hacking biology to produce energy and fuels€¦ · hacking biology to produce energy and fuels...

Hacking Biology to Produce Energy and

FuelsJoseph Laureanti, Chemist

Pacific Northwest National Laboratory

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We value your feedback!

https://www.surveymonkey.com/r/PNNL061620


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Everything We Do Requires Energy, Much Of That Comes From Carbon Sources

Coal

Natural gas

Petroleum

NuclearRenewables

https://www.eia.gov/energyexplained/us-energy-facts/#:~:text=After%20record%20high%20energy%20production,primary%20energy%20production%20in%202019.

https://www.eia.gov/energyexplained/us-energy-facts/#:%7E:text=After%20record%20high%20energy%20production,primary%20energy%20production%20in%202019.

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n


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n

O2

H2OCO2

Energy


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Carbon Based Energy Sources Are Problematic

https://scripps.ucsd.edu/programs/keelingcurve/

https://scripps.ucsd.edu/programs/keelingcurve/

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Goal: Store Energy In Chemical Bonds

Chemical Fuels

Renewable Energy

Catalysts

Fuels from abundant substratesCO2

CH3OH

H2O

H2+O2

N2

NH3

https://www.plymouthenergy.com/iea-notes-potential-for-renewable-energy-in-future/


8https://www.cleanpng.com/png-cartoon-royalty-free-stock-photography-illustratio-499070/

Biology Is Great At Chemistry

https://www.cleanpng.com/png-cartoon-royalty-free-stock-photography-illustratio-499070/


Biology is great at chemistry.Far greater than we are at chemistry.

However, nature has had billions of years to perfect chemical reactions.


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Learning About Renewability And Sustainability

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17 National Labs Throughout The United States

http://large.stanford.edu/courses/2017/ph241/longstaff2/

http://large.stanford.edu/courses/2017/ph241/longstaff2/

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Pacific Northwest National Lab –A Place Where We Solve Big Problems

Scientific Discovery

National Security

Energy Independence

Environmental Management

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PNNL is Focused on DOE’s MISSIONSandAddressing CriticalNATIONAL NEEDS

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Institute For Integrated Catalysis At PNNL: Ideas From Start To Finish

Largest non-industrial catalysis R&D organization in the U.S.

Integrates staff from different disciplines

Over 100 staff members across all disciplines

Bridge for fundamental and applied catalysis

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PNNL is an ECONOMICENGINE

Employees

$1.01BAnnual Spending

$465MTotal Payroll

265Inventions

193

Patents

34Licenses

4,722Total Economic Output

Jobs Generated in Washington

Companieswith PNNL Roots

7,180

$1.46B

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50+ Years

Developing Goodwill

$28.5M$0.52M

Philanthropic Investments

347,00030,000

Team Battelle Volunteer Hours

>12056

Community Organizations

Decades

FY19

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Employees have volunteered more than 500,000 hours since team Battelle began at PNNL in 1999.

Sharing Science With Our Community

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Grasping Scale Is Not A Simple Task

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Interdisciplinary Work Is Essential To Understand Bio-Inorganic System

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We See Macromolecules, Yet Cellular Functions Rule Our World

https://www.thoughtco.com/animal-cells-vs-plant-cells-373375https://www.vectorstock.com/royalty-free-vector/structure-of-a-bacterial-cell-cartoon-vector-9812792

https://www.thoughtco.com/animal-cells-vs-plant-cells-373375

https://www.vectorstock.com/royalty-free-vector/structure-of-a-bacterial-cell-cartoon-vector-9812792

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Proteins, Enzymes, And Small Molecules Drive Life As We Know It, We Just Don’t See It

https://chem.libretexts.org/Courses/University_of_Kentucky/UK%3A_CHE_103_-_Chemistry_for_Allied_Health_(Soult)/Chapters/Chapter_15%3A_Metabolic_Cycles/15.4%3A_The_Electron_Transport_Chain


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Proteins, Enzymes, And Small Molecules Drive Life As We Know It, We Just Don’t See It

https://www.rcsb.org/3d-view/5Z62/1https://chem.libretexts.org/Courses/University_of_Kentucky/UK%3A_CHE_103_-_Chemistry_for_Allied_Health_(Soult)/Chapters/Chapter_15%3A_Metabolic_Cycles/15.4%3A_The_Electron_Transport_Chain

https://www.rcsb.org/3d-view/5Z62/1


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Let’s Try Some Technology

• https://account.altvr.com/worlds/1355452616871510998/spaces/1442927460000727719

https://account.altvr.com/worlds/1355452616871510998/spaces/1442927460000727719

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Energy Storage In Chemical Bonds

Chemical Fuels

Renewable Energy

Catalysts


CH3OH

H2O

H2+O2

N2

NH3



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Enzymes Are Nature’s Catalysts

Carbon monoxide dehydrogenase Nitrogenase

Multi-copper oxidases

2e- + 2H+ ⇌ H2

CO + H2O ⇌ CO2 + H2

O2 + 4e- + 4H+ → 2H2O

N2 + 8H+ + 8e- ⇌ 2NH3 + H2

Synthetic catalysts are typically unable to match the catalytic performance of enzymes

[FeFe]-hydrogenase

Enzymes control a large variety of challenging reactionsEfficient and fastFinely tuned ensemble of featuresComplex architecture

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Enzymatic Control of Catalysis: Outer Coordination Sphere

e-

H+

• Channels• Ion channels (hydrophilic)• Gas channels (hydrophobic)• Electron shuttles

• Controlling the environment around the active site• Charge• Hydrophobicity/hydrophilicity• Weak interactions• Variety of functional groups

• Ligand dynamics• Structural change/Allostery

• Cooperativity[FeFe]-Hydrogenase

2H+ + 2e-H2

Ginovska, et al., BBA Bioenergetics, 2014, 1837, 131

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Enzymatic Control of Catalysis: Outer Coordination Sphere

e-

H+

• Channels• Ion channels (hydrophilic)• Gas channels (hydrophobic)• Electron shuttles

• Controlling the environment around the active site• Charge• Hydrophobicity/hydrophilicity• Weak interactions• Variety of functional groups

• Ligand dynamics• Structural change/Allostery

• Cooperativity[FeFe]-Hydrogenase

2H+ + 2e-H2

Ginovska, et al., BBA Bioenergetics, 2014, 1837, 131

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Can We Mimic the Effects of the Scaffold in CO Dehydrogenase into Molecular Catalysts?

• In CODH, positively charged groups are thought to stabilize the transition state during CO2reduction

• Initial questions:• Does changing the potential

around the active site affect activity?

• Do positively charged groups stabilize the transition state?

Wang et. al, JACS, 2013, 135,9493

CO Dehydrogenase

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Can We Mimic the Effects of the Scaffold in CO Dehydrogenase into Molecular Catalysts?

• In CODH, positively charged groups are thought to stabilize the transition state during CO2reduction

• Initial questions:• Does changing the potential

around the active site affect activity?

• Do positively charged groups stabilize the transition state?

Wang et. al, JACS, 2013, 135,9493

CO Dehydrogenase

39-Schwizer, F.; Ward, T.R. Chemical Reviews 2018 118 (1), 142-231. DOI: 10.1021/acs.chemrev.7b00014-Laureanti, J.A., O’Hagan, M., Shaw, W.J., Sustainable Energy Fuels, 2019,3, 3260-3278

Hacking Biology

40-Schwizer, F.; Ward, T.R. Chemical Reviews 2018 118 (1), 142-231. DOI: 10.1021/acs.chemrev.7b00014-Laureanti, J.A., O’Hagan, M., Shaw, W.J., Sustainable Energy Fuels, 2019,3, 3260-3278

Hacking Biology

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Goal: Learn Design Principles from the Second and Outercoodination Spheres

M89C M89C’Not a catalyst!

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Confirming We Made The Correct Product

PDB ID = 6DO0

LmrR+(Rh+Mal), -HATU

Rh-LmrR

[Rh(PNP)2]+

LmrR before coupling

Laureanti, J.A.; O’Hagan, M. ACS Catalysis 2019 9 (1), 620-625. DOI: 10.1021/acscatal.8b02615

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Locations Where We Placed A Positive Charge

LmrR ScaffoldV15RW96RW96HR98A

D100RD100H | R98AD100K | R98A

W96R | D100A | R98A

Laureanti, J., et al., (2020). Organometallics https://dx.doi.org/10.1021/acs.organomet.9b00843

https://dx.doi.org/10.1021/acs.organomet.9b00843

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Sometimes You Win, Sometimes You Don’t

Laureanti, J.A.; Shaw, W.J. ACS Organometallics. Just Accepted.

2e- + H+

H-

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Electrostatics Show Increase In Positive Charge

D100R D100H/R98A WT

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Molecular Dynamics Suggest Localization of CO2Molecules at Active Site

RhCO2 WT

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Molecular Dynamics Suggest Localization of CO2Molecules at Active Site

RhCO2 R100RhCO2 WT

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We Stored Energy In Chemical Bonds

Chemical Fuels

Renewable Energy

Catalysts


CH3OH

H2O

H2+O2

N2

NH3


H2 + Rh Rh(H)2 + CO2 Liquid Fuel


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Take Home Message

• We need a ton of energy to power our daily lives.

• We employed lessons from nature to design catalytic systems.

• We want to store energy in chemical bonds.Allows fuels to be transported with ease

• Complex alone not a catalystWhen in the protein environment, activity is turned on

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Acknowledgements

Research was funded by the Laboratory Directed Research and Development program at Pacific Northwest National Laboratory. A portion of this work was performed in part using the Molecular Sciences Computing Facility (MSCF) in the William R. Wiley Environmental Molecular Sciences Laboratory, a US Department of Energy (DOE) national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located and the Pacific Northwest National Laboratory (PNNL).

SULI Student InternsQiwen Su – 2017Sriram Katipamula – 2018Margaret Hebert – 2019Noah Garret – 2020Emma Hanson – 2020

PNNL StaffDr. Wendy ShawDr. Nathan BakerBojana GinovskaDr. Simone RaugeiDr. Garry BuchkoDr. John LinehanDr. Neeraj Kumar Dr. Eric WiednerDr. Aaron AppelJuan Brandi-LozanoDavid EngelDr. Greg SchenterDr. Ba TranDr. Samantha Johnson

CollaboratorsDr. Molly O’Hagan (MSU)Dr. John Peters (WSU)Dr. Oleg Zadvornyy (WSU)Dr. Xavier Martinez (CNRS)Dr. Marc Baaden (CNRS)Dr. David Kennedy (UT)

PNNL PostDocsDr. Avery VilbertDr. Aaron WalshDr. Peter DunnDr. Jeremy Dr. Ben NeisenDr. Andrew Preston

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We value your feedback!



THANK YOU!

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