• Bulletin of the Korean Chemical Society
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• 제35권8호
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• pp.2410-2414
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• 2014

A kinetic study is reported on nucleophilic substitution reactions of Y-substituted-phenyl picolinates (7a-7h) with a series of cyclic secondary amines in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. Comparison of the kinetic results with those reported previously for the corresponding reactions of Y-substituted-phenyl benzoates (1a-1f) reveals that 7a-7h are significantly more reactive than 1a-1f. The Br${\o}$nsted-type plot for the aminolysis of 4-nitrophenyl picolinate (7a) is linear with ${\beta}_{nuc}=0.78$, which is typical for reactions proceeding through a stepwise mechanism with expulsion of the leaving group being the rate-determining step. The Br${\o}$nsted-type plots for the piperidinolysis of 7a-7h and 1a-1f are also linear with ${\beta}_{lg}=-1.04$ and -1.39, respectively, indicating that the more reactive 7a-7h are less selective than the less reactive 1a-1f to the leaving-group basicity. One might suggest that the enhanced reactivity of 7a-7h is due to the inductive effect exerted by the electronegative N atom in the picolinyl moiety, while the decreased selectivity of the more reactive substrates is in accord with the reactivity-selectivity principle. However, the nature of intermediate (e.g., a stabilized cyclic intermediate through the intramolecular H-bonding interaction for the reactions of 7a-7h, which is structurally not possible for the reactions of 1a-1f) is also responsible for the enhanced reactivity with a decreased selectivity.

• 한국초전도ㆍ저온공학회논문지
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• 제18권1호
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• pp.37-40
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• 2016

We have investigated the addition effect of NiO magnetic nanoparticles on crystal structure, microstructure as well as superconducting properties of $MgB_2$. NiO-added $MgB_2$ samples were prepared by the solid-state reaction method. The superconducting transition temperature ($T_c$) of 37.91 K was obtained for pure $MgB_2$, and $T_c$ was found to decrease systematically on increasing the addition level of NiO. X-ray diffraction (XRD) analysis revealed that no substitution of Ni for Mg in the lattice of $MgB_2$ was occurred. The microstructural analysis shows that the pure $MgB_2$ sample consists of plate shape $MgB_2$ grains, and the grains get refined to smaller size with the addition of NiO nanoparticles. At 5 K, high values of critical current density ($J_c$) were obtained for small amount NiO-added $MgB_2$ samples as compared to pure sample. The enhancement in $J_c$ could be attributed to the refinement of $MgB_2$ grains which leads to high density of grain boundaries in NiO-added $MgB_2$ samples.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2005년도 추계학술대회 논문집 Vol.18
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• pp.210-211
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• 2005

[ $(K_{0.5}Na_{0.5})NbO_3$ ](KNN) 세라믹스의 소결 특성과 압전 특성을 높이기 위해 B-site에 Sb를 치환하여 Sb함량에 따른 특성을 측정 하였다. Sb 의 함량을 0mol $\sim$ 0.1mol 까지 첨가한 결과 소결 밀도는 Sb의 첨가량이 많아질수록 증가하다 Sb-0.08mol에서 4.40g/$cm^3$으로 가장 높은 밀도를 가졌으며, 여기서의 전기기계 결합 계수가(Kp) 0.45로 높은 값을 나타내었다. 상전 이 온도는 375$^{\circ}C$로 순수한 KNN 의 420$^{\circ}C$ 보다 약 45$^{\circ}C$정도 떨어졌으나 orthorhombic에 서 tetragonal 로 바뀌는 전이 온도는 KNN이 220$^{\circ}C$, KNNS 가 225$^{\circ}C$로 크게 변하지 않았다.

• Korea-Australia Rheology Journal
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• 제13권1호
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• pp.29-35
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• 2001

The development of filament stretching extensional rheometers over the past decade has enabled the systematic measurement of the transient extensional stress growth in dilute and semi-dilute polymer solutions. The strain-hardening in the extensional viscosity of dilute solutions overwhelms the perturbative effects of capillarity, inertia & gravity and the kinematics of the extensional deformation become increasingly homogeneous at large strains. This permits the development of a robust open-loop control algorithm for rapidly realizing a deformation with constant stretch history that is desired for extensional rheometry. For entangled fluids such as concentrated solutions and melts the situation is less well defined since the material functions are governed by the molecular weight between entanglements, and the fluids therefore show much less pronounced strain-hardening in transient elongation. We use experiments with semi-dilute/entangled and concentrated/entangled monodisperse polystyrene solutions coupled with time-dependent numerical computations using nonlinear viscoelastic constitutive equations such as the Giesekus model in order to show that an open-loop control strategy is still viable for such fluids. Multiple iterations using a successive substitution may be necessary, however, in order to obtain the true transient extensional viscosity material function. At large strains and high extension rates the extension of fluid filaments in both dilute and concentrated polymer solutions is limited by the onset of purely elastic instabilities which result in necking or peeling of the elongating column. The mode of instability is demonstrated to be a sensitive function of the magnitude of the strain-hardening in the fluid sample. In entangled solutions of linear polymers the observed transition from necking instability to peeling instability observed at high strain rates (of order of the reciprocal of the Rouse time for the fluid) is directly connected to the cross-over from a reptative mechanism of tube orientation to one of chain extension.

• Journal of Magnetics
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• 제18권4호
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• pp.386-390
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• 2013

This paper studies the effects of A-site substitution by barium on the magnetic and magnetocaloric properties of $Pr_{0.5}Sr_{0.5-x}Ba_{x}MnO_{3}$ (x = 0, 0.04, 0.08 and 0.1). The tetragonal crystal structures of the samples are confirmed by room temperature X-ray diffraction. The dependence of the Curie temperature ($T_C$) and the magnetic entropy change (${\Delta}S_M$) on the Ba doping content has been investigated. The samples of all doping contents undergo the second order phase transition. As the concentration of Ba increased, the maximum entropy change ($|{\Delta}S_M|_{max}$) increased gradually, from 1.15 J $kg^{-1}$ $K^{-1}$ (x = 0) to 1.36 J $kg^{-1}$ $K^{-1}$ (x = 0.1), in a magnetic field change of 1.5 T. The measured value of $T_C$ is 265 K, 275 K, 260 K and 250 K for x = 0, 0.04, 0.08 and 0.1, respectively. If combining these samples for magnetic refrigeration, the temperature range of ~220 K and 290 K, where |${\Delta}S_M$|max is stable at ~1.27 J $kg^{-1}$ $K^{-1}$ and RCP = 88.9 $J{\cdot}kg^{-1}$ for ${\Delta}H$ = 1.5 T. $Pr_{0.5}Sr_{0.5-x}Ba_{x}MnO_{3}$ compounds, are expected to be suitable for magnetic-refrigeration application due to these magnetic properties.

• Bulletin of the Korean Chemical Society
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• 제35권1호
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• pp.177-181
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• 2014

Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for the reactions of Y-substituted-phenyl benzoates (5a-j) with potassium ethoxide (EtOK) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. [EtOK] curve upward regardless of the electronic nature of the substituent Y in the leaving group. Dissection of $k_{obsd}$ into the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOK (i.e., $k_{EtO^-}$ and $k_{EtOK}$, respectively) has revealed that the ion-paired EtOK is more reactive than the dissociated $EtO^-$. The Br${\phi}$nsted-type plots for the reactions with the dissociated $EtO^-$ and ion-paired EtOK exhibit highly scattered points with ${\beta}_{lg}$ = -$0.5{\pm}0.1$. The Hammett plots correlated with ${\sigma}^o$ constants result in excellent linear correlations, indicating that no negative charge develops on the O atom of the leaving Y-substituted-phenoxide ion in transition state. Thus, it has been concluded that the reactions with the dissociated $EtO^-$ and ion-paired EtOK proceed through a stepwise mechanism, in which departure of the leaving group occurs after the RDS, and that $K^+$ ion catalyzes the reactions by increasing the electrophilicity of the reaction center through a four-membered cyclic TS structure.

• Journal of Microbiology
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• 제45권5호
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• pp.418-421
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• 2007

The nucleotide at position 791(G791) of E. coli 16S rRNA was previously identified as an invariant residue for ribosomal function. In order to characterize the functional role of G791, base substitutions were introduced at this position, and mutant ribosomes were analyzed with regard to their protein synthesis ability, via the use of a specialized ribosome system. These ribosomal RNA mutations attenuated the ability of ribosomes to conduct protein synthesis by more than 65%. A transition mutation (G to A) exerted a moderate effect on ribosomal function, whereas a transversion mutation (G to C or U) resulted in a loss of protein synthesis ability of more than 90%. The sucrose gradient profiles of ribosomes and primer extension analysis showed that the loss of protein-synthesis ability of mutant ribosomes harboring a base substitution from G to U at position 791 stems partially from its inability to form 70S ribosomes. These findings show the involvement of the nucleotide at position 791 in the association of ribosomal subunits and protein synthesis steps after 70S formation, as well as the possibility of using 16S rRNA mutated at position 791 for the selection of second-site revertants in order to identify ligands that interact with G791 in protein synthesis.

• Bulletin of the Korean Chemical Society
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• 제30권7호
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• pp.1579-1582
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• 2009

The reaction rates of 4-X-2,6-dinitrochlorobenzenes (X = $NO_2,\;CN,\;CF_3$) with Y-substituted pyridines (Y = 3-$OCH_3,\;H,\;3-CH_3,\;4-CH_3$) in methanol-acetonitrile mixtures were measured by conductometry at 25 ${^{\circ}C}$. It was observed that the rate constant increased in the order of X = 4-$NO_2\;>\;4-CN\;>\;4-CF_3$ and the rate constant also increased in the order of Y = 4-$CH_3\;>\;3-CH_3\;>\;H\;>\;3-OCH_3$. When the solvent composition was varied, the rate constant increased in order of MeCN > 50% MeOH > MeOH. The electrophilic catalysis by methanol may be ascribed to the formation of hydrogen bonds between alcoholic hydrogen and nitrogen of pyridines in ground state. Based on the transition parameters, ${\rho}_S,\;{\rho}_N,\;{\beta}_Y,\;{\rho}_{XY}$ and solvent effects, the reaction seems to proceed via $S_N$Ar-Ad.E mechanism. We also estimated the isokinetic solvent mixtures (${\rho}_{XY}$ = 0) based on cross-interaction constants, where the substituent effects of the substrate and nucleophile are compensated.

• BMB Reports
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• 제37권2호
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• pp.246-253
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• 2004

Constitutional RB1 gene mutations were studied in a series of 21 families with unilateral and bilateral retinoblastoma patients. Peripheral blood lymphocytes were analyzed by "exon by exon" PCR-heteroduplex and sequencing. Mutations were identified in 6 (29%) of the patients. One mutation corresponded to an intronic polymorphism in g.174351T > A. The other five mutations resulted C to T exonic transitions, four were CGA sequences (g.65386, g.150037 in two patients, and g.162237), creating stop codons and presumably truncated proteins. The fifth one was new and resulted in alanine to valine substitution (g.73774). Two patients had the same the germline truncated mutation (g.150037C > T), one with a familial bilateral early onset retinoblastoma and one with a sporadic unilateral late onset retinoblastoma. The later type has not been previously described. This finding is discussed in the genotype/phenotype correlation context. Additionally, a single nucleotide change was found in six studied samples, where a C to T homozygous transversion was identified in intron 26 (IVS26 + 28). It is worthy the non concordance of the nucleotide with the published sequence. This analysis proved to be a useful method for the detection of mutations in the RB1 gene, and contributed to the adequate genetic counseling to patients and relatives.

• Bulletin of the Korean Chemical Society
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• 제30권1호
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• pp.214-218
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• 2009

Second-order rate constants ($k_N$) have been measured for nucleophilic substitution reactions of S-4-nitrophenyl thiobenzoate with a series of alicyclic secondary amines in $H_2O$ containing 20 mol % DMSO at 25.0 ${\pm}$ 0.1 ${^{\circ}C}$. The Br$\phi$nsted-type plot exhibits a downward curvature, i.e., $\beta_{nuc}$ decreases from 0.94 to 0.34 as the amine basicity increases. The reactions in the aqueous DMSO have also been suggested to proceed through a zwitterionic tetrahedral intermediate (T${\pm}$) with change in the RDS on the basis of the curved Br$\phi$nsted-type plot. The reactions in the aqueous DMSO exhibit larger $k_N$ values than those in the aqueous EtOH. The macroscopic rate constants ($k_N$) for the reactions in the two solvent systems have been dissected into the microscopic rate constants ($k_1\;and\;k_2/k_{-1}$ ratio) to investigate effect of medium on reactivity in the microscopic level. It has been found that the $k_2/k_{-1}$ ratios are similar for the reactions in the two solvent systems, while $k_1$ values are larger for the reactions in 20 mol % DMSO than for those in 44 wt % EtOH, indicating that the larger $k_1$ is mainly responsible for the larger $k_N$. It has been suggested that the transition state is more stabilized in 20 mol % DMSO through mutual polarizability interaction than in 44 wt % EtOH through H-bonding interaction.