Catalytic Asymmetric Construction of α‐Quaternary Cyclopentanones and Its Application to the Syntheses of (−)‐1,14‐Herbertenediol and (−)‐Aphanorphine

A novel and efficient strategy to build α‐benzylic quaternary cyclopentanones with excellent enantioselectivities (up to 96 % ee) and high yields (up to 99 % yield) has been developed, and its application demonstrated by the first catalytic asymmetric total synthesis of (?)‐1,14‐herbertenediol and the formal synthesis of (?)‐aphanorphine.     

大脉冲电流下钨铜电极水和空气中的烧蚀特性

针对水中、空气中脉冲放电条件下金属电极烧蚀速率及烧蚀机理差异,对脉冲大电流作用下水中、空气中钨铜电极的烧蚀特性进行了对比研究。在保证放电电流波形一致性的前提下,通过采用高精度天平测量并获取了水中、空气中钨铜电极的阴、阳极烧蚀速率及总烧蚀速率,并对电极表面进行了二次电子观察和背散射电子观察分析。结果表明,大脉冲电流作用下,水中钨铜电极烧蚀较空气中更为严重,钨铜电极的烧蚀主要是金属蒸发引起的汽相侵蚀。由于水介质较空气具有不可压缩性,水中放电电弧集中,电极表面电弧斑点处电流密度和电流作用时间较空气中更为严重,同时由于水中脉冲放电时发生的高温物理化学反应,是造成水中电极烧蚀要高于空气中的根本原因。     

Biological evaluation of 2-methylpyrimidine derivatives as active pan Bcr-Abl inhibitors

We designed a series of 2-methylpyrimidine derivatives as new BCR-ABL inhibitors using scaffold-hopping strategy.These synthetic compounds exhibited significant inhibition against a broad spectrum of Bcr-Abl mutants including the gatekeeper T315I mutant.Compound 7u showed very potent kinase inhibitory activities against Bcr-Abl WT,Bcr-Abl E255K,Bcr-Abl Q252H,Bcr-Abl G250E and Bcr-Abl T315I,with IC50 values of 0.13 nM,0.17 nM,0.24 nM,0.19 nM and 0.65μM,respectively.This compound also displayed anti-proliferation activity against K562 cell line with an IC50 value of 1.1 nM,thus representing a new lead for further optimization.     

Reversible Optical Writing and Data Storage in an Anthracene‐Loaded Metal–Organic Framework

Metal–organic frameworks (MOFs) enable the design of host–guest systems with specific properties. In this work, we show how the confinement of anthracene in a well‐chosen MOF host leads to reversible yellow‐to‐purple photoswitching of the fluorescence emission. This behavior has not been observed before for anthracene, either in pure form or adsorbed in other porous hosts. The photoresponse of the host–guest system is caused by the photodimerization of anthracene, which is greatly facilitated by the pore geometry, connectivity, and volume as well as the structural flexibility of the MOF host. The photoswitching behavior was used to fabricate photopatternable and erasable surfaces that, in combination with data encryption and decryption, hold promise in product authentication and secure communication applications.     

2,6-二甲基-4-苯基-1,4-二氢吡啶-3,5-二甲酸乙酯的合成和晶体结构

标题化合物C1 9H2 3NO4由苯甲醛、尿素、乙酰乙酸乙酯在微波辐射下干反应而得。结构通过单晶X 射线衍射法测定 ,其晶体属单斜晶系 ,空间群P2 1 /c ,a =9.745(2 ) ,b =7.388(2 ) ,c =2 4 .354(5) ,β =92 .60 (3)°,V =1 751 .6(6) 3,Z =4,Mr=32 9.38,Dc=1 2 4 9g/cm3,μ(MoKα) =0 .0 87mm- 1 ,F(0 0 0 ) =70 4。晶体结构用直接法解出 ,经全矩阵最小二乘法对原子参数进行修正 ,最终的偏离因子为R =0 .0 4 1 6,wR =0 .1 1 75。在晶体结构中 ,二氢吡啶环与苯环之间的二面角为 92 .1 4°。     

Self-assembling gold nanoparticles on thiol-functionalized poly(styrene-co-acrylic acid) nanospheres for fabrication of a mediatorless biosensor

A novel strategy to construct a sensitive mediatorless sensor of H₂O₂ was described. At first, a cleaned gold electrode was immersed in thiol-functionalized poly(styrene-co-acrylic acid) (St-co-AA) nanosphere latex prepared by emulsifier-free emulsion polymerization St with AA and function with dithioglycol to assemble the nanospheres, then gold nanoparticles were chemisorbed onto the thiol groups and formed monolayers on the surface of poly(St-co-AA) nanospheres. Finally, horseradish peroxidase (HRP) was immobilized on the surface of the gold nanoparticles. The sensor displayed an excellent electrocatalytical response to reduction of H₂O₂ without the aid of an electron mediator. The biosensor showed a linear range of 8.0 μmol L⁻¹–7.0 mmol L⁻¹ with a detection limit of 4.0 μmol L⁻¹. The biosensor retained more than 97.8% of its original activity after 60 days’ storage. Moreover, the studied biosensor exhibited good current reproducibility and good fabrication reproducibility.     

Characterization of a pectic polysaccharide from the fruit of <Emphasis Type="Italic">Ziziphus jujuba</Emphasis>

A pectic polysaccharide was isolated from the fruits of Ziziphus jujuba Mill. cv. jinsixiaozao Hort. and its structure was characterized by acid hydrolysis, methylation, and NMR spectroscopies. The purified fraction Ju-B-7 had a molecular mass of over 2000 kDa. Chemical and spectroscopic analyses indicated that Ju-B-7 is composed mainly of α-1,4-linked D-galactopyranosyluronic acid and 1,2-linked L-rhamnose with a molar ratio of 8.1:1. It can significantly stimulate spleen cell proliferation in vitro (P<0.01, 10 μmg/mL). Published in Khimiya Prirodnykh Soedinenii, No. 4, pp. 311–312, July–August, 2007.     

Two-fluid and population balance models for subcooled boiling flow

Population balance equations combined with a three-dimensional two-fluid model are employed to predict subcooled boiling flow at low pressure in a vertical annular channel. The MUSIG (MUltiple-SIze-Group) model implemented in the computer code CFX4.4 is further developed to accommodate the wall nucleation at the heated wall and condensation in the subcooled boiling regime. Comparison of model predictions against local measurements is made for the void fraction, bubble Sauter mean diameter and gas and liquid velocities covering a range of different mass and heat fluxes and inlet subcooling temperatures. Additional comparison using empirical relationships for the active nucelation site density and local bubble diameter is also investigated. Good agreement is achieved with the local radial void fraction, bubble Sauter diameter and liquid velocity profiles against measurements. However, significant weakness of the model is evidenced in the prediction of the vapour velocity. Work is in progress to circumvent the deficiency through the consideration of additional momentum equations or developing an algebraic slip model to account for bubble separation.     

Mesoporous tungsten titanate as matrix for matrix-assisted laser desorption/ionization time-of-flight mass spectrometry analysis of biomolecules

In this paper, mesoporous tungsten titanate (WTiO) with different nano-pore structures was utilized as matrix for the analysis of short peptides by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). Effect of characteristic features of mesoporous matrices on laser desorption/ionization process was investigated. Experiments showed that the ordered two-dimensional and three-dimensional mesoporous matrices were superior in performance to the non-ordered WTiO matrix. The dramatic enhancement of signal sensitivity by the ordered mesoporous matrices can be reasonably attributed to the ordered structure, which facilitated the understanding on structure-function relationship in mesoporous cavity for laser desorption process of adsorbed biomolecules. With the ordered mesoporous matrix, the short peptides are successfully detected. The presence of trace alkali metal salt effectively increased the analyte ion yields and the MALDI-TOFMS using the inorganic mesoporous matrices displayed a high salt tolerance. The developed technique also showed a satisfactory performance in peptide-mapping and amino-acid sequencing analysis.