Partial wetting of chemically patterned surfaces: the effect of drop size

Partial wetting of chemically heterogeneous substrates is simulated. Three-dimensional sessile drops in equilibrium with smooth surfaces supporting ordered chemical patterns are considered. Significant features are observed as a result of changing the drop volume. The number of equilibrated drops is found either to remain constant or to increase with growing drop volume. The shape of larger drops appears to approach that of a spherical cap and their three-phase contact line seems, on a larger scale, more circular in shape than that of smaller drops. In addition, as the volume is increased, the average contact angle of drops whose free energy is lowest among all equilibrium-shaped drops of the same volume appears to approach the angle predicted by Cassie. Finally, contrary to results obtained with two-dimensional drops, contact angle hysteresis observed in this system is shown to exhibit a degree of volume dependence in the advancing and receding angles. Qualitative differences in the wetting behavior associated with the two different chemical patterns considered here, as well as differences between results obtained with two-dimensional and three-dimensional drops, can possibly be attributed to variations in the level of constraint imposed on the drop by the different patterns and by the dimensionality of the system.     

High-performance liquid chromatography of biogenic amines, derivatized with 9-fluorenylmethyl chloroformate

A procedure was elaborated for the analysis of three biogenic amines posing a considerable health hazard. The method takes advantage of the characteristics of the 9-fluorenylmethyl chloroformate (FMOC) derivative, namely specificity, stability and compatibility for either fluorescence or UV-absorbance detection. The FMOC-tyramine derivative was probably adsorbed to labware when acetone served as the solvent for FMOC. Methanol, substituted for acetone, removed this problem. Excellent linearity was obtained with standard solutions of tyramine, tryptamine and phenylethylamine. Meat samples, spiked with the mentioned amines, also showed good linearity. Perchloric acid was chosen for deproteinization, as potassium perchlorate may be eliminated on neutralization. Histamine failed to react with FMOC or was not detected under the test conditions.     

On minimal factorizations of rational matrix functions

The theory of factorization of rational matrix functions W() = = C(I-A)^–1B + D, as presented in the book Bart-Gohberg-Kaashoek [1], is extended here to the case where D = W() is not invertible, and applied to factorizations of monic matrix polynomials.     

In vitro selection of self-cleaving DNAs

Background: Ribozymes catalyze an important set of chemical transformations in metabolism, and ‘engineered’ ribozymes have been made that catalyze a variety of additional reactions. The possibility that catalytic DNAs or ‘deoxyribozymes’ can be made has only recently been addressed. Specifically, it is unclear whether the absence of the 2′ hydroxyl renders DNA incapable of exhibiting efficient enzyme-like activity, making it impossible to discover natural or create artificial DNA biocatalysts.Results: We report the isolation by in vitro selection of two distinct classes of self-cleaving DNAs from a pool of random-sequence oligonucleotides. Individual catalysts from ‘class I’ require both Cu²⁺ and ascorbate to mediate oxidative self-cleavage. Individual catalysts from class II use Cu²⁺ as the sole cofactor. Further optimization of a class II individual by in vitro selection yielded new catalytic DNAs that facilitate Cu²⁺-dependent self-cleavage with rate enhancements exceeding 1000 000-fold relative to the uncatalyzed rate of DNA cleavage.Conclusions: Despite the absence of 2′ hydroxyls, single-stranded DNA can adopt structures that promote divalent-metal-dependent self-cleavage via an oxidative mechanism. These results suggest that an efficient DNA enzyme might be made to cleave DNA in a biological context.     

Pulsed Electron-Nuclear Double Resonance in the Fourier Regime

Nuclear magnetic resonance (NMR) spectroscopy provides atomic-level molecular structural information. However, in molecules containing unpaired electron spins, NMR signals are difficult to measure directly. In such cases, data is obtained using the electron-nuclear double resonance (ENDOR) method, where nuclei are detected through their interaction with nearby unpaired electron spins. Unfortunately, electron spins spread the ENDOR signals, which challenges current acquisition techniques, often resulting in low spectral resolution that provides limited structural details. Here, we show that by using miniature microwave resonators to detect a small number of electron spins, integrated with miniature NMR coils, one can excite and detect a wide bandwidth of ENDOR data in a single pulse. This facilitates the measurement of ENDOR spectra with narrow lines spread over a large frequency range at much better spectral resolution than conventional approaches, which helps reveal details of the paramagnetic molecules’ chemical structure that were not accessible before.     

Breakdown of hydration repulsion between charged surfaces in aqueous Cs+ solutions

Using a surface force balance, we have measured the normal and shear forces between mica surfaces across aqueous caesium salt solutions (CsNO(3) and CsCl) up to 100 mM concentrations. In contrast to all other alkali metal ions at these concentrations, we find no evidence of hydration repulsion between the mica surfaces on close approach: the surfaces appear to be largely neutralized by condensation of the Cs ions onto the charged lattice sites, and are attracted on approach into adhesive contact. The contact separation at adhesion indicates that the condensed Cs ions protrude by 0.3 +/- 0.2 nm from each surface, an observation supported both by the relatively weak adhesion energies between the surfaces, and the relatively weak frictional yield stress when they are made to slide past each other. These observations show directly that the hydration shells about the Cs(+) ions are removed as the ions condense into the charged surface lattice. This effect is attributed to the low energies-resulting from their large ionic radius-required for dehydration of these ions.     

Selective adsorption of poly(ethylene oxide) onto a charged surface mediated by alkali metal ions

Using a surface force balance, we have measured normal and shear interactions between mica surfaces across pure water and across 0.1 M aqueous solutions of LiNO3, NaNO3, KNO3, and CsNO3, both prior to adding polymer and following addition of 1.5 x 10(-4) w/w poly(ethylene oxide) (PEO, Mw = 170 kD) and overnight incubation. Our results reveal that while the PEO adsorbs strongly from the KNO3 and CsNO3 solutions, unexpectedly it does not adsorb at all from the LiNO3 and NaNO3 salt solutions. We attribute this to the different nature of the hydration layers about the alkali metal ions: these favor liganding to the negatively charged mica surface of the etheric -O- group on the ethylene oxide monomer for the case of the more weakly hydrated K+ and Cs+, but not for the case of Na+ or Li+ with their more strongly bound water. A simple model relating the electrostatic energy changes occurring upon such liganding to the experimentally measured hydration energies of the different alkali metal ions supports this attribution.     

Interfacial characterization of chemical solution‐deposited thin films of PbSe on GaAs(100)

The microstructure and composition of the interfacial layer between chemically deposited PbSe and GaAs substrates were studied using high‐resolution transmission electron microscopy (HRTEM), Auger electron spectroscopy (AES), x‐ray photoelectron spectroscopy (XPS) and energy‐filtered TEM. The thickness of the interfacial layer varied significantly from direct contact of the film with the substrate to 5 nm in the thickest regions. The results established the presence of a discontinuous, amorphous intermediate layer of Ga₂O₃ at the PbSe/GaAs interface. Copyright © 2008 John Wiley & Sons, Ltd.     

Piatetski-Shapiro phenomenon in the uniqueness problem

We extend the phenomenon discovered by Piatetski-Shapiro (1954) to $l^q$ spaces. To be precise, for any $q>2$ we construct a compact K on the circle, which supports a distribution S with Fourier transform $\stackrel{?}{S}\in l^q$, but does not support such a measure. To cite this article: N. Lev, A. Olevskii, C. R. Acad. Sci. Paris, Ser. I 340 (2005).