Immobilizing redox enzymes at mesoporous and nanostructured electrodes

Three key challenges are stimulating intensive research in the development of productive direct electron transfer mode enzyme electrodes: proper enzyme orientation, high enzyme loading, and full retention of enzyme activity. In this review, we summarize some significant advances that have been reported in the last years on the design of mesoporous and nanostructured electrodes as enzyme scaffolds and of innovative methodologies for wiring enzymes to electrodes. Particular attention is given to investigations on physical factors that determine a favorable enzyme immobilization, to provide rational guidelines for the design of productive enzymatic electrodes. Finally, some emerging trends focused on the spatial organization of either single enzymes or enzyme cascades are also briefly addressed.     

Glycosyl azide—a novel substrate for enzymatic transglycosylations

Glycosyl azides are new efficient donors for glycosidases. Their high water solubility facilitates transglycosylations with comparable or better yields than common O-glycosides. The azido group totally changes the β-GalNAc-ase/β-GlcNAc-ase ratio in β-N-acetylhexosaminidases (from the usual 0.3-1.0 to <0.01), contrary to all known aglycons.     

Synthesis of β-phenyl-δ,ε-unsaturated amino acids and stereoselective introduction of side chain groups into [4,3,0]-bicyclic β-turn dipeptides

(2S,3S)- and (2R,3R)-2-amino-3-phenyl-5-hexenoic acids have been synthesized in large scale by using Ni(II)-complexes as a template. The amino acids were used in the synthesis of [4,3,0]-bicyclic β-turn mimetics by a convergent methodology. The unique advantage of this strategy is the convenience of introducing side chain groups with predetermined chiralities on both the five- and six-membered heterocyclic rings.     

General Aspects and Optimization of Enantioselective Biocatalysis in Organic Solvents: The Use of Lipases [New Synthetic Methods (76)]

Enantioselective biocatalysis in nonaqueous media is becoming increasingly important in preparative synthetic chemistry. This article discusses (1) the general catalytic properties of enzymes in nonaqueous environments, (2) the basic principles that govern lipase-catalyzed enantioselective esterification and transesterification reactions in organic media for the preparation of optically active acids and alcohols, (3) the determination of kinetic and thermodynamic parameters, and (4) the quantitative analysis of published data.     

Current methods for site-directed structure generation

Summary There has been a rapid growth of interest in techniques for site-directed drug design, fuelled by the increasing availability of structural models of proteins of therapeutic importance, and by studies reported in the literature showing that potent chemical leads can be obtained by these techniques. Structure generation programs offer the prospect of discovering highly original lead structures from novel chemical families. Due to the fact that this technique is more-or-less still in its infancy, there are no case studies available that demonstrate the use of structure generation programs for site-directed drug design. Such programs were first proposed in 1986, and became commercially available in early 1992. They have shown their ability to reproduce, or suggest reasonable alternatives for, ligands in well-defined binding sites. This brief review will discuss the recent advances that have been made in the field of site-directed structure generation.     

Inhibitors of biotin biosynthesis as potential herbicides

Isosteric derivatives and analogues of the 7-keto-8-aminopelargonic acid (KAPA), 7,8-diaminopelargonic acid (DAPA) and desthiobiotin (DTB) vitamer intermediates involved in the biosynthetic pathway of biotin were prepared and evaluated as potential herbicides. The most active compound was desmethyl-KAPA which displayed a GR₅₀ (concentration of the active compound that causes a 50% growth inhibition) value of 8 ppm, where values <50 ppm are considered herbicidal. Other KAPA analogs where the terminal Me group was replaced by bulkier substituents such as Et, i-Pr and HOCH₂ showed moderate activity.