Degradation of VOCs by phototcatalytic oxidation reactor using TiO2 pellets

Volatile Organic Compounds (VOCs) are air pollutants that come from burning fossil fuels and industrial emissions. They have potentially adverse health effects being carcinogenic and highly persistent in the environment. The use of photocatalytic oxidation to remove VOCs has the potential to be applied in indoor air quality improvement and industrial emission control. A fixed bed photocatalytic reactor was designed and built. UV black light lamps were installed in the reactor to provide a source of UV radiation. A non-film titania media as pellets were placed on the three fixed beds within the reactor. Toluene and acetone were used as indicators of VOCs during the experiment. With a flow rate of 12.75l/min, the oxidation efficiencies were obtained at four different concentrations of acetone laden gas streams ranging from 40ppm to 250ppm. It was found that the lower the acetone concentration of the untreated inlet gas, the higher the oxidation efficiency. The oxidation efficiency was in the range of 40–70% for various concentrations of untreated gases. Two concentrations of toluene laden gas stream were also tested using the same reactor. The oxidation efficiencies were found as 50% for 120ppm toluene gas and 45% for 300ppm toluene gas. It was found that the times required for toluene to reach oxidization equilibrium have been halved than for acetone gas stream. Other parameters such as flow rate and UV intensity were also altered to see their effects on the oxidation efficiency. A full spectrum scan was carried out using a Bio-rad Infrared spectrometer. It was found that the main components of the treated gas stream from the outlet of the reactor were CO2 and water along with small amount of untreated acetone. The suspected intermediates of aliphatic hydrocarbons and CO were found in very minimal amounts or undetectable. The research experiments supported that the TiO2 pellets can work effectively in a fixed bed photocatalytic reactor and achieve significant oxidation efficiencies for degradation of toluene and acetone as indicators of VOCs.

Chemiluminescence from the oxidation of urea and ammonia with hypobromite and N-bromosuccinimide

The spectral distribution for the chemiluminescent oxidation of ammonia with hypobromite is significantly different to that for the oxidation of ammonia with N-bromosuccinimide. Therefore, in contrast to the assumptions of several authors, the action of N-bromosuccinimide is not solely derived from the in situ formation of hypobromite. Neither the oxidation of urea with hypobromite nor the oxidation of urea with N-bromosuccinimide involves an initial hydrolysis of urea to ammonia in the alkaline solution. However, these two reactions lead to a common emitter. The addition of xanthene dyes, such as dichlorofluorescein, enhance the chemiluminescence intensity by energy transfer to the efficient fluorophore, but reaction between the sensitiser and hypobromite can result in a significant increase in the background signal. A list of potential interferences has been compiled; particular attention was paid to guanidino compounds, as the chemiluminescence accompanying the oxidation of this functional group has not been previously discussed.

Effects of alternative dietary lipid sources on performance, tissues chemical composition, mitochondrial fatty acid oxidation capabilities, and sensory characteristics in brown trout (Salmo trutta L.)

The efficiency of five dietary lipid sources (fish oil as control—C; canola oil—CO; poultry fat—PF; pork lard—PL; and oleine oil—OO) were evaluated in juvenile brown trout (58.4±0.7 g) in an experiment conducted over 70 days at 14.6±0.4 °C. The best growth was observed in fish fed the C diet whereas the PL diet fed fish had the best feed utilization. Significant differences in carcass and muscle proximate composition, but not in liver, were noted among fish fed the different dietary treatments. The fatty acid composition of muscle largely reflected that of the diets, while total cholesterol was not affected. The atherogenicity and the thrombogenicity qualities of the trout flesh were modified by the lipid sources. Sensory analysis did not show any significant differences among the cooked fillets with respect to dietary treatments, while in uncooked products, some significant differences were observed. The carnitine palmitoyltransferase I and II (CPT-I and CPT-II) activities of liver and white muscle were assayed for a better understanding of the potential β-oxidation capability of the different dietary lipid sources. The hepatic, but not white muscle CPT-I and CPT-II activities were affected by dietary treatments. This study showed that alternative lipid sources could be used effectively for oil coating extruded diets for brown trout.

Evaluating the stability of disulfide bridges in proteins: a torsional potential energy surface for diethyl disulfide

Disulfide bonds formed by the oxidation of cysteine residues in proteins are the major form of intra- and inter-molecular covalent linkages in the polypeptide chain. To better understand the conformational energetics of this linkage, we have used the MP2(full)/6-31G(d) method to generate a full potential energy surface (PES) for the torsion of the model compound diethyl disulfide (DEDS) around its three critical dihedral angles (χ2, χ3, χ2′). The use of ten degree increments for each of the parameters resulted in a continuous, fine-grained surface. This allowed us to accurately predict the relative stabilities of disulfide bonds in high resolution structures from the Protein Data Bank. The MP2(full) surface showed significant qualitative differences from the PES calculated using the Amber force field. In particular, a different ordering was seen for the relative energies of the local minima. Thus, Amber energies are not reliable for comparison of the relative stabilities of disulfide bonds. Surprisingly, the surface did not show a minimum associated with χ2 − 60°, χ390, χ2′ − 60°. This is due to steric interference between Hα atoms. Despite this, significant populations of disulfides were found to adopt this conformation. In most cases this conformation is associated with an unusual secondary structure motif, the cross-strand disulfide. The relative instability of cross-strand disulfides is of great interest, as they have the potential to act as functional switches in redox processes.

The whole-body fatty acid balance method : examples of its potential for feed efficiency and product quality optimisation in fish and poultry

Dietary lipids and fatty acids are not only fundamental in determining animal performance, but also determine the eating qualities of animal products. Several methods have been used to quantify fatty acid metabolism but most involve expensive in vitro approaches that are not suitable for most laboratories. Furthermore, there is considerable variation between methods with regard to enzyme activity, which makes comparison of results between studies difficult. The recently developed whole-body fatty acid balance method (WBFABM) is a simple and reliable in vivo method for assessing fatty acid metabolism, including rates of liponeogenesis and de novo fatty acid production, β-oxidation of fatty acids and bioconversion (elongation and desaturation) of fatty acids to long-chain polyunsaturated fatty acids. Initially developed for implementation with a fish model, the WBFABM has proven to be a simple and effective method that can be used in any laboratory equipped with a gas chromatography unit. Since its development, it has been used in several farmed finfish feeding trials and in broiler chicken feeding trials. The WBFABM is currently used at research institutions worldwide and its use is increasing in popularity among animal scientists. With this method, it is possible to track the fate of individual dietary fatty acids within the body. The WBFABM could contribute significantly to information generated by animal feeding trials.

A potential copper-regulatory role for cytosolic expression of the DNA repair protein XRCC5

Copper (Cu) has a critical role in the generation of oxidative stress during neurodegeneration and cancer. Reactive oxygen species generated through abnormal elevation or deficiency of Cu can lead to lipid, protein, and DNA damage. Oxidation of DNA can induce strand breaks and is associated with altered cell fate including transformation or death. DNA repair is mediated through the action of the multimeric DNA-PK repair complex. The components of this complex are the Ku autoantigens, XRCC5 and XRCC6 (Ku80 and Ku70, respectively). How this repair complex responds to perturbed Cu homeostasis and Cu-mediated oxidative stress has not been investigated. We previously reported that XRCC5 expression is altered in response to cellular Cu levels, with low Cu inhibiting XRCC5 expression and high Cu levels enhancing expression. In this study we further investigated the interaction between XRCC5 and Cu. We report that cytosolic XRCC5 is increased in response to Cu, but not zinc, iron, or nickel, and the level of cytosolic XRCC5 correlates with protection against oxidative damage to DNA. These observations were made in both HeLa cells and fibroblasts. Cytosolic XRCC5 interacted with the Cu chaperone and detoxification protein human Atox1 homologue (HAH), and down regulation of XRCC5 expression using siRNA led to enhanced HAH expression when cells were exposed to Cu. XRCC5 could also be purified from cytosolic extracts using a Cu-loaded column. These findings provide further evidence that cytosolic XRCC5 has a key role in protection against DNA oxidation from Cu, through either direct sequestration or signaling through other Cu-detoxification molecules. Our findings have important implications for the development of therapeutic treatments targeting Cu in neurodegeneration and/or cancer.

A potential-controlled switch on/off mechanism for selective excitation in mixed electrochemiluminescent systems

We demonstrate the complete, rapid, and reversible switching between the emissions from two electrogenerated chemiluminescence (ECL) systems contained within the same solution, controlled by simple modification of the applied potential. The fundamental bases of the approach are the ability to selectively 'switch on' luminophores at distinct oxidation potentials, and an intriguing observation that the emission from the well-known electrochemiluminescent complex, fac-Ir(ppy)3, (where ppy is 2-phenylpyridinato), can be selectively 'switched-off' at high overpotentials. The dependence of this phenomenon on high concentrations of the co-reactant implicates quenching of the excited [Ir(ppy)3]* state by electron transfer. Rapid spectral scanning during modulation of the applied potential reveals well resolved maxima for mixtures comprising either green and red or green and blue luminophores, illustrating the vast potential of this approach for multiplexed ECL detection.

Redox sulfur chemistry of the copper chaperone Atox1 is regulated by the enzyme glutaredoxin 1, the reduction potential of the glutathione couple GSSG/2GSH and the availability of Cu(I)

Glutaredoxins have been characterised as enzymes regulating the redox status of protein thiols via cofactors GSSG/GSH. However, such a function has not been demonstrated with physiologically relevant protein substrates in in vitro experiments. Their active sites frequently feature a Cys-xx-Cys motif that is predicted not to bind metal ions. Such motifs are also present in copper-transporting proteins such as Atox1, a human cytosolic copper metallo-chaperone. In this work, we present the first demonstration that: (i) human glutaredoxin 1 (hGrx1) efficiently catalyses interchange of the dithiol and disulfide forms of the Cys(12)-xx-Cys(15) fragment in Atox1 but does not act upon the isolated single residue Cys(41); (ii) the direction of catalysis is regulated by the GSSG/2GSH ratio and the availability of Cu(I); (iii) the active site Cys(23)-xx-Cys(26) in hGrx1 can bind Cu(I) tightly with femtomolar affinity (K(D) = 10(-15.5) M) and possesses a reduction potential of E(o)' = -118 mV at pH 7.0. In contrast, the Cys(12)-xx-Cys(15) motif in Atox1 has a higher affinity for Cu(I) (K(D) = 10(-17.4) M) and a more negative potential (E(o)' = -188 mV). These differences may be attributed primarily to the very low pKa of Cys23 in hGrx1 and allow rationalisation of conclusion (ii) above: hGrx1 may catalyse the oxidation of Atox1(dithiol) by GSSG, but not the complementary reduction of the oxidised Atox1(disulfide) by GSH unless Cu(aq)(+) is present at a concentration that allows binding of Cu(I) to reduced Atox1 but not to hGrx1. In fact, in the latter case, the catalytic preferences are reversed. Both Cys residues in the active site of hGrx1 are essential for the high affinity Cu(I) binding but the single Cys(23) residue only is required for the redox catalytic function. The molecular properties of both Atox1 and hGrx1 are consistent with a correlation between copper homeostasis and redox sulfur chemistry, as suggested by recent cell experiments. These proteins appear to have evolved the features necessary to fill multiple roles in redox regulation, Cu(I) buffering and Cu(I) transport.

Conditions favoring the formation of monomeric Pt(III) derivatives in the electrochemical oxidation of trans-[Pt(II){(p-BrC6F4)NCH2CH2NEt2}Cl(py)]

Characterization of the anticancer active compound trans-[Pt^II{(p-BrC6F4)NCH2CH2NEt2}Cl(py)] is described along with identification of electrochemical conditions that favor formation of a monomeric one-electron-oxidized Pt^III derivative. The square-planar organoamidoplatinum(II) compound was synthesized through a carbon dioxide elimination reaction. Structural characterization by using single-crystal X-Ray diffraction reveals a trans configuration with respect to donor atoms of like charges. As Pt^III intermediates have been implicated in the reactions of platinum anticancer agents, electrochemical conditions favoring the formation of one-electron-oxidized species were sought. Transient cyclic voltammetry at fast scan rates or steady-state rotating disc and microelectrode techniques in a range of molecular solvents and an ionic liquid confirm the existence of a well-defined, chemically and electrochemically reversible one-electron oxidation process that, under suitable conditions, generates a Pt^III complex, which is proposed to be monomeric [Pt^III{(p-BrC6F4)NCH2CH2NEt2}Cl(py)]⁺. Electron paramagnetic resonance spectra obtained from highly non-coordinating dichloromethane/([Bu4N][B(C6F5)4]) solutions, frozen to liquid nitrogen temperature immediately after bulk electrolysis in a glove box, support the Pt^III assignment rather than formation of a Pt^II cation radical. However, the voltammetric behavior is highly dependent on the timescale of the experiments, temperature, concentration of trans-[Pt^II{(p-BrC6F4)NCH2CH2NEt2}- Cl(py)], and the solvent/electrolyte. In the low-polarity solvent CH2Cl2 containing the very weakly coordinating electrolyte [Bu4N][B(C6F5)4], a well-defined reversible one-electron oxidation process is observed on relatively long timescales, which is consistent with the stabilization of the cationic platinum(III) complex in non-coordinating media. Bulk electrolysis of low concentrations of [Pt{(p-BrC6F4)NCH2CH2NEt2}Cl(py)] favors the formation of monomeric [Pt^III{(p-BrC6F4)NCH2CH2NEt2}Cl(py)]⁺. Simulations allow the reversible potential of the Pt^II/Pt^III process and the diffusion coefficient of [Pt^III{(p-BrC6F4)- NCH2CH2NEt2}Cl(py)]⁺ to be calculated. Reversible electrochemical behavior, giving rise to monomeric platinum(III) derivatives, is rare in the field of platinum chemistry.

Disruption of the class IIa HDAC corepressor complex increases energy expenditure and lipid oxidation

Drugs that recapitulate aspects of the exercise adaptive response have the potential to provide better treatment for diseases associated with physical inactivity. We previously observed reduced skeletal muscle class IIa HDAC (histone deacetylase) transcriptional repressive activity during exercise. Here, we find that exercise-like adaptations are induced by skeletal muscle expression of class IIa HDAC mutants that cannot form a corepressor complex. Adaptations include increased metabolic gene expression, mitochondrial capacity, and lipid oxidation. An existing HDAC inhibitor, Scriptaid, had similar phenotypic effects through disruption of the class IIa HDAC corepressor complex. Acute Scriptaid administration to mice increased the expression of metabolic genes, which required an intact class IIa HDAC corepressor complex. Chronic Scriptaid administration increased exercise capacity, whole-body energy expenditure and lipid oxidation, and reduced fasting blood lipids and glucose. Therefore, compounds that disrupt class IIa HDAC function could be used to enhance metabolic health in chronic diseases driven by physical inactivity.