• Title/Summary/Keyword: Hydrolysis rate

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Burke-Schumann analysis of silica formation by hydrolysis in an external chemical vapor deposition process (외부 화학증착 공정에서의 가수분해반응으로 인한 실리카 생성에 대한 버크-슈만 해석)

  • Song, Chang-Geol;Hwang, Jeong-Ho
    • Transactions of the Korean Society of Mechanical Engineers B
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    • v.20 no.5
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    • pp.1671-1678
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    • 1996
  • In external chemical vapor deposition processes including VAD and OVD the distribution of flame-synthesized silica particles is determined by heat and mass transfer limitations to particle formation. Combustion gas flow velocities are such that the particle diffusion time scale is longer than that of gas flow convection in the zone of particle formation. The consequence of these effects is that the particles formed tend to remain along straight smooth flow stream lines. Silica particles are formed due to oxidation and hydrolysis. In the hydrolysis, the particles are formed in diffuse bands and particle formation thus requires the diffusion of SiCl$\_$4/ toward CH$\_$4//O$\_$2/ combustion zone to react with H$\_$2/O diffusing away from these same zones on the torch face. The conversion kinetics of hydrolysis is fast compared to diffusion and the rate of conversion is thus diffusion-limited. In the language of combustion, the hydrolysis occurs as a Burke-Schumann process. In selected conditions, reaction zone shape and temperature distributions predicted by the Burke-Schumann analysis are introduced and compared with experimental data available. The calculated centerline temperatures inside the reaction zone agree well with the data, but the calculated values outside the reaction zone are a little higher than the data since the analysis does not consider diffusion in the axial direction and mixing of the combustion products with ambient air. The temperatures along the radial direction agree with the data near the centerline, but gradually diverge from the data as the distance is away from the centerline. This is caused by the convection in the radial direction, which is not considered in the analysis. Spatial distribution of silica particles are affected by convection and diffusion, resulting in a Gaussian form in the radial direction.

Prediction of Sucrose Hydrolysis Rate using Equivalent Time at A Reference Temperature under Regular Temperature Fluctuations (규칙적인 온도변화에서 표준온도 상당시간을 이용한 Sucrose 가수분해속도의 예측)

  • Cho, Hyung-Yong;Hong, Seok-In;Kim, Young-Sook;Pyun, Yu-Ryang
    • Korean Journal of Food Science and Technology
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    • v.25 no.6
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    • pp.643-648
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    • 1993
  • A simple approximate model using equivalent time at a reference temperature ($t_{eq}$) was derived to predict quality changes caused by temperature fluctuations. The validity and effectiveness of this model have been assessed with experimental data of sucrose hydrolysis. Kinetic parameters of sucrose hydrolysis were estimated by one step method using equivalent time at a reference temperature with linearly increasing temperature profile. Sucrose hydrolysis was a first order reaction, and the activation energy was 25.84 kcal/mol. The extent of sucrose hydrolysis of liquid model system under accelerated test with sinusoidal temperature fluctuations were determined. The proposed model yielded accurate prediction with the correlation coefficient in the range of $0.92{\sim}0.99$.

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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
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    • v.24 no.1
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    • pp.65-69
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    • 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.

Catalytic Effect of $MO_4^{2-_4}$ (M=Cr, Mo and W) on Hydrolyses of Carbon and Phosphorus Esters

  • An, Byeong Tae;Park, Hui Seon;Lee, Eun Ju;Eom, Ik Hwan
    • Bulletin of the Korean Chemical Society
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    • v.21 no.9
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    • pp.905-908
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    • 2000
  • Second-order rate constants have been measured spectrophotometrically for the hydrolysis of p-nitrophenyl ac-etate (PNPA) and p-nitrophenyl diphenylphosphinate (PNPDPP) with MO42- (M = Cr, Mo and W) in phos-phate buffer (pH = 8.00) at 35.0 $^{\circ}C.$ Thes e MO42- species exhibit large catalytic effect in the hydrolysis of PNPA and PNPDPP except WO42- in the reaction with PNPA. The catalytic effect of these MO42- species has been observed to be much more significantin the hydrolysis of PNPDPP than in the hydrolysis of PNPA. Since the smallest CrO42-would be most highly solvated by H2O molecules, CrO42- is expected to exhibit the least catalytic effect, if solvation effect is the most important factor. However, in fact, CrO42- shows the highest cat-alytic effect toward PNPA, indicating that solvation effect is not solely responsible for the catalytic effect. The most basic CrO42- shows the highest catalytic effect, while the least basic WO42- is least reactive toward PNPA, indicating that the basicity of MO4 2- might bean important factor. However, in the hydrolysis of PNPDPP, no correlation is observed between the basicity and catalytic effect, suggesting thatbasicity alone can not be re-sponsible for the catalytic effect shown by the MO42- species. Formation of a chelate is suggested to be respon-sible for the high catalytic effect of MO42- in the hydrolysis reaction of PNPA and PNPDPP. The formation of chelate is considered to be more suitable for the reaction with PNPDPP than with PNPA based on the larger catalytic effect observed in the reaction with PNPDPP than with PNPA.

Kinetics and Mechanism of Hydrolysis of Benzenesulfonylimido Phosgene (Benzenesulfonylimido Phosgene 의 加水分解 反鷹메카니즘과 反鷹速度論的 硏究)

  • Sung, Nack-Do;Han, Sun-Ho;Kwon, Ki-Sung;Kim, Tae-Rin
    • Journal of the Korean Chemical Society
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    • v.28 no.4
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    • pp.259-264
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    • 1984
  • The rate constants for the hydrolysis of benzenesulfonylimido phosgene at various pH were determined by ultraviolet spectrophotometry in 1 : 4 dioxane-water mixed solvents at 25$^{\circ}$C and a rate equation which can be applied over a wide pH range was obtained. Based on the Grunwald-Winstein equation, m = 0.4 was obtained. The thermodynamic activation parameters for the hydrolysis were ${\Delta}H^{\neq}$ = 15kcal mol$^{-1}$, ${\Delta}S^{\neq}$ = 21e.u. at pH 4.0 and $ {\Delta}H^{\neq}$ = 8kcal. mol$^{-1}$, ${\Delta}S^{\neq}$ = -39e.u. at pH 11.0, respectively. It was concluded that the hydrolysis of benzenesulfonylimido phosgene in 1 : 4 dioxane-water mixed solvents proceed via nucleophilic addition-elimination.

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Thermal and Mechanical Properties with Hydrolysis of PLLA/MMT Nanocomposite (PLLA/MMT 나노복합재료의 가수분해에 따른 열적, 기계적 물성)

  • Lee Jong Hun;Lee Yun Hui;Lee Doo Sung;Lee Youn-Kwan;Nam Jae-Do
    • Polymer(Korea)
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    • v.29 no.4
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    • pp.375-379
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    • 2005
  • The morphology and therma]/viscoelastic characteristics were investigated for PLLA/MMT nanocomposite manufactured by incorporating inorganic nanosized silicate nanoplatelets into biodeuadable poly(l-lactic acid) (PLLA). The XRD difiactogram and TEM image may be regarded as a formation of homogeneously dispersed nanocomposites. The melting energy(${\Delta}H_m$) was increased during hydrolysis process because of increase of crystallinity. As MMT played a role of reinforcing agent, the storage modulus was increase in case of PLLA/MMT nanocomposite, it was well coincided with our previous results. From SEM image, many tiny pinholes formed by spinodal decomposition were observed on the surface, and the shape of nanocomposite was maintained during hydrolysis process. In this study, it was shown that the control of biodegradation rate, thermal/mechnical property was possibile by incorporating MMT.

Optical Resolution of Racemic Ibuprofen by Candida Rugosa Lipase Catalyzed esterification (Candida Rugosa Lipase에 의한 Ibuprofen 에스테르화 반응과 광학분할)

  • 홍중기;김광제;소원욱;문상진;이용택
    • KSBB Journal
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    • v.17 no.6
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    • pp.543-548
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    • 2002
  • The enantioselective esterification of racemic ibuprofen catalyzed by a Candida rugosa lipase was studied according to reaction conditions such as a lipase concentration, reaction temperature, alcohol chain length and alcohol concentration. The S-(+)-ibuprofen alkyl esters prepared were converted to S-(+)-ibuprofen by hydrolysis with sulfuric acid as a catalyst. High conversions in the esterifications were obtained at 60$^{\circ}C$ and an equimolar ratio of octanol to ibuprofen. The initial reaction rate of the esterification decreased with increasing octanol concentration. Conversion and initial reaction rate increased with increasing alcohol chain length. Values of enantiomeric excess(ee) according to esterification reaction conditions did not change below 60$^{\circ}C$. On the other hand, values of conversion and ee for the chemical hydrolysis of S-(+)-ibuprofen alkyl esters were independent of alcohol alkyl chain length. Optical resolution of racemic ibuprofen was achieved by lipase catalyzed esterification and chemical hydrolysis. The separation method provided a high yield and enantioselectivity for the production of S-(+)-ibuprofen from racemic ibuprofen.

Synthesis and Characterization of Novel pH-Sensitive Hydrogels Containing Ibuprofen Pen dents for Colon-Specific Drug Delivery

  • Mahkam, Mehrdad;Poorgholy, Nahid;Vakhshouri, Laleh
    • Macromolecular Research
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    • v.17 no.9
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    • pp.709-713
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    • 2009
  • The aim of this study was to develop novel intestinal specific drug delivery systems with pH sensitive swelling and drug release properties. The carboxyl group of ibuprofen was converted to a vinyl ester group by reacting ibuprofen and vinyl acetate as an acylating agent in the presence of catalyst. The glucose-6-acrylate-1, 2, 3, 4-tetraacetate (GATA) monomer was prepared under mild conditions. Cubane-1, 4-dicarboxylic acid (CDA) linked to two 2-hydroxyethyl methacrylate (HEMA) group was used as the crosslinking agent (CA). Methacrylic-type polymeric prodrugs were synthesized by the free radical copolymerization of methacrylic acid, vinyl ester derivative of ibuprofen (VIP) and GATA in the presence of cubane cross linking agent. The structure of VIP was characterized and confirmed by FTIR, $^1H$ NMR and $^{13}C$ NMR spectroscopy. The composition of the cross-linked three-dimensional polymers was determined by FTIR spectroscopy. The hydrolysis of drug polymer conjugates was carried out in cel-lophane membrane dialysis bags, and the in vitro release profiles were established separately in enzyme-free simulated gastric and intestinal fluids (SGF, pH 1 and SIF, pH 7.4). The detection of a hydrolysis solution by UV spectroscopy at selected intervals showed that the drug can be released by hydrolysis of the ester bond between the drug and polymer backbone at a low rate. Drug release studies showed that increasing the MAA content in the copolymer enhances the rate of hydrolysis in SIP. These results suggest that these polymeric prodrugs can be useful for the release of ibuprofen in controlled release systems.

Pretreatment of Waste-activated Sludge for Enhancement of Methane Production (메탄발효 효율향상을 위한 하.폐수 슬러지의 전처리 기술)

  • NamKung, Kyu-Cheol;Jeon, Che-Ok
    • Microbiology and Biotechnology Letters
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    • v.38 no.4
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    • pp.362-372
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    • 2010
  • Although different disposal routes of waste-activated sludge are possible, anaerobic digestion plays an important role for its abilities to further transform organic matter into methane. The potential of using methane as energy source has long been widely recognised and the present paper extensively reviews the principles of anaerobic digestion, the process parameters and hydrolysis. Hydrolysis is recognised as rate-limiting step in the complex digestion process. To accelerate the digestion and enhance the production of biogas, various pre-treatments can be used to improve the rate-limiting hydrolysis. These treatments include mechanical, thermal, chemical and biological interventions to the feedstock. All pre-treatments result in a lysis or disintegration of sludge cells, thus releasing and solubilizing intracellular material into the water phase and transforming refractory organic material into biodegradable species. The reader will finally be guided to extensive discussion for anaerobic digestion processes.

Stability of pipethanate hydrochloride in aqueous solution

  • Kim, Chonng-Kook;Cha, Hyun-Sook
    • Archives of Pharmacal Research
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    • v.4 no.2
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    • pp.109-115
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    • 1981
  • In the present investigation, an attempt has been made to apply the methods of classical chemical kinetics to the hydrolytic reaction of pipethanate hydrochloride. By successively keeping all but one variable essentially constant, it has been possible to resolve the overall effect of the individual contributing factors. Since nearly all commercial pipethanate preparations are formulated with antacid, studies were made at several constant hydrogen ion concentration ranging pH 0.4 to 7.5. Rate measurement was also carried out in temperature ranging from $25^{\circ}C$ to $60^{\circ}C$. The hydrolysis of pipethanate is found to be of first order with respect to pipeethanate concentration over an experimental range of hydrogen ion concentration (pH 0407.5). The apparent activation energy(Ea) at pH 7.5 is 18.30 Kcal/mole and the frequency factor is $1.1408 {\times}10^{9}sec^{-1}$. The rate of the hydrolysis has a minimum at pH 2.5-3.5. In this region the half-life of pipethanate was about15.3 days at $60^{\circ}C$. The catalytic effect of water was found to be $K_{H_2O}$ = $3.16{\times}10^{-5}min^{-1}$ at $60^{\circ}C$. The catalytic constants of the hydroxyl ions and hydrogen ions at $60^{\circ}C$ were also found to be $K_{OH}$ = $4.5519{\times}10^{-5}min^{-1}$ and $K_{H}+$ = $1.1568{\times}10^{-2}min^{-1}$, respectively. This reaction appears to be primarily base catalyzed hydrolysis and pipethanate is relatively reluctant toward acid catalyzed hydrolysis. A positive primary salt effect was noted in the solution of phpethanate at pH 7.5 and at $60^{\circ}C$.

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