Determination of ionizable groups of proteins by potentiometric titration in concentrated solutions of guanidine hydrochloride

A linearization method based on modified Gran functions, and a general nonlinear regression program were used to study potentiometric titration curves of denatured ovalbumin and lysozyme in 6 mol L^–1 guanidine hydrochloride medium with the aim of determining the ionizable species. With both numerical techniques it was possible to determine the sum of the carboxylic groups, the imidazol, the α-amine, and the sum of ɛ-amine, phenolic and sulfhydryl groups, if the protein is completely denatured, and assumes a randomly coiled conformation. A total of 87.8 ± 2.5 and 20.7 ± 0.6 groups per mol were determined in the ovalbumin and lysozyme, respectively. These values are very close to the 88 and 21 groups expected by aminoacid composition of both proteins, indicating that all ionizable groups were exposed to the solvent. For ovalbumin the distribution of groups was very similar to that expected by the aminoacid composition, but for lysozyme some anomalies were observed, suggesting the existence of interactions between ionizable groups, altering the dissociation constants. Received: 9 December 1996 / Revised: 27 February 1997 / Accepted: 4 March 1997     

Preparation and characterization of theβ-cyclodextrin inclusion complex with phenylpropiolic acid

The preparation of a 1:1 complex involving-cyclodextrin (-CD) and phenylpropiolic acid (PPA) is reported. The new inclusion complex of-CD has been characterized on the basis of its chemical analysis, thermal behavior, infrared spectrum, X-ray powder pattern and¹³C-NMR spectrum in DMSO solution.     

Thermal behavior of some antihistamines

Thermogravimetry (TG), differential scanning calorimetry (DSC), polarized light thermal microscopy (PLTM), as well as X-ray powder diffraction (XRD) and Fourier transformed infrared spectroscopy (FTIR) were used to study the thermal behavior and the chemical structure of cimetidine, famotidine, ranitidine-HCl, and nizatidine. The TG–DSC curves show that the famotidine and ranitidine-HCl suffer decomposition during melting and they are thermally less stable in comparison with cimetidine and nizatidine, the latter being the most stable of all the drugs studied in this study. The DSC curves of famotidine and ranitidine-HCl show exothermic peaks immediately after the melting, confirming the occurrence of thermal decomposition. The DSC curves also show that the cimetidine and nizatidine have some thermal stability after melting. The thermal events shown in the PLTM images are consistent with the results shown in the TG–DSC and DSC curves. The XRD patterns show that the cimetidine and famotidine are less crystalline compared with ranitidine-HCl and nizatidine. The theoretical FTIR bands are in agreement with those obtained experimentally, and in some cases, no difference is observed between the theoretical and experimental values, even being identical in one of the cases.     

Thermoanalytical study of nimesulide and their recrystallization products obtained from solutions of several alcohols

Thermogravimetry, differential scanning calorimetry, and vibrational infrared spectroscopy were used to study nimesulide and its recrystallization products that were obtained from solutions of several alcohols. The thermoanalytical measurements were performed in both air and nitrogen atmospheres and the results suggest that, under the experimental conditions used in this paper, it was possible to obtain neither polymorphic nor pseudopolymorphic forms of this drug. In this investigation, quantum chemical approach methods were used to determine the molecular structures using the Becke three-parameter hybrid method and the Lee–Yang–Parr correlation functional. The performed molecular calculations were done with the Gaussian 09 routine and the theoretical calculation results were correlated with the experimental IR vibrational spectrum.     

Nanostructures of sodium titanate/zirconium oxide

In this work is reported the synthesis of nanotubes and nanoribbons from mixed oxides (Ti_1−x Zr _x O₂·nH₂O), employing hydrothermal treatment in a highly alkaline medium. The morphology and crystal structure of the products obtained via hydrothermal treatment depend on the value of x. For example, for x equal to 0 and 0.50 were observed the presence of nanotubes (diameter around 9 nm) and nanoribbons (diameter around 200 nm), respectively. However, for x values above 0.50, there was no morphological change. Regarding the crystalline structure of these samples, for x equal to 0 was observed the sodium titanate phase; already for x values up to 0.50, we observed the presence of two crystalline phases: sodium titanate and tetragonal ZrO₂. For x values above 0.50, only tetragonal ZrO₂ was observed. Furthermore, only the product obtained from x equal to 0.15 was observed the presence of three-dimensional flower-like arrangements. The results obtained by the characterization techniques showed the segregation of zirconium after hydrothermal treatment of precursors with x less or equal to 0.50. Thus, we describe the important role that Ti/Zr molar ratio of the precursor plays on the morphology and crystalline phase of the products formed by hydrothermal treatment.     

Characterization of galactooligosaccharides derived from lactulose

Galactooligosaccharides are non-digestible carbohydrates with potential ability to modulate selectively the intestinal microbiota. In this work, a detailed characterization of oligosaccharides obtained by transgalactosylation reactions of the prebiotic lactulose, by using β-galactosidases of different fungal origin (Aspergillus oryzae, Aspergillus aculeatus and Kluveromyces lactis), is reported. Oligosaccharides of degree of polymerization (DP) up to 6 were detected and quantified by HPLC-ESI MS from a complex mixture produced by transgalactosylation reaction with A. oryzae (GOSLuAo), whereas only carbohydrates up to DP4 and DP5 were found for those obtained from the reaction with β-galactosidases from K. lactis (GOSLuKl) and A. aculeatus (GOSLuAa), respectively. Disaccharides (galactosyl-galactoses and galactosyl-fructoses) and trisaccharides were characterised in the three mixtures by GC-MS as their trimethylsilyl oximes. Galactosyl- and digalactosyl-glycerols were produced during the transgalactosylation reaction of lactulose with β-galactosidases from A. aculeatus and K. lactis, due to the presence of glycerol as enzyme stabiliser.     

Green synthesis of colloidal silver nanoparticles using natural rubber latex extracted from Hevea brasiliensis

Colloidal silver nanoparticles were synthesized by an easy green method using thermal treatment of aqueous solutions of silver nitrate and natural rubber latex (NRL) extracted from Hevea brasiliensis. The UV–Vis spectra detected the characteristic surface plasmonic absorption band around 435 nm. Both NRL and AgNO₃ contents in the reaction medium have influence in the Ag nanoparticles formation. Lower AgNO₃ concentration led to decreased particle size. The silver nanoparticles presented diameters ranging from 2 nm to 100 nm and had spherical shape. The selected area electron diffraction (SAED) patterns indicated that the silver nanoparticles have face centered cubic (fcc) crystalline structure. FTIR spectra suggest that reduction of the silver ions are facilitated by their interaction with the amine groups from ammonia, which is used for conservation of the NRL, whereas the stability of the particles results from cis-isoprene binding onto the surface of nanoparticles. Therefore natural rubber latex extracted from H. brasiliensis can be employed in the preparation of stable aqueous dispersions of silver nanoparticles acting as a dispersing and/or capping agent. Moreover, this work provides a new method for the synthesis of silver nanoparticles that is simple, easy to perform, pollutant free and inexpensive.     

Flatness of Gaussian curvature and area of ideal triangles

Let M be aC ^k ,k 4, compact surface of genus greater than two whose curvature is negative in all points but along a simple closed geodesic (t) where the curvature is zero at every point. We show that the area of ideal triangles having a lifting of as an edge is infinite. This provides a family of surfaces having ideal triangles of infinite area whose geodesic flows are equivalent to Anosov flows, in contrast with the well-known examples of surfaces with flat strips which also have ideal triangles of infinite area. By the CAT-comparison theory we can deduce, using these surfaces as models, that aC compact surface of non-positive curvature having one geodesic along which the curvature is zero has ideal triangles of infinite area.Partially supported by CNPq of Brazilian Government