The Quantum Yield of Oxidation of Hevea Rubber and GR-S

1948 ◽  
Vol 21 (3) ◽  
pp. 639-653 ◽  
Author(s):  
E. J. Hart ◽  
M. S. Matheson
Keyword(s):  
Quantum Yield ◽  
Room Temperature ◽  
Wave Length ◽  
Radical Reaction ◽  
Quantum Yields ◽  
Initial Reaction ◽  
Free Radical Reaction ◽  
Stable Intermediate ◽  
A Chain ◽  
Reaction Chain

Abstract The initial quantum yields of photoöxidation for purified Hevea rubber have been measured for various mercury arc lines in the wave length region 2537– 17,400 A˚. All experiments were carried out at room temperature and at an oxygen pressure of one atmosphere. At the outset of irradiation all quantum yields of combined oxygen are less than unity, although the quantum efficiency rises above 1.0 at 2537 and 3130 A˚. as photoöxidation proceeds. The low quantum yield suggests that in its initial stages (less than 0.1 per cent oxygen combined on the rubber) photoöxidation is not a chain reaction. It is postulated as the first step in rubber photoöxidation that the light activated rubber group reacts with oxygen to give a relatively stable intermediate which does not immediately dissociate to give a free radical reaction chain. The quantum yields of photoöxidation of purified GR-S were also measured under the same conditions as used for rubber. At each wave length the quantum yield was lower than for rubber, indicating formation of a stable intermediate in the initial reaction also.

The photochemical decomposition of t -butyl hydroperoxide in solution

1953 ◽  
Vol 220 (1142) ◽  
pp. 322-339 ◽  
Keyword(s):  
Quantum Yield ◽  
Wave Length ◽  
Butyl Alcohol ◽  
Quantum Yields ◽  
Oxidation Reactions ◽  
Butyl Hydroperoxide ◽  
Acetone Water ◽  
Photochemical Decomposition ◽  
Solvent Molecules ◽  
A Chain

The photochemical decomposition of t -butyl hydroperoxide by light of wave-length 3130 Å has been investigated in three solvents. Reaction mechanisms are elucidated by consideration of the products and the quantum yields of decomposition. In carbon tetrachloride a chain reaction occurs in which the quantum yield of 3.2 at 20° C increases to 5.3 at 50° C. The main products are t -butyl alcohol and oxygen with smaller amounts of acetone, water and compounds arising from the oxidation of methyl radicals. The same series of reactions takes place in n -hexane, but superimposed are oxidation reactions involving solvent molecules which ultimately lead to the formation of alcohols. The quantum yield in this solvent is 3.9 and independent of temperature. When the peroxide is irradiated in dioxan solution immediate hydrogenation of the radicals produced in the primary photo-chemical act prevents the formation of reaction chains and the quantum yield is unity. The interaction of the radicals with solvent molecules is such that some of the etheric oxygen of the dioxan is transformed into alcoholic hydroxyl during the course of the reaction, and the fragmentation of dioxan gives formaldehyde Experiments with a dioxan solution using light of wave-length 2450 to 2800 Å show no fundamental change in the mode of decomposition of the peroxide, but an increase in concentration of the products of dioxan decomposition indicates a more vigorous attack by the radicals on the solvent.

Reactions of Thiyl Radicals. XI. Further Investigations of Thiol–Disulfide Photolyses in the Liquid Phase

1973 ◽  
Vol 51 (9) ◽  
pp. 1410-1415 ◽  
Author(s):  
Donna D. Carlson ◽  
Arthur R. Knight
Keyword(s):  
Liquid Phase ◽  
Room Temperature ◽  
Liquid Mixtures ◽  
Quantum Yields ◽  
Chain Reaction ◽  
Photochemical Process ◽  
High Quantum Efficiency ◽  
Thiyl Radicals ◽  
Exchange Processes ◽  
A Chain

The photolysis of C2H5SH liquid at 2537 Å has been shown to give H2 and C2H5SSC2H5 at equal rates with a quantum yield of 0.25. The photolysis of ethanethiol – methyl disulfide liquid mixtures leads, via a chain reaction involving propagation by attack of thiyl radicals on the disulfide S—S bond, to the formation with high quantum efficiency of CH3SH, C2H5SSC2H5 and, as an intermediate that is consumed after long exposures, CH3SSC2H5. The net result of the sequence of exchange processes is the essentially irreversible conversion of the methyl disulfide into methanethiol. The same overall reaction occurs thermally at room temperature, but the rate is appreciably less than that of the photochemical process. The quantum yields of formation of the unsymmetrical disulfides arising from the photochemically initiated exchange reaction in equimolar mixtures of CH3SSCH3 + n-C3H7SSC3H7 and C2H5SSC2H5 + n-C3H7SSC3H7 have been shown to be 6.9 and 4.4, compared to 355 for CH3-SSCH3 + C2H5SSC2H5 mixtures. In all three types of system examined in this investigation all thiyl radicals can be accounted for stoichiometrically on the basis of exchange and combination reactions alone, indicating negligible disproportionation of these species in condensed phase.

Photochemische 2+2-Cycloadditionen von Äthylen und Acetylen an 1.3-Cyclohexadien unter erhöhtem Druck / Photochemical 2+2-Cycloadditions of Ethylene and Acetylene to 1,3-Cyclohexadiene under High Pressure

1977 ◽  
Vol 32 (1) ◽  
pp. 47-52 ◽  
Author(s):  
Marlis F. Mirbach ◽  
Manfred J. Mirbach ◽  
Alfons Saus
Keyword(s):  
High Pressure ◽  
Quantum Yield ◽  
Room Temperature ◽  
Kinetic Scheme ◽  
Solvent Mixture ◽  
Experimental Results ◽  
Quantum Yields ◽  
Ethylene Pressure ◽  
Formal Kinetic

The photochemical cycloaddition of 1,3-cyclohexadiene (CHD) to ethylene and acetylene at pressures above 10 bar is described. Upon sensitized irradiation (2-acetylnaphthaline) CHD adds to ethylene at room temperature in dichloromethane to give cis-bicyclo[4,2,0]-oct-2-ene (1) along with dimers of cyclohexadiene. The yield of cross adduct increases with ethylene pressure (10-50 bar) whereas dimerisation decreases. Quantum yields of cross addition and dimerisation at 12 M ethylene were determined to be 0.31 and 0.35 respectively. At a pressure of 15 bar acetylene CHD reacts with acetylene to give bicyclo-[4,2,0]octa-2,7-diene (2) and bicyclo[2,2,2]octa-2,5-diene (3) as the major and minor products respectively. In a solvent mixture containing 60 vol-% CH2Cl2 and 40 vol-% acetone (2) is formed with a quantum yield of φ = 0.2. The experimental results are explained by a formal kinetic scheme.

Absolute Quantum Yields for Exciplex Fluorescence

1990 ◽  
Vol 44 (1) ◽  
pp. 101-105 ◽  
Author(s):  
S. J. Hale ◽  
L. A. Melton
Keyword(s):  
Quantum Yield ◽  
Temperature Dependence ◽  
Room Temperature ◽  
Quantum Yields ◽  
Absolute Quantum Yield ◽  
The Absolute ◽  
Visualization Systems ◽  
Methyl Naphthalene ◽  
Absolute Quantum ◽  
Exciplex Fluorescence

The absolute quantum yields for exciplex fluorescence in four solutions which have potential as exciplex-based vapor/liquid visualization systems have been measured. The room-temperature absolute quantum yields for 10% dibutyl-aniline/0.4%, 1-cyanonaphthalene, 12.5% 1-methyl-naphthalene/0.5% N,N,N′,N′-tetramethyl- p-phenylenediamine (TMPD), 10% trihexylamine/1.0% 1-cyanonaphthalene, and 10% naphthalene/1.0% TMPD in hexadecane or cyclohexane are 0.03 ± 0.005, 0.05 ± 0.002 (308 nm), 0.02 ± 0.001, and 0.16 ± 0.021, respectively. The temperature dependence of the absolute quantum yield for the 10% naphthalene/1% TMPD in the hexadecane system was measured over the range of 23 to 260°C and was found to decrease by 20–30% at 260°C.

Kinetics and mechanisms of the pyrolysis of diethyl ether II. The reaction inhibited by nitric oxide

1964 ◽  
Vol 278 (1375) ◽  
pp. 517-526 ◽  
Keyword(s):  
Nitric Oxide ◽  
Diethyl Ether ◽  
High Pressures ◽  
Radical Reaction ◽  
Free Radical Reaction ◽  
Order Component ◽  
Maximal Inhibition ◽  
First Order ◽  
A Chain ◽  
Low Pressures

The pyrolysis of diethyl ether, inhibited by nitric oxide, was studied in the temperature range of 560 to 640 °C, and at pressures between 10 and 360 mmHg. About 7 mm of nitric oxide gave maximal inhibition. The degree of maximal inhibition varied with the temperature but was independent of the ether pressure. As the nitric oxide pressure was increased beyond 35 to 40 mm the rate increased linearly. In the maximally inhibited region the order with respect to ether varied between 1 at high temperatures and low pressures to 3/2 at low temperatures and high pressures. A chain mechanism is proposed, in which nitric oxide is involved in both initiation and termination, and leads to a rate expression showing both first-order and three-halves-order dependence on ether pressure. The first-order component of the reaction is concluded to consist of both a molecular split into ethanol and ethylene and a free-radical reaction.

Fluorescence Quantum Yields of 2-Substituted 3-Methylquinoxalines in Liquid Solutions at Room Temperature

1991 ◽  
Vol 46 (8) ◽  
pp. 700-702
Author(s):  
A. Kawski ◽  
K. Nowaczyk ◽  
B. Kuklinski
Keyword(s):  
Quantum Yield ◽  
Fluorescence Spectra ◽  
Room Temperature ◽  
Atomic Weight ◽  
Modulation Method ◽  
Quantum Yields ◽  
Strong Decrease ◽  
Polar Solvents ◽  
Fluorescence Quantum Yields ◽  
Liquid Solutions

AbstractA sensitivity modulation method was employed to measure the fluorescence spectra and quantum yields of weakly fluorescent 2-substituted (NH2, O, OCH3, CI, Br) 3-methylquinoxalines in n-hexane and methanol at room temperature. A strong decrease in the quantum yield with increasing atomic weight of the substituents was observed in n-hexane. In polar solvents, the CI substituent is the strongest quencher although its atomic weight is 2.254 times smaller than that of Br

Two channel competitive photodecomposition reaction of gaseous bromoethane at 193.1 nm

1983 ◽  
Vol 61 (11) ◽  
pp. 2486-2489 ◽  
Author(s):  
Kyung-Hoon Jung ◽  
Chong Mok Lee ◽  
Hee Soo Yoo
Keyword(s):  
Room Temperature ◽  
Vacuum Ultraviolet ◽  
Constant Pressure ◽  
Radical Reaction ◽  
Quantum Yields ◽  
Radical Scavenger ◽  
Reaction Products ◽  
Principal Reaction ◽  
Ultraviolet Photolysis ◽  
Pressure Independent

The vacuum ultraviolet photolysis of gas phase bromoethane at 193.1 nm (6.42 eV) was studied over the pressure range of 1.1–303.2 Torr at room temperature using a carbon atom lamp. The pressure effect with and without inert gas, i.e., He or N2, was investigated. A scavenger effect of the reaction was also observed by adding NO as a radical scavenger. The principal reaction products were C2H6, C2H4, 1,1-C2H4Br2, and n-C4H10. The quantum yields of C2H4 and C2H6 were found to increase slightly with the reactant pressure. When the pressure of He or N2 was varied at a constant pressure of C2H5Br, however, the quantum yields of C2H4 and C2H6 were found to be pressure independent. Addition of NO completely suppressed the formation of C2H6, C2H4Br2, and C4H10, and partially reduced that of C2H4. These results were interpreted in terms of two channel competition between the molecular elimination and the formation of radicals. Two different decomposition modes were 82% radical reaction and 18% molecular elimination.

The Structure of Radiation Cross-Linked Poly (ethylene oxide) Gels

1971 ◽  
Vol 29 ◽  
pp. 76-77
Author(s):  
C. E. Cluthe ◽  
G. G. Cocks
Keyword(s):  
Molecular Weight ◽  
Ethylene Oxide ◽  
Parallel Plate ◽  
Average Molecular Weight ◽  
Radical Reaction ◽  
Free Radical Reaction ◽  
Nitrogen Gas ◽  
Poly Ethylene Oxide ◽  
Poly Ethylene ◽  
Initial Viscosity

Aqueous solutions of a 1 weight-per cent poly (ethylene oxide) (PEO) were degassed under vacuum, transferred to a parallel plate viscometer under a nitrogen gas blanket, and exposed to Co60 gamma radiation. The Co60 source was rated at 4000 curies, and the dose ratewas 3.8x105 rads/hr. The poly (ethylene oxide) employed in the irradiations had an initial viscosity average molecular weight of 2.1 x 106.The solutions were gelled by a free radical reaction with dosages ranging from 5x104 rads to 4.8x106 rads.

scholarly journals Ruthenium-based PACT agents based on bisquinoline chelates: synthesis, photochemistry, and cytotoxicity

2021 ◽  
Author(s):  
Anja Busemann ◽  
Ingrid Flaspohler ◽  
Xue-Quan Zhou ◽  
Claudia Schmidt ◽  
Sina K. Goetzfried ◽  
...  
Keyword(s):  
Quantum Yield ◽  
Singlet Oxygen ◽  
Cancer Cells ◽  
Cellular Uptake ◽  
Ruthenium Complex ◽  
Human Cancer ◽  
Light Irradiation ◽  
Quantum Yields ◽  
Light Activation ◽  
Human Cancer Cells

AbstractThe known ruthenium complex [Ru(tpy)(bpy)(Hmte)](PF6)2 ([1](PF6)2, where tpy = 2,2’:6’,2″-terpyridine, bpy = 2,2’-bipyridine, Hmte = 2-(methylthio)ethanol) is photosubstitutionally active but non-toxic to cancer cells even upon light irradiation. In this work, the two analogs complexes [Ru(tpy)(NN)(Hmte)](PF6)2, where NN = 3,3'-biisoquinoline (i-biq, [2](PF6)2) and di(isoquinolin-3-yl)amine (i-Hdiqa, [3](PF6)2), were synthesized and their photochemistry and phototoxicity evaluated to assess their suitability as photoactivated chemotherapy (PACT) agents. The increase of the aromatic surface of [2](PF6)2 and [3](PF6)2, compared to [1](PF6)2, leads to higher lipophilicity and higher cellular uptake for the former complexes. Such improved uptake is directly correlated to the cytotoxicity of these compounds in the dark: while [2](PF6)2 and [3](PF6)2 showed low EC50 values in human cancer cells, [1](PF6)2 is not cytotoxic due to poor cellular uptake. While stable in the dark, all complexes substituted the protecting thioether ligand upon light irradiation (520 nm), with the highest photosubstitution quantum yield found for [3](PF6)2 (Φ[3] = 0.070). Compounds [2](PF6)2 and [3](PF6)2 were found both more cytotoxic after light activation than in the dark, with a photo index of 4. Considering the very low singlet oxygen quantum yields of these compounds, and the lack of cytotoxicity of the photoreleased Hmte thioether ligand, it can be concluded that the toxicity observed after light activation is due to the photoreleased aqua complexes [Ru(tpy)(NN)(OH2)]2+, and thus that [2](PF6)2 and [3](PF6)2 are promising PACT candidates. Graphic abstract

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