具有普遍意义的数学物理方法。在本项研究工作中，通过能基础数学中的约当引理的推广，发现一个特例：对非连接图，Lippmann-Schwingwer方程存在收敛的解，因此多体散射形式理论，有可能重新建立。由于核力和多体问题是当今核物理研究的两大难点，世界各国的科学家都在努力以图攻克它们，而且多体问题还是物理学的其它许多领域的难题，因而多体散射还是引起诸多研究学科广泛兴趣的课题。通过发展一些新的数学理论和方法，我们已得到一些有意义的结果。4.将量子分子动力学这种中高能量区域所用的理论分析方法扩展至较低能区，通过对相空间中初始位置和动量抽样增加限制条件。如结合能和实验值要求一致，平均核势，核内Pauli阻塞更强一些，在演化中能量和动量守恒等等。得到一个很稳定的初始基态。均方半径保持不弥散的时间可达1600fm/c，用于研究10.6MeV/u Ne~(20)+Al~(27)的实验分析过程中。另外，量子统计模型（QSM）主要描述中心核-核碰撞，将它和碎裂模型结合，作一些改进后，可以对核-核碰撞进行统一描述。5.在中能核反应研究中发现，核反应过程中有大量的中子，轻带电粒子以及中等质量碎片发射出来，可以将这些粒子发射机制大致分为两大类。其中一类可以归结为动力学发射过程的产物。另一类则可以归于统计发射的产物。在低能核反应中，其发射能谱的斜率的负倒数，可作为复合核的核温度。而在中能重离子核反应中，其发射能谱变得很复杂，不再具有Maxwell分布。通常的三源拟合所给出的温度参数，已不能反映物理实质。提出多阶矩分析方法用于分析中能核反应中统计发射规律及受动力学过程的影响。

A study of fucoidan from the brown seaweed Chorda filum

Fucoidan fractions from the brown seaweed Chorda filum were studied using solvolytic desulfation.Methylation analysis and NMR spectroscopy were applied for native and desulfated polysaccharides.Homefucan sulfate from C.filum was shown to contain poly-a-(1-3)-fucopyranoside backbone with a high degree of branching,mainly of a-(1-2)-linked single units.Some fucopyranose residues are sulfated at O-4(mainly) and O-2 positions.Some a-(1-3)-linked fucose residues were shown by NMR to be 2-O-acetylated.The 1H and 13C NMR spectra of desulfated,deaceylated fucan were complerely assigned.THe spectral data obtained correspond to a quasiregular polysaccharide structure with a branched hexasaccharide repeating unit.Other fucoidan frations from C.filum have more complex carbohydrate composition and give rather complex methvlation patterns.