Addition of sodium camptothecin (2a, Fig. 1) in comparable low concentrations to the glycopeptide antitumor antibiotic bleomycin (BLM) leads to enhanced rates of single-strand scission of PM2-covalently closed circular DNA, whereas sodium camptothecin alone has no effect. A similar enhancement of DNA scission by sodium camptothecin is produced with the 1 : 1 bleomycin-iron complex alone or in conjunction with NADPH as an additional reductant. The interpretation that camptothecin may substitute for the reducing requirement of the antibiotic is supported by its oxidation at 37°C by the 1 : 1 bleomycin iron complex, by iron salts or more efficiently by hydrogen peroxide to the known hemiacetal (3, Fig. 1).Electrochemical studies of 2a, its analogues and selected model compounds established that the α-pyridone ring D is most susceptible to a one-electron reduction at a reversible potential of ?0.95 ± 0.01 V. The reduced camptothecin is a transient species readily capable of donating an electron. This process may by compatible with a coupled reduction of the sequestered Fe(III) in the glycopeptide antibiotic necessary for the expression of antibiotic and antitumor properties. The results may provide a mechanistic rationale for the observed potentiation of the antitumor activity of bleomycin by camptothecin in vivo. 相似文献
Industrial enzymatic reactions requiring 1,4-NAD(P)H2 to perform redox transformations often require convoluted coupled enzyme regeneration systems to regenerate 1,4-NAD(P)H2 from NAD(P) and recycle the cofactor for as many turnovers as possible. Renewed interest in recycling the cofactor via electrochemical means is motivated by the low cost of performing electrochemical reactions, easy monitoring of the reaction progress, and straightforward product recovery. However, electrochemical cofactor regeneration methods invariably produce adventitious reduced cofactor side products which result in unproductive loss of input NAD(P). We review various literature strategies for mitigating adventitious product formation by electrochemical cofactor regeneration systems, and offer insight as to how a successful electrochemical bioreactor system could be constructed to engineer efficient 1,4-NAD(P)H2-dependent enzyme reactions of interest to the industrial biocatalysis community. 相似文献
Surface modifications of anode materials are important for enhancing power generation of microbial fuel cell (MFC). Membrane free single-chamber air-cathode MFCs, MFC-A and MFC-N, were constructed using activated carbon fiber felt (ACF) anodes treated by nitric acid and ethylenediamine (EDA), respectively. Experimental results showed that the start-up time to achieve the maximum voltages for the MFC-A and MFC-N was shortened by 45% and 51%, respectively as compared to that for MFC-AT equipped with an unmodified anode. Moreover, the power output of MFCs with modified anodes was significantly improved. In comparison with MFC-AT which had a maximum power density of 1304 mW/m2, the MFC-N achieved a maximum power density of 1641 mW/m2. The nitric acid-treated anode in MFC-A increased the power density by 58% reaching 2066 mW/m2. XPS analysis of the treated and untreated anode materials indicated that the power enhancement was attributable to the changes of surface functional groups. 相似文献
In the past 20 years, inorganic fuel cells have been transformed from novelty devices to practical energy transfer-energy storage units. However, the advantage of the high operating efficiency afforded by these fuel cells is partially offset by (a) the limited viability and high cost of the catalysts, (b) the highly corrosive electrolytes, and (c) the elevated operating temperatures. The possibility exists to reduce some of these problems through the development of bioelectrochemical fuel cells. Such biological/electrochemical systems incorporate either microorganisms or enzymes as an active component within the specified electrode compartments. Recent studies with microorganisms as part of the anode compartment have been aimed at defining the mechanism of the observed electrochemical reactions. Recent investigations on the use of cell-free enzyme preparations in the electrode compartments have dealt primarily with developing methodology and defining mechanisms for enhancing the rate of electron transfer from the enzyme-cofactor active site to the solid electrode surface. Applications of this developing technology have been envisioned for analytical chemistry, medical devices, energy transfer, electrochemical synthesis, and detoxification. In this review, the theory and problems of bioelectrochemical fuel cells are described and related to research, both recent and proposed, for the practical development of this area. 相似文献
1. 1. Cycles of oxidation followed by reduction at pH 7.2 have been induced in uncoupled anaerobic mung bean mitochondria treated with succinate and malonate by addition of oxygen-saturated medium. Under the conditions used, cytochromes b557, b553, c549 (corresponding to c1 in mammalian mitochondria) and ubiquinone are completely oxidized in the aerobic state, but become completely reduced in anaerobiosis.
2. 2. The time course of the transition from fully oxidized to fully reduced in anaerobiosis was measured for cytochromes c549, b557, and b553. The intramitochondrial redox potential (IMPh) was calculated as a function of time for each of the three cytochromes from the time course of the oxidized-to-reduced transition and the known midpoint potentials of the cytochromes at pH 7.2. The three curves so obtained are superimposable, showing that the three cytochromes are in redox equilibrium under these conditions during the oxidized-to-reduced transition.
3. 3. This result shows that the slow reduction of cytochrome b557 under these conditions, heretofore considered anomalous, is merely a consequence of its more negative midpoint potential of +42 mV at pH 7.2, compared to +75 mV for cytochrome b553 and +235 mV for cytochrome c549. Cytochrome b557 is placed on the low potential side of coupling site II and transfers electrons to cytochrome c549via the coupling site.
4. 4. The time course of the transition from fully oxidized to fully reduced was also measured for ubiquinone. Using the change in intramitochondrial potential IMPh with time obtained from the three cytochromes, the change in redox state of ubiquinone with IMPh was calculated. When replotted as IMPhversus the logarithm of the ratio (fraction oxidized)/(fraction reduced), two redox components with n = 2 were found. The major component is ubiquinone with a midpoint potential Em7.2 = + 70 mV. The minor component has a midpoint potential Em7.2 = − 12 mV; its nature is unknown.
Abbreviations: IMPh, intramitochondrial potential, referred to the normal hydrogen electrode; Em7.2, midpoint potential at pH 7.2 相似文献