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.     

Odd/even effect in the chain length on the enthalpy of micellization of gemini surfactants in aqueous solution

The micellization properties of cationic symmetric gemini surfactants, [CmH(2m+1)(CH3)2N(CH2)6N(CH3)2CmH(2m+1)]Br2 (designated as CmC6CmBr2, with m = 7, 8, 9, 10, 11, 12, and 16), has been investigated by isothermal titration microcalorimetry. The critical micelle concentration (CMC) and enthalpy of micellization (DeltaHmic) were determined from calorimetric titration curves. The linear decreasing of log CMC with increasing the length of the hydrophobic chain is consistent with an increase in the hydrophobicity of the alkyl chain. Interestingly, with increasing the length of the alkyl chain, the DeltaHmic values of the surfactants with even numbered alkyl chains vary from endothermic to exothermic, whereas the DeltaHmic values of the surfactants with odd numbered alkyl chains are all endothermic and tend to become more endothermic. The pronounced even/odd effect in DeltaHmic is discussed with respect to the "donor-acceptor" interaction.     

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     

Accurate local spin-polarized exchange potential: Reconciliation of generalized Slater and Kohn–Sham methods

Using simple physical arguments, a local spin-polarized exchange potential, V_xσ, is constructed from the single-particle Hartree–Fock (HF ) potentials (generalized Slater method) that reduces to the usual Kohn–Sham (KS ) result in the uniform gas limit. Numerical results for 10 closed subshell atoms demonstrate that the total energy calculated employing this V_xσ is closer to the exact KS results than those of other standard exchange approximations with electron densities and highest occupied orbital eigenvalues that closely approximate the HF results.     

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.     

胆汁酸盐对胆红素钙沉淀过程的影响

研究了六种人胆汁主要胆汁酸盐对胆红素钙沉淀形成过程的影响。用曲线拟合法处理数据取得热力学及动力学参数。结果表明,六种胆汁酸盐都表现动力学和热力学抑制,而且抑制作用有浓度依赖关系。在一定条件下出现诱导期。虽然不同胆汁酸盐的作用结果相似,但在相同条件下,二羟基胆汁酸和三羟基胆汁酸影响程度不同。     

Predictions of moiré excitons in twisted two-dimensional organic–inorganic halide perovskites

Recent breakthrough in synthesizing arbitrary vertical heterostructures of Ruddlesden–Popper (RP) perovskites opens doors to myriad quantum optoelectronic applications. However, it is not clear whether moiré excitons and flat bands can be formed in such heterostructures. Here, we predict from first principles that twisted homobilayers of RP perovskite, MA₂PbI₄, can host moiré excitons and yield flat energy bands. The moiré excitons exhibit unique and hybridized characteristics with electrons confined in a single layer of a striped distribution while holes localized in both layers. Nearly flat valence bands can be formed in the bilayers with relatively large twist angles, thanks to the presence of hydrogen bonds that strengthen the interlayer coupling. External pressures can further increase the interlayer coupling, yielding more localized moiré excitons and flatter valence bands. Finally, electrostatic gating is predicted to tune the degree of hybridization, energy, position and localization of moiré excitons in twisted MA₂PbI₄ bilayers.

Excitonic states in twisted MA₂PbI₄ bilayers were calculated by first-principles calculations.