Photorelease of phosphates: Mild methods for protecting phosphate derivatives.

We have developed a new photoremovable protecting group for caging phosphates in the near UV. Diethyl 2-(4-hydroxy-1-naphthyl)-2-oxoethyl phosphate (14a) quantitatively releases diethyl phosphate upon irradiation in aq MeOH or aq MeCN at 350 nm, with quantum efficiencies ranging from 0.021 to 0.

-Hydroxyphenacyl photoremovable protecting groups - Robust photochemistry despite substituent diversity.

A broadly based investigation of the effects of a diverse array of substituents on the photochemical rearrangement of hydroxyphenacyl esters has demonstrated that common substituents such as F, MeO, CN, COR, CONH, and CH have little effect on the rate and quantum efficiencies for the photo-Favorskii rearrangement and the release of the acid leaving group or on the lifetimes of the reactive triplet state. A decrease in the quantum yields across all substituents was observed for the release and rearrangement when the photolyses were carried out in buffered aqueous media at pHs that exceeded the ground-state p of the chromophore where the conjugate base is the predominant form. Otherwise, substituents have only a very modest effect on the photoreaction of these robust chromophores.

Collagen cross linking agents: design and development of a multifunctional cross linker.

A new cross linking reagent based on the first-generation polyamidoamine dendrimer (G.1 PAMAM) has been synthesized by reaction of the PAMAM with eight equivalents of p-nitrophenyl diazopyruvate. The resulting water-soluble octadiazopyruvoyl PAMAM (8G.

Bonding corneal tissue: applications of photoactivated diazopyruvoyl cross-linking agent.

Photoactivated bis-diazopyruvamide-N,N'-bis(3-diazopyruvoyl)-2,2'-(ethylenedioxy)bis-(ethylamine), (DPD)-was previously shown to bond materials containing type I collagen. However, tensile strength of bonded collagenous tissue ( approximately 78% water) was low compared with that of dehydrated collagenous gelatin ( approximately 14% water). Here we investigated the role of water in corneal tissue bond strength and in bonding corneal tissue to glass.

A photoactivated diazopyruvoyl cross-linking agent for bonding tissue containing type-I collagen.

On the basis of the earlier examples of diazopyruvoyl (DAP) groups reported by Lawton for covalent binding and cross-linking of proteins and oligopeptides and our recent demonstration that a coumaryl diazopyruvamide was used to label Type-I collagen, we have extended our investigations to the synthesis and cross-linking capabilities of a bis-DAP polyethylene glycol to cross-link Type-I collagen. The new photoactivated cross-linking agent, N,N'-bis(3-diazopyruvoyl)-2,2'-(ethylenedioxy)bis(ethylamine) (DPD, 2), has been designed and synthesized specifically to "weld" collagenous tissues by cross-linking Type-I collagen. A working model for the photochemical welding studies of collagenous tissues was developed using gelatin strips (gel strips) composed of denatured Type-I collagen.