(Research Description PDF - 665 kb)
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.
Terephthalic and Trimellitic Based Acids and Carboxylate Derivatives Thereof, John W. Frost, Adeline Miermont, Dirk Schweitzer, Vu Bui, Douglas A Wicks, U.S. Patent 8,367,858, February 5, 2013.
Cyclohexane 1,4-Carboxylates, John W. Frost, Adeline Miermont, Dirk Schweitzer, Vu Bui, Douglas A Wicks, U.S. Patent 8,367,859, February 5, 2013.
Biobased Polyesters, John W. Frost, Adeline Miermont, Dirk Schweitzer, Vu Bui, Edward Paschke, Douglas A Wicks, U.S. Patent 8,415,496, April 9, 2013.
Methods and Materials for the Production of Shikimic Acid, John W. Frost, U.S. Patent 8,372,621, February 12, 2013.
Biosynthesis of Phloroglucinol and Preparation of 1,3-Dihydroxybenzene Therefrom, John W. Frost, U.S. Patent 8,329,445, December 11, 2012.
Catalytic Deamination for Caprolactam Production, John W. Frost, U.S. Patent 8,283,466, October 9, 2012.
B.S., 1977, Purdue Univ.
Ph.D., 1981, Massachusetts Institute of Technology.
|Award||Organization||Division||Level Code||Type Code||Start Date||End Date|
|Science and Technology Awards from Corp! magazine||Draths Corporation||Professional||Professional Activities||2010||2010|
|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"||Professional||Administration||2002|
|Distinguished Faculty Award||Michigan State University||College of Natural Science||Professional||Honors||2000|
|Session Organizer||"Industrial Chemicals" 21st Symposium on Biotechnology for Fuels and Chemicals||Professional||Administration||1999|
|Participant||EPA/NSF||Joint Technology for a Sustainable Environment Review Workshop||Professional||Professional Activities||1999|
|Co-Chairperson||National Science Foundation/DOE||Workshop on Molecular Energy and Environmental Science||Professional||Administration||1999|
|The Presidential Green Chemistry Challenge Award||Environmental Protection Agency||Professional||Honors||1998|
|Participant||National Institutes of Health||Metabolic Engineering Workshop - this gathering advised NIH on the establishment of an initiative in metabolic engineering.||Professional||Professional Activities||1995|
|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||Professional||Professional Activities||1994|
|Organizing Committee Member||Council for Chemical Research Workshop on Environmental Chemistry||Professional||Professional Activities||1994|
|Co-Chairperson||"Biocatalysis" Gordon Research Conference||Professional||Administration||1992|
|Co-organizer||"Workshop in Environmental Chemistry" National Science Foundation||Professional||Administration||1992|
|Cyanamid Faculty Award||Professional||Honors||1991|
|Co-organizer||"Strategies and Opportunities at the Interface Between Chemistry, Chemical Engineering and Life Sciences" The 39th Industrial Affiliates Symposium, Stanford University||Professional||Administration||1988|
|"Environmental Chemistry and Chemical Processes" National Science Foundation Workshop||Professional||Administration||1987|
|Teacher-Scholar Award||Camille and Henry Dreyfus Foundation||Professional||Honors||1987||1992|
|Organizer||"Environmental Chemistry and Chemical Processes" National Science Foundation Workshop||Professional||Administration||1987|
|Alfred P. Sloan Fellowship||Alfred P. Sloan Foundation||Professional||Fellowship||1987||1989|
|Summer Faculty Fellowship||Rohm and Haas||Professional||Fellowship||1985|
|Ph.D.||Massachusetts Institute of Technology||Graduate||Degree||1981|
|Postdoctoral Fellowship||National Institutes of Health||Postdoctoral||Fellowship||1981||1983|
|Postdoctoral Fellowship||Harvard University||Postdoctoral||Fellowship||1981||1983|
|Bachelor of Science||Purdue University||Undergraduate||Degree||1977|
|Phi Beta Kappa||Phi Beta Kappa||Undergraduate||Honors||1977|
|Graduate with Distinction||Purdue University||Undergraduate||Honors||1977|
|Phi Kappa Phi||Phi Kappa Phi||Undergraduate||Honors||1977|
Okemos-based Draths Corp., founded by John and Karen Frost, is relocating to Delhi Twp.
Two companies that originated from Intellectual property created by Department faculty have won 2010 Science and Technology Awards from Corp! magazine. They are Draths Corporation which is based on the biocatalysis research of John and Karen Frost, and Biophotonic Solutions which was founded by Marco Dantus for marketing technology that grew from his research into ultrafast optical phenomena. The awards were presented at a ceremony held in Troy, MI on April 20.
Professor John Frost and Dr. Karen Draths, who have taken a leave of absence from their jobs at Michigan State University in December 2006 to start Draths Corporation, have more recently developed a microbial process for making phloroglucinol, a chemical to replace formaldehyde, a carcinogen, in adhesive resins. more
Warren Beck, Marcos Dantus, Michael Feig, John Frost, Jim Geiger, Ned Jackson, Rob Maleczka, Jim McCusker, Aaron Odom, Piotr Piecuch, Tom Pinnavaia, Greg Swain, and Bill Wulff received new grants during Fall 2005.
John Frost has developed technology that can be used to produce shikimic acid, the starting material for Tamiflu(oseltamivir) a drug that will be important in combating avian flu if such a pandemic develops. New York Times Article