Protonation equilibria and solubility of l-cystine

l-Cystine is the natural least soluble of the naturally occurring amino acids. Its solubility is a function of the hydrogen ion concentration depending on its protonation. This paper presents an investigation on properties of l-cystine in a constant ionic medium of NaCl at different concentrations (3.00,2.00,1.00,0.500,0.150 mol dm(-3)) and at 25 degrees C. In such experimental conditions, solubility and its changes as a function of hydrogen ion concentration were determined. Protonation of cystine was studied in acid and basic solution, by measuring the electromotive force of galvanic cell involving a glass electrode. Four protonation constants for l-cystine were determined in all the selected concentrations of ionic medium. The different values obtained for the constants in ionic medium of different concentration could be explained both with the variation of activity coefficients or with the complex formation between l-cystine and sodium ions. Variations of solubility for different concentration of NaCl were observed as well.     

The shape of leucine in the gas phase.

Two structures of neutral leucine are detected in the jet-cooled rotational spectrum of a laser-ablation molecular-beam Fourier transform microwave (LA-MB-FTMW) experiment. The comparison between the experimental rotational and (14)N nuclear quadrupole coupling constants and those calculated ab initio provides conclusive evidence for the identification of the conformers. The most stable species is stabilized by a N-H...O=C intramolecular hydrogen bond and a cis-COOH interaction, while a higher-energy conformer exhibits a N...H-O intramolecular hydrogen bond and trans-COOH, as in lower aliphatic amino acids. The isobutyl side chain adopts the same configuration in the two conformers of leucine, characterized by a trans arrangement of the C'-C(alpha)-C(beta)-C(gamma)-C(delta) chain. The differences with the preferred side chain configurations observed in valine and isoleucine are discussed.     

Self-organization of the ternary didecyldimethylammonium bromide/octyl-beta-D-glucopyranoside/water system

The spontaneous and thermodynamically stable mixed vesicles constituted by a double-chain cationic surfactant with 10 carbon atoms hydrophobic tail, didecyldimethylammonium bromide (di-C(10)DMAB), and a nonionic single-chain surfactant, octyl-beta-d-glucopyranoside (OBG), have been characterized in aqueous media by means of a series of experimental techniques, as well as a theoretical approach. Conductivity data allow for the determination of the concentrations at which the monomer-to-vesicle (CVC) and/or vesicle-to-micelle (CMC) transitions occur. Electrophoretic mobilities, obtained from laser-doppler-electrophoresis experiments, permit the determination of zeta-potentials and, from them, the surface charge density of the vesicle aggregates. Cryogenic transmission electron microscopy (cryo-TEM) provides pictures of the vesicles, their size and shape being, thus, determined. Finally, the sensitivity of the emission spectra of some fluorescent probes, such as the cationic TNS and the nonionic PRODAN, to the polarity of the environment, allow for a complete study of different pre- and post-vesicle microdomains, of variable rigidity and micropolarity. This, in turn, yield interesting information about the vesicle surface and bilayer, as well as, about the existence of clusters and/or nanoaggregates prior to the formation of vesicles, as was proposed by us in a previous paper.     

Use of Legendre moments for the fast comparison of two-dimensional polyacrylamide gel electrophoresis maps images

In this paper, Legendre moments are calculated to extract the global information from a set of two-dimensional polyacrylamide gel electrophoresis map images. The dataset contains 18 samples belonging to two different cell lines (PACA44 and T3M4) of control (untreated) and drug-treated pancreatic ductal carcinoma cells. The aim of this work was to obtain the correct classification of the 18 samples, using the Legendre moments as discriminant variables. For each image the Legendre moments up to a maximum order of 100 were computed. The stepwise linear discriminant analysis (LDA) was performed in order to select the moments with the highest discriminating power. The results demonstrate that the Legendre moments can be successfully applied for fast classification purposes and similarity analysis.     

Shape of 4S- and 4R-hydroxyproline in gas phase

The alpha-amino acids 4(S)-hydroxyproline and 4(R)-hydroxyproline have been studied under isolation conditions in gas phase using laser-ablation molecular-beam Fourier transform microwave spectroscopy. Two conformers of each molecule have been detected in the jet-cooled rotational spectrum. The most stable conformer in both molecules exhibits an intramolecular N...H-O hydrogen bond (configuration 1) between the hydrogen atom of the carboxylic group and the nitrogen atom. The second conformer is characterized by an intramolecular N-H...O=C hydrogen bond (configuration 2). The conformers of 4(R)-hydroxyproline adopt a C(gamma)-exo puckering, while those of 4(S)-hydroxyproline present a C(gamma)-endo ring conformation. These ring conformations, which show the same propensity observed in collagen-like peptides, are stabilized by additional intramolecular hydrogen bonds involving the 4-hydroxyl group, with the exception of the most stable form of 4(S)-hydroxyproline for which a n-pi interaction between the oxygen atom of the 4-hydroxyl group and the carboxyl group carbon seems to be established. A gauche effect could be also contributing to stabilize the observed conformers.     

Optimisation of the formulation of a bubble bath by a chemometric approach market segmentation and optimisation

The optimisation of the formulation of a commercial bubble bath was performed by chemometric analysis of Panel Tests results. A first Panel Test was performed to choose the best essence, among four proposed to the consumers; the best essence chosen was used in the revised commercial bubble bath. Afterwards, the effect of changing the amount of four components (the amount of primary surfactant, the essence, the hydratant and the colouring agent) of the bubble bath was studied by a fractional factorial design. The segmentation of the bubble bath market was performed by a second Panel Test, in which the consumers were requested to evaluate the samples coming from the experimental design. The results were then treated by Principal Component Analysis. The market had two segments: people preferring a product with a rich formulation and people preferring a poor product. The final target, i.e. the optimisation of the formulation for each segment, was obtained by the calculation of regression models relating the subjective evaluations given by the Panel and the compositions of the samples. The regression models allowed to identify the best formulations for the two segments ofthe market.     

Spin control in ladderlike hexanuclear copper(II) complexes with metallacyclophane cores

Two new hexanuclear oxamatocopper(II) complexes 3 and 4 have been synthesized from the binuclear copper(II) complexes of the meta- and para-phenylenebis(oxamate) ligands, respectively. Complexes 3 and 4 possess an overall ladderlike structure made up of two oxamate-bridged linear trinuclear units ("rails") connected through two phenylenediamidate bridges ("rungs") between the central copper atoms to give metallacyclic cores of the meta- and para-cyclophane type, respectively. They show different ground spin states, S = 1 (3) or S = 0 (4), depending on the substitution pattern in the aromatic spacers. The triplet state molecule 3 containing two spin doublet Cu(II)3 units connected by two m-phenylenediamidate bridges represents a successful extension of the concept of "ferromagnetic coupling units" to metal complexes, which is a well-known approach toward high spin organic radicals.     

Absolute configuration of amino alcohols by 1H-NMR

A general NMR spectroscopy protocol for determination of absolute configuration of 1,2-amino alcohols, that allows differentiation of the four possible stereoisomers by analysis of the 1H NMR spectra of their bis-MPA derivatives, is described.     

Charge transport versus recombination in dye-sensitized solar cells employing nanocrystalline TiO2 and SnO2 films

We report a comparison of charge transport and recombination dynamics in dye-sensitized solar cells (DSSCs) employing nanocrystalline TiO(2) and SnO(2) films and address the impact of these dynamics upon photovoltaic device efficiency. Transient photovoltage studies of electron transport in the metal oxide film are correlated with transient absorption studies of electron recombination with both oxidized sensitizer dyes and the redox couple. For all three processes, the dynamics are observed to be 2-3 orders of magnitude faster for the SnO(2) electrode. The origins of these faster dynamics are addressed by studies correlating the electron recombination dynamics to dye cations with chronoamperometric studies of film electron density. These studies indicate that the faster recombination dynamics for the SnO(2) electrodes result both from a 100-fold higher electron diffusion constant at matched electron densities, consistent with a lower trap density for this metal oxide relative to TiO(2), and from a 300 mV positive shift of the SnO(2) conduction band/trap states density of states relative to TiO(2). The faster recombination to the redox couple results in an increased dark current for DSSCs employing SnO(2) films, limiting the device open-circuit voltage. The faster recombination dynamics to the dye cation result in a significant reduction in the efficiency of regeneration of the dye ground state by the redox couple, as confirmed by transient absorption studies of this reaction, and in a loss of device short-circuit current and fill factor. The importance of this loss pathway was confirmed by nonideal diode equation analyses of device current-voltage data. The addition of MgO blocking layers is shown to be effective at reducing recombination losses to the redox electrolyte but is found to be unable to retard recombination dynamics to the dye cation sufficiently to allow efficient dye regeneration without resulting in concomitant losses of electron injection efficiency. We conclude that such a large acceleration of electron dynamics within the metal oxide films of DSSCs may in general be detrimental to device efficiency due to the limited rate of dye regeneration by the redox couple and discuss the implications of this conclusion for strategies to optimize device performance.     

Stereospezifität der neuroleptischen Wirkung und Chiralität von (+)-3-{2-[4-(8-Fluor-2-methyl-10,11-dihydrodibenzo[b,f]thiepin-10-yl)-1-piperazinyl]-äthyl}-2-oxazolidinon (16). 4. Mitteilung über tricyclische Antidepressiva und Neuroleptica

Stereospecifity of the neuroleptic activity and chirality of (+)-3-{2-[4-(8-fluoro-2-methyl-10, 11-dihydrodibenzo[b,f]thiepin-10-yl)-1-piperazinyl]ethyl}-2-oxazolidinone (16). The synthesis and stereospecific neuroleptic action in animals of the (+)-enantiomer of 3-{2-[4-(8-fluoro-2-methyl-10,11-dihydrodibenzo [b,f]thiepin-10-yl)-1-piperazinyl]ethyl}-2-oxazolidinone ( 16 ) are briefly described. The (10S)-configuration of this compound was determined by X-ray diffraction.