Growth of NaBi（WO4）2 Dendrite and Mechanism

The solid-liquid interface motion of NaBi（WO4）2 （NBWO） melt crystal growth is observed in an in situ system, in which the whole processes of interface transition from fiat interface and cellular to dendrite are visualized. The spacing of the dendrite under smaller temperature gradient turns out to be larger than that under larger temperature gradient, which is found to be sensitive to the temperature distribution. The mechanism of dendrite growth of NBWO is studied based on the model of the growth units of anion coordination polyhedra. The { 001} face has two apex links, so it shows higher stability and has high growth rate and forms the arm of dendrite, whereas the {010} face has only one apex link, and thus shows relative slower growth rate and firstly forms the branches.     

In Situ Observation of Skeletal Shape Transition during BaB2O4 Crystal Growth in High-Temperature Solution

The transition from a fiat solid-liquid interface to a skeletal shape during BaB2O4 （BBO） single crystal growth in Li2B4O7 flux is observed in real time by an optical high-temperature in-situ observation system. The movement of crystal step is also investigated. The observation results demonstrate that the steps propagate along and parallel to the fiat interface when the crystal size is small. Nevertheless, they will ‘bend＇ close to the face centre if the crystal size becomes greater. Atomic force microscopy reveals that more deposition places near the face centre give rise to the bending of advancing steps and thus the formation of a vicinal interface structure. Measurements of step velocity show that the velocity keeps nearly constant at different moments for one specific step, whereas the step on a newly formed layer advanced faster than that on a previously formed one when the crystal size is larger than 210μm or so. Thus interracial morphological instability occurs and a skeletal interface is obtained.     

Eucaglobulin, A New Complex of Gallotannin and Monoterpene from Eucalyptus globulus

EucalyPtusgl0bulusLabill.(Myrtaceae)isakindofmedicinalplantwidelydistributedintheYunnanpr0vinceofChina.ItSleaves,rootSandffoitShavebeenusedastraditionalremediesforthetreatmentofinfluenza,dysentery,enteritis,rheumatalgiaandbleeding.BesidesvolatileterpenoidconstituentSintheessential0iloftheleavesandfruits,theoccurrenceofanumber0fphloroglucinol-sesquiterpene-or-m0n0terpene-c0upledcomPoundsnamedmacrocarpals'andeugl0bals'intheleavesandbudshasbeenrepofted.Inordertostudythechendcalandbioactivecon…     

高固含量聚合物乳液制备方法新进展

高固含量一直是聚合物乳液制备追求的目标 ,本文将高固含量 (>6 0 % )聚合物乳液的制备方法按机理分为控制乳胶粒直径分布 ,增大乳胶粒直径和使乳胶粒发生形变三类 ,详细评述了各种制备方法的研究进展 ,并对高固含量乳液制备的发展进行了展望。     

血橙中微量元素的测定

采用电感耦合等离子体原子发射光谱仪(ICP-AES),对血橙果肉汁、皮、籽中10种微量元素进行了测定。结果表明,血橙果肉汁、皮、籽中含有Ca、Mg、Fe、Zn、Mn、Cu、Ni等丰富的人体必需微量元素,且血橙果皮、籽中的微量元素含量普遍高于果肉汁中的微量元素的含量,这为血橙药效功能的进一步研究和资源综合开发利用提供一定的科学依据。     

A new ligand system based on a bipyridine-functionalized calix[4]arene backbone leading to mono- and bimetallic complexes

The synthesis of a new ligand system for mono- and bimetallic complexes based on a calixarene is described. Ligand BBPC (3, bis(bipyridine)-calix[4]arene) is obtained in three steps in 40% overall yield by first brominating one of the methyl groups of the 4,4'-dimethyl-2,2'-bipyridine in two steps and subsequently reacting it with p-tert-butylcalix[4]arene under basic conditions. Reaction of BBPC (3) with 2 equiv of [Rh(NBD)(2)]BF(4) or [Rh(NBD)(CH(3)CN)(2)]BF(4) (NBD = norbornadiene) produces the bimetallic compound BBPC[Rh(NBD)BF(4)](2) (4). Treatment of the ligand with PdCl(2)(CH(3)CN)(2) leads to the isolation of the bimetallic complex BBPC[PdCl(2)](2) (5). When the nickel precursor NiBr(2)(DME) (DME = dimethoxyethane) is reacted with BBPC, the bimetallic complex BBPC[NiBr(2)](2) (6) is isolated which, upon crystallization from methanol, gives the mononuclear bis(bipyridine) complex BBPC[NiBr(OMe)] (7). Full characterization includes X-ray structural studies of complexes 4, 5, and 7. The bimetallic compounds 4 and 5 show metal to metal distances of 4.334 A (for 4) and 3.224 A (for 5). For all three complexes, unique molecular packing arrangements were found, based on hydrophobic/hydrophilic interactions.     

过碳酸钠-醋酸酐作用下的Baeyer-Villiger反应

在醋酸酐介质中, 过碳酸钠可以与酮进行Baeyer-Villiger反应, 将它们氧化成相应的酯。其中脂环酮的反应结果较好, 环内酯的产率约为80%。芳香酮除芳环被活化的以外, 效果欠佳。当反应施加超声辐射后可显著加快反应速度, 并对过碳酸钠的作用机理进行了讨论。     

Nucleophilic de-coordination and electrophilic regeneration of "hemilabile" pincer-type complexes: formation of anionic dialkyl, diaryl, and dihydride Pt(II) complexes bearing no stabilizing pi-acceptors

Novel anionic dialkyl, diaryl, and dihydride platinum(II) complexes based on the new "long-arm" hemilabile PCN-type ligand C6H4[CH2P(tBu)2](CH2)2N(CH3)2 with the general formula Li+[Pt(PCN)(R)2]- (R=Me (4), Ph (6) and H (9)) were prepared by reaction of [Pt(PCN)(R)] complexes (obtained from the corresponding chlorides) with an equivalent of RLi, as a result of the opening of the chelate ring. Alkylating agents based on other metals produce less stable products. These anionic d8 complexes are thermally stable although they bear no stabilizing pi acceptors. They were characterized by 1H, 31P[1H], 13C, and 7Li NMR spectroscopy; complex 9 was also characterized by single crystal X-ray crystallography, showing that the Li+ ion is coordinated to the nitrogen atom of the open amine arm and to the hydride ligand (trans to the P atom) of a neighboring molecule (H--Li=2.15 A), resulting in a dimeric structure. Complexes 4 and 9 exhibit high nucleophilic reactivity, upon which the pincer complex is regenerated. Reaction of 4 with water, methyl iodide, and iodobenzene resulted in the neutral complex [Pt(PCN)(CH3)] (3) and methane, ethane, or toluene, respectively. Labeling studies indicate that the reaction proceeds by direct electrophilic attack on the metal center, rather than attack on the alkyl ligand. The anionic dihydride complex 9 reacted with water and methyl iodide to yield [Pt(PCN)(H)] (8) and H2 or methane, respectively.     

Solvent-stabilized alkylrhodium(III) hydride complexes: a special mode of reversible C-H bond elimination involving an agostic intermediate

Reaction of the complex [Rh(coe)2(solv)n]BF4 (coe=cyclooctene) with the phosphane 1-di-tert-butylphosphinomethyl-2,4,6-trimethylbenzene (1) results in selective C-H bond activation, yielding the spectroscopically characterized solvento complexes [(solv)nRhH(CH2C6H2(CH3)2[CH2P(tBu)2]]]BF4 (solv = acetone, 2a; THF, 2b; methanol, 2c). The stability of these complexes is solvent dependent, alcohols providing significant stabilization. Although cis-alkylrhodium hydride complexes containing labile ligands are generally unstable, 2a-c are stable at room temperature. Complex [ (acetone)(ketol)RhH[CH2C6H2(CH3)2[CH2P(t-Bu)2]]]BF4 (2d, ketol 4-hydroxy-4-methyl-2-pentanone, the product of acetone aldol condensation), crystallized from a solution of 2a in acetone and was structurally characterized. Unusual solvent- and temperature-dependent selectivity in reversible C-H bond elimination of these complexes, most probably controlled by a special mode of strong agostic interactions, is observed by spin saturation transfer experiments.