Positivity of entropy production in nonequilibrium statistical mechanics

We analyze different mechanisms of entropy production in statistical mechanics, and propose formulas for the entropy production ratee() in a state . When is steady state describing the long term behavior of a system we show thate()0, and sometimes we can provee()>0.     

On two--block--factor sequences and one--dependence

The distributions of two--block--factors arising from i.i.d. sequences are observed to coincide with the distributions of the superdiagonals of jointly exchangeable and dissociated arrays . An inequality for superdiagonal probabilities of the arrays is presented. It provides, together with the observation, a simple proof of the fact that a special one--dependent Markov sequence of Aaronson, Gilat and Keane (1992) is not a two--block factor.

     

硫酸钡改性新型甲基化环糊精毛细管色谱柱柱行为的研究

在硫酸钡微晶对毛细管内壁改性的基础上,系统制备了甲基环糊精与不同混合固定液的毛细管色谱柱,从柱的分离选择性,惰性,柱效和分析准确性等方面作了较为系统的研究,并对环糊精的分离机理作了初步探索。     

End-functionalized polyethylene oxide coated silica particles for packed capillary column supercritical fluid chromatography

Summary Polyethylene oxide (PEO)-based polymers with hydroxy, methoxy, and aminopropoxy terminal groups were coated on diol functionalized and hexamethyldisilazane end-capped silica particles. Proton-donor and proton-acceptor test solutes, including carboxylic acids, hydroxy-containing compounds, arylamines, and alkylamines were used to evaluate the chromatographic performances of these polymer coated particles under SFC conditions with neat CO₂ as mobile phase. It was found that the particles coated with hydroxy-terminated PEO were suitable for the separation of proton-donor compounds such as hydroxy-containing compounds and carboxylic acids, and the particles coated with aminopropoxy-terminated PEO could be used for the separation of amines. That is, the proton-accepting stationary phase is suitable for the separation of proton accepting solutes, including strong basic alkylamines (pK_b4), using neat CO₂ as mobile phase, while the protondonating stationary phase is suitable for the separation of proton-donating compounds such as carboxylic acids (pK_a4). Hydrogen bond basicity was found to be a critical factor for the chromatography of basic amines. Low volatility acidic and basic drugs were chromatographed using the new stationary phases. The stability of the PEO coated particles was determined by measuring the loss of organic carbon under SFC conditions. It was found that approximately 18 % of the coating (average molecular weight of 15,000) was washed out of the particles by supercritical CO₂ after 7 h at 350 atm and 50°C     

Cyclical games with prohibitions

We consider a certain combinatorial game on a digraph for two cases of the price function. For one case the game in question extends the cyclical game studied in Ehrenfeucht and Mycielski (1979) and Gurvitch, Karzanov and Khachiyan (1988) which, in its turn, is a generalization of the well-known problem of finding a minimum mean cycle in an edge-weighted digraph. We prove the existence of optimal uniform stationary strategies for both cases and give algorithms to find such strategies.This work was partially supported by Chaire municipale, Mairie de Grenoble.     

Synthesis and performance of HPTLC plates modified with cyanopropyl- and octadecyl-trichlorosilane

Chemical modification of commercial high performance thin-layer chromatography plates with various mixtures of cyano-propyltrichlorosilane and octadecyltrichlorosilane is described. Surface coverage by different treatments is demonstrated as well as the variations in chromatographic performance. With regard to the development in aqueous media the utility of CN/ ODS plates compared to ODS plates is also shown.     

Characterization of OV-1/FFAP-mixture coated glass capillary columns used for the separation of free fatty acids

As an alternative to acid pretreated UCON and FFAP capillaries for the analysis of wide-boiling free fatty acid mixtures, OV-1 : FFAP phase mixtures were used on high-temperature silylated inert glass capillary columns. The HETP-carrier gas velocity curves, peak asymmetry factors, coating efficiency, gas phase and stationary phase contributions to the mass transfer resistance were determined for various OV-1 : FFAP ratios. Mixed-phase capillaries showed optimum performance at a 2 : 1 OV-1 : FFAP ratio. The thermal and long-term stability of OV-1-stabilized FFAP columns surpassed those of the UCON and pure FFAP reference column used.     

A unique reversal of elution order during direct enantiomeric resolution of amide derivatives of 1-phenyl-2-aminopropane by high performance liquid chromatography on chiral stationary phases

Enantiomeric amide derivatives of (S)- and (R)-1-phenyl-2-aminopropane (dextro- and levoamphetamine, respectively) were resolved by high performance liquid chromatography on commercially available ionically and covalently bonded chiral stationary phases ((R)-N-(3,5-dinitrobenzoyl)phenylglycine). Ten enantiomeric amide pairs were synthesized and chromatographed on the columns by using a mobile phase of hexane-isopropanol (97 : 3), a flow rate of 2 ml/min, and a column temperature of 20°C. The (R)-isomer of all 10 amides eluted first on the covalent column as did the (R)-isomer of nine derivatives on the ionic column. however, the 3,5-dinitrobenzoyl amide of (S)- amphetamine eluted before the (R)-isomer on the ionic column. This reversal in enantiomeric elution order reveals the complexity of the interactions occurring on these columns and emphasizes the hazards of relying on observed elution order as an a priori indication of absolute configuration.     

A refined physico-chemical model of solute retention in reversed-phase high-performance liquid chromatography with ternary mobile phases

Summary In our previous publication we have introduced a new model of solute retention in RP-HPLC systems with ternary mobile phases of the B+AB₁+AB₂ type (B: acetonitrile or tetrahydrofuran; AB₁: methanol; AB₂: water). That model proposed no stoichiometric differentiation between acetonitrile and tetrahydrofuran, alternatively present in the solvent system; moreover, it made some very rough assumptions only as to the intermolecular interactions among the mobile phase constituents.This paper introduces a significant refinement to the already established retention model, which is based on the simple quantitative relationships between acetonitrile and tetrahydrofuran, and the remaining components of the ternary liquid system. The refined model is tested with same experimental data.     

Chromatographic evaluation of perphenylcarbamoylated β-cyclodextrin bonded stationary phase for micro-high performance liquid chromatography and pressurized capillary electrochromatography

Application of mono (6^A-N-ethylenediamine-6^A-deoxy) perphenylcarbamoylated β-cyclodextrin (β-CD) bonded stationary phase (CSP) in micro-high performance liquid chromatography (micro-HPLC) and pressurized capillary electrochromatography (p-CEC) was firstly presented. A series of racemic α-amidophosphonates were resolved in reversed- and normal-phase modes on this CSP. The investigated chromatographic parameters include retention factor (k′), separation factor (α) and resolution (Rs) of solutes. In addition, the structural variation of the solutes and the experimental factors affecting chiral separations have been examined, including the percentage of alcohol modifier, the linear velocity (u) of the mobile phase, electrical field strength, etc. Baseline separation was achieved for most of the entities. Hydrophobic interaction, steric effect and π-π interaction contribute to the possible mechanism. Comparative results indicate that higher Rs value up to 3.1 was found in micro-HPLC, higher efficiency up to 29,970 in p-CEC.