Mandler D, Willner I. Photosensitized NAD(P)H regeneration systems. Application in the reduction of butan-2-one, pyruvic, and acetoacetic acids and in the reductive amination of pyruvic and oxoglutaric acid to amino acid. J. Chem. Soc., Perkin Trans. 2Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999). 1986;(6) :805 - 11.Abstract
NADH and NADPH were formed by a photosensitized enzyme-catalyzed process. NADPH was formed in the presence of ferredoxin NADP-reductase with Ru(bpy)32+ (bpy = 2,2'-bipyridine) as photosensitizer, Me viologen as primary electron acceptor, and (NH4)3 EDTA or 2-mercaptoethanol. Zn(II) meso-tetramethylpyridiniumporphyrin was used as photosensitizer for the photoinduced prodn. of NADH with the same reaction components but with lipoamide dehydrogenase as the enzyme catalyst. The photoinduced NADH/NADPH regeneration systems were coupled to secondary enzyme-catalyzed processes, e.g. the redn. of butan-2-one to butan-2-ol, pyruvic acid to lactic acid, or acetoacetic acid to β-hydroxybytyric acid; coupling to the reductive amination of pyruvic acid to alanine and of α-oxoglutaric acid to glutamic acid was also possible. The products showed high optical purity and the enzymes and coenzymes showed high turnover nos. and stability. [on SciFinder(R)]
Willner I, Goren Z, Mandler D, Maidan R, Degani Y. Transformation of single-electron transfer photoproducts into multielectron charge relays: the functions of water-oil two-phase systems and enzyme catalysis. J. Photochem.Journal of Photochemistry. 1985;28 (2) :215 - 28.Abstract
Water-in-oil microemulsions provide an organized environment that effectively controls photosensitized electron transfer processes. Effective charge sepn. and stabilization of the intermediate photoproducts against back electron transfer processes are achieved by means of hydrophobic and hydrophilic interactions of the photoproducts with the water-oil phases. Water-oil 2-phase systems also provide a means for induced disproportionation of a photogenerated 1-electron transfer product to the corresponding 2-electron charge relay. This induced disproportionation can be achieved by design of opposite soly. properties of the comproportionation products in the 2 phases. The 2-electron charge relay mediates the redn. of meso-1,2-dibromostilbene to trans-stilbene. An alternative route for generating multielectron charge relays involves the enzyme-catalyzed prodn. of NADPH using the 4,4'-bipyridinium radical cation as an electron carrier. NADPH is subsequently utilized in the redn. of 2-butanone to (-)-2-butanol in the presence of the enzyme alc. dehydrogenase. [on SciFinder(R)]
Mandler D, Degani Y, Willner I. Photoredox reactions in water-in-oil microemulsions. The functions of amphiphilic viologens in charge separation and electron transfer across a water-oil boundary. J. Phys. Chem.Journal of Physical Chemistry. 1984;88 (19) :4366 - 70.Abstract
Photosensitized redn. of a series of dialkyl-4,4'-bipyridinium salts, CnV2+, with Cn alkyl of n = 1, 4, 6, 8, 14, and 18 was examd. in water-in-oil microemulsions, by using Ru(bpy)32+ (bpy = 2,2'-bipyridine) [15158-62-0] as sensitizer and (NH4)3 EDTA [15934-01-7] as electron donor. With the amphiphilic electron acceptors (n = 8-18) the water-in-oil microemulsion media effect the charge sepn. of the initial encounter cage complex, and stabilize the photoproducts, CnV+ and Ru(bpy)33+, against the recombination process. Consequently, enhanced quantum yields for CnV+. formation are obsd. under continuous illumination. [on SciFinder(R)]
Mandler D, Willner I. Solar light induced formation of chiral 2-butanol in an enzyme-catalyzed chemical system. J. Am. Chem. Soc.Journal of the American Chemical Society. 1984;106 (18) :5352 - 3.Abstract
The photosensitized prodn. of chiral (-)-2-butanol is accomplished in a chem.-enzyme catalyzed-system in which ruthenium-tris-bipyridine, Ru(bipy)32+, photosensitizes the redn. of dimethyl-4,4'-bipyridinium (methylviologen, MV2+), and the sensitizer is recycled by oxidn. of (NH4)3EDTA. The primary reduced photoproduct, MV+·, mediates the redn. of NADP to NADPH in the presence of ferredoxin-NADP reductase. The final step in the cycle involves the redn. of 2-butanone by NADPH in the presence of alc. dehydrogenase. The optical purity of the formed (-)-2-butanol is 100%. The net reaction that corresponds to the redn. of 2-butanone by (NH4)3EDTA is an endoergic process by ∼33 kcal/mol EDTA consumed. [on SciFinder(R)]