• Title/Summary/Keyword: D2 isotope

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A Kinetic Study on Solvolysis of Diphenyl Thiophosphorochloridate

  • Koh, Han-Joong;Kang, Suk-Jin;Kevill, Dennis N.
    • Bulletin of the Korean Chemical Society
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    • v.30 no.2
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    • pp.383-388
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    • 2009
  • Rates of solvolyses of diphenyl thiophosphorochloridate ($(PhO)_2$PSCl, 1) in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone and 2,2,2-trifluoroethanol (TFE) are reported. For four representative solvents, studies were made at several temperatures and activation parameters were determined. The 30 solvents gave a reasonably precise extended Grunwald-Winstein plot, correlation coefficient (R) of 0.989. The sensitivity values (l = 1.29 and m = 0.64) of diphenyl thiophosphorochloridate ($(PhO)_2$PSCl, 1) were similar to those obtained for diphenyl phosphorochloridate ($(PhO)_2$POCl, 2), diphenylphosphinyl chloride ($Ph_2$POCl, 3) and diphenylthiophosphinyl chloride ($Ph_2$PSCl, 4). As with the previously studied of 3~4 solvolyses, an $S_N$ pathway is proposed for the solvolyses of diphenyl thiophosphorochloridate (1). The activation parameters, ${\Delta}H^{\neq}\;(=11.6{\sim}13.9\;kcal{\cdot}mol^{-1})\;and\;{\Delta}S^{\neq}\; (=\;-32.1\;{\sim}\;-42.7\;cal{\cdot}mol^{-1}{\cdot}K^{-1})$, were determined, and they were in line with values expected for an $S_N$2 reaction. The large kinetic solvent isotope effects (KSIE, 2.44 in MeOH/MeOD and 3.46 in $H_2O/D_2$O) are also well explained by the proposed $S_N$2 mechanism.

The Different Isotopic Signatures of Co-existing Zooplankton Species in Two Alpine Lakes (두 삼림호수에 공존하는 동물플랑크톤종의 다른 안정동위원소비)

  • Lee, Jae-Yong;Kim, Bom-Chul;Yoshioka, Takahito;Hino, Shuji
    • Korean Journal of Ecology and Environment
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    • v.41 no.3
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    • pp.294-300
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    • 2008
  • The stable isotopes ratios ($\delta^{13}C\;and\;\delta^{15}N$) of two coexisting species of zooplankton (Daphnia longispina and Acanthodiaptomus pacificus) and POM were determined in two alpine lakes in Japan. The difference of $\delta^{13}C$ between A. pacificus and D. longispina was 4.1$\pm$0.9‰ in Lake Shirakoma, which was larger than in Lake Panke. Whereas the difference of $\delta^{15}N$ between A. pacificus and D. longispina (2.6$\pm$0.8‰) was larger in Lake Panke than in Lake Shirakoma. $\delta^{13}C$ of POM (-26.6$\pm$1.2‰) in Lake Shirakoma was different from those of zooplankton; it was heavier than those of D. longispina and A. pacificus by 3.7$\pm$1.6‰ and 7.8$\pm$1.0‰, respectively. Whereas $\delta^{15}N$ of POM (2.0$\pm$0.8‰) was similar with those of both A. pacificus and D. longispina. This implies that the two lakes may have different trophic structure and food sources for zooplankton, and each species are grazing on selectively different components of POM. The temporal variation of $\delta^{13}C$ for each zooplankton species was associated with lipid contents of zooplankton in both lakes. The results showed that stable isotope composition of zooplankton can be an useful information for understanding energy pathways and trophic structures in lakes.

Allochthonous Organic Matter Contribution to Foodweb in Shingu Agricultural Researvoir after Rainfall Period (강우기 후 신구 농업용 저수지 먹이망에 미치는 외부기원 유기물의 영향 - 안정동위원소비 활용 -)

  • Kim, Min-Seob;Lee, Yeon-Jung;An, Kwang-Guk;Kim, Baik-Ho;Hwang, Soon-Jin;Shin, Kyung-Hoon
    • Korean Journal of Ecology and Environment
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    • v.47 no.1
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    • pp.53-61
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    • 2014
  • The origin of particulate organic matter (POM) and food web structure were investigated in Shingu reservoir based on stable isotope analysis from pre-monsoon (July) to post-monsoon (September) 2007. According to the depth in Shingu reservoir, the $^{13}C$ and $^{15}N$ values of POM for pre-monsoon period were nonsignificant distinction, while it was significant variation after rainfall period. The ${\delta}^{13}C$ values of POM in premonsoon period ranged from -25.1‰ to -26.1‰ in whole water column, but the ${\delta}^{13}C$ values of POM in post-monsoon period showed relatively wide range between -23.2‰ and -27.5‰. The apparently lighter values (average -27.5‰) in near bottom water (7 m water depth) demonstrate that POM in high turbid water in post-monsoon period may be derived from the outside terrestrial plants (allochthonous) through heavy rainfall during the summer monsoon period. After rainfall period, $^{13}C$ and $^{15}N$ values of D. brachyurum showed -23.3‰ and 12.2‰, respectively, while B. longirostris showed -27.1% and 8.7%, respectively. It suggested that D. brachyurum mainly feed on POM in autochthonous organic matter pool, but B. longirostris mainly consumed POM in allochthonous organic matter pool after rainfall period. Carbon and nitrogen stable isotope ratios were markedly different among secondary consumers. The carp (C. carpio) and catfish (S. asotus) were in the higher trophic level and crucian carp (C. auratus) and mudfish (M. mizolepis) were in the lower trophic level. $^{13}C$ and $^{15}N$ values of Z. platypus didn't significantly changed between before and after rainfall period. But P. parva and C. auratus apparently changed the $^{13}C$ and $^{15}N$ values after rainfall period. It is suggested that P. parva and C. auratus seem to feed allochthonous food source while Z. platypus depend on autochthonous food source.

NMR study of the interaction of T4 Endonuclease V with DNA

  • Lee, Bong-Jin;Im, Hoo-Kang;Hyungmi Lihm;Yu, Jun-Suk
    • Proceedings of the Korean Society of Applied Pharmacology
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    • 1995.04a
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    • pp.80-80
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    • 1995
  • T4 Endonuclease V (Mw 16,000) acts as a repair enzyme for UV induced pyrimidine dimers in DNA. Many researchers have studied the biochemical characteristics of the enzyme. However the precise action mechanism of T4 endo V has not fully elucidated yet. In our laboratory NMR spectroscopy technique is being used for the structural study of T4 endo V. Because of its low temperature stability and high content of ${\alpha}$-helix, the conventional $^1$H NMR technique was inapplicable. Therefore we utilized stable isotope labeling technique and so far prepared about 10 amino acid specific labeled proteins. The HSQC spectra of amino acid specific labeled proteins will help us to interpret the triple resonance 3D, 4D data which are under processing, We also studied the behaviors of specific amino acid residues whose roles might be critical. When the enzyme labeled by $\^$15/N-Thr was mixed with the substrate oligonucleotide (semispecific -TT- sequence), one crosspeak in its HSQC spectrum was completely desappeared, which means that one of seven Thr residues is in the binding site of the enzyme with DNA, This result is well consistent with previous report that implicated the Thr 2 residue in the activity of the enzyme. Similar studies were carried on the behaviors of Arg and Tyr residues.

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Diagnostics of Diffuse Two-Phase Matter Using Techniques of Positron Annihilation Spectroscopy in Gamma-Ray and Optical Spectra

  • Doikov, Dmytry;Yushchenko, Alexander;Jeong, Yeuncheol
    • Journal of Astronomy and Space Sciences
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    • v.36 no.3
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    • pp.115-119
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    • 2019
  • This paper is a part of the series on positron annihilation spectroscopy of two-phase diffuse gas-and-dust aggregates, such as interstellar medium and the young remnants of type II supernovae. The results obtained from prior studies were applied here to detect the relationship between the processes of the annihilation of the K-shell electrons and incident positrons, and the effects of these processes on the optical spectra of their respective atoms. Particular attention was paid to the Doppler broadening of their optical lines. The relationship between the atomic mass of the elements and the Doppler broadening, ${\Delta}{\lambda}_D$ (${\AA}$), of their emission lines as produced in these processes was established. This relationship is also illustrated for isotope sets of light elements, namely $^3_2He$, $^6_3Li$, $^7_3Be$, $^{10}_5B$ and $^{11}_5B$. A direct correlation between the ${\gamma}-line$ luminosity ( $E_{\gamma}=1.022MeV$) and ${\Delta}{\lambda}_D$ (${\AA}$) was proved virtually. Qualitative estimates of the structure of such lines depending on the positron velocity distribution function, f(E), were made. The results are presented in tabular form and can be used to set up the objectives of further studies on active galactic nuclei and young remnants of type II supernovae.

Kinetics and Mechanism of the Addition of Benzylamines to Benzylidene Meldrum's Acids in Acetonitrile

  • Oh, Hyuck-Keun;Kim, Tae-Soo;Lee, Hai-Whang;Lee, Ik-Choon
    • Bulletin of the Korean Chemical Society
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    • v.24 no.2
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    • pp.193-196
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    • 2003
  • Nucleophilic addition reactions of benzylamines $(XC_6H_4CH_2NH_2)$ to benzylidene Meldrum's acids (BMA; $YC_6H_4CH=C(COO)_2C(CH_3)_2$) have been investigated in acetonitrile at 20.0 ℃. The rates of addition are greatly enhanced due to the abnormally high acidity of Meldrum's acid. The magnitudes of the Hammett $({\rho}_X\;and\;{\rho}_Y)$ and Bronsted $({\rho}_X$)$ coefficients are rather small suggesting an early transition state. The sign and magnitude of the cross-interaction constant, ${\rho}_{XY}$ (= -0.33), and kinetic isotope effects $(k_H/k_D\;{\stackrel}{~}{=}\;1.5-1.7)$ involving deuterated benzylamine nucleophilies $(XC_6H_4CH_2ND_2)$ are indicative of hydrogen-bonded cyclic transition state. The activation parameters, ${\Delta}H^{\neq}\;{\stackrel}{~}{=}\;4\;kcal\;mol^{-1}\;and\;{\Delta}S^{\neq}\;{\stackrel}{~}{=}\;-37\;e.u.$, are also in line with the proposed mechanism.

Preliminary study on the use of near infrared spectroscopy for determination of plasma deuterium oxide in dairy cattle

  • Purnomoadi, Agung;Nonaka, Itoko;Higuchi, Kouji;Enishi, Osamu;Amari, Masahiro;Terada, Fuminori
    • Proceedings of the Korean Society of Near Infrared Spectroscopy Conference
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    • 2001.06a
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    • pp.4101-4101
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    • 2001
  • Information of body composition (fat and protein) in living animal is important to determine the nutrients requirement. Deuterium oxide (D2O) dilution techniques, as one of isotope dilution techniques have been useful for the prediction of body composition. However, the determination of D2O concentration is time consuming and complicated. Therefore this study was conducted to develop a new method to predict D2O concentration in plasma using near infrared spectroscopy technique (NIRS). Four dairy cows in early lactation were used. They were fed total mixed ration containing conr silage, timothy hay, and concentrates to make 17.0%CP and 14.0 MJDE/kgDM. Dosing D2O was at week 1,3 and 5 after parturition. After dosing D2O, the blood was collected from hour 0 to 72. Blood samples were then centrifuge at 3,000 rpm for 10 minutes to obtain plasma. D2O concentration was analyzed by gas chromatograph (deuterium oxide analyzable system, HK102, Shokotsusyou) after extracted from plasma by liophilization. Plasma sample was scanned by NIRS using Pacific Scientific (Neotec) model 6500 (Perstorp Analytical, Silver Spring, MD) in the range of wavelength from 1100 to 2500 nm. Calibration equation was developed using multiple linear regression. Sample from one animal (cow #550; n: 74) was used for developing the calibration while the rest three animals were used for validating the equation. The range, R and SEC of the calibration set samples were 135-925 ppm, 0.93 and 48.1 ppm, respectively. Validation of the calibration equation for three individual cows was done and the average of NIR predicted value of D2O at each collection time from three weeks injection showed a high correlation. The range, r and 53 of plasma from cow #474 were 322-840 ppm,0.93 and 53.1; cow #478 were 146-951 ppm,0.95 and 39.8; cow #942 were 313-885 ppm,0.95 and 37.2, respectively. Judgement of accuracy based on ratio of standard deviation and standard error in validation set samples (RPD) for cow #474, #478 and #942 were 2.2,4.3 and 3.4, respectively. The error in application due to the variation between individual was considered smaller than the bias from collection period, however, this prediction can be overcome with correction of standard zero-minute concentration of blood. The results of this preliminary study on the use of NIRS for determination of D2O in plasma showed very promising as shown by a convenient and satisfy accuracy. Further study on various physiological stage of animal should be done.

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Examination of lysine requirement of healthy young male adults on a Chinese habitual diet by the modified indicator amino acid oxidation method

  • Tian, Ying;Peng, Jing;Chen, Yu;Gong, Junjun;Xu, Huiqing
    • Nutrition Research and Practice
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    • v.8 no.1
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    • pp.59-65
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    • 2014
  • There is currently no reference for intake of lysine for Chinese people; therefore, the present study was conducted to determine the lysine requirement of Chinese young male adults on a habitual Chinese mixed diet based on the modified indicator amino acid oxidation method. Seven young men with a mean age of $23.7{\pm}2.2$ years that were healthy based on questionnaire, physical examinations and screening tests were evaluated. Subjects were evaluated over five consecutive 7 day periods, during which time they were administered decreasing amounts of lysine via the diet (65, 55, 45, 35, $25mg{\cdot}kg^{-1}{\cdot}d^{-1}$). Subjects were allowed to adapt from day 1 to 6 and the isotopes were measured on day 7 in each period. The subjects' body weights, body compositions and plasma proteins were also examined during the study. Amino acid kinetics were measured based on the indicator amino acid oxidation technique using the $^{13}CO_2$ release rate and phenylalanine oxidation rate to estimate lysine requirements. Body weights, body compositions, and plasma proteins of subjects did not change significantly relative to those at baseline. The mean and the upper 95% CI of lysine requirements of Chinese habitual diets were determined to be 58.41 and $70.09mg{\cdot}kg^{-1}{\cdot}d^{-1}$, respectively, based on the $^{13}CO_2$ release rate and 54.28 and $65.14mg{\cdot}kg^{-1}{\cdot}d^{-1}$, respectively, based on the phenylalanine oxidation rate.

Environmental Geochemistry and Contamination Assessment of the Tohyun Mine Creek, Korea (토현광산 수계의 환경지구화학적 특성과 오염도 평가)

  • 이찬희;이현구;이종창;전서령
    • Economic and Environmental Geology
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    • v.34 no.5
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    • pp.471-483
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    • 2001
  • The pH values of the mine and surface water from the Tohyun mine creek were higher compared with those of groundwater, and 2nd round samples in same sites were even alkaline. The stream and mine waters belong to the characteristics of (Ca+Mg)-(SO$_4$) and (Ca+Mg)-(HCO$_3$) types, and groundwaters have to the (Ca+Mg+Na+K)-(HCO$_3$+SO$_4$) type. As the 2nd samples. concentrations of mostly anions are increasing compared with the forder samples. However, the mostly cation concentrations are decreasing. The hydrogeochemistry indicate that water quality is different chemical characteristics and evolution trends. The range of $\delta$D and $\delta$$^{18}$ valutes (relative to SMOW) in the waters are shown in -62.2 to -70.1$\textperthousand$, and -8.1 to -9.4$\textperthousand$. The values are plowed parallel to $\delta$D=8$\delta$$^{18}$ O+ (6$\pm$4). The d values of groundwater show 2.4, which is lower than the surface (5.2) and mine (7.6) waters. Strontium concentra titans range from 0.025 to 11.844 mg/$\ell$ in all kinds of water samples, but the groundwater has the highest contents The $^{87}$ Sr/$^{86}$ Sr ratios (0.7115 to 0.7129) show more lightened to the groundwater. The $\delta$$^{18}$ O value, Ca and Sr contents are decreased with $^{87}$ Sr/$^{86}$ Sr increasing, because it is support to the altitude effects of the sampling sites rather than a water-rock interaction of environmental isotope. Using computer code of WATEQ4F, saturation indices of albite, Quartz, gibssite and gypsum are calculated to be soluble. The calcite and dolomite show super saturation state, however, clay mineral species are plotted boundary between undersaturation and supersaturation. In the Tohyun mine creek, reaction materials with ore wastes arid precipitation have influence upon increasing EC and TDS of the waters independent of pH. The SO$_4$ concentrations in the mine water is 181.845 mg/$\ell$. This is abruptly increase in surface water and then detected 249.727 mg/$\ell$ in the groundwater. As a results of the calculated sulfate mineral solubilities, the sulfate ions became saturation states an above 150 mg/$\ell$ concentrations.

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Analytic simulator and image generator of multiple-scattering Compton camera for prompt gamma ray imaging

  • Kim, Soo Mee
    • Biomedical Engineering Letters
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    • v.8 no.4
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    • pp.383-392
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    • 2018
  • For prompt gamma ray imaging for biomedical applications and environmental radiation monitoring, we propose herein a multiple-scattering Compton camera (MSCC). MSCC consists of three or more semiconductor layers with good energy resolution, and has potential for simultaneous detection and differentiation of multiple radio-isotopes based on the measured energies, as well as three-dimensional (3D) imaging of the radio-isotope distribution. In this study, we developed an analytic simulator and a 3D image generator for a MSCC, including the physical models of the radiation source emission and detection processes that can be utilized for geometry and performance prediction prior to the construction of a real system. The analytic simulator for a MSCC records coincidence detections of successive interactions in multiple detector layers. In the successive interaction processes, the emission direction of the incident gamma ray, the scattering angle, and the changed traveling path after the Compton scattering interaction in each detector, were determined by a conical surface uniform random number generator (RNG), and by a Klein-Nishina RNG. The 3D image generator has two functions: the recovery of the initial source energy spectrum and the 3D spatial distribution of the source. We evaluated the analytic simulator and image generator with two different energetic point radiation sources (Cs-137 and Co-60) and with an MSCC comprising three detector layers. The recovered initial energies of the incident radiations were well differentiated from the generated MSCC events. Correspondingly, we could obtain a multi-tracer image that combined the two differentiated images. The developed analytic simulator in this study emulated the randomness of the detection process of a multiple-scattering Compton camera, including the inherent degradation factors of the detectors, such as the limited spatial and energy resolutions. The Doppler-broadening effect owing to the momentum distribution of electrons in Compton scattering was not considered in the detection process because most interested isotopes for biomedical and environmental applications have high energies that are less sensitive to Doppler broadening. The analytic simulator and image generator for MSCC can be utilized to determine the optimal geometrical parameters, such as the distances between detectors and detector size, thus affecting the imaging performance of the Compton camera prior to the development of a real system.