Surface of room temperature ionic liquid [bmim][PF6] studied by polarization- and experimental configuration-dependent sum frequency generation vibrational spectroscopy

Understanding and control of the surface properties such as molecular orientations are of great importance in numerous applications of ionic liquids. However, there remain discrepancies among the previous experimental and theoretical studies on the surface orientation and structures of room temperature ionic liquids(RTIL) systems. In this article, the orientation of 1-butyl-3-methylimidazolium([bmin]) cation at the air/liquid interface of a characteristic RTIL, 1-butyl-3-methylimidazolium hexafluorophosphate([bmim][PF6]), was investigated by the sum frequency generation vibrational spectroscopy(SFG-VS). Detailed polarization and experimental configuration analyses of the SFG-VS spectra showed the possibility of a small spectral splitting in the CH3 symmetric stretching region, which can be further attributed to the probable existence of multiple orientations for the interfacial [bmim] cations. In addition, the(N)–CH3 vibrations were absent, ruling out the prediction by several recent molecular dynamics simulations which state that portions of the [bmim] cations orient with a standing-up(N)–CH3 group at the ionic liquid surface. Hence, new realistic theoretical models have to be developed to reflect the complex nature of the ionic liquid surface.     

Scale-up of bubbling fluidized beds with continuous particle flow based on particle-residence-time distribution

Few studies have investigated scale-up of the residence-time distribution（RTD） of particles in bubbling fluidized beds（BFBs） with continuous particle flow.Two approaches were investigated in this study:first,using well-known scaling laws that require changes in particle properties and gas velocity;second,using a simple approach keeping the same particles and gas velocity for different beds.Our theoretical analysis indicates it is possible to obtain similar RTDs in different BFBs with scaling laws if the plug-flow residence time(t_plug) is changed as m^0.5,where m is the scaling ratio of the bed;however,neither approach can ensure similar RTDs if t_plugis kept invariant.To investigate RTD variations using two approaches without changing t_plug,we performed experiments in three BFBs.The derivatives d?（θ）/dθ（where E（θ） is the dimensionless RTD density function and θ is the dimensionless time） in the early stage of the RTDs always varied with m-1,which was attributed to the fact that the particle movement in the early stage were mainly subject to dispersion.Using the simple approach,we obtained similar RTDs by separately treating the RTDs in the early and post-stages.This approach guarantees RTD similarity and provides basic rules for designing BFBs.     

Enhanced release of the poorly soluble drug itraconazole loaded in ordered mesoporous silica

It is known that the energy of the amorphous state of itraconazole loaded in ordered mesoporous materials is high relative to that of the crystalline state and is responsible for enhanced solubility and dissolution rate. We investigated the effects of particle size(0.7–5μm), mesostructure(2D p6 mm, cubic Ia-3d and cubic Fm-3m) and pore size(2.2–15.4 nm) of mesoporous silicas on the release performance of itraconazole. Results indicated that the release performance was not influenced by the particle sizes tested here, that the release performance increased with increasing pore diameter due to the lower probability of drug molecules colliding to recrystallize in large pores, and that the release performance was decreased in the cage-type pore structure(Fm-3m) compared to that in the cylindrical pore structures(p6mm and Ia-3d) because of the small entrance to the cagelike pores that retards the drug release.     

VIBRATION AND SOUND RADIATION OF AN ASYMMETRIC LAMINATED PLATE IN THERMAL ENVIRONMENTS

Analytical studies on the vibration and sound radiation characteristics of an asymmetric laminated rectangular plate are carried out in this paper. Theoretical formulations, in which the effects of thermal environments are taken into account, are derived for the vibration and sound radiation based on both first-order shear deformation plate theory and Rayleigh integral. It is found that the natural frequencies, the resonant amplitudes of vibration response and the sound pressure level decrease with the temperature rising. The natural frequencies of asymmetric plates are smaller than those of symmetric plates and the velocity responses of asymmetric plates are larger than those of symmetric plates.     

Ratiometric mode with dyads: a breakthrough in dynamic trapping and quantification for redox regulation in living cells

Redox-based post-translational modification of protein thiols has become an attractive strategy in cellular homeostasis and cell signaling.Due to the reductive end of the redox buffer network,the vicinal dithiol-containing proteins(VDPs)maintains an appropriate oxidation-reduction state of proteins through the reversible transformation from vicinal dithiols to disulfide,which is responsible for a variety of     

Hemin-histamine-montmorillonite clay conjugate as a model biocatalyst to mimic natural peroxidase

We successfully synthesized the first hemin-montmorillonite bio-conjugate with an amino acid residue to mimic natural peroxidase enzyme. Histamine was intercalated in montmorillonite by cation exchange, then a hemin molecule was loaded onto the histamine-montmorillonite with an adsorption capacity of 7.0 mg g-1. The hemin-histamine-montmorillonite conjugate shows high peroxidase activity as indicated by the oxidation of guaiacol, which is attributed to the activation of hemin by Fe–N complex formation between the imidazole group in histamine and the iron ion in the hemin molecule. Temperature- dependent peroxidase activity for this synthesized biomimetic material indicates that raising the reaction temperature could significantly enhance the activity of the conjugate. The biomimetic catalyst has good reusability; nearly 100% activity can be retained after three cycles. Because montmorillonite clay is widely distributed in the environment, this material offers great potential for in situ and ex situ remediation of many organic contaminants in surface/subsurface soils.     

Direct synthesis of propylene carbonate from propylene and carbon dioxide catalyzed by quaternary ammonium heteropolyphosphatotungstate–TBAB system

In this paper,we have developed a highly efficient method for the direct preparation of propylene carbonate from propylene and carbon dioxide(CO2) using quaternary ammonium heteropolyphosphatotungstate–quaternary ammonium halide catalytic system with anhydrous hydrogen peroxide as an oxidant through one-pot two-step process.The effects of the amount of tetrabutylammonium bromide(TBAB),the concentration of hydrogen peroxide and other reaction conditions were investigated.The catalyst system gave an optimum propylene oxide yield(91%) at75°C in oxidation step and the highest propylene carbonate yield(99%) at 140°C and 3.0 MPa in cycloaddition step.Based on the results,a reaction mechanism has been proposed.     

Preparation,characterization and hydrodesulfurization performances of Co-Ni2P/SBA-15 catalysts

A series of Co-Ni2P/SBA-15 catalysts with various Co contents, Ni2P contents and P/Ni molar ratios were prepared by impregnating nickel nitrate, diammonium hydrogen phosphate, and then cobalt nitrate into SBA-15 support followed by temperature-programmed reduction in a H2 flow. The catalyst structure was characterized by X-ray diffraction(XRD), high resolution-transmission electron microscopy(HR-TEM)and N2adsorption-desorption techniques and their catalytic performance of the hydrodesulfurization(HDS) of dibenzothiophene(DBT) was evaluated. The effects of Co contents, Ni2 P contents and P/Ni molar ratios on the catalyst structure and HDS of DBT over the Co-Ni2P/SBA-15 catalyst were investigated. The results indicated that the mesoporous structure was mainly maintained and the nickel phosphides were well dispersed in all of the characterized catalysts. The 4Co-25Ni2P/SBA-15(P/Ni = 0.8) catalyst with the Co and Ni2 P contents of 4 wt% and25 wt%, respectively, and the P/Ni molar ratio of 0.8 showed the highest catalytic performance for HDS of DBT. Under the reaction conditions of 380?C and 3.0 MPa, the DBT conversion can reach 99.62%. The HDS of DBT proceeded mainly via the direct desulfurization(DDS)pathway with biphenyl(BP) as the dominant product on all of the catalysts and the BP selectivity was slightly enhanced after the introduction of Co promoters.     

各向异性本构关系在板料成形数值模拟中的应用

对几种能表达面内各向异性的屈服准则Hill、Barlat-Lian、Barlat进行了比较。以弹性变形服从各向同性广义虎克定律的情况下，给出了基于张量算法推导的弹塑性本构关系的一般表达式，并由此导出了相应屈服准则的弹塑性本构关系的显式表达。借助ABAQUS软件本构模块用户子程序接口，分别实现了这些屈服准则在ABAQUS的嵌入。以模拟方形盒的拉延过程为例，分析了不同的屈服准则在板料成形过程数值模拟中的应用。模拟结果表明，基于弹塑性本构关系一般表达所列出的相应屈服准则的显式表达式是正确的；在采用壳元来模拟板料成形时，采用Barlat准则的模拟结果和采用Barlat-Lian准则的结果差别不大。