Pair correlation functions and a free energy functional for the nematic phase

In this paper we have presented the calculation of pair correlation functions in a nematic phase for a model of spherical particles with the long-range anisotropic interaction from the mean spherical approximation (MSA) and the Percus-Yevick (PY) integral equation theories. The results found from the MSA theory have been compared with those found analytically by Holovko and Sokolovska [J. Mol. Liq. 82, 161 (1999)]. A free energy functional which involves both the symmetry conserving and symmetry broken parts of the direct pair correlation function has been used to study the properties of the nematic phase. We have also examined the possibility of constructing a free energy functional with the direct pair correlation function which includes only the principal order parameter of the ordered phase and found that the resulting functional gives results that are in good agreement with the original functional. The isotropic-nematic transition has been located using the grand thermodynamic potential. The PY theory has been found to give a nematic phase with pair correlation function harmonic coefficients having all the desired features. In a nematic phase the harmonic coefficient of the total pair correlation function h(x1,x2) connected with the correlations of the director transverse fluctuations should develop a long-range tail. This feature has been found in both the MSA and PY theories.     

Application of Doehlert design in optimizing the determination of degraded products of nerve agents by ion-pair liquid chromatography electrospray ionization tandem mass spectrometry

A qualitative method was developed for the determination of degraded products of nerve agents by using ion-pair liquid chromatography electrospray ionization tandem mass spectrometry (IP-LC-ESI-MS(n)). Generally, alkylphosphonic acids (APAs) and O-alkyl alkylphosphonic acids (AAPAs) give deprotonated molecular ion [M-H](-) in negative mode. Interestingly, first time we obtained the molecular radical anion [M](.-) of phosphonic acids in negative mode by using tri-n-butyl amine as an ion-pairing agent. We interpreted this observation as an indication of electrochemical reduction of phosphonic acids in electrospray needle. Three variables such as sheath gas flow, electrospray needle voltage and pH of the mobile phase were investigated to enhance the molecular radical anion [M](.-) signal of each analyte. The Doehlert design was used to obtain the region in which the optimum value of such variables is simultaneously achieved. Limit of detection achieved was 0.5 microg mL(-1) for AAPAs and 10 microg mL(-1) for APAs. Excellent precision was observed with less than 8.61% RSD. Finally, the method was applied for the detection of ethyl methylphosphonic in aqueous extract of soil sample.     

In situ derivatization hollow fiber mediated liquid phase microextraction of alkylphosphonic acids from water

Alkylphosphonic acids (APAs), particularly the methyl-, ethyl-, isopropyl- and n-propyl-phosphonic acids are important markers of extremely toxic nerve agents. Hence, their detection and identification is of vital importance to verification of chemical weapons convention (CWC). Verification analysis of CWC requires development of fast, reliable, simple and reproducible sample preparation methods of water and soil samples. Present investigation is focused on the optimization of alkylation of APAs in water with subsequent extraction of alkylated acids by hollow fiber liquid phase microextraction (HF-LPME). This simple and sensitive sample preparation of APAs from water offered better recoveries in comparison to conventionally used extraction technique. Under optimized conditions, the APAs were detected at the concentration of 0.5-0.75 microg/mL with S/N ratio > or = 5, whereas the LODs for alkyl APAs (monobasic APAs) were achieved up to 0.1 microg/mL. The developed method was finally tested with water samples supplied in 19th official proficiency test conducted by the OPCW.     

The perturbative proton form factor reexamined

We recalculate the proton Dirac form factor based on the perturbative QCD factorization theorem, which includes Sudakov suppression. The evolution scale of the proton wave functions and the infrared cutoffs for the Sudakov re-summation are carefully chosen such that the soft divergences from large coupling constants are diminished and perturbative QCD predictions are stabilized. We find that the King–Sachrajda model for the proton wave function leads to results which are in better agreement with experimental data than those from the Chernyak–Zhitnitsky wave function. Received: 27 November 1998 / Published online: 7 April 1999     

Kinetics of PdII‐catalyzed polymerization of methyl methacrylate by triethanolamine in the presence of CCl4

Polymerization of methyl methacrylate (MMA) with triethanolamine (TEA) and carbon tetrachloride has been investigated in the presence of PdCl₂ and in a dimethylsulfoxide (DMSO) medium by employing a dilatometric technique at 60°C. The rate of polymerization has been obtained under the conditions [CCl₄]/[TEA] ≤ 1. The kinetic date indicate the possible participation of the charge‐transfer complex formed between the {amine–Pd^II} complex and CCl₄ in the polymerization of MMA. In the absence of either CCl₄ or amine, no polymerization of MMA was observed under the present experimental conditions. The rate of polymerization was inhibited by hydroquinone, suggesting a free‐radical initiation. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 171–177, 2000     

Zirconium-Based Metal Organic Frameworks for the Capture of Carbon Dioxide and Ethanol Vapour. A Comparative Study

This paper reports on the comparison of three zirconium-based metal organic frameworks (MOFs) for the capture of carbon dioxide and ethanol vapour at ambient conditions. In terms of efficiency, two parameters were evaluated by experimental and modeling means, namely the nature of the ligands and the size of the cavities. We demonstrated that amongst three Zr-based MOFs, MIP-202 has the highest affinity for CO₂ (−50 kJ·mol⁻¹ at low coverage against around −20 kJ·mol⁻¹ for MOF-801 and Muc Zr MOF), which could be related to the presence of amino functions borne by its aspartic acid ligands as well as the presence of extra-framework anions. On the other side, regardless of the ligand size, these three materials were able to adsorb similar amounts of carbon dioxide at 1 atm (between 2 and 2.5 µmol·m⁻² at 298 K). These experimental findings were consistent with modeling studies, despite chemisorption effects, which could not be taken into consideration by classical Monte Carlo simulations. Ethanol adsorption confirmed these results, higher enthalpies being found at low coverage for the three materials because of stronger van der Waals interactions. Two distinct sorption processes were proposed in the case of MIP-202 to explain the shape of the enthalpic profiles.     

Pd(II) inhibition during hexacyanoferrate(III) oxidation of sugars: A kinetic study

An inhibition effect of PdCl₂ on the rate of oxidation of sugars by alkaline hexacyanoferrate(III) has been observed. The order of reactions in hexacyanoferrate(III) and OH⁻ is zero and unity, respectively, while that in sugars decreases from unity at higher sugar concentration. The kinetic data and spectrophotometric evidence support the formation of {Pd^II − (sugar)} and {Pd^II − sugar)₂} complexes and their resistance to react with Fe(CN)₆³⁻ © 1996 John Wiley & Sons, Inc.     

Wave induced sliding at the interface between a layered elastic medium and a half-space

The sliding interface between an unrestrained elastic half-space and a grounded layered half-space excited by an incident harmonic wave is investigated. The problem is formulated considering various possible boundary conditions and boundary inequalities at the sliding interface. The Coulomb friction model without distinction between the static and kinetic coefficients of friction is considered to govern the sliding condition. Three possible bands at the interface, namely slip, stick, and separation, are considered. The interface is assumed to be preloaded under normal and shear stresses. The solution is developed by modifying the problem of welded interface, which then is reduced to a set of algebraic equations. The effects of the incident angle, layer thickness, friction coefficient and externally applied stresses on the drift velocity of the unrestrained half-space are studied numerically for a pair of materials. It is shown that the sliding interface, and hence the drift velocity of unrestrained half-space is noticeably influenced by the layered medium. These results are expected to be useful for the development of a new kind of ultrasonic drive in future.