Thermal behaviour of amorphous Li2ZrO3 prepared by sol-gel technique

The results of the investigations of thermal behaviour of Li₂ZrO₃, prepared in the amorphous state by means of sol-gel technique are demonstrated. The thermal treatment was carried out in air under constant heating rate of 5 deg·min^–1 and cooling rate of 2.5 deg·min^–1. The methods of DTA, TG, Emanation Thermal Analysis (ETA) and dilatometry were used, for characterization of the thermal behaviour in dynamic conditions. The X-ray diffraction patterns were used for characterization of the phase changes observed by TA Methods.

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Zusammenfassung Ergebnisse aus Untersuchungen des thermischen Verhaltens von Li₂ZrO₃, hergestellt mittels einer Sol-Gel-Technik im amorphen Zustand werden dargelegt. Die thermische Behandlung wurde in Luft bei einer konstanten Aufheizgeschwindigkeit von 5 Grad·min^–1 und einer Abkühlgeschwindigkeit von 2,5Grad·min^–1 durchgeführt. Zur Beschreibung des thermischen Verhaltens unter dynamischen Verhältnissen wurden DTA, TG, Emanationsthermoanalyse und Dilatometrie angewendet. Zur näheren Charakterisierung der bei TG beobachteten Phasenumwandlungen wurde Röntgendiffraktion verwendet.

     

Molecular recognition and crystal energy landscapes: an X-ray and computational study of caffeine and other methylxanthines

We introduce a new approach to crystal-packing analysis, based on the study of mutual recognition modes of entire molecules or of molecular moieties, rather than a search for selected atom-atom contacts, and on the study of crystal energy landscapes over many computer-generated polymorphs, rather than a quest for the one most stable crystal structure. The computational tools for this task are a polymorph generator and the PIXEL density sums method for the calculation of intermolecular energies. From this perspective, the molecular recognition, crystal packing, and solid-state phase behavior of caffeine and several methylxanthines (purine-2,6-diones) have been analyzed. Many possible crystal structures for anhydrous caffeine have been generated by computer simulation, and the most stable among them is a thermodynamic, ordered equivalent of the disordered phase, revealed by powder X-ray crystallography. Molecular recognition energies between two caffeine molecules or between caffeine and water have been calculated, and the results reveal the largely predominant mode to be the stacking of parallel caffeine molecules, an intermediately favorable caffeine-water interaction, and many other equivalent energy minima for lateral interactions of much less stabilization power. This last indetermination helps to explain why caffeine does not crystallize easily into an ordered anhydrous structure. In contrast, the mono- and dimethylxanthines (theophylline, theobromine, and the 1,7-isomer, for which we present a single-crystal X-ray study and a lattice energy landscape) do crystallize in anhydrous form thanks to the formation of lateral hydrogen bonds.     

Selection of thermotolerant yeasts for simultaneous saccharification and fermentation (SSF) of cellulose to ethanol

A total of 27 yeast strains belonging to the groupsCandida, Saccharomyces, andKluyveromyces were screened for their ability to grow and ferment glucose at temperatures ranging 32-45°C. K. marxianus andK. fragilis were found to be the best ethanol producing organisms at the higher temperature tested and, so, were selected for subsequent simultaneous saccharification and fermentation (SSF) studies.     

Discriminating the helical forms of peptides by NMR and molecular dynamics simulation

The HNCO NMR pulse sequence was applied to three selectively labeled (15)N and (13)C isotopic homologues of the peptide Ac-WAAAH(AAARA)(3)A-NH(2) to probe directly for hydrogen bonds between residues 8 and 11 (characteristic of a 3(10)-helix), 8 and 12 (alpha-helix), and 8 and 13 (pi-helix). The experiments demonstrate conclusively, and in agreement with circular dichroism studies, that the center of the peptide is alpha-helical; there is no discernible 3(10)- or pi-helix at these specific positions. Molecular dynamics simulations of the preceding peptide and Ac-(AAAAK)(3)A-NH(2) in water using the potential energy parameter set CHARMM22/CMAP correctly yield an alpha-helix, in contrast to simulations with the set CHARMM22, which result in a pi-helix.     

Crystal structure and reactivity of 2-chloro-3,5-dinitrothiophene and of 2-phenylsulphonyl-3,5-dinitrothiophene with nucleophiles

The geometry obtained by a crystal structure determination of the title compounds, as compared with that of the analogous benzene derivatives, along with results of ab initio calculations, is used to interpret the different S_NAr reactivities in some thiophene and benzene compounds. The smaller rotation of the nitro groups with respect to the aromatic rings observed in thiophene derivatives should be considered a relevant factor in the higher reactivity in the thiophene series.     

Influence of medium and temperature on the hydrolysis kinetics of propacetamol hydrochloride: determination using derivative spectrophotometry

Propacetamol hydrochloride (PRO) is a water-soluble prodrug of paracetamol (PA) which can be parenterally administered as analgesic for the treatment of postoperative pain, acute trauma, and gastric and/or intestinal disorders where oral administration is not possible. In these circumstances, PRO can be administered in physiologic or glucose solutions since it is rapidly and quantitatively hydrolyzed into PA by plasma estearases. We have studied the degradation kinetics of PRO in 5% glucose and 0.9% saline solutions at 4 degrees C and 25 degrees C (storage and room temperatures, respectively). The analytic technique used to determine PRO and PA quantitatively was first-derivative spectrophotometry. The degradation process of PRO can be best fitted to a second-order kinetics with independence of the medium used (saline or glucose solution). The hydrolysis kinetics of PRO conversion into PA depends on the temperature but not on the assay medium (saline or glucose solution). The degradation rate constants obtained for PRO were approximately 4.5 times higher at 25 degrees C than at 4 degrees C. The values of t(90%) for PRO were 3.17 h and 3.61 h at 25 degrees C, and 13.42 h and 12.36 h at 4 degrees C when the tests were performed in 5% glucose and 0.9% saline solutions, respectively.     

YETI: An interactive molecular mechanics program for small-molecule protein complexes

YETI, an interactive molecular mechanics program for drug-design applications on small-molecule protein complexes, is described. To model short-range interactions in better agreement with experimental data, its force-field energy expression includes directional potential functions for H-bonds, salt linkages, and metal ligand interactions. The program works on an internal coordinate concept and uses a conjugate-gradient minimizer. YETI is available for distribution through the author. The program has been used to model details of small-molecule binding to the enzyme human carbonic anhydrase I. The impact of the directional potential functions on the geometry of H-bonds and metal-ligand interactions is discussed.     

N,O-heterocyclics. 13. Isoxazolidinium salts as synthons to N,N, O-trisubstituted hydroxylamines

Substituted isoxazolidinium salts react with lithium aluminium hydride to yield open-ring products which have hydroxylamine structures. The bimolecular reaction-mechanism has been investigated by substituent effect and the structure of the products ascertained by spectroscopic methods with the aid of the MIKE technique. The overall process of the ring-opening substitution is controlled by the polarisation of the C? N bond with steric and conformational factors acting mainly at the C-5 position of the nucleus. The mechanism of isoxazolidinium ion reaction defines the use of these synthons towards the synthesis of N,N,O-trisubstituted hydroxylamines and substituted 1,3-amino-alcohols.     

Copper bronze catalyzed Heck reaction in ionic liquids

Heck reaction of aryl iodides and activated aryl bromides catalyzed by copper bronze in tetrabutylammonium bromide as solvent and tetrabutylammonium acetate as base was developed. The effective catalysts are Cu nanoparticles deriving from the reaction of iodobenzene with copper bronze. These nanoparticles are very stable in tetraalkylammonium salts, are easily recycled, and can be stored for months without a loss of catalytic efficiency. [reaction: see text]