The role of Mittag-Leffler functions in anomalous relaxation

The inertia-corrected Debye model of rotational Brownian motion of polar molecules was generalized by Coffey et al. [Phys. Rev. E, 65, 32 102 (2002)] to describe fractional dynamics and anomalous rotational diffusion. The linear- response theory of the normalized complex susceptibility was given in terms of a Laplace transform and as a function of frequency. The angular-velocity correlation function was parametrized via fractal Mittag-Leffler functions. Here we apply the latter method and complex-contour integral- representation methods to determine the original time-dependent amplitude as an inverse Laplace transform using both analytical and numerical approaches, as appropriate. (C) 2004 Elsevier B.V. All rights reserved.

Microscopic models for dielectric relaxation in disordered systems

It is shown how the Debye rotational diffusion model of dielectric relaxation of polar molecules (which may be described in microscopic fashion as the diffusion limit of a discrete time random walk on the surface of the unit sphere) may be extended to yield the empirical Havriliak-Negami (HN) equation of anomalous dielectric relaxation from a microscopic model based on a kinetic equation just as in the Debye model. This kinetic equation is obtained by means of a generalization of the noninertial Fokker-Planck equation of conventional Brownian motion (generally known as the Smoluchowski equation) to fractional kinetics governed by the HN relaxation mechanism. For the simple case of noninteracting dipoles it may be solved by Fourier transform techniques to yield the Green function and the complex dielectric susceptibility corresponding to the HN anomalous relaxation mechanism.

Electron-induced hydrogen loss in uracil in a water cluster environment

Low-energy electron-impact hydrogen loss due to dissociative electron attachment (DEA) to the uracil and thymine molecules in a water cluster environment is investigated theoretically. Only the A'-resonance contribution, describing the near-threshold behavior of DEA, is incorporated. Calculations are based on the nonlocal complex potential theory and the multiple scattering theory, and are performed for a model target with basic properties of uracil and thymine, surrounded by five water molecules. The DEA cross section is strongly enhanced when the attaching molecule is embedded in a water cluster. This growth is due to two effects: the increase of the resonance lifetime and the negative shift in the resonance position due to interaction of the intermediate negative ion with the surrounding water molecules. A similar effect was earlier found in DEA to chlorofluorocarbons. 

Rotational spectra induced by vibrations

Mizushima and Venkateswarlu showed in 1953 that certain molecules have the property that excited vibrational states may possess rotational spectra even when the rotational spectrum of the ground vibrational state is forbidden by symmetry. We call such a spectrum a vibrationally induced rotational spectrum, and have made a systematic examination of the point groups which permit such behaviour. We also give formulae for the approximate line frequencies and intensities in these spectra, and discuss some of the problems involved in observing them. The spectra can only arise from degenerate vibrational states, and are of three possible types: i) symmetric top perpendicular spectra, shown by molecules belonging to the point groups Dnh, Dn and Cnh, where n is odd; (ii) symmetric top parallel spectra, shown by molecules belonging to Dnd and S2n, where n is even; and (iii) spherical top spectra, shown by molecules belonging to T or Td. Excited vibrational states of polar molecules of point groups Cnv or Cn, where n is odd, may also possess vibrationally induced perpendicular components of type (i), in addition to their ordinary parallel spectra. In addition to the above limitations on the point groups there are, in general, limitations on the symmetry species of the degenerate vibrational states.

Thomas-Fermi ground state of dipolar fermions in a circular storage ring

Recent developments in the field of ultracold gases has led to the production of degenerate samples of polar molecules. These have large static electric-dipole moments, which in turn causes the molecules to interact strongly. We investigate the interaction of polar particles in waveguide geometries subject to an applied polarizing field. For circular waveguides, tilting the direction of the polarizing field creates a periodic inhomogeneity of the interparticle interaction. We explore the consequences of geometry and interaction for stability of the ground state within the Thomas-Fermi model. Certain combinations of tilt angles and interaction strengths are found to preclude the existence of a stable Thomas-Fermi ground state. The system is shown to exhibit different behavior for quasi-one-dimensional and three-dimensional trapping geometries.

Cytotoxicity of Diepoxybutane and Epichlorohydrin in Relation to Stages of the Cell Cycle

Work conducted in the Millard Biochemistry Research Laboratory examines the dual nature of molecules as carcinogens and anti-tumor agents through the molecular mechanisms of duplex DNA damage by bifunctional alkylating agents. Diepoxybutane (DEB) and epichlorohydrin (ECH) are polar molecules that form covalent DNA interstrand lesions by cross-linking the N7 position of deoxyguanosine residues. A recent experiment indicated that ECH preferentially targets nuclear DNA over mitochondrial DNA, whereas DEB shows similar rates of lesion formation for both loci. It was concluded that preferential targeting of nuclear DNA results from relatively poor uptake of ECH across the mitochondrial membrane. The objective of my honors research was to determine if the cytotoxicities of DEB and ECH vary according to the presence of the nuclear envelope in 6C2 chicken erythro-progenitor cells. The cytotoxicity of DEB and ECH was compared between cells randomly distributed throughout the cell cycle (Go/G, and S » G2/M) and cells enriched in G2/M stages. Results indicated that ECH is more cytotoxic than DEB in both unsynchronized control 6C2 cells and synchronized 6C2 cells enriched in G2/M stages of the cell cycle. Treatment with either bifunctional alkylating agent induced greater cytotoxicity in 6C2 cells enriched in G2/M stages than in unsynchronized control 6C2 cells, suggesting that the presence of the nuclear envelope-or any plasma membrane-may inhibit the reactivity of DEB and ECH.

A REVIEW OF OPTICALLY PUMPED FAR-INFRARED LASER LINES FROM METHANOL ISOTOPES

The technique of optical pumping in polar molecules is the most efficient for Far-Infrared (FIR) laser generation, providing also a versatile and powerful tool for molecular spectroscopy in this spectral region. Methanol (CH3OH) and its isotopic varieties are the best media for optically pumped FIR laser, with over thousand lines observed, and the most widely used for investigations and applications. In this sense, it is important organize and make available catalogues of FIR laser lines as complete as possible. Since the last critical reviews of 1984 [1] on methanol and its isotopic varieties [2,3,4], over hundred papers have been published dealing with hundreds of new FIR laser lines. In 1992 a review of FIR laser lines from CH3OH was presented [5]. In this communication we extend this work to the other methanol isotopes, namely CH3OD, CD3OH, CD3OD, (CH3OH)-C-13, (CD3OH)-C-13, (CD3OD)-C-13, (CH3OH)-O-18, CH2DOH, CHD2OH and CH2DOD.

Estudo de solvatocromismo em líquidos moleculares orgânicos via método seqüencial Monte Carlo/Mecânica Quântica

Utilizou-se o método seqüencial Monte Carlo / Mecânica Quântica para obterem-se os desvios de solvatocromismo e os momentos de dipolo dos sistemas de moléculas orgânicas: Uracil em meio aquoso, -Caroteno em Ácido Oléico, Ácido Ricinoléico em metanol e em Etanol e Ácido Oléico em metanol e em Etanol. As otimizações das geometrias e as distribuições de cargas foram obtidas através da Teoria do Funcional Densidade com o funcional B3LYP e os conjuntos de funções de base 6-31G(d) para todas as moléculas exceto para a água e Uracil, as quais, foram utilizadas o conjunto de funções de base 6-311++G(d,p). No tratamento clássico, Monte Carlo, aplicou-se o algoritmo Metropólis através do programa DICE. A separação de configurações estatisticamente relevantes para os cálculos das propriedades médias foi implementada com a utilização da função de auto-correlação calculada para cada sistema. A função de distribuição radial dos líquidos moleculares foi utilizada para a separação da primeira camada de solvatação, a qual, estabelece a principal interação entre soluto-solvente. As configurações relevantes da primeira camada de solvatação de cada sistema foram submetidas a cálculos quânticos a nível semi-empírico com o método ZINDO/S-CI. Os espectros de absorção foram obtidos para os solutos em fase gasosa e para os sistemas de líquidos moleculares comentados. Os momentos de dipolo elétrico dos mesmos também foram obtidos. Todas as bandas dos espectros de absorção dos sistemas tiveram um desvio para o azul, exceto a segunda banda do sistema de Beta-Caroteno em Ácido Oléico que apresentou um desvio para o vermelho. Os resultados encontrados apresentam-se em excelente concordância com os valores experimentais encontrados na literatura. Todos os sistemas tiveram aumento no momento de dipolo elétrico devido às moléculas dos solventes serem moléculas polares. Os sistemas de ácidos graxos em álcoois apresentaram resultados muito semelhantes, ou seja, os ácidos graxos mencionados possuem comportamentos espectroscópicos semelhantes submetidos aos mesmos solventes. As simulações através do método seqüencial Monte Carlo / Mecânica Quântica estudadas demonstraram que a metodologia é eficaz para a obtenção das propriedades espectroscópicas dos líquidos moleculares analisados.

Effect of temperature on salt-salt aqueous biphasic systems: manifestations of upper critical solution temperature

Water-miscible ionic liquids (ILs) may be salted out using kosmotropic salts such as potassium phosphate (K3PO4) to form salt-salt aqueous biphasic systems (ABS). The effect of temperature on these systems has been studied using phase diagrams and it is observed that the degree of binodal shift decreases (requiring lower IL and kosmotropic salt concentrations) with the increase of temperature following the trend [C(4)mim]Cl > [C(4)py]Cl > [C(4)mmim] Cl > [N-4444]Cl. This trend can be correlated with the decreasing hydrogen bonding abilities of each salt. The phase behavior was also interpreted on the basis of critical solution temperature behavior of pure aqueous ionic liquid solutions. Additionally, the distribution of alcohols in these systems was studied as a function of temperature and it was found that the distribution ratios did not change with changes in temperature. The Gibbs energy of transfer of a methylene group in these systems and correlation to tie-line length was also determined. It was concluded that while the miscibility of alcohols increases in the ILs with increasing temperature, phase divergence in the aqueous biphasic system decreases, and thus these competing forces tend to cancel each other out for small polar molecules. A comparison is provided for the response to temperature in the currently studied salt-salt systems and analogous ABS formed by the addition of hydrophilic polymers to kosmotropic salts (polymer-salt) or other polymers (polymer-polymer).

Loading a K-39 crossed optical dipole trap from a magneto-optical trap

In this work, we have applied sub-Doppler laser cooling to a K-39 magneto-optical trap in order to load a 1071 nm crossed optical dipole trap. The number of atoms loaded into the dipole trap was characterized as a function of the frequency and intensity of the cooling and repump laser beams. For the optimum conditions, the dipole trap has about 2 x 10(6) atoms at an atomic density of 2 x 10(12) cm(-3), with a temperature of about 10 mu K. This technique is a very simple procedure to load a K-39 optical dipole trap without a previous magnetic evaporative cooling step and may find application in other atomic physic systems.

Targeting the Blood-brain Barrier with a Non-canonical Iron-mimicry Mechanism

Treatment of central nervous system (CNS) diseases is limited by the blood-brain barrier (BBB), a selective vascular interface restricting passage of most molecules from blood into brain. Specific transport systems have evolved allowing circulating polar molecules to cross the BBB and gain access to the brain parenchyma. However, to date, few ligands exploiting such systems have proven clinically viable in the setting of CNS diseases. We reasoned that combinatorial phage-display screenings in vivo would yield peptides capable of crossing the BBB and allow for the development of ligand-directed targeting strategies of the brain. Here we show the identification of a peptide mediating systemic targeting to the normal brain and to an orthotopic human glioma model. We demonstrate that this peptide functionally mimics iron through an allosteric mechanism and that a non-canonical association of (i) transferrin, (ii) the iron-mimic ligand motif, and (iii) transferrin receptor mediates binding and transport of particles across the BBB. We also show that in orthotopic human glioma xenografts, a combination of transferrin receptor over-expression plus extended vascular permeability and ligand retention result in remarkable brain tumor targeting. Moreover, such tumor targeting attributes enables Herpes simplex virus thymidine kinase-mediated gene therapy of intracranial tumors for molecular genetic imaging and suicide gene delivery with ganciclovir. Finally, we expand our data by analyzing a large panel of primary CNS tumors through comprehensive tissue microarrays. Together, our approach and results provide a translational avenue for the detection and treatment of brain tumors.

Rotational constants and structure of para-difluorobenzene determined by femtosecond Raman coherence spectroscopy: A new transient type

Femtosecond Raman rotational coherence spectroscopy (RCS) detected by degenerate four-wave mixing is a background-free method that allows to determine accurate gas-phase rotational constants of non-polar molecules. Raman RCS has so far mostly been applied to the regular coherence patterns of symmetric-top molecules, while its application to nonpolar asymmetric tops has been hampered by the large number of RCS transient types, the resulting variability of the RCS patterns, and the 10³–10⁴ times larger computational effort to simulate and fit rotational Raman RCS transients. We present the rotational Raman RCS spectra of the nonpolar asymmetric top 1,4-difluorobenzene (para-difluorobenzene, p-DFB) measured in a pulsed Ar supersonic jet and in a gas cell over delay times up to ~2.5 ns. p-DFB exhibits rotational Raman transitions with ΔJ = 0, 1, 2 and ΔK = 0, 2, leading to the observation of J −, K −, A −, and C–type transients, as well as a novel transient (S–type) that has not been characterized so far. The jet and gas cell RCS measurements were fully analyzed and yield the ground-state (v = 0) rotational constants Aₒ = 5637.68(20) MHz, Bₒ = 1428.23(37) MHz, and Cₒ = 1138.90(48) MHz (1σ uncertainties). Combining the Aₒ, Bₒ, and Cₒ constants with coupled-cluster with single-, double- and perturbatively corrected triple-excitation calculations using large basis sets allows to determine the semi-experimental equilibrium bond lengths rₑ(C₁–C₂) = 1.3849(4) Å, rₑ(C₂–C³) = 1.3917(4) Å, rₑ(C–F) = 1.3422(3) Å, and rₑ(C₂–H₂) = 1.0791(5) Å.

On the equilibrium and dynamic behavior of alcohol vapors in activated carbon

As alcohol molecules such as methanol and ethanol have both polar and non-polar groups, their adsorption behavior is governed by the contributions of dispersion interaction (alkyl group) and hydrogen bonding (OH group). In this paper, the adsorption behavior of alcohol molecules and its effect on transport processes are elucidated. From the total permeability (B-T) of alcohol molecules in activated carbon, an adsorption mechanism is proposed, describing well the experimental data, by taking combination effects of clustering, entering micropores, layering and pore filling processes. Unlike the case of non-polar compounds, it was found that at low pressures there are two rises in the BT of alcohol molecules in activated carbon. The first rise is due to the major contribution of surface diffusion to the transport (which is the case of non-polar molecules) and the second one may be associated with cluster formation at the edge of micropores and entering micropores when the clusters are sufficiently large enough to induce a dispersive energy. In addition the clusters formed may enhance surface diffusion at low pressures and hinder gas phase diffusion and flow in meso/macropores. (c) 2006 Elsevier Ltd. All fights reserved.

Flow Characteristics of Non-Polar Organic Liquids with Small Molecules in a Microchannel

用去离子水及有机液体在内径约为25μm的石英圆管内进行了流量特性实验.液体分子量范围为18～160,动力黏性系数的范围为0.5～1 mPa.s.实验雷诺数范围为Re<8.所用有机液体为:四氯化碳、乙基苯及环己烷都是非极性液体,其分子结构尺度小于1 nm.实验结果表明,在定常层流条件下,圆管内的液体流量与两端压力差成正比,其压力-流量关系仍符合经典的Hagen-Poiseuille流动.这说明非极性小分子有机液体在本实验所用微米尺度管道中其流动规律仍符合连续介质假设.鉴于微尺度流动实验的特殊性,文中还介绍了微流动实验装置,分析了微尺度流动测量误差来源及提高测量精度的措施.

Simplified theory of wideband spectra of liquid H2O and D2O (from 0 to 1000 cm(-1)) due to reorienting polar and vibrating H-bonded water molecules

A semi-phenomenological molecular model is presented, which is capable of describing with the use of analytical formulae, the wideband dielectric(1) and far-infrared spectra of ordinary and heavy water. In the model the vector of a dipole moment is presented as a sum of two components. The absolute value of the first one is constant; the second one changes harmonically with time. The key aspect of this work is consideration of FIR spectra due to the second component. In the context of the modified hybrid model presented in the work, reorientation of the dipoles in the rectangular potential well is considered, as a result of which the librational (near 700 cm (-1)) and translational (near 200 cm (-1)) absorption bands and the microwave Debye relaxation spectrum arise. It is shown that the time-dependent part of a dipole moment contributes most to the translational band, the relevant mechanism is taken to be stretching vibration of the H-bonded molecules. Previous linear-response molecular models were unsuccessful in describing this band (in heavy water) in terms of the complex dielectric permittivity. The spatial and time scales characteristic of water are estimated. (C) 2002 Elsevier Science B.V. All rights reserved.