Photoreduction of CHCl3 in Aqueous SPEEK/HCO2- Solutions Involving Free Radicals.

Exposure of sulfonated poly(ether etherketone), SPEEK, in aqueous solutions to 350 nm photons induced reduction of CHCl3 to CH2Cl2 and chloride ions in the presence of HCO2H/HCO2- buffers or poly(vinyl alcohol), PVA. The kinetics of the SPEEK-sensitized photoreaction was characterized by quantum yields of halide ion formation, ϕ(Cl-), evaluated from in situ determinations of [Cl-]. Particularly efficient reductions took place when formate buffers served as H atom donors in the absence of air and with excess CHCl3. The dependence of ϕ(Cl-) on the inverse square root of the light intensity together with postirradiation formation of Cl- in the dark indicated that the CHCl3 photoreduction occurred via a chain process. EPR determinations identified the α-hydroxy radical of SPEEK and •CHCl2 as chain carriers. Most of the kinetic findings were rationalized in terms of a free radical mechanism where dimerizations of the radicals acted as termination steps. Photoreduction of CHCl3 was also detected in the presence of air albeit with lower quantum efficiencies. Observations made during postirradiation experiments indicated that a chain process was also operative under such conditions.

Radical Chain Reduction of CCl4 Initiated by Illumination of SPEEK Solutions.

Efficient reduction of CCl4 took place upon exposure to 350-nm photons of aqueous solutions containing sulfonated poly(ether etherketone) (SPEEK) as a sensitizer and either poly(vinyl alcohol) (PVA) or HCO2H/HCO2- buffer. The photoreaction formed chloride ions whose concentration increased linearly with time in solutions free of O2, whereas slower reductions occurred in the presence of air. Utilization of formate buffer as the H-atom donor yielded photoreactions at least 10 times faster than those in the presence of PVA and generated CHCl3 as another reaction product. The quantum yield of chloride ion formation, ø(Cl-), was found to be a function of both the SPEEK concentration and concentration of formate buffer. Whereas the quantum efficiency increased steadily with decreasing solution acidity, a drastic surge in the reaction rate occurred in neutral solutions. ø(Cl-) first increased rapidly to a maximum value exceeding 1 at pH 7.3 and then decreased thereafter. The dependence of r(Cl-) on (I0)1/2, where I0 is the light intensity, and the occurrence of postirradiation formation of Cl- through the reduction of CCl4 in the dark are further evidence that the photoreaction proceeded by a chain process. Several of the kinetic features were rationalized by means of a mechanism involving the α-hydroxy radicals of SPEEK and •CCl3 as chain carriers.

Photogeneration of H2O2 in Water-Swollen SPEEK/PVA Polymer Films.

Efficient reduction of O2 took place via illumination with 350 nm photons of cross-linked films containing a blend of sulfonated poly(ether etherketone) and poly(vinyl alcohol) in contact with air-saturated aqueous solutions. Swelling of the solid macromolecular matrices in H2O enabled O2 diffusion into the films and also continuous extraction of the photogenerated H2O2, which was the basis for a method that allowed quantification of the product. Peroxide formed with similar efficiencies in films containing sulfonated polyketones prepared from different precursors and the initial photochemical process was found to be the rate-determining step. Generation of H2O2 was most proficient in the range of 4.9 ≤ pH ≤ 8 with a quantum yield of 0.2, which was 10 times higher than the efficiencies determined for solutions of the polymer blend. Increases in temperature as well as [O2] in solution were factors that enhanced the H2O2 generation. H2O2 quantum yields as high as 0.6 were achieved in H2O/CH3CN mixtures with low water concentrations, but peroxide no longer formed when film swelling was suppressed. A mechanism involving reduction of O2 by photogenerated α-hydroxy radicals from the polyketone in competition with second-order radical decay processes explains the kinetic features. Higher yields result from the films because cross-links present in them hinder diffusion of the radicals, limiting their decay and enhancing the oxygen reduction pathway.

Photogeneration of H2O2 in SPEEK/PVA aqueous polymer solutions.

Photolysis of air-saturated aqueous solutions containing sulphonated poly(ether etherketone) and poly(vinyl alcohol) results in the generation of hydrogen peroxide. Consumption of oxygen and H2O2 formation are initially concurrent processes with a quantum yield of peroxide generation of 0.02 in stirred or unstirred solutions within the range of 7 ≤ pH ≤ 9. The results are rationalized in terms of O2 reduction by photogenerated α-hydroxy radicals of the polymeric ketone in competition with radical-radical processes that consume the macromolecular reducing agents. Generation of H2O2 is controlled by the photochemical transformation that produces the polymer radicals, which is most efficient in neutral and slightly alkaline solutions. Quenching of the excited state of the polyketone by both H3O(+) and OH(-) affect the yields of the reducing macromolecular radicals and of H2O2. Deprotonation of the α-hydroxy polymeric radicals at pH > 9 accelerate their decay and contribute to suppressing the peroxide yields in basic solutions. Maxima in [H2O2] are observed when illuminations are performed with static systems, where O2 reduction is faster than diffusion of oxygen into the solutions. Under such conditions H2O2 can compete with O2 for the reducing radicals resulting in a consumption of the peroxide.

Sulfonated poly(ether ether ketone)/poly(vinyl alcohol) sensitizing system for solution photogeneration of small Ag, Au, and Cu crystallites.

Illumination of air-free aqueous solutions containing sulfonated poly(ether ether ketone) and poly(vinyl alcohol) with 350 nm light results in benzophenone ketyl radicals of the polyketone. The polymer radicals form with a quantum yield 0.02 and decay with a second-order rate constant 6 orders of magnitude lower than that of typical alpha-hydroxy radicals. Evidence is presented that the polymeric benzophenone ketyl radicals reduce Ag+, Cu2+, and AuCl4- to metal particles of nanometer dimensions. Decreases in the reduction rates with increasing Ag(I), Cu(II), and Au(III) concentrations are explained using a kinetic model in which the metal ions quench the excited state of the polymeric benzophenone groups, which forms the macromolecular radicals. Quenching is fastest for Ag+, whereas Cu2+ and AuCl4- exhibit similar rate constants. Particle formation becomes more complex as the number of equivalents needed to reduce the metal ions increases; the Au(III) system is an extreme case where the radical reactions operate in parallel with secondary light-initiated and thermal reduction channels. For each metal ion, the polymer-initiated photoreactions produce crystallites possessing distinct properties, such as a very strong plasmon in the Ag case or the narrow size distribution exhibited by Au particles.

Polymer-initiated photogeneration of silver nanoparticles in SPEEK/PVA films: direct metal photopatterning.

Cross-linking of sulfonated poly(ether-ether)ketone-poly(vinyl alcohol) (SPEEK-PVA) materials yields flexible polymer films, possessing high light-sensitivity and ion-exchange capabilities. Adsorbed Ag+ ions are photoreduced in the film under illumination (lambda = 350 nm), leading to metal nanoparticle formation in places where the film has been exposed to the light. Nanoparticles form via reduction of Ag+ by the polymeric alcohol radicals, generated in the system as a result of photochemical H-abstraction from PVA molecules by the excited carbonyl triplet state of SPEEK. Use of the films for direct metal photopatterning is demonstrated.

Attitudes toward people with disabilities and judgments of employment potential.

The relationship between employers' expressed attitudes toward people with disabilities and their impressions of the employment potential of female job applicants was investigated. 120 subjects viewed videotapes of a simulated interview situation which included either an able-bodied applicant, one on crutches, or one in a wheelchair. The dependent measures included a scale for employment characteristics and management potential and the Attitudes Toward Disabled Persons Scale. Analysis of variance showed the applicants depicted as disabled were rated higher on the employment characteristics and management potential scales than the able-bodies applicant. Mean scores on the Attitudes Toward Disabled Persons Scale were also higher for all depictions of physical condition than published norm indicate. This group of employers appeared to be positively oriented toward people with disabilities.

Metabolic effects of liquid protein.

In the first experiment, the liquid protein product (LP) tested would not support growth in rats when fed at the 8% protein level in an otherwise nutritionally adequate diet. The product was composed of an imbalanced mixture of amino acids which could not be used optimally for protein synthesis and which resulted in appetite depression. Total plasma nonessential amino acids increased significantly in the rats receiving LP, while total plasma essential amino acids were not significantly different. In the second experiment, the LP reducing diet caused rapid weight loss. Adequate vitamin-mineral supplementation given to the rats receiving the LP diet apparently prevented heart and plasma electrolyte abnormalities.