[Cu(2,2''-bpy)Cl2]和[Cu(1,10-phen)C12]在多金属氧酸盐上的多相化:选择性氧化四氢化萘的新催化剂

Mononuclear Cu(II)bipyridine(1)and phenantroline complexes(2)were synthesized and immobilized by different procedures on H3PW12O40 polyoxometalate(POM).Characterization by XRD and SEM-EDX were performed to assess the preservation of the Keggin structure and stoichiometry of the complex.The immobilized complexes were tested as heterogeneous catalysts for the partial oxidation of tetralin(1,2,3,4-tetrahydronaphthalene)using hydrogen peroxide as oxidant in acetonitrile/water as solvent.[Cu(2,2'-bpy)Cl][H2PW12O...     

Theoretical Study and NBO Analysis of the Decomposition Kinetics of Oxetane, 2-Methyloxetane and 2,2-Dimethyloxetane

A theoretical study of the thermal decomposition kinetics of oxetane (1), 2-methyloxetane (2), and 2,2-dimethyloxetane (3) has been carried out at the B3LYP/6-311+G**, B3PW91/6-311+G**, and MPW1PW91/6-311+G** levels of theory. The MPW1PW91/6-311+G** method was found to give a reasonable good agreement with the experimental kinetics and thermodynamic parameters. The decomposition reaction of compounds 1～3 yields formaldehyde and the corresponding substituted olefin. Based on the optimized ground state geometries using MPW1PW91/6-311+G** method, the natural bond orbital (NBO) analysis of donor-acceptor (bond-antibond) interactions revealed that the stabilization energies associated with the electronic delocalization from σC3-C4 bonding to σ*O1-C2 antibonding orbitals decrease from compounds 1 to 3. The σC3-C4→σO1-C2 resonance energies for compounds 1～3 are 2.63, 2.59 and 2.45 kcal mol-1, respectively. Further, the results showed that the energy gaps between σC3-C4 bonding and σ*O1-C2 antibonding orbitals decrease from compounds 1 to 3. Also, the decomposition process in these compounds are controlled by σ→σ* resonance energies. Moreover, the obtained order of energy barriers could be explained by the number of electron-releasing methyl groups substituted to the Csp3 atom (which is attached to oxygen atom). NBO analysis shows that the occupancies of σCsp3-O bonds decrease for compounds 1～3 as 3<2<1, and those of σCsp3-O bonds increase in the opposite order (3 > 2 > 1). This fact illustrates a comparatively easier thermal decomposition of the sCsp3-O bond in compound 3 compared to compound 2, and in compound 2 compared to compound 1. NBO results indicate that these reactions are occurring through a concerted and asynchronous four-membered cyclic transition state type of mechanism.     

具时滞带非单调反应函数的半比例依赖捕食被捕食系统的持久性

研究了具时滞半比例依赖的捕食被捕食非单调函数反应系统的持久性,得到了比较弱的由积分形式表述的充分条件.     

N-羟基邻苯二甲酰亚胺与8-羟基喹啉氧钒(Ⅳ)配合物协同催化分子氧氧化乙苯

研究了钒化合物对N-羟基邻苯二甲酰亚胺(NHPI)催化分子氧氧化乙苯反应中的调变效应.结果表明,由8-羟基喹啉及其衍生物与乙酰丙酮氧钒(Ⅳ)配位制得的8-羟基喹啉氧钒(Ⅳ)配合物的催化活性比乙酰丙酮氧钒(Ⅳ),NH4VO3和V2O5的高.在优化的反应条件下,乙苯转化率和苯乙酮选择性可分别达60％～69％和97％.基于液...     

Effects of CRAC Channel on Spatiotemporal Ca2＋ Patterns in T Cells

A reaction-diffusion model is built to investigate the temporal and spatial patterns of cytoplasmic Ca2＋ dynamics under the effects of Ca2＋-release activated Ca2＋ （CRAC） channels in T cells. Simulation results show a strong dependence of the modulation mode of Ca2＋ oscillation and dynamic patterns of Ca2＋ wave on the influx rate through the CRAC channel （ksoc）. When ksoc is small, cytoplasmic Ca2＋ is modulated as a frequency-modulation （FM） signal, whereas it shows an amplitude modulation （AM） mode after ksoc passes through a critical value. The heterogeneity in spatial Ca2＋ distribution is mostly arising from the influx through CRAC channels in both FM and AM modes. During each Ca2＋ spike, a more sustained cytoplasmic Ca2＋ gradient is maintained in the AM mode rather than in the FM mode.     

共掺氧化镱对掺铋硅酸盐玻璃的发光性能调控

掺铋玻璃及其光纤材料在近红外（中心波长1300nm）具有200-400nm的超宽带发光特性，是用作超宽带光纤放大、可调谐激光以及飞秒激光的理想基质材料。武汉光电国家实验室李进延教授带领的新型光纤材料与器件团队从事新型光纤材料与器件的前沿研究。     

CuNaY分子筛的制备及其催化甲醇氧化羰基化

采用多种铜盐溶液与NaY分子筛离子交换制备了CuNaY催化剂,通过加入氨水提高溶液pH值以及高温活化,显著提高了该催化剂对甲醇氧化羰基化合成碳酸二甲酯的反应活性。不同的铜盐水溶液交换制备的CuNaY催化剂催化活性不同,添加氨水将溶液pH值调节为11后,离子交换制备的CuNaY催化剂的催化活性和DMC选择性明显升高且趋于一致。经元素分析、XRD、XPS和H₂-TPR表征可知,加入氨水可促进Cu²⁺离子交换的进行,提高CuNaY催化剂中Cu的交换量,催化剂中约75%的Cu²⁺定位于分子筛的超笼中。     

氧化石墨催化醇和酚的四氢吡喃化保护与脱保护

氧化石墨作为一种高效、低毒、易得、可重复使用的弱酸性催化剂用于醇和酚的四氢吡喃化保护与脱保护反应.反应在室温下短时间内即可完成,产物收率高,分子中的碳碳不饱和键不受影响,氧化石墨可重复使用至少4次.该方法具有操作简便、安全、经济、环境友好等优点.     

Studies on the Molecular Chain Conformation Stability of Aminated Konjac Glucomannan

Konjac glucomannan （KGM） was aminated by 2-chloroethyl-amine （CEA） as reagent so as to study the influence of concentration of CEA （based on the amount of KGM）, concentration of NaOH, reaction time and temperature on the extent of amination. And the molecular simulation technology was adopted to analyze the conformation stability of aminate （AKGM）. The results indicate that when the amount of CEA is higher, the extent of amination is higher. The optimum concentration of NaOH, reaction time and temperature are 10% NaOH, 70 ℃ and 45 rain, respectively. IR shows KGM is successfully aminated. The conformation of AKGM is in a random clew-like shape.     

叶片大小与树木高度

 高大的树木往往叶片也较小,美国哈佛大学的詹森(KaareJensen)和加利福尼亚大学戴维斯分校的兹维尼奇(MaciejZwieniecki)认为其原因就在于树木的循环系统。葡萄糖来自于光合作用,尽管叶片加速了这一进程,但是树干、枝杈和茎却可能成为运输瓶颈。在某些情况下,叶片较大并无价值。因为树木越高大,这种瓶颈效果就越显著。当然,叶片也不能太小。