• Title/Summary/Keyword: Hydrolysis Reaction

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Theoretical Studies on the Competitive Sn2 Reactions of O-Imidomethyl Derivatives of Phenols with OH-

  • Kim, Chang Gon;Jeong, Dong Su;Kim, Chan Gyeong;Lee, Bon Su;Jeong, Yeong Jin;Lee, Byeong Jun;Lee, Ik Jun
    • Bulletin of the Korean Chemical Society
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    • v.22 no.1
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    • pp.25-29
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    • 2001
  • Nucleophilic substitution reactions of O-imidomethyl derivatives of phenols with OH- were studied theoretically using the semiempirical AM1 and Solvation Model 2.1 (SM2.1) methods in the gas phase and aqueous solution, respectively. In the gas phase, the two reaction paths, in which the imide (1a) or phenol (1b) is functioning as a leaving group, can occur competitively. In contrast, in aqueous solution, path (1b) becomes more favorable than (1a) because the transition states (TS) of path (1b) are more stabilized by solvent. Differences in solvation energies are caused by the structural differences of TS, i.e., the TS via path (1b) is more dissociative than that via path (1a). Therefore we conclude that the solvent effects play an important role in the hydrolysis of O-imidomethyl derivatives of phenols. However, reactivity is dependent on the acidities of both the imide and the phenol fragments since the ρz values vary progressively from 4.2 (Z' = I) to 2.5 (Z' = IV) as the acidities of imide increase. These are in good agreement with the experimental results.

Highly Porous Pillared Clay with Multistacked $SiO_2/TiO_2$ Nanosols

  • 조진호;박주형;윤주병
    • Bulletin of the Korean Chemical Society
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    • v.19 no.11
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    • pp.1185-1188
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    • 1998
  • Layered nanocomposite, SiO2/TiO2 sol pillared clay, has been prepared by the ion exchange reaction of Na' ion in montmorillonite with positively charged mixed SiO2/TiO2 sol. The nanosized sol particles were synthesized by mixing SiO2 sol solution with TiO2 one, which is obtained by acidic hydrolysis of TEOS and TiCl4, respectively. From powder XRD, the basal spacing (d001) of the sample calcined at 400 ℃ was found to be ca. 60 Å, due to the multistacking of nanosized SiO2 and TiO2 sol particles, which was confirmed by the pore size analysis from 129Xe NMR and micropore analysis calculated from nitrogen adsorption. The BET specific surface area shows the value of 684 m2g-1 (Langmuir 1115 m2g-1), which is the highest among various pillared clays ever reported previously, and the total porosity is found to be 0.51 mlg-1, and the pores are mainly composed of micropore with a size of ca. 11.8 Å. This result agrees with the adsorption capacity obtained from water adsorption. According to diffuse reflectance ultraviolet-visible spectroscopy, it is found that the TiO2 particles stabilized in the interlayer space of montmorillonite are quantum-sized of ca. 20 Å.

Synthesis of Monodispersed and Spherical $SiO_2-coated Fe_2O_3$ Nanoparticle

  • Han, Yang Su;Yun, Seon Mi;Kim, Dong Guk
    • Bulletin of the Korean Chemical Society
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    • v.21 no.12
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    • pp.1193-1198
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    • 2000
  • The preparation of nanocrystalline hematite, ${\alpha}-Fe_2O_3$, paricles and their surface coating with silica layers are described. The hematite particles with the size of 30~60 nm are firstly prepared by thermal decomposition of trinuclear acetate-hydroxo iron (III) nitrate complex, $[Fe_3$(OCOCH_3)_7$OH${\cdot}$2H_2O]NO_3$, at $400^{\circ}C$. Subsequently the hematite surfaces are coated with siliva layers by a controlled hydrolysis and condensation reaction of TEOS with varying the TEOS concentration and pH. Monodispersed and spherical $SiO_2-coatedFe_2O_3$ particles with the average particle diameter of ~90 nm and extremely narrow size distribution can be obtained at the pH of 11 and the TEOS concentration of 0.68M, which are found to be the optimum conditions in the present study in achieving the homogeneous deposition of silica layers on hematite surfaces. Diffuse reflectance UV-Vis spectra reveal that the characteristic optical reflectance of ${\alpha}-Fe_2O_3$ particles is preserved almost constant even after coating the surfaces, suggesting that the $SiO_2$ layers can be regarded as protecting layers without degrading the optical properties of hematite particles.

Synthesis of Acetins from Glycerol using Lipase from Wheat Extract

  • Pradima, J;Rajeswari, M Kulkarni;Archna, Narula;Sravanthi, V;Rakshith, R;Nawal, Rabia Nizar
    • Korean Chemical Engineering Research
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    • v.57 no.4
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    • pp.501-506
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    • 2019
  • New technology-driven biocatalysts are revolutionizing the biochemical industries. With maximum utilization of renewable feedstock, biocatalysts have been the basis for a major breakthrough. Lipases are the most widely established catalysts used for hydrolysis, esterification and transesterification reactions. In this research, a biochemical process that combines extraction of lipase enzyme from germinated wheat seeds and its application to valorize glycerol to acetins by esterification is presented. Acetins are among highly rated, value-added products derived from glycerol. The favorable conditions for the enzymatic conversion of glycerol were observed as glycerol to acetic acid molar ratio (1:5), reaction temperature ($40^{\circ}C$) and the amount of enzyme (20% v/v). 65.93% of glycerol conversion was achieved for duration of 15 h with the use of tert-butanol solvent. This method proposes to explore the viability of a biological route to convert glycerol derived from biodiesel industry to acetins with further streamlining.

Oxygen Control in CdS Thin Film by UV Illumination in Chemical Bath Deposition (용액성장법에서 자외선 조사를 이용한 CdS의 산소함량 제어)

  • Baek, Hyeon-ji;Oh, Ji-A;Seo, Young-Eun;Shin, Hye-Jin;Cho, Sung-Wook;Jeon, Chan-Wook
    • Current Photovoltaic Research
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    • v.7 no.2
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    • pp.33-37
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    • 2019
  • In this paper, we compared the performance of $Cu(In,Ga)(S,Se)_2$ (CIGSSe) thin film solar cell with CdS buffer layer deposited by irradiating 365 nm UV light with 8 W power in Chemcial Bath Deposition (CBD) process. The effects of UV light irradiation on the thin film deposition mechanism during CBD-CdS thin film deposition were investigated through chemical and electro-optical studies. If the UV light is irradiated during the solution process, the hydrolysis of Thiourea is promoted even during the same time, thereby inhibiting the formation of the intermediate products developed in the reaction pathway and decreasing the pH of the solution. As a result, it is suggested that the efficiency of the CdS/CIGSSe solar cell is increased because the ratio of the S element in the CdS thin film increases and the proportion of the O element decreases. This is a very simple and effective approach to control the S/O ratio of the CdS thin film by the CBD process without artificially controlling the process temperature, solution pH or concentration.

Production of Cyanocarboxylic Acid by Acidovorax facilis 72W Nitrilase Displayed on the Spore Surface of Bacillus subtilis

  • Zhong, Xia;Yang, Shaomin;Su, Xinying;Shen, Xiaoxia;Zhao, Wen;Chan, Zhi
    • Journal of Microbiology and Biotechnology
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    • v.29 no.5
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    • pp.749-757
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    • 2019
  • Nitrilase is a valuable hydrolase that catalyzes nitriles into carboxylic acid and ammonia. Its applications, however, are severely restricted by the harsh conditions of industrial reaction processes. To solve this problem, a nitrilase from Acidovorax facilis 72W was inserted into an Escherichia coli-Bacillus subtilis shuttle vector for spore surface display. Western blot, enzyme activity measurements and flow cytometric analysis results all indicated a successful spore surface display of the CotB-nit fusion protein. In addition, the optimal catalytic pH value and temperature of the displayed nitrilase were determined to be 7.0 and $50^{\circ}C$, respectively. Moreover, results of reusability tests revealed that 64% of the initial activity of the displayed nitrilase was still retained at the $10^{th}$ cycle. Furthermore, hydrolysis efficiency of upscale production of cyanocarboxylic acid was significantly higher in the displayed nitrilase-treated group than in the free group expressed by E. coli (pET-28a-nit). Generally, the display of A. facilis 72W nitrilase on the spore surface of Bacillus subtilis may be a useful method for immobilization of enzyme and consequent biocatalytic stabilization.

Gallic acid caused cultured mice TM4 Sertoli cells apoptosis and necrosis

  • Li, Wanhong;Yue, Xiangpeng;Li, Fadi
    • Asian-Australasian Journal of Animal Sciences
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    • v.32 no.5
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    • pp.629-636
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    • 2019
  • Objective: The study was designed to determine the cytotoxic effect of gallic acid (GA), obtained by the hydrolysis of tannins, on mice TM4 Sertoli cells apoptosis. Methods: In the present study, non-tumorigenic mice TM4 Sertoli cells were treated with different concentrations of GA for 24 h. After treatment, cell viability was evaluated using WST-1, mitochondrial dysfunction, cells apoptosis and necrosis was detected using JC-1, Hoechst 33342 and propidium iodide staining. The expression levels of Cyclin B1, proliferating cell nuclear antigen (PCNA), Bcl-2-associated X protein (BAX), and Caspase-3 were also detected by quantitative real-time polymerase chain reaction and Western-blotting. Results: The results showed that 20 to $400{\mu}M$ GA inhibited viability of TM4 Sertoli cells in a dose-dependent manner. Treatment with $400{\mu}M$ GA significantly inhibited PCNA and Cyclin B1 expression, however up-regulated BAX and Caspase-3 expression, caused mitochondrial membrane depolarization, activated Caspase-3, and induced DNA damage, thus, markedly increased the numbers of dead cells. Conclusion: Our findings showed that GA could disrupt mitochondrial function and caused TM4 cells to undergo apoptosis and necrosis.

Improved immune-enhancing activity of egg white protein ovotransferrin after enzyme hydrolysis

  • Lee, Jae Hoon;Kim, Hyeon Joong;Ahn, Dong Uk;Paik, Hyun-Dong
    • Journal of Animal Science and Technology
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    • v.63 no.5
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    • pp.1159-1168
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    • 2021
  • Ovotransferrin (OTF), an egg protein known as transferrin family protein, possess strong antimicrobial and antioxidant activity. This is because OTF has two iron binding sites, so it has a strong metal chelating ability. The present study aimed to evaluate the improved immune-enhancing activities of OTF hydrolysates produced using bromelain, pancreatin, and papain. The effects of OTF hydrolysates on the production and secretion of pro-inflammatory mediators in RAW 264.7 macrophages were confirmed. The production of nitric oxide (NO) was evaluated using Griess reagent and the expression of inducible nitric oxide synthase (iNOS) were evaluated using quantitative real-time polymerase chain reaction (PCR). And the production of pro-inflammatory cytokines (tumor necrosis factor [TNF]-α and interleukin [IL]-6) and the phagocytic activity of macrophages were evaluated using an ELISA assay and neutral red uptake assay, respectively. All OTF hydrolysates enhanced NO production by increasing iNOS mRNA expression. Treating RAW 264.7 macrophages with OTF hydrolysates increased the production of pro-inflammatory cytokines and the phagocytic activity. The production of NO and pro-inflammatory cytokines induced by OTF hydrolysates was inhibited by the addition of specific mitogen-activated protein kinase (MAPK) inhibitors. In conclusion, results indicated that all OTF hydrolysates activated RAW 264.7 macrophages by activating MAPK signaling pathway.

A Kinetic Study of the Fe(Ⅲ)-Catalyzed Aquation of Bis(malonato)Diaquochromate(Ⅲ) Ion

  • Shim, Jeong-Ae;Moon, Jung-Dae;Park, Heung-Jae;Choi, Sung-Nak
    • Bulletin of the Korean Chemical Society
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    • v.11 no.4
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    • pp.318-323
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    • 1990
  • The bis(malonato)diaquochromate(III) ion, $Cr(C_3H_2O_4)_2^-$ in acidic solution hydrolyzes to give $Cr(C_3H_2O_4)^{+}.$ This reaction is catalyzed by ferric ion and the rate law for this cation catalyzed-aquation in a $HClO_4/NaClO_4$ medium, $I = 1.00 M, is-d[Cr(C_3H_2O_4)_2^-]/dt = ({\kappa}_1[Fe^{3+}] + {\kappa}_2[H^+])[Cr(C_3H_2O_4)_2^-]$ where ${\kappa}_1(25^{\circ}C) = 4.72×10^{-5} M^{-1}sec^{-1} ({\Delta}H^{\neq} = 22.5 Kcal/mol, {\Delta}S^{\neq} = - 2.58 eu) and {\kappa}_2(25^{\circ}C) = 4.75{\times}10^{-5} M^{-1}sec^{-1} ({\Delta}H^{\neq} = 21.2 Kcal/mol, {\Delta}S^{\neq} = - 7.13 eu).$ Rapid preequilibrium association of basic Cr-bound oxygen with $Fe^{3+},$ followed by rate-determining ring opening, is proposed to account for the ${\kappa}_1,$ hydrolysis pathway.

Electrochemical and surface investigations of copper corrosion in dilute oxychloride solution

  • Gha-Young Kim ;Junhyuk Jang;Jeong-Hyun Woo;Seok Yoon;Jin-Seop Kim
    • Nuclear Engineering and Technology
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    • v.55 no.8
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    • pp.2742-2746
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    • 2023
  • The corrosion behavior of copper immersed in dilute oxychloride solution (100 mM) was studied through surface investigation and in-situ monitoring of open-circuit potential. The copper corrosion was initiated with copper dissolution into a form of CuCl-2, resulting in mass decrease within the first 40 h of immersion. This was followed by a hydrolysis reaction initiated by the CuCl-2 at the copper surface, after which oxide products were formed and deposited on the surface, resulting in a mass increase. The formation of nucleation sites for copper oxide and its lateral extension during the corrosion process were examined using focused ion beam (FIB)-scanning electron microscopy (SEM). The presence of metastable compounds such as atacamite (CuCl2·3Cu(OH)2) on the corroded copper surface was revealed by X-ray photoelectron spectra (XPS) and transmission electron microscopy (TEM)-energy dispersive spectrometry (EDS) analysis.