• Title/Summary/Keyword: reactivity

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A Kinetic Study on Aminolysis of 2-Pyridyl X-Substituted Benzoates: Effect of Changing Leaving Group from 4-Nitrophenolate to 2-Pyridinolate on Reactivity and Mechanism

  • Lee, Jong-Pal;Bae, Ae-Ri;Im, Li-Ra;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.31 no.12
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    • pp.3588-3592
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    • 2010
  • Second-order rate constants ($k_N$) have been measured spectrophotometrically for nucleophilic substitution reactions of 2-pyridyl X-substituted benzoates 8a-e with a series of alicyclic secondary amines in $H_2O$ at $25.0{\pm}0.1^{\circ}C$. The $k_N$ values for the reactions of 8a-e are slightly smaller than the corresponding reactions of 4-nitrophenyl X-substituted benzoates 1a-e (e.g., $kN^{1a-e}/k_N^{8a-e}$ = 1.1 ~ 3.1), although 2-pyridinolate in 8a-e is ca. 4.5 $pK_a$ units more basic than 4-nitrophenolate in 1a-e. The Br$\o$nsted-type plot for the aminolysis of 8c (X = H) is linear with $\beta_{nuc}$ = 0.77 and $R^2$ = 0.991 (Figure 1), which is typical for reactions reported previously to proceed through a stepwise mechanism with breakdown of a zwitterionic tetrahedral intermediate $T^{\pm}$ being the rate-determining step (RDS), e.g., aminolysis of 4-nitrophenyl benzoate 1c. The Hammett plot for the reactions of 8a-e with piperidine consists of two intersecting straight lines (Figure 2), i.e., $\rho$ = 1.71 for substrates possessing an electron-donating group (EDG) while $\rho$ = 0.86 for those bearing an electron-withdrawing group (EWG). Traditionally, such a nonlinear Hammett plot has been interpreted as a change in RDS upon changing substituent X in the benzoyl moiety. However, it has been proposed that the nonlinear Hammett is not due to a change in RDS since the corresponding Yukawa-Tsuno plot exhibits excellent linear correlation with $\rho$ = 0.85 and r = 0.62 ($R^2$ = 0.995, Figure 3). Stabilization of substrates 8a-e in the ground state has been concluded to be responsible for the nonlinear Hammett plot.

Synthesis of Polyester Polyols by Using Double Metal Cyanide Catalyst and Physical Properties of Polyurethanes Produced by the Polyols (이중금속시안염 촉매에 의한 폴리에스테르 폴리올 제조 및 이를 이용한 폴리우레탄의 물성)

  • Kim, In-Ki;Seo, Hyun-Sook;Ha, Chang-Sik;Park, Dae-Won;Kim, Il
    • Clean Technology
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    • v.14 no.1
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    • pp.29-34
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    • 2008
  • Copolymerizations of propylene oxide (PO) and phthalic anhydride (PA) have been performed in the presence of double metal cyanide (DMC) catalyst as a means of incorporating ester groups in the polyol backbone. DMC catalyst was effective for the copolymerization and the reactivity ratios measured by modified Kelen-$T{\ddot{u}}d{\ddot{o}}s$ equation were $r_1(PA)\;=\;0$, and $r^2(PO)\;=\;0.248$. Four different Polyol samples containing 1.0, 2.1, 7.52, and 11.42 mol% of PA unit were utilized for the synthesis of thermoplastic polyurethanes of their hard segments of 19 wt%. As the incorporated amount of PA increases, the elongation of the resulting polyurethane decreases and the tensile strength and the tensile modulus increase. The modulation of the incorporated amount of PA into polyol backbone was proven to be a feasible way to tune the physical properties of polyurethanes.

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Physiologic state and behavioral response to sponge bathing in premature infants (스폰지 목욕에 대한 미숙아의 생리적상태 및 행동반응)

  • Lee Hae Kyung;Hong Kyung Ja;Nam Eun Sook;Lee Young Hee;Jung Eun Ja
    • Child Health Nursing Research
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    • v.6 no.1
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    • pp.32-50
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    • 2000
  • A descriptive exploratory design was used in this study to evaluate the effects of sponge bathing on physiological(heart rate, heart period, vagal tone, oxygen saturation, respiration) and behavioral responses in newly born 40 preterm infants from intensive care unit of S University Hospital in Seoul. Data has been collected from October, 1997 to March, 1999. The infants were between 27-33 weeks gestational age at birth, and were free of congenital defects. The subjects entered the protocol when they were medically stable (determined by initiation of feeding and discontinuation of all respiratory support) but still receiving neonatal intensive care. The infants' physiologic parameters were recorded a 10 - minute before, during, and after bathing. Continuous heart rate data were recorded on a notebook computer from the infant's EKG monitor. The data were digitized off-line on software(developed by Lee and Chang in Wavelet program) which detected the peak of the R wave for each heart beat and quantified sequential R-R intervals in msec(i.e. heart periods). Heart period data were edited to remove movement artifact. Heart period data were quantified as : 1) mean heart period; 2) vagal tone. Vagal tone was quantitfied with a noninvasive measure developed by Porges(1985) in Mxedit software. To determine behavioral status, tools were developed by Scafidi et al(1990) were used. Collected data were analyzed with the SPSS program using paried t-test, ANOVA, and Pearson correlation. The result were as follow. 1. The results of the ANOVAs indicated that vagal tone were signifcantly lower during bathing than baseline and post-bathing. There were significant differences in heart period and heart rate levels across the bathing. But the mean oxygen saturations and respirations were no differences. Also, there were no significant differences on behavioral sign, motor activity, behavioral distress, weight changes, morbidity, and hospitalization period. 2. To evaluate the relation between vagal tone and subsequent parameters, the two groups (the high group had 19 subjects and low group had 21subjects) were divided by the mean baseline vagal tone. Vagal tone measured prior to bathing were significantly associated with respiration before bathing, vagal tone during bathing, and the magnitude of change in both vagal tone. But, other subsequent reactivities were no differences in two groups. 3. Correlations were also calculated between vagal tone and the subsequent physiological reactivities from baseline through after- bathing. Correlations were significant between baseline vagal tone and baseline heart rate, between baseline vagal tone and baseline heart period, between baseline vagal tone and oxygen saturation after bathing. In summary, the bathing in this study showed a stressful stimulus on premature infants through there was significance in the physiological parameters. In addition, our study represents the documentation that vagal tone reactivity in response to clearly defined external stimulation provides an index of infant's status.

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The Study on development of a SAW SO$_2$ gas sensor (표면탄성파를 이용한 아황산 가스센서 개발에 관한 연구)

  • Lee, Young-Jin;Kim, Hak-Bong;Roh, Yong-Rae;Cho, Hyun-Min;Baik, Sung;,
    • The Journal of the Acoustical Society of Korea
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    • v.16 no.2
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    • pp.89-94
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    • 1997
  • A new type SO$_2$ gas sensor with a particular inorganic thin film on SAW devices was developed. The sensor consisted of twin SAW oscillators of the center frequency of 54 MHz fabricated on the LiTaO$_3$ piezoelectric single crystal. One delay line of the sensor was coated with a CdS thin film that selectively adsorbed and desorbed SO$_2$, while the other was uncoated for use as a stable reference. Deposition of the CdS thin film was carried out by the spray pyrolysis method using an ultrasonic nozzle. The sensor could measure the concentration in air less than 0.25 parts per million of SO$_2$. Stability of the sensor turned out to be as good as less than 20ppm, recovery time after each measurement was as short as 5 minutes. Repeatability of the measurement was confirmed through so many reiterated experiments. Hence, the SAW sensor developed through this work showed promising performance as a microsensing tool of SO$_2$. Further work required to improve the performance of the sensor includes enhancement of the reactivity of the CdS thin film with SO$_2$ through appropriate dopant addition, an increase of the center frequency of the SAW device.

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INNOVATIVE CONCEPT FOR AN ULTRA-SMALL NUCLEAR THERMAL ROCKET UTILIZING A NEW MODERATED REACTOR

  • NAM, SEUNG HYUN;VENNERI, PAOLO;KIM, YONGHEE;LEE, JEONG IK;CHANG, SOON HEUNG;JEONG, YONG HOON
    • Nuclear Engineering and Technology
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    • v.47 no.6
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    • pp.678-699
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    • 2015
  • Although the harsh space environment imposes many severe challenges to space pioneers, space exploration is a realistic and profitable goal for long-term humanity survival. One of the viable and promising options to overcome the harsh environment of space is nuclear propulsion. Particularly, the Nuclear Thermal Rocket (NTR) is a leading candidate for nearterm human missions to Mars and beyond due to its relatively high thrust and efficiency. Traditional NTR designs use typically high power reactors with fast or epithermal neutron spectrums to simplify core design and to maximize thrust. In parallel there are a series of new NTR designs with lower thrust and higher efficiency, designed to enhance mission versatility and safety through the use of redundant engines (when used in a clustered engine arrangement) for future commercialization. This paper proposes a new NTR design of the second design philosophy, Korea Advanced NUclear Thermal Engine Rocket (KANUTER), for future space applications. The KANUTER consists of an Extremely High Temperature Gas cooled Reactor (EHTGR) utilizing hydrogen propellant, a propulsion system, and an optional electricity generation system to provide propulsion as well as electricity generation. The innovatively small engine has the characteristics of high efficiency, being compact and lightweight, and bimodal capability. The notable characteristics result from the moderated EHTGR design, uniquely utilizing the integrated fuel element with an ultra heat-resistant carbide fuel, an efficient metal hydride moderator, protectively cooling channels and an individual pressure tube in an all-in-one package. The EHTGR can be bimodally operated in a propulsion mode of $100MW_{th}$ and an electricity generation mode of $100MW_{th}$, equipped with a dynamic energy conversion system. To investigate the design features of the new reactor and to estimate referential engine performance, a preliminary design study in terms of neutronics and thermohydraulics was carried out. The result indicates that the innovative design has great potential for high propellant efficiency and thrust-to-weight of engine ratio, compared with the existing NTR designs. However, the build-up of fission products in fuel has a significant impact on the bimodal operation of the moderated reactor such as xenon-induced dead time. This issue can be overcome by building in excess reactivity and control margin for the reactor design.

Enhanced Properties of Epoxy Molding Compound by Plasma Polymerization Coating of Silica (실리카의 플라즈마 중합 코팅에 의한 에폭시 봉지재의 물성 향상 연구)

  • Roh, J.H.;Lee, J.H.;Yoon, T.H.
    • Journal of Adhesion and Interface
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    • v.2 no.2
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    • pp.1-10
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    • 2001
  • Silica for Epoxy Molding Compound (EMC) was coated via plasma-polymerization with RF plasma (13.56 MHz) as a function of treatment time, power and pressure. 1,3-diaminopropane, allylamine, pyrrole, 1,2-epoxy-5-hexene, allylmercaptan or allylalcohol were utilized for plasma polymerization coating and adhesion of coated silica was evaluated by measuring flexural strength. CTE and water absorption of EMC were also measured, and fracture surface of flexural specimen was analyzed by SEM in order to elucidate the failure mode. The plasma polymer coated silica was analyzed by FT-IR and reactivity of plasma polymer coating with epoxy resin was evaluated with DSC in order to investigate the adhesion mechanism. The EMC prepared from the silica coated with 1,3-diaminopropane or allylamine exhibited high flexural strength, low CTE, and low water absorption compared with the control sample, and also exhibited 100% cohesive failure mode. These results can be attributed to the chemical reaction between the functional groups in the plasma polymer coating and epoxy resin, and also consistent with the results from FT-IR and DSC analysis.

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Preparation and Stability of Silyl Adlayers on 2×1-Reconstructed and Modified Si(100) Surfaces (Si(100)-2×1 표면과 개질된 Si(100) 표면 상에서 실릴 (Silyl) 흡착충의 형성과 안정성)

  • Jo, Sam-K.
    • Journal of the Korean Vacuum Society
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    • v.18 no.1
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    • pp.15-23
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    • 2009
  • Saturation-coverage silyl, $-SiH_3(a)$, overlayers were prepared from $Si_2H_6$ adsorption on three comparative surfaces: clean unmodified; D-precovered; and atomically roughened Si(100). Together with its precursor-mediated adsorption behavior, the surface reactivity of $Si_2H_6$ was found to be the highest on the unmodified Si(100)-$2{\times}1$ surface. This was correlated with its dissociative adsorption mechanism, in which both the $H_3Si-SiH_3$ bond scission and the dual surface $Si-SiH_3(a)$ bond formation require a surface dangling bond 'pair'. The unusually high thermal stability of $-SiH_3(a)$ on the unmodified surface was ascribed to a nearly close-packed $-SiH_3(a)$ coverage of ${\sim}0.9$ monolayer and the consequent lack of dangling bonds on the silyl-packed surface.

Development of Sandwich ELISA for the Detection of Mackerel in Processed Foods (가공식품 중 고등어의 검출을 위한 ELISA의 개발)

  • Shon, Dong-Hwa;Kim, Mi-Hye
    • Korean Journal of Food Science and Technology
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    • v.44 no.1
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    • pp.1-7
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    • 2012
  • There have been few studies related to ELISA for mackerel. In this study we developed a sandwich ELISA for mackerel in processed foods using rabbit polyclonal antibodies against mackerel parvalbumin, the major allergen of mackerel and heat-stable protein. The parvalbumin was purified by ammonium sulfate precipitation and Sephadex G-50 column chromatography. From the standard ELISA curves, the detection limit of parvalbumin was 3 ng/mL and the detection range of mackerel was 5-5,000 ${mu}g/mL$. We further investigated the cross-reactivity of the antibodies toward mackerel, mackerel pike, salmon, flatfish, armorclad rockfish, cod fish, squid, shrimp, blue crab, and lobster. The antibodies were specific for mackerel only. The mean assay recoveries in cooked cream soup, baby food, sausage, and sauce spiked with 0.01 to 0.3% mackerel were 104, 101, 54, and 0%, respectively. In sample tests of 16 commercial items, the qualitative coincidence ratio of assay result and indication was 75%.

Detection of Peanuts in Commercially Processed Foods by an Enzyme-Linked Fluorescent Immunoassay (Enzyme-linked fluorescent immunoassay에 의한 가공식품 중 땅콩의 검출)

  • Kim, Mi-Hye;Kim, Hyun-Jung;Shon, Dong-Hwa
    • Korean Journal of Food Science and Technology
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    • v.41 no.1
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    • pp.111-115
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    • 2009
  • In this study we analysed for peanuts in processed foods using an enzyme-linked fluorescent immunoassay (ELFA), and compared the results with labeled ingredients. Crude peanut protein (CPP) was immunized into rabbits to produce specific antibodies(Ab). A sandwich ELFA was established using anti-CPP Ab and Ab-horseradish peroxidase (HRP) conjugate. The cross-reactivities of the Ab toward CPP, peanuts, almonds, soybeans, and walnuts were 100, 9.8, $1.1{\times}10^{-2},\;4.4{\times}10^{-3}$, and 0%, respectively. The samples included 19 items consisting of biscuits, snacks, chocolates, and so on. The results from the sandwich ELFA showed that peanuts were contained in 7 of the processed food items, among which, 5 items were labeled as having peanuts present but 2 items were not. One of the 2 items that was peanut-detected but unlabeled was a biscuit labeled to contain almonds and assayed to contain $2.1{\times}10^{-3}%$ peanuts, which might have been due to the weak cross-reactivity of the Ab toward almonds. The other item was a snack labeled to contain soybeans and assayed to contain 0.098% peanuts, which might have been due to peanut cross-contamination during processing, since the crossreactivity of the Ab toward soybeans was very weak. These results suggest that ELFA is a good tool to detect peanuts in processed foods, and allergens in certain processed foods should be labeled correctly.

Quality Evaluation of the High-purity Limestones for Lime Manufacturing Based on the Measurements of Shape Factor and Grain Boundary Frequency (형상계수 및 경계빈도수 측정에 의거한 생석회 제조용 고품위석회석의 품질 평가)

  • Noh, Jin-Hwan;Lee, Hyun-Chul
    • Journal of the Mineralogical Society of Korea
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    • v.22 no.4
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    • pp.371-383
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    • 2009
  • Crystallinity and textural relations, which are crucial in terms of the quality concept of high-purity limestone, have not been effectively applicable to the limestone evaluation as crude ore due to the difficulties in precise measurements. To overcome the above, as a new method of ore characterization, a measurement of shape factor and grain boundary frequency utilizing the image analysing system was adopted in this study. Some domestic limestones used for lime manufacturing were investigated by such a quality evaluation method, and its results are discussed and correlated each other samples. As the result, even though calcite contents of crude ore, i.e., limestone grade and its crystal size are similar, quality of manufactured lime is remarkably different depending on the degree of shape factor and grain boundary frequency. In other words, as the more irregular in crystal shape and the higher the grain boundary frequency, the manufactured quick lime became more superior in all terms of lime quality such as rate of calcination, porosity, reactivity, sintering and decrepitation effect. However, because the quick lime become easily overheated in case of relatively higher degree in shape factor and grain boundary effect, a technology minimizing heating time is necessary for the manufacturing of high quality lime. In limestone industry, such a ore characterization method will be much more reasonable than the conventional method by measurement of mean size, because the method may collectively comprise crystal shape and other textural factors which can not be numerically evaluated in the past.