• Journal of the Mineralogical Society of Korea
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• v.28 no.1
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• pp.61-69
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• 2015

While the macroscopic properties and eruption style of basaltic and phonolitic melts are different, the microscopic origins including atomic structures are not well understood. Here we report the atomic structure differences of glass in diopside-anorthite eutectic composition (basaltic glass) and phonolitic glass using high-resolution 1D and 2D solid-state Nuclear Magnetic Resonance (NMR). The $^{27}Al$ MAS NMR spectra for basaltic glass and phonolitic glass show that the full width at half maximum (FWHM) of Al for basaltic glass is about twice than phonolitic glass, suggesting the topological disorder of basaltic magma is larger than that of phonolitic magma. The $^{27}Al$ 3QMAS NMR spectra for basaltic glass and phonolite glass show much improved resolution than the 1D MAS NMR, resolving Al and Al. Approximately 3.3% of Al is observed for basaltic glass, demonstrating the configurational disorder of basaltic magma is larger than phonolitic magma. This result confirms that the topological disorder of Al in basaltic glass is larger than that of phonolitic glass. The observed structural differences between basaltic glass and phonolitic glass can provide an atomistic origin for change of the macroscopic properties with composition including viscosity.

• Journal of the Mineralogical Society of Korea
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• v.25 no.4
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• pp.283-293
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• 2012

In order to have better insights into the chemical differentiation of Earth from its magma ocean phase to the current stratified structure, detailed information of crystallization kinetics of silicate melts consisting of the magma ocean is essential. The structural transitions in oxide glasses and melts upon crystallization provide improved prospects for a systematic and quantitative understanding of the crystallization processes. Here, we report the $^{27}Al$ 3QMAS NMR spectra for sol-gel synthesized $Al_2O_3$ glass with varying temperature and annealing time. The NMR spectra for the amorphous $Al_2O_3$ show well-resolved Al coordination environments, characterized with mostly $^{[4,5]}Al$ and a minor fraction of $^{[6]}Al$. The fraction of $^{[5]}Al$ in the alumina phase decreases with increasing annealing time at constant temperature. The NMR results of $Al_2O_3$ phases also imply that multiple processes (e.g., crystallization and/or changes in structural disorder within glasses) could involve upon its phase transition. The current results and method can be useful to understand crystallization kinetics of diverse natural and multi-component silicate glasses and melts. The potential result may yield atomic-level understanding of Earth's chemical evolution and differentiation from the magma ocean.

• Journal of the Mineralogical Society of Korea
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• v.24 no.4
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• pp.301-312
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• 2011

The study on the atomic structure of iron-bearing silicate glasses has significant geological implications for both diverse igneous processes on Earth surface and ultra-low velocity zones at the core-mantle boundary. Here, we report experimental results on the effect of iron content on the atomic structure in iron-bearing alkali silicate glasses ($Na_2O-Fe_2O_3-SiO_2$ glasses, up to 16.07 wt% $Fe_2O_3$) using $^{29}Si$ and $^{17}O$ solid-state NMR spectroscopy. $^{29}Si$ spin-lattice ($T_1$) relaxation time for the glasses decreases with increasing iron content due to an enhanced interaction between nuclear spin and unpaired electron in iron. $^{29}Si$ MAS NMR spectra for the glasses show a decrease in signal intensity and an increase in peak width with increasing iron content. However, the heterogeneous peak broa-dening in $^{29}Si$ MAS NMR spectra suggests the heterogeneous distribution of $Q^n$ species around iron in iron-bearing silicate glasses. While nonbridging oxygen ($Na-O-Si$) and bridging oxygen (Si-O-Si) peaks are partially resolved in $^{17}O$ MAS NMR spectrum for iron-free silicate glass, it is difficult to distinguish the oxygen clusters in iron-bearing silicate glass. The Lorentzian peak shape for $^{29}Si$ and $^{17}O$ MAS NMR spectra may reflect life-time broadening due to spin-electron interaction. These results demonstrate that solid-state NMR can be an effective probe of the detailed structure in iron-bearing silicate glasses.

• Journal of the Korean Magnetic Resonance Society
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• v.15 no.1
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• pp.54-68
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• 2011

$^1H$ nuclear magnetic resonance (NMR) spectroscopy of biological samples has been proven to be an effective and nondestructive approach to probe drug toxicity within an organism. In this study, ketoprofen toxicity was investigated using $^1H$-NMR spectroscopy coupled with multivariate statistical analysis. Histopathologic test of ketoprofen-induced acute gastrointestinal damage in rats demonstrated a significant dose-dependent effect. Furthermore, principal component analysis (PCA) derived from $^1H$-NMR spectra of urinary samples showed clear separation between the vehicle-treated control and ketoprofen-treated groups. Moreover, PCA derived from endogenous metabolite concentrations through targeted profiling revealed a dose-dependent metabolic shift between the vehicle-treated control, low-dose ketoprofen-treated (10 mg/kg body weight), and high-dose ketoprofen-treated (50 mg/kg) groups coinciding with their gastric damage scores after ketoprofen administration. The resultant metabolic profiles demonstrated that the ketoprofen-induced gastric damage exhibited energy metabolism perturbations that increased urinary levels of citrate, cis-aconitate, succinate, and phosphocreatine. In addition, ketoprofen administration induced an enhancement of xenobiotic activity in fatty oxidation, which caused increase levels of N-isovalerylglycine, adipate, phenylacetylglycine, dimethylamine, betaine, hippurate, 3-indoxylsulfate, N,N-dimethylglycine, trimethyl-N-oxide, and glycine. These findings demonstrate that $^1H$-NMR-based urinary metabolic profiling can be used for noninvasive and rapid way to diagnose adverse drug effects and is suitable for explaining the possible biological pathways perturbed by nonsteroidal anti-inflammatory drug toxicity.

• BMB Reports
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• v.35 no.3
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• pp.343-347
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• 2002

The human protein tyrosine kinase-6 (PTK6) polypeptide that is deduced from the cDNA sequence contains a Src homology (SH) 3 domain, SH2 domain, and catalytic domain of tyrosine kinase. We initiated biochemical and NMR characterization of PTK6 SH3 domain in order to correlate the structural role of the PTK6 using circular dichroism and heteronuclear NMR techniques. The circular dichroism data suggested that the secondary structural elements of the SH3 domain are mainly composed of $\beta$-sheet conformations. It is most stable when the pH is neutral based on the pH titration data. In addition, a number of cross peaks at the low-field area of the proton chemical shift of the NMR spectra indicated that the PTK6 SH3 domain retains a unique and folded conformation at the neutral pH condition. For other pH conditions, the SH3 domain became unstable and aggregated during NMR measurements, indicating that the structural stability is very sensitive to pH environments. Both the NMR and circular dichroism data indicate that the PTK6 SH3 domain experiences a conformational instability, even in an aqueous solution.

• Journal of the Korean Magnetic Resonance Society
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• v.19 no.3
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• pp.137-142
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• 2015

NMR-based structural studies on membrane proteins are appreciated quite challenging due to various reasons, generally including the narrow dispersion of NMR spectra, the severe peak broadening, and the lack of long range NOEs. In spite of the poor biophysical properties, structural studies on membrane proteins have got to go on, considering their functional importance in biological systems. In this review, we provide a simple overview of the techniques generally used in structural studies of membrane proteins by solution NMR, with experimental examples of a helical membrane protein, caveolin 3. Detergent screening is usually employed as the first step and the selection of appropriate detergent is the most important for successful approach to membrane proteins. Various tools can then be applied as specialized NMR techniques in solution that include sample deteuration, amino-acid selective isotope labeling, residual dipolar coupling, and paramagnetic relaxation enhancement.

• Journal of the Korean Chemical Society
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• v.51 no.6
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• pp.520-525
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• 2007

Three-component coupling of thiourea/urea, various structurally diverse aromatic aldehydes and ammonium acetate is catalyzed by activated fly ash in dry media under microwave irradiation to give 6-aryl-1,2,4,5-tetrazinan- 3-thiones/ones in good yields. The structure of 6-aryl-1,2,4,5-tetrazinan-3-thiones/ones have been elucidated on the basis of their melting points, elemental analysis, MS, IR, 1H NMR, D2O exchange, 13C NMR and two dimensional NMR spectral studies including Homonuclear Correlation (HOMOCOR) and Heteronuclear Single Quantum Correlation (HSQC) spectra.

• Analytical Science and Technology
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• v.17 no.2
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• pp.98-107
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• 2004

In this study, $^1H$ NMR spectroscopy and HPLC were used to identify the type and quantity of each component in an acrylic coating materials applied for an automotive part. By the $^1H$ NMR analysis, it was found that this acrylic coating contained about 88.40 wt% of poly methyl methacrylate (PMMA), 7.05 wt% of methyl methacrylate (MMA), and 2.36 wt% of allyl methacrylate. Polymer additives such as a benzotriazole light stabilizer (Hisorb 328), an oxanilide light stabilizer, butylated hydroxy toluene (BHT), and dimethyl phthalate (DMP) were also identified and measured quantitatively from the $^1H$ NMR spectra. However, only two light stabilizers were identified by reverse phase (RP) HPLC analysis using Bondapak C18 column, methanol mobile phase, and a PDA (Photodiode array) detector. The contents of two light stabilizers in the acrylic coating were measured by a quantitative analysis through UV-Vis spectroscopy and compared with the NMR data. The analytical informations from $^1H$ NMR spetra were better than those from HPLC-PDA plot.

• Journal of the Korean Chemical Society
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• v.51 no.6
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• pp.526-535
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• 2007

Ru(II)-terpyridine complexes (8, 9, 11) linked with adamantyl or β-cyclodextrin moieties were synthesized and characterized based on their 1H and 13C NMR spectra as well as MS spectra. Ru(II)-terpyridine complexes (8, 11) linked with adamantyl moiety were readily dissolved in aqueous solution via encapsulation by β-cyclodextrin when they were mixed with an equimolar amount of β-cyclodextrin. In the similar way, the adamantane guest of the Ru(II)-terpyridine complexes (8, 11) were encapsulated by β-cyclodextrin moiety of the ruthenium complex 9 to afford supramolecular assemblies in aqueous environment. Formation of assemblies was corroborated by 1H NMR spectroscopy.

• Journal of the Korean Chemical Society
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• v.54 no.5
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• pp.506-514
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• 2010

A new series of ligands N-[(benzoylamino)-thioxomethyl]-amino acid (HL) were synthesized by reaction of benzoylisothiocyanate with various amino acids namely aspartic acid [BATA] (1), glutamic acid [BATG] (2), methionine [BATM] (3), leucine [BATL] (4), and tryptophan [BATT] (5). The ligands were characterized by elemental analysis, IR and NMR spectra. Some transition metal complexes ($ML_2$) for these ligands (6-8) were prepared; [M=Cu(II), Co(II), or Ni(II)], and characterized by elemental analysis, IR and $^1H$ NMR spectra. Antibacterial study showed that all the ligands have no antibacterial activity, whereas ($ML_2$) complexes; [M = Cu(II), Co(II), or Ni(II)] have antibacterial activity towards (Gram -ive) Escherichia (NCTC5933) and (Gram +ive) Staphylococcus (NCTC6571) and have no toxicity on (BALB/C) Albino mice.