The second acidic constant of salicylic acid

The second dissociation constant of salicylic acid (H2L) has been determined, at 25 degrees C, in NaCl ionic media by UV spectrophotometric measurements. The investigated ionic strength values were 0.16, 0.25, 0.50, 1.0, 2.0 and 3.0 M. The protolysis constants calculated at the different ionic strengths yielded, with the Specific Interaction Theory, the infinite dilution constant, log beta1(0) = 13.62 +/- 0.03, for the equilibrium L2- + H+ <==> HL-. The interaction coefficient between Na+ and L2-, b(Na+, L2-) = 0.02 +/- 0.07, has been also calculated.     

Influence of substituted 1,4-anthraquinones on the chlorophyll fluorescence and photochemical activity of pea thylakoid membranes

The effect of substituted 1,4-anthraquinones on the photochemical activity and chlorophyll fluorescence of thylakoid membranes was examined. Both the fluorescence and the photochemical activity depend on the 1,4-anthraquinone substituent. Stronger quinone-induced quenching of the chlorophyll fluorescence than quinone-induced changes in the activity of photosystem II is observed. The type (Cl or Br) and the position (Cl) of the chalogen atom strongly influence the degree of inhibition of PSII electron transport and the quenching of chlorophyll fluorescence. The data suggest that the quenching of chlorophyll fluorescence is due rather to the interaction of the 1,4-anthraquinones and chlorophyll molecules than to an indirect effect caused by stimulation of the photochemistry.     

Separation and determination of denatured alpha(s1)-, alpha(s2)-, beta- and kappa-caseins by hydrophobic interaction chromatography in cows', ewes' and goats' milk,milk mixtures and cheeses

Caseins alpha(s1)-, alpha(s2)-, beta- and kappa- from raw cows', ewes' and goats' milk were separated and determined by hydrophobic interaction chromatography (HIC) by using a Propyl column (Eichrom) in the presence of 8.0 M urea in the mobile phase. The method is based on fast and easy solubilization of real raw samples by 4.0 M guanidine thiocyanate followed by the HIC analysis, without any preliminary precipitation or separation of the casein fraction. Elution conditions have been optimized by analyzing commercial single bovine standard caseins and their mixture. In the optimized chromatographic conditions the four casein fractions were separated in less than 45 min. A linear relationship between the concentration of casein and peak area (UV absorbance detector at 280 nm) has been obtained over the concentration range of 0.5 to 40 microM. The detection limit for alpha-, beta- and kappa-caseins ranged between 0.35 and 0.70 microM. The precision of the method was evaluated, the coefficient of variation for alpha-, beta- and kappa-casein determination ranging between 3.0 and 6.0%. The method has been validated by the analysis of reference skim milk powder (BCR-063R) certificated for total nitrogen content. The method was applied to commercial casein mixture and to the qualitative and quantitative analysis of casein fractions in unprocessed, raw cows', goats' and ewes' milk (10 samples analyzed for each species), in one sample of unprocessed buffalos' milk and in commercial cheeses (mozzarella, robiola, ricotta and stracchino). Binary mixtures of milk (cow/goat and cow/ewe) were also analyzed and the ratio between casein peak areas (alpha(s1)/kappa, alpha(s2)/beta, beta/kappa and alpha(s2)/alpha(s1)) of the HIC chromatograms was proposed and discussed in order to evaluate a possible application of this method to detect milk adulteration.     

Mixed‐Ligand Complexes of Zinc(II) with α‐Hydroxycarboxylates and Aromatic N‐N Donor Ligands: Synthesis,Crystal Structures and Effect of Weak Interactions on their Crystal Packing

Several new two‐ligand complexes of zinc(II) with the aromatic N, N‐donor ligands 2, 2′‐bipyridine or 1, 10‐phenanthroline and one of three different α‐hydroxycarboxylates (HL′) derived of the α‐hydroxycarboxylic acids (H₂L′) (2‐methyllactic, H₂mL; mandelic, H₂M or benzilic, H₂B) were prepared. The compounds of formula [Zn(HL′)₂(NN)]·nH₂O (HL′ = HM, HB) were isolated as white powders and characterized by elemental analysis, IR spectroscopy and thermogravimetric analysis. The complexes of general formula [Zn(HL′)(NN)₂](HL′)·nH₂O (HL′ = HmL, HM) and [Zn(HB)₂(NN)₂], were obtained as single crystals and were characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis and X‐ray diffractometry. In all cases, the zinc atom is in a distorted octahedral environment. In [Zn(HL′)(NN)₂](HL′)·nH₂O the α‐hydroxycarboxylato ligands behave as bidentate chelating monoanion and an α‐hydroxycarboxylate as counterion is also present. In [Zn(HB)₂(NN)₂], the monoanionic benzilato ligand behaves as monodentate through one oxygen atom of the carboxylate function. The effect of the classical and no‐classical hydrogen bonding and of the π‐π and C‐H…π interactions in the 3D supramolecular arrangement of these molecular complexes is analyzed.     

Quantitation of reduced glutathione and cysteine in human immunodeficiency virus-infected patients

Plasma viral load (VL) values and CD4(+) cell count are employed clinically for initiation of therapy in the treatment of patients infected with human immunodeficiency virus (HIV), as previous clinical studies have shown a marked prevalence of acquired immunodeficiency syndrome (AIDS) development in seropositive individuals with VL values over 30 000 copies/mL. Many studies have shown that reduced glutathione (GSH) and cysteine (Cys) deficiency play an important role in the infection. We have developed capillary zone electrophoresis (CZE)-based assays and have used them to investigate the relationship between plasma and intracellular thiol levels and HIV-1 viremia in plasma. Blood samples from healthy volunteers and seropositive patients undergoing different antiretroviral regimes were analyzed in the study. The VL assay was based on CZE-UV detection of viral RNA at 260 nm. Determination of endogenous reduced Cys and GSH was achieved by CZE-UV detection of their mercurial complexes at 200 nm. We found that a decrease in GSH and Cys levels may be associated with disease progress. In fact, reduced GSH and Cys levels appear progressively reduced with increasing VL.     

Role of LHCII organization in the interaction of substituted 1,4-anthraquinones with thylakoid membranes

The chlorophyll fluorescence, photochemical activity and surface electric properties of thylakoid membranes with different stoichiometry of pigment-protein complexes and organization of the light-harvesting chlorophyll a/b protein complex of photosystem II (LHCII) were studied in the presence of substituted 1,4-anthraquinones. Data show strong dependence of the quenching of the chlorophyll fluorescence on the structural organization of LHCII. The increase of the LHCII oligomerization, which is associated with significant reduction of the transmembrane electric charge asymmetry and electric polarizability of the membrane, correlates with enhanced quenching effect of substituted 1,4-athraquinones. Crucial for the large quinone-induced changes in the membrane electric dipole moments is the structure of the quinone molecule. The strongest reduction in the values of the dipole moments is observed after interaction of thylakoids with 3-chloro-9-hydroxy-1,4-anthraquinone (TF33) which has the highest quenching efficiency. The quinone induced changes in the photochemical activity of photosystem II (PSII) correlate with the total amount of the supramolecular LHCII-PSII complex and depend on the number of substituents in the 1,4-anthraquinone molecule.     

Changes in the energy distribution between chlorophyll-protein complexes of thylakoid membranes from pea mutants with modified pigment content. I. Changes due to the modified pigment content

The low-temperature (77 K) emission and excitation chlorophyll fluorescence spectra in thylakoid membranes isolated from pea mutants were investigated. The mutants have modified pigment content, structural organization, different surface electric properties and functions [Dobrikova et al., Photosynth. Res. 65 (2000) 165]. The emission spectra of thylakoid membranes were decomposed into bands belonging to the main pigment protein complexes. By an integration of the areas under them, the changes in the energy distribution between the two photosystems as well as within each one of them were estimated. It was shown that the excitation energy flow to the light harvesting, core antenna and RC complexes of photosystem II increases with the total amount of pigments in the mutants, relative to the that to photosystem I complexes. A reduction of the fluorescence ratio between aggregated trimers of LHC II and its trimeric and monomeric forms with the increase of the pigment content (chlorophyll a, chlorophyll b, and lutein) was observed. This implies that the closer packing in the complexes with a higher extent of aggregation regulates the energy distribution to the PS II core antenna and reaction centers complexes. Based on the reduced energy flow to PS II, i.e., the relative increased energy flow to PS I, we hypothesize that aggregation of LHC II switches the energy flow toward LHC I. These results suggest an additive regulatory mechanism, which redistributes the excitation energy between the two photosystems and operates at non-excess light intensities but at reduced pigment content.     

Die Bildung von kristallinem Böhmit in gemeinsam gefällten AlFe(III)-Hydroxiden unter hydrothermalen Bedingungen

Under mild hydrothermal conditions originally amorphous aluminium hydroxide coprecipitated with iron(III)ions as Al_0,5Fe_0,5(OH)₃ transforms into aluminium hydroxide crystalline phases which are not observed in products of ageing of pure aluminium hydroxide.By X-ray diffraction analysis, IR spectroscopic studies and microscopic observations it has been found that due to the presence of iron(III) hydroxide it is possible to stabilize the trihydoxide of aluminium i.e. bayerite until 130–140°C. Moreover, with increasing temperature well crystallized boehmite is obtained instead of the usually formed pseudoboehmite.Experiments revealed that the formation of crystalline boehmite does not take place as a process of pseudoboehmit crystallites growth but only as a result of bayeriteboehmite transformation.

     

Thermal, rheological, and barrier properties of waterborne acrylic nanocomposite coatings based on boehmite or organo-modified montmorillonite

An organo-modified montmorillonite (Cloisite^®30B) or an unmodified boehmite (Disperal^®40) have been added to two acrylic latex dispersions (one of them UV-curable) for obtaining nanocomposite coatings. X-ray diffraction and transmission electron microscopy show a high degree of exfoliation in the nanocoatings based on montmorillonite, together with the deagglomeration of the micrometer-sized boehmite powder and the presence of single boehmite crystallites within the polymer matrix. Such morphologies are found to enhance the thermal and thermo-oxidative stability of the latexes and to significantly decrease their oxygen permeability, as well.