Solid‐state NMR study on changes of phosphate and proton species in metal pyrophosphate composite (MP2O7–MO2) ceramics

In order to investigate the effects of composite production and the role of the counter cation for metal phosphate conductors, changes in the solid‐state nuclear magnetic resonance (NMR) spectra and magnetic relaxation times caused by the removal of volatile products and water washing were examined for various metal pyrophosphate (MP₂O₇–MO₂; M = Sn, Si, Ti, and Zr). Acidic species could be detected by ¹H MAS NMR spectra for all the composites except ZrP₂O₇–ZrO₂ that had the lowest conductivity. The ³¹P DD‐MAS NMR spectra for MP₂O₇–MO₂ composites showed different signal patterns depending on the counter cations participating in the ion exchange as a result of different microstructures. Combinational analysis of ³¹P DD‐MAS and ³¹P CP‐MAS NMR spectra of the composites indicated that protonic bulk phosphates were observed at slightly lower fields than non‐protonic bulk phosphates in all of the MP₂O₇–MO₂ composites. After water washing, the acidic species and the protonic bulk phosphates of MP₂O₇–MO₂ composites disappeared or were reduced to trace amounts. The T₁H values of the water‐washed composites lengthened because of removal of orthophosphoric acid, although the T₁P values remained almost unchanged. The results of the solid‐state NMR studies suggest that the protonic bulk phosphates of MP₂O₇–MO₂ composites do not generally distribute in the bulk but exist in the interface between excess H₃PO₄ and the bulk. Copyright © 2016 John Wiley & Sons, Ltd.     

Layered metal(IV) phosphonate materials: Solid‐state 1H, 13C, 31P NMR spectra and NMR relaxation

Multinuclear solid‐state NMR and powder X‐ray diffraction data collected for phosphonate materials Zr(O₃PC₆H₄PO₃) · 3.6H₂O and Sn(O₃PC₆H₄PO₃)_0.85(O₃POH)_0.30 · 3.09H₂O have resulted in the layered structure, where the phosphonic acids cross‐link the layers. The main structural motif (the 111 connectivity in the PO₃ group) has been established by determination of chemical shift anisotropy parameters for phosphorus nuclei in the phosphonate groups. An analysis of the variable‐temperature ³¹P T₁ measurements and the shapes of the phosphorus resonances in the ³¹P static NMR spectra have resulted in the dipolar mechanism of the phosphorus spin‐lattice relaxation, where the rotating phenylene rings reorient dipolar vectors P^…H as a driving force of the relaxation process. It has been found that water protons do not affect the ³¹P T₁ times. The activation energy of the phenylene rotation in both compounds has been determined as low as 12.5 kJ/mol. The interpretation of the phosphorus relaxation data has been independently confirmed by the measurements of ¹H T₁ times for protons of the phenylene rings.     

Solid‐state 1H → 19F/19F → 1H CP/MAS NMR study of poly(vinylidene fluoride)

Solid‐state ¹H → ¹⁹F and ¹⁹F → ¹H cross‐polarization magic angle spinning (CP/MAS) NMR spectra have been investigated for a semicrystalline fluoropolymer, namely poly(vinylidene fluoride) (PVDF). The ¹H → ¹⁹F CP/MAS spectra can be fitted by five Lorentzian functions, and the amorphous peaks were selectively observed by the DIVAM CP pulse sequences. Solid‐state spin‐lock experiments showed significant differences in T_1ρ^F and T_1ρ^H between the crystalline and amorphous domains, and the effective time constants, T_HF* and T_1ρ*, which were estimated from the ¹H → ¹⁹F CP curves, also clarify the difference in the strengths of dipolar interactions. Heteronuclear dipolar oscillation behaviour is observed in both standard CP and ¹H → ¹⁹F inversion recovery CP (IRCP) experiments. The inverse ¹⁹F → ¹H CP‐MAS and ¹H → ¹⁹F CP‐drain MAS experiments gave complementary information to the standard ¹H → ¹⁹F CP/MAS spectra in a manner reported in our previous papers for other fluoropolymers. The value of N_F/N_H (where N is a spin density) estimated from the CP‐drain curve is within experimental error equal to unity, which is consistent with the chemical structure. Copyright © 2001 John Wiley & Sons, Ltd.     

Solid‐state NMR studies of 1,3‐imidazolidine‐2‐selenone and some related compounds

Solid‐state cross‐polarization magic angle spinning ¹³C, ⁷⁷Se and ¹⁵N NMR spectra were recorded for 1,3‐imidazolidine‐2‐selenone, its N‐substituted derivatives and some related compounds. The spinning sideband manifold intensities were used to obtain principal values of ¹³C and ⁷⁷Se chemical shift tensors. Large selenium chemical shift anisotropies were observed for these selenones. Copyright © 2003 John Wiley & Sons, Ltd.     

Solid‐state 31P NMR investigation on the status of guanine nucleotides in paclitaxel‐stabilized microtubules

Microtubule dynamics is a target for many chemotherapeutic drugs. In order to understand the biochemical effects of paclitaxel on the GTPase activity of tubulin, the status of guanine nucleotides in microtubules was investigated by ³¹P cross‐polarization magic angle spinning (CPMAS) NMR. Microtubules were freshly prepared in vitro in the presence of paclitaxel and then lyophilized in sucrose buffer for solid‐state NMR experiments. A ³¹P CPMAS NMR spectrum with the SNR of 25 was successfully acquired from the lyophilized microtubule sample. The broadness of the ³¹P spectral lines in the spectrum indicates that the molecular environments around the guanine nucleotides inside tubulin may not be as crystalline as reported by many diffraction studies. Deconvolution of the spectrum into four spectral components was carried out in comparison with the ³¹P NMR spectra obtained from five control samples. The spectral analysis suggested that about 13% of the nucleotides were present as GTP and 37% as GDP in the β‐tubulin (E‐site) of the microtubules. It was found that most of the GDPs were present as GDP‐P_i complex in the microtubules, which seems to be one of the effects of paclitaxel binding. Copyright © 2015 John Wiley & Sons, Ltd.     

Phosphorylated amino acids: model compounds for solid-state 31P NMR spectroscopic studies of proteins

Solid-state 31P NMR spectroscopy was applied to measure the isotropic chemical shifts, chemical shift anisotropies and asymmetry parameters of three phosphorylated amino acids, O-phospho-L-serine, O-phospho-L-threonine and O-phospho-L-tyrosine. The cross-polarization buildup rates and longitudinal relaxation times of 31P and 1H were-determined and compared with the values measured for a triphosphate (GppCH2p) bound to a crystalline protein (Ras). It is shown that the phosphorylated amino acids are well-suited model compounds, e.g. for the optimization of experiments on crystalline proteins. Two-dimensional exchange experiments on O-phospho-L-tyrosine indicate the existence of an exchange between the two different conformations of the molecule.     

Complete 1H, 13C, 19F and 31P NMR data assignment of CWC‐related chemicals N,N‐dialkyl‐P‐alkyl phosphonamidic fluorides

The complete multinuclear ¹H, ¹³C, ³¹P and ¹⁹F NMR data of symmetrically substituted amines containing N,N‐dialkyl‐P‐alkyl phosphonamidic fluorides are presented. Assignment was achieved, using various one‐and two‐dimensional NMR experiments. Copyright © 2010 John Wiley & Sons, Ltd.     

NOESY,HOESY, T1 and solid‐state NMR studies on [RuH(η6‐toluene)(Binap)](CF3SO3): a molecule with a strongly distorted piano‐stool structure

Detailed solution‐NMR studies on the distorted ruthenium hydride complex [RuH(η⁶‐toluene)(Binap)](CF₃SO₃) (2) are reported. NOE‐spectroscopy, together with low‐temperature ¹H and ³¹P NMR data, reveals restricted rotation around a P—C bond for a specific axial P—phenyl ring with the activation energy determined via simulation. From ¹⁹F, ¹H HOESY data, the approach of the triflate anion relative to the hydride ligand is established. Comparison of the quadrupole coupling constant C_QF from both solution‐ and solid‐state MAS‐NMR on the deuteride [RuD(η⁶‐benzene)(Binap)](CF₃SO₃) (1‐D) provide information on the nature of the Ru—H bond. Copyright © 2003 John Wiley & Sons, Ltd.     

Modification and intercalation of layered zirconium phosphates: a solid‐state NMR monitoring

Several layered zirconium phosphates treated with Zr(IV) ions, modified by monomethoxy‐polyethyleneglycol‐monophosphate and intercalated with doxorubicin hydrochloride have been studied by solid‐state MAS NMR techniques. The organic components of the phosphates have been characterized by the ¹³C{¹H} CP MAS NMR spectra compared with those of initial compounds. The multinuclear NMR monitoring has provided to establish structure and covalent attachment of organic/inorganic moieties to the surface and interlayer spaces of the phosphates. The MAS NMR experiments including kinetics of proton‐phosphorus cross polarization have resulted in an unusual structure of zirconium phosphate 6 combining decoration of the phosphate surface by polymer units and their partial intercalation into the interlayer space. Copyright © 2016 John Wiley & Sons, Ltd.     

Physicochemical characterization of the dimeric lanthanide complexes [en{Ln(DO3A)(H2O)}2] and [pi{Ln(DTTA)(H2O)}2]2-: a variable-temperature 17O NMR study

The Gd(III) complexes of the two dimeric ligands [en(DO3A)2] {N,N'-bis[1,4,7-tris(carboxymethyl)-1,4,7,10-tetraazacyclododecan-10-yl-methylcarbonyl]-N,N'-ethylenediamine} and [pi(DTTA)2]8- [bisdiethylenetriaminepentaacetic acid (trans-1,2-cyclohexanediamine)] were synthesized and characterized. The 17O NMR chemical shift of H2O induced by [en{Dy(DO3A)}2] and [pi{Dy(DTTA)}2]2- at pH 6.80 proved the presence of 2.1 and 2.2 inner-sphere water molecules, respectively. Water proton spin-lattice relaxation rates for [en{Gd(DO3A)(H2O)}2] and [pi{Gd(DTTA)(H2O)}2]2- at 37.0 +/- 0.1 degrees C and 20 MHz are 3.60 +/- 0.05 and 5.25 +/- 0.05 mM(-1) s(-1) per Gd, respectively. The EPR transverse electronic relaxation rate and 17O NMR transverse relaxation time for the exchange lifetime of the coordinated H2O molecule and the 2H NMR longitudinal relaxation rate of the deuterated diamagnetic lanthanum complex for the rotational correlation time were thoroughly investigated, and the results were compared with those reported previously for other lanthanide(III) complexes. The exchange lifetimes for [en{Gd(DO3A)(H2O)}2] (769 +/- 10 ns) and [pi{Gd(DTTA)(H2O)}2]2- (910 +/- 10 ns) are significantly higher than those of [Gd(DOTA)(H2O)]- (243 ns) and [Gd(DTPA)(H2O)]2- (303 ns) complexes. The rotational correlation times for [en{Gd(DO3A)(H2O)}2] (150 +/- 11 ps) and [pi{Gd(DTTA)(H2O)}2]2- (130 +/- 12 ps) are slightly greater than those of [Gd(DOTA)(H2O)]- (77 ps) and [Gd(DTPA)(H2O)]2- (58 ps) complexes. The marked increase in relaxivity (r1) of [en{Gd(DO3A)(H2O)}2] and [pi{Gd(DTTA)(H2O)}2]2- result mainly from their longer rotational correlation time and higher molecular weight.     

Solid‐state NMR studies of cis‐1,4‐polyisoprene crosslinked with dicumyl peroxide in the presence of triallyl cyanurate

The network of dicumyl peroxide (DCP)/triallyl cyanurate (TAC) crosslinked cis‐1,4‐polyisoprene was studied by solid‐state NMR techniques such as direct‐polarization (DP), cross‐polarization (CP), and proton T₂ experiments. Line broadening and cis/trans isomerization of mobile carbons were observed in the DP experiments. The information on rigid carbons of network structures was observed with the CP technique. Motional heterogeneity was examined by proton T₂ relaxation experiments. Decreases in long T₂ (T_2L) values from the mobile non‐network structures and short T₂ (T_2S) values from the rigid network structures were observed with an increase in peroxide or coagent concentration. The percentage of T_2S in T₂ relaxation, which is related to network density, was observed to increase with peroxide and coagent addition. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1417–1423, 2000     

1H, 13C, 17O NMR and quantum‐chemical study of the stereochemistry of the sulfoxide and sulfone derivatives of 3‐arylidene‐1‐thioflavan‐4‐one epoxides

The oxidation of the trans,cis‐( 2 ) and trans,trans‐epoxides ( 3 ) of differently substituted (Z)‐3‐arylidene‐1‐thioflavan‐4‐ones ( 1 ) with dimethyldioxirane (DMD) yielded the appropriate sulfoxides ( 4, 5 ) and sulfones ( 6, 7 ). The structures were elucidated by the extensive application of one‐ and two‐dimensional ¹H, ¹³C and ¹⁷O NMR spectroscopy. The conformational analysis was achieved by the application of ³J(C,H) coupling constants, NOESY responses and ab initio calculations. The preferred ground‐state conformers (twisted envelope‐A, twisted envelope‐B for 6 and twisted envelope‐A, envelope‐B for 7 ) were obtained as global minima of the theoretical ab initio MO study and also the examination of the ¹⁷O and ¹³C chemical shifts, calculated for the global minima structures of the sulfone isomers by the GIAO method. Analogous results, obtained for the sulfoxide isomers ( 4, 5 ), not only led to the preferred conformers but also gave evidence for the trans arrangement of the 2‐Ph group and the oxygen atom of the S?O group. Chemical shift differences between the isomers, sulfoxides and sulfones were corroborated by ab initio calculations of the anisotropic effects of the oxirane ring and the S?O and SO₂ groups. Copyright © 2003 John Wiley & Sons, Ltd.     

Probing the interaction of the potassium channel modulating KCNE1 in lipid bilayers via solid‐state NMR spectroscopy

KCNE1 is known to modulate the voltage‐gated potassium channel α subunit KCNQ1 to generate slowly activating potassium currents. This potassium channel is essential for the cardiac action potential that mediates a heartbeat as well as the potassium ion homeostasis in the inner ear. Therefore, it is important to know the structure and dynamics of KCNE1 to better understand its modulatory role. Previously, the Sanders group solved the three‐dimensional structure of KCNE1 in LMPG micelles, which yielded a better understanding of this KCNQ1/KCNE1 channel activity. However, research in the Lorigan group showed different structural properties of KCNE1 when incorporated into POPC/POPG lipid bilayers as opposed to LMPG micelles. It is hence necessary to study the structure of KCNE1 in a more native‐like environment such as multi‐lamellar vesicles. In this study, the dynamics of lipid bilayers upon incorporation of the membrane protein KCNE1 were investigated using ³¹P solid‐state nuclear magnetic resonance (NMR) spectroscopy. Specifically, the protein/lipid interaction was studied at varying molar ratios of protein to lipid content. The static ³¹P NMR and T₁ relaxation time were investigated. The ³¹P NMR powder spectra indicated significant perturbations of KCNE1 on the phospholipid headgroups of multi‐lamellar vesicles as shown from the changes in the ³¹P spectral line shape and the chemical shift anisotropy line width. ³¹P T₁ relaxation times were shown to be reversely proportional to the molar ratios of KCNE1 incorporated. The ³¹P NMR data clearly indicate that KCNE1 interacts with the membrane. Copyright © 2017 John Wiley & Sons, Ltd.     

Fingerprints of Phalaenopsis Tissues in Growth and Spike Induction Periods—A Solid‐state 13C NMR Approach

Solid‐state Nuclear Magnetic Resonance (ss‐NMR) ¹³C single‐pulse excitation spectroscopy in combination with the magic‐angle spinning (MAS) technique was applied to a series of Phalaenopsis tissues, including the leaf, sheath, stem, and root, at different growth and spiking periods. Compared with{¹H}/¹³C cross‐polarization MAS spectra, the ¹³C single‐pulse excitation MAS spectra displayed very distinct spectral patterns, recognizable as fingerprints of the tissues studied. ¹Here, we demonstrate that solid‐state ¹³C single‐pulse excitation NMR spectroscopy provides a direct and robust analytical tool for studying the various tissues of Phalaenopsis in different growth and spiking induction periods.     

Complete NMR assignment of (+)‐10β,14‐dihydroxy‐allo‐aromadendrane

The assignment of ¹H and ¹³C NMR of the sesquiterpene (+)‐10β,14‐dihydroxy‐allo‐aromadendrane by means of two‐dimensional NMR is reported. Copyright © 2003 John Wiley & Sons, Ltd.     

Engineering of an all‐heteronuclear 5‐qubit NMR quantum computer

The realization of an all‐heteronuclear 5‐qubit nuclear magnetic resonance quantum computer is reported, from the design and synthesis of a suitable molecule through the engineering of a prototype 6‐channel probe head. Full control over the quantum computer is shown by a benchmark experiment. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and Characterization of the New Lacunar Zincophosphate [C6H10N2][ZnP2O8H2]·0.6H2O

The new zincophosphate of chemical formula [C₆H₁₀N₂][ZnP₂O₈H₂] · 0.6H₂O was hydrothermally synthesized with p‐phenylenediamine as structure‐directing agent. The title compound crystallizes in the trigonal symmetry (proposed space group P3m1), where inorganic zincophosphate chains form layers due to the half occupancy of the unique crystallographic zinc site. The layers are separated from each other by p‐phenylenediammonium dications with hydrogen bonding scheme involving the ammonium protons that reveals a pillar‐like 3D structure aspect. The compound was characterized by powder X‐ray diffraction, multinuclear solid‐state NMR, scanning electron microscopy, chemical analysis, and thermogravimetric analysis.     

Comparison of the substituent effects on the 13C NMR with the 1H NMR chemical shifts of CHN in substituted benzylideneanilines

Fifty‐two samples of substituted benzylideneanilines XPhCH?NPhYs (XBAYs) were synthesized, and their NMR spectra were determined in this paper. Together with the NMR data of other 77 samples of XBAYs quoted from literatures, the ¹H NMR chemical shifts (δ_H(CH?N)) and ¹³C NMR chemical shifts (δ_C(CH?N)) of the CH?N bridging group were investigated for total of 129 samples of XBAYs. The result shows that the δ_H(CH?N) and δ_C(CH?N) have no distinctive linear relationship, which is contrary to the theoretical thought that declared the δ_H(CH?N) values would increase as the δ_C(CH?N) values increase. With the in‐depth analysis, we found that the effects of σ_F and σ_R of X/Y group on the δ_H(CH?N) and the δ_C(CH?N) are opposite; the effects of the substituent specific cross‐interaction effect between X and Y (Δσ²) on the δ_H(CH?N) and the δ_C(CH?N) are different; the contributions of parameters in the regression equations of the δ_H(CH?N) and the δ_C(CH?N) [Eqns 4 and 7), respectively] also have an obvious difference. Copyright © 2015 John Wiley & Sons, Ltd.     

Determination of 31P,31P coupling constants in cyclotriphosphazenes and their influence on 1H and 13C NMR spectra of phosphorus substituents

¹H and ¹³C NMR spectra of symmetrically substituted cyclotriphosphazenes exhibit second‐order effects. The influence of the ³¹P,³¹P coupling constants between ring phosphorus atoms on these effects was studied. Some values of this coupling constant between phosphorus bearing identical substituents were measured using ¹³C satellites of the ³¹P signals or by introduction of a chiral substituent on the third phosphorus atom. Copyright © 2003 John Wiley & Sons, Ltd.     

Isoquinoline alkaloids: a 15N NMR and x‐ray study. Part 2

Continuing our systematic ¹⁵N NMR study of isoquinoline alkaloids, we report a contribution extending our previous paper. The ¹⁵N NMR chemical shifts and ¹⁵N,¹H long‐range coupling pathways of tertiary and quaternary isoquinoline alkaloids of several constitutional types are presented. The selected compounds belong to the protoberberine, proaporphine, pavinane, rhoeadine and phtalideisoquinoline classes of alkaloids and were investigated by gradient‐selected inverse‐detected multiple bond correlation experiments (GHMBC and GSQMBC). In addition, x‐ray data and the principal geometric parameters of stylopine, mecambridine, norchelerythrine, isothebaine and mecambrine are reported and discussed. Copyright © 2002 John Wiley & Sons, Ltd.