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Destruction of environmental organic pollutants by supercritical water oxidation.

The supercritical water oxidation of two environmental pollutants in the form of diesel fuel and two waste landfill leachate samples have been examined in relation to sub-critical and supercritical water oxidation conditions. Supercritical water oxidation involves reactions in an aqueous fluid phase under conditions below and around the critical point of water (T(c) = 374 degrees C, P(c) = 22.1 MPa). Experiments were carried out using a batch autoclave reactor at temperatures between 300 degrees C and 380 degrees C corresponding to pressures between 10.5 MPa and 22.8 MPa. The oxidative decomposition of the diesel fuel, which was loaded onto a sand matrix to simulate a contaminated land sample, was determined in relation to process conditions. The results showed that almost complete destruction of the components of the diesel fuel could be achieved. In addition, intermediate oxygenated compounds were formed and identified. The level of loading of the diesel fuel onto the sand matrix influenced the level of compound decomposition and the amount of intermediate oxygenated compounds formed. The characteristics of the waste landfill leachates were determined and were shown to be highly chemically complex. The high chloride concentration of the leachate resulted in significant corrosion of the reactor. However, almost complete oxidation of the organic components of the leachate could be achieved under supercritical water oxidation conditions.

Alkanes↗

Emissions of regulated pollutants from a spark ignition engine. Influence of fuel and air/fuel equivalence ratio.

A spark ignition engine is used to determine the influence of fuel composition and air/fuel equivalence ratio on the exhaust emissions of regulated pollutants. Two specific fuel matrices are used: the first contains eight hydrocarbons and the second contains four oxygenated compounds. A specific experimental design is used for these tests. Fuel aromatics increase the exhaust CO, HC, and NOx at stoichiometry, lean and rich conditions. Lambda is more important than fuel composition in the case of CO and HC. At stoichiometry, the addition of oxygenated compounds can decrease exhaust CO, HC, and NOx up to 30%, 50%, and 60%, respectively. Under these conditions, the addition of 5% of 2-propanol is the most effective for the reduction of CO, the addition of 20% of ethanol forthe reduction of HC, and this of 5% of methyl tributyl ester (MTBE) for the NOx. The addition of oxygenated compounds can decrease CO by 30% at lean conditions, while no decrease is observed at rich ones; HC and NOx can decrease up to 30% and 80%, respectively, under lean conditions and 50% under rich ones. At all lambda tested, exhaust NOx increases with the addition of 20% of 2-propanol.

Air Pollutants↗

Complexes of trivalent oxygenated phosphorus compounds with cytochrome P-450 and cytochrome P-420: the origin of double Soret spectra.

Trivalent oxygenated phosphorus ligands include alkyl and aryl phosphites, (RO)3P, phosphonites, (RO)2PR, and phosphinites, ROPR2. All such compounds tested, with the exception of triphenyl phosphite, interact with ferrous cytochrome P-450 and its denatured form, cytochrome P-420, to produce complexes having two peaks in the Soret region of their optical difference spectra. Careful evaluation of these spectra indicate that they arise for different reasons for each of the two cytochromes. Clear evidence shows that cytochrome P-450 is not denatured by these ligands. The high affinity of these ligands for heme iron is indicated by small Ks values. The experimental results are used to substantiate a theory of the origin of microsomal double Soret spectra and the nature of the environments available for microsomal cytochromes P-450 and P-420.

Animals↗

Vasoactive intestinal peptide inhibits the respiratory burst in human monocytes by a cyclic AMP-mediated mechanism.

The neuropeptide vasoactive intestinal peptide (VIP) was shown to inhibit the production of reactive oxygen compounds (respiratory burst) in monocytes activated by serum opsonized zymosan. Reactive oxygen compounds are of importance for host defence against micro-organisms and cancer, but normal tissues are also susceptible to damage from these reactive substances. Maximum inhibition of respiratory burst was 40% by 0.1 microM VIP (ID100), while ID50 for the VIP effect was 0.36 nM VIP. PHM-27, closely related to VIP on the basis of the amino acid sequence, inhibited the respiratory burst with much lower potency (ID50 = 60 nM, ID100 = 1 microM). Secretin, related to VIP and PHM-27, produced no effect on the respiratory burst in monocytes. VIP was also shown to stimulate the cyclic AMP production in monocytes in a dose dependent manner. IBMX and forskolin, as well as the cyclic AMP analogue butyryl cyclic AMP were shown to produce an inhibition of the respiratory burst. In conclusion, this study showed that VIP inhibited the respiratory burst in monocytes by a cyclic AMP-mediated mechanism, and serves to establish still another role for VIP as a mediator in the neuro-immune axis.

1-Methyl-3-isobutylxanthine↗

Structure-activity relationship studies of 3-aroylindoles as potent antimitotic agents.

The concise synthesis and structure-activity relationship (SAR) studies of 3-aroylindoles were carried out in an effort to improve the potency and solubility of anticancer drug candidate BPR0L075 (8) by exploring structure modifications through three regimens: substitution of the B ring, at the N1 position, and of the 3-carbonyl linker. The SAR information revealed that the methoxy group of the B ring could be replaced with an electron-donating group such as methyl (in compound 9) or N,N-dimethylamino (in compound 13) while retaining both strong cytotoxic and antitubulin activities. The introduction of amide (compounds 30-33) and carbamate (compounds 34-37) functionalities at the N1 position of 8 gave analogues with potent antiproliferative activities. The cytotoxic potency of 8 was improved by replacing the carbonyl group with sulfide (compound 41) or oxygen (compound 43), indicating that the carbonyl moiety is important but not essential. The N,N-dimethylamino derivative 13 not only displayed potent cytotoxicity and antitubulin activity, but also showed a markedly improved physicochemical profile relative to the parent compound.

Animals↗

Effects of iron and oxygen species scavengers on Listeria spp. chemiluminescence.

Listeria monocytogenes and Listeria innocua are able, under certain conditions, to produce chemiluminescence (CL), which is amplified by luminol. Kinetic studies of CL by L. monocytogenes and L. innocua show a close parallelism between CL and growth curves during the exponential phase, with a maximum of CL reached just before entrance of bacteria into the stationary phase. CL is tightly correlated with the release of oxygen compounds. The reactive oxygen species scavengers tryptophan, mannitol, and tiron, as well as cellobiose and high temperature, were assessed with regard to CL in the two Listeria species. Only tiron strongly reduced the CL emitted by L. monocytogenes and L. innocua. On the other hand, charcoal pretreatment of the growth medium inhibited the CL, whereas ferric citrate strongly increased the CL of L. monocytogenes and L. innocua. These data suggest that iron and superoxide radical are implicated in the CL produced by these bacteria, but this phenomenon is not correlated to virulence.

1,2-Dihydroxybenzene-3,5-Disulfonic Acid Disodium ↗

[Extraction and determination of volatile constituents in leaves of Eucalyptus citriodora].

The volatile constituents in leaves of Eucalyptus citriodora, including oil fraction and water-soluble fraction, were extracted and determined. Oil fraction of volatile components was obtained through steam distillation. Ether was used as the solvent to extract the water-soluble fraction of volatile compounds from the liquid left after steam distillation in order to know the quantity and constituents of volatile compounds dissolved in the water phase. The oil yield in the oil fraction was 1.36%, and the oil yield in the water-soluble fraction was 0.48% (both on fresh weight basis). Both oil fraction and water-soluble fraction were analyzed by gas chromatography-mass spectrometry (GC-MS) method. The results showed that 37 compounds (97.36%) in the oil fraction and 10 compounds (82.05%) in the water-soluble fraction were identified. There were 12 hydrocarbon compounds and 25 oxygenated compounds identified in oil fraction. The major constituents in oil fraction were citronellal (57.00%), followed by citronellol (15.89%) and citronellyl acetate (15.33%). Alcohols dominated the compounds in water-soluble fraction. cis-p-Menthane-3, 8-diol (53.43%) and trans-p-menthane-3, 8-diol (16. 48%) were found to be the major compounds, which have the activity to repel insects. It is concluded that the comprehensive utilization value of leaves of Eucalyptus citriodora was enhanced owing to the extraction of water-soluble volatile components.

Acyclic Monoterpenes↗

Acceleration of the oxygen reaction in CuA-deficient Nitrosomonas europaea cytochrome c oxidase as revealed by the flow-flash measurement.

The oxygen reaction of Nitrosomonas europaea cytochrome c oxidase containing either 2Cu or 1Cu per two heme a molecules was investigated by the flow-flash technique at 20 degrees C. The reaction profiles of the bacterial enzyme were essentially the same as those of bovine heart cytochrome c oxidase, although the rate of the primary oxygen compound formation was much slower. The 1Cu enzyme exhibited higher rates for both primary oxygen compound formation and intramolecular electron transfer than the 2Cu enzyme. This result clearly indicates that CuA is not essential functionally for the oxidation of ferrous heme a moieties, and suggests its structural importance in maintaining the molecular integrity of N. europaea cytochrome oxidase.

Copper↗

Phenols in hydrothermal petroleums and sediment bitumen from Guaymas Basin, Gulf of California.

The aliphatic, aromatic and polar (NSO) fractions of seabed petroleums and sediment bitumen extracts from the Guaymas Basin hydrothermal system have been analyzed by gas chromatography and gas chromatography-mass spectrometry (free and silylated). The oils were collected from the interiors and exteriors of high temperature hydrothermal vents and represent hydrothermal pyrolyzates that have migrated to the seafloor by hydrothermal fluid circulation. The downcore sediments are representative of both thermally unaltered and thermally altered sediments. The survey has revealed the presence of oxygenated compounds in samples with a high degree of thermal maturity. Phenols are one class of oxygenated compounds found in these samples. A group of methyl-, dimethyl- and trimethyl-isoprenoidyl phenols (C27-C29) is present in all of the seabed NSO fractions, with the methyl- and dimethyl-isoprenoidyl phenols occurring as major components, and a trimethyl-isoprenoidyl phenol as a minor component. A homologous series of n-alkylphenols (C13-C33) has also been found in the seabed petroleums. These phenols are most likely derived from the hydrothermal alteration of sedimentary organic matter. The n-alkylphenols are probably synthesized under hydrothermal conditions, but the isoprenoidyl phenols are probably hydrothermal alteration products of natural product precursors. The suites of phenols do not appear to be useful tracers of high temperature hydrothermal processes.

Chromatography, Gas↗

[Protective effect of nitric oxide on pancreas and its relation to sulfhydryl compounds and oxygen free radicals].

OBJECTIVE: To investigate the effect of endogenous nitric oxide (NO) on acute necrosis pancreatitis in rats and its relation to sulfhydryl compounds and lipid peroxidation. METHODS: Acute necrosis pancreatitis in rats was induced by retrograde sodium taurocholate (5%) infusion into the pancreatobiliary duct (1 ml/kg body weight), and N(G)-nitro-L-arginine (L-NNA) was used as the inhibitor of endogenous NO. The effect of endogenous NO on pancreatic injury, serum amylase level, the pancreatic tissue levels of sulfhydryl compounds, and malonaldehyde (MDA, the end product of lipid peroxidation) was evaluated, respectively. RESULTS: Sodium taurocholate administration induced evident pancreatic tissue edema and acinar necrosis, and intrapancreatic hemorrhage occurred in 2/7 rats. Both serum amylase and tissue MDA [(1.25 +/- 0.28) nmol/mg x pr vs. (0.5 +/- 0.03) nmol/mg x pr, P < 0.05] were significantly increased, but tissue sulfhydryl compounds were decreased markedly. Pretreatment with the NO inhibitor, L-NNA (12.5 mg/kg body weight), significantly intensified acinar necrosis and increased the intrapancreatic hemorrhage (10/12). L-NNA also resulted in a further increase of serum amylase and tissue MDA [(3.0 +/- 0.40) vs. (1.25 +/- 0.28) nmol/mg x pr, P < 0.05], but it had no effect on the tissue sulfhydryl compounds. CONCLUSION: Endogenous NO has the effect of pancreatic protection, and its antioxidation may be responsible, at least in part, for the protective mechanisms. Sulfhydryl compounds may not be involved in NO's pancreatic protection mechanisms.

Amylases↗

Histomorphometric, ultrastructural and microhardness evaluation of the osseointegration of a nanostructured titanium oxide coating by metal-organic chemical vapour deposition: an in vivo study.

Over the past decade the increase of elderly population has determined a rise in the incidence of bone fractures, and the improvement of the implant-bone interface remains an open problem. Metal-organic chemical vapour deposition (MOCVD) has recently been proposed as a technique to coat orthopaedic and dental prostheses with metal nanostructured oxide films either through the decomposition of oxygenated compounds (single-source precursors) or the reaction of oxygen-free metal compounds with oxygenating agents. The present study was performed to assess the in vivo biocompatibility of commercially pure Ti (control material: TI/MA) implants ( psi 2 mm x 5 mm length) coated with nanostructured TiO2 films by MOCVD (Ti/MOCVD) and then inserted into rabbit femoral cortical (middhiaphysis) and cancellous (distal epiphysis) bone. Histomorphometric, ultrastructural and microhardness investigations were carried out. Four and 12 weeks after surgery, significant (p<0.0005) increases in AI of Ti/MOCVD implants were observed as compared to Ti/MA implants (distal femoral epiphysis: 4 weeks=8.2%, ns; 12 weeks=52.3%, p <0.005; femoral diaphysis: 4 weeks=20.2%, p <0.0005; 12 weeks=10.7%, p <0.005). Bone microhardness results showed significant increases for the Ti/MOCVD versus Ti/MA implants at 200 microm in the femoral diaphysis (4 weeks=14.2, p <0.005) and distal femoral epiphysis (12 weeks=14.5, p <0.01) at 4 and 12 weeks, respectively. In conclusion, the current findings demonstrate that the nanostructured TiO2 coating positively affects the osseointegration rate of commercially pure Ti implants and the bone mineralization at the bone-biomaterial interface in both cortical and cancellous bone.

Animals↗

In vitro biocompatibility of titanium oxide for prosthetic devices nanostructured by low pressure metal-organic chemical vapor deposition.

Metal-Organic Chemical Vapor Deposition (MOCVD) has recently been proposed to coat orthopedic and dental prostheses with metal nanostructured oxide films through the decomposition of oxygenated compounds (single-source precursors) or the reaction of oxygen-free metal compounds with oxygenating agents. The present study was carried out to assess the in vitro biocompatibility in terms of cell proliferation and activation, of commercially pure Ti (control material: TI/MA) coated with nanostructured TiO2 film by MOCVD (Ti/MOCVD) using osteoblast-like cell cultures (MG-63). Evaluations were performed at 3, 7 and 14 days. Cell proliferation showed a similar trend for Ti/MA and TilMOCVD compared to polystyrene; cell number increased with time from seeding to day 7 (p < 0.005), and then decreased progressively until day 14 (ranging from -14% to -47%). The ALP level and OC production showed no significant differences between Ti/MOCVD and Ti/MA at each experimental time. Significantly higher ALP levels were found in Ti/MA at 3 days and in Ti/MOCVD at 7 and 14 days when compared to the polystyrene group. OC production decreased over time and the highest values were observed at 3 days, when it was significantly higher in the Ti/MA than in the polystyrene group (50%, p < 0.05). CICP synthesis was positively affected by the presence of Ti/MOCVD and was higher in Ti/MOCVD than in the polystyrene group. No significant differences were found between Ti/MOCVD and Ti/MA in terms of IL-6 and TGF-beta1 synthesis at any experimental time. In conclusion, the current findings demonstrate that the nanostructured TiO2 coating positively affects the osteoblast-like cell behavior in terms of cell proliferation and activity, thus confirming its high level of in vitro biocompatibility in accordance with expectations.

Biocompatible Materials↗