Differential Cocrystallization Behavior of Isomeric Pyridine Carboxamides toward Antitubercular Drug Pyrazinoic Acid

Pyrazinoic acid, the active form of the antitubercular pro-drug Pyrazinamide, is an amphiprotic molecule containing carboxylic acid and pyridine groups and therefore can form both salts and cocrystals with relevant partner molecules. Cocrystallization of pyrazinoic acid with isomeric pyridine carboxamide series resulted in a dimorphic mixed-ionic complex with isonicotinamide and in eutectics with nicotinamide and picolinamide, respectively. It is observed that with alteration of the carboxamide position, steric and electrostatic compatibility issues between molecules of the combination emerge and affect intermolecular interactions and supramolecular growth, thus leading to either cocrystal or eutectic for different pyrazinoic acid-pyridine carboxamide combinations. Intermolecular interaction energy calculations have been performed to understand the role of underlying energetics on the formation of cocrystal/eutectic in different combinations. On the other hand, two molecular salts with piperazine and cytosine and a gallic acid cocrystal of the drug were obtained, and their X-ray crystal structures were also determined in this work.

The Self-Association of Graphane Is Driven by London Dispersion and Enhanced Orbital Interactions

We investigated the nature of the cohesive energy between graphane sheets via multiple CH center dot center dot center dot HC interactions, using density functional theory (DFT) including dispersion correction (Grimmes D3 approach) computations of n]graphane sigma dimers (n = 6-73). For comparison, we also evaluated the binding between graphene sheets that display prototypical pi/pi interactions. The results were analyzed using the block-localized wave function (BLW) method, which is a variant of ab initio valence bond (VB) theory. BLW interprets the intermolecular interactions in terms of frozen interaction energy (Delta E-F) composed of electrostatic and Pauli repulsion interactions, polarization (Delta E-pol), charge-transfer interaction (Delta E-CT), and dispersion effects (Delta E-disp). The BLW analysis reveals that the cohesive energy between graphane sheets is dominated by two stabilizing effects, namely intermolecular London dispersion and two-way charge transfer energy due to the sigma CH -> sigma*(HC) interactions. The shift of the electron density around the nonpolar covalent C-H bonds involved in the intermolecular interaction decreases the C-H bond lengths uniformly by 0.001 angstrom. The Delta E-CT term, which accounts for similar to 15% of the total binding energy, results in the accumulation of electron density in the interface area between two layers. This accumulated electron density thus acts as an electronic glue for the graphane layers and constitutes an important driving force in the self-association and stability of graphane under ambient conditions. Similarly, the double faced adhesive tape style of charge transfer interactions was also observed among graphene sheets in which it accounts for similar to 18% of the total binding energy. The binding energy between graphane sheets is additive and can be expressed as a sum of CH center dot center dot center dot HC interactions, or as a function of the number of C-H bonds.

Correlation equations for average deposition rate coefficients of nanoparticles in a cylindrical pore

Nanoparticle deposition behavior observed at the Darcy scale represents an average of the processes occurring at the pore scale. Hence, the effect of various pore-scale parameters on nanoparticle deposition can be understood by studying nanoparticle transport at pore scale and upscaling the results to the Darcy scale. In this work, correlation equations for the deposition rate coefficients of nanoparticles in a cylindrical pore are developed as a function of nine pore-scale parameters: the pore radius, nanoparticle radius, mean flow velocity, solution ionic strength, viscosity, temperature, solution dielectric constant, and nanoparticle and collector surface potentials. Based on dominant processes, the pore space is divided into three different regions, namely, bulk, diffusion, and potential regions. Advection-diffusion equations for nanoparticle transport are prescribed for the bulk and diffusion regions, while the interaction between the diffusion and potential regions is included as a boundary condition. This interaction is modeled as a first-order reversible kinetic adsorption. The expressions for the mass transfer rate coefficients between the diffusion and the potential regions are derived in terms of the interaction energy profile. Among other effects, we account for nanoparticle-collector interaction forces on nanoparticle deposition. The resulting equations are solved numerically for a range of values of pore-scale parameters. The nanoparticle concentration profile obtained for the cylindrical pore is averaged over a moving averaging volume within the pore in order to get the 1-D concentration field. The latter is fitted to the 1-D advection-dispersion equation with an equilibrium or kinetic adsorption model to determine the values of the average deposition rate coefficients. In this study, pore-scale simulations are performed for three values of Peclet number, Pe = 0.05, 5, and 50. We find that under unfavorable conditions, the nanoparticle deposition at pore scale is best described by an equilibrium model at low Peclet numbers (Pe = 0.05) and by a kinetic model at high Peclet numbers (Pe = 50). But, at an intermediate Pe (e.g., near Pe = 5), both equilibrium and kinetic models fit the 1-D concentration field. Correlation equations for the pore-averaged nanoparticle deposition rate coefficients under unfavorable conditions are derived by performing a multiple-linear regression analysis between the estimated deposition rate coefficients for a single pore and various pore-scale parameters. The correlation equations, which follow a power law relation with nine pore-scale parameters, are found to be consistent with the column-scale and pore-scale experimental results, and qualitatively agree with the colloid filtration theory. These equations can be incorporated into pore network models to study the effect of pore-scale parameters on nanoparticle deposition at larger length scales such as Darcy scale.

Multi-scale analysis of AFM tip and surface interactions

Thoroughly understanding AFM tip-surface interactions is crucial for many experimental studies and applications. It is important to realize that despite its simple appearance, the system of tip and sample surface involves multiscale interactions. In fact, the system is governed by a combination of molecular force (like the van der Waals force), its macroscopic representations (such as surface force) and gravitational force (a macroscopic force). Hence, in the system, various length scales are operative, from sub-nanoscale (at the molecular level) to the macroscopic scale. By integrating molecular forces into continuum equations, we performed a multiscale analysis and revealed the nonlocality effect between a tip and a rough solid surface and the mechanism governing liquid surface deformation and jumping. The results have several significant implications for practical applications. For instance, nonlocality may affect the measurement accuracy of surface morphology. At the critical state of liquid surface jump, the ratio of the gap between a tip and a liquid dome (delta) over the dome height (y(o)) is approximately (n-4) (for a large tip), which depends on the power law exponent n of the molecular interaction energy. These findings demonstrate that the multiscale analysis is not only useful but also necessary in the understanding of practical phenomena involving molecular forces. (c) 2007 Elsevier Ltd. All rights reserved.

Topics in LIGO-related physics: interferometric speed meters and tidal work

In the quest to develop viable designs for third-generation optical interferometric gravitational-wave detectors, one strategy is to monitor the relative momentum or speed of the test-mass mirrors, rather than monitoring their relative position. The most straightforward design for a speed-meter interferometer that accomplishes this is described and analyzed in Chapter 2. This design (due to Braginsky, Gorodetsky, Khalili, and Thorne) is analogous to a microwave-cavity speed meter conceived by Braginsky and Khalili. A mathematical mapping between the microwave speed meter and the optical interferometric speed meter is developed and used to show (in accord with the speed being a quantum nondemolition observable) that in principle the interferometric speed meter can beat the gravitational-wave standard quantum limit (SQL) by an arbitrarily large amount, over an arbitrarily wide range of frequencies . However, in practice, to reach or beat the SQL, this specific speed meter requires exorbitantly high input light power. The physical reason for this is explored, along with other issues such as constraints on performance due to optical dissipation.

Chapter 3 proposes a more sophisticated version of a speed meter. This new design requires only a modest input power and appears to be a fully practical candidate for third-generation LIGO. It can beat the SQL (the approximate sensitivity of second-generation LIGO interferometers) over a broad range of frequencies (~ 10 to 100 Hz in practice) by a factor h/h_SQL ~ √W^(SQL)_(circ)/W_circ. Here W_circ is the light power circulating in the interferometer arms and W_SQL ≃ 800 kW is the circulating power required to beat the SQL at 100 Hz (the LIGO-II power). If squeezed vacuum (with a power-squeeze factor e^-2R) is injected into the interferometer's output port, the SQL can be beat with a much reduced laser power: h/h_SQL ~ √W^(SQL)_(circ)/W_circe^-2R. For realistic parameters (e^-2R ≃ 10 and W_circ ≃ 800 to 2000 kW), the SQL can be beat by a factor ~ 3 to 4 from 10 to 100 Hz. [However, as the power increases in these expressions, the speed meter becomes more narrow band; additional power and re-optimization of some parameters are required to maintain the wide band.] By performing frequency-dependent homodyne detection on the output (with the aid of two kilometer-scale filter cavities), one can markedly improve the interferometer's sensitivity at frequencies above 100 Hz.

Chapters 2 and 3 are part of an ongoing effort to develop a practical variant of an interferometric speed meter and to combine the speed meter concept with other ideas to yield a promising third- generation interferometric gravitational-wave detector that entails low laser power.

Chapter 4 is a contribution to the foundations for analyzing sources of gravitational waves for LIGO. Specifically, it presents an analysis of the tidal work done on a self-gravitating body (e.g., a neutron star or black hole) in an external tidal field (e.g., that of a binary companion). The change in the mass-energy of the body as a result of the tidal work, or "tidal heating," is analyzed using the Landau-Lifshitz pseudotensor and the local asymptotic rest frame of the body. It is shown that the work done on the body is gauge invariant, while the body-tidal-field interaction energy contained within the body's local asymptotic rest frame is gauge dependent. This is analogous to Newtonian theory, where the interaction energy is shown to depend on how one localizes gravitational energy, but the work done on the body is independent of that localization. These conclusions play a role in analyses, by others, of the dynamics and stability of the inspiraling neutron-star binaries whose gravitational waves are likely to be seen and studied by LIGO.

Studying adsorbent dynamics on a quartz crystal resonator using its nonlinear electrical response

The quartz crystal resonator has been traditionally employed in studying surface-confined physisorbed films and particles by measuring dissipation and frequency shifts. However, theoretical interpretation of the experimental observations is often challenged due to limited understanding of physical interaction mechanisms at the interfaces involved. Here we model a physisorbed interaction between particles and gold electrode surface of a quartz crystal and demonstrate how the nonlinear modulation of the electric response of the crystal due to the nonlinear interaction forces may be used to study the dynamics of the particles. In particular, we show that the graphs of the deviation in the third Fourier harmonic response versus oscillation amplitude provide important information about the onset, progress and nature of sliding of the particles. The graphs also present a signature of the surface-particle interaction and could be used to estimate the interaction energy profile. Interestingly, the insights gained from the model help to explain some of the experimental observations with physisorbed streptavidin-coated polystyrene microbeads on quartz resonators. © 2012 Elsevier B.V. All rights reserved.

Depolarization blueshift in intersubband transitions of triangular quantum wires

Major State Basic Research Project 973 program of China 2006CB604907;National Science Foundation of China 60776015 60976008;863 High Technology R&D Program of China 2007AA03Z402

InAs/GaAs single-electron quantum dot qubit

The time evolution of the quantum mechanical state of an electron is calculated in the framework of the effective-mass envelope function theory for an InAs/GaAs quantum dot. The results indicate that the superposition state electron density oscillates in the quantum dot, with a period on the order of femtoseconds. The interaction energy E-ij between two electrons located in different quantum dots is calculated for one electron in the ith pure quantum state and another in the jth pure quantum state. We find that E-11]E-12]E-22, and E-ij decreases as the distance between the two quantum dots increases. We present a parameter-phase diagram which defines the parameter region for the use of an InAs/GaAs quantum dot as a two-level quantum system in quantum computation. A static electric field is found to efficiently prolong the decoherence time. Our results should be useful for designing the solid-state implementation of quantum computing. (C) 2001 American Institute of Physics.

Molecular weight dependence of phase Behavior of PEO/P(EO-b-DMS) blends: Application of Sanchez-Lacombe lattice fluid theory

Molecular weight dependence of phase separation behavior of the Poly (ethylene oxide) (PEO)/Poly(ethylene oxide-block-dimethylsiloxane) (P(EO-b-DMS)) blends was investigated by both experimental and theoretical methods. The cloud point curves of PEO/P(EO-b-DMS) blends were obtained by turbidity method. Based on Sanchez-Lacombe lattice fluid theory (SLLFT), the adjustable parameter, epsilon*(12)/k (quantifying the interaction energy between different components), was evaluated by fitting the experimental data in phase diagrams. To calculate the spinodals, binodals, and the volume changes of mixing for these blends, three modified combining rules of the scaling parameters for the block copolymer were introduced.

Pressure effects on thermodynamics of phase behavior in polystyrene/methylcyclohexane solutions

The calculations presented in this paper are based on the Sanchez-Lacombe (SL) lattice fluid theory. The interaction energy parameter, g*(12)/k, required in this approach was obtained by fitting the cloud points of polystyrene (PS) /methyleyclohexane (MCH) polymer solutions under pressure. The SL lattice fluid theory was used to calculate the spinodals, the binodals, and the Flory-Huggins (FH) interaction parameter of the solutions. The calculated results show that the SL lattice fluid theory can describe the dependences of thermodynamics of PS/MCH solutions on temperature and pressure very well. However, the calculated enthalpy and the excess volume changes indicate that the Clausius-Clapeyron equation cannot be suitable to describe pressure effect on PS/MCH solutions. Further analysis on the thermodynamics of this system under pressure shows that the role of entropy is more important than the excess volume in the present case.

Crystallization behavior of poly(epsilon-caprolactone) in poly(epsilon-caprolactone) and poly(vinyl methyl ether) mixtures

The morphological development and crystallization behavior of poly(epsilon-caprolactone) (PCL) in miscible mixtures of PCL and poly(vinyl methyl ether) (PVME) were investigated by optical microscopy as a function of the mixture composition and crystallization temperature. The results indicated that the degree of crystallinity of PCL was independent of the mixture composition upon melt crystallization because the glass-transition temperatures of the mixtures were much lower than the crystallization temperature of PCL. The radii of the PCL spherulites increased linearly with time at crystallization temperatures ranging from 42 to 49 degrees C. The isothermal growth rates of PCL spherulites decreased with the amount of the amorphous PVME components in the mixtures. Accounting for the miscibility of PCL/PVME mixtures, the radial growth rates of PCL spherulites were well described by a kinetic equation involving the Flory-Huggins interaction parameter and the free energy for the nuclei formation in such a way that the theoretical calculations were in good agreement with the experimental data. From the analysis of the equilibrium melting point depression, the interaction energy density of the PVME/PCL system was calculated to be -3.95 J/cm(3).

Calculating the equation of state parameters and predicting the spinodal curve of isotactic polypropylene/poly(ethylene-co-octene) blend by molecular dynamics simulations combined with Sanchez-Lacombe lattice fluid theory

Molecular dynamics simulations are adopted to calculate the equation of state characteristic parameters P*, rho*, and T* of isotactic polypropylene (iPP) and poly(ethylene-co-octene) (PEOC), which can be further used in the Sanchez-Lacombe lattice fluid theory (SLLFT) to describe the respective physical properties. The calculated T* is a function of the temperature, which was also found in the literature. To solve this problem, we propose a Boltzmann fitting of the data and obtain T* at the high-temperature limit. With these characteristic parameters, the pressure-volume-temperature (PVT) data of iPP and PEOC are predicted by the SLLFT equation of state. To justify the correctness of our results, we also obtain the PVT data for iPP and PEOC by experiments. Good agreement is found between the two sets of data. By integrating the Euler-Lagrange equation and the Cahn-Hilliard relation, we predict the density profiles and the surface tensions for iPP and PEOC, respectively. Furthermore, a recursive method is proposed to obtain the characteristic interaction energy parameter between iPP and PEOC. This method, which does not require fitting to the experimental phase equilibrium data, suggests an alternative way to predict the phase diagrams that are not easily obtained in experiments.

Monte Carlo simulation of miscibility of polymer blends with repulsive interactions: effect of chain structure

The effects of the chain structure and the intramolecular interaction energy of an A/B copolymer on the miscibility of the binary blends of the copolymer and homopolymer C have been studied by means of a Monte Carlo simulation. In the system, the interactions between segments A, B and C are more repulsive than those between themselves. In order to study the effect of the chain structure of the A/B copolymer on the miscibility, the alternating, random and block copolymers were introduced in the simulations, respectively. The simulation results show that the miscibility of the binary blends strongly depends on the intramolecular interaction energy ((ε) over bar (AB)) between segments A and B within the A/B copolymers. The higher the repulsive interaction energy, the more miscible the A/B copolymer and homopolymer C are. For the diblock copolymer/homopolymer blends, they tend to form micro phase domains. However, the phase domains become so small that the blend can be considered as a homogeneous phase for the alternating copolymer/ homopolymer blends. Furthermore, the investigation of the average end-to-end distance ((h) over bar) in different systems indicates that the copolymer chains tend to coil with the decrease Of (ε) over bar (AB) whereas the (h) over bar of the homopolymer chains depends on the chain structure of the copolymers.

Effects of pressure and molecular weight on the miscibility of polystyrene and cyclohexane

With the aid of Sanchez-Lacombe lattice fluid theory (SLLFT), the phase diagrams were calculated for the system cyclohexane (CH)/polystyrene (PS) with different molecular weights at different pressures. The experimental data is in reasonable agreement with SLLFT calculations. The total Gibbs interaction energy, g*(12) for different molecular weights PS at different pressures was expressed, by means of a universal relationship, as g(12)* =f(12)* + (P - P-0) nu*(12) demixing curves were then calculated at fixed (near critical) compositions of CH and PS systems for different molecular weights. The pressures of optimum miscibility obtained from the Gibbs interaction energy are close to those measured by Wolf and coworkers. Furthermore, a reasonable explanation was given for the earlier observation of Saeki et al., i.e., the phase separation temperatures of the present system increase with the increase of pressure for the low molecular weight of the polymer whereas they decrease for the higher molecular weight polymers. The effects of molecular weight, pressure, temperature and composition on the Flory Huggins interaction parameter can be described by a general equation resulting from fitting the interaction parameters by means of Sanchez-Lacombe lattice fluid theory.

Phase-separation behavior of the system PES/phenoxy: An application of the Sanchez-Lacombe lattice fluid theory

Cloud-point curves reported for the system polyethersulfone (PES)/phenoxy were calculated by means of the Sanchez-Lacombe (SL) lattice fluid theory. The one adjustable parameter epsilon(12)*/k (quantifying the interaction energy between mers of the different components) can be evaluated by comparison of the theoretical and experimental phase diagrams. The Flory-Huggins (FH) interaction parameters are computed based on the evaluated epsilon(12)*/k and are approximately a linear function of volume fraction and of inverse temperature. The calculated enthalpies of mixing of PES/phenoxy blends for different compositions are consistent with the experimental values obtained previously by Singh and Walsh [1].