Existence and stability results for the hyperbolic Stefan problem with relaxation

Summary The aim of this paper is to study a phase transition model, based on the Cattaneo-Fourier constitutive law for the heat flux and on a relaxed constitutive law for the phase variable. In turn, the model describes fast processes of melting and crystallization with supercooling and superheating effects. We give existence and stability results for the former phase transition problem. Uniqueness is deduced from the stability result On leave from: Lavrent'ev Institute of Hydrodynamics, 630090 Novosibirsk, Academy of Sciences of Russia, Russia.     

Effect of Detachments in Asymmetric Simple Exclusion Processes

Asymmetric simple exclusion processes are important for understanding low-dimensional multi-particle dynamic phenomena. The effect of irreversible detachments of particles on dynamics of asymmetric simple exclusion processes is studied using analytical and computer simulation techniques. In the simplest model, where particles can only detach from a single site in the bulk of the system, a theory is presented and used to calculate explicitly phase diagrams and particle density profiles. The complexity of the phase behavior is discussed in terms of a recent domain-wall theory for driven lattice systems. The theoretical results qualitatively and quantitatively agree with computer Monte Carlo simulations.     

Statistical evaluation of electrospray tandem mass spectra for optimized peptide fragmentation

Liquid chromatography-tandem mass spectrometry (LC-MS/MS) has become the method of choice for the analysis of complex peptide mixtures. It combines the separation power of nanoflow LC with highly specific sequence analysis, allowing automated peptide sequencing with high resolution and throughput. For peptide fragmentation, the current experimental setup uses predefined parameters based on the mass-to-charge ratio of the individual precursor. Suitable parameters are typically established by empirical evaluation of fragment spectra of individual peptides used as standards. As a result, nonoptimal fragment spectra are obtained if peptides show fragmentation behavior different from these standards, which often result in the loss of sequence-specific fragment ion information. Here we describe a statistical approach for the systematic evaluation of the quality of individual peptide fragment spectra based on the calculation of their arithmetic mean and standard deviation. The method utilizes the dependence of these parameters on the difference in electric potential across the collision cell to determine the value that results in maximum information content. We show that the method is applicable to fragment spectra generated from a variety of multiply-charged tryptic peptides, over a wide concentration range, and on different types of mass analyzers. We also show how this novel approach can be used to define optimized collision energy settings over a wide mass-to-charge range.     

2,4,5,7-Tetranitrofluorescein in solutions: novel type of tautomerism in hydroxyxanthene series as detected by various spectral methods

Stepwise dissociation and tautomerism of 2,4,5,7-tetranitrofluorescein (TNF) were studied by using vis-spectroscopy in dimethylsulfoxide (DMSO), in aqueous acetone, and in cetyl-trimethylammonium chloride (CTAC) micellar solutions at ionic strength of the bulk phase 4.00M KCl. The pK(a) values in DMSO and 90 mass% (CH3)2CO as well as the 'apparent'pK(a)(a) values of the substance in micellar media were determined spectrophotometrically. The neutral (molecular) form H2R is found to be completely converted into the colorless lactone. Moreover, the lactonic structure, yellow due to 'nitrophenolate' absorption band, predominates also in the case of TNF dianion R2-. Contrary to the unsubstituted fluorescein, and like 2,4,5,7-tetrabromofluorescein (eosin), the monoanion HR- of TNF with lambda(max) 522-525 nm and E(max) approximately (60-62)x10(3) dm(3)mol(-1)cm(-1) exists mainly as a deeply and intensively colored structure with non-ionized carboxylic and ionized hydroxylic group; its fluorescence spectra in various media are registered. In 90% acetone, the Stokes shift is 1.17x10(3)cm(-1), fluorescence lifetime equals 2.3 ns. An extremely expressed trend to dianion-lactone formation of R2- ion of TNF is confirmed in the systems studied. For TNF in DMSO, in aqueous acetone, in surfactant micelles, and in trichloromethane extracts of ionic associatiates with N(n-Bu)4+ and N(n-Hept)4+, the deeply colored 'quinon-phenolate' dianion, typical for all hydroxyxanthenes, is not registered at all. The sequence of dissociation of functional groups in solution is confirmed using IR spectroscopy in DMSO.     

Alternating field-induced phase transition in zigzag carbon nanotubes

We predict the possibility of spontaneous emergence of a constant electric field in carbon nanotubes if a high-frequency electric field is applied to them. The effect can be related to the nonequilibrium state of the electron subsystem of carbon nanotubes. The characteristics of the spontaneous field with respect to the parameters of the problem under consideration are revealed.     

Statistical analysis of the autoregressive modeling of reverberant speech

Hands-free speech input is required in many modern telecommunication applications that employ autoregressive (AR) techniques such as linear predictive coding. When the hands-free input is obtained in enclosed reverberant spaces such as typical office rooms, the speech signal is distorted by the room transfer function. This paper utilizes theoretical results from statistical room acoustics to analyze the AR modeling of speech under these reverberant conditions. Three cases are considered: (i) AR coefficients calculated from a single observation; (ii) AR coefficients calculated jointly from an M-channel observation (M > 1); and (iii) AR coefficients calculated from the output of a delay-and sum beamformer. The statistical analysis, with supporting simulations, shows that the spatial expectation of the AR coefficients for cases (i) and (ii) are approximately equal to those from the original speech, while for case (iii) there is a discrepancy due to spatial correlation between the microphones which can be significant. It is subsequently demonstrated that at each individual source-microphone position (without spatial expectation), the M-channel AR coefficients from case (ii) provide the best approximation to the clean speech coefficients when microphones are closely spaced (<0.3m).     

Host-guest complexes of carotenoids with beta-glycyrrhizic acid

The structure, stability, and reactivity of the host-guest complexes between a set of carotenoids and the triterpene glycoside, beta-glycyrrhizic acid (GA), were investigated by different physicochemical techniques: high-performance liquid chromatography, optical absorption, and fluorescence spectroscopy. It has been demonstrated recently that the molecular complexes of GA with a number of drugs are characterized by reduced toxicity and increased therapeutic activity of these drugs. In the present work it was found that carotenoids form 1:2 complexes with GA in aqueous solutions as well as in polar organic solvents, methanol, acetonitrile, and dimethylsulfoxide. We assume that the structure of the complex is a cycliclike dimer of GA encapsulating a carotenoid molecule. The stability constants in all solvents are near 10(4) M(-1). In addition, GA forms inclusion complexes with carotenoid radical cations, which results in their stabilization. Complex formation (a) decreases the rate of electron transfer from carotenoids to electron acceptors (Fe3+ or quinone) and (b) considerably increases the lifetime of the carotenoid-quinone charge-transfer complex and the yield of the major product (a carotenoid-quinone adduct). A thermodynamic study shows that hydrophobic interactions are the main driving force of the carotenoid-GA complex formation. These results are important for understanding both the nature of GA complexes and the influence of GA on the therapeutic activity of some drugs. Furthermore, carotenoid-GA complexes could be used for the design of artificial light-harvesting, photoredox, and catalytic systems.     

Superglass phase of 4He

We study different solid phases of 4He, by means of path integral Monte Carlo simulations based on a recently developed worm algorithm. Our study includes simulations that start off from a high- gas phase, which is then "quenched" down to T = 0.2 K. The low-T properties of the system crucially depend on the initial state. While an ideal hcp crystal is a clear-cut insulator, the disordered system freezes into a superglass, i.e., a metastable amorphous solid featuring off-diagonal long-range order and superfluidity.