K Takegoshi

Kyoto University, Kioto, Kyōto, Japan

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Publications (137)512.89 Total impact

  • [Show abstract] [Hide abstract]
    ABSTRACT: The effect of (1)H decoupling in magic-angle spinning solid-state NMR is studied under radiofrequency irradiation causing simultaneous nutations around a pair of orthogonal axes. Double-nutation with an arbitrary pair of nutation frequencies is implemented through modulation of the amplitude, phase, and frequency of the transmitting pulses. Similarity and difference of double-nutation decoupling and two-pulse phase-modulation decoupling schemes [A. E. Bennett, C. M. Rienstra, M. Auger, K. V. Lakshmi, and R. G. Griffin, J. Chem. Phys. 103, 6951-6958 (1995) and I. Scholz, P. Hodgkinson, B. H. Meier, and M. Ernst, J. Chem. Phys. 130, 114510 (2009)] are discussed. The structure of recoupling bands caused by interference of the (1)H spin nutation with sample spinning is studied by both experiments and numerical simulations.
    The Journal of Chemical Physics 12/2014; 141(22):224202. · 3.12 Impact Factor
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    ABSTRACT: Proton multiple-quantum (MQ) spin-counting experiment has been employed to study arrangement of hydrogen atoms in 9 Å/11 Å natural/synthetic tobermorites. Even though all tobermorite samples give similar characterless, broad static-powder 1H NMR spectra, their MQ spin-counting spectra are markedly different; higher quanta in 11 Å tobermorite do not grow with the MQ excitation time, while those in 9 Å one do. A statistical analysis of the MQ results recently proposed [26] is applied to show that hydrogens align in 9 Å tobermorite one dimensionally, while in 11 Å tobermorite they exist as a cluster of 5–8 hydrogen atoms.
    Cement and Concrete Research 12/2014; 66:115–120. · 3.85 Impact Factor
  • Naoki Ichijo, Kazuyuki Takeda, K. Takegoshi
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    ABSTRACT: We propose a new passive shimming strategy for variable-field NMR experiments, in which the magnetic field produced by paramagnetic shim pieces placed inside the magnet bore compensates the inhomogeneity of a variable-field magnet for a wide range of magnet currents. Paramagnetic shimming is demonstrated in (7)Li, (87)Rb, and (45)Sc NMR of a liquid solution sample in magnetic fields of 3.4, 4.0, and 5.4T at a fixed carrier frequency of 56.0MHz. Since both the main-field inhomogeneity and the paramagnetic magnetization are proportional to the main-magnet current, the resonance lines are equally narrowed by the improved field homogeneity with an identical configuration of the paramagnetic shim pieces. Paramagnetic shimming presented in this work opens the possibility of high-resolution variable-field NMR experiments.
    Journal of Magnetic Resonance 09/2014; · 2.32 Impact Factor
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    ABSTRACT: We propose a cross polarization (CP) sequence effective under magic-angle spinning (MAS) which is tolerant to RF field inhomogeneity and Hartmann-Hahn mismatch. Its key feature is that spin locking is not used, as CP occurs among the longitudinal (Z) magnetizations modulated by the combination of two pulses with the opposite phases. We show that, by changing the phases of the pulse pairs synchronized with MAS, the flip-flop term of the dipolar interaction is restored under MAS.
    Journal of Magnetic Resonance 08/2014; · 2.32 Impact Factor
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    ABSTRACT: We explore modulation-sideband recoupling conditions of the (13)C-(13)C Second-order Hamiltonian among Analogous nuclei plus pulse sequence (SHA+), and found that this sequence can be used in two different recoupling regimes. The first regime, νR>Δνiso(max), is recommended for broad-band recoupling to avoid any rotational resonance broadening. In this regime, the spinning speed should be only slightly larger than Δνiso(max), to obtain the best transfer efficiency. The second regime, νR<Δνiso(max), can be used to observe long-range constraints with lower spinning speed, which increases the transfer efficiency, and may allow using bigger rotors to increase the S/N ratio.
    Solid State Nuclear Magnetic Resonance 08/2013; · 2.86 Impact Factor
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    ABSTRACT: Pradimicins (PRMs) and benanomicins are the only family of non-peptidic natural products with lectin-like properties, that is, they recognize D-mannopyranoside (Man) in the presence of Ca(2+) ions. Coupled with their unique Man binding ability, they exhibit antifungal and anti-HIV activities through binding to Man-containing glycans of pathogens. Notwithstanding the great potential of PRMs as the lectin mimics and therapeutic leads, their molecular basis of Man recognition has yet to be established. Their aggregate-forming propensity has impeded conventional interaction analysis in solution, and the analytical difficulty is exacerbated by the existence of two Man binding sites in PRMs. In this work, we investigated the geometry of the primary Man binding of PRM-A, an original member of PRMs, by the recently developed analytical strategy using the solid aggregate composed of the 1:1 complex of PRM-A and Man. Evaluation of intermolecular distances by solid-state NMR spectroscopy revealed that the C2-C4 region of Man is in close contact with the primary binding site of PRM-A, while the C1 and C6 positions of Man are relatively distant. The binding geometry was further validated by co-precipitation experiments using deoxy-Man derivatives, leading to the proposal that PRM-A binds not only to terminal Man residues at the non-reducing end of glycans, but also to internal 6-substituted Man residues. The present study provides new insights into the molecular basis of Man recognition and glycan specificity of PRM-A.
    Chemistry - A European Journal 07/2013; 19(32). · 5.93 Impact Factor
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    ABSTRACT: The aggregation of 42-residue amyloid β-protein (Aβ42) is involved in the pathogenesis of Alzheimer's disease (AD). Numerous flavonoids exhibit inhibitory activity against Aβ42 aggregation, but their mechanism remains unclear in molecular level. Here we propose the site-specific inhibitory mechanism of (+)-taxifolin, a catechol-type flavonoid, whose 3',4'-dihydroxyl groups of the B-ring plays a critical role. Addition of sodium periodate, an oxidant, strengthened suppression of Aβ42 aggregation by (+)-taxifolin, whereas no inhibition was observed under anaerobic conditions, suggesting the inhibition to be associated with the oxidation to form o-quinone. Since the formation of Aβ42-taxifolin adduct was suggested by mass spectrometry, Aβ42 mutants substituted at Arg5, Lys16, and/or Lys28 with norleucine (nL) were prepared to identify the residues involved in the conjugate formation. (+)-Taxifolin did not suppress the aggregation of Aβ42 mutants at Lys16 and/or Lys28 except for the mutant at Arg5. In addition, the aggregation of Aβ42 was inhibited by other catechol-type flavonoids, while that of K16nL-Aβ42 was not. In contrast, some non-catechol-type flavonoids suppressed the aggregation of K16nL-Aβ42 as well as Aβ42. Furthermore, interaction of (+)-taxifolin with β-sheet in Aβ42 was not observed using solid-state NMR unlike curcumin of non-catechol-type. These results demonstrate that catechol-type flavonoids could specifically suppress Aβ42 aggregation by targeting Lys-residues. Although the anti-AD activity of flavonoids has been ascribed to their anti-oxidative activity, the mechanism that the o-quinone reacts with Lys-residues of Aβ42 might be more intrinsic. The Lys-residues could be targets for Alzheimer's therapy.
    Journal of Biological Chemistry 06/2013; · 4.60 Impact Factor
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    ABSTRACT: A novel statistical approach for analyzing (1)H multiple-quantum (MQ) spin dynamics in so-called spin-counting solid-state NMR experiments is presented. The statistical approach is based on the percolation theory with Monte Carlo methods and is examined by applying it to the experimental results of three solid samples having unique hydrogen arrangement for 1-3 dimensions: the n-alkane/d-urea inclusion complex as a one-dimensional (1D) system, whose (1)H nuclei align approximately in 1D, and magnesium hydroxide and adamantane as a two-dimensional (2D) and a three-dimensional (3D) system, respectively. Four lattice models, linear, honeycomb, square and cubic, are used to represent the (1)H arrangement of the three samples. It is shown that the MQ dynamics in adamantane is consistent with that calculated using the cubic lattice and that in Mg(OH)2 with that calculated using the honeycomb and the square lattices. For n-C20H42/d-urea, these 4 lattice models fail to express its result. It is shown that a more realistic model representing the (1)H arrangement of n-C20H42/d-urea can describe the result. The present approach can thus be used to determine (1)H arrangement in solids.
    Physical Chemistry Chemical Physics 04/2013; · 4.20 Impact Factor
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    ABSTRACT: Alzheimer's disease (AD) is caused by abnormal deposition (fibrillation) of a 42-residue amyloid β-protein (Aβ42) in the brain. During the process of fibrillation, the Aβ42 takes the form of protofibrils with strong neurotoxicity, and is thus believed to play a crucial role in the pathogenesis of AD. To elucidate the supramolecular structure of the Aβ42 protofibrils, the intermolecular proximity of the Ala-21 residues in the Aβ42 protofibrils was analyzed by (13)C-(13)C rotational resonance experiments in the solid state. Unlike the Aβ42 fibrils, an intermolecular (13)C-(13)C correlation was not found in the Aβ42 protofibrils. This result suggests that the β-strands of the Aβ42 protofibrils are not in an in-register parallel orientation. Aβ42 monomers would assemble to form protofibrils with the β-strand conformation, then transform into fibrils by forming intermolecular parallel β-sheets.
    Biochemical and Biophysical Research Communications 11/2012; · 2.28 Impact Factor
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    ABSTRACT: We explore the possibility for elemental analysis by NMR. To keep the efficiency of the signal acquisition common for all spin species, we propose to fix the frequency and vary the magnetic field to cover the isotopes involved in a sample. We introduce constant-frequency receptivity for quantitative elemental analysis in the frequency-fixed NMR experiment. Field-variable NMR experiments are demonstrated using a cryogen-free superconducting magnet. In addition to elemental analysis in liquid solution, solid-state NMR under magic-angle spinning is also described.
    Journal of Magnetic Resonance 09/2012; 224:48-52. · 2.30 Impact Factor
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    ABSTRACT: I still see you: A new pulse sequence, SHA+, little sensitive to dipolar truncation, allows direct or relayed polarization transfer between (13) C atoms, distant by 3.5-9.6 Å, in amyloid fibrils. SHA+ can also be used in a broadband way with the weak rf-condition of ν(1) /ν(R) ≈0.2-0.3 which permits the investigation of temperature-sensitive biological systems.
    ChemPhysChem 08/2012; · 3.36 Impact Factor
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    ABSTRACT: Two-dimensional (2D) covariance NMR spectroscopy, which has originally been established to extract homonuclear correlations (HOMCOR), is extended to include heteronuclear correlations (HETCOR). In a (13)C/(15)N 2D chemical shift correlation experiment, (13)C and (15)N signals of a polycrystalline sample of (13)C, (15)N-labeled amino acid are acquired simultaneously using a dual-receiver NMR system. The data sets are rearranged for the covariance data processing, and the (13)C-(15)N heteronuclear correlations are obtained together with the (13)C-(13)C and (15)N-(15)N homonuclear correlations. The present approach retains the favorable feature of the original covariance HOMCOR that the spectral resolution along the indirect dimension is given by that of the detection dimension. As a result, much fewer amounts of data are required to obtain a well-resolved 2D spectrum compared to the case of the conventional 2D Fourier-Transformation (FT) scheme. Hence, one can significantly save the experimental time, or enhance the sensitivity by increasing the number of signal averaging within a given measurement time.
    Physical Chemistry Chemical Physics 06/2012; 14(27):9715-21. · 4.20 Impact Factor
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    ABSTRACT: In oxides, the substitution of non-oxide anions (F(-),S(2-),N(3-) and so on) for oxide introduces many properties, but the least commonly encountered substitution is where the hydride anion (H(-)) replaces oxygen to form an oxyhydride. Only a handful of oxyhydrides have been reported, mainly with electropositive main group elements or as layered cobalt oxides with unusually low oxidation states. Here, we present an oxyhydride of the perhaps most well-known perovskite, BaTiO(3), as an O(2-)/H(-) solid solution with hydride concentrations up to 20% of the anion sites. BaTiO(3-x)H(x) is electronically conducting, and stable in air and water at ambient conditions. Furthermore, the hydride species is exchangeable with hydrogen gas at 400 °C. Such an exchange implies diffusion of hydride, and interesting diffusion mechanisms specific to hydrogen may be at play. Moreover, such a labile anion in an oxide framework should be useful in further expanding the mixed-anion chemistry of the solid state.
    Nature Material 04/2012; 11(6):507-11. · 36.43 Impact Factor
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    ABSTRACT: Pradimicin A (PRM-A) is a unique antibiotic with a lectin-like ability to recognize d-mannopyranosides (Man) in the presence of Ca(2+) ion. BMY-28864 (1) is a water-soluble analogue of PRM-A, which has been extensively used for studies on the mode of Man recognition and antifungal action of pradimicins. Although it has been assumed that PRM-A and 1 bind Man in a similar fashion, direct experimental evidence has yet to be provided. In this report, we compared Ca(2+) and Man binding of 1 with that of PRM-A through two solid-state NMR experiments. The solid-state (113)Cd NMR analysis using (113)Cd(2+) ion as a surrogate for Ca(2+) ion suggested the similarity in Ca(2+) coordination of PRM-A and 1. The dipolar assisted rotational resonance (DARR) analysis using (13)C-labeled 1 clearly showed that 1 as well as PRM-A binds Man near its carboxyl group. These results collectively indicate that the mode of binding of Ca(2+) ion and Man is nearly identical between PRM-A and 1.
    Bioorganic & medicinal chemistry letters 12/2011; 22(2):1040-3. · 2.65 Impact Factor
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    ABSTRACT: We study the QUantitative Cross-Polarization (QU-CP) method proposed by Hou et al. (Chem. Phys. Lett. 421 (2006) 356) under the moderate MAS speed of 23 kHz, re-examining its two building blocks, namely, the CP polarization transfer from (1)H to (13)C, and the thermal equalization of the (13)C magnetizations. We show that the nuclear-integrated cross-polarization (NI-CP) scheme is conveniently used for (1)H-(13)C polarization transfer, because of its simplicity, robustness to rf-mismatch, and compatibility with fast sample spinning. In the mixing part, in addition to dipolar-assisted rotational-resonance (DARR) recoupling, we examine the Phase-Alternated Recoupling Irradiation Schemes (PARIS and PARIS(xy)), and Second-order Hamiltonian among Analogous Nuclei Generated by Hetero-nuclear Assistance Irradiation (SHANGHAI) sequences, and show that SHANGHAI gives the best performances in equalizing the (13)C magnetizations.
    Journal of Magnetic Resonance 11/2011; 214(1):340-5. · 2.30 Impact Factor
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    ABSTRACT: Pradimicin A (PRM-A) is an actinomycete-derived antibiotic with the lectin-like property of being able to recognize D-mannopyranoside (Man) in the presence of Ca(2+) ion. PRM-A and its derivatives have been attracting a great deal of attention as the only family of natural carbohydrate receptors with nonpeptidic skeleton and, more recently, as conceptually novel drug candidates for human immunodeficiency virus (HIV). Despite its scientific interest and potential therapeutic importance, understanding how PRM-A recognizes Man has been severely limited. Conventional interaction analysis of PRM-A with Man in solution has been frustrated by aggregation of PRM-A and the three-component equilibrium consisting of the [PRM-A(2)/Ca(2+)], [PRM-A(2)/Ca(2+)/Man(2)], [PRM-A(2)/Ca(2+)/Man(4)] complexes, and their mixed oligomers. In this Article, we demonstrate the interaction analysis of PRM-A with methyl α-D-mannopyranoside (Man-OMe) in the solid state, which benefits from aggregate-forming propensity of PRM-A and eliminates the problem associated with the complicated equilibrium in solution. Isothermal titration calorimetry (ITC) analysis and coprecipitation experiments revealed that the primary Man binding of PRM-A is markedly tighter than the secondary one, leading to preparation of the solid aggregate solely composed of the [PRM-A(2)/Ca(2+)/Man-OMe(2)] complex. The simple 1:1 complexes of biosynthetically (13)C-enriched PRM-As and [(13)C(6)]Man-OMe facilitated the analysis of the primary Man binding of PRM-A by two-dimensional dipolar-assisted rotational resonance (2D-DARR), which clearly identified that the cavity consisted of D-alanine moiety and ABC rings of PRM-A is the Man binding site. Interestingly, the proposed Man binding site of PRM-A seems to resemble the typical architecture of artificial carbohydrate receptors.
    Journal of the American Chemical Society 09/2011; 133(43):17485-93. · 11.44 Impact Factor
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    ABSTRACT: Aggregation of 42-residue amyloid β-protein (Aβ42) plays a pivotal role in the etiology of Alzheimer's disease (AD). Curcumin, the yellow pigment in the rhizome of turmeric, attracts considerable attention as a food component potentially preventing the pathogenesis of AD. This is because curcumin not only inhibits the aggregation of Aβ42 but also binds to its aggregates (fibrils), resulting in disaggregation. However, the mechanism of interaction between curcumin and the Aβ42 fibrils remains unclear. In this study, we analyzed the binding mode of curcumin to the Aβ42 fibrils by solid-state NMR using dipolar-assisted rotational resonance (DARR). To improve the quality of 2D spectra, 2D DARR data were processed with the covariance NMR method, which enabled us to detect weak cross peaks between carbons of curcumin and those of the Aβ42 fibrils. The observed (13)C-(13)C cross peaks indicated that curcumin interacts with the 12th and 17-21st residues included in the β-sheet structure in the Aβ42 fibrils. Interestingly, aromatic carbons adjacent to the methoxy and/or hydroxy groups of curcumin showed clear cross peaks with the Aβ42 fibrils. This suggested that these functional groups of curcumin play an important role in its interaction with the Aβ42 fibrils.
    Bioorganic & medicinal chemistry 08/2011; 19(20):5967-74. · 2.82 Impact Factor
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    ABSTRACT: In this work, we examine the fluctuation of the intensity and the phase of an NMR signal during repetition of experiments and investigate possibilities of using these information to judge suspicious peaks, whose true colors may be noises or genuine signals. We firstly analyze the intensity and the phase of an NMR signal separately, and show that for the accumulated spectral profile the contribution of the intensity is less than that of the phase. Secondly we show that we can de-noise a noisy spectrum by using the standard deviation of phase at each spectral point. We then compare the de-noising effect of the present approach and that of the phase-covariance method proposed recently, which is an alternative method of appreciating phase distribution. Finally, effects of the dispersion component are discussed.
    Journal of Magnetic Resonance 07/2011; 211(1):52-9. · 2.30 Impact Factor
  • Angewandte Chemie International Edition 06/2011; 50(27):6084-8. · 11.34 Impact Factor
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    ABSTRACT: Sensitive 2D solid-state (13)C-(13)C correlation spectra of amyloid β fibrils have been recorded at very fast spinning frequencies and very high magnetic fields. It is demonstrated that PARIS-xy recoupling using moderate rf amplitudes can provide structural information by promoting efficient magnetization transfer even under such challenging experimental conditions. Furthermore, it has been shown both experimentally and by numerical simulations that the method is not very sensitive to dipolar truncation effects and can reveal direct transfer across distances of about 3.5-4 Å.
    Journal of Biomolecular NMR 03/2011; 50(2):129-36. · 3.31 Impact Factor

Publication Stats

1k Citations
512.89 Total Impact Points


  • 1982–2014
    • Kyoto University
      • • Division of Chemistry
      • • Graduate School of Science / Faculty of Science
      Kioto, Kyōto, Japan
  • 2011–2013
    • RIKEN
      • Synthetic Cellular Chemistry Laboratory
      Вако, Saitama, Japan
    • Tohoku University
      • Graduate School of Pharmaceutical Sciences
      Sendai-shi, Miyagi-ken, Japan
  • 2009
    • National Institute for Materials Science
      Tsukuba, Ibaraki, Japan
  • 2008–2009
    • JEOL
      Edo, Tōkyō, Japan
  • 2004
    • National Institute of Agrobiological Sciences
      Tsukuba, Ibaraki, Japan
  • 1989–1997
    • Hokkaido University
      • • Division of Biological Sciences (Biology)
      • • Department of Biological Sciences (Biology)
      • • Faculty of Science
      Sapporo-shi, Hokkaido, Japan
  • 1996
    • Mie University
      Tu, Mie, Japan