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Magic-angle Spinning (magic-angle + spinning)
Kinds of Magic-angle Spinning Selected AbstractsHighly Ordered Interstitial Water Observed in Bone by Nuclear Magnetic Resonance,JOURNAL OF BONE AND MINERAL RESEARCH, Issue 4 2005Erin E Wilson Abstract NMR was used to study the nanostructure of bone tissue. Distance measurements show that the first water layer at the surface of the mineral in cortical bone is structured. This water may serve to couple the mineral to the organic matrix and may play a role in deformation. Introduction: The unique mechanical characteristics of bone tissue have not yet been satisfactorily connected to the exact molecular architecture of this complex composite material. Recently developed solid-state nuclear magnetic resonance (NMR) techniques are applied here to the mineral component to provide new structural distance constraints at the subnanometer scale. Materials and Methods: NMR dipolar couplings between structural protons (OH, and H2O) and phosphorus (PO4) or carbon (CO3) were measured using the 2D Lee-Goldburg Cross-Polarization under Magic-Angle Spinning (2D LG-CPMAS) pulse sequence, which simultaneously suppresses the much stronger proton-proton dipolar interactions. The NMR dipolar couplings measured provide accurate distances between atoms, e.g., OH and PO4 in apatites. Excised and powdered femoral cortical bone was used for these experiments. Synthetic carbonate (,2-4 wt%)-substituted hydroxyapatite was also studied for structural comparison. Results: In synthetic apatite, the hydroxide ions are strongly hydrogen bonded to adjacent carbonate or phosphate ions, with hydrogen bond (O-H) distances of ,1.96 Å observed. The bone tissue sample, in contrast, shows little evidence of ordered hydroxide. Instead, a very ordered (structural) layer of water molecules is identified, which hydrates the small bioapatite crystallites through very close arrangements. Water protons are ,2.3-2.55 Å from surface phosphorus atoms. Conclusions: In synthetic carbonated apatite, strong hydrogen bonds were observed between the hydroxide ions and structural phosphate and carbonate units in the apatite crystal lattice. These hydrogen bonding interactions may contribute to the long-range stability of this mineral structure. The biological apatite in cortical bone tissue shows evidence of hydrogen bonding with an ordered surface water layer at the faces of the mineral particles. This structural water layer has been inferred, but direct spectroscopic evidence of this interstitial water is given here. An ordered structural water layer sandwiched between the mineral and the organic collagen fibers may affect the biomechanical properties of this complex composite material. [source] NMR nomenclature: Nuclear spin properties and conventions for chemical shifts (IUPAC recommendations 2001),CONCEPTS IN MAGNETIC RESONANCE, Issue 5 2002Robin K. Harris Abstract A unified scale is recommended for reporting the NMR chemical shifts of all nuclei relative to the 1H resonance of tetramethylsilane. The unified scale is designed to provide a precise ratio, ,, of the resonance frequency of a given nuclide to that of the primary reference, the 1H resonance of tetramethylsilane (TMS) in dilute solution (volume fraction, , < 1%) in chloroform. Referencing procedures are discussed, including matters of practical application of the unified scale. Special attention is paid to recommended reference samples and values of , for secondary references on the unified scale are listed, many of which are the results of new measurements. Some earlier recommendations relating to the reporting of chemical shifts are endorsed. The chemical shift, ,, is redefined to avoid previous ambiguities but to leave practical usage unchanged. Relations between the unified scale and recently published recommendations for referencing in aqueous solutions (for specific use in biochemical work) are discussed, as well as the special effects of working in the solid state with magic-angle spinning. In all, nine new recommendations relating to chemical shifts are made. Standardized nuclear spin data are also presented in tabular form for the stable (and some unstable) isotopes of all elements with non-zero quantum numbers. The information given includes quantum numbers, isotopic abundances, magnetic moments, magnetogyric ratios and receptivities, together with quadrupole moments and linewidth factors (where appropriate). © 2001 IUPAC. Concepts Magn Reson 14:326,346, 2002 [source] Luminescent Polyoxotungstoeuropate Anion-Pillared Layered Double HydroxidesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 4 2006Filipa L. Sousa Abstract Novel luminescent polyoxometalate anion-pillared layered double hydroxides (LDHs) were prepared by aqueous ion exchange of a Zn,Al LDH precursor in nitrate form with the europium-containing polyoxotungstate anions [EuW10O36]9,, [Eu(BW11O39)(H2O)3]6, and [Eu(PW11O39)2]11,. The host,guest interaction has a strong influence on the nature of the final intercalated species, as evidenced by elemental analysis, powder X-ray diffraction (XRD), infra-red (IR) and Raman spectroscopy, solid state magic-angle spinning (MAS) 11B and 31P NMR spectroscopy, and photoluminescence spectroscopy. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Solid-State NMR Investigations of the Unusual Effects Resulting from the Nanoconfinement of Water within Amphiphilic Crosslinked Polymer NetworksADVANCED FUNCTIONAL MATERIALS, Issue 21 2009Ryutaro Ohashi Abstract Two types of solid-state 19F NMR spectroscopy experiments are used to characterize phase-separated hyperbranched fluoropolymer,poly(ethylene glycol) (HBFP,PEG) crosslinked networks. Mobile (soft) domains are detected in the HBFP phase by a rotor-synchronized Hahn echo under magic-angle spinning conditions, and rigid (hard) domains by a solid echo with no magic-angle spinning. The mobility of chains is detected in the PEG phase by 1H,,,13C cross-polarization transfers with 1H spin-lock filters with and without magic-angle spinning. The interface between HBFP and PEG phases is detected by a third experiment, which utilized a 19F,,,1H,(spin diffusion),1H,,,13C double transfer with 13C solid-echo detection. The results of these experiments show that composition-dependent PEG inclusions in the HBFP glass rigidify on hydration, consistent with an increase in macroscopic tensile strength. [source] Direct Synthesis of Highly Stable Mesoporous Molecular Sieves Containing Zeolite Building Units,ADVANCED FUNCTIONAL MATERIALS, Issue 2 2005A. Sakthivel Abstract A novel, one-step synthesis of a highly stable mesoporous molecular sieve (MMS-H), which has a structure analogous to MCM-48 but which contains zeolite building units, is reported. A variety of experimental techniques,X-ray diffraction (XRD), N2 adsorption/desorption, transmission electron microscopy (TEM), Fourier-transform infrared (FTIR) spectroscopy, hyperpolarized 129Xe,NMR, and solid-state 27Al and 31P,magic-angle spinning (MAS) NMR spectroscopies,have been used to characterize the framework structure, porosity, and acidity of this novel mesoporous/microporous composite material, which is also found to possess superior thermal, hydrothermal, steam, and mechanical stabilities. [source] Recyclable Polymer- and Silica-Supported Ruthenium(II)-Salen Bis-pyridine Catalysts for the Asymmetric Cyclopropanation of OlefinsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 9 2009Christopher Abstract Homogeneous ruthenium(II)-salen bis-pyridine complexes are known to be highly active and selective catalysts for the asymmetric cyclopropanation of terminal olefins. Here, new methods of heterogenization of these Ru-salen catalysts on polymer and porous silica supports are demonstrated for the facile recovery and recycle of these expensive catalysts. Activities, selectivities, and recyclabilities are investigated and compared to the analogous homogeneous and other supported catalysts for asymmetric cyclopropanation reactions. The catalysts are characterized with a variety of methods including solid state cross-polarization magic-angle spinning (CP MAS) 13C and 29Si,NMR, FT-IR, elemental analysis, and thermogravimetric analysis. Initial investigations produced catalysts possessing high selectivities but decreasing activities upon reuse. Addition of excess pyridine during the washing steps between cycles was observed to maintain high catalytic activities over multiple cycles with no impact on selectivity. Polymer-supported catalysts showed superior activity and selectivity compared to the porous silica-supported catalyst. Additionally, a longer, flexible linker between the Ru-salen catalyst and support was observed to increase enantioselectivity and diastereoselectivity, but had no effect on activity of the resin catalysts. Furthermore, the polymer-supported Ru-salen-Py2 catalysts were found to generate superior selectivities and yields compared to other leading heterogeneous asymmetric cyclopropanation catalysts. [source] Two- and three-dimensional multinuclear stray-field imaging of rotating samples with magic-angle spinning (STRAFI-MAS): From bio to inorganic materialsJOURNAL OF MAGNETIC RESONANCE IMAGING, Issue 2 2010Alan Wong PhD Abstract Purpose: To revisit and illustrate the potential of a simple and effective multidimensional stray-field imaging technique with magic-angle spinning, known as STRAFI-MAS. Materials and Methods: STRAFI-MAS images are acquired with a standard NMR magnet and a traditional magic-angle sample spinning (MAS) probe. The stray-field gradients are achieved by placing the MAS probe, along the z -direction, at a distance from the center of the magnet. No pulsed-field gradients are applied. The multidimensional spatial encoding is carried out by synchronizing the radiofrequency pulses with the sample MAS rotation. Results: Two-dimensional (2D) and 3D multinuclear images of various phantoms, including a tibia bone and silicon carbide, are recorded. Images of inorganic solids containing quadrupolar nuclei, 23Na and 27Al, are also explored for the first time by STRAFI-MAS. Conclusion: We have demonstrated that STRAFI-MAS is a simple and user-friendly technique for multidimensional imaging without the need of imaging equipment. With the current advancements in NMR and MRI methodologies, STRAFI-MAS is expected to be further developed and improved. We anticipate that STRAFI-MAS can spark a wide spectrum of interest, from material to bio science, where can benefit from high-resolution images. J. Magn. Reson. Imaging 2010;32:418,423. © 2010 Wiley-Liss, Inc. [source] Quantitation of crystalline and amorphous forms of anhydrous neotame using 13C CPMAS NMR spectroscopyJOURNAL OF PHARMACEUTICAL SCIENCES, Issue 12 2005Thomas J. Offerdahl Abstract Although most drugs are formulated in the crystalline state, amorphous or other crystalline forms are often generated during the formulation process. The presence of other forms can dramatically affect the physical and chemical stability of the drug. The identification and quantitation of different forms of a drug is a significant analytical challenge, especially in a formulated product. The ability of solid-state 13C NMR spectroscopy with cross polarization (CP) and magic-angle spinning (MAS) to quantify the amounts of three of the multiple crystalline and amorphous forms of the artificial sweetener neotame is described. It was possible to quantify, in a mixture of two anhydrous polymorphic forms of neotame, the amount of each polymorph within 1,2%. In mixtures of amorphous and crystalline forms of neotame, the amorphous content could be determined within 5%. It was found that the crystalline standards that were used to prepare the mixtures were not pure crystalline forms, but rather a mixture of crystalline and amorphous forms. The effect of amorphous content in the crystalline standards on the overall quantitation of the two crystalline polymorphic forms is discussed. The importance of differences in relaxation parameters and CP efficiencies on quantifying mixtures of different forms using solid-state NMR spectroscopy is also addressed. © 2005 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 94:2591,2605, 2005 [source] Synthesis and characterization of synthetic polymer colloids colloidally stabilized by cationized starch oligomersJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 7 2009Marianne Gaborieau Abstract A method is developed for anchoring enzymatically degraded cationized starch as electrosteric stabilizers onto synthetic latices, using cerium(IV) to create free-radical grafting sites on the starch. Direct anchoring of debranched starch onto a poly(methyl methacrylate) seed latex yields a latex stabilized by well-defined oligosaccharides. Using ,-amylase to randomly cleave starch to form (1,4)-,-glucans, and a comonomer, N -isopropyl acrylamide (NIPAM), whose corresponding polymer exhibits a lower critical solution temperature (LCST), creates a means to synthesize block (or graft) oligomers of oligosaccharide and synthetic polymer, which are water soluble at room temperature. Above 30 °C, they become amphiphilic and form self-emulsifying nanoparticles (sometimes termed "frozen micelles") from which a synthetic latex is grown after addition of methyl methacrylate, the collapsed NIPAM-containing entities functioning as a type of in situ seed. This synthesis of stable synthetic latex particles is shown to have a high grafting efficiency. The starch fragments were characterized by 1H solution-state NMR before grafting, and 13C solid-state cross-polarization magic-angle spinning (CP-MAS) NMR was used to characterize the starch oligomers actually grafted on the final latex. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1836,1852, 2009 [source] Supramolecular inclusion complexes of star-shaped poly(,-caprolactone) with ,-cyclodextrinJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 20 2005Lu Wang Abstract Both star-shaped poly(,-caprolactone) (PCL) having 4 arms (4sPCL) and 6 arms (6sPCL) and linear PCL having 1 arm (LPCL) and 2 arms (2LPCL) were synthesized and then investigated for inclusion complexation with ,-cyclodextrin (,-CD). The supramolecular inclusion complexes (ICs) were in detail characterized by 1H NMR, differential scanning calorimetry, thermogravimetric analysis, wide angle X-ray diffraction, solid-state carbon nuclear magnetic resonance spectroscopy using cross-polarization and magic-angle spinning, and Fourier transform infrared, respectively. The stoichiometry (CL:CD, mol:mol) of all ICs increased with the increasing branch arm of PCL polymers, and it was in the order of ,-CD-6sPCL1 ICs > ,-CD-4sPCL ICs > ,-CD-2LPCL ICs > ,-CD-LPCL ICs. All analyses indicated that the branch arms of star-shaped PCL polymers were included into the hydrophobic ,-CD cavities and their original crystalline properties were completely suppressed. Moreover, the ICs of star-shaped PCL with ,-CD had a channel-type crystalline structure similar to that formed between the linear PCL and ,-CD. Furthermore, the thermal stability of the free PCL polymers probably controlled that of the guest polymers included in the ICs. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4721,4730, 2005 [source] Conductivity and characterization of polyurea electrolytes with carboxylic acidJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 24 2003Shao-Ming Lee Abstract Polyurea, which was synthesized from 4,4,-diphenylmethane diisocyanate, Jeffamine-ED2001 (weight-average molecular weight: 2000), and 3,5-diaminobanzoic acid (DABA) were doped with lithium perchlorate (LiClO4) as the polyelectrolyte. Differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy, and 7Li magic-angle spinning (MAS) solid-state NMR were used to monitor changes in the morphology of polyurea electrolytes corresponding to the concentration of LiClO4 dopants. DSC showed the glass-transition temperature of the hard and soft segments increases with salt concentration. FTIR indicated the carboxylic group of DABA coordinates with the Li+ ion, and the ordered hydrogen-bonded urea carbonyl groups are destroyed when the salt concentration exceeds 0.5 mmole of LiClO4 (gPUrea),1. The 7Li MAS solid-state NMR investigation of the polyurea electrolytes revealed the presence of two Li+ environments at lower temperature. Impedance spectroscopy measurements showed that the conductivity behavior followed the Arrhenius equation, and the maximum conductivity occurred when the crystalline structure of polyurea was disrupted. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 4007,4016, 2003 [source] Synthesis and characterization of chemically bonded stationary phases on hydride surfaces by hydrosilation of alkynes and dienesJOURNAL OF SEPARATION SCIENCE, JSS, Issue 18 2005Joseph J. Pesek Abstract A hydrosilation reaction was used to bind four compounds with one or more alkyne groups or two alkene functionalities. The diffuse reflectance infrared Fourier transform, the 29Si cross-polarization magic-angle spinning (CP-MAS) NMR, and the 13C CP-MAS NMR spectra were used to characterize the various bonded materials. The bonded phase density was determined from carbon elemental analysis. The two ten-carbon hydrophobic stationary phases were characterized chromatographically and static stability tests were run in acidic and basic solutions. [source] Further Conventions for NMR Shielding and Chemical Shifts (IUPAC Recommendations 2008),MAGNETIC RESONANCE IN CHEMISTRY, Issue 6 2008Applied Chemistry Physical, Biophysical Chemistry Division, International Union of Pure Abstract IUPAC has published a number of recommendations regarding the reporting of nuclear magnetic resonance (NMR) data, especially chemical shifts. The most recent publication [Pure Appl. Chem.73, 1795 (2001)] recommended that tetramethylsilane (TMS) serve as a universal reference for reporting the shifts of all nuclides, but it deferred recommendations for several aspects of this subject. This document first examines the extent to which the 1H shielding in TMS itself is subject to change by variation in temperature, concentration, and solvent. On the basis of recently published results, it has been established that the shielding of TMS in solution [along with that of sodium-3-(trimethylsilyl)propanesulfonate, DSS, often used as a reference for aqueous solutions] varies only slightly with temperature but is subject to solvent perturbations of a few tenths of a part per million (ppm). Recommendations are given for reporting chemical shifts under most routine experimental conditions and for quantifying effects of temperature and solvent variation, including the use of magnetic susceptibility corrections and of magic-angle spinning (MAS). This document provides the first IUPAC recommendations for referencing and reporting chemical shifts in solids, based on high-resolution MAS studies. Procedures are given for relating 13C NMR chemical shifts in solids to the scales used for high-resolution studies in the liquid phase. The notation and terminology used for describing chemical shift and shielding tensors in solids are reviewed in some detail, and recommendations are given for best practice. © 2008 IUPAC. Reprinted with permission from Pure Appl. Chem. 2008; 80: 59. This article can be freely downloaded from http://www.iupac.org/publications/pac/80/1/0059/ and can be copied, provided acknowledgement to IUPAC is given. [source] High-resolution magic-angle spinning NMR for the identification of reaction products directly from thin-layer chromatography spotsMAGNETIC RESONANCE IN CHEMISTRY, Issue 10 2007Scott A. Bradley Abstract We have investigated the prospect of identifying organic reaction products directly from separated thin-layer chromatography (TLC) spots with high-resolution magic-angle spinning (HRMAS) NMR. The concept is to use the TLC spots for NMR analysis so that spectra can be obtained before the reaction is worked up, but without having to elute the product from the TLC stationary phase. Thus, the separated spot is scraped from the plate, transferred to an HRMAS sample rotor, and suspended with a deuterated solvent. Herein, we describe the effects of having the stationary phase present during NMR acquisition. Using a Varian 4 mm gHX Nanoprobe and rotenone as a test compound, we found that the presence of the stationary phase during NMR acquisition resulted in (i) a large, broad ,background' signal near 4.6 ppm and (ii) a decrease in the signal-to-noise ratio due to the adsorption of the product molecules to the adsorbent. However, both effects could be adequately and conveniently eliminated. The background signal was removed by using either a CPMG pulse sequence or chemical exchange. The adsorption was avoided by using a more polar solvent system. Finally, we found that spectra with good signal-to-noise ratio and resolution could be acquired in a matter of minutes even for cases of limited product concentration. Therefore, we believe the technique has value and provides the organic chemist with another option to obtain NMR data critical for structural elucidation or verification. Copyright © 2007 John Wiley & Sons, Ltd. [source] Solid-state NMR characterization of 69Ga and 71Ga in crystalline solidsMAGNETIC RESONANCE IN CHEMISTRY, Issue 9 2006Jason T. Ash Abstract Gallium model systems containing four- and six-coordinate gallium sites have been investigated using solid-state NMR. Measurement of the isotropic chemical shift and electric field gradient (EFG) have been performed at 9.4 T on ,-Ga2O3, ,-Ga2O3, LiGaO2, NaGaO2, KGaO2, Ga2(SO4)3, and LaGaO3 using a variety of techniques on both NMR active nuclei (69Ga and 71Ga) including static, high speed magic-angle spinning (MAS), satellite transition (ST) spectroscopy, and rotor-assisted population transfer (RAPT). The chemical shift is found to correlate well with the coordination number, with four-coordinate gallium having values of approximately 50 ppm and six-coordinate gallium having values near 225 ppm (referenced to 1 M gallium nitrate solution). The magnitude of the EFG is found to be correlated to the distortion of the gallium polyhedra, with the strained systems having EFGs of 3 × 1021 Vm,2 or more, while the less strained systems have values of 1.5 × 1021 Vm,2 or less. A plot of chemical shift versus EFG suggests that solid-state NMR of gallium oxyanions can be more discriminating than liquid state NMR chemical shifts alone. Copyright © 2006 John Wiley & Sons, Ltd. [source] NMR nomenclature: nuclear spin properties and conventions for chemical shifts.MAGNETIC RESONANCE IN CHEMISTRY, Issue 7 2002Applied Chemistry., IUPAC Recommendations 2001., International Union of Pure Abstract An Addendum has been published for this article in Magnetic Resonance in Chemistry 40(9) 2002, 622. A unified scale is recommended for reporting the NMR chemical shifts of all nuclei relative to the 1H resonance of tetramethylsilane. The unified scale is designed to provide a precise ratio, ,, of the resonance frequency of a given nuclide to that of the primary reference, the 1H resonance of tetramethylsilane (TMS) in dilute solution (volume fraction, , < 1%) in chloroform. Referencing procedures are discussed, including matters of practical application of the unified scale. Special attention is paid to recommended reference samples, and values of , for secondary references on the unified scale are listed, many of which are the results of new measurements. Some earlier recommendations relating to the reporting of chemical shifts are endorsed. The chemical shift, ,, is redefined to avoid previous ambiguities but to leave practical usage unchanged. Relations between the unified scale and recently published recommendations for referencing in aqueous solutions (for specific use in biochemical work) are discussed, as well as the special effects of working in the solid state with magic-angle spinning. In all, nine new recommendations relating to chemical shifts are made. Standardized nuclear spin data are also presented in tabular form for the stable (and some unstable) isotopes of all elements with non-zero quantum numbers. The information given includes quantum numbers, isotopic abundances, magnetic moments, magnetogyric ratios and receptivities, together with quadrupole moments and linewidth factors (where appropriate). Copyright 2001 IUPAC. Reprinted with permission from Pure Appl. Chem. 2001; 73: 1795. [source] Influence of hemicelluloses on the structure and properties of Lyocell fibersPOLYMER ENGINEERING & SCIENCE, Issue 5 2007Huiru Zhang In the present paper the difference in the structure and properties of Lyocell fibers with different hemicelluloses content was investigated. The supermolecular structure and the morphological characterization were compared. The fibril aggregation size was estimated by the cross-polarization magic-angle spinning carbon-13 nuclear magnetic resonance (CP/MAS13C-NMR) spectroscopy. Meanwhile, the difference in the mechanical, the fibrillation resistance and the dyeing properties of Lyocell fiber with different hemicelluloses content was also analyzed. POLYM. ENG. SCI., 47:702,706, 2007. © 2007 Society of Plastics Engineers. [source] Chemical shift assignment of the transmembrane helices of DsbB, a 20-kDa integral membrane enzyme, by 3D magic-angle spinning NMR spectroscopyPROTEIN SCIENCE, Issue 2 2008Ying Li Abstract The Escherichia coli inner membrane enzyme DsbB catalyzes disulfide bond formation in periplasmic proteins, by transferring electrons to ubiquinone from DsbA, which in turn directly oxidizes cysteines in substrate proteins. We have previously shown that DsbB can be prepared in a state that gives highly resolved magic-angle spinning (MAS) NMR spectra. Here we report sequential 13C and 15N chemical shift assignments for the majority of the residues in the transmembrane helices, achieved by three-dimensional (3D) correlation experiments on a uniformly 13C, 15N-labeled sample at 750-MHz 1H frequency. We also present a four-dimensional (4D) correlation spectrum, which confirms assignments in some highly congested regions of the 3D spectra. Overall, our results show the potential to assign larger membrane proteins using 3D and 4D correlation experiments and form the basis of further structural and dynamical studies of DsbB by MAS NMR. [source] X-ray Diffraction and Solid-State NMR Studies of a Germanium Binuclear ComplexCHEMISTRY - A EUROPEAN JOURNAL, Issue 2 2006Luís Mafra Abstract A compound formulated as (C4H12N2)[Ge2(pmida)2(OH)2],4,H2O (where pmida4,=N -(phosphonomethyl)iminodiacetate and C4H12N22+=piperazinedium cation), containing the anionic [Ge2(pmida)2(OH)2]2, complex, has been synthesised by the hydrothermal approach and its structure determined by single-crystal X-ray diffraction analysis. Several high-resolution solid-state magic-angle spinning (MAS) NMR techniques, in particular two-dimensional 1H,X(13C,31P) heteronuclear correlation (HETCOR) and 1H,1H homonuclear correlation (HOMCOR) experiments incorporating a frequency-switched Lee,Goldburg (FS-LG) decoupling scheme, have been employed for the first time in such a material. Using these tools in tandem affords an excellent general approach to study the structure of other inorganic,organic hybrids. We assigned the NMR resonances with the help of C,,,H and P,,,H internuclear distances obtained through systematic statistical analyses of the crystallographic data. The compound was further characterised by powder X-ray diffraction techniques, IR and Raman spectroscopy, and by elemental and thermal analyses (thermogravimetric analysis and differential scanning calorimetry). [source] Preparation and Characterization of Inclusion Complexes of ,-Cyclodextrin with Ionic LiquidCHEMISTRY - A EUROPEAN JOURNAL, Issue 20 2005Yan-An Gao Abstract The solubilities of ,-cyclodextrin (,-CD), ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF6), and their mixture in water were determined, and the conductivity of these aqueous solutions was measured. It was demonstrated that ,-CD and bmimPF6 could enhance the solubility of each other, and the solubility curves of each were linear with gradients of about 1. The conductivity decreased remarkably with increasing , - CD concentration, and a discernible break in the conductivity curve could be observed when ,-CD and bmimPF6 were equimolar in the solution. The solubility and conductivity results indicated that inclusion complexes (ICs) of 1:1 stoichiometry were formed. The inclusion compounds were further characterized by using powder X-ray diffraction (XRD) analysis, 13C CP/MAS (cross-polarization magic-angle spinning) NMR and 1H NMR spectroscopy, and thermogravimetric analysis (TGA). The results showed that the ICs were a fine crystalline powder. The host,guest system exhibited a channel-type structure and each glucose unit of ,-CD was in a similar environment. The decomposition temperature of the ICs was lower than that of bmimPF6 and ,-CD individually. [source] Synthesis of Large-Pore Urea-Bridged Periodic Mesoporous OrganosilicasCHEMISTRY - AN ASIAN JOURNAL, Issue 4 2009Ling Gao Abstract Bringing order: A new class of periodic mesoporous organosilicas (PMOs) with a urea-bridged organosilica precursor under acid-catalyzed and inorganic-salt-assisted conditions was obtained. The large-pore hybrid materials have ordered mesostructure with uniform pore size distributions, which can be seen from the TEM images. In this article we report the successful synthesis of a new class of periodic mesoporous organosilicas (PMOs) with a urea-bridged organosilica precursor under acid-catalyzed and inorganic-salt-assisted conditions. The large-pore hybrid materials have an ordered mesostructure with uniform pore size distributions, excellent thick framework walls, thermal stability, and specific functional groups. The composition of the mesoporous organosilicas was characterized by FTIR spectroscopy, 13C cross-polarization magic-angle spinning (CP,MAS) NMR spectroscopy, and 29Si MAS NMR spectroscopy. [source] Sensitivity Enhancement in Two-Dimensional Solid-State NMR Spectroscopy by Transverse MixingCHEMPHYSCHEM, Issue 6 2004Robert Tycko Dr. Abstract The sensitivity of two-dimensional (2D) 13C,13C solid-state NMR spectroscopy under magic-angle spinning (MAS) is shown to be enhanced by the use of transverse polarization transfer in place of the conventional longitudinal polarization transfer. Experimental results are reported for 2D spectroscopy of a 20-residue, filament-forming peptide derived from the E. coli RecA protein, containing five uniformly 13C-labeled residues, performed at 14.1 T with high-speed MAS and with finite-pulse radio-frequency-driven recoupling of dipolar interactions in the mixing period. Significant sensitivity enhancements observed at short mixing periods result from a more rapid build-up of cross-peaks under transverse mixing than under longitudinal mixing and from the gain inherent in 2D measurements in which both orthogonal transverse polarization components in the t1 period contribute to each free-induction decay signal detected in the t2 period. [source] Catalytic Performances of Binder-free ZSM-5 Catalysts for Dehydration of Crude Methanol to Dimethyl EtherCHINESE JOURNAL OF CHEMISTRY, Issue 2 2010Jing Wang Abstract A series of binder-free ZSM-5 catalysts and a binder-containing catalyst were prepared and characterized with X-ray diffraction (XRD), X-ray fluorescence (XRF), 27Al magic-angle spinning (MAS) nuclear magnetic resonance (NMR), N2 sorption and ammonia temperature-programmed deposition (TPD) methods. The catalytic activity and selectivity in the dehydration of crude methanol to dimethyl ether (DME) were evaluated in a fixed-bed reactor for the catalysts. The outstanding structural characters such as high zeolite contents, sufficiently open channels and richness in mesopores have been proved on these binder-free catalysts. The influence of the solid-acidity, which is closely related to the framework silica alumina ratio (SAR) of the catalysts, on the catalytic properties has been discussed. A binder-free catalyst with a better potential in application has been selected for its high activity and selectivity, long life-time and non-sensitivity to water contents in the feed. The reason for its excellent performance of the catalyst was discussed. [source] | ||||||||||||||||