Periodic patterns and energy states of buckled films on compliant substrates

Thin stiff films on compliant elastic substrates subject to equi-biaxial compressive stress states are observed to buckle into various periodic mode patterns including checkerboard, hexagonal and herringbone. An experimental setting in which these modes are observed and evolve is described. The modes are characterized and ranked by the extent to which they reduce the elastic energy of the film-substrate system relative to that of the unbuckled state over a wide range of overstress. A new mode is identified and analyzed having nodal lines coincident with an equilateral triangular pattern. Two methods are employed to ascertain the energy in the buckled state: an analytical upper-bound method and a full numerical analysis. The upper-bound is shown to be reasonably accurate to large levels of overstress. For flat films, except at small states of overstress where the checkerboard is preferred, the herringbone mode has the lowest energy, followed by the checkerboard, with the hexagonal, triangular, and one-dimensional modes lowering the energy the least. At low overstress, the hexagonal mode is observed in the experiments not the square mode. It is proposed that a slight initial curvature of the film may play role in selecting the hexagonal pattern accompanied by a detailed analysis. An intriguing finding is that the hexagonal and triangular modes have the same energy in the buckled state and, moreover, a continuous transition between these modes exists involving a linear combination of the two modes with no change in energy. Experimental observations of various periodic modes are discussed with reference to the energy landscape. Discrepancies between observations and theory are identified and open issues are highlighted.     

Seasonal Variation in Urocanic Acid Isomers in Human Skin

Abstract— Urocanic acid (UCA) is a major chromophore for UV in the skin and has been suggested to act as an initiator of UV-induced immunosuppression. It converts from the naturally occurring trans-isomer to the cis-isomer on UV exposure. Isomerization is dose dependent until the photostationary state is reached, and the seasonal variation in irradiance from the sun may lead to changes in the percentage of UCA present as cis -UCA throughout the year. Thirty young healthy subjects, skin types I-IV, were followed from early summer till spring. At each of six visits (June, July, August, October, December, March), pigmentation and the concentration of UCA isomers were measured at six body sites: forehead, upper chest, upper back, outer upper arm, inner upper arm and buttock. In exposed as well as unexposed regions a variation in pigmentation was found, peak values being recorded in August. Total UCA concentration was lower in July and August than in the rest of the year, irrespective of body site. In July, the percentage of cis -UCA was close to the maximal obtainable (50-60%) at all sites except the buttock. In the three winter months the percentage of cis-UCA was below 7% in all regions except for the forehead, where the mean cis -UCA was 18% in October and March. No consistent relationship was found between UCA isomers and pigmentation or skin type.     

Combinatorial investigations of interfacial failure

Conventional measurements of interfacial strength focus on a single variable, whereas many variables couple nontrivially and simultaneously to define this property. We present a combinatorial methodology that allows the effects of multivariable environments on interfacial strength to be investigated in a high‐throughput, parallel, and quantitative manner. This technique is largely based on the theory of Johnson, Kendall, and Roberts that quantifies adhesion through the contact and separation of a spherical lens and flat substrate. For our experiments, we fabricated a combinatorial library consisting of a two‐dimensional array of spherical caps and a complementary substrate. The array of spherical caps was brought into contact and subsequently separated from the substrate, whereas the relative displacement and contact area of the individual lenses were recorded. With gradient library‐fabrication methods, two adhesion‐controlling parameters can be continuously varied along the orthogonal axes of the array. In this manner, each lens quantifies the interfacial strength at a unique point in parameter space. We demonstrate this multilens contact‐adhesion test by measuring the effect of temperature and coating thickness on the self‐adhesion of polystyrene thin films. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 883–891, 2003     

Mupirocin H, a novel metabolite resulting from mutation of the HMG-CoA synthase analogue, mupH in Pseudomonas fluorescens

Mutation of the HMG-CoA synthase encoding mupH gene in Pseudomonas fluorescens gives rise to a new metabolite formed from a truncated polyketide intermediate, providing in vivo evidence for the roles of mupH and cognate genes found in several "AT-less" and other bacterial PKS gene clusters responsible for the biosynthesis of diverse metabolites containing acetate/propionate derived side chains.     

Barriers to energy migration in mixed-ligand zinc(II) complexes

Spectroscopic investigations of Zn(4-Cl-PhS)₂(dmphen) (4-Cl-PhS = anion of 4-chlorobenzenethiol; DMPHEN = 2,9-dimethyl-1,10-phenanthroline) in the p2₁/N and p2₁/C crystal phases and in polymethylmethacrylate (PMMA) are reported. The results demonstrate the existence of an intramolecular barrier to energy migration between 3ππ* and ligand-to-ligand charge-transfer levels.     

Bet nitrogen adsorption studies of iron oxides from natural and synthetic sources.

A vacuum microbalance technique has been used to obtain the surface areas and porosities of iron oxyhydroxides derived from Fe(III) and Fe(II) sources. The pore shape of the Fe(III)-derived material was of the wide-bodied, narrow-necked type, whereas the Fe(II)-derived precipitates were composed of parallel plates or slit-shaped pores. The surface area of the Fe(II)-derived material was found to be influenced by the temperature of the precipitate formation. These differences in surface character are discussed in relation to the adsorption of trace constituents at the iron oxyhydroxide-water interface.