抗坏血酸有机锗倍半氧化物的合成及抗癌活性研究

通过三氯锗仿与抗坏血酸分子的加成反应,合成了一种新型有机锗倍半氧化物,产物的结构通过元素分析、IR及UV光谱等方法进行了表征．生物活性实验表明合成物对小鼠S-180肿瘤生长具有显著的抑制作用．     

Highly Stable trans‐Cyclooctene Amino Acids for Live‐Cell Labeling

trans‐Cyclooctene groups incorporated into proteins via non‐canonical amino acids (ncAAs) are emerging as specific handles for bioorthogonal chemistry. Here, we present a highly improved synthetic access to the axially and the equatorially linked trans‐cyclooct‐2‐ene isomers ( 1 a , b ). We further show that the axially connected isomer has a half‐life about 10 times higher than the equatorial isomer and reacts with tetrazines much faster, as determined by stopped‐flow experiments. The improved properties resulted in different labeling performance of the insulin receptor on the surface of intact cells.     

Is it possible to use Charge Transfer Bands to Measure Impurity-Ligand Distances? Experimental and Theoretical Results on Cu 2+ Doped (C 2 H 5 NH 3 ) 2 CdCl 4

The present work is focused on the effects produced by hydrostatic pressure on Cu 2+ (<100 ppm) doped (C 2 H 5 NH 3 ) 2 CdCl 4 single crystal. The energy E u ( ~ ) of the e u ( ~ ) M b 1 g (～ x 2 m y 2 ) charge-transfer transition of (C 2 H 5 NH 3 ) 2 CdCl 4 : Cu 2+ undergoes a red shift of 1400 cm m 1 on passing from ambient pressure to 40 kbar. To understand this fact theoretical calculations of the {\rm CuCl}^{4-}_{6} complex using four different methods have been carried out. Based on these calculations, it is concluded that the experimental red shift undergone by E u ( ~ ) can only be reasonably explained through a decrease of ～25 pm in R ax and an increase of ～7 pm in R eq leading to a decrement of the {\rm CuCl}^{4-}_{6} volume. Variations of any metal-halide distances down to 0.1 pm can be well detected through the shifts of the charge-transfer band energy upon pressure.     

Mechanism‐Dependent Modulation of Ultrafast Interfacial Water Dynamics in Intrinsically Disordered Protein Complexes

The recognition of intrinsically disordered proteins (IDPs) is highly dependent on dynamics owing to the lack of structure. Here we studied the interplay between dynamics and molecular recognition in IDPs with a combination of time‐resolving tools on timescales ranging from femtoseconds to nanoseconds. We interrogated conformational dynamics and surface water dynamics and its attenuation upon partner binding using two IDPs, IBB and Nup153FG, both of central relevance to the nucleocytoplasmic transport machinery. These proteins bind the same nuclear transport receptor (Importinβ) with drastically different binding mechanisms, coupled folding–binding and fuzzy complex formation, respectively. Solvent fluctuations in the dynamic interface of the Nup153FG‐Importinβ fuzzy complex were largely unperturbed and slightly accelerated relative to the unbound state. In the IBB‐Importinβ complex, on the other hand, substantial relative slowdown of water dynamics was seen in a more rigid interface. These results show a correlation between interfacial water dynamics and the plasticity of IDP complexes, implicating functional relevance for such differential modulation in cellular processes, including nuclear transport.     

Asteriscunolides A,B, C and D,the first humulanolides; Two pairs of conformationally stable stereoisomers

Following a preliminary comunication on Asteriscunolide A (the first reported natural humulanolide), three more configurationally and/or conformationally isomeric Asteriscunolides ( B, C and D ) from the same plant ($\text{Asteriscus aquaticus}$ L.) are described. The absolute configurations and the stable conformations of all four Asteriscunolides are established by an array of spectroscopic methods (CD, ¹H and ¹³C NMR) without resorting to X ray analysis.     

Local symmetry change in BaF2:Mn2+ at approximately 50 K: microscopic insight

The microscopic origin of the abrupt cubic-tetrahedral symmetry change associated with the local a(2u) vibrational mode observed by electron paramagnetic resonance in BaF(2):Mn(2+) at approximately 50 K is explored by means of density functional theory calculations. It is found that while the a(2u) vibrational frequencies calculated for MnF(8) (6-) in CaF(2) (168 cm(-1)) and SrF(2) (132 cm(-1)) are real, in the case of BaF(2):Mn(2+), the adiabatic potential curve along this mode exhibits a double well with a small barrier of 50 cm(-1). Although the ground and first excited vibrational states are localized around the energy minima, the rest of the excited states resemble those of a harmonic oscillator centered at Q(a(2u))=0. Moreover, only the inclusion of the anharmonic coupling between a(2u) and t(1u) modes allows one to understand the T(d)-O(h) transition temperature. It is shown that both the unusually high Mn(2+)-F(-) distance in BaF(2):Mn(2+) and the pseudo-Jahn-Teller interaction of the t(2g)(xy;xz;yz) antibonding orbital with filled t(1u) orbitals favor the a(2u) instability. The calculated a(2u) force constant for different electronic states supports this conclusion.     

电感耦合等离子体原子发射光谱法测定钛酸钡纳米粉体中7种杂质元素

钛酸钡纳米粉体样品用盐酸溶解,在所得样品溶液中用电感耦合等离子体原子发射光谱法测定了以氧化物存在于样品中的7种杂质元素(包括镁、锶、钾、钠、铝、硅及铁),对测定的光谱条件进行了试验并优化达到上述各元素的测定上限为0.1%(质量分数).测得方法的检出限(3S/b)为(单位μg·L-1):2.0(铝),1.0(铁),20.0(钾),0.2(镁),4.0(钠),3.0(硅)及0.5(锶).应用此方法分析了两件实样,所得结果的相对标准偏差(n=6)小于等于2.0%,对其中4种杂质元素(镁、钾、钠和锶)同时用HG/T 3587-1999标准中的方法作分析校核,所得结果与此方法结果一致.