• Title/Summary/Keyword: Substitution reaction

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Preparation and Physicochemical Characteristics of Octenyl Succinated Rice Starches Based on Amylose Content (아밀로오스 함량에 따른 옥테닐호박산 쌀전분의 제조 및 이화학적 특성)

  • Jung, Myung-Hoon;Youn, Kwang-Sup
    • Korean Journal of Food Science and Technology
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    • v.44 no.5
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    • pp.577-582
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    • 2012
  • The purpose of this study was to investigate the preparation and physicochemical characteristics of n-octenylsuccinylated (OSAn) rice starches with different rice amylose contents. Amylose contents of Jinsumi flour and Milyang 261 flour were 15.42 and 20.31%, respectively. After processing by alkali treatment, amylose contents of Jinsumi rice starch and Milyang 261 rice starch were 34.21% and 39.32%, respectively. After OSAn treatment, the degree of substitution and reaction efficiency of Jinsumi starch were higher than those of Milyang 261. The stability of the modified Jinsumi emulsion was higher than that of the Milyang 261 emulsion. Viscosity of the Jinsumi emulsion was higher than that of the Milyang 261 emulsion. When the emulsions were spray dried, modified Jinsumi rice starch showed excellent coating efficiency compared to that of modified Milyang 261 rice starch. Therefore, Jinsumi was more suitable than Milyang 261 to apply for encapsulation as wall materials.

Structure-Reactivity Relationship of Benzyl benzenesulfonates (Part 2). Nucleophilic Substitution Reaction of Benzyl Derivatives (Benzyl benzenesulfonate류의 구조-반응성 관계 (2보). 벤질 유도체의 친핵성 치환반응)

  • Cheong, Duk-Young;Kim, Sung-Hong;Lee, Myung-Ho;Yoh, Soo-Dong;Fujio, Mizue;Tsuno, Yuho
    • Journal of the Korean Chemical Society
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    • v.39 no.8
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    • pp.643-649
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    • 1995
  • The Menschutkin type reactions of substituted(Z)-benzyl systems with substituted(Y)-pyridines and N,N-dimethyl aniline have been studied by the electro-conductometric method in acetonitrile at 35$^{\circ}C$ and 50$^{\circ}C$. On the plot of $k_{obs}$ versus concentrations of nucleophile under pseudo-first order conditions, 3,$4-(CH_3/O)_2$-benzyl bromide and $4-CH_3O$-benzyl bromide were a positive intercept at zero concentration of nucleophile. The $k_1$ value for each compound was invariant with the different nucleoephile. However, $4-CH_3-$ and other electron withdrawing substituents of benzyl bromides did not show the positive intercept. These results are suggested that the reactions have been proceeding simultaneously and independently for the activated benzyl bromides via direct bimolecular and intimate ion pair intermediate.

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Kinetics and Mechanism of the Pyridinolysis of Aryl Ethyl Chlorothiophosphates in Acetonitrile

  • Adhikary, Keshab Kumar;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.32 no.11
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    • pp.3947-3951
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    • 2011
  • The nucleophilic substitution reactions of Y-aryl ethyl chlorothiophosphates with X-pyridines are studied kinetically in acetonitrile at $55.0^{\circ}C$. The Hammett and Bronsted plots for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a break point at X = 3-Me. The substituents of X = 4-CN and 4-Ac show great positive deviations from both the Hammett and Bronsted plots. The Hammett plots for substituent Y variations in the substrates exhibit biphasic concave upwards with a minimum point at Y = H. The obtained values of the cross-interaction constants (${\rho}_{XY}$) are all in spite of the biphasic free energy correlations for both substituent X and Y variations, since the ${\rho}_X$values with both the strongly and weakly basic pyridines are almost constant. A stepwise mechanism with a rate-limiting leaving group departure from the intermediate is proposed where the distance between X and Y does not vary from the intermediate to the second transition state. A frontside attack is proposed with the strongly basic pyridines based on the considerably great magnitudes of ${\rho}_X$ and ${\beta}_X$ values and a backside attack is proposed with the weakly basic pyridines based on the relatively small magnitudes of ${\rho}_X$ and ${\beta}_X$. The positive deviations of the two strong ${\pi}$-acceptor parasubstituents, X = 4-Ac and 4-CN, from both the Hammett and Bronsted plots are rationalized by the great extents of bond formation and breaking.

Pycnometric and Spectroscopic Studies of Red Phosphors Ca2+(1-1.5x)WO4:Eu3+x and Ca2+(1-2x)WO4:Eu3+x,Na+x

  • Cho, Seon-Woog
    • Bulletin of the Korean Chemical Society
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    • v.34 no.9
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    • pp.2769-2773
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    • 2013
  • Red phosphors $Ca_{(1-1.5x)}Eu_xWO_4$ and $Ca_{(1-2x)}Eu^_xNa_xWO_4$ were synthesized with various concentrations x of $Eu^{3+}$ ions by using a solid-state reaction method. The crystal structure of the red phosphors were found to be a tetragonal scheelite structure with space group $I4_1/a$. X-ray diffraction (XRD) results show the (112) main diffraction peak centered at $2{\theta}=28.71^{\circ}$, and indicate that there is no basic structural deformation caused by the vacancies ${V_{Ca}}^{{\prime}{\prime}}$ or the $Eu^{3+}$ (and $Na^+$) ions in the host crystals. Densities of $Ca_{(1-1.5x)}Eu_xWO_4$ were measured on a (helium) gas pycnometer. Comparative results between the experimental and theoretical densities reveal that $Eu^{3+}$ (and $Na^+$) ions replace the $Ca^{2+}$ ions in the host $CaWO_4$. Also, the photoluminescence (PL) emission and photoluminescence excitation (PLE) spectra show the optical properties of trivalent $Eu^{3+}$ ions, not of divalent $Eu^{2+}$. Raman spectra exhibit that, without showing any difference before and after the doping of activators to the host material $CaWO_4$, all the gerade normal modes occur at the identical frequencies with the same shapes and weaker intensities after the substitution. However, the FT-IR spectra show that some of the ungerade normal modes have shifted positions and different shapes, caused by different masses of $Eu^{3+}$ ions (or $Na^+$ ions, or ${V_{Ca}}^{{\prime}{\prime}}$ vacancies) from $Ca^{2+}$.

Effect of Ni dopant on the multiferroicity of BiFeO3 ceramic

  • Hwang, J.S.;Yoo, Y.J.;Kang, J.H.;Lee, K.H.;Lee, B.W.;Park, S.Y.;Lee, Y.P.
    • Proceedings of the Korean Vacuum Society Conference
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    • 2016.02a
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    • pp.139.1-139.1
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    • 2016
  • Multiferroic materials are of great interest because of its potential applications in the design of devices combining magnetic, electronic and optical functionalities. Among various multiferroic materials, $BiFeO_3$(BFO) is known to be one of the intensively focused mainly due to the possibility of multiferroism at device working temperature (> $200^{\circ}C$). However, leakage current and weak polarization resulting from oxygen deficiency and crystalline defect should be resolved. Furthermore the magnetic ordering of pure BFO mainly prefers to have antiferromagnetic coupling. Up to now many attempts have been performed to improve the ferromagnetic and the ferroelectric properties of BFO by doping. In this work, we investigated the effects of Ni substitution on the multiferroism of bulk BFO. Four BFO samples (a pure BFO and three Ni-doped BFO's; $BiFe_{0.99}Ni_{0.01}O_3$, $BiFe_{0.98}Ni_{0.02}O_3$ and $BiFe_{0.97}Ni_{0.03}O_3$) were synthesized by the standard solid-state reaction and rapid sintering technique. The XRD results reveal that Ni atoms are substituted into Fe-sites and give rise to phase transition of cubic to rhombohedal. By using vibrating sample magnetometer and standard ferroelectric tester, the multiferroic properties at room temperature were characterized. We found that the magnetic moment of Ni-doped BFO turned out to be maximized for 3% of Ni dopant.

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Associations between an MDM2 gene polymorphism and ulcerative colitis by ARMS-PCR

  • Doulabi, Mahsa Sadat Hashemi;Moghaddam, Reza Goleyjani;Salehzadeh, Ali
    • Genomics & Informatics
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    • v.18 no.1
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    • pp.9.1-9.5
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    • 2020
  • Ulcerative colitis is a form of inflammatory bowel disease characterized by chronic inflammation of the colon and rectum. The abnormal lesions in the digestive system caused by ulcerative colitis and intermittent colitis are of major clinical importance. MDM2 is a phospho-protein that functions as a ubiquitin ligase for p53. Recently, a T>G substitution in the promoter of the MDM2 gene (rs309) has been identified. In this case-control study, 174 ulcerative colitis biopsy samples and 82 control samples were collected from colonoscopy centers, hospitals, and clinics in Mazandaran and Gilan Provinces in Iran from October 2014 to May 2015. This MDM2 polymorphism was investigated in DNA samples (extracted from biopsy samples) by amplification-refractory mutation system polymerase chain reaction. The mean age of patients with ulcerative colitis was 46.5 years (range, 28 to 69 years) and that of control individuals was 45.3 years (range, 26 to 71 years). Seventy-eight patients (44.82%) were men and 96 (55.18%) were women. The distribution of the TT, TG, and GG genotypes was 17.93%, 27.59%, and 34.48%, respectively, in the ulcerative colitis patients and 31.70%, 24.40%, and 43.90%, respectively, in the control individuals (odds ratio of GG for ulcerative colitis, 7.142; 95% confidence interval, 2.400 to 9.542; p = 0.001). It was found that a single-nucleotide polymorphism at rs309 in the MDM2 gene was associated with ulcerative colitis. A direct relationship was found between age and ulcerative colitis, while no relationship was found with sex. This finding is of note because the occurrence of intestinal inflammation and subsequent ulcers can precede the development of cancer.

Preparation of High Range Water Reducer Containing Carboxylic Acid and Their Cement Absorptivity(I) (카르본산계 고성능감수제의 제조 및 그들의 시멘트 흡착성(I))

  • 김화중;강인규;김성훈;김우성;권영도
    • Magazine of the Korea Concrete Institute
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    • v.7 no.2
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    • pp.175-182
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    • 1995
  • Styrene-Maleic anhydride copolymer (SMA) was prepared by the radical copolmerization of styrene and maleic anhydride using ${\alpha}-{\alpha}'$ azobis(isobutyronitrile) as an initiatrr. SMA was further reacted with m-amino phenol to obtain aminophenol-substituted SMR (mSMA). Sulfonated SMA and mSMA were also prepared by the reaction of copolymers with sulfuric acid The copolyniers were characterized by infrared spectroscopy. It was found from the results of elemental analysis that the substitution degree of aminophenol in the mSMR is 44% and the degree is lowered to 35% after sulfonation. The percentage of copolymers adsorbed on the surface of cement particles was increased with a decrease of added copolymers. While, the arnourit of sulfonated SMA absorbed on the surface of cement particles was larger than that of the sulfonated mSMA The copolymers synthesized in this study are probably expected as a high range water reducer for coiicxte.

Synthesis and Characterization of Multi-Block Sulfonated Poly (Arylene Ether Sulfone) Polymer Membrane with Different Hydrophilic Moieties for PEMFC (서로 다른 친수성구조를 가지는 고분자전해질 연료전지용 멀티블록형 술폰산화 폴리아릴렌에테르술폰 전해질막의 합성 및 특성 분석)

  • Yuk, Jinok;Lee, Sojeong;Yang, Tae-Hyun;Bae, Byungchan
    • Journal of the Korean Electrochemical Society
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    • v.18 no.2
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    • pp.75-80
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    • 2015
  • Multi-block sulfonated poly(arylene ether sulfone) (SPAES) copolymer was synthesized via nucleophilic aromatic substitution reaction for proton exchange membrane fuel cell application. After synthesizing the hydrophilic and hydrophobic precursor oligomers having different end-groups (F-terminated or OH-terminated), the effect of end group on the molecular weight was investigated. Hydrophilic oligomers with hydroquinone showed better performance as fuel cell membranes. SPAES membranes showed comparable proton conductivity to that of Nafion at $80^{\circ}C$ and above 70% RH. In particular, SPAES 9 with hydroquinone showed higher proton conductivity than SPAES 10 in the whole RH range studied. Increased local concentration of sulfonic acids within hydrophilic block might develop the hydrophilic-hydrophobic phase separation in the block copolymers.

Photoaddition Reactions of Silyl Ketene Acetals with Aromatic Carbonyl Compounds: A New Procedure for β-Hydroxyester Synthesis

  • Yoon, Ung-Chan;Kim, Moon-Jung;Moon, Jae-Joon;Oh, Sun-Wha;Kim, Hyun-Jin;Mariano, Patrick S.
    • Bulletin of the Korean Chemical Society
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    • v.23 no.9
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    • pp.1218-1242
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    • 2002
  • Photochemical reactions of aromatic carbonyl compounds with silyl ketene acetals have been explored. Irradiation of acetonitrile or benzene solutions containing aryl aldehydes or ketones in the presence of silyl ketene acetals is observed to promo te formation of ${\beta}-hydroxyester$, 2,2-dioxyoxetane and 3,3-dioxyoxetane products. The ratios of these photoproducts, which arise by competitive single electron transfer (SET) and classical Paterno-Buchi mechanistic pathways, is found to be dependent on the degree of methyl-substitution on the vinyl moieties of the ketene acetals in a manner which reflects expected alkyl substituent effects on the oxidation potentials of these electron rich donors. An analysis of the product distribution arising by irradiation of a solution containing butyrophenone (6) and the silyl ketene acetal 9, derived from methyl isobutyrate, provides an estimate of the rate constants for the competitive Norrish type Ⅱ, SET and Paterno-Buchi processes occuring. Finally, sequences involving silyl ketene acetal-aryl aldehyde or ketone photoaddition followed by 2,2-dioxyoxetane hydrolysis represent useful procedures for Claisen-condensation type, ${\beta}-hydroxyester$ synthesis.

A Study on the U(VI), Ca(II) and Lu(III) Metal Ions Utilizing Nitrogen-Donator Synthetic Resin (질소-주게 합성수지를 이용한 U(VI), Ca(II) 및 Lu(III) 금속 이온들에 관한 연구)

  • 정만태
    • Journal of environmental and Sanitary engineering
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    • v.15 no.1
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    • pp.25-33
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    • 2000
  • The new ion exchange resin was synthesized from chloromethylated styrene-1,4-divinylbenzene(DVB) with 1-aza-15-crown-5 macrocyclic ligand by substitution reaction. The effect of pH, time, dielectric constant of solvent and cross-linked of the matrix on the adsorption for $UO_2^{2+}$, $Ca^{2}$ and $Lu^{3+}$ was investigated. The metal ion was not adsorbed on the resins below pH 3 but above pH 4 fast adsorption behavior was showed. The optimum equilibrium time for adsorption of metallic ions was two hours. The adsorption selectivity determined in ethanol matrix was in increasing order $UO_2^{2+}>Ca^{2}>Lu^{3+}$. The adsorption power was in the order of 1%, 2%, 10% and 20% -crosslinked resin, but adsorption properties of resins decreased in proportion to the order of dielectric constant of solvents used. In addition, these metal ions could be separated in the column packed with 1% crosslinked resin by pH2.5 $HNO_3$ as an eluent.

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