Retinal venous blood carbon monoxide response to bright light in male pigs: A preliminary study.

The physical mechanism by which light is absorbed in the eye and has antidepressant and energizing effects in Seasonal Affective Disorder and other forms of psychiatric major depression is of scientific interest. This study was designed to explore one specific aspect of a proposed humoral phototransduction mechanism, namely that carbon monoxide (CO) levels increase in retinal venous blood in response to bright light. Eleven mature male pigs approximately six months of age were kept for 7days in darkness and fasted for 12h prior to surgery. Following mild sedation, anesthesia was induced. Silastic catheters were inserted into the dorsal nasal vein through the angular vein of the eye to reach the ophthalmic sinus, from which venous blood outflowing from the eye area was collected. The animals were exposed to 5000lx of fluorescent-generated white light. CO levels in the blood were analyzed by gas chromatography before and after 80min of light exposure. At baseline, mean CO levels in the retinal venous blood were 0.43±0.05(SE)nmol/ml. After bright light, mean CO levels increased to 0.54±0.06nmol/ml (two-tailed t-test p<0.05). This study provides preliminary mammalian evidence that acute bright light exposure raises carbon monoxide levels in ophthalmic venous blood.

NIR-Responsive On-Demand Release of CO from Metal Carbonyl-Caged Graphene Oxide Nanomedicine.

On-demand release of carbon monoxide (CO) is realized through a novel near-infrared-responsive nanomedicine in favor of the enhancement of therapy efficacy and biosafety of CO therapy.

Visible-light photoredox catalysis: selective reduction of carbon dioxide to carbon monoxide by a nickel N-heterocyclic carbene-isoquinoline complex.

The solar-driven reduction of carbon dioxide to value-added chemical fuels is a longstanding challenge in the fields of catalysis, energy science, and green chemistry. In order to develop effective CO2 fixation, several key considerations must be balanced, including (1) catalyst selectivity for promoting CO2 reduction over competing hydrogen generation from proton reduction, (2) visible-light harvesting that matches the solar spectrum, and (3) the use of cheap and earth-abundant catalytic components. In this report, we present the synthesis and characterization of a new family of earth-abundant nickel complexes supported by N-heterocyclic carbene-amine ligands that exhibit high selectivity and activity for the electrocatalytic and photocatalytic conversion of CO2 to CO. Systematic changes in the carbene and amine donors of the ligand have been surveyed, and [Ni((Pr)bimiq1)](2+) (1c, where (Pr)bimiq1 = bis(3-(imidazolyl)isoquinolinyl)propane) emerges as a catalyst for electrochemical reduction of CO2 with the lowest cathodic onset potential (E(cat) = -1.2 V vs SCE). Using this earth-abundant catalyst with Ir(ppy)3 (where ppy = 2-phenylpyridine) and an electron donor, we have developed a visible-light photoredox system for the catalytic conversion of CO2 to CO that proceeds with high selectivity and activity and achieves turnover numbers and turnover frequencies reaching 98,000 and 3.9 s(-1), respectively. Further studies reveal that the overall efficiency of this solar-to-fuel cycle may be limited by the formation of the active Ni catalyst and/or the chemical reduction of CO2 to CO at the reduced nickel center and provide a starting point for improved photoredox systems for sustainable carbon-neutral energy conversion.

Fat content influences the color, lipid oxidation, and volatiles of irradiated ground beef.

Ground beef with 10%, 15%, or 20% fat were added with none, 0.05% ascorbic acid + 0.01%alpha-tocopherol, or 0.05% ascorbic acid + 0.01%alpha-tocopherol + 0.01% sesamol, and irradiated at 0 or 2.5 kGy. The meat samples were displayed under fluorescent light for 14 d at 4 degrees C. Color, lipid oxidation, volatiles, oxidation-reduction potential (ORP), and carbon monoxide (CO) production were determined during storage. Irradiation increased lipid oxidation and total volatiles of ground beef regardless of fat contents. Ascorbic acid + alpha-tocopherol + sesamol treatment was the most effective in reducing lipid oxidation during storage. The production of ethanol in nonirradiated ground beef increased dramatically after 7 d of storage due to microbial growth. Total aldehydes and hexanal increased drastically in irradiated control over the storage period, but hexanal increased the most by irradiation. L*-values was decreased by irradiation, but increased in all meat regardless of fat contents as storage period increased. Irradiation reduced the redness, but fat contents had no effect on the a*-value of ground beef. Sesamol lowered, but ascorbic acid + alpha-tocopherol maintained the redness of irradiated beef up to 2 wk of storage. The yellowness of meat was significantly decreased by irradiation. The reducing power of ascorbic acid + alpha-tocopherol lasted for 3 d, after which ORP values increased. Irradiation increased CO production regardless of fat content in ground beef. In conclusion, up to 20% fat had no effect on the quality change of irradiated ground beef if ascorbic acid + alpha-tocopherol was added.

Photocatalytic degradation of NOx gases using TiO2-containing paint: a real scale study.

An indoor car park was appropriately equipped in order to test the de-polluting efficiency of a TiO(2)-containing paint in an indoor polluted environment, under real scale configuration. Depollution tests were performed in an artificially closed area of the parking, which was polluted by a car exhaust during the testing period. The ceiling surface of the car park was covered with white acrylic TiO(2)-containing paint (PP), which was developed in the frame of the EU project 'PICADA' (Photocatalytic Innovative Coverings Application for Depollution Assessment). The closed area was fed with car exhaust gases. As soon as the system reached steady state, the UV lamps were turned on for 5h. The difference between the final and the initial steady state concentration indicates the removal of the pollutants due to both the photocatalytic paint and car emission reduction. Results showed a significant photocatalytic oxidation of NO(x) gases. The photocatalytic removal of NO and NO(2) was calculated to 19% and 20%, respectively, while the photocatalytic rate (microgm(-2)s(-1)) ranged between 0.05 and 0.13 for NO and between 0.09 and 0.16 for NO(2).

Infrared spectroscopic and theoretical studies on the reactions of copper atoms with carbon monoxide and nitric oxide molecules in rare-gas matrices.

Reactions of laser-ablated Cu atoms with CO and NO mixtures in solid argon and neon have been investigated using matrix-isolation infrared spectroscopy. Copper carbonyls and copper nitrosyls have been observed, whereas copper carbonyl nitrosyl complexes are absent from the present experiments. New products, (CuCO)2, [NO]Cu[NO], Cu2(mu2-NO), and Cu(NO)2Cu, have been formed in the copper experiments and characterized using infrared spectroscopy on the basis of the results of the isotopic shifts, mixed isotopic splitting patterns, stepwise annealing, the change of reagent concentration and laser energy, and comparison with theoretical predictions. Density functional theory calculations have been performed on these copper carbonyls and copper nitrosyls, which support the identification of these products from the matrix infrared spectrum. A plausible reaction mechanism has been proposed to account for the formation of copper carbonyls and copper nitrosyls. Similar matrix experiments with Ag and Au produce no new species.

Pyrolysis experiment of simulated exogenous complex organics synthesized from the gas mixtures of CO, NH3, and H2O by 3 MeV proton irradiation.

High molecular weight organic matter synthesized from mixtures of carbon monoxide, ammonia and water gases similar to those found in the interstellar medium were irradiated with a 3 MeV proton beam and analyzed by Curie point pyrolysis with detection by gas chromatograph and mass spectrometer (Pyr-GC-MS). A wide variety of organic compounds, not only a number of amide compounds, but also heterocyclic and polycyclic aromatic hydrocarbons (PAHs), were detected among the products of the pyrolysis. The present data shows that primary and primitive organic matter serving as precursors to bioorganic compounds such as amino acids, nucleic acid bases and sugar might have been formed in a gaseous mixture of similar composition to that of the interstellar dust environment.

Amino acid formation in gas mixtures by high energy particle irradiation.

Amino acids were formed from carbon monoxide, nitrogen and water, which are possible constituents of the primitive earth's atmosphere, by irradiation with high energy particles (components of cosmic rays). Glycine yield was proportional to the total energy deposited to the gas mixture, and its G-value was as high as 0.02 when the carbon monoxide/nitrogen ratio was 1. Based on an estimate of the effective energies of various types of energy sources available in the primitive earth's atmosphere for amino acid synthesis, it is suggested that cosmic rays were one of the most important energy sources for the synthesis of amino acids on the primitive earth.