title: Generating singlet oxygen bubbles: a new mechanism for gas-liquid oxidations in water.
abstract: Laser-coupled microphotoreactors were developed to bubble singlet oxygen [(1)O(2) ((1)Δ(g))] into an aqueous solution containing an oxidizable compound. The reactors consisted of custom-modified SMA fiberoptic receptacles loaded with 150 μm silicon phthalocyanine glass sensitizer particles, where the particles were isolated from direct contact with water by a membrane adhesively bonded to the bottom of each device. A tube fed O(2) gas to the reactor chambers. In the presence of O(2), singlet oxygen was generated by illuminating the sensitizer particles with 669 nm light from an optical fiber coupled to the top of the reactor. The generated (1)O(2) was transported through the membrane by the O(2) stream and formed bubbles in solution. In solution, singlet oxygen reacted with probe compounds (9,10-anthracene dipropionate dianion, trans-2-methyl-2-pentanoate anion, N-benzoyl-D,L-methionine, or N-acetyl-D,L-methionine) to give oxidized products in two stages. The early stage was rapid and showed that (1)O(2) transfer occurred via bubbles mainly in the bulk water solution. The later stage was slow; it arose only from (1)O(2)-probe molecule contact at the gas/liquid interface. A mechanism is proposed that involves (1)O(2) mass transfer and solvation, where smaller bubbles provide better penetration of (1)O(2) into the flowing stream due to higher surface-to-volume contact between the probe molecules and (1)O(2).
authors.affiliation: Department of Chemistry, Brooklyn College, City University of New York, Brooklyn, New York 11210, United States.
authors.forename: Dorota
authors.initials: D
authors.lastname: Bartusik
authors.forename: David
authors.initials: D
authors.lastname: Aebisher
authors.forename: BiBi
authors.initials: B
authors.lastname: Ghafari
authors.forename: Alan M
authors.initials: AM
authors.lastname: Lyons
authors.forename: Alexander
authors.initials: A
authors.lastname: Greer
mesh_terms: D005740:Gases / Q000737:chemistry; D007211:Indoles / Q000138:chemical synthesis / Q000737:chemistry; D007834:Lasers; D015394:Molecular Structure; D017646:Organosilicon Compounds / Q000138:chemical synthesis / Q000737:chemistry; D010084:Oxidation-Reduction; D010777:Photochemistry / Q000295:instrumentation / Q000379:methods; D017319:Photosensitizing Agents / Q000138:chemical synthesis / Q000737:chemistry; D026082:Singlet Oxygen / Q000737:chemistry*; D014867:Water / Q000737:chemistry*
chemical_list: D005740:Gases; D007211:Indoles; D017646:Organosilicon Compounds; D017319:Photosensitizing Agents; D014867:Water; C082854:silicon phthalocyanine; D026082:Singlet Oxygen