• Title/Summary/Keyword: Kinetics and mechanism

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Synthesis and Properties of Ionic Polyacetylene Composite from the In-situ Quaternization Polymerization of 2-Ethynylpyridine Using Iron (III) Chloride (염화 철(III)을 이용한 2-에티닐피리딘의 in-situ4차염화중합을 통한 이온형 폴리아세틸렌 복합체의 합성과 특성)

  • Taehyoung Kim;Sung-Ho Jin;Jongwook Park;Yeong-Soon Gal
    • Applied Chemistry for Engineering
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    • v.35 no.4
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    • pp.296-302
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    • 2024
  • An ionic conjugated polymer-iron (III) chloride composite was prepared via in-situ quaternization polymerization of 2-ethynylpyridine (2EP) using iron (III) chloride. Various instrumental methods revealed that the chemical structure of the resulting conjugated polymer (P2EP)-iron (III) chloride composite has the conjugated backbone system having the designed pyridinium ferric chloride complexes. The polymerization mechanism was assumed to be that the activated triple bond of 2-ethynylpyridinium salt, formed at the first reaction step, is easily susceptible to the step-wise polymerization, followed by the same propagation step that contains the propagating macroanion and monomeric 2-ethynylpyridinium salts. The electro-optical and electrochemical properties of the P2EP-FeCl3 composite were studied. In the UV-visible spectra of P2EP-FeCl3 composite, the absorption maximum values were 480 nm and 533 nm, and the PL maximum value was 598 nm. The cyclic voltammograms of the P2EP-FeCl3 composite exhibited irreversible electrochemical behavior between the oxidation and reduction peaks. The kinetics of the redox process of composites were found to be very close to a diffusion-controlled process from the plot of the oxidation current density versus the scan rate.

Humeral Torque in Youth Baseball Pitchers: Implications for the Development of Little League Shoulder and Humeral Retroversion (청소년기 야구 투수의 상완골 회전력: 소아 야구 견 및 상완골 후염의 발달에 미치는 영향)

  • Kim Young-Kyu;Sabick Michelle B.;Torry Michael R.;Hawkins Richard J.
    • Journal of Korean Orthopaedic Sports Medicine
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    • v.2 no.1
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    • pp.62-70
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    • 2003
  • Purpose: We examined the kinematics and kinetics of the shoulder in youth baseball pitchers in light of the mechanisms of development of little league shoulder and humeral retrotorsion. Materials and Methods: The joint kinematics and the net force and torque acting on the humerus were calculated in fourteen youth pitchers throwing in a simulated game. Results: The major force component acting on the humerus was a tensile force of 378$\pm$81 N that peaked just after ball release. The predominant torque on the humerus was an external rotation torque about the long axis of the humerus. This torque reached a peak value of 35.3$\pm$6.7 Nm about 73$\%$through the pitching motion. This torque is approximately 66$\%$ of the torque required to fracture of the adult humerus. Conclusions: The direction of the humeral torque was consistent with the development of increased humeral retrotorsion in the throwing arm. Shear stress arising from the high torque during the late cocking phase likely leads to deformation the relatively weak proximal humeral epiphysis. The external rotation torque applied to the humerus during the pitch also agrees with the proposed mechanism for development little league shoulder, which has been hypothesized to be due to rotational stresses acting on the epiphysis during the throwing motion.

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The Evidence for Pepsin-Catalyzed Transpeptidation (펩신촉매에 의한 Transpeptide의 생성)

  • 조용권
    • Journal of Life Science
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    • v.8 no.4
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    • pp.410-415
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    • 1998
  • Procine pepsin hydrolysis of hexapeptide L-S-pNF-Nle-A-OMe in the presence of dipeptide L-L generates a new peak on HPLC analysis of reaction mixtures that is not seen when enzyme is incubated with either peptide alone. The peaks can be detected spectroscopically at either 214 or 254 nm, the latter consistent with a new peptide containing the p-nitro-F residue. The data suggest acyl transpeptidation between E(L-S-pNF) and L-L to form L-S-pNF-L-L. Consistent with this inference are (1) the ability of L-L-NH$_{2}$ and inability of Boc-L-L to undergo a similar transpeptidation reaction, and (2) the data from electrospray mass spectrum. This synthesis requires that Nle-A-L-OMe be released before L-S-pNF, an order opposite to that proposed on the basis of product inhibition kinetics. Consistent with this inference are reciprocal solvent isotope effects ; normal isotope effects of 1.736$\pm$0.121 on the formation of Nle-A-L-OMe and 2.281$\pm$0.184 in the formation of L-S-pNF, coupled to an inverse isotope effects of 0.576$\pm$0.045 on the formation of L-S-pNF-L-L. Because transpeptidation precedes faster in D$_{2}$O, the isotopically-sensitive step must occur after release of Nle-A-L-OMe. Isotopically-enhanced transpeptidation is consistent with the Uni-Bi iso memchanism postulated on the basis of an isotope effects on Vmax but not on Vmax/Km$^{1)}$ and confirmed by isotope effects on the onset of inhibition by pepstatin$^{2)}$.

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Adsorption Characteristics of Reactive Red 120 by Coal-based Granular Activated Carbon : Isotherm, Kinetic and Thermodynamic Parameters (석탄계 입상활성탄에 의한 Reactive Red 120의 흡착 특성 : 등온선, 동력학 및 열역학 파라미터)

  • Lee, Jong Jib
    • Applied Chemistry for Engineering
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    • v.31 no.2
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    • pp.164-171
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    • 2020
  • Adsorption characteristics of reactive red 120 (RR 120) dye by a coal-based granular activated carbon (CGAC) from an aqueous solution were investigated using the amount of activated carbon, pH, initial concentration, contact time and temperature as adsorption variables. Isotherm equilibrium relationship showed that Langmuir's equation fits better than that of Freundlich's equation. The adsorption mechanism was considered to be superior to the adsorption of monolayer with uniform energy distribution. From the evaluated Langmuir separation coefficients (RL = 0.181~0.644), it was found that this adsorption process belongs to an effective treatment area (RL = 0~1). The adsorption energy determined by Temkin's equation and Dubinin-Radushkevich's equation was E = 15.31~7.12 J/mol and B = 0.223~0.365 kJ/mol, respectively. The adsorption process showed the physical adsorption (E < 20 J/mol and B < 8 kJ/mol). The adsorption kinetics followed the pseudo first order model. The adsorption reaction of RR 120 dye on CGAC was found to increase spontaneously with increasing the temperature because the free energy change decreased with increasing the temperature. The enthalpy change (12.747 kJ/mol) indicated an endothermic reaction. The isosteric heat of adsorption (△Hx = 9.78~24.21 kJ/mol) for the adsorption reaction of RR 120 by CGAC was revealed to be the physical adsorption (△Hx < 80 kJ/mol).

Chronic Ca2+ influx through voltage-dependent Ca2+ channels enhance delayed rectifier K+ currents via activating Src family tyrosine kinase in rat hippocampal neurons

  • Yang, Yoon-Sil;Jeon, Sang-Chan;Kim, Dong-Kwan;Eun, Su-Yong;Jung, Sung-Cherl
    • The Korean Journal of Physiology and Pharmacology
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    • v.21 no.2
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    • pp.259-265
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    • 2017
  • Excessive influx and the subsequent rapid cytosolic elevation of $Ca^{2+}$ in neurons is the major cause to induce hyperexcitability and irreversible cell damage although it is an essential ion for cellular signalings. Therefore, most neurons exhibit several cellular mechanisms to homeostatically regulate cytosolic $Ca^{2+}$ level in normal as well as pathological conditions. Delayed rectifier $K^+$ channels ($I_{DR}$ channels) play a role to suppress membrane excitability by inducing $K^+$ outflow in various conditions, indicating their potential role in preventing pathogenic conditions and cell damage under $Ca^{2+}$-mediated excitotoxic conditions. In the present study, we electrophysiologically evaluated the response of $I_{DR}$ channels to hyperexcitable conditions induced by high $Ca^{2+}$ pretreatment (3.6 mM, for 24 hours) in cultured hippocampal neurons. In results, high $Ca^{2+}$-treatment significantly increased the amplitude of $I_{DR}$ without changes of gating kinetics. Nimodipine but not APV blocked $Ca^{2+}$-induced $I_{DR}$ enhancement, confirming that the change of $I_{DR}$ might be targeted by $Ca^{2+}$ influx through voltage-dependent $Ca^{2+}$ channels (VDCCs) rather than NMDA receptors (NMDARs). The VDCC-mediated $I_{DR}$ enhancement was not affected by either $Ca^{2+}$-induced $Ca^{2+}$ release (CICR) or small conductance $Ca^{2+}$-activated $K^+$ channels (SK channels). Furthermore, PP2 but not H89 completely abolished $I_{DR}$ enhancement under high $Ca^{2+}$ condition, indicating that the activation of Src family tyrosine kinases (SFKs) is required for $Ca^{2+}$-mediated $I_{DR}$ enhancement. Thus, SFKs may be sensitive to excessive $Ca^{2+}$ influx through VDCCs and enhance $I_{DR}$ to activate a neuroprotective mechanism against $Ca^{2+}$-mediated hyperexcitability in neurons.

Kinetic Study of Macrocyclic Ligand-Metal Ion Complexes (거대고리 리간드와 금속이온과의 착물에 관한 반응속도론적 연구)

  • Moon-Hwan Cho;Jin-Ho Kim;Hyu-Bum Park;Si-Joon Kim
    • Journal of the Korean Chemical Society
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    • v.33 no.4
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    • pp.366-370
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    • 1989
  • A new macrocyclic ligand 1,15,18-triaza-3,4;12,13-dibenzo-5,8,11-cycloeicosane (NdienOdien$H_4$ = $N_3O_3$) has been synthesized and identified by element analysis, NMR and IR spectrophotometry. Stepwise protonation constants of ligand are determined by potentiometry in 95% methanol solution(I = 0.1 mol $dm^{-3}$, $Me_4$NCl). log $K_1$;log $K_2$;log $K_3$ = 9.1;8.1;3.6.The kinetics of the acid-promoted dissociation reactions of complex cations of nickel(II) and copper(III) with NdienOdien and NdienOen macrocyclic ligands having, respectively, 17 and 20 ring members, have been studied spectrophotometrically in HCl$O_4$ NaCl$O_4$ aqueous solutions. From the temperature effect on kinetic constant ($k_{obs}$), the parameters of activation(${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$) of dissociation reaction for $ML^{2+}$ with $H^+$ ion have been determined. We have proposed the possible mechanism of the reaction from the data obtained.

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Kinetic Study of the Fischer-Tropsch Synthesis and Water Gas Shift Reactions over a Precipitated Iron Catalyst (철 촉매를 이용한 Fischer-Tropsch 합성 반응과 수성 가스 전환 반응에 대한 반응 속도 연구)

  • Yang, Jung-Il;Chun, Dong Hyun;Park, Ji Chan;Jung, Heon
    • Korean Chemical Engineering Research
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    • v.50 no.2
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    • pp.358-364
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    • 2012
  • The kinetics of the Fischer-Tropsch synthesis and water gas shift reactions over a precipitated iron catalyst were studied in a 5 channel fixed-bed reactor. Experimental conditions were changed as follows: synthesis gas $H_2$/CO feed ratios of 0.5~2, reactants flow rate of 60~80 ml/min, and reaction temperature of $255{\sim}275^{\circ}C$ at a constant pressure of 1.5 MPa. The reaction rate of Fischer-Tropsch synthesis was calculated from Eley-Rideal mechanism in which the rate-determining step was the formation of the monomer species (methylene) by hydrogenation of associatively adsorbed CO. Whereas water gas shift reaction rate was determined by the formation of a formate intermediate species as the rate-determining step. As a result, the reaction rates of Fischer-Tropsch synthesis for the hydrocarbon formation and water gas shift for the $CO_2$ production were in good agreement with the experimental values, respectively. Therefore, the reaction rates ($r_{FT}$, $r_{WGS}$, $-r_{CO}$) derived from the reaction mechanisms showed good agreement both with experimental values and with some kinetic models from literature.

Fluoride Sorption Property of Lanthanum Hydroxide (란탄수산화물의 불소 흡착 특성)

  • Kim, Jung-Hwan;Park, Hyun-Ju;Jung, Kyung-Hun
    • Journal of Korean Society of Environmental Engineers
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    • v.32 no.7
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    • pp.714-721
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    • 2010
  • This research was undertaken to evaluate the feasibility of lanthanum hydroxide for fluoride removal from aqueous solutions. A batch sorption experiments were conducted to study the influence of various factors such as pH, contact time, initial fluoride concentration and temperature on the sorption of fluoride on lanthanum hydroxide. The optimum fluoride removal was observed in the $pH_{eq}{\leq}8.8$. Sorption equilibrium of fluoride on lanthanum hydroxide was better described by the Freundlish isotherm model than by the Langmuir isotherm model. The adsorption energy obtained from D-R model was 9.21 kJ/mol indicating an ion-exchange process as primary adsorption mechanism. The pseudo-second-order kinetic model described well the experimental kinetic data. Thermodynamic parameters such as ${\Delta}Go^{\circ}$, ${\Delta}H^{\circ}$ and ${\Delta}S^{\circ}$ indicated that the nature of fluoride sorption is spontaneous and endothermic. The used lanthanum hydroxide could be regenerated by washing with NaOH solution. Also, the results applied to real ground water indicate that fluoride selectivity and removal capacity of lanthanum hydroxide were superior to those of PA anion-exchange resin.

Kinetic Measurement of the Step Size of DNA Unwinding by Bacteriophage T7 DNA Helicase gp4 (T7 박테리오파지 gp4 DNA helicase에 의한 DNA unwinding에서 step size의 반응속도론적 측정)

  • Kim, Dong-Eun
    • Journal of Life Science
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    • v.14 no.1
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    • pp.131-140
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    • 2004
  • T7 bacteriophage gp4 is the replicative DNA helicase that unwinds double-stranded DNA by utilizing dTTP hydrolysis energy. The quaternary structure of the active form of T7 helicase is a hexameric ring with a central channel. Single-stranded DNA passes through the central channel of the hexameric ring as the helicase translocates $5'\rightarrow3'$ along the single-stranded DNA. The DNA unwinding was measured by rapid kinetic methods and showed a lag before the single-stranded DNA started to accumulate exponentially. This behavior was analyzed by a kinetic stepping model for the unwinding process. The observed lag phase increased as predicted by the model with increasing double-stranded DNA length. Trap DNA added in the reaction had no effect on the amplitudes of double-stranded DNA unwound, indicating that the $\tau7$ helicase is a highly processive helicase. Global fitting of the kinetic data to the stepping model provided a kinetic step size of 10-11 bp/step with a rate of $3.7 s^{-1}$ per step. Both the mechanism of DNA unwinding and dTTP hydrolysis and the coupling between the two are unaffected by temperature from $4∼37^{\circ}C$. Thus, the kinetic stepping for dsDNA unwinding is an inherent property of tile replicative DNA helicase.

Fine Structure and Detoxification Kinetics in Kupffer Cells after Injection of Endotoxin in Rats (내독소 투여에 의한 Kupffer 세포의 미세형태학적 해독반응)

  • Choi, Joon-Hyuk;Choi, Won-Hee;Lee, Tae-Sook
    • Journal of Yeungnam Medical Science
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    • v.10 no.2
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    • pp.313-337
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    • 1993
  • The aim of this study was to clarify the role of Kupffer cells in the mechanism of endotoxin-induced liver injury. The study on fine structure of Kupffer cells was performed after the injection of endotoxin. The endotoxin(Escherichia coli lipopolysaccharide 026 : B6. 1.5mg/100 g of body weight) was intraperitoneally injected in Sprague-Dewley rats. Animals were sacrificed at 1/4, 1/2, 1, 2, 4, 8, 16, 24, 72 and 120 hours after the injection of endotoxin. Livers were extirpated and processed to be examined by light and electron microscopy. The results obtained were summerized as follows: Early changes observed in liver after endotoxin injection included the increased number and hypertrophy of Kupffer cells, infiltration of neutrophils and presence of fibrin thrombi within the sinusoids. The continuous increase of the Kupffer cells in number with hypertrophy, congestion and infiltration of inflammatory cells within the sinusoids were observed. Hepatocytes showed fatty change and occasional necrosis. At 72 hours the congestion decreased. At 120 hours the number of Kupffer cells was increased, but the morphology of Kupffer cells became similar to that of the control group. The numbers and sizes of primary and secondary lysosomes and amount of euchromatin of Kupffer cells increased. Swellings and increase in number of mitochondria, Golgi complex, smooth endoplasmic reticulum, rough endoplasmic reticulum were evident. Microthrombi were present within the sinusoids. The swelling of rough endoplasmic reticulum and mitochondria, decrease of glycogen particles, fatty change, hypoxic vacuoles, pyknotic nuclei and occasional necrosis were observed in hepatocytes. At 72 hours the number of secondary lysosomes in Kupffer cells decreased. At 120 hours the morphology of Kupffer cells became similar to that of the control group. According to these results, it was postulated that the endotoxin was initially taken up by pinocytosis into Kupffer cells and degraded in secondary lysosomes of activated Kupffer cells. Kupffer cells may play an important role in the defense mechanism of liver during endotoxemia. The dysfunction of Kupffer cells and ischemia by sinusoidal microthrombi may cause liver injury.

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