New metalloligands [M(SC[O]Ph)(4)](-): synthesis and characterization of polymeric [A(MeCN)(x)[M(SC[O]Ph)(4)]] compounds (A = Li,Na and K; M = Ga and In; x = 0-2)

Exploiting the ability of the [M(SC[O]Ph)(4)](-) anion to behave like an anionic metalloligand, we have synthesized [Li[Ga(SC[O]Ph)(4)]] (1), [Li[In(SC[O]Ph)(4)]] (2), [Na[Ga(SC[O]Ph)(4)]] (3), [Na(MeCN)[In(SC[O]Ph)(4)]] (4), [K[Ga(SC[O]Ph)(4)]] (5), and [K(MeCN)(2)[In(SC[O]Ph)(4)]] (6) by reacting MX(3) and PhC[O]S(-)A(+) (M = Ga(III) and In(III); X = Cl(-) and NO(3)(-); and A = Li(I), Na(I), and K(I)) in the molar ratio 1:4. The structures of 2, 4, and 6 determined by X-ray crystallography indicate that they have a one-dimensional coordination polymeric structure, and structural variations may be attributed to the change in the alkali metal ion from Li(I) to Na(I) to K(I). Crystal data for 2 x 0.5MeCN x 0.25H(2)O: monoclinic space group C2/c, a = 24.5766(8) A, b = 13.2758(5) A, c = 19.9983(8) A, beta = 108.426(1) degrees, Z = 8, and V = 6190.4(4) A(3). Crystal data for 4: monoclinic space group P2(1)/c, a = 10.5774(7) A, b = 21.9723(15) A, c = 14.4196(10) A, beta = 110.121(1) degrees, Z = 4, and V = 3146.7(4) A(3). Crystal data for 6: monoclinic space group P2(1)/c, a = 12.307(3) A, b = 13.672(3) A, c = 20.575(4) A, beta = 92.356(4) degrees, Z = 4, and V = 3458.8(12) A(3). The thermal decomposition of these compounds indicated the formation of the corresponding AMS(2) materials.     

蛋白质组学和代谢组学在微生物代谢工程中的应用

构建微生物细胞工厂是化学品、生物能源以及药物分子可持续生产的可行性策略。然而，微生物的代谢复杂、调控严谨，制约着目标产物高效合成。蛋白质组学和代谢组学可以从系统生物学角度分析酶和代谢物组分，从而理解复杂的生物系统，为微生物代谢工程改造提供重要线索。该文介绍了蛋白质组学和代谢组学在微生物代谢工程中的应用，包括基因组尺度代谢模型构建、菌株生物合成优化、指导菌株耐受性改造、限速步骤预测、植物次级代谢途径挖掘，从而为微生物合成天然产物提供新的基因或途径。在此基础上，该文还展望了生物大数据未来的发展方向。     

“受阻路易斯酸碱对”催化的2,3-二取代2H-1,4-苯并噁嗪氢化反应机理研究

在受阻路易斯酸碱对（FLPs）催化的2，3-二取代2H-1，4-苯并噁嗪氢化反应中，3号位取代基不同会导致反应效率极大改变，因此我们选取反应活性具有较大差别的三种底物作为模型化合物对其反应机理进行了研究，建立了氢化反应势能面.发现当B（C₆F₅）₃与2，3-二苯基2H-1，4-苯并噁嗪或2-甲基-3-苯基2H-1，4-苯并噁嗪混合后，会形成FLPs与路易斯酸碱加合物的混合物.而将B（C₆F₅）₃与2，3-二甲基2H-1，4-苯并噁嗪混合后主要形成没有催化活性的路易斯酸碱加合物，因其能量低于FLPs，在催化体系中不容易转化为FLPs，这导致三种模型化合物在FLPs催化的氢化反应中效率不同.进一步的取代基电子效应及位阻效应计算表明：B（C₆F₅）₃与2-甲基-3-取代2H-1，4-苯并噁嗪混合后形成的路易斯酸碱加合物和FLPs化合物之间稳定性差别源于3位取代基空间位阻不同.     

微过氧化物酶-8与Eu3+相互作用的机理

用紫外-可见(UV-Vis)吸收光谱和电化学方法研究Eu3+与微过氧化物酶-8(MP-8)相互作用的机理,发现Eu3+优先与MP-8中血红素基团的2个丙酸基的羧基氧发生强的配位作用,导致MP-8分子中血红素基团的非平面性、暴露程度和电化学可逆性的增加.过剩的Eu3+与MP-8分子中肽链上的含氧基团发生弱的相互作用,对血红素基团结构的影响较小.     

平行光栅对在刻线不平行时的色散研究

 利用三维空间光线追迹法，分析了啁啾脉冲放大系统中的压缩光栅对，在刻线不平行而光栅面平行时光的衍射特性。导出了此时光通过光栅对的群延时，数值计算了系统2阶和3阶色散量，以及这些色散量在光栅对严格平行时的相对误差。得出了中心波长光的接收位置相对于光栅对严格平行时的偏移量，并且分析了它与入射角的变化关系。     

水平极化电磁脉冲模拟器空间场的数值模拟

 采用时域有限差分方法，对水平极化电磁脉冲模拟器所产生的电磁场进行数值模拟，在时域中计算了电磁场的时间 空间分布。讨论了电磁脉冲模拟器产生的电磁脉冲波形和场的空间变化、均匀性等重要因素。结果表明，模拟器产生的电磁脉冲前沿为10ns，接近脉冲电压前沿，波形与脉冲电压波形（双指数波）相差较大；峰值场强在对称轴上并非与距离成反比，而是随距离增大而迅速减弱；该模拟器的双锥 笼形天线能在大范围内（大于等于50m,水平方向）产生均匀分布、高峰值场强、快前沿的电磁脉冲。     

荧光标记-高效液相色谱测定多肽（PC2～PC6）的研究

基于多肽(Polypeptides PC2~PC6)中富有巯基(-SH)官能团,其与单溴二胺(Monobromobimanes mBBr)能够发生缩合反应,生成具有荧光信号的多肽衍生物;通过优化色谱分离条件,建立了高效液相色谱(荧光检测器)测定多肽的方法;试验中利用质谱鉴定了PCs与mBBr缩合反应的比例关系。结果显示,通过比较PCs标记前后化合物的质谱图,PCs与mBBr反应比例关系为1∶1,稳定性好;高效液相色谱-荧光法测定多肽化合物,五种化合物间分离度较好,出峰时间集中在16.6~22.0min间;PC2,PC3,PC4,PC5和PC6线性相关性系数>0.999 1,方法定量限分别为0.3,0.05,0.3,0.5和0.8 mg·L-1,回收率范围为83.0%~102.0%;重线性较好,RSD<2.0%,该方法实现了多肽类化合物快速、准确定量分析。     

Hexacyanoferrate‐based ionic liquids as Fenton‐like catalysts for deep oxidative desulfurization of fuels

Two hexacyanoferrate‐based ionic liquids, [C₄Py]₃Fe(CN)₆ and [C₁₆Py]₃Fe(CN)₆, were synthesized and characterized using Fourier transform infrared and mass spectroscopies and CHN analysis. They were employed as Fenton‐like catalysts in extraction and catalytic oxidative desulfurization of model oil with dibenzothiophene (DBT), benzothiophene (BT), 4,6‐dimethyldibenzothiophene (4,6‐DMDBT), 4‐methyldibenzothiophene (4‐MDBT) and 3‐methylbenzothiophene (3‐MBT) as substrates. Various polar solvents, such as ionic liquids, water and organic solvents, were applied to choose a suitable extractant. The results showed the removal of DBT reached 97.1% with [C₄Py]₃Fe(CN)₆ as a catalyst and 1‐n‐octyl‐3‐methylimidazolium hexafluorophosphate ([C₈mim]PF₆) as an extractant under optimal conditions. The activity of sulfur removal followed the order DBT > 3‐MBT > BT > 4‐MDBT >4,6‐DMDBT. The effect of water content on sulfur removal was investigated by adding various concentrations of H₂O₂. It was found that excess water had a positive effect on sulfur removal but the catalysts were less sensitive than [FeCl₄^?]‐based catalysts to water. The mechanism was studied using electron spin‐resonance spectroscopy and gas chromatography–mass spectrometry. O₂^?? may be the active oxygen species in the catalytic oxidative desulfurization process and the oxidation products of various sulfur compounds were the corresponding sulfoxides and sulfones. Copyright © 2016 John Wiley & Sons, Ltd.     

One-step preparation of branched PEG functionalized AIE-active luminescent polymeric nanoprobes

The synthesis of amphiphilic aggregation-induced emission(AIE) dyes based organic nanoparticles has recently attracted increasing attention in the biomedical fields. These AIE dyes based nanoparticles could effectively overcome the aggregation caused quenching effect of conventional organic dyes, making them promising candidates for fabrication of ultrabright organic luminescent nanomaterials. In this work, AIE-active luminescent polymeric nanoparticles(4-NH_2-PEG-TPE-E LPNs) were facilely fabricated through Michael addition reaction between tetraphenylethene acrylate(TPE-E) and 4-arm-poly(ethylene glycol)-amine(4-NH_2-PEG) in rather mild ambient. The 4-NH_2-PEG can not only endow these AIE-active LPNs good water dispersibility, but also provide functional groups for further conjugation reaction. The size, morphology and luminescent properties of 4-NH_2-PEG-TPE-E LPNs were characterized by a series of techniques in detail. Results suggested that these AIE-active LPNs showed spherical morphology with diameter about 100–200 nm. The obtained 4-NH_2-PEG-TPE-E LPNs display high water dispersibility and strong fluorescence intensity because of their self assembly and AIE properties of TPE-E.Biological evaluation results demonstrated that 4-NH_2-PEG-TPE-E LPNs showed negative toxicity toward cancer cells and good fluorescent imaging performance. All of these features make 4-NH_2-PEG-TPE-E LPNs promising candidates for biological imaging and therapeutic applications.     

Synthesis,structure and catalytic polymerization activity of half‐sandwich cyclometallated iridium complexes

A series of mononuclear half‐sandwich cyclometallated iridium complexes with Schiff base ligands were synthesized in good yields. Five air‐stable C,N‐chelate mode complexes were obtained smoothly through metal‐mediated C─H bond activation. Treatments of dimeric metal complexes [Cp*IrCl₂]₂ with ligands L1–L5 afforded the corresponding C,N‐chelate mononuclear half‐sandwich iridium(III) complexes 1 – 5 . These iridium complexes exhibit high catalytic activity for norbornene polymerization. Both steric and electronic effects of the substituted groups have influences on the behaviors of the polymerization process. All complexes were characterized using infrared and NMR spectroscopies and elemental analysis. Molecular structures of complexes 1 , 2 and 5 were further confirmed using single‐crystal X‐ray analysis.