果糖1,6-二磷酸酯酶的代谢调控

<正> 果糖1,6-二磷酸酯酶(FBPase 1)在生物体内糖异生代谢途径中起着重要的作用。当二价金属离子存在时,它催化果糖1,6-二磷酸(Fru-1,6-P_2)水解生成果糖6-磷酸(Fru-6-P)和无机磷。它是一个由4个相同亚单位构成的蛋白质,其亚单位分子量约为35 000～40 000。FBPase 1可被蛋白水解酶降解修饰,使其最适pH从7.5变为9.2。该酶受AMP及果糖2,6-二磷酸(Fru-2,6-P_2)

Metamorphic InGaAs quantum wells for light emission at 1.3-1.6 mu m

Metamorphic InGaAs quantum well structures grown on GaAs reveal strong light emission at 1.3-1.6 mu m, smooth surface with an average roughness below 2 nm. and good rectifying I-V characteristics. Dark line defects are found in the QW Post growth thermal annealing further improves the luminescence efficiency but does not remove those dark line defects. Some challenges of epitaxial growth using this method for laser applications are discussed. (c) 2006 Elsevier B.V. All rights reserved.

2-C-支链-1,6-脱水吡喃葡萄糖的开环反应及吡喃烯糖的合成研究

在糖化学合成中，1,6-脱水吡喃糖不仅是合成具有生物活性低聚糖、糖共体、抗原、抗体以及天然产物等化合物重要原料，而且还是许多具有生物活性的天然产物的结构单元。同时，它还具有[3,2,1]的双环缩醛结构，使其在糖化学合成中具有高的立体选择性和区域选择性，同时减少了C-1 和C-6 位的保护和去保护的优点。此外，环内的缩醛开环后，又可以相应地在C-1 和C-6 位进行官能团转化以及糖苷化反应。 本文报道了一种新的1,6-脱水吡喃糖的合成方法，并设计合成了2-C-支链-1,6-脱水吡喃葡萄糖1-195、1-197、1-198 以及2-C-支链-6-硫代1,6-脱水吡喃葡萄糖1-225。到目前为止，1,6-脱水糖开环并进行糖苷化反应，存在选择性较差、产率低的缺点。我们发现，在乙腈做溶剂的条件下，NiCl5 能高立体选择性高产率地催化化合物1-195、1-197、1-198 开环并与ROH、RSH 发生糖苷化反应。在NiCl5-乙腈条件下，合成了一系列2-C-支链-α-糖苷和2-C-支链-β-硫代糖苷，并对2-C-支链1,6-脱水吡喃葡萄糖的生成机理以及开环机理进行了探讨。 烯糖在糖化学合成中是重要的起始原料，从Fischer 首次合成烯糖至今，一直不断地有新的合成方法出现。但目前文献报道的方法存在所用试剂有毒、价格贵和操作繁琐等缺点。我们对Fischer-Zach 方法进行了改进， 发现Zn-NaH2PO4-H2O 和Zn-PEG600-H2O 体系都能很好地合成烯糖。该方法具有条件温和、绿色环保、操作简单的优点。在Zn-NaH2PO4 溶液或Zn-PEG600 条件下，以溴代糖为原料，高产率地合成一系列的烯糖。 The 1,6-anhydrohexopyranoses are crucial subunits of myriad bioactive nature products, as well as important syntons of carbohydrate chemistry which have been extensively used to prepare the biologically potential oligosaccharides, glycoconjugates, antibiotics, and structurally varied nature products. Their particular [3.2.1] bicyclic skeleton makes them have high regio- and stereo-control in a variety of reactions, and such structure avoids protecting hydroxyl groups at C1 and C6.Additionally, the cleavage of the internal acetal under acidic conditions could be beneficial for further transformations of functional group and glycosylation of the corresponding pyranosyl sugar at the C6 or C1 site. Herein we developed a novel approach to prepare the 1,6-anhydrohexopyranose, and synthesized the 2-C-branched-1,6-anhydrohexopyranose 1-195, 1-197, 1-198 and 2-C-branched-6-thio-1,6-anhydrohexopyranose 1-225. Until now, glycosylation of 1,6-anhydrohexopyranoses has been limited because of the low yields and low stereoselectivity. In this paper, we found that NiCl5-MeCN system could selectively cleave the ring of 1,6-anhydrohexopyranoses with alcohols and thiols at room temperature in high yields. A series of 2-C-branched-α-glycosides and 2-C-branched-β-thioglycosides have been synthesized via NiCl5-catalyzed. Furthermore, we investigated the formation and ring-opening mechanism of 2-C-acetylmethyl-1,6-anhydrohexopyranose. Glycals are significant starting material in carbohydrate chemistry. After the Fischer-Zach method for forming glucal was reported for the first time, the numerous synthetic methods for glycals have been explored. However, there are several drawbacks in the existing methods, such as the usage of very expensive and toxic reagents, intricate operation, and the influence of acid-sensitive and base-sensitive functional group. We improved the Fischer-Zach method and developed a facile, mild and environmentally benign methodology towards the synthesis of the glycals in Zn-NaH2PO4-H2O or Zn-PEG600-H2O system. Our method involves the treatment of glycosyl bromides with Zn in NaH2PO4 aqueous solution or PEG600-H2O at room temperature, affording various glycals in excellent yields.

General SU(2)(L) x SU(2)(R) x U(1)(EM) sigma model with external sources, dynamical breaking and spontaneous vacuum symmetry breaking

We give a general SU(2)(L) x SU(2)(R) x U(1)(EM) sigma model with external sources, dynamical breaking and spontaneous vacuum symmetry breaking, and present the general formulation of the model. It is found that sigma and pi(0) without electric charges have electromagnetic interaction effects coming front the internal structures. A general Lorentz transformation relative to external sources J(gauge) - (J(A mu) J(A mu)(kappa)) derived, using the general Lorentz transformation and the four-dimensional current of nuclear matter of the ground si ate with J(gauge) = 0, we give the four-dimensional general relations between the different currents of nuclear matter systems with J(gauge) not equal 0 and those with J(gauge) = 0. The relation of the density's coupling with external magnetic field is derived, which conforms well to dense nuclear matter in a strong magnetic field. We show different condensed effects in strong interaction about fermions and antifermions, and give the concrete scalar and pseudoscalar condensed expressions of sigma(0) and pi(0) bosons. About different dynamical breaking and spontaneous vacuum symmetry breaking, the concrete expressions of different mass spectra are obtained in field theory. This paper acquires the running spontaneous vacuum breaking value sigma'(0), and obtains the spontaneous vacuum breaking in tenus of the running sigma'(0), which make nucleon, sigma, and pi particles gain effective masses. We achieve both the effect of external sources and nonvanishing value of the condensed scalar and pseudoscalar paticles. It is deduced that the masses of nucleons, sigma and pi generally depend on different external sources.

两种新的手性1,6-双膦的合成

由D-甘露醇出发合成了两种新型的手性1,6-双膦:1,6-双(二苯膦基)-2,3,4,5-二亚(艹卡)基-D-甘露醇和1,6-双(二苯膦基)-3,4-亚(艹卡)基-2,5-亚甲基-D-甘露醇。 以这两种手性配位体的Rh(Ⅰ)配合物为催化剂用于α-乙酰氨基肉桂酸的不对称氢化反应,但都未观察到对映选择性,而且由第一种配位体参加的反应,也未显示氢化活性,对此本文也作了初步的说明。

Theoretical study on adsorption of Na+ and Na+(H2O)(n) (n=1-6) on a clean Si(111) surface

To model the adsorption of Na+ in aqueous solution on the semiconductor surface, the interactions of Na+ and Na+(H2O)(n) (n = 1-6) with a clean Si(111) surface were investigated by using hybrid density functional theory (B3LYP) and Moller-Plesset second-order perturbation (MP2) methods. The Si(111) surface was described with Si8H12, Si16H20, and Si22H21 Cluster models. The effect of the basis set superposition error (BSSE) was taken into account by applying the counterpoise (CP) correction. The calculated results indicated that the interactions between the Na+ cation and the dangling bonds of the Si(111) surface are primarily electrostatic with partial orbital interactions. The magnitude of the binding energies depends weakly on the adsorption sites and the size of the clusters. When water molecules are present, the interaction between the Nal and Si(I 11) surfaces weakens and the binding energy has the tendency to saturate. On a Si22H21 cluster described surface, the optimized Na+-surface distance for Na+(H2O)(5) adsorbed at on-top site is 4.16 angstrom and the CP-corrected binding energy (MP2) is -35.4 kJ/mol, implying a weakly adsorption of hydrated Na+ cation on clean Si(111) surface.