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the food-producing redox reactions of photosynthesis …
Cellulose, a main component of green plants, is the most abundant organic chemical on Earth, produced 1011 tons per year in the biosphere. The polysaccharide consists of D-glucose units linked by beta-1,4-glycosidic bonds and has been widely utilized in diverse engineering fields because of its biocompatibility, abundance, and high chemical stability. In this work, we have demonstrated the utility of carboxymethyl cellulose (CMC) fibers as a sacrificial template to produce binary and tertiary metal oxides fibers. The electrostatic interaction between metal ions and the carboxyl groups in CMC fibers induced a hierarchical structure of metal oxides. The morphologies of synthesized metal oxides (e.g., CeO2, ZnO, and CaMn2O4) could be controlled according to synthetic conditions, such as metal precursor concentration, calcination temperature, and the amount of CMC fibers. Thus-synthesized CMC-templated metal oxide fibers exhibited enhanced performances for photocatalytic, photochemical, and electrocatalytic reactions. The CeO2 fibers showed much higher photocatalytic activity than CeO2 nanoparticles due to superior ability to generate reactive oxygen species which can degrade organic pollutants. We also demonstrated that hierarchical ZnO fibers hybridized with g-C3N4 could provide directional charge transfer pathway and showed their utility for biocatalyzed artificial photosynthesis through visible light-driven chemical NADH regeneration coupled with redox enzymatic reaction. The electrochemical properties of CaMn2O4 fibers enabled bi-functional reactions of oxygen reduction and evolution reactions. We expect that the economical and environmentally friend approach could be extended to green synthesis of hierarchically structured materials of other metal oxides.
In biological systems, the Redox Potential must be kept reduced to perpetuate the life process. In other words, the concentration of DHA (an oxidized form of ascorbic acid), must be kept to a minimum.
During injuries or stress which expose body tissues to atmospheric oxygen or disease, several reactions are triggered in polyunsaturated fatty acids (PUFAs) present in cellular membranes which produce hormones called prostaglandins that repair damage.
Under oxidizing stress (injury or disease) or impaired ability to manufacture NADH (aging or disease), the concentration of DHA can rise as the redox potential slips. This is a potentially life-threatening state for fish or any other animal.
5.6 Redox Reactions in Organic Chemistry and Biochemistry
In the past 50 years, cytochrome P450 monooxygenases (P450s) have been given significant attention for the synthesis of natural products (e.g., vitamins, steroids, lipids) and pharmaceuticals. Despite their potential, however, costly nicotinamide cofactors such as NAD(P)H are required as reducing equivalents; thus, in situ regeneration of NAD(P)H is essential to sustaining P450-catalyzed reactions. Furthermore, poor stability of P450s has been considered as a hurdle, hampering industrial implementations of P450-catalyzed reactions. Herein we describe the development of an economic and robust process of P450-catalyzed reactions by the combination of P450 immobilization and solar-induced NADPH regeneration. The P450 monooxygenase could be efficiently immobilized on a P(3HB) biopolymer, which enabled simple purification from the E. coli host. We clearly demonstrated that the P450-P(3HB) complex exhibited much higher enzymatic yield and stability than free P450 did against changes of pH, temperature, and concentrations of urea and ions. Using the robust P450-P(3HB) complex and solar-tracking module, we successfully conducted P450-catalyzed artificial photosynthesis under the irradiation of natural sunlight in a preparative scale (500 mL) for multiple days. To the best of our knowledge, this is the largest reactor volume in P450-catalyzed reactions reported so far. We believe that our robust platform using simple immobilization and abundant solar energy promises a significant breakthrough for the broad applications of cytochrome P450 monooxygenases.
Cytochromes P450 (P450 or CYP) belong to a superfamily of multifunctional monooxygenases that contain heme molecules (i.e., Fe-porphyrin) as a prosthetic group. They can catalyze various oxidative metabolic reactions of endogenous and exogenous compounds in living organisms. Their catalytic diversity and vast substrate range with regio- and stereo-specificity have high potential in applications to drug metabolism as well as in the fine chemical synthesis of steroids, lipids, vitamins, and natural products. Here, we have designed a novel visible light-driven platform for cofactor-free, whole-cell P450 photo-biocatalysis using eosin Y (EY) as a photosensitizer. EY can easily enter into the cytoplasm of Escherichia coli and bind specifically to the heme domain of P450. The catalytic turnover of P450 was mediated through the direct transfer of photo-induced electrons from the photosensitized EY to the P450 heme domain under visible light illumination. The photoactivation of the P450 catalytic cycle in the absence of cofactors and redox partners is successfully conducted using many bacterial P450s (variants of P450 BM3) and human P450s (CYPs 1A1, 1A2, 1B1, 2A6, 2E1, and 3A4) for the bioconversion of different substrates, including marketed drugs (simvastatin, lovastatin, and omeprazole) and a steroid (17beta-estradiol), to demonstrate general applicability of the light-driven, cofactor-free system.
Half reaction method of balancing redox reactions …
Depending on the type of microorganism, the reduced ferredoxin which supplies electrons for this process is generated byphotosynthesis, respiration or fermentation.
Bio Chemistry as it relates to Redox Balance:
There are enzymes within a body that are reactive oxygen species (ROS) and others that are reactive nitrogen species (RNS). A disturbance in the oxidationreduction state of the cell, in which ROS production exceeds antioxidant defenses, is called oxidative stress.
By analogy, nitrosative stress is an impairment in nitric oxide (NO) signaling caused by increased amounts of RNS, which may be caused by, or associated with, a disturbance in the Redox state. As discussed earlier, free radicals are highly reactive molecules with unpaired electrons.
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Internet Chemistry - University of Hawaii
In nature, quinone plays a vital role in numerous electrochemical reactions for energy transduction and storage; such processes include respiration and photosynthesis. For example, fast proton-coupled electron transfer between primary and secondary quinones in green plants triggers the rapid charge separation of chlorophyll molecules, achieving unparalleled photosynthesis with near-unity quantum yield. In addition, quinone-rich polymers such as eumelanin and polydopamine show unique optical and electrical properties (e.g., strong broadband absorbance or a switching response to external stimuli), mostly arising from their chemically disordered structures. Understanding the unique features of quinone and its derivatives can provide solutions to the construction of bio-inspired systems for energy harvesting and conversion. This paper reviews recent advances in the design of quinone-functionalized hybrid materials based on quinones redox, electrical, optical, and metal chelating/reducing properties to determine these materials applications in energy-harvesting and -storage systems, such as artificial photosynthetic platforms, rechargeable batteries, pseudocapacitors, phototransistors, plasmonic light harvesting platforms, and dye-sensitized solar cells.
Oxidation-reduction reaction | chemical ..
FROM WASTE TO VALUABLES: Human urine is studied as a potential source of energy for light-driven redox biocatalytic reactions. The urea-rich human urine functions as an efficient chemical fuel in a photoelectrochemical cell regenerating nicotinamide cofactor (NADH), an essential hydride mediator that is required for numerous redox biocatalytic reactions. We demonstrate the utility of human urine as a chemical fuel for driving redox biocatalysis in a photoelectrochemical cell. Ni(OH)2-modified alpha-Fe2O3 is selected as a photoanode for the oxidation of urea in human urine and black silicon (bSi) is used as a photocathode material for NADH regeneration. The electrons extracted from human urine are used for the regeneration of NADH. The catalytic reactions at both the photoanode and the photocathode were significantly enhanced by light energy that lowered the overpotential and generated high currents in the full cell system.
Chemical formula for photosynthesis
Efficient harvesting of unlimited solar energy and its conversion into valuable chemicals is one of the ultimate goals of scientists. With the ever-increasing concerns about sustainable growth and environmental issues, numerous efforts have been made to develop artificial photosynthetic process for the production of fuels and fine chemicals mimicking natural photosynthesis. Despite the research progresses made over the decades, the technology is still in its infancy because of the difficulties in kinetic coupling of whole photocatalytic cycles. Here, we report a new type of artificial photosynthesis system that can avoid such problems by integrally coupling biocatalytic redox reactions with photocatalytic water-splitting. We found that photocatalytic water-splitting reaction can be efficiently coupled with biocatalytic redox reactions by using tetra-cobalt polyoxometalate and Rh-based organometallic compound as hole and electron scavengers, respectively, for photoexcited Ru(bpy)32+ dye. Based on these results, we could successfully photosynthesize a model chiral compound (L-glutamate) using a model redox enzyme (glutamate dehydrogenase) upon in-situ photo-regeneration of cofactors.
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