Removal and recovery of nitriles from gaseous streams: An IR study of acetonitrile adsorption on and desorption from inorganic solids

The adsorption and the desorption of acetonitrile over several different inorganic solids (such as silicas, aluminas, modified aluminas, silica-aluminas, metal oxides, protonic zeolites, alkali-metal zeolites, and clays) have been investigated by IR spectroscopy. Different kinds of interactions (weak to strong hydrogen-bonding, coordination on Lewis acid sites, different kinds of surface chemical reactions) have been observed. The temperature needed for acetonitrile desorption from these solids has also been determined. Silicas and alkali metal zeolites have been found to allow molecular adsorption without reactivity and to allow desorption in mild conditions.     

Differentiation of human serum samples by surface plasmon resonance monitoring of the integral glycoprotein interaction with a lectin panel

Bacterial infection and inflammation result in massive changes in serum glycoproteins. These changes were investigated by the interaction of the saccharide glycoprotein moiety with lectins. A panel of eight lectins (Canavalia ensiformis, Bandeiraea simplicifolia BS-I, Arachis hypogaea, Phytolacca americana, Phaseolus vulgaris, Artocarpus integrifolia, Triticum vulgaris and Pisum sativum) was used to differentiate human serum glycoproteins obtained from patients with various bacterial infections. Lectin functionalised sensing layers were created on gold-coated wafers and lectin-glycoprotein interactions were monitored by surface plasmon resonance. The interaction of the lectin panel with serum glycoproteins produces unique patterns. Principal component analysis (PCA) was used to analyse the patterns. The actual panel of eight lectins enabled discrimination between sera obtained from patients sick with bacterial infection and healthy patients. Extended lectin panels have the potential to distinguish between types of bacterial infection and identify specific disease state.     

Correlation between the surface free energy of modified and non-modified glasses with controlled porosity and their sorption properties

Summary Contact angles for water and diiodomethane drops were measured on the surface of thermally and chemically (by Carbowax 20M bonding) modified porous glasses and on the surface of naphthalene, diphenyl and anthracene. Using the obtained results to a modified Young equation, dispersion and nondispersion components of the surface free energy of these glasses and organic substances were calculated. The work of adhesion (W_A) for benzene, naphthalene, diphenyl, anthracene, nitrobenzene was estimated and correlated with the capacity factors, (k′) of these substances. On the basis of experimental and calculated data it can be stated that the thermal treatment of porous glasses increases, their hydrophobicity but the Carbowax layer causes hydrophilicity. There is a linear relationship between k′ and W_A which can be helpful for predicting retention data of chromatographed substances on the base of surface free energy which can be calculated from contact angle measurements.     

Thermochemistry of hydride and phenyl groups on the surface of amorphous silicon dioxide

The thermodynamic properties of hydride and phenyl groups on the surface of amorphous silicon dioxide are investigated in the presented work. The characteristics of the surface silane centers (SiH) are determined from the data obtained by infrared spectroscopy and caloric measurements. The conversions of hydrogen and benzene with the surface are described by thermodynamic calculations at reactions take place in the gaseous phase.To model the reaction between hydrogen and the surface the thermodynamic data for (OH)_4−nSi_n (n=0-4) in the gaseous phase are used. The surface groups and the model molecules are comparable because the thermodynamic characteristics depend only from the local environment.The thermodynamic properties of (OH)₃SiC₆H₅ in the gaseous phase are determined to describe the reaction between benzene and the surface. The predications of these calculations are confirmed by the spectroscopic results. The properties of the surface phenyl groups (SiC₆H₅) are concluded from these data.     

Impact of surface hydroxylation in MgO-/SnO-nanocluster modified TiO2 anatase (101) composites on visible light absorption,charge separation and reducibility

Anatase TiO₂ surfaces, whether oxidised or hydroxylated, can be modified by nanoclusters of SnO and MgO to give a red shift in light absorption, enhanced charge separation and high reducibility.     

Direct estimation of the electrostatic interaction between colloidal particle and chemically modified glass surface by the evanescent wave light scattering microscope method

The profile of the interaction potential between polystyrene latex particle and chemically modified glass surface was estimated directly by the evanescent wave light scattering microscope (EVLSM) method; this enables us to measure the distance between particle and surface as a function of time in the order of less than a millisecond. The minimum of the potential profile, which is the result of an electrostatic repulsion and an apparent attraction by gravity between the particle and surface, was clearly observed. To change the electrostatic nature, the glass surface was chemically modified by treatment with a silanization reagent and a vinyl monomer with a sulfonate group. As the absolute value of the zeta potential of the glass surface became larger, the position of the potential minimum on the interaction potential profile shifted away from the glass surface, reflecting an increase of electrostatic repulsion between the particle and the wall. The ionic strength dependence of the potential profile was also clearly observed. In conclusion, EVLSM is a powerful tool for the quantitative estimation of particle-wall interactions. Received: 3rd March 1998 Accepted in revised form: 26 August 1998     

A study on the surface free energy of modified silica fillers and poly(ethylene terephthalate) fibers by inverse gas chromatography

The surface free energy of modified silica fillers and poly(ethylene terephthalate) (PET) fibers was analyzed by inverse gas chromatography in order to investigate the relationship between their surface characteristics and the performance of the composite formed from these materials. The adsorption isotherms of n-heptane and 1-propanol were determined by the elution-peak-maximum method. The dispersive and polar components of the surface free energy were determined by use of the Young–Dupré equation and the Fowkes equation on the basis of the saturated spreading pressure derived from the Gibbs adsorption equation. The acidity and the basicity of the surface were estimated by the specific retention volume of each probe molecule with different donor number and acceptor number. It was found that the dispersive component of the surface free energy for modified silica fillers was mostly lower than that for original silica filler. The polar component of the surface free energy for ethylene glycol modified silica filler became large, while that for n-butanol modified silica filler decreased remarkably. It was also found that original silica filler exhibited high acidity, while modified silica fillers exhibited low acidity. Although these methods have been applied to PET fibers, the surface free energy could not be determined quantitatively because of the surface change during the pretreatment of PET fibers. It was observed that the polar component of the surface free energy decreased when the pretreatment was made at a temperature higher than the glass-transition temperature of PET. It became clear that the interaction between modified silica fillers and PET fibers correlated well with the basicity of the fillers, but not with their acidity. Received: 18 October 1999 Accepted: 8 February 2000     

Cu单原子修饰对Fe(111)表面CO吸附性能及电子性质调变的第一性原理研究

采用密度泛函理论方法研究了Cu单原子修饰对Fe(111)表面CO吸附性能和电子性质的调变作用,其中,Cu单原子修饰研究了吸附和取代两种方式。结果表明,CO在Cu修饰的Fe(111)面吸附能力都会变弱,一是Cu原子自身提供的位点对CO的吸附较弱;二是Cu会使其附近的Fe对CO的吸附变弱。分析电子性质表明,Cu作用于Fe表面后,会导致Cu附近Fe原子部分电子向Cu原子转移,进而削弱了Fe与吸附分子间电子交互作用而改变Fe原子的吸附能力。故Cu原子改性Fe表面可以很好地调变CO的吸附、解离及后续反应催化活性,这为进一步探究Cu改性Fe表面的合成气催化反应机理提供了基础信息。     

Comparison of various capillary electrophoretic approaches for the study of drug–protein interaction with emphasis on minimal consumption of protein sample and possibility of automation†

The binding ability of a drug to plasma proteins influences the pharmacokinetics of a drug. As a result, it is a very important issue in new drug development. In this study, affinity capillary electrophoresis, capillary electrophoresis with frontal analysis, and Hummel Dreyer methods with internal and external calibration were used to study the affinity between bovine serum albumin and salicylic acid. The binding constant was measured by all these approaches including the equilibrium dialysis, which is considered to be a reference method. The comparison of results and other considerations showed the best electrophoretic approach to be capillary electrophoresis‐frontal analysis, which is characterized by the high sample throughput with the possibility of automation, very small quantities of biomacromolecules, simplicity, and a short analysis time. The mechanism of complex formation was then examined by capillary electrophoresis with frontal analysis. The binding parameters were determined and the corresponding thermodynamic parameters such as Gibbs free energy ΔG⁰, enthalpy ΔH⁰, and entropy changes ΔS⁰ at various temperatures were calculated. The results showed that the binding of bovine serum albumin and salicylic acid was spontaneous, and that hydrogen bonding and van der Waals forces played a major role in the formation of the complex.     

Chiral vanadyl salen complex anchored on supports as recoverable catalysts for the enantioselective cyanosilylation of aldehydes. Comparison among silica, single wall carbon nanotube, activated carbon and imidazolium ion as support

The activity and enantiomeric excess (ee) (in some cases >85%) obtained for the asymmetric addition of trimethylsilyl cyanide to aldehydes using different heterogeneous chiral catalysts are compared. A library of recoverable catalysts was developed by immobilization of a chiral vanadyl salen complex having a terminal carbon-carbon double bond onto a series of scaffolds including silica, single-wall carbon nanotubes, activated carbon and room-temperature ionic liquids. The covalent linkage has been achieved by radical initiated addition of mercapto groups to CC. The highest enantiomeric excesses, similar to those obtained in the homogeneous phase, were achieved using silica as support or with the homogeneous tetra-tert-butyl salen catalyst dissolved in an imidazolium ionic liquid. The use of silica as support permits an easier separation and reuse of the catalyst from the reaction media.     

Mechanistic studies on the chiral recognition of polysaccharide-based chiral stationary phases using liquid chromatography and vibrational circular dichroism: Reversal of elution order of N-substituted alpha-methyl phenylalanine esters

Enantiomeric separation of two aromatic α-substituted alanine esters was achieved on two commercially available polysaccharide-based chiral stationary phases (CSPs): amylose tris(3,5-dimethylphenylcarbamate) (ADMPC) and cellulose tris(3,5-dimethylphenylcarbamate) (CDMPC). The interactions between enantiomeric analytes and the CSPs were investigated using chromatographic methods and vibration circular dichroism (VCD). The two analytes differ on the aromatic portion of the molecules where one analyte has a π-acceptor aromatic ring (1) while the other has a π-donor aromatic ring (2). When an ADMPC CSP was employed, an increase in the polarity of the mobile phase leads to a reversal of the elution order for the two enantiomers of 1. The elution order of compound 2 was not affected by the polarity of the mobile phase. In order to gain an understanding of these phenomena, the enantiomeric separation of 1 and 2 was also performed on the CDMPC CSP. Interestingly, no reversal of elution order was observed upon the chromatographic separation of both pairs of enantiomers of compounds 1 and 2 upon increasing the solvent polarity when a CDMPC CSP was utilized. To understand the underlying mechanism governing these chiral separations, VCD was applied to study the structure of the ADMPC and CDMPC polymers and their conformational behaviors under chromatographic conditions. For the first time the conformations of the side chains of both polymers were revealed based on the VCD spectra along with DFT calculations. Furthermore, the interactions between the two analytes and the two CSPs were directly probed by VCD. By comparing the spectral differences of the two CSPs in the presence of the two analytes, the detailed interactions involving different functional groups associated with the chiral recognition were elucidated and thus explained the unusual reversal of elution order associated with increasing solvent polarity.