• Title/Summary/Keyword: base substitution

Search Result 133, Processing Time 0.024 seconds

Correlation of the Rates of Solvolysis of Methyl Fluoroformate Using the Extended Grunwald-Winstein Equation

  • Seong, Mi-Hye;Choi, Song-Hee;Lee, Yong-Woo;Kyong, Jin-Burm;Kim, Dong-Kook;Kevill, Dennis N.
    • Bulletin of the Korean Chemical Society
    • /
    • v.30 no.10
    • /
    • pp.2408-2412
    • /
    • 2009
  • The specific rates of solvolysis of methyl fluoroformate have been measured at $40.0\;{^{\circ}C}$ in several hydroxylic solvents. Analysis with the extended Grunwald-Winstein equation leads to sensitivities toward changes in solvent nucleophilicity (l) of $1.33\;{\pm}\;0.10$ and toward changes in solvent ionizing power (m) $0.73\;{\pm}\;0.06$. For methanolysis, a solvent deuterium isotope effect of 3.98 is compatible with the incorporation of general-base catalysis into the substitution process. For four representative solvents, studies were made at several temperatures and activation parameters determined. These observations are also compared with those previously reported for alkyl halogenoformate esters and mechanistic conclusions are drawn.

Correlation of the Rates of Solvolysis of Isopropyl Fluoroformate Using the Extended Grunwald-Winstein Equation

  • Lee, So-Hee;Rhu, Chan-Joo;Kyong, Jin-Burm;Kim, Dong-Kook;Dennis N. Kevill
    • Bulletin of the Korean Chemical Society
    • /
    • v.28 no.4
    • /
    • pp.657-661
    • /
    • 2007
  • The specific rates of solvolysis of isopropyl fluoroformate are well correlated using the extended Grunwald-Winstein equation, with a sensitivity (l ) to changes in solvent nucleophilicity (NT) and a sensitivity (m) to changes in solvent ionizing power (YCl). The sensitivities (l = 1.59 ± 0.16 and m = 0.80 ± 0.06) toward changes in solvent nucleophilicity and solvent ionizing power, and the kF/kCl values are very similar to those for solvolyses of n-octyl fluoroformate, suggesting that the addition step of an addition-elimination mechanism is rate-determining. For methanolysis, a solvent deuterium isotope effect of 2.53 is compatible with the incorporation of general-base catalysis into the substitution process. The large negative values for the entropies of activation are consistent with the bimolecular nature of the proposed rate-determining step. These observations are also compared with those previously reported for the corresponding chloroformate and fluoroformate esters.

Prediction of Critical Heat Flux in Fuel Assemblies Using a CHF Table Method

  • Chun, Tae-Hyun;Hwang, Dae-Hyun;Bang, Je-Geon;Baek, Won-Pil;Chang, Soon-Heung
    • Proceedings of the Korean Nuclear Society Conference
    • /
    • 1997.10a
    • /
    • pp.534-539
    • /
    • 1997
  • A CHF table method has been assessed in this study for rod bundle CHF predictions. At the conceptual design stage for a new reactor, a general critical heat flux (CHF) prediction method with a wide applicable range and reasonable accuracy is essential to the thermal-hydraulic design and safety analysis. In many aspects, a CHF table method (i.e., the use of a round tube CHF table with appropriate bundle correction factors) can be a promising way to fulfill this need. So the assessment of the CHF table method has been performed with the bundle CHF data relevant to pressurized water reactors (PWRs). For comparison purposes, W-3R and EPRI-1 were also applied to the same data base. Data analysis has been conducted with the subchannel code COBRA-IV-I. The CHF table method shows the best predictions based on the direct substitution method. Improvements of the bundle correction factors, especially for the spacer grid and cold wall effects, are desirable for better predictions. Though the present assessment is somewhat limited in both fuel geometries and operating conditions, the CHF table method clearly shows potential to be a general CHF predictor.

  • PDF

Synthesis and E-Beam-Mediated Gas Phase Fragmentation of Thiol-Containing Furoxans for Nanopatterned Alkyne Formation on Gold Surface

  • Koo, Hyun-Seo;Park, Kyung-Moon;Hwang, Kwang-Jin
    • Bulletin of the Korean Chemical Society
    • /
    • v.31 no.12
    • /
    • pp.3583-3587
    • /
    • 2010
  • Furoxanthiols PFT and BPFT possessing thiomethyl or thiobenzyl groups in the furoxan ring were designed and synthesized as potential light-sensitive alkyne precursors on a gold surface. The synthesis of thiofuroxans PFT and BPFT was performed from the corresponding halofuroxans 1b and 2c, respectively, by the substitution with potassium thioacetate in ethyl acetate/ethanol or DMF, followed by basic hydrolysis as the key reactions. Electron-beammediated fragmentation of furoxans 1c and 2d in a mass spectrometer afforded the corresponding aryl alkyne fragments, with the evolution of NO in high preference. In the cases of thiofuroxans PFT and BPFT, carbon-sulfur bond cleavage was observed as a representative fragmentation, producing M-SH and M-SAc peaks, which competed with the release of NO. In the fragmentation of mono-aryl furoxan 1c, the release of molecule of NO was predominately observed to produce an M-NO fragment as a base peak by the formation of trimembered thiiranium or azirine intermediate.

Inhibitory Effect of Vitamin C on Mutagenicity of 6-Sulfooxymethylbenzo[a]pyrene

  • Cho, Young-Sik;Hong, Sun-Taek;Chung, An-Sik
    • Toxicological Research
    • /
    • v.12 no.1
    • /
    • pp.21-27
    • /
    • 1996
  • Vitamin C has been well known to be a potential chemopreventive agent for several toxic compounds. It reduced the mutation frequencies of 6-sulfooxymethylbenzo[a]pyrene (SMBP) and 6hydroxymethylbenzo[a]pyrene (HMBP) in Salmonella typhimurium TA98 and TA100, indicating that corbic acid affects both frameshift and base-pair substitution mtltations. A similar type of dose-response relationship was shown in the V79 cells, although the inhibitory effect was less dramatic compared with that in S. typhimurium. However, SMBP or HMBP binding to calf thymus DNA was not affected by the presence of vitamin C, suggesting that SMBP seems to be much more reactive to calf thymus DNA than vitamin C. This was supported by migration pattern and fluorescence intensity of SMBP-modified plasmid on the gel. These restilts were not correlated with mutation tests in bacterial and mammalian cell systems. It has been already reported that vitamin C inactivates SMBP through the formation of covalently bound addact. It was found from HPLC analysis that the reaction between vitamin C and SMBP was accomplished within just 5 min and then produced the several products. These findings indicate that the beneficiary of vitamin C is not merely derived from the covalent adducts. On the other hand, the addition of DNA to incubation mixture reduced the amounts of vitamin C adducts while the magnitude of HMBP peak increased, suggesting that DNA accelerates the SMBP hydrolysis to intercept the interaction between SMBP and vitamin C or forms rapidly complex with SMBP.

  • PDF

Genetic Toxicity Test of 1,2-Dibromoethane by Ames, Micronucleus, Comet Assays and Microarray Analysis

  • Kim, Ki-Y.;Kim, Ji-H.;Kwon, Kyoung-J.;Go, Seo-Y.;Min, Kyung-N.;Lee, Woo-S.;Park, Sue-N.;Shee, Yhun-Y.
    • Biomolecules & Therapeutics
    • /
    • v.14 no.4
    • /
    • pp.246-252
    • /
    • 2006
  • 1,2-Dibromoethane(DBE) has been widely used as a soil fumigant, an additive to leaded gasoline and an industrial solvent. In this study, we have carried out in vitro genetic toxicity test of 1,2-dibromoethane and microarray analysis of differentially expressed genes in response to 1,2-dibromoethane. 1,2-Dibromoethane showed mutations in base substitution strain TA1535 both with and without exogenous metabolic activation. 1,2-Dibromoethane showed mutations in frame shift TA98 both with and without exogenous metabolic activation. 1,2-Dibromoethane showed DNA damage based on single cell gel/comet assay in L5178Y cells both with and without exogenous metabolic activation. 1,2-Dibromoethane increased micronuclei in CRO cells both with and without exogenous metabolic activation. Microarray analysis of gene expression profiles in L5178Y cells in response to 1,2-dibromoethane selected differentially expressed 241 genes that would be candidate biomarkers of genetic toxic action of 1,2-dibromoethane.

Synthesis and Characterization of Poly(arylene ether)s Containing Benzoxazole Pendants from Novel Aromatic Difluoride Monomer

  • Kim, Ji Hyeong;Bang, Sang U;Kim, Yeong Jun
    • Bulletin of the Korean Chemical Society
    • /
    • v.21 no.9
    • /
    • pp.896-900
    • /
    • 2000
  • A study was done on the synthesis of new poly(arylene ether)s and poly(arylenesulfide) with rigid benzoxazole pendants using nucleophilic aromatic substitution reaction. As a new aromatic monomer, 1,4-bis(2-benzox-azolyl)-2,5-difluorobenzene [I] w as synthesized in three steps starting from 1,4-dibromo-2,5-difluorobenzene. A model reaction of difluoro monomer [I] with two equivalents of m-cresol or thiophenol in a typical ether con-densation reaction conditions gave very high yields ( > 93%) of the desired disubstituted product, suggesting the feasibility of polymer formation in these reaction system. Monomer[I] was polymerized with bisphenols and bisbenzenethiol in NMP using K2CO3 as base. The molecular weight of the resulting polymers, however,seemed relatively low according to their solution viscosity values ( ηinh = 0.15-0.29 dL/g). The poly(arylene ether)s were soluble in several common organic solvents including chloroform, pyridine and N,N'-dimethylfor-mamide. The poly(arylene sulfide) was, however, ony soluble in strong acids like sulfuric acid and trifluoro-acetic acid. The glass transition temperatures were found to be 175-215 $^{\circ}C.$ These polymers were stable up to 380-420 $^{\circ}C$ in both nitrogen and air, as determined by the temperature that a significant weight loss began to appear on TGA.

Application of zeolite/kaolin combination for replacement of partial cement clinker to manufacture environmentally sustainable cement in Oman

  • Abdul-Wahab, Sabah A.;Hassan, Edris M.;Al-Jabri, Khalifa S.;Yetilmezsoy, Kaan
    • Environmental Engineering Research
    • /
    • v.24 no.2
    • /
    • pp.246-253
    • /
    • 2019
  • This study was conducted to explore the optimum proportion of zeolite and zeolite-kaolin as additives to cement clinker and gypsum samples, while maintaining the strength properties of produced environmentally sustainable cements. According to the British standard method, zeolite was added to cement clinker in proportions of 5-12% and 10-12% by weight, respectively, in the preparation of samples of zeolite-containing cement and zeolite-kaolin-based cement. Kaolin was used as a second additive as 10-20% of the total weight. The compressive strength tests were performed on base cement samples according to a standard procedure given in ASTM C109 Compressive Strength of Hydraulic Cement. These values were compared with those of the reference sample and the Omani allowable limits. The results indicated that the best compressive strength values were obtained with 88% cement clinker, 5% gypsum, and 7% zeolite for the zeolite-containing cement. Quantities of 70% cement clinker, 5% gypsum, 10% zeolite, and 15% kaolin gave the best results for zeolite-kaolin-based cement, resulting in a substitution of than 25% cement clinker. The study concluded that the partial cement clinker replacement using zeolite/kaolin combination may have a great influence on the reduction of $CO_2$ emission and energy saving in cement manufacturing.

A Study on the Improvement Policy of the Localization Parts of the Defense Sector (국방분야 부품국산화개발 정책개선 방안)

  • Jung, Suk-Yun;Eom, Jung-Ho
    • Journal of National Security and Military Science
    • /
    • s.15
    • /
    • pp.117-151
    • /
    • 2018
  • The development of local defense parts has played a role a pure function such as maintenance of stable procurement source of military goods, provision of timely supply, establishment of self-defense base, creation of import substitution effect considering the whole life-cycle cost, reduction of foreign currency and protection of domestic defense industry. However, as the development success rate is deteriorating, it is time to analyze the related policies and improve the system. In order to improve the success rate of development of parts for the defense sector, it is necessary to unify the separated policies by the development-related departments and strengthen the policy support for the development companies to actively participate in the development. In addition, it is necessary to improve the paradigm for the selection of development items and change the authority of selecting development items and to delegate authority to create synergies. Parts localization development policy improvement is military support side it will contribute to strengthening defense power management by organically combining with technological development aspect and economical aspect. Development items will be linked to defense exports, which will have a remarkable effect on sales growth and job creation effects. The development of local defense parts is spreading.

  • PDF

Characterization of the Acetolactate synthase (ALS) gene and Molecular Assay of Mutations Associated with Sulfonylurea Herbicide Resistance of Monochoria vaginalis (물달개비의 Acetolactate synthase (ALS) 유전자의 특성과 Sulfonylurea 제초제 저항성과 관련 돌연변의 분자생물학적 접근)

  • Park, Tae-Seon;Park, Hong-Kyu;Ku, Bon-Il;Kim, Young-Doo;Ko, Jae-Kwon;Lee, In-Yong;Park, Jae-Eup
    • The Korean Journal of Pesticide Science
    • /
    • v.13 no.4
    • /
    • pp.290-297
    • /
    • 2009
  • This research aims to contribute the characterization of acetolactate synthase (Ec 4.1.3.18; ALS) and the resistance mechanism by sequence analysis of ALS gene of the sulfonylurea-resistant and -susceptible Monochoria vaginalis. The ALS gene was obtained from susceptible (S) and resistant (R) M. vaginalis to sulfonylurea herbicides (SUs). The 815 bp the fragment and the genomic DNA sequence coding for acetolactate synthase (ALS) of S and R biotypes of M. vaginalis were cloned and sequenced. Nineteen clones were divided greatly into 4 groups as result of sequencing. The first group was not difference to S type, the second group was amino acid of P197S which found point mutations causing substitution of serine for proline at amino acid 197, the third group was observed greatly other part of 6 places than group 1, and the fourth group appeared the intergrade of group 1 and 3. Therefore, it could be assumed what ALS gene of various types can be one plant. The peptide of the 13 amino acid Domain A region for ALS genes from R biotype of M. vaginalis differed from that of the S biotype by one base substitution at proline codon of Domain A. It could also be confirmed that point mutation of serine for proline at amino acid 197.