Rhodium‐Catalyzed Oxidative Benzannulation of N‐Pivaloylanilines with Internal Alkynes through Dual C−H Bond Activation: Synthesis of Highly Substituted Naphthalenes

An efficient method was developed for the synthesis of highly substituted naphthalenes through rhodium‐catalyzed oxidative benzannulation of N‐pivaloylanilines with internal alkynes. The benzannulation reaction proceeded smoothly through dual C?H bond activation to produce the corresponding highly substituted naphthalene products in satisfactory to good yields.     

Polyproline-rod approach to isolating protein targets of bioactive small molecules: isolation of a new target of indomethacin

Identification of protein targets of bioactive small molecules has been a technical hurdle of chemical genetics. Here we report a polyproline-rod approach to isolating protein targets of small molecules from cell lysates. The results indicate that insertion of a long, rigid polyproline helix between a small-molecule bait and a biotin tag boosts the capacity of affinity purification and thereby permits isolation of low-abundance or low-affinity proteins. In the course of the proof-of-concept experiments, we isolated glyoxalase 1 (GLO1) as a new target of indomethacin, a widely used antiinflammatory drug. Molecular biological experiments suggest that inhibition of GLO1 enzyme activity is related to the clinically recognized beneficial side effects of the indomethacin family of nonsteroidal antiinflammatory drugs.     

Application of fluorescence resonance energy transfer (FRET) to investigation of light-induced conformational changes of the phoborhodopsin/transducer complex

The photoreceptor phoborhodopsin (ppR; also called sensory rhodopsin II) forms a complex with its cognate the Halobacterial transducer II (pHtrII) in the membrane, through which changes in the environmental light conditions are transmitted to the cytoplasm in Natronomonas pharaonis to evoke negative phototaxis. We have applied a fluorescence resonance energy transfer (FRET)-based method for investigation of the light-induced conformational changes of the ppR/pHtrII complex. Several far-red dyes were examined as possible fluorescence donors or acceptors because of the absence of the spectral overlap of these dyes with all the photointermediates of ppR. The flash-induced changes of distances between the donor and an acceptor linked to cysteine residues which were genetically introduced at given positions in pHtrII(1-159) and ppR were determined from FRET efficiency changes. The dye-labeled complex was studied as solubilized in 0.1% n-dodecyl-beta-D-maltoside (DDM). The FRET-derived changes in distances from V78 and A79 in pHtrII to V185 in ppR were consistent with the crystal structure data (Moukhametzianov, R. et al. [2006] Nature, 440, 115-119). The distance from D102 in pHtrII linker region to V185 in ppR increased by 0.33 angstroms upon the flash excitation. These changes arose within 70 ms (the dead time of instrument) and decayed with a rate of 1.1 +/- 0.2 s. Thus, sub-angstrom-scale distance changes in the ppR/pHtrII complex were detected with this FRET-based method using far-red fluorescent dyes; this method should be a valuable tool to investigate conformation changes in the transducer, in particular its dynamics.     

Determination of vanillin and related flavor compounds in cocoa drink by capillary electrophoresis

In the first part of this study, the stability of five terpenes (alpha-pinene, limonene, camphor, citronellol, and carvacrol) under subcritical water conditions was investigated. The stability studies were carried out at four different temperatures (100, 150, 200, and 250 degrees C) with two different heating times (30 and 300 min). When water temperature was increased, the degradation of terpenes became more serious. Prolonged exposure time to each heating temperature also caused decreased terpene stability. The terpene recoveries were determined by conducting subcritical water extraction of sand spiked with terpenes. The recoveries are typically around 70 to 80% for extractions at 100 degrees C. Terpene recoveries were decreased with increasing water temperature due to poorer stability of terpenes. After the degradation and recovery studies, basil and oregano leaves were extracted using water at both 100 and 150 degrees C. The concentrations of each individual terpene in the water extract generally ranged from trace quantity to 65 microg terpene/g herb. However, the concentration of carvacrol in the oregano-water extract at 150 degrees C was found to be as high as 4270 microg carvacrol/g oregano.     

Study on multimers and their structures in molecular association mixture

Self-association system of(R)-1,3-butanediol in dilute carbon tetrachloride(CCl4)solution is studied as a model of molecular association mixture.Analysis methods including FSMWEFA(fixed-size moving window evolving factor analysis)combined with PCA(principal component analysis),SIMPLISMA (simple-to-use interactive self-modeling mixture analysis),and ITTFA(iterative target transformation factor analysis)are adopted to resolve infrared spectra of(R)-1,3-butanediol solution.Association number and equilibrium constant are computed.(R)-1,3-butanediol in dilute inert solution is determined as a monomer-trimer equilibrium system.Theoretical investigation of trimer structures is carried out with DFT(density functional theory),and structural factors are analyzed.     

A convergent approach to the formal total synthesis of hemibrevetoxin B

A convergent synthesis of the key synthetic intermediate of hemibrevetoxin B was achieved via the intramolecular allylation of an α-chloroacetoxy ether and subsequent ring-closing metathesis.     

Catalytic Alkynylation of Polyfluoroarenes by Amide Base Generated In Situ

We herein demonstrate that the amide base generated in situ from CsF and N(TMS)₃ catalyzes the deprotonative coupling reactions of terminal alkynes with polyfluoroarenes, wherein mono- and dialkynylations occur efficiently for penta- and hexafluorobenzenes, respectively. Tetraalkynylated products could also be synthesized from dialkynylated compounds.     

Palladium(II)-catalyzed carboxylation of benzene and other aromatic compounds with carbon monoxide under very mild conditions

Aromatic compounds such as benzene, toluene, chlorobenzene, anisole, and naphthalene were carboxylated by palladium(II) acetate catalyst with carbon monoxide in the presence of potassium peroxodisulfate in trifluoroacetic acid (TFA) at room temperature under atmospheric pressure. The aromatic carboxylic acids were formed in good yields; for example, the carboxylation of benzene with carbon monoxide proceeds quantitatively under the optimal conditions.     

Lewis acid mediated claisen-type rearrangement of aryl dienyl ethers

In the presence of BF₃·.OEt₂, aryl dienyl ethers were rearranged under mild conditions to afford dienyl phenols in good yields.     

基于毛细管电泳的环介导恒温扩增技术检测方法研究

以大肠杆菌(E.coli)为对象,采用环介导恒温扩增技术(LAMP)对其扩增,在实验室自制的毛细管电泳-诱导荧光平台上建立了LAMP产物的检测新方法。引物F3,B3,FIP,BIP扩增的E.coli LAMP产物大小为240 bp。优化的毛细管电泳条件为:毛细管有效长度/总长度(10 cm/15 cm),筛分介质溶液为0.5%羟乙基纤维素(1 300 K),电场强度(100 V/cm),进样条件(100 V/cm,1.0 s)。毛细管电泳时,DNA长度在100~500 bp范围内与其迁移时间呈线性关系,相关系数为0.996。在相同毛细管电泳条件下对E.coli LAMP产物进行分析,并利用这种线性关系在电泳图中对E.coli LAMP产物与假阳性产物做区分,结果表明,毛细管电泳技术不仅可在15 min内实现LAMP产物及附加产物的快速检测,而且可快速区分LAMP阳性及假阳性实验产物。采用建立的毛细管电泳快速检测LAMP产物的方法,对AB0174 E.coli基因实施了LAMP,结果表明该方法适合DNA LAMP产物的快速检测。