From D-glucose to biologically potent L-hexose derivatives: synthesis of alpha-L-iduronidase fluorogenic detector and the disaccharide moieties of bleomycin A2 and heparan sulfate

A novel and convenient route for the synthesis of biologically potent and rare L-hexose derivatives from D-glucose is described. Conversion of diacetone-alpha-D-glucose (14) into 1,2:3,5-di-O-isopropylidene-beta-L-idofuranose (19) was efficiently carried out in two steps. Orthogonal isopropylidene rearrangement of compound 19 led to 1,2:5,6-di-O-isopropylidene-beta-L-idofuranose (27), which underwent regioselective epimerization at the C3 position to give the L-talo- and 3-functionalized L-idofuranosyl derivatives. Hydrolysis of compound 19 under acidic conditions furnished 1,6-anhydro-beta-L-idopyranose (35) in excellent yield, which was successfully transformed into the corresponding L-allo, L-altro, L-gulo, and L-ido derivatives via regioselective benzylation, benzoylation, triflation and nucleophilic substitution as the key steps. Applications of these 1,6-anhydro-beta-L-hexopyranoses as valuable building blocks to the syntheses of 4-methylcoumarin-7-yl-alpha-L-iduronic acid and the disaccharide moieties of bleomycin A(2) as well as heparan sulfate are highlighted.     

MH—Ni电池封口化成及其性能

在硼氢化钾碱性溶液中对金属氢化物（ＭＨ）电极的表面进行化学还原处理，提高了ＭＨ电极的放电容量、活化性能和电催化活性．用其为负极组装的ＡＡ型ＭＨ－Ｎｉ电池进行了封口化成，电池放电容量达到１１５０ｍＡｈ，５Ｃ下电池的放电容量达到０．２Ｃ下容量的８０％以上，电池在１Ｃ１００％ＤＯＤ（放电深度）充放电条件下，循环寿命由原来的１００次左右提高到２００次以上     

Kinetics and mechanism of emulsifier-free emulsion polymerization. II. Styrene/water soluble comonomer (sodium methallyl sulfonate) system

The emulsifier-free emulsion polymerizations of styrene in the presence of about 1 wt% (related to styrene) of the water soluble comonomer, sodium methallyl sulfonate (NaMS), which has short hydrophobic group and strong hydrophilic ionic group, and of the initiator, potassium persulfate, are carried out. Under constant ionic strength, the number density of polymer particles (N_p) is found to depend on 0.5-power of the initiator concentration and shows a minimum in the comonomer concentration plot. Under constant concentration of monomer, comonomer and initiator, N_p is found to depend on ?1.1-power of the ionic strength. In the earlier period, the presence of styrene oligomer having MW about 1000 and water soluble poly(NaMS) or copolymer with high NaMS content suggests a micellar nucleation mechanism, by which the styrene oligomer behaves as emulsifier and the poly(NaMS) can either stabilize or destabilize the existing particles, depending on its concentration in the aqueous phase. The particle size is rather uniform having an uniformity very close to 1 (ca. 1.001) throughout the entire process. It is much larger than that of the conventional emulsion polymerization or emulsifier-free emulsion polymerization with the other comonomers by about 3 to 4 times in diameter or 27 to 64 times in volume, leading to that the average radical number in the particle could be much greater than 0.5. The (conversion)^2/3 versus time plot is found to be linear from 6 to 50% conversion. During this period, for the conversion from 10 to 40% the polymerization rate increases twice but the particle volume increases four-fold. In addition, MWD shows bimodal (excluding the styrene oligomer peak in the earlier period) during the growth period. But the lower MW peak shifts to higher MW and become larger, while the higher MW peak decreases, and finally the MWD becomes single mode after 58.6% conversion. These results suggest a “gradient polymerization” or “transition stage to core-shell structure” in the earlier stage of particle growth and a “shell part polymerization” in the later stage.     

Synthesis of trans-1,2-diphenyl-3,4-bis[4-(2,6-diphenyl-4H- pyranylidenyl)]cyclobutane: correction and structure proof

The reaction of phenyl lithium acetylide ($\text{2}$) with 2,6-diphenylpyrylium perchlorate ($\text{1}$) is solvent dependent. With diethyl ether as solvent, the isolated product differed from that previously reported and is reassingned as 2,6-diphenyl-4-phenylacetylenyl-4$\text{H}$-pyran ($\text{5}$). On the other hand, in THF the title compound ($\text{6}$) was obtained; its structure confirmed by single-crystal x-ray crystallography.     

硅氧聚合度对细胞毒性的影响

本文采用家兔肺泡巨噬细胞(AM)存活率和细胞过氧化脂质(LPO)值为测定指标,研究了硅氧的聚合度对其细胞毒性的影响。结果表明:各种聚合度的硅氧都有一定的细胞毒性,聚合度愈大,细胞毒性也愈大。胶体SiO_2的粒径增大,其细胞毒性降低。十硅酸盐及粒径小于5nm的硅溶胶的细胞毒性大于α-石英。聚合度小于6的低聚硅酸及其盐、粒径18nm以上的硅溶胶以及硅胶H的毒性皆小于α-石英。本实验细胞存活率降低和过氧化脂质值升高的趋势基本一致,这表明硅氧可能主要与细胞表面膜作用,膜上磷脂等表面活性物质被氧化和变性,从而导致细胞损伤。     

2,5-Dimethylthiophene coordination to three metal centers in the complexes (η4, S-μ3-2,5-Me2T)(IrCp*) [M(CO)2Cp]2 where MMo or W

The 2,5-dimethylthiophene (2,5-Me₂T) ligand in the isomers Cp*Ir(η⁴-2,5-Me₂T) (1) and Cp*Ir(C,S-2,5-Me₂T) (2) is activated to react with the dimers Cp(CO)₂M?M(CO)₂Cp[M?Mo (3), W (4)] to give complexes (5,6) in which the thiophene is coordinated to three metals. Oxidation of 5 with Cp₂Fe⁺ removes the Mo dimer to give Cp*Ir(η⁵-2,5-Me₂T)²⁺. Reaction of 5 with CO displaces the Mo as [CpMo(CO)₃]₂ to give Cp*Ir(CO)(C,S-2,5-Me₂T) (7). Ultraviolet photolysis of 1 provides a convenient route to the ring-opened isomer 2. Despite the remarkable nature of the thiophene coordination in 5 and 6, its reactivity does not suggest new pathways that would lead to the hydrodesulfurization of thiophenes.     

马来酸酐与1，2－环己烷二羧酸二异丁酯的气液平衡

采用小沸点仪测定了马来酸酐和1,2－环己烷二羧酸二异丁酯二元系统在不同配料组成条件下的温度与压力数据，并通过内插法得到不同压力下的温度与配料组成的数据.进一步采用单纯形法优化NRTL方程参数，推算了平衡气液相组成，发现该二元系统具有最高压力恒沸点，且该恒沸点随压力的变化显著.当压力降低至20 kPa时, 由温度随气相组成的变化趋势知该恒沸点将趋于消失.     

负载贵金属光催化剂的光催化活性研究

在注入V离子的二氧化钛光催化剂上负载贵金属,制备了在可见光照射下具有高光催化活性的功能型光催化剂,研究在可见光和太阳光照射下丙炔的光催化水解反应，利用这些改性的二氧化钛构筑太阳能到化学能的转换系统.研究结果发现了V/Pt光催化剂在丙炔和水的光催化水解反应中，由于贵金属的存在，有利于促进发生加氢反应；导致丙烯的生成量增加.在可见光下的光催化活性也和负载贵金属所处的氧化状态有着密切的关系，贵金属完全被还原到0价是提高光催化活性的必要条件.     

Two 3D supramolecular polymers constructed from an amino acid and a high-nuclear Ln6Cu24 cluster node

The first successful attempt to construct 3D supramolecular frameworks with high-nuclear 3d-4f heterometallic clusters as a node is reported. The self-assembly of Ln3+, Cu2+ and amino acid in solution leads to the formation of two polymers, 35-nuclear complex [Sm6Cu29] 1 with a primitive cubic net-like structure and 36-nuclear complex [Nd6Cu30] 2 with a face-centred cubic network type structure. Glycine and L-proline, respectively, were used as ligands. It should be noted that 2 has a chiral framework. X-ray structure analyses show that 1 crystallizes in the triclinic P1 space group (a=19.6451(8), b=20.4682(8), c=20.7046(8) A, alpha=89.453(1), beta=66.290(1), gamma=68.572(1) degrees, V=7003.0(5) A3 and Z=1) and 2 belongs to the cubic P2(1)3 space group (a=b=c=32.4341(3) A, V=34 119.7(5) A3 and Z=4). Both complexes utilize Ln6Cu24 octahedral clusters as nodes and trans-Cu(amino acid)2 groups as bridges. Electrical conductivity measurements reveal that both polymers behave as semiconductors.     

四磺酸基酞菁锌在水和非水溶剂中的电化学性质研究

在非水溶剂（二甲基亚砜（ＤＭＳＯ）及Ｎ,Ｎ＿二甲基甲酰胺（ＤＭＦ））中的伏安曲线．呈现三对电流峰,表明存在三个可逆或准可逆酞菁配体的单电子转移过程,而在水溶液中则不呈现准可逆行为,且波形改变很大．此外,还比较了四磺酸基酞菁锌的水溶液在自然光和红光（６００～７００ｎｍ）照射下的循环伏安曲线,其氧化还原峰的数目和峰电位基本不变,但在红光照射下比自然光照射下的峰电流明显增大．