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Biocatalysis and Fine Chemicalsrenewable resources Aspartate Cysteine Glutamate Glycine Lysine Methionine Phenylalanine Threonine Tryptophane Vitamin B1 Pantothenate Vitamin B2 Vitamin B6 Vitamin B12 Vitamin C Vitamin D Biotin Folate Amino acids Vitamins by fermentation

Biocatalysis and Fine Chemicals

renewable resources Aspartate Cysteine Glutamate Glycine Lysine Methionine Phenylalanine Threonine Tryptophane Vitamin B1 Pantothenate Vitamin B2 Vitamin B6 Vitamin B12 Vitamin C Vitamin D Biotin Folate Amino acids Vitamins by fermentation

Riboflavin (Vitamin B2) vitamin (e.g. multivitamin juices) colorant (E-101), e.g. for soft drinks and yogurt animal feed additives > 3000 t/year (Hoffmann-La Roche, BASF, ADM) chemical production (from D-ribose, with 3,4-xylidine in methanol,... with phenyl diazonium halogenide, cyclocondensation with barbituric acid) maximum yield of 60 lot of waste, organic solvents, 25% more energy compared to a biotechnological production

since 1946-68 and then again from 1974 with Ashbya gossypii (filamentous fungus) BASF (Germany): since 1996 exclusively by fermentation with A. gossypii ADM (USA) by Candida famata (yeast) Roche (Switzerland) by Bacillus subtilis (gram-positive bacterium) (50% of the costs of the chemical process)

Metabolic Engineering

Productivity Development time Mutagenesis Metabolic Engineering slides kindly provided by Dr. O. Zelder (BASF) Obviously, we hope to gain new momentum by metabolic engineering

Riboflavin = yellow color = yellow colonies

Vitamin B2 - Synthesis in Ashbya gossypii

16 C3 C18 C2 C4 B2 GTP Catabolism Central Metabolism Biosynthesis B2-Bio-synthesis CO2 Glyoxylate Bypass Purinbio- synthesis Oil β-Oxidation C3 C5

Overproduction of biosynthesis enzymes

Diese waren rib 3,4 und 5.

Vitamin B2 - Synthesis in Ashbya gossypii

16 C3 C18 C2 C4 B2 GTP Catabolism Central Metabolism Biosynthesis B2-Bio-synthesis CO2 Glyoxylate Bypass Purinbio- synthesis Oil β-Oxidation C3 C5

Blockage of Purin Catabolism

N N N N O H H H H O O H 2 O P i Adenosin Nucleotidase Inosin H 2 O P i Guanosin Nucleotidase Ribose-1P P i Hypoxanthin Purin- nucleosid- Phosphorylase (PNP) Ribose-1P P i Guanin Purin- nucleosid- Phosphorylase (PNP) Adenosin- Desaminase H 2 O NH 4 + Guanin- Desaminase H 2 O NH 4 + Xanthin- Oxidase- O 2 +H 2 O H 2 O 2 H 2 O P i Nucleotidase H 2 O O 2 +H 2 O Xanthin- Oxidase- H 2 O P i Xanthosin Nucleotidase Ribose-1P P i Xanthin Purin- nucleosid- Phosphorylase (PNP) AMP- Desaminase H 2 O NH 4 + H N N N N R i b O H N H 2 P N N N N R i b O H O H AMP GMP IMP XMP N N N N R i b O P P N N N N R i b N H 2 P

Purine biosynthesis in A. gossypii

O H O H O H O O P H 2 O O H O H O O P H 2 P 2 O H O H O O P H 2 N H 2 O O H O H O N N N N H O N H 2 P 3 GTP Guanosintriphosphate Ribose-5-Phosphate PRPP Phosphoribosylpyrophosphate PRS1 ADE4 Feedback-Inhibition by Purines The purine biosynthesis starts from ribose-5-phosphate and consists of a large number of enzymatic steps. The pathway is controled by feedback inhibition of the first two steps by purines. That means that increasing end product concentration will decrease the biosynthetic power. Our goal here was to remove the feedback inhibition of this two enzymatic steps. The PRS1 gene responsible for the first step is well known from medicine. Gicht is a disorder of the purine metabolism and has ists molecular reason in mutation in the human PRS1 gene leading to feedback resistant enzyme. We transferred the Gicht causing mutations from the human gene to the gene of Ashbya gossypii. The introduced point mutations result in a reduced sensitivity towards high purine concentrations. Also the second step Glutamin-PRPP Amidotransferase of the purine biosynthetic pathway encoded by the ADE4 gene is inhibited by purines. Fortunately, there was a crystal structure of this enzyme from Bacillus in the database and our molecular modellers were able to identify the critical amino acid residues by molecular modelling employing the Bacillus structure and the Ashbya DNA sequence.

PRPP-Synthase (PRS1) Feedback-deregulation

Purine - Biosynthesis in A. gossypii

O H O H O H O O P H 2 O O H O H O O P H 2 P 2 O H O H O O P H 2 N H 2 O O H O H O N N N N H O N H 2 P 3 GTP Guanosintriphosphate Ribose-5-Phosphate PRPP Phosphoribosylpyrophosphate PRS1 ADE4 Feedback-Inhibition by Purines Feedback-Inhibition by Purines The purine biosynthesis starts from ribose-5-phosphate and consists of a large number of enzymatic steps. The pathway is controled by feedback inhibition of the first two steps by purines. That means that increasing end product concentration will decrease the biosynthetic power. Our goal here was to remove the feedback inhibition of this two enzymatic steps. The PRS1 gene responsible for the first step is well known from medicine. Gicht is a disorder of the purine metabolism and has ists molecular reason in mutation in the human PRS1 gene leading to feedback resistant enzyme. We transferred the Gicht causing mutations from the human gene to the gene of Ashbya gossypii. The introduced point mutations result in a reduced sensitivity towards high purine concentrations. Also the second step Glutamin-PRPP Amidotransferase of the purine biosynthetic pathway encoded by the ADE4 gene is inhibited by purines. Fortunately, there was a crystal structure of this enzyme from Bacillus in the database and our molecular modellers were able to identify the critical amino acid residues by molecular modelling employing the Bacillus structure and the Ashbya DNA sequence.

Glutamine-PRPP-Amidotransferase from Bacillus subtilis

Glutamine-PRPP-Amidotransferase (ADE4) Feedback-Deregulation

Expression of the deregulated ADE-4 gene in Ashbya gossypii

Vitamin B2 - Synthesis in Ashyba gossypii

16 C3 C18 C2 C4 B2 GTP Catabolism Central Metabolism Biosynthesis B2-Bio-synthesis CO2 Glyoxylate Bypass Purinbio- synthesis Oil β-Oxidation C3 C5

increase transcription or copy number of ICL1 encoding isocitrate lyase Glyoxylate cycle

A. gossypii

Candida famata

B. subtilis

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Name: 
Lecture_Cosenza_4
Author: 
t
Company: 
BASF
Description: 
Biocatalysis and Fine Chemicalsrenewable resources Aspartate Cysteine Glutamate Glycine Lysine Methionine Phenylalanine Threonine Tryptophane Vitamin B1 Pantothenate Vitamin B2 Vitamin B6 Vitamin B12 Vitamin C Vitamin D Biotin Folate Amino acids Vitamins by fermentation
Tags: 
vitamin | synthesi | purin | gossypii | ribos | biosynthesi | gtp | prpp
Created: 
10/13/2004 5:29:41 AM
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20
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