• Bulletin of the Korean Chemical Society
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• v.10 no.6
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• pp.591-595
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• 1989

The$^{13}C$ NMR shifts of a series of para-substituted 9-aryl-tricyclo$[3.3.1.0^{2,8}]$non-9-yl and 8-aryl-tetracyclo$[3.2.1.0^{2,7}.0^{4,6}]$-oct-8-yl cations were measured in $FSO_3H/SO_2ClF \;at\; -90^{\circ}C\; or\; -70^{\circ}C$ in order to examine whether the ${\rho}^{c+}$ values can be used to explain the mechanism for the stabilization of the geometrically rigid cyclopropylcarbinyl cations. Plots of the ${\Delta}{\delta}^{c+}$ shifts against ${\sigma}^{c+}$ reveal excellent linear correlation. The tricyclononyl systems yield a ${\rho}^{c+}$ value of -4.95 with a correlation coefficient r = 0.9948. The tetracyclo-octanyl systems give a ${\rho}^{c+}$ value of -6.39 with r = 0.9943. A fair parallelism exists between the results of $^{19}F$ nmr studies and the change of ${\rho}^{c+}$ values in these cations. Accordingly, the present study established that the ${\rho}^{c+}$ value can be used as a mearsure of the geometric influence for the charge delocalization in cyclopropylcarbinyl cations.

• Bulletin of the Korean Chemical Society
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• v.34 no.8
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• pp.2276-2280
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• 2013

The accurate prediction of vertical excitation energies is very important for the development of new materials in the dye and pigment industry. A time-dependent density functional theory (TD-DFT) approach coupled with 22 different exchange-correlation functionals was used for the prediction of vertical excitation energies in the halogenated copper phthalocyanine molecules in order to find the most appropriate functional and to determine the accuracy of the prediction of the absorption wavelength and observed spectral shifts. Among the tested functional, B3LYP functional provides much more accurate vertical excitation energies and UV-vis spectra. Our results clearly provide a benchmark calibration of the TD-DFT method for phthalocyanine based dyes and pigments used in industry.

• Bulletin of the Korean Chemical Society
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• v.32 no.7
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• pp.2332-2338
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• 2011

In this study, we proposed a new promising idea of utilizing moving window principal component analysis (MWPCA) as a sensitive diagnostic tool to detect the presence of peak position shift. In this approach, the moving window is constructed from a small data segment along the wavenumber axis. For each window bound by a narrow wavenumber region, separate PCA analysis was applied. Simulated spectra with complex spectral feature variations were analyzed to explore the possibility of MWPCA technique. This MWPCA-based detection of the peak shift, potentially coupled with 2D correlation analysis to provide additional verification, may offer an attractive solution.

• Bulletin of the Korean Chemical Society
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• v.8 no.2
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• pp.122-126
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• 1987

Oribtal energies for AuH and AgH are calculated by an all-electron relativistic self-consistent-field method using Slater type basis functions. Major relativistic effects for AgH are spin-orbit splittings and those for AuH are large shifts in orbital energies in addition to spin-orbit splittings. Relativistic effects on orbital energies in AgH and AuH imply that changes in correlation energies for relativistic calculations of AuH will be significantly larger than those of AgH, providing partial explanation for the large discrepencies in equilibrium bond length and the dissociation energy between experiments and theoretical estimates for AuH. Large relativistic effects on orbital energies indicate that relativistic contributions should be included for the correct interpretation of ionization potentials for these molecules. Relativistic effects are also evident in dipole moments for these molecules.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.339-339
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• 2006

In this study, the microvoids in glassy polymers were investigated by Xe sorption and $^{129}Xe$ NMR measurements. Xe sorption isotherms of glassy polymers have been successfully interpreted by the dual-mode sorption model. $^{129}Xe$ NMR chemical shift of the $^{129}Xe$ in the samples show nonlinear low-field shift with increasing sorption amount of Xe because of a fast exchange of Xe atoms between Henry and Langmuir sites, whereas it has showed linear shift against sorption amount of Xe into the Langmuir site. From this Xe-density dependence of the $^{129}Xe$ NMR chemical shift, it has been able to estimate mean size of the microvoids in glassy polymer. It is confirmed that there is correlation between ${C_H}'$ and volume or number of microvoids. From these findings, it is demonstrated that $^{129}Xe$ NMR spectroscopy is a powerful technique to determine the mean size and number of microvoids in glassy polymers.

• Bulletin of the Korean Chemical Society
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• v.14 no.5
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• pp.546-548
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• 1993

The discrete structure of substituted 9-benzonorbornenyl cation 3a and 3c was studied using the empirical ${\Delta}$J equation which was developed by Kelly and coworker$^5$. The ${\Delta}$J values of substituted 9-benzonorbornenyl cations were obtained from p-methyl-6,7-dimethyl benzonorbornen-9-yl (3a) and 9-methyl-6,7-dimethyl benzonorbonen-9-yl (3c) cations under stable ion conditions, and were compared with those of the corresponding ketone analog; these cations were generated by dissolving the corresponding carbinols in superacid at -120$^{\circ}$C and the nmr spectra taken at -60$^{\circ}$C~-90$^{\circ}$C. The ${\Delta}$J values are 8.7 Hz for the bridgehead carbons in cation 3c and 3.1 Hz for cation 3b. The ${\Delta}$J values at C5,8 in fused benzene ring are 14.3 Hz for cation 3c and 8.7 Hz for cation 3a. The excellent correlation of the ${\Delta}$J values with 1$^9F$ chemical shifts of p-fluorophenyl-6,7-dimethylbenzonorbornenyl cation (3d) indicate that ${\Delta}$J value is a reliable probe to charge density at adjacent cationic carbon. These NMR parameters strongly support that the symmetrically ${\pi}$-bridged nonclassical structure (type 2) of substituted 9-benzonorbornenyl cations in stable ion conditions.

• Journal of the Korean Magnetic Resonance Society
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• v.27 no.4
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• pp.35-41
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• 2023

From a marine sponge Dysidea species, four new furanosesquiterterpenoids were isolated and characterized. Their structural elucidation was achieved through an extensive analysis employing NMR, MS data, and DFT method. Notably, all compounds shared as identical molecular formula. Compound 2 was identified as a derivative of compound 1, while compounds 3 and 4 exhibited an identical planar structure. Determination of the configurations of chiral centers in compounds 1 and 2 involved a comparative analysis between measured and calculated ECD spectra, along with the application of DP4+ probability analysis. Distinctly, the configurations of isomers 3 and 4 were established by scrutinizing proton chemical shifts based on the NOE correlation.

• Bulletin of the Korean Chemical Society
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• v.32 no.11
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• pp.4011-4015
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• 2011

We explored the interpretation of the well-accepted correlation between the apparent peak maximum position shift and extent of molecular interactions, like hydrogen bonding and dipole-dipole interactions, based on the overlapped multiple band model. The simulation of two overlapped Lorentzian bands was carried out to interpret how the maximum position of a composite peak relates to the relative contributions of two species representing the different levels of molecular interactions, i.e., free (or very weekly bound) vs. strongly bound. To demonstrate the validity of our interpretation of the origin of the peak position shift, the temperaturedependent IR spectra of ethylene glycol were also analyzed. It was found through the analysis of simulated and experimental spectra that the apparent peak shift in certain case can be safely interpreted as the measure of the strength of hydrogen bonding. The result of this study gives a new insight to interpret molecular interactions probed by vibrational spectroscopy.

• Journal of Microbiology and Biotechnology
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• v.34 no.3
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• pp.580-588
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• 2024

Microbial communities in mangrove forests have recently been intensively investigated to explain the ecosystem function of mangroves. In this study, the soil microbial communities under young (<11 years-old) and old (>17 years-old) mangroves have been studied during dry and wet seasons. In addition, biogeochemical properties of sediments and methane emission from the two different mangrove ages were measured. The results showed that young and old mangrove soil microbial communities were significantly different on both seasons. Seasons seem to affect microbial communities more than the mangrove age does. Proteobacteria and Chloroflexi were two top abundant phyla showing >15%. Physio-chemical properties of sediment samples showed no significant difference between mangrove ages, seasons, nor depth levels, except for TOC showing significant difference between the two seasons. The methane emission rates from the mangroves varied depending on seasons and ages of the mangrove. However, this did not show significant correlation with the microbial community shifts, suggesting that abundance of methanogens was not the driving factor for mangrove soil microbial communities.

• Journal of the Korean Magnetic Resonance Society
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• v.12 no.1
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• pp.14-25
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• 2008

To investigate the 3-bond connectivity of human brain metabolites by scalar coupling interaction through 2D-correlation spectroscopy (COSY) techniques using high field NMR spectroscopy. All NMR experiments were performed at 298K on Unity Inova 500 or 600 (Varian Inc.) equipped with a triple resonance probe head with z-shield gradient. Human brain metabolites were prepared with 10% $D_2O$. Two dimensional 2D COSY spectra were acquired with 4096 complex data points in $t_2$ and 128 or 256 increments in $t_1$ dimension. The spectral width was 9615.4 Hz and solvent suppression was achieved using presaturation using low power irradiation of the water resonance during 2s of relaxation delay. NMR data were processed using VNMRJ (Varian Instrument) software and all the chemical shifts were referenced to the methyl resonance of N-acetyl aspartate (NAA) peak at 2.0 ppm. Total 10 metabolites such as N-acetyl aspartate (NAA), creatine (Cr), choline (Cho), glutamine (Gln), glutamate (Glu), myo-inositol (Ins), lactate (Lac), taurine (Tau), ${\gamma}$-aminobutyricacid (GABA), alanine (Ala) were included for major target metabolites. Symmetrical 2D-COSY spectra were successfully acquired. Total 14 COSY cross peaks were observed even though there were parallel/orthogonal noisy peaks induced by water suppression. Except for Cr, all of human brain metabolites produced COSY cross peaks. The spectra of NAA methyl proton at 2.02 ppm and Glu methylene proton ($CH_2(3)$) at 2.11 ppm and Gln methylene proton ($CH_2(3)$) at 2.14 ppm were overlapped in the similar resonance frequency between 2.00 ppm and 2.15 ppm. The present study demonstrated that in vitro 2D-COSY represented the 3-bond connectivity of human brain metabolites by scalar coupling interaction. This study could aid in better understanding the interactions between human brain metabolites in vivo 2D-COSY study. Also it would be helpful to determine the molecular stereochemistry in vivo by using two-dimensional MR spectroscopy.