• Title/Summary/Keyword: cross-reactions

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Kinetics and Mechanism of the Anilinolysis of Bis(aryl) Chlorophosphates in Acetonitrile

  • Barai, Hasi Rani;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.32 no.6
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    • pp.1939-1944
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    • 2011
  • The nucleophilic substitution reactions of bis(Y-aryl) chlorophosphates (1) with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at 35.0 $^{\circ}C$. The kinetic results of 1 are compared with those of Y-aryl phenyl chlorophosphates (2). The substrate 1 has one more identical substituent Y compared to substrate 2. The cross-interaction between Y and Y, due to additional substituent Y, is significant enough to result in the change of the sign of cross-interaction constant (CIC) from negative ${\rho}_{XY}$ = -1.31 (2) to positive ${\rho}_{XY}$ = +1.91 (1), indicating the change of reaction mechanism from a concerted $S_N2$ (2) to a stepwise mechanism with a rate-limiting leaving group departure from the intermediate (1). The deuterium kinetic isotope effects (DKIEs) involving deuterated anilines ($XC_6H_4ND_2$) show secondary inverse, $k_H/k_D$ = 0.61-0.87. The DKIEs invariably increase as substituent X changes from electron-donating to electron-withdrawing, while invariably decrease as substituent Y changes from electron-donating to electron-withdrawing. A stepwise mechanism with a rate-limiting bond breaking involving a predominant backside attack is proposed on the basis of positive sign of ${\rho}_{XY}$ and secondary inverse DKIEs.

Study on Neutron Capture Probability of Praseodymium at Thermal Neutron Energy (열중성자에 대한 프라세오디뮴의 중성자포획확률에 대한 연구)

  • Lee, Samyol;Lee, Sangbock;Jungran Yoon;Kim, Jeongkoo
    • The Journal of the Korea Contents Association
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    • v.4 no.2
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    • pp.76-82
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    • 2004
  • The thermal neutron capture cross-section (at 2,200 m/s value) of the $^{141}$Pr(n,$\gamma$)$^{142}$Pr reaction was measured by an activation method by using the heavy water ($D_2$O) thermal neutron facility at the KUR(Kyoto University Reactor). The thermal neutron fiux used in this experiment was monitored with the$^{197}$Au(n,$\gamma$)$^{198}$Au standard cross-section. The previous results and the evaluated data of JENDL-3.2, ENDF/B-VI, and JEF-2.2 were in good agreement with the current result.

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Local tissue effects of various barrier membranes in a rat subcutaneous model

  • Naenni, Nadja;Lim, Hyun-Chang;Strauss, Franz-Josef;Jung, Ronald E.;Hammerle, Christoph H.F.;Thoma, Daniel S.
    • Journal of Periodontal and Implant Science
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    • v.50 no.5
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    • pp.327-339
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    • 2020
  • Purpose: The purpose of this study was to examine the local tissue reactions associated with 3 different poly(lactic-co-glycolic acid) (PLGA) prototype membranes and to compare them to the reactions associated with commercially available resorbable membranes in rats. Methods: Seven different membranes-3 synthetic PLGA prototypes (T1, T2, and T3) and 4 commercially available membranes (a PLGA membrane, a poly[lactic acid] membrane, a native collagen membrane, and a cross-linked collagen membrane)-were randomly inserted into 6 unconnected subcutaneous pouches in the backs of 42 rats. The animals were sacrificed at 4, 13, and 26 weeks. Descriptive histologic and histomorphometric assessments were performed to evaluate membrane degradation, visibility, tissue integration, tissue ingrowth, neovascularization, encapsulation, and inflammation. Means and standard deviations were calculated. Results: The histological analysis revealed complete integration and tissue ingrowth of PLGA prototype T1 at 26 weeks. In contrast, the T2 and T3 prototypes displayed slight to moderate integration and tissue ingrowth regardless of time point. The degradation patterns of the 3 synthetic prototypes were similar at 4 and 13 weeks, but differed at 26 weeks. T1 showed marked degradation at 26 weeks, whereas T2 and T3 displayed moderate degradation. Inflammatory cells were present in all 3 prototype membranes at all time points, and these membranes did not meaningfully differ from commercially available membranes with regard to the extent of inflammatory cell infiltration. Conclusions: The 3 PLGA prototypes, particularly T1, induced favorable tissue integration, exhibited a similar degradation rate to native collagen membranes, and elicited a similar inflammatory response to commercially available non-cross-linked resorbable membranes. The intensity of inflammation associated with degradable dental membranes appears to relate to their degradation kinetics, irrespective of their material composition.

Specific and common antigens of Clonorchis sinensis and Opisthorchis viverrini (Opisthorchidae, Trematoda)

  • Choi, Min-Ho;Ryu, Jin-Sook;Lee, Me-Jeong;Li, Shun-Yu;Chung, Byung-Suk;Chai, Jong-Yil;Sithithaworn, Paiboon;Tesana, Smarn;Hong, Sung-Tae
    • Parasites, Hosts and Diseases
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    • v.41 no.3
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    • pp.155-163
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    • 2003
  • The antigenic characterizations and serological reactions of human liver flukes, Clonorchis sinensis and Opisthorchis viverrini, were analyzed by immunoblot. The antigenic profiles of the crude extract of Clonorchis contained major proteins of 8, 26-28, 34-37, 43, and 70 kDa, and those of Opisthorchis 34-37, 43, 70, and 100 kDa. Of these, the 8, 26-28 and 34-37 kDa bands of Clonorchis and the 100 kDa of Opisthorchis were major components of each excretory-secretory antigen. The 8 and 26-28 kDa bands were specific to Clonorchis but the 100 kDa of Opisthorchis cross-reacted with the sera of clonorchiasis, and the 34-37, 70 and 100 kDa bands cross-reacted with sera of other helminthiases. The frequency and intensity of the immunoblot reactions were positively correlated with the intensity of the liver fluke infection.

Nucleophilic Substitution Reactions of N-Methyl α-Bromoacetanilides with Benzylamines in Dimethyl Sulfoxide

  • Adhikary, Keshab Kumar;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.32 no.3
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    • pp.857-862
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    • 2011
  • Kinetic studies of the reactions of N-methyl-Y-${\alpha}$-bromoacetanilides with substituted X-benzylamines have been carried out in dimethyl sulfoxide at $25.0^{\circ}C$. The Hammett plots for substituent X variations in the nucleophiles (log $k_N$ vs ${\sigma}_X$) are slightly biphasic concave upwards/downwards, while the Bronsted plots (log $k_N$ vs $pK_a$) are biphasic concave downwards with breakpoints at X = H. The Hammett plots for substituent Y variations in the substrates (log $k_N$ vs ${\sigma}_Y$) are biphasic concave upwards/downwards with breakpoints at Y = H. The cross-interaction constant $\rho_{XY}$ values are all negative: $\rho_{XY}$ = -0.32 for X = Y = electron-donating; -0.22 for X = electron-withdrawing and Y = electron-donating; -1.80 for X = electron-donating and Y = electronwithdrawing; -1.43 for X = Y = electron-withdrawing substituents. Deuterated kinetic isotope effects are primary normal ($k_H/k_D$ > 1) for Y = electron-donating, while secondary inverse ($k_H/k_D$ < 1) for Y = electronwithdrawing substituent. The proposed mechanisms of the benzylaminolyses of N-methyl-Y-${\alpha}$-bromoacetanilides are a concerted mechanism with a five membered ring TS involving hydrogen bonding between hydrogen (deuterium) atom in N-H(D) and oxygen atom in C = O for Y = electron-donating, while a concerted mechanism with an enolate-like TS in which the nucleophile attacks the ${\alpha}$-carbon for Y = electronwithdrawing substituents.

Sensitivity and uncertainty quantification of neutronic integral data in the TRIGA Mark II research reactor

  • Makhloul, M.;Boukhal, H.;Chakir, E.;El Bardouni, T.;Lahdour, M.;Kaddour, M.;Ahmed, Abdulaziz;Arectout, A.;El Yaakoubi, H.
    • Nuclear Engineering and Technology
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    • v.54 no.2
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    • pp.523-531
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    • 2022
  • In order to study the sensitivity and the uncertainty of the Moroccan research reactor TRIGA Mark II, a model of this reactor has been developed in our ERSN laboratory for use with the N-Particle MCNP Monte Carlo transport codes (version 6). In this article, the sensitivities of the effective multiplication factor of this reactor are evaluated using the ENDF/B-VII.0, ENDF/B-VII.1 and JENDL-4.0 libraries and in 44 energy groups, for the cross sections of the fuel (U-235 and U-238) and the moderator (H-1 and O-16). However, the quantification of the uncertainty of the nuclear data is performed using the nuclear code NJOY99 for the generation and processing of covariance matrices. On the one hand, the highest uncertainty deviations, calculated using the ENDFB-VII.1 and JENDL4.0 evaluations, are 2275, 386 and 330 pcm respectively for the reactions U235(n, f), $ U_{235}(n\bar{\nu})$ and H1(n, γ). On the other hand, these differences are very small for the neutron reactions of O-16 and U-238. Regarding the neutron spectra, in CT-mid plane, they are very close for the three evaluations (ENDF/B-VII.0, ENDF/B-VII.1 and JENDL-4.0). These spectra present two peaks (thermal and fission) around the energies 0.05 eV and 1 MeV.

Preparation and Characterization of Ion-exchange Membrane Using sPEEK for Fuel Cell Application (Sulfonated-PEEK를 이용한 연료전지용 이온교환막의 제조 및 특성평가)

  • Jang, Won-Gi;Ye, Se-Hui;Kang, Seung-Kyu;Kim, Ji-Tae;Byun, Hong-Sik
    • Membrane Journal
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    • v.21 no.3
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    • pp.270-276
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    • 2011
  • A nascent membrane was prepared by using the solution evaporation method with a solution of sPEEK, EdAn (cross-linking reagent), and PEA (grafting reagent) in DMAc. Then, after the imination and sulfonation process the cross-linked and grafted ion-exchange membrane, CG-sPEEK, was obtained. The sulfonation and imination reactions were confirmed by FTIR analysis. In order to evaluate the possibility of prepared membrane for the use of an ion-exchange membrane in PEMFC, proton conductivity, water uptake and volume change were measured and compared with a commercial membrane, Nafion 115. It was revealed that since the proton conductivity (0.17 S/cm) of prepared membrane were much higher than those of Nafion 115 (0.10 S/cm) the prepared membrane could be used for the ion-exchange membrane in PEMFC. However, the high water uptake (130%) of CG-sPEEK should be reduced for the dimension stability.

Effects of repeated tuberculin skin testings on immune responses in experimental monkeys

  • Min, Fangui;Wang, Jing;Yuan, Wen;Kuang, Huiwen;Zhao, Weibo
    • Journal of Animal Science and Technology
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    • v.56 no.8
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    • pp.32.1-32.4
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    • 2014
  • Though many alternative methods to tuberculin skin testing (TST) have been established and evaluated in recent years, sensitivities and specificities of most methods could not meet the requirements of golden standards. In this study, we sought to identify whether repeated TSTs could affect the immune responses in experimental monkeys. Nine natural tuberculosis (TB) monkeys receiving repeated TSTs biweekly were used to demonstrate the effect on TST responsiveness. Two healthy monkeys were administrated with repeated TSTs to analyze the immune response profiling. Intrapalpebral reactions in TB infections gradually weakened or presented intermittent positive reactions. The leukocyte counts, cytokine responses, and antibody responses to all antigens except Old tuberculin (OT) and MPT64L showed no specific changes for TB in healthy monkeys. Positive antibody responses to OT and MPT64L emerged during the first half experimental period, which may cause by their cross-reactivity with mycobacterial species. Results showed that repeated TSTs had no significant effects on immune responses in healthy monkeys but a progressive reduction in TST responsiveness in TB infections.

Numerical study of effect of membrane properties on long-cycle performance of vanadium redox flow batteries

  • Wei, Zi;Siddique, N.A.;Liu, Dong;Sakri, Shambhavi;Liu, Fuqiang
    • Advances in Energy Research
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    • v.4 no.4
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    • pp.285-297
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    • 2016
  • Fundamental understanding of vanadium ion transport and the detrimental effects of cross-contamination on vanadium redox flow battery (VRFB) performance is critical for developing low-cost, robust, and highly selective proton-conducting membranes for VRFBs. The objective of this work is to examine the effect of conductivity and diffusivity, two key membrane parameters, on long-cycle performance of a VRFB at different operating conditions using a transient 2D multi-component model. This single-channel model combines the transport of vanadium ions, chemical reactions between permeated ions, and electrochemical reactions. It has been discovered that membrane selecting criterion for long cycles depends critically on current density and operating voltage range of the cell. The conducted simulation work is also designed to study the synergistic effects of the membrane properties on dynamics of VRFBs as well as to provide general guidelines for future membrane material development.

Nucleophilic Substitution Reactions of α-Bromoacetanilides with Benzylamines

  • Adhikary, Keshab Kumar;Kim, Chan-Kyung;Lee, Bon-Su;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.29 no.1
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    • pp.191-196
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    • 2008
  • Kinetic studies of the reactions of a-bromoacetanilides [YC6H4NHC(=O)CH2Br] with substituted benzylamines (XC6H4CH2NH2) have been carried out in dimethyl sulfoxide at 35.0 oC. The Hammett plots for substituent (Y) variations in the substrate (log kN vs. sY) are biphasic concave upwards/downwards with breaks at Y = 4-Cl (sY = 0.23). The Hammett coefficients rY and the cross-interaction constant rXY (= +0.16) are positive for sY 0.23, while the rY values are positive/negative [rY > 0 for X = (4-MeO and 4-Me) and rY < 0 for X = (H, 4-Cl and 3-Cl)] and the rXY (= -1.51) value is negative for sY ³ 0.23. Based on these and other results, the benzylaminolyses of a-bromoacetanilides are proposed to proceed through rate-limiting expulsion of the bromide leaving group from a zwitterionic tetrahedral intermediate, T, with a bridged transition state for s Y 0.23, while the reaction proceeds through concerted mechanism with an enolate-like TS in which the nucleophile attacks the a-carbon for s Y ³ 0.23.