胶体晶体自组装排列进展

自组装排列胶体晶体是发展光子晶体等亚微米周期有序结构及新型光电子器件十分重要的环节.高电荷密度单分散胶体球在较弱的离子强度和稀浓度下会自发排列形成紧密堆积的周期性结构(ccp),常常是面心立方(fcc),科学家们以此为基础发展了多种结晶化胶体粒子的方法,包括重力场沉积、电泳沉积、胶体外延技术、垂直沉积、流通池、物理束缚排列及其他的许多方法.目前排列的胶体粒子基本为球形,材料也多为SiO2、PS、PMMA,此外一些复合粒子,主要为核壳粒子的排列这里也稍作介绍,这些方法及其变通的使用可以形成类蛋白石及反蛋白石结构,最终实现光子带隙及其它多种用途。     

Baker＇s Yeast Mediated Reduction of Optically Active Diketone

Baker‘s yeast mediated reduction of optically active diketone is described. The two keto groups are efficiently differentiated and the ee value of the recovered material is considerably raised. It affords highly optically active key intermediates efficiently for the synthesis of natural polyhydroxylated agarofuran products.     

Electronic structure and molecular orbital study of the first excited state of the high‐efficiency blue OLED material bis(2‐methyl‐8‐quinolinolato)aluminum(III) hydroxide complex from ab initio and TD‐B3LYP

Bis(2‐methyl‐8‐quinolinolato)aluminum(III) hydroxide complex (AlMq₂OH) is used in organic light‐emitting diodes (OLEDs) as an electron transport material and emitting layer. By means of ab initio Hartree–Fock (HF) and density functional theory (DFT) B3LYP methods, the structure of AlMq₂OH was optimized. The frontier molecular orbital characteristics and energy levels of AlMq₂OH have been analyzed systematically to study the electronic transition mechanism in AlMq₂OH. For comparison and calibration, bis(8‐quinolinolato)aluminum(III) hydroxide complex (Alq₂OH) has also been examined with these methods using the same basis sets. The lowest singlet excited state (S₁) of AlMq₂OH has been studied by the singles configuration interaction (CIS) method and time‐dependent DFT (TD‐DFT) using a hybrid functional, B3‐LYP, and the 6‐31G* basis set. The lowest singlet electronic transition (S₀ → S₁) of AlMq₂OH is π → π* electronic transitions and primarily localized on the different quinolate ligands. The emission of AlMq₂OH is due to the electron transitions from a phenoxide donor to a pyridyl acceptor from another quinolate ligand including C → C and O → N transference. Two possible electron transfer pathways are presented, one by carbon, oxygen, and nitrogen atoms and the other via metal cation Al³⁺. The comparison between the CIS‐optimized excited‐state structure with the HF ground‐state structure indicates that the geometric shift is mainly confined to the one quinolate and these changes can be easily understood in terms of the nodal patterns of the highest occupied and lowest unoccupied molecular orbitals. On the basis of the CIS‐optimized structure of the excited state, TD‐B3‐LYP calculations predict an emission wavelength of 499.78 nm. An absorption wavelength at 380.79 nm on the optimized structure of B3LYP/6‐31G* was predicted. They are comparable to AlMq2OH 485 and 390 nm observed experimentally for photoluminescence and UV‐vis absorption spectra of AlMq₂OH solid thin film on quartz, respectively. Lending theoretical corroboration to recent experimental observations and supposition, the reasons for the blue‐shift of AlMq2OH were revealed. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2004     

Supramolecular assemblies of a naturally derived sophorolipid

Acidic sophorolipid (SL) molecules derived from yeasts represent a novel type of asymmetrical bolaamphiphiles due to their unique structural features that include an asymmetrical polar head size (disaccharide vs COOH), a kinked hydrophobic core (cis-9-octadecenoic chain), and a non-amide polar-nonpolar linkage. Light microscopy, small- and wide-angle X-ray scattering, FT-IR spectroscopy, and dynamic laser light scattering were used to investigate the supramolecular structures of the self-assembled aggregates of SL molecules at different pH values. In acidic conditions (pH < 5.5), giant twisted and helical ribbons of 5-11 microm width and several hundreds of micrometers length were observed for the first time. Increase in solution pH values slowed ribbon formation, decreased ribbon yield, and increased the helicity and entanglements of the giant ribbons. An interdigitated lamellar packing model of acidic SL-COOH molecules with a long period of 2.78 nm, stabilized by both the strong hydrophobic association between the cis-9-octadecenoic chains and strong disaccharide-disaccharide hydrogen bonding, is proposed. The neutralization of SL-COOH in water to SL-COONa produced clear solutions with the formation of short-range ordered aggregates. At concentrations below 1.0 mg/mL, the size of self-assembled aggregates increased as the concentration increased. At concentrations above 1.0 mg/mL, narrowly distributed micellar aggregates with a constant hydrodynamic radius (R(h)) of about 100 nm are formed. The large micelles show strong angular dependence with the fast mode appearing at scattering angle theta >/= 60 degrees.     

Interactive effects of ultraviolet-B radiation and temperature on cotton physiology, growth, development and hyperspectral reflectance

Current conditions of 2-11 kJ m(-2) day(-1) of UV-B radiation and temperatures of >30 degrees C during flowering in cotton cultivated regions are projected to increase in the future. A controlled environment study was conducted in sunlit growth chambers to determine the effects of UV-B radiation and temperature on physiology, growth, development and leaf hyperspectral reflectance of cotton. Plants were grown in the growth chambers at three day/night temperatures (24/16 degrees C, 30/22 degrees C and 36/28 degrees C) and three levels of UV-B radiation (0, 7 and 14 kJ m(-2) day(-1)) at each temperature from emergence to 79 days under optimum nutrient and water conditions. Increases in main stem node number and the node of first fruiting branch and decrease in duration to first flower bud (square) and flower were recorded with increase in temperature. Main effects of temperature and UV-B radiation were significant for net photosynthetic rates, stomatal conductance, total chlorophyll and carotenoid concentrations of uppermost, fully expanded leaves during squaring and flowering. A significant interaction between temperature and UV-B radiation was detected for total biomass and its components. The UV-B radiation of 7 kJ m(-2) day(-1) reduced boll yield by 68% and 97% at 30/22 degrees C and 36/28 degrees C, respectively, compared with yield at 0 kJ m(-2) day(-1) and 30/22 degrees C. No bolls were produced in the three temperature treatments under 14 kJ m(-2) day(-1) UV-B radiation. The first-order interactions between temperature, UV-B radiation and leaf age were significant for leaf reflectance. This study suggests a growth- and process-related temperature dependence of sensitivity to UV-B radiation.     

Direct optical detection of singlet oxygen from a single cell

Singlet oxygen has been detected in single nerve cells by its weak 1270 nm phosphorescence (a1deltag --> X3sigmag-) upon irradiation of a photosensitizer incorporated in the cell. Thus, one can now consider the application of direct optical imaging techniques to mechanistic studies of singlet oxygen at the single-cell level.     

A QM/MM study of a nucleophilic aromatic substitution reaction catalyzed by 4-chlorobenzoyl-CoA dehalogenase

Calculated using a QM/MM method, the free energy profile for the conversion of 4-chlorobenzoate to 4-hydroxybenzoate catalyzed by 4-chlorobenzoyl-CoA dehalogenase indicates the existence of a stable Meisenheimer complex.     

Electronic gel protein transfer and identification using matrix-assisted laser desorption/ionization-mass spectrometry

An electronic protein transfer technique is described for achieving the rapid and efficient recovery of sodium dodecyl sulfate (SDS)-protein complexes from polyacrylamide gels. This process involves the use of small-dimension capillaries in physical contact with a resolved protein band within the polyacrylamide gel, providing a large potential drop and high electric field strength at the capillary/gel interface. Several factors controlling the electronic protein transfer, including the applied electric field strength, the electrophoresis buffer concentration, and the capillary dimension, are studied to further enhance the use of field-amplification for sample stacking of extracted SDS-protein complexes. As a result of sample stacking, the extracted proteins from a 50 ng gel loading are present in a narrow ( approximately 80 nL) and highly concentrated (0.46 mg/mL or 3.3 x 10(-5) M for cytochrome c) solution plug. Three model proteins with molecular mass ranging from 14 kDa (cytochrome c) to 116 kDa (beta-galactosidase) are stained by Coomassie blue and electrophoretically extracted from gels with protein loadings as low as 50 ng. The capillary format of the electronic protein transfer technique allows direct deposition of extracted proteins onto a matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) target. Various matrices and solvent compositions are evaluated for the analysis of extracted and concentrated SDS-protein complexes using MALDI-MS. The electronic protein transfer technique, when operated under optimized conditions, is demonstrated for the effective (>70% recovery), speedy (less than 5 min), and sensitive MS identification of gel resolved proteins (as low as 50 ng).     

Research Progress and Application of Ion Funnel Technique

Ion funnel is a new-style ion guider which can reduce spatial divergence and energy dispersity of the transmission ions by using radio frequency (RF) electric field to confine the ions radially and the direct current (DC) axial electric field to move the ions toward the exit, and thus it can greatly increase the ion transmission efficiency and improve the sensitivity of the mass spectrometry. Since ion funnel was invented in 1997, it has attracted a close attention of mass spectrometry scientists all over the world. Ion funnel has been used in various kinds of mass spectrometry, and built a bridge with high efficiency ion transmission between low vacuum ionization source and high vacuum mass analyzer. In this paper, the principle, technology development, and application progress of ion funnel are reviewed, and the future prospects are prospected.