Photocatalytic oxidation of multicomponent mixtures of estrogens (estrone (E1), 17β-estradiol (E2), 17α-ethynylestradiol (EE2) and estriol (E3)) under UVA and UVC radiation: Photon absorption, quantum yields and rate constants independent of photon absorption

2010 ◽  
Vol 99 (3-4) ◽  
pp. 388-397 ◽  
Author(s):  
Gianluca Li Puma ◽  
Valeria Puddu ◽  
Hin Kit Tsang ◽  
Alexander Gora ◽  
Bea Toepfer
Keyword(s):  
Rate Constants ◽  
Photocatalytic Oxidation ◽  
Photon Absorption ◽  
Quantum Yields ◽  
Multicomponent Mixtures ◽  
17Β Estradiol ◽  
Uvc Radiation

Mechanistic studies of aromatic ketone-sensitized photoreduction of bis(acetylacetonato)copper(II)

1983 ◽  
Vol 61 (5) ◽  
pp. 801-808 ◽  
Author(s):  
Yuan L. Chow ◽  
Gonzalo E. Buono-Core ◽  
Bronislaw Marciniak ◽  
Carol Beddard
Keyword(s):  
Rate Constant ◽  
Rate Constants ◽  
Flash Photolysis ◽  
Decay Rates ◽  
Polynuclear Aromatic Hydrocarbons ◽  
Aromatic Ketone ◽  
Quantum Yields ◽  
Triplet States ◽  
Quenching Rate ◽  
Triplet Energy

Bis(acetylacetonato)copper(II), Cu(acac)2, quenches triplet excited states of ketones and polynuclear aromatic hydrocarbons efficiently, but only aromatic ketones with high triplet energy successfully sensitize photoreduction of Cu(acac)2 in alcohols under nitrogen to give derivatives of aeetylacetonatocopper(I), Cu(acac). For the triplet state benzophenone-sensitized photoreduction of Cu(acac)2, the quantum yields of photoreduction (ΦC) and those of benzophenone disappearance (ΦB) were determined in methanol with various concentrations of Cu(acac)2. The values of the quenching rate constant, kq, determined from these two types of monitors on the basis of the proposed mechanism were in good agreement (6.89 ~ 7.35 × 109 M−1 s−1). This value was higher, by a factor of about two, than that obtained from the monitor of the benzophenone triplet decay rates generated by flash photolysis in the presence of Cu(acac)2. The quenching rate constants of various aromatic ketone and hydrocarbon triplet states by Cu(acac)2 were determined by flash photolysis to be in the order of the diffusion rate constant and the quantum yields of these photoreductions were found to be far from unity. Paramagnetic quenching, with contributions of electron exchange and charge transfer, was proposed as a possible quenching mechanism. For a series of aromatic ketone sensitizers with higher triplet energy, this mechanism was used to rationalize the observed high quenching rate constants in contrast to the low quantum yields of photoreduction.

Wavelength controlled production of SO4- radicals in the ultraviolet photolysis of ceric sulfate solutions

1984 ◽  
Vol 37 (3) ◽  
pp. 475 ◽  
Author(s):  
RW Matthews
Keyword(s):  
Rate Constants ◽  
Photochemical Reaction ◽  
Transfer Reaction ◽  
Quantum Yields ◽  
Oh Radical ◽  
Transfer Energy ◽  
Fluorescence Measurements ◽  
Sulfate Solutions ◽  
Ultraviolet Photolysis ◽  
Primary Photochemical Reaction

Solutions of cerium(III)/(IV) and formic acid in 0.4 M sulfuric acid have been photolysed under 254 nm and 365 nm light. Marked differences in the reaction kinetics and quantum yields are observed at the two different wavelengths. At 365 nm, the reactions leading to cerium(IV) reduction are caused almost exclusively by the SO4- radical. The ratio of rate constants, k(SO4- + CeIII)/ k(SO4- + HCOOH), is 116 � 11 and the quantum yield of sulfate radicals, ф(SO4-), is 0.023 � 0.002. At 254 nm, the reactions leading to cerium(IV) reduction are caused mainly by the OH radical, but approximately 35% of the oxidizing radicals formed in the primary photochemical reaction are SO4-. Cerium(III) species, excited at 254 nm, transfer energy to cerium(IV) and this results in an additional yield of OH and SO4- radicals. Fluorescence measurements confirmed the efficiency of the energy transfer reaction. The ratio of rate constants, k(OH+CeIII)/k(OH+HCOOH), is 2.22 � 0.18 and ф(CeIV*) and ф(CelIII*) giving oxidizing radicals are 0.116 � 0.010 and 0.0083 � 0.0008 respectively. Thus about 5 times more total oxidizing radicals are produced from excited cerium(IV) species at 254 nm than at 365 nm.

Assessing Estrogenic Activities of Selected Endocrine Disrupting Chemicals and their Combination Effects

2013 ◽  
Vol 765-767 ◽  
pp. 2944-2948 ◽  
Author(s):  
Xiao Ling Shao ◽  
Wen Qi Zhong ◽  
Xiao Yan Ma ◽  
Ang Gao ◽  
Xiang Yang Wu ◽  
...  
Keyword(s):  
Binary Systems ◽  
Endocrine Disrupting Chemicals ◽  
Concentration Addition ◽  
Multicomponent Mixtures ◽  
Yeast Two Hybrid ◽  
Yeast Two Hybrid System ◽  
Endocrine Disrupting ◽  
17Β Estradiol ◽  
Ethylhexyl Phthalate ◽  
Two Hybrid

Yeast two-hybrid system was used to investigate the estrogenic activities of 13 kinds of representative endocrine disrupting chemicals (EDCs) and their combinary effects. Results show that the order of estrogenic potencies for these chemicals is: 17α-ethynylestradiol>diethylstilbestrol >17β-estradiol>estrone>estriol>branchedp-nonylphenol>4-t-octylphenol>bisphenol A>diethyl phthalate>4-n-nonylphenol>di-(2-ethylhexyl) phthalate>dibutyl phthalate>dimethyl phthalate. The mixture effects of multiple EDCs were compared to those obtained from individual chemicals, using the model of concentration addition. Results reveal that the estrogenicities of multicomponent mixtures of more than three (including three) of EDCs follow antagonistic effects, while there is no definite conclusion for binary systems. The less than additive effects were also confirmed in the spiked experiments conducted in the extracts of real water samples.

Inorganic greywater matrix impact on photocatalytic oxidation: does flocculation of TiO2 nanoparticles impair process efficiency?

2011 ◽  
Vol 63 (12) ◽  
pp. 2808-2813 ◽  
Author(s):  
A. Armanious ◽  
A. Özkan ◽  
U. Sohmen ◽  
H. Gulyas
Keyword(s):  
Rate Constants ◽  
Electric Double Layer ◽  
Photocatalytic Oxidation ◽  
Process Efficiency ◽  
Point Of Zero Charge ◽  
Inorganic Salts ◽  
Co2 Absorption ◽  
Oh Radical ◽  
Radical Scavengers ◽  
Subsequent Formation

This study was conducted in order to clarify whether photocatalyst flocculation – as observed in biologically pretreated greywater – contributes to photocatalytic oxidation (PCO) efficiency impairment. Aqueous solutions of tetraethyleneglycol dimethylether spiked with different inorganic salts in concentrations as found in biologically treated greywater were investigated with respect to TiO2 flocculation and PCO mineralisation kinetics. Flocculation of the photocatalyst primarily depended on pH (which was affected by the salts) and how close pH was to the point of zero charge (PZC). Photocatalyst agglomeration was maximum at pH 5.5. With salt concentrations >7 mmol L−1, flocculation was strong even at pH far above PZC due to electric double layer compression. PCO rate constants were not unequivocally related to flocculation. Increasing pH was observed as the clearest factor deteriorating PCO efficiency. This was interpreted to result from impaired adsorbability of negatively charged oxidation intermediates as well as from enhanced CO2 absorption with increasing pH and subsequent formation of HCO3− anions which are OH radical scavengers.

The determination of oxidation rates and quantum yields during the photocatalytic oxidation of As(III) over TiO2

2021 ◽  
pp. 113628
Author(s):  
Hany Fathy Heiba ◽  
Jay C. Bullen ◽  
Andreas Kafizas ◽  
Camille Petit ◽  
Stephen J Skinner ◽  
...  
Keyword(s):  
Photocatalytic Oxidation ◽  
Quantum Yields ◽  
Oxidation Rates

scholarly journals Laboratory-scale photomineralisation of n-alkanes in aqueous solution, by photocatalytic membranes immobilising titanium dioxide

2005 ◽  
Vol 7 (2) ◽  
pp. 79-85 ◽  
Author(s):  
Ignazio Renato Bellobono ◽  
Franca Morazzoni ◽  
Riccardo Bianchi ◽  
Emilia Simona Mangone ◽  
Rodica Stanescu ◽  
...  
Keyword(s):  
Aqueous Solution ◽  
Photocatalytic Oxidation ◽  
Point Of View ◽  
Laboratory Scale ◽  
Kinetic Constants ◽  
Quantum Yields ◽  
Oxidation Of Methane ◽  
Oxygen Donor ◽  
Absorbed Power ◽  
Kinetics Of

Kinetics of photocatalytic oxidation of methane, ethane,n-heptane,n-decane, andn-dodecane, to yield intermediates, and photomineralisation of intermediates, to yield carbon dioxide and water, was studied in aqueous solution, by a laboratory-scale photoreactor and photocatalytic membranes immobilizing30±3wt.% ofTiO2, in the presence of stoichiometric hydrogen peroxide as oxygen donor. The whole volume of irradiated solution was4.000±0.005L, the ratio between this volume and the geometrical apparent surface of the irradiated side of the photocatalytic membrane was3.8±0.1cm, and the absorbed power 0.30W/cm (cylindrical geometry). A kinetic model was used, by which mineralisation of substrate toCO2was supposed to occur, by kinetic constantsk1, through one single intermediate, mediating the behaviour of all the numerous real intermediates formed in the path from the substrate toCO2(kinetic constants of formation of the latter beingk2). A competitive Langmuirian adsorption of both substrate and “intermediate” was also supposed to be operative, as expressed by apparent adsorption constantsk1andk2, possessing a, partly at least, kinetic significance. By Langmuir-Hinshelwood treatment of initial rate data, starting values of thekandKcouples were obtained, from which, by a set of differential equations, the final optimised parameters,k1andk1,k2andK2, were calculated, able fit the whole photomineralisation curve, and not only its initial segment, as the Langmuirian parameters do. The parameters of present work are critically compared with those obtained in two preceding set of studies relative ton-alkanoic acids and ton-alkanols. They are interpreted on the basis of a closer behaviour of hydrocarbons to alkanols, from the photocatalytic point of view, than to carboxylic acids are. Discussion of limiting effective quantum yields, and their comparison with maximum, theoretical values, are also carried out.

ABSORPTION, EMISSION AND NONLINEAR SPECTROSCOPIC CHARACTERIZATION OF REACTIVE DYE

2006 ◽  
Vol 15 (04) ◽  
pp. 481-490
Author(s):  
SHENG-LI GUO ◽  
ZHUN GUO ◽  
T. SUSDORF ◽  
TIAN-DE CAO
Keyword(s):  
Ground State ◽  
Nonlinear Optical ◽  
Spectroscopic Characterization ◽  
Reactive Dye ◽  
Mode Locking ◽  
Photon Absorption ◽  
Quantum Yields ◽  
Saturable Absorption ◽  
Potential Candidate ◽  
Reactive Orange

An optical spectroscopic characterization is carried out on a reactive dye (reactive orange 1). This dye is widely applied in textile coloration. It is a potential candidate for photonics applications. Its absorption cross-section spectra are measured. A fluorescence spectroscopic characterization is undertaken by measuring the fluorescence quantum distributions and fluorescence quantum yields. The saturable absorption is studied by nonlinear transmission measurements with intense picosecond laser pulses (second harmonic pulses of a mode-locked Nd :glass laser). The nonlinear optical absorption and refraction coefficients are measured by using the top-hat Z-scan technique at a wavelength of 532 nm with 35 ps duration pulses. Reactive orange 1 has the two-photon absorption coefficient of 1.20 cm/GW and the nonlinear refraction coefficient of -7.33 × 10-6 cm2/GW, respectively. In reactive orange 1, there occurs fast ground-state recovery by internal conversion likely via conical intersections. Low excited-state absorption and fast ground-state absorption recovery make it an ideal candidate for passive mode-locking of picosecond and femtosecond lasers as well as for fast nonlinear optical gating.

Synthesis, DNA photocleavage, singlet oxygen photogeneration and two photon absorption properties of ruthenium-phenanthroline porphyrins

2015 ◽  
Vol 19 (09) ◽  
pp. 1046-1052 ◽  
Author(s):  
Ze-Bin Xu ◽  
Fa-Quan Yu ◽  
Fengshou Wu ◽  
Heng Zhang ◽  
Kai Wang ◽  
...  
Keyword(s):  
Singlet Oxygen ◽  
Cross Section ◽  
Therapeutic Agents ◽  
Photon Absorption ◽  
Quantum Yields ◽  
Absorption Properties ◽  
Dna Photocleavage ◽  
Two Photon Absorption ◽  
Two Photon ◽  
Photochemical Properties

Through a new synthetic route, three ruthenium-phenanthroline porphyrins (RPP1, RPP2 and RPP3) were prepared. Their photophysical and photochemical properties, such as DNA photocleavage activity, singlet-oxygen photogeneration and two-photon absorption (2PA) were evaluated. These porphyrins 1–3 had substantial photocleavage activities, with 71%, 74% and 38% observed at 20 μM. The porphyrins with different substituents on phenathroline group had similar singlet oxygen quantum yields, with ΦΔ values at 0.52, 0.47 and 0.41, respectively. The 2PA cross-section (σ(2)) values of RPP 1–3, measured by the Z-scan method, were calculated to be 152, 172 and 135 GM, respectively, which were around 5-fold higher than that of H2TPP . Thus, these porphyrins, with their good photocleavage activities, 1 O 2 quantum yields and high 2PA cross section, suggest great potential as photodynamic therapeutic agents.

Laser flash photolysis studies of the formation and reactivities of phenyl(naphthyl)methyl carbocations generated from phosphonium salt precursors

1992 ◽  
Vol 70 (6) ◽  
pp. 1784-1794 ◽  
Author(s):  
E. O. Alonso ◽  
L. J. Johnston ◽  
J. C. Scaiano ◽  
V. G. Toscano
Keyword(s):  
Rate Constants ◽  
Phosphonium Salt ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Ion Pairs ◽  
Laser Flash ◽  
Product Formation ◽  
Quantum Yields ◽  
Back Reaction ◽  
Transient Experiments

The photolysis of several substituted phenyl(naphthyl)methyl triphenylphosphonium chlorides has been examined using a combination of laser flash photolysis experiments and product studies. Both carbocation and radical intermediates have been characterized in the transient experiments, with the relative yields depending strongly on the solvent. For example, in alcohols, acetonitrile, or aqueous solvents cation formation predominates while acetonitrile/dioxane mixtures (5–10%) are required for the observation of radicals. Quantum yields for cation formation vary from 0.79 in methanol to 0.093 in 1:4 acetonitrile/dioxane, as measured by product studies and transient experiments, respectively. The addition of perchlorate salts leads to dramatic enhancements in the cation lifetimes; the effects are particularly pronounced for acetonitrile/dioxane mixtures where the cation yields also increase by factors of 3–4. In this case the effects are attributed primarily to replacement of chloride by perchlorate in the initial ion pairs. The combined data from both solvent and perchlorate salt effects on the cation lifetimes and yields suggest that the excited state of the phosphonium salt cleaves homolytically, followed by electron transfer within the initial radical/triphenylphosphine radical cation pair to generate carbocation, as opposed to direct heterolytic cleavage. The cation yields also indicate that back reaction to regenerate starting material, as well as product formation within the initial geminate cage, occur in some solvents. The effects of solvent and added perchlorate salts on the rate constants for reaction with nucleophiles have been examined. For example, rate constants that vary by an order of magnitude have been measured for quenching by azide ion in various aqueous acetonitrile and trifluoroethanol mixtures.

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