Estimating the virial coefficients of small polar molecules

We adapt existing models for estimating the second and third virial coefficients of small molecules to the halogenated methanes and ethanes. We compare the results with the abundant new, high-qualityPVT data resulting from the search for alternative refrigerants. The present model provides an accurate method for calculating densities, and therefore it should provide reliable thermodynamic properties and fugacity coefficients. We give equations and parameters useful for estimating the properties of pure refrigerants and their mixtures when noPVT data are available.Nomenclature B Second virial coeficient - B ₁₂ Mixture cross second virial - B _h Second virial of a hard sphere fluid - _i (T) Temperature function, second virial, Eq. (7) - C Third virial coefficient - C ₁₁₂,C ₁₂₂ Mixture cross third virials - C _h Third virial of a hard sphere fluid - N Avogadro's number Virial Coefficients P _c Critical pressure - P _c12 Characteristic critical pressure of a binary mixture - T _c Critical temperature - T _c12 Characteristic critical temperature of a binary mixture - T _r Reduced temperature,T/T _c - Parameter measuring polar contribution toB, Eq. (3) - b Volume of a hard sphere molecule - f ^(f) Polynomials determining temperature dependence of the nonpolar part ofB - k ₁₂ Binary interaction parameter for mixtures, Eq. (9a) - _c Critical volume - _e Molecular polarizability - Dipole moment - _R Reduced dipole moment, Eq. (4) - _R12 Mixture reduced dipole moment, second virial - _R112, _R122 Mixture reduced dipole moment, third virial - Pitzer acentric factor - ₁₂ Mixture acentric factor - (r) Intermolecular potential - _c Critical density (1/_c)     

Synthesis and characterization of poly(1-sila-cis-pent-3-enes) substituted with pendant pyridinyl groups

Poly[1-methyl-1-[3-(3-pyridinyl)propyl]-1-sila-cis-pent-3-ene], poly[1-phenyl-1-[3-(3-pyridinyl)propyl)-1-sila-cis-pent-3-ene], and poly[1-phenyl-1-(4-pyridinyl)-1-sila-cis-pent-3-ene] were synthesized by the anionic ring-opening polymerization of 1-methyl-1-[3-(3-pyridinyl)propyl]-1-silacyclopent-3-ene, 1-phenyl-1-[3-(3-pyridinyl)propyl]-1-silacyclopent-3-ene, and 1-phenyl-1-(4-pyridinyl)-1-silacyclopent-3-ene, respectively. These are the first polycarbosilanes which contain heterocyclic pyridine units as side-chain substituents. These polymers were characterized by¹H,¹³C, and²⁹Si NMR as well as by IR and UV spectroscopy. The molecular weight distributions were determined by gel permeation chromatography, glass transition temperatures, by differential seanning calorimetry: (DSC) and thermal behavior, by thermogravimetric analysis. (TGA).     

Extreme-ultraviolet interferometry at 15.5 nm using multilayer optics

The development of multilayer mirror technology capable of operating in the range of 3-30 nm and the construction of thin membranes with excellent uniformity and strength have made it possible to design and implement a Mach-Zehnder interferometer operating at 15.5 nm. We have tested this interferometer by using a soft x-ray laser as a source, and we show its use in probing high-density plasmas.     

Microwave-Assisted Fabrication of Superamphiphobic Surfaces on Aluminum Substrates

The field of superamphiphobic surface fabrication has evolved rapidly in the last decade; however, research on important issues such as sustainability and green chemistry procedures is still scarce. Herein, a simple method of microwave irradiation (MW) to minimize energy consumption during the preparation of superamphiphobic aluminum (Al) surfaces is reported. Al substrates are first etched in diluted HCl solutions to generate a microstructure and then irradiated in a commercial microwave unit for several time intervals, temperatures, and pressures. The surfaces are then coated with different compounds, and the wettability is tested with high and very-low surface tension liquids. Optical profilometry and scanning electron microscopy images show that the density of hierarchical micro-nanostructures increases with MW time, temperature, and pressure. At 170 °C and 7.9 bar, the surfaces present a high density of structures and re-entrant topographies. The obtained coatings display excellent repellence to liquids with surface tensions as low as 27.5 mN m⁻¹. X-ray photoelectron spectroscopy data show the importance of efficient surface functionalization for the production of superamphiphobicity in Al substrates. The results show that MW irradiation of Al substrates can be a green and efficient method for fabricating superamphiphobic surfaces.     

In vitro studies of PDR brachytherapy

BACKGROUND: Calculations on the basis of the LQ-model have been focussed on the possible radiobiological equivalence between common continuous low dose rate irradiation (CLDR) and a superfractionated irradiation (PDR = pulsed dose rate) provided that the same total dose will be prescribed in the same overall time as with the low doserate. A clinically usable fractionation scheme for brachytherapy was recommended by Brenner and Hall and should replace the classical CLDR brachytherapy with line sources with an afterloading technique using a stepping source. The hypothes is that LDR equivalency can be achieved by superfractionation was tested by means of in vitro experiments on V79 cells in monolayer and spheroid cultures as well as on HeLa monolayers. MATERIALS AND METHODS: Simulating the clinical situation in PDR brachytherapy, fractionation experiments were carried out in the dose rate gradient of afterloading sources. Different dose levels were produced with the same number of fractions in the same overall incubation time. The fractionation schedules which were to be compared with a CLDR reference curve were: 40 x 0.47 Gy, 20 x 0.94 Gy, 10 x 1.88 Gy, 5 x 3.76 Gy, 2 x 9.4 Gy given in a period of 20 h and 1 x 18.8 Gy as a "single dose" exposition. As measured by flow cytometry, the influence of the dose rate in the pulse on cell survival and on cell cycle distribution under superfractionation was examined on V79 cells. RESULTS: V79 spheroids as a model for a slowly growing tumor, reacted according to the radiobiological calculations, as a CLDR equivalency was achieved with increasing fractionation. Rapidly growing V79 monolayer cells showed an inverse fractionation effect. A superfractionated irradiation with pulses of 0.94 Gy/h respectively 0.47 Gy/0.5 h was significantly more effective than the CLDR irradiation. This inverse fractionation effect in log-phase V79 cells could be attributed to the accumulation of cycling cells in the radiosensitive G2/M phase (G2 block) during protected exposure which was drastically more pronounced for the pulsed scheme. HeLa cells were rather insensitive to changes of fractionation. Superfractionation as well as hypofractionation yielded CLDR equivalent survival curves. CONCLUSIONS: The fractionation scheme, derived from the PDR theory to achieve CLDR equivalent effects, is valid for many cell lines, however not for all. Proliferation and dose rate dependend cell cycle effects modify predictions derived from the sublethal damage recovery model and can influence acute irradiation effects significantly. Dose rate sensitivity and rapid proliferation favour cell cycle effects and substantiate, applied to the clinical situation, the possibility of a higher effectiveness of the pulsed irradiation on rapidly growing tumors.     

Combination of fiber-guided pulsed erbium and holmium laser radiation for tissue ablation under water

Because of the high absorption of near-infrared laser radiation in biological tissue, erbium lasers and holmium lasers emitting at 3 and 2 μm, respectively, have been proven to have optimal qualities for cutting or welding and coagulating tissue. To combine the advantages of both wavelengths, we realized a multiwavelength laser system by simultaneously guiding erbium and holmium laser radiation by means of a single zirconium fluoride (ZrF(4)) fiber. Laser-induced channel formation in water and poly(acrylamide) gel was investigated by the use of a time-resolved flash-photography setup, while pressure transients were recorded simultaneously with a needle hydrophone. The shapes and depths of vapor channels produced in water and in a submerged gel after single erbium and after combination erbium-holmium radiation delivered by means of a 400-μm ZrF(4) fiber were measured. Transmission measurements were performed to determine the amount of pulse energy available for tissue ablation. The effects of laser wavelength and the delay time between pulses of different wavelengths on the photomechanical and photothermal responses of meniscal tissue were evaluated in vitro by the use of histology. It was observed that the use of a short (200-μs, 100-mJ) holmium laser pulse as a prepulse to generate a vapor bubble through which the ablating erbium laser pulse can be transmitted (delay time, 100 μs) increases the cutting depth in meniscus from 450 to 1120 μm as compared with the depth following a single erbium pulse. The results indicate that a combination of erbium and holmium laser radiation precisely and efficiently cuts tissue under water with 20-50-μm collateral tissue damage.     

Structural and residual stress changes in Mo/a-Si multilayer thin films with annealing

The thermal and mechanical stability of molybdenum and amorphous silicon (Mo/a-Si) optical multilayers (3 and 4 nm nominal thickness of Mo and Si) at 316 °C were studied by annealing experiments. Growth of amorphous Mo-Si interlayers with a stoichiometry of 12 was observed at the Mo/a-Si interfaces. In addition, residual stresses significantly changed in the crystalline Mo and amorphous Si layers with annealing. High resolution electron microscopy, selected area electron diffraction, and X-ray diffraction of the crystalline Mo revealed that tensile stresses increased from 2 to about 10 GPa in the lateral direction (parallel to the interface plane). The compressive strains that developed in the vertical direction (perpendicular to the interface plane) are consistent with Poisson's ratio. Laser deflectometer measurements of thicker (0.1 m) amorphous silicon layers may indicate compressive-stress relaxation in the amorphous silicon with annealing, consistent with other investigations. Overall, the residual stress in a 40-bilayer film changes from about –0.5 to about +1.5 GPa. Structural transformation after relatively short annealing times at the interfaces in the thin amorphous Mo-Si interlayers may rationalize increased tensile strains in the Mo layers.     

Nutritional regulation of the activities of lipogenic enzymes of rat liver and brown adipose tissue

Nutrition-induced effects on the activity of enzymes of lipogenesis, fatty acid synthase (FAS: EC 2.3.1.85), ATP citrate lyase (ACL: EC 4.1.3.8), malic enzyme (ME; EC 1.1.1.40), glucose-6-phosphate dehydrogenase (G6PDH: EC 1.1.1.49) and 6-phosphogluconate dehydrogenase (PGDH; EC 1.1.1.44) were investigated in liver and interscapular brown adipose tissue (BAT) of rats. The lipogenic enzymes could be grouped into two categories according to their response to dietary manipulations: FAS and ACL, both key enzymes of lipogenesis, responded fast and strongly to dietary manipulations. ME, G6PDH and PGDH, enzymes which also contribute to metabolic pathways other than lipogenesis, responded in a more sustained and less pronounced fashion. Feed deprivation caused the specific activities of lipogenic enzymes to decline several-fold. Refeeding of previously fasted (up to 3 days) animals increased the activities dramatically (10-to 25-fold) to far above pre-fasting levels ("overshoot"). Repetition of the fasting/refeeding regimen increasingly impaired the ability of both tissues to synthesize overshooting enzyme activities in the subsequent refeeding period. The fasting-induced decline of the activities was prevented when sugars were provided to the animals via drinking water. The sugars displayed different effectivities: sucrose = glucose > fructose > maltose > > lactose. Sugars as the sole nutrient after fasting were also able to induce overshooting enzyme activities. Again, activities of FAS and ACL responded in a more pronounced fashion than the other three enzymes. Transition from feeding one diet to feeding a new diet of different composition led to adaptation of the lipogenic enzyme activities to levels characteristic for the new diet. Replacing a low-carbohydrate with a high-carbohydrate diet proceeded with major alterations of enzyme activities. This process of attaining a new level took up to 20 days and involved pronounced oscillations of the specific activities. In contrast, when a high-carbohydrate diet was replaced with another diet. particular one high in fat, transition to new enzyme activities was completed within 2-3 days and proceeded without oscillations. All dietary manipulations caused more pronounced responses in young (35d-old) than in adult (180d-old) animals.     

Specification and refinement of networks of asynchronously communicating agents using the assumption/commitment paradigm

This paper presents an assumption/commitment specification technique and a refinement calculus for networks of agents communicating asynchronously via unbounded FIFO channels in the tradition of Kahn.

We define two types of assumption/commitment specifications, namely simple and general specifications.

It is shown that semantically, any deterministic agent can be uniquely characterized by a simple specification, and any nondeterministic agent can be uniquely characterized by a general specification.

We define two sets of refinement rules, one for simple specifications and one for general specifications. The rules are Hoare-logic inspired. In particular the feedback rules employ invariants in the style of a traditional while-rule.

Both sets of rules have been proved to be sound and also (semantic) relative complete.

Conversion rules allow the two logics to be combined. This means that general specifications and the rules for general specifications have to be introduced only at the point in a system development where they are really needed.