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Visible light induced biohydrogen production from sucrose using the photosensitization of Mg chlorophyll-a.

A photoinduced hydrogen production system, coupling sucrose degradation with invertase and glucose dehydrogenase (GDH) and hydrogen production with colloidal platinum as a catalyst using the visible light-induced photosensitization of Mg chlorophyll-a (Mg Chl-a), has been developed. Continuous hydrogen gas production was observed when the reaction mixture containing sucrose, invertase, GDH, nicotinamide adenine dinucleotide (NAD(+)), Mg Chl-a, methyl viologen (MV(2+), an electron relay reagent), and colloidal platinum was irradiated by visible light.

Chlorophyll↗

Biohydrogen production from sucrose using the visible light sensitization of artificial Zn chlorophyll-a.

A photoinduced hydrogen production system that couples sucrose degradation with invertase and glucose dehydrogenase (GDH) and hydrogen production with colloidal platinum as a catalyst using visible light-induced photosensitization of artificial Zn chlorophyll-a (Zn Chl-a) has been developed. Continuous hydrogen gas production over more than 240 min was observed when the reaction mixture containing sucrose, invertase, GDH, nicotinamide adenine dinucreotide (NAD(+)), Zn Chl-a, methyl viologen (MV(2+), an electron relay reagent), and colloidal platinum was irradiated by visible light. Zn Chl-a was superior to that of Mg Chl-a in photostability and photosensitization activity.

Chlorophyll↗

Biohydrogen production as a function of pH and substrate concentration.

The conversion of organics in wastewaters into hydrogen gas could serve the dual role of renewable energy production and waste reduction. The chemical energy in a sucrose rich synthetic wastewater was recovered as hydrogen gas in this study. Using fractional factorial design batch experiments, the effect of varying pH (4.5-7.5) and substrate concentration (1.5-44.8 g COD/L) and their interaction on hydrogen gas production were tested. Mixed bacterial cultures obtained from a compost pile, a potato field, and a soybean field were heated to inhibit hydrogen-consuming methanogens and to enrich sporeforming, hydrogen-producing acidogens. It was determined that the highest rate (74.7 mL H2/(L*h)) of hydrogen production occurred at a pH of 5.5 and a substrate concentration of 7.5 g COD/Lwith a conversion efficiency of 38.9 mL H2/(g COD/L). The highest conversion efficiency was 46.6 mL H2/(g COD/L).

Algorithms↗

The relative effectiveness of pH control and heat treatment for enhancing biohydrogen gas production.

Hydrogen gas can be recovered from the microbial fermentation of organic substrates at high concentrations when interspecies hydrogen transfer to methanogens is prevented. Two techniques that have been used to limit methanogenesis in mixed cultures are heat treatment, to remove nonsporeforming methanogens from an inoculum, and low pH during culture growth. We found that high hydrogen gas concentrations (57-72%) were produced in all tests and that heat treatment (HT) of the inoculum (pH 6.2 or 7.5) produced greater hydrogen yields than low pH (6.2) conditions with a nonheat-treated inoculum (NHT). Conversion efficiencies of glucose to hydrogen (based on a theoretical yield of 4 mol-H2/mol-glucose) were as follows: 24.2% (HT, pH = 6.2), 18.5% (HT, pH = 7.5), 14.9% (NHT, pH = 6.2), and 12.1% (NHT, pH = 7.5). The main products of glucose (3 g-COD/L) utilization (> or = 99%) in batch tests were acetate (3.4-24.1%), butyrate (6.4-29.4%), propionate (0.3-12.8%), ethanol (15.4-28.8%), and hydrogen (4.0-8.1%), with lesser amounts of acetone, propanol, and butanol (COD basis). Hydrogen gas phase concentrations in all batch cultures reached a maximum of 57-72% after 30 h but thereafter rapidly declined to nondetectable levels within 80 h. Separate experiments showed substantial hydrogen losses could occur via acetogenesis and that heat treatment did not prevent acetogenesis. Heat treatment consistently eliminated the production of measurable concentrations of methane. The disappearance of ethanol produced during hydrogen production was likely due to acetic acid production as thermodynamic calculations show that this reaction is spontaneous once hydrogen is depleted. Overall, these results show that low pH was, without heat treatment, sufficient to control hydrogen losses to methanogens in mixed batch cultures and suggest that methods will need to be found to limit acetogenesis in order to increase hydrogen gas yields by batch cultures.

Bacteria, Anaerobic↗

Inhibition of biohydrogen production by undissociated acetic and butyric acids.

Glucose fermentation to hydrogen results in the production of acetic and butyric acids. The inhibitory effect of these acids on hydrogen yield was examined by either adding these acids into the feed of continuous flow reactors (external acids), or by increasing glucose concentrations to increase the concentrations of acids produced by the bacteria (self-produced). Acids added to the feed at a concentration of 25 mM decreased H2 yields by 13% (acetic) and 22% (butyric), and 60 mM (pH 5.0) of either acid decreased H2 production by >93% (undissociated acid concentrations). H2 yields were constant at 2.0 +/- 0.2 mol H2/mol glucose for an influent glucose concentration of 10-30 g/L. At 40 g glucose/L, H2 yields decreased to 1.6 +/- 0.1 mol H2/mol glucose, and a switch to solventogenesis occurred. A total undissociated acid concentration of 19 mM (self-produced acids) was found to be a threshold concentration for significantly decreasing H2 yields and initiating solventogenesis. Hydrogen yields were inhibited more by self-produced acids (produced at high glucose feed concentrations) than by similar concentrations of externally added acids (lower glucose feed concentrations). These results show the reason hydrogen yields can be maximized by using lower glucose feed concentrations is that the concentrations of self-produced volatile acids (particularly butyric acid) are minimized.

Acetates↗

Improvement of biohydrogen production from solid wastes by intermittent venting and gas flushing of batch reactors headspace.

Headspace of batch minireactors was intermittently vented and gas flushed with N2 in order to enhance H2 production (PH) by anaerobic consortia degrading organic solid wastes. Type of inocula (meso and thermophilic), induction treatment (heat-shock pretreatment, HSP, and acetylene, Ac), and incubation temperature (37 and 55 degrees C) were studied by means of a factorial design. On average, it was found that mesophilic incubation had the most significant positive effect on PH followed by treatment with Ac, although the units with the best performance (high values of PH, initial hydrogen production rate, and short lag time) were those HSP-induced units incubated at 37 degrees C (type of inocula was not significant). In this way, after 720 h of incubation PH was inhibited in those units by H2 partial pressure (pH2) of 0.54 atm. Venting and gas flushing with N2 was efficient to eliminate that inhibition achieving additional hydrogen generation in subsequent incubation cycles although smaller than the first one. Thus, four cycles of PH were obtained from the same substrate with neither addition of inocula nor application of induction treatment obtaining an increment of 100% in the generated H2. In those subsequent cycles there was a positive correlation between PH and organic acids/solvent ratio; maximum values were found in the first cycle. Solventogenesis could be clearly distinguished in third and fourth production cycles, probably due to a metabolic shift originated by high organic acid concentrations.

Acids↗

Visible and near-IR light induced biohydrogen production using the system containing Mg chlorophyll-a from Spirulina and colloidal platinum.

Photoinduced hydrogen production with Mg chlorophyll-a from Spirulina as a visible and near-IR light photosensitizer by use of three component system consisting of nicotineamide adenine dinucleotide phosphate, reduced form (NADPH) as an electron donor, methylviologen as electron relay reagent and colloidal platinum as hydrogen production catalyst was investigated. After 4 h irradiation, the amount of hydrogen production with Mg chlorophyll-a and MgTPP, which was artificial model compound for chlorophyll, were c.a. 2.7 and 1.8 micromol, respectively. When the near-IR light was irradiated, little change of hydrogen production was observed. Thus, the effective visible and near IR light induced hydrogen production system with colloidal platinum was established using Mg chlorophyll-a.

Bacterial Proteins↗

Food particles as a site for biohydrogenation of unsaturated fatty acids in the rumen.

On incubation of linoleic acid with strained rumen contents from sheep, it was observed that conversion of linoleic acid into C(18:1)trans-11 monoenoic acid and subsequently into stearic acid was largely associated with the food-particle fraction. The bacteria, protozoa and cell-free supernatant together contributed less than 30% to the overall change in the added C(18:2) fatty acid.

Animals↗

Preparation of (S)2-methylsuccinate and (2S,3S) [2,3-2H]2-methylsuccinate by biohydrogenation of 2-methylfumarate.

2-Methylfumarate can be hydrogenated by resting cells of Proteus mirabilis under an atmosphere of hydrogen gas. Optically pure (S)2-methylsuccinate is formed in a yield greater than 95%. The hydrogen addition, presumably catalyzed by the fumarate reductase, occurs in a trans fashion, as with succinate dehydrogenase of mammalian systems. Only one reactive enzyme-substrate complex with 2-methylfumarate seems to be possible.

Fumarates↗

Ruminal biohydrogenation of fatty acids from high-oleate sunflower seeds.

The objective of these experiments was to examine methods of modifying the fatty acid composition of bovine tissues. In the first experiment, four steers were fitted with duodenal fistulas and were assigned to four diets in a Latin square design. The steers were fed a control diet or the same diet containing 10% high-oleate partially crushed sunflower seeds, serum-coated sunflower seeds, and heat-treated, serum-coated sunflower seeds for 5 d. Samples of digesta and feces were collected on d 5. The inclusion of sunflower seeds (plain or serum-coated) in the diet increased (P less than .05) the digesta concentration of stearate. The percentage of stearate in the digesta and feces was increased (P less than .05) from 51 to 67% and from 64 to 74%, respectively, when steers were fed the untreated sunflower seed. The fecal concentration of oleate was increased (P less than .05) by dietary sunflower seeds in steers that were fed the serum-coated, unheated sunflower seeds. In a second experiment, heifers (four per group) were fed a corn-based control diet or diets containing 10% of high-oleate sunflower oil encapsulated with calcium alginate, either plain, coated with blood meal, or with blood meal integrated into the pellet. After 50 d on treatment, samples of perianal adipose tissue were obtained by biopsy. The fatty acid composition of the adipose tissue was not modified by the inclusion of the encapsulated oleate in the diet. In summary, limited ruminal bypass of sunflower seed oleate was accomplished with sunflower seed but not with encapsulated oleate.

Adipose Tissue↗