• Bulletin of the Korean Chemical Society
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• 제32권7호
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• pp.2301-2305
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• 2011

The potential energy surface (PES) for the loss of HCN or HNC from the pyrazine molecular ion was determined based on quantum chemical calculations using the G3//B3LYP method. Four possible dissociation pathways to form four $C_3H_3N^{+{{\bullet}}$ isomers were examined. A Rice-Ramsperger-Kassel-Marcus quasi-equilibrium theory model calculation was performed to predict the dissociation rate constant and the product branching ratio on the basis of the obtained PES. The resultant rate constant for the HCN loss agreed with the previous experimental result. The kinetic analysis predicted that the formation of $CH=CHN{\equiv}CH^{+{\bullet}}+HCN$ was predominant, which occurred by three consecutive steps, a C-C bond cleavage to form a linear intermediate, a rearrangement to form an H-bridged intermediate, and elimination of HCN.

• Bulletin of the Korean Chemical Society
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• 제26권4호
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• pp.641-644
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• 2005

Nucleophilic addition reactions of benzylamines $(XC_6H_4CH_2NH_2)\;to\;{\beta}$-cyanostilbenes ($YC_6H_4CH=C(CN)C_6H_4$Y’) have been studied in acetonitrile at 30.0 oC. A greater degree of N-$C_{\alpha}$ bond formation (larger ${\beta}_X$) is obtained with a stronger electron-withdrawing substituent in either ${\alpha}-\;(\delta\sigma_Y\;{\gt}\;0)\;or\;{\beta}-ring\;(\delta\sigma_{Y'}\;{\gt}$ 0). A stronger charge development is observed in the TS on $C_{\beta}\;(\rho_{Y'}$= 1.06 for X=Y=H) rather than on $C_{\alpha}\;(\rho_{Y}$ = 0.62 for X=Y’H) indicating the lag in the resonance development into the activating group (CN) on $C_{\beta}$ in the transition state. Similarly, the magnitude of $\rho$$_{XY'}$(−0.72) is greater than $\rho_{XY}$ (−0.66) due to a stronger interaction of the nucleophile with $\beta$-ring than $\alpha$-ring. The positive sign of $\rho_{YY'}$correctly reflects $\pi$ bond cleavage between the two rings in the TS. Relatively large kinetic isotope effects ($k_H/k_D\;{\geq}$ 2.0) involving deuterated nucleophiles ($XC_6H_4CH_2ND_2$) suggest a four-membered cyclic TS in which concurrent N-C$_{\alpha}$ and H(D)-C$_{\beta}$ bond formation occurs.

• 한국수산과학회지
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• 제49권5호
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• pp.628-634
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• 2016

We investigated the characteristics and rate of development of allotriploid embryos derived from a cross between female olive flounder Paralichthys olivaceus and male starry flounder Platichthys stellatus. The allotriploidy was induced by cold shocking fertilized eggs three minutes post-fertilization at 3°C for 45 minutes. The average cellular DNA content of the allotriploid embryos was 2.06±0.03 pg/cell, which is equal to the sum of the cellular DNA content of a diploid olive flounder (1.42 pg/cell) and a haploid starry flounder (0.66 pg/haploid cell). The first cleavage, midblastula, gastrula and Kupffer's vesicle appearance stages of the allotriploid eggs began at 1.5, 8, 13 and 26 hours after cold shocking at 18°C, respectively. The developmental rate of allotriploid eggs was equivalent to that of diploid and triploid olive flounder eggs at 10, 14 and 18°C. However, the hatching times of allotriploid eggs, 7 h at 10°C, 5 h at 14°C and 4 h at 18°C, were earlier than those of diploid and triploid olive flounder.

• Journal of Applied Biological Chemistry
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• 제43권3호
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• pp.147-151
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• 2000

A gene, nprM, from Bacillus megaterium ATCC 14945 was obtained by PCR using primers synthesized based on two nprM sequences from two different strains, and cloned into Escherichia coli. The gene nprM encoded an extracellular neutral protease, and the molecular mass of the expressed enzyme was estimated to be approximately 36kDa on a denaturating gel. The enzyme was activated by $Ca^{2+}$, and the optimum concentration of $Ca^{2+}$ was 5 mM. The enzyme was inhibited by EDTA but not by PMSF. The optimal pH and temperature of the cloned enzyme were $50^{\circ}C and pH 7.5-8.0, respectively, and were similar to those of the enzyme from the gene gonor cell. The cloned NprM caused internal cleavage of the native endoglucanase of B. subtilis BSE616 as a model foregin protein, and resulted in a small truncated but still active endoglucanase.

• Bulletin of the Korean Chemical Society
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• 제19권4호
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• pp.462-466
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• 1998

The homobimetallic anion, $({\eta}^5-MeCp)Mn(CO)_2Mn(CO)_5-M^+\; (M^+=Na^+, PPN^+$) was disrupted by $PR_3\;(R=C_6H_5,\;C_2H_5,\;OCH_3)$ in THF at various temperatures (r.t. ∼65℃) under the pseudo first order reaction conditions where excess of $PR_3$ was employed under a nitrogen atmosphere. For the reaction involving $PPN^+$ analog, Mn-Mn heterolytic cleavage occurred, leading to $PPN^+Mn(CO)_5^-\; and \;({\eta}^5-MeCp)Mn(CO)_2PR_3$ as products; however, in case of $Na^+\; analog,\; Na^+$ seems to play a novel counter ion effect on the disruption reaction by transferring one terminal CO from the $Mn(CO)_5$ moiety on to the $({\eta}^5-MeCp)Mn(CO)_2$ of the corresponding homobimetallic complex, eventually resulting in $Na^+Mn(CO)_4PR_3^-\;and\;({\eta}^5-MeCp)Mn(CO)_3$. This reaction is of overall first order with respect to [homobimetallic complex] with the activation parameters (ΔH≠=23.0±0.7 kcal/mol, ΔS≠= - 8.7±0.8 e.u. for $Na^+$ analog; ΔH≠=28.8±0.4 kcal/mol, ΔS≠=15.7±0.6 e.u. for $PPN^+$ analog reaction).

• Bulletin of the Korean Chemical Society
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• 제16권1호
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• pp.53-58
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• 1995

Heats of solution of aniline (AN), benzylamine (BA), ethyl-(EBS) and 2-phenylethyl benzenesulfonates (PEB) are calorimetrically measured in acetonitrile-methanol mixtures at 25.0 $^{\circ}C$. The activation parameters, ${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$ and ${\Delta}G^{\neq}$, are determined for the reactions of EBS and PEB with AN and BA using the kinetic data at three temperatures. Calorimetric transfer enthalpies of initial state, ${\delta}H_t^{0{\rightarrow}x})$(IS), and kinetically derived activation enthalpies, ${\delta}\;{\Delta}H^{\neq}$, in the MeCN-MeOH mixtures are combined to determine the transfer enthalpies of transition state, ${\delta}H_t^{0{\rightarrow}x})$(TS); ${\delta}H_t^{0{\rightarrow}x})$(IS) = ${\delta}{\Delta}H^{\neq}\;+\;{\delta}H_t^{0{\rightarrow}x}$(IS) The preferential solvation of anionic charge in the TS predicts a loose TS with a greater degree of bond cleavage for the reactions of PEB than for EBS, and also for the reactions with BA compared to the reactions with AN.

• Corrosion Science and Technology
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• 제4권5호
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• pp.211-216
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• 2005

Failure analysis of the latch ram ball and the C-ram ball with the trade name AFBMA Gr. 50 Colmonoy No. 6, has been performed to identify the root cause of the failure. The study required the extraction of the both failed and normal balls from the nuclear fuel exchanger. Microstructures of both balls were examined after polishing and etching. Breaking tests of both the ball revealed similarity in cleavage surfaces. Fracture surfaces of both failed ball and normal ball after breaking test were examined with SEM and EDX. Microstructure of the ball revealed an austenite phase with coarse Cr rich precipitate. Indented marks observed on the surface of the failed ball are believed to be produced by overloading. In the light of the afore mentioned observations and studies, the failure mechanism of the ball in nuclear fuel exchanger seem to be caused by impact or mechanical overloading on ball.

• 한국가축번식학회지
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• 제23권3호
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• pp.271-278
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• 1999

본 연구는 핵이식 기술에 의한 재구축 배의 작성과정에서 핵의 세포주기단계에 따른 재구축 배의 염색체의 핵상변화를 검토하고, 염색체의 핵상변화와 핵이식란의 체외발육과의 관계를 검토하였다. 공핵란은 nocodazole 처리에 의해 분할구가 분열기에 정지되도록 한 후, 분열개시 1.5 시간 이내, 분열 후 3 시간째 핵 및 무처리 분할구 핵올 활성화 전 (metaphase-II기 : M II기 ), 후 (S 기)의 탈핵 미수정란 세포질에 이식하였다. MII기 수핵란에 핵이식 된 재구축 배의 극체상 방출, 미성숙 염색체응축, 염색질구조 변화 등과 같은 핵형 변화 형태 및 재구축 배의 발육능은 핵의 세포주기 단계에 의해 영향을 받았으며, 극체상 방출 유무에 따라서도 재구축 배의 발육율에 차이가 있었다. S기 수핵란에 핵이식 된 경우에는 이식된 핵의 형태변화가 거의 없었다. 본 연구의 결과는 재구축 배의 핵형 변화가 핵 및 세포질의 세포주기단계에 따라 다양하며, 이것이 핵이식 재구축 배의 발육에 영향을 미칠 수 있음을 확증한다.

• 한국정밀공학회:학술대회논문집
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• 한국정밀공학회 2007년도 추계학술대회 논문집
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• pp.83-84
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• 2007

• Bulletin of the Korean Chemical Society
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• 제7권2호
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• pp.111-113
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• 1986

The axial alcohol in trans-3,3,5-trimethylcyclohexanol was oxidized more readily than the equatorial alcohol in cis-3,3,5-trimethylcyclohexanol by NBS in aqueous dioxane. On the contrary, the equatorial alcohol was preferentially oxidized to the axial one by 10% aqueous sodium hypochlorite in the presence of tetrabutylammonium hydrogen sulfate (TBHS). The specificity indicates the presence of two different mechanism. In acidic medium, the cleavage of C-H bond is rate determining step while the reactivity of the alcohol is important in the presence of TBHS. The mechanism in basic medium without TBHS will be discussed.