Elastic constants of solids and fluids with initial pressure via a unified approach based on equations-of-state

The second and third-order Brugger elastic constants are obtained for liquids and ideal gases having an initial hydrostatic pressure p₁. For liquids the second-order elastic constants are C₁₁ = A + p₁, C₁₂ = A − p₁, and the third-order constants are C₁₁₁ = −(B + 5A + 3p₁), C₁₁₂ = −(B + A − p₁), and C₁₂₃ = A − B − p₁, where A and B are the Beyer expansion coefficients in the liquid equation of state. For ideal gases the second-order constants are C₁₁ = p₁γ + p₁, C₁₂ = p₁γ − p₁, and the third-order constants are C₁₁₁ = −p₁(γ² + 4γ + 3), C₁₁₂ = −p₁(γ² − 1), and C₁₂₃ = −p₁ (γ² − 2γ + 1), where γ is the ratio of specific heats. The inequality of C₁₁ and C₁₂ results in a nonzero shear constant C₄₄ = (1/2)(C₁₁ − C₁₂) = p₁ for both liquids and gases. For water at standard temperature and pressure the ratio of terms p₁/A contributing to the second-order constants is approximately 4.3 × 10⁻⁵. For atmospheric gases the ratio of corresponding terms is approximately 0.7. Analytical expressions that include initial stresses are derived for the material ‘nonlinearity parameters’ associated with harmonic generation and acoustoelasticity for fluids and solids of arbitrary crystal symmetry. The expressions are used to validate the relationships for the elastic constants of fluids.     

Biological activities of ophiobolin K and 6-epi-ophiobolin K produced by the endophytic fungus Aspergillus calidoustus

Endophytic fungi represent ubiquitous microbial organisms able to live in the tissues of different plants around the world and represent a prolific source of bioactive metabolites. In the present study, the endophytic fungus Aspergillus calidoustus was isolated from the medicinal plant Acanthospermum australe (Asteraceae), and identified using molecular, physiological and morphological methods. A methylene chloride crude extract of A. calidoustus has been produced and subjected to antifungal bioassay-directed fractionation which resulted in the isolation of the two bioactive compounds: ophiobolin K and 6-epi-ophiobolin K. These pure compounds displayed antifungal activity against fungal plant pathogens, protozoal activity against Trypanosoma cruzi, and cytotoxic activity against human tumoral cell lines. The results show that A. calidoustus was able to produce the antifungal and cytotoxic metabolites ophiobolin K and 6-epi-ophiobolin K, which may help the fungus to colonise and occupy the substratum as well as survive in natural environments.     

Ice nucleation on hydrophilic silicon

We have used Fourier transform infrared spectroscopy to study thin water films on a hydrophilic silicon surface in the temperature range from 20 to -20 degrees C. Throughout that range, the spectra of the water adjacent to the silicon surface are consistent with that of bulk water near 25 degrees C. Thicker films (>1 microm) freeze at -11+/-1 degrees C. We reconcile the apparent paradox of a thin film of water which is quite liquidlike at a temperature where freezing of thicker films occurs by hypothesizing that the nucleation event in the thicker film is triggered by a critical ice embryo which forms at some small distance from the silicon surface, as opposed to in direct contact with it.     

Heat of freezing for supercooled water: measurements at atmospheric pressure

Unlike reversible phase transitions, the amount of heat released upon freezing of a metastable supercooled liquid depends on the degree of supercooling. Although terrestrial supercooled water is ubiquitous and has implications for cloud dynamics and nucleation, measurements of its heat of freezing are scarce. We have performed calorimetric measurements of the heat released by freezing water at atmospheric pressure as a function of supercooling. Our measurements show that the heat of freezing can be considerably below one predicted from a reversible hydrostatic process. Our measurements also indicate that the state of the resulting ice is not fully specified by the final pressure and temperature; the ice is likely to be strained on a variety of scales, implying a higher vapor pressure. This would reduce the vapor gradient between supercooled water and ice in mixed phase atmospheric clouds.     

Computationally derived rules for persistence of C60 nanowires on recumbent pentacene bilayers

The tendency for C(60) nanowires to persist on two monolayers of recumbent pentacene is studied using molecular dynamics (MD) simulations. A review of existing experimental literature for the tilt angle adopted by pentacene on noble metal surfaces shows that studies cover a limited range from 55° to 90°, motivating simulation studies of essentially the entire range of tilt angles (10°-90°) to predict the optimum surface tilt angle for C(60) nanowire formation. The persistence of a 1D nanowire depends sensitively on this tilt angle, the amount of initial tensile strain, and the presence of surface step edges. At room temperature, C(60) nanowires oriented along the pentacene short axes persist for several nanoseconds and are more likely to occur if they reside between, or within, pentacene rows for ? ≤ ～60°. The likelihood of this persistence increases the smaller the tilt angle. Nanowires oriented along the long axes of pentacene molecules are unlikely to form. The limit of stability of nanowires was tested by raising the temperature to 400 K. Nanowires located between pentacene rows survived this temperature rise, but those located initially within pentacene rows are only stable in the range ?(1) = 30°-50°. Flatter pentacene surfaces, that is, tilt angles above about 60°, are subject to disorder caused by C(60) molecules "burrowing" into the pentacene surface. An initial strain of 5% applied to the C(60) nanowires significantly decreases the likelihood of nanowire persistence. In contrast, any appreciable surface roughness, even by half a monolayer in height of a third pentacene monolayer, strongly enhances the likelihood of nanowire formation due to the strong binding energy of C(60) molecules to step edges.     

Photochemical studies of 4-tert-butyl-4'-methoxydibenzoylmethane (BM-DBM).

Kinetic UV-VIS absorption data following 355 and 266 nm nanosecond laser flash photolysis of 4-tert-butyl-4'-methoxydibenzoylmethane (BM-DBM) solutions is presented. The kinetics of the decay of the non-chelated enol (NCE) produced following 355 nm excitation of BM-DBM solutions are analysed in terms of mixed 1st- and 2nd-order kinetics. The temperature dependences of the component rate constants are unusual and both 1st- and 2nd-order components display negative activation energies, which are explained by invoking pre-equilibria. In addition, it is shown for the first time that 266 nm laser photolysis of BM-DBM solutions leads to formation of the triplet state of the keto (K) form with a lifetime of approximately 500 ns. Under these conditions the triplet state of the K form is quenched by oxygen.