• Journal of applied mathematics & informatics
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• v.6 no.3
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• pp.697-726
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• 1999

In this paper we develop a now procedure to control stepsize for linear multistep methods applied to semi-explicit index 1 differential-algebraic equations. in contrast to the standard approach the error control mechanism presented here is based on monitoring and contolling both the local and global errors of multistep formulas. As a result such methods with the local-global stepsize control solve differential-algebraic equation with any prescribed accuracy (up to round-off errors). For implicit multistep methods we give the minimum number of both full and modified Newton iterations allowing the iterative approxima-tions to be correctly used in the procedure of the local-global stepsize control. We also discuss validity of simple iterations for high accuracy solving differential-algebraic equations. Numerical tests support the the-oretical results of the paper.

• Bulletin of the Korean Chemical Society
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• v.32 no.7
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• pp.2306-2310
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• 2011

The nucleophilic substitution reactions of diethyl thiophosphinic chloride with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at 55.0 $^{\circ}C$. The values of deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) invariably increase from secondary inverse ($k_H/k_D$ < 1) to primary normal (kH/kD > 1) as the nucleophiles change from the strongly basic to weakly basic anilines. The secondary inverse with the strongly basic anilines and primary normal DKIEs with the weakly basic anilines are rationalized by the gradual transition state (TS) variation from a predominant backside attack, via invariably increasing the fraction of a frontside attack, to a predominant frontside attack, in which the reaction mechanism is a concerted $S_N2$ pathway. A frontside attack involving a hydrogen bonded, four-center-type TS is substantiated by the primary normal DKIEs.

• Journal of Integrative Natural Science
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• v.5 no.3
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• pp.175-181
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• 2012

Oxepane high explosives substituted to explosive group such as azido, nitrato and hydrazino are investigated theoretically the acid catalyzed reaction using the semiempirical MINDO/3, MNDO and AM1 methods to use as the guidelines of high explosives. The nucleophilicity and basicity of oxepane high explosives can be explained by the value of negative charge on oxygen atom of oxepane and the reactivity in propagation step can be represented by the value of positive charge on carbon atom and low electrophile LUMO energy. It was known that carbenium ion was favorable due to the stable energy (19.507~32.101 Kcal/mol) between oxonium ion and carbenium ion in the process of cyclic oxonium ion of oxepane high explosives being converted to open carbenium ion in oxepane high explosives. The value of concentration of cyclic oxonium ion and open carbenium ion in equilibrium status was found to be a major determinant of mechanism, it was expected to react faster in the prepolymer propagation step in SN1 mechanism than in that of $S_N2$.

• Journal of the Korean Chemical Society
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• v.20 no.6
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• pp.453-459
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• 1976

Rate constants for the reaction of methyl chloroformate with substituted anilines, and for the halogen exchanges in phenyl chloroformate have been determined in acetone. Although the rate data can be interpreted equally well with the addition-elimination mechanism($S_AN$) involving an intermediate, results of MO and isotope effect studies strongly favor the synchronous ($S_N2$) mechanism for the reactions studied. It was concluded that for the fast reacting nucleophiles the transition state is of "late" type while for the slow reacting nucleophiles it is of "early" type.

• Bulletin of the Korean Chemical Society
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• v.35 no.7
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• pp.2081-2085
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• 2014

Second-order rate constants ($k_N$) have been measured spectrophotometrically for the reactions of phenyl 2- pyridyl carbonate (6) with a series of cyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. The Br${\o}$nsted-type plot for the reaction of 6 is linear with ${\beta}_{nuc}$ = 0.54, which is typical for reactions reported previously to proceed through a concerted mechanism. Substrate 6 is over $10^3$ times more reactive than 2-pyridyl benzoate (5), although the reactions of 6 and 5 proceed through the same mechanism. A combination of steric hindrance, inductive effect and resonance contribution is responsible for the kinetic results. The reactions of 6 and 5 proceed through a cyclic transition state (TS) in which H-bonding interactions increase the nucleofugality of the leaving group (i.e., 2-pyridiniumoxide). The enhanced nucleofugality forces the reactions of 6 and 5 to proceed through a concerted mechanism. In contrast, the corresponding reaction of 4-nitrophenyl 2-pyridyl carbonate (7) proceeds through a stepwise mechanism with quantitative liberation of 4-nitrophenoxide ion as the leaving group, indicating that replacement of the 4-nitrophenoxy group in 7 by the PhO group in 6 changes the reaction mechanism (i.e., from a stepwise mechanism to a concerted pathway) as well as the leaving group (i.e., from 4-nitrophenoxide to 2-pyridiniumoxide). The strong electron-withdrawing ability of the 4-nitrophenoxy group in 7 inhibits formation of a H-bonded cyclic TS. The presence or absence of a H-bonded cyclic TS governs the reaction mechanism (i.e., a concerted or stepwise mechanism) as well as the leaving group (i.e., 2-pyridiniumoxide or 4-nitrophenoxide).

• Journal of the Korean Institute of Telematics and Electronics A
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• v.31A no.1
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• pp.54-60
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• 1994

In this paper, we present the analytical models for the change of the lateral electric field distribution and the velocity saturation region length with the electron trapping of stressed SC-PMOSFET in the saturation region. To derive the hot-electron-induced lateral electric field of stressed SC-PMOSFET. Ko's pseudo two dimensional box model in the saturation region which illustrates the analysis of the velocity saturation region is modified under the condition of electron trapping in the oxide near the drain region. From the results, we have the following lateral electric field in the y-direction, that is, E(y) ES1satT.cosh(y/l) qNS1tT.sinh(y/l)/lCox. It is shown that the trapped electrons influence the field in the drain region. decreasing the lateral electric field. Calculated velocity saturaion length increases with the trapped electrons. increasing the drain current of stressed SCPMOSFET. This results well explain the HEIP phenomenon of PMOSFET's.

• Journal of the Korea Institute of Military Science and Technology
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• v.3 no.1
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• pp.164-175
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• 2000

Three compounds of Cu(II)-loaded N,N,N'-trimethylethylenediaminated Merrifield-type polymers were synthesized with yields higher than 80%, and the hydrolysis reaction rates of O-isopropylmethyl-phosphonofluoridate(GB) and O-pinacolylmethylphosphonofluoridate (GD) catalyzed by them have been surveyed. GB and GD hydrolysis by Cu(II)-loaded polymers occurs via intermediate complex mechanism where rapid equilibrium to form intermediate complex between substrate and Cu(II)-loaded polymers($K_f$) is followed by rate determining hydrolysis step($k_1$). The measured activation parameters for $k_1$ are ${\Delta}H^{\ddag}$ : $17.75{\pm}0.98kJ/mol$ ${\Delta}S^{\ddag}$ / : $-218.42{\pm}3.35J/mol$ K, $E^{\circ}_a$ : $20.22{\pm}0.98kJ/mo1$ for GB and ${\Delta}H^{\ddag}$ / : $11.16{\pm}1.15kJ/mol,$${\Delta}S^{\ddag}$ /: $-258.57{\pm}3.93J/mol$ K, $E^{\circ}_a$ : $13.64{\pm}1.15 kJ/mol$ for GD. Standard enthalpy/entropy changes corresponding to the intermediate complex formation constant $K_f$ are ${\Delta}H^{\circ}$ : $37.05{\pm}2.19 kJ/mo1,$$ {\Delta}S^{\circ}$ : $163.12{\pm}7.49 J/mol$ K and ${\Delta}H^{\circ}$ : 418.59{\pm}2.04 kJ/mol,$ ${\Delta}S^{\circ}$ : 4111.92{\pm}6.98 J/mol$ K for GB and GD, respectively, The electron push-pull mechanism by Cu(II)-loaded polymers lowers the P-F bond breaking energy(~400 kJ/mol) to less than 1/20 compared to the case in which no Cu(II)-loaded resin presents. Analysis of $K_f$ and 4k_1$ over pH=6.5~8.0 range suggest that the GB and GD hydrolysis occurs intramolecularily with $pK_a$ =7.29 for ligated $H_2O$ and $t_{1/2}$=36.9 sec, $pK_a$ = 7.06 and $t_{1/2}$=177.7 sec for GB and GD, respectively.

• Journal of the Korean Chemical Society
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• v.42 no.2
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• pp.150-155
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• 1998

Kinetic studies on the reaction of isoquinoline with para-substituted benzylbromides were conducted under various pressures (1 ~1000 bar) in acetonitrile. From the rate constants obtained, the activation parameters such as$\DeltaV^{\neq}, \Delta\beta^{\neq}, \DeltaH^{\neq}, \DeltaS^{\neq}, \DeltaG^{\neq}$ and Ea were evaluated. Reaction rate increasing the pressure and temperature. The activation compressibility coefficient and the activation entropy showed negative values. From the substituent effect and the results, it was found that the reaction proceeds through $S_N2$ mechanism, but the structure of transition state was slightly changed with substituents and pressure.

• Journal of the Korean Chemical Society
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• v.36 no.2
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• pp.180-184
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• 1992

Kinetic studies for the reaction of pyridine with substituted benzoyl chlorides were conducted under various pressures (1-1000 bar) in acetonitrile. From rate constants, the activation parameters (${\Delta}V^{\neq}$, ${\Delta}{\beta}^{\neq}$,${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$ and ${\Delta}G^{\neq}$) were evaluated. Rates of these reaction increased with an increase in the pressure. The activation volume, the activation compressibility coefficient and the activation entropy were negative. From substituents effect and these results, it was found that these reactions proceed through $S_N2$ mechanism, but the structure of transition state was slightly changed with substituents and pressure.

• Journal of Physiology & Pathology in Korean Medicine
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• v.31 no.1
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• pp.65-74
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• 2017

Sleep deprivation is an extremely common event in today's society. It has caused learning cognitive skill deterioration and poor concentration, increased disease such as heart disease, diabetes and obesity, sexual function decrease, infertility increase, depression and autonomic nervous system disorder. Sleep deprivation-induced stress caused NADPH oxidase and oxidative stress. And this oxidative stress induces apoptosis. Lilii bulbus and Nelumbins semen are known to mental and physical relaxation effects. In this study, we induced sleep deprivation(SD) in Sprague-Dawley rats in water for 5 days and thereafter administered orally L. bulbus and N. semen for 5 days. Brain tissues were observed by histochemical, immunohistochemical and tunel staining. The immunoreactives of Tumor necrosis factor ${\alpha}$, Neuronal nitric oxide synthases, Phospho-SAPK/JNK and gp91-phox of the L. bulbus administered group and N. semen administered group were weaker than those of sleep deprivation group. In the L. bulbus administered group and N. semen administered group, apoptosis was decreased than that of sleep deprivation group. Proapoptotic p53, Bax, Cleaved caspase 3 immunoreactives of the administered group were weaker than those of sleep deprivation group, whereas anti-apoptotic Bcl-2 immunoreactity was stronger in the L. bulbus administered group and N. semen administered group. Antioxidant mechanism such as DJ-1, superoxide dismutase 1, Nuclear factor-like 2 immunoreactives of the L. bulbus and N. semen administered group were stronger than those of sleep deprivation group. These results demonstrate that L. bulbus, N. semen had the neuroprotective effects on the sleep deprivation-induced oxidative stress in the hippocampus.