A rapid determination of nuclear quadrupole resonance frequencies using field-cycling magnetic resonance and frequency modulated RF excitations.

A modification of Slusher-Hahn's double resonance technique is described and experimentally tested. It is based on application of multiple frequency sweeps and can be used for a rapid location of nuclear quadrupole resonance (NQR) frequencies. The resolution of the present technique is relatively low but, when the NQR frequencies are located, it is easy to use either the Slusher-Hahn's technique or pulse NQR to determine the NQR frequencies with a higher precision.

¹H-²H cross-relaxation study in a partially deuterated nematic liquid crystal.

A detailed study of the cross-relaxation effects between the ¹H and ²H spins systems is presented in the nematic phase of a 5-cyanobiphenyl (5CB) liquid crystal, partially deuterated at α position (5CB-αd2). The proton spin-lattice relaxation time was measured at a frequency range from 5 kHz to 100 MHz at a temperature 5 K below the nematic-isotropic phase transition. In the low frequency domain, the spin-lattice relaxation rate (T1⁻¹) dispersion clearly differs from that of the fully protonated 5CB homologue. At two distinct frequencies, T1⁻¹ presents two distinct local maxima and for low frequencies T1⁻¹ presents a stronger frequency dependence when compared with what is observed for 5CB. The T1⁻¹ dispersion obtained for 5CB-αd2 for frequencies above 60 kHz was interpreted in terms of the relaxation mechanisms usually accepted to interpret the spin-lattice relaxation in nematic phases in general and 5CB in particular. For lower frequencies it was necessary to consider cross-relaxation contributions between the proton and deuterium reservoirs. A detailed model interpretation of the deuterium quadrupolar dips with respect to the proton-spin relaxation is presented. The analysis of the quadrupolar relaxation independently confirms that the order director fluctuations is the dominant mechanism of proton relaxation in the low frequency domain.

An innovative method for the non-destructive identification of photodegradation products in solid state: 1H-14N NMR-NQR and DFT/QTAIM study of photodegradation of nifedipine (anti-hypertensive) to nitrosonifedipine (potential anti-oxidative).

Stability of the antihypertensive drug nifedipine (NIF) has been studied experimentally in solid state by (1)H-(14)N NMR-NQR double resonance (NQDR) and theoretically by the Density Functional Theory (DFT). Photodegradation of NIF to its metabolite in vivo nitrosonifedipine, NO-NIF (antioxidative agent) upon long term daylight exposure was detected and the changes in the molecular structure of NIF were analysed. The photoconversion of NIF to NO-NIF in solid was found to be accompanied with the electron density redistribution at nitrogen sites (NH to N and NO(2) to NO) and proved to be successfully detected with identification of photoproducts by (1)H-(14)N NQDR and DFT methods. The increase in the e(2)qQ/h and η describing EFG tendency towards non-spherical symmetry was significantly greater upon the reduction of NO(2) site than upon hydrogen abstraction from NH site. The level of sensitivity of detection of the photodegradation product was about 1% of the original sample. The Quantum Theory of Atoms in Molecules (QTAIM) analysis has been found useful in predicting photoreactive sites in the molecules and finding the explanation of differences in reactivity between parent NIF and its photoproduct NO-NIF. Using NIF as a model, this study demonstrates the suitability of NQDR supported by DFT for non-destructive determination of the photodegradation products in solid state.

Conformations and intermolecular interactions pattern in solid chloroxylenol and triclosan (API of anti-infective agents and drugs). A (35)Cl NQR, (1)H-(14)N NQDR, X-ray and DFT/QTAIM study.

Two antibacterial and antifungal agents, chloroxylenol (4-chloro-3,5-dimethyl-phenol) and triclosan (5-chloro-2-(2',4'-dichlorophenoxy)-phenol), were studied experimentally in solid state with an X-ray, (35)Cl-nuclear quadrupole resonance (NQR) and (17)O-nuclear quadrupole double resonance (NQDR) spectroscopies and, theoretically, with the density functional theory/quantum theory of atoms in molecules (DFT/QTAIM). The crystallographic structure of triclosan, which crystallises in space group P31 with one molecule in the asymmetric unit [a = 12.64100(10), b = 12.64100(10), c = 6.71630(10) Å], was solved with an X-ray and refined to a final R-factor of 2.81% at room temperature. The NQR frequencies of (35)Cl and (17)O were detected with the help of the density functional theory (DFT) assigned to particular chlorine and oxygen sites in the molecules of both compounds. The NQR frequencies at (35)Cl sites in chloroxylenol and triclosan were found to be more differentiated than frequencies at the (17)O site. The former better describes the substituent withdrawing effects connected to π-electron delocalization within the benzene rings and the influence of temperature; whereas, those at the (17)O site provide more information on O-H bond and intermolecular interactions pattern. The conformation adopted by diphenyl ether of triclosan in solid state was found to be typical of diphenyl ethers, but the opposite to those adopted when it was bound to different inhibitors. According to an X-ray study, temperature had no effect on the conformation of the diphenyl ring of triclosan, which was the same at 90 K and at room temperature (RT). The scattering of NQR frequencies reproduced by the DFT under assumption of the X-ray data at 90 K and RT is found to be a good indicator of the quality of resolution of the crystallographic structure.

Nature of isomerism of solid isothiourea salts, inhibitors of nitric oxide synthases, as studied by 1H-14N nuclear quadrupole double resonance, X-ray, and density functional theory/quantum theory of atoms in molecules.

Isothioureas, inhibitors of nitric oxide synthases, have been studied experimentally in solid state by nuclear quadrupole double resonance (NQDR) and X-ray methods and theoretically by the quantum theory of atoms in molecules/density functional theory. Resonance frequencies on (14)N have been detected and assigned to particular nitrogen sites in each molecule. The crystal packings of (S)-3,4-dichlorobenzyl-N-methylisothiouronium chloride with the disordered chlorine positions in benzene ring and (S)-butyloisothiouronium bromide have been resolved in X-ray diffraction studies. (14)N NQDR spectra have been found good indicators of isomer type and strength of intra- or intermolecular N-H···X (X = Cl, Br) interactions. From among all salts studied, only for (S)-2,3,4,5,6-pentabromobenzylisothiouronium chloride are both nitrogen sites equivalent, which has been explained by the slow exchange. This unique structural feature can be a key factor in the high biological activity of (S)-2,3,4,5,6-pentabromobenzylisothiouronium salts.

Zeeman shift--a tool for assignment of 14N NQR lines of nonequivalent 14N atoms in powder samples.

The use of Zeeman perturbed 14N nuclear quadrupole resonance (NQR) to determine the ν+ and ν-14N lines in polycrystalline samples with several nonequivalent nitrogen atoms was investigated. The 14N NQR line shift due to a weak external Zeeman magnetic field was calculated, assuming isotropic distribution of EFG tensor directions. We calculated the broad line distribution of the ν+ and ν- line shifts and experimentally confirmed the calculated Zeeman field dependence of singularities (NQR peaks) in cyclotrimethylenetrinitramine (RDX) and aminotetrazole monohydrate (ATMH). The calculated and measured frequency shifts agreed well. The proposed measurement method enabled determination of which 14N NQR lines in ATMH belong to ν+ and which to ν- transitions.

14N NQR study of polymorphism and hydrogen bonding in molecular complex isonicotinamide-oxalic acid (2:1).

The complete (14)N nuclear quadrupole resonance (NQR) spectra have been measured in the two polymorphic crystalline phases of the molecular complex isonicotinamide-oxalic acid (2:1) by nuclear quadrupole double resonance. The observed NQR frequencies, quadrupole coupling constants, and asymmetry parameters (η) have been assigned to the two nitrogen positions (ring and amide) in a molecule on the basis of the intensity and multiplicity of the double resonance signals. The NQR data for the ring nitrogen in both polymorphic phases deviate from the correlation relations observed in substituted pyridines. This deviation is analyzed in a model, where it is assumed that an additional electric charge on the nitrogen atom changes the NQR parameters. The model suggests that this additional electric charge is negative so that the N···H-O hydrogen bond seem to be partially ionic, of the type N(-)···H-O.

Measurement of dipolar structure of 17O nuclear quadrupole resonance lines by three-frequency irradiation.

A modification of nuclear quadrupole double resonance with coupled multiplet is proposed which can be used for the measurement of the dipolar structure of the 17O nuclear quadrupole resonance lines in case of a strong 1H--17O dipolar interaction. The technique is based on magnetic field cycling between a high magnetic field and zero magnetic field and on the simultaneous application of three rf magnetic fields with the frequencies that are close to the three 17O NQR frequencies nu(5/2-1/2)>nu(5/2-3/2)nu(3/2-1/2) during the time spent in zero static magnetic field. When the sum of the two lower irradiation frequencies nu(1)+nu(2) is not equal to the highest irradiation frequency nu, the three-frequency irradiation increases the proton relaxation rate in zero magnetic field and consequently decreases the proton NMR signal at the end of the magnetic field cycle. The new technique is theoretically analyzed and compared to the single-frequency and two-frequency irradiation techniques. It is shown that the sensitivity of the new technique exceeds the sensitivity of the two-frequency irradiation technique. As a test of the new technique we measured the shape of the highest-frequency 17O NQR line in paraelectric KH2PO4.

Structural study of selected polyhalogenated benzimidazoles (protein kinase CK2 inhibitors) by nuclear quadrupole double resonance, X-ray, and density functional theory.

Protein kinase CK2 inhibitors, polyhalogenated benzimidazoles, have been studied experimentally in solid state by NMR-NQR double resonance and X-ray and theoretically by the density functional theory (DFT). Six resonance frequencies on (14)N have been detected and assigned to particular nitrogen sites in each polyhalogenated benzimidazole molecule. The effects of prototropic annular tautomerism and polymorphism related to stable cluster formation due to intermolecular hydrogen bonding interactions on the (14)N NQR parameters have been analyzed within the DFT and AIM (atoms in molecules) formalism. The studies suggest that all polyhalogenobenzimidazoles are isostructural and can exhibit polymorphism and that (14)N NQR is very sensitive to hydrogen bondings but less sensitive to the specific arrangement of the hydrogen bonded molecules. NQDR and DFT results suggest the presence of the prototropic annular tautomerism 50:50, which is in a good agreement with the X-ray and (1)H NMR data.

Hydrogen bonding and stacking pi-pi interactions in solid 6-thioguanine and 6-mercaptopurine (antileukemia and antineoplastic drugs) studied by NMR-NQR double resonance spectroscopy and density functional theory.

A chemotherapeutic drug 6-thioguanine (2-amino-1,7-dihydro-6H-purine-6-thione, 6-TG) has been studied experimentally in the solid state by NMR-NQR double resonance and theoretically by the density functional theory. Fourteen resonance frequencies on (14)N have been detected and assigned to particular nitrogen sites in the 6-TG molecule. A valid assignment of NQR frequencies for 6-mercaptopurine (6-MP) has been proposed. The effects of molecular aggregations, related to intermolecular hydrogen bonding and stacking pi-pi interactions on the NQR parameters have been analyzed within the DFT and AIM (atoms in molecules) formalism for 6-TG and 6-mercaptopurine (6-MP). The so-called global reactivity descriptors have been calculated to compare the properties of molecules of 6-TG and 6-MP, to check the effect of -NH(2) group as well as to identify the differences in crystal packing.

Double resonance experiments in low magnetic field: dynamic polarization of protons by (14)N and measurement of low NQR frequencies.

The possibilities of dynamically polarizing proton spin system via the quadrupole (14)N spin system in low magnetic field are analyzed. The increase of the proton magnetization is calculated. The polarization rate of the proton spin system is related to the transition probabilities per unit time between the (14)N quadrupole energy levels and proton energy levels. The experiments performed in 1,3,5-triazine confirm the results of the theoretical analysis. A new double resonance technique is proposed for the measurement of nuclear quadrupole resonance frequencies nu(Q) of the order of 100kHz and lower. The technique is based on magnetic field cycling between a high and a low static magnetic field and observation of the proton NMR signal in the high magnetic field. In the low magnetic field the quadrupole nuclei and protons resonantly interact at the proton Larmor frequency nu(H)=nu(Q)/2. The quadrupole nuclei are simultaneously excited by a resonant rf magnetic field oriented along the direction of the low static magnetic field. The experimental procedure is described and the sensitivity of the new technique is estimated. Some examples of the measurement of low (14)N and (2)H nuclear quadrupole resonance frequencies are presented.

1H-17O nuclear quadrupole double resonance in phenylphosphinic acid and phenylphosphonic acid. 17O quadrupole coupling in P = O and P-O-H bonds.

The (17)O nuclear quadrupole resonance (NQR) frequencies have been measured in phenylphosphinic acid and phenylphosphonic acid using nuclear quadrupole double resonance. The quadrupole coupling constants have been determined with an uncertainty of +/- 10 kHz and the asymmetry parameter eta with an uncertainty of +/- 0.01. The results are compared to the published results of the theoretical calculation and the high-field solid-state NMR measurements. The position of hydrogen in the O-H...O hydrogen bond in phenylphosphinic acid has also been determined. On the basis of the present and the previously published data we show that the principal values of the electric-field-gradient tensor in P = O and P-O-H bonds correlate. A correlation between the nuclear quadrupole parameters and the length of the P-O bond is also observed.

Sensitivity of nuclear-quadrupole double-resonance detection of half-integer spin nuclei.

The sensitivity of the Slusher and Hahn's nuclear quadrupole double resonance technique is calculated in general for an arbitrary nuclear spin S of the quadrupole nuclei and for an arbitrary asymmetry parameter eta of the electric field gradient tensor. The nuclear spin S=5/2 ((17)O, (25)Mg, ...) is treated in details. The influence of the cross-relaxation rate between the quadrupole nuclei and the abundant spin system on the sensitivity of double resonance is discussed. The results of the theoretical analysis are applied in the analysis of the (1)H-(17)O nuclear quadrupole double resonance spectra in p-toluenesulfonamide and 2-nitrobenzoic acid. The 17O nuclear quadrupole resonance frequencies from a sulfonamide group are determined for the first time. The proton-oxygen cross-relaxation rates and the proton local frequency in zero external magnetic field are experimentally determined from the nuclear quadrupole double resonance spectra.

Measurement of the (14)N nuclear quadrupole resonance frequencies by the solid effect.

(1)H-(14)N nuclear quadrupole double resonance using magnetic field cycling between high and low magnetic field and solid effect in the low magnetic field is analyzed in details. The transition probabilities per unit time for the solid-effect transitions are calculated. The double resonance spectra are calculated in the limiting cases of fast and slow nitrogen spin-lattice relaxation. The double resonance spectra are measured in histamine and quinolinic acid. The experimental spectra are analyzed and the (14)N NQR frequencies are determined.

Temperature dependence of nonequivalent potential wells for pyridinium ion reorientation in pyridinium tetrachloroiodate(III), PyHICl4, studied by 1H-14N nuclear quadrupole double resonance.

The reorientation of a pyridinium ion in the paraelectric and antiferroelectric phase of PyHICl(4) is investigated using (1)H-(14)N nuclear quadrupole double resonance (NQDR). The (14)N nuclear quadrupole resonance frequencies are measured. The temperature variations of the principal values of the time-averaged electric-field-gradient (EFG) tensor at the nitrogen position are used to determine the occupation probabilities of the six orientations of a pyridinium ion in both crystallographic phases. The energy difference between various orientations is determined. The molar transition entropy associated with the reorientation of the pyridinium ions is calculated and compared to the experimental value.

14N NQR study of nicotinamide and related compounds.

14N nuclear quadrupole resonance (NQR) frequencies have been measured in picolinamide, nicotinamide, isonicotinamide, 2,6-pyridine dicarboxamide, and acetamide by double resonance. The 14N NQR spectra in picolinamide, nicotinamide, isonicotinamide, and 2,6-pyridine dicarboxamide show the presence of two distinct nitrogen positions: the ring position with the quadrupole coupling constant about 4,5 MHz and the amide position with the quadrupole coupling constant about 2.6 MHz. The NQR data are related to the structure of the investigated compounds and to the N--H...O hydrogen bonds.

Field-cycling NMR relaxometry of a liquid crystal above in mesoscopic confinement.

We measured the proton spin-lattice relaxation times in the isotropic phase of liquid crystal 4-n-pentyl-4-cyanobiphenyl (5CB) confined into porous glass (CPG) with the average pore diameter approximately 72 nm. The analysis of T1(-1) frequency dispersions, spanning over four decades, shows that the main relaxation mechanism induced by the ordered surface layer are molecular reorientations mediated by translational displacements (RMTD). The RMTD contribution to T1(-1) is proportional to the inverse square root of Larmor frequency, a consequence of the equipartition of diffusion modes along the surface. Low and high frequency cutoffs of the RMTD mechanism clearly reveal that the surface alignment of liquid crystal is random planar with the size of uniformly oriented patches approximately 5 nm, depending on the treatment of the CPG matrix. According to the size of the uniformly oriented patches varies also the thickness of the ordered surface layer and its temperature behavior. The surface-induced order parameter is found to be temperature independent and determined by the local short range surface interactions.

Dynamics of the pinned modulation wave in incommensurate bis (4-chlorophenyl) sulfone (BCPS).

We show that both the anomalously huge resonance-frequency dependence of the (35)Cl nuclear quadrupole resonance (NQR) spin-lattice relaxation time in BCPS, reported here for the first time, and its anomalous temperature dependence can be explained by large-scale fluctuations of the pinned modulation wave instead of small-scale fluctuations (phasons and amplitudons). The results were obtained by measuring the laboratory (T(1Q)) and rotating frame (T(1Q,rho)) (35)Cl relaxation times. This is the first time that an effective resonance frequency dependence of the spin-lattice relaxation rate was measured in pure NQR.

(1)H-(17)O nuclear-quadrupole double-resonance study of hydrogen disorder in 2-nitrobenzoic acid.

Temperature dependence of (17)O nuclear quadrupole resonance frequencies was measured in solid 2-nitrobenzoic acid by a (1)H-(17)O nuclear quadrupole double resonance technique. The experimental results show the presence of a fast exchange of hydrogen atoms between two nonequivalent positions within the O-H ellipsis O hydrogen bonds. The hydrogen disorder is ascribed to concerted jumps of two hydrogen atoms within the hydrogen bonds connecting two molecules in a dimer. The energy difference DeltaE of the two hydrogen configurations is equal to DeltaE = 60 meV = 5.8 kJ/mol. The dipole structure of the (17)O NQR lines from the C-O-H oxygen positions was also measured at -100 degrees C and at room temperature. The orientation of the principal axes of the electric field gradient tensor with respect to the O-H bond and the sign of the quadrupole coupling constant were determined. The oxygen-hydrogen distance R(O-H), as determined from the dipole structure of the (17)O NQR lines is at -100 degrees C equal to 0.099 nm. At room temperature we observe a longer distance, R(O-H) = 0.101 nm, in agreement with the hydrogen intrabond exchange.

T1 rho in nuclear quadrupole resonance: a theoretical study.

A new NQR method of measuring the spectral density of slow motions in solids is proposed. It is shown that also in NQR a 90 degrees phase shift of a resonant rf magnetic field following a 90 degrees pulse locks the nuclear magnetization in a 'rotating frame' similarly as in NMR. The spin-lattice relaxation time T1 rho of the locked magnetization is calculated in general for an arbitrary spin. It is assumed that the fluctuations of the EFG tensor dominate the spin-lattice relaxation. The calculations show that T1 rho depends on the spectral density J(omega) of the electric quadrupole fluctuations at the NQR frequencies, and also at a low frequency omega. Here omega approximately gamma B1 kHz depends on the orientation of the rf magnetic field in the principal-axis system of the EFG tensor. The term containing J(omega) in the expression for T1 rho-1 depends on the orientation of the rf magnetic field in the principal-axis system of the EFG tensor, only through the orientation dependence of omega. This term vanishes when the electric quadrupole fluctuations do not modulate the frequency of the NQR transition excited by the rf magnetic field. Two particular examples: I = 1 and I = 3/2 are worked out in details.