- Chemical Synthesis of d -glycero- d -manno-Heptose 1,7-Bisphosphate and Evaluation of Its Ability to Modulate NF-κB Activation
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D-glycero-d-manno-Heptose 1,7-bisphosphate (HBP) is the precursor for heptose residues found in Gram-negative bacterial membrane surface glycoproteins and glycolipids. HBP β-anomer was recently reported to be a pathogen-associated molecular pattern (PAMP) that regulates TIFA-dependent immunity. Herein, we report the chemical synthesis of HBP α- and β-anomers, which highlights a C-7 carbon homologation via the Corey-Chaykovsky reaction, and the introduction of a phosphate group at the anomeric position using the Mitsunobu reaction. Furthermore, NF-κB reporter assaying revealed that HBP β-anomer activates the NF-κB signaling pathway.
- Inuki, Shinsuke,Aiba, Toshihiko,Kawakami, Shota,Akiyama, Taishin,Inoue, Jun-Ichiro,Fujimoto, Yukari
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p. 3079 - 3082
(2017/06/23)
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- The cofactor Mg2+ - A key switch for effective continuous enzymatic production of GDP-mannose using recombinant GDP-mannose pyrophosphorylase
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The aim of the presented work is the chemoenzymatic synthesis of GDP- mannose (GDP-Man). Mannose-1-phosphate (Man-1-P) is synthesised by a very convenient chemical method and is activated with GTP and recombinant GDP- mannose pyrophosphorylase (GDP-Man PP) to give GDP-Man. The productivity of the process is improved using reaction engineering techniques. Detailed kinetic studies, modelling of the reaction and simulations of different reaction systems revealed that besides a strong product inhibition the cofactor Mg2+ is a key switch for effective enzymatic synthesis. Using a two-stage cascade of enzyme membrane reactors, GDP-Man could be produced continuously with a space-time yield of 28 gL-1 d-1 and an enzyme consumption of 0.9 Ug-1, which means a six-fold improvement related to batch synthesis.
- Fey, Sven,Elling, Lothar,Kragl, Udo
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p. 475 - 481
(2007/10/03)
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- Chemo-enzymic Synthesis of Guanosine 5'-Diphosphomannose (GDP-Mannose) and Selected Analogues
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Guanosine 5'-diphosphomannose (GDP-mannose, 1) has been prepared via two routes from α-D-mannose 1-phosphate 5.The non-enzymic route involves coupling of the phosphate 5 to guanosine 5'-monophosphate dibutyl phosphinothioic anhydride (GMP-anhydride 11) to give compound 1 in 40percent yield.The enzymic routes require coupling of compound 5 with guanosine 5'-triphosphate (GTP) catalysed by GDP-mannose pyrophosphorylase (37percent).
- Pallanca, Jane E.,Turner, Nicolas J.
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p. 3017 - 3022
(2007/10/02)
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- DIBENZYL PHOSPHORFLUORIDATE, A NEW PHOSPHORYLATING AGENT
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The first synthesis of dibenzyl phosphorofluoridate and its utility as a phosphorylating agent are described.
- Watanabe, Yutaka,Hyodo, Nobuyuki,Ozaki, Shoichiro
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p. 5763 - 5764
(2007/10/02)
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- Glycosyl Imidates, 10. - Glycosyl Phosphates from Glycosyl Trichloroacetimidates
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The glycosyl trichloroacetimidates 1-α,β, 8-α, 11-α, 13-α, 15-α, and 17-α directly transfer the glycosyl moiety to phosphoric acid mono- and diesters.The acidity of the phosphoric acid derivatives used was sufficient for the activation of the trichloroacetimidates, therefore an additional acidic catalyst was not required.From the β-imidate 1-β α-glycosyl phosphate and from the α-imidates preferentially β-glycosyl phosphates were obtained.Reaction of dibenzyl phosphate (2a) and cetyl phosphate (2c) with 1-α demonstrated that β/α-anomerization iscatalyzed by traces of acid.The glycosyl phosphates 3a-α, 3a-β - 3c-β, 3f-α, 9a-β, and 9c-β were partly or totally deprotected.The structures of the synthezised compounds were assigned by 1H NMR spectroscopy and by comparison with literature data.
- Schmidt, Richard R.,Stumpp, Michael
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p. 680 - 691
(2007/10/02)
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