A5082428188- Carbohydrate Chemistry and Synthesis
- Glycosylation and Glycoproteins Research
- Legume Nitrogen Fixing Symbiosis
- Click Chemistry and Applications
- Marine Biology and Environmental Chemistry
- Metal-Catalyzed Oxygenation Mechanisms
- Diatoms and Algae Research
- Enzyme Catalysis and Immobilization
- Chemical Synthesis and Analysis
- Genomics and Phylogenetic Studies
- Polyoxometalates: Synthesis and Applications
- Enzyme Production and Characterization
- Oxidative Organic Chemistry Reactions
- Covalent Organic Framework Applications
- Advanced NMR Techniques and Applications
- Computational Drug Discovery Methods
- Porphyrin and Phthalocyanine Chemistry
- Catalytic C–H Functionalization Methods
- Lanthanide and Transition Metal Complexes
Delft University of Technology
2017-2024
Leiden University
2018-2023
Abstract Controlling the chemical glycosylation reaction remains major challenge in synthesis of oligosaccharides. Though 1,2- trans glycosidic linkages can be installed using neighboring group participation, construction cis is difficult and has no general solution. Long-range participation (LRP) by distal acyl groups may steer stereoselectivity, but contradictory results have been reported on role strength this stereoelectronic effect. It exceedingly to study bridging dioxolenium ion...
Abstract The reactivity of both coupling partners—the glycosyl donor and acceptor—is decisive for the outcome a glycosylation reaction, in terms yield stereoselectivity. Where donors is well understood can be controlled through manipulation functional/protecting‐group pattern, acceptor alcohols poorly understood. We here present an operationally simple system to gauge reactivity, which employs two conformationally locked with stereoselectivity that critically depends on nucleophile. A wide...
The reactivity of the acceptor alcohol can have a tremendous influence on outcome glycosylation reaction, both in terms yield and stereoselectivity. Through systematic survey 67 alcohols reactions with two glucosyl donors we here reveal how carbohydrate depends its configuration substitution pattern. study shows functional groups flanking show that nature relative orientation play an essential role. empiric guidelines revealed will aid rational optimization be important tool assembly...
Abstract The reactivity of both coupling partners—the glycosyl donor and acceptor—is decisive for the outcome a glycosylation reaction, in terms yield stereoselectivity. Where donors is well understood can be controlled through manipulation functional/protecting‐group pattern, acceptor alcohols poorly understood. We here present an operationally simple system to gauge reactivity, which employs two conformationally locked with stereoselectivity that critically depends on nucleophile. A wide...
A peroxygenase-catalysed hydroxylation of organosilanes is reported. The recombinant peroxygenase from Agrocybe aegerita (AaeUPO) enabled efficient conversion a broad range silane starting materials in attractive productivities (up to 300 mM h-1 ), catalyst performance 84 s-1 and more than 120 000 catalytic turnovers). Molecular modelling the enzyme-substrate interaction puts basis for mechanistic understanding AaeUPO selectivity.
Abstract Biocatalytic oxidation reactions of toluene derivates to the corresponding aldehydes are typically challenged by regio‐ and chemoselectivity issues. In this contribution we address both challenges a combined reactant‐ reaction engineering approach. We demonstrate that peroxygenase‐catalysed transformation ring‐substituted toluenes proceeds highly regioselectively in benzylic position. Furthermore, neat conditions not only enable attractive product concentrations (up 185 mM) but also...
Surface PEGylation of nanoparticles designed for biomedical applications is a common and straightforward way to stabilize the materials in vivo administration increase their circulation time. This strategy becomes less trivial when MRI active porous nanomaterials are concerned as function relies on water/proton-exchange between pores bulk water. Here we present comprehensive study effects relaxometric properties nanozeolite LTL (dimensions 20 × 40 nm) ion-exchanged with paramagnetic GdIII...
Drug discovery programs of covalent irreversible, mechanism-based enzyme inhibitors often focus on optimization potency as determined by IC50-values in biochemical assays. These assays do not allow the characterization binding activity (Ki) and reactivity (kinact) individual kinetic parameters inhibitors. Here, we report development a substrate assay to study influence acidity (pKa) heterocyclic leaving group triazole urea derivatives diacylglycerol lipase (DAGL)-α Surprisingly, found that...
Abstract A peroxygenase‐catalysed hydroxylation of organosilanes is reported. The recombinant peroxygenase from Agrocybe aegerita ( Aae UPO) enabled efficient conversion a broad range silane starting materials in attractive productivities (up to 300 mM h −1 ), catalyst performance 84 s and more than 120 000 catalytic turnovers). Molecular modelling the enzyme‐substrate interaction puts basis for mechanistic understanding UPO selectivity.
Controlling the chemical glycosylation reaction remains major challenge in synthesis of oligosaccharides. Though 1,2- trans glycosidic linkages can be installed using neighboring group participation, construction cis is difficult and has no general solution. Long-range participation (LRP) by distal acyl groups may steer stereoselectivity, but contradictory results have been reported on role strength this stereoelectronic effect. It exceedingly to study bridging dioxolenium ion intermediates...
Abstract Ene‐reductases from the old yellow enzyme (OYE) family have been traditionally employed in reduction of conjugated C═C double bonds. This study explores underutilized oxidative potential OYEs, demonstrating their capability to catalyze enantioselective desaturation carbonyl compounds. Utilizing a deprotonated tyrosine residue as catalytic base, we developed method enable OYE‐catalyzed at ambient temperature and alkaline pH without need for high‐temperature conditions. Through...
Controlling the chemical glycosylation reaction remains major challenge in synthesis of oligosaccharides. Though 1,2-<i>trans</i> glycosidic linkages can be installed using neighboring group participation, construction 1,2-<i>cis</i> is difficult and has no general solution. Long-range participation (LRP) by distal acyl groups may steer stereoselectivity, but contradictory results have been reported on role strength this stereoelectronic effect. It exceedingly to...
Die Stereoselektivität von Glykosylierungen kann ganz zentral der Reaktivität des Akzeptor-Glykosids (des Nukleophils in Reaktion) abhängen. J. D. Codée et al. berichten ihrer Zuschrift auf S. 8372 ff. über ein einfaches System, um die Beziehung zwischen Glykosyl-Akzeptors und Glykosylierung zu kartieren. Feinabstimmung durch sorgfältige Wahl Schutzgruppen ermöglicht stereoselektive 1,2-cis-Glykosylierungen. Carbenchemie Proteinmarkierung Breslow-Intermediate