• The Korean Journal of Food And Nutrition
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• v.7 no.1
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• pp.29-35
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• 1994

Photolysis of diazotetracyanocyclopentadiene has been investigated by means of IR and UV-vis spec troscopy in Ar matrix. Parent carbene is produced in low yield and could be detected by UV-vis spectroscopy and IR spectroscopy. The carbene produced from the diazo compound is very photolabile and also decay thermally at temperature as low as 10K. When the diazo compound is photolyzed the Arrhenius plots show a tunneling effect that is not shown as non linearity.

• Journal of Photoscience
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• v.7 no.1
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• pp.15-19
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• 2000

The photochemical reaction mechanism has been investigated for methanol insertion into the p-substituted phenylketo carbenes. The triplet spin state of phenyl koto carbene is stabilized by the neighbored carbonyl electrons. When the phenylketo carbene reacts with methanol, the ylied intermediate is formed, then moves to the activated transition state.

• The Korean Journal of Food And Nutrition
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• v.11 no.3
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• pp.267-271
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• 1998

The photochemical carcinogenic reaction mechanism and molecular carcinogenic intensity through the reaction of dibromo carbene and diazomethane with dehydroacetic acid and coumarin have been studied under the two kinds of photolysis. The reaction intensities show the degree of carcinogenic activity. Under the condition of UV/vis light source, the yield of high toxic carcinogenetic carbene intermediate is produced less than those of the laser flash photolysis.

• Bulletin of the Korean Chemical Society
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• v.10 no.4
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• pp.374-377
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• 1989

Photolysis of dichlorodiphenylmethane in glassy 2-MeTHF at 77K results in the formation of diphenylcarbene and the diphenylchloromethyl radical, which were detected by their flourescence emission and excitation spectra. The relative yield of the carbene to radical is shown to vary dramatically as a function of irradiation time. The photolability of the radical is also demonstated. These results were interpreted in terms of a two step mechanism, where the diphenylchloromethyl radical is an intermediate in the formation of diphenylcarbene.

• Bulletin of the Korean Chemical Society
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• v.26 no.12
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• pp.1981-1985
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• 2005

Kinetic studies have been performed for alkaline hydrolysis of a series of [(methoxy)(p-substituted styryl)carbene]pentacarbonyl chromium(0) complexes ($(CO)_5$Cr=$C(OCH_3)CH=CHC_6H_4X$, X = p-$OCH_3$, p-$CH_3$, H, p-Cl, p-$NO_2$). Second-order rate constants $(k_{{OH}^-})$ for the alkaline hydrolysis in 50% acetonitrile-water(v/v) were determined spectrophotometrically at various temperatures. At a low pH region (pH < 7.5), the observed rate constant $(k_{obs})$ remained constant with a small value, while in a high pH region (pH > 9.5), $k_{obs}$ increases linearly with increasing the pH of the medium. The second-order rate constants $(k_{{OH}^-})$ increase as the substituent X changes from a strong electron donating group to a strong electron withdrawing group. The Hammett plot obtained for the alkaline hydrolysis is consisted of two intersecting straight lines. The nonlinear Hammett plot might be interpreted as a change in the rate-determining step. However, the fact that the corresponding Yukawa-Tsuno plot is linear with $\rho$ and r values of 0.71 and 1.14, respectively indicates that the nonlinear Hammett plot is not due to a change in the rate-determing step but is due to ground-state stabilization through resonance interaction. The positive $\rho$ value suggests that nucleophilic attack by $OH^-$ to form a tetrahedral addition intermediate is the rate-determining step. The large negative ${\Delta}S^\neq$ value determined in the present system is consistent with the proposed mechanism.

• The Korean Journal of Food And Nutrition
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• v.10 no.1
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• pp.6-13
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• 1997

Reactivity and reaction mechanism for the photosensitized generation of hydroxyl radical by various coumarin derivatives are investigated by means of ESR and laser flash photolysis methods. The nine kinds of coumarin derivatives show to be proceeded through the OH·radical generation mechanism, however 1-ethyl-3-nitro-1-nitrosoguanidine decomposes and produces the carbene intermediate before OH·radical generation reaction occurs. The nine coumarin derivatives show the signals, which are corresponded to DMPO-OH spin adducts. NaN3, EtOH and HCOONa act as a strong photosensitizer to quench OH·radical. The decay rate constants of the hydrated electrons in the case of added N2O show higher than added K3Fe(CN)6.