• Title/Summary/Keyword: Isotope effect

Search Result 242, Processing Time 0.032 seconds

Infrared Stimulated Luminescence (IRSL) Dating of a Tidal Flat, West Coast of Korea (적외선 여기 루미네센스를 이용한 조간대 퇴적층의 연대추정)

  • Choi, Man-Sik;Han, Jeong-Hee;Choi, Jeong-Heon;Cheong, Chang-Sik;Hong, Duk-Geun
    • The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
    • /
    • v.7 no.1
    • /
    • pp.1-7
    • /
    • 2002
  • Optical dating, using infrared stimulation of K-feldspar grains, was undertaken to determine the sedimentation rate of a recently deposited tidal flat on the western coast of Korea. Very low luminescence of the natural surface sample confirms that the materials we investigated were well bleached at deposition. The five IRSL ages obtained show a reasonable stratigraphic correlation with the expected sedimentation rate of approximately 50cm/100yr. In addition the recuperation effect due to thermal transfer was discussed. We conclude that the optical dating used here shows a great promise to determine the sedimentation rates of tidal flats.

Investigation on the Stability of Uric Acid and its Isotope (1,3-15N2) in Ammonium Hydroxide for the Absolute Quantification of Uric Acid in Human Serum

  • Lee, Sun Young;Kim, Kwonseong;Oh, Han Bin;Hong, Jongki;Kang, Dukjin
    • Mass Spectrometry Letters
    • /
    • v.8 no.3
    • /
    • pp.59-64
    • /
    • 2017
  • In clinical diagnosis, it's well known that the abnormal level of uric acid (UA) in human body is implicated in diverse human diseases, for instance, chronic heart failure, gouty arthritis, diabetes, and so on. As a primary method, an isotope dilution mass spectrometry (IDMS) has been used to obtain the accurate quantity of UA in blood or serum and also develop the certificated reference material (CRM) so as to provide a SI-traceability to clinical laboratories. Due to the low solubility of UA in water, an ammonium hydroxide ($NH_4OH$) has been considered as a promising solvent to increase the solubility of UA that enables the preparation of both UA and its isotope standard solution for next IDMS-based absolute quantification. But, because of using this $NH_4OH$ solvent, it gives rise to the unwanted degradation of UA. In this study, we sought to optimize condition for the stability of UA in $NH_4OH$ solution by varying the mole ratios of UA to $NH_4OH$, followed by ID-LC-MRM analysis. In addition, we also inspected minutely the effect of the storage temperatures. Additionally, we also performed the quantitative analysis of UA in the KRISS serum certificated reference material (CRM, 111-01-02A) with diverse mixing ratios of UA to $NH_4OH$ and then compared those values to its certification value. Based on our experiments, adjusting the mole ratio of 1/2 ($UA/NH_4OH$) with the storage temperature of $-20^{\circ}C$ is an effective way to secure both the solubility and stability of UA in $NH_4OH$ solution for next IDMS-based quantification of UA in serum.

Temporal Variations in Isotope Ratios and Concentrations of Nitrate-nitrogen in Groundwater as Affected by Chemical Fertilizer and Livestock Manure

  • Yoo, Sun-Ho;Choi, Woo-Jung;Han, Gwang Hyun;Park, Jung-Geun;Lee, Sang-Mo;Jin, Sheng-ai
    • Journal of Applied Biological Chemistry
    • /
    • v.42 no.4
    • /
    • pp.186-190
    • /
    • 1999
  • Isotope ratio ($^{15}N/^{14}N$) and nitrate-nitrogen concentration in groundwater were measured to investigate the effect of chemical fertilizer and livestock manure on temporal variations in nitrate-nitrogen concentration and to estimate the contribution of fertilizer and manure to groundwater contamination by nitrate. Four study wells from a rural area in Kyonggi province were selected. One well was located on an upper site from a livestock feedlot, and the others were situated at lower sites from the feedlot. The ${\delta}^{15}N$ values were analyzed by a stable isotope ratio mass spectrometer (Micromass, VG Optima IRMS). Reproducibility of the method and precision of the mass spectrometer were below 1.0 and 0.1‰, respectively Even though study wells were located at the same area, nitrate-nitrogen concentrations and ${\delta}^{15}N$ values differed and fluctuated during the sampling period. The ${\delta}^{15}N$ values of well located at upper site from the feedlot were extremely variable (-1.48~20.80‰). The ranges of ${\delta}^{15}N$ value of three wells situated at lower sites from the feedlot were 11.83~20.73 (ave. 16.11), 8.90~11.73 (ave.11.01), and 5.29~12.73‰ (ave. 8.21‰) with increasing distance from the feedlot. The average values of contribution proportion of nitrogen derived from livestock manure to nitrate-nitrogen in groundwater were 79% for the well closet to the feedlot, 44% for the well most distant from the feedlot, and 56% for the well in between the two wells.

  • PDF

Identification of Pitfalls Related to the Analysis of Liquid Chromatography-Tandem Mass Spectrometry and Liquid Chromatography-Time of Flight Mass Spectrometry (액체크로마토그래프-질량분석기를 이용한 정성 및 정량 오류의 확인)

  • Kwon, Jin-Wook;Cho, Yoon-Jae;Rhee, Gyu-Seek
    • Korean Journal of Environmental Agriculture
    • /
    • v.34 no.3
    • /
    • pp.230-237
    • /
    • 2015
  • BACKGROUND: To identify the sources of inaccuracy in LC/MS/MS methods used in the routine quantitation of small molecules are described and discussed. METHODS AND RESULTS: Various UPLC coupled to triple quadrupole mass spectrometer and time of flight (TOF) were used to identify the potential sources of inaccuracy and inducing the pitfalls of qualification and quntitation during the veterinary drug residue analysis. Some of stable isotope labelled veterinary drugs, which were used as internal standards, presented "cross-talk", regardless of manufactures of mass spectrometer and types of spectrometer. Group of sulfonamides also presented inaccuracy qualification and quantitation due to the multi-residue analytical method with the same fragment ions at the close retention times. CONCLUSION: The phenomena of "cross-talk" occurring between subsequently monitored transition from stable isotope labelled and isotope non-labelled authentic chemical were identified. To prevent errors and achieve more accurate data during the analysis of small molecules by LC/MS/MS SRM method, Followings should be taken care of and kept checking; purity and concentration of stable isotope as an internal standard, prevention of carry-over during the separation in column, minimizing the ion suppression by matrix effect, identification of retention time, precursor ion and product ion, and full knowledge of data processing including smoothing and peak integration.

Dual Substituent Effects on Anilinolysis of Bis(aryl) Chlorothiophosphates

  • Barai, Hasi Rani;Lee, Hai Whang
    • Bulletin of the Korean Chemical Society
    • /
    • v.34 no.12
    • /
    • pp.3597-3601
    • /
    • 2013
  • The reactions of bis(Y-aryl) chlorothiophosphates (1) with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at $55.0^{\circ}C$. The Hammett plots for substituent Y variations in the substrates show biphasic concave upwards with a break point at Y = H. The cross-interaction constants (${\rho}_{XY}$) are positive for both electron-donating and electron-withdrawing Y substituents. The kinetic results of 1 are compared with those of Y-aryl phenyl chlorothiophosphates (2). The cross-interaction between Y and Y, due to additional substituent Y, is significant enough to result in the change of the sign of ${\rho}_{XY}$ from negative with 2 to positive with 1. The effect of the cross-interaction between Y and Y on the rate changes from negative role with electron-donating Y substituents to positive role with electron-withdrawing Y substituents, resulting in biphasic concave upward free energy correlation with Y. A stepwise mechanism with a rate-limiting leaving group departure from the intermediate involving a predominant frontside attack hydrogen bonded, four-center-type transition state is proposed based on the positive sign of ${\rho}_{XY}$ and primary normal deuterium kinetic isotope effects.

[18F]FET PET is a useful tool for treatment evaluation and prognosis prediction of anti-angiogenic drug in an orthotopic glioblastoma mouse model

  • Kim, Ok-Sun;Park, Jang Woo;Lee, Eun Sang;Yoo, Ran Ji;Kim, Won-Il;Lee, Kyo Chul;Shim, Jae Hoon;Chung, Hye Kyung
    • Laboraroty Animal Research
    • /
    • v.34 no.4
    • /
    • pp.248-256
    • /
    • 2018
  • O-2-$^{18}F$-fluoroethyl-l-tyrosine ($[^{18}F]FET$) has been widely used for glioblastomas (GBM) in clinical practice, although evaluation of its applicability in non-clinical research is still lacking. The objective of this study was to examine the value of $[^{18}F]FET$ for treatment evaluation and prognosis prediction of anti-angiogenic drug in an orthotopic mouse model of GBM. Human U87MG cells were implanted into nude mice and then bevacizumab, a representative anti-angiogenic drug, was administered. We monitored the effect of anti-angiogenic agents using multiple imaging modalities, including bioluminescence imaging (BLI), magnetic resonance imaging (MRI), and positron emission tomography-computed tomography (PET/CT). Among these imaging methods analyzed, only $[^{18}F]FET$ uptake showed a statistically significant decrease in the treatment group compared to the control group (P=0.02 and P=0.03 at 5 and 20 mg/kg, respectively). This indicates that $[^{18}F]FET$ PET is a sensitive method to monitor the response of GBM bearing mice to anti-angiogenic drug. Moreover, $[^{18}F]FET$ uptake was confirmed to be a significant parameter for predicting the prognosis of anti-angiogenic drug (P=0.041 and P=0.007, on Days 7 and 12, respectively, on Pearson's correlation; P=0.048 and P=0.030, on Days 7 and 12, respectively, on Cox regression analysis). However, results of BLI or MRI were not significantly associated with survival time. In conclusion, this study suggests that $[^{18}F]FET$ PET imaging is a pertinent imaging modality for sensitive monitoring and accurate prediction of treatment response to anti-angiogenic agents in an orthotopic model of GBM.

A study of activity ratios of uranium isotope in the groundwater using liquid scintillation counter (액체섬광계수기를 이용한 지하수 내 우라늄 동위원소 측정법에 관한 연구)

  • Cho, Soo-Young;Song, Kyung-Sun;Lee, Kil-Yong;Yoon, Yoon-Yeol;Kim, Won-Baek;Ko, Kyung-Sok
    • Analytical Science and Technology
    • /
    • v.25 no.2
    • /
    • pp.146-151
    • /
    • 2012
  • An analytical method was developed for the measurement of uranium isotope in ground water using the liquid scintillation counting technique. A LKB Wallac Quantulus 1220 liquid scintillation counter (LSC) equipped with pulse shape analyzer (PSA) and a solvent extraction method were used for the measurement of uranium isotope in ground water samples. The effect of solution volume on the extraction efficiency was evaluated for 100 to 1000 mL solutions using a NIST standard reference material (NIST SRM 4321C). The effect of groundwater pH on the extraction efficiency was also investigated for pH ranging from 0.5 to 10. It was found that the extraction efficiency had a strong dependence on pH showing a maximum at pH 2. In contrast, the effect of groundwater volume on the extraction efficiency was negligible in the range investigated. According to the method, the extraction efficiency of uranium isotopes was near 96% and the lower detection limit for uranium was 0.018 Bq/L with the counting time of 300 min. The result of this study was also verified by the conventional ICP-MS measurement. It is demonstrated that the suggested method is valuable to the determination of the optimum extraction and measurement conditions for uranium in ground water. The method was successfully applied to the ground water at four locations near the Daejeon province. It was found that the uranium content and the isotopic ratio of $^{234}U/^{238}U$ at the locations ranged 0.59~6.69 Bq/L and 0.72~1.40, respectively.

Variation of Nitrate Concentrations and δ15N Values of Seawater in the Drake Passage, Antarctic Ocean (남극해 드레이크해협 해수의 질산염 농도와 질소동위원소 값의 변화)

  • Jang, Yang-Hee;Khim, Boo-Keun;Shin, Hyoung-Chul;Sigman, Daniel M.;Wang, Yi;Hong, Chang-Su
    • Ocean and Polar Research
    • /
    • v.30 no.4
    • /
    • pp.407-418
    • /
    • 2008
  • Seawater samples were collected at discrete depths from five stations across the polar front in the Drake Passage (Antarctic Ocean) by the $20^{th}$ Korea Antarctic Research Program in December, 2006. Nitrate concentrations of seawater increase with depth within the photic zone above the depth of Upper Circumpolar Deep Water (UCDW). In contrast, ${\delta}^{15}N$ values of seawater nitrate decrease with depth, showing a mirror image to the nitrate variation. Such a distinct vertical variation is mainly attributed to the degree of nitrate assimilation by phytoplankton as well as organic matter degradation of sinking particles within the surface layer. The preferential $^{14}{NO_3}^-$ assimilation by the phytoplankton causes $^{15}{NO_3}^-$ concentration to become high in a closedsystem surface-water environment during the primary production, whereas more $^{14}{NO_3}^-$ is added to the seawater during the degradation of sinking organic particles. The water-mass mixing seems to play an important role in the alteration of ${\delta}^{15}N$ values in the deep layer below the UCDW. Across the polar front, nitrate concentrations of surface seawater decrease and corresponding ${\delta}^{15}N$ values increase northward, which is likely due to the degree of nitrate utilization during the primary production. Based on the Rayleigh model, the calculated ${\varepsilon}$ (isotope effect of nitrate uptake) values between 4.0%o and 5.8%o were validated by the previously reported data, although the preformed ${\delta}^{15}{{NO_3}^-}_{initial}$ value of UCDW is important in the calculation of ${\varepsilon}$ values.

Solvolysis of 2-Thiophenesulfonyl Chloride (2-염화티오펜술포닐의 가용매 분해반응)

  • Jin-Chel Choi;Jieun Oh;Dae Ho Kang;In Sun Koo;Ikchoon Lee
    • Journal of the Korean Chemical Society
    • /
    • v.37 no.8
    • /
    • pp.695-701
    • /
    • 1993
  • Rate constants of solvolysis of 2-thiophenesulfonyl chloride were determined in aqueous binary mixtures with methanol, ethanol, acetone in water and in methanol. These data are interpreted using the equation of Grunwald-Winstein and Kivinen relationship. Also, kinetic solvent isotope effects in water and in methanol and product selectivities in alcohol-water mixtures were determined. Kinetic solvent isotope effect for hydrolysis of 2-thiopenesulfonyl chloride was 2.24 and 1.47 for methanol and water, respectively. Selectivity values for formation of ester relative to acid in ethanol-water mixtures show maximum S value. From kinetic solvent isotope effect in methanol and water, selectivity data in aqueous alcoholic solvents and solvent effects, it is proposed that the reaction channel favoured in low polarity solvents is general-base catalysis and/or is possibly addition elimination (S$_A$N) reaction pathway and in high polarity solvents iS S$_N$2 reaction mechanism.

  • PDF

Kinetics and Mechanism of the Anilinolysis of Diisopropyl Thiophosphinic Chloride in Acetonitrile

  • Ul Hoque, Md. Ehtesham;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
    • /
    • v.32 no.11
    • /
    • pp.3880-3886
    • /
    • 2011
  • The nucleophilic substitution reactions of diisopropyl thiophophinic chloride (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $65.0^{\circ}C$. The anilinolysis rate of 3 is rather slow to be rationalized by the conventional stereoelectronic effects. The obtained deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are secondary inverse ($k_H/k_D$ = 0.80-0.96). The anilinolyses of ten P=S systems in MeCN are reviewed on the basis of DKIEs and selectivity parameters to obtain systematic information on the DKIEs and mechanism for thiophosphoryl transfer reactions. The steric effects of the two ligands on reactivity, DKIEs, mechanism, and substituent effects of the nucleophile (X) on the DKIEs are discussed.