• Title/Summary/Keyword: Kinetic studies

Search Result 730, Processing Time 0.024 seconds

Equilibrium, Isotherm, Kinetic and Thermodynamic Studies for Adsorption of 7-Epi-10-deacetylpaclitaxel from Taxus chinensis on Sylopute (실로퓨트에 의한 Taxus chinensis 유래 7-에피-10-디아세틸파클리탁셀의 흡착에 대한 평형, 등온흡착식, 동역학 및 열역학적 특성)

  • Park, Sae-Hoon;Kim, Jin-Hyun
    • Korean Chemical Engineering Research
    • /
    • v.58 no.1
    • /
    • pp.113-121
    • /
    • 2020
  • In batch experiments, the adsorption of 7-epi-10-deacetylpaclitaxel was studied using Sylopute. Experimental equilibrium data were applied to Langmuir, Freundlich, Temkin and Dubinin-Radushkevich isotherm models. Among the four isotherm models tested, the Langmuir isotherm model gave the highest accuracy. The adsorption capacity was found to decrease with increases in temperature and the adsorption of 7-epi-10-deacetylpaclitaxel onto Sylopute was a favorable physical process. Adsorption kinetic data agreed very well with the pseudo-second-order kinetic model, while boundary layer diffusion and intraparticle diffusion did not play a key role in the adsorption process. The process of 7-epi-10-deacetylpaclitaxel adsorption onto Sylopute was exothermic and nonspontaneous. Also, the adsorption isosteric heat was independent of surface loading indicating an energetically homogeneous adsorbent.

Kinetic Studies of the Solvolyses of 4-Nitrophenyl Phenyl Thiophosphorochloridate

  • Koh, Han-Joong;Kang, Suk-Jin
    • Bulletin of the Korean Chemical Society
    • /
    • v.30 no.10
    • /
    • pp.2413-2418
    • /
    • 2009
  • Rates of solvolyses of 4-nitrophenyl phenyl thiophosphorochloridate (4-N$O_2$PhOP(S)(Cl)OPh, $\underline{1}$) in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone, and 2,2,2-trifluroethanol (TFE) are reported. Thermodynamic parameters were determined at several temperatures in three representative solvents. The extended Grunwald-Winstein equation was applied to 29 solvents and the correlation coefficient (R) showed 0.959. The sensitivities (l = 1.37 and m = 0.62) are similar to those obtained for diphenyl thiophosphorochloridate (($PhO)_2$PSCl, $\underline{2}$), diphenyl phosphorochloridate (($PhO)_2$POCl, $\underline{3}$), diphenyl phosphinic chloride ($Ph_2$POCl, $\underline{4}$), and diphenyl thiophosphinic chloride ($Ph_2$PSCl, $\underline{5}$). The solvolytic reaction mechanism of 4-nitrophenyl phenyl thiophosphorochloridate ($\underline{1}$) is suggested to be proceeded a $S_N$2 process as previously reported result. The activation enthalpies are shown as slightly low as ${\Delta}H^{\neq}\;=\;9.62\;to\;11.9\;kcal{\cdot}mol^{-1}$ and the activation entropies are shown as slightly high negative value as ${\Delta}S^{\neq}\;=\;-34.1\;to\;-44.9\;cal{\cdot}mol^{-1}{\cdot}K^{-1}$ compared to the expected $S_N$2 reaction mechanism. Kinetic solvent isotope effects are accord with a typical $S_N$2 mechanism as shown in the range of 2.41 in MeOH/ MeOD and 2.57 in $H_2O/D_2O$ solvent mixtures.

Effect of current density and contact time on membrane fouling in electrocoagulation-MBR and their kinetic studies on fouling reduction rate (전기응집-MBR 공정의 전류밀도와 접촉시간이 막 오염에 미치는 영향과 막 오염 저감 속도론적 고찰)

  • Um, Se-Eun;Chang, In-Soung
    • Journal of Korean Society of Water and Wastewater
    • /
    • v.31 no.4
    • /
    • pp.321-328
    • /
    • 2017
  • Recently EC-MBR (Elctrocoagulation - Membrane Bio Reactor) has been suggested as one of alternative processes to overcome membrane fouling problems. Most important operational parameters in the EC-MBR are known to current density and contact time. Their effect on membrane filtration performances has been reported well, however, quantitative interrelationship between both parameters not been investigated yet. The purpose of this study is to give a kinetic model suggesting the current density and the contact time required to reduce the membrane fouling. The 4 different set of current densities (2.5, 6, 12 and $24A/m^2$) and contact times (0, 2, 6 and 12 hr) were selected as operational parameters. After each electro-coagulation under the 16 different conditions, a series of membrane filtration was carried out. The membrane fouling decreased as the current density and contact time increased, Total fouling resistances under different conditions, $R_t(=R_c+R_f)$ were calculated and compared to those of the controls ($R_0$), which were calculated from the data of experiments without electro-coagulation. A kinetic approach for the fouling reduction rate ($R_t/R_0$) was carried out and the equation ${\rho}^{0.46}_it=7.0$ was obtained, which means that the product of current density and the contact time needed to reduce the fouling in certain amounts (in this study, 10% of fouling reduction) is always constant.

Acetylcholinesterase(AChE)-Catalyzed Hydrolysis of Long-Chain Thiocholine Esters: Shift to a New Chemical Mechanism

  • Jung, Dai-Il;Shin, Young-Ju;Lee, Eun-Seok;Moon, Tae-sung;Yoon, Chang-No;Lee, Bong-Ho
    • Bulletin of the Korean Chemical Society
    • /
    • v.24 no.1
    • /
    • pp.65-69
    • /
    • 2003
  • The kinetic and chemical mechanisms of AChE-catalyzed hydrolysis of short-chain thiocholine esters are relatively well documented. Up to propanoylthiocholine (PrTCh) the chemical mechanism is general acid-base catalysis by the active site catalytic triad. The chemical mechanism for the enzyme-catalyzed butyrylthiocholine(BuTCh) hydrolysis shifts to a parallel mechanism in which general base catalysis by E199 of direct water attack to the carbonyl carbon of the substrate. [Selwood, T., et al. J. Am. Chem. Soc. 1993, 115, 10477- 10482] The long chain thiocholine esters such as hexanoylthiocholine (HexTCh), heptanoylthiocholine (HepTCh), and octanoylthiocholine (OcTCh) are hydrolyzed by electric eel acetylcholinesterase (AChE). The kinetic parameters are determined to show that these compounds have a lower Michaelis constant than BuTCh and the pH-rate profile showed that the mechanism is similar to that of BuTCh hydrolysis. The solvent isotope effect and proton inventory of AChE-catalyzed hydrolysis of HexTCh showed that one proton transfer is involved in the transition state of the acylation stage. The relationship between the dipole moment and the Michaelis constant of the long chain thiocholine esters showed that the dipole moment is the most important factor for the binding of a substrate to the enzyme active site.

Nucleophilic Substitution Reactions of N-Methyl α-Bromoacetanilides with Benzylamines in Dimethyl Sulfoxide

  • Adhikary, Keshab Kumar;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
    • /
    • v.32 no.3
    • /
    • pp.857-862
    • /
    • 2011
  • Kinetic studies of the reactions of N-methyl-Y-${\alpha}$-bromoacetanilides with substituted X-benzylamines have been carried out in dimethyl sulfoxide at $25.0^{\circ}C$. The Hammett plots for substituent X variations in the nucleophiles (log $k_N$ vs ${\sigma}_X$) are slightly biphasic concave upwards/downwards, while the Bronsted plots (log $k_N$ vs $pK_a$) are biphasic concave downwards with breakpoints at X = H. The Hammett plots for substituent Y variations in the substrates (log $k_N$ vs ${\sigma}_Y$) are biphasic concave upwards/downwards with breakpoints at Y = H. The cross-interaction constant $\rho_{XY}$ values are all negative: $\rho_{XY}$ = -0.32 for X = Y = electron-donating; -0.22 for X = electron-withdrawing and Y = electron-donating; -1.80 for X = electron-donating and Y = electronwithdrawing; -1.43 for X = Y = electron-withdrawing substituents. Deuterated kinetic isotope effects are primary normal ($k_H/k_D$ > 1) for Y = electron-donating, while secondary inverse ($k_H/k_D$ < 1) for Y = electronwithdrawing substituent. The proposed mechanisms of the benzylaminolyses of N-methyl-Y-${\alpha}$-bromoacetanilides are a concerted mechanism with a five membered ring TS involving hydrogen bonding between hydrogen (deuterium) atom in N-H(D) and oxygen atom in C = O for Y = electron-donating, while a concerted mechanism with an enolate-like TS in which the nucleophile attacks the ${\alpha}$-carbon for Y = electronwithdrawing substituents.

Study of the Kinetic Effects on Relativistic Unmagnetized Shocks using 3D PIC Simulations

  • Choi, Eun Jin;Min, Kyoung W.;Choi, Cheongrim;Nishikawa, Ken-Ichi
    • The Bulletin of The Korean Astronomical Society
    • /
    • v.37 no.2
    • /
    • pp.101.2-101.2
    • /
    • 2012
  • Shocks are ubiquitous in astrophysical plasmas: bow shocks are formed by the interaction of solar wind with planetary magnetic fields, and supernova explosions and jets produce shocks in interstellar and intergalactic spaces. The global morphologies of these shocks are usually described by a set of magnetohydrodynamic (MHD) equations which tacitly assumes local thermal equilibrium, and the resulting Rankine-Hugoniot shock jump conditions are applied to obtain the relationship between the upstream and downstream physical quantities. While thermal equilibrium can be achieved easily in collisional fluids, it is generally believed that collisions are infrequent in astrophysical settings. In fact, shock widths are much smaller than collisional mean free paths and a variety of kinetic phenomena are seen at the shock fronts according to in situ observations of planetary shocks. Hence, both the MHD and kinetic equations have been adopted in theoretical and numerical studies to describe different aspects of the physical phenomena associated with astrophysical shocks. In this paper, we present the results of 3D relativistic particle-in-cell (PIC) simulations for ion-electron plasmas, with focus on the shock structures: when a jet propagates into an unmagnetized ambient plasma, a shock forms in the nonlinear stage of the Weibel instability. As the shock shows the structures that resemble those predicted in MHD systems, we compare the results with those predicted in the MHD shocks. We also discuss the thermalization processes of the upstream flows based on the time evolutions of the phase space and the velocity distribution, as well as the wave spectra analyses.

  • PDF

SCK Tumor Cell Killing by Hyperthermia in the Presence of Heat Protector and Heat Sensitizer (열보호제와 열증감제의 존재하에서 온열처리에 의한 SCK 종양세포의 치사기작)

  • 강만식;서미영;정주영
    • The Korean Journal of Zoology
    • /
    • v.32 no.2
    • /
    • pp.134-141
    • /
    • 1989
  • The present investigation aims at elucidating a possible mechanism of heat inactivation of SCK ceils by comparing the kinetics of cell lethality and protein degradation in the presence of heat protector or heat sensitizer. The effect of heat sensitizer and protector was exhibited in both cell survival and protein degradation kinetics, the magnitude of the effect being much profound for the protector compared to the sensitizer. A conclusion to he drawn from the present experiment is that there is no direct correlation between cell lethality and protein degradation. Rather, protein degradation, which might occur in the membrane, causes cell inactivation indirectly, possibly by altering the cellular environment. Accordingly, further studies are needed to get insight into the mechanism of cell inactivation by hyperthermia.

  • PDF

Comparison of Dynamic Knee Valgus During Single-leg Step Down Between People With and Without Pronated Foot Using Two-dimensional Video Analysis

  • Kim, Hyun-sook;Yoo, Hwa-ik;Hwang, Ui-jae;Kwon, Oh-yun
    • Physical Therapy Korea
    • /
    • v.28 no.4
    • /
    • pp.266-272
    • /
    • 2021
  • Background: Considering the kinetic chain of the lower extremity, a pronated foot position (PFP) can affect malalignment of the lower extremity, such as a dynamic knee valgus (DKV). Although the DKV during several single-leg movement tests has been investigated, no studies have compared the differences in DKV during a single-leg step down (SLSD) between subjects with and without PFP. Objects: The purpose of this study was to compare the DKV during SLSD between subjects with and without PFP. Methods: Twelve subjects with PFP (9 men, 3 women) and 15 subjects without PFP (12 men, 3 women) participated in this study. To calculate the DKV, frontal plane projection angle (FPPA), knee-in distance (KID), and hip-out distance (HOD) during SLSD were analyzed by two-dimensional video analysis software (Kinovea). Results: The FPPA was significantly lower in PFP group, compared with control group (166.4° ± 7.5° and 174.5° ± 5.5°, p < 0.05). Also, the KID was significantly greater in PFP group, compared with control group (12.7 ± 3.9 cm and 7.3 ± 2.4 cm, p < 0.05). However, the HOD not significantly differed between two groups (12.7 ± 1.7 cm and 11.4 ± 2.5 cm, p > 0.05). Conclusion: The PFP is associated with lower FPPA and greater KID. When assess the DKV during SLSD, the PFP should be considered as a crucial factor for occurrence of DKV.

Immediate Effect of Serratus Posterior Inferior Muscle Direction Taping on Thoracolumbar Junction Rotation Angle During One Arm Lifting in the Quadruped Position

  • Kim, Nu-ri;Ahn, Sun-hee;Gwak, Gyeong-tae;Yoo, Hwa-ik;Kwon, Oh-yun
    • Physical Therapy Korea
    • /
    • v.28 no.3
    • /
    • pp.227-234
    • /
    • 2021
  • Background: The serratus posterior inferior (SPI) muscle originates from the spinous process of T11-L2 and inserts at the lower border of the 9-12th ribs. This muscle is involved in thoracolumbar rotation and stability. Several positions can be used to improve trunk stability; the quadruped position is a good position for easily maintaining a neutral spine. In particular, during one arm lifting, various muscles act to maintain a neutral trunk position, and the SPI is one of these muscles. If trunk stability is weakened, uncontrolled trunk rotation may occur at this time. Tape can be used to increase trunk stability. There have been no studies on the effect of taping applied to the SPI muscle on thoracolumbar junction (TLJ) stability. Objects: This study compared the TLJ rotation angle between three different conditions (without taping, transverse taping, and SPI muscle direction taping). Methods: Thirty subjects were recruited to the study (18 males and 12 females). The TLJ rotation angle was measured during one arm lifting in a quadruped position (ALQP). Two taping methods (transverse and SPI muscle direction taping) were applied, and the TLJ rotation angle was measured in the same movement. Results: SPI muscle direction taping significantly reduced TLJ rotation compared to that without taping (p < 0.001) and with transverse taping (p < 0.001). There was a significant difference in the TLJ rotation angle between transverse taping and SPI muscle direction taping (p < 0.017). Conclusion: SPI muscle direction taping reduces the TLJ rotation angle during ALQP. Therefore, SPI muscle direction taping is one method to improve TLJ stability and reduce uncontrolled TLJ rotation during ALQP.

Evaluation of Structural Performance for High Strength Rockfall Protection Fence according Reinforcement of H-Beam using Numerical Analysis (수치해석을 통한 지주 보강에 따른 고강도 낙석 방지울타리 구조성능 평가)

  • Hyunwoo Jin;Sanghoon Seo;Duho Lee;Youngcheol Hwang
    • Journal of the Korean GEO-environmental Society
    • /
    • v.24 no.1
    • /
    • pp.25-36
    • /
    • 2023
  • In Korea, the rockfall prevention fence is designed with 50kJ of rockfall kinetic energy in order to prevent damages such as falling rocks and landslides. In the case of rockfall kinetic energy, it is highly dependent on the shape of the slope on which it occurs. As a previous study, a fence performance evaluation was conducted for 100kJ rockfall impact energy using ETAG 27. However, previous studies have focused on newly installed rockfall prevention fences. In this study, a reinforcing materials was installed on the existing rockfall prevention fence through numerical analysis, and the structural performance of the high-strength rockfall prevention fence capable of defending against 120kJ of rockfall kinetic energy was evaluated.