Glucose biomimetics

Parmpi P, Kofinas P. Biomimetic glucose recognition using molecularly imprinted polymer hydrogels. Biomaterials 2004, 25, 1969-1973. 

Hilt JZ, Byrne ME, Peppas NA. Microfabrication of intelligent biomimetic networks for recognition of D-glucose. Chemistry of Materials 2006, 18, 5869-5875. 

Beyond the complete assembly of biomimetic membranes, interfacial supramolec-ular assemblies which incorporate biocomponents represent an important approach to replicating the biological functions outside of living systems. For example, the ability to link or wire otherwise electro-inactive enzymes to electrodes so that they can efficiently transport electrons allows sensitive and selective sensors to be developed for important bioactive molecules, e.g. glucose, lactate, urea, etc. 

The use of peroxide sensors has been extended to the sensing of glucose, lactate, alcohol, oxalate, glutamate and other amino acids by coimmobilization of the respective oxidase on top of the peroxidase [7,8,228,229], and furthermore, to afl nity-based assays [130,131,217,273]. An octane sensor was created by layering a porphyrin type P450-mimics on a screen-printed HRP-modified carbon electrode (Fig. 2.13) [106]. The biomimetic catalyst (iron(III)-meso-tetrakis-(pentafluorophenyl)-p-tetrasulfonatopor-phyrin chloride) was linked to the electrode with polyallylamine on the basis... 

The construction of only the (S)-hexahydroxydiphenyl unit, a structural analog of secondary plant metabolite ellagitannins, by biomimetic cyclization of suitably protected glucose-derived digaUoyl esters has been achieved by use of lead tetraacetate (Scheme 13.32). No quinone ketal-type product was detected, in contrast to the simpler system described below (Scheme 13.37). 

P. Manini, M. d Ischia, and G. Prota, An unusual decarboxylative Maillard reaction between l-DOPA and o-glucose under biomimetic conditions Factors governing competition with Pictet-Spengler condensation, J. Org. Chem., 66 (2001) 5048-5053. 

The approach using cyclodextrin as a binding site has also been developed. Cyclodextrins are widely utilized in biomimetic chemistry as simple models for an enzyme because they have the ability to form inclusion complexes with a variety of molecules and because they have catalytic activity toward some reactions. Kojima et al. (1980, 1981) reported the acceleration in the reduction of ninhydrin and some dyes by a 1,4-dihydronicotinamide attached to 3 Cyclodextrin. Saturation kinetics similar to enzymatic reactions were observed here, which indicates that the reduction proceeds through a complex. Since the cavity of the cyclodextrin molecule has a chiral environment due to the asymmetry of D-glucose units, these chiralities are expected to be effective for the induction of asymmetry into the substrate. Asymmetric reduction with NAD(P)H models of this type, however, has not been reported. Asymmetric reduction by a 1,4-dihydronicotinamide derivative took place in an aqueous solution of cyclodextrin (Baba et al. 1978), although the optical yield from the reduction was quite low. Trifluoromethyl aryl ketones were reduced by PNAH in 1.1 to 5.8 % e.e. in the presence of 3-cyclodextrin. Sodium borohydride works as well (Table 18). In addition to cyclodextrin, Baba et al. also found that the asymmetric reductions can be accomplished in the presence of bovine serum albumin (BSA) which is a carrier protein in plasma. 

Carbohydrates have again been used as chiral precursors for the total synthesis of other natural products, including thromboxane Bj, ( —)-isoavenaciolide, and insect pheromones - but pride of place must be given to a total synthesis of (-l-)-biotin from o-glucose in which a biomimetic transformation was used in forming the tetrahydrothiophen ring (Chapter 23). 

Gun J., Lev O. Sol-gel derived, ferrocenyl-modified silicate-graphite composite electrode Wiring of glucose oxidase. Anal. Chim. Acta 1996b 336(1-3) 95-106 Guo Y.Z., Guadalupe A.R. Screen-printable surfactant-induced sol-gel graphite coirposites for electrochemical sensors. Sensors Actuators B Chem. 1998 46(3) 213-219 Haupt K., Mosbach K. Molecularly imprinted pol3uners and their use in biomimetic sensors. Chem. Rev. 2000 100(7) 2495-2504... 

The Perrier reaction has also been used to prepare some novel methyl-branched tetrahydroxycyclohexanone daivatives such as (48) and (49). Purther applications of the same reaction has led to the preparation of 23,6-tri-O-benzyl-D-myo-inositol from D-glucose, via the intermediate Cj-symmetric cyclohexene (50) and to a biomimetic synthesis of D-myo-inositol derivatives as illustrated in Scheme 11. ... 

Dai X-H, Dong C-M, Yan D (2008) Supramolecular and biomimetic polypseudorotaxane/ glycopolymer biohybrids synthesis, glucose-surfaced nanoparticles, and recognition with lectin. J Phys Chem B 112(12) 3644-3652... 

---