• Title/Summary/Keyword: Photochemical Reaction

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A Novel Photoreaction of (2-Hydroxyethoxyphenyl)pentamethyldisilane

  • Park, Seung Ki;Seong, Won-Je
    • Bulletin of the Korean Chemical Society
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    • v.30 no.6
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    • pp.1331-1336
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    • 2009
  • Photolysis of (2-hydroxyethoxyphenyl)pentamethyldisilane 2 in benzene provides a novel intramolecular cyclization photoproduct 9 which was probably formed from the intramolecular reaction to form a seven-membered ring in silatriene intermediate 7 and then the photochemical disrotatory ring closure of 1,3-butadiene moiety to cyclobutene. Irradiation of 2 in methanol afforded photoproducts 5 and 6 which were formed by the nucleophilic attack of methanol to $\beta$ or $\alpha$ silicon atom in pentamethyldisilanyl group of the photoexcited state of 2. Compounds 10 and 11 were also formed by the same way as in the formation of the photoproducts 5 and 6 in the photolysis of (2-allyloxyethoxyphenyl)pentamethyldisilane 3 in methanol solvent. Photoreaction of (2-acetoxyethoxyphenyl) pentamethyldisilane 4 in methanol gave a photoproduct 12 which was formed via the elimination of dimethylsilylene species in the photoexcited state of 4.

Photoreactions of Photofunctional polymer Bearing Acyloxyimino Groups and Its Applications (아실옥사이미노기를 갖는 광기능성고분자의 광반응과 이용)

  • Song, Gyeong-Hyeon
    • The Journal of Natural Sciences
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    • v.5 no.1
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    • pp.59-65
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    • 1992
  • In this study, new photosensitive polymers bearing acyloxyimino(AOI) group were prepared and the relationship between photochemical reactions of the polymers and changes of their physical properties was investigated. It was found that main reaction of these copolymers depended on the structure of polymer mainchain. From the view point of amino groups formation, acryl type polymers were superior to methacryl type polymers. On the other hand, in the case of mathacryl type polymers, mainchain scissions and formation of double bonds occurred very effectively. Applications of these copolymers to photofunctional polymers were also discussed.

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Paeparation and Properties of Epoxy Copolymers Containing Oxime-urethane Groups as Photobase Generators

  • Chae, Gyu Ho;Song, Hye Bong;Seon, Ho Yong;Jang, Ji Yeong
    • Bulletin of the Korean Chemical Society
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    • v.21 no.7
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    • pp.690-696
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    • 2000
  • Epoxy copolymers containing oxime urethane groups were prepared by the polymerization of glycidyl methacrylate and N-[5-(benzophenoneoximinocarbonylamino)pentanyl]maleimide (BOPM). Their physical properties were characterized by GPC, DSC and TGA analyses. Photochemical changes of the copolymers were studied by UV, IR spectroscopy, and contact angle measurements. A photoinduced cross-linking reaction in copolymer films was observed by measuring the insoluble fraction. Irradiation of the copolymers at 254 nm UV light leads to the formation of pendant amino groups by photodissociation of the oxime-urethane groups. Treatment of the amino groups with HCl resulted in the formation of ammonium salts, which changed the polymer surface to be hydrophilic. An insoluble fraction of the copolymers increased with irradiation time, heating time, and heating temperature. Cross-linking of the epoxy resin effectively catalyzed by the photogenerated pendant amines upon heating.

The Photochemical Reactivities of Benzenes Tethered to Haloarene

  • 박용태;김영희;황철균;성대동
    • Bulletin of the Korean Chemical Society
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    • v.17 no.6
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    • pp.506-510
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    • 1996
  • The syntheses and photoreactions of haloarenes, in which the aryl and haloaryl moieties are tethered by a simple alkyl group, were studied. For 2-benzyl-1-halobenzene, in which two aryl moieties were connected by methylene group, photoreduced product, diphenylmethane, was obtained along with the minor formation of the photocyclized product, fluorene, in acetonitrile solvent. For 1-halo-2-phenethylbenzene, in which two aryl moieties were connected by ethylene group, photocyclized products, 9,10-dihydrophenanthrene and phenanthrene, were obtained along with the minor formation of photoreduced product, bibenzyl, in acetonitrile solvent. The photoreaction selectivities in several solvent systems were studied: In cyclohexane, 2-benzyl-1-chlorobenzene was photoreduced more effective than 2-benzyl-1-bromobenzene; In the presence of NaOH, 1-halo-2-phenethylbenzenes gave 9,10-dihydrophenanthrene and, in the presence of toluene, they gave phenanthrene. A radical reaction mechanism is proposed for the explanation of the reactions. This study shows that the photoreaction of haloarene, in which haloaryl and aryl moieties are tethered by ethylene group, can be used for ring formation of 9,10-dihydrophenanthrene otherwise difficultly accessible.

Theoretical Studies on the Photochemical Reactions of 5,7-Dimethoxycoumarin with Adenosine. The Electronic States of 5,7-Dimethoxycoumarin and their Photoadducts

  • Kim, Ja-Hong;Han, Goang-Lae;Song, Young-Chil;Sohn, Sung-Ho
    • Bulletin of the Korean Chemical Society
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    • v.10 no.3
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    • pp.223-226
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    • 1989
  • The chemical reactivity of 5,7-dimethoxycoumarine with adenosine has been calculated by the frontier electron and PPP-Cl MO methods. Results suggest that the major reactivity of the 5,7-dimethoxycoumarin is highest at the carbon-4 (position 4), whereas the electrophilic reactivity is generally spread all over the 5,7-dimethoxycoumarin molecule. These results are consistent with the experimental photoaddition reaction products. The small change of bond orders on excitation does not give enough reactivity to triplet states or the efficient intersystem crossing from $T_1\;to\;S_0$ inhibits photoaddition of 5,7-dimethoxycoumarine to adenosine. Although the relative intensity of the singlet band appears to be considerably higher than the triplet band intensity, its integrated intensity, i.e. oscillator strength, is comparable to that of the 5,7-dimethoxycoumarin and adenosine bands.

Quantitative Determination of Acetone formed in the Thermal and Photochemical Decompositions of Azobisisobutyronitrile

  • Yoon, Heung-Sick;Kim ,Kyong-Tae
    • Bulletin of the Korean Chemical Society
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    • v.6 no.5
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    • pp.284-287
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    • 1985
  • Cyanoisopropyl radical derived from azobisisobutyronitrile (AIBN) by either thermolysis or photolysis reacts with oxygen to give cyanoisopropylperoxy radical which then was converted to acetone and cyano radical and/or acetyl cyanide and methyl radical. Of these products, acetone formed was quantitatively determined by the addition of thianthrene cation radical perchlorate to the reaction mixture. The results showed that 55.7 mmol, 16.9 mmol, and 16.0 mmol of acetone were formed for 7 hours from 1 mol of AIBN at $82{\pm}1^{\circ}C$ in acetonitrile, carbon tetrachloride, and benzene, respectively. However, 22.2 mmol of acetone was formed from photolysis of 1 mmol of AIBN in acetonitrile. The value decreased to 13.2 mmol by bubbling argon into the solvent prior to photolysis.

Theoretical Studies on the Photochemical Reaction of Psoralen with Purine and Pyrimidine Base

  • Kim Ja Hong;Sohn Sung Ho
    • Bulletin of the Korean Chemical Society
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    • v.13 no.2
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    • pp.173-176
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    • 1992
  • The spectroscopic studies of the 5,7-dimethoxycoumarin(5,7-DMC) and 4,5',8-trimethylpsoralen(TMP) and the conformational stability of 5,7-DMC-thymidine, 4,5',8-TMP-thymine were carried out by the CNDO/S and molecular mechanics calculation. Theoretical transition energies and direction of polarizations calculated by the CNDO/S method have been used for the interpretation of the observed results. The calculated absorption spectra of 5,7-DMC are qualitatively similar to experimental ones with their characteristic visible bands. MM2 force field calculation on the possible $C_4-cyclophotoadducts$ formed between 5,7-DMC and thymidine through a cycloaddition. of $C_3$, $C_4$ bond of 5,6-DMC to $C_5$, $C_6$ bond of thymidine showed the most stable photocycloadduct to have the anti-head to tail configuration. The major photoadduct of 4,5',8-TMP-thymine has the cis-anti configuration.

Effect of Partial Shading by Agrivoltaic Systems Panel on Electron Transport Rate and Non-photochemical Quenching of Crop (영농형 태양광 패널의 부분 차광 생육 환경이 작물 전자전달효율과 비광화학적 형광소멸에 미치는 영향)

  • Cho, Yuna;Kim, Hyunki;Jo, Euni;Oh, Dohyeok;Jeong, Hoejeong;Yoon, Changyong;An, Kyunam;Cho, Jaeil
    • Korean Journal of Agricultural and Forest Meteorology
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    • v.23 no.2
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    • pp.100-107
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    • 2021
  • An agrivoltaic system (AVS) is a system of innovation that comprises productions of photovoltaic power and agricultural crops on the same area. However, the decline in crop yield will be fatally occurred because the pigments of crop absorbs less light energy under AVS. In addtion, the photosynthetic capacity of crop grown under the partial shading of AVS is not well reported. In this study, the electron transport rate (ETR) and non-photochemical fluorescence quenching (NPQ) of soybean and rice under the AVS in Boseong and Naju was investigated using chlorophyll fluorescence measurement. The ETR value of soybean and rice under AVS were not significantly differed by location. It represents that the photophosphorylation rate of the crops is not critically different. It means that the decreases in total photosynthesis under AVS were mostly affected by the amount of light absorbed by leaves. Under AVS the photosynthesis of crops will be lower than field crops grown in open fields. This is because the crops under AVS observed higher NPQ, which means that the available energy cannot distribute to photophosphorylation reaction.

Enhancement of Ozone and Carbon Monoxide Associated with Upper Cut-off Low during Springtime in East Asia

  • Moon, Yun-Seob;Drummond, James R.
    • Journal of Korean Society for Atmospheric Environment
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    • v.26 no.5
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    • pp.475-489
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    • 2010
  • In order to verify the enhancement of ozone and carbon monoxide (CO) during springtime in East Asia, we investigated weather conditions and data from remote sensors, air quality models, and air quality monitors. These include the geopotential height archived from the final (FNL) meteorological field, the potential vorticity and the wind velocity simulated by the Meteorological Mesoscale Model 5 (MM5), the back trajectory estimated by the Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model, the total column amount of ozone and the aerosol index retrieved from the Total Ozone Mapping Spectrometer (TOMS), the total column density of CO retrieved from the Measurement of Pollution in the Troposphere (MOPITT), and the concentration of ozone and CO simulated by the Model for Ozone and Related Chemical Tracers (MOZART). In particular, the total column density of CO, which mightoriginate from the combustion of fossil fuels and the burning of biomass in China, increased in East Asia during spring 2000. In addition, the enhancement of total column amounts of ozone and CO appeared to be associated with both the upper cut-off low near 500 hPa and the frontogenesis of a surface cyclone during a weak Asian dust event. At the same time, high concentrations of ozone and CO on the Earth's surface were shown at the Seoul air quality monitoring site, located at the surface frontogenesis in Korea. It was clear that the ozone was invaded by the downward stretched vortex anomalies, which included the ozone-rich airflow, during movement and development of the cut-off low, and then there was the catalytic photochemical reaction of ozone precursors on the Earth's surface during the day. In addition, air pollutants such as CO and aerosol were tracked along both the cyclone vortex and the strong westerly as shown at the back trajectory in Seoul and Busan, respectively. Consequently, the maxima of ozone and CO between the two areas showed up differently because of the time lag between those gases, including their catalytic photochemical reactions together with the invasion from the upper troposphere, as well as the path of their transport from China during the weak Asian dust event.

Observation of Secondary Organic Aerosol and New Particle Formation at a Remote Site in Baengnyeong Island, Korea

  • Choi, Jinsoo;Choi, Yongjoo;Ahn, Junyoung;Park, Jinsoo;Oh, Jun;Lee, Gangwoong;Park, Taehyun;Park, Gyutae;Owen, Jeffrey S.;Lee, Taehyoung
    • Asian Journal of Atmospheric Environment
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    • v.11 no.4
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    • pp.300-312
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    • 2017
  • To improve the understanding of secondary organic aerosol (SOA) formation from the photo-oxidation of anthropogenic and biogenic precursors at the regional background station on Baengnyeong Island, Korea, gas phase and aerosol chemistries were investigated using the Proton Transfer Reaction Time of Flight Mass Spectrometer (PTR-ToF-MS) and the Aerodyne High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS), respectively. HR-ToF-AMS measured fine particles ($PM_1$; diameter of particle matter less than $1{\mu}m$) at a 6-minute time resolution from February to November 2012, while PTR-ToF-MS was deployed during an intensive period from September 21 to 29, 2012. The one-minute time-resolution and high mass resolution (up to $4000m{\Delta}m^{-1}$) data from the PTR-ToF-MS provided the basis for calculations of the concentrations of anthropogenic and biogenic volatile organic compounds (BVOCs) including oxygenated VOCs (OVOCs). The dominant BVOCs from the site are isoprene (0.23 ppb), dimethyl sulphide (DMS, 0.20 ppb), and monoterpenes (0.38 ppb). Toluene (0.45 ppb) and benzene (0.32 ppb) accounted for the majority of anthropogenic VOCs (AVOCs). OVOCs including acetone (3.98 ppb), acetaldehyde (2.67 ppb), acetic acid (1.68 ppb), and formic acid (2.24 ppb) were measured. The OVOCs comprise approximately 75% of total measured VOCs, suggesting the occurrence of strong oxidation processes and/or long-range transported at the site. A strong photochemical aging and oxidation of the atmospheric pollutants were also observed in aerosol measured by HR-ToF-AMS, whereby a high $f_{44}:f_{43}$ value is shown for organic aerosols (OAs); however, relatively low $f_{44}:f_{43}$ values were observed when high concentrations of BVOCs and AVOCs were available, providing evidence of the formation of SOA from VOC precursors at the site. Overall, the results of this study revealed several different SOA formation mechanisms, and new particle formation and particle growth events were identified using the powerful tools scanning mobility particle sizer (SMPS), PTR-ToF-MS, and HR-ToF-AMS.