Synthesis of Carbazoles and Related Heterocycles from Sulfilimines by Intramolecular C−H Aminations

While direct nitrene insertions into C?H bonds have become an important tool for building C?N bonds in modern organic chemistry, the generation of nitrene intermediates always requires transition metals, high temperatures, ultraviolet or laser light. We report a mild synthesis of carbazoles and related building blocks through a visible light‐induced intramolecular C?H amination reaction. A striking advantage of this new method is the use of more reactive aryl sulfilimines instead of the corresponding hazardous azides. Different catalysts and divergent light sources were tested. The reaction scope is broad and the product yield is generally high. An efficient gram‐scale synthesis of Clausine C demonstrates the applicability and scalability of this new method.     

减少纳米MOS器件栅电流的研究分析

采用Schroedinger-Poisson方程自洽全量子求解法研究了MOS器件不同介质材料和栅结构栅电流,该模型对栅电流中的三维电流成分用行波统一地计算;对二维栅电流成分通过反型层势阱中准束缚态的隧穿率计算。模拟得出栅极电流与实验结果符合。研究结果表明,采用高愚栅介质材料、p-MOSFET或双栅结构对栅电流的减少有明显的作用,这一结果可望对器件性能作出预计并对其研制提供指导。     

Boussinesq方程行波解的存在性

利用平面动力系统方法的分支理论,研究了Boussinesq方程,通过对Boussinesq方程进行行波变换,得到了相应行波系统的首次积分和平衡点,给出了不同参数条件下的相图,证实了Boussinesq方程存在孤立波解和周期波解。     

高双折射微结构光纤特性的研究

采用基于单轴各向异性完美匹配层吸收边界的频域有限差分方法研究一种椭圆芯高双折射微结构光纤的特性.通过计算,分析了空气孔尺寸和孔距对模式双折射、泄漏损耗以及模式截止波长的影响;综合研究了双折射微结构光纤的几种特性及其相互之间的影响和制约关系;并首次采用有效面积的方法研究高双折射微结构光纤的模式截止特性,分析单模传输条件;从而为高双折射微结构光纤的设计提供了一定的理论依据.     

Synthetic Diphenylacetylene-Based Retinoids Induce DNA Damage in Chinese Hamster Ovary Cells without Altering Viability

All-trans-retinoic acid (ATRA), the active metabolite of vitamin A, plays a pivotal role in cell differentiation, proliferation and embryonic development. It is an effective therapy for dermatological disorders and malignancies. ATRA is prone to isomerization and oxidation, which can affect its activity and selectivity. Novel diphenylacetylene-based ATRA analogues with increased stability can help to overcome these problems and may offer significant potential as therapeutics for a variety of cancers and neurodegenerative diseases, including amyotrophic lateral sclerosis. Here, we investigated the effects of these retinoids on cell viability and genotoxicity in the widely used model system of the rapidly proliferating Chinese hamster ovary cell line. DC360 is a fluorescent ATRA analogue and DC324 is a non-active derivative of DC360. EC23, DC525, DC540, DC645, and DC712 are promising analogues with increased bioactivity. The cytotoxic activity of the compounds was evaluated by ATP assay and DNA damage was tested by comet assay. No cytotoxicity was observed in the 10⁻⁶–10⁻⁵ M concentration range. All compounds induced DNA migration similar to ATRA, but DC324, DC360 and EC23 did so to a greater extent, particularly at higher concentrations. We believe that retinoid receptor-independent genotoxicity is a general characteristic of these compounds; however, further studies are needed to identify the molecular mechanisms and understand their complex biological functions.     

Catalytic properties of mesoporous materials supported heteropoly acids for Baeyer-Villiger oxidation of cyclic ketones

Three mesoporous molecular sieves loaded silicotungstic acids, named HSiW/SBA-15, HSiW/MCM-41, HSiW/MCM-48, were prepared and characterised by XRD, FT-IR, TEM and SEM. The catalytic performance of the prepared materials for the Baeyer-Villiger oxidation of cyclic ketones was carried out in the presence of 30%H₂O₂ under mild conditions. These loading materials were proved to be efficient and reusable catalysts, they all exhibited excellent catalytic performance for the Baeyer-Villiger oxidation of cyclic ketones with 30% H₂O₂ as oxidant. Many cyclic ketones were efficiently converted to the corresponding lactones with up to 90% conversions and high selectivities under the optimum reaction conditions.

Cyclic ketones were efficiently oxidised by mesoporous materials sopported silicotungstic acid to the corresponding lactones with 30%H₂O₂ as oxidant. All of the catalysts showed promising recyclability in the reactions.     

Development,Validation, and Application of the UPLC-DAD Methodology for the Evaluation of the Qualitative and Quantitative Composition of Phenolic Compounds in the Fruit of American Cranberry (Vaccinium macrocarpon Aiton)

Phenolic compounds in the fruit of American cranberry (Vaccinium macrocarpon Aiton) determine the antioxidant, anti-inflammatory, anticancer, and other biological effects. The berries are used in the production of medicinal preparations and food supplements, which highlights the importance of qualitative and quantitative analysis of phenolic compounds in cranberry fruit raw material. The aim of our study was to develop and validate an efficient, cost-effective, reproducible, and fast UPLC-DAD methodology for the evaluation of the qualitative and quantitative composition of phenolic compounds in raw material and preparations of American cranberry fruit. During the development of the methodology, chlorogenic acid and the following flavonols were identified in cranberry fruit samples: myricetin-3-galactoside, quercetin-3-galactoside, quercetin-3-glucoside, quercetin-3-α-L-arabinopyranoside, quercetin-3-α-L-arabinofuranoside, quercetin-3-rhamnoside, myricetin, and quercetin. The developed and optimized UPLC-DAD methodology was validated according to the guidelines of the International Council for Harmonization (ICH), evaluating the following parameters: range, specificity, linearity (R² > 0.999), precision (%RSD < 2%), LOD (0.38–1.01 µg/mL), LOQ (0.54–3.06 µg/mL), and recovery (80–110%). The developed methodology was applied to evaluate the qualitative and quantitative composition of phenolic compounds in fruit samples of cranberry cultivars ‘Baifay’, ‘Bergman’, ‘Prolific’, and ‘Searles’, as well as ‘Bain-MC’ and ‘BL-12′ clones. In the tested samples, the majority (about 70%) of the identified flavonols were quercetin derivatives. The greatest amount of quercetin-3-galactoside (1035.35 ± 4.26 µg/g DW) was found in fruit samples of the ‘Searles’ cultivar, and the greatest amount of myricetin-3-galactoside (940.06 ± 24.91 µg/g DW) was detected in fruit samples of the ‘Woolman’ cultivar.     

灵芝子实体水溶性多糖的分离和分子量测定

用磷酸盐缓冲液、热水、碱和热碱水分别从灵芝子实体分离出五种水溶性杂多糖ＧＬ１、ＧＬ２、ＧＬ３、ＧＬ４和ＧＬ５．紫外光谱、红外光谱、气相色谱及硫酸咔唑分析结果表明，它们主要由葡聚糖、木糖、甘露糖、半乳糖组成，ＧＬ３、ＧＬ４和ＧＬ５含葡萄糖醛酸．由粘度、光散射和膜渗透压法测定了特性粘度［η］、重均分子量Ｍｗ及数均分子量Ｍｎ，ＧＬ２、ＧＬ３和ＧＬ５多糖的Ｍｗ值分别为１２４×１０４、１２８×１０４和５８×１０４．实验结果表明这些杂多糖含水溶性Ｄ 葡聚糖，并且初步推断，用磷酸盐缓冲液提取出的杂多糖ＧＬ２中包含刚性链β Ｄ 葡聚糖     

INFLUENCE OF MOLECULAR WEIGHT AND PERIODATE-MODIFICATION OF β-D-GLUCANS FROM PORIA COCOS SCLEROTIUM ON ANTITUMOR ACTIVITIES*

In this work, influence of molecular weight and periodate modification ofβ-D-glucans isolated from Poria cocos sclerotium on the antitumor activities against Sar-coma 180 and Ehrlich ascites carcinoma (EAC) tumor was studied. The results show thattwo glucans PC3 (linear β-(1→3)-D-glucan) and PC4 [β-(1→3)-D-glucan with a fewof branches and glucuronic acid] are devoid of antitumor activity. However, when theglucans were modified by periodate oxidation, borohydride reduction and mild hydrolysisor partially hydrolysis, the derivatives have obvious antitumor activities. The decreasein molecular weight of glucans after periodate modification hardly affects their antitumoractions, but on the other hand, the decrease of molecular weight without periodate modi-fication could lead to an enhancement of the antitumor activities. Moreover, the glucansand these derivatives have much higher enhancement ratios of body weight of mice thanthat of 5-Fluorouracil (5-Fu), suggesting that they are less toxic than 5-Fu.     

Partial Oxidation of Methane to Synthesis Gas over Hexaaluminates LaMAl11O19-δ catalysts

A series of M-substituted hexaaluminates LaMAl11O19-δ (M=Fe, Co, Ni, Mn, and Cu)were prepared and characterized by XRD, XPS, TPR and TGA techniques, respectively. They exhibited different reducibility and catalytic activity for partial oxidation of methane (POM) to synthesis gas. Among the LaMAl11O19-δ samples, LaNiAl11O19-δ showed the best catalytic activity for the topic reaction and selectivity for synthesis gas at 780 ℃ for 2 h. The conversion of CH4 was over 99.2%, and the product selectivity for both CO and H2 was above 90.3%.