• Bulletin of the Korean Chemical Society
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• v.25 no.1
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• pp.90-96
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• 2004

The conformations of dicyclopropyl, isopropyl cyclopropyl, and diisopropylcarbenes were optimized using density functional theory (B3LYP/6-31G(d)). We showed that the optimized geometries of carbenes with cyclopropyl groups are fully in accord with those expected for bisected W-shaped conformations, in which the effective hyperconjugation of a cyclopropyl group with singlet carbene can occur. The stabilization energies were evaluated at the B3LYP/6-311+G(3df, 2p)//B3LYP/6-31G(d) + ZPE level using an isodesmic equation. The relative stability of carbenes is in the order $(c-Pr)_2$C: > (i-Pr)(c-Pr)C: > $(i-Pr)_2$C:, and a cyclopropyl group stabilizes carbene more than an isopropyl group by nearly 9 kcal/mol. Energies for the decomposition of diazo compounds to carbenes increase in the order $(c-Pr)_2$ < (i-Pr)(c-Pr) < $(i-Pr)_2$ by ~9 kcal/mol each. From a singlettriplet energy gap ($E_{ST}$) calculation, the singlet level is lower than the triplet level and the $E_{ST}$ shows a trend similar to the stabilization energy calculations. For comparison, the optimized geometries and stabilization energies for the corresponding carbocations were also studied at the same level of calculation. The greater changes in geometries and the higher stabilization energies for carbocations compared to carbenes can explain the greater hyperconjugation effect.

• Bulletin of the Korean Chemical Society
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• v.20 no.11
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• pp.1281-1287
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• 1999

The low-lying electronic states of diazirine and 3,3'-dimethyldiazirine have been studied by high level ab initio quantum chemical methods. The equilibrium geometries of the ground state and the first excited singlet and triplet states have been optimized using the Hartree-Fock (HF) and complete active space SCF (CASSCF) methods, as well as using the Møller-Plesset second order perturbation (MP2) theory and the single configuration interaction (CIS) theory. It was found that the first excited singlet state is of 1 B1 symmetry resulting from the n- π* transition, while the first excited triplet state is of 3 B2 symmetry resulting from the π- π* transition. The harmonic vibrational frequencies have been calculated at the optimized geometry of each electronic state, and the scaled frequencies have been compared with the experimental frequencies available. The adiabatic and vertical transition energies from the ground electronic state to the low-lying electronic states have been estimated by means of multireference methods based on the CASSCF wavefunctions, i.e., the multiconfigurational quasidegenerate second order perturbation (MCQDPT2) theory and the CASSCF second-order configuration interaction (CASSCF-SOCI) theory. The vertical transition energies have also been calculated by the CIS method for comparison. The computed transition energies, particularly by MCQDPT2, agree well with the experimental observations, and the electronic structures of the molecules have been discussed, particularly in light of the controversy over the existence of the so-called second electronic state.

• Bulletin of the Korean Chemical Society
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• v.13 no.2
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• pp.166-172
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• 1992

Studies have been conducted to explore single electron transfer (SET) induced photocyclization reactions of N-(trimethylsilylmethoxyalkyl)phthalimides(alkyl=E thyl, n-propyl, n-butyl, n-pentyl, and n-octyl). Photocyclizations occur in methanol in high yields to produce cyclized products in which phthalimide carbonyl carbon is bonded to the carbon of side chain in place of the trimethylsilyl group. Mechanism for these photocyclizations involving intramolecular SET from oxygen in the $\alpha-silylmethoxy$ groups to the singlet excited state phthalimide moieties followed by desilylation of the intermediate $\alpha-silylmethoxy$ cation radicals and cyclization by radical coupling are proposed. In contrast, photoreaction of N-(trimethylsilylmethoxyethyl) phthalimide in acetone follows different reaction routes to produce two cyclized products in which carbon-carbon bond formation takes place between the phthalimide carbonyl carbon and the carbon $\alpha$ to silicon and oxygen atoms via triplet carbonyl hydrogen abstraction triplet carbonyl silyl group abstraction pathways. The normal singlet SET pathway dominates these triplet processes for photoreaction of this substance in methanol. The efficient and regioselective cyclization reactions observed for photolysis in methanol represent synthetically useful processes for construction of medium and large ring heterocyclic compounds.

• Bulletin of the Korean Chemical Society
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• v.28 no.10
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• pp.1656-1660
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• 2007

Using solid inorganic peroxides (including Li2O2, Na2O2, SrO2 and BaO2) as starting materials, three reaction paths for singlet oxygen (1O2) production were developed and studied. Their 1O2 emission spectra in the near- IR region and visible region from these reaction paths were simultaneously recorded by a near-IR sensitive Optical Multichannel Analyzer and a visible sensitive Optical Spectrum Analyzer, respectively. The comparison of their 1O2 emission spectra indicated that: (1) in term of the efficiency for 1O2 production, the gasliquid- solid reaction path (in which Cl2 or HCl and H2O reacted with the solid inorganic peroxides suspension in CCl4) was prior to the gas-solid reaction path (in which Cl2 or HCl reacted with the solid inorganic peroxides suspension in CCl4), but was inferior to the gas-liquid reaction path (in which Cl2 or HCl reacted with the solid inorganic peroxides solution in H2O or D2O); (2) the alkali metal peroxides (such as Li2O2 and Na2O2) was prior to the alkaline earth metal peroxides (such as SrO2 and BaO2) as the solid reactants, and Cl2 was favorable than HCl as the gas reactant in efficiency for 1O2 production in these reaction paths.

• Journal of Dairy Science and Biotechnology
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• v.28 no.2
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• pp.13-18
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• 2010

Electron Spin Resonance (ESR) spectroscopy has been used to detect the presence of radiation-induced free radicals in biological samples since the mid 1950s and to irradiate foods containing cellulose, crystalline sugar, and bone. Therefore, we analyzed the ESR spectrum of irradiated infant formula and its ingredients in this study. Samples were irradiated with 2 different radiation sources of $^{60}Co$ gamma rays and electron beams (EBs), and the absorbed doses were 0, 1, 3, 5, and 7 kGy. ESR measurements were performed under normal atmospheric conditions using a JEOL JES-FA100 spectrometer equipped with an X-band bridge. Irradiated infant formula showed anunsymmetrical spectrum ($g_1$=2.0050, $g_2$=2.0006); in contrast, non-irradiated samples showed asymmetrical spectrum. The ingredients of irradiated samples showed a multi-component ESR signal in glucose and lactose and a singlet-type spectrum in milk powder (g=2.0050). $R^2$ of the dose-response curve showed a fine linearity of over 0.95 across the entire sample. We also compared the spectra of identical samples irradiated with $^{60}Co$ gamma rays and EBs, because EBs can be used for food irradiation in foreign countries, although this is not permitted in Korea. However, we could not find any significant differences according to the types of radiation source. Thus, ESR spectroscopy can be used to detect irradiated infant formula and several types of primary ingredients in this formula.

• Food Science and Preservation
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• v.20 no.5
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• pp.684-690
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• 2013

The antioxidant and photoprotective effects of various extracts from the roots of Rumex crispus L. were evaluated. The concentrations ($IC_{50}$) of various extracts required to exert a 50% reducing effect on a DPPH radical were found to be 0.005~0.093 mg/mL. The ethyl acetate extract showed a more remarkable effect than the positive control ascorbic acid. The concentrations ($QC_{50}$) of the butanol and ethyl acetate extracts required to exert a 50% reducing effect on the singlet oxygen $^1O_2$ were found to be 0.464 and 0.365 mg/mL, respectively. Both extracts were also found to protect the in vitro biological system from the detrimental effect of a singlet oxygen $^1O_2$ on type II photosensitization in E. coli and genomic DNA. Among all the tested extracts, the ethyl acetate and butanol extracts contained higher amounts of total phenolic contents. The results suggest that our study may contribute to the development of new bioactive products with potential applications to the reduction of photo-produced oxidative stress involving reactive oxygen species in living organisms.

• Food Science and Preservation
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• v.22 no.1
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• pp.129-133
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• 2015

The antioxidant potentials of ten kinds of medicinal plants used as natural dyeing agents were tested. Among the plant extracts and floral waters that were examined in this study, the antioxidant activities of the DPPH and ABTS radical scavengers increased with increasing amounts of the extracts. The hot-water extracts from Aphis chinensis, Caesalpinia sappan L., Rumex crispus L., and Areca catechu effectively inhibited the DPPH and ABTS radicals at concentration below 0.1 mg/mL. The floral water obtained through steam distillation from Areca catechu, Rubia akane Nakai, Coptis chinensis, and Phellodendron amurense showed relatively valid antioxidant activities. In particular, the natural colorants extracted from Rumex crispus L., Areca catechu, and Aphis chinensis effectively suppressed the photogenerated singlet oxygen induced by a photosensitizer in in-vitro assay systems. The concentrations ($IC_{50}$) of the hot-water Aphis chinensis extract required to exert a 50% reduction effect on DPPH, ABTS, and singlet oxygen were found to be 8.5, 8.0, and $210{\mu}g/mL$, respectively. The study results suggest that extracts derived from naturally occurring colorants as well as floral waters could be used as natural antioxidants in the food and health-care industries.

• Environmental Analysis Health and Toxicology
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• v.10 no.3_4
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• pp.21-28
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• 1995

The photodegradation of TCBs in humic acid solutions at pH 7 was evaluated under laboratory sunlight simulated irradiation for 8 and 42 days. The irradiation to TCBs in solution in the presence of humic acid produced trichlorophenols, dichlorophenols in addition to the minor photodegraded products such as dichlorobutadiene, dichlorobenzaldehyde and pentachlorobiphenyls. The formation of photodegradation products indicate that the excited singlet oxygen and solvated electrons play a major contributors to the photodegradation process.

• Proceedings of the Korean Society of Crop Science Conference
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• 2006.04a
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• pp.596-597
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• 2006

• Journal of Photoscience
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• v.4 no.2
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• pp.53-59
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• 1997

Absorption and fluorescence studies of E-1-(p-methoxyphenyl)-2-(p-nitrophenyl) ethene in homogeneous solvents, polymer matrix and normal and reverse micelles showing strong solvatochromic fluorescent emission properties with quasi-planar intramolecular charge transfer characteristics in the electronically excited singlet state are discussed.