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A breadboard GC detector based on Penning ionization electron spectroscopy in plasma (PIES) was investigated. The PIES detector was set up in series with a gas chromatograph and a thermal conductivity detector. Two-dimensional PIES chromatograms were recorded for carbon monoxide, carbon dioxide, and methane. The analytes were identified independently of the GC retention time, and their concentrations were measured in a range between I and 100 ppm. PIES spectra for methane were observed for the first time and displayed two characteristic peaks with electron energies of 7.1 and 5.4 eV. Rate coefficients for Penning ionization due to collisions between [2.sup.3]S helium metastable atoms and analyte molecules under study were found to be [k.sup.*.sub.co] = (0.7 [+ or -] 0.2) x [10.sup.-10], [k.sup.*.sub.co2] = (1.8 [+ or -] 0.7) x [10.sup.-10], [k.sup.*.sub.7.1 CH4] = (4.7 [+ or -] 0.6) x [10.sup.-10], and [k.sup.*.sub.5.4 CH4] = (8 [+ or -] 2) x [10.sup.-10] [cm.sup.3]/s. The work provides the basis for the development of a portable and robust analytical platform capable of in situ real-time monitoring of greenhouse gases, with a perspective toward laboratory-on-chip realization.

The aim of this study was to develop a novel approach to the spatial characterization of multicomponent samples, based on the emergent technique of microthermal analysis. More specifically, we present an assessment of the use of scanning thermal microscopy as a means of component mapping via thermal conductivity; we include a new statistical approach to data handling, which allows reduction of topographic effects. We also introduce a novel three-dimensional mapping technique based on localized thermomechanical analysis. Tablets of paracetamol and hyproxypropyl methylcellulose (HPMC) and 50:50 mixes of the two were prepared and the materials characterized in scanning and localized modes using a TA Instruments 2990 microthermal analyzer with a Thermomicroscopes Explorer AFM head and Wollaston wire thermal probe. L-TMA studies of the pure components indicated markedly differing thermal responses, with the paracetamol showing a sharp melting accompanied by a probe pull-in effect, while HPMC showed only thermal expansion over the temperature range studied. Thermal conductivity and topographic images indicated that two-dimensional differentiation between the components was possible in scanning mode. A means of delineating the relative contribution of the topographic and conductivity effects was developed based on a regression analysis of the thermal conductivity measurements on a set of terms representing the local surface curvature. The results of three-dimensional imaging using a grid of L-TMA measurements is presented. This technique utilized the distinct thermal responses of the two components to allow the probe to melt through the paracetamol down to the underlying HPMC. The advantages and limitations of this novel imaging method are discussed in the context of pharmaceutical and broader uses of the approach.

Microwave-assisted organic synthesis in nonpolar solvents is investigated utilizing cylinders of sintered silicon carbide SiC, a chemically inert and strongly microwave absorbing material, as passive heating elements PHEs. Microwave energy is absorbed due to this heating, which subsequently transfer the generated thermal energy through conduction phenomena to the reaction mixture.

We demonstrate in this work and in the accompanying paper that it is possible to measure simultaneously heat capacity and expansibility of biomolecules in a single DSC experiment. In this study, we provide the theoretical basis for this new method based on rigorous statistical thermodynamics. The theoretical treatment presented here demonstrates that there are two additive contributions to the heat capacity at variable pressure, viz. (1) the isobaric heat capacity and (2) an expansibility term, and that these contributions can be experimentally separated to obtain simultaneously both heat capacity and expansibility in continuous DSC temperature scans preformed under pressure modulation. Equations that describe the mixed heat capacity and expansibility signal are derived, and experimental strategies as well as data extraction procedures are discussed.

A new method is described that permits the continuous and synchronous determination of heat capacity and expansibility data. We refer to it as pressure-modulated differential scanning calorimetry (PMDSC), as it involves a standard DSC temperature scan and superimposes on it a pressure modulation of preselected format. The power of the method is demonstrated using salt solutions for which the most accurate heat capacity and expansibility data exist in the literature. As the PMDSC measurements could reproduce the parameters with high accuracy and precision, we applied the method also to an aqueous suspension of multilamellar DSPC vesicles for which no expansibility data had been reported previously for the transition region. Excellent agreement was obtained between data from PMDSC and values from independent direct differential scanning densimetry measurements. The basic theoretical background of the method when using sawtooth-like pressure ramps is given under Supporting Information, and a complete statistical thermodynamic derivation of the general equations is presented in the accompanying paper.

The use of ionic liquids (ILs) as a solvent for thermal lens measurements has been investigated. It was found that ILs provide a better medium for thermal lens measurements than water. Specifically, not only the ILs offer at least 20 times higher sensitivity than water but that the enhancement can be appropriately adjusted by changing either the cation or the anion of the ILs. For example, the sensitivity in [[BMIm].sup.+][[Tf.sub.2]N].sup.-] is ~26 times higher than in water. It can be increased up to 31 times by changing the anion to [[P[F.sub.6].sup.-] (i.e., [[BMIm].sup.+][[P[F.sub.6]].sup.-]) or to 35 times by changing the cation to [[OMIm].sup.+] (i.e., [[OMIm].sup.+][[Tf.sub.2]N].sup.-]). In fact, the sensitivity of thermal lens measurements in ILs is comparable to those in volatile organic solvents such as benzene, carbon tetrachloride, and hexane. However, the ILs are more desirable as they have virtually no vapor pressure. Furthermore, additional sensitivity enhancement (up to 42 times higher than that in water) can be achieved by simply adding surfactants into the ILs. Based on the thermal conductivity (k) and dn/dT values, calculated from the measured thermal time constant [t.sub.c] and thermal lens strength [theta], it is evident that the observed sensitivity enhancement by the ILs is due to their relatively better thermooptical properties. More specifically, the enhancement is due not to the relatively modest lowering of the thermal conductivity but rather to the substantial increase in their dn/dT values. Because of the relationship between dn/dT and d[rho]/dT, it is expected that ILs can serve as an attractive and superior solvent not only for thermal lens measurements but also for other photothermal and photoacoustic techniques as well. Also equally important is the fact that the thermal lens technique in particular and photothermal techniques, in general, can offer a unique means to determine themooptical and thermal physical properties of the ILs (e.g., thermal conductivity, thermal diffusivity, and phase transition temperatures). This type of data is currently lacking but is of extreme importance for implementing ILs as a solvent in various industrial applications.

The continuum Navier-Stokes and heat conduction equations for stochastic rotation dynamics, a particle based algorithm for simulating a fluid is derived using a kinetic theory approach. The expressions for the viscosity and thermal conductivity in two or three dimensions are obtained and analyzed.

A simple one-step polymer-incorporation sol-gel process together with a surface modification and an ambient pressure drying processes were developed to prepare silica-poly(vinyclpyrrolidone) composite aerogels. The products obtained could find useful long-term, large scale applications of thermal insulation for energy saving practices.

Nonequilibrium molecular dynamics simulations with the nonpolarizable SPC/E and the polarizable COS/G2 force fields were employed to calculate the thermal conductivity and other associated properties of methane hydrate over a temperature range from 30 to 260 K. The low thermal conductivity of methane hydrate compared to ice Ih attributed the differences between the two lattice structures.

A unified nanothermodynamic model was developed to study the origin of the size effects in the thermal conductivity and diffusivity of nanostructural semiconductors. The results provide insight into the fundamental understanding of high-performance nanostructural semiconductors which could be used in optoelectronic and thermoelectric devices.

Single-sided transient plane source method is used for determining the thermal conductivity and thermal diffusivity of compacted methane hydrate sample at various temperatures and pressures. The simulation thermal conductivity results have helped in predicting gas hydrate stability in sediments for producing/estimating methane release into the environment due to gradual warming.

The physical properties of proton conducting polymer membranes based on a protic ionic liquid (IL) are examined. The results have shown a change in the glass transition temperature and in the temperature dependence of the conductivity with increasing polymer content, which are related to the physical confinement of the IL in the polymer membrane.

The nonequillibrium molecular dynamics calculations are used to investigate the thermal conductivity of the amorphous phase of polyamide-6,6. The analysis shows that the thermal, as well as the heat capacity are highly dependent on the number of degrees of freedom.

Various light-induced processes from the ultrafast charge photogeneration too much slower decay of the charges by recombination are being observed and studied. The analysis reveals that the geminate charge recombination directly competes with an efficient charge collection in copolymer/fullerene blends under solar illumination conditions.

The paramagnetic chiral semiconductor is synthesized by combining paramagnetic iron containing anion and bis (ethylenedithiol tetrathiafulvalene) (BEDT-TTF). The alpha phase induced by chirality presents a semiconductor behavior while beta phase presents a semiconductor behavior.

The structural, microstructural, and electronic properties of iodine intercalated [[[Bi.sub.(0.82)]Ca[O.sub.2]].sub.2][[Co[O.sub.2]].sub.(1.69)] misfit cobaltite are discussed. The coupling between the block-layer structure and the transport properties are described along with the description of some doping effects in the quasi-2D studied phase.

The concentration of aqueous solutes above the critical point of water is determined by using a pulsed, two-beam, thermal lensing experiment. It is found to be linear with concentration in the sub-millimolar range.

A total of six generalized solvation heat capacities, each of which contain unique physical information, were defined by extension of the partial molar heat capacity associated with a constant-pressure solvation process. The results were used to experimentally quantify the generalized heat capacities pertaining to the self-solvation of xenon, difluoromethane, n-hexane, and water, as well as the hydration of xenon, cyclohexane, and three hard sphere solutes.

The anomalous ionic conductivities of 0.5[Li.sub.2]S + 0.5[(1-x)Ge[S.sub.2] + xGe[O.sub.2]] glasses are investigated. The addition of oxides has contracted the glass structure leading to an increase in the conductivity activation energy and a decrease in the conductivity.

Thermal conduction described by Newton's law of cooling and by Fourier's transport equation and chemical reactions based on mass action kinetics where a simple example of a reaction mechanism with one intermediate is investigated. When there is strict proportionality between fluxes and forces, then the entropy production rate is an extremum at the stationary state even if the stationary state is far away from equilibrium.

The reverse nonequilibrium molecular dynamics (RNEMD) method for thermal conductivity of molecular liquids is discussed. The value of thermal conductivity is affected by the force field but thermal conductivities are insensitive to variations in its control parameters.

The single-walled carbon nanotubes exhibit chemical properties similar to those exhibited by other molecular compounds, such as fullerenes. The nanotubes are display solubility in organic solvents, undergo chemical transformation, and covalent binding. These one-dimensional structures are of nanometer size with electronic properties ranging from metallic to semiconducting and high thermal conductivity.

Heat capacities of tetragonal hen egg-white lysozyme crystals containing different amounts of water are measured in the temperature region between 8 and 300 K. A broad glass transition was observed at about 150 K fro the crystals with more than 24.0 wt % water content.