• Bulletin of the Korean Chemical Society
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• v.20 no.1
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• pp.85-88
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• 1999

Me3NO selectively abstracts the proton from [IrH(CO)(PPh3)2L(A)]0.1+,2+ (1) (A: -CCPh, Cl-, CH3CN and L: CH3CN, Cl-, C1O4-) to give the trans-elimination products, Ir(CO)(PPh3)2(A) (2). The reductive elimination of H+ and Cl- from Ir(H)Cl2(CO)(PPh3)2 (lb) to give IrCl(CO)(PPh3)2 (2b) is first order in both lb and Me3NO. The rate law d[2b]/dt=kobs[lb]=k2[lb][Me3NO] suggests the formation of (PPh3)2(CI)2(CO)Ir-H-ON+Me3 in the rate determining step (k2) followed by the fast dissociation of both H-ON+Me3 and the trans ligand Cl-. The rate significantly varies with the cis liaand A and the trans ligand L and is slower with both A and L being Cl- than other ligands. Me3NO selectively eliminates CO from [Ir(H)2(CO)(PPh3)2L]0,+ (3) (L=CH3CN, C1O4-) to produce [Ir(H)2(PPh3)2L'(CH3CN)]+ (4) (L'=CH3CN, PPh3) in the presence of L. Me3NO does not readily remove either H+ or CO from cis, trans- and trans, trans-lr(H)(-CCPh)2(CO)(PPh3)2 and cis, trans-Ir(H)2Cl(CO)(PPh3)2. The choice whether hydridocarbonyls, 1 and 3 undergo the deprotonation or decarbonylation may be understood mostly in terms of thermodynamic stability of the products and partly by kinetic preference of Me3NO on proton and CO.

• Journal of the Korean Chemical Society
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• v.37 no.2
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• pp.199-205
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• 1993

The decomposition of hydrogen peroxide by copper-amines complexes was studied in the pH range of 7.3∼11.3 by measuring the rate of the decreasing concentration of $H_2O_2$. Decomposition rate of hydrogen peroxide increased with increasing pH, and then decreased with increasing pH successively. The mechanism for this type of reaction involves the formation of peroxo complexes in the rate-determining step preceding deprotonation of hydrogen peroxide and copper-amines complexes.

• Molecular & Cellular Toxicology
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• v.4 no.2
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• pp.170-176
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• 2008

The quantitative structure-activity relationship (QSAR) of a set of 35 flavonoid compounds presenting antioxidant activity was established by means of Genetic Algorithm-Multiple Linear Regression (GA-MLR) technique. Four-parametric models for two sets of data, the 1,1-diphenyl-2-picryl hydrazyl (DPPH) radical scavenging activity $(R^2=0.788,\;Q^2_{cv}=0.699\;and\;Q^2_{ext}=0.577)$ and scavenging activity of reactive oxgen species (ROS) induced by $H_2O_2 (R^=0.829,\;Q^2_{cv}=0.754\;and\;Q^2_{ext}=0.573)$ were obtained with low external predictive ability on a mass basis, respectively. Each model gave some different mechanistic aspects of the flavonoid compounds tested in terms of the radical scavenging activity. Topological charge, H-bonding complex and deprotonation processes were likely to be involved in the radical scavenging activity.

• Journal of Photoscience
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• v.10 no.1
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• pp.89-96
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• 2003

Two important types of $\alpha$-heterolytic fragmentation reactions of aminium radicals are discussed. In these fragmentation processes, transfer of electrofugal groups from the aminium radicals to either Lowry-Bronsted or Lewis bases produces $\alpha$-amino radicals. The results of recent studies that provided key information about the dynamics of the important aminium radical fragmentation reactions, deprotonation, desilylation, are summarized. Finally, selected examples, which demonstrate how knowledge of the relative rates of aminium radical cleavage can be used to design synthetically relevant SET-promoted photocyclization reactions, are presented.

• Journal of Pharmaceutical Investigation
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• v.21 no.3
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• pp.149-153
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• 1991

Polyethylene oxide (PEO)-polymethacrylic acid (PMAA) interpenetrating polymer networks (IPN) were synthesized via radical polymerization of PMAA and simultaneous crosslinking of PEO using triisocyanate. The equilibrium swelling of PEO-PMAA IPN was determined at different pHs. The swelling of PEO-PMAA IPN, ranged from 20% to 90%, was more sensitive than that of homo polymer PMAA gel This is probably due to protonation and deprotonation of the PMAA network and interpolymer complex formation between PEO and PMAA. Several model drugs were loaded into the IPN matrices and the release mechanisms were investigated. The release of nonionizable drugs such as ftorafur and prednisolone was controlled by swelling of the matrices. However, he release of propranolol, positively charged drug, was more affected by the ionic interaction between the drug and PMAA newtork, and the interpolymer complexation.

• Bulletin of the Korean Chemical Society
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• v.35 no.11
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• pp.3313-3318
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• 2014

The reaction mechanism of Lead ions catalyzing complexation reactions between TIPP and metal ions was investigated by researching the kinetics of the formation of metalloporphyrins by UV/Vis-spectra, and verified by exploring the formation of metalloporphyrins catalyzed by acetic acid. Kinetics studies suggested that the fluctuations of reaction rate indicated the formation of metalloporphyrin was step-wise, including the pre-equilibrium step (the coordination of the pyrrolenine nitrogens to $Mn^+$) and the rate-controlling step (the deprotonation of the pyrrole proton). In the pre-equalization step, a sitting-atop (SAT) structure formed first with the complexation between larger radius of $Pb^{2+}$ and TIPP, changed the activation, then $Pb^{2+}$ left with the smaller radius of metal ions attacking from the back of the porphyrin ring center. In the rate-controlling step, two pyrrole protons dissociated to restore a stable structure. This was verified by adding acetic acid at different reaction times.

• Bulletin of the Korean Chemical Society
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• v.26 no.3
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• pp.423-427
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• 2005

The bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex-272) and sodium diethyl- dithiocarbamate (NaDDC) ligands were used to extract of metal ions ($Cd^{2+},\;Co^{2+},\;Cu^{2+},\;Pb^{2+},\;Zn^{2+}$) in supercritical $CO_2$. Experiments showed a strong synergistic effect and better extraction efficiency if the two ligands were used together. In-situ UV-visible observation indicates that NaDDC in the water/supercritical $CO_2$ started to decompose slowly. The synergistic effect seems to come from the deprotonation of the organophosphorus ligand by amines from the decomposed NaDDC. The enhancing role of amines was confirmed using the mixture of Cyanex-272 and diethylamine(DEA) in the metal extraction.

• Bulletin of the Korean Chemical Society
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• v.27 no.8
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• pp.1099-1114
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• 2006

Our studies in the area of single electron transfer (SET) photochemistry have led to the discovery of efficient processes, in which regioselective formation of carbon-centered radicals takes place by nucleophile assisted desilylation of $\alpha$-trialkylsilyl substituted ether, thioether, amine and amide centered cation radicals. The rates of bimolecular desilylation of the intermediate cation radicals exceed those of other cation radical $\alpha$-fragmentation processes (e.g.,-deprotonation). This sereves as the basis for the design of highly regioselective, SET-induced photomacrocyclization reactions of polyether, polythioether, polyamide, and polypeptide linked phthalimides. Photocyclization reactions of trimethylsilyl-terminated substrates in these families are unique in that they produce polyfunctionalized macrocyclic substances in a highly efficient and regioselective manner. In addition, our studies in this area have led to important information about the factors that govern chemical and quantum efficiencies that should be applicable to a wide variety of redox processes promoted by SET from substrates containing more than one electron donor site.

• Journal of Photoscience
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• v.1 no.2
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• pp.89-94
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• 1994

The reaction of decaborane with trimethylsilyldiazomethane gives 1, 2-bis (trimethylsilyl)-1, 2-carba-closo-dodecaborane(12). This compound is similar to the icosahedral cage structure of o-carborane. This formation of the first adduct proceeds through deprotonation of the acidic center of B(9) and B(6) by intermolecular attack by the lone electron pair of the carbene, : CHSiMe$_3$. The yield of product is influenced by irradiation and thermal conditions.

• Macromolecular Research
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• v.14 no.5
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• pp.510-516
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• 2006

Lactide was produced from oligomeric PLA by back-biting reaction of the OH end groups. For optimization of the reaction conditions, the effects of temperature, pressure, PLA molecular weight, and catalyst type on the lactide synthesis were examined. The fraction of D,L-lactide decreased with increasing temperature. Among the various Sn-based catalysts, the D,L-lactide fraction was maximized when SnO was used. A higher yield with lower racemization was observed at lower pressure. The conversion of PLA was maximized at an oligomeric PLA molecular weight of ca. 1380. The yield of lactide increased but the fraction of D,L-lactide decreased with increasing molecular weight. The highest conversion with the lowest racemization degree was obtained at a catalyst concentration of 0.1 wt%. The lactide was more sensitive to racemization because of the entropic effect.