• 제목/요약/키워드: Substitution reaction

검색결과 580건 처리시간 0.045초

팔라듐 촉매화 비닐 치환 반응을 이용한 Conjugated Dienals의 합성 (Synthesis of Conjugated Dienals by Palladium-Catalyzed Vinyl Substitution Reaction)

  • 이종태;김진일
    • 대한화학회지
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    • 제28권5호
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    • pp.335-341
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    • 1984
  • ${\alpha},{\beta}$-불포화 알데히드의 아세탈은 브롬화 방향족화합물들과 팔라듐 촉매와 트리에틸아민 존재하에서 쉽게 반응하여 방향족의 conjugated enals을 생성하였다. 불포화 아세탈로서 acrolein diethyl acetal과 methacrolein diethyl acetal을 사용하여 이들을 메틸기와 이소프로필기로 치환된 브롬화 방향족화합물들과 $100^{\circ}C$에서 반응시킨 뒤 생성물들을 옥살산 수용액으로 처리하여 방향족의 conjugated enals를 합성하였다. o-bromotoluene과 methacrolein diethyl acetal과의 반응을 제외하고는 모두 60% 이상의 좋은 수득율을 얻을 수 있었으며 생성물의 구조는 proton NMR과 IR스펙트럼으로 확인하였다. 3-bromopropenal dimethyl acetal 및 (E)-3-bromo-2-methylpropenal diethyl acetal을 할로겐화 비닐화합물의 반응 부위로 하고 1-알켄과 ethyl acrylate등을 올레핀 반응 부위로 하는 반응물들의 역조합(reverse combination)에 의하여 지방족의 2,4-dienals를 50% 이상의 수득율로 합성 할 수 있다.

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Tetramethyltin과 Iodine의 친전자 치환반응에 대한 압력의 영향 (The Effect of Pressure on the Electrophilic Substitution Reaction of Tetramethyltin with Iodine)

  • 권오천;이훈영
    • 대한화학회지
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    • 제37권6호
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    • pp.555-561
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    • 1993
  • 메탄올용매내에서 요오드와 테트라메틸주석 사이의 Iododestannylation에 대한 반응속도를 분광학적 방법으로 연구하였다. 이 결과로부터 일시적인 전하이동착물의 흡수 스펙트럼이 관찰되었으며, 흡수 스펙트럼의 후속적인 감소현상으로 요오드에 의한 테트라메틸주석의 분해반응임을 알았다. 따라서 iododestannylation에 대한 속도상수를 온도 10, 25 및 35$^{\circ}C$ 압력을 1600 bar 까지 변화시켜 가면서 측정하였으며, 이때의 반응속도상수는 온도와 압력에 따라 증가함을 알았다. 이 반응속도상수로부터 ${\Delta}V^\neq,\;{\Delta}{\beta}^{\neq},\;{\Delta}H^{\neq},\;{\Delta}S^{\neq}$${\Delta}G^{\neq}$의 값을 구하였다. 활성화 부피와 활성화 압축율계수는 모두 음의 값이며, 활성화 엔탈피는 양의 값을, 활성화 엔트로피는 음의 값을 나타내었다. 이들 값으로부터 전이상태의 용매구조변화 및 메카니즘을 규명하였다. 이러한 사실로부터 본 반응은 $S_E2$ 메카니즘이 지배적이며 압력이 증가함에 따라 $S_E2$의 성격이 약화됨을 알았다

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불균일계 술폰화에 의한 한외여과용 폴리에테르 술폰 막소재 합성과 fouling 감소효과 (Synthesis of Sulfonated Polyethersulfone Membrane Material for Ultrafiltration by Heterogeneous Sulfonation and Fouling Reduction Effect)

  • 김인철;최중구;최남석;김종호;탁태문
    • 멤브레인
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    • 제8권4호
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    • pp.210-219
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    • 1998
  • Fouling을 줄이기 위한 한외여과용 친수성 막을 제조하기 위해서 chlorosulfonic acid(CSA)를 사용하여 이온교환용량이 다른 여러 종류의 sulfonated polyethersulfone(SPES)을 불균일계에서 제조하고 특성조사를 하였다. CSA농도, 반응온도, 반응시간 등의 반응조건에 따른 반응도와 분해정도를 알아본 결과 10$\circ$C 이상의 온도와 0.05 mol 이상의 CSA 농도에서 효과적으로 반응이 일어나지만 고분자 주쇄의 분해가 심하게 일어나는 경향을 나타내었다. 술폰산기의 치환여부는 FTIR과 $^1$H-NMR로 확인할 수 있었다. 불균일계에서 개질된 SPES 한외여과막의 단백질에 의한 fouling 감소효과를 알아보기 위해 같은 투과성능을 갖는 막을 비용매인 DCM과 pore 형성제 PVP를 첨가제로 사용하여 막을 제조하였다. 이온교환용량이 증가함에 따라 투과속도는 감소하고 배제율은 상당히 증가되었다. 이런 결과는 SEM에 의해서도 확인할 수 있었다. Finger 구조가 사라지면서 top layer의 두께도 증가하였다. 비용매인 DCM에 의해서 치밀한 막을, pore 형성제인 PVP에 의해서 다공성 막을 제조할 수 있었다. 이온교환 용량이 높을수록 친수성이 증가하여 fouling을 감소시킬 수 있었다.

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Sequential use of real-time polymerase chain reaction and enzyme-linked immunosorbent assay techniques verifies adulteration of fermented sausages with chicken meat

  • Benli, Hakan;Barutcu, Elif
    • Animal Bioscience
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    • 제34권12호
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    • pp.1995-2002
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    • 2021
  • Objective: Detection of adulteration in processed meats is an important issue for some countries due to substitution of beef with a cheaper source of protein like poultry. In this study, the presence of chicken meat was investigated using real-time polymerase chain reaction (real-time PCR) and enzyme-linked immunosorbent assay (ELISA) techniques to verify adulteration of fermented sausage samples. Methods: A total of 60 commercial samples were collected from 20 establishments in three replicates including 10 fermented sausage manufacturers and 10 butchers to investigate the presence of chicken meat with the sequential use of real-time PCR and ELISA techniques. In addition, pH, moisture content, water activity and color values of the samples were determined. Results: Both real-time PCR and ELISA showed agreement on the presence or absence of chicken meat in 55 out of 60 fermented sausage samples and chicken meat was identified with both methods in 16 samples. Five samples produced inconsistent results for the presence of chicken meat in the first run. Nevertheless, the presence of chicken meat was verified with both methods when these samples were analyzed for the second time. In addition, the average physico-chemical values of the fermented sausage samples tested positive for chicken meat were not significantly different from some of those fermented sausage samples tested negative for the chicken meat. Conclusion: The sequential use of real-time PCR and ELISA techniques in fermented sausages could be beneficial for the government testing programs to eliminate false negatives for detection of adulteration with chicken meat. Furthermore, consumers should not rely on some of the quality cues including color to predict the adulteration of fermented sausages with chicken meat since there were no statistical differences among some of the samples tested positive and negative for chicken meat.

Electrochemical Oxygen Evolution Reaction on NixFe3-xO4 (0 ≤ x ≤ 1.0) in Alkaline Medium at 25℃

  • Pankaj, Chauhan;Basant, Lal
    • Journal of Electrochemical Science and Technology
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    • 제13권4호
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    • pp.497-503
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    • 2022
  • Spinel ferrites (NixFe3-xO4; x = 0.25, 0.5, 0.75 and 1.0) have been prepared at 550℃ by egg white auto-combustion route using egg white at 550℃ and characterized by physicochemical (TGA, IR, XRD, and SEM) and electrochemical (CV and Tafel polarization) techniques. The presence of characteristic vibration peaks in FT-IR and reflection planes in XRD spectra confirmed the formation of spinel ferrites. The prepared oxides were transformed into oxide film on glassy carbon electrodes by coating oxide powder ink using the nafion solution and investigated their electrocatalytic performance for OER in an alkaline solution. The cyclic voltammograms of the oxide electrode did not show any redox peaks in oxygen overpotential regions. The iR-free Tafel polarization curves exhibited two Tafel slopes (b1 = 59-90 mV decade-1 and b2 = 92-124 mV decade-1) in lower and higher over potential regions, respectively. Ni-substitution in oxide matrix significantly improved the electrocatalytic activity for oxygen evolution reaction. Based on the current density for OER, the 0.75 mol Ni-substituted oxide electrode was found to be the most active electrode among the prepared oxides and showed the highest value of apparent current density (~9 mA cm-2 at 0.85 V) and lowest Tafel slope (59 mV decade-1). The OER on oxide electrodes occurred via the formation of chemisorbed intermediate on the active sites of the oxide electrode and follow the second-order mechanism.

실대형 모형 실험을 이용한 강관합성 말뚝의 수평 거동 특성 평가 (Assessment of Lateral Behavior of Steel-concrete Composite Piles Using Full-scale Model Tests)

  • 권형민;이주형;박재현;정문경
    • 대한토목학회논문집
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    • 제29권5C호
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    • pp.199-206
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    • 2009
  • 본 연구에서는 수평하중을 받는 강관합성 말뚝의 역학적 특성을 평가하기 위하여 서로 다른 단면 특성을 가진 모형 말뚝에 대하여 실내 모형 실험을 수행하였다. 지반 반력의 효율적인 모사를 위하여 스프링 장치를 이용한 지반 반력 시스템을 개발하였으며, 축하중 및 수평하중을 독립적으로 재하할 수 있는 하중 재하 시스템을 적용하여 사용하중 상태에서의 말뚝의 수평방향 거동 특성을 평가하였다. 강관합성 말뚝은 기존의 현장타설 말뚝에 비하여 증가된 수평저항 특성을 보여주며, 강관 합성 효과에 의하여 강관 및 철근 콘크리트의 수치합 보다 큰 수평 극한강도를 발휘하는 것을 확인하였다. 또한, 전단 연결재의 사용에 따른 강관-콘크리트의 일체화 거동을 검토하였으며, 고강도 콘크리트의 사용에 따른 강관합성 말뚝의 하중 지지성능을 평가하였다. 이와 함께, 강관합성 말뚝의 강관에 의한 내부 철근망의 대체 가능성 여부를 평가하였다.

Metal Ion Catalysis and Inhibition in Nucleophilic Substitution Reactions of 4-Nitrophenyl Nicotinate and Isonicotinate with Alkali Metal Ethoxides in Anhydrous Ethanol

  • Choi, Seo-Young;Hong, Yeon-Ju;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • 제32권6호
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    • pp.1951-1956
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    • 2011
  • A kinetic study is reported on nucleophilic substitution reactions of 4-nitrophenyl nicotinate 5 and isonicotinate 6 with alkali metal ethoxide EtOM (M = K, Na, and Li) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. Plots of pseudo-first-order rate constant $k_{obsd}$ vs. EtOM concentration exhibit upward curvature for the reactions of 5 and 6 with EtOK and EtONa but are almost linear for those with EtOLi. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constant for the reaction with dissociated $EtO^-$ and ion-paired EtOM, respectively) has shown that $k_{EtOK}$ ${\geq}$ $k_{EtONa}$ > $k_{EtO^-}$ but $k_{EtOLi}$ < $k_{EtO^-}$. It has been concluded that $K^+$ and $Na^+$ ions catalyze the reactions by increasing the electrophilicity of the carbonyl carbon atom through formation of a 4-membered cyclic transition state $TS_3$ or $TS_4$. However, $M^+$ ion catalysis has been found to be much less significant for the reactions of 5 and 6 than for the corresponding reactions of 4-nitrophenyl picolinate 4, which was reported to proceed through a 5-membered cyclic transition state $TS_2$. Although 5 and 6 are significantly more reactive than 4-nitrophenyl benzoate 3, the reactions of 5 and 6 result in smaller $k_{EtOK}/k_{EtO^-}$ ratios than those of 3. The electron-withdrawing ability of the nitrogen atom in the acyl moiety of 5 and 6 has been suggested to be responsible for the increase in reactivity and the decrease in the $k_{EtOK}/k_{EtO^-}$ ratio.

Rapid Identification of Ginseng Cultivars (Panax ginseng Meyer) Using Novel SNP-Based Probes

  • Jo, Ick-Hyun;Bang, Kyong-Hwan;Kim, Young-Chang;Lee, Jei-Wan;Seo, A-Yeon;Seong, Bong-Jae;Kim, Hyun-Ho;Kim, Dong-Hwi;Cha, Seon-Woo;Cho, Yong-Gu;Kim, Hong-Sig
    • Journal of Ginseng Research
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    • 제35권4호
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    • pp.504-513
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    • 2011
  • In order to develop a novel system for the discrimination of five ginseng cultivars (Panax ginseng Meyer), single nucleotide polymorphism (SNP) genotyping assays with real-time polymerase chain reaction were conducted. Nucleotide substitution in gDNA library clones of P. ginseng cv. Yunpoong was targeted for the SNP genotyping assay. From these SNP sites, a set of modified SNP specific fluorescence probes (PGP74, PGP110, and PGP130) and novel primer sets have been developed to distinguish among five ginseng cultivars. The combination of the SNP type of the five cultivars, Chungpoong, Yunpoong, Gopoong, Kumpoong, and Sunpoong, was identified as 'ATA', 'GCC', 'GTA', 'GCA', and 'ACC', respectively. This study represents the first report of the identification of ginseng cultivars by fluorescence probes. An SNP genotyping assay using fluorescence probes could prove useful for the identification of ginseng cultivars and ginseng seed management systems and guarantee the purity of ginseng seed.

$LaAlO_3-BaZrO_3$계 perovskites의 제조 및 유전특성 (Fabrication and dielectric properties of $LaAlO_3-BaZrO_3$ perovskites)

  • 이소희;김신;신현호
    • 한국전기전자재료학회:학술대회논문집
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    • 한국전기전자재료학회 2007년도 하계학술대회 논문집 Vol.8
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    • pp.325-325
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    • 2007
  • The perovskites in the $LaAlO_3-BaZrO_3$ system (i.e., $(1-x)LaAlO_3-xBaZrO_3$ were fabricated by a solid state reaction and their dielectric properties were investigated. For the compositions of x=0.1~0.9, the mixture of $LaAlO_3$ with a rhombohedral structure and $BaZrO_3$ with a cubic was observed when the sintering was conducted at $1500^{\circ}C$, indicating that the solubility of constituent elements was very low and a narrow solid solution region might exist. The large difference of ionic radii between $La^{3+}$ ion (0.136nm, C.N.=12) and $Ba^{2+}$ ion (0.161nm) or $Al^{3+}$ ion (0.0535nm, C.N.=6) and $Zr^{4+}$ ion (0.072nm) might hinder the mutual substitution. Within the compositions of x=0~0.7, the dielectric constant of the mixture increased with the amount of $BaZrO_3$, i.e., x value, which was in good agreement with the logarithmic mixing rule (In $_{r,i}={\Sigma}v_iln\;_{r,i}$). The increase in $BaZrO_3$ doping decreased $Q{\times}f$ value significantly due to the low $Q{\times}f$ value of $BaZrO_3$ itself, a poor microstructure of the mixture with an increased grain boundary area per volume, and defects in the cation and oxygen sub-lattices which were respectively caused by the evaporation of barium during the sintering process and the substitution of Ba on La-site or Al on Zr-site.

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Simultaneously Enhanced Magnetic and Ferroelectric Properties of $Bi_{0.9}Dy_{0.1}Fe_{0.97}Co_{0.03}O_3 $ compound

  • 유영준;황지섭;박정수;이주열;강지훈;이광훈;이보화;김기원;이영백
    • 한국진공학회:학술대회논문집
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    • 한국진공학회 2013년도 제45회 하계 정기학술대회 초록집
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    • pp.147-147
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    • 2013
  • Multiferroic material $BiFeO_3$ (BFO) is a typical multiferroic material with a room-temperature magnetoelectric coupling in view of high magnetic- and ferroelectric-ordering temperatures (Neel temperature $T_N$ ~ 647 K and Curie temperature TC ~1,103 K). Rare-earth ion substitution at the Bi sites is very interesting, which induces suppressed volatility of the Bi ion and improved ferroelectric properties. At the same time, the Fe-site substitution with magnetic ions is also attracting, since the enhanced ferromagnetism was reported. In this study, BFO, $Bi_{0.9}Dy_{0.1}FeO_3$ (BDFO), $BiFe_{0.97}Co_{0.03}O_3$ (BFCO) and $Bi_{0.9}Dy_{0.1}Fe_{0.97}Co_{0.03}O_3 $ (BDFCO) compounds were prepared by conventional solid-state reaction and wet-mixing method. High-purity $Bi_2O_3$, $Dy_2O_3$, $Fe_2O_3$ and $Co_3O_4$ powders with the stoichiometric proportions were mixed, and calcined at $500^{\circ}C$ for 24 h. The samples were immediately put into an oven, which was heated up to 800oC and sintered in air for 1 h. The crystalline structure of samples was investigated at room temperature by using a Rigaku Miniflex powder diffractometer. The field-dependent magnetization measurements were performed with a vibrating-sample magnetometer. The electric polarization was measured at room temperature by using a standard ferroelectric tester (RT66B, Radiant Technologies). Dy and Co co-doping at the Bi and the Fe sites induce the enhancement of both magnetic and ferroelectric properties of $BiFeO_3$.

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