• Title/Summary/Keyword: Addition-elimination (A-E)

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Correlation of the Rates of Solvolyses of 4-Methylthiophene-2-carbonyl Chloride Using the Extended Grunwald-Winstein Equation

  • Choi, Ho-June;Koo, In-Sun
    • Bulletin of the Korean Chemical Society
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    • v.33 no.2
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    • pp.499-504
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    • 2012
  • The specific rates of sovolysis of 4-methylthiophene-2-carbonyl chloride (1) have been determined in 26 pure and binary solvents at $25.0^{\circ}C$. Product selectivities are reported for solvolyses of 1 in aqueous ethanol and methanol binary mixtures. Comparison of the specific rates of solvolyses of 1 with those for p-methoxybenzoyl chloride (2) in terms of linear free energy relationships (LFER) are helpful in mechanistic considerations, as is also treatment in terms of the extended Grunwald-Winstein equation. It is proposed that the solvolyses of 1 in binary aqueous solvent mixtures proceed through an SN1 and/or ionization (I) pathway rather than through an associative $S_N2$ and/or addition-elimination (A-E) pathway.

Effect of S.E.C Mixing on the Properties of Concrete (S.E.C 방식에 의한 콘크리트의 혼합효과에 관한 연구)

  • 김기형;박원태;최재진
    • Journal of the Korean Society of Safety
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    • v.12 no.2
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    • pp.133-139
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    • 1997
  • Conventional concrete mixing method is to put all of the materials simultaneously into a mixer and mix for a required time. However, recently concrete researchers have reported that mixing sequence iufluences the properties of concrete. This study discusses the influence of mixing sequence and partitioning addition of mixing water. Concrete, by method of partitioning addition of mixing water, was found to have substantially stronger strength than conventional concrete with the same water-cement ratio. This means that a higher strength concrete could be obtained by using “Sand Enveloped with Cement”(S.E.C) mixing technique. Both a high bond strength between cement paste and aggregate, and elimination of bleeding both contribute to improving the strength of S. E. C concrete.

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A non-replicating oncolytic vector as a novel therapeutic tool against cancer

  • Kaneda, Yasufumi
    • BMB Reports
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    • v.43 no.12
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    • pp.773-780
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    • 2010
  • Cancers are still difficult targets despite recent advances in cancer therapy. Due to the heterogeneity of cancer, a single-treatment modality is insufficient for the complete elimination of cancer cells. Therapeutic strategies from various aspects are needed. Gene therapy has been expected to bring a breakthrough to cancer therapy, but it has not yet been successful. Gene therapy also should be combined with other treatments to enhance multiple therapeutic pathways. In this view, gene delivery vector itself should be equipped with intrinsic anti-cancer activities. HVJ (hemagglutinating virus of Japan; Sendai virus) envelope vector (HVJ-E) was developed to deliver therapeutic molecules. HVJ-E itself possessed anti-tumor activities such as the generation of anti-tumor immunities and the induction of cancer-selective apoptosis. In addition to the intrinsic anti-tumor activities, therapeutic molecules incorporated into HVJ-E enabled to achieve multi-modal therapeutic strategies in cancer treatment. Tumor-targeting HVJ-E was also developed. Thus, HVJ-E will be a novel promising tool for cancer treatment.

Real-Time Forward Kinematics of the 6-6 Stewart Platform with One Extra Linear Sensor (한 개의 선형 여유센서를 갖는 스튜어트 플랫폼의 실시간 순기구학)

  • Lee, Tae-Young;Shim, Jae-Kyung
    • Proceedings of the KSME Conference
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    • 2000.11a
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    • pp.541-547
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    • 2000
  • This paper presents the closed-form forward kinematics of the 6-6 Stewart platform of planar base and moving platform. Based on algebraic elimination method and with one extra linear sensor, it first derives an 8th-degree univariate equation and then finds tentative solution sets out of which the actual solution is to be selected. In order to provide more exact solution despite the error between measured sensor value and the theoretical one, a correction method is also used. The overall procedure requires so little computation time that it can be efficiently used for realtime applications. In addition, unlike the iterative schemes e.g. Newton-Raphson, the algorithm does not require initial estimates of solution and is free of the problems that it does not converge to actual solution within limited time. The presented method has been implemented in C language and a numerical example is given to confirm the effectiveness and accuracy of the developed algorithm.

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Understand the Molecular Orbital Theory on the Hydrolytic Reactivity of Herbicide Flumioxazine (제초제 Flumioxazine의 가수분해 반응성에 관한 분자 궤도론적 이해)

  • Sung, Nack-Do;Jung, Hoon-Sung
    • The Korean Journal of Pesticide Science
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    • v.8 no.4
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    • pp.265-271
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    • 2004
  • Hydrolytic reactivities of N-phenylphthalimid herbicide flumioxazine (S) were disccused using molecular orbital (MO) theoretical method. It is revealed that below pH 5.0, the protonation $(SH^+)$ to carbonyl oxygens atom $(O_{21})$ of 1,2-dicarboximino group by general acid catalysis $(k_A)$ with hydronium ion $(H_3O^+)$ proceeds via charge controled reaction. Whereas, the specific base catalysis $(k_{OH})$ with hydroxide anion via orbital controled reaction occurs above pH 8.0. We may concluded that in the range of pH $5.0\sim8.0$, the hydrolysis proceeds through nucleophilic addition elimination $(Ad_{N-E})$ reaction, these two reactions occur competitively.

Correlation of the Rates of Solvolysis of 1-Piperidincarbonyl Chloride Using the Extended Grunwald-Winstein Equation

  • Choi, Ho-June;Ali, Dildar;Lee, Jong-Pal;Yang, Ki-Yull;Park, Jong-Keun;Koo, In-Sun
    • Bulletin of the Korean Chemical Society
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    • v.32 no.11
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    • pp.3941-3946
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    • 2011
  • The specific rates of sovolysis of 1-piperidincarbonyl chloride (1) have been determined in 26 pure and binary solvents at $25.0^{\circ}C$. Comparison of the specific rates of solvolyses of 1 with those for p-methoxybenzoyl chloride and those for 4-morpholinecarbonyl chloride in terms of linear free energy relationships (LFER) are helpful in mechanistic considerations, as is also treatment in terms of the extended Grunwald-Winstein equation. It is proposed that the solvolyses of 1 in binary aqueous solvent mixtures proceed through an ionization [I] pathway rather than through an $S_N1/S_N2$ and/or ionization/(ionization-elimination) = [I/(I-E)] pathway.

Saturable Disposition of Taurine in the Cerebrospinal Fluid of the Rat

  • Chung, Suk-Jae
    • Proceedings of the Korean Society of Applied Pharmacology
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    • 1996.11a
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    • pp.99-113
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    • 1996
  • Taurine, a ${\beta}$-amino acid, plays an important role as a neuromodulator and is necessary for the normal development of the brain. Since de novo synthesis of taurine in the brain is minimal and in vivo studies suggest that taurine does not cross the blood-brain barrier, the blood-cerebrospinal fluid (CSF) barrier is likely to play a role in taurine transport between the central nervous system and the systemic circulation. Therefore, we examined in vivo elimination of taurine from the CSF in the rat to characterize in vivo kinetics of elimination for taurine from the CSF is consistent with the in vitro study. Using a stereotaxic device, cannulaes were placed into the lateral ventricle and the cisterna magna of the rat. Radio-labelled taurine and inulin (a marker of CSF flow) were injected into the lateral ventricle, and the concentrations of the labelled compounds in the CSF were monitored for up to 3 hrs in the cisterna magna. The apparent clearance of taurine from CSF was greater than the estimated CSF flow (p<0.005), indicating that there is a clearance process in addition to the CSF flow. Taurine distribution into the choroid plexus was at least 10 fold higher than that found in other brain areas (e.g., cerebellum, olfactory bulb and cortex). When unlabelled taurine was co-administered with radio-labelled taurine, the apparent clearance of the labeled taurine was reduced (p<0.01), suggesting a saturable disposition of taurine from CSF. Distribution of taurine into the choroid plexus, cerebellum, olfactory bulb and cortex was similarly diminished, indicating that the saturable uptake of taurine into these tissues is responsible for the non-linear disposition. A pharmacokinetic model involving first order elimination and saturable distribution described these data adequately. The Michaelis-Menten rate constant estimated from in vivo elimination study is similar to that obtained in the in vitro uptake experiment Collectively, our results demonstrate that taurine is transported in the choroid plexus via a taurine is cleared from the CSF via a saturable process. This process may be functionally relevant to taurine homeostasis in the brain.

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Real-Time Forward Kinematics of the 6-6 Stewart Platform with One Extra Linear Sensor (한 개의 선형 여유센서를 갖는 스튜어트 플랫폼의 실시간 순기구학)

  • Sim, Jae-Gyeong;Lee, Tae-Yeong
    • Transactions of the Korean Society of Mechanical Engineers A
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    • v.25 no.9
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    • pp.1384-1390
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    • 2001
  • This paper deals with the forward kinematics of the 6-6 Stewart platform of planar base and moving platform using one extra linear sensor. Based on algebraic elimination method, it first derives an 8th-degree univariate equation and then finds tentative solution sets out of which the actual solution is to be selected. In order to provide more exact solution despite the error between measured sensor value and the theoretic alone, a correction method is also used in this paper. The overall procedure requires so little computation time that it can be efficiently used for real-time applications. In addition, unlike the iterative scheme e.g. Newton-Raphson, the algorithm does not require initial estimates of solution and is free of the problems that it does not converge to actual solution within limited time. The presented method has been implemented in C language and a numerical example is given to confirm the effectiveness and accuracy of the developed algorithm.

Sodium Dependent Taurine Transport into the Choroid Plexus, the Blood-Cerebrospinal Fluid Barrier

  • Chung, Suk-Jae;Ramanathan, Vikram;Brett, Claire M.;Giacomini, Kathleen M.
    • Journal of Pharmaceutical Investigation
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    • v.25 no.3
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    • pp.7-20
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    • 1995
  • Taurine, a ${\beta}-amino$ acid, plays an important role as a neuromodulator and is necessary for the normal development of the brain. Since de novo synthesis of taurine in the brain is minimal and in vivo studies suggest that taurine dose not cross the blood-brain barrier, we examined whether the choroid plexus, the blood-cerebrospinal fluid (CSF) barrier, plays a role in taurine transport in the central nervous system. The uptake of $[^3H]-taurine$ into ATP depleted choroid plexus from rabbit was substantially greater in the presence of an inwardly directed $Na^+$ gradient taurine accumulation was negligible. A transient in side-negative potential gradient enhanced the $Na^+-driven$ uptake of taurine into the tissue slices, suggesting that the transport process is electrogenic, $Na^+-driven$ taurine uptake was saturable with an estimated $V_{max}$ of $111\;{\pm}\;20.2\;nmole/g/15\;min$ and a $K_M\;of\;99.8{\pm}29.9\;{\mu}M$. The estimated coupling ratio of $Na^+$ and taurine was $1.80\;{\pm}\;0.122.$ $Na^+-dependent$ taurine uptake was significantly inhibited by ${\beta}-amino$ acids, but not by ${\alpha}-amino$ acids, indicating that the transporter is selective for ${\beta}-amino$ acids. Since it is known that the physiological concentration of taurine in the CSF is lower than that in the plasma, the active transport system we characterized may face the brush border (i.e., CSF facing) side of the choroid plexus and actively transport taurine out of the CSF. Therefore, we examined in vivo elimination of taurine from the CSF in the rat to determine whether elimination kinetics of taurine from the CSF is consistent with the in vitro study. Using a stereotaxic device, cannulaes were placed into the lateral ventricle and the cisterna magna of the rat. Radio-labelled taurine and inulin (a marker of CSF flow) were injected into the lateral ventricle, and the concentrations of the labelled compounds in the CSF were monitored for upto 3 hrs in the cisterna magna. The apparent clearance of taurine from CSF was greater than the estimated CSF flow (p<0.005) indicating that there is a clearance process in addition to the CSF flow. Taurine distribution into the choroid plexus was at least 10 fold higher than that found in other brain areas (e. g., cerebellum, olfactory bulb and cortex). When unlabelled taurine was co-administered with radio-labelled taurine, the apparent clearance of taurine was reduced (p<0.0l), suggesting a saturable disposition of taurine from CSF. Distribution of taurine into the choroid plexus, cerebellum, olfactory bulb and cortex was similarly diminished, indicating that the saturable uptake of taurine into these tissues is responsible for the non-linear disposition. A pharmacokinetic model involving first order elimination and saturable distribution described these data adequately. The Michaelis-Menten rate constant estimated from in vivo elimination study is similar to that obtained in the in vitro uptake experiment. Collectively, our results demonstrate that taurine is transported in the choroid plexus via a $Na^+-dependent,saturable$ and apparently ${\beta}-amino$ acid selective mechanism. This process may be functionally relevant to taurine homeostasis in the brain.

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Effects of $\beta$-Mercaptoethanol and Hydrogen Peroxide on Enzymatic Conversion of Human Proinsulin to Insulin

  • Son, Young-Jin;Kim, Chang-Kyu;Choi, Byoung-Taek;Park, Yong-Cheol;Seo, Jin-Ho
    • Journal of Microbiology and Biotechnology
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    • v.18 no.5
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    • pp.983-989
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    • 2008
  • Human insulin is a hormone well-known to regulate the blood glucose level. Recombinant preproinsulin, a precursor of authentic insulin, is typically produced in E. coli as an inactive inclusion body, the solubilization of which needs the addition of reducing agents such as $\beta$-mercaptoethanol. To make authentic insulin, recombinant preproinsulin is modified enzymatically by trypsin and carboxypeptidase B. The effects of $\beta$-mercaptoethanol on the formation of human insulin derivatives were investigated in the enzymatic modification by using commercially available human proinsulin as a substrate. Addition of 1 mM $\beta$-mercaptoethanol induced the formation of various insulin derivatives. Among them, the second major one, impurity 3, was found to be identical to the insulin B chain fragment from $Phe_1$ to $Glu_{21}$. Minimization of the formation of insulin derivatives and concomitant improvement of the production yield of human insulin were achieved by the addition of hydrogen peroxide. Hydrogen peroxide bound with $\beta$-mercaptoethanol and thereby reduced the negative effects of $\beta$-mercaptoethanol considerably. Elimination of the impurity 3 and other derivatives by the addition of over 10 mM hydrogen peroxide in the presence of $\beta$-mercaptoethanolled to a 1.3-fold increase in the recovery efficiency of insulin, compared with those for the case without hydrogen peroxide. The positive effects of hydrogen peroxide were also confirmed with recombinant human preproinsulin expressed in recombinant E. coli as an inclusion body.