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					June 8, 2001




Memo to:         Potential Applicants for Funding

From:            Prof. J. M. DeSimone, Director
                 Prof. R. G. Carbonell, Co-Director
                 Prof. G. W. Roberts, Technical Program Coordinator

                 NSF Science and Technology Center for
                 Environmentally Responsible Solvents and Processes

Re: Request for Technical Proposals for Center Funding for the Period
                          11/1/2001-10/31/2003


This memorandum is an invitation to submit proposal(s) for research funding by the NSF Science
and Technology Center for Environmentally Responsible Solvents and Processes under
Cooperative Agreement CHE-9876674. There will be two solicitations. In the first, the primary
subject of this memorandum, we solicit proposals for two-year programs supporting one or more
of three “Application Domains” (Macromolecular Synthesis and Engineering; Dissolution and
Deposition; and Small Molecule Systems described below). Approximately 90% of annual
operating funds will be used to support these projects. Participation in the first solicitation will be
limited to existing Principal Investigators and their Departmental colleagues plus invited
researchers whose expertise complements our existing programs and needs. Remaining funds
will be allocated to projects supported under the second solicitation, which will encompass “seed
programs”. The latter generally will be smaller projects aimed at assuring vitality of the Center
through continual renewal and expansion into diverse areas not presently covered by Center
programs. Outside departments and institutions will be included. Details of this second
solicitation will be issued in August 2001.
                                      Table of Contents
I.     Summary                                                                         1

II.    Background                                                                      2

         A.   CERSP vision, mission and goals
         B.   Application Domains
         C.   Overarching goals and general objectives
         D.   Strategic targets
         E.   Matrix of application domains and functional efforts

III.   Pre-proposal                                                                    5

         A. Purpose
         B. Format and Content

IV. Proposal Format and Content                                                        5

         A. Project Title and Principal Investigator(s)
         B. Research plan
                 1. Overall objective
                 2. Approach
                 3. Relation to overarching Center goals
                          a. Overarching goal(s) supported
                          b. Position in research matrix
                 4. Potential impact
         C. Connectivity
                 1. Related work
                          a. Other Center proposal(s) supported (past and planned)
                          b. Additional Center goals (other than primary) supported
                          c. Additional functional efforts supported
                 2. Collaborations planned outside the Center
                 3. Resource and/or facilities sharing
         D. Education and Outreach
                 1. Past K-12 support
                 2. Proposed K-12 support
                 3. Participation in PDP (past and proposed future)
         E. Funding
                 1. Standard funding option selected
                 2. Additional and complementary funding

V.     Selection criteria                                                              8

VI. Expectations                                                                       8

VII. Schedule and Inquiries                                                            9

VIII. Appendix. Details of Strategic Needs                                            10

                                                    ii
I.    Summary of RFP Announcement for NSF Science and Technology
       Center for Environmentally Responsible Solvents and Processes
This flyer announces an invitation to submit proposal(s) for research funding by the NSF Science
and Technology Center for Environmentally Responsible Solvents and Processes under
Cooperative Agreement CHE-9876674. This solicitation for proposals is for two-year programs
supporting one or more of three “Application Domains” including:

       Macromolecular Synthesis and Engineering
Work in this area relates to all aspects of polymer synthesis and selected downstream processes.
The goal is to develop fundamental understanding of kinetic and transport mechanisms,
thermodynamics, phase equilibria, and factors affecting polymeric materials’ structure and
function in CO2-related systems in order to demonstrate feasibility of sustainable polymerization
and processing technology.
       Dissolution and Deposition
Work in this area focused on useful in cleaning or lithographic processes; deposition, such as
might be useful in making films, coatings or devices; and materials which might be employed in
either of these processes. The goal is to develop fundamental understanding of phenomena
involved in dissolution of materials and formation of thin films, coatings and structures at CO 2
interfaces in order to demonstrate feasibility of sustainable processes, materials, and devices.
       Small Molecule Systems
  This domain includes a wide variety of research areas such as inorganic and biological catalysis.
  The overarching goal is to develop fundamental understanding of small molecule reactions and
  synthesis, separations and materials formation in supercritical and near-supercritical CO2-based
  systems in order to identify sustainable new processes involving small molecules as candidates
  for further development.
.
Schedule and proposed selection criteria are given below.

                                  Schedule for Proposal Submission

        Videoconference review with faculty                                 June 14*
        Pre-proposal titles due (intent to respond)                         June 28
        Proposals due                                                       Aug 6
        Final selection of projects                                         Sep 13
        Funding commences                                                   Nov 1

* A videotape of this conference will be available for those unable to attend.


                                Selection Criteria for Technical Projects

        Primary Criteria                                    Secondary Criteria

        Fit to strategic plan                               Collaboration plan
        Potential impact                                    K-12 outreach record and plan
        Scientific merit                                    Outside funds attracted

        Approximately 90% of annual operating funds will be used to support these projects.
Participation in this solicitation will be limited to existing Principal Investigators and their
Departmental colleagues plus invited researchers whose expertise complements our existing
programs and needs. For a detailed RFP, contact Vicki Haithcock at vph@email.unc.edu

                                                    1
II. Background
A. CERSP Vision, Mission and Goals

The vision, mission and goals of the Center have been developed through several iterations, in
conjunction with stakeholder groups, including industrial partners, National Lab affiliates and
faculty and with guidance of our External Advisory Board. These are given in Table 1, and the
strategic planning process which defined these is detailed on our website www.nsfstc.unc.edu
(Research Areas/Strategic Planning of Research).




                      Table 1. CERSP Science and Technology
                             Vision, Mission, and Goals
                            CERSP Science and Technology Vision

     Enabling a revolution in green chemistry through cutting-edge science and engineering

                           CERSP Science and Technology Mission

   To identify and enable a new generation of sustainable processes, especially for improved
   products, by developing and encouraging the application of a robust body of fundamental
                       knowledge in CO2-related science and technology

                            CERSP Science and Technology Goals

         To create a strong body of integrated basic knowledge targeted at supporting
             selected applications in macromolecular synthesis and engineering;
                   dissolution and deposition; and small molecule systems

         To explore new frontiers in basic science and technology for environmentally
                             responsible solvents and processes


B. Application Domains

The ”selected applications” referenced in Table 1 give rise to “application domains” which support
the goals of the CERSP. These domains are
      Macromolecular Synthesis and Engineering
      Dissolution and Deposition;
      Small Molecule Systems
Over thirty-five potential application targets have been identified within these domains. The first
of these relates to all aspects of polymer synthesis and selected downstream processes. The
second relates to dissolution, such as might be useful in cleaning or lithographic processes;
deposition, such as might be useful in making films, coatings or devices; and materials which
might be employed in either of these processes. The third domain, “Small Molecule Systems”,
includes a wide variety of research areas such as inorganic and biological catalysis. Selection of
these domains by the faculty was further validated by an independent survey of members of the
Kenan Center for Utilization of CO2 in Manufacturing.

Applications are viewed as a test bed for evaluation of ideas. PIs should be alert to fundamental
issues that may be generalized and have impact well outside the target application.

                                                 2
C. Overarching Goals and General Objectives

In keeping with CERSP’s strategic plan, all technical programs should be aligned with the vision,
mission, and goals in Table 1 and with the overarching goals listed in Table 2.




               Table 2. Overarching Goals of Application Domains

                         Overarching Goal of Application Domain I:
                         Macromolecular Synthesis and Engineering

          To develop fundamental understanding of kinetic and transport mechanisms,
          thermodynamics, phase equilibria, and factors affecting polymeric materials’
                        structure and function in CO2-related systems

               In order to demonstrate feasibility of sustainable polymerization and
                                     processing technology

                         Overarching Goal of Application Domain II:
                                Dissolution and Deposition

          To develop fundamental understanding of phenomena involved in dissolution
        of materials and formation of thin films, coatings and structures at CO 2 interfaces

       In order to demonstrate feasibility of sustainable processes, materials, and devices

                         Overarching Goal of Application Domain III:
                                  Small Molecule Systems

 To develop fundamental understanding of small molecule reactions and synthesis, separations
       and materials formation in supercritical and near-supercritical CO2-based systems

            In order to identify sustainable new processes involving small molecules
                               as candidates for further development



D. Strategic Targets

During the initial two years’ operation of the Center, certain strategic targets have become
apparent. The list in Table 3 is offered as guidance as to where greatest programmatic impact is
expected, organized by Application Domain. Details are given in the Appendix. As “impact” is
one of the key factors in project selection, proposals addressing these issues may be expected to
receive stronger attention. However, this list is not intended to be the sole focus of the Center,
just a stimulus for ideas. Some iteration with potential PIs is anticipated during the selection
process so as to avoid overlap while assuring that key topics are covered. A “pre-proposal title”
or intent to respond is requested by June 28 so PIs can be alerted to modify their targets if
necessary before spending a great deal of time in preparing the proposal. (See Section III.)

                                                  3
                               Table 3. Strategic Targets#
Macromolecular Synthesis and Engineering
       * Low delta P separation of monomers from high P CO2 streams
       * Synthesis of water-soluble polymers
       * Theory and model to predict phase equilibria
       * Control of polymer properties
       * Low temperature free radical initiators
Dissolution and Deposition
       * “Dry” microelectronic processes/devices such as
               CMP                      CVD                       quantum dots
               lithography              metal films               nanoporous films
       * Coatings for biomedical applications
Small Molecule Systems
       * CO2 activation
       * Use of CO2/H2O emulsions for chemical synthesis, separations and materials formation
       * Synthesis of pharmaceuticals
       * Synthesis and recovery of products from fermentation broths
       * Organic transformations avoiding solvents
       * Oxidation and hydrogenation in CO2
       * Powder and particle technology
       * Extraction of products from organic and aqueous solvents and solid phases
       * Design of surfactants to solubilize organics in dry CO 2
       * Use of CO2 for petroleum processing
Cross-cutting
       * Sensors
       * Low-cost, light-weight equipment for high pressure
       * Cost effective surfactants
       * Rapid fluid handling

# Details for most of these are given in the Appendix

E. Matrix of application domains and functional efforts

In order to facilitate collaboration within cross-cutting or functional groups (e.g., surfactant
studies) proposers will be asked to use the functions listed in Table 4 to communicate to
evaluators and colleagues the combination of function and application reflected in your proposal.


               Table 4. Technical Task-Function Interaction Matrix
        Function                                        Task (Application Domain)
                                                 |Macromolec |Dissol/Deposit |Small Molec |
Surfactants & interfacial phenomena              |____________|____________|____________|
Separations processes                            |____________|____________|____________|
Modeling and simulations                         |____________|____________|____________|
Spectroscopy                                     |____________|____________|____________|
Kinetics and mass transport                      |____________|____________|____________|
Thermodynamics                                   |____________|____________|____________|
Reactor design                                   |____________|____________|____________|
Other (specify)                                  |____________|____________|____________|

                                                 4
III. Pre-proposal

A. Purpose

The pre-proposal is a brief concept statement. Its purpose is to provide a mechanism for early
dialog among Center leadership and potential respondents. This stage is intended to provide
guidance to respondents in preparing the best set of proposals possible. There are at least three
mutual benefits for respondents and the Center. (1) Excessive overlaps can be avoided in
proposals. More positively stated, opportunities for close collaboration can be identified between
respondents who propose similar work. (2) At an early stage, gaps can be identified in project
areas that need to be filled. If no one within the constituent university departments is able or
willing to fill those gaps, it may be necessary to identify and invite outside researchers to
participate. (3) It may be possible to identify potential collaboration targets between researchers
from different fields working on different aspects of similar areas. For example, theorists
developing molecular models would do well to focus on systems of interest to experimentalists in
related areas. And experimentalists should provide bases to test developing models.

These pre-proposals will be reviewed and prompt feedback given to guide you in preparing an
effective and successful proposal.

B. Format and Content

Respondents are to submit pre-proposals by June 28, 2001 (as electronic copies, preferably in
MS Word 2000 format) to Vicki Haithcock at vph@email.unc.edu. Respondents are requested to
maintain a copy for their records (If any computer incompatibilities exist these will be dealt with
individually.)

   1. Project title and Principle Investigator(s)

Please be brief but descriptive in developing your title. Use no more than 12 words, terms (e.g.,
CO2) or abbreviations. If more than one PI is named, please indicate which is to be considered
lead investigator. Please include contact information (phone, FAX, e-mail).

   2. Research Concept

This section should be 6-8 lines, including a brief statement of research objective and your
proposed research approach.


IV. Proposal Format and Content

Respondents are to submit proposals in the following format. An electronic copy of the full
proposal is to be sent as outlined in Section III above by August 6, 2001.

A. Project Title and Principal Investigator(s)

Please be brief but descriptive in developing your title. Use no more than 12 words, terms (e.g.,
CO2) or abbreviations. If more than one PI is named, please indicate which is to be considered
the lead. Please include contact information (phone, FAX, e-mail).

                                                    5
B. Research Plan

This section should be 2-3 pages and include all of the following elements.

   1. Overall objective

The overall research objective should be stated in a brief paragraph. In addition, a one-line
synopsis should be included which can be directly excerpted in listing the Center’s key objectives.

   2. Approach

What specifically do you plan to do? What is your strategy?

   3. Relation to overarching Center goals

All research programs selected in the first solicitation must be clearly aligned with one or more of
the three Application Domains listed above. Some projects may relate to predictive models
(mathematical or physical); diagnostic or characterization tools and techniques (e.g., for
measurements); and/or broadly applicable equipment and/or processes. As the Center’s work is
fundamental, this is expected and encouraged. However, it should also be clear how that model,
tool or technique will be used directly to achieve the goals of at least one Application Domain. (If
your proposal does not support one of these Domains but supports higher-level Center vision,
mission and goals, it may be a candidate for “seed” funding.)

        a. Overarching goal(s) supported

With which of the three overarching goals (Table 2) does your project best align? There may be
more than one, but pick the one where the success (or failure) of your project would have the
greatest impact. This alignment will be used in our official reporting to NSF and on our website
but will not affect collaborative opportunities or group meeting assignments. Collaboration is
expected within cross-cutting functions as well as application domains and thus grad students
and post docs are expected to attend as many weekly seminars as possible.

        b. Position in the research matrix

Please refer to Table 4 in the Background section. Copy the matrix and complete it as follows.
Find the functional area(s) that most nearly describe(s) your proposal. Mark the boxes in the
matrix where the functional area contributes to an application. Use “@” for very important and “o”
for somewhat important. Leave blank if there is little or no overlap. For example, if your proposal
would measure polymerization kinetics using a spectroscopic technique, there would be an “@” in
the box where spectroscopy and macromolecules intersect. However, that technique might also
be used to follow dissolution kinetics. Depending upon the likelihood of this application, either
“@” or “o” would go into that box. If the technique could also be used to follow an organic
condensation reaction in CO2, that box would be appropriately marked as well. For each mark
that is made in the matrix, there should be a brief explanation.

   4. Potential impact

What difference will your project make? How will the Center benefit/suffer if your proposal is/is
not funded? The matrix above and connectivity section below should be considered.


                                                 6
C. Connectivity

If this proposal extends an existing project, briefly, what new collaborations have you established
as a result of your funding to date? Whether new or existing project, what new ones are planned?
Sharing of graduate students and/or post-docs on related projects is an excellent way to develop
connectivity. PIs are encouraged to collaborate on proposals to develop such connections.

   1. Related work
       a. Other Center proposal supported (past and planned)
       b. Additional Center goals (other than primary) supported
       c. Additional functional efforts supported
   2. Collaborations planned outside the Center
   3. Resource and/or facilities sharing

D. Education and Outreach

Include all research group participation, but highlight your personal involvement. The expectation
is that you participate in ongoing K-12 programs, not necessarily “invent” new ones.

   1. Past and proposed K-12 support
   2. Past and proposed support of higher education initiatives
   3. Past and proposed participation in Personal Development Program

E. Funding

   1. The standard funding module allows for the following allocations for each of two years.
(Second year funding is contingent upon satisfactory completion of a semiannual review.)

     One summer month for PI
     One full-time grad student or half-time post-doc, preferably shared with another Center PI
     Provision for supplies ($4000 per year)
     Travel ($500 per year)
Please advise as to which option (one graduate student or ½ post doc) you select. Also, if you
propose sharing, please state with whom. Undergraduate support may be available upon
request, certainly so at NC A&T.

   2. Additional and complementary funding

Be advised that very little if any additional capital is likely to be available. Proposals should not
be predicated upon capital availability nor availability of funds beyond the standard module
described above.

Please indicate plans to obtain complementary funding. Also, if you are presently receiving STC
funding, what Center-related proposals have you filed to date and with what results?




                                                  7
V. Selection Criteria
Table 5 summarizes selection criteria for complete proposals received by August 6, 2001.


                 Table 5. Selection Criteria for Technical Projects
                Criterion                                                  Relative Priority

        Fit to strategic plan (application domain)                 --|
        Potential impact on CERSP programs                           |          Primary
        Scientific merit (apart from other considerations)         --|

        Collaboration plan (inside and outside CERSP)              --|
        K-12 outreach record and plan                                |         Secondary
        Outside funds attracted                                    --|



Proposals will receive informal peer review. Reviewers may include scientists and engineers
from inside and outside constituent universities, national labs and affiliates, and the technical
subcommittee of our External Advisory Board. The Technical Executive Committee shown in
Table 6 will select projects based upon these reviews, individual merits per criteria in Table 5 plus
judgment as to the best overall combination of programs. Selections will be announced by mid-
September.


                       Table 6. Technical Executive Committee
   Prof. George Roberts (NCSU), Chair                          Prof. Joseph DeSimone (UNC-CH)
   Prof. Ruben Carbonell (NCSU)                                Dr. Everett Baucom (UNC-CH)
   Prof. Keith Johnston (UT-A)                                 Prof. Godfrey Uzochukwu (NCA&T)


VI. Expectations

As stated in Section IV.E.1 Principal Investigators will review projects semiannually to assist in
establishing collaborations and to assure continuing alignment with strategic plans and continuing
contribution to Center objectives. Additional expectations include

               For PIs
                - Monitor project progress vs. proposal commitments
                - Participate in semiannual organization meetings, NSF and EAB reviews
                - Establish collaborations supporting the Center
                - Support students and post-docs in their obligations
                - Timely response to administrative requests

               For students and post-docs, participation in
                - All weekly Center seminars
                - K-12 outreach programs
                - Personal Development Program
                - Kenan Center and NSF poster reviews

                                                  8
VII. Schedule and Inquiries
There will be two solicitations. In the first, we solicit proposals for two-year programs supporting
one or more of three “Application Domains” (Macromolecular Synthesis and Engineering;
Dissolution and Deposition; and Small Molecule Systems described below). Approximately 90%
of annual operating funds will be used to support these projects. Participation in the first
solicitation will be limited to existing PIs and/or institutions plus invited researchers whose
expertise complements our existing expertise and needs. Table 7 gives the schedule. Remaining
funds will be allocated to projects supported under the second solicitation, which will encompass
“seed programs”. The latter generally will be smaller projects aimed at assuring vitality of the
Center through continual renewal and expansion into diverse areas not presently covered by
Center programs. Outside departments and institutions will be included. Details of this second
solicitation will be issued in August 2001.




                    Table 7. Schedule for RFP (First Solicitation)
        Videoconference review with PIs                                     June 14*
        Pre-proposal titles due (intent to respond)                         June 28
        Response to pre-proposals                                           July 9
        Proposals due                                                       Aug 6
        Final selection of projects                                         Sep 13
        Funding commences                                                   Nov 1

* A videotape of this conference will be available for those unable to attend



The overarching goal of the “Seed Program” is given in Table 8. This is clearly an experiment in
renewal with only a one-year commitment (pending approvals). If it serves its purpose, the intent
is to continue it at least until 2005.


                                  Table 8. Seed Program
                          Overarching Goal of CERSP Seed Program

                  To provide a mechanism for exploration of innovative ideas in
                           areas outside existing application domains

                 In order to foster renewal and to assure continued Center vitality




Tentative schedule for the “seed program” solicitation is given in Table 9. In general, proposal
requirements will be modest—a single page description of the idea, how it might contribute to
achieving the Center’s goals, and how the project would be continued if successful. However,
these proposals generally should not address existing Application Domains. Each project will
likely be administered under a Memorandum of Understanding. Funding is for one year and is
flexible but must be matched by the recipient. It is envisioned that proposals could be
submitted at any time with awards made at least quarterly.

                                                  9
               Table 9. Schedule for Seed Program RFP (Tentative)
        RFP II issued                                                       Oct    4
        Videoconference review with PIs                                     Oct   11
        Proposal review begins                                              Nov   26
        Initial funding commences                                           Jan    1, 2002



Inquiries

Inquiries regarding this RFP should be directed to Prof. George Roberts (919-515-7328 or
groberts@eos.ncsu.edu.) Alternatively, contact Ev Baucom at baucome@email.unc.edu.



VIII. Appendix: Details of Strategic Needs

A. MACROMOLECULAR SYNTHESIS AND ENGINEERING



   1. Low Delta P Monomer Separations from High P CO2 Streams

There is need for the separation of monomers and organic residues, such as ethylene, styrene, or
phenol, from high-pressure CO2 streams with minimum need to re-pressurize. This would allow
continuous polymerization, solid-state polymerization or residue removal in reactor and stripping
systems to minimize costly and complex recompression cycles.

   2. Synthesis of Water Soluble Polymers

Bone-dry powders of hydroscopic, water-soluble polymers is an important target of opportunity for
CO2-based polymerization processes.


   3. Theory and Model to Predict Phase Equilibria for Precipitations

During most precipitations in scCO2, the formed polymer precipitates as a separate phase.
Therefore, it is possible for polymerization to take place in both the supercritical fluid and the
CO2-swollen polymer particles. The partitioning of relevant species: CO 2, monomers, and
initiator, between the polymer and the supercritical fluid is being measured for the poly(vinylidene
fluoride) (PVDF) and poly(tetrafluoroethylene) systems. Similar measurements undoubtedly will
be required as other polymers are investigated.

Simple models, e.g., Sanchez-Lacombe, do not appear to describe the available data, even for
binary systems such as CO2-PVDF. Research is needed to evaluate more sophisticated
equations of state, and to develop new models that will describe the phase equilibria in systems
with up to four partitioning components.


                                                  10
   4. Control of Polymer Properties

Macromolecular synthesis and processing is one of the most active areas of research in the
CERSP. Many of the investigations to date have been focused on understanding the physical
phenomena involved in polymerizations in scCO2, the kinetics of the reactions, and polymer
recovery. Some important features of polymer structure and composition have not received much
attention. These include: morphology, molecular weight distribution, monomer sequencing,
copolymer composition, and end group identification. Proposals are solicited that involve
innovative methods for measurement and control of the polymer characteristics listed above, for
polymerizations that are carried out in scCO2.

   5. Low Temperature Free-Radical Initiators

Polymerizations in scCO2 must take place at relatively low temperatures (ca. 110 °C) so that the
density of the supercritical fluid will be high at reasonable pressures (ca. 5000 psig.). In a
continuous polymerization, the average residence time must be reasonable low (ca. 1hr.) and the
monomer conversion per pass should be about 50% in order to avoid excessive reactor capital
cost and excessive recycle cost. This requires an initiator that has a short half-life (< ca. 20 min.)
at a low temperature (< ca 60 °C). The initiator must also be safe to use on a continuous basis in
the laboratory and in a commercial plant. The initiators that have been used in research to date
do not approach these requirements.

Research is needed to increase the range of free-radical initiators that can be used for
polymerizations in scCO2. In view of the need to handle quantities of the initiator safely, redox
systems may offer the best possibilities.


B. DISSOLUTION AND DEPOSITION

   1. "Dry" Microelectronic Processes

The microelectronic industry continues to grow rapidly. Many of the processes used in the
fabrication of ICs, MEMs and memory devices depend on the use of large volumes of water and
organic solvents. In addition, the high surface tension and the relatively high viscosity of water
and organic solvents can lead to challenges when processing next generation structures that are
mechanically fragile and/or can be difficult to coat with uniform thin films. Proposals are
encouraged to consider the fundamentals associated with converting traditionally "wet"
processes based on water and organic solvents to "dry" processes in the microelectronics
industry including chemical-mechanical polishing, lithography, CVD, metal film deposition,
quantum dots, nanoporous films, SAMs, etc.

   2. Coatings for Biomedical Applications

Carbon dioxide is an ideal solvent for the deposition of thin films for biomedical applications.
These films may be deposited as self-assembled monolayers, from either liquid or supercritical
states. They may also be deposited using free meniscus and spin coating approaches. Since
carbon dioxide has a low viscosity and surface tension, ultra thin films are favored. Because it
can evaporate completely it will leave no residue on materials that are to come in contact with
living systems. Since carbon dioxide has a very low surface energy it can wet almost any
surface. Novel materials need to be synthesized that are carbon dioxide soluble, but could
render hydrophobic materials such as perfluorinated polymers hydrophilic to reduce adsorption
and deposition of proteins, cells and the formation of tissue. This can lead to materials with
superior mechanical properties whose surfaces are compatible with biological systems.

                                                   11
C. SMALL MOLECULE SYSTEMS


   1. Activation of Carbon Dioxide

The use of CO2 in chemical synthesis is attractive for many reasons, e.g., its low cost, its
environmentally-benign characteristics, and the resulting reduction in net CO 2 emissions. There
are two major impediments to increased use of CO2 as a reactant. First, CO2 is not very
reactive. This makes it likely that some form of catalysis that "activates" CO 2 will be required.
Second, because CO2 has a large negative free energy of formation, reactions with CO2 as a
reactant usually have an unfavorable equilibrium.

Proposals are solicited that involve the synthesis of useful small molecules or macromolecules
from CO2. The proposal should address the question of how an unfavorable reaction equilibrium
might be overcome, if this question is relevant to the chemistry involved. The proposal also
should address any issues related to catalysis of the reaction(s) that will be studied.

   2. Development and Use of CO2/H2O Microemulsions and Emulsions for Chemical Synthesis
      Separations and Materials Formation

The formation of microemulsions and emulsions of water and CO 2 offers the opportunity to bring
hydrophilic molecules into close proximity with CO2. These emulsions may be applied in a wide
variety of reaction, separation and materials formation processes that expand substantially the
CO2 platform.

   3. Synthesis of Pharmaceuticals

The manufacture of small molecule drugs is usually carried out in organic solvents using
homogeneous and heterogeneous catalysts or in aqueous systems by fermentation or enzymatic
reactions. In either case, product purification is difficult and results in significant amounts of
contaminated water or waste solvents. Novel catalytic routes are sought in which the synthesis of
pharmaceuticals can be carried out in carbon dioxide with adjuncts to control the solubility of
reactants, catalyst and product species. The catalysts can either be immobilized enzymes or
metallic species or they can be suspended in micelles and other aggregate structures in solution.

   4. Synthesis and Recovery of Products from Fermentation Broths

   5. Organic Transformations Avoiding Solvents

The chemical industry uses large amounts of solvents in the manufacture of specialty chemicals,
intermediates and pharmaceuticals. Proposals are encouraged to explore the feasibility of
conducting various synthetic transformations in CO 2, especially those that would be important to
demonstrate in an effort to reduce the use of organic solvents and water in currently used
processes.

   6. Oxidations and Hydrogenations in CO2

Partial oxidation and hydrogenation are important steps in the synthesis of many small
molecules. Both types of reaction are exothermic, so that excellent temperature control is
important to high reaction selectivity. Moreover, many hydrogenations are carried out in three-
phase systems, where hydrogen gas must dissolve in a liquid, and the solubility of H 2 in the liquid

                                                  12
may have an important effect on reaction behavior. Carrying out oxidation and/or hydrogenation
reactions in liquid or supercritical carbon dioxide (scCO 2) can have potential benefits. The higher
heat capacity of liquid or scCO2 relative to gases can help to moderate reaction exotherms for
gas-phase reactions. Moreover, H2 generally is more soluble in scCO2 than in conventional liquid
solvents. Proposals are solicited that involve the synthesis of useful small molecules using liquid
or scCO2 as a reaction medium.


   7. Powder and Particle Technology

Novel methods are needed that would utilize the transport and thermodynamic properties of
carbon dioxide to facilitate the formation of novel particulate species either by spraying from liquid
systems (swollen by carbon dioxide) or from supercritical state or by reaction. There is particular
interest in the formation of nanoparticles and encapsulated materials for drug delivery as well as
particles that can be used for powder coatings, insulators, conductors and magnetic media.
General principles of aggregation and stabilization of colloidal suspensions need to be examined.
There is also a great deal of interest in novel methods for isolating and precipitating these novel
structures.

   8. Extraction of Products from Organic and Aqueous Solvents and Solid Phases

Carbon dioxide with suitable additives to aid the formation of microemulsions, emulsions, micelles
and other aggregated structures might be able to extract small and large molecules from organic
and aqueous solvents, as well as solid phases This might lead to effective and energy efficient
separation and fractionation methods that utilize the tunable physical properties of carbon dioxide
to affect separations by extraction.

   9. Design of Surfactants to Solubilize Organics in Dry CO2

  10. Use of Carbon Dioxide for Petroleum Processing

Production and fractionation of oil is an expensive and energy intensive process. It would be
attractive to have novel methods of petroleum production utilizing carbon dioxide and co-solvents
that could be carried out at lower temperatures and that would not result in environmental
contamination. Among the potential applications one can list oil recovery from underground
deposits, underwater deposits and tar sands.




D. CROSS-CUTTING ACTIVITIES


   1. Sensors

It is becoming increasingly clear that sensors can and will play an important role in monitoring
CO2-based processes including polymerizations, separations, cleaning processes, extractions,
etc. Proposals are encouraged in the design of sensors and the research that supports sensor
design.




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   2. Low Cost, Light Weight High-Pressure Equipment

Stainless steel high-pressure equipment is expensive, large and heavy. This creates significant
barriers to the development of high-pressure technologies utilizing carbon dioxide and other
supercritical fluids. Research is needed on novel reinforced materials that will have the ability to
safely withstand pressures as high as 5,000 psi, but that can be formed in various shapes and
sizes. These materials need to be impermeable to most organic molecules and water.

   3. Cost-effective Surfactants

Surfactants for CO2 will be playing an increasingly important role in a number of applications,
including in polymer synthesis and processing, reaction systems, separations including materials
synthesis, surface modification, bioseparations, and in cleaning. Proposals are sought for the
study, design and synthesis of cost effective surfactants and the characterization of the properties
of interfaces containing these surfactants that can contribute to the CO 2 technology platform
reaching its full potential.

   4. Thermal and Transport Issues of Rapid Supercritical Fluid Handling

The steps of pressurizing and venting high-pressure systems can be time-consuming and result
in significant temperature swings on the operating equipment. It would be attractive to have novel
ways of pressurizing and venting vessels that would minimize recompression times and costs and
at the same time help minimize temperature variations.




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