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Pyun, Sang Yong,Cho, Bong Rae Korean Chemical Society 2013 Bulletin of the Korean Chemical Society Vol.34 No.7
Reactions of 4-nitrophenyl 2-thiophenecarboxylate (1a-e) with $R_2NH/R_2NH{_2}^+$ in 20 mol % DMSO (aq) have been studied kinetically. The $2^{nd}$ order kinetics, ${\beta}_{nuc}$ = 0.88-0.98, and linear Hammett and Yukawa-Tsuno plots observed for these reactions indicate an addition-elimination mechanism in which the $2^{nd}$ step is rate limiting. The ${\beta}_{nuc}$ value increased with a stronger electron-withdrawing 5-thienyl substituent, the Hammett plots are linear except for X = MeO, and Yukawa-Tsuno plots are linear with ${\rho}$ = 0.79-1.32 and r = 0.28-0.93, respectively. The ${\rho}$ value increased and r value decreased with a stronger nucleophile, indicating an increase in the electron density at the C=O bond and a decrease in the resonance demand. These results have been interpreted with enhanced N-C bond formation in the transition state with the reactivity increase.
Pyun, Sang Yong,Kim, Ju Chang,Cho, Bong Rae Korean Chemical Society 2014 Bulletin of the Korean Chemical Society Vol.35 No.7
Ketene-forming elimination from 2-X-4-nitrophenyl furylacetates (1a-d) promoted by $R_2NH-R_2NH_2{^+}$ in 70 mol % MeCN(aq) has been studied kinetically. When X = Cl and $NO_2$, the reactions exhibited second-order kinetics as well as Br$\ddot{o}$nsted ${\beta}$ = 0.37-0.54 and $|{\beta}_{lg}|$ = 0.31-0.45. The Br$\ddot{o}$nsted ${\beta}$ decreased with a poorer leaving group and $|{\beta}_{lg}|$ increased with a weaker base. The results are consistent with an E2 mechanism. When the leaving group was changed to a poorer one [X= H (1a) and $OCH_3$ (1b)], the reaction mechanism changed to the competing E2 and E1cb mechanisms. A further change to the E1cb mechanism was realized for the reaction of 1a with $i-Pr_2NH/i-Pr_2NH_2{^+}$ in 70 mol % MeCN-30 mol % $D_2O$. By comparing the kinetic results in this study with the existing data for $ArCH_2C(O)OC_6H_3-2-X-4-NO_2$, the effect of the ${\beta}$-aryl group on the ketene-forming elimination was assessed.
Pyun, Sang-Yong,Byun, Woong-Sub,Cho, Bong-Rae Korean Chemical Society 2011 Bulletin of the Korean Chemical Society Vol.32 No.6
Nitrile-forming eliminations from $(E)-2,4,6-(NO_2)_3C_6H_2CH=NOC_6H_4-2-X-4-NO_2$ (1) promoted by $R_3NH/R_3NH^+$ in 70 mol % MeCN(aq) have been studied kinetically. When X = $NO_2$, the reactions exhibited second-order kinetics as well as Br$\"{o}$nsted ${\beta}$ = 0.63 and ${\mid}{\beta}_{lg}{\mid}$ = 0.34-0.46, and an E2 mechanism is evident. As the leaving group was made poorer (X = H, Cl, and $CF_3$), Br$\"{o}$nsted ${\beta}$ value increased from 0.63 to 0.85-0.89 without much change in the ${\mid}{\beta}_{lg}{\mid}$ value E2, indicating that structure of the transition state changed to an E1cb-like with extensive $C_{\beta}-H$ bond cleavage, significant negative charge development at the ${\beta}$-carbon, and limited $C_{\alpha}$-OAr bond cleavage.
Interaction between thyroglobulin and ADAMTS16 in premature ovarian failure
Pyun, Jung-A,Kim, Sunshin,Kwack, KyuBum The Korean Society for Reproductive Medicine 2014 Clinical and Experimental Reproductive Medicine Vol.41 No.3
Objective: The aim of the present study was to examine whether interactions between polymorphisms in the thyroglobulin and ADAM metallopeptidase with thrombospondin type 1 motif, 16 (ADAMTS16) genes are associated with the development of premature ovarian failure (POF). Methods: A total of 75 patients with POF and 196 controls were involved in this study. We used a GoldenGate assay to genotype single nucleotide polymorphisms (SNPs). Logistic regression analysis was performed to identify POF-associated polymorphisms and synergistic interactions between polymorphisms in the thyroglobulin and ADAMTS16 genes. Results: Single gene analyses using logistic regression analysis showed no significant association between polymorphisms in the two genes and POF. In the results from interaction analyses, we found seven synergistic interactions between the polymorphisms in thyroglobulin and ADAMTS16, although there was no combination showing p-values lower than the significant threshold using the Bonferroni correction. When the AG genotype was present at the rs853326 missense SNP, the A and G alleles at the tagging SNPs rs16875268 and rs13168665 showed significant interactions (odds ratios=5.318 and 16.2 respectively; 95% confidence intervals, 1.64-17.28 and 2.08-126.4; p=0.0054 and 0.0079). Conclusion: Synergistic interactions between polymorphisms in the thyroglobulin and ADAMTS16 genes were associated with an increased risk of POF development in Korean women.
Lithium intercalation into a plasma-enhanced-chemical-vapour-deposited carbon film electrode
Pyun Su-II The Korean Electrochemical Society 1999 한국전기화학회지 Vol.2 No.1
Electrochemical lithium intercalation into a PECVD (plasma enhanced chemical vapour deposited) carbon film electrode was investigated in 1 M $LiPF_6-EC$ (ethylene carbonate) and DEC (diethyl carbonate) solution during lithium intercalation and deintercalation, by using cyclic voltammetry supplemented with ac-impedance spectroscopy. The size of the graphitic crystallite in the a- and c-axis directions obtained from the carbon film electrode was much smaller than those of the graphite one, indicating less-developed crystalline structure with hydrogen bonded to carbon, from the results of AES (Auger electron spectroscopy), powder XRD (X-ray diffraction) method, and FTIR(Fourier transform infra-red) spectroscopy. It was shown from the cyclic voltammograms and ac-impedance spectra of carbon film electrode that a threshold overpotential was needed to overcome an activation barrier to entrance of lithium into the carbon film electrode, such as the poor crystalline structure of the carbon film electrode showing disordered carbon and the presence of residual hydrogen in its structure. The experimental results were discussed in terms of the effect of host carbon structure on the lithium intercalation capability.
Pyun Su-Il,Moon Sung-Mo The Korean Electrochemical Society 1998 한국전기화학회지 Vol.1 No.1
This work presents the way how to evaluate the degree of reversibility of the discharging process undergone by the nickel hydroxide film cathodically deposited on pure nickel as a positive electrode for electrochemical capacitor using the combined cyclic voltammetry and potential drop method, supplemented by galvanostatic discharge and open-circuit potential transient methods. The time interval necessary just to establish the current reversal of anodic to cathodic direction from the moment just after applying the potential inversion of anodic to cathodic direction, was obtained on cyclic voltammogram. The cathodic charge density passed upon dropping the applied potential, was calculated on potentiostatic current density-time curve. Both the time interval and the cathodic charge density in magnitude can be regarded as being measures of the degree of reversibility of the discharging process undergone by the positive active material for supercapacitor, i.e. , the longer the time interval is, the lower is the degree of reversibility and the greater the cathodic charge density is, the higher is the degree of reversibility. From the applied potential dependences of the time interval and cathodic charge density, discharge at $0.42 V_{SCE}$ was determined to be the most reversible.
Pyun, Jung Eun,Choi, Da Min,Lee, Jung Hwa,Yoo, Kee Hwan,Shim, Jung Ok The Korean Society of Pediatric Gastroenterology 2015 Pediatric gastroenterology, hepatology & nutrition Vol.18 No.1
Gastroesophageal reflux disorder (GERD) is the most common esophageal disorder in children. Achalasia occurs less commonly but has similar symptoms to GERD. A nine-year old boy presented with vomiting, heartburn, and nocturnal cough. The esophageal impedance-pH monitor revealed nonacidic GERD (all-refluxate clearance percent time of 20.9%). His symptoms persisted despite medical treatment for GERD, and he was lost to follow up. Four years later, he presented with heartburn, solid-food dysphagia, daily post-prandial vomiting, and failure to thrive. Endoscopy showed a severely dilated esophagus with candidiasis. High-resolution manometry was performed, and he was diagnosed with classic achalasia (also known as type I). His symptoms resolved after two pneumatic dilatation procedures, and his weight and height began to catch up to his peers. Clinicians might consider using high-resolution manometry in children with atypical GERD even after evaluation with an impedance-pH monitor.