Biomedical subjects

Jérôme Hirschinger

Publications and source records attributed to Jérôme Hirschinger.

6 recordsLinked to original sources

PubMed2006

13C/15N distance determination by CPMAS NMR in uniformly 13C labeled molecules.

The REDOR and CPMAS techniques are applied for measuring 13C-15N dipolar coupling constants in glycine. It is shown that the selective CP or SPECIFIC CP technique removes the coherent evolution of the spin system under homonuclear 13C-13C J couplings. While the large coupling constant (approximately 900 Hz) is readily determined because of the presence of large oscillations in the CPMAS dynamics, their absence precludes the measurement of the small coupling constant (approximately 200 Hz). The experimental results and numerical simulations demonstrate that the determination of 13C-15N coupling constants of medium size (<1 kHz) by the CPMAS technique is mainly limited by the strength of the 1H decoupling field and the size of the 13C and 15N chemical shift anisotropies.

Journal Article↗

PubMed2005

1H/31P distance determination by solid state NMR in multiple-spin systems.

The results of two techniques of dipolar recoupling, REDOR and CPMAS, are compared in the case of a coupled multiple-spin system. A fundamentally different behavior is observed for these two techniques. In REDOR, the terms associated with each interaction S-I(k) commute with each other and no truncation takes place so that each addition of spin I(k) causes a splitting with its dipolar frequency. In CPMAS, the flip-flop terms of the dipolar Hamiltonian do not commute with the dominant term from the strongly coupled spin pair so that the weak coupling terms from the neighboring spin I(k) are effectively truncated by the dominant pair interaction. Spin dynamics calculations are in agreement with the experimental data in a cubane shaped cluster.

Journal Article↗

PubMed2004

NMR polarization echoes in a nematic liquid crystal.

We have modified the polarization echo (PE) sequence through the incorporation of Lee-Goldburg cross polarization steps to quench the 1H-1H dipolar dynamics. In this way, the 13C becomes an ideal local probe to inject and detect polarization in the proton system. This improvement made possible the observation of the local polarization P(00)(t) and polarization echoes in the interphenyl proton of the liquid crystal N-(4-methoxybenzylidene)-4-butylaniline. The decay of P(00)(t) was well fitted to an exponential law with a characteristic time tau(C) approximately 310 micros. The hierarchy of the intramolecular dipolar couplings determines a dynamical bottleneck that justifies the use of the Fermi Golden Rule to obtain a spectral density consistent with the structural parameters. The time evolution of P(00)(t) was reversed by the PE sequence generating echoes at the time expected by the scaling of the dipolar Hamiltonian. This indicates that the reversible 1H-1H dipolar interaction is the main contribution to the local polarization decrease and that the exponential decay for P(00)(t) does not imply irreversibility. The attenuation of the echoes follows a Gaussian law with a characteristic time tau(phi) approximately 527 micros. The shape and magnitude of the characteristic time of the PE decay suggest that it is dominated by the unperturbed homonuclear dipolar Hamiltonian. This means that tau(phi) is an intrinsic property of the dipolar coupled network and not of other degrees of freedom. In this case, one cannot unambiguously identify the mechanism that produces the decoherence of the dipolar order. This is because even weak interactions are able to break the fragile multiple coherences originated on the dipolar evolution, hindering its reversal. Other schemes to investigate these underlying mechanisms are proposed.

Journal Article↗

PubMed2004

51V magic angle spinning NMR in VOPO4 phases.

51V magic angle spinning NMR was applied to the alpha(II), beta and gamma phases of VOPO4 at three magnetic field strengths (4.7, 7.1, and 11.7 T). The 51V quadrupole and chemical shift tensors were determined by iterative fitting of the NMR lineshapes at the three magnetic field strengths. The applicability of the method is illustrated by comparison with literature data. Although determined chemical shift tensors are completely axially symmetric and of the same magnitude, all studied phases can clearly be distinguished by their quadrupole coupling tensor. Relationships between the 51V NMR data and structural characteristics such as crystal symmetries are discussed.

Crystallography↗

PubMed2003

59Co, 23Na NMR and electric field gradient calculations in the layered cobalt oxides NaCoO2 and HCoO2.

59Co and 23Na NMR has been applied to the layered cobalt oxides NaCoO(2) and HCoO(2) at three different magnetic field strengths (4.7, 7.1 and 11.7T). The 59Co and 23Na quadrupole and anisotropic shift tensors have been determined by iterative fitting of the NMR line shapes at the three magnetic field strengths. Due to the large 59Co quadrupole interaction in NaCoO(2), a frequency-swept irradiation procedure was used to alleviate the limited bandwidth of the excitation. While the 59Co and 23Na shift and quadrupole coupling tensors in NaCoO(2) are found to be coincident and axially symmetric in agreement with the crystal symmetry requirements, the fits of the 59Co NMR spectra clearly show the presence of structural disorder in HCoO(2). The 23Na chemical shift anisotropy can be reproduced by shift tensor calculations using a point dipole model and considering that the magnetic susceptibility in NaCoO(2) is due to Van Vleck paramagnetism for Co(3+). Electric field gradient calculations using either the empirical point charge model or the ab initio full potential-linearized augmented plane wave method are compared with the experimental NMR data.

Cobalt↗

PubMed2002

Synthesis and characterization of a novel cyclic aluminophosphinate: structure and solid-state NMR study.

We present the structure and a multinuclear solid-state NMR study of a new cyclic aluminophosphinate. The crystallographic structure of [Al(2)(HC(6)H(5)PO(2))(2)(C(4)H(9)OH)(8)]Cl(4) (compound 1) was obtained at low temperature (a = 11.830(7) A, b = 14.216(6) A, c = 17.790(6) A, beta = 91.25(4) degrees, monoclinic, P21/c, Z = 2). (13)C IRCP (inversion recovery cross polarization) and NQS (non quaternary suppression) NMR experiments allowed the complete assignment of the quaternary carbon atom of the phenyl ring and the precise determination of the isotropic /(1)J(P-C)/ coupling constant. (31)P CP MAS dynamics was carefully studied by varying the contact time. Dipolar oscillations even at slow MAS were observed. Up to 11 kHz, these oscillations were more pronounced, and the P-H distance was easily extracted. (27)Al NMR quadrupolar parameters for 1 were obtained with very good accuracy, and unusual satellite transition splitting was observed. Furthermore, the isotropic lines of the inner and outer transitions were clearly observable, leading to the unambiguous determination of the quadrupolar parameters.

Journal Article↗