[New approach to the study of interaction of amino acid side groups with aryl azides]. / Novyi podkhod k izucheniiu vzaimodeistviia aminokislot po ikh bokovym radikalam s arilazidami.

A new approach to the study of the interaction of amino acid side chains with photoreactive aryl azides was proposed. This approach was based on the drawing together of the reacting groups by the attachment of the reacting compounds to complementary oligonucleotides. Cystamine, histamine, and 1,6-hexamethylenediamine mimicking the cystine, histidine, and lysine residues, respectively, were attached to the 3'-terminal phosphate of the oligonucleotide GGTATCp through a phosphamide bond and used as the targets for photomodification. Derivatives of the oligonucleotide pGATACCAA with the fragment N3C6H4NH- attached directly to its 5'-end by a phosphamide bond or through the spacer -(CH2)nNH- (where n is 2, 4, and 6) were used as photoreagents. Their derivatives containing the same spacer and the N3C6F4CO-NH(CH2)3NH- or 2-N3,5-NO2-C6H3CO-NH(CH2)3NH- residues were also used. The duplexes were photomodified by irradiation with 300-350 nm wavelength light. The maximal yields of the photo-cross-linking were from 22 to 68%. The reagents containing p-azidoaniline residue were found to be the most effective toward the targets. The maximum yields of the photomodification products modeling the side chains of cysteine and lysine were found to vary from 40 to 67% and to depend on the length and the structure of the spacers used. The duplex with the target bearing the imidazole residue (the histidine model) manifested a yield decreased to 25%. This fact was in a good agreement with the data of computer modeling that indicated an unfavorable mutual displacement of the imidazole residue and the photoreactive group.

Free radical production by Nd:YAG laser photodisruption.

BACKGROUND AND OBJECTIVES: Plasma and cavitation bubble formation during optical breakdown in aqueous media may produce hydroxyl (*OH) radicals. The authors' objectives were to detect *OH produced by a neodymium:yttrium-aluminum-garnet (Nd:YAG) laser photodisruptor and to determine *OH concentration in relation to laser energy. MATERIALS AND METHODS: *OH was assayed by measuring absorbance of triiodide (I3-) in a potassium iodide (KI) solution exposed to optical breakdown by an Nd:YAG laser. The concentration-dependent reduction of radical production in relation to cystamine concentration was evaluated. RESULTS: I3- concentration increased linearly with total irradiation energy and decreased exponentially with increasing cystamine concentration. *OH concentration was calculated using extinction coefficients of I3- and chemical equations relating I3- formation to *OH. CONCLUSIONS: The authors calculated that approximately 4 x 10(-12) moles of *OH are produced in a typical posterior capsulotomy of 100 mJ of total energy. This *OH concentration could produce strand breaks in approximately 0.4% of vitreous hyaluronic acid molecules, but is unlikely to produce clinical effects.