激光大气等离子体时间演化特性的光谱研究

采用延时光谱法和谱线演化法 ,对YAG脉冲激光器 1 0 6 μm光束击穿一个大气压的空气所产生的等离子体进行了时间分辨光谱研究。对激光大气等离子体连续光谱的短波带与长波带分别进行了时间分辨测量 ,结果表明两者的衰变速率均在等离子体激发约 0 5微秒以后明显变慢。分析认为这种衰变速率的变慢可能与空气中氧对自由电子的吸附与去吸附有关。对激光大气等离子体线状光谱所作的时间分辨测量则表明 ,大部分线状光谱的演化寿命大于其标称寿命 ,部分线状光谱还呈现“衰变—增涨—衰变”的复杂形式。分析认为线状光谱的这些演化特征可能与等离子体在衰变期间的各种复合过程和能量转移过程有关。     

Homonuclear decoupled 13C chemical shift anisotropy in 13C doubly labeled peptides by selective-pulse solid-state NMR

We describe a new experiment for measuring homonuclear-decoupled anisotropic chemical shift patterns in doubly 13C-labeled compounds under magic-angle spinning. The experiment combines a pair of selective and non-selective 180 degrees pulses to suppress the 13C-13C scalar and dipolar interactions. This is combined with the recently developed SUPER technique to recouple the chemical shift anisotropy. Demonstrations on 13Calpha and 13CO-labeled amino acids and peptides show that accurate chemical shift powder patterns can be obtained. This permits the use of chemical shift anisotropy for conformational studies of suitably extensively 13C-labeled peptides and proteins.     

Lasonolide A: structural revision and total synthesis

The proposed structure of lasonolide A was synthesized employing radical cyclization reactions of beta-alkoxyacrylates for preparation of the tetrahydropyranyl units A and B, but the spectroscopic data did not match those of the natural product. Both enantiomers of a revised structure featuring 17E,25Z double bonds were synthesized, and the (-)-isomer was found to be the biologically active enantiomer.     

Identification using LC-MSn of co-metabolites in the biosynthesis of the polyketide toxin mycolactone by a clinical isolate of Mycobacterium ulcerans

LC-MSn analysis of mycolactone toxin from extracts of Mycobacterium ulcerans has shown that minor co-metabolites, including two previously unreported, differ structurally from mycolactone only in a small portion of the polyketide side-chain.     

Synthesis of new 3'-, 5-, and N(4)-modified 2'-O-methylcytidine libraries on solid support

A versatile solid phase combinatorial approach was developed and utilized for the rapid synthesis of new 2'-O-methylcytidine nucleoside libraries 1-7 containing 672 compounds with 3'-deoxy-3'-C-methyl, 3'-deoxy-3'-C-hydroxymethyl, and 5-alkyl/alkynyl modifications. The modified uridine scaffolds 8-10, 23-25, and 31 were loaded onto the 4-methoxytrityl chloride (MMT-Cl) polystyrene resin through the hydroxyl groups at the 5'-position as well as on the substituents at the 3'- and 5-positions. The scaffolds loaded on the resin were orthogonally protected by MMT group on the resin itself and TBDMS or acetyl protecting groups. The 4-position of the uridine derivatives was activated by 2,4,6-triisopropyl benzene sulfonyl chloride for further derivatization. The resins 14-16, 28-30, and 32 loaded with the corresponding activated scaffolds were reacted with the selected and validated amino building blocks in the 96 well format on the semiautomated synthesizer. The high-quality 2'-O-methylcytidine libraries 1-7 were thus generated and characterized by liquid chromatography-mass spectrometry (LC-MS) analysis with 63-99% successful rates.     

C-H and C-C bond activation of primary amines through dehydrogenation and transimination

[structure: see text]. Dehydrogenation and subsequent transimination of primary amines offer a new pathway for C-H bond activation, ortho-alkylation, and C-C bond activation to afford a variety of ketones in the reaction of 1-alkene by a cocatalyt system of Rh(I) and 2-amino-3-picoline.     

Structure of the Ba-induced Si(111)- (3 x 2) reconstruction

The Ba/Si(111) surface, previously known as a 3 x 1 phase, is found to have a 3 x 2 periodicity and a semiconducting band gap. The substrate reconstructs into the honeycomb chain-channel (HCC) structure with Ba atoms in the channel, as in the alkali-metal-induced Si(111)-(3 x 1). However, the metal coverage is determined to be 1/6 monolayers, half the alkali-metal coverage. We propose that the structure and the metal coverage determined for the Ba adsorbate is universal for other alkaline-earth-metal adsorbates. With the alkali-metal-induced 3 x 1 case, our results lead to a rule that one donated electron per 3 x 1 surface unit is necessary to stabilize the HCC reconstruction of Si.