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Copyright © National Academy of Sciences. All rights reserved.
Bioinspired Chemistry for Energy: A Workshop Summary to the Chemical Sciences Roundtable
http://www.nap.edu/catalog/12068.html
v
BOARD ON CHEMICAL SCIENCES AND TECHNOLOGY
Cochairs
F. FleMing CriM, University of Wisconsin, Madison
gary s. CalaBrese, Corning, Inc., Corning, New York
Members
BenJaMin anderson, Eli Lilly K.K., Kobe, Japan
PaBlo deBenedetti, Princeton University, Princeton, New Jersey
ryan r. dirkx, Arkema, Inc., King of Prussia, Pennsylvania
george W. Flynn, Columbia University, New York
MauriCio Futran, Bristol-Myers Squibb Company, New Brunswick, New Jersey
Mary galvin-donoghue, Air Products and Chemicals, Allentown, Pennsylvania
Paula t. haMMond, Massachusetts Institute of Technology, Cambridge
rigoBerto hernandez, Georgia Institute of Technology, Atlanta
JaMes l. kinsey, Rice University, Houston, Texas
Martha a. kreBs, California Energy Commission, Sacramento
Charles t. kresge, Dow Chemical Company, Midland, Michigan
JosePh a. Miller, Corning, Inc., Corning, New York
sCott J. Miller, Yale University, New Haven, Connecticut
gerald v. PoJe, Independent Consultant, Vienna, Virginia
donald Prosnitz, The Rand Corporation, Walniut Creek, California
thoMas h. uPton, ExxonMobil Chemical Company, Baytown, Texas
National Research Council Staff
kathryn hughes, Postdoctoral Fellow
tina M. MasCiangioli, Program Officer
eriCka M. MCgoWan, Associate Program Officer
syBil a. Paige, Administrative Associate
JessiCa Pullen, Research Assistant
kela l. Masters Senior Program Assistant
FederiCo san Martini, Program Officer
dorothy zolandz, Director
Copyright © National Academy of Sciences. All rights reserved.
Bioinspired Chemistry for Energy: A Workshop Summary to the Chemical Sciences Roundtable
http://www.nap.edu/catalog/12068.html
Copyright © National Academy of Sciences. All rights reserved.
Bioinspired Chemistry for Energy: A Workshop Summary to the Chemical Sciences Roundtable
http://www.nap.edu/catalog/12068.html
vii
The Chemical Sciences Roundtable (CSR) was established in 1997 by the National
Research Council. It provides a science-oriented apolitical forum for leaders in the chemical
sciences to discuss chemistry-related issues affecting government, industry, and universi-
ties. Organized by the National Research Council’s Board on Chemical Sciences and
Technology, the CSR aims to strengthen the chemical sciences by fostering communication
among the people and organizations—spanning industry, government, universities, and
professional associations—involved with the chemical enterprise. One way it does this
is by organizing workshops that address issues in chemical science and technology that
require national attention.
In May 2007, the CSR organized a workshop on the topic “Bioinspired Chemistry for
Energy.” This document summarizes the presentations and discussions that took place at
the workshop and includes poster presenter abstracts. In accordance with the policies of
the CSR, the workshop did not attempt to establish any conclusions or recommendations
about needs and future directions, focusing instead on issues identified by the speakers.
In addition, the organizing committee’s role was limited to planning the workshop. The
workshop summary has been prepared by the workshop rapporteurs Sandi Schwartz, Tina
Masciangioli, and Boonchai Boonyaratanakornkit as a factual summary of what occurred
at the workshop.
Preface
Copyright © National Academy of Sciences. All rights reserved.
Bioinspired Chemistry for Energy: A Workshop Summary to the Chemical Sciences Roundtable
http://www.nap.edu/catalog/12068.html
Copyright © National Academy of Sciences. All rights reserved.
Bioinspired Chemistry for Energy: A Workshop Summary to the Chemical Sciences Roundtable
http://www.nap.edu/catalog/12068.html
ix
This workshop summary has been reviewed in draft form by persons chosen for their
diverse perspectives and technical expertise in accordance with procedures approved by the
National Research Council’s Report Review Committee. The purpose of this independent
review is to provide candid and critical comments that will assist the institution in making
its published workshop summary as sound as possible and to ensure that the summary meets
institutional standards of objectivity, evidence, and responsiveness to the workshop charge.
The review comments and draft manuscript remain confidential to protect the integrity of
the deliberative process. We wish to thank the following individuals for their review of
this workshop summary:
Kyu Yong Choi, University of Maryland, College Park
Louis Graziano, Rohm and Haas Company, Spring House, Pennsylvania
Paula T. Hammond, Massachusetts Institute of Technology, Cambridge
Levi T. Thompson, University of Michigan, Ann Arbor
Although the reviewers listed above have provided many constructive comments
and suggestions, they were not asked to endorse the workshop summary nor did they see
the final draft of the workshop summary before its release. The review of this workshop
summary was overseen by Jennie Hunter-Cevera, University of Maryland, Rockville.
Appointed by the National Research Council, she was responsible for making certain that
an independent examination of this workshop summary was carried out in accordance with
institutional procedures and that all review comments were carefully considered. Respon-
sibility for the final content of this workshop summary rests entirely with the authors and
the institution.

Acknowledgment of Reviewers
Copyright © National Academy of Sciences. All rights reserved.
Bioinspired Chemistry for Energy: A Workshop Summary to the Chemical Sciences Roundtable
http://www.nap.edu/catalog/12068.html
Copyright © National Academy of Sciences. All rights reserved.
Bioinspired Chemistry for Energy: A Workshop Summary to the Chemical Sciences Roundtable
http://www.nap.edu/catalog/12068.html
xi
1 Overview—The Role of Bioinspired Chemistry in Improving 1
Alternative Energy Technologies
2 Government, Industry, and Academic Perspectives on Bioinspired Chemistry 7
for Energy
3 Fundamental Aspects of Bioinspired Chemistry for Energy 15
4 Robust Implementation of Bioinspired Chemistry for Energy 25
5 Partnerships and Integration 31
6 Research Challenges, Education, and Training 33
Appendixes
A Workshop Agenda 39
B Biographies 41
C Poster Abstracts 45
D Workshop Attendees 53
E Origin of and Information on the Chemical Sciences Roundtable 55
Contents
Copyright © National Academy of Sciences. All rights reserved.
Bioinspired Chemistry for Energy: A Workshop Summary to the Chemical Sciences Roundtable
http://www.nap.edu/catalog/12068.html
Copyright © National Academy of Sciences. All rights reserved.
Bioinspired Chemistry for Energy: A Workshop Summary to the Chemical Sciences Roundtable
http://www.nap.edu/catalog/12068.html
1
1
Overview—The Role of Bioinspired Chemistry in
Improving Alternative Energy Technologies
Understanding the basic processes of photosynthesis
and chemical conversion may enable scientists to create
systems that mimic biomolecules and produce energy more
efficiently. Some of the losses in photovoltaic energy conver-
sion might be overcome with biomimetic processes.
1
Much
work has been conducted in the development of artificial
photosynthetic antennas, which provide rapid electron-
transfer, as well as artificial reaction centers that generate a
chemical potential by providing long-lived charged separa-
tion.
2
As in photosynthesis, light energy can be harvested
to drive a sequential reaction in which water is oxidized
to hydrogen (for the hydrogen economy) and oxygen.
3

Extensive progress has been made in catalyzing the forma-
tion of hydrogen from protons. Several catalysts have been
developed to mimic hydrogenase activity.
4,5
However, a rate
limiting step in water oxidation that remains to be overcome
is the stitching together of oxygen atoms to form O
2
via
bioinspired catalysts.
6
In an effort to advance the understanding of “bioinspired
chemistry for energy,” this workshop featured presentations, a
poster session, and discussions on chemical issues by experts
1
LaVan, D. A. and J. N. Cha. 2006. Approaches for Biological and
Biomimetic Energy Conversion. Proceedings of the National Academy of
Sciences 103(14): 5251-5255.
2
Gust, D., A. Moore, and T. Moore. 2001. Mimicking Photosynthetic So-
lar Energy Transduction. Accounts of Chemical Ressearch 34(1): 40-48.
3
Dismukes, C. 2001. Photosynthesis: Splitting Water. Science 292 (5516):
447-448.
4
Liu, T. and M. Darensbourg. 2007. A Mixed-Valent, Fe(II)Fe(I), Diiron
Complex Reproduces the Unique Rotated State of the [FeFe] Hydrogenase
Active Site. Journal of the American Chemical Society 129(22): 7008-7009.
5
Rauchfuss, T. 2007. Chemistry: A Promising Mimic of Hydrogenase
Activity Science 316(5824): 553-554.
6
Service, R. F. 2007. Daniel Nocera Profile: Hydrogen Economy? Let
Sunlight Do the Work Science 315(5813): 789.
from government, industry, and academia (see Appendix A
for workshop agenda). Speakers at the workshop
• Summarized the current energy challenges, such as
carbon emissions, population growth, and cost, and presented
opportunities to address these challenges, such as developing
sustainable energy sources.
• Provided an overview of the fundamental aspects
and robust implementations of bioinspired chemistry from
government, academic, and industrial perspectives.
• Explored the role of fundamental chemistry in bio-
catalysis applications for energy systems.
• Addressed how improvements in bioinspired
catalysis might be harnessed for improved energy systems.
• Discussed the most promising research develop-
ments in bioinspired chemistry for energy systems.
• Identified future research directions.
WORKSHOP STRUCTURE
The main speaker sessions are briefly described below.
A more detailed summary of the speaker comments can be
found in the chapters indicated in parentheses. The three
main speaker sessions were:
1. Government, industry, and academic perspectives
on bioinspired chemistry for energy (Chapter 2).
2. Fundamental aspects of bioinspired chemistry for
energy (Chapter 3).
3. Robust implementation of bioinspired catalysis
(Chapter 4).
In addition, two overarching themes were highlighted
throughout the sessions: (1) partnership and integration (see
Copyright © National Academy of Sciences. All rights reserved.
Bioinspired Chemistry for Energy: A Workshop Summary to the Chemical Sciences Roundtable
http://www.nap.edu/catalog/12068.html
2 BIOINSPIRED CHEMISTRY FOR ENERGY
Chapter 5) and (2) research challenges, education, and train-
ing (see Chapter 6).
Opening remarks were made by Douglas Ray, Pacific
Northwest National Laboratory followed by an overview
perspective given by John Turner, National Renewable
Energy Laboratory. Next, government perspectives on
bioinspired chemistry for energy were presented by Eric
Rohlfing, Office of Basic Energy Sciences Department of
Energy; Michael Clarke, Chemistry Division, National
Science Foundation; Judy Raper, Division of Chemical, Bio-
engineering, Environmental, and Transport Systems National
Science Foundation; and Peter Preusch, National Institute
of General Medical Science, National Institutes of Health.
The government perspectives were followed by industry
perspectives on bioinspired chemistry for energy with presen-
tations given by Henry Bryndza, DuPont; Brent Erickson,
Biotechnology Industry Organization; and Magdalena
Ramirez, British Petroleum. The overview session con-
cluded with open discussion moderated by Sharon Haynie,
DuPont.
The first technical session covered fundamental aspects
of bioinspired chemistry for energy, and included the fol-
lowing topics and speakers: Hydrogen-Processing Catalysts
for Replacement of Platinum in Fuel Cell Electrodes:
Hydrogenases, Marcetta Darensbourg, Texas A&M Uni-
versity; The Lesson from the Hydrogenases? New Chemistry
(Happens to Be Strategic), Thomas Rauchfuss, University
of Illinois at Urbana-Champaign; Self-Assembly of Arti-
ficial Photosynthetic Systems for Solar Energy Conver-
sion, Michael Wasielewski, Northwestern University and
Argonne National Laboratory; and Sustained Water Oxida-
tion by Bioinspired Catalysts: The Real Thing Now, Charles
Dismukes, Princeton University. The talks were followed by
open discussion, moderated by Sharon Haynie.
Speakers discussing fundamental aspects were asked to
address the following questions: What are the design princi-
ples that enable biomolecular machines to effect selective and
efficient atom- and group-transfer processes useful for energy
conversions? What are the fundamental mechanisms of multi-
electron transfer in biological systems? What are the principles
of energy storage and production in biology? How do biologi-
cal systems such as catalysts composed of seemingly fragile
peptide residues achieve durability and robustness?
The technical session on fundamental aspects of bio-
inspired chemistry for energy concluded with remarks by
Sharon Haynie, followed a poster session in which students
and junior researchers presented emerging ideas in the realm
of bioinspired chemistry for energy. Abstracts for the poster
presenters are in Appendix C. The first day of the workshop
adjourned after the poster session.
Day two of the workshop opened with remarks by
Leonard Buckley, Naval Research Laboratory, followed
by the academic perspective on bioinspired chemistry, Solar
Fuels: A Reaction Chemistry of Renewable Energy presented
by Daniel Nocera, Massachusetts Institute of Technology.
Next, there was a technical session on robust imple-
mentation of bioinspired catalysts, which included the
following topics and speakers: Mimicking Photosynthetic
Energy Transduction, Thomas Moore, Arizona State Uni-
versity; Biological Transformations for Energy Production:
An Overview of Biofuel Cells, G. Tayhas Palmore, Brown
University; and Bioinspired Initiatives at DuPont, Mark
Emptage, DuPont. Open discussion was then moderated by
Leonard Buckley.
Speakers addressing robust implementation responded
to the following questions: How can bioinspired design prin-
ciples be replicated in synthetic and semisynthetic catalysts
and catalytic processes? Can discovery methods (e.g., bio-
informatics) be harnessed to encode designer catalytic sites?
To what extent can protein scaffolds be replicated with more
easily synthesized supports, and can we use these principles
to design sequential catalytic assemblies?
The workshop concluded with remarks by Leonard
Buckley.
OPENING REMARKS
Douglas Ray of the Pacific Northwest National Labora-
tory welcomed about 75 workshop participants and provided
some initial thoughts on the energy crisis and how chemistry
can play a role. With about 86 percent of energy currently
coming from coal, gas, and oil, and only 7 percent from
renewables (mostly conventional hydroelectric and bio-
mass; see Figure 1.1),
7
Ray noted it is important to consider
whether renewables, such as solar energy, hydrogen fuel, and
biofuels, could reach the necessary scale needed to support
current energy demand. He questioned whether our quality
of life would be affected by the energy sources used. Ray
also explained that progress in the energy field will depend
on how scientists shape the future. He explained that trans-
formational science—which focuses on translating what
can be learned from biology to energy issues—is critical for
changes to take place.
Workshop Charge
Ray then motivated the workshop participants to take
advantage of this opportunity to reach across disciplines and
learn from one another. He hoped that the workshop discus-
sion would bring together traditional scientific disciplines
to identify new science directions. Ray talked about what
can be learned from biology and how that knowledge can be
translated into more robust applications through chemistry.
The forum was an opportunity to create new understanding
and identify a research agenda for the future. Ray concluded
7
Energy Information Agency. 2007. Renewable Energy Annual, 2005
Edition. Table 1. http://www.eia.doe.gov/cneaf/solar.renewables/page/
rea_data/rea_sum.html (accessed 11/16/07).