A Diels-Alder route to angularly functionalized bicyclic structures

A Diels-Alder-based route to trans-fused angularly functionalized bicyclic structures has been developed. This transformation features the use of a tetrasubstituted dienophile in the cycloaddition step.     

An efficient large-scale synthesis of gemcitabine employing a crystalline 2,2-difluoro-α-ribofuranosyl bromide

An efficient large-scale synthesis of gemcitabine was achieved without chromatography or fractional crystallization. The key steps include stereospecific conversion of a novel β-ribofuranosyl phosphate into a highly crystalline α-ribofuranosyl bromide and coupling of the α-ribofuranosyl bromide and trimethylsilyl cytosine to produce a β-nucleoside. p-Phenylbenzoyl group was introduced for the protection of one of hydroxy groups in order to enhance the crystallinity of intermediates. Continuous removal of trimethylsilyl bromide, generated during the coupling reaction, by distillation from the reaction medium substantially enhanced the β-selectivity of the crucial coupling reaction.     

基于近红外光谱的人参与西洋参的快速鉴别研究

基于近红外光谱分析技术结合模式判别方法建立了一种人参和西洋参鉴别的新方法。收集根状、根须和粉末状的样品共90份,在有聚乙烯包装袋的情况下直接采集近红外光谱,去除原始光谱中包装袋的显著吸收后进行了MSC与一阶导数处理,然后采用移动窗口偏最小二乘法选择了建模光谱区间,分别建立了PLS-DA,PCA-DA和SVM判别模型,并对3种模型作了对比分析,结果表明SVM判别效果最优,其对预测集的正确判别率为100%。该方法准确、便捷,可实际应用于企业原料药材的质量控制,实现对原料药材的快速筛查。     

NMR and Excess Volumes Studies in DMF–Alcohol Mixtures

Chemical shifts of the alcohol and DMF protons in DMF–alcohol mixtures with the mole fraction of alcohol are reported in order to study the hydrogen bond interaction present in the mixtures. The densities of DMF–methanol mixture at 22°C are also measured. Excess volumes and excess chemical shifts are correlated by the Redlich–Kister equation. The relation between excess volumes and excess chemical shifts in the mixtures is discussed. It is found that the maximum excess chemical shifts ^E(CHO-OH) and ^E(CH₃-OH) are positioned at about mole fraction methanol = 0.57 for the DMF–methanol system, as is V ^E. The results show that the NMR spectral method offers a valuable approach to similar future studies of interactions in mixtures.     

Kinetics and mechanism of the pyridinolysis of phenacyl bromides in acetonitrile

Kinetic studies of the reactions of substituted phenacyl bromides (YC6H4COCH2Br) with pyridines (XC5H4N) are carried out in acetonitrile at 45.0 degrees C. A biphasic Bronsted plot is obtained with a change in slope from a large (betaX approximately equals 0.65-0.80) to a small (betaX approximately 0.36-0.40) value at pKa = 3.2-3.6, which can be attributed to a change in the rate-determining step from breakdown to formation of a tetrahedral intermediate in the reaction path as the basicity of the pyridine nucleophile increases. This mechanism is supported by the faster rates with pyridines than with anilines and the change of cross-interaction constant rhoXY from a large positive (rhoXY = +1.4) to a small positive (rhoXY approximately +0.1) value. The large magnitude of Hammett rhoX (= -5.5 to -6.9) values for the pyridines with electron-withdrawing substituents and positive deviations of the pi-acceptors, p-CH3CO and p-CN, are quite similar to those for the pyridinium ion formation equilibria. The activation parameters are also in line with the proposed mechanism.     

A Cyanine-based Liposomal Nanophotosensitizer for Enhanced Cancer Chemo-Photodynamic Therapy

Currently, chemotherapy is one of the most important treatment modalities for malignant tumors in the clinic, however, it exhibits some shortcomings, such as poor selectivity, limited efficacy and serious adverse effects. Therefore, synergistic therapy and accurate drug delivery at tumor sites become a promising strategy for achieving tumor eradication. Herein, a smart NIR fluorescence imaging-guided nanoliposome was fabricated by encapsulating a chemotherapeutic drug(doxorubicin, DOX), liposomes(L) and a near-infrared(NIR) photosensitizer(CY) to form L@CY@DOX, which could realize enhanced therapeutic efficacy of chemo-PDT in cancer therapy(PDT=photodynamic therapy). L@CY@DOX can induce mitochondrial apoptosis and produce severe toxicity at the cellular level, and L@CY@DOX can enrich in the tumor site, which significantly induces tumor death. In vitro and in vivo studies demonstrated that L@CY@DOX exhibited great antitumor efficacy compared with each one of these monotherapies, indicating that the combination of chemotherapy and PDT possessed potential development prospects and is anticipated in clinical application.     

Capillary Electrophoresis-Indirect Laser-Induced Fluorescence Detection of Neomycin in Fish

Chromatographia - A capillary electrophoresis-indirect laser-induced fluorescence detection method was established for neomycin detection in fish. With rhodamine 6G as the background fluorescent...     

A cosolvent pretreatment: effect of solvent–water on enzymatic hydrolysis of glucan,lignin structure,and dynamics

Cellulose - In this study, a biomass pretreatment strategy with a recyclable cosolvent (toluene sulfonic acid/ethanol) was developed. The low boiling point solvent (78.15 °C),...     

Crosslinking polydopamine/cellulose nanofibril composite aerogels by metal coordination bonds for significantly improved thermal stability,flame resistance,and thermal insulation properties

Cellulose nanofibril (CNF) aerogels have attracted great interests in recent years due to the low cost, sustainability and biocompatibility of raw CNF. However, the poor thermal stability and flammable feature of CNF aerogels have limited their wider applications. In this paper, polydopamine/CNF composite aerogels with good comprehensive properties are fabricated by modification of CNF with polydopamine and metal coordination bonds crosslinking. The microstructure and properties of composite aerogels are thoroughly characterized by a variety of tests. It is found that the microstructure of aerogels are more regular and the compressive strength of aerogels are enhanced by the incorporation of polydopamine and Fe³⁺ crosslinking. Importantly, the thermal stability and flame resistance of aerogels are significantly improved, which permit the application of composite aerogels in high-temperature thermal insulation. In addition, the reversible characteristic of metal coordination bonds allows the water induced healing of fractured composite aerogels. This study is expected to provide information for future development of green and high-performance aerogels.

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Development and testing of a Frisch-Grid Ionization Chamber for the measurement of low activity of alpha-particle emitters

Journal of Radioanalytical and Nuclear Chemistry - A Frisch-grid Ionization Chamber (FGIC) for the measurement of low activity of alpha-particle emitters has been built. The design and performance...