Enantioselective Cross-couplings between Halide Derivatives and Organometallics by Using Iron and Cobalt Catalysts: Formation of C−C Bonds

This review highlights the recent achievements of iron- and cobalt-catalyzed enantioselective cross-couplings of halide derivatives with organometallic reagents for the construction of C-C bonds. Synthetic applications of enantioselective cross-couplings to natural products and biologically active compounds are also covered showing the power of these cross-couplings in organic synthesis.     

Gold‐Catalyzed Tandem Cycloisomerization–Halogenation of Chiral Homopropargyl Sulfonamides

Two new gold‐catalyzed tandem cycloisomerization–halogenation reactions of chiral homopropargyl sulfonamides have been developed. Various enantioenriched 3,3‐diiodopyrrolidin‐2‐ols and 3‐fluoropyrrolidin‐2‐ols were obtained in moderate‐to‐good yields with excellent enantio‐ and diastereoselectivity.     

Synthesis of 2-aminooxazolines from isonitriles and iodine

A novel one-pot protocol for the synthesis of substituted 2-aminooxazoline from isonitriles and 2-aminoethanol was developed and the reactions involved imidoyl diiodide intermediates,which were generated by mixing isonitriles and iodine in CH₂C1₂ at room temperature.     

Application of Graphene as a Sorbent for Simultaneous Preconcentration and Determination of Trace Amounts of Cobalt and Nickel in Environmental Water and Vegetable Samples

A new method using a column packed with graphene as adsorbent was developed for the preconcentration of trace amounts of cobalt (Co) and nickel (Ni) prior to their determinations by flame atomic absorption spectrometry. Several factors influencing the extraction efficiency of Co and Ni and their subsequent determinations, such as pH, amounts of the chelating agent, flow rates of sample and eluent solution, eluent type and its volume, breakthrough volume, and adsorption capacity were established. Under the optimum conditions, the calibration graphs were linear in the range of 4.0‐200.0 μg L^?1 and 5.0‐200.0 μg L^?1 with detection limits of 0.36 μg L^?1 and 0.51 μg L^?1 for Co and Ni, respectively. Good relative standard deviations for ten determinations of 100.0 μg L^?1 of Co and Ni were 3.2 and 3.6%, respectively. The results for determination of Co and Ni in tap water, river water, sea water, vegetable and spiked samples have demonstrated the accuracy and applicability of the proposed method. To validate the proposed method, three certified reference materials of environment water (GSBZ 50030‐94 and GSB 07‐1186‐2000) and tomato leaf (GSBZ 51001‐94) were analyzed, and the determined values were in good agreement with the certified values.     

Influence of Intermolecular Interactions on Valence Tautomeric Behaviors in Two Polymorphic Dinuclear Cobalt Complexes

Two polymorphic structures have been well determined in a valence tautomeric (VT) dinuclear cobalt complex. These polymorphs showed distinct thermal‐ and photomagnetic behavior, and are thus ideal for studying the “pure” intermolecular factors to VT transitions. In polymorph 1A , the VT cations are arranged head‐to‐waist with their neighbors and exhibit weak π???π interactions, resulting in a gradual and incomplete thermal VT transition. In contrast, the cations in polymorph 1B are arranged head‐to‐tail and exhibit relatively strong π???π interactions, leading to an abrupt and complete thermal VT transition with adjustable hysteresis loop at around room temperature. The VT process for both polymorphs can be induced by light, but the light‐excited state of 1B? 2H₂O has a higher thermal relaxation temperature than that of 1A? 3H₂O.     

Extinction Effects of Multiplicative Non-Gaussian L′evy Noise in a Tumor Growth System with Immunization

The extinction phenomenon induced by multiplicative non-Gaussian Levy noise in a tumor growth model with immune response is discussed. Under the influence of the stochastic immune rate, the model is analyzed in terms of a stochastic differential equation with multiplicative noise. By means of the theory of the infinitesimal generator of Hunt processes, the escape probability, which is used to measure the noise-induced extinction probability of tumor cells, is explicitly expressed as a function of initial tumor cell density, stability index and noise intensity. Based on the numerical calculations, it is found that for different initial densities of tumor cells, noise parameters play opposite roles on the escape probability. The optimally selected values of the multiplicative noise intensity and the stability index are found to maximize the escape probability.     

冶金法生产太阳能级硅的除硼方法、技术及工艺

太阳能作为一种绿色可再生能源受到了广泛关注,而杂质去除是从冶金级硅中获得太阳能级硅所需的纯化过程,对硅基太阳能电池的制备至关重要。冶金法制备太阳能级多晶硅新工艺技术由于其能耗低、成本低和污染少等优点,成为研究开发的热点,但如何有效地去除硼是我们面临的最严峻的挑战之一。本文综述了硼的热力学和动力学性质(溶解度、扩散率、扩散系数、传质系数和活度系数)以及近年来除硼的相关课题研究(吹气、炉渣处理、等离子体处理、酸浸和溶剂精炼)。研究发现,溶剂精炼是一种很有前途的获取高纯硅的方法,硅的富集率以及硼的去除率均可达到90%以上,而添加剂能够加强硼化物的形成和析出来改进除硼工艺,且后续几乎可被完全消除,不会对精炼硅造成污染,这将更加有效除硼并增加工艺实用性。最后本文对几种除硼工艺进行了比较分析,并对冶金法的应用前景进行了展望。     

Temperature memory effect and its stability revealed via differential scanning calorimetry in ethylene‐vinyl acetate within glass transition range

In this article, we reveal the temperature memory effect (TME) in a commercial thermoplastic polymer, namely ethylene‐vinyl acetate (EVA), within its glass transition range via a series of differential scanning calorimeter (DSC) tests. In addition, we investigate the influence of heating holding time and also compare the observed TME in current study with that of shape memory alloys (SMAs). It is concluded that the TME via DSC (without any macroscopic shape change) is achievable within the glass transition range of a polymer. Conversely, although the observed TME shares the many similar features as those in SMAs, due to the nature of micro‐Brownian motion in the glass transition of polymers, the resulted TME is strongly affected by the heating holding time. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1731–1737     

一例具有单分子磁体行为的单核钴-氮氧自由基异自旋配合物

合成并表征了一例2p-3d异自旋配合物[Co （hfac）₂（NIT-PyzMe-PhCHO）]（1），其中hfac=六氟乙酰丙酮，NIT-PyzMe-PhCHO=2-（3-（1H-咪唑-1-亚甲基）苯甲醛）-4，4，5，5-四甲基咪唑啉-1-氧基-3-氧化物。配合物1是单核结构，Co^Ⅱ离子与直接配位的氮氧基团之间存在强的反铁磁耦合。此外，与磁弛豫相关的频率依赖的虚部信号证实了其单分子磁体行为。