• Title/Summary/Keyword: Selective hydrolysis

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Synthesis and Characterization of Various Di-N-Functionalized Tetraaza Macrocyclic Copper(II) Complexes

  • Kang, Shin-Geol;Kim, Na-Hee;Lee, Rae-Eun;Jeong, Jong-Hwa
    • Bulletin of the Korean Chemical Society
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    • v.28 no.10
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    • pp.1781-1786
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    • 2007
  • Two copper(II) complexes, [CuL3](ClO4)2 bearing one N-CH2CH2CONH2 group as well as one N-CH2CH2CN group and [CuL4](ClO4)2 bearing two N-CH2CH2CONH2 groups, have been prepared by the selective hydrolysis of [CuL2](ClO4)2 (L2 = C-meso-1,8-bis(cyanoethyl)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). The complex [CuL5](ClO4)2 bearing one N-CH2CH2C(=NH)OCH3 and one N-CH2CH2CN groups has been prepared as the major product from the reaction of [CuL2](ClO4)2 with methanol in the presence of triethylamine. In acidic aqueous solution, the N-CH2CH2C(=NH)OCH3 group of [CuL5](ClO4)2 undergoes hydrolysis to yield [CuL6](ClO4)2 bearing both N-CH2CH2COOCH3 and N-CH2CH2CN groups. The crystal structure of [CuL5](ClO4)2 shows that the complex has a slightly distorted square-pyramidal coordination polyhedron with an apical Cu-N (N-CH2CH2C(=NH)OCH3 group) bond. The apical Cu-N bond distance (2.269(3) A) is ca. 0.06 A longer than the apical Cu-O (N-CH2CH2CONH2 group) bond of [CuL4](ClO4)2. The pendant amide group of [CuL3](ClO4)2 is involved in coordination. The carboxylic ester group of [CuL6](ClO4)2 is also coordinated to the metal ion in various solvents but is removed from the coordination sphere in the solid state.

Isotope-Dilution Mass Spectrometry for Quantification of Urinary Active Androgens Separated by Gas Chromatography

  • Lee, Su-Hyeon;Choi, Man-Ho;Lee, Won-Yong;Chung, Bong-Chul
    • Mass Spectrometry Letters
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    • v.1 no.1
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    • pp.29-32
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    • 2010
  • Cross reacting antibodies can cause an overestimation of the results of immunoassays. Therefore, alternative methods are needed for the accurate quantification of steroids. Gas chromatography combined with isotope-dilution mass spectrometry (GC-IDMS) is developed to quantify urinary active androgens, testosterone, epitestosterone and dihydrotestosterone, which are clinically relevant androgens to both hair-loss and prostate diseases. The method devised involves enzymatic hydrolysis with $\beta$-glucuronidase, solid-phase extraction, liquid-liquid extraction using methyl tert-butyl ether and subsequent conversion to pentafluorophenyldimethylsilyl-trimethylsilyl (flophemesyl-TMS) derivatives for sensitive and selective analysis in selected-ion monitoring mode. Flophemesyl-TMS derivatization not only eliminates matrix interference but also has a good peak resolution within a 6 min-run. A selective and sensitive GC technique with flophemesyl-TMS derivatives also allows accurate quantitative analysis of three active androgens when combined with IDMS. The limit of quantification of the three analytes was <50 pg/mL, and extraction recoveries ranged from 91.9 to 102.1%. The precision and accuracy were 1.2~6.5% and 89.0~106.7%, respectively. This GC-IDMS method can be useful for evaluating the drug efficacy and monitoring the biological processes responsible for male-pattern baldness and prostate diseases.

Preparation of an Amino Acid Based DTPA as a BFCA for Radioimmunotherapy

  • Choi, Kang-hyuk;Hong, Young-Don;Pyun, Mi-Sun;Choi, Sun-Ju
    • Bulletin of the Korean Chemical Society
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    • v.27 no.8
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    • pp.1194-1198
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    • 2006
  • For the purpose of developing more effective chelating agents, we have synthesized a diethylene triamine pentaacetic acid(DTPA) analogue by using an amino acid. S-(N-Boc-aminophenyl)-Cys(t-Bu4-DTPA) methylester was prepared in 6 steps with total yield of 47.9%. For the sake of introducing a biomolecule to the DTPA derivative, a selective hydrolysis was performed with 3 M HCl/Ethylacetate = 1 : 3 ($25{^{\circ}C}$, 30 min, vigorous stirring). $^{166}Ho$-Cys-DTPA and $^{166}Ho$-Biotin-Cys-DTPA were prepared by mixing $^{166}Ho$ with DTPA derivatives at room temp in a HCl solution (pH = 5) and the radiochemical stabilities (> 99%) were maintained for over 6 hrs in vitro.

Characterization of Pyribenzoxim Metabolizing Enzymes in Rat Liver Microsomes

  • Liu Kwang-Hyeon;Moon Joon-Kwan;Seo Jong-Su;Park Byeoung-Soo;Koo Suk-Jin;Lee Hye-Suk;Kim Jeong-Han
    • Toxicological Research
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    • v.22 no.1
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    • pp.1-8
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    • 2006
  • The primary metabolism of pyribenzoxim was studied in rat liver microsomes in order to identify the cytochrome P450 (CYP) isoform(s) and esterases involved in the metabolism of pyribenzoxim. Chemical inhibition using CYP isoform-selective inhibitors such as ${\alpha}$-naphthoflavone, tolbutamide, quinine, chlorzoxazone, troleandomycin, and undecynoic acid indicated that CYP1A and CYP2D are responsible for the oxidative metabolism of pyribenzoxim. And inhibitory studies using eserine, bis-nitrophenol phosphate, dibucaine, and mercuric chloride indicated pyribenzoxim hydrolysis involved in microsomal carboxylesterases containing an SH group (cysteine) at the active center.

Free and Glycosidically Bound Volatile Components in Tobacco Leaves(Nicotiana tabacum L.) (잎담배중 유리 및 Glycoside형태로 존재하는 휘발성 향기성분)

  • 김영회;나도영;김옥찬;서철원;김용태
    • Journal of the Korean Society of Tobacco Science
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    • v.14 no.1
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    • pp.79-86
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    • 1992
  • Free and glycosidically bound volatiles from three green tobacco leaves(NC 82, KF 109 and Br-21) were separated by nonionic resin Amberlite XAD-2 adsorption column chromatography and election by selective solvents. Aglycones from the glycosidically bound fractions were released by enzymatic hydrolysis with almond B-glucosidase. A total of 20 components identified from free and glycosidically bound fractions, the major components were benzaldehyde, benzyl alcohol, 2-phenylethyl alcohol, 3-oxo- -ionol, 3-hydroxy-B-ionone, 3-oxo-7, 8-dihydro-n-ionol and scopoletin. Six Cl.B norisoprenoids identified in this study, which have been described to possess a characteristic tobacco aroma-enhancing effect, were not presented in free forms but rather bound glycosidic forms.

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Synthesis of Amphiphilic Poly(alkyl methacrylate-b-methacrylic acid) by Group Transfer Polymerization and Selective Hydrolysis

  • Soon Ki Kwon;Weon Jung Choi;Yun Hi Kim;Sam Kwon Choi
    • Bulletin of the Korean Chemical Society
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    • v.13 no.5
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    • pp.479-482
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    • 1992
  • Several poly(alkyl methacrylate-b-t-butyl methacrylate) diblock copolymers were synthesized by group transfer polymerization. The molecular weight of poly(t-butyl methacrylate) segments and the composition of the resulting block copolymers were controlled by the monomer feed ratios and mole ratios of monomer to initiator. The poly(t-butyl methacrylate) block was quantitatively hydrolyzed to poly(methacrylic acid) block by refluxing with a catalytic amount of p-toluenesulfonic acid in dioxane at $100^{\circ}C$ for 12 hrs. The thermogravimetric analysis of poly(alkyl methacrylate-b-t-butyl methacrylate) exhibited the lose of isobutylene and subsequent anhydride formation in the range of $205-300^{\circ}C$.

Food application of enzymes derived from microorganisms degrading chitin and chitosan (키틴과 키토산 분해 미생물 유래 효소의 식품에의 이용)

  • Park, Jae Kweon
    • Food Science and Industry
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    • v.53 no.1
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    • pp.43-55
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    • 2020
  • Most reports demonstrated the substrate specificity-based kinetic properties of chitin or chitosan degrading enzymes. However, there is virtually less information on the high quality and quantity production of chitin or chitosan hydrolysates having a larger than (GlcN)7 from the hydrolysis of high molecular weight chitosan using specific enzymes and their biological activity. Therefore, the production of such molecules and the discovery of such enzyme sources are very important. Fortunately, the author has established a mass production method of chitosan hydrolysates (GlcN)n, n=2-13 that have been characterized as a potent antioxidant substance, as well as antifungal and antibacterial activities against Penicillium species and highly selective pathogenic bacteria. In addition, preclinical studies using (GlcN)n, n=5-25 demonstrated that these molecules played a very important role in maintaining biometric balance. Collectively, it is implicated that the application of these mixed substances to foods with significant biological activity is very encouraging.

An Asymmetric Synthesis of (+)-Polyoxamic acid

  • Lee, Ki-Han;Oh, Chang-Young;Lee, Kee-Young;Kim, Yong-Hyun;Lee, Yiu-Suk;Joo, Jae-Eun;Ham, Won-Hun
    • Proceedings of the PSK Conference
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    • 2002.10a
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    • pp.362.3-362.3
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    • 2002
  • The Polyoxin complex is an antifungal antibiotics produced by Streptomyces cacaoi var. asoensis that exhibit marked and selective activity against pytopathogenic fungi. They incorporate carbamoylated dipeptides attached to the sugar moiety. Controlled alkaline hydrolysis of polyoxins result in several products. one of which has been identified as (+)-(2S. 3S, 4S)-2-amino-3. 4. 5-trihydroxypentonic acid(polyoxamic acid). A variety of chemical syntheses of polyoxamic acid have been developed over several years. (omitted)

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Study on Enhancement of Ammonia Generation for Effective Collision Frequency (유효충돌빈도를 고려한 암모니아 생성 증대기법 연구)

  • Sejin Kim;Yongseok CHoi;Hyunchul Park
    • Journal of Aerospace System Engineering
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    • v.17 no.6
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    • pp.1-8
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    • 2023
  • Research, such as developing alternative energy in the transportation field, including aviation, is being actively conducted to solve the issue of current climate change. Interest in ammonia fuel as a carbon free energy (CFE) source is increasing due to the ease of liquefaction and transportation and similarity in energy density to that of methanol. However, explosiveness and toxicity of ammonia make it difficult to handle. Therefore, in this study, stable ammonia production was attempted using relatively easy-to-handle urea water solution (UWS). High temperature steam was used to promote the hydrolysis of ammonia. In order to determine the causes for ammonia production below the theoretical equivalent ratio, it was suggested that there were not enough collisions to promote the hydrolysis based on the kinetic theory of gases. The hydrolysis of unreacted isocyanic acid (HNCO) was tested according to the change in water supply. As a result, an increased amount of ammonia produced was confirmed. The increased amount of ammonia produced in a certain section was dependent on the steam temperature and the flow rate of water supplied.

Highly sensitive and selective detection of cyanide in aqueous solutions using a surface acoustic wave chemical sensor (표면음향파 화학센서를 이용한 수용액 중 시안화이온의 선택적인 고감도 검출)

  • Lee, Soo Suk
    • The Journal of the Acoustical Society of Korea
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    • v.35 no.6
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    • pp.473-479
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    • 2016
  • We report a highly selective and sensitive 200 MHz Surface Acoustic Wave (SAW) sensor that can detect cyanide ion in aqueous solution using surface immobilized thioester molecules in combination with gold nanoparticles (AuNPs). To construct the sensor device, a monolayer of thioester compound was immobilized on the SAW sensor surface. At the sensor surface, hydrolysis of thioester group by nucleophilic addition of cyanide occurred and the resulting free thiol unit bound to AuNP to form thiol-AuNP conjugate. For the signal enhancement, gold staining signal amplification process was introduced subsequently with gold (III) chloride trihydrate and reducing agent, hydroxylamine hydrochloride. The SAW sensor showed a detection ability of $17.7{\mu}M$ for cyanide in aqueous solution and demonstrated a saturation behavior between the frequency shift and the concentration of cyanide ion. On the other hand, our SAW sensor had no activities for other anions such as fluoride ion, acetate ion and sulfate ion, moreover, no significant interference observed by other anions. Finally, all the experiments were carried out in-house developed sensor and fluidics modules to obtain highly reproducible results.