• 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.

• YAKHAK HOEJI
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• v.33 no.3
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• pp.203-205
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• 1989

A method is presented for calculating the $^{13}C$ chemical shifts produced in liquid solution by referenced relative to RF frequency. The method is useful to get the real variations of chemical shifts in magnetic field by eliminating the affects of the variation of a reference substance.

• Journal of the Korean Wood Science and Technology
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• v.17 no.4
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• pp.44-56
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• 1989

To recover much residual lignin from the black liquor of kraft pulp. the black liquor was extracted and purified with many organic solvents. Many kinds of lignins were isolated from each fraction obtained and the characteristics of these lignins investigated by $^{13}C$-NMR spectroscopy. If M$\ddot{o}$rck's method was compared with Kirk's method. M$\ddot{o}$rck's method was better than Kirk's method because the particular signals of each lignin occur more in the former than m the latter. Especially the $^{13}C$-NMR spectrum of the MCS fraction identifies with those of other researchers. The experiment that the kraft lignin from Pinus densiflora S. et Z. found in Korea was investigated by $^{13}C$-NMR spectroscopy was performed first in Korea.

• Journal of Microbiology and Biotechnology
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• v.15 no.6
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• pp.1330-1336
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• 2005

Polyhydroxyalkanoic acid (PHA) inclusion bodies were analyzed in situ by $^{13}C$-nuclear magnetic resonance ($^{13}C$-NMR) spectroscopy. The PHA inclusion bodies studied were composed of poly(3-hydroxybutyrate) or poly(3hydroxybutyrate-co-4-hydroxybutyrate), which was accumulated in Hydrogenophaga pseudoflava, and medium-chain-length PHA (MCL-PHA), which was accumulated in Pseudomonas fluorescens BM07 from octanoic acid or 11-phenoxyundecanoic acid (11-POU). The quantification of the $^{13}C$-NMR signals was conducted against a standard compound, sodium 2,2-dimethyl-2-silapentane-5-sulfonate (DSS). The chemical shift values for the in vivo NMR spectral peaks agreed well with those for the corresponding purified PHA polymers. The intracellular degradation of the PHA inclusions by intracellular PHA depolymerase(s) was monitored by in vivo NMR spectroscopy and analyzed in terms of first-order reaction kinetics. The H. pseudoflava cells were washed for the degradation experiment, transferred to a degradation medium without a carbon source, but containing 1.0 g/l ammonium sulfate, and cultivated at $35^{\circ}C$ for 72 h. The in vivo NMR spectra were obtained at $70^{\circ}C$ for the short-chain-length PHA cells whereas the spectra for the aliphatic and aromatic MCL-PHA cells were obtained at $50^{\circ}C\;and\;80^{\circ}C$, respectively. For the H. pseudoflava cells, the in vivo NMR kinetics analysis of the PHA degradation resulted in a first-order degradation rate constant of 0.075/h ($r^{2}$=0.94) for the initial 24 h of degradation, which was close to the 0.050/h determined when using a gas chromatographic analysis of chloroform extracts of sulfuric acid/methanol reaction mixtures of dried whole cells. Accordingly, it is suggested that in vivo $^{13}C$-NMR spectroscopy is an important tool for studying intracellular PHA degradation in terms of kinetics.

• Elastomers and Composites
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• v.19 no.1
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• pp.32-45
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• 1984

• Journal of Photoscience
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• v.9 no.2
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• pp.110-113
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• 2002

We demonstrate here a dynamic structure of bacteriorhodopsin (bR) as revealed by $^{13}$ C NMR studies on [3_$^{13}$ C]_,[1-$^{13}$ C]Ala- and/or Val-labeled wild type and a variety of site-directed mutants at ambient temperature. For this purpose, well-resolved (up to twelve) I$^{13}$ C NMR peaks were assigned with reference to the displacement of peaks due to the conformation-dependent I$^{13}$ C chemical shifts and reduced peak-intensities due to site-directed mutations. Revealed bR structure was not rigid as anticipated from 2D crystals of hexagonal array but a dynamically heterogeneous, undergoing a variety of local fluctuations depending upon specific site with frequency range of 10$^2$ -10$^{8}$ Hz. In particular, dynamics- dependent suppression of peaks turned out to be very sensitive to the motion of 10$^{-4}$ s and 10$^{-5}$ s interfered with frequency of magic angle spinning and proton decoupling, respectively. It is also noteworthy that such dynamic feature is strongly dependent upon the manner of 2D crystalline packing: $^{13}$ C NMR peaks of monomeric bR yielded either highly broadened or completely suppressed signals, depending upon the type of $^{13}$ C-labeled amino-acid residues.

• Analytical Science and Technology
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• v.9 no.2
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• pp.168-178
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• 1996

Molecular structures of petroleum fractions(diesel fuel, bunker-C oil, lubricant base stocks) have been analyzed and compared in terms of the compositions (aromatics, naphtherucs, paraffinics), aromatics(benzene-nuclear and bonded alkyl groups), C2(methylene) carbon atoms % $C_{\alpha}$ and $C_{\beta}$ carbon stom % in alkyl groups and paraffins(branched and normal) by near-infrared and $^{13}C$-NMR spectroscopy.

• Bulletin of the Korean Chemical Society
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• v.23 no.12
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• pp.1729-1732
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• 2002

The LB71350,(3S, 4R)-Epoxy-(5S)-[[N-(1-methylethoxy)carbonyl]-3-(methylsulfonyl)-L-valinyl]amino]-N-[2-methyl-(1R)-[(phenyl)carbonylpropyl-6-phenylhexanamide, is a novel HIV protease inhibitor. Its equilibrium solubility at room temperature was less than $40{\mu}g/mL.$ It was speculated that the low aqueous solubility might be due to the high crystalline lattice energy resulting from intermolecular hydrogen bonds. The present study was carried out to learn the solid-state characteristics of LB71350 using analytical methods such as NMR, FT-IR and XRD. $^{13}C$ Solid-state NMR, solution NMR, and FT-IR spectra of the various solid forms of LB71350 were used to identify the conformation and structure of the solid forms. The chemical shifts of $^{13}C$ solid-state NMR spectra suggest that the crystalline form might have 3 intermolecular hydrogen bondings between monomers.

• 한국신재생에너지학회:학술대회논문집
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• 2006.06a
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• pp.395-398
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• 2006

동일한 조건에서 순수한 물과 계면활성제인 DBS(dodecyl bezebe sulfonic acid) 25ppm을 첨가한 물에 대해 천연가스 하이드레이트를 제조시 가스의 함유량은 각각 80배와 160배로 2배의 차이가 발생한다. 이에 대해 본 연구에서는 결정 생성 형태의 관찰 및 $^{13}C$ NMR을 사용한 분광학적 구조 분석으로부터 이의 원인을 찾고자 하였다. 순수한 물과 DBS를 미량 함유한 물을 사용하여 whiskery 결정을 생성시킨 결과, 순수한 물을 사용한 경우보다 섬유 다발 형태가 매우 활발한 형태의 결정 형태로 가스하이드 레이트가 생성됨을 알 수 있었다. 또한 400MHz의 NMR을 사용한 분광학적 구조 분석으로부터 천연가스하이드레이트는 구조-I과 구조-II가 혼재된 결정 구조를 이루고 있음을 알 수 있었다. 또한 DBS를 함유한 물에 의해 제조된 천연가스하이드레이트는 arge cage를 많이 생성시키는 역할을 하는 분석 결과를 보였고 이것이 가스 함유량을 증대시키는 원인 중의 하나임을 알 수 있었다.

• Progress in Superconductivity
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• v.12 no.1
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• pp.51-56
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• 2010

$^{13}C$ NMR (nuclear magnetic resonance) measurements have been performed to investigate the local electronic structure of a superconducting graphite intercalation compound $CaC_6$ ($T_c$ = 11.4 K). A large number of single crystals were stacked and sealed in a quartz tube for naturally abundant $^{13}C$ NMR. The spectrum, Knight shift, linewidth, and spin-lattice relaxation time $T_1$ were measured in the normal state as a function of temperature down to 80 K at 8.0 T perpendicular to the c-axis. The $^{13}C$ NMR spectrum shows a single narrow peak with a very small Knight shift. The Knight shift and the linewidth of the $^{13}C$ NMR are temperature-independent around, respectively, +0.012% and 1.2 kHz. The spin-lattice relaxation rate, $1/T_1$, is proportional to temperature confirming a Korringa behavior as for non-magnetic metals. The Korringa product is measured to be $T_1T\;=\;210\;s{\cdot}K$. From this value, the Korringa ratio is deduced to be $\xi$ = 0.73, close to unity, which suggests that the independent-electron description works well for $CaC_6$, without complications arising from correlation and many-body effects.