• 제목/요약/키워드: Hydrogen isotope

검색결과 149건 처리시간 0.051초

Evaluation of Flow and Transport Model in Integrated Surface and Subsurface Systems

  • 김성균;박영진;배광옥;이강근
    • 한국지하수토양환경학회:학술대회논문집
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    • 한국지하수토양환경학회 2005년도 총회 및 춘계학술발표회
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    • pp.324-327
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    • 2005
  • 지하수와 지표수를 연계하여 flow와 transport를 모의하는 프로그램인 HydroSphere를 Canada Ontario주의 Canadian Forces Base Borden에서의 실험 (Abdul ,1985) 자료를 이용하여 평가해 보았고, 유성지역 소유역에서의 강수, 지표수, 지하수의 수소동위원소 모니터링 (박준형, 고용권, 박경우, 정형재, 김교원, 2003) 자료를 이용하여 평가해 볼 예정이다.

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Kinetics and Mechanism of the Aminolysis of O-Methyl-S-Phenylthiocarbonates in Methanol

  • Song, Ho-Bong;Choi, Moon-Ho;Koo, In-Sun;Oh, Hyuck-Keun;Lee, Ik-choon
    • Bulletin of the Korean Chemical Society
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    • 제24권1호
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    • pp.91-94
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    • 2003
  • Kinetic studies of the reaction of O-methyl-S-phenylthiocarbonates with benzylamines in methanol at 45.0 ℃ have been carried out. The reaction proceeds by a stepwise mechanism in which the rate-determining step is the breakdown of the zwitterionic tetrahedral intermediate, $T^{\pm}$, with a hydrogen-bonded four-center type transition state (TS). These mechanistic conclusions are drawn based on (ⅰ) the large magnitude of ${\rho}_X\;and\;{\rho}_Z$, (ⅱ) the normal kinetic isotope effects $(k_H/k_D\;>\;1.0)$ involving deuterated benzylamine nucleophiles, (ⅲ) the positive sign of ${\rho}_{XZ}$ and the larger magnitude of ${\rho}_{XZ}$ than that for normal $S_N2$ processes, and lastly (ⅳ) adherence to the reactivity-selectivity principle (RSP) in all cases.

Nucleiphilic Substitution Reactions of Thiophenyl Dimethylacetates and Trimethylacetates wkth Benzylamines in Acetonitfile

  • 오혁근;박치열;이재문;이익춘
    • Bulletin of the Korean Chemical Society
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    • 제22권4호
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    • pp.383-387
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    • 2001
  • The kinetics and mechanism of the reactions of thiophenyl dimethylacetates (TDA) and trimethylacetates (TTA) with benzylamines in acetonitrile are studied. The reactions are first order in both the amine and the substrate. Relatively large values of ${\beta}X(\betanuc$ = 1.1-1.5; TDA and 1.1-1.5; TTA) and ${\beta}Z({\beta}lg$ = -1.8~-2.0; DTA and -1.3~-1.6; TTA) for benzylamines, significantly large kH/kD values (=1.2-1.5; DTA and 1.2-1.5; TTA) involving deuterated benzylamines, and large ${\rho}XZ$ (=0.82; TDA and 1.05; TTA) values are interpreted to indicate stepwise acyl transfer mechanism, but with the hydrogen bonded four center type transition state for benzylamine. The relatively greater magnitudes of ${\rho}XZ$ and the secondary kinetic isotope effects involving deuterated nucleophiles are in line with the proposed mechanism.

Kinetics and Mechanism of the Aminolysis of Thiophenyl Acetates in Acetonitrile

  • 오혁근;양진희;이해황;이익춘
    • Bulletin of the Korean Chemical Society
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    • 제20권12호
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    • pp.1418-1420
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    • 1999
  • Kinetics and mechanism of the aminolysis of Z-thiophenyl acetates with X-benzylamines are investigated in acetonitrile at 45.0 ℃. The magnitudes of Bronsted coefficients β$_x$ (=1.3~-1.6) and β$_z$ (= -2.1~-2.4) are all large and cross-interaction constant ρxz is relatively large and positive (0.90). These trends are consistent with the rate-limiting breakdown of a tetrahedral intermediate, $T^±$. The proposed mechanism is also supported by adherence of the rate data to the reactivity-selectivity principle (RSP). The kinetic isotope effects, $k_H/k_D$, are greater than unity (1.3-1.4) suggesting a possibility of hydrogen-bonded four-centered transition state. The activation parameters, ΔH$^≠$ and ΔS$^≠$, are consistent with this transition-state structure.

Kinetics and Mechanism of the Aminolysis of Phenylacetyl Chlorides in Acetonitrile

  • 이해황;이지원;고한중;이익천
    • Bulletin of the Korean Chemical Society
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    • 제19권6호
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    • pp.642-645
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    • 1998
  • The aminolysis reactions of phenylacetyl chlorides with anilines and N,N-dimethylanilines (DMAS) in acetonitrile at -15.0 ℃ are investigated. The magnitude of ρx (= -2.8 ∼ -2.9) and ρy (= 0.9 ∼ 1.3, after correcting for the fall-off), and the negative sign of ρxy (= -0.12) for the reactions with anilines suggest an associative SN2 mechanism. For the reactions with DMAs, the magnitude of these Hammett coefficients increases so that tighter bond making in the transition state (TS) is predicted. A nonlinear Hammett plots obtained for the DMAs with an electron acceptor substituent is interpreted to result from a more advanced degree of leaving group departure to assist closer approach of the bulky DMA in the TS. The normal secondary kinetic isotope effects $(k_H/k_D>1.0)$ involving deuterated anilines suggest partial deprotonation by hydrogen bonding to the departing chloride ion.

Kinetics and Mechanism of the Benzylaminolysis of O,O-Diphenyl S-Aryl Phosphorothioates in Dimethyl Sulfoxide

  • Adhikary, Keshab Kumar;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • 제32권5호
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    • pp.1625-1629
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    • 2011
  • Kinetic studies of the reactions of O,O-diphenyl Z-S-aryl phosphorothioates with X-benzylamines have been carried out in dimethyl sulfoxide at 55.0 $^{\circ}C$. The Hammett (log $k_2$ vs ${\sigma}_X$) and Bronsted [log $k_2$ vs $pK_a(X)$] plots for substituent X variations in the nucleophiles are biphasic concave downwards with a maximum point at X = H, and the unusual positive ${\rho}_X$ and negative ${\beta}_X$ values are obtained for the strongly basic benzylamines. The sign of the cross-interaction constant (${\rho}_{XZ}$) is negative for both the strongly and weakly basic nucleophiles. Greater magnitude of ${\rho}_{XZ}$ value is observed with the weakly basic nucleophiles (${\rho}_{XZ}$ = -2.35) compared to with the strongly basic nucleophiles (${\rho}_{XZ}$ = -0.03). The deuterium kinetic isotope effects ($k_H/k_D$) involving deuterated benzylamines [$XC_6H_4CH_2ND_2$] are primary normal ($k_H/k_D$ > 1). The proposed mechanism is a concerted $S_N2$ involving a frontside nucleophilic attack with a hydrogen bonded, four-center-type transition state for both the strongly and weakly basic nucleophiles. The unusual positive ${\rho}_X$ and negative ${\beta}_X$ values with the strongly basic benzylamines are rationalized by through-space interaction between the ${\pi}$-clouds of the electron-rich phenyl ring of benzylamine and the phenyl ring of the leaving group thiophenoxide.

Quantitative Speciation of Selenium in Human Blood Serum and Urine with AE- RP- and AF-HPLC-ICP/MS

  • Jeong, Ji-Sun;Lee, Jonghae;Pak, Yong-Nam
    • Bulletin of the Korean Chemical Society
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    • 제34권12호
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    • pp.3817-3824
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    • 2013
  • Various separation modes in HPLC, such as anion exchange (AE), reversed-phase (RP), and affinity (AF) chromatography were examined for the separation of selenium species in human blood serum and urine. While RP- and AE-HPLC were mainly used for the separation of small molecular selenium species, double column AF-HPLC achieved the separation of selenoproteins in blood serum efficiently. Further, the effluent of AF-HPLC was enzymatically hydrolyzed and then analyzed with RP HPLC for selenoamino acid study. The versatility of the hybrid technique makes the in-depth study of selenium species possible. For quantification, post column isotope dilution (ID) with $^{78}Se$ spike was performed. ORC ICP/MS (octapole reaction cell inductively coupled plasma/mass spectrometry) was used with 4 mL $min^{-1}$ Hydrogen as reaction gas. In urine sample, inorganic selenium and SeCys were identified. In blood serum, selenoproteins GPx, SelP and SeAlb were detected and quantified. The concentration for GPx, SelP and SeAlb was $22.8{\pm}3.4\;ng\;g^{-1}$, $45.2{\pm}1.7\;ng\;g^{-1}$, and $16.1{\pm}2.2\;ng\;g^{-1}$, respectively when $^{80}Se/^{78}Se$ was used. The sum of these selenoproteins ($84.1{\pm}4.4\;ng\;g^{-1}$) agrees well with the total selenium concentration measured with the ID method of $87.0{\pm}3.0\;ng\;g^{-1}$. Enzymatic hydrolysis of each selenium proteins revealed that SeCys is the major amino acid for all three proteins and SeMet is contained in SeAlb only.

무주지역 소유역내 지표수와 지하수의 안정동위원소 조성의 시공간적 변화 (Temporal and Spatial Variation of Stable Isotopic Compositions of Surface Water and Ground Water in a Small Catchment, Muju, Korea)

  • 한원식;우남칠;이광식;이기철
    • 자원환경지질
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    • 제36권5호
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    • pp.329-338
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    • 2003
  • 이 연구는 무주군 적상산 부근에 위치하는 소유역(100$Km^2$)에서 지표수와 천부 지하수의 안정동위원소 조성의 시공간적 변화를 조사하기 위해서 실시되었다. 시료채취는 2001년 8월(여름)과 10월(가을), 2002년 4월(봄), 3회에 걸쳐 실시되었다. 지표수의 동위원소 조성은 계절에 따라 뚜렷이 구분되어 도시되지만 천부 지하수에서는 이러한 변화가 줄어든 것이 관찰되었다. 하지만 지표수와 지하수의 안정동위원소 조성의 변화 폭은 계절별로 서로 유사하게 나타나고 있다. 이것은 이 지역에서 강수, 지표수 및 지하수 사이의 상호작용이 매우 활발하며 지속적으로 일어나고 있음을 의미한다. 무주지역 지표수의 안정동위원소 조성은 남쪽에 위치하는 섬진강의 조성보다는 가벼운 “위도효과”를 나타내고 있다. 또한 하천수에는 동위원소 조성의 계절변화와 아울러 강수의 “고도효과”와 “우량효과”가 잘 반영되어 있음이 관찰되었다.

18F 동위원소 피폭에 의한 금붕어 장관 평활근의 수축활성 (Contractile Activity of Goldfish Intestine Exposed to 18F Isotope)

  • 문경희;옥치일;조승일;이종규;길상형;서원찬;이병우;손희영;고혜진;박남규
    • 한국수산과학회지
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    • 제41권2호
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    • pp.89-93
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    • 2008
  • Goldfish were exposed to radioactive isotope $^{18}F$, which is used for positron emission tomography (PET). $^{18}F$ is created when the oxygen in water combines with hydrogen on exposure to positrons accelerated by a cyclotron. The temporal change in intestine contractility was measured by physiograph after the exposure to $^{18}F$. The distance between the goldfish and 580 mCi of $^{18}F$ was approximately 4 cm and the exposure was for 4 hrs. The absorption level calculated from the distance, exposure time, and half-life of $^{18}F$ was approximately 2 Gy. The contractile activity of goldfish intestine was lowest on the first day and increased gradually to 100% of the control level by a period of between 5 and 36 days.

만경-동진강 유역 지하수의 화학적 특성에 대한 농업용수 측면의 예비적 평가 (A Preliminary Assessment of Groundwater Chemistry for Agricultural Water Supply in the Mangyeong-Dongjin Watershed)

  • 최한나;권홍일;윤윤열;김용철;고동찬
    • 한국지하수토양환경학회지:지하수토양환경
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    • 제26권1호
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    • pp.65-75
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    • 2021
  • We investigated hydrochemical and stable isotope characteristics of groundwater in a large agricultural plain, the Honam plain, to evaluate the adequacy of agricultural water supply. For preliminary assessment for the area, we collected 23 groundwater samples from domestic wells and conducted hydrochemical and water stable isotope analysis. Groundwater in the study area is mainly Ca-HCO3 type resulting from water-rock interactions. Stable oxygen and hydrogen isotopic compositions indicated that recharge water is derived from precipitation while some sampling sites had evaporation signatures. Irrigation water quality using sodium absorption ratio and salinity hazard showed most of the groundwater samples were found to be suitable for irrigation. The groundwater in the southwestern part of the study area was affected by both seawater intrusion and agricultural activities, indicating a higher possibility of groundwater contamination near the coastal areas. Elevated concentrations of nitrate and phosphate ions in the groundwater are considered to be influenced by anthropogenic activities such as fertilizer application. It is expected that this study would be able to provide preliminary information on groundwater quality for agricultural water supply in the Mangyeong-Dongjin watershed.