Weakly bound atomic trimers in ultracold traps

The scaling dependence of the recombination parameter as a function of the ratio between the energies of the atomic dimer and the most excited trimer states was derived. The scaling function tends to a unversal function in the limit of zero-range interaction or infinite scattering length. This paper reports on how one can obtain the trimer binding energy of a trapped atomic system, from the three-body recombination rate and the corresponding two-body scattering length.

Conformational basis for the biological activity of TOAC-labeled angiotensin II and bradykinin: Electron paramagnetic resonance, circular dichroism, and fluorescence studies

N-Terminally and internally labeled analogues of the hormones angiotensin (AII, DRVYIHPF) and bradykinin (BK, RPPGFSPFR) were synthesized containing the paramagnetic amino acid 2,2,6,6-tetramethylpiperidine-1-oxyl-4-amino-4- carboxylic acid (TOAC). TOAC replaced Asp 1 (TOAC 1-AII) and Val 3 (TOAC 3-AII) in AII and was inserted prior to Arg 1 (TOAC 0-BK) and replacing Pro 3 (TOAC 3-BK) in BK. The peptide conformational properties were examined as a function of trifluoroethanol (TFE) content and pH. Electron paramagnetic resonance spectra were sensitive to both variables and showed that internally labeled analogues yielded rotational correlation times (TC) considerably larger than N-terminally labeled ones, evincing the greater freedom of motion of the N-terminus. In TFE, τ C increased due to viscosity effects. Calculation of τ Cpeptide/τ CTOAC ratios indicated that the peptides acquired more folded conformations. Circular dichroism spectra showed that, except for TOAC 1-AII in TFE, the N-terminally labeled analogues displayed a conformational behavior similar to that of the parent peptides. In contrast, under all conditions, the TOAC 3 derivatives acquired more restricted conformations. Fluorescence spectra of All and its derivatives were especially sensitive to the ionization of Tyr 4. Fluorescence quenching by the nitroxide moiety was much more pronounced for TOAC 3-AII The conformational behavior of the TOAC derivatives bears excellent correlation with their biological activity, since, while the N-terminally labeled peptides were partially active, their internally labeled counterparts were inactive [Nakaie, C. R., et al., Peptides 2002, 23, 65-70]. The data demonstrate that insertion of TOAC in the middle of the peptide chain induces conformational restrictions that lead to loss of backbone flexibility, not allowing the peptides to acquire their receptor-bound conformation. © 2004 Wiley Periodicals, Inc.

Helivypolide G. A novel dimeric bioactive sesquiterpene lactone

Helivypolide G was isolated from leaves of Helianthus annuus L. cv. Stella. In the course of our ongoing research for new allelochemicals from Helianthus annuus, a novel dimeric bioactive sesquiterpene lactone, helivypolide G has been isolated and characterized from the medium polar active fractions of the leaves of cultivar variety Stella. The monomers are connected through carbons C-15 of each unit and an oxygen bridge, forming an enolic oxane ring. © 2004 Elsevier Ltd. All rights reserved.

Structure and weak hydrogen bonds in liquid acetaldehyde

Monte Carlo simulations have been performed to investigate the structure and hydrogen bonds formation in liquid acetaldehyde. An all atom model for the acetaldehyde have been optimized in the present work. Theoretical values obtained for heat of vaporisation and density of the liquid are in good agreement with experimental data. Graphics of radial distribution function indicate a well structured liquid compared to other similar dipolar organic liquids. Molecular mechanics minimization in gas phase leads to a trimer of very stable structure. The geometry of this complex is in very good agreement with the rdf. The shortest site-site correlation is between oxygen and the carbonyl hydrogen, suggesting that this correlation play a important role in the liquid structure and properties. The O⋯H average distance and the C-H⋯O angle obtained are characteristic of weak hydrogen bonds.

Synthesis and spectroscopic characterization of new metal(II) complexes with methionine sulfoxide

Methionine sulfoxide complexes of iron(II) and copper(II) were synthesized and characterized by chemical and spectroscopic techniques. Elemental and atomic absorption analyses fit the compositions K2[Fe(metSO) 2]SO4 · H2O and [Cu(metSO)2] · H2O. Electronic absorption spectra of the complexes are typical of octahedral geometries. Infrared spectroscopy suggests coordination of the ligand to the metal through the carboxylate and sulfoxide groups. An EPR spectrum of the Cu(II) complex indicates tetragonal distortion of its octahedral symmetry. 57Fe Mössbauer parameters are also consistent with octahedral stereochemistry for the iron(II) complex. The complexes are very soluble in water.

Synthesis and characterization of poly-o-toluidine: Kinetic and structural aspects

Poly(o-methylaniline) (poly-o-toluidine, PTOL) was synthesized by chemical oxidation of o-toluidine with ammonium peroxydisulfate in an aqueous 1.0 mol L -1 HCl solution. The progress of polymerization was followed by measuring the open-circuit potential (OCP) of a Pt electrode immersed in the reaction medium with the polymerization time. The chemical synthesis of PTOL was carried out at different monomer:oxidant (M:O) molar ratios (4:1, 2:1, 1.5:1, 1:1, and 0.66:1), and the products obtained were characterized by infrared spectroscopy, gel permeation chromatography, and X-ray diffraction. The molecular weight and percentage of crystallinity of PTOL are higher for samples synthesized in an excess of the monomer, i.e. at higher M:O ratios. However, the yield of PTOL prepared at higher M:O ratios is considerably low, in particular at a 4:1 M:O ratio, which is the M:O ratio most commonly used in the literature to synthesize polyaniline and its derivatives.

Four new metal complexes with the amino acid deoxyalliin

The solid complexes [Co(C6H10NO2S) 2], [Ni(C6H10NO2S)2], [Cu(C6H10NO2S)2] and [Fe(C 6H10NO2S)2] were obtained from the reaction of cobalt(II), nickel(II), copper(II) and iron(II) salts with the potassium salt of the amino acid deoxyalliin (S-allyl-L-cysteine). Electronic absorption spectra of the complexes are typical of octahedral structures. Infrared spectroscopy confirms the ligand coordination to the metal ions through (COO-) and (NH2) groups. EPR spectrum of the Cu(II) complex indicates a slight distortion of its octahedral symmetry. Mössbauer parameters permitted to identify the presence of iron(II) and iron(III) species in the same sample, both of octahedral geometry. Thermal decomposition of the complexes lead to the formation of CoO, NiO, CuO and Fe2O3 as final products. The compounds show poor solubility in water and in the common organic solvents. ©2005 Sociedade Brasileira de Química.

Effect of lithium doping on the evolution of rheological and structural properties during gelation of siloxane-poly(oxypropylene) nanocomposites

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Effect of post-polymerization heat treatments on the cytotoxicity of two denture base acrylic resins

Introduction: Most denture base acrylic resins have polymethylmethacrylate in their composition. Several authors have discussed the polymerization process involved in converting monomer into polymer because adequate polymerization is a crucial factor in optimizing the physical properties and biocompatibility of denture base acrylic resins. To ensure the safety of these materials, in vitro cytotoxicity assays have been developed as preliminary screening tests to evaluate material biocompatibility. 3H-thymidine incorporation test, which measures the number of cells synthesizing DNA, is one of the biological assays suggested for cytotoxicity testing. Aim: The purpose of this study was to investigate, using 3H-thymidine incorporation test, the effect of microwave and water-bath post-polymerization heat treatments on the cytotoxicity of two denture base acrylic resins. Materials and Methods: Nine disc-shaped specimens (10 x 1 mm) of each denture base resin (Lucitone 550 and QC 20) were prepared according to the manufacturers' recommendations and stored in distilled water at 37°C for 48 h. The specimens were assigned to 3 groups: 1) post-polymerization in a microwave oven for 3 min at 500 W; 2) post-polymerization in water-bath at 55°C for 60 min; and 3) without post-polymerization. For preparation of eluates, 3 discs were placed into a sterile glass vial with 9 mL of Eagle's medium and incubated at 37°C for 24 h. The cytotoxic effect of the eluates was evaluated by 3H-thymidine incorporation. Results: The results showed that the components leached from the resins were cytotoxic to L929 cells, except for the specimens heat treated in water bath (p<0.05). Compared to the group with no heat treatment, water-bath decreased the cytotoxicity of the denture base acrylic resins. Conclusion: The in vitro cytotoxicity of the tested denture base materials was not influenced by microwave post-polymerization heat treatment.

Magnetic resonance study of the crystallization behavior of InF3-based glasses doped with Cu2+, Mn2+ and Gd3+

The crystallization of fluoroindate glasses doped with Gd3+, Mn2+ and Cu2+ heat treated at different temperatures, ranging from the glass transition temperature (Tg) to the crystallization temperature (Tc), are investigated by electron paramagnetic resonance (EPR) and 19F nuclear magnetic resonance (NMR). The EPR spectra indicate that the Cu2+ ions in the glass are located in axially distorted octahedral sites. In the crystallized glass, the g-values agreed with those reported for Ba2ZnF6, which correspond to Cu2+ in a tetragonal compressed F- octahedron and to Cu2+ on interstitial sites with a square-planar F- co-ordination. The EPR spectra of the Mn2+ doped glasses exhibit a sextet structure due to the Mn2+ hyperfine interaction. These spectra suggest a highly ordered environment for the Mn2+ ions (close to octahedral symmetry) in the glass. The EPR spectra of the recrystallized sample exhibit resonances at the same position, suggesting that the Mn2+ ions are located in sites of highly symmetric crystalline field. The increase of the line intensity of the sextet and the decrease of the background line in the thermal treated samples suggest that the Mn2+ ions move to the highly ordered sites which contribute to the sextet structure. The EPR spectra of the Gd3+ doped glasses exhibit the typical U-spectrum of a s-state ion in a low symmetry site in disordered systems. The EPR of the crystallized glasses, in contrast, have shown a strong resonance in g ≈ 2.0, suggesting Gd3+ ions in environment close to cubic symmetry. The 19F NMR spin-lattice relaxation rates were also strongly influenced by the crystallization process that takes over in samples annealed above Tc. For the glass samples (doped or undoped) the 19F magnetization recoveries were found to be adjusted by an exponential function and the spin-lattice relaxation was characterized by a single relaxation time. In contrast, for the samples treated above Tc, the 19F magnetization-recovery becomes non-exponential. A remarkable feature of our results is that the changes in the Cu2+, Mn2+, Gd3+ EPR spectra and NMR relaxation, are always observed for the samples annealed above Tc. © 2006 Elsevier B.V. All rights reserved.

Orphan nuclear receptor NGFI-B forms dimers with nonclassical interface

The orphan receptor nerve growth factor-induced B (NGFI-B) is a member of the nuclear receptor's subfamily 4A (Nr4a). NGFI-B was shown to be capable of binding both as a monomer to an extended half-site containing a single AAAGGTCA motif and also as a homodimer to a widely separated everted repeat, as opposed to a large number of nuclear receptors that recognize and bind specific DNA sequences predominantly as homo- and/or heterodimers. To unveil the structural organization of NGFI-B in solution, we determined the quaternary structure of the NGFI-B LBD by a combination of ab initio procedures from small-angle X-ray scattering (SAXS) data and hydrogen-deuterium exchange followed by mass spectrometry. Here we report that the protein forms dimers in solution with a radius of gyration of 2.9 nm and maximum dimension of 9.0 nm. We also show that the NGFI-B LBD dimer is V-shaped, with the opening angle significantly larger than that of classical dimer's exemplified by estrogen receptor (ER) or retinoid X receptor (RXR). Surprisingly, NGFI-B dimers formation does not occur via the classical nuclear receptor dimerization interface exemplified by ER and RXR, but instead, involves an extended surface area composed of the loop between helices 3 and 4 and C-terminal fraction of the helix 3. Remarkably, the NGFI-B dimer interface is similar to the dimerization interface earlier revealed for glucocorticoid nuclear receptor (GR), which might be relevant to the recognition of cognate DNA response elements by NGFI-B and to antagonism of NGFI-B-dependent transcription exercised by GR in cells. Published by Cold Spring Harbor Laboratory Press. Copyright © 2007 The Protein Society.

Optimization of a novel nitric oxide sensor using a latex rubber matrix

This study present a novel NO sensor made of a spin trap (iron(II)-diethyldithiocarbamate complex, FeDETC) incorporated in a latex rubber matrix and works as a trap for NO, which is detectable by Electron Paramagnetic Resonance (EPR). We explored the optimization of our sensors changing systematically two fabrication parameters: the latex rubber matrix temperature of polymerization and FeDETC concentration inside the matrix. The sensor was prepared in four different temperatures: 4, 10, 20 and 40°C. The FeDETC concentration was also varied from 0.975 to 14.8 mM. We observed a variation of the EPR signals from the sensors prepared at different conditions. We found a high stability of the EPR response from our sensor, 40 days at RT. The best sensor was made with a latex rubber matrix polymerized at 10°C and with a FeDETC concentration of 14.8 mM. In vivo tests show good biocompatibility of our sensor. © 2007 Asian Network for Scientific Information.

Myotoxic phospholipases A2 isolated from Bothrops brazili snake venom and synthetic peptides derived from their C-terminal region: Cytotoxic effect on microorganism and tumor cells

This paper reports the purification and biochemical/pharmacological characterization of two myotoxic phospholipases A2 (PLA2s) from Bothrops brazili venom, a native snake from Brazil. Both myotoxins (MTX-I and II) were purified by a single chromatographic step on a CM-Sepharose ion-exchange column up to a high purity level, showing Mr ∼ 14,000 for the monomer and 28,000 Da for the dimer. The N-terminal and internal peptide amino acid sequences showed similarity with other myotoxic PLA2s from snake venoms, MTX-I belonging to Asp49 PLA2 class, enzymatically active, and MTX-II to Lys49 PLA2s, catalytically inactive. Treatment of MTX-I with BPB and EDTA reduced drastically its PLA2 and anticoagulant activities, corroborating the importance of residue His48 and Ca2+ ions for the enzymatic catalysis. Both PLA2s induced myotoxic activity and dose-time dependent edema similar to other isolated snake venom toxins from Bothrops and Crotalus genus. The results also demonstrated that MTXs and cationic synthetic peptides derived from their 115-129 C-terminal region displayed cytotoxic activity on human T-cell leukemia (JURKAT) lines and microbicidal effects against Escherichia coli, Candida albicans and Leishmania sp. Thus, these PLA2 proteins and C-terminal synthetic peptides present multifunctional properties that might be of interest in the development of therapeutic strategies against parasites, bacteria and cancer. © 2008 Elsevier Inc. All rights reserved.

Research of new mixed-chelate copper complexes with quinoxaline N 1,N 4,-dioxide derivatives and alanine as ligands, potential antimycobacterial agents

Three new mixed-chelate copper complexes with 3-aminoquinoxaline-2-carbonitrile N 1,N 4-dioxide derivatives and alanine as ligands were synthesized in solid state. The spectroscopic characterization (FTIR, EPR, UV-Vis) showed that copper coordinated through the amine and the N-oxide groups of the quinoxaline derivatives and the amine and carboxylate moieties from alanine forming a dimeric species. The tree complexes showed in vitro activity against M. tuberculosis H 37Rv (ATCC 27294) similar to that of ethambutol while they are inactive against E. coli and S. aureus.

The Rv1712 locus from Mycobacterium tuberculosis H37Rv codes for a functional CMP kinase that preferentially Phosphorylates dCMP

The Mycobacterium tuberculosis cmk gene, predicted to encode a CMP kinase (CMK), was cloned and expressed, and its product was purified to homogeneity. Steady-state kinetics confirmed that M. tuberculosis CMK is a monomer that preferentially phosphorylates CMP and dCMP by a sequential mechanism. A plausible role for CMK is discussed. Copyright © 2009, American Society for Microbiology. All Rights Reserved.