HDL composition and HDL antioxidant capacity in patients on regular haemodialysis

Recent evidence suggests that HDL can directly inhibit LDL oxidation, a key early stage in atherogenesis. Patients with chronic renal failure are at increased cardiovascular risk, have reduced HDL levels and altered HDL composition. We have therefore investigated whether compositional changes in HDL lead to decreased HDL antioxidant capacity in these patients. In comparison to control subject HDL, patient HDL contained less total cholesterol, cholesterol esters, phospholipids and alpha-tocopherol. LDL, HDL and LDL + HDL were standardised for protein and oxidised in the presence of Cu2+. The rate of propagation during HDL oxidation was reduced in the patient group (3.28 +/- 0.65 x 10(-5) vs. 4.60 +/- 0.97 x 10(-5) abs. U/min, P

Adsorption mechanisms of removing heavy metals and dyes from aqueous solution using date pits solid adsorbent

A potential usefulness of raw date pits as an inexpensive solid adsorbent for methylene blue (MB), copper ion (Cu2+), and cadmium ion (Cd2+) has been demonstrated in this work. This work was conducted to provide fundamental information from the study of equilibrium adsorption isotherms and to investigate the adsorption mechanisms in the adsorption of MB, Cu2+, and Cd2+ onto raw date pits. The fit of two models, namely Langmuir and Freundlich models, to experimental data obtained from the adsorption isotherms was checked. The adsorption capacities of the raw date pits towards MB and both Cu2+ and Cd2+ ions obtained from Langmuir and Freundlich models were found to be 277.8, 35.9, and 39.5 mg g(-1), respectively. Surface functional groups on the raw date pits surface substantially influence the adsorption characteristics of MB, Cu2+, and Cd2+ onto the raw date pits. The Fourier transform infrared spectroscopy (FTIR) studies show clear differences in both absorbances and shapes of the bands and in their locations before and after solute adsorption. Two mechanisms were observed for MB adsorption, hydrogen bonding and electrostatic attraction, while other mechanisms were observed for Cu2+ and Cd2+. For Cu2+, binding two cellulose/lignin units together is the predominant mechanism. For Cd2+. the predominant mechanism is by binding itself using two hydroxyl groups in the cellulose/lignin unit. (C) 2009 Elsevier B.V. All rights reserved.

Simultaneous, long-term monitoring of valve and cardiac activity in the blue mussel Mytilus edulis exposed to copper

Valve and cardiac activity were simultaneously measured in the blue mussel (Mytilus edulis) in response to 10 d copper exposure. Valve movements, heart rates and heart-rate variability were obtained non-invasively using a Musselmonitor(R) (valve activity) and a modified version of the Computer-Aided Physiological Monitoring system (CAPMON; cardiac activity). After 2 d exposure of mussels (4 individuals per treatment group) to a range of dissolved copper concentrations (0 to 12.5 mu M as CuCl2) median valve positions (% open) and median heart rates (beats per minute) declined as a function of copper concentration. Heart-rate variability (coefficient of variation for interpulse durations) rose in a concentration-dependent manner. The 48 h EC50 values (concentrations of copper causing 50% change) for valve positions, heart rates and heart-rate variability were 2.1, 0.8, and 0.06 mu M, respectively. Valve activity was weakly correlated with both heart rate (r = 0.48 +/- 0.02) and heart-rate variability (r = 0.32 +/- 0.06) for control individuals (0 mu M Cu2+). This resulted from a number of short enclosure events that did not coincide with a change in cardiac activity. Exposure of mussels to increasing copper concentrations (greater than or equal to 0.8 mu M) progressively reduced the correlation between valve activity and heart rates (r = 0 for individuals dosed with greater than or equal to 6.3 mu M Cu2+), while correlations between valve activity and heart-rate variability were unaffected. The poor correlations resulted from periods of valve flapping that were not mimicked by similar fluctuations in heart rate or heart-rate variability. The data suggest that the copper-induced bradycardia observed in mussels is not a consequence of prolonged valve closure.

Kinetics and mechanism of a fast leuco-Methylene Blue oxidation by copper(II)-halide species in acidic aqueous media

The kinetics of a fast leuco-Methylene Blue (LMB) re-oxidation to Methylene Blue (MB) by copper(II)-halide (Cl-, Br-) complexes in acidic aqueous media has been studied spectrophotometrically using a stopped-flow technique. The reaction follows a simple first order rate expression under an excess of the copper(II) species (and H+(aq)), and the pseudo-first order rate constant (k'(obs)) is largely independent of the atmosphere used (air, oxygen, argon). The rate law, at constant Cl- (Br-) anion concentration, is given by the expression: (d[MB+])/dt = ((k(a)K[H+] + k(b))/(1 + K[H+])).[Cu-II][LMB] = k'(obs)[LMB], where K is the protonation constant, and k(a) and k(b) are the pseudo-second order rate constants for protonated and deprotonated forms of LMB, respectively The rate law was determined based on the observed k'(obs) vs. [Cu-II] and [H+] dependences. The rate dramatically increases with [Cl-] over the range: 0.1-1.5 M, reflecting the following reactivity order: Cu2+(aq)

On the Mechanism of Lewis Acid Catalyzed Glucose Transformations in Ionic Liquids

<p>A complementary computational and experimental study of the reactivity of Lewis acidic CrCl2, CuCl2 and FeCl2 catalysts towards glucose activation in dialkylimidazolium chloride ionic liquids is performed. The selective dehydration of glucose to 5-hydroxymethylfurfural (HMF) proceeds through the intermediate formation of fructose. Although chromium(II) and copper(II) chlorides are able to dehydrate fructose with high HMF selectivity, reasonable HMF yields from glucose are only obtained with CrCl2 as the catalyst. Glucose conversion by CuCl2 is not selective, while FeCl2 catalyst does not activate sugar molecules. These differences in reactivity are rationalized on the basis of in situ X-ray absorption spectroscopy measurements and the results of density functional theory calculations. The reactivity in glucose dehydration and HMF selectivity are determined by the behavior of the ionic liquid-mediated Lewis acid catalysts towards the initial activation of the sugar molecules. The formation of a coordination complex between the Lewis acidic Cr2+ center and glucose directs glucose transformation into fructose. For Cu2+ the direct coordination of sugar to the copper(II) chloride complex is unfavorable. Glucose deprotonation by a mobile Cl- ligand in the CuCl42- complex initiates the nonselective conversion. In the course of the reaction the Cu2+ ions are reduced to Cu+. Both paths are prohibited for the FeCl2 catalyst.</p>

Coordination Properties of Ionic Liquid-Mediated Chromium(II) and Copper(II) Chlorides and Their Complexes with Glucose

<p>The structural and coordination properties of complexes formed upon the interaction of copper(II) and chromium(II) chlorides with diallrylimidazolium chloride (RMlm(+)Cl(-)) ionic liquids and glucose are studied by a combination of density functional theory (DFT) calculations and X-ray absorption spectroscopy (XAS). In the absence of the carbohydrate substrate, isolated mononuclear four-coordinated MeCl42- species (Me = Cu, Cr) dominate in the ionic liquid solution. The organic part of the ionic liquid does not directly interact with the metal centers. The interactions between the RMlm(+) cations and the anionic metal chloride complexes are limited to hydrogen bonding with the basic Cl- ligands and the overall electrostatic stabilization of the anionic metal complexes. Exchange of Cl ligands by a hydroxyl group of glucose is only favorable for CrCl42-. For Cu2+ complexes, the formation of hydrogen bonded complexes between CuCl42- and glucose is preferred. No preference for the coordination of metal chloride species to specific hydroxyl group of the carbohydrate is found. The formation of binuclear metal chloride complexes is also considered. The reactivity and selectivity patterns of the Lewis acid catalyzed reactions of glucose are discussed in the framework of the obtained results.</p>

Adsorption of metal ions on nitrogen surface functional groups in activated carbons

<p>A commercially available coconut-shell-derived active carbon was oxidized with nitric acid, and both the original and oxidized active carbons were treated with ammonia at 1073 K to incorporate nitrogen functional groups into the carbon. An active carbon with very high nitrogen content (similar to9.4 wt % daf) was also prepared from a nitrogen-rich precursor, polyacrylonitrile (PAN). These nitrogen-rich carbons had points of zero charge (pH(pzc)) similar to H-type active carbons. X-ray absorption near-edge structure (XANES) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and temperature-programmed desorption (TPD) were used to characterize the nitrogen functional groups in the carbons. The nitrogen functional groups present on the carbon surface were pyridinic, pyrrolic (or indolic), and pyridonic structures. The adsorption of transition metal cations Cd2+, Ni2+, and Cu2+ from aqueous solution on the suite of active carbons showed that adsorption was markedly higher for carbons with nitrogen functional groups present on the surface than for carbons with similar pH(pzc) values. In contrast, the adsorption characteristics of Ca2+ from aqueous solution were similar for all the carbons studied. Flow microcalorimetry (FMC) studies showed that the enthalpies of adsorption of Cd2+(aq) on the active carbons with high nitrogen contents were much higher than for nitric acid oxidized carbons studied previously, which also had enhanced adsorption characteristics for metal ion species. The enthalpies of adsorption of Cu2+ were similar to those obtained for Cd2+ for specific active carbons. The nitrogen functional groups in the carbons act as surface coordination sites for the adsorption of transition metal ions from aqueous solution. The adsorption characteristics of these carbons are compared with those of oxidized carbons.</p>

The adsorption, storage and release of nitric oxide using ion exchanged zeolites

<p>Zeolites exchanged with transition metal cations Co2+, Mn2+, Zn2+ and Cu2+ are capable of storing and delivering a large quantity of nitric oxide in a range of 1.2-2.7 mmolg(-1). The metal ion exchange impacts the pore volumes of zeolite FAU more significantly than LTA. The storage of NO mainly involves coordination of NO to metal cation sites. By exposing zeolites to a moisture atmosphere, the stored nitric oxide can be released. The NO release takes more than 2 hours for the NO concentration decreasing below similar to 5ppb in outlet gas. Its release rate can be controlled by tailoring zeolite frameworks and optimising release conditions.</p>

Adsorption properties of HKUST-1 toward hydrogen and other small molecules monitored by IR

<p>Among microporous systems metal organic frameworks are considered promising materials for molecular adsorption. In this contribution infrared spectroscopy is successfully applied to highlight the positive role played by coordinatively unsaturated Cu2+ ions in HKUST-1, acting as specific interaction sites. A properly activated material, obtained after solvent removal, is characterized by a high fraction of coordinatively unsaturated Cu2+ ions acting as preferential adsorption sites that show specific activities towards some of the most common gaseous species (NO, CO2, CO, N-2 and H-2). From a temperature dependent IR study, it has been estimated that the H-2 adsorption energy is as high as 10 kJ mol(-1). A very complex spectral evolution has been observed upon lowering the temperature. A further peculiarity of this material is the fact that it promotes ortho-para conversion of the adsorbed H-2 species.</p>

Catalytic conversion of sodium lignosulphonate to vanillin –engineering aspects. Part 1 Effect of processing conditionson vanillin yield and selectivity

The commercial production of vanillin from sodium lignosulfonate under highly alkaline conditions, catalyzed by Cu2+ at elevated temperature and pressures up to 10 bar, has been simulated in a 3-L stirred reactor. Initially, the process was operated in the presence of nitrogen in dead-end mode, and it was shown that vanillin and vanillic acid were formed by hydrolysis at temperatures of 120, 140, and 160 °C. At the two higher temperatures, the amount of vanillin produced was the same. Subsequently, experiments were conducted at the same elevated pressures and temperatures with addition of air or oxygen-enriched air once the temperature in the reactor had reached temperatures similar to those used when only hydrolysis occurred. In this case, the concentration of vanillin at 140 and 160 °C was equal to that due to hydrolysis, and the subsequent 2-fold increase was due to oxidation. In addition, both vanillic acid and acetovanillone (which has rarely been reported) were produced, as was hydrogen. Thus, for the first time, it has been shown that the production of vanillin (and other compounds) from sodium lignosulfonate at elevated temperatures involves hydrolysis and oxidation, with hydrolysis starting at just above 100 °C, that is, much lower than has previously been reported. Approximately 50% is produced by each mechanism. In addition, the orders of the reactions of the different steps were estimated, and the reaction mechanisms are discussed.

A retrievable and highly selective fluorescent probe for monitoring dihydrogen phosphate ions based on a naphthalimide framework

<p>A novel selective fluorescent chemosensor based on naphthalimide derivatives (AN-SB) was synthesized and characterized. Once combined with Cu2+, compound AN-SB could give rise to a visible yellow to orange color change and fluorescence quenching, while other metal ions showed subtle disturbance. The complex (AN-SB-Cu2+) formed by Cu2+ and AN-SB displayed high specificity for H2PO4-. Among the various anions, only H2PO4- induced the revival of color and fluorescence of AN-SB, resulting in "off-on" type sensing of H2PO4- anion. The signal transduction occured via reversible formation-separation of complex AN-SB-Cu2+, however, slight changes were observed in the presence of other anions. (C) 2013 Elsevier B.V. All rights reserved.</p>

Understanding catalytic reactions over zeolites: A density functional theory study of selective catalytic reduction of NOX by NH3 over Cu-SAPO-34

Metal exchanged CHA-type (SAPO-34 and SSZ-13) zeolites are promising catalysts for selective catalytic reduction (SCR) of NOx by NH3. However, the understanding of the process at the molecular level is still limited, which hinders the identification of its mechanism and the design of more efficient zeolite catalysts. In this work, modelling the reaction over Cu-SAPO-34, a periodic density functional theory (DFT) study of NH3-SCR was performed using hybrid functional with the consideration of van der Waals (vdW) interactions. A mechanism with a low N–N coupling barrier is proposed to account for the activation of NO. The redox cycle of Cu2+ and Cu+, which is crucial for the SCR process, is identified with detailed analyses. Besides, the decomposition of NH2NO is shown to readily occur on the Brønsted acid site by a hydrogen push-pull mechanism, confirming the collective efforts of Brønsted acid and Lewis acid (Cu2+) sites. The special electronic and structural properties of Cu-SAPO-34 are demonstrated to play an essential role the reaction, which may have a general implication on the understanding of zeolite catalysis.