Stoichiometric and catalytic reactions of gold utilizing ionic liquids

The first thiazolium gold(III) compound that qualifies as an ionic liquid has been prepared and crystallographically characterized. Hydration of phenylacetylene with this compound as catalyst precursor in ionic liquids indicates that gold(Ill)based ionic liquids could serve both as solvents and catalysts for organic transformations. The potential re-use of catalysts is an advantage achieved by recycling the ionic liquid phase. Various imidazolium-derived ionic liquids as well as the new thiazolium compound can be converted into gold carbene complexes by sequential deprotonation and coordination, opening the way for in situ catalyst tailoring. (C) 2002 Elsevier Science B.V. All rights reserved.

Transesterification of vegetable oils on basic large mesoporous alumina supported alkaline fluorides-Evidences of the nature of the active site and catalytic performances

KF, LiF and CsF/A(2)O(3) catalysts with different loadings from 1 to 20 wt% were prepared using aqueous solutions of the alkaline fluoride compounds by wet impregnation of basic mesoporous MSU-type alumina. The catalysts were activated under At at 400 degrees C for 2 h and monitored by in situ XRD measurements. The catalysts were also characterized using several techniques: N-2 adsorption/desorption isotherms at -196 degrees C, FTIR, DR-UV-vis, CO2-TPD, XRD, Al-27 CP/MAS NMR. These characterizations led to the conclusion that the deposition of alkaline fluorides on the alumina surface generates fluoroaluminates and aluminate species. The process is definitivated at 400 degrees C. The fluorine in these structures is less basic than in the parent fluorides, but the oxygen becomes more basic. The catalysts were tested for the transesterification of fatty esters under different experimental conditions using conventional heating, microwave and Ultrasound irradiation. Recycling experiments showed that these catalysts are stable for a limited number of cycles. (C) 2009 Elsevier Inc. All rights reserved.

Selective catalytic reduction of O-2 with excess H-2 in the presence of C2H4 or C3H6

The selective reduction of molecular oxygen with excess H-2 in the presence of alkenes was achieved successfully for the first time: silver supported on alumina catalysts exhibited full conversion of O-2 at temperature as low as 50 degrees C, while the conversion of ethene or propene remained essentially zero up to 250 degrees C.

Catalytic Hydrogenolysis of Aromatic Ketones in Mixed Choline-Betainium Ionic Liquids

The palladium-catalyzed hydrogenolysis of aromatic ketones to alkylbenzenes was studied in mixtures of ionic liquids to explore the promotional effect of these reaction media. Choline-based ionic liquids displayed complete miscibility with the aromatic ketone substrate at reaction temperature and a clear phase separation of the derived alkylbenzene product at room temperature. Selected ionic liquids were then assessed as reaction media in the hydrogenolysis of aromatic ketones over palladium catalysts. A binary mixture of choline and betainium bis(trifluoromethylsulfonyl)imide ionic liquids resulted in the highest conversion and selectivity values in the hydrogenolysis of acetophenone. At the end of the reaction, the immiscible alkylbenzene separates from the ionic liquid mixture and the pure product phase can be isolated by simple decantation. After optimization of the reaction conditions, high yields (>90%) of alkylbenzene were obtained in all cases. The catalyst and the ionic liquid could be used at least three times without any loss of activity or selectivity.

Role of creatine supplementation on exercise-induced cardiovascular function and oxidative stress

Many degenerative diseases are associated with increased oxidative stress. Creatine has the potential to act as an indirect and direct antioxidant; however, limited data exist to evaluate the antioxidant capabdities of creatine supplementation within in vivo human systems. This study aimed to investigate the effects of oral creatine supplementation on markers of oxidative stress and antioxidant defenses following exhaustive cycling exercise. Following preliminary testing and two additional familiarization sessions, 18 active males repeated two exhaustive incremental cycling trials (T1 and T2) separated by exactly 7 days. The subjects were assigned, in a double-blind manner, to receive either 20 g of creatine (Cr) or a placebo (P) for the 5 days preceding T2. Breath-by-breath respiratory data and heart rate were continually recorded throughout the exercise protocol and blood samples were obtained at rest (preexercise), at the end of exercise (postexercise), and the day following exercise (post24 h). Serum hypdroperoxide concentrations were elevated at postexercise by 17 +/- 5% above preexercise values (p = 0.030). However, supplementation did not influence lipid peroxidation (serum hypdroperoxide concentrations), resistance of low density lipoprotein to oxidative stress (t(1/2max) LDL oxidation) and plasma concentrations of non-enzymatic antioxidants (retinol, alpha-carotene, beta-carotene, alpha-tocopherol, gamma-tocopherol, lycopene and vitamin Q. Heart rate and oxygen uptake responses to exercise were not affected by supplementation. These findings suggest that short-term creatine supplementation does not enhance non-enzymatic antioxidant defence or protect against lipid peroxidation induced by exhaustive cycling in healthy males.

Expression of the counter-regulatory peptide intermedin is augmented in the presence of oxidative stress in hypertrophied cardiomyocytes.

Background: Intermedin (IMD), a novel cardiac peptide related to adrenomedullin (AM), protects against myocardial ischemia-reperfusion injury and attenuates ventricular remodelling. IMD’s actions are mediated by a calcitonin receptor-like receptor in association with receptor activity modifying proteins (RAMPs 1-3). Aim/method: using the spontaneously hypertensive rat (SHR) and normotensive Wistar Kyoto (WKY) rat at 20 weeks of age, to examine (i) the presence of myocardial oxidative stress and concentric hypertrophy; (ii) expression of IMD, AM and receptor components. Results: In left and right ventricular cardiomyocytes from SHR vs. WKY cell width (26% left, 15% right) and mRNA expression of hypertrophic markers ANP (2.7 fold left, 2.7 fold right) and BNP (2.2 fold left, 2.0 fold right) were enhanced. In left ventricular cardiomyocytes only (i) oxidative stress was indicated by increased membrane protein carbonyl content (71%) and augmented production of O2- anion (64%); (ii) IMD (6.8 fold), RAMP1 (2.5 fold) and RAMP3 (2.0 fold) mRNA was increased while AM and RAMP2 mRNA was not altered; (iii) abundance of RAMP1 (by 48%), RAMP2 (by 41%) and RAMP3 (by 90%) monomers in cell membranes was decreased. Conclusion: robust augmentation of IMD expression in hypertrophied left ventricular cardiomyocytes indicates a prominent role for this counter-regulatory peptide in the adaptation of the SHR myocardium to the stresses imposed by chronic hypertension. The local concentration and action of IMD may be further enhanced by down-regulation of NEP within the left ventricle.

Lanthanide(III) nitrobenzenesulfonates as new nitration catalysts: The role of the metal and of the counterion in the catalytic efficiency

Lanthanide(III) complexes of p-nitrobenzenesulfonic acid, Ln(p-NBSA)(3), m-nitrobenzenesulfonic acid, Ln(m-NBSA)(3), and 2,4-nitrobenzenesulfonic acid, Ln(2,4-NBSA)(3), were prepared, characterized and examined as catalyst for the nitration of benzene, toluene, xylenes, naphthalene, bromobenzene and chlorobenzene. The initial screening of the catalysts showed that lanthanum(III) complexes were more effective than the corresponding ytterbium(III) complexes, and that catalysts containing the bulky 2,4-NBSA ligand were less effective than the catalyst containing p-NBSA (nosylate) or m-NBSA ligands. Examination of a series of Ln(p-NBSA)(3) and Ln(m-NBSA)(3) catalysts revealed that there is a clear correlation between the ionic radii of the lanthanide(III) ions and the yields of nitration, with the lighter lanthanides being more effective. The X-ray single crystal structure of Yb(m-NBSA)(3).6H(2)O shows that two m-NBSA ligands are directly bound to the metal centre while the third ligand is not located in the first coordination sphere, but it is hydrogen bonded to one of the water molecules which is coordinated to ytterbium(III). NMR studies suggest that this structure is preserved under the conditions used in the nitration reaction. The structure of Yb(m-NBSA)(3) is markedly different from the structure of the well-known ytterbium(III) triflate catalyst. The coordination of the nitrobenzenesulfonate counterion to the lanthanide(III) ion suggests that steric effects might play an important role in determining the efficiency of these novel nitration catalysts. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004).

Upregulation of Oxidative Stress Markers in Human Microvascular Endothelial Cells by Complexes of Serum Albumin and Digestion Products of Glycated Casein

The extent of absorption of dietary advanced glycation end products (AGEs) is not fully known. The possible physiological impact of these absorbed components on inflammatory processes has been studied little and was the aim of this investigation. Aqueous solutions of bovine casein and glucose were heated at 95 degrees C for 5 h to give AGE-casein (AGE-Cas). Simulated stomach and small intestine digestion of AGE-Cas and dialysis (molecular mass cutoff of membrane = 1 kDa) resulted in a low molecular mass (LMM) fraction of digestion products, which was used to prepare bovine serum albumin (BSA)-LMM-AGE-Cas complexes. Stimulation of human microvascular endothelial cells with BSA-LMM-AGE-Cas complexes significantly increased mRNA expression of the receptor of AGE (RAGE), galectin-3 (AGE-113), tumor necrosis factor alpha, and a marker of the mitogen-activated protein kinase pathway (MAPK-1), as well as p65NF-kappa B activation. Cells treated with LMM digestion products of AGE-Cas significantly increased AGE-R3 mRNA expression. Intracellular reactive oxygen species production increased significantly in cells challenged with BSA-LMM-AGE-Cas and LMM-AGE-Cas. In conclusion, in an in vitro cell system, digested dietary AGEs complexed with serum albumin play a role in the regulation of RAGE and down-stream inflammatory pathways. AGE-R3 may protect against these effects.