• 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.

• 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.

• 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.

• Mass Spectrometry Letters
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• v.2 no.2
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• pp.37-40
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• 2011

Saccharin is a commonly used artificial sweetener in foodstuffs. However, for its carcinogenic dispute, it has been regulated by government bodies. In this study, isotope dilution mass spectrometry (ID-MS) was introduced for the accurate quantification of saccharin. To employ ID-LC/MS, we obtained its isotope analogue, $^{13}C_1$-sodium saccharin, by customized synthesis. Samples were spiked with $^{13}C_1$-sodium saccharin and analyzed with LC/MS in negative mode. Chromatographic conditions were optimized for the adequate chromatographic retention and separation of saccharin with a $C_{18}$ column. MS was operated with electrospray ionization by the selected ion monitoring (SIM) mode of $[M-H]^-$ for saccharin (m/z 182) and $[M-Na]^-$ for its isotope analogue (m/z 183). To validate the ID-LC/MS method for accurate measurement, we prepared a batch of a candidate material by sortifying quasi-tea-drinks with saccharin and analyzed samples gravimetrically fortified in various levels of concentration. The repeatability and reproducibility of this method was tested by analyzing the reference material. Result show that ID-LC/MS is a reliable method for the quantitative analysis of saccharin.

• ALGAE
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• v.32 no.4
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• pp.349-357
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• 2017

Korean mariculture Undaria pinnatifida was collected during the months of January, February, March, and December of 2010, as well as from January of 2011 to investigate the changes in the carbon and nitrogen stable isotope ratios (${\delta}^{13}C$ and ${\delta}^{15}N$) and heavy metal with respect to it growth and to identify the factors that influence such changes. The blades of U. pinnatifida showed ${\delta}^{13}C$ and ${\delta}^{15}N$ in the range (mean) of -13.11 to -19.42‰ (-16.93‰) and 2.99 to 7.57‰ (4.71‰), respectively. Among samples with the same grow-out period, those that weighed more tended to have higher ${\delta}^{13}C$ suggesting a close association between the carbon isotope ratio and growth rate of U. pinnatifida. Indeed, we found a very high positive linear correlation between the monthly average ${\delta}^{13}C$ and the absolute growth rate in weight ($r^2=0.89$). Nitrogen isotope ratio tended to be relatively lower when nitrogen content in the blade was higher, probably due to the strengthening of isotope fractionation stemming from plenty of nitrogen in the surrounding environment. In fact, a negative linear correlation was observed with the nitrate concentration in the nearby seawaters ($r^2=0.83$). Concentrations of Cu, Cd, Pb, Cr, Hg, and Fe in the blades showed a rapid decrease in their concentration per unit weight in the more mature U. pinnatifida. Specifically, compared to adult samples, Cu, Hg, and Pb were concentrated by 30, 55, and 73 folds, respectively, in the young blades. Therefore, U. pinnatifida tissue ${\delta}^{13}C$ is as an indirect indicator of its growth rate, while ${\delta}^{15}N$ values and heavy metal concentrations serve as tracers that reflect the environmental characteristics.

• Journal of Ginseng Research
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• v.41 no.2
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• pp.195-200
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• 2017

Background: The natural ratios of carbon (C), nitrogen (N), and sulfur (S) stable isotopes can be varied in some specific living organisms owing to various isotopic fractionation processes in nature. Therefore, the analysis of C, N, and S stable isotope ratios in ginseng can provide a feasible method for determining ginseng authenticity depending on the cultivation land and type of fertilizer. Methods: C, N, and S stable isotope composition in 6-yr-old ginseng roots (Jagyeongjong variety) was measured by isotope ratio mass spectrometry. Results: The type of cultivation land and organic fertilizers affected the C, N, and S stable isotope ratio in ginseng (p < 0.05). The ${\delta}^{15}N_{AIR}$ and ${\delta}^{34}S_{VCDT}$ values in ginseng roots more significantly discriminated the cultivation land and type of organic fertilizers in ginseng cultivation than the ${\delta}^{13}C_{VPDB}$ value. The combination of ${\delta}^{13}C_{VPDB}$, ${\delta}^{15}N_{AIR}$, or ${\delta}^{34}S_{VCDT}$ in ginseng, except the combination ${\delta}^{13}C_{VPDB}-^{34}S_{VCDT}$, showed a better discrimination depending on soil type or fertilizer type. Conclusion: This case study provides preliminary results about the variation of C, N, and S isotope composition in ginseng according to the cultivation soil type and organic fertilizer type. Hence, our findings are potentially applicable to evaluate ginseng authenticity depending on cultivation conditions.

• Journal of the korean society of oceanography
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• v.32 no.1
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• pp.28-37
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• 1997

Two marine bivalve shells were collected from the eastern and western coastal regions of Korea, respectively. Stable oxygen and carbon isotope profiles are constructed using the incremental sampling along the axis of maximum growth to provide the continuous ${\delta}^{18}$O and ${\delta}^{13}$C records, which register the physical, biological and chemical properties of seawater where the organisms live. Cycles in the ${\delta}^{18}$O profiles are interpreted as annual along with the identification of annual growth bands; the maximum ${\delta}^{18}$O values correspond with the coldest temperature of seawater whereas the minimum ${\delta}^{18}$O values with the warmest temperature. The primary control on the amplitude of the ${\delta}^{18}$O profiles is seasonal variation of seawater temperature. The offset of the baseline between ${\delta}^{18}$O values of the two specimens is attributed to differences in both temperature and seawater ${\delta}^{18}$O values between two localities. The ${\delta}^{13}$C profiles show the similar seasonality of carbon cycling associated with phytoplankton productivity. The offset in the ${\delta}^{13}$C profiles between two specimens may be, as in the case of oxygen isotope profile, attributed to the different ${\delta}^{13}$C value of the seawater DIC (dissolved inorganic carbon) between the western coast and the eastern coast. Relationships between the shell isotopic composition and the coastal water properties of shell growth are readily interpreted from the ${\delta}^{18}$O-${\delta}^{13}$C pair diagram of the shell isotope data, similar to the use of salinity-${\delta}^{18}$O diagram for identifying water masses. The preliminary stable isotope results of this study suggest that mollusk shell isotope geochemistry may be useful to monitor the properties of water masses in the coastal and inner shelf setting around Korea and improve the interpretation of paleoceanography, provided the fossil mollusks are well preserved.

• Journal of the Korean Magnetic Resonance Society
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• v.15 no.2
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• pp.115-127
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• 2011

A newly developed cost-effective approach to prepare $^{15}N/^{13}C$-labeled protein for NMR studies is presented. This method has been successfully applied to isotopically labeling of PTK6 SH2 domain and MTH 1880 protein. The production method generates cell density using a growing media containing $^{15}NH_4Cl$, $^{12}C_6$-D-glucose. Following a doubling time period for unlabeled metabolite exhaustion and then addition $^{13}C_6$-D-glucose into a M9 growing media, the cells are induced. Our results demonstrate that in order to get full incorporation of $^{13}C$, the isotopes are not totally required during the initial growth phase before induction. The addition of small amounts of $^{13}C_6$-D-glucose to the induction phase is sufficient to obtain more than 95% incorporation of isotopes into the protein. Our optimized protocol is two-thirds less costly than the classical method using $^{13}C$ isotope during the entire growth phase.

• Bulletin of the Korean Chemical Society
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• v.32 no.10
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• pp.3618-3623
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• 2011

This paper presents a stable isotope chemistry of bone collagen and carbonate. Bone carbonate has the potential to provide additional isotopic information. However, it remains controversial as to whether archaeological bone carbonate retains its original biogenic signature. I used a novel application of bone density fractionation and checked the integrity of ${\delta}^{13}C_{apa}$ values using radiocarbon dating. Diagenesis in archaeological bone carbonate still remains to be resolved in extracting biogenic information. The combined use of bone density fractionation and differential dissolution method shows a large shift in the ${\delta}^{13}C_{apa}$ values. Although ${\delta}^{13}C_{apa}$ values are improved in lighter density fractions, a large percentage of contamination in bone carbonate was reported via $^{14}C$ dating compared to that noted with bone collagen.

• The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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• v.13 no.1
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• pp.83-88
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• 2008

Using micromill, discrete carbonate powders from the otolith of Argyrosomus argentatus were sampled along the growth band, and high-resolution stable isotope profiles were obtained. The ${\delta}^{18}O$ and ${\delta}^{13}C$ values are increasing gradually from the core to the margin. However, such increases do not seem to be attributed to the environmental property changes during the growth, but to the dominant effect of metabolic carbons during the early growth, and then, the isotopic composition seems to be equilibrium to the environmental condition. This paper allows the diverse applicability of high-resolution isotope research to the fish otoliths in the future.