• Bulletin of the Korean Chemical Society
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• v.32 no.spc8
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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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• v.19 no.8
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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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• v.22 no.5
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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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• v.19 no.6
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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.

• Analytical Science and Technology
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• v.8 no.4
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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.

• Proceedings of the Korean Environmental Sciences Society Conference
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• 2003.11a
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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.

• Analytical Science and Technology
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• v.7 no.2
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• pp.213-224
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• 1994

Several isotopomers of cyclooctanone were prepared by selective deuterium substitution. Intrinsic isotope effects on $^{13}C$ NMR chemical shifts of these isotopomers were investigated systematically at low temperature. These istope effects were discussed in relation to the preferred boat-chair conformation of cyclooctanone. Deuterium isotope effects on NMR chemical shifts have been known for a long time. Especially in a conformationally mobile molecule, isotope perturbation could affect NMR signals through a combination of isotope effects on equilibria and intrinsic effects. The distinction between intrinsic and nonintrinsic effects is quite difficult at ambient temperature due to involvement of both equilibrium and intrinsic isotope effects. However if equilibria between possible conformers of cyclooctanone are slowed down enough on the NMR time scale by lowering temperature, it should be possible to measure intrinsic isotope shifts from the separated signals at low temperature. $^{13}C$ NMR has been successfully utilized in the study on molecular conformation in solution when one deals with stable conformers or molecules were rapid interconversion occurs at ambient temperature. The study of dynamic processes in general requires analysis of spectra at several temperature. Anet et al. did $^1H$ NMR study of cyclooctanone at low temperature to freeze out a stable conformation, but were not able initially to deduce which conformation was stable because of the complexity of alkyl region in the $^1H$ NMR spectrum. They also reported the $^1H$ and $^{13}C$ NMR spectra of the $C_9-C_{16}$ cycloalkanones with changing temperature from $-80^{\circ}C$ to $-170^{\circ}C$, but they did not report a variable temperature $^{13}C$ NMR study of cyclooctanone. For the analysis of the intrinsic isotope effect with relation to cylooctanone conformation, $^{13}C$ NMR spectra are obtained in the present work at low temperatures (up to $-150^{\circ}C$) in order to find the chemical shifts at the temperature at which the dynamic process can be "frozen-out" on the NMR time scale and cyclooctanone can be observed as a stable conformation. Both the ring inversion and pseudorotational processes must be "frozen-out" in order to see separate resonances for all eight carbons in cyclooctanone. In contrast to $^1H$ spectra, slowing down just the ring inversion process has no apparent effects on the $^{13}C$ spectra because exchange of environments within the pairs of methylene carbons can still occur by the pseudorotational process. Several isotopomers of cyclooctanone were prepared by selective deuterium substitution (fig. 1) : complete deuterium labeling at C-2 and C-8 positions gave cyclooctanone-2, 2, 8, $8-D_4$ : complete labeling at C-2 and C-7 positions afforded the 2, 2, 7, $7-D_4$ isotopomer : di-deuteration at C-3 gave the 3, $3-D_2$ isotopomer : mono-deuteration provided cyclooctanone-2-D, 4-D and 5-D isotopomers : and partial deuteration on the C-2 and C-8 position, with a chiral and difunctional case catalyst, gave the trans-2, $8-D_2$ isotopomer. These isotopomer were investigated systematically in relation with cyclooctanone conformation and intrinsic isotope effects on $^{13}C$ NMR chemical shifts at low temperature. The determination of the intrinsic effects could help in the analysis of the more complex effects at higher temperature. For quantitative analysis of intrinsic isotope effects, the $^{13}C$ NMR spectrum has been obtained for a mixture of the labeled and unlabeled compounds because the signal separations are very small.

• Nuclear Engineering and Technology
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• v.51 no.5
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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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• v.51 no.6
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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.

• Journal of Life Science
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• v.8 no.4
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• pp.410-415
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• 1998

Procine pepsin hydrolysis of hexapeptide L-S-pNF-Nle-A-OMe in the presence of dipeptide L-L generates a new peak on HPLC analysis of reaction mixtures that is not seen when enzyme is incubated with either peptide alone. The peaks can be detected spectroscopically at either 214 or 254 nm, the latter consistent with a new peptide containing the p-nitro-F residue. The data suggest acyl transpeptidation between E(L-S-pNF) and L-L to form L-S-pNF-L-L. Consistent with this inference are (1) the ability of L-L-NH$_{2}$ and inability of Boc-L-L to undergo a similar transpeptidation reaction, and (2) the data from electrospray mass spectrum. This synthesis requires that Nle-A-L-OMe be released before L-S-pNF, an order opposite to that proposed on the basis of product inhibition kinetics. Consistent with this inference are reciprocal solvent isotope effects ; normal isotope effects of 1.736$\pm$0.121 on the formation of Nle-A-L-OMe and 2.281$\pm$0.184 in the formation of L-S-pNF, coupled to an inverse isotope effects of 0.576$\pm$0.045 on the formation of L-S-pNF-L-L. Because transpeptidation precedes faster in D$_{2}$O, the isotopically-sensitive step must occur after release of Nle-A-L-OMe. Isotopically-enhanced transpeptidation is consistent with the Uni-Bi iso memchanism postulated on the basis of an isotope effects on Vmax but not on Vmax/Km$^{1)}$ and confirmed by isotope effects on the onset of inhibition by pepstatin$^{2)}$.