Macroscopic Fluctuation Theory for Stationary Non-Equilibrium States

We formulate a dynamical fluctuation theory for stationary non-equilibrium states (SNS) which is tested explicitly in stochastic models of interacting particles. In our theory a crucial role is played by the time reversed dynamics. Within this theory we derive the following results: the modification of the Onsager–Machlup theory in the SNS; a general Hamilton–Jacobi equation for the macroscopic entropy; a non-equilibrium, nonlinear fluctuation dissipation relation valid for a wide class of systems; an H theorem for the entropy. We discuss in detail two models of stochastic boundary driven lattice gases: the zero range and the simple exclusion processes. In the first model the invariant measure is explicitly known and we verify the predictions of the general theory. For the one dimensional simple exclusion process, as recently shown by Derrida, Lebowitz, and Speer, it is possible to express the macroscopic entropy in terms of the solution of a nonlinear ordinary differential equation; by using the Hamilton–Jacobi equation, we obtain a logically independent derivation of this result.     

羧基膦酸改性氧化锆固定相的制备及其色谱性能

用十二胺-N乙酸-N亚甲基膦酸（DAPA）改性氧化锆制备了一种新的锆基质色谱固定相（DAPAZ），研究发现，DAPA在氧化锆表面有两种结合方式：红外光谱中1611cm^-1处的特征吸收表明羧基主要与胺基形成偶极离子，以羧酸根离子形式存在，大部分的DAPA分子通过膦酸基团与氧化锆结合；而与钼酸的显色反应则表明有少量DAPA以羧居与氧化锆结合，另外，对固定相的屏蔽效应、碱性条件（pH9．5）下的稳定性等色谱性能的研究也证实这两种吸附方式同时存在，但以膦酸基结合为主。     

A Unified Approach to the Proportional Relation for Discrete-Time Single-Server Queues

It is well known that a simple relation called proportional relation holds for some queueing models, that is, the stationary queue length distribution of one system can be expressed as the product of a constant and the distribution of another system which is different only in the buffer capacity. Recently, the proportional relation has been verified for various discrete-time single-server queues with correlated arrivals, where it has been also shown that the proportional constant can be expressed in terms of the distribution of one system. This implies that the stationary queue length distribution of one system can be completely expressed in terms of the distribution of the other system. In this paper, we consider a generalized model of discrete-time single-server queue, which covers all previous ones, and give a simple and unified proof to the proportional relation as well as the expression of the proportional constant.     

Chromatographic retention and thermodynamics of the adsorption of α-phenylcarboxylic acid enantiomers on a chiral stationary phase with a grafted antibiotic eremomycin: Effect of eluent pH

The effect of the pH of aqueous–ethanol mobile phases on the retention and adsorption thermodynamics of the optical isomers of several α-phenylcarboxylic acids on a chiral stationary phase “Nautilus-E” with a grafted antibiotic, eremomycin, was studied. It was determined that ionic interactions dominated in the retention of α-phenylcarboxylic acid enantiomers. It was revealed that the Nautilus-E adsorbent was most selective to acids, the adsorption of which is an enthalpy-controlled process. It was found that the nature of adsorption was changed by varying the eluent pH. The dissociation constants of α-phenylcarboxylic acids have been determined by chromatographic method in aqueous–ethanol solution. A statistical analysis of the phenomenon of enthalpy-entropy compensation was performed, and a manifestation of the false compensation effect was established. It was shown that the spatial configuration of the molecule and the presence of polar groups on a chiral carbon atom in its structure have a greater influence on the chiral recognition mechanism of acid enantiomers using the Nautilus-E CSP.     

Synthesis, characterization, and high-performance liquid chromatographic evaluation of C14 stationary phases containing branched and unbranched alkyl groups

Reversed-phase materials with branched and unbranched alkyl groups were prepared by modifying porous, spherical silica gel in a two-step reaction—immobilization of a trifunctional alkoxysilane (3-glycidoxypropyltrimethoxysilane) on the silica surface followed by reaction with a branched and an unbranched octanoic acid. The chromatographic sorbents were characterized by solid-state ²⁹Si and ¹³C NMR spectroscopy. The chromatographic behaviour of the stationary phases was evaluated by use of a test mixture according to the Standard Reference Material 870 set from the US National Institute of Standards and Technology, in order to study the effect of branched and unbranched alkyl chains.     

Covalently bonded DNA aptamer chiral stationary phase for the chromatographic resolution of adenosine

In this work, a target-specific aptamer chiral stationary phase (CSP) based on the oligonucleotidic selector binding to silica particles through a covalent linkage was developed. An anti-d-adenosine aptamer was coupled, using an in-situ method, by way of an amide bond to macroporous carboxylic acid based silica. Frontal chromatography analysis was performed to evaluate the column properties, i.e., determination of the stationary phase binding capacity and the dissociation constant of the target-immobilized aptamer complex. It was found that such covalent immobilization was able to maintain the aptamer binding properties at a convenient level for an efficient enantioseparation. Subsequently, the separation of adenosine enantiomers was investigated under different operating conditions, including changes in the eluent’s ionic strength and the proportion of organic modifiers as well as column temperatures. It was demonstrated that, under various conditions of use and storage, the present CSP was stable over time.     

Generalized stationary random fields with linear regressions - an operator approach

Existence, -stationarity and linearity of conditional expectations of square integrable random sequences satisfying

for a real sequence is examined. The analysis is reliant upon the use of Laurent and Toeplitz operator techniques.

     

Column temperature programming in enantioseparation of dihydropyrimidinone compounds using derivatized cellulose and amylose chiral stationary phases

We report the application of column temperature programs as a tool to examine unusual temperature-induced behaviors of polysaccharide chiral stationary phases (CSPs). Using dihydropyrimidinone (DHP) compounds as probes we observed the heating (10-50 degrees C) and cooling (50-10 degrees C) van't Hoff plots of retention factors and/or selectivities of DHP compounds were not superimposable on AD, IA, and AS-H columns solvated with ethanol (EtOH)/n-hexane (n-Hex) mobile phases. The plots were not superimposable on AD, IB, and AS-H columns solvated with 2-propanol (2-PrOH)/n-Hex mobile phases. The thermally induced path-dependant behaviors were caused by slow equilibration as evidenced by the disappearance of the hysteresis in the second heating to cooling cycle and in a cooling to heating cycle. From the step-temperature program (10-50-10 degrees C), only EtOH solvated AD and AS-H phases showed the change of retention factors and/or selectivities with time while only 2-PrOH solvated AS-H phase showed similar behaviors.     

Kinetic and equilibrium study of the enantioseparation of paroxetine intermediate on amylose and tartaric acid-based chiral stationary phases

trans-(-)-Paroxetine is a selective 5-hydroxytryptamine (5-HT) reuptake inhibitor currently used as an antidepressant. trans-(+/-)-3-Ethoxycarbonyl-4-(4'-fluorophenyl)-1-methylpiperidine-2,6-dione is an important intermediate of trans-(-)-paroxetine. It was separated on amylose and tartaric acid-based chiral stationary phases by HPLC. The equilibrium constants and overall mass transfer coefficients together with the axial dispersion coefficients were experimentally determined by moment analysis based on the lumped kinetic model of chromatography. In case of Kromasil CHI-TBB, the equilibrium constants measured were found to be 8.36 and 9.37 for trans-(+) and trans-(-) enantiomers, respectively. For Chiralpak AD-H, the equilibrium constants were 6.68 and 4.13 for trans-(+) and trans-(-) enantiomers, respectively. The axial dispersion coefficients of both enantiomers on Kromasil CHI-TBB column were about one order of magnitude greater than on Chiralpak AD-H. Fast kinetics of mass transfer in both chiral stationary phases was observed. Their overall mass transfer coefficients on Kromasil CHI-TBB and Chiralpak AD-H were 32.12, 33.18, 26.50, 46.85 s(-1) for trans-(+) and trans-(-) enantiomers, respectively. The parameters obtained were utilized to simulate the elution profiles, and the simulated and experimental results match well, which confirmed that the parameters obtained in this study were valid.