• Bulletin of the Korean Chemical Society
• /
• v.12 no.4
• /
• pp.429-433
• /
• 1991

The photoinduced electron transfer reactions of N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) in various polar solvents were studied by measuring time-resolved fluorescence. The temperature dependence on the fluorescence decay rate in acetonitrile, methanol, ethanol and buthanol was carried out to obtain the activation energy and Arrehnius factor for the photoinduced electron transfer reaction. It was found that as the dielectric constant of the solvent increases, the activation energy and the reaction rate increase. This implys that the Arrehnius factor is important in controlling the photoinduced electron transfer reaction rate. In water, TMPD exists in three forms (cationic, protonated and neutral forms) due to the high dielectric constant and strong proton donating power of water. The photoinduced electron transfer reaction was found to be very fast (< 50 ps) and also the long liverd component in the fluorescence decay profile attributable to the photoexcited protonated form of TMPD was observed. Probably, the reaction pathway and the reaction coordinate seem to be different depending on the solvents studied here.

• Bulletin of the Korean Chemical Society
• /
• v.16 no.9
• /
• pp.886-891
• /
• 1995

Electroactive monolayers based on zirconium(Ⅳ) phosphonate film were prepared on gold and tin oxide electrodes by sequential layer-by-layer depostion technique. High transfer coefficient values and surface coverages of surface bound redox molecules were obtained from the electrochemical measurements of heterogeneous electron transfer rates for monolayer modified electrodes. 1,10-Decanediylbis(phosphonic acid) (DBPA) monolayer as insulating barrier was effective in blocking electron transfer. However, these film modified oxide electrode shows voltammetric behavior of diffusion/permeation process taking place at very small exposed area of modified electrode through channels due to structural defects within film when a very fast redox couple such as Ru(NH3)63+ is hired.

• Applied Biological Chemistry
• /
• v.17 no.2
• /
• pp.143-148
• /
• 1974

The interaction of the carcinogenic mycotoxin, Aflatoxin $B_1$, with the electron-donating molecule, benzene, was studied spectrophotometrically. The formation of charge-transfer complex between Aflatoxin $B_1$ and benzene in the presence of zinc chloride was observed and the apparent equilibrium constant of this charge-transfer complex was found to be 0.198 (liter $mole^{-1}$). It is assumed that, as the result of this study, some charge-transfer complexes could be formed between the weak electron-accepting Aflatoxin $B_1$ and strong electron-donating molecules, and the spectral changes occurred in the binding of Aflatoxin $B_1$ with proteins or DNA is attributed to the existence of charge-transfer type interaction.

• Rapid Communication in Photoscience
• /
• v.4 no.2
• /
• pp.37-40
• /
• 2015

To examine the photosensitized biomolecules damaging activity, dimethoxyP(V)tetrakis(2-naphthyl)porphyrin (NP) and dimethoxyP(V)tetraphenylporphyrin (PP) were synthesized. The naphthyl moiety of NP hardly deactivated the photoexcited P(V)porphyrin ring in ethanol. In aqueous solution, the naphthyl moiety showed the quenching effect on the photoexcited porphyrin ring, possibly through electron transfer and self-quenching by a molecular association. Binding interaction between human serum albumin (HSA), a water soluble protein, and these porphyrins could be confirmed by the absorption spectral change. The apparent association constant of NP was larger than that of PP. It is explained by that more hydrophobic NP can easily bind into the hydrophobic pockets of HSA. The photoexcited PP effectively induced damage of the tryptophan residue of HSA, through electron transfer-mediated oxidation and singlet oxygen generation. NP also induced HSA damage during photo-irradiation and the contributions of the electron transfer and singlet oxygen mechanisms were speculated. The electron transfer-mediated mechanism to the photosensitized protein damage should be advantageous for photodynamic therapy in hypoxic condition. The quantum yield of the HSA photodamage by PP was significantly larger than that of NP. The quenching effect of the naphthyl moiety is considered to suppress the photosensitized protein damage. In conclusion, the naphthalene substitution to the P(V)porphyrins can enhance the binding interaction with hydrophobic biomacromolecules such as protein, however, this substitution may reduce the photodynamic effect of P(V)porphyrin ring in aqueous media.

• Journal of Microbiology and Biotechnology
• /
• v.32 no.3
• /
• pp.287-293
• /
• 2022

The hydroxylation of methane (CH₄) is crucial to the field of environmental microbiology, owing to the heat capacity of methane, which is much higher than that of carbon dioxide (CO₂). Soluble methane monooxygenase (sMMO), a member of the bacterial multicomponent monooxygenase (BMM) superfamily, is essential for the hydroxylation of specific substrates, including hydroxylase (MMOH), regulatory component (MMOB), and reductase (MMOR). The diiron active site positioned in the MMOH α-subunit is reduced through the interaction of MMOR in the catalytic cycle. The electron transfer pathway, however, is not yet fully understood due to the absence of complex structures with reductases. A type II methanotroph, Methylosinus sporium 5, successfully expressed sMMO and hydroxylase, which were purified for the study of the mechanisms. Studies on the MMOH-MMOB interaction have demonstrated that Tyr76 and Trp78 induce hydrophobic interactions through π-π stacking. Structural analysis and sequencing of the ferredoxin domain in MMOR (MMOR-Fd) suggested that Tyr93 and Tyr95 could be key residues for electron transfer. Mutational studies of these residues have shown that the concentrations of flavin adenine dinucleotide (FAD) and iron ions are changed. The measurements of dissociation constants (K_ds) between hydroxylase and mutated reductases confirmed that the binding affinities were not significantly changed, although the specific enzyme activities were significantly reduced by MMOR-Y93A. This result shows that Tyr93 could be a crucial residue for the electron transfer route at the interface between hydroxylase and reductase.

• Journal of Power Electronics
• /
• v.18 no.1
• /
• pp.300-308
• /
• 2018

An online estimation method for wireless power transfer (WPT) systems is presented without using any measurement of the secondary side or the load. This parameter estimation method can be applied with a controlling strategy that removes both the receiving terminal controller and the wireless communication. This improves the reliability of the system while reducing its costs and size. In a wireless power transfer system with an LCCL impedance matching circuit under a rectifier load, the actual load value, voltage/current and mutual inductance can be reflected through reflected impedance measuring at the primary side. The proposed method can calculate the phase angle tangent value of the secondary loop circuit impedance via the reflected impedance, which is unrelated to the mutual inductance. Then the load value can be determined based on the relationships between the load value and the secondary loop impedance. After that, the mutual inductance and transfer efficiency can be computed. According to the primary side voltage and current, the load voltage and current can also be detected in real-time. Experiments have verified that high estimation accuracy can be achieved with the proposed method. A single-controller based on the proposed parameter estimation method is established to achieve constant current control over a WPT system.

• Bulletin of the Korean Chemical Society
• /
• v.26 no.11
• /
• pp.1706-1710
• /
• 2005

The excited-state intramolecular proton transfer (ESIPT) fluorescence in the 2-(2'-hydroxyphenyl)benzoxazole (HBO) derivatives with different electron donor and acceptor substituents was studied by spectroscopic and theoretical methods. Changes in the electronic transition, energy levels, and orbital diagrams of HBO analogues were investigated by the semi-empirical molecular orbital calculation and were correlated with the experimental spectral position of ESIPT keto emission. It was found that the presence of substituents, regardless of their nature, resulted in the red-shifted absorption relative to HBO. However, the spectral change of the ESIPT fluorescence was differently affected by the nature of substituent: hypsochromic shift with electron donor and bathochromic shift with electron acceptor.

• Journal of the Korean Chemical Society
• /
• v.45 no.1
• /
• pp.61-66
• /
• 2001

Stabilized Cross-linking Enzyme Crystals(CLEC) can be used as not only biocatalysts but also as enzyme sensors. PMS(Phenylmethyl Sulfate)was shown more efficience than any other electron mediator transfers toward HLADH(Horse Liver Alcohol Dehydrogenase)that were examined. NQS(naphtoquinonesulphonate), phenothiazine and ferrocene aldehyde had respectively just 52%, 37%, 35% electron transfer efficiency as compared to PMS . HLADH-CLEC was very stable toward elctron transfer mediators such as PMS, NQS and ferrocene aldehyde in which HLADH-solution was unstable.

• Journal of Photoscience
• /
• v.8 no.3_4
• /
• pp.99-104
• /
• 2001

Studies have been conducted to explore single electron transfer (SET) promoted photocyclization reactions of ($\omega$-phthalimidoalkylthio)acetic acids (alkyl=ethyl, n-propyl, n-butyl, n -hexyl and n-nonyl). Photocyclizations occur in methanol in modest yields to produce cyclized products in which phthalimide carbonyl carbon is bonded to the carbon of side chain in place of the carboxylic group. The initially formed cyclized products undergo efficient water eliminations to produce enthiol ethers in secondary ground state reactions.

• Journal of Photoscience
• /
• v.5 no.3
• /
• pp.125-129
• /
• 1998

Occurrence of an electron (or H atom equivalent to one electron plus H+) transfer from $\alpha$- tocopherol $\alpha$(TOH) to a number of photosensitizers in theri triplet states were investigated by monitoring the ESR signal of $\alpha$-chromaoxyl radical ($\alpha$(TO.) in ethanolic solutions of $\alpha$TOH and the sensitizers under continuous illumination. Every sensitizer molecule examined, such as protocholorophyllide (Pchl), hematoporphyrin and rose bengal which are generally regarded as efficient type II photosensitizers and thus have long-lived triplet states, was found to actively participate in an electro transfer reaction with $\alpha$TOH even under air-saturation conditions, generating $\alpha$TOH complex as an intermediate in a fashion of Michaelis-Menten type of reaction. For the reaction of $\alpha$TOH with triplet Pchl, the rate law was derived by applying the steady approximation for the binary complex, triplet Pchl-$\alpha$TOH , which turned out to be well consistent with the kinetic data.