Density functional theory calculation on the C―H bond insertion reaction of dibromocarbene with acetaldehyde

The insertion reaction mechanism of CBr_2 with CH_3CH_O has been studied by using the B3LYP/6-31G(d) method. The geometries of reactions, transition state and products were completely optimized. All the energy of the species was obtained at the CCSD(T)/6-31G(d) level. All the transition state is verified by the vibrational analysis and the internal reaction coordinate (IRC) calculations. The results show that the propionaldehyde (~HP1) is the main product of CH_2 insertion with CH_3CH_O. The calculated results indicated that all the major pathways of the reaction were obtained on the singlet potential energy surface. The singlet CBr_2 not only can insert the C_α-H [reaction I(1)]) but also can react with C_β-H [reaction II(1)]. The statistical thermodynamics and Eyring transition state theory with Wigner correc- tion are used to study the thermodynamic and kinetic characters of I(1) and II(1) in temperature range from 100 to 2200 K. The results show that the appropriate reaction temperature rang is 250 to 1750 K and 250 to 1600 K at 1.0 atm for I(1) and II(1) respectively. The rate constant and equilibrium constant are distinct in the range from 250 to 1000 K so that I(1) more easily occurs, while the reactions are not selected in the temperature range of 1000-1600 K     

Effects of Ca on the distribution, structure and morphology of aluminum species in polyaluminum chloride

The flocculation efficiency of polyaluminum chloride (PAC) is closely related to the distribution and structure of its AI species, and Al13 is the optimal species in PAC for flocculation. A series of PAC containing Ca was prepared by adding Ca before and after the basifying reaction. The effects of Ca on the Al species were studied by ^27Al nuclear magnetic resonance (NMR) and atomic force microscope (AFM) techniques. The experimental results show that the introduction of Ca increases the content of Alm and Al13 in PAC and decreases their chemical shifts in NMR spectra due to the electric repulsion between the positive Ca species and AI species and the formation of AI-O-Ca complexes.With the rise of Ca/AI molar ratio, the AI species in PAC tend to scatter. It is observed that the formerly branch-aggregated clusters are tending to form granule-aggregated ones whose diameter gets smaller and smaller, and the floccule aggregates are formed at a higher Ca/Al molar ratio. The introduction of Ca to PAC, which increases the Al13 content, is certainly to enhance the flocculation efficiency of PAC in water treatment.     

Discussion of the Constitutive Relation on Cyclic Stress-Strain of Engineering Materials

Based on the experimental results and analysis of the cyclic deformation, there is an obvious yield stage on the cyclic stress-strain curve at the stage of small plastic deformation (in room or low temperatures). This phenomenon is similar to that of monotonic tensile curve case. But for the former the deformation amount at which the yield begins is much smaller than that for the latter. The cyclic stress-strain constitutive relation needs to be further studied according to the actual cyclic stress-strain curve. The conventional constitutive equation σ=Aεn is based on the results only corresponding to the cyclic strengthening stage. It is not appropriate for the stage of the small plastic deformation and the stage of yield.     

Investigating the Microstructure of Slenderized Wool Fibers at Different Stretching Ratios by Raman Spectroscopy

The molecular conformation and the microstructure of the slenderized wool fibers have been studied by the Raman spectroscopy. The typical bands analyzed in this paper include the amideⅠand amide Ⅲ regions, the C-C skeletal vibration region, and the S-S and C-S bond vibration regions. The experimental results show that ⅰ) the Raman spectroscopy can reveal the secondary structural transformation from α-helical to β-pleated sheet begin at the early stage of stretching; ⅱ) the stretching mechanism of wool fibers can be divided into two different mechanisms, I.e. The secondary structural transformation and the slippage of the polypeptide chain; and ⅲ) the stretching leads to the increasing of the amount of the disordered conformation and the decreasing of the amount of S-S bonds.     

<Emphasis Type="Italic">In situ</Emphasis> FTIR investigation on phase transformations in BN nanoparticles

Fourier transformation infrared spectrum （FTIR） was employed to investigate phase transformation of nanoparticle BN, containing eBN, rBN, wBN and cBN, in which eBN and rBN are the main components. We found that part of eBN was converted into rBN at 200--350℃. At and above 400℃, eBN transformed into wBN, and some of wBN were converted into cBN simultaneously. This conclusion is supported by the results from high- resolution transmission electron microscopic （HRTEM） and Raman spectroscopic measurements. In this work, the converting processes between different BN phases were continuously monitored by in situ FTIR spectroscopy. The results will be helpful for synthesis of cBN at moderate conditions.     

Evaluation of the Potential of the Ternary Aluminides in Nb-Ti-Al system for Hiyh Temperature Application

Being aimed to developing intermetallic base structural materials to be worked at above 1000℃, a systematic investigation has been performed of the fundamental crystallographic structure, phase constitution map, density-composition dependence, oxidation resistance and general mechanical behaviour for the ternary intermetallic alloys in the Nb-Ti-Al system. Promissing results have been obtained at the initial stage in the current program. The 1100℃ high temperature strength at the strain rate of 10-2/s and 10-5/s for the ternary compound NbTiAl3 (γ1) base alloys are generally much higher than that of the binary compound TiAl (γ), especially in the γ1 + α2 phase region, it is as high as twice as that of TiAl. The densities are 4.1-4.79g/cm3, depending on relative amount of the intermetallics involved and the density difference between the intermetallics. The oxidation resistance at the temperature of 900-1200℃ of the compound NbTiAl3 is relatively low but still acceptable. However, by adjusting the     

Relationship among the secretion of extracellular polymeric substances,heat resistance,and bioleaching ability of Metallosphaera sedula

This paper describes the investigation of the secretion of extracellular polymeric substances (EPS) by an extremely thermoacidophilic archaea, Metallosphaera sedula (M. sedula), during the bioleaching of pyrite under different temperatures and discusses the relationship among the EPS secretion, its heat resistance, and its ability to bioleach pyrite. The investigation results indicate that the amount of extracellular proteins is significantly higher than the amount of extracellular polysaccharides in the extracted EPS whether free cells or attached cells; these results are quite different from the behavior of mesophilic Acidithiobacillus ferrooxidans. Although the growth of M. sedula is inhibited at 80℃, the bioleaching ability of M. sedula is only slightly lower than that at the optimum growth temperature of 72℃ because of the heat resistance mechanism based on EPS secretion. The secretion of more extracellular proteins is an important heat resistance mechanism of M. sedula.     

Shape controllable preparations of PbS nanocrystals using cysteine as the precursor of S^2- ions

Flowerlike, spherical and cubic PbS nanoparticles have been successfully synthesized by refluxing cysteine and lead nitrate in an alkaline solu- tion. The influences of the cysteine to Pb2 molar ratio, the pH value of the reaction mixture as well as the refluxing time on the shape of PbS nanoparticles were investigated. Detailed experimental results demonstrated that a higher molar ratio of cysteine to Pb2 (5.2:1) and shorter refluxing time favor the for- mation of flowerlike PbS nanoparticles at pH 9.0. While lower pH value (8.0) favors the formation of spherical PbS nanoparticles, and higher pH value (10.0), however, favors the formation of cubic PbS nanoparticles. The mechanism for the shape control of PbS nanoparticles is discussed.     

Molecular modeling of the ion channel-like nanotube structure of amyloid β-peptide

The ion channel-like nanotube structure of the oligomers of amyloid β-peptide (Aβ) was first investi-gated by molecular modeling. The results reveal that the hydrogen bond net is one of the key factors to stabilize the structure. The hydrophobicity distribution mode of the side chains is in favor of the structure inserting into the bilayers and forming a hydrophilic pore. The lumen space is under the control of the negative potential,weaker but spreading continuously,to which the cation selectivity attributes; meanwhile,the alternate distribution of the stronger positive and negative potentials makes the electrostatic distribution of the structure framework balance,which is also one of the key factors stabilizing the structure. The results lay the theoretical foundation for illuminating the structure stability and the ion permeability,and give a clue to elucidating the molecular mechanism of Alzheimer's dis-ease (AD) and designing novel drugs to prevent or reverse AD at the root.     

Leaching of a copper flotation concentrate with ammonium persulfate in an autoclave system

The leaching behavior of a copper flotation concentrate was investigated using ammonium persulfate (APS) in an autoclave system. The decomposition products of APS, active oxygen, and acidic medium were used to extract metals from the concentrate. Leaching experiments were performed to compare the availability of APS as an oxidizing agent for leaching of the concentrate under atmospheric conditions and in an autoclave system. Leaching temperature and APS concentration were found to be important parameters in both leaching systems. Atmospheric leaching studies showed that the metal extractions increased with the increase in APS concentration and temperature (up to 333 K). A similar tendency was determined in the autoclave studies up to 423 K. It was also determined that the metal extractions decreased at temperatures above 423 K due to the passivation of the particle surface by molten elemental sulfur. The results showed that higher copper extractions could be achieved using an autoclave system.     

C-H···Pd(II) interaction-driven homochiral M helix formation of neutral (R,R)-bis(pyrrol-2-ylmethyl- eneamino) cyclohexane palladium(II) complex

A chiral complex of (R,R)-Pd was prepared by reaction of optically pure (R,R)-bis(pyrrol-2-ylmethyl-eneamino) cyclohexane ligand with Pd(OAc)2·2H2O under the base condition at room temperature. The weak intermolecular C-H···Pd interaction was found to be responsible for the homochiral M helix for-mation of the neutral,chiral,mononuclear (R,R)-Pd in the crystal packing.     

A novel heteroseneous reaction for generating gaseous nitrous acid

The short-lived reactive specimen nitrous acid HONO was generated in the gas phase by the heterogeneous reaction of gaseous HCl with AgNO2 which can generate higher concentration of HONO than other methods. We investigated the process from generation to dissociation in the gas phase under different controlled temperatures, and discussed the ionization and reaction on the solid surface by combination of the photoelectron spectroscopy and photoionization mass spectroscopy （PES-PIMS） and in situ diffuse reflectance infrared Fourier transform spectroscopy （DRIFTS）.     

The uptake of ethyl iodide on black carbon surface

The importance of the iodine chemistry in the atmosphere has been demonstrated by recent obserations. The uptake of ethyl iodine on black carbon surface was inestigated at 298 K for the first time. Degussa FW2 （an amorphous black carbon comprising medium oxides） was used as black carbon sample. Black carbon surface was found to be deactiated in reaction with C2H51, and the uptake coefficient （r） was dependent on the time of exposure. The alue of （2.3±0.9）×10^-2 was determined for the initial uptake coefficient （No）. The result suggests that the heterogeneous loss of C2H51 on carbonaceous aerosols may be important under the atmospheric conditions.     

Styrene polymerization catalyzed by nickel complexes bearing hydroxyindanone-iminate ligands

Activated by methylaluminoxane, mononuclear bis（hydroxyindanone-iminate）nickel complexes Ni[ArN=CC2H3（CH3）C6H2（R）O]2 （Ar = 2,6-i-Pr2C6H3, R=Me（1）, R=CI（2）, and R=H（3）） showed good activity for the styrene polymerization. The effect of many reaction parameters including the AI/Ni ratio, temperature, and reaction time on catalytic activities of catalytic systems and the molecular weights of the obrained polystyrene was ascertained. The highest activity of 1.34×10^5g（PS）·mol^-1（Ni）·h^-1 was obtained under the optimum reaction condition. The ^13C NMR spectra of the polymers revealed that the polymer was isotactic-rich atactic polystyrene. And the coordination mechanism was confirmed by the analyses of the polymer chain end-groups.     

Influence of O2/Ar ratio on the properties of transparent conductive niobium-doped ZnO films

Niobium-doped ZnO transparent conductive films are deposited on glass substrates by radio frequency sputtering at 300℃. The influence of O2/Ar ratio on the structural, electrical and optical properties of the as-deposited films is investigated by X-ray diffraction, Hall measurement and optical transmission spectroscopy. The lowest resistivity of 4.0×10^-4Ω· cm is obtained from the film deposited at the O2/Ar ratio of 1/12. The average optical transmittance of the films is over 90%.     

An exceptionally well-preserved fossil Kalligrammatid from the Jehol Biota

A new species of Neuroptera, Sophogramma lii sp. nov. is described and illustrated in this paper. This new species is assigned to Sophogramma Ren of Kalligrammatidae, mainly based on its humeral recurrent veins, the basal cell present between posterior branch of media at base of wing, etc. The new species is distinguished from all other Sophogramma species on the difference of wing venation. This exceptionally well-preserved specimen is recovered from the Yixian Formation, Huangbanjigou, located near Beipiao City, in western Liaoning Province. The genus diagnosis has been emended based on new characters shown in this new species. Based on a summary of localities, distribution and geological ages of all genera and species of the Kalligrammatidae, we suggest that Kalligrammatids might have originated in Eastern Asia, especially in China. Function of the wing pigmentation is discussed briefly. Supported by National Natural Science Foundation of China (Grant Nos. 30430100 and 40872022), Beijing Natural Science Foundation Program (Grant No. 5082002), Scientific Research Key Program (Grant No. KZ200910028005) and PHR Project of of Beijing Municipal Commission of Education, Science-Technology Basic Condition Platform from the Ministry of Science and Technology of the People’s Republic of China (Grant No. 2005DKA21402)     

Effect of the contact distance on transport properties of an orsanic molecular device

Using a spatially symmetric phenyldithiolate molecule sandwiched between two gold electrodes as model system and through shifting one electrode from symmetric contact site to form asymmetric contact, we investigated the properties of electronic transport in such a device by the first-principles. It was found that the/（G ）-V characteristics of a device show significant asymmetry and the magnitudes of current and conductance depend remarkably on the variation of molecule-metal distance at one of the two contacts. Namely, an asymmetric contact would lead to the weak rectifying effects on the current-voltage characteristics of a molecular device. The analysis shows that the HOMO is responsible for the resonant tunneling and its shift due to the charging of the device while the bias voltage is the intrinsic origin of asymmetric/（G）- Vcharacteristics.     

Microbial community structure in major habitats above 6000 m on Mount Everest

Bacterial abundance in surface snow between 6600 and 8000 m a.s.l. on the northern slope of Mt. Ev- erest was investigated by flow cytometry. Bacterial diversity in serac ice at 6000 m a.s.l., glacier melt- water at 6350 m, and surface snow at 6600 m a.s.l. was examined by constructing a 16S rRNA gene clone library. Bacterial abundance in snow was higher than that in the Antarctic but similar to other mountain regions in the world. Bacterial abundance in surface snow increased with altitude but showed no correlation with chemical parameters. Bacteria in the cryosphere on Mt. Everest were closely related to those isolated from soil, aquatic environments, plants, animals, humans and other frozen environ- ments. Bacterial community structures in major habitats above 6000 m were variable. The Cyto- phaga-Flavobacterium-Bacteroides (CFB) group absolutely dominated in glacial meltwater, while β-Proteobacteria and the CFB group dominated in serac ice, and β-Proteobacteria and Actinobacteria dominated in surface snow. The remarkable differences among the habitats were most likely due to the bacterial post-deposition changes during acclimation processes.     

Protein synthesis inhibition in the basolateral nucleus of amygdala facilitates extinction of auditory fear memory

It is known that consolidation of fear conditioning requires de novo protein synthesis in the amygdala. However, there is controversy about the role of protein synthesis in post-retrieval extinction of fear memory. The present study investigated the effect of protein synthesis inhibition (PSI) in the baso- lateral nucleus of amygdala (BLA) on post-retrieval extinction of auditory fear memory. Intra-BLA infu- sion of the protein synthesis inhibitor anisomycin ‘0’ h post-retrieval facilitated the extinction, but was ineffective if the memory was not retrieved. Anisomycin had no effect on the extinction when it was infused 6 h post-retrieval. The present results suggest that there exists a protein-synthesis-dependent mechanism in the BLA that retards extinction of auditory fear memory.     

Enhanced parametric amplification in slow-light photonic crystal waveguides

We demonstrate both theoretically and numerically that slow light can enhance the parametric process of silicon in photonic crystal line-defect waveguides. Specifically, to get the desired gain, the pump power for a given gain medium length or the gain medium length for given pump power can be reduced by （c/vgn）^2 when slow light waveguides are used, where n is the material index of conventional waveguide, vg is the group velocity of the slow light waveguide and c is the light velocity in vacuum.