RABA (Reductive Alkylation By Acetone): A novel stable isotope labeling approach for quantitative proteomics

Quantitative proteomics is challenging and various stable isotope based approaches have been developed to meet the challenge. Hereby we describe a simple, efficient, reliable, and inexpensive method named reductive alkylation by acetone (RABA) to introduce stable isotopes to peptides for quantitative analysis. The RABA method leads to alkylation of N-terminal and lysine amino groups with isopropyl moiety. Using unlabeled (d₀) and deuterium labeled (d₆) acetone, a 6 Da mass split is introduced to each isopropyl modification between the light and heavy isotope labeled peptides, which is ideally suited for quantitative analysis. The reaction specificity, stoichiometry, labeling efficiency, and linear range of the RABA method have been thoroughly evaluated in this study using standard peptides, tryptic digest of proteins, as well as human cell lysate. Reliable quantitative results have been consistently obtained in all experiments. We also applied the RABA method to quantitative analysis of proteins in spinal cords of transgenic mouse models of amyotrophic lateral sclerosis. Highly homologous proteins (transgenic human SOD1 and endogenous mouse SOD1) were distinguished and quantified using the method developed in this study. In addition, the quantitative results using the RABA approach were independently validated by Western blot.     

Novel ring-cleaving reaction of 4-nitro-1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophane with nucleophiles

When 4-nitro-AF4 is treated with nucleophiles such as alkoxides and cyanide, a novel ring opening, cyclophane destroying reaction is observed whereby, via an S_NAr mechanism, the nucleophile attacks the bridgehead aryl carbon vicinal to the nitro group with subsequent aryl-CF₂ bond cleavage.     

双圈连通图的L(2,1)-labelling

给定图G,G的一个L(2,1)-labelling是指一个映射f:V(G)→{0,1,2,…},满足:当dG(u,v)=1时,f(u)-f(v)≥2;当dG(u,v)=2时,f(u)-f(v)≥1.如果G的一个L(2,1)-labelling的像集合中没有元素超过k,则称之为一个k-L(2,1)-labelling.G的L(2,1)-labelling数记作l(G),是指使得G存在k-L(2,1)-labelling的最小整数k.如果G的一个L(2,1)-labelling中的像元素是连续的,则称之为一个no-holeL(2,1)-labelling.本文证明了对每个双圈连通图G,l(G)=△ 1或△ 2.这个工作推广了[1]中的一个结果.此外,我们还给出了双圈连通图的no-hole L(2,1)-labelling的存在性.     

Path Decomposition of Graphs with Given Path Length

A path decomposition of a graph G is a list of paths such that each edge appears in exactly onepath in the list.G is said to admit a {P_l}-decomposition if G can be decomposed into some copies of P_l,whereP_l is a path of length l-1.Similarly,G is said to admit a {P_l,P_k}=decomposition if G can be decomposed intosome copies of P_l or P_k.An k-cycle,denoted by C_k,is a cycle with k vertices.An odd tree is a tree of which allvertices have odd degree.In this paper,it is shown that a connected graph G admits a {P_3,P_4}-decompositionif and only if G is neither a 3-cycle nor an odd tree.This result includes the related result of Yan,Xu andMutu.Moreover,two polynomial algorithms are given to find {P_3}-decomposition and {P_3,P_4}-decompositionof graphs,respectively.Hence,{P_3}-decomposition problem and {P_3,P_4}-decomposition problem of graphs aresolved completely.     

A theoretical kinetics study on low-temperature oxidation of n-C4H9 radicals

The low-temperature oxidation mechanism of n?butyl radicals (n-C₄H₉) has been investigated by high level quantum chemical calculations coupled with the Rice–Ramsperger–Kassel–Marcus/Master Equation (RRKM/ME) theory. The potential energy surfaces (PES) were explored at the QCISD(T)/CBS//B3LYP/6-311++G(d,p) level. The temperature- and pressure-dependent rate constants were computed and fitted in modified Arrhenius parameters. The major reaction channels were discussed to more deeply understand the competing relationships between chain branching, chain propagation and termination reactions. The results show that the 1,5 H-shift reaction is more competitive than the 1,6 H-shift and 1,4 H-shift for isomerization reactions of n?butyl peroxy radicals, and the concerted HO₂ elimination channel to form butene becomes more important at high temperatures. Furthermore, based on our calculations, a revised kinetic model was developed to describe n-butane oxidation. Good consistency between model predictions and experimental data was shown. This study enhances our understanding of the combustion mechanism of n-butane and can be used as a reliable reference for mechanistic understanding of larger alkanes.     

Enhanced electron transfer ability <Emphasis Type="Italic">via</Emphasis> coordination in block copolymer/porphyrin/fullerene micelle

Inspired by structures of antenna-reaction centers in photosynthesis, the complex micelle was prepared from zinc tetra-phenyl porphyrin (ZnTPP), fullerene derivative (PyC₆₀) and poly(ethylene glycol)-block-poly(ε-caprolactone) (PEG-b-PCL). The core-shell structure made the hydrophobic donor-acceptor system work in aqueous. In micellar core, coordination interaction occurred between ZnTPP and PyC₆₀ molecules which ensured the enhanced energy migration from the donor to the acceptor. The enhanced interaction between porphyrin and fullerene was confirmed by absorption, steady-state fluorescence and transient fluorescence. The generation of singlet oxygen and superoxide radical was detected by iodide method and reduction of nitro blue tetrazolium, respectively, which confirmed that electron transfer reaction in the complex micellar core occurred. Moreover, the complex micelle exhibited effective electron transfer performance in photodebromination of 2,3-dibromo-3-phenylpropionic acid. The complex micellar structure endowed the donor-acceptor system with improved stability under irradiation. This strategy could be helpful for designing new electron transfer platform and artificial photosynthetic system.     

大雷诺数线性剪切流绕圆柱的分离流动

本文采用离散涡方法计算了大雷诺数下线性剪切流绕圆柱的分离流动,计算结果给出阻力系数、横向力系数、边界层分离点、斯特罗哈数及尾流中旋涡的分布图案,计算数据与已有的实验数据相吻合。     

Ionic Liquid‐Hemoglobin‐Carbon Paste Composite Bioelectrode and Its Electrocatalytic Activity

A new carbon ionic liquid paste bioelectrode was fabricated by mixing hemoglobin (Hb) with graphite powder, ionic liquid 1‐ethyl‐3‐methylimidazolium tetrafluoroborate (EMIMBF₄) and liquid paraffin homogeneously. Nafion film was cast on the electrode surface to improve the stability of bioelectrode. Direct electrochemistry of Hb in the bioelectrode was carefully investigated. Cyclic voltammetric results indicated that a pair of well‐defined and quasi‐reversible electrochemical responses appeared in pH 7.0 phosphate buffer solution (PBS), indicating that direct electron transfer of Hb was realized in the modified electrode. The formal potential (E^0′) was calculated as ?0.316 V (vs. SCE), which was the typical characteristic of the electrochemical reaction of heme Fe(III)/Fe(II) redox couple. Based on the cyclic voltammetric results the electrochemical parameters of the electrode reaction were calculated. This bioelectrode showed high electrocatalytic activity towards the reduction of trichloroacetic acid (TCA) with good stability and reproducibility.