14N nuclear quadrupole resonance in carcinostatic phosphamides

Nitrogen-14 nuclear quadrupole resonance spectra of the anti-cancer drugs cyclophosphamide monohydrate, isonphosphamide and triphosphamide have been detected at 77 K. The electron distribution in the vicinity of the nitrogens possessing trigonal bonding configurations have been calculated in the framework of the Townes and Dailey theory.     

14N nuclear quadrupole resonance of some sulfa drugs

The 14N nuclear quadrupole double resonance spectra of different polymorphs of sulfanilamide, sulfadiazine, sulfamerazine and sulfamethazine have been measured and the 14N quadrupole coupling tensors have been determined. The obtained 14N spectra are compared with those of other sulfa drugs like sulfathiazole. It is shown that different polymorphs can be easily discriminated. The application of this technique for non-destructive analysis, polymorph determination and quality control in the production of pharmaceuticals is stressed.     

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.     

N nuclear quadrupole resonance in the barbiturates

The ¹⁴N nuclear quadrupole resonance frequencies at 77 K are reported for several barbiturates. Differences between charge densities in the π and various σ orbitals at the nitrogen site are obtained. The charge distributions are correlated with various substituents, and are discussed with emphasis on the effects of phenyl substituents, hydrogen bonding, and formation of the sodium salt.     

Detection of plastic explosives in luggage with14N nuclear quadrupole resonance spectroscopy

Nuclear quadrupole resonance (NQR) of¹⁴N nuclei has many advantages as a method for detecting nitrogen-containing explosives, the most important are very high chemical specificity, true noninvasive operation and detection of bulk explosive in situ only (no vapor or particular capture needed). One of the most high explosives is hexogen (RDX) often used by terrorists in plasticized forms. The ring nitrogen nuclei in an RDX molecule generate three sets of NQR frequencies corresponding to three physically nonequivalent positions of the molecule in the crystal lattice. The prototype device we have constructed is intended for inspection of suitcases for the presence of plastic explosives containing RDX or octogen by¹⁴N quadrupole resonance. It is essentially a fully automated PC-controlled pulsed FT NQR spectrometer equipped with a large volume (70 1) radio-frequency (RF) sample coil to accommodate a typical suitcase. The device consists of a measure chamber with an RF coil, tuning and matching box, an RF pulse transmitter and a control PC with dedicated cards like digital receiver, frequency synthesizer, pulse programmer and probe-tuning controller. The control software finds the NQR lines and measures their frequencies. An alarm is produced if any of these frequencies matches the characteristic NQR frequency of the explosive and the signal-tonoise ratio exceeds the preset threshold. Multipulse sequences of the type SORC (strong off-resonance comb) or SLSE (spin-locked spin echo) were used in order to increase the allowed data acquisition rate. We could detect 230 g of PMW-8, a plastic explosive (containing 81% of RDX) in 10 s or 100 g in 30 s. Detection probability was not less than 90%.     

Two-dimensional exchange nuclear quadrupole resonance spectroscopy of molecular crystals

A theoretical treatment of the 2D exchange NQR pulse sequence is presented and applied to the quantitative study of exchange processes in molecular crystals. It takes into account the off-resonance irradiation, which critically influences the spin dynamics. The response of a system of spins I = 3/2 in zero applied field, experiencing electric quadrupole couplings, to the three-pulse sequence is analysed. All the tools and mathematical expressions to predict the time evolution of the signal created by a pure NQR multipulse sequence are presented explicitly. The mixing dynamics by exchange and the expected cross-peak intensities as a function of the frequency offset have been derived. The theory is illustrated by a study of the optimization procedure, which is of crucial importance for the detection of the cross- and diagonalpeaks in a 2D exchange spectrum. The systems investigated here were hexachloroethane and tetrachloroethylene, which show threefold and twofold reorientational jumps about the carbon-carbon axis, respectively.     

Special features of remote observations of weak signals from 14N nuclear quadrupole resonance

The case of excitation of nuclear quadrupole resonance (NQR) in nitrogen-containing compounds is examined for significant sample removal under conditions of strong dispersion of the registered signal. Principal limitations on the sensitivity of remote NQR observations are demonstrated. A method of registering resonant lines after fading of the main signal is suggested. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 8, pp. 8–11, August, 2008.     

Nitrogen-14 nuclear quadrupole resonance study of hydrazine monohydrate

¹⁴N NQR in hydrazine monohydrate has been investigated from 4.2 K to 140 K. A molecular motion with an activation energy of about 7.5 kcal/mol became active at about 120 K. Echo envelope modulation due to intramolecular dipolar coupling was observed.     

Two-frequency method for increasing the signal-to-noise ratio for nuclear quadrupole resonance14N low-frequency transitions

A method is proposed for increasing the signal-to-noise ratio during detection of NQR¹⁴N low-frequency transitions, consisting in a preliminary saturation of the _o(_–) transition before accumulation of the multiplet signals of the spin echo or induction signals, observed during the action of a series of 90 pulses on the _–(_o) transition. The gain in signal-to-noise ratio achieved by the two-frequency action is calculated theoretically, and the maximum value is found to be 3/(3 –) for _– and 3(1 + )/4 for _o. It is shown that the envelope of the induction signal for an increase in the time between the 90 pulses decreases according to one exponent for _o, while for _– and ₊ it decreases according to two exponents, and the approach to equilibrium of the system of¹⁴N nuclei is oscillatory in nature.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 61–64, November, 1987.     

Hydrogen bonds in single crystals of para and meta-aminobenzonitrile as revealed by the Zeeman effect on the nuclear quadrupole resonance of 14N

The |e ² qQ/h| and η values for both the cyano and the amino-nitrogen of the title compounds are reported at room temperature as well as at 273 K and 77 K. From Zeeman effects on single crystals of both compounds the orientation of the principal axes of the electric field gradient (efg) on both nitrogen nuclei, as well as a number of data on the crystallographic and molecular structure, are obtained. A reliable interpretation is given of the experimental resonance frequencies, which are also safely assigned to the right nitrogen atoms. By studying the dependence of the resonance linewidth on the orientation, with respect to the efg principal axes, of the Zeeman field B ₀, the spatial distribution of the hydrogen nuclei around the ¹⁴N nuclei is determined. In this way hydrogen bonds are shown to exist in both single crystals. An analysis based on the Townes and Dailey theory allows an estimate to be made of the possible variation of the population of the cyano-nitrogen lone-pair orbital when involved in hydrogen bonds.     

14N and35Cl nuclear quadrupole double resonance study of the structural phase transitions in N-octylammoniumchloride

The structural phase transitions between the non-intercalated phases of the layer structure compound N-octylammoniumchloride have been studied via proton-¹⁴N and proton-³⁵Cl nuclear quadrupole double resonance. The results have been related to an order-disorder model of the octylammonium chains. The temperature dependence of the order parameters of the –NH₃ head groups has been determined.     

Secondary signals in two-frequency nuclear quadrupole resonance on (14)N nuclei with I=1

Our experimental and theoretical studies show that using two-frequency excitation of (14)N nuclei it is possible to observe secondary NQR signals at one of the three possible transitions due to irradiation of another adjacent transition. As a result of the pulse sequence applied to the adjacent transition the spin-echo signals on the detected transition are observed after essential time interval from the initial single pulse on this frequency. Experiments have been performed on the (14)N nuclei in the sodium nitrite (NaNO(2)) and the military explosive hexahydro-1,3,5-trinitro-s-triazine C(3)H(6)N(6)O(6) (RDX).     

Ab initio calculation of 14N nuclear quadrupole coupling constants

The use of ab initio Hartree-Fock electric field gradient calculations to predict nitrogen nuclear quadrupole coupling constants is examined using basis sets of split valence to triple zeta plus polarization size. From results on 20 to 35 molecules for each basis, such calculations are shown to be of predictive value if systematic errors are eliminated by using regression-derived scaling factors, and the reliability of each basis is assessed. For field gradient calculations on larger molecules, a significantly better alternative to a minimal basis which adds little extra computational cost, is proposed.     

Theoretical study of14N pure quadrupole resonance in amino acids

The theoretical hybridization model of Vega is adapted to the tetrahedral environment around the nitrogen nucleus in eleven amino acids to estimate the orbital occupation numbers using the experimental values of the quadrupole coupling constant and asymmetry parameter of¹⁴N quadrupole resonance and the results are discussed.     

Diffusion in nuclear quadrupole resonance

With the aid of the method of random trajectories, formulas have been obtained for the first time for diffusion damping of the amplitudes of nuclear quadrupole spin echo signals because of molecular vibration-rotation in a two-frequency four-pulse program for spin 5/2 and zero asymmetry parameter. The formulas are similar to the result of Hahn for diffusion in NMR.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 6, pp. 14–16, June, 1985.     

14N and35Cl nuclear quadrupole double resonance study of the phase transitions in n-decylammoniumchloride and n-hexylammoniumchloride

The structural phase transitions between the intercalated and the non-intercalated phases of the layer structure compound n-decylammoniumchloride and n-hexylammoniumchloride have been studied via proton-¹⁴N and proton-³⁵Cl nuclear quadrupole double resonance. The results have been related to an order-disorder model of the alkylammonium chains. The temperature dependence of the order parameters of the –NH₃ head groups has been determined.     

Density functional theory calculations of nuclear quadrupole coupling constants with calibrated 14N quadrupole moments

Density functional calculations of the electric field gradient tensor at the nitrogen nucleus in 13 test molecules, containing 14 nitrogen sites, have been performed using the linear combination of Gaussian-type orbital Kohn-Sham density functional theory (LCGTO-KSDFT) approach. Local and gradient corrected functionals were used for all-electron calculations. All the molecular structures were optimized at their respective levels of theory with extended basis sets. Calibrated ¹⁴N nuclear quadrupole moments were obtained through a fitting procedure between calculated electric field gradients and experimental nuclear quadrupole coupling constants of the test set of molecules for each basis set and functional considered. With these calibrated ¹⁴N nuclear quadrupole moments, the nuclear quadrupole coupling constants of the following selected systems were determined: fluoromethylisonitrile, pyridine, pyrrole, imadazole, pyrazole, 1,8-bis(dimethyl-amino)naphthalene, cyclotetramethylenetetranitramine, cocaine and heroin.     

14N Pulsed nuclear quadrupole resonance. 2. Effect of a single radio-frequency pulse in the general case

A novel theory, based on density operator calculations, is provided for assessing the nuclear quadrupole resonance behaviour of a spin 1 (¹⁴N) subjected to a single radio-frequency pulse. It is for a powder sample in zero magnetic field for an electric field gradient tensor without symmetry. A complete set of equations is obtained for the quantities of interest. It is derived from the general Liouville–von Neumann equation and from a proper basis on which the density operator is expanded. Theoretical results, in terms of signal evolution as a function of the pulse length (nutation experiments), show that the same nutation curve is expected for the three different transitions which exist when the electric field gradient tensor is without symmetry. This latter nutation curve is, however, different from that which prevails in the case of an axially symmetric tensor, this apparent discrepancy being easily resolved on theoretical grounds. Experimental data (for NaNO₂, electric field gradient tensor without symmetry) are checked against values of the radio-frequency field amplitude provided by NMR measurements performed with the same equipment. Good agreement between theory and experiment is obtained.     

Improving N nuclear quadrupole resonance detection of trinitrotoluene using off-resonance effects

The off-resonance dependence of the amplitudes of the six dominant ¹⁴N nuclear quadrupole resonance (NQR) lines in commercial polymorphic trinitrotoluene (TNT) sample were experimentally determined for a wide range of experimental parameters when irradiated with the spin-lock spin-echo (SLSE) pulse sequence. We find that the amplitudes off-resonance dependence follows a sinc-like function with an additional modulation due to the spacing between the RF pulses. This dependence can be very well modeled with expressions we have derived for a single site ¹⁴N NQR in paranitrotoluene (PNT). The results can be immediately used for the reduction of the number of free parameters used in the robust signal processing models for the TNT NQR detectors.