Mixtures of tertiary amine functionalized azo-containing mesogens with acid-functionalized polymers

A tertiary amine functionalized 4-nitro-4′-alkoxy azobenzene mesogen with a 10 or 12 carbon spacer (azo-nN) was synthesized and complexed in equimolar proportions with poly(acrylic acid) (PA-H) and poly(sulfonic acid) (PSS-H), and investigated by thermogravimetric analysis, differential scanning calorimetry, polarizing optical microscopy, Fourier transform infrared spectroscopy and X-ray diffraction. The neat azo-nN is characterized by a partial bilayer S_A mesophase at higher temperatures, and a highly ordered phase, in which the molecules are stacked orthogonally in bilayers, at lower temperatures. As supported by infrared analysis, for the azo-nN/PA-H mixture, the complexation is partial while for the same azo-nN/PSS-H mixture, complete proton transfer occurs. When the azo-nN is blended with the PA-H, regarded as a weak acid, a biphasic system is generated and the thermotropic behavior of neat mesogen is not significantly affected. In contrast, by mixing the same mesogen with a PSS-H (regarded as a strong acid), the thermotropic behavior is significantly influenced: the complexation generated a partial or interdigitated smectic A or tilted smectic C lamellar phase.     

Amino acid profiles and liposomes: Their role as chemosensory information carriers in the marine environment

Yellowfin tuna enhance their hunting success in the vast pelagic environment by using their sense of smell to detect intact (uninjured) prey that are beyond visual range. However, the olfactory cues that tuna use would normally face huge and rapid dilution in the open ocean. We demonstrate that these prey odors are complexed within biologically derived lipid structures that probably delay the dilution of the amino acids to subthreshold concentrations and provide persistent arousal and search cues for the tuna. This may be the first demonstration of an extracorporeal biological function for liposomes. Tuna may also form chemical search images to maximize feeding efficiency. We demonstrate that the amino acid profiles of various prey species are consistent over time and between schools, which makes the formation of search images feasible.     

Discovery–Versus Hypothesis–Driven Detection of Protein–Protein Interactions and Complexes

Protein complexes are the main functional modules in the cell that coordinate and perform the vast majority of molecular functions. The main approaches to identify and quantify the interactome to date are based on mass spectrometry (MS). Here I summarize the benefits and limitations of different MS-based interactome screens, with a focus on untargeted interactome acquisition, such as co-fractionation MS. Specific emphasis is given to the discussion of discovery- versus hypothesis-driven data analysis concepts and their applicability to large, proteome-wide interactome screens. Hypothesis-driven analysis approaches, i.e., complex- or network-centric, are highlighted as promising strategies for comparative studies. While these approaches require prior information from public databases, also reviewed herein, the available wealth of interactomic data continuously increases, thereby providing more exhaustive information for future studies. Finally, guidance on the selection of interactome acquisition and analysis methods is provided to aid the reader in the design of protein-protein interaction studies.     

Preparation and Bioactivity of Iridium(III) Phenanthroline Complexes with Halide Ions and Pyridine Leaving Groups

A series of half-sandwich structural iridium(III) phenanthroline (Phen) complexes with halide ions (Cl⁻, Br⁻, I⁻) and pyridine leaving groups ([(η⁵-Cp^X)Ir(Phen)Z](PF₆)_n, Cp^x: electron-rich cyclopentadienyl group, Z: leaving group) have been prepared. Target complexes, especially the Cp^xbiph (biphenyl-substituted cyclopentadienyl)-based one, showed favourable anticancer activity against human lung cancer (A549) cells; the best one ( Ir8 ) was almost five times that of cisplatin under the same conditions. Compared with complexes involving halide ion leaving groups, the pyridine-based one did not display hydrolysis but effectively caused lysosomal damage, leading to accumulation in the cytosol, inducing an increase in the level of intracellular reactive oxygen species and apoptosis; this indicated an anticancer mechanism of oxidation. Additionally, these complexes could bind to serum albumin through a static quenching mechanism. The data highlight the potential value of half-sandwich iridium(III) phenanthroline complexes as anticancer drugs.     

DMFC阳极催化剂用GRQD-NiCo2O4复合物的制备与电催化活性分析

采用水热法制备GRQD-NiCo₂O₄复合物,利用XRD、SEM及TEM分析其微结构,并探讨其作为DMFC阳极催化剂使用时的电化学性能。微结构分析表明所得GRQD-NiCo₂O₄复合物皆为具NiCo₂O₄单一相的尖晶石结构,且GRQD质量浓度高于0.25 g/mL后表面形貌将转变GRQD与NiCo₂O₄相互结合的状态。电化学分析表明添加GRQD可有效增强NiCo₂O₄的导电性并提升其电化学稳定性,其中GRQD质量浓度为0.25 g/mL时所得样品经500次循环测试后电流密度约为77.5 A/g,与循环5次后相比其电流密度剩余量最大（约为69.7%）,该样品作为DMFC阳极催化剂使用时性价比最佳。     

取代水杨醛Schiff碱金属配合物催化氧化脱硫性能

以水杨醛类Schiff碱为配体,与Co(NO_3)_2、Cu(NO_3)_2反应合成6种Salen(M)型配合物Ⅰ～Ⅵ。以1-己硫醇、二丁基硫醚和2-甲基噻吩为模型化合物配制模拟油体系,考察了配合物Ⅰ～Ⅵ的催化氧化脱硫性能,并分析了配合物结构与氧化脱硫性能的关系。结果表明,6种配合物在75 min时的总脱硫效果为Ⅵ>Ⅴ>Ⅳ>Ⅰ>Ⅲ>Ⅱ,Ⅵ的总脱硫率为31.9%。对1-己硫醇及二丁基硫醚脱除效果最佳的是Ⅴ,脱除率分别为74.2%和65.1%;对2-甲基噻吩脱除效果最好的是Ⅰ,脱除率为26.8%。构效关系研究表明,中心金属离子与O_2的配位能力越强,配体的共轭体系越大、电子云密度越高,配合物的脱硫性能越好;通过IR和离子色谱对单一硫化物模拟油体系氧化前后的产物进行分析发现,硫化物氧化后皆生成相应的砜类或亚砜类,且1-己硫醇和二丁基硫醚被进一步氧化生成SO_3~(2–)或SO_4~(2–)。     

Simulation of Fe-Al compounds developed during single superphosphate manufacture

In order to analyse iron phosphate complexes and gel-like phases encountered in the single superphosphate process, experiments were performed with a free-Al, Fe apatite crystal of Durango from Mexico phosphate rock and sulfuric acid. Reaction products were studied by X-ray diffraction and surface analysis methods namely X-ray photoelectron spectroscopy and scanning electron microscopy. Results show that in a free Al, Fe-system, part of the Ca(H₂PO₄ )₂.H₂O (MCPM) forms before precipitation of any CaSO₄(CS) and gel-like phase such H₂SO₄.yH₃PO₄.xH₂O is formed. When iron is added, the precipitation rate of (CS) and (MCPM) increases and Fe₃(H₃O)H₈(PO₄)₆.6H₂O is formed. When Fe and Al are added, a gel-like phase is quickly formed with a molar ratio that changes with time and develops into crystalline compounds. The composition of this gel may be represented as a mixture of two phases: H₂SO₄.yH₃PO₄.xH₂O and a gel containing Al-Fe-Si.     

聚甲基丙烯酰氧乙基二甲基丁烷基溴化铵共振光散射法测定核酸

通过光谱法研究聚甲基丙烯酰氧乙基二甲基丁烷基溴化铵(PMDB)和核酸的作用。结果表明通过共振光散射法用PMDB检测微量的DNA可靠、准确和简单。     

S-苄基-L-半胱氨酸的合成

由溴化苄和L-半胱氨酸直接合成S-苄基-L-半胱氨酸,通过正交试验及统计分析,检验了各影响因子的显著性,确定了最佳工艺条件为：反应时间2.5h,反应温度45℃,原料配比n（溴化苄）：n（L-半胱氨酸）=1：1.在此条件下反应,摩尔产率可达到95%.     

Electrochemical investigations of copper behaviour in different cupric complex solutions: Voltammetric study

The electrochemical behaviour of copper has been investigated in different cupric complex solutions by cyclic voltammetry. In pyridinic and picolinic solutions the reduction of cupric complex occurred in two stages leading to Cu(I) and Cu(0), respectively. The electrodeposited copper is oxidized in two steps leading to Cu(I) and Cu(II) as in ammoniacal cupric complex solutions. In glycine, alanine, sulfamic acid and ethylenediamine solutions, the cuprous complex is an intermediate in the cupric complex reduction but it is not detected during the oxidation of the electrodeposited copper in these solutions. In EDTA and triethanolamine solutions, the cuprous complex is not observed. The rate of copper etching was determined in pyridinic and ammoniacal cupric solutions and was shown to be faster in ammoniacal cupric solutions than in the pyridinic solutions.