MCM-41-supported bidentate phosphine palladium(0) complex: a highly active and recyclable catalyst for the Sonogashira reaction of aryl iodides

The first MCM-41-supported bidentate phosphine palladium(0) complex has been prepared. This complex is a highly efficient catalyst for Sonogashira reaction and can be reused at least 10 times without any decrease in activity.     

Gap exponents for percolation processes with triangle condition

A study is made of the gap exponents for percolation processes with the triangle condition in the subcritical region. It is show that the gaps are given by _t =2 fort=2, 3,. Scaling theory predicts thatP _p (¦C ₀¦S(p))–(p _c –p) andE _p (1/¦C ₀¦; ¦C ₀¦S(p))–(p _c –p)³, whereS(p) is the typical cluster size. It is found that (p _c –p)P _p (|C ₀S(p) ^1–)(p _c –p)^1–2 and (p _c –p)³E _p (1/|C ₀|;|C ₀|S(p) ^1–))(p _c –p)^3–4.     

Characterization of N-terminal processing of group VIA phospholipase A<Subscript>2</Subscript> and of potential cleavage sites of amyloid precursor protein constructs by automated identification of signature peptides in LC/MS/MS analyses of proteolytic digests

Dysregulation of proteolytic processing of the amyloid precursor protein (APP) contributes to the pathogenesis of Alzheimer's Disease, and the Group VIA phospholipase A(2) (iPLA(2)beta) is the dominant PLA(2) enzyme in the central nervous system and is subject to regulatory proteolytic processing. We have identified novel N-terminal variants of iPLA(2)beta and previously unrecognized proteolysis sites in APP constructs with a C-terminal 6-myc tag by automated identification of signature peptides in LC/MS/MS analyses of proteolytic digests. We have developed a Signature-Discovery (SD) program to characterize protein isoforms by identifying signature peptides that arise from proteolytic processing in vivo. This program analyzes MS/MS data from LC analyses of proteolytic digests of protein mixtures that can include incompletely resolved components in biological samples. This reduces requirements for purification and thereby minimizes artifactual modifications during sample processing. A new algorithm to generate the theoretical signature peptide set and to calculate similarity scores between predicted and observed mass spectra has been tested and optimized with model proteins. The program has been applied to the identification of variants of proteins of biological interest, including APP cleavage products and iPLA(2)beta, and such applications demonstrate the utility of this approach.     

On-line preconcentration of arsenic from water samples with an anion-exchanger column coupled to a hydride generation ICP system

Summary An on-line anion-exchange preconcentration hydride generation ICP system for the determination of total inorganic arsenic in water is described. The column was packed with strongly basic anion-exchange resin (AG 1-X8). Experimental conditions including pH of the sample solution, eluent, flow rate of eluent, oxidation states of arsenic and competing anion ions were studied. Compared with the conventional continuous hydride generation ICP, a 9.2-fold improvement in sensitivity was obtained with RSD 1–2% at 100 ng/ml. The detection limit (3) was 0.08 ng/ml. The recoveries in water samples were satisfactory. The system provides complete automation of sample loading, eluting and regenerating of the resin.On leave from Shanghai Institute of Metallurgy, Chinese Academy of Sciences, Shanghai, China 200050     

Fluorescent sensors for the enantioselective recognition of mandelic acid: signal amplification by dendritic branching

Novel chiral bisbinaphthyl compounds have been synthesized for the enantioselective fluorescent recognition of mandelic acid. By introducing dendritic branches to the chiral receptor unit, the fluorescence signals of the receptors are significantly amplified because of the light-harvesting effect of the dendritic structure. This has greatly increased the sensitivity of the sensors in the fluorescent recognition. Study of the three generation sensors demonstrates that the generation zero sensor is the best choice for the recognition of mandelic acid because of its greatly increased fluorescence signal over the core and its high enantioselectivity. This sensor is potentially useful for the high throughput screening of chiral catalysts for the asymmetric synthesis of alpha-hydroxycarboxylic acids.     

Ultrafast collective dynamics in the charge-density-wave conductor K(0.3)MoO(3)

Low-energy coherent charge-density wave excitations are investigated in blue bronze (K(0.3)MoO(3)) and red bronze (K(0.33)MoO(3)) by femtosecond pump-probe spectroscopy. A linear gapless, acousticlike dispersion relation is observed for the transverse phasons with a pronounced anisotropy in K(0.33)MoO(3). The amplitude mode exhibits a weak (opticlike) dispersion relation with a frequency of 1.67 THz at 30 K. Our results show for the first time that the time-resolved optical technique provides momentum resolution of collective excitations in strongly correlated electron systems.     

Concise synthesis of acyl migration-blocked 1,1-difluorinated analogues of lysophosphatidic acid

Lysophosphatidic acid (LPA, 1- or 2-acyl-sn-glycerol 3-phosphate) is an important phospholipid mediator produced by activated platelets and by ovarian cancer cells. Efforts to understand LPA signaling through G-protein-coupled receptors are hampered by the facile acyl migration that results in equilibration to a mixture of the 1- or 2-acyl species under physiological conditions. We describe a new and efficient route to enantiomerically homogeneous lysophospholipid analogues from D-mannitol 1,2:5,6-bis-acetonide to give two 1,1-difluorodeoxy analogues of (2R)-acyl-sn-glycerol 3-phosphate. These compounds are migration-blocked analogues of the labile sn-2 LPA species. The (19)F NMR of diastereotopic fluorines of the difluoromethyl group shows an unexpected solvent dependence.