Off-resonance effects in (14)N NQR signals from the pulsed spin-locking (PSL) and three-pulse echo sequence; a study for monoclinic TNT.

In NQR detection applications signal averaging by the summation of rapidly regenerated signals from multiple pulse sequences of the pulsed spin-locking (PSL) type is often used to improve sensitivity. It is important to characterise and if possible minimise PSL sequence off-resonance effects since they can make it difficult to optimise detection performance. We illustrate this with measurements of the variation of the decay time T2e and the amplitude of PSL signal trains with pulse spacing and excitation offset frequency for the 870 kHz ν+(14)N NQR line of monoclinic TNT under carefully stabilised temperature conditions. We have also carried out a similar study of signals from monoclinic TNT and 1H-1,2,3-triazole generated by a three-pulse echo sequence and the results are shown to agree well with a theoretical treatment appropriate to polycrystalline NQR samples such as TNT for which spin I=1, asymmetry parameter η≠0 and T1≫T2. Based on this theory we derive simple models for calculating TNT PSL signal trains and hence the pulse spacing and off-resonance dependence of signal amplitude and T2e which we compare to our experimental data. We discuss the influence of PSL echo summation on off-resonance effects in detected signal intensity and show how a phase-alternated multiple pulse sequence can be used in combination with the PSL sequence to eliminate variation in detection performance due to off-resonance effects.

(14)N NQR, relaxation and molecular dynamics of the explosive TNT.

Multiple pulse sequences are widely used for signal enhancement in NQR detection applications. Since the various (14)N NQR relaxation times, signal decay times and frequency of each NQR line have a major influence on detection sequence performance, it is important to characterise these parameters and their temperature variation, as fully as possible. In this paper we discuss such measurements for a number of the ν+ and ν- NQR lines of monoclinic and orthorhombic TNT and relate the temperature variation results to molecular dynamics. The temperature variation of the (14)N spin-lattice relaxation times T1 is interpreted as due to hindered rotation of the NO2 group about the C-NO2 bond with an activation energy of 89 kJ mol(-1) for the ortho and para groups of monoclinic TNT and 70 kJ mol(-1) for the para group of orthorhombic TNT.

Nitrogen-14 nuclear quadrupole resonance spectroscopy: a promising analytical methodology for medicines authentication and counterfeit antimalarial analysis.

We report the detection and analysis of a suspected counterfeit sample of the antimalarial medicine Metakelfin through developing nitrogen-14 nuclear quadrupole resonance ((14)N NQR) spectroscopy at a quantitative level. The sensitivity of quadrupolar parameters to the solid-state chemical environment of the molecule enables development of a technique capable of discrimination between the same pharmaceutical preparations made by different manufacturers. The (14)N NQR signal returned by a tablet (or tablets) from a Metakelfin batch suspected to be counterfeit was compared with that acquired from a tablet(s) from a known-to-be-genuine batch from the same named manufacturer. Metakelfin contains two active pharmaceutical ingredients, sulfalene and pyrimethamine, and NQR analysis revealed spectral differences for the sulfalene component indicative of differences in the processing history of the two batches. Furthermore, the NQR analysis provided quantitative information that the suspected counterfeit tablets contained only 43 ± 3%, as much sulfalene as the genuine Metakelfin tablets. Conversely, conventional nondestructive analysis by Fourier transform (FT)-Raman and FT-near infrared (NIR) spectroscopies only achieved differentiation between batches but no ascription. High performance liquid chromatography (HPLC)-UV analysis of the suspect tablets revealed a sulfalene content of 42 ± 2% of the labeled claim. The degree of agreement shows the promise of NQR as a means of the nondestructive identification and content-indicating first-stage analysis of counterfeit pharmaceuticals.

Variable-pitch rectangular cross-section radiofrequency coils for the nitrogen-14 nuclear quadrupole resonance investigation of sealed medicines packets.

The performance of rectangular radio frequency (RF) coils capable of being used to detect nuclear quadrupole resonance (NQR) signals from blister packs of medicines has been compared. The performance of a fixed-pitch RF coil was compared with that from two variable-pitch coils, one based on a design in the literature and the other optimized to obtain the most homogeneous RF field over the whole volume of the coil. It has been shown from (14)N NQR measurements with two medicines, the antibiotic ampicillin (as trihydrate) and the analgesic medicine Paracetamol, that the latter design gives NQR signal intensities almost independent of the distribution of the capsules or pills within the RF coil and is therefore more suitable for quantitative analysis.

14N quadrupole resonance and 1H T1 dispersion in the explosive RDX.

The explosive hexahydro-1,3,5-trinitro-s-triazine (CH2-N-NO2)3, commonly known as RDX, has been studied by 14N NQR and 1H NMR. NQR frequencies and relaxation times for the three ν+ and ν- lines of the ring 14N nuclei have been measured over the temperature range 230-330 K. The 1H NMR T1 dispersion has been measured for magnetic fields corresponding to the 1H NMR frequency range of 0-5.4 M Hz. The results have been interpreted as due to hindered rotation of the NO2 group about the N-NO2 bond with an activation energy close to 92 kJ mol(-1). Three dips in the 1H NMR dispersion near 120, 390 and 510 kHz are assigned to the ν0, ν- and ν+ transitions of the 14NO2 group. The temperature dependence of the inverse line-width parameters T2∗ of the three ν+ and ν- ring nitrogen transitions between 230 and 320 K can be explained by a distribution in the torsional oscillational amplitudes of the NO2 group about the N-NO2 bond at crystal defects whose values are consistent with the latter being mainly edge dislocations or impurities in the samples studied. Above 310 K, the 14N line widths are dominated by the rapid decrease in the spin-spin relaxation time T2 due to hindered rotation of the NO2 group. A consequence of this is that above this temperature, the 1H T1 values at the quadrupole dips are dominated by the spin mixing time between the 1H Zeeman levels and the combined 1H and 14N spin-spin levels.

Magnetic field-cycling NMR and (14)N, (17)O quadrupole resonance in the explosive pentaerythritol tetranitrate (PETN).

The explosive pentaerythritol tetranitrate (PETN) C(CH(2)-O-NO(2))(4) has been studied by (1)H NMR and (14)N NQR. The (14)N NQR frequency and spin-lattice relaxation time T(1Q) for the nu(+) line have been measured at temperatures from 255 to 325K. The (1)H NMR spin-lattice relaxation time T(1) has been measured at frequencies from 1.8kHz to 40MHz and at temperatures from 250 to 390K. The observed variations are interpreted as due to hindered rotation of the NO(2) group about the bond to the oxygen atom of the CH(2)-O group, which produces a transient change in the dipolar coupling of the CH(2) protons, generating a step in the (1)H T(1) at frequencies between 2 and 100kHz. The same mechanism could also explain the two minima observed in the temperature variation of the (14)N NQR T(1Q) near 284 and 316K, due in this case to the transient change in the (14)N...(1)H dipolar interaction, the first attributed to hindered rotation of the NO(2) group and the second to an increase in torsional amplitude of the NO(2) group due to molecular distortion of the flexible CH(2)-O-NO(2) chain which produces a 15% increase in the oscillational amplitude of the CH(2) group. The correlation times governing the (1)H T(1) values are approximately 25 times longer than those governing the (14)N NQR T(1Q), explained by the slow spin-lattice cross-coupling between the two spin systems. At higher frequencies, the (1)H T(1) dispersion results show well-resolved dips between 200 and 904kHz assigned to level crossing with (14)N and weaker features between 3 and 5MHz tentatively assigned to level crossing with (17)O.

Spectral estimation of irregularly sampled exponentially decaying signals with applications to RF spectroscopy.

The problem of estimating the spectral content of exponentially decaying signals from a set of irregularly sampled data is of considerable interest in several applications, for example in various forms of radio frequency spectroscopy. In this paper, we propose a new nonparametric iterative adaptive approach that provides a solution to this estimation problem. As opposed to commonly used methods in the field, the damping coefficient, or linewidth, is explicitly modeled, which allows for an improved estimation performance. Numerical examples using both simulated data and data from NQR experiments illustrate the benefits of the proposed estimator as compared to currently available nonparametric methods.

Quantitative 35Cl nuclear quadrupole resonance in tablets of the antidiabetic medicine Diabinese.

Pulsed (35)Cl nuclear quadrupole resonance (NQR) experiments have been performed on 250-mg tablets of the antidiabetic medicine Diabinese to establish the conditions needed for noninvasive quantitative analysis of the medicine in standard bottles. One important condition is the generation of a uniform radio-frequency (RF) field over the sample, which has been achieved by two designs of sample coil: one of variable pitch, and the other a resonator that has been fabricated from a single turn of copper sheet with a longitudinal gap bridged by tuning capacitors. The results from blind tests show that the number of tablets in a bottle could be predicted to within +/-3%.

Potential of nuclear quadrupole resonance in pharmaceutical analysis.

Nuclear quadrupole resonance is a radio frequency (rf) spectroscopic technique, closely related to NMR, which can be used to detect signals from solids containing nuclei with spin quantum number >1/2. It is nondestructive, highly specific and noninvasive, requires no static magnetic field, and as such is currently used in the detection of explosives and narcotics. Recent technological advances in pulsed NQR methods have shortened detection times, eliminated spurious signals, and enhanced the sensitivity of detection of 14N frequencies, which lie in the low rf range of 0.4-6 MHz, encouraging a wider range of "real world" applications. This Perspective highlights some of the advantages of NQR, the applications in which it could be used, such as the quantification of pharmaceuticals and the identification of polymorphs. Other roles could include detection, analysis, and quality control of pharmaceuticals at all stages of manufacture. Finally, recent advances which enhance even further the sensitivity of detection will be discussed.