Publications

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Ananyev, GM, Gates C, Dismukes GC.  2016.  The Oxygen quantum yield in diverse algae and cyanobacteria is controlled by partitioning of flux between linear and cyclic electron flow within photosystem II.. Biochim Biophys Acta.. 1857(9):1380-1391. Abstract
We have measured flash-induced oxygen quantum yields (O2-QYs) and primary charge separation (Chl variable fluorescence yield, Fv/Fm) in vivo among phylogenetically diverse microalgae and cyanobacteria. Higher O2-QYs can be attained in cells by releasing constraints on charge transfer at the Photosystem II (PSII) acceptor side by adding membrane-permeable benzoquinone (BQ) derivatives that oxidize plastosemiquinone QB- and QBH2. This method allows uncoupling PSII turnover from its natural regulation in living cells, without artifacts of isolating PSII complexes. This approach reveals different extents of regulation across species, controlled at the QB- acceptor site. Arthrospira maxima is confirmed as the most efficient PSII-WOC (water oxidizing complex) and exhibits the least regulation of flux. Thermosynechococcus elongatus exhibits an O2-QY of 30%, suggesting strong downregulation. WOC cycle simulations with the most accurate model (VZAD) show that a light-driven backward transition (net addition of an electron to the WOC, distinct from recombination) occurs in up to 25% of native PSIIs in the S2 and S3 states, while adding BQ prevents backward transitions and increases the lifetime of S2 and S3 by 10-fold. Backward transitions occur in PSIIs that have plastosemiquinone radicals in the QB site and are postulated to be physiologically regulated pathways for storing light energy as proton gradient through direct PSII-cyclic electron flow (PSII-CEF). PSII-CEF is independent of classical PSI/cyt-b6f-CEF and provides an alternative proton translocation pathway for energy conversion. PSII-CEF enables variable fluxes between linear and cyclic electron pathways, thus accommodating species-dependent needs for redox and ion-gradient energy sources powered by a single photosystem.
Ananyev, GM, Carrieri D, Dismukes GC.  2008.  Optimization of metabolic capacity and flux through environmental cues to maximize hydrogen production by the cyanobacterium "Arthrospira (Spirulina) maxima". Applied and Environmental Microbiology. 74:6102-6113. AbstractWebsite
Environmental and nutritional conditions that optimize the yield of hydrogen (H-2) from water using a two-step photosynthesis/ fermentation (P/F) process are reported for the hypercarbonate-requiring cyanobacterium "Arthrospira maxima." Our observations lead to four main conclusions broadly applicable to fermentative H-2 production by bacteria: (i) anaerobic H-2 production in the dark from whole cells catalyzed by a bidirectional [NiFe] hydrogenase is demonstrated to occur in two temporal phases involving two distinct metabolic processes that are linked to prior light-dependent production of NADPH (photosynthetic) and dark/anaerobic production of NADH (fermentative), respectively; (ii) H-2 evolution from these reductants represents a major pathway for energy production (ATP) during fermentation by regenerating NAD(+) essential for glycolysis of glycogen and catabolism of other substrates; (iii) nitrate removal during fermentative H-2 evolution is shown to produce an immediate and large stimulation of H-2, as nitrate is a competing substrate for consumption of NAD(P) H, which is distinct from its slower effect of stimulating glycogen accumulation; (iv) environmental and nutritional conditions that increase anaerobic ATP production, prior glycogen accumulation (in the light), and the intracellular reduction potential (NADH/NAD(+) ratio) are shown to be the key variables for elevating H-2 evolution. Optimization of these conditions and culture age increases the H-2 yield from a single P/F cycle using concentrated cells to 36 ml of H-2/g (dry weight) and a maximum 18% H-2 in the headspace. H-2 yield was found to be limited by the hydrogenase-mediated H-2 uptake reaction.
Ananyev, GM, Skizim NJ, Dismukes CG.  2012.  Enhancing biological hydrogen production from cyanobacteria by removal of excreted products.. Journal of biotechnology. 162(1):97-104. Abstract
Hydrogen is produced by a [NiFe]-hydrogenase in the cyanobacterium Arthrospira (Spirulina) maxima during autofermentation of photosynthetically accumulated glycogen under dark anaerobic conditions. Herein we show that elimination of H₂ backpressure by continuous H₂ removal ("milking") can significantly increase the yield of H₂ in this strain. We show that "milking" by continuous selective consumption of H₂ using an electrochemical cell produces the maximum increase in H₂ yield (11-fold) and H₂ rate (3.4-fold), which is considerably larger than through "milking" by non-selective dilution of the biomass in media (increases H₂ yield 3.7-fold and rate 3.1-fold). Exhaustive autofermentation under electrochemical milking conditions consumes >98% of glycogen and 27.6% of biomass over 7-8 days and extracts 39% of the energy content in glycogen as H₂. Non-selective dilution stimulates H₂ production by shifting intracellular equilibria competing for NADH from excreted products and terminal electron sinks into H₂ production. Adding a mixture of the carbon fermentative products shifts the equilibria towards reactants, resulting in increased intracellular NADH and an increased H₂ yield (1.4-fold). H₂ production is sustained for a period of time up to 7days, after which the PSII activity of the cells decreases by 80-90%, but can be restored by regeneration under photoautotrophic growth.
Ananyev, GM, Zaltsman L, Vasko C, Dismukes GC.  2001.  The inorganic biochemistry of photosynthetic oxygen evolution/water oxidation. Biochimica et Biophysica Acta (BBA) - Bioenergetics. 1503:52-68.Website
Ananyev, GM, Nguyen T, Putnam-Evans C, Dismukes GC.  2005.  Mutagenesis of CP43-arginine-357 to serine reveals new evidence for (bi)carbonate functioning in the water oxidizing complex of Photosystem II. Photochemical & Photobiological Sciences. 4:991-998.Website
Ananyev, GM, Dismukes GC.  2005.  How fast can Photosystem II split water? Kinetic performance at high and low frequencies Photosynthesis Research. 84:355-365.Website
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Bartlett, JE, Baranov SV, Ananyev GM, Dismukes GC.  2008.  Calcium controls the assembly of the photosynthetic water-oxidizing complex: a cadmium(II) inorganic mutant of the Mn4Ca core. Philosophical Transactions of the Royal Society B-Biological Sciences. 363:1253-1261. AbstractWebsite
Perturbation of the catalytic inorganic core (Mn4Ca1OxCly) of the photosystem II-water-oxidizing complex (PSII-WOC) isolated from spinach is examined by substitution of Ca2+ with cadmium(II) during core assembly. Cd2+ inhibits the yield of reconstitution of O-2-evolution activity, called photoactivation, starting from the free inorganic cofactors and the cofactor-depleted apo-WOC-PSII complex. Ca2+ affinity increases following photooxidation of the first Mn2+ to Mn3+ bound to the 'high-affinity' site. Ca2+ binding occurs in the dark and is the slowest overall step of photoactivation (IM1/IM*(1) -> step). Cd2+ competitively blocks the binding of Ca2+ to its functional site with 10-to 30-fold higher affinity, but does not influence the binding of Mn2+ to its high-affinity site. By contrast, even 10-fold higher concentrations of Cd2+ have no effect on O-2-evolution activity in intact PSII-WOC. Paradoxically, Cd2+ both inhibits photoactivation yield, while accelerating the rate of photoassembly of active centres 10-fold relative to Ca2+. Cd2+ increases the kinetic stability of the photooxidized Mn3+ assembly intermediate(s) by twofold (mean lifetime for dark decay). The rate data provide evidence that Cd2+ binding following photooxidation of the first Mn3+, IM1/IM*(1), causes three outcomes: (i) a longer intermediate lifetime that slows IM1 decay to IM0 by charge recombination, (ii) 10-fold higher probability of attaining the degrees of freedom (either or both cofactor and protein d.f.) needed to bind and photooxidize the remaining 3 Mn2+ that form the functional cluster, and (iii) increased lability of Cd2+ following Mn-4 cluster assembly results in (re) exchange of Cd2+ by Ca2+ which restores active O-2-evolving centres. Prior EPR spectroscopic data provide evidence for an oxo-bridged assembly intermediate, Mn3+ (mu-O2-) Ca2+, for IM*(1). We postulate an analogous inhibited intermediate with Cd2+ replacing Ca2+.
Brimblecombe, R, Koo A, Dismukes CG, Swiegers GF, Spiccia L.  2010.  A Tandem Water-Splitting Device Based on a Bio-inspired Manganese Catalyst. ChemSusChem. 3:1146-1150.Website
Brimblecombe, R, Chen J, Wagner P, Buchhorn T, Dismukes CG, Spiccia L, Swiegers GF.  2011.  Photocatalytic oxygen evolution from non-potable water by a bioinspired molecular water oxidation catalyst. Journal of Molecular Catalysis A: Chemical. 338:1-6.Website
Brimblecombe, R, Bond AM, Dismukes CG, Swiegers GF, Spiccia L.  2009.  Electrochemical investigation of Mn4O4-cubane water-oxidizing clusters. Physical Chemistry Chemical Physics. 11:6441-6449. AbstractWebsite
High valence states in manganese clusters are a key feature of the function of one of the most important catalysts found in nature, the water-oxidizing complex of photosystem II. We describe a detailed electrochemical investigation of two bio-inspired manganese-oxo complexes, [Mn4O4L6] (L = diphenylphosphinate (1) and bis(p-methoxyphenyl)phosphinate (2)), in solution, attached to an electrode surface and suspended within a Nafion film. These complexes contain a cubic [Mn4O4]6+ core stabilized by phosphinate ligands. They have previously been shown to be active and durable photocatalysts for the oxidation of water to dioxygen. A comparison of catalytic photocurrent generated by films deposited by two methods of electrode immobilization reveals that doping of the catalyst in Nafion results in higher photocurrent than was observed for a solid layer of cubane on an electrode surface. In dichloromethane solution, and under conditions of cyclic voltammetry, the one-electron oxidation processes 1/1+ and 2/2+ were found to be reversible and quasi-reversible, respectively. Some decomposition of 1+ and 2+ was detected on the longer timescale of bulk electrolysis. Both compounds also undergo a two-electron, chemically irreversible reduction in dichloromethane, with a mechanism that is dependent on scan rate and influenced by the presence of a proton donor. When immersed in aqueous electrolyte, the reduction process exhibits a limited level of chemical reversibility. These data provide insights into the catalytic operation of these molecules during photo-assisted electrolysis of water and highlight the importance of the strongly electron-donating ligand environment about the manganese ions in the ability of the cubanes to photocatalyze water oxidation at low overpotentials.
Brimblecombe, R, Koo A, Dismukes CG, Swiegers GF, Spiccia L.  2010.  Solar Driven Water Oxidation by a Bioinspired Manganese Molecular Catalyst. Journal of the American Chemical Society. 132:2892-2894. AbstractWebsite
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Brimblecombe, R, Dismukes CG, Swiegers GF, Spiccia L.  2009.  Molecular water-oxidation catalysts for photoelectrochemical cells. Dalton Transactions. :9374-9384. AbstractWebsite
Photoelectrochemical cells that efficiently split water into oxygen and hydrogen, "the fuel of the future", need to combine robust water oxidation catalysts at the anode (2H2O [rightward arrow] O2 + 4H+ + 4e-) with hydrogen reduction catalysts at the cathode (2H+ + 2e-[rightward arrow] H2). Both sets of catalysts will, ideally, operate at low overpotentials and employ light-driven or light-assisted processes. In this Perspective article, we focus on significant efforts to develop solid state materials and molecular coordination complexes as catalyst for water oxidation. We briefly review the field with emphasis on the various molecular catalysts that have been developed and then examine the activity of molecular catalysts in water oxidation following their attachment to conducting electrodes. For such molecular species to be useful in a solar water-splitting device it is preferable that they are securely and durably affixed to an electrode surface. We also consider recent developments aimed at combining the action of molecular catalysts with light absorption so that light driven water oxidation may be achieved.
Brimblecombe, R, Swiegers G F, Dismukes  CG, Spiccia L.  2008.  Sustained Water Oxidation Photocatalysis by a Bioinspired Manganese Cluster. Angewandte Chemie International Edition. 47:7335-7338.Website
Brimblecombe, R, Kolling DRJ, Bond AM, Dismukes CG, Swiegers GF, Spiccia L.  2009.  Sustained Water Oxidation by [Mn4O4]7+ Core Complexes Inspired by Oxygenic Photosynthesis. Inorganic Chemistry. 48:7269-7279. AbstractWebsite
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Burrows, EH, Bennette NB, Carrieri D, Dixon JL, Brinker A, Frada M, Bakdassabim S N, Falkowski PG, Dismukes GC.  2012.  Dynamics of Lipid Biosynthesis and Redistribution in the Marine Diatom Phaeodactylum tricornutum under Nitrate Deprivation. Bioenerg. Res. 5:876-885. Abstract
One approach to achieve continuous overproduction of lipids in microalgal “cell factories” relies upon depletion or removal of nutrients that act as competing electron sinks (e.g., nitrate and sulfate). However, this strategy can only be effective for bioenergy applications if lipid is synthesized primarily de novo (from CO2 fixation) rather than from the breakdown and interconversion of essential cellular components. In the marine diatom, Phaeodactylum tricornutum, it was determined, using 13C-bicarbonate, that cell growth in nitrate (NO 3 − )-deprived cultures resulted predominantly in de novo lipid synthesis (60 % over 3 days), and this new lipid consisted primarily of triacylglycerides (TAGs). Nearly complete preservation of 12C occurred in all previously existing TAGs in NO 3 − -deprived cultures and thus, further TAG accumulation would not be expected from inhibition of TAG lipolysis. In contrast, both high turnover and depletion of membrane lipids, phosphatidylcholines (PCs), were observed in NO 3 − -deprived cultures (both the headgroups and fatty acid chains), while less turnover was observed in NO 3 − replete cultures. Liquid chromatography-tandem mass spectrometry mass spectra and 13C labeling patterns of PC headgroups provided insight into lipid synthesis in marine diatoms, including suggestion of an internal pool of glycine betaine that feeds choline synthesis. It was also observed that 16C fatty acid chains incorporated into TAGs and PCs contained an average of 14 13C carbons, indicating substantial incorporation of 13C-bicarbonate into fatty acid chains under both nutrient states.
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Carrell, TG, Cohen S, Dismukes CG.  2002.  Oxidative catalysis by Mn4O46+ cubane complexes. Journal of Molecular Catalysis A: Chemical. 187:3-15.Website
Carrell TG, Smith PF, Dennes J, Dismukes CG.  2014.  Entropy and enthalpy contributions to the kinetics of proton coupled electron transfer to the Mn4O4(O2PPh2)6 cubane.. Physical chemistry chemical physics : PCCP. 16(24):11843-7. Abstract
The dependence of rate, entropy of activation, and ((1)H/(2)H) kinetic isotope effect for H-atom transfer from a series of p-substituted phenols to cubane Mn4O4L6 (L = O2PPh2) () reveals the activation energy to form the transition state is proportional to the phenolic O-H bond dissociation energy. New implications for water oxidation and charge recombination in photosystem II are described.