• Title/Summary/Keyword: Fluorescence quantum yield

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The Mechanism of the Photocyclization of N-(2-Haloarylmethyl)Pyridinium and N-(arylmethyl)-2-Halopyridinium Salts

  • Yong-Tae Park;Chang-Han Joo;Chung-Do Choi;Kum-Soo Park
    • Bulletin of the Korean Chemical Society
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    • v.12 no.2
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    • pp.163-169
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    • 1991
  • The photochemical and photophysical properties of N-(2-haloarylmethyl)pyridinium, N-(arylmethyl)-2-halopyridinium, N-(2-haloarylmethyl)-2-halopyridinium salts and N-(2-halobenzyl)-isoquinolinium salt are studied. The pyridinium salts photocyclize to afford isoindolium salts, while the isoquinolium salts do not. In the photocyclization of N-(2-chlorobenzyl)-2-chloropyridinium salts, pyrido[2,1-a]-4-chloroisoindolium salt is formed by the cleavage of chlorine of pyridinium ring. This indicates that the excited moiety is not the phenyl ring, but the pyridinium ring. The triplet states of the pyridinium salts are believed to be largely involved in the photocyclization, since oxygen retards most of the reaction. Some assistance of a ${\pi}$-complex between the excited chlorine moiety of the salt and phenyl plane of the same molecule is required to explain the reactivity of the salts. N-(Benzyl)-2-chloropyridinium salt is two times more reactive than N-(2-chlorobenzyl)pyridinium salt. N-(Benzyl)-2-chloropyridinium salt can form ${\pi}-complex$ effectively because of the electron-rich phenyl group. The ${\pi}$-complex affords an intermediate, phenyl radical by cleaving the chlorine atom. The photocyclized product, isoindolium salt is obtained by losing the hydrogen atom from the phenyl radical. The reactive pyridinium salts 1a, 2a and 3a have a low fluorescence quantum yield (${\Phi}F$ < 0.01) and a higher triplet energy (ET > 68 kcal/mole) than the unreactive quinolinium salt. The unreactivity of isoquinolinium salt can be understood in relation to its high fluorescence quantum yield and its low triplet energy $(E_T = 61 kcal/mole).$.

Photosynthetic Responses of the Benthic Diatom Nitzschia sp. to Selected Heavy Metals and Herbicides (일부 중금속과 제초제에 대한 저서규조류 Nitzschia sp.의 광합성 반응)

  • Kang, Eun-Ju;Choi, Tae-Seob;Kim, Kwang-Young
    • ALGAE
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    • v.22 no.4
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    • pp.319-323
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    • 2007
  • This study was conducted with using chlorophyll a fluorescence (indicated as photosynthetic activity) to examine the toxic effect of 96 h exposure of heavy metals and herbicides on the benthic diatom Nitzschia sp. which was isolated from pristine sediment in Pamquat Harbour, Nova Scotia, Canada. Samples of benthic diatom were exposed to 0, 0.01, 0.1 and 1 mg L–1 of copper, 0, 1, 10 and 100 mg L–1 of chrome (VI), 0, 2.45, 24.5 and 245 mg L–1 of paraquat dichloride, and 0, 4.37, 43.7 and 437 mg L–1 of alachlor during 96 hours. The effective quantum yield of photochemistry (ΔF/Fm’) was evaluated by subjecting light acclimated samples to saturating pulses of light using a pulse amplitude modulated (PAM) fluorometer. The impact of heavy metals on Nitzschia sp. photosynthesis was not severe in < 1 mg L–1 but in the high concentrations (> 1 mg L–1) clearly increased toxic stress during 96 h. Herbicides had a limited impact during the exposure period but clearly increased stress on the benthic diatom with increasing concentrations. Acute response of Nitzschia sp. to selected heavy metals and herbicides was characterized, and the capacity of a benthic diatom to tolerate and recover from toxic stress was assessed.

Acclimation of maximum quantum yield of PSII and photosynthetic pigments of Panax quinquefolius L. to understory light

  • Fournier, Anick R.;T.A., John;Khanizadeh, Shahrokh;Gosselin, Andre;Dorais, Martine
    • Journal of Ginseng Research
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    • v.32 no.4
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    • pp.347-356
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    • 2008
  • Forest-grown American ginseng (Panax quinquefolius L.) is exposed to daily and seasonal light variations. Our goal was to determine the effect of understory light changes on the maximum quantum yield of photosystem II, expressed as $F_v/F_m$, and photosynthetic pigment composition of two-year-old plants. Understory light photon flux density and sunfleck durations were characterized using hemispherical canopy photography. Our results showed that understory light significantly affected the $F_v/F_m$ of American ginseng, especially during the initial development of the plants when light levels were the highest, averaging 28 mol $m^{-2}d^{-1}$. Associated with low $F_v/F_m$ during its initial development, American ginseng had the lowest levels of epoxidation state of the xanthophyll cycle of the season, suggesting an active dissipation of excess light energy absorbed by the chlorophyll pigments. As photon flux density decreased after the deployment of the forest canopy to less than 10 mol $m^{-2}d^{-1}$, chlorophyll a/b decreased suggesting a greater investment in light harvesting pigments to reaction centers in order to absorb the fleeting light energy.

Physiological Responses of the Three Deciduous Hardwood Seedlings Growing Under Different Shade Treatment Regimes (상이한 피음조건에서 자라는 3개 활엽수의 생리적 반응)

  • Kim, Gil-Nam;Cho, Min-Seok;Lee, Soo-Won
    • Journal of Bio-Environment Control
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    • v.19 no.1
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    • pp.36-48
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    • 2010
  • This present study was conducted to investigate photosynthetic characteristics, chlorophyll fluorescence, chlorophyll contents of Betula platyphylla var. japonica, Prunus leveilleana, Magnolia sieboldii, growing under four different light intensity regimes (full sun, and 64~73%, 35~42%, 9~16% of full sun). As result, Betula platyphylla var. japonica showed outstanding photosynthetic capacity and apparent quantum yield in full sun and showed low shade tolerance. Prunus leveilleana showed good photosynthetic capacity and apparent quantum yield in 64~73% or 35~42% of full sun and showed common shade tolerance. However, Magnolia sieboldii showed good photosynthetic capacity and apparent quantum yield in 35~42% of full sun, while the lowest in full sun. Magnolia sieboldii showed the highest shade tolerance compared to the other species. As the shading level increased, the total chlorophyll contents of all species increased with significant difference.

A New Analytical Method to Determine the Purity of Synthetic Fluorophores using Single Molecule Detection Technique

  • Song, Nam-Yoong;Kim, Hyong-Ha;Park, Tae-Sook;Yoon, Min-Joong
    • Journal of Photoscience
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    • v.12 no.2
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    • pp.87-93
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    • 2005
  • A new assay technique to distinguish between pure compounds and the isomeric mixtures has been suggested using single molecule (SM) fluorescence detection technique. Since the number of emission spots in a fluorophorespread film prepared from a genuine dye solution was determined by experimental condition, the deviation of spot numbers from the expected values could be considered to be an indication of lower purity of the sample solution. The lower limit of sample concentration for this assay was determined to be $5{\times}10^{-10}$ M to show uniform number of expected spots within 10% uncertainties in our experimental condition. An individual fluorescence intensity distribution for a mixture of isomers having doubly different emissivities was simulated by adding distributions obtained from Cy3 and nile red (NR) independently. The result indicated that the mixture could be identified from the pure compounds through the difference in the number of Gaussian functions to fit the distribution. This new assay technique can be applied to the purity test for synthetic biofluorophores which are usually prepared in small quantities not enough for classical ensemble assays.

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Copper and Zinc Uptake Capacity of a Sorghum-Sudangrass Hybrid Selected for in situ Phytoremediation of Soils Polluted by Heavy Metals (식물정화를 위한 중금속 내성 작물의 선발과 수수-수단그라스 교잡종의 구리와 아연 흡수능력)

  • Oh, Soon-Ja;Koh, Seok-Chan
    • Journal of Environmental Science International
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    • v.24 no.11
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    • pp.1501-1511
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    • 2015
  • As essential trace elements, copper and zinc play important roles in many physiological events in plants. In excess, however, these elements can limit plant growth. This study selected a heavy metal-tolerant plant by analyzing seed germination and biomass of alfalfa (Medicago sativa), canola (Brassica campestris subsp. napus var. nippo-oleifera), Chinese corn (Setaria italica), and a sorghum-sudangrass hybrid (Sorghum bicolor ${\times}$ S. sudanense), and determined heavy metal uptake capacity by analyzing biomass, chlorophyll a fluorescence, and heavy metal contents under high external copper or zinc levels. The seed germination rate and biomass of the sorghum-sudangrass hybrid were higher under copper or zinc stress compared to the other three plants. The plant biomass and photosynthetic pigment contents of the sorghum-sudangrass hybrid seedlings were less vulnerable under low levels of heavy metals (${\leq}50ppm$ copper or ${\leq}400ppm$ zinc). The maximum quantum yield of PSII ($F_v/F_m$) and the maximum primary yield of PSII ($F_v/F_o$) decreased with increasing copper or zinc levels. Under high copper levels, the decline in $F_v/F_m$ was caused only by the decline in $F_m$, and was accompanied by an increase in non-photochemical quenching (NPQ). The $F_v/F_m$ declined under high levels of zinc due to both a decrease in the maximum fluorescence ($F_m$) and an increase in the initial fluorescence ($F_o$), and this was accompanied by a marked decrease in photochemical quenching (qP), but not by an increase in NPQ. Accumulations of copper and zinc were found in both aboveand below-ground parts of plants, but were greater in the below-ground parts. The uptake capacity of the sorghum-sudangrass hybrid for copper and zinc reached 4459.1 mg/kg under 400 ppm copper and 9028.5 mg/kg under 1600 ppm zinc. Our results indicate that the sorghum-sudangrass hybrid contributes to the in situ phytoremediation of copper or zinc polluted soils due to its high biomass yield.

Different Susceptibilities to Low Temperature Photoinhibition in the Photosynthetic Apparatus Among three Cultivars of Cucumber (Cucumis sativus L.)

  • Oh, Kwang-Hoon;Lee, Woo-Sung;Lee, Choon-Hwan
    • Journal of Photoscience
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    • v.8 no.3_4
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    • pp.105-112
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    • 2001
  • Susceptibility to low temperature photoinhibition in photosynthetic apparatus was compared among three cucumber cultivars, Gahachungjang (GH), Banbaekjijeo (BB) and Gaeryangsymji (GR). By chilling in the light for 6 h, a sustained decrease in the potential quantum yield (Fv/Fm) and the oxidizable P700 contents was observed, and the decrease was less in GH than in BB and GR. Although the difference was small, some $\Phi_{PSII}$ remained in GH after light-chilling for 6 h indicating that a few electrons can flow around photosystem II(PSII). As a consequence, the primary electron acceptor of PSII, $Q_{A}$, was reduced slowly and was not fully reduced after light-chilling for 6 h in GH. Although the amplitude was small, the development of NPQ was also faster in GH, indicating a higher capacity for non-photochemical energy dissipation. The relative fraction of a fast relaxing component of NPQ (qf) was higher in GH. After light-chilling for 5 h, the values of qf in BB and GR became much smaller than that in GH, indicating BB and GR suffered more significant uncoupling of ATPase and/or irreversible damages in PSII. When fluorescence induction transients were recorded after chilling, significant differences in quenching coefficients (qQ and qN) were observed among the three cultivars.

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Detection of Volatile Organic Compounds (VOCs) using Organic-Inorganic Hybrid Perovskite Nanoparticles (유무기 페로브스카이트 나노입자의 휘발성 유기화합물 감응특성)

  • Choi, Hansol;Choi, Jihoon
    • Korean Journal of Materials Research
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    • v.30 no.10
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    • pp.515-521
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    • 2020
  • Organic-inorganic hybrid perovskite nanocrystals have attracted a lot of attention owing to their excellent optical properties such as high absorption coefficient, high diffusion length, and photoluminescence quantum yield in optoelectronic applications. Despite the many advantages of optoelectronic materials, understanding on how these materials interact with their environments is still lacking. In this study, the fluorescence properties of methylammonium lead bromide (CH3NH3PbBr3, MAPbBr3) nanoparticles are investigated for the detection of volatile organic compounds (VOCs) and aliphatic amines (monoethylamine, diethylamine, and trimethylamine). In particular, colloidal MAPbBr3 nanoparticles demonstrate a high selectivity in response to diethylamine, in which a significant photoluminescence (PL) quenching (~ 100 %) is observed at a concentration of 100 ppm. This selectivity to the aliphatic amines may originate from the relative size of the amine molecules that must be accommodated in the perovskite crystals structure with a narrow range of tolerance factor. Sensitive PL response of MAPbBr3 nanocrystals suggests a simple and effective strategy for colorimetric and fluorescence sensing of aliphatic amines in organic solution phase.

Over-expression of Cu/ZnSOD Increases Cadmium Tolerance in Arabidopsis thaliana

  • Cho, Un-Haing
    • Journal of Ecology and Environment
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    • v.30 no.3
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    • pp.257-264
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    • 2007
  • Over-expression of a copper/zinc superoxide dismutase (Cu/ZnSOD) resulted in substantially increased tolerance to cadmium exposure in Arabidopsis thaliana. Lower lipid peroxidation and $H_2O_2$ accumulation and the higher activities of $H_2O_2$ scavenging enzymes, including catalase (CAT) and ascorbate peroxidase (APX) in transformants (CuZnSOD-tr) compared to untransformed controls (wt) indicated that oxidative stress was the key factor in cadmium tolerance. Although progressive reductions in the dark-adapted photochemical efficiency (Fv/Fm) and quantum efficiency yield were observed with increasing cadmium levels, the chlorophyll fluorescence parameters were less marked in CuZnSOD-tr than in wi. These observations indicate that oxidative stress in the photosynthetic apparatus is a principal cause of Cd-induced phytotoxicity, and that Cu/ZnSOD plays a critical role in protection against Cd-induced oxidative stress.

Excitation Mechanism of Fluorescent Polycyclic Aromatic Amines and Polycyclic Aromatic Hydrocarbons in Peroxyoxalate Chemiluminescence Reactions

  • Sung Chul Kang;Kang-Jin Kim
    • Bulletin of the Korean Chemical Society
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    • v.11 no.3
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    • pp.224-227
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    • 1990
  • The excitation mechanism of polycyclic aromatic amines (amino-PAHs) and polycyclic aromatic hydrocarbons(PAHs) for the chemiluminescence arising from the reaction between oxalate ester, bis(2,4,6-trichlorophenyl)oxalate (TCPO) or bis(2,4-dinitrophenyl)oxalate (DNPO) and hydrogen peroxide has been studied in terms of the excitation efficiencies to singlet excitation energies and the oxidative half-wave potentials. As a results of the study, the excitations of both amino-PAHs and PAHs appear to involve the charge transfer type of energy transfer. However the chemiluminescence efficiency corrected for fluorescence quantum yield of the amino-PAHs are varied more sensitively to the oxidative half-wave potential than that of PAHs possibly due to the large difference in solvation energy between the compounds and their ions.