Biocatalysis at the Austrian Center of Industrial Biotechnology

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Biocatalytic Synthesis enzymatic solutions for chemical problems

Enzyme Engineering & Technology enzymes designed for industry

science is our success

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Synthesis - enzymatic solutions for chemical problems - Enzyme Engineering & Technology - eynzmes designed for industry - Biocatalytic Synthesis - enzymatic solutions for

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chemical problems - Enzyme Engineer


Contents

Reductive Biotransformations

4-5

Oxidative Biotransformations

6-7

C-C Bond Formation

8-9

C-C Bond Breaking

9

Enzymatic Isomerisation

10

Hydrolysis / Esterification

11-12

Enzymatic Cascades

12-13

Glycozyme Technology

14-15

API Modification

16

In-silico Search for Novel Biocatalysts

17

About acib

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Contact

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Reductive Biotransformations Reduction of Carboxylic Acids

(CAR = carboxylate reductase, ADH = alcohol dehydrogenase; ChemCatChem 2014, 6, 1089-1095; Biotechnol. J. 2014, 9, 822-843; Chemical Monthly, 2016, 147, 575-578; Adv. Synth. Catal., 2016, in press, DOI: 10.1002/ adsc.201600914.)

Reduction of Aldehydes and Ketones

(ADH = alcohol dehydrogenase; Angew. Chem., Int. Ed. 2002, 41, 1014; Angew. Chem., Int. Ed. 2008, 47, 714; ChemCatChem 2013, 5, 1744.)

Reduction of C=C-Bonds

(X = electron-withdrawing group; Angew. Chem., Int. Ed. 2007, 46, 3934; Chem. Eur. J. 2012, 18, 10367; Curr. Opin. Chem. Biol. 2007, 11, 203; J. Biotechnol. 2012, 162, 381; Nat. Commun. 2014, 5, 4150.)

Reduction of Imines

(IRED = imine reductase; Adv. Synth. Catal. 2015, 357, 1655.)

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Reductive Biotransformations Reductive Amination of Aldehydes and Ketones

(TA = ω-transaminase; Angew. Chem., Int. Ed. 2008, 47, 9337; Angew. Chem., Int. Ed. 2012, 27, 1; Org. Process Res. Dev. 2013, 17, 751; ACS Catal. 2014, 4, 129.)

Structure of an Ene-Reductase

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Oxidative Biotransformations Oxidation of Alcohols / Aldehydes

(ADH = alcohol dehydrogenase; Angew. Chem., Int. Ed. 2002, 41, 1014; Angew. Chem., Int. Ed. 2008, 47, 714; J. Am. Chem. Soc. 2008, 130, 13969; ChemCatChem 2013, 5, 1744.)

C=C-Bond Cleavage

(Angew. Chem., Int. Ed. 2006, 45, 5201; J. Am. Chem. Soc. 2009, 131, 5368; Chem. Commun. 2012, 48, 3303; Adv. Synth. Catal. 2013, 355, 3321.)

Enzymatic De-Amination

(TA = ω-transaminase; AO = α-amino oxidase; Angew. Chem., Int. Ed. 2008, 47, 9337; Angew. Chem., Int. Ed. 2012, 27, 6817; Org. Process Res. Dev. 2013, 17, 751; ACS Catal. 2014, 4, 129.)

Enzymatic De-Alkylation (Angew. Chem. Int. Ed. 2015, 54, 15051.)

Enzymatic Hydration (Angew. Chem., Int. Ed. 2013, 52, 2293.)

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Oxidative Biotransformations Oxidative Decarboxylation

(Angew. Chem. Int. Ed. 2015, 54, 8819–8822; Chem. Commun., 2016, 51, 1918; Eur. J. Org. Chem., 2016, 2473– 3477.)

Enzymatic Hydroxylation

(Nat. Biotechnol. 2002, 20, 1135.)

Baeyer-Villiger Oxidation

(hFMO = human flavin containing monooxygenase; ACS Chem. Biol., 2016, 11, 1039-1048.)

Oxyfunctionalisation of Amino Acids (aKG = a-ketoglutarate; AAD = amino acid dioxygenase; Front. Microbiol., 2016, 7, 425.)

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C-C Bond Formation Bio-Carboxylation

(Chem. Soc. Rev. 2010, 39, 313; Org. Lett. 2012, 14, 1974; J. Biotechnol. 2013, 168, 264; RSC Adv. 2014, 4, 9673.)

Bio-Friedel-Crafts Acylation

(unpublished results)

Biocatalytic Alkaloid Synthesis (BBE = berberine bridge enzyme; STR = strictosidine synthase; NCS = norcoclaurine synthase; Angew. Chem., Int. Ed. 2011, 50, 1068; Org. Process Res. Dev. 2013, 17, 751; Angew. Chem., Int. Ed. 2014, 53, 3731.)

Trifluoromethylation

(TFMS = trifluoromethylsulfonic acid; TBHP = tert-butylhydroperoxide; Nat. Commun. 2016, in press, DOI: 10.1038/ncomms13323.) Synthesis - enzymatic solutions for chemical problems - Enzyme Engineering & Technology - eynzmes designed for industry - Biocatalytic Synthesis - enzymatic solutions for

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C-C Bond Formation Cyanohydrin Synthesis/Henry Reaction

(HNL = hydroxynitrile lyase; Angew. Chem., Int. Ed. 2006, 45, 3454; Adv. Synth. Catal. 2007, 349, 1445; ChemCatChem 2015, 7, 325; Angew. Chem., Int. Ed. 2003, 42, 4815; Curr. Biotechnol., 2015, 4, 111-117.)

C-C Bond Breaking Asymmetric Synthesis of Optically Pure Îą-Substituted Carboxylic Acids

(AMDase = arylmalonate decarboxylase; ChemCatChem, 2016, 8, 916; Appl. Microbiol. Biotechnol., 2016, 20, 8621.)

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Enzymatic Isomerisation Racemization of Arylpropionates

(APR = arylpropionate racemase; ChemBioChem, 2016, 16, 1943; Cat. Sci. Technol., 2016, 6, 4397.)

Isomerisations of C=C-Bonds

(ChemBioChem, 2012, 13, 2346–2351.)

Disproportionation: Biocatalytic Cannizzaro Reaction

(ADH = alcohol dehydrogenase; ChemCatChem, 2013, 5, 1744–1748.)

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Hydrolysis / Esterification Hydrolysis of Lactams

(ChemCatChem 2014, 6, 2517.)

Bio-Mitsunobu-Inversion

(Angew. Chem., Int. Ed. 2002, 41, 1014; Angew. Chem., Int. Ed. 2005, 44, 6381; Angew. Chem., Int. Ed. 2013, 52, 3277; Eur. J. Org. Chem. 2013, 356; Trends Biotechnol. 2013, 31, 468; Appl. Microbiol. Biotechnol. 2014, 4, 1485.)

C-C Bond Hydrolysis

(Adv. Synth. Catal. 2013, 355, 1677; Adv. Synth. Catal. 2013, 355, 1703; Top. Catal. 2014, 57, 376.)

Nitrile Hydrolysis

(Tetrahedron 2005, 61, 4249-4260; ChemCatChem 2010, 2, 267-269; Enz. Microb. Technol. 2010, 47, 140-146; OBC 2015, 13, 7803-7812.)

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Hydrolysis / Esterification Enantioselective Ester Formation in Aqueous Systems

(AT= acyl transferase; to be published.)

Enzymatic Phosphorylation

(PPi = phyrophosphate; Eur. J. Org. Chem., 2016, 45–50.)

Enzymatic Cascades Chemoenzymatic Preparation of Bio-Based AntiOxidants

(PAD = phenolic acid decarboxylase; Angew. Chem., Int. Ed., 2016, in press, DOI: 10.1002/anie.201607777.)

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Enzymatic Cascades Direct Amination of Alcohols

(ADH = alcohol dehydrogenase; TA = ω-transaminase; Angew. Chem., Int. Ed. 2012, 51, 9156; ACS Catal. 2014, 4, 129.)

6-Aminohexanoic Acid from Cyclohexanol

(ADH = alcohol dehydrogenase; BVMO = Baeyer-Villiger monooxygenase, TA = ω-transaminase; Angew. Chem., Int. Ed. 2014, 53, 14153; ACS Catal. 2014, 4, 129.)

Cyclohexylamines from Diketones

(TA = ω-transaminase; Adv. Synth. Catal. 2013, 355, 1703.)

Vinylation of Phenols

(Angew. Chem. Int. Ed. 2015, 45, 10899.)

ring & Technology - eynzmes designed for industry - Biocatalytic Synthesis - enzymatic solutions for chemical problems - Enzyme Engineering & Technology - eynzmes designed

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Glycozyme Technology Regioselective Glycosyltransfer

(Biocat. Biotrans. 2010, 28, 10; Pure Appl. Chem. 2013, 85, 1865; PCT Int. Appl. 2015, WO 2015001033.)

Small Molecule Glycosylation

(Angew. Chem., Int. Ed. 2008, 47, 10086; PCT Int. Appl. 2008, WO 2008034158.)

Regioselective Glucosylation – Flavonoid Glycosylation

(Green Chem. 2014, 16, 4417.)

Synthesis - enzymatic solutions for chemical problems - Enzyme Engineering & Technology - eynzmes designed for industry - Biocatalytic Synthesis - enzymatic solutions for

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Glycozyme Technology Nucleotid Sugar Synthesis

(SPase = sucrose phosphorylase; AGP = α-D-glucose 1-phosphate phosphatase; PPase = pyrophosphatase; NTPase = nucleotide transferase; GTP = guanosine 5′-triphosphate; D-Glc = D-glucose; D-Fru = D-fructose; Pi = inorganic phosphate; Adv. Synth. Catal., submitted.)

Diasterioselecitve Synthesis of Glycosyl Phosphates

(SPase = sucrose phosphorylase; AGP = α -D-glucose 1-phosphate phosphatase; D-Glc = D-glucose; D-Fru = Dfructose; Pi = inorganic phosphate; Angew. Chem.,Int. Ed., 2015, 54,15867.)

ring & Technology - eynzmes designed for industry - Biocatalytic Synthesis - enzymatic solutions for chemical problems - Enzyme Engineering & Technology - eynzmes designed

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API-Modification with Human Enzymes Chemo- & Regioselective Oxidation of Soft Nucleophiles

(Chem. Commun. 2012, 48, 6001-6003; ChemCatChem 2014, 6, 1028-1042; Microb. Cell Fact. 2015, 14:82, 1-10; J. Biotechnol. 2016, 235, 3.)

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In-silico Search for Novel Biocatalysts Traditional screening for novel enzymes requires time-consuming experiments and expensive activity assays in the wet-lab. To reduce costs, the prediction and identification of enzyme functionalities is a major challenge of modern bioinformatics. However, the computational annotation of proteins proves to be difficult, erroneous and lacks the possibility to identify completely independent novel biocatalysts because they rely on the correlation of (sequence) similarities with the known functions of the template and are bound to find “more of the same”.

Catalophore Search for Novel Enzymes acib-researchers developed a patented bioinformatics method1 to mine structural databases using three dimensional search templates which cover the arrangement of chemical functional groups or pre-calculated point-clouds representing the “empty space” of active sites. These search templates are termed “catalophores” (i.e. carrier of the catalytic function). The searches are independent of structural or sequence similarities to currently employed enzymes. Therefore, these identified enzymes may feature different physico-chemical properties such as stability, selectivity or substrate tolerance. A successful test-case led to the identification of two “novel” ene-reductases2, by searching with patterns obtained from classical old yellow enzymes. The identified enzymes showed significant conversions on typical old yellow enzyme substrates and even allowed access to enantiomers that could not be obtained using current enzyme portfolio, although the overall sequence and structural similarity are below 10%. Catalophore used for the identification of the old-yellow enzyme example; a) schematic mechanism of the reaction mechanism; b) 3D active site constellation (“catalphore“) ; c) catalophore motif indicating used atom types; d) geometrical representation of the search motif used for the database search.

(1. PCT/EP2013/074556, 2014, ACIB GmbH and University of Graz; 2. Nat. Commun. 2014, 5, 4150.)

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about acib next step in industrial research The Austrian Centre of Industrial Biotechnology (acib) is an international research center with 200+ employees based in Austria with with collaborative links to Germany, Slovenia, Italy, Spain and Poland. acib can draw on 25+ years of experience to apply sophisticated, new methods in industrial production – focused on biocatalysis, enzymes, polymers, (pharmaceutical) protein production & purification, cell line development, bioinformatics and synthetic biology. Together with 130+ industrial and scientific partners acib adopts the tools and methods of nature for i) new production processes & products with improved ecological efficiency, ii) new production processes with higher economic efficiency, iii) products with higher quality and purity, iv) functional innovative products for everyday use and v) sophisticated computational methods for the health care, pharmaceutical or chemical industry... acib – science ist our success.

The competence centre acib is funded in the framework of COMET – Competence Centers for Excellent Technologies – by BMVIT, BMWFW and the provinces of Lower Austria, Styria, Tyrol and Vienna. The COMET programme is conducted by FFG.

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contact Dr. Martin Trinker

Prof. Kurt Faber

Research Management

t: +43 316 380 5332

Business Development

m: kurt.faber@uni-graz.at

t: +43 316 873 9316 fax: +43 316 873 9302 m: martin.trinker@acib.at acib GmbH

Prof. Wolfgang Kroutil t: +43 316 380 5350 m: wolfgang.kroutil@uni-graz.at

austrian centre of industrial biotechnology Petersgasse 14 8010 Graz Austria

Dr. Christoph Winkler t: +43 316 380 8646 m: christoph.winkler@uni-graz.at acib GmbH c/o Department of Chemistry, University of Graz 8010 Graz Austria

w: www.acib.at w: biocatalysis.uni-graz.at www.xing.com/companies/acibgmbh www.linkedin.com/company/acib-gmbh www.facebook.com/acibgmbh

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Notes

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Notes

ring & Technology - eynzmes designed for industry - Biocatalytic Synthesis - enzymatic solutions for chemical problems - Enzyme Engineering & Technology - eynzmes designed

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Notes

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Notes

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