Direct Photolysis of 2-Propanol Vapor

1972 ◽  
Vol 50 (14) ◽  
pp. 2217-2223 ◽  
Author(s):  
O. S. Herasymowych ◽  
A. R. Knight

The photolysis of 2-propanol vapor in the 1800–2000 Å wavelength range has been investigated. The volatile products of the reaction and their quantum yields at 80 °C and 200 Torr substrate pressure are H2 (0.64), CH3COCH3 (0.34), CH4 (0.39), CH3CHO (0.29), CO (0.15), and C2H6 (0.08). A mechanism is proposed that accounts for the observed rate variations with substrate pressure, exposure time, temperature, and pressure of inert addend. Acetone and acetaldehyde undergo significant secondary decomposition and this is the source of CO, CH4, and C2H6. Acetaldehyde is formed in the unimolecular decomposition of C3H7O radicals produced in the primary process.The effects of CO2 and CF4 as inert addends have been examined and it has been established that the quantum yield enhancement through collision induced predissociation that has been reported to occur in methanol is not a characteristic of the 2-propanol photolysis.

1973 ◽  
Vol 51 (1) ◽  
pp. 147-148 ◽  
Author(s):  
O. Sonia Herasymowych ◽  
Arthur R. Knight

Hydrogen and methane yields from the 1849 Å photolysis of methanol vapor in an all-quartz system have been investigated as a function of exposure time and pressure of CH3OH and added CO2.Product yields are decreased by the inert addend, and by the substrate itself at high pressures, in contrast to the collision-induced quantum yield enhancement reported to be occurring in this system.


1962 ◽  
Vol 40 (6) ◽  
pp. 1134-1139 ◽  
Author(s):  
Arthur R. Knight ◽  
Harry E. Gunning

The reaction of isopropanol vapor with Hg 6(3P1) atoms has been investigated under static conditions at 25 °C under continuous and intermittent illumination. The effect of added inert gas and isolation of the 2537 Å Hg resonance line were also studied.The products of the reaction are H2 (0.72), CH3COCH3 (0.25), CO, CH4, C2H6, CH3CHO, and H2O, with the numbers in parentheses representing the quantum yields at zero exposure time. The non-volatile product remaining in the cell was a mixture of C6-glycols, containing 98.6% pinacol, 1.2% 2-methyl-2,4-pentanediol, and ca. 0.2% or less of 2,5-hexanediol.Under intermittent illumination, the quantum yield of hydrogen production, measured as a function of light period, tL, rose linearly with log tL, and had a constant value of unity for tL < 0.45 msec. A mechanism is proposed involving the primary formation with perfect efficiency of isopropoxy radicals and H atoms.


1972 ◽  
Vol 50 (13) ◽  
pp. 2010-2016 ◽  
Author(s):  
B. L. Kalra ◽  
A. R. Knight

The photodecomposition of cyclohexane sensitized by Cd(3P1) atoms has been studied in the vapor phase at 355 °C. The primary decomposition gives hydrogen atoms and cyclohexyl radicals. The volatile products of the decomposition are H2, cyclohexene, propylene, ethane, ethylene, methane, propane, butadiene, and methylcyclopentane. Products other than H2 and cyclo-C6H10 arise from unimolecular reactions of cyclohexyl radicals, the most important such process being the production of propylene and allyl radicals. Hydrogen yields decrease rapidly with time because of H-atom scavenging reactions involving olefinic products. The quantum yield of molecular hydrogen formation at the shortest exposure time examined is 0.53.


Author(s):  
Anja Busemann ◽  
Ingrid Flaspohler ◽  
Xue-Quan Zhou ◽  
Claudia Schmidt ◽  
Sina K. Goetzfried ◽  
...  

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


Instruments ◽  
2021 ◽  
Vol 5 (2) ◽  
pp. 17
Author(s):  
Eldred Lee ◽  
Kaitlin M. Anagnost ◽  
Zhehui Wang ◽  
Michael R. James ◽  
Eric R. Fossum ◽  
...  

High-energy (>20 keV) X-ray photon detection at high quantum yield, high spatial resolution, and short response time has long been an important area of study in physics. Scintillation is a prevalent method but limited in various ways. Directly detecting high-energy X-ray photons has been a challenge to this day, mainly due to low photon-to-photoelectron conversion efficiencies. Commercially available state-of-the-art Si direct detection products such as the Si charge-coupled device (CCD) are inefficient for >10 keV photons. Here, we present Monte Carlo simulation results and analyses to introduce a highly effective yet simple high-energy X-ray detection concept with significantly enhanced photon-to-electron conversion efficiencies composed of two layers: a top high-Z photon energy attenuation layer (PAL) and a bottom Si detector. We use the principle of photon energy down conversion, where high-energy X-ray photon energies are attenuated down to ≤10 keV via inelastic scattering suitable for efficient photoelectric absorption by Si. Our Monte Carlo simulation results demonstrate that a 10–30× increase in quantum yield can be achieved using PbTe PAL on Si, potentially advancing high-resolution, high-efficiency X-ray detection using PAL-enhanced Si CMOS image sensors.


Solar Energy ◽  
2020 ◽  
Vol 206 ◽  
pp. 473-478 ◽  
Author(s):  
Fan Sui ◽  
Mingyue Pan ◽  
Zhengyan Wang ◽  
Ming Chen ◽  
Wenjie Li ◽  
...  

1970 ◽  
Vol 48 (8) ◽  
pp. 1333-1334 ◽  
Author(s):  
B. L. Kalra ◽  
A. R. Knight

The photodecomposition of acetone vapor at 255 °C sensitized by Cd 3P1 atoms has been investigated. On irradiation of the Cd–acetone system at 3261 Å, both direct and sensitized reaction occur. CO and CH4 are the only significant volatile products, and their yield is decreased by addition of SF6 as inert quenching gas. The required participation of triplet acetone molecules in the sensitized reaction and the virtual identity of the direct and sensitized decompositions provide additional evidence for the importance of this excited species in direct photolysis.


1981 ◽  
Vol 59 (11) ◽  
pp. 1607-1609 ◽  
Author(s):  
Karl R. Kopecky ◽  
Rodrigo Rico Gomez
Keyword(s):  

The quantum yields for photolysis of 0.25 M solutions of bicyclo[3.1.0]hexan-3-one, 1,5-dimethylbicyclo[3.1.0]hexan-3-one, and tricyclo[4.3.1.0]decan-8-one in pentane or cyclohexane with 313 nm light are 0.44, 0.52, and 0.32, respectively.


2021 ◽  
pp. 1-10
Author(s):  
Ibrahim Erden ◽  
Betül Karadoğan ◽  
Fatma Aytan Kılıçarslan ◽  
Göknur Yaşa Atmaca ◽  
Ali Erdoğmuş

This work describes the synthesis, spectral and fluorescence properties of bis 4-(4-formyl-2,6-dimethoxyphenoxy) substituted zinc (ZnPc) and magnesium (MgPc) phthalocyanines. The new compounds have been characterized by elemental analysis, UV-Vis, FT-IR, 1H-NMR and mass spectra. Afterward, the effects of including metal ion on the photophysicochemical properties of the complexes were studied in biocompatible solvent DMSO to analyze their potential to use as a photosensitizer in photodynamic therapy (PDT). The fluorescence and singlet oxygen quantum yields were calculated as 0.04–0.15 and 0.70–0.52 for ZnPc and MgPc, respectively. According to the results, MgPc has higher fluorescence quantum yield than ZnPc, while ZnPc has higher singlet oxygen quantum yield than MgPc. The results show that the synthesized complexes can have therapeutic outcomes for cancer treatment.


1968 ◽  
Vol 46 (4) ◽  
pp. 527-530 ◽  
Author(s):  
N. J. Friswell ◽  
R. A. Back

The Hg(63P1)-sensitized decomposition of HNCO vapor has been briefly studied at 26 °C with HNCO pressures from about 3 to 30 Torr. The products detected were the same as in the direct photolysis, CO, N2, and H2. The quantum yield of CO was appreciably less than unity, compared with a value of 1.5 in the direct photolysis under similar conditions. From this and other observations it is tentatively concluded that a single primary process occurs:[Formula: see text]From a study of the mercury-photosensitized reactions in mixtures of HNCO with H2, it was concluded that hydrogen atoms react with HNCO to form CO but not N2. The initial step is probably addition to form NH2CO. From the competition between reaction [1] and the corresponding quenching by H2, the cross section for reaction [1] was estimated to be 2.3 times that of hydrogen.


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