Synthesis and Crystal Structure of a Novel 1D Coordination Polymer:[Pr(BYBA)_3(H_2O)_2]·[Pr(BYBA)_3(H_2O)]

The novel coordination polymer [Pr(BYBA)3(H2O)2]·[Pr(BYBA)3(H2O)] (BYBAH=2-benzoylbenzoic acid) was yielded by hydrothermal synthesis,determined by single-crystal X-ray diffraction,and characterized by FT-IR and UV-Vis spectra. The crystal crystallizes in the triclinic system,space group P1 with a=9.112(3),b=14.644(5),c=27.076(11),α=84.223(3),β= 87.816(4),γ=88.902(4)o,V=3592(2)3,C84H60O21Pr2,Mr=1687.14,Z=2,F(000)=1700,Dc= 1.560 g/cm3,μ=1.419 mm-1,the final R=0.0485 and wR=0.1258 for 13035 observed reflections with I > 2σ(I). The compound contains two different building units,[Pr2(BYBA)6(H2O)4] and [Pr2(BYBA)6(H2O)2]. It is noticeable that [Pr2(BYBA)6(H2O)4] is an isolated binuclear building block,in which the Pr3+ ion centers are both located in an eight-coordinated environment. However,in [Pr2(BYBA)6(H2O)2] the Pr3+ ion centers are located in a nine-coordinated environment and connected by BYBA ligands to form 1D chains.     

新型2-氧代-1,2,4-三唑并[3,2-d][1,5]苯并氧氮杂类稠杂环的合成

将取代色满酮(1)与芳肼反应生成的腙与HNCO发生[3+2]环加成反应,加成产物(2)经氧化得到偕偶氮异氰酸酯(3).化合物3在HBF4的催化下发生环化-重排反应,得到新颖的三环系2-氧代-1,2,4-三唑并[3,2-d][1,5]苯并氧氮杂化合物5a～5g.     

Recycling Chiral Organocatalyst （4S）-Phenoxy-（S）-proline for Direct Asymmetric Aldol Reaction in Ionic Liquid （bmim）PF6

Room temperature ionic liquid (bmim)PF6 was evaluated for recycling an organocatalyst (4S)-phenoxy-(S)-proline for direct asymmetric aldol reactions. The desired aldol products were obtained with good yields up to 93.2% and enantioselectivities up to 88.5%, and isolation of the products by simple extraction allowed recycling the ionic liquid containing the immobilized catalyst in subsequent reactions without significant decrease of yields and enantioselectivities.     

High-level expression of soluble human β-defensin-2 fused with green fluorescent protein in Escherichia coli cell-free system

Human β-defensin-2 (hBD2), a small cationic peptide, exhibits a broad range of antimicrobial activity and does not acquire any microbial resistance. To produce this uneasily detectable, degradable, and toxic polypeptide efficiently, an alternative approach based on the Escherichia coli cell-free biosynthesis system was proposed. The approach implies that a polypeptide of interest is synthesized as a fusion protein linked to a green fluorescent protein (GFP) through a cleavable spacer. With batch-mode operation, a significant amount of hBD2 fused with GFP (0.25 mg/mL) can be expressed in this cell-free system. The productivity of the fusion protein can be improved up to 1.2 mg/mL by employing a continuous-exchange cell-free system. Furthermore, the GFP moiety provides directly visible and quantitative monitoring of the polypeptide synthesis, and the product is soluble and stable. This work will be helpful in allowing the rapid and visible expression of other similar defensins using an in vitro cell-free system.     

A combined diffraction and dielectric properties investigation of Ba3MnNb2O9 complex perovskites

A combined synthesis, diffraction and dielectric properties investigation of the dependence (and effect) of Mn²⁺/Nb⁵⁺ ordering in Ba₃MnNb₂O₉ (BMN) upon annealing atmosphere and processing conditions has been carried out. Annealing in different atmospheres was not found to significantly alter either nominal stoichiometry or structure type. The obtained structure type (disordered metrically cubic or ordered trigonal) as well as the measured electrical properties (in particular, the dielectric loss) were, however, found to be sensitive to the synthesis route. Samples obtained via solid-state reaction were found to be predominantly of 1:2 Mn²⁺/Nb⁵⁺ ordered, trigonal structure type whereas samples obtained via an aqueous solution route were found to be of a Mn²⁺/Nb⁵⁺ ‘disordered’, metrically cubic structure type. All solid-state synthesized samples showed reasonable dielectric properties. The microwave dielectric constant and dielectric quality factor, Q, at 8 GHz of an as-synthesized BMN sample were 38 and 100, respectively. By contrast, the dielectric loss of the metrically cubic, Mn²⁺/Nb⁵⁺ ‘disordered’ samples obtained via an aqueous solution synthesis process were significantly worse.     

A non-catalytic approach to the synthesis of 5,6-dihydrobenzo[h]quinolines

A concise synthesis of highly functionalized 5,6-dihydrobenzo[h]quinoline-3-carbonitriles is delineated through base induced ring transformation of 4-sec-amino-2-oxo-5,6-dihydro-2H-benzo[h]chromene-3-carbonitriles with S-methylisothiourea sulfate and 1-carboxamidinepyrazole hydrochloride, separately, in DMF. Under analogous reaction conditions the ring transformation of 4-sec-amino-2-oxo-5,6-dihydro-2H-benzo[h]chromene-3-carbonitriles by formamidine acetate provided 4-sec-amino-benzo[h]quinoline-3-carbonitriles in moderate yields, while with benzamidine hydrochloride, the reaction followed the same mechanism to yield 2-phenyl-4-sec-amino-5,6-dihydrobenzo[h]quinoline-3-carbonitriles.     

An unusual synthesis of tetrahydrobenzo[f]isoquinolines

A facile and short synthesis of 2-oxo-4-sec-amino-2,3,5,6-tetrahydrobenzo[f]isoquinoline-1-carbonitriles has been delineated through base catalyzed ring transformation of 5,6-dihydro-2-oxo-4-sec-amino-2H-benzo[h]chromene-3-carbonitrile by cyanoacetamide in excellent yields.     

FTIR and WAXS analysis of periodate oxycellulose: Evidence for a cluster mechanism of oxidation

Cellulose paper (Whatman no.1, chromatographic grade) was oxidised with 0.1 M sodium metaperiodate at different oxidation levels (0–11 days at room temperature), and analysed with FTIR before and after chemical treatments (reduction, further oxidation, alkaline hydrolysis). The deconvolution of infrared data allowed us to verify that periodate oxidises cellulose in isolated domains, leading to the decrease of crystallinity, in agreement with the results of wide angle X-ray scattering (WAXS). In particular, the alkaline hydrolysis (β-alkoxy fragmentation) followed by mild acid treatment removed the oxidised groups and recovered most of the crystallinity of cellulose, as determined by the FTIR crystallinity index.     

LiNi0.8Co0.2O2 / MWNTs复合物超级电容器电极材料的研究

Multiwalled carbon nanotubes (MWNTs) were used as the conductive additive in the electrode materials. The electrochemical properties of supercapacitors based on LiNi_0.8Co_0.2O₂ / MWNTs composite and LiNi_0.8Co_0.2O₂/acetylene black composite and MWNTs in 1.0 mol·L^-1 LiClO₄ / EC+DEC [V(EC)∶V(DEC)=1∶1] electrolyte were investigated by means of constant charge/discharge current tests, respectively. The experimental results show that the LiNi_0.8Co_0.2O₂ / MWNTs composite has better performance than that of others, and the maximum specific capacitance of the supercapacitor can reach 271.6 F·g^-1, while the energy density is up to 339.5 Wh·kg^-1. Furthermore, it is remarkable that the performance of MWNTs is better than that of acetylene black as the conductive additive.     

离子液体介质中FeCl3•6H2O催化下芳香醛与5,5-二甲基-1,3-环己二酮的缩合反应

考察了在离子液体1-正丁基-3-甲基咪唑四氟硼酸盐([bmim][BF₄])介质中, 芳香醛与5,5-二甲基-1,3-环己二酮的缩合反应. 实验结果表明, 在催化量的FeCl₃•6H₂O存在下, 该反应可高产率地生成氧杂蒽二酮类化合物3; 而在TMSCl/FeCl₃•6H₂O复合催化体系的催化下, 则得到氧杂蒽二酮类化合物的开环衍生物4, 反应具有非常好的选择性. 该论文提供的方法操作简单、产率高、选择性好而且对环境友好. 在反应结束后, 所用催化剂及离子液体都很容易回收, 并能有效重复使用.