• Journal of the Mineralogical Society of Korea
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• v.22 no.4
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• pp.343-352
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• 2009

High-resolution Solid-state NMR provides element specific and quantitative information and also resolves, otherwise overlapping atomic configurations in multi-component non-crystalline silicates. Here we report the preliminary results on the effect of composition on the structure of CMAS (CaO-MgO-$Al_2O_3-SiO_2$) silicate glasses, as a model system for basaltic magmas, using the high-resolution 1D and 2D solid-state NMR. The $^{27}Al$ MAS NMR spectra for the CMAS silicate glasses show that four-coordinated Al is predominant, demonstrating that $Al^{3+}$ is network forming cation. The peak position moves toward lower frequency about 4.7 ppm with increasing $X_{MgO}$ due to an increase in $Q^4$(4Si) fraction with increasing Si content, indicating that Al are surrounded only by bridging oxygen. $^{17}O$ MAS NMR spectra for $CaAl_2SiO_6$ and $CaMgSi_2O_6$ glasses qualitatively suggest that NBO fraction in the former is smaller than that in $CaMgSi_2O_6$ glasses. As $^{17}O$ 3QMAS NMR spectrum of model quaternary aluminosilicate glass resolved distinct bridging and non-bridging oxygen environments, atomic structure for natural magmas can also be potentially probed using high-resolution 3QMAS NMR.

• Journal of the Mineralogical Society of Korea
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• v.25 no.4
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• pp.271-282
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• 2012

We explore the effect of removal of organic ligand on the atomic configurations around oxygen in hydroxyl groups in amorphous silica gel (synthesized through hydrolysis of $SiCl_4$ in diethyl-ether) using high resolution $^{17}O$ solid state NMR spectroscopy. $^1H$ and $^{29}Si$ MAS NMR spectra for amorphous silica gel showed diverse hydrogen environments including water, hydroxyl groups (e.g., hydrogen bonded silanol, isolated silanol), and organic ligands (e.g., alkyl chain) that may interact with surface hydroxyls in the amorphous silica gel, for instance, forming silica-organic ligand complex (e.g., Si-$O{\cdots}R$). These physically and chemically adsorbed organic ligands were partly removed by ultrasonic cleaning under ethanol and distilled water for 1 hour. Whereas $^{17}O$ MAS NMR spectra with short pulse length ($0.175{\mu}s$) at 9.4 T and 14.1 T for as-synthesized amorphous silica gel showed the unresolved peak for Si-O-Si and Si-OH structures, the $^{17}O$ MAS NMR spectra with long pulse length ($2{\mu}s$) showed the additional peak at ~0 ppm. The peak at ~0 ppm may be due to Si-OH structure with very fast relaxation rate as coupled to liquid water molecules or organic ligands on the surface of amorphous silica gel. The observation of the peak at ~0 ppm in $^{17}O$ MAS NMR spectra for amorphous silica gel became more significant as the organic ligands were removed. These results indicate that the organic ligands on the surface of amorphous silica gel interact with oxygen atoms in Si-OH and provide the information about atomic structure of silanol and siloxane in amorphous silica gel. The current results could enhance the understanding of dehydration mechanism of diverse silicates, which is known as atomic scale origins of intermediate depth (approximately, 70~300 km) earthquakes in subduction zone.

• Journal of the Korean Magnetic Resonance Society
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• v.23 no.2
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• pp.56-60
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• 2019

Study on the structure and dynamics of molecules at the atomic level is of great significance for understanding their function and stability as well as roles for various chemico-physical and biological processes. $^{17}O$ NMR spectroscopy has appeared as an elegant technique for investigating of the physicochemical and structural properties of oxygen-containing compounds such as metal organic frameworks and nanosized oxides. This method has drawn much attention as it provides unique insights into the properties of targets based on atomistic information of local oxygen environments which is otherwise difficult to obtain using other methods. In this mini review, we introduce and discuss the recent study and developments of $^{17}O$ NMR techniques which are tailored for the investigation on the structure and dynamics of water and inorganic materials.

• 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.

• Investigative Magnetic Resonance Imaging
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• v.5 no.1
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• pp.33-37
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• 2001

Purpose : The water exchange rate between bulk water and bound water is an important parameter in deciding the efficiency of paramagnetic contrast agents. In this study, we evaluated the water exchange rates of various Gd-chelates using oxygen-17 NMR technique. Material and Methods : The samples (Gd-DTPA, Gd-DTPA-BMA, Gd-DOTA, Gd-EOB-DTPA) were prepared by mixing 5% $^{17}O-enriched$ water (Isotech, USA). The pH of the samples was adjusted to physiological value [pH=7.0] by buffer solution. The variable temperature $^{17}O-NMR$ measurements were performed using Bruker-600 (14.1 T, 81.3 MHz) spectrometer. Bruker VT-1000 temperature control units were used to stabilize the temperature. The $^{17}O$ spin-spin relaxation times (T2) were measured using Carr-Purcell-Meiboom-Gill (CPMG)I pulse sequence with 24 echo trains. The variable temperature T2 relaxation data were then fitted into Solomon-Bloembergen equations using least square fit algorithm to estimate the water exchange times. Results : From the measured $^{17}O-NMR$ relaxation rates, the determined water exchange rates at 300K are $0.42{\;}{\mu}s$ for Gd-DTPA, $1.99{\;}{\mu}s$ for Gd-DTPA-BMA, $0.27{\;}{\mu}s$ for Gd-DOTA, and $0.11{\;}{\mu}s$ for Gd-EOB-DTPA. The Gd-DTPA-BMA showed slowest exchange whereas Gd-EOB-DTPA had fastest water exchange rate. In addition, it was found that the water exchange rates (${\tau}_m$) of all samples had exponential temperature dependence with different decay constant. Conclusion : $^{17}O-NMR$ relaxation rate measurements, when combined with variable temperature technique, provide a solid tool for studying water exchange rate, which is very important in investigating the detailed mechanism of relaxation enhancement effect of the paramagnetic contrast agents.

• Journal of the Korean Magnetic Resonance Society
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• v.17 no.2
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• pp.86-91
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• 2013

Detailed information about the structural nature of three-coordinate borons in ${\beta}-BaB_2O_4$ is obtained through $^{11}B$ MAS NMR and $^{11}B$ single-crystal NMR. The three-coordinate $BO_3$ of the two borons B(1) and B(2) in ${\beta}-BaB_2O_4$ were distinguished. The spin-lattice relaxation time in the laboratory frame $T_1$ for B(1) and B(2) slowly decreases with increasing temperature, whereas the spin-lattice relaxation time in the rotating frame $T_{1{\rho}}$ for B(1) and B(2), which differs from $T_1$, is nearly constant. The B(1) and B(2) of the two types were distinguished by $^{11}B$ MAS NMR and $^{11}B$ single-crystal NMR.

• Bulletin of the Korean Chemical Society
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• v.21 no.9
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• pp.913-918
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• 2000

Vanadium oxide catalyst supported on TiO2-ZrO2 has been prepared by adding Ti(OH)4-Zr(OH)4 powder to an aqueous solution of ammonium metavanadate followed by drying and calcining at high temperatures. The char-acterization ofthe prepared catalysts was performed using solid-state 51V NMR and FTIR.In thecase ofcalci-nation temperature at 773 K, vanadium oxide was in a highly dispersed state for the samples containing low loading V2O5 below 25 wt %, but for samplescontaining high loading V2O5 equal to or above 25 wt %, vana-dium oxidewas well crystallized due to the V2O5 loading exceeding the formation of monolayer on the surface of TiO2-ZrO2.The ZrV2O7 compound was formed through the reactionof V2O5 and ZrO2 at 773-973 K, where-as the V3Ti6O17 compound was formedthrough the reaction of V2O5 and TiO2 at 973-1073 K. The V3Ti6O17 compound decomposed to V2O5 and TiO2 at 1173 K, which were confirmed by FTIR and 51V NMR.

• Journal of the Mineralogical Society of Korea
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• v.19 no.4 s.50
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• pp.347-353
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• 2006

The atomic-nano scale structures of multi-component aluminosilicate glasses have not been well understood in spite of its implications fur dynamics and generation of magma in the natural system due to lack of suitable spectroscopic and scattering experiments. Here, we report O-17 MAS and isotropic projection of 3QMAS NMR spectra for quaternary Na-Ca silicate glasses $[(CaO)_x(Na_2O)_{1-x}]\;(A1_2O_3)_{0.5}(SiO_2)_6,\;CNAS)$ at 14.1 Tesla where atomic configurations around bridging oxygen (Si-O-Si, Si-O-Al) and non bridging oxygen (Na-O-Si, Ca-O-Si, (Na, Ca)-O-Si) are partially resolved. With increasing Na content, the fraction of Na-O-Si increases while those for bridging oxygens remain constant. The Na/Ca ratio apparently affects the peak widths of bridging oxygen peaks (e.g., Si-O-Si)) and thus the topological entropy as well as chemical shifts of the bridging oxygen peaks, implying that both BOs and NBOs are strongly interacting with network modifying cations The effect of cation field strength on the degree of Al-avoidance was also discussed.

• Journal of the Korean Magnetic Resonance Society
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• v.17 no.1
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• pp.24-29
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• 2013

The structural characteristics of 4-coordinate $BO_4$ [B(1)] and 3-coordinate $BO_3$ [B(2)] groups in $BiB_3O_6$ were studied by $^{11}B$ magic angle spinning (MAS) and single-crystal nuclear magnetic resonance (NMR) spectroscopy. The spin-lattice relaxation time in the laboratory frame, $T_1$, for $^{11}B$ decreased slowly with increasing temperature, whereas the spin-lattice relaxation times in the rotating frame, $T_{1{\rho}}$, for B(1) and B(2), which differed from $T_1$, were nearly constant. Further, $T_{1{\rho}}$ for B(1) and B(2) showed very similar trends, although the $T_{1{\rho}}$ value of B(2) was shorter than that of B(1). The 3-coordinate $BO_3$ and 4-coordinate $BO_4$ were distinguished by $^{11}B$ MAS NMR spectrum and $T_{1{\rho}}$.

• Bulletin of the Korean Chemical Society
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• v.17 no.5
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• pp.457-460
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• 1996

The principal elements of the 31P NMR chemical shielding tensors have been determined for three binuclear platinum diphosphite complexes, K4[Pt2(P2O5H2)4·2H2O ("Pt2"), K4[Pt2(P2O5H2)4Cl2]·2H2O ("Pt2Cl2"), and K4[Pt2(P2O5H2)4Br2]·2H2O ("Pt2Br2"), by using a Herzfeld-Berger graphical method for interpreting the 31P MAS spectrum. The orientations of 31P chemical shielding tensor relative to the molecular axis system are partially assigned with combination of the longitudinal relaxation study of HPO32- and the reference to known tensor orientations of related sites; the most chemical shielding component, δ33, is directed along the P-Pt bond axis. A discussion is given in which the experimental principal elements of the 31P chemical shielding tensor are related with the Pt-Pt bond distances in binuclear platinum diphosphite complexes.