• Analytical Science and Technology
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• v.7 no.1
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• pp.91-102
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• 1994

The monomer compositions in a series of propylene heterophasic copolymer, propylene random copolymer, propylene random terpolymer and ethylene-propylene-ENB terpolymer have been determined from $^{13}C-NMR$ spectra. The simplified and highly resolved $^{13}C-NMR$ spectra made it possible to assign unambiguousely and calculate the monomer composition. A complete sets of NMR chemical shift assignments and the way to measure the quantity of monomer are newly given in diverse polymers. Furthermore complete dyad, triad, tetrad and pentad distributions have been able to be determined. These NMR quantitative analytical results for monomer compostition have consistent with those from Infrared spectral data.

• 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.

• Molecules and Cells
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• v.24 no.3
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• pp.437-440
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• 2007

$OGL-20P^T$-358 is a novel 66 amino acid residue protein from the hyperthermophile Thermococcus thioreducens sp. nov., strain $OGL-20P^T$, which was collected from the wall of the hydrothermal black smoker in the Rainbow Vent along the mid-Atlantic ridge. This protein, which has no detectable sequence homology with proteins or domains of known function, has a calculated pI of 4.76 and a molecular mass of 8.2 kDa. We report here the backbone $^1H$, $^{15}N$, and $^{13}C$ resonance assignments of $OGL-20P^T$-358. Assignments are 97.5% (316/324) complete. Chemical shift index was used to determine the secondary structure of the protein, which appears to consist of primarily ${\alpha}$-helical regions. This work is the foundation for future studies to determine the three-dimensional solution structure of the protein.

• Journal of Environmental Health Sciences
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• v.27 no.1
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• pp.36-43
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• 2001

Chitosans were prepared from red crab chitin under various alkali treatment conditions(different alkali concentrations, reaction times and temperatures) and theirphysicochemical properties were investigated. The nitrogen content and deacetylation degree of red crab chitin were 6.15% and 22.17A%, respectively. By the IR spectra, red crab and reference chitin showed the sharp bands at 1650 $cm^{-1}$ / and 1550 $cm^{-1}$ /, which are characteristic of chitin. The nitrogen contents of prepared chitosans ranged from 6.19~7.48%. Thedeacetylation degree was increased from 63~76% and 48~78% with increasing reaction time and temperature, whereas viscosity was decreased. The nitrogen content and yield of red crab chitosan perpared from chitin with 50% NaOH, 1:25(w/v) for 3.0 hr at 120$cm^{-1}$ / were 7.26% and 85.0%, respectively. and viscosity, deacetylation degree and molecular weight, 67.0 mPa.s, 75.0% and 6.5$\times$10$^{5}$ Dalton, respectively. From the IR spectra, the amide absorption bands of red crab and reference chitosan became very weak, similarly. And at solid state $^{13}$ C-NMR spectra, C=O(carbonyl carbon) signals absent, whereas $CH_3$(methyl carbon) was residues. Chemical shift of $^{13}$ C-NMR spectra of red crab and reference chitosans were in good agreement with slight experimental deviation.

• Macromolecular Research
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• v.10 no.1
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• pp.34-39
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• 2002

Cure behavior of an epoxy resin was investigated at different cure temperatures (110, 120, 130, 140, and 150 $^{\circ}C$) and cure times in the presence of 2 wt% of an N-benzylpyrazinium hexafluoroantimonate (BPH) cationic catalyst by means of differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The glass transition temperature ( $T_{g}$) and chemical conversion (x) at the different temperatures were determined from DSC thermograms. The $T_{g}$ and x vs. In time data were superposed up to $T_{g}$ = 10$0^{\circ}C$ and x = 0.70 by shifting horizontally at a reference temperature of $T_{g}$ = 13$0^{\circ}C$. It is interesting that the $T_{g}$ and x of the superposed data increase rather slowly in the early stage of cure and rapidly thereafter. Therefore, the increase of the $T_{g}$ and x can be divided into two regions; $R_{I}$= -18.4(= $T_{go}$ ) ~5$^{\circ}C$ and $R_{II}$ = 5 ~ 10$0^{\circ}C$ in $T_{g}$, and $R_{I}$ : 0~0.24 and $R_{II}$ : 0.24~0.70 in x. The $R_{I}$ is closely related to the initiation reactions between BPH and epoxy and between hydroxy group and epoxy in this epoxy/catalyst system. From the kinetic analysis of the $T_{g}$-shift, activation energy was 12.5 kcal/mol. The relationship between $T_{g}$ and x was also considered. The gelation and vitrification times for different cure temperatures were obtained from DMA curves.urves. DMA curves.urves.

• Investigative Magnetic Resonance Imaging
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• v.20 no.1
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• pp.53-60
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• 2016

Purpose: To develop a technique for quantifying the $^{13}C$-metabolites by performing frequency-selective hyperpolarized $^{13}C$ magnetic resonance spectroscopy (MRS) in vitro which combines simple spectrally-selective excitation with spectrally interleaved acquisition. Methods: Numerical simulations were performed with varying noise level and $K_p$ values to compare the quantification accuracies of the proposed and the conventional methods. For in vitro experiments, a spectrally-selective excitation scheme was enabled by narrow-band radiofrequency (RF) excitation pulse implemented into a free-induction decay chemical shift imaging (FIDCSI) sequence. Experiments with LDH / NADH enzyme mixture were performed to validate the effectiveness of the proposed acquisition method. Also, a modified two-site exchange model was formulated for metabolism kinetics quantification with the proposed method. Results: From the simulation results, significant increase of the lactate peak signal to noise ratio (PSNR) was observed. Also, the quantified $K_p$ value from the dynamic curves were more accurate in the case of the proposed acquisition method compared to the conventional non-selective excitation scheme. In vitro experiment results were in good agreement with the simulation results, also displaying increased PSNR for lactate. Fitting results using the modified two-site exchange model also showed expected results in agreement with the simulations. Conclusion: A method for accurate quantification of hyperpolarized pyruvate and the downstream product focused on in vitro experiment was described. By using a narrow-band RF excitation pulse with alternating acquisition, different resonances were selectively excited with a different flip angle for increased PSNR while the hyperpolarized magnetization of the substrate can be minimally perturbed with a low flip angle. Baseline signals from neighboring resonances can be effectively suppressed to accurately quantify the metabolism kinetics.

• Bulletin of the Korean Chemical Society
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• v.12 no.2
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• pp.130-137
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• 1991

The following new cryptand 221 complexes of lanthanides(Ⅲ) and dioxouranium(Ⅵ) nitrate have been synthesized: $(Ln(C_{16}H_{32}N_2O_5)(H_2O)_2(NO_3)_3\ and \((UO_2)_2(C_{16}H_{32}N_2O_5)(H_2O)_4(NO_3)_4$. These complexes have been identified by elemental analysis, moisture titration, conductivity measurements and various spectroscopic techniques. The proton and carbon-13 NMR as well as calorimetric measurements were used to study the interaction of cryptand 221 with La(Ⅲ), Pr(Ⅲ ), Ho(Ⅲ) and $UO_2(Ⅱ)$ ions in nonaqueous solvents. The bands of metal-oxygen atoms, metal-nitrogen atoms and O-U-O in the IR spectra shift upon complexation to lower frequencies, and the vibrational spectra ({\delta}NMN$) of metal-amide complexes in the crystalline state exhibit lattice vibrations below 300 $cm^{-1}$. The NMR spectra of the lanthanides(Ⅲ) and dioxouranium(Ⅵ) nitrate complexes in nonaqueous solvents are quite different, indicating that the ligand exists in different conformation, and also the $^1H$ and $^{13}C-NMR$ studies indicated that the nitrogen atom of the ring has greater affinity to metal ions than does the oxygen atom, and the planalities of the ring are lost by complexation with metal ions. Calorimetric measurements show that cryptand 221 forms more stable complexes with $La^{3+}$ and $Pr^{3+}$ ions than with $UO^{22+}$ ion, and $La^{3+}/Pr^{3+}$ and $UO^{22+}/Pr^{3+}$ selectivity depends on the solvents. These changes on the stabilities are dependent on the basicity of the ligand and the size of the metal ions. The absorption band (230-260 nm) of the complex which arises from the direct interaction of macrocyclic donor atoms with the metal ion is due to n-{\delta}*$ transition and also that (640-675 nm) of $UO^{22+}$-cryptand 221 complex, which arises from interaction between two-dioxouranium(Ⅵ) ions in being out of cavity of the ligand ring is due to d-d* transition.

• Applied Chemistry for Engineering
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• v.4 no.4
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• pp.770-775
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• 1993

Chemical structure of poly(ethylene terephthalate-co-1, 4-cyclohexylene dimethylene terephthalate), P(ET-CT) copolyesters was investigated by High Resolution NMR analysis. The copolymer composition and isomeric ratio were determined by methylene resonance peaks which were separated into three peaks corresponding to ET, trans CT and cis CT units, respectively. The copolymer sequence distribution was evaluated from the carbon resonance peaks connected to carbonyl groups in benzene, indicating died distribution. According to statistics model, these copolyesters are almost random copolymers. The copolymer sequence distribution could be simulated and its averaged length was calculated by random copolymer statistics.

• Journal of the Korean Magnetic Resonance Society
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• v.21 no.4
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• pp.139-144
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• 2017

Ni(II) containing coenzyme F430 catalyzes the reduction of $CO_2$ in methanogen. Macrocyclic Ni(II) complexes with N,O shiff bases have been received a great attention since metal ions play an important role in the catalysis of reduction. The reducing power of metal complexes are supposed to be dependent on oxidoreduction state of metal ion and structural properties of macrocyclic ring moiety that can enhance electrochemical properties in catalytic process. Six different ${\alpha}$-oximinoketone compounds, precursor of macrocyclic ligands used in $CO_2$ reduction coenzyme F430 model complexes, were synthesized with yields over 90% and characterized by NMR. The molecular geometries of ${\alpha}$-oximinoketone analogues were fully optimized at Beck's-three-parameter hybrid (B3LYP) method in density functional theory (DFT) method with $6-31+G^*$ basis set using the ab initio program. In order to understand molecular planarity and substitutional effects that may enhance reducing power of metal ion are studied by computing the structure-dependent $^{13}C$-NMR chemical shift and comparing with experimental results.

• Journal of the Korean Magnetic Resonance Society
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• v.3 no.1
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• pp.52-59
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• 1999

Authors synthesized common intermediates which are applicable for potential antibiotics. Their complete 13C and 1H NMR chemical shift data as well as carbon-and proton-fluorine coupling constants are reported. The knowledge of proton and carbon-fluorine coupling constants may help one assign the NMR data of the fluorinated quinolone derivatives. These results agree with the data published previously.