In vivo infection by Trypanosoma cruzi: The conserved FLY domain of the gp85/trans-sialidase family potentiates host infection

Trypanosoma cruzi is a protozoan parasite that infects vertebrates, causing in humans a pathological condition known as Chagas` disease. The infection of host cells by T. cruzi involves a vast collection of molecules, including a family of 85 kDa GPI-anchored glycoproteins belonging to the gp85/trans-sialidase superfamily, which contains a conserved cell-binding sequence (VTVXNVFLYNR) known as FLY, for short. Herein, it is shown that BALB/c mice administered with a single dose (1 mu g/animal, intraperitoneally) of FLY-synthetic peptide are more susceptible to infection by T. cruzi, with increased systemic parasitaemia (2-fold) and mortality. Higher tissue parasitism was observed in bladder (7.6-fold), heart (3-fold) and small intestine (3.6-fold). Moreover, an intense inflammatory response and increment of CD4(+) T cells (1.7-fold) were detected in the heart of FLY-primed and infected animals, with a 5-fold relative increase of CD4(+)CD25(+)FoxP3(+) T (Treg) cells. Mice treated with anti-CD25 antibodies prior to infection, showed a decrease in parasitaemia in the FLY model employed. In conclusion, the results suggest that FLY facilitates in vivo infection by T. cruzi and concurs with other factors to improve parasite survival to such an extent that might influence the progression of pathology in Chagas` disease.

cis-4-decenoic acid provokes mitochondrial bioenergetic dysfunction in rat brain

Aims: In the present work we investigated the in vitro effect of cis-4-decenoic acid, the pathognomonic metabolite of medium-chain acyl-CoA dehydrogenase deficiency, on various parameters of bioenergetic homeostasis in rat brain mitochondria. Main methods: Respiratory parameters determined by oxygen consumption were evaluated, as well as membrane potential, NAD(P)H content, swelling and cytochrome c release in mitochondrial preparations from rat brain, using glutamate plus malate or succinate as substrates. The activities of citric acid cycle enzymes were also assessed. Key findings: cis-4-decenoic acid markedly increased state 4 respiration, whereas state 3 respiration and the respiratory control ratio were decreased. The ADP/O ratio, the mitochondrial membrane potential, the matrix NAD(P)H levels and aconitase activity were also diminished by cis-4-decenoic acid. These data indicate that this fatty acid acts as an uncoupler of oxidative phosphorylation and as a metabolic inhibitor. cis-4-decenoic acid also provoked a marked mitochondrial swelling when either KCl or sucrose was used in the incubation medium and also induced cytochrome c release from mitochondria, suggesting a non-selective permeabilization of the inner mitochondria! membrane. Significance: It is therefore presumed that impairment of mitochondrial homeostasis provoked by cis-4-decenoic acid may be involved in the brain dysfunction observed in medium-chain acyl-CoA dehydrogenase deficient patients. (C) 2010 Elsevier Inc. All rights reserved.

Total Trans Fatty Acid Analysis in Spreadable Cheese by Capillary Zone Electrophoresis

An alternative method for determination of total trans fatty acids expressed as elaidic acid by capillary zone electrophoresis (CZE) under indirect UV detection at 224 nm within an analysis time of 7.5 min was developed. The optimized running electrolyte includes 15.0 mmol L(-1) KH(2)PO(4)/Na(2)HPO(4) buffer (pH similar to 7.0), 4.0 mmol L(-1) SDBS, 8.0 mmol L(-1) Brij35, 45%v/v ACN, 8% methanol, and 1.5% v/v n-octanol. Baseline separation of the critical pair C18-9cis/C18:1-9t: with a resolution higher than 1.5 was achieved using C15:0 as the internal standard. The optimum capillary electrophoresis (CE) conditions for the background electrolyte were established with the aid of Raman spectroscopy and experiments of a 3(2) factorial design. After response factor (R(F)) calculations, the CE method was applied to total trans fatty acid (TTFA) analysis in a hydrogenated vegetable fat (HVF) sample, and compared with the American Oil Chemists` Society (AOCS) official method by gas chromatography (GC). The methods were compared with an independent sample t test, and no significant difference was found between CE and GC methods within the 95% confidence interval for six genuine replicates of TTFA analysis (p-value > 0.05). The CE method was applied to TTFA analysis in a spreadable cheese sample. Satisfactory results were obtained, indicating that the optimized methodology can be used for trans fatty acid determination for these samples.

Formation of out of plane oxime metallacycles in [Cu(2)] and [Cu(4)] complexes

The reaction Of Cu(ClO(4))(2)center dot 6H(2)O with dimethylglyoxime (H(2)dmg) in a 1:1 mole ratio in aqueous methanol at room temperature affords the dinuclear complex [Cu(2)(mu-Hdmg)(4)] (1). Reaction of 1 with [Cu(bpy)(H(2)O)(2)](ClO(4))(2) (bpy = 2,2`-bipyridine) in a 1:1 mole ratio in aqueous methanol at room temperature yields the tetranuclear complex [Cu(2)(mu-HdMg)(2)(mu-dMg)(2)(bpy)(2)(H(2)O)(2)](ClO(4))(2) (2). The direct reaction of Cu(ClO(4))(2)center dot 6H(2)O with H(2)dmg and bpy in a 2:21 mole ratio in aqueous methanol at room temperature also yields 2 quantitatively. The complexes 1 and 2 were structurally characterized by X-ray crystallography. Unlike the binding in Ni/Co-dmg, two different types of N-O bridging modes during the oxime based metallacycle formation and stacking of square planar units have been identified in these complexes. The neutral dinuclear complex 1 has CuN(4)O coordination spheres and complex 2 consists of a dicationic [Cu(2)(mu-HdMg)(2)(mu-dMg)(2)(bpy)(2)(H(2)O)(2)](2+) unit and two uncoordinated ClO(4)(-) anions having CuN(4)O and CuN(2)O(3) coordination spheres. The two copper(II) ions are at a distance of 3.846(8) angstrom in 1 for the trans out of plane link and at 3.419(10) and 3.684(10) angstrom in 2 for the trans out of plane and cis in plane arrangements, respectively. The average Cu-N(oxime) distances are 1.953 and 1.935 angstrom, respectively. The average basal and apical Cu-N(oxime) distances are 1.945, 2.295 and 2.429 angstrom. The UV-Vis spectra of 2 is similar to the spectrum of the reaction mixture of 1 and [Cu(bpy)(H(2)O)(2)](2+). Variable temperature magnetic properties measurement shows that the interaction between the paramagnetic copper centers in complex I is antiferromagnetic in nature. The EPR spectra of frozen solution of the complexes at 77 K consist of axially symmetric fine-structure transitions (Delta M(S) = 1) and half-field signals (Delta M(S) = 2) at ca. 1600 G, suggesting the presence of appreciable Cu-Cu interactions. (C) 2009 Elsevier Ltd. All rights reserved.

Synthesis and Characterization of Magnetic Composites Based on Cis-Polyisoprene and CoFe(2)O(4) Nanoparticles

CoFe(2)O(4) nanoparticles were obtained by the co-precipitation method. They were further modified by the adsorption of ricinoleic acid (RA). The non-modified and modified CoFe(2)O(4)/RA nanoparticles were characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM), Raman, and Fourier transform infrared (FTIR) spectroscopy. The modified particles present a mean diameter < 20 nm. The adsorption of RA on the CoFe(2)O(4) surface is characterized by the IR absorptions of the RA while in the Raman spectrum the predominant signals are those from the CoFe(2)O(4). The cis-polyisoprene (PI) composite was prepared by dissolving PI in cyclohexane followed by the addition of a magnetic fluid based on CoFe(2)O(4)/RA nanoparticles dispersed in cyclohexane. After solvent evaporation a magnetic composite was obtained and characterized by AFM, Raman, and FTIR measurements. AFM images show uniformly CoFe(2)O(4)/RA particles distributed in the PI matrix. Raman spectra obtained for the composites reveal the characteristic Raman peaks of PI and CoFe(2)O(4) nanoparticles.

Photoswitches and Luminescent Rigidity Sensors Based on fac-[Re(CO)(3)(Me(4)phen)(L)](+)

The fac-[Re(CO)(3)(Me(4)phen)(trans-L)](+) complexes, Me(4)phen = 3,4,7,8-tetramethyl-1,10-phenanthroline and L = 4-styrylpyridine, stpy, or 1,2-bis(4-pyridyl)ethylene, bpe, were synthesized and characterized by their spectroscopic, photochemical, and photophysical properties. The complexes exhibit trans-to-cis isomerization upon 313, 334, 365, and 404 nm irradiation, and the true quantum yields can be efficiently determined by absorption changes combined with (1)H NMR data. For fac-[Re(CO)(3)(Me(4)phen)(trans-bpe)](+) similar quantum yields were determined at all wavelengths investigated. However, a lower value (phi(true) = 0.35) was determined for fac-[Re(CO)(3)(Me(4)phen)(trans-stpy)](+) at 404 nm irradiation, which indicates different pathways for the photoisomerization process. The photoproducts, fac-[Re(CO)(3)(Me(4)phen)(cis-L)](+), exhibit luminescence at room temperature with two maxima ascribed to the (3)IL(Me4phen) and (3)MLCT(Re -> Me4phen) excited states. The luminescence properties were investigated in different media, and the behavior in glassy EPA at 77 K showed that the contribution of each emissive state is dependent on the excitation wavelength. The photochemical and photophysical behavior of the complexes were rationalized in terms of the energy gap of excited states and can be exploited in photoswitchable luminescent rigidity sensors.

Chemoselective screening for the reduction of a chiral functionalised (+/-)-2-(phenylthio)cyclohexanone by whole cells of Brazilian micro-organisms

The use of whole cells of micro-organisms to bring about the biotransformation of an organic compound offers a number of advantages, but problems caused by enzymatic Promiscuity may be encountered upon With Substrates hearing more than one functional group. A one-pot screening method, in which whole fungal cells were incubated with a Mixture of 4-rnethylcyclohexanone I and phenyl methyl Sulfide 2, has been employed to determine the chemoselectivity of various biocatalysts. The hyphomycetes, Aspergillus terreus CCT 3320 and A. terreus URM 3571, catalysed the oxidation of 2 accompanied by the reduction of I to 4-methylcyclohexanol 1a and, for strain A. terreus CCT 3320, the Baeyer-Villiger oxidation of 1. The Basidomycetes, Trametes versicolor CCB 202, Pycnoporus sanguineus CCB 501 and Trichaptum byssogenum CCB 203, catalysed the oxidation of 2 and the reduction 1, but no Baeyer-Villiger reaction products were detected. In contrast. Trametes rigida CCB 285 catalysed the biotransformation of 1 to 1a, exclusively, in the absence of any detectable Sulfide oxidation reactions. The chemoselective reduction Of (+/-)-2-(phenylthio)cyclohexanone 3 by T. rigida CCB 285 afforded exclusively the (+)-cis-(1R,2S) and (+)-trans-(1S,2S) diastereoisomers of 2-(phenylthio)cyclohexan-1-ol 3a in moderate yields (13% and 27%, respectively) and high enantiomeric excesses (>98%). Chemoselective screening for the reduction of a ketone and/or the oxidation Of a Sulfide group in one pot by whole cells of micro-organisms represents an attractive technique with applications in the development of synthesis of complex molecule hearing different functional groups. (C) 2008 Published by Elsevier Ltd.

Preparation and characterization of the novels terpolymers of poly-{trans-[RuCl(2)(vpy)(4)]-styrene-divinylbenzene} and styrene-divinylbenzene-vinylpiridine impregnated with silver nanoparticles

This paper reports the preparation and characterization of poly-{trans-[RuCl(2)(vpy)(4)]-styrene-divinylbenzene} and styrene-divinylbenzene-vinylpiridine filled with nanosilver. Theses materials were synthesized by non aqueous polymerization through a chemical reaction using benzoyl peroxide as the initiator. The nanosilver was obtained from chemical reduction using NaBH(4) as reducing agent and sodium citrate as stabilizer. The nanometric dimension of nanosilver was monitored by UV-visible and confirmed through TEM. The morphology was characterized by SEM and the thermal properties were done by TGA and DSC. The antimicrobial action of the polymers impregnated with nanosilver was evaluated using both microorganisms, Staphylococcus aureus and Escherichia coli. The antimicrobial activity of the poly-{trans-[RuCl(2)(vpy)(4)]-styrene-divinylbenzene} filled with nanosilver was confirmed by the presence of an inhibition halo of the bacterial growth in seeded culture media, but was not confirmed to the styrene-divinylbenzene-vinylpiridine. The present work suggest that trans - [RuCl(2)(vpy)(4)] complex facilitate the release of silver ion from the media.

Azo-hydrazone tautomerism in protonated aminoazobenzenes: Resonance Raman spectroscopy and quantum-chemical calculations

The protonation effect on the vibrational and electronic spectra of 4-aminoazobenzene and 4-(dimethylamino)azobenzene was investigated by resonance Raman spectroscopy, and the results were discussed on the basis of quantum-chemical calculations. Although this class of molecular systems has been investigated in the past concerning the azo-hydrazone tautomerism, the present work is the first to use CASSCF/CASPT2 calculations to unveil the structure of both tautomers as well the nature of the molecular orbitals involved in chromophoric moieties responsible for the resonance Raman enhancement patterns. More specifically both the resonance Raman and theoretical results show clearly that in the neutral species, the charge transfer transition involves mainly the azo moiety, whereas in the protonated forms there is a great difference, depending on the tautomer. In fact, for the azo tautomer the transition is similar to that observed in the corresponding neutral species, whereas in the hydrazone tautomer such a transition is much more delocalized due to the contribution of the quinoid structure. The characterization of protonated species and the understanding of the tautomerization mechanism are crucial for controlling molecular properties depending on the polarity and pH of the medium.

Tellurium in organic synthesis: a new approach to trisubstituted gamma-butyrolactones with trans-trans relative stereochemistry. Total enantioselective synthesis of (-)-Blastmycinolactol, (+)-Blastmycinone, (-)-NFX-2, and (+)-Antimycinone

The total synthesis of (-)-Blastmycinolactol, (+)-Blastmycinone, (-)-NFX-2, and (+)-Antimycinone was accomplished in few steps in high yields and ee, starting from enantiomerically enriched (S)-Z-vinylic hydroxytellurides. (C) 2010 Published by Elsevier Ltd.

Excited-State Dynamics in fac-[Re(CO)(3)(Me(4)phen)(L)](+)

Excited-state dynamics in fac-[Re(CO)(3)(Me(4)phen)(cis-L)](+) (Me(4)phen = 3,4,7,8-tetramethyl-1,10-phenanthroline, L = 4-styrylpyridine (stpy) or 1,2-bis(4-pyridyl)ethylene (bpe)) were investigated by steady-state and time-resolved techniques. A complex equilibrium among three closely lying excited states, 3IL(cis-L), (3)MLCT(Re -> me4phen), and (3)IL(Me4phen), has been established. Under UV irradiation, cis-to-trans isomerization of coordinated cis-L is observed with a quantum yield of 0.15 in acetonitrile solutions. This photoreaction competes with radiative decay from (3)MLCT(Re -> Me4phen) and (3)IL(Me4phen) excited states, leading to a decrease in the emission quantum yield relative to the nonisomerizable complex fac-[Re(CO)(3)(Me(4)phen)(bpa)](+) (bpa = 1,2-bis(4-pyridyl)ethane). From temperature-dependent time-resolved emission measurements in solution and in poly(methyl methacrylate) (PMMA) films, energy barriers (Delta E(a)) for interconversion between (3)MLCT(Re -> me4Phen) and (3)IL(Me4phen) emitting states were determined. For L = cis-stpy, Delta E(a) = 11 (920 cm(-1)) and 15 kJ mol(-1) (1254 cm(-1)) in 5:4 propionitrile/butyronitrile and PMMA, respectively. For L = cis-bpe, Delta E(a) = 13 kJ mol(-1) (1087 cm(-1)) in 5:4 propionitrile/butyronitrile. These energy barriers are sufficient to decrease the rate constant for internal conversion from higher-lying (3)IL(me4phen) state to (3)MLCT(Re -> Me4phen), k(i) congruent to 10(6) s(-1). The decrease in rate allows for the observation of intraligand phosphorescence, even in fluid medium at room temperature. Our results provide additional insight into the role of energy gap and excited-state dynamics on the photochemical and photophysical properties of Re(I) polypyridyl complexes.

Total syntheses of trikentrins and of herbindoles

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(1)H NMR spectroscopy as a tool to determine accurate photoisomerization quantum yields of stilbene-like ligands coordinated to rhenium(I) polypyridyl complexes

In this work, the use of proton nuclear magnetic resonance, (1)H NMR, was fully described as a powerful tool to follow a photoreaction and to determine accurate quantum yields, so called true quantum yields (Phi(true)), when a reactant and photoproduct absorption overlap. For this, Phi(true) for the trans-cis photoisomerization process were determined for rhenium(I) polypyridyl complexes, fac-[Re(CO)(3)(NN)(trans-L)](+) (NN = 1,10-phenanthroline, phen, or 4,7-diphenyl-1,10-phenanthroline, ph(2)phen, and L = 1,2-bis(4-pyridyl) ethylene, bpe, or 4-styrylpyridine, stpy). The true values determined at 365 nm irradiation (e. g. Phi(NMR) = 0.80 for fac-[Re(CO)(3)(phen)(trans-bpe)](+)) were much higher than those determined by absorption spectral changes (Phi(UV-Vis) = 0.39 for fac-[Re(CO)(3)(phen)(trans-bpe)](+)). Phi(NMR) are more accurate in these cases due to the distinct proton signals of trans and cis-isomers, which allow the actual determination of each component concentration under given irradiation time. Nevertheless when the photoproduct or reactant contribution at the probe wavelength is negligible, one can determine Phi(true) by regular absorption spectral changes. For instance, Phi(313) nm for free ligand photoisomerization determined both by absorption and (1)H NMR variation are equal within the experimental error (bpe: Phi(UV-Vis) = 0.27, Phi(NMR) = 0.26; stpy: Phi(UV-Vis) = 0.49, Phi(NMR) = 0.49). Moreover, (1)H NMR data combined with electronic spectra allowed molar absorptivity determination of difficult to isolate cis-complexes. (C) 2009 Elsevier B. V. All rights reserved.

Stereoselective synthesis of azetidine-derived glutamate and aspartate analogues from chiral azetidin-3-ones

The stereoselective syntheses of cis conformationally constrained glutamate and aspartate analogues, containing an azetidine framework were accomplished from (S)-N-tosyl-2-phenylglycine in moderate overall yields. The key steps in these syntheses involved an efficient Wittig olefination of an azetidin-3-one, followed by a highly stereoselective rhodium catalyzed hydrogenation. The route could also be applied to the synthesis of a trans glutamate analogue, since epimerization of cis to trans isomer could be performed using DBU in toluene at reflux. (C) 2008 Elsevier Ltd. All rights reserved.

Excited-state dynamics of polyfluorene derivatives in solution

The excited-state dynamics of two polyfluorene copolymers, one fully conjugated containing phenylene vinylene units alternated with 9,9`-dihexylfluorenyl groups and the other segmented by -(CH2)(8)- spacer, were studied in dilute solution of different solvents using a picosecond single-photon timing technique. The excited-state dynamics of the segmented copolymer follows the Forster resonant energy-transfer model which describes intrachain energy-transfer kinetics among random oriented chromophores. Energy transfer is confirmed by analysis of fluorescence anisotropy relaxation with the measurement of a short decay component of about 60 ps. The fluorescence decay surface of the fully conjugated copolymer is biexponential with decay times of about 470 and 900 ps, ascribed to deactivation of chain moieties containing trans and cis isomers already in a photostationary condition. Thus, energy transfer is very fast due to the conjugated nature and rigid-rod-like structure of this copolymer chain.