Ipolamiide and fulvoipolarniide from Stachytarpheta glabra (Verbenaceae): A structural and spectroscopic characterization

The phenylethanoid glycoside acteoside and the iridoids ipolamiide and 4-methoxycarbonyl-7-methylcyclopenta[c]pyran (fulvoipolamiide) were isolated from the leaves of Stachytarpheta glabra. The solid state structure of fulvoipolamiide was confirmed by X-ray diffraction studies. The molecules of fulvoipolamiide are displayed in layers parallel to the crystallographic axis a. This molecule is planar with electron delocalization in the fused ring system and the pyran rings of adjacent layers in the solid state structure are involved in a pi-pi stacking interaction. Raman spectroscopy has also been used to characterize the most important bands present in the spectra of fulvoipolamiide and ipolamiide, and comparison made with literature allows the assignment of some key markers, specially the bands in the 1600-1700 cm(-1) range. (C) 2007 Elsevier B.V. All rights reserved.

Effect of Ti and C additions on structural and magnetic properties of (Pr,Nd)-Fe-B nanocrystalline magnetic materials

Effects of titanium carbide (TiC) addition on structural and magnetic properties of isotropic (Pr,Nd)-Fe-B nanocrystalline magnetic materials have been investigated. In this work, we investigate the effect of TiC addition on a (Pr,Nd)-poor and B-rich composition, as well as on a B-poor and (Nd, Pr)-rich composition. Rapidly solidified (Pr, Nd)-Fe-B alloys were prepared by melt-spinning. The compositions studied were (Pr(1-x)Nd(x))(4)Fe(78)B(18) (x = 0, 0.5, and 1) with addition of 3 at% TiC. Unlike the (Pr(x)Nd(1-x))(9.5)Fe(84.5)B(6) materials that present excellent values for coercive. field and energy product, the (Pr,Nd)-poor and B-rich composition alloys with TiC addition present lower values. Rietveld analysis of X-ray data and Mossbauer spectroscopy revealed that samples are predominantly composed of Fe(3)B and alpha-Fe. For the RE-rich compositions (Pr(x)Nd(1-x))(9.5)Fe(84.5)B(6) (x = 0.1, 0.25, 0.5, 0.75, and 1) with the addition of 3 at% TiC, the highest coercive field and energy product (8.4 kOe and 14.4 MGOe, respectively) were obtained for the composition Pr(9.5)Fe(84.5)B(6). (c) 2008 Elsevier B.V. All rights reserved.

Structural and morphological studies on SiOxNy thin films

In this work, the structure and morphology of silicon oxynitride films deposited by the PECVD technique were studied. The films were deposited under two different conditions: (a) SiOxNy with chemical compositions varying from SiO2 to Si3N4 via the control of a N2O + N-2 + SiH4 gas mixture, and (b) Si-rich SiOxNy films via the control of a N2O + SiH4 gas mixture. The analyses were performed using X-ray near edge spectroscopy (XANES) at the Si-K edge, transmission electron microscopy (TEM) and Rutherford backscattering spectroscopy (RBS). For samples with chemical composition varying from SiO2 to Si3N4, the diffraction patterns obtained by TEM exhibited changes with the chemical composition, in agreement with the XANES results. For silicon-rich silicon oxynitride samples, the formation of a-Si clusters was observed and the possibility of obtaining Si nanocrystals after annealing depending on the composition and temperature was realized. (C) 2007 Elsevier B.V. All rights reserved.

Anodic porous alumina structural characteristics study based on SEM image processing and analysis

The present work reports the porous alumina structures fabrication and their quantitative structural characteristics study based on mathematical morphology analysis by using the SEM images. The algorithm used in this work was implemented in 6.2 MATLAB software. Using the algorithm it was possible to obtain the distribution of maximum, minimum and average radius of the pores in porous alumina structures. Additionally, with the calculus of the area occupied by the pores, it was possible to obtain the porosity of the structures. The quantitative results could be obtained and related to the process fabrication characteristics, showing to be reliable and promising to be used to control the pores formation process. Then, this technique could provide a more accurate determination of pore sizes and pores distribution. (C) 2008 Elsevier Ltd. All rights reserved.

Predicting the columnar-to-equiaxed transition for a distribution of nucleation undercoolings

A deterministic mathematical model for steady-state unidirectional solidification is proposed to predict the columnar-to-equiaxed transition. In the model, which is an extension to the classic model proposed by Hunt [Hunt JD. Mater Sci Eng 1984;65:75], equiaxed grains nucleate according to either a normal or a log-normal distribution of nucleation undercoolings. Growth maps are constructed, indicating either columnar or equiaxed solidification as a function of the velocity of isotherms and temperature gradient. The fields A columnar and equiaxed growth change significantly with the spread of the nucleation undercooling distribution. Increasing the spread Favors columnar solidification if the dimensionless velocity of the isotherms is larger than 1. For a velocity less than 1, however, equiaxed solidification is initially favored, but columnar solidification is enhanced for a larger increase in the spread. This behavior was confirmed by a stochastic model, which showed that an increase in the distribution spread Could change the grain structure from completely columnar to 50% columnar grains. (c) 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Structural and physicochemical characterization of RS prepared using hydrolysis and heat treatments of chickpea starch

The aim of this study was to evaluate the production and the structural and physicochemical properties of RS obtained by molecular mass reduction (enzyme or acid) and hydrothermal treatment of chickpea starch. Native and gelatinized starch were submitted to acid (2 M HCl for 2.5 h) or enzymatic hydrolysis (pullulanase, 40 U/g per 10 h), autoclaved (121 degrees C/30 min), stored under refrigeration (4 degrees C/24 h), and lyophilized. The hydrolysis of starch increased the RS content from 16% to values between 20 and 32%, and the enzymatic treatment of the gelatinized starch was the most efficient. RS showed an increase in water absorption and water solubility indexes due to hydrolytic and thermal process. The processes for obtaining RS changed the crystallinity pattern from C to B. Hydrolysis treatments caused an increase in relative crystallinity due to the greater retrogradation caused by the reduction in MW. RS obtained from hydrolysis showed a reduction in viscosity, indicating the rupture of molecules. The viscosity seemed to be inversely proportional to the RS content in the sample.

Atmospheric Absorption of Fluoride by Cultivated Species. Leaf Structural Changes and Plant Growth

Fluoride (F) is an air pollutant that causes phytotoxicity. Besides the importance of this, losses of agricultural crops in the vicinity of F polluting industries in Brazil have been recently reported. Injuries caused to plant leaf cell structures by excess F are not well characterized. However, this may contribute to understanding the ways in which plant physiological and biochemical processes are altered. A study evaluated the effects of the atmospheric F on leaf characteristics and growth of young trees of sweet orange and coffee exposed to low (0.04 mol L(-1)) or high (0.16 mol L(-1)) doses of HF nebulized in closed chamber for 28 days plus a control treatment not exposed. Gladiolus and ryegrass were used as bioindicators in the experiment to monitor F exposure levels. Fluoride concentration and dry mass of leaves were evaluated. Leaf anatomy was observed under light and electron microscopy. High F concentrations (similar to 180 mg kg(-1)) were found in leaves of plants exposed at the highest dose of HF. Visual symptoms of F toxicity in leaves of citrus and coffee were observed. Analyses of plant tissue provided evidence that F caused degeneration of cell wall and cytoplasm and disorganization of bundle sheath, which were more evident in Gladiolus and coffee. Minor changes were observed for sweet orange and ryegrass. Increase on individual stomatal area was also marked for the Gladiolus and coffee, and which were characterized by occurrence of opened ostioles. The increased F absorption by leaves and changes at the structural and ultrastructural level of leaf tissues correlated with reduced plant growth.

Enhanced fibroblast adhesion and proliferation on electrospun fibers obtained from poly(isosorbide succinate-b-L-lactide) block copolymers

Block copolymers containing isosorbide succinate and L-lactic acid repeating units with different mass compositions were synthesized in two steps: bulk ring-opening copolymerization from L-lactide and poli(isosorbide succinate) (PIS) preoligomer, in the presence of tin(II) 2-ethylhexanoate as catalyst. followed by chain extension in solution by using hexamethylene diisocyanate. Poly(L-lactide) (PLLA) and a chain extension product from PIS were also obtained, for comparison. SEC, (1)H and (13)C NMR, MALDI-TOFMS, WAXD, DSC, TG, and contact angle measurements were used in their characterization. The incorporation of isosorbide succinate into PLLA main backbone had minor effect on the thermal stability and the T(g) of the products. However, it reduced the crystallinity and increased the surface energy in relation to PLLA. Nonwoven mats of the block copolymers and PLLA obtained by electrospinning technique were submitted to fibroblasts 3T3-L1 cell culture. The copolymers presented enhanced cell adhesion and proliferation rate as revealed by MTT assay and SEM images. (C) 2009 Elsevier Ltd. All rights reserved.

Expanding cyclitol structural diversity by biocatalysis and metalocatalysis. A click chemistry approach

The palladium catalyzed cross-coupling reaction of phenyltrifluoroborate with a chemoenzymatically derived bromoazidoconduritol, combined with 1,3-dipolar cycloaddition, with a variety of alkynes is described. Fourteen new compounds were synthesized in moderate to good yields. The click chemistry reaction can be effected by using sodium ascorbate and CuSO(4) center dot 5H(2)O as catalyst in toluene-H(2)O at room temperature.

DSC estimation of structural and textural parameters of SBA-15 silica using water probe

The aim of this study was to use DSC and X-ray diffraction measurements to determine the pore size and pore wall thickness of highly ordered SBA-15 materials. The DSC curves showed two endothermic events during the heating cycle. These events were due to the presence of water inside and outside of mesopores. The results of pore radius, wall thickness and pore volume measurements were in good agreement with the results obtained by nitrogen adsorption measurement, XRD and transmission electron microscopy.

Detailed H-1 and C-13 NMR structural assignment and relative stereochemistry determination for three closely related sesquiterpene lactones

A complete analysis of H-1 and C-13 NMR spectra of the trypanocidal sesquiterpene lactone eremantholide C and two of its analogues is described. These structurally similar sesquiterpene lactones were submitted to H-1 NMR, C-13 (H-1) NMR, gCOSY, gHSQC, gHMBC, J-resolved and DPFGSE-NOE NMR techniques. The detailed analysis of those results, correlated to some computational calculations (molecular mechanics), led to the total and unequivocal assignment of all H-1 and C-13 NMR data. The determination of all H-1/H-1 coupling constants and all signal multiplicities, together with the elimination of previous ambiguities were also achieved. Copyright (C) 2008 John Wiley & Sons, Ltd.

Structural characterization of exopolysaccharides from biofilm of a cariogenic streptococci

Soluble (EPS-SOL), as well as insoluble extracellular polysaccharide (EPS-INSOL), extracted from biofilm of Streptococcus mutans, were analyzed by nuclear magnetic resonance spectroscopy, methylation analysis, and a controlled Smith degradation. EPS-SOL was a branched alpha-glucan containing a (1 -> 6)-and (1 -> 3)-linkages. EPS-INSOL was a branched alpha-glucan with similar linkages, but with a (1 -> 3)-linked main-chain partially substituted at O-6 with Glcp-(1 -> 6)-Glcp-side chains. Biofilm EPS had a distinct chemical structure compared with those synthesized by plankton cells or by purified enzymes from S. mutans, which could indicate different mechanisms for its degradation. (C) 2011 Published by Elsevier Ltd.

Photocytotoxic activity of a nitrosyl phthalocyanine ruthenium complex - A system capable of producing nitric oxide and singlet oxygen

The synthesis, structural aspects, pharmacological assays, and in vitro photoinduced cytotoxic properties of [Ru(NO)(ONO)(pc)] (pc = phthalocyanine) are described. Its biological effect on the B16F10 cell line was studied in the presence and absence of visible light irradiation. At comparable irradiation levels, [Ru(NO) (ONO)(pc)] was more effective than [Ru(pc)] at inhibiting cell growth, suggesting that occurrence of nitric oxide release following singlet oxygen production upon light irradiation may be an important mechanism by which the nitrosyl ruthenium complex exhibits enhanced biological activity in cells. Following visible light activation, the [Ru(NO)(ONO)(pc)] complex displayed increased potency in B16F10 cells upon modifications to the photoinduced dose; indeed, enhanced potency was detected when the nitrosyl ruthenium complex was encapsulated in a drug delivery system. The liposome containing the [Ru(NO)(ONO)(pc)] complex was over 25% more active than the corresponding ruthenium complex in phosphate buffer solution. The activity of the complex was directly proportional to the ruthenium amount present inside the cell, as determined by inductively coupled plasma mass spectroscopy. Flow cytometry analysis revealed that the photocytotoxic activity was mainly due to apoptosis. Furthermore, the vasorelaxation induced by [Ru(NO)(ONO)(pc)], proposed as NO carrier, was studied in rat isolated aorta. The observed vasodilation was concentration-dependent. Taken together, the present findings demonstrate that the [Ru(NO)(ONO)(pc)] complex induces vascular relaxation and could be a potent anti-tumor agent. Nitric oxide release following singlet oxygen production upon visible light irradiation on a nitrosyl ruthenium complex produces two radicals and may elicit phototoxic responses that may find useful applications in photodynamic therapy. Crown Copyright (C) 2011 Published by Elsevier Inc. All rights reserved.

On the mechanisms of phenothiazine-induced mitochondrial permeability transition: Thiol oxidation, strict Ca(2+) dependence, and cyt c release

Phenothiazines (PTZ) are drugs widely used in the treatment of schizophrenia. Trifluoperazine, a piperazinic PTZ derivative, has been described as inhibitor of the mitochondrial permeability transition (MPT). We reported previously the antioxidant activity of thioridazine at relatively low concentrations associated to the inhibition of the MPT (Brit. J. Pharmacol., 2002;136:136-142). In this study, it was investigated the induction of MPT by PTZ derivatives at concentrations higher than 10 mu M focusing on the molecular mechanism involved. PTZ promoted a dose-response mitochondrial swelling accompanied by mitochondrial transmembrane potential dissipation and calcium release, being thioridazine the most potent derivative. PTZ-induced MPT was partially inhibited by CsA or Mg(2+) and completely abolished by the abstraction of calcium. The oxidation of reduced thiol group of mitochondrial membrane proteins by PTZ was upstream the VIP opening and it was not sufficient to promote the opening of PTP that only occurred when calcium was present in the mitochondrial matrix. EPR experiments using DMPO as spin trapping excluded the participation of reactive oxygen species on the PTZ-induced MPT. Since 117 give rise to cation radicals chemically by the action of peroxidases and cyanide inhibited the PTZ-induced swelling, we propose that VIZ bury in the inner mitochondrial membrane and the chemically generated 117 cation radicals modify specific thiol groups that in the presence of Ca(2+) result in MPT associated to cytochrome c release. These findings contribute for the understanding of mechanisms of MET induction and may have implications for the cell death induced by PTZ. (C) 2010 Elsevier Inc. All rights reserved.

Impact of adenosine nucleotide translocase (ANT) proline isomerization on Ca(2+)-induced cysteine relative mobility/mitochondrial permeability transition pore

Mitochondrial membrane carriers containing proline and cysteine, such as adenine nucleotide translocase (ANT), are potential targets of cyclophilin D (CyP-D) and potential Ca(2+)-induced permeability transition pore (PTP) components or regulators; CyP-D, a mitochondrial peptidyl-prolyl cis-trans isomerase, is the probable target of the PTP inhibitor cyclosporine A (CsA). In the present study, the impact of proline isomerization (from trans to cis) on the mitochondrial membrane carriers containing proline and cysteine was addressed using ANT as model. For this purpose, two different approaches were used: (i) Molecular dynamic (MD) analysis of ANT-Cys(56) relative mobility and (ii) light scattering techniques employing rat liver isolated mitochondria to assess both Ca(2+)-induced ANT conformational change and mitochondrial swelling. ANT-Pro(61) isomerization increased ANT-Cys(56) relative mobility and, moreover, desensitized ANT to the prevention of this effect by ADP. In addition, Ca(2+) induced ANT ""c"" conformation and opened PTP; while the first effect was fully inhibited, the second was only attenuated by CsA or ADP. Atractyloside (ATR), in turn, stabilized Ca(2+)-induced ANT ""c"" conformation, rendering the ANT conformational change and PTP opening less sensitive to the inhibition by CsA or ADP. These results suggest that Ca(2+) induces the ANT ""c"" conformation, apparently associated with PTP opening, but requires the CyP-D peptidyl-prolyl cis-trans isomerase activity for sustaining both effects.