Biocatalysis

John Frost

University Distinguished Professor

528A CEM

517-353-0502



Primary Research Area

Organic (Or)

Other Area(s) of Interest

Biological (Bi)

Research

(Research Description PDF)

Green chemistry is being elaborated that enables CO2 fixed by plants to be converted into chemicals currently derived from the BTX (benzene toluene xylene) fraction of petroleum refining. Nonrenewable fossil fuel feedstocks, carcinogenic starting materials and toxic intermediates are avoided. In addition, an array of new monomers is being synthesized to identify structures that are: (a) free of endocrine disruption activity, and (b) lead to polymers and plasticizers characterized by novel materials properties.

Current commercial synthesis of p-hydroxybenzoic acid begins with BTX-derived benzene and proceeds through cumene and phenol as intermediates. Carboxylation of potassium phenolate affords p-hydroxybenzoic acid monomer, which typically constitutes 50% of the mass of liquid crystalline polymers. A green synthetic alternative has been elaborated whereby p-hydroxybenzoic acid is synthesized in a single step in high conversion and good selectivity from nontoxic shikimic acid. Shikimic acid, in turn, is microbially synthesized from plant-derived glucose or isolated directly from plants such as Ginkgo biloba. Shikimic acid’s solubility in n-butanol and propensity to crystallize from n-butanol facilitate its isolation from fermentation broth or plant tissue. Green synthesis of p-hydroxybenzoic acid eliminates the need for using carcinogenic benzene as a starting material and toxic phenol as an intermediate.

BTX-derived xylene is industrially oxidized to terephthalic acid, which is polymerized with ethylene glycol to produce poly(ethylene terephthalate) PET. Over 50 × 109 kg of terephthalic acid are globally produced each year. Two green synthetic alternative routes have been developed. Isoprene and acrylic acid microbially synthesized from glucose undergo a cycloaddition to form 4-methylcyclohex-3-ene-1-carboxylic acid. Dehydrogenation affords terephthalic acid. Alternatively, cis,cis-muconic acid microbially synthesized from glucose is isomerized and the resulting trans,trans-muconic acid reacted in a cycloaddition with bioethanol-derived ethene to yield cyclohex-2-ene-1,4-dicarboxylic acid. Dehydrogenation affords terephthalic acid. In addition to use of renewable feedstocks, the new routes enable the first practical synthesis of substituted terephthalates when substituted acrylic acids and substituted ethenes are employed. Furthermore, a parallel world of 1,4-cyclohexane and 1,4-cyclohexene 1,4- dicarboxylic acids has been created, which affords unique opportunities to avoid aromatic-associated, endocrine disruption activity while enabling the fabrication of novel materials.

 

Selected Publications

B-O-B catalyzed cycloadditions of acrylic acids, Zhang, P.; Kriegel, R. M.; Frost, J. W. ACS Sustainable Chem. Eng. 2016, 4, 6991-6995.

Synthesis of Terephthalic Acid from Methane, Zhang, P.; Nguyen, V.; Frost, J. W., ACS Sustainable Chem. Eng. 2016, 4, 5998-6001.

Synthesis of Biobased Terephthalic Acid from Cycloaddition of Isoprene with Acrylic Acid, K.K. Miller, P. Zhang, Y. Nishizawa- Brennen, and J. W. Frost, ACS Sustainable Chem. Eng. 2014, 2, 2053−2056.

CV

B.S., 1977, Purdue Univ.

Ph.D., 1981, Massachusetts Institute of Technology.

Awards/Honors

2010 - 2010 Science and Technology Awards from Corp! magazine Draths Corporation
2002 Organizer U.S. Department of Energy (DOE) Catalysis Workshop - biocatalysis working group and authored sections dealing with biocatalysis in the report entitled "Opportunities for Catalysis Science in the 21st Century"
2000 Distinguished Faculty Award Michigan State University (College of Natural Science)
1999 Co-Chairperson National Science Foundation/DOE (Workshop on Molecular Energy and Environmental Science)
1999 Participant EPA/NSF (Joint Technology for a Sustainable Environment Review Workshop)
1999 Session Organizer "Industrial Chemicals" 21st Symposium on Biotechnology for Fuels and Chemicals
1998 The Presidential Green Chemistry Challenge Award Environmental Protection Agency
1995 Participant National Institutes of Health (Metabolic Engineering Workshop - this gathering advised NIH on the establishment of an initiative in metabolic engineering.)
1994 Facilitator U.S. Environmental Protection Agency and the National Science Foundation "Workshop on Green Syntheses and Processing in Chemical Manufacturing" benign organic synthesis working group
1994 Organizing Committee Member Council for Chemical Research Workshop on Environmental Chemistry
1992 Co-Chairperson "Biocatalysis"Gordon Research Conference
1992 Co-organizer "Workshop in Environmental Chemistry" National Science Foundation
1991 Cyanamid Faculty Award
1988 Co-organizer "Strategies and Opportunities at the Interface Between Chemistry, Chemical Engineering and Life Sciences" The 39th Industrial Affiliates Symposium, Stanford University
1987 - 1992 Teacher-Scholar Award Camille and Henry Dreyfus Foundation
1987 - 1989 Lilly Grantee
1987 Organizer National Science Foundation Workshop
1987 - 1989 Alfred P. Sloan Fellowship Alfred P. Sloan Foundation
1985 Summer Faculty Fellowship Rohm and Haas
1985 Searle Scholar