Recent advances in UV-visible reflectance spectroelectrochemistry

UV-visible spectroelectrochemistry is used in situ during electrochemical experiments to examine chemical processes occurring either in solution or at the electrode surface. The technique has recently been applied to the study of polymer modified electrodes, surface adsorbed species and surface plasmons, and soluble reactive organic intermediates, in addition to many other areas of general interest. Substantial improvements have been made recently in the sensitivity of the method, which allow electrochemical kinetic and mechanistic studies on very small concentrations of electrogenerated chromophores.     

NMR-spectroscopic mapping of an engineered cavity in the I14A mutant of HPr from Staphylococcus carnosus using xenon

The interaction between the histidine-containing phosphocarrier protein HPr and xenon atoms in solution is studied in the present paper. Wild-type HPr as well as the exchange mutant I14A have been studied. Specific binding of xenon into an engineered cavity created via the exchange of amino acid residue I14 by alanine could be shown using 1H-15N heteronuclear single-quantum coherence (HSQC) spectroscopy. Xenon binding results in pronounced changes of the 1H and 15N chemical shifts of amide groups close to the cavity. In addition to this observation which allows the NMR-spectroscopic mapping of such cavities, we have shown that the entire molecule is slightly rearranged as a result of xenon binding. In contrast, wild-type HPr only exhibits minor chemical shift changes due to the nonspecific interactions with the xenon atoms in solution.     

Light collimation and focusing by a thin flat metallic slab

We present experimental and theoretical work showing that a flat metallic slab can collimate and focus light impinging on the slab from a point source. The effect is optimized when the radiation is around the bulk, not at the surface, plasma frequency. Also, the smaller the imaginary part of the permittivity is, the better the collimation. Experiments for Ag in the visible as well as calculations are presented. We also discuss the interesting case of Al, whose imaginary part of permittivity is very small at the plasma frequency in UV radiation. Generalization to other materials and radiations are also discussed.     

The effect of molecular shape on the thermotropic liquid crystal behavior of monolauroylated amino acid glyceride conjugates

Monoacylglycerol amino acid conjugates constitute a novel class of specific biocompatible surfactants that can be considered analogues to partial glycerides and lysophospholipids. They consist of one aliphatic chain and one polar head, i.e., the amino acid, linked through a glycerol moiety. In a previous work, we synthesized monolauroylated amino acid glyceride conjugates, 1-O-lauroyl-rac-glycero-3-O-(N(alpha)-acetyl-L-amino acid), changing the amino acid headgroup systematically: arginine (compound 2), aspartic acid (compound 3), glutamic acid (compound 4), asparagine (compound 5), glutamine (compound 6), and tyrosine (compound 7), to elucidate the structure-properties relationship governing the occurrence of their polymorphism. The thermotropism of the new compounds was measured with polarizing light microscopy, differential scanning calorimetry, and X-ray diffraction and compared with the classical monoglyceride rac-1-lauroylglycerol (compound 1). The experiments were performed for a sequence of heating, cooling, and reheating scans. The results showed that compounds 1-6 exhibit a thermotropic smectic phase. As a consequence, the substitution of the polar head did not engender any curvature into the system, which might lead to the formation of cubic or columnar phases. Interestingly, liquid crystalline phases were not found in the case of compound 7. Small-angle X-ray diffraction data in the gel phase revealed that the substitution of the polar head by the different amino acid structures did not modify significantly the lamellar repeat distance relative to that of the reference one. The observed area per molecule, however, was larger for the new compounds. Consequently, interdigitation was promoted in compounds 2-7. The diffraction patterns were analyzed in terms of electron density profiles, using a modified Caillé theory plus a Gaussian electron density representation (MCG method) on X-ray diffraction data.     

Crystallization monitoring by quantitative image analysis

Crystals have well defined geometric characteristics. A geometry-based algorithm has been developed to study images of crystals and to calculate their macroscopic structural characteristics. The procedure has been applied to single monocrystals and crystal populations for which shape distributions can be determined and used to quantify the shape homogeneity of a crystallizer production.     

Evidence for double dissociation in K-p interactions at 14.3 GeV/c

We have studied the reaction K^-p → K^-π⁺π^-π⁺π^-p at 14.3 GeV/c to search for evidence of the double dissociation process $\text{K}{}^{\mathrm{-}}\text{p}\text{→}\text{QN}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}{}^1$. In the channel $\text{K}{}^{\mathrm{-}}\text{p}\text{→}\text{K}{}^{10}\text{(890)}$π₁^-π₂^-Δ⁺⁺ (1236) there is evidence for simultaneous production of low-mass enhancements in the $\text{K}{}^{10}\text{π}{}_1{}^{\mathrm{-}}$ and Δ⁺⁺(1236)π₂^- subsystems which correspond to the $\text{Q}\text{→}\text{K}{}^1\text{(890)π}$ and $\text{N}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}{}^1\text{→ Δπ}$ decay modes. In this particular final state the double fragmentation system is produced with a cross section of the order of a few microbarns. Our data are consistent with the factorizable pomeron exchange model of double diffractive dissociation.     

Instrumental factors influencing absorption measurements for fluid food color determination

The differences in color coordinates obtained from the use of different spectral features in the calculation are studied. Seven groups of food (olive oil, vanilla milkshake, brandy, honey, grape juice, vinegar, and orange juice) and an anthocyanin petunidin solution (natural pigment present in several vegetables) with different pH values were selected. Tristimulus values were calculated by considering the different sources of errors (truncation, abridgement, or different bandwidths). Results obtained were corrected by using the methods recommended (see References). These methods of abridgment work well in general, although in some circumstances (20 nm bandwidth or larger), specific spectral weighting functions have to be used to obtain a negligible error. Therefore, it is interesting to know how much difference can be expected from those factors in order to avoid confusion between color differences attributable to instruments and those attributable to actual color changes.