• Title/Summary/Keyword: N transfer

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Photochemical Reactions of Saccharin-$\alpha$-Silylamine Systems. Desilylmethylation of $\alpha$-Silylamine via Single Electron Transfer Pathway

  • Ung Chan Yoon;Young Sim Koh;Hyun Jin Kim;Dong Yoon Jung;Dong Uk Kim;Sung Ju Cho;Sang Jin Lee
    • Bulletin of the Korean Chemical Society
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    • v.15 no.9
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    • pp.743-748
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    • 1994
  • Photochemical reactions of saccharin with tertiary amines were explored. Saccharin was found to undergo an acid-base reaction with N-trimethylsilylmethyl-N,N-diethyl amine to form N-trimethylsilylmethyl-N,N-diethyl ammonium saccharin salt which is in equilibrium with free saccharin and N-trimethylsilylmethyl-N,N-diethyl amine insolution. Photoreaction of N-trimethylsilylmethyl-N,N-diethyl ammonium saccharin in $CH_3OH\;or\;CH_3CN$ results in the generation of desilylmethylated product, N,N-diethyl ammonium saccharin mainly along with benzamide. Photoreaction of N-methylsaccharin with N-trimethylsilylmethyl-N,N-diethyl amine in $CH_3OH$ leads to the production of o-(N-methylcarbamoyl)-N-ethylbenzenesulfonamid e as the major product along with N-methylbenzamide as the minor product. On the other hand, photoreaction of N,N,N-triethyl ammonium saccharin, generated from saccharin and triethylamine, produces N-methylbenzamide as the exclusive product. These photoreactions are quenched by oxygen indicating that triplets of saccharin and N-methylsaccharin are the reactive excited states. Based on the consideration of the redox potentials of saccharin and N-trimethylsilylmethyl-N,N-diethyl amine, and the nature of photoproducts, pathways involving initial triplet state single electron transfer are proposed for photoreactions of the saccharins with the ${\alpha}$-silylamine.

Energy Transfer Pathway in Luminescent Lanthanide Complexes Based on Dansyl-N-methylaminobenzoic Acid through Intramolecular Charge Transfer State for Near Infrared Emission

  • Roh, Soo-Gyun;Baek, Nam-Seob;Kim, Yong-Hee;Kim, Hwan-Kyu
    • Bulletin of the Korean Chemical Society
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    • v.28 no.8
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    • pp.1249-1255
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    • 2007
  • We have investigated the photophysical properties of dansyl-N-methylaminobenzoic acid (DABAH) as a ligand and its lanthanide (Ln3+)-cored complexes (Ln3+-(DABA)3(terpy)) in order to determine the main energy transfer pathway for sensitized near infrared emission of Ln3+ ions (Ln3+ = Nd3+ and Er3+) in Ln3+- (DABA)3(terpy). The fluorescence spectrum of DABAH shows a large Stokes shift with increasing solvent polarity. This large Stokes shift might be due to the formation of a twisted intramolecular charge transfer (TICT) state, as demonstrated by the large dipole moment in the excited state. It is in good agreement with the result that the phosphorescence even in the Gd3+-cored complex based on the DABAH ligand was not observed, maybe due to the highly forbidden character of the S1 → T1 transition in the DABAH ligand. A short decay component (ca. 1 ns) was observed in Er3+-(DABA)3(terpy) whereas the fluorescence lifetimes of DABAH and its Gd3+-(DABA)3(terpy) are observed about ~10 ns. The short component could be originated from the energy transfer process between the ligand and the Ln3+ ion. Based on the fluorescence of DABAH its Ln3+- (DABA)3(terpy), the sensitization of Ln3+ luminescence in the Ln3+-(DABA)3(terpy) takes place by the energy transfer via the TICT state of DABAH in the excited singlet state rather than via the excited triplet state.

Effect of Estrus Synchronization Protocols and Gonadotropin Releasing Hormone Treatments on the Pregnancy and Fetal Loss Rate after Transfer of Korean Native Cattle Embryos to Holstein Recipients

  • Kim, So-Seob;Ryoo, Zae-Young;Park, Yong-Soo
    • Journal of Embryo Transfer
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    • v.23 no.2
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    • pp.109-114
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    • 2008
  • This study examined pregnancy and fetal loss rates according to different estrus synchronization protocols and injection of gonadotropin releasing hormone (GnRH) after transfer of Korean Native Cattle embryos to Holstein recipients. In Experiment 1, recipients received no treatment (Control, n = 119); two injections of prostaglandin$F_{2{\alpha}}$ ($PGF_{2{\alpha}}$ ) 11 days apart (PGF group, n = 120); GnRH (day 0)-$PGF_{2{\alpha}}$ (day 7)-GnRH (day 9) (Ovsynch group, n = 120); and CIDR (day 0)-$PGF_{2{\alpha}}$ and CIDR removal (day 7)-GnRH (day 9) (CIDR group, n = 110). In Experiment 2, the control group was received no treatment of GnRH. The treatment groups were received GnRH at embryo transfer (ET) (day 0), 7 days later, 14 days later, ET and 7 days later, 7 and 14 days later, or ET, 7 and 14 days later. Recipients were assigned to treatment randomly and received two in vitro produced blastocysts. Pregnancy was diagnosed at day 60 by palpation per rectum. Fetal loss to term was determined by palpation every 90 days thereafter. In Experiment 1, the pregnancy rate in the CIDR group (59.1%) were higher than in the Control group (42.0%) (p<0.01); fetal loss rates were similar for all groups (12.0 to 18.5%). In Experiment 2, the pregnancy rate in Day 0+7+14 group was higher (60.2%) than the control (40.2%) (p<0.01) and resulted in a lower fetal loss (p<0.05) than the control (4.6 vs. 11.4%). There were no significant difference between other treatment and the control (p>0.05). These results show that pregnancy rates of bovine embryos can be enhanced by CIDR insertion or GnRH $3{\times}$ treatment. Additionally, fetal loss may be reduced with GnRH treatment after ET.

Nitrogen Fixation of legumes and Cropping System for Organic Forage Production (두과 작물의 질소고정과 유기조사료생산을 위한 작부체계)

  • 이효원;박형수
    • Korean Journal of Organic Agriculture
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    • v.10 no.1
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    • pp.49-63
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    • 2002
  • In order to supply 85% of total organic feed in ruminants and 80% in non-ruminants for organic animal production, nitrogen fixation ability of legume should be used in domestic roughages production. 50% of Europe organic farmer use intercropping legume in as green manure. This article is dealing with amount of biologically fixed nitrogen used by legumes and methods for estimating the transfer of biologically fixed N in rotation and separating the N benefit into fixed N and non-fixed N components are reviewed. Available data indicate that transfer amount of N to non legumes was from 50∼9.6(kg/ha) in legume-cereal rotations and proportion of legume N varied with seasons, 90% in summer, 50% in autumn. The important point in cropping system for legumes have to be included for organic forage production 6 year rotation is based on pasture system of 3 year pasture + 2 year annual(com, sudangrass), again pasture. Rye, barly and Italian ryegrass+legumes(vetch, crimson and pea) can be one of option in spring, com, soybean, sudangrass and Japanese bamyard millet would be seeded after spring harvest in the field. Farmer can make good use of rice paddy field as forge production potential area after harvesting rice. Italian, burly and rye+vetch and crimsonclover may be grown in autumn or spring time at the rice field.

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Characteristics of Products in the Reaction 40 MeV/nucleon $^{14}N+Ag$

  • Chung, Yong-Hee;Porile, N. T.
    • Bulletin of the Korean Chemical Society
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    • v.15 no.11
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    • pp.971-975
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    • 1994
  • Cross sections and recoil properties have been measured for the fragments produced in the interaction of silver with 40 MeV/nucleon $^{14}N$ ions using off-line ${\gamma}$-ray spectroscopy. The data were used to obtain the isobaric-yield distribution, the mass yield distribution, and the fractional momentum transfer. The values of forward-to-backward ratios were measured to be very large, indicating that substantial momentum transfer occurs at this energy regime. The results are compared with other studies of the interaction of silver with intermediate-energy heavy ions.

Syntheses and Phase-transfer Catalytic Activities of Monoazacrown Ethers

  • Shim Jae Hu;Chung Kwang Bo;Masao Tomoi
    • Bulletin of the Korean Chemical Society
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    • v.13 no.3
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    • pp.252-255
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    • 1992
  • Preparative methods for and catalytic activities of monoaza-18-crown-6 or monoaza-15-crown-5 in the reaction of 1-bromooctane with aqueous KI or NaI were investigated. Monoazacrown ethers were prepared by debenzylation of N-benzylmonoazacrown ethers, obtained from the reaction of N-benzyldiethanolamine and oligoethylene glycol ditosylate. The phase-transfer catalytic activity of N-benzylmonoazacrown ethers was higher than that of the corresponding monoazacrown ethers.

Delete and Generate: Korean style transfer based on deleting and generating word n-grams (Delete-Generate: 단어 n-gram의 삭제 및 생성에 기반한 한국어 스타일 변환)

  • Choi, Heyon-Jun;Na, Seung-Hoon
    • Annual Conference on Human and Language Technology
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    • 2019.10a
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    • pp.400-403
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    • 2019
  • 스타일 변환(Style Transfer)은 주어진 문장의 긍정이나 부정 같은 속성을 변경하여 다른 속성을 갖는 문장으로 변환하는 과정을 의미한다. 본 연구에서는 스타일 변환을 위한 단어 n-그램 삭제의 기준을 확장하였고, 네이버 영화리뷰 데이터셋을 통해 이를 스타일 변환 이후 원래 문장의 스타일로부터 얼마나 차이가 나게 되었는지를 측정하였다. 측정은 감성분석기를 통해 이루어졌고, 기존 방법에 비해 6.28%p정도 높은 75.13%의 정확도를 보였다.

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Studies of Silyl-Transfer Photochemical Reactions of N-[(Trimethylsilyl)alkyl]saccharins

  • Cho, Dae-Won;Oh, Sun-Wha;Kim, Dong-Uk;Park, Hea-Jung;Xue, Jin-Ying;Yoon, Ung-Chan;Mariano, Patrick S.
    • Bulletin of the Korean Chemical Society
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    • v.31 no.9
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    • pp.2453-2458
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    • 2010
  • Photochemical studies of N-[(trimethylsilyl)alkyl]saccharins were carried out to investigate their photochemical behavior. Depending on the nature of the substrate and the solvent system employed, reactions of these substances can take place by either SET-promoted silyl migration from carbon to either the amide carbonyl or sulfonyl oxygen or by a N-S homolysis route. The results of the current studies show that an azomethine ylide, arising from a SET-promoted silyl migration pathway, is generated in photoreactions of N-[(trimethylsilyl)methyl]saccharin and this intermediate reacts to give various photoproducts depending on the conditions employed. In addition, irradiation of N-[(trimethylsily)ethyl]saccharin produces an excited state that reacts through two pathways, the relative importance is governed by solvent polarity and protic nature. Finally, photoirradiation of N-[(trimethylsilyl)propyl]saccharin in a highly polar solvent system comprised of 35% aqueous MeOH gives rise to formation of a tricyclic pyrrolizidine and saccharin that generated via competitive SET-promoted silyl transfer and $\gamma$-hydrogen abstraction pathways.

Homolytic Reactions of Isonitriles (이소니트릴의 자유라디칼반응)

  • Sung Soo Kim
    • Journal of the Korean Chemical Society
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    • v.24 no.3
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    • pp.250-258
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    • 1980
  • Various radicals may add to isonitriles to give imidoyl radcals RN=CR'. This may be also generated via abstraction of imidoyl hydrogen from imine in the following manner: RN=CR' + R"${\cdot}{\rightarrow}$ RN=CR' + R"-H Imidoyl radicals would be stabilized via two pathways, ${\beta}$-cleavage and atom transfer reactions. ${\beta}$-Cleavage may occur in two directions depending upon structure of the radicals. Cyanide transfer and the "so-called" normal ${\beta}$-cleavage are the two modes of ${\beta}$-cleavage. Addition of t-butoxy radical to t-butyl isocyanide 7 generates an imidoyl radical t-Bu-N=C-O-Bu-t, which undergoes ${\beta}$-cleavage to give t-butyl isocyanate and t-butyl radical. Addition of phenyl radical to 7 forms the intermediate radical t-Bu-N=$C-C_6H_5$, which decomposes to give benzonitrile and t-butyl radical. The t-butyl radical generated from the ${\beta}$-cleavage adds to 7 giving the radical t-Bu-N=C-Bu-t, which cleaves only to pivalonitrile and t-butyl radical, inducing radical chain isomerization. Trimethylsilyl radical adds to 7 to give the intermediate t-Bu-N=$C-Si(CH_3)_3$, which collapses to $(CH_3)_3$SiCN and a t-butyl radical.

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