Some aspects of approach to equilibrium in classical and quantum systems

Investigations of general properties of time evolution of both classical and quantum systems show that the evolution (on a microscopic level) is reversible, and, if there is an approach to equilibrium, it exists only in the sense of weak convergence and necessarily in both directions of time. In this connection attempts to derive irreversibility and the approach to equilibrium in the sense of strong convergence and without any loss of information (using the so-called Lyapunov converters) are discussed. After demonstrating their drawbacks, an alternative approach is proposed based on the spectral properties of the generator of the group. The relevant spectral criteria for the approach of both classical and quantum ensembles to equilibrium are given, and the decisive role of loss of information in obtaining stronger variants of convergence is emphasized. The asymmetry between initial and any other state —consisting of different levels of information needed to prepare the states—is proposed as an adequate explanation of irreversibility. The importance of the method of complex scaling in this context is discussed, and its application in proving some spectral properties in the quantal Hamiltonian formulation is stressed.     

2‐Triazolylpyrimido[1,2,3‐cd]purine‐8,10‐diones via 1,3‐dipolar cycloadditions to 2‐ethynylpyrimido[1,2,3‐cd]purine‐8,10‐dione

This paper presents the synthesis of a series of 5,6‐dihydro‐4H,8H‐pyrimido[1,2,3‐cd]purine‐8,10(9H)‐dione ring system derivatives with a [1,2,3]triazole ring bonded in position 2. The procedure is based on cycloaddition of substituted alkyl azides to the terminal triple bond of 5,6‐dihydro‐2‐ethynyl‐9‐methyl‐4H,8H‐pyrimido[1,2,3‐cd]purine‐8,10(9H)‐dione ( 4 ). This cycloaddition produced two regioisomers ?5,6‐dihydro‐9‐methyl‐2‐(1‐substituted‐1H‐[1,2,3]triazol‐5‐yl)‐4H,8H‐pyrimido[1,2,3‐cd]purine‐8,10(9H)‐dione ( 7 ) and 2‐(1‐substituted‐1H‐[1,2,3]triazol‐4‐yl) derivative 8 . The required 2‐ethynyl deriva tive 4 was obtained from the starting 2‐unsubstituted compound 1 by bromination to yield the 2‐bromo derivative 2 , which was converted by Sonogashira reaction to trimethylsilylethyne 3 and finally, the protective trimethylsilyl group was removed by hydrolysis.     

Determination of brominated phenols in water samples by on-line coupled isotachophoresis with capillary zone electrophoresis

A method for determination of nine brominated phenols as environmental risk compounds was developed by on-line coupled capillary isotachophoresis and capillary zone electrophoresis (ITP–CZE). For ITP step, 1 × 10⁻² mol L⁻¹ hydrochloric acid with 3 × 10⁻² mol L⁻¹ ammediol pH 9.1 was used as the leading electrolyte, and 3 × 10⁻² mol L⁻¹ β-alanine with 2 × 10⁻² mol L⁻¹ sodium hydroxide pH 10.05 was used as the terminating electrolyte. As the background electrolyte for CZE separation, 2.5 × 10⁻² mol L⁻¹ β-alanine with 2.5 × 10⁻² mol L⁻¹ lysine pH 9.6 was used. All electrolytes contained 0.05% or 0.1% (m/v) hydroxyethylcellulose to suppress the electroosmotic flow. UV detection at wavelength 220 nm was used. Detection limits in order of tens of nmol L⁻¹ were achieved. Good repeatability of migration times (less than 0.33% RSD) and good repeatability of peak areas (less than 7.19% RSD) at concentration level 5 × 10⁻⁸ mol L⁻¹ were observed. Developed ITP–CZE method was applied to determination of brominated phenols in spiked tap and river water samples.     

Using of S-(-)-2-hydroxymethyl-1,1-dimethylpyrrolidinium tetrafluoroborate as additive to the background electrolyte in capillary electrophoresis

We synthesised and used new type of quaternary ammonium salt [S-(-)-2-hydroxymethyl-1,1-dimethylpyrrolidinium tetrafluoroborate] as effective additive to acidic background electrolytes. We used this quaternary ammonium salt as effective agent for capillary zone electrophoresis separation of model mixture of five tricyclic antidepressants (amitriptyline, nortriptyline, imipramine, desipramine and clomipramine) as model analytes. We observed that addition of S-(-)-2-hydroxymethyl-1,1-dimethylpyrrolidinium tetrafluoroborate ([HMDP](+) [BF(4)](-)) to acidic background electrolytes leads to suppression of magnitude of electroosmotic flow (EOF) and gradually change the direction of the EOF. Baseline separation of five TAs was achieved by using of 91.1 mmol L(-1) (20 gL(-1)) of [HMDP](+) [BF(4)](-) in 25 mmol L(-1) sodium phosphate pH 2.5, where electroosmotic mobility was -11.3 x 10(-9) m(2) V(-1) s(-1). We achieved baseline separation of five TAs with using of [HMDP](+) [BF(4)](-) as water solution too. We observed that [HMDP](+) [BF(4)](-) can be used as buffer additive, which offers relatively smaller anodic electroosmotic flow instead of cationic surfactants that are mostly used for genarating of anodic electroosmotic flow in capillary electrophoresis.     

CZE Separation of New Drugs for Treatment of Leukemia

Imatinib, bosutinib, dasatinib, pazopanib, erlotinib, canertinib and vatalanib are new developed anticancer drugs, especially for treatment of leukemia. In this article, a fast and high throughput capillary zone electrophoresis method has been developed and validated for analysis of these new drugs in pharmaceutical formulas. The method can be easily utilized for determination of all the drugs in one run what is advantageous for the quality control in pharmaceutical industry because there is no need for changing and optimization of separation conditions when changing the analyte. The separation was performed using an uncoated fused silica capillary with 100 mmol L⁻¹ sodium phosphate buffer pH 2.75, voltage of 25 kV, hydrodynamic injection time of 5 s by 50 mbar, and detection at 214 nm. Under these conditions, the analysis took about 8 min. The validation of all the drugs resulted in recoveries in the range of 84–100 %. The method showed to be precise for all the drugs with RSDs of migration times lower than 0.9 % (interday precision). A very good linearity in the validated range (5–100 μg mL⁻¹) and the limits of detection (LODs) in the range of 0.5–2.0 (μg mL⁻¹) were achieved. Finally, we proved that the method is robust by the Youden’s test. Therefore, our method can be successfully applied for analysis of the real pharmaceutical samples.

     

Two-step resonance energy transfer between dyes in layered silicate films

Single- and two-step fluorescence resonance energy transfer (FRET) was investigated between laser dyes rhodamine 123 (R123), rhodamine 610 (R610), and oxazine 4 (Ox4). The dye molecules played the role of molecular antennas and energy donors (ED, R123), energy acceptors (EA, Ox4), or both (R610). The dye cations were embedded in the films based on layered silicate laponite (Lap) with the thickness of several μm. Optically homogeneous films were prepared directly from dye/Lap colloids. Dye concentration in the films was high enough for FRET to occur but sufficiently low to prevent the formation of large amounts of molecular aggregates. The films were characterized by absorption and fluorescence spectroscopies, and their optical properties were compared with colloid precursors and dye aqueous solutions. The phenomenon of FRET was confirmed by means of steady-state and time-resolved fluorescence spectroscopies. Significant quenching of ED emission in favor of the luminescence from EA molecules was observed. FRET led to the decrease in the lifetimes of excited states of ED molecules. Molecular orientation of dye molecules was determined by polarized absorption and fluorescence spectroscopies. Almost parallel orientation with respect to silicate surface (～30°) was determined for all fluorescent species of the dyes. Theoretical model on relationship between anisotropy and molecular orientation of the fluorophores fits well with measured data. The analysis of anisotropy measurements confirmed the significant role of FRET in the phenomenon of light depolarization.     

Analysis of antiepileptic drugs by capillary gas chromatography with on-column injection

A simple and quick gas chromatographic method has been developed for the determination of up to six commonly used antiepileptic drugs in human serum. The antiepileptics are isolated from serum by solid phase extraction on to a reversed phase sorbent and recovered with ethyl acetate as eluent. The ethyl acetate eluate is suitable for direct on-column injection on to a phenyl methyl siloxane capillary column; hydrogen is used as carrier gas and the compounds are separated with a two-ramp temperature program. Detection is by FID. The reproducibility of the method varies between 2 and 6% RSD, depending on the drug and the level analyzed; limits of detection were found to be 14–51 pg and minimum assayed concentrations in serum were between 14 and 51 ng/ml.     

Comparative DFT study on the <Emphasis Type="Italic">α</Emphasis>-glycosidic bond in reactive species of galactosyl diphosphates

Correct prediction of the structure and energetics along the reaction pathway of the formation or dissociation of the glycosidic bond in sugar phosphates is crucial for the understanding of catalytic mechanism and for the determination of transition state structures of sugar-phosphate processing enzymes. The performance of seven density functional theory (DFT) methods (BLYP, B3LYP, MPW1PW91, MPW1K, MPWB1K, M05 and M05-2X) and two wave function methods (HF and MP2) was tested using four structural models with the activated sugar-phosphate α-glycosidic linkage. The models were chosen based on the crystal structure of the retaining glycosyltransferase LgtC complex with methyl α-d-galactopyranose diphosphate and its 2-fluoro derivative. Results of the MP2 method were used as a benchmark for the other methods. Two structural trends were observed in the calculations: predicted length of the activated C1-O1 glycosidic bond of 1.49–1.63 Å was significantly larger than values of a standard C1-O1 glycosidic bond in crystal structures of carbohydrates (1.39–1.48 Å), and the calculated value depended on the DFT method used. The MPW1K, M05 and M05-2X functionals provided results in closest agreement with those from the MP2 method, the difference being less than 0.02 Å in the calculated glycosidic bond lengths. On the contrary, the BLYP and B3LYP functionals failed to predict sugar diphosphate in the (-sc) conformation as a stable structure. Instead, the only stationary points localized along the C1-O1 dissociation coordinate were oxocarbenium ions at the distance of approximately 2.8 Å. The M05-2X, MPW1K and MPWB1K functionals gave the most reasonable prediction of the thermochemical kinetic parameters, where the formation of the oxocarbenium ion has a slightly endothermic character (0.4–1.7 kJ mol^?1) with an activation barrier of 7.9–9.2 kJ mol^?1.     

Dynamics of Foaming of Polystyrene Particles

September 24, 2006 Summary: In this work, we address the industrially relevant problem of the foaming of expandable polystyrene (PS) impregnated by pentane as a traditional down-stream processing in the suspension polymerization of styrene. Once the polystyrene foam is formed by means of a proper foaming agent, e.g., pentane or fluoro- or chloro-hydrocarbons, the blowing agent diffuses out from the cellular structure. Environmental efforts call for the reduced consumption of blowing agents. The dynamics of foaming of polystyrene particles was recorded video-microscopically in our laboratory as the sequence of images of expanding particle located in the small pressure cell placed under the microscope with sufficient depth of focus. The amount of pentane sorbed in PS was controlled by the length of the impregnation period and was determined independently by gravimetric measurements. Strong dependence of the structure of the produced foam and of the foaming dynamics on the amount of sorbed pentane, temperature and particle size is reported and explanations for some observed foaming phenomena are provided.