Dismukes Lab

Research Overview

To mitigate many of the potentially deleterious environmental and agricultural consequences associated with current landbased-biofuel feedstocks, we advocate the use of biofuels derived from aquatic microbial oxygenic photoautotrophs (AMOPs), more commonly known as algae, cyanobacteria and diatoms. Our research on AMOPs addresses:

  1. Demonstrated productivity in mass culturing and future potential as biomass energy crops

  2. Use as cell factories for production of gaseous fuels (H2, CH4)

  3. Fundamental photosynthetic physiology and mechanisms

  4. Genetic transformants for understanding mechanisms and improving fuel production.

Announcements
  • Congratulations Hiba Shaqra!

    Please join me in congratulating Hiba Shaqra on her nomination by Rutgers University for a Goldwater fellowship. This is considered the most prestigious undergraduate fellowship in the natural sciences, mathematics and engineering in America.

     

    Hiba is a junior majoring in Molecular Biology and Biochemistry | Arabic, Chemistry, and Mathematics minors. She has been working closely with Apostolos Zournas for the last two years in the Waksman Institute. Pat on the back to Apostolos for awesome mentoring!
  • Catalysis Research

    We develop selective and robust catalysts that electrochemically convert carbon dioxide (CO2) into sustainable chemical feedstocks and could ultimately be coupled to the recycling of environmental CO2. The catalysts employed are transition metal phosphides and their doped derivatives that form distinct crystalline structure types, enabling selection of chemical reactivity towards desired products including high molecular weight solid polymers. Selecting the catalyst’s elemental composition and crystal structure allows for tuning of the chemical, physical, and… Read More

Contact Information

Chemistry & Chemical Biology
610 Taylor Road
Wright Rieman Labs 102
Piscataway, NJ 08854
United States

(848) 445-6786
dismukes@rutgers.edu
Links

Selected Publications

Complete list of publications: [Google Scholar] [Pubmed]

'Birth defects’ of photosystem II make it highly susceptible to photodamage during chloroplast biogenesis.

Shevela, D., G. Ananyev, A.K. Vatland, J. Arnold, F. Mamedov, L. Eichacker, G.C. Dismukes and J. Messinger, 'Birth defects’ of photosystem II make it highly susceptible to photodamage during chloroplast biogenesis. Physiol. Plant., 2019. https://doi.org/10.1111/ppl.12932

Understanding Water and Gas Transport in Algal-Fungal Symbionts: Integrating Laboratory Experiments and Numerical Modeling of Lichens

Potkay, A., M.-C.t. Veldhuis, G. Ananyev, G.C. Dismukes and Y. Fan, Understanding Water and Gas Transport in Algal-Fungal Symbionts: Integrating Laboratory Experiments and Numerical Modeling of Lichens. in preparation, 2019.

Crossing the Thauer limit: rewiring cyanobacterial metabolism to maximize fermentative H2 production

Kumaraswamy, G.K., A. Krishnan, G. Ananyev, D.A. Bryant and G.C. Dismukes, Crossing the Thauer limit: rewiring cyanobacterial metabolism to maximize fermentative H2 production. Energy & Environmental Science, 2019. Advance article(c8ee03606c): p. c8ee03606c.

Fluorescence induction technique for studies of photosynthetic electron transport across multiple time domains: Application to CO2-fixation rates and fluxes.

Ananyev, G., A. Zournas, C. Gates, M.-c.t. Veldhuis and G.C. Dismukes, Fluorescence induction technique for studies of photosynthetic electron transport across multiple time domains: Application to CO2-fixation rates and fluxes. in preparation, 2019.

The Catalytic Cycle of Water Oxidation in Crystallized Photosystem II Complexes: Performance and Requirements for Formation of Intermediates.

Ananyev, G., S. Roy-Chowdhury, C. Gates, P. Fromme and G.C. Dismukes, The Catalytic Cycle of Water Oxidation in Crystallized Photosystem II Complexes: Performance and Requirements for Formation of Intermediates. ACS Catalysis, 2019. 9(2): p. 1396-1407.

Desiccation tolerant lichens facilitate in vivo H/D isotope effect measurements in oxygenic photosynthesis.

Vinyard, D.J., G.M. Ananyev and G.C. Dismukes, Desiccation tolerant lichens facilitate in vivo H/D isotope effect measurements in oxygenic photosynthesis. Biochimica et Biophysica Acta (BBA) - Bioenergetics, 2018. 1859(10): p. 1039-1044.

Rerouting of Metabolism into Desired Cellular Products by Nutrient Stress: Fluxes Reveal the Selected Pathways in Cyanobacterial Photosynthesis.

Qian, X., Y. Zhang, D.S. Lun and G.C. Dismukes, Rerouting of Metabolism into Desired Cellular Products by Nutrient Stress: Fluxes Reveal the Selected Pathways in Cyanobacterial Photosynthesis. ACS Synthetic Biology, 2018. 7(5): p. 1465-1476.

Rewiring of cyanobacterial metabolism for hydrogen production: Synthetic biology approaches and challenges. Synthetic Biology of Cyanobacteria

Krishnan, A., X. Qian, G. Ananyev, D.S. Lun and G.C. Dismukes, Rewiring of cyanobacterial metabolism for hydrogen production: Synthetic biology approaches and challenges. Synthetic Biology of Cyanobacteria, in Adv Exp Med Biol. , W.Z.a.X. Song, Editor. 2018, Springer: Singapore. p. 171-213.

Resolving Ambiguous Protonation and Oxidation States in the Oxygen Evolving Complex of Photosystem II.

Chen, H., G.C. Dismukes and D.A. Case, Resolving Ambiguous Protonation and Oxidation States in the Oxygen Evolving Complex of Photosystem II. The Journal of Physical Chemistry B, 2018. 122(37): p. 8654-8664.

Reconciling Structural and Spectroscopic Fingerprints of the Oxygen-Evolving Complex of Photosystem II: A Computational Study of the S2 State

Chen, H., D.A. Case and G.C. Dismukes, Reconciling Structural and Spectroscopic Fingerprints of the Oxygen-Evolving Complex of Photosystem II: A Computational Study of the S2 State. The Journal of Physical Chemistry B, 2018. 122(50): p. 11868-11882.

Nickel phosphides catalyze the electrochemical CO2 reduction to C3 and C4 products at low overpotential

Calvinho, K.U.D., A.B. Laursen, K.M.K. Yap, T.A. Goetjen, S. Hwang, N. Murali, B. Mejia-Sosa, A. Lubarski, K.M. Teeluck, E. Garfunkel, M. Greenblatt and G.C. Dismukes, Nickel phosphides catalyze the electrochemical CO2 reduction to C3 and C4 products at low overpotential. Energy and Environmental Science, 2018. 11(9): p. 2550-2559.

The multiplicity of roles for (bi)carbonate in photosystem II operation in the hypercarbonate-requiring cyanobacterium Arthrospira maxima

Ananyev, G., C. Gates and G.C. Dismukes, The multiplicity of roles for (bi)carbonate in photosystem II operation in the hypercarbonate-requiring cyanobacterium Arthrospira maxima. Photosynthetica, 2018. 56(1): p. 217-228. doi.org/10.1007/s11099-018-0781-0

Climbing the volcano of electrocatalytic activity while avoiding catalyst corrosion: Ni3P a hydrogen evolution electrocatalyst stable in both acid and alkali

A. B. Laursen, R. B. Wexler, M. J. Whitaker, E. Izett, R. Rucker, H. Wang, J. Li, M. Greenblatt, A. M. Rappe and G.C. Dismukes, Climbing the volcano of electrocatalytic activity while avoiding catalyst corrosion: Ni3P a hydrogen evolution electrocatalyst stable in both acid and alkali. ACS Catalysis, 2018(8): p. 4408−4419. https://doi.org/10.1021/acscatal.7b04466

Flux balance analysis of photoautotrophic metabolism: Uncovering new biological details of subsystems involved in cyanobacterial photosynthesis

Qian, X., M.K. Kim, G.K. Kumaraswamy, A. Agarwal, D.S. Lun and G.C. Dismukes, Flux balance analysis of photoautotrophic metabolism: Uncovering new biological details of subsystems involved in cyanobacterial photosynthesis. Biochim Biophys Acta, 2017. 1858(4): p. 276-287. https://doi.org/10.1016/j.bbabio.2016.12.007

Biogenesis and Assembly of the CaMn4O5 Core of Photosynthetic Water Oxidases and Inorganic Mutants, in Metalloprotein Active Site Assembly

Gates, C., G. Ananyev and C.C. Dismukes, Biogenesis and Assembly of the CaMn4O5 Core of Photosynthetic Water Oxidases and Inorganic Mutants, in Metalloprotein Active Site Assembly, M.K. Johnson and R.A. Scott, Editors. 2017, John Wiley & Sons, Ltd, : Chichester, West Sussex PO19 8SQ, UK. p. 1-15.

The Oxygen quantum yield in diverse algae and cyanobacteria is controlled by partitioning of flux between linear and cyclic electron flow within photosystem II

Ananyev, G., C. Gates and G. Dismukes, The Oxygen quantum yield in diverse algae and cyanobacteria is controlled by partitioning of flux between linear and cyclic electron flow within photosystem II. . Biochimica et Biophysica Acta (BBA)-Bioenergetics, 2017. 1857 (9): p. 1380-1391. doi: 10.1016/j.bbabio.2016.04.056

Natural and Synthetic Variants of the Tricarboxylic Acid Cycle in Cyanobacteria: Introduction of the GABA Shunt into Synechococcus sp. PCC 7002

Zhang, S., X. Qian, S. Chang, G.C. Dismukes and D.A. Bryant, Natural and Synthetic Variants of the Tricarboxylic Acid Cycle in Cyanobacteria: Introduction of the GABA Shunt into Synechococcus sp. PCC 7002. Front Microbiol, 2016. 7: p. 1972. doi: 10.3389/fmicb.2016.01972

Natural isoforms of the Photosystem II D1 subunit differ in photoassembly efficiency of the water-oxidizing complex

 Vinyard, D.J., J.S. Sun, J. Gimpel, G.M. Ananyev, S.P. Mayfield and G. Charles Dismukes, Natural isoforms of the Photosystem II D1 subunit differ in photoassembly efficiency of the water-oxidizing complex. Photosynth Res, 2016. 128(2): p. 141-50. doi: 10.1007/s11120-015-0208-8

Coordination Geometry and Oxidation State Requirements of Corner Sharing MnO6 Octahedra for Water Oxidation Catalysis: An Investigation of Manganite (γ-MnOOH)

Smith, P.F., B.J. Deibert, S. Kaushik, G. Gardner, S. Hwang, H. Wang, J.F. Al-Sharab, E. Garfunkel, L. Fabris, J. Li and G.C. Dismukes, Coordination Geometry and Oxidation State Requirements of Corner Sharing MnO6 Octahedra for Water Oxidation Catalysis: An Investigation of Manganite (γ-MnOOH). ACS Catalysis, 2016. 6(3): p. 2089–2099. https://doi.org/10.1021/acscatal.6b00099

Inactivation of nitrate reductase alters metabolic branching of carbohydrate fermentation in the cyanobacterium Synechococcus sp. strain PCC 7002.

Qian, X., G.K. Kumaraswamy, S. Zhang, C. Gates, G.M. Ananyev, D.A. Bryant and G.C. Dismukes, Inactivation of nitrate reductase alters metabolic branching of carbohydrate fermentation in the cyanobacterium Synechococcus sp. strain PCC 7002. Biotechnol Bioeng, 2016. 113(5): p. 979-88. doi: 10.1002/bit.25862

Optimizing “Artificial Leaf” Photoanode-Photocathode-Catalyst Interface Systems for Solar Water Splitting

Porter, S.H., S. Hwang, V. Amarasinghe, E. Taghaddos, V. Manichev, M. Li, G. Gardner, A. Safari, E. Garfunkel, M. Greenblatt and G.C. Dismukes, Optimizing “Artificial Leaf” Photoanode-Photocathode-Catalyst Interface Systems for Solar Water Splitting. ECS Transactions, 2016. 72(37): p. 1-19. https://doi.org/10.1149/07237.0001ecst

Consequences of ccmR deletion on respiration, fermentation and H2 metabolism in cyanobacterium Synechococcus sp. PCC 7002

Krishnan, A., S. Zhang, Y. Liu, K.A. Tadmori, D.A. Bryant and C.G. Dismukes, Consequences of ccmR deletion on respiration, fermentation and H2 metabolism in cyanobacterium Synechococcus sp. PCC 7002. Biotechnol Bioeng, 2016. 113(7): p. 1448-59. doi: 10.1002/bit.25913

Thin Film Catalysts: Ni5P4 (Cathodic) and LiCoO2 (Anodic) for Electrolysis of Water

Hwang, S., S.H. Porter, G. Gardner, A.B. Laursen, H. Wang, M. Li, V. Amarasinghe, E. Taghaddos, A. Safari, E. Garfunkel, M. Greenblatt and G.C. Dismukes, Thin Film Catalysts: Ni5P4 (Cathodic) and LiCoO2 (Anodic) for Electrolysis of Water. ECS Transactions, 2016. 72(23): p. 31-51. https://doi.org/10.1149/07223.0031ecst

The strontium inorganic mutant of the water oxidizing center (CaMn4O5) of PSII improves WOC efficiency but slows electron flux through the terminal acceptors

Gates, C., G. Ananyev and G.C. Dismukes, The strontium inorganic mutant of the water oxidizing center (CaMn4O5) of PSII improves WOC efficiency but slows electron flux through the terminal acceptors. Biochim Biophys Acta, 2016. 1857(9): p. 1550-1560.  doi: 10.1016/j.bbabio.2016.06.004

Structural basis for differing electrocatalytic water oxidation by the cubic, layered and spinel forms of lithium cobalt oxides

Gardner, G., J. Al-Sharab, N. Danilovic, Y.B. Go, K. Ayer, M. Greenblatt and G.C. Dismukes, Structural basis for differing electrocatalytic water oxidation by the cubic, layered and spinel forms of lithium cobalt oxides. Energy Environ. Sci., 2016. 9: p. 184--192. DOI: 10.1039/c5ee02195b

The unexpected extremophile: Tolerance to fluctuating salinity in the green alga Picochlorum

Foflonker, F., G. Ananyev, H. Qiu, A. Morrison, B. Palenik, G.C. Dismukes and D. Bhattacharya, The unexpected extremophile: Tolerance to fluctuating salinity in the green alga Picochlorum. Algal Research-Biomass Biofuels and Bioproducts, 2016. 16: p. 465-472. doi.org/10.1016/j.algal.2016.04.003

X-ray Emission Spectroscopy of Mn Coordination Complexes Toward Interpreting the Electronic Structure of the Oxygen-Evolving Complex of Photosystem II

Davis, K.M., M.C. Palenik, L.F. Yan, P.F. Smith, G.T. Seidler, G.C. Dismukes and Y.N. Pushkar, X-ray Emission Spectroscopy of Mn Coordination Complexes Toward Interpreting the Electronic Structure of the Oxygen-Evolving Complex of Photosystem II. Journal of Physical Chemistry C, 2016. 120(6): p. 3326-3333.

Photosystem II-cyclic electron flow powers exceptional photoprotection and record growth in the microalga Chlorella ohadii

Ananyev, G., C. Gates, A. Kaplan and G.C. Dismukes, Photosystem II-cyclic electron flow powers exceptional photoprotection and record growth in the microalga Chlorella ohadii. Biochim Biophys Acta, 2016. 1858(11): p. 873-883. doi: 10.1016/j.bbabio.2017.07.001

Selective CO 2 Reduction to C 3 and C 4 Oxyhydrocarbons on Nickel Phosphides at Overpotentials as Low as 10 MV.

Calvinho, Karin U. D., Anders B. Laursen, Kyra M. K. Yap, Timothy A. Goetjen, Shinjae Hwang, Bryan Mejia-Sosa, Alexander Lubarski, et al. 2018. “Selective CO 2 Reduction to C 3 and C 4 Oxyhydrocarbons on Nickel Phosphides at Overpotentials as Low as 10 MV.” Energy & Environmental Science. The Royal Society of Chemistry. doi:10.1039/C8EE00936H.

Instrument Development

Analytical Chemistry Tools:

LC-Tandem MS/MS: The Dismukes lab is equipped with commercial QQQ and Q-TOF mass spectrometers coupled to LC chromatographic separation systems for nano-flow LC and 2D nano-cube LC. These are among the most sensitive mass spectrometers available (lod = Femtogram). They feature robust operation and amenability towards the detection of small, polar metabolites. The use of isotopic-labeled inputs also allows for the direct time-resolved monitoring of pathway fluxes. Chemical extraction parameters have been optimized for Synechococcus sp. PCC7002. Cellular metabolites are extracted by ice cold extraction buffer. The extracts are subsequently separated using Reversed-phase Ion-pairing (RIP) chromatography, the effluent of which is analyzed using a Agilent 6400 Series Triple Quadrupole (QQQ) mass spectrometer. Targeted metabolites are detected via predetermined mass breakdown channels, and concentrations are estimated based on compound-specific calibration curves.

LCMS
LCMS

Catalysis Research

We develop selective and robust catalysts that electrochemically convert carbon dioxide (CO2) into sustainable chemical feedstocks and could ultimately be coupled to the recycling of environmental CO2. The catalysts employed are transition metal phosphides and their doped derivatives that form distinct crystalline structure types, enabling selection of chemical reactivity towards desired products including high molecular weight solid polymers. Selecting the catalyst’s elemental composition and crystal structure allows for tuning of the chemical, physical, and electrical properties to achieve the best match with desired product and application.

Transition metal phosphides are efficient hydrogen evolution catalysts due to their ability to abstract protons from water and transfer electrons to them, forming adsorbed hydrides. Since CO2 reduction also requires multiple transfers of adsorbed hydrogen and electrons, these catalysts are also effective for the reduction of CO2. Additionally, these catalysts bind CO2 relatively strongly, allowing for the formation of C3, C4 and Cn products at ambient conditions and aqueous solution. It is also our belief that when utilizing iron and nickel phosphides, the reaction proceeds through hydride transfer, and therefore carbon monoxide is not an intermediate. This opens up a new reaction pathway with minimal overpotential requirements. 

CO2RR Revised
CO2RR Revised

PSII

Natural photosynthesis dominates the biosphere as the most widespread and successful metabolism on Earth. Among photosynthetic organisms the oxygenic phototrophs are the most prolific, comprising all known species of cyanobacteria, algae, and higher plants. The early ancestors of these organisms transformed the surface of Earth beginning circa 3 billion years ago from a drab alumino-silicate composite to a lush green carpet visible from Outer Space. These organisms power the planet using the Photosystem II (PSII) enzyme to split water, yielding O2, hydrogen reductants, and proton gradients (energy). Remarkably, only one PSII enzyme has evolved on Earth.

Our goal is to reveal the range of kinetic and energetic performance by photosynthetic water oxidation enzymes in vivo, selected from diverse microbial phototrophs, cyanobacteria and microalgae. The outcome is a fundamental understanding of the principles of light energy conversion to chemical energy and the mechanisms used to oxidize water in nature. Supported by DOE-BES.

Tobacco Replacement
Tobacco Replacement

BioEnergy Research

  • Cyanobacterial fermentative H2 production
  • Algal photo-H2 production
  • Food vs. Biomass energy feedstocks:
  • Cofermentation for enhanced biomass conversion efficiency
  • Lipid biosynthesis and conversion to fuels
  • High throughput screening for lipid productive algal strains
Summary
Summary

Carbon Metabolic Fluxomics

Photoautotrophic carbon fluxomics

Our goal is to use flux balance analysis (FBA, left figure) and isotopically nonstationary metabolic flux analysis (INST-MFA, right figure) to quantitatively understand carbon flux distributions and pathway utilizations of the cyanobacterium Synechococcus sp. PCC 7002 during photosynthesis. The outcome also helps discover new roles of existing metabolic pathways.

flux balance analysis (FBA, left figure) and isotopically nonstationary metabolic flux analysis (INST-MFA, right figure)
flux balance analysis (FBA, left figure) and isotopically nonstationary metabolic flux analysis (INST-MFA, right figure)

Current Lab Members

Principal Investigator
  • Dr. G. Charles Dismukes
    Dr. G. Charles Dismukes

    dismukes@chem.rutgers.edu

    G. Charles Dismukes is a Distinguished Professor at Rutgers University on the faculties of the Chemistry & Chemical Biology Department and the Waksman Institute of Microbiology. He is a member of the executive committee of the Institute for Advanced Materials and Device Nanotechnology (IAMDN), the Rutgers Energy Institute (REI), and the graduate training faculty in Microbiology and Biochemistry.

    The Dismukes research group investigates the science of catalysis particularly photo- and electro-catalysis, using an integrated theoretical-experimental approach that incorporates knowledge from biology, chemistry and physics to understand the fundamental principles and translate that knowledge into proof of principle devices and solutions. They study systems extending from natural photosynthetic organisms and isolated enzymes to artificial photosynthetic constructs and solar fuel cells.

    Topics include water splitting, carbon dioxide capture and reduction to chemicals, carbon metabolism in phototrophs, dinitrogen capture and reduction.

Graduate Students
  • Waksman Person
    Christopher Turner

    chris.turner@rutgers.edu

Undergraduate Students
  • Waksman Person
    Sofia Dvinskikh

    sofia.dvinskikh@rutgers.edu

Alumni

Former Research Associates
  • Gennady Ananyev

Former Graduate Students
  • Yuan Zhang