• Bulletin of the Korean Chemical Society
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• 제32권spc8호
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• pp.3003-3008
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• 2011

Reactions of benzyl alcohol and its derivatives by [Ru$^{IV}$(tpy)(dcbpy)(O)]$^{2+}$ (tpy = 2,2':6',2"-terpyridine; dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) leading to the corresponding benzaldehydes in acetonitrile and water have been studied. Kinetic studies show that the reaction is first-order in both alcohol and oxidant, with k = 1.65 (${\pm}$ 0.1) $M^{-1}s^{-1}$ at $20^{\circ}C$, ${\Delta}H^{\ddag}$ = 4.3 (${\pm}$ 0.1) kcal/mol, ${\Delta}S^{\ddag}$ = -22 (${\pm}$ 1) eu, and $E_a$ = 4.9 (${\pm}$ 0.1) kcal/mol. High ${\alpha}$ C-H kinetic isotope effects are observed, but O-H solvent isotope effects are negligible. Spectral evidences with the isotope effects suggest that oxidation of benzyl alcohols occurs by a two-electron, hydride transfer. The catalytic cycles of aerobic benzyl alcohol oxidation are employed.

• Bulletin of the Korean Chemical Society
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• 제19권8호
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• pp.836-840
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• 1998

The intrinsic and equilibrium isotope effects on the 13C NMR chemical shift of the cyclooctanone-2-D were investigated. Equilibrium constants and changes in the free energies, enthalpy, entropy, which are derived from the temperature dependence of the isotope shifts, are reported for this isotopomer.

• Bulletin of the Korean Chemical Society
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• 제22권5호
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• pp.503-506
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• 2001

Separation of lithium isotopes was investigated by chemical ion exchange with a hydrous manganese(IV) oxide ion exchanger using an elution chromatography. The capacity of manganese(IV) oxide ion exchanger was 0.5 meq/g. One molar CH3COO Na solution was used as an eluent. The heavier isotope of lithium was enriched in the solution phase, while the lighter isotope was enriched in the ion exchanger phase. The separation factor was calculated according to the method of Glueckauf from the elution curve and isotopic assays. The single stage separation factor of lithium isotope pair fractionation was 1.021.

• Bulletin of the Korean Chemical Society
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• 제19권6호
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• pp.634-641
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• 1998

Quasiclassical trajectory calculations were carried out for the reactions of $H+H_2$ (V=O, J=O) and its isotope variants on the Siegbahn-Liu-Truhlar-Horowitz potential energy surface for the relative energies E between 6 and 150 kcal/mol. The goal of the work was to understand the inter- and intramolecular isotope effects. We examine the relative motion of reactants during the collision using the method of analysis that monitors the intermolecular properties (internuclear distances, geometry of reactants, and final product). As in other works, we find that the heavier the incoming atom is, the greater the reaction cross section is at the same collision energy. Using the method of analysis we prove that the intermolecular isotope effect is contributed mainly by differences in reorientation due to the different reduced masses. We show that above E=30 kcal/mol recrossing also contributes to the intermolecular isotope effect. For the intramolecular isotope effect in the reactions of H+HD and T+HD, we reach the same conclusions as in the systems of $O(^3P)+HD$, F+HD, and Cl+HD. That is, the intramolecular isotope effect below E=150 kcal/mol is contributed by reorientation, recrossing, and knockout type reactions.

• 분석과학
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• 제8권4호
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• pp.427-434
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• 1995

Inductively coupled plasma mass spectrometry combined with the isotope dilution method is used for the determination of lithium. The isotope dilution method is based on the addition of a known amount of enriched isotope (spike) to a sample. The analyte concentration is obtained by measuring the altered isotope ratio. The spike solution is calibrated through so called reverse isotope dilution with a primary standard. The spike calibration is an important step to minimize error in the determined concentration. It has been found essential to add spike to a sample and the primary standard so that the two isotope ratios should be as dose as possible. Since lithium is neither corrosive nor toxic, lithium is used as a chemical tracer in the nuclear power plants to measure feedwater flow rate. 99.9% $^7Li$ was injected into a feedwater line of an experimental system and sample were taken downstream to be spiked with 95% $^6Li$ for the isotope dilution measurements. Effects of uncertainties in the spike enrichment and isotope ratio measurement error at various spike-to-sample ratios are presented together with the flow rate measurement results in comparison with a vortex flow meter.

• 한국환경과학회:학술대회논문집
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• 한국환경과학회 2003년도 International Symposium on Clean Environment
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• pp.198-203
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• 2003

The effects of salmon carcasses on forest and stream ecosystems were determined by nitrogen stable isotope analysis in natural streams in Hokkaido, Northern Japan, where numerous chum salmon (Oncoryhncus keta) were migrated upstream ITom ocean to spawn in autumn. The leaves and soils surrounding riparian forest and stream dwelling invertebrates were collected before and after migration. The nitrogen stable isotope ratio $({\delta}^{15}N)$ of riparian vegetation (Salix spp.) were different depending on the presence of salmon and distance from the stream. The $({\delta}^{15}N)$ of stream dwelling invertebrates were different between salmon present and absent stream. This difference was tested using the experiment channel by implanting salmon carcasses. The nitrogen stable isotope ratio of epilithic algae and leaf shredding animals were nearly 3 higher in the salmon implanted treatment suggesting that around 20％ of salmon derived nitrogen was uptake either in algae and leaf shredding invertebrates. These results suggest that the salmon carcasses effects not only on stream primary production but also on primary consumers, which decompose leaves fertilized with nitrogen from carcasses.

• 분석과학
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• 제7권2호
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• pp.213-224
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• 1994

선택적으로 중수소를 치환시킨 싸이클로옥타논의 여러 동위원소 이성질체들을 합성하였다. 고유동위원소 효과에 의해 영향을 받는 $^{13}C$ NMR 화학적 이동값들을 각 이성질체에 대해 저온에서 계통적으로 관찰하였다. 특히 싸이클로옥타논이 선호하는 안정한 형태 이성질체인 클 boat-chair 형과 연관시켜 이 효과들을 논의하였다.

• Nuclear Engineering and Technology
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• 제51권5호
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• pp.1355-1364
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• 2019

A recently published nuclear forensics methodology for source discrimination of separated weapons-grade plutonium utilizes intra-element isotope ratios and a maximum likelihood formulation to identify the most likely source reactor-type, fuel burnup and time since irradiation of unknown material. Sensitivity studies performed here on the effects of random measurement error and the uncertainty in intra-element isotope ratio values show that different intra-element isotope ratios have disproportionate contributions to the determination of the reactor parameters. The methodology is robust to individual errors in measured intra-element isotope ratio values and even more so for uniform systematic errors due to competing effects on the predictions from the selected intra-element isotope ratios suite. For a unique sample-model pair, simulation uncertainties of up to 28% are acceptable without impeding successful source-reactor discrimination. However, for a generic sample with multiple plausible sources within the reactor library, uncertainties of 7% or less may be required. The results confirm the critical role of accurate reactor core physics, fuel burnup simulations and experimental measurements in the proposed methodology where increased simulation uncertainty is found to significantly affect the capability to discriminate between the reactors in the library.

• Journal of Applied Biological Chemistry
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• 제51권6호
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• pp.262-271
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• 2008

Natural abundances of stable isotopes of nitrogen and carbon (${\delta}^{15}N$ and ${\delta}^{13}C$) are being widely used to study N and C cycle processes in plant and soil systems. Variations in ${\delta}^{15}N$ of the soil and the plant reflect the potentially variable isotope signature of the external N sources and the isotope fractionation during the N cycle process. $N_2$ fixation and N fertilizer supply the nitrogen, whose ${\delta}^{15}N$ is close to 0%o, whereas the compost as. an organic input generally provides the nitrogen enriched in $^{15}N$ compared to the atmospheric $N_2$. The isotope fractionation during the N cycle process decreases the ${\delta}^{15}N$ of the substrate and increases the ${\delta}^{15}N$ of the product. N transformations such as N mineralization, nitrification, denitrification, assimilation, and the $NH_3$ volatilization have a specific isotope fractionation factor (${\alpha}$) for each N process. Variation in the ${\delta}^{13}C$ of plants reflects the photosynthetic type of plant, which affects the isotope fractionation during photosynthesis. The ${\delta}^{13}C$ of C3 plant is significantly lower than, whereas the ${\delta}^{13}C$ of C4 plant is similar to that of the atmospheric $CO_2$. Variation in the isotope fractionation of carbon and nitrogen can be observed under different environmental conditions. The effect of environmental factors on the stomatal conductance and the carboxylation rate affects the carbon isotope fractionation during photosynthesis. Changes in the environmental factors such as temperature and salt concentration affect the nitrogen isotope fractionation during the N cycle processes; however, the mechanism of variation in the nitrogen isotope fractionation has not been studied as much as that in the carbon isotope fractionation. Isotope fractionation factors of carbon and nitrogen could be the integrated factors for interpreting the effects of the environmental factors on plants and soils.

• 생명과학회지
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• 제8권4호
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• pp.410-415
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• 1998

HPLC 및 electrospary mass spectrum으로부터 L-L dipeptide의 존제하에서 pepsin은 hexapeptide인 L-S-pNF-Nle-A-OMe를 가수분해하여 가수분해물외의 새로운 생성물을 합성하는 것이 확인되었다. 이 생성물은 254nm에서 p-nitro-Phe 잔기를 포함하는 peptide였다. 실험결과로부터 E(L-S-pNF)와 L-L 사이의 acyl transpeptidation에 의해 L-S-pNF-L-L가 생성됨을 뒷받침한다. 이러한 transpeptidation 결과는 product 저해실험에 의한 결과에 기초한 것과는 반대로 L-S-pNF가 해리되기전에 Nle-A-L-OMe가 먼저 한다는 것을 보여준다. 그리고, electrospray mass spectrum 으로부터 위에서 검출된 새로운 펩티드에 해당하는 peak (MW 636.1)을 얻었는데, 이는 새 펩티드의 생성을 확실히 증명하는 증거이다. 한편, Nle-A-L-OMe 생성에 대한 solvent isotope effect는 1.736$\pm$0.121이며 L-S-pNF는 2.28$\pm$0.184 그리고 L-S-pNF-L-L의 생성에는 inverse isotope effect로서 0.576$\pm$0.045였는데, 이는 상기 생성물 해리 순서를 확인시켜 준다. D$_{2}$에서 transpeptidation은 더 빠르기 때문에 isotopically-sensitive단계는 Nle-A-L-OMe해리후에 존재하는 것을 알 수 있다. 본 실험결과는, Rebholz and Northrop$^{1)}$ 및 Cho등의 $^{2)} iso-mechanism이론의 타당성을 제시한다.