• Title/Summary/Keyword: Secondary alcohols

Search Result 49, Processing Time 0.033 seconds

Synthesis of Alcohol-oxidase in Pichia pastoris on Various Carbon Sources (여러가지 탄소원에 의한 Pichia pastoris의 Alcohol-oxidase 생성)

  • Lee, Myung-Suk;Hur, Sung-Ho
    • Journal of the Korean Society of Food Science and Nutrition
    • /
    • v.18 no.4
    • /
    • pp.435-443
    • /
    • 1989
  • The regulation of the synthesis of alcohol-oxidase(E. C. 1. 1. 3. 13) was investigated in the methanol-utilizing yeasts during growth on different carbon sources. For this experiment, Pichia pastoris CBS 2612 and Pichia pastoris CBM 10 were cultured in mineral salt medium by changing its carbon sources. The production of alcohol-oxidase was varied by the carbon sources. For example, alcohol-oxidase was undetectable in all strains submitted to the test in the medium with glucose, but its production was rapidely increased when the carbon source was changed from glucose to methanol after 48hrs of incubation. Moreover, this enzyme was not synthesized during growth on the primary aliphatic alcohols alone(ethanol, propanol, butanol or pentanol) or on the mixed substrates(0.5% methanol+0.5% primary aliphatic alcohols). When cells were grown on the various carbon sources(glucose, xylose, lactose, glycerol, galactose, saccharose, sorbose, lactic acid or acetic acid), The alcohol-oxidase activity was detected a very little amounts. These carbon sources together with methnol yieled far better synthesis of alcohol-oxidase than in case of carbon sources alone. Especially, the alcohol-oxidase activity of the cells grown on sorbose, lactose or lactic acid together with methanol was far better or similar than that of cells grown on methanol alone. The apparent Km values for the methanol of Pichia pastoris CBS 2612 and Pichia pastoris CBM 10 enzymes were 1.92 and 210 mM, respectively. It is also active towards alcohols of shorter alkyl-chain length than $C_7$, insaturated alcohols(allylalcohol, crotyl-alcohol) and secondary alcohols (iso-amylacohol, iso-butylalcohol). The affinity of alcohol-oxidase for this alcohols decreased with the increasing length of the alkyl-chain.

  • PDF

A Selectivity Character for the Phase Transfer Reactions of Alcohols by Tetra-n-Butyl Ammonium Chloride (Tetra-n-Butyl Ammonium Chloride에 의한 알코올류의 상전이 반응에 대한 선택 특이성)

  • Jee, Jong-Gi;Cboi, Won-Bok;Lee, Kwang-Pill
    • Analytical Science and Technology
    • /
    • v.8 no.1
    • /
    • pp.33-40
    • /
    • 1995
  • Only trace amounts of hydroxide ion can be extracted from aqueous phase into organic phase by Tetra-n-Butyl Ammonium Chloride(TBAC). Addition of small amounts of primary alcohols, particularly certain dials, dramatically changes the behavior of Phase Transfer Catalysis systems, and surprising amounts of base can be found in the organic phase. Quantitative measurements were carried out for the extraction amounts of primary alkoxides, secondary alkoxides, and diol anions into organic phase. On the other hand, the selectivity constants for extraction of primary alcohols and benzylalcohol could be separated to the equilibrium constants of the ion pairs such as $Q^+RO^-$ and $Q^+Cl^-$ in the aqueous and organic phases and this distribution coefficients between phases on anions respectively. In a word, the colligated property for the selectivity of $Q^+RO^-$ in which $Q^+$ is quaternary cation and $RO^-$ alkoxide ion could be discussed in more detail by using of the corresponding free energies to the various constants mentioned.

  • PDF

Reaction of Lithium n-Butylborohydride with Selected Organic Compounds Containing Representative Functional Groups

  • Chong-Suh Pyun;Jong-Chan Son;Nung-Min Yoon
    • Bulletin of the Korean Chemical Society
    • /
    • v.4 no.1
    • /
    • pp.3-9
    • /
    • 1983
  • Lithium n-butylborohydride was prepared from borane-dimethylsulfide (BMS) and n-butyllithium, and the approximate rates and stoichiometrics of its reactions with selected organic compounds containing representative functional groups were studied in THF at room temperature. Phenol and benzenetiol liberated hydrogen quickly and quantitatively, and the reactions of primary alcohols, 2,6-di-ter-butylphenol and 1-hexanethiol liberated hydrogen quantitatively within 3 hrs, whereas the reactions of secondary and tertiary alcohols were very slow. Aldehydes and ketones were reduced rapidly and quantitatively to the corresponding alcohols. Cinnamaldehyde utilized 1 equiv. of hydride rapidly, suggesting the reduction to cinnamyl alcohol. Carboxylic acids evolved 1 equiv. of hydrogen rapidly and further reduction was not observed. Anhydrides utilized 2 equiv. of hydride rapidly but further hydride uptake was very slow, showing a half reduction. Acid chlorides were reduced to the alcohol stage very rapidly. All the esters examined were reduced to the corresponding alcohol rapidly. Lactones were also reduced rapidly. Expoxides took up 1 equiv. of hydride at a moderate rate to be reduced to the corresponding alcohols. Nitriles and primary amides were inert to this hydride system, whereas tertiary amide underwent slow reduction. Nitroethane and nitrobenzene were reduced slowly, however azobenzene and azoxybenzene were quite inert. Cyclohexanone oxime evolved 1 equiv. of hydrogen rapidly, but no further reduction was observed. Phenyl isocyanate and pyridine N-oxide were proceeded slowly, showing 1.74 and 1.53 hydride uptake, respectively in 24 hours. Diphenyl disulfide was reduced rapidly, whereas di-n-butyl disulfide, sulfone and sulfonic acids were inert or sluggish. n-Hexyl iodide and benzyl bromide reacted rapidly, but n-octyl bromide, n-octyl chloride, and benzyl chloride reacted very slowly.

Kinetic Study on the Oxidation Reaction of Alcohols by Cr(VI)-Quinoline Compound (크롬(VI)-퀴놀린 화합물에 의한 알코올류의 산화반응에 대한 반응속도론적 연구)

  • Park, Young-Cho;Kim, Soo-Jong
    • Journal of Convergence for Information Technology
    • /
    • v.11 no.9
    • /
    • pp.109-114
    • /
    • 2021
  • Cr(VI)-quinoline compound[(C9H7NH)2Cr2O7] was synthesized by the reaction between of quinoline and chromium(VI) trioxide, and structure was FT-IR, elemental analysis. The oxidation ability of benzyl alcohol greatly depends upon the dielectric constant of the used organic solvent, where carbon tetrachloride was worst and N,N'-dimethylformamide was best solvent. Noticeably, in N,N'-dimethylformamide solvent, Cr(VI)-quinoline compound oxidized substituted benzyl alcohols. The Hammett reaction constant(ρ)=-0.69(303K). As a resuit, Cr(VI)-quinoline compound was found as efficicent oxidizing agent that converted benzyl alcohol, allyl alcohol, primary alcohol and secondary alcohols to the corresponding aldehydes or ketones. Cr(VI)-quinoline compound was selective oxidizing agent of benzyl alcohol, allyl alcohol and primary alcohol in the presence of secondary alcohol ones.

Effect of Ether-Typed Alcohols on Pore Formation in Preparing an Asymmetrically Porous Polysulfone Membrane (다공성 폴리술폰 비대칭막 제조시 에테르형 알코올의 공경형성에 미치는 영향)

  • Choi, Yong-Jin;Kang, Byung-Chul
    • Membrane Journal
    • /
    • v.20 no.2
    • /
    • pp.135-141
    • /
    • 2010
  • Various asymmetric Polysulfone membranes were prepared for a MBR process. Ether-typed alcohols (co-solvent) were added into a dope solution in order to control the pore size of membrane, whose effect on water permeability were investigated. Pore size of the prepared membranes were more affected by molecular-structure of co-solvent than by boiling point of theirs. With the increasing order of methoxy ($CH_3$-O-) < secondary propanol ($-CH_2$-CH(OH)$-CH_3$) < ethoxy ($CH_3-CH_2$-O-), water permeability of the prepared membrane increased. The phenomenon might attribute to the difference of molecularly steric hinderance of co-solvent (eg, Methoxy propanol, Ethoxy ethanol, Methoxy ethanol) in dope solution during the phase inversion. By the addition of ether typed alcohol into a dope solution, the pore size of MF (microfiltration) could be controlled. Also, Membrane prepared was applied to a MBR process and the system was stably operated for 2 months.

Reaction of Sodium Tris(diethylamino)aluminum Hydride with Selected Organic Compounds Containing Representative Functional Groups

  • Cha, Jin-Soon;Jeoung, Min-Kyoo;Kim, Jong-Mi;Kwon, Oh-Oun;Lee, Keung-Dong;Kim, Eun-Ju
    • Bulletin of the Korean Chemical Society
    • /
    • v.15 no.10
    • /
    • pp.881-888
    • /
    • 1994
  • The approximate rates and stoichiometry of the reaction of excess sodium tris(diethylamino)aluminum hydride (ST-DEA) with selected organic compounds containing representative functional groups under standardized conditions(tetrahydrofuran, $0{\circ}$) were studied in order to characterize the reducing characteristics of the reagent for selective reductions. The reducing ability of STDEA was also compared with those of the parent sodium aluminum hydride (SAH) and lithium tris(diethylamino)aluminum hydride (LTDEA). The reagent appears to be milder than LTDEA. Nevertheless, the reducing action of STDEA is very similar to that observed previously for LTDEA, as is the case of the corresponding parent sodium and lithium aluminum hydrides. STDEA shows a unique reducing characteristics. Thus, benzyl alcohol, phenol and 1-hexanol evolved hydrogen slowly, whereas 3-hexanol and 3-ethyl-3-pentanol, secondary and tertiary alcohols, were essentially inert to STDEA. Primary amine, such as n-hexylamine, evolved only 1 equivalent of hydrogen slowly. On the other hand, thiols examined were absolutely stable. STDEA reduced aidehydes and ketones rapidly to the corresponding alcohols. The stereoselectivity in the reduction of cyclic ketones by STDEA was similar to that by LTDEA. Quinones, such as p-benzoquinone and anthraquinone, were reduced to the corresponding 1,4-dihydroxycyclohexadienes without evolution of hydrogen. Carboxylic acids and anhydrides were reduced very slowly, whereas acid chlorides were reduced to the corresponding alcohols readily. Esters and epoxides were also reduced readily. Primary carboxamides consumed hydrides for reduction slowly with concurrent hydrogen evolution, but tertiary amides were readily reduced to the corresponding tertiary amines. The rate of reduction of aromatic nitriles was much faster than that of aliphatic nitriles. Nitrogen compounds examined were also reduced slowly. Finally, disulfide, sulfoxide, sulfone, and cyclohexyl tosylate were readily reduced without evolution of hydrogen. In addition to that, the reagent appears to be an excellent partial reducing agent: like LTDEA, STDEA converted ester and primary carboxamides to the corresponding aldehydes in good yields. Furthermore, the reagent reduced aromatic nitriles to the corresponding aldehydes chemoselectively in the presence of aliphatic nitriles. Consequently, STDEA can replace LTDEA effectively, with a higher selectivity, in most organic reductions.

Overexpression, Purification, and Biochemical Characterization of the Thermostable NAD-dependent Alcohol Dehydrogenase from Bacillus stearothermophilus

  • Shim, Eun-Jung;Jeon, Sang-Hoon;Kong, Kwang-Hoon
    • Journal of Microbiology and Biotechnology
    • /
    • v.13 no.5
    • /
    • pp.738-744
    • /
    • 2003
  • The gene ADH encoding NAD-dependent alcohol dehydrogenase from Bacillus stearothennophilus was cloned and overexpressed as a GST fusion protein at a high level in Escherichia coli. The expressed fusion protein was purified simply by glutathione affinity chromatography. GST fusion protein was then cleaved by thrombin, while soluble enzyme was further purified by glutathione affinity chromatography. The recombinant enzyme had the same elctrophoretic mobility as the native enzyme from Bacillus stearothennophilus. The recombinant enzyme catalyzed the oxidation of a number of alcohols and exhibited high activities towards secondary alcohols. The $K_m\;and\;V_{max}$ values of the recombinant enzyme for ethanol were 5.11 mM and 61.35 U/mg, respectively. Pyridine and imidazole notably inhibited the enzymatic activity. The activity of the recombinant enzyme optimally proceeded at pH 9.0 and $70^{\circ}C$. The midpoint of the temperature-stability curve for the recombinant enzyme was approximately $68^{\circ}C$, and the enzyme was not completely inactivated even at $85^{\circ}C$. The recombinant enzyme showed a high resistance towards denaturing agents (0.05% SDS, 0.1 M urea). Therefore, due to its stability and relatively broad substrate specificity, the recombinant enzyme could be utilized in bio-industrial processes and biosensors.

Selective Reduction by Lithium Bis- or Tris(dialkylamino)aluminum Hydrides. VIII. Reaction of Lithium Tripiperidinoaluminum Hydride in Tetrahydrofuran with Selected Organic Compounds Containing Representative Functional Groups

  • 차진순;이재철;주영철
    • Bulletin of the Korean Chemical Society
    • /
    • v.18 no.8
    • /
    • pp.890-895
    • /
    • 1997
  • The approximate rates and stoichiometry of the reaction of excess lithium tripiperidinoaluminum hydride (LTPDA), an alicyclic aminoaluminum hydride, with selected organic compounds containing representative functional groups under the standardized conditions (tetrahydrofuran, 25°) were examined in order to define the reducing characteristics of the reagent for selective reductions. The reducing ability of LTPDA was also compared with those of the parent lithium aluminum hydride (LAH) and lithium tris(diethylamino)aluminum hydride (LTDEA), a representative aliphatic aminoaluminum hydride. In general, the reactivity of LTPDA toward organic functionalities is weaker than LTDEA and much weaker than LAH. LTPDA shows a unique reducing characteristics. Thus, benzyl alcohol, phenol and thiols evolve a quantitative amount of hydrogen rapidly. The rate of hydrogen evolution of primary, secondary and tertiary alcohols is distinctive. LTPDA reduces aldehydes, ketones, esters, acid chlorides and epoxides readily to the corresponding alcohols. Quinones, such as p-benzoquinone and anthraquinone, are reduced to the corresponding diols without hydrogen evolution. Tertiary amides and nitriles are also reduced readily to the corresponding amines. The reagent reduces nitro compounds and azobenzene to the amine stages. Disulfides are reduced to thiols, and sulfoxides and sulfones are converted to sulfides. Additionally, the reagent appears to be a good partial reducing agent to convert primary carboxamides into the corresponding aldehydes.

Kinetics and Mechanism of the Oxidation of Alcohols by C9H7NHCrO3Cl (C9H7NHCrO3Cl에 의한 알코올류의 산화반응에서 속도론과 메카니즘)

  • Park, Young-Cho;Kim, Young-Sik;Kim, Soo-Jong
    • Journal of the Korea Academia-Industrial cooperation Society
    • /
    • v.19 no.8
    • /
    • pp.378-384
    • /
    • 2018
  • $C_9H_7NHCrO_3Cl$ was synthesized by reacting $C_9H_7NH$ with chromium (VI) trioxide. The structure of the product was characterized by FT-IR (Fourier transform infrared) spectroscopy and elemental analysis. The oxidation of benzyl alcohol by $C_9H_7NHCrO_3Cl$ in various solvents showed that the reactivity increased with increasing dielectric constant(${\varepsilon}$) in the following order: DMF (N,N'-dimethylformamide) > acetone > chloroform > cyclohexane. The oxidation of alcohols was examined by $C_9H_7NHCrO_3Cl$ in DMF. As a result, $C_9H_7NHCrO_3Cl$ was found to be an efficient oxidizing agent that converts benzyl alcohol, allyl alcohol, primary alcohols, and secondary alcohols to the corresponding aldehydes or ketones (75%-95%). The selective oxidation of alcohols was also examined by $C_9H_7NHCrO_3Cl$ in DMF. $C_9H_7NHCrO_3Cl$ was the selective oxidizing agent of benzyl, allyl and primary alcohol in the presence of secondary ones. In the presence of DMF with an acidic catalyst, such as $H_2SO_4$, $C_9H_7NHCrO_3Cl$ oxidized benzyl alcohol (H) and its derivatives ($p-OCH_3$, $m-CH_3$, $m-OCH_3$, m-Cl, and $m-NO_2$). Electron donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. The Hammett reaction constant (${\rho}$) was -0.69 (308K). The observed experimental data were used to rationalize hydride ion transfer in the rate-determining step.

Amount and Chemical Characteristics of the Epicuticular Waxes on Leaves at Active Tillering and Heading Stages of Rice Varieties (벼 품종들의 분얼성기 및 출수기의 엽표면Wax의 양 및 화학적 조성)

  • Yong Woong, Kwon;Bong Jin, Chung
    • KOREAN JOURNAL OF CROP SCIENCE
    • /
    • v.37 no.2
    • /
    • pp.185-197
    • /
    • 1992
  • Differences in the amount and chemical characteristics of the epicuticular waxes on rice leaves were studied for the active tillering and heading stages of rice varieties differing widely in gross leaf-surface property and genetics. The amount of waxes on surfaces of rice leaf-blades was determined by extraction with chloroform and chemical composition of the waxes was characterized by thin layer chromatography, gas liquid chromatography and infrared spectrophotometry. The amount of waxes varied by variety and significantly with growth stage. The amount at the heading stage was 1.7 to 3.6 mg/g fresh weight of leaves, which was two to three times as much as that at the tillering stage of 0.8 to 1.8 mg/g fresh weight. The waxes consisted of seven chemical classes, namely diols, fatty acids, fatty alcohols, fatty aldehydes, fatty esters, saturated and unsaturated hydrocarbons. Diols and unsaturated hydrocarbons were identified as new chemical classes of the rice epicuticular waxes. The polar constituents such as dials, fatty acids and fatty alcohols and the non-polars such as fatty aldehydes, fatty esters, and saturated and unsaturated hydrocarbons were identified at the heading stage, but at the tillering stage only the non-polar compounds were identified. In the carbon numbers (C) of the chemical classes, diols were composed entirely of C30 and acids were mainly of C30 and C31. In alcohols, primary alcohols were composed of C13 and C32, and the secondary alcohols were of C14, C16 and / or C30 regardless of the rice varieties. The acid portion of fatty esters, mainly composed of C22 and C23, showed low cabon numbers compared with the aldehydes. The alcohol portion of them showed a wide distribution in carbon numbers from C13 to C26 depending on the rice varieties. Hydrocarbons had odd carbon numbers, consisting mainly of C29 and C31.

  • PDF