• 제목/요약/키워드: cross-reactions

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A Mechanistic Study on the Nucleophilic Addition Reactions of Benzylamines to the Activated Olefins

  • Oh, Hyuck-Keun
    • Bulletin of the Korean Chemical Society
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    • 제29권6호
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    • pp.1195-1198
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    • 2008
  • Kinetic studies of the additions of benzylamines to a noncyclic dicarbonyl group activated olefin, methyl $\alpha$-acetyl-$\beta$ -phenylacrylates (MAP), in acetonitrile at 30.0 ${^{\circ}C}$ are reported. The rates are lower than those for the cyclic dicarbonyl group activated olefins. The addition occurs in a single step with concurrent formation of the $C_\alpha$ -N and $C_\beta$ -H bonds through a four-center hydrogen bonded transition state. The kinetic isotope effects ($k_H/k_D$ > 1.0) measured with deuterated benzylamines ($XC_6H_4CH_2ND_2$) increase with a stronger electron acceptor substituent ($\delta\sigma$ X > 0) which is the same trend as those found for other dicarbonyl group activated series (1-4). The sign and magnitude of the cross-interaction constant, ρXY, is comparable to those for the normal bond formation processes in the $S_N2$ and addition reactions. The relatively low ${\Delta}H^\neq$ and large negative ${\Delta}S^\neq$ values are also consistent with the mechanism proposed.

Kinetic and Mechanism of the Addition of Benzylamines to α-Phenyl-β-thiophenylacrylonitriles in Acetonitrile

  • Hwang, Jae-young;Yang, Ki-yull;Koo, In-Sun;Sung, Dae-Dong;Lee, Ik-choon
    • Bulletin of the Korean Chemical Society
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    • 제27권5호
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    • pp.733-738
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    • 2006
  • Nucleophilic addition reactions of p-substitutedbenzylamines $(XC _6H_4CH _2NH _2)$ to $\alpha$-phenyl-$\beta$-thiophenyl-acrylonitriles ($YC _4SH _2CH=C(CN)C_6H_4$Y') have been studied in acetonitrile at 25.0, 30.0, and 35.0 ${^{\circ}C}$. The reactions take place in single step in which the $C_\beta$ -N bond formation and proton transfer to $C_\alpha$ of $\alpha$-phenyl-$\beta$-thiophenylacrylonitriles occur concurrently with four-membered cyclic transition structure. These mechanistic conclusions are drawn based on (i) the large negative $\rho$x and large positive $\rho$Y' values and also large magnitude of $\rho$X, (ii) the negative sign and large magnitude of the cross-interaction constants ($\rho$XY), (iii) the normal kinetic isotope effects ($k_H/k_D$ > 1.0), and (iv) relatively low $\Delta H ^\neq$ and large negative $\Delta S ^\neq$ values.

Transition State Variation in the Anilinolysis of O-Aryl Phenyl Phosphonochloridothioates in Acetonitrile

  • Adhikary, Keshab Kumar;Lumbiny, Bilkis Jahan;Dey, Shuchismita;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • 제32권8호
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    • pp.2628-2632
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    • 2011
  • The nucleophilic substitution reactions of Y-O-aryl phenyl phosphonochloridothioates with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are kinetically investigated in acetonitrile at $55.0^{\circ}C$. The deuterium kinetic isotope effects (DKIEs) invariably increase from an extremely large secondary inverse ($k_H/k_D$ = 0.439; min) to a primary normal ($k_H/k_D$ = 1.34; max) as both substituents of nucleophile (X) and substrate (Y) change from electron-donating to electron-withdrawing. These results are opposite to the DKIEs on Y-O-aryl methyl phosphonochloridothioates, and can be rationalized by the gradual transition state (TS) variation from backside to frontside attack. The trigonal bipyramidal pentacoordinate TS is proposed for a backside attack, while the hydrogen-bonded, four-center-type TS is proposed for a frontside attack. The negative values of the cross-interaction constants (${\rho}_{XY(H)}$ = -0.38 for $XC_6H_4NH_2$ and ${\rho}_{XY(D)}$ = -0.29 for $XC_6H_4ND_2$) indicate that the reactions proceed by a concerted $S_N2$ mechanism.

균사 외피 항체를 이용한 Streptomyces 속 균주들의 혈청학적 유사성 분석 (Serotaxonomical Analyses of Some Streptomyces Strains Using Antibodies against Cell Envelope)

  • 조성기;김재헌
    • 미생물학회지
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    • 제43권2호
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    • pp.137-141
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    • 2007
  • Streptomyces 5균주 간의 유사도를 혈청학적 방법으로 측정하였다. 항원으로는 충분히 생장한 균체의 외피를 Tween 20으로 용출시킨 용액을 사용하였고 항체는 토끼를 면역시켜 얻었다. 면역확산과 ELISA 결과 항원-항체 반응의 정도가 균주간의 분류학적 유사성과 비례적으로 반영되지 않았다. 즉 군집 A에 속하는 균주들 사이의 항원-항체 반응이 낮게 측정된 반면에 군집 F의 Streptomyces Iavendulae와 군집 A의 Streptomyces viridochromogenes가 특이적으로 비교적 높게 나타났다.

발단 방사화 검출기를 이용한 핵분열 즉발 중성자 에너지 스펙트럼 측정방법 (Method for Measuring Prompt Fission Neutron Energy Spectrum by Means of Threshold Activation Detectors)

  • 노성기;신희성;박종묵
    • Nuclear Engineering and Technology
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    • 제22권4호
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    • pp.410-415
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    • 1990
  • MN(Madland-Nix) 모형에 바탕을 둔 핵분열 즉발 중성자 에너지 스펙트럼을 핵분열 유기중성자의 에너지 함수로서 구했다. 이 중성자 스펙트럼을 $^{27}$ Al(n,$\alpha$), $^{32}$S(n,p) 및 $^{115}$ In(n,n') 발단 방사화 검출기의 여기함수에 증율시켜 평균핵반응 단면적을 계산하고 상호간의 비, 즉, 중성자 스펙트럼 지수를 구했다. 그 결과 핵분열 유기중성자의 에너지에 따라 중성자 스펙트럼은 변하며 그에 따라 중성자 스펙트럼 지수도 변함을 보였다. 이것은 곧 중성자 스펙트럼 지수를 실험적으로 결정하므로써 핵분열 즉발 중성자 에너지 스펙트럼을 결정할 수 있음을 의미한다.

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An Application of High-Power Ultrasound to Rubber Recycling

  • Hong, Chang-Kook;Isayev, A.I.
    • Elastomers and Composites
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    • 제38권2호
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    • pp.103-121
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    • 2003
  • The application of powerful ultrasound to rubber recycling is a very recent field of study. An ultrasonic field creates high frequency extension-contraction stresses by acoustic cavitation. The breakdown of rubber network occurs primarily around pulsating cavities due to the highest level of strain produced by high-power ultrasound. Stronger reductions of cross-link density were observed at a higher pressure, indicating an important role of pressure during ultrasonic recycling. Visible bubbles were observed during ultrasonic treatment as a proof of acoustic cavitation. Shearing effect has a significant influence on improving the efficiency of ultrasonic treatment. After the ultrasonic treatment, the cross-link densities of NR/SBR blends were lower than those of NR and SBR due to the reduced degree of unsaturation and chemical reactions. Carbon black fillers increase the probability of bond scission during ultrasonic treatment, due to the restricted mobility. The mechanical properties of ground tire rubber (GRT)/HDPE blends were improved by ultrasonic treatment and dynamic revulcanization. Ultrasonic treatment of GRT in the presence of HDPE matrix was found to give better mechanical properties due to the chemical reactions between rubber and plastic phases.

안느 에베르의 중·단편집 『격류』에 드러나는 소외의 시대상 (Phases of Alienation in Le Torrent by Anne Hébert)

  • 강충권
    • 비교문화연구
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    • 제39권
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    • pp.7-32
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    • 2015
  • In 1950, Anne $H{\acute{e}}bert$ published Le Torrent, a collection of seven short stories. These stories containing many shocking themes and expressions have placed her one of the pioneers of modern novels in Quebec. This paper tries to analyze several phases of alienation described in the novels and the reactions of alienated caracters in their situation. Some examples of alienated and mentally or physically deformed characters in Le Torrent are Fran?ois, $St{\acute{e}}phanie$, Stella, etc. Although the author wanted readers to interpret these characters on ther individual level, this paper interprets them differently. The result of this study is as following. Alienation doesn't come from one's interior but his exterior. Society and history are major agents of alienation. The injustice of life imposed on the caracters results from political and religious underdevelopment, cultural lowness, absence of social security system and of universal education at that time. The conquest of Quebec by England left a deep and historical wound on the French Canadians. This fact is, in my opinion, one of the essential themes of Anne $H{\acute{e}}bert^{\prime}s$ novels. In spite of all these alienating situations, the reactions showed by the caracters of the novels are limited to escapist illusion, self-destruction, mistaken revenge, eternal submission, etc. In conclusion, Le Torrent by Anne $H{\acute{e}}bert$ which deeply approached themes of violence and alienation could be called authentic landscape of the inner world of Quebecois before 'la Revolution tranquille.'

Study on (n, α) reactions for the production of 51Cr, 89Sr, 99Tc, 131I, 133Xe, 137Cs and 153Sm radioisotopes used in nuclear medicine

  • Hallo M. Abdullah;Ali H. Ahmed
    • Nuclear Engineering and Technology
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    • 제55권9호
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    • pp.3352-3358
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    • 2023
  • Nuclear medicine seems to be a decent choice of medicine in the recent decade. The radioactive isotopes 51Cr, 89Sr, 99Tc, 131I, 133Xe, 137Cs and 153Sm are extremely essential in nuclear medicine. The excitation functions of the 54Fe (n, α) 51Cr, 92Zr (n, α) 89Sr, 102Rh (n, α) 99Tc, 134Cs (n, α) 131I, 136Ba (n, α) 133Xe, 140La (n, α) 137Cs and 156Gd (n, α) 153Sm reactions were calculated in this study using the EMPIRE 3.2.3 and TALYS 1.95 nuclear codes. Additionally, the cross sections at 14-15 MeV were calculated using empirical formulae and the experimental data. The computer codes were compared to the experimental data and Empirical formulas as well as the evaluated data (TENDL 2021, JENDL 3.3, JENDL 5, JEFF 3.3, EAF 2010, CENDL 3.1, CENDL 3.2, ROSFOND 2010, FENDL 3.2 b, and BROND 3.1).

Study on (n,p) reactions of 58Ni, 99Tc, 99Ru, 131Xe, 133Cs and 186Os radioisotopes used in medicine

  • Hallo M. Abdullah;Ali H. Ahmed
    • Nuclear Engineering and Technology
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    • 제55권1호
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    • pp.304-309
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    • 2023
  • In the last decade, nuclear medicine appears to be a good choice of medicine. 58Co, 99Mo, 99Tc, 99Re, 133Xe and 186Re are very important radionuclides for nuclear medicine. In this study, the excitation functions of 58Ni (n, p) 58Co, 99Tc (n, p) 99Mo, 99Ru (n, p) 99Tc, 131Xe (n, p) 131I, 133Cs (n, p) 133Xe and 186Os (n, p) 186Re nuclear reactions were calculated at neutron energies between 1 and 20 MeV using TALYS 1.95 and EMPIRE 3.2 nuclear codes. Furthermore, the cross sections were calculated with the empirical formula derived in our past study at 14-15 MeV. The obtained results were compared with the measured values in EXFOR library, and with the evaluated data of (JENDL-4.0/HE, JEFF-3.3, TENDL-2019, ENDF/B-VIII.0, IRDFF-II, JENDL/ImPACT-18). The results are in good agreement with those of the evaluated data libraries and experimental results and indicates that these radioisotopes can be produced by smaller cyclotrons.

Formation of Cross-Linked Products of The Reaction Center D1 Protein in Photosystem II under Light Stress

  • Uchida, Suguru;Kato, Yoji;Yamamoto, Yasusi
    • Journal of Photoscience
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    • 제9권2호
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    • pp.382-384
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    • 2002
  • When illuminated with strong visible light, the reaction center Dl protein of photo system II is photodamage and degraded. Reactive oxygen species and endogenous cationic radicals generated by photochemical reactions are the cause of the damage to the Dl protein. Recently we found that the photodamaged Dl protein cross-links with the surrounding polypeptides such as D2 and CP43 in photosystem II. As the cross-linking reaction is dependent on the presence of oxygen, reactive oxygen species are suggested to be involved. Among the reactive oxygen species examined, ? OH was most effective in the formation of the cross-linked products. These results indicate that the cross-linking is mostly due to ? OH generated at photosystem II. The cross-linking site of the Dl protein is not known. As several tyrosine residues exist at the D­E loop of the Dl protein, there is a possibility that di-Tyr is formed between the D­E loop of the Dl protein and surrounding polypeptides during the strong illumination. Therefore, we examined the formation of di-Tyr using the monoclonal antibody against di-Tyr under excess illumination of the photosystem II membranes. The results obtained here suggest that no di-Tyr is formed during the excess illumination of photosystem II.

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