η6-苊烯三羰基铬配合物的合成、结构及光谱性质研究

采用苊烯配体与三胺基三羰基铬在四氢呋喃中回流反应,合成了η6-苊烯三羰基铬配合物.通过元素分析、IR、1HNMR、13CNMR、MS和X射线单晶衍射对其结构进行了表征,比较了标题配合物与其自由配体的光物理行为.晶体结构分析表明,标题配合物属单斜晶系,空间群P21/c,Z=4,a=0.8719(7)nm,b=1.2436(10)nm,c=1.1504(9)nm,β=111.835(13)°,Cr(CO)3基团可与苊烯配体中的2个苯环中的任意一个配位,形成2个异构体(R,S),并以1:1的比例在其晶胞单元中反向面对面堆积,这种异构体共存于晶体中归属于Cr(CO)3基团在配体芳环之间的配位移动重排(IRHRs).     

Separation and determination of biphenyl nitrile compounds by microemulsion electrokinetic chromatography with mixed surfactants

A mixture of six biphenyl nitrile compounds and three related substances with high hydrophobicity and similar structures was successfully separated by microemulsion electrokinetic chromatography (MEEKC) within 30 min. The microemulsion system contained 100 mM sodium dodecyl sulfate (SDS), 80 mM sodium cholate (SC), 0.81% v/v heptane, 7.5% v/v n-butanol, 10% v/v acetonitrile, and 10 mM borate. The addition of SC, organic modifiers, sample preparation, and temperature all showed remarkable effects on the separation. The capacity factor (k) was calculated by using dodecyl benzene as the marker for microemulsion, and the calculated partition coefficient log P(o/w) of the solutes was in the range of 3.35-7.38. The log k values matched well with the log P(o/w) with a correlation coefficient of 0.96. In addition, the linear correlation coefficients of each compound between peak area and concentration were from 0.996 to 0.998 with the repeatability RSD value < 1.2% for migration time and < 4.8% for peak area, and the highest theoretic plate number was > 586000. MEEKC was compared with micellar electrokinetic chromatography (MEKC) indicating that the former method is more suitable for this separation and can be used for the quality control of biphenyl nitrile compounds in the synthesis of liquid crystals.     

Differentiation and quantitation of isomeric dipeptides by low-energy dissociation of copper(II)-bound complexes

Application of the kinetic method based on the dissociation of transition metal centered cluster ions is extended from chiral analysis (Tao, W. A.; Zhang, D.; Nikolaev, E. N.; Cooks, R. G. J. Am. Chem. Soc. 2000, 122, 10598) to quantitative analysis of isomeric mixtures, including those with Leu/Ile substitutions. Copper(II)-bound complexes of pairs of peptide isomers are generated by electrospray ionization mass spectrometry and the trimeric complex [CuII(ref)2(A) - H]+ (analyte A, a mixture of isomeric peptides; reference compound ref, usually a peptide) is caused to undergo collisional dissociation. Competitive loss of the neutral reference compound or the neutral analyte yields two ionic products and the ratio of rates of the two competitive dissociations, viz. the product ion branching ratio R is shown to depend strongly on the regiochemistry of the analyte in the precursor [CuII(A)(ref)2 - H]+ complex ion. Calibration curves are constructed by relating the branching ratio measured by the kinetic method, to the isomeric composition of the mixture to allow rapid quantitative isomer analysis.     

微乳液体系中过硫酸钾氧化碘离子的动力学研究

分别在不同盐浓度的自由水和不同液滴尺寸的微乳液中测量了过硫酸钾氧化碘 离子的化学反应速率常数，获得微乳液不核中水的活度，探讨了水的活度及体系中 离子强度与反应速率的关系，发现当表面活性剂与水的摩尔比R≤20时，水的活度 随微反应器尺寸减小而快速下降。     

分散聚合水基聚苯胺乳胶微球制备与表征

水溶性空间稳定剂聚乙烯吡咯烷酮（PVP）存在时，采用分散聚合制备水溶性单分散的聚苯胺(PAn)乳胶粒子，采用透射电子显微镜（TEM）观察粒子形态及尺寸；利用紫外-可见吸收光谱对胶体分散体系进行表征.实验结果表明，当PAn含量较少（w< 16.78％）时， PAn-PVP复合乳胶粒子呈米粒状；当PAn含量较大（w >23.22％）时， PAn-PVP复合乳胶粒子呈球形.     

Triboelectric pulsed direct current for self-powered sterilization of cellulose fiber

A variety of liquid energy exists in papermaking engineering and has not yet been developed and utilized. In addition, for the papermaking industry, the presence of slime can seriously affect the quality of the finished paper and can lead to paper breaking. The current slime control strategies cannot completely solve the problem and also have some low toxicity. In this study, a method of self-powered sterilization of cellulose fibers by using triboelectric pulsed direct current is reported. A liquid–solid triboelectric nanogenerator (L–S TENG) was used to convert the liquid energy of nanocellulose suspension into electrical energy and convert this electrical energy into pulsed direct current for self-powered sterilization of cellulose fiber. A hydrophobic coating material is used as solid triboelectric material and electrode for sterilization. Driven by L–S TENG, the electrodes exhibited an excellent sterilization rate against four microorganisms including Escherichia coli, Aspergillus niger, Candida albicans, and Klebsiella pneumoniae, which from slime in the papermaking industry. This study could provide a basic research theory for liquid energy harvesting in the papermaking industry, and also provide a new strategy for pulp sterilization.

Graphical abstract

     

Chemoproteomic profiling of kinases in live cells using electrophilic sulfonyl triazole probes

Sulfonyl-triazoles are a new class of electrophiles that mediate covalent reaction with tyrosine residues on proteins through sulfur-triazole exchange (SuTEx) chemistry. Recent studies demonstrate the broad utility and tunability of SuTEx chemistry for chemical proteomics and protein ligand discovery. Here, we present a strategy for mapping protein interaction networks of structurally complex binding elements using functionalized SuTEx probes. We show that the triazole leaving group (LG) can serve as a releasable linker for embedding hydrophobic fragments to direct molecular recognition while permitting efficient proteome-wide identification of binding sites in live cells. We synthesized a series of SuTEx probes functionalized with a lipid kinase fragment binder for discovery of ligandable tyrosines residing in catalytic and regulatory domains of protein and metabolic kinases in live cells. We performed competition studies with kinase inhibitors and substrates to demonstrate that probe binding is occurring in an activity-dependent manner. Our functional studies led to discovery of probe-modified sites within the C2 domain that were important for downregulation of protein kinase C-alpha in response to phorbol ester activation. Our proof of concept studies highlight the triazole LG of SuTEx probes as a traceless linker for locating protein binding sites targeted by complex recognition elements in live cells.

Sulfonyl-triazole probes modified with a kinase recognition element are developed for live cell activity-based profiling to identify tyrosine sites located in catalytic and regulatory domains that are important for kinase function.     

Molecular Dynamics Simulation of the Self-assembled Monolayers of 1-Adamantanethiolate and Its Derivatives on Au（111） Surfaces

The self-assembled monolayers （SAMs） of 1-adamantanethiolate and its derivatives on Au（111） surface were investigated. Density functional theory （DFT） calculation indicates that the most stable configuration for absorption is at the face centered cubic （fcc）-bridge site. Canonical ensemble molecular dynamics （MD） simulations were carried out to study the structures and energies of the SAMs. The ordered structures of the SAMs were analyzed by means of radial distribution function and the relative stability of the SAMs was compared. It was concluded by the comparison of various contributions to the SAM formation energy that the formation of the SAMs was determined by the intermolecular nonbonding interaction and the chemical bonding interaction of sulfur and gold.     

呋喃西林水溶液在光和热作用下的稳定性

The influence of both light and heat on the stability of nitrofurazone aqueous solution was studied. Results show that in either heating experiments or the exposure to light at high temperatures, the degradation rate obeyed zero-order kinetics. The total rate constant ktotal caused by both light and heat can be divided into two parts: ktotal =kdark klight, where kdark and klight are the degradation rate constants caused by heat and light, respectively. The klight can be expressed as klight=Alight*exp(-Ea,light/RT)*E, where E is the illuminance of light, and Alight and Ea,light both are experimental constants. The values of these kinetic parameters were determined based on the experiments in the dark and upon exposure to three different light sources. Results show that the values of Alight and Ea, light varied with the light source. To save time, labor, and drugs, exponential heating experiments were employed and compared with the isothermal experiments. Results indicated that kinetic parameters obtained by exponential heating experiments are comparable to those obtained by isothermal experiments either in the dark or upon exposure to light.     

Adaptation of Cu/ZnO/Al_2O_3 to Temperature Change in Methanol Synthesis from CO_2 Hydrogenation

The induction behavior in CO2 hydrogenation was studied by varying the reaction temperature to investigate the adaptation of the Cu/ZnO/Al2O3 catalyst to the temperature change. The results indicated that a used catalyst had a tendency to keep the last running state in new reaction conditions for MeOH formation, and that this tendency was related to the difference in Cu/Cun+ ratio caused by CO2 and CO produced at different reaction temperatures. However, the reverse water-gas shift reaction (RWGS) induced at four temperatures was completely different from that of methanol synthesis. It implied that the two so-called competitive reactions in CO2+H2, RWGS and methanol synthesis, have different active centers.