Intramolecular,Stoichiometric (Li,Mg, Zn) and Catalytic (Ni,Pd, Pt) Metallo-Ene Reactions in Organic Synthesis [New Synthetic Methods (75)]

Metallo-ene reactions, hardly recognized until very recently, have experienced a breathtaking development when applied in an intramolecular sense. Efficient regio- and stereoselective magnesium-ene cyclizations have served as a cornerstone for numerous syntheses of structurally diverse natural products (e.g., sesquiterpenes of marine or plant origin, alkaloids, fragrances, insect defense compounds, and a fungitoxin). A brilliant example is the synthesis of the elusive odorant (+)-khusimone which outshines 20 years of work in the field of tricyclovetivane synthesis. Palladium-, platinum-, and nickel-catalyzed versions of the metallo-ene reaction are in a comparatively early stage of exploration, but, nevertheless, reveal intriguing potential. Hence an almost 100% stereospecific C? O→C? ;Pd-→ C? C chirality transfer permits simple and selective, cis- or trans-annelation processes. The mild cyclization conditions are compatible with various functional groups, such as nitrogen moieties, which offer interesting perspectives for the preparation of heterocycles (e.g., alkaloids) difficult to obtain by other methods. Carbon monoxide insertion reactions of the cyclized σ-metal intermediates were shown to afford annelated cyclopentanones and cyclopentenones with concomitant stereocontrolled formation of four carbon–carbon bonds. These and other observations, highlighted in this article, provide a platform for further extensions and applications of this powerful method in organic synthesis.     

Synthesis of N,N-diethyldithiocarbamate functionalized 1,4-polyisoprene, from natural rubber and synthetic 1,4-polyisoprene

N,N-Diethyldithiocarbamate functionnalized 1,4-polyisoprenes were prepared from 1,4-polyisoprenes (natural or synthetic). The syntheses were performed by nucleophilic addition of N,N-diethyldithiocarbamate salts upon oxirane rings of epoxidized units according to a SN2 mechanism with ring opening. Studies on model molecules of epoxidized 1,4-polyisoprene units (1,2-epoxy-1-methylcyclohexane and 4,5-epoxy-4-methyloctane) were previously achieved to develop the procedure. The best yields were obtained at low temperature in polar medium, and more especially in water with sodium N,N-diethyldithiocarbamate (DEDT-Na) as reagent. A diastereospecific addition was noted when reaction was performed in water with DEDT-Na. Afterwards, the developed procedure was successfully generalized to epoxidized synthetic polyisoprenes and epoxidized natural rubber (in THF, then in latex medium). Excellent results were obtained in latex medium with epoxidized natural rubber (ENR) latices. As with the models, a diastereospecific addition of sodium N,N-diethyldithiocarbamate trihydrate onto epoxidized 1,4-polyisoprene units of ENR was observed at the condition to bring the latex medium to pH 8 before introduction of DEDT-Na. Influence of temperature, drc, and DEDT-Na concentration were successively examined to determine the best conditions of the addition on ENR latices.     

槲皮素包裹修饰硅包银纳米颗粒作为荧光传感器对铜离子的识别作用

制备了一种基于天然产物槲皮素接枝硅包银核壳结构的纳米荧光传感器(Ag@SiO₂@Qc),对铜离子具有好的选择性和灵敏性。Ag@SiO₂@Qc与Cu2+离子结合后,荧光发射强度发生猝灭,并且可通过荧光滴定光谱得到了荧光滴定曲线：y = -32.864x+587.59(R2=0.998),其线性范围分别为：3×10-7~4.8×10-6 mol·L-1,最低检测限为1.0×10-7 mol·L-1。并且将Ag@SiO₂@Qc应用于环境中水样的检测结果的准确度好,精密度高,而且更加环保、方便、快捷,具有很大发展潜力与应用价值。     

激光拉曼光谱法测定天然气组成标准研究

进行了天然气组成分析-激光拉曼光谱法标准化研究,探讨了激光拉曼天然气组成分析方法标准化的可行性。采用激光拉曼光谱进行天然气组成分析,无需将天然气中各组分分离便可实现多组分同步检测,减少分析时长,提高测量的实时性,实现快速分析,通过国内外激光拉曼天然气分析方法和标准的研究和实验,掌握了国内外激光拉曼天然气分析方法技术现状及发展方向,积累了激光拉曼天然气分析试验数据,结果表明激光拉曼天然气分析具有可快速检测(10 s)、连续记录和操作简单的优点,适用于天然气录井、井站、集气站原料气气质分析和天然气净化处理中过程控制中实时快速获取气质数据,建议制定激光拉曼光谱天然气分析方法标准,测量组分为CO₂,N₂,H₂S,CH₄,C₂H₆,C₃H₈,测量范围分别为：CH₄：75%~99.9%,C₂H₆：0.005%~20%,C₃H₈：0.005%~10%,H₂S：0.001 5%~10%,N₂：0.02%~10%,CO₂：0.01%~10%(上述浓度均为摩尔分数),为上游领域天然气勘探开发及过程控制服务。     

Mapping of an ultrasonic bath for ultrasound assisted extraction of mangiferin from Mangifera indica leaves

The present work deals with the mapping of an ultrasonic bath for the maximum extraction of mangiferin from Mangifera indica leaves. I₃⁻ liberation experiments (chemical transformations) and extraction (physical transformations) were carried out at different locations in an ultrasonic bath and compared. The experimental findings indicated a similar trend in variation in an ultrasonic bath by both these methods. Various parameters such as position and depth of vessel in an ultrasonic bath, diameter and shape of a vessel, frequency and input power which affect the extraction yield have been studied in detail. Maximum yield of mangiferin obtained was approximately 31 mg/g at optimized parameters: distance of 2.54 cm above the bottom of the bath, 7 cm diameter of vessel, flat bottom vessel, 6.35 cm liquid height, 122 W input power and 25 kHz frequency. The present work indicates that the position and depth of vessel in an ultrasonic bath, diameter and shape of a vessel, frequency and input power have significant effect on the extraction yield. This work can be used as a base for all ultrasonic baths to obtain maximum efficiency for ultrasound assisted extraction.     

Microwave dielectric and magnetic properties of superparamagnetic 8-nm Fe3O4 nanoparticles

The superparamagnetic 8-nm Fe₃O₄ nanoparticles were successfully prepared by chemical oxidation process. For the complex permittivity, the dual dielectric relaxation processes have been proved by two overlapped Cole–Cole semicircles, and the natural resonance frequency is 3.03 GHz for the complex permeability. The maximum reflection loss value reaches −55.5 dB at 6.11 GHz with 3.85 mm in the thickness of the absorbers for the superparamagnetic 8-nm Fe₃O₄ nanoparticles which is better than that of 150 nm and 30 nm Fe₃O₄ nanoparticles. It is believed that the superparamagnetic 8-nm Fe₃O₄ nanoparticles can be used as a kind of candidate for microwave absorber.     

2-F-环氧丁烷与几种生物小分子间的赝氢键结构

采用密度泛函B3LYP(Becke,three-parameter,Lee-Yang-PaH)/6-311++G**和HF(Hartree Fock)/6-311++G**方法,从理论上探讨了2-F-环氧丁烷分别与几种常见而重要的生物小分子咪唑(Iminazole)、噻唑(Thiazole)和恶唑(Oxazo1e)等分子间的弱相互作用,发现分子间同时存在N…H常规氢键和C-F…H-C赝氢键结构.弱相互作用能计算表明3个复合物的相对稳定性相当.计算结果表明,在C-F…H-C赝氢键结构中,与电子的直接供体F密切相关的共价键C-F键长增大,伸缩振动的频率红移,而作为电子受体的H-C基团,其C-H键伸缩振动光谱蓝移;另外,电子密度拓扑性质表明C-F…H-C赝氢键的共价性及离子性均与常规氢键相当.     

Vibration and instability analysis of tubular nano- and micro-beams conveying fluid using nonlocal elastic theory

A nonlocal Euler–Bernoulli elastic beam model is developed for the vibration and instability of tubular micro- and nano-beams conveying fluid using the theory of nonlocal elasticity. Based on the Newtonian method, the equation of motion is derived, in which the effect of small length scale is incorporated. With this nonlocal beam model, the natural frequencies and critical flow velocities for the case of simply supported system and for the case of cantilevered system are obtained. The effect of small length scale (i.e., the nonlocal parameter) on the properties of vibrations is discussed. It is demonstrated that the natural frequencies are generally decreased with increasing values of nonlocal parameter, both for the supported and cantilevered systems. More significantly, the effect of small length scale on the critical flow velocities is visible for fluid-conveying beams with nano-scale length; however, this effect may be neglected for micro-beams conveying fluid.