355nm Nd∶YAG激光在H_2中的高效一级斯托克斯转换

对脉冲Nd∶YAG激光(355 nm)在H2和H2∶He-Ar混合气体中的受激拉曼散射(SRS)进行了研究。在0.5 MPa的氢气中,同时测量到从二级反斯托克斯到三级斯托克斯的多波长输出,其总转化效率达88%;而高压下只剩下一级和二级斯托克斯输出,其中二级斯托克斯最大能量转化效率达44%(对应量子效率为63%)。由于高级斯托克斯的竞争,纯氢气中一级斯托克斯的最大能量转换效率不超过43%。通过向3 MPa氢气中掺入2 MPaAr气后,很好地抑制了二级斯托克斯的产生,从而获得了能量转换效率高达71%(对应量子效率为83%)的一级斯托克斯输出。对四波混频和级联受激拉曼散射在氢气多级斯托克斯产生中的作用以及惰性气体对它们的影响进行了讨论。     

射流式单重态氧发生器研究

单重态氧O2 (a1Δg)是迄今唯一能用纯化学反应高效产生的具有长寿命的亚稳激发态分子 .为了考察提出的用两个O2 (1Δ)能量汇集反应生成氧第二单重激发态O2 (b1Σ+ g)以实现近可见短波长化学激光方案的现实性 ,设计和实验了一个氯流量为 3～ 10mmol/s的射流式单重态氧发生器 (JSOG) .考察了三种具有不同孔径和孔数目的喷头、氯气流量和脱水冷阱温度等对JSOG出口的O2 (1Δ)浓度、O2 (1Δ)分压、氯利用率及水蒸气含量的影响 .发现用聚氯乙烯管作冷阱时 ,最佳冷阱介质温度为 - 140～ - 15 0℃ ,对此提出了O2 (1Δ)表面脱活与脱水互相竞争的解释 .在最佳条件下 ,可将O2 (1Δ)气中水分压降低至 4Pa ,这一结果是首次报导     

Photoluminescence properties of the composite of porous alumina and poly (2,5-dibutoxy-1,4 phenylenevinylene)

The spin coating method was used to assemble polymer (Poly (2,5-dibutoxy-1,4-phenylenevinylene)) (DBO-PPV) into the pores of porous alumina which was prepared by anodization. Four peaks in the photoluminescence (PL) spectra of the composite, with contributions from the DBO-PPV and porous alumina, were found. It was also found that the light emitting from the porous alumina could excite the photoluminescence of DBO-PPV. The nanometer effect of the porous alumina can lead to a blue shift of 90 nm of the PL peaks of DBO-PPV.     

A density functional study on a biomimetic non-heme iron catalyst: insights into alkane hydroxylation by a formally HO-FeV=O oxidant

The reactivity of [HO-(tpa)Fe(V)=O] (TPA=tris(2-pyridylmethyl)amine), derived from O-O bond heterolysis of its [H(2)O-(tpa)Fe(III)-OOH] precursor, was explored by means of hybrid density functional theory. The mechanism for alkane hydroxylation by the high-valent iron-oxo species invoked as an intermediate in Fe(tpa)/H(2)O(2) catalysis was investigated. Hydroxylation of methane and propane by HO-Fe(V)=O was studied by following the rebound mechanism associated with the heme center of cytochrome P450, and it is demonstrated that this species is capable of stereospecific alkane hydroxylation. The mechanism proposed for alkane hydroxylation by HO-Fe(V)=O accounts for the experimentally observed incorporation of solvent water into the products. An investigation of the possible hydroxylation of acetonitrile (i.e., the solvent used in the experiments) shows that the activation energy for hydrogen-atom abstraction by HO-Fe(V)=O is rather high and, in fact, rather similar to that of methane, despite the similarity of the H-CH(2)CN bond strength to that of the secondary C-H bond in propane. This result indicates that the kinetics of hydrogen-atom abstraction are strongly affected by the cyano group and rationalizes the lack of experimental evidence for solvent hydroxylation in competition with that of substrates such as cyclohexane.     

铌酸锂单晶光纤包层研究

通过镁离子内扩散铌酸锂单晶光纤，以改变晶纤表层的折射率，首次在国内实现了沿不同轴向生长、不同掺杂的铌酸锂单晶光纤的芯－包层波导结构。通过匹配扩散温度、扩散时间、ＭｇＯ膜厚等扩散参数及选择合适的晶纤直径，实现了晶纤具有阶跃和抛物折射率分布的包层，并对包层晶纤的模式特性进行了观察，得到低次模传输。     

Application of high-field NMR and cryogenic probe technologies in the structural elucidation of poecillastrin a,a new antitumor macrolide lactam from the sponge poecillastra species

Poecillastrin A (1), a new polyketide-derived macrolide lactam, was isolated from a deep-water collection of the marine sponge Poecillastra species. The structure of poecillastrin A (1) was assigned using NMR data acquired at 500 MHz with an inverse-detection cryogenic probe and at 800 MHz with a room-temperature probe.     

转动分辨的NH3X→C′→Ã跃迁的离子凹陷光谱

NH_3Ã(~1A_2~″)是一个快速预解离态, 以往的光谱研究从未得到它的转动分辨光谱。我们用两个脉冲染料激光器研究了NH_3C′→X的3+1多光子电离光谱和NH_3X→C′→Ã的折叠光学双共振多光子电离光谱, 称为“离子凹陷光谱”。对前者观察到了较高分辨的转动光谱, 得出C′v_2~′=O的高精度转动常数。通过谱线宽度, 得到了C′v_2~′=0,1,2能级的预解离寿命。从离子凹陷光谱上, 首次观察到了C′→Ã跃迁的0-0, 1-1, 2-2等带的转动分辨光谱。由双共振选择定则简化的光谱使漫散至～50 cm~(-1)线宽的转动线得以分开, 由此得到Ãv_2~″=0,1,2能级的转动常数和各谱带的带原点。在消除功率加宽的情况下, 测出Ãv_2~′=1能级的寿命。这种方法对研究分子的快速预解离态有一定的普遍意义。     

Mechanistic studies on the formation and reactivity of dioxygen adducts of diiron complexes supported by sterically hindered carboxylates

Dioxygen activation by enzymes such as methane monooxygenase, ribonucleotide reductase, and fatty acid desaturases occurs at a nonheme diiron active site supported by two histidines and four carboxylates, typically involving a (peroxo)diiron(III,III) intermediate in an early step of the catalytic cycle. Biomimetic tetracarboxylatodiiron(II,II) complexes with the familiar "paddlewheel" topology comprising sterically bulky o-dixylylbenzoate ligands with pyridine, 1-methylimidazole, or THF at apical sites readily react with O(2) to afford thermally labile peroxo intermediates that can be trapped and characterized spectroscopically at low temperatures (193 K). Cryogenic stopped-flow kinetic analysis of O(2) adduct formation carried out for the three complexes reveals that dioxygen binds to the diiron(II,II) center with concentration dependences and activation parameters indicative of a direct associative pathway. The pyridine and 1-methylimidazole intermediates decay by self-decomposition. However, the THF intermediate decays much faster by oxygen transfer to added PPh(3), the kinetics of which has been studied with double mixing experiments in a cryogenic stopped-flow apparatus. The results show that the decay of the THF intermediate is kinetically controlled by the dissociation of a THF ligand, a conclusion supported by the observation of saturation kinetic behavior with respect to PPh(3), inhibition by added THF, and invariant saturation rate constants for the oxidation of various phosphines. It is proposed that the proximity of the reducing substrate to the peroxide ligand on the diiron coordination sphere facilitates the oxygen-atom transfer. This unique investigation of the reaction of an O(2) adduct of a biomimetic tetracarboxylatodiiron(II,II) complex provides a synthetic precedent for understanding the electrophilic reactivity of like adducts in the active sties of nonheme diiron enzymes.     

一氧化碳的双共振多光子电离研究

用两束脉冲染料激光进行了CO的光学双共振四光子电离, 获得了转动分辩的CO A~(1Π)←X~(1Σ~+)和B~(1Σ~+)←A~(1Π)跃迁的光谱。观察到了在此2+1光子相继吸收中特有的选择定则。动力学研究表明CO基态到A~(1Π)态的双光子吸收是速率决定步骤, 其吸收截面约为1×10~(-49) cm~4 s。还测定了A~(1Π)态的单态转动传能截面。对于宇称指数e守恒、△J×±1的过程的截面约为0.05 nm; 随△J值增大而减小。对相同的△J, e正负变号的过程的截面总是小于e不变过程的截面。