Study of the antimicrobial peptide indolicidin and a mutant in micelle medium by molecular dynamics simulation

The antimicrobial peptide indolicidin (IND) and the mutant CP10A in hydrated micelles were studied using molecular dynamics simulations in order to observe whether the molecular dynamics and experimental data could be sufficiently correlated and a detailed description of the interaction of the antimicrobial peptides with a model of the membrane provided by a hydrated micelle system could be obtained. In agreement with the experiments, the simulations showed that the peptides are located near the surface of the micelles. Peptide insertions agree with available experimental data, showing deeper insertion of the mutant compared with the peptide IND. Major insertion into the hydrophobic core of the micelle by all tryptophan and mutated residues of CP10A in relation to IND was observed. The charged residues of the terminus regions of both peptides present similar behavior, indicating that the major differences in the interactions with the micelles of the peptides IND and CP10A occur in the case of the hydrophobic residues.

Photophysical properties of a photocytotoxic fluorinated chlorin conjugated to four beta-cyclodextrins

A meso-tetrakis(pentafluorophenyl)-chlorin with the reduced pyrrole ring linked to an isoxazolidine ring (FC) has been conjugated to four beta-cyclodextrins (CDFC). The CDFC exhibits excellent water solubility and is a potent photosensitizer towards proliferating NCTC 2544 human keratinocytes. The study by conventional steady state absorption and fluorescence spectroscopies and by time-resolved femto- and nanosecond laser flash spectroscopies suggests that in ethanol and pH 7 buffer the beta-cyclodextrins embed the highly hydrophobic tetrakis(pentafluorophenyl)-chlorin macrocycle and strongly interact with the chlorin rings in the singlet and triplet manifolds. In these solvents, femtosecond spectroscopy suggests that the conjugate undergoes a rapid relaxation in the upper excited singlet states induced by photochemical and/or conformation change(s) at a rate of about 5 ps(-1) to fluorescent states whose lifetime is similar to 8 ns. This interaction is destroyed upon addition of Triton X100 to buffer. Both FC and CDFC strongly fluoresce (Phi(F) similar to 0.5) in micelles. Similar behavior is observed at the triplet level. In ethanol and water, the initial transient triplet state absorbance decays within 1-3 mu s yielding a longer lived triplet with spectral properties indistinguishable from that of original difference absorbance spectra. The determination of the molar absorbance in the 440-460 nm region (similar to 35 000 M(-1) cm(-1)) leads to an estimate of similar to 0.2 for the triplet formation quantum yield of FC in toluene and of FC and CDFC in Triton X100 micelles. Quenching of the CDFC triplets by dioxygen in buffer produces (1)O(2) in a good yield consistent with the effective photocytotoxicity of the chlorin-cyclodextrins conjugate towards cultured NCTC 2544 human keratinocytes. By contrast, FC which aggregates in buffer produces little if any (1)O(2).

Thermodiffusion in a multicomponent lyotropic mixture in the vicinity of the critical micellar concentration by using the Z-scan technique

Thermodiffusion in a lyotropic mixture of water and potassium laurate is investigated by means of an optical technique (Z scan) distinguishing the index variations due to the temperature gradient and the mass gradients. A phenomenological framework allowing for coupled diffusion is developed in order to analyze thermodiffusion in multicomponent systems. An observable parameter relating to the mass gradients is found to exhibit a sharp change around the critical micellar concentration, and thus may be used to detect it. The change in the slope is due to the markedly different values of the Soret coefficients of the surfactant and the micelles. The difference in the Soret coefficients is due to the fact that the micellization process reduces the energy of interaction of the ball of amphiphilic molecules with the solvent.

The role of oxygen vacancy in the photoluminescence property at room temperature of the CaTiO(3)

In this paper, electron paramagnetic resonance, photoluminescence (PL) emission, and quantum mechanical calculations were used to observe and understand the structural order-disorder of CaTiO(3), paying special attention to the role of oxygen vacancy. The PL phenomenon at room temperature of CaTiO(3) is directly influenced by the presence of oxygen vacancies that yield structural order-disorder. These oxygen vacancies bonded at Ti and/or Ca induce new electronic states inside the band gap. Ordered and disordered CaTiO(3) was obtained by the polymeric precursor method. (C) 2009 American Institute of Physics. [DOI: 10.1063/1.3190524]

A preliminary study of the incorparation of NPK fertilizer into chitosan nanoparticles

The use of slow release fertilizer has become a new trend to save fertilizer consumption and to minimize environmental pollution. Due to its polymeric cationic, biodegradable, bioabsorbable, and bactericidal characteristics, chitosan (CS) nanoparticle is an interesting material for use in controlled release systems. However, there are no attempts to explore the potential of chitosan nanoparticles as controlled release for NPK fertilizers. In this work chitosan nanoparticles were obtained by polymerizing methacrylic acid for the incorporation of NPK fertilizers. The interaction and stability of chitosan nanoparticle suspensions containing nitrogen (N), phosphorus (P) and potassium (K) were evaluated by FTIR spectroscopy, particle size analysis and zeta-potential. The FTIR results indicated the existence of electrostatic interactions between chitosan nanoparticles and the elements N, P and K. The stability of the CS-PMAA colloidal suspension was higher with the addition of nitrogen and potassium than with the addition of phosphorus, due to the higher anion charge from the calcium phosphate than the anion charges from the potassium chloride and urea. The mean diameter increase of the CS-PMAA nanoparticles in suspension with the addition of different compounds indicated that the elements are being aggregated on the surface of the chitosan nanoparticles.

Photochemistry of anthocyanins and their biological role in plant tissues

Anthocyanins, the major red, purple, and blue pigments of plants, absorb visible as well as UV radiation and are effective antioxidants and scavengers of active oxygen species. In plant leaves, one of the functional roles proposed for anthocyanins is protection of the photosynthetic apparatus from the effects of excess incident visible or UV-B radiation and photooxidative stress. In essence, a photoprotective role requires that the excited singlet states of both complexed and uncomplexed anthocyanins deactivate back to the ground state so quickly that intersystem crossing, photoreaction, and diffusion-controlled quenching processes cannot compete. Studies of the photochemical properties of synthetic analogs of anthocyanins and of several naturally occurring anthocyanins show that this is indeed the case, uncomplexed anthocyanins decaying back to the ground state via fast (subnanosecond) excited-state proton transfer (ESPT) and anthocyanin-copigment complexes by fast (sub-picosecond) charge-transfer-mediated internal conversion.

Protein-polysaccharide viscoelastic matrices: synergic effects of amylose on lysozyme physical gelation in aqueous dimethylsulfoxide

A synergic effect of amylose on rheological characteristics of lysozyme physical gels evolved out of dimethylsulfoxide-water was verified and analyzed. The dynamics of the gels were experimentally approached by oscillatory rheology. The synergic effect was characterized by a decrease in the threshold DMSO volume fraction required for lysozyme gelation, and by a significant strengthening of the gel structure at over-critical solvent and protein concentrations. Drastic changes in the relaxation and creep curve patterns for systems in the presence of amylose were verified. Complex viscosity dependence on temperature was found to conform to an Arrhenius-like equation, allowing the determination of an activation energy term (Ea, apparent) for discrimination of gel rigidity. A dilatant effect was found to be induced by temperature on the flow behavior of lysozyme dispersions in DMSO-H(2)O in sub-critical conditions for gelation, which was greatly intensified by the presence of amylose in the samples. That transition was interpreted as reflecting a change from a predominant colloidal flow regime, where globular components are the prevailing structural elements, to a mainly fibrillar, polymeric flow behavior.

Spectroscopic, structural, and functional characterization of the alternative low-spin state of horse heart cytochrome c

The alternative low-spin states of Fe3+ and Fe2+ cytochrome c induced by SDS or AOT/hexane reverse micelles exhibited the heme group in a less rhombic symmetry and were characterized by electron paramagnetic resonance, UV-visible, CD, magnetic CD, fluorescence, and Raman resonance. Consistent with the replacement of Met 80 by another strong field ligand at the sixth heme iron coordination position, Fe3+ ALSScytc exhibited 1-nm Soret band blue shift and e enhancement accompanied by disappearance of the 695-nm charge transfer band. The Raman resonance, CD, and magnetic CD spectra of Fe3+ and Fe2+ ALSScytc exhibited significant changes suggestive of alterations in the heme iron microenvironment and conformation and should not be assigned to unfold because the Trp(59) fluorescence remained quenched by the neighboring heme group. ALSScytc was obtained with His(33) and His(26) carboxyethoxylated horse cytochrome c and with tuna cytochrome c (His(33) replaced by Asn) pointing out Lys(79) as the probable heme iron ligand. Fe3+ ALSScytc retained the capacity to cleave tert-butylhydroperoxide and to be reduced by dithiothreitol and diphenylacetaldehyde but not by ascorbate. Compatible with a more open heme crevice, ALSScytc exhibited a redox potential similar to 200 mV lower than the wild-type protein (1220 mV) and was more susceptible to the attack of free radicals.

Polymer matrix sensitizing effect on photoluminescence properties of Eu(3+)-beta-diketonate complex doped into poly-beta-hydroxybutyrate (PHB) in film form

In this work is reported the sensitization effect by polymer matrices on the photoluminescence properties of diaquatris(thenoyltrifluoroacetonate)europium(III), [Eu(tta)(3)(H(2)O)(2)], doped into poly-beta-hydroxybutyrate (PHB) with doping percentage at 1, 3, 5, 7 and 10% (mass) in film form. TGA results indicated that the Eu(3+) complex precursor was immobilized in the polymer matrix by the interaction between the Eu(3+) complex and the oxygen atoms of the PHB polymer when the rare earth complex was incorporated in the polymeric host. The thermal behaviour of these luminescent systems is similar to that of the undoped polymer, however, the T(onset) temperature of decomposition decreases with increase of the complex doping concentration. The emission spectra of the Eu(3+) complex doped PHB films recorded at 298 K exhibited the five characteristic bands arising from the (5)D(0) -> (7)F(J) intraconfigurational transitions (J = 0-4). The fact that the quantum efficiencies eta of the doped film increased significantly revealed that the polymer matrix acts as an efficient co-sensitizer for Eu(3+) luminescent centres and therefore enhances the quantum efficiency of the emitter (5)D(0) level. The luminescence intensity decreases, however, with increasing precursor concentration in the doped polymer to greater than 5% where a saturation effect is observed at this specific doping percentage, indicating that changes in the polymeric matrix improve the absorption property of the film, consequently quenching the luminescent effect.

Effect of terbium(III) on the binding of aromatic guests with sodium taurocholate aggregates

The effect of binding Tb(3+) to sodium taurocholate aggregates containing polyaromatic hydrocarbon guests was examined using pyrene and 1-ethylnaphthalene as guests that bind to the primary aggregate, and 1-naphthyl-1-ethanol as a secondary aggregate guest. Time-resolved fluorescence quenching studies were used to study the binding site properties, while laser flash photolysis quenching studies provided information on the dynamics of the guest-aggregate system. Both the primary and secondary aggregate binding sites became more compact in the presence of bound Tb(3+), while only the primary aggregate became more accessible to anionic molecules. The binding dynamics for the guest-primary aggregate system became faster when Tb(3+) was bound to the aggregate. In contrast, for the guest-secondary aggregate the presence of Tb(3+) resulted in a small decrease in the dissociation rate constant. The influence of bound Tb(3+) on the primary and secondary bile salt aggregates is significantly different, which affects how these aggregates can be used as supramolecular host systems to modify guest reactivity.

(4-Hydroxy-2,5-dimethylphenyl)phenylmethanone

The title compound, C(15)H(14)O(2), was obtained by Friedel-Crafts acylation between 2,5-dimethylphenol and benzoyl chloride in the presence of aluminium chloride as a catalyst. The dihedral angle between the benzene rings is 61.95 (4)degrees. In the crystal, O-H center dot center dot center dot O hydrogen bonding and C-H center dot center dot center dot O weak interactions lead to polymeric C(6), C(8) and C(11) chains along the a, b and c-axis directions, respectively.

Laser-induced breakdown spectroscopy and chemometrics for classification of toys relying on toxic elements

Quality control of toys for avoiding children exposure to potentially toxic elements is of utmost relevance and it is a common requirement in national and/or international norms for health and safety reasons. Laser-induced breakdown spectroscopy (LIBS) was recently evaluated at authors` laboratory for direct analysis of plastic toys and one of the main difficulties for the determination of Cd. Cr and Pb was the variety of mixtures and types of polymers. As most norms rely on migration (lixiviation) protocols, chemometric classification models from LIBS spectra were tested for sampling toys that present potential risk of Cd, Cr and Pb contamination. The classification models were generated from the emission spectra of 51 polymeric toys and by using Partial Least Squares - Discriminant Analysis (PLS-DA), Soft Independent Modeling of Class Analogy (SIMCA) and K-Nearest Neighbor (KNN). The classification models and validations were carried out with 40 and 11 test samples, respectively. Best results were obtained when KNN was used, with corrected predictions varying from 95% for Cd to 100% for Cr and Pb. (C) 2011 Elsevier B.V. All rights reserved.

Simultaneous flow injection preconcentration of lead and cadmium using cloud point extraction and determination by atomic absorption spectrometry

A flow injection (FI) micelle-mediated separation/preconcentration procedure for the determination of lead and cadmium by flame atomic absorption spectrometry (FAAS) has been proposed. The analytes reacted with 1-(2-thiazolylazo)-2-naphthol (TAN) to form hydrophobic chelates, which were extracted into the micelles of 0.05% (w/v) Triton X-114 in a solution buffered at pH 8.4. In the preconcentration stage, the micellar solution was continuously injected into a flow system with four mini-columns packed with cotton, glass wool. or TNT compresses for phase separation. The analytes-containing micelles were eluted from the mini-columns by a stream of 3 mol L(-1) HCl solution and the analytes were determined by FAAS. Chemical and flow variables affecting the preconcentration of the analytes were studied. For 15 mL. of preconcentrated solution, the enhancement factors varied between 15.1 and 20.3, the limits of detection were approximately 4.5 and 0.75 mu g L(-1) for lead and cadmium, respectively. For a solution containing 100 and 10 mu g L(-1) of lead and cadmium, respectively, the R.S.D. values varied from 1.6 to 3.2% (n = 7). The accuracy of the preconcentration system was evaluated by recovery measurements on spiked water samples. The method was susceptible to matrix effects, but these interferences were minimized by adding barium ions as masking agent in the sample solutions, and recoveries from spiked sample varied in the range of 95.1-107.3%. (C) 2008 Elsevier B.V. All rights reserved.

Environment-friendly soy flour-based resins without formaldehyde

Glyoxalated soy flour adhesives for wood particleboard added with a much smaller proportion of glyoxalated lignin or tannin and without any addition of either formaldehyde or formaldehyde-based resin are shown to yield results satisfying the relevant standard specifications for interior wood boards. Adhesive resin formulations in which the total content of natural material is either 70 or 80% of the total resin solids content gave good results. The resins comprising 70% by weight of natural material can be used in a much lower proportion on wood chips and can afford pressing times fast enough to be significant under industrial panel pressing conditions. The best formulation of all the ones tried was the one based on glyoxalated precooked soy flour (SG), to which a condensed tannin was added in water solution and a polymeric isocyanate (pMDI), where the proportions of the components SG/T/pMDI was 54/16/30 by weight. (C) 2008 Wiley Periodicals, Inc.

Synthesis of Nb(2)O(5)center dot nH(2)O nanoparticles by water-in-oil microemulsion

Hydrous niobium oxide (Nb(2)O(5)center dot nH(2)O) nanoparticles had been Successfully prepared by water-in-oil microemulsion. They were characterized by X-ray diffraction (XRD), thermal analysis (TG/DTG), Fourier transform infrared spectroscopy (FTIR), BET surface area measurement, transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The results showed that the nanoparticle was exactly Nb(2)O(5)center dot nH(2)O with spherical shape. Their BET surface area was 60 m(2) g(-1). XRD results showed that Nb(2)O(5)center dot nH(2)O nanoparticles with crystallite size in nanometer scale were formed. The crystallinity and crystallity size increased with increasing annealing temperature. TT-phase of Nb(2)O(5) was obtained when the sample is annealed at 550 degrees C. (C) 2009 Elsevier B.V. All rights reserved.