Al 27 NMR local study of the Al0.5TiZrPdCuNi alloy in high-entropy alloy and metallic glass forms

We report a Al27 nuclear magnetic resonance (NMR) local spectroscopic study of the NMR lineshape and Knight shift of a six-component Al0.5TiZrPdCuNi metallic alloy that can be prepared either as a crystalline high-entropy alloy (HEA) or as an amorphous metallic glass (MG) at the same chemical composition. For both structural modifications of the material (HEA and MG), we have determined the distribution of electric-field-gradient (EFG) tensors and the local electronic density of states (DOS) g(ϵF) at the Fermi level at the position of Al27 nuclei. A theoretical I=52 quadrupole-perturbed NMR spectrum, pertinent to both cubic HEAs and amorphous MGs, has been derived using the Gaussian isotropic model of the EFG tensor distribution, and excellent fits of the experimental spectra were obtained. The EFG distribution function of the MG state is about twice broader than that of the HEA state, reflecting the existence of a (distorted) crystal lattice in the latter and its absence in the former. The T2 dependence of the Knight shift indicates that the DOS is changing rapidly with energy within the Fermi level region for both structural modifications. The local DOS at the Al27 sites of the HEA sample is ∼10% larger than that of the MG state, indicating comparable degrees of disorder

Sensitivity of Proton NMR Relaxation and Proton NMR Diffusion Measurements to Olive Oil Adulterations with Vegetable Oils

Olive oils and, in particular, extra-virgin olive oils (EVOOs) are one of the most frauded food. Among the different adulterations of EVOOs, the mixture of high-quality olive oils with vegetable oils is one of the most common in the market. The need for fast and cheap techniques able to detect extra-virgin olive oil adulterations was the main motivation for the present research work based on H-1 NMR relaxation and diffusion measurements. In particular, the H-1 NMR relaxation times, T-1 and T-2, measured at 2 and 100 MHz on about 60 EVOO samples produced in Italy are compared with those measured on four different vegetable oils, produced from macadamia nuts, linseeds, sunflower seeds, and soybeans. Self-diffusion coefficients on this set of olive oils and vegetable oil samples were measured by means of the H-1 NMR diffusion ordered spectroscopy (DOSY) technique, showing that, except for the macadamia oil, other vegetable oils are characterized by an average diffusion coefficient sensibly different from extra-virgin olive oils. Preliminary tests based on both NMR relaxation and diffusometry methods indicate that eventual adulterations of EVOO with linseed oil and macadamia oil are the easiest and the most difficult frauds to be detected, respectively

Observing short-range orientational order in small-molecule liquids

AG and TA acknowledge the funding from Slovenian Research Agency, Basic core funding grant P1-0125. SNF, MGH acknowledge the FCT—Portuguese Foundation for Science and Technology projects PIDDAC (POCI-01-0145-FEDER-007688, Reference UIDB/50025/2020-2023). Publisher Copyright: © 2022, The Author(s).Local molecular ordering in liquids has attracted a lot of interest from researchers investigating crystallization, but is still poorly understood on the molecular scale. Classical nucleation theory (CNT), a macroscopic thermodynamic description of condensation, has shortcomings when dealing with clusters consisting of tens of molecules. Cluster formation and local order fluctuations in liquid media are difficult to study due to the limited spatial resolution of electron- and photon-imaging methods. We used NMR relaxometry to demonstrate the existence of dynamic clusters with short-range orientational order in nominally isotropic liquids consisting of elongated molecules. We observed clusters in liquids where the local ordering is driven by polar, steric, and hydrogen-bond interactions between the molecules. In the case of a liquid crystal, measuring the local orientational order fluctuations allowed us to observe the size of these clusters diverging when approaching the phase transition from the isotropic to the nematic phase. These fluctuations are described in terms of rotational elasticity as a consequence of the correlated reorientations of the neighbouring molecules. Our quantitative observations of the dynamic clusters in liquids, numbering about ten or fewer molecules, indicate that this is a general phenomenon in various types of liquids.publishersversionpublishe

Study of Liquid Crystals Showing Two Isotropic Phases by ¹H NMR Diffusometry and ¹H NMR Relaxometry

In this work, we report a study of two thermotropic liquid crystalline samples showing a not common mesophase behavior. The samples, namely a di-benzyloxy biphenyl derivative labelled 9/2 RS/RS, and a bimesogenic liquid crystal labelled L1, show a direct transition between two isotropic phases followed, at lower temperatures, by the optically isotropic, 3D structured, cubic phase. These systems have been investigated by means of 1H NMR diffusometry and 1H NMR relaxometry in order to characterize their isotropic–isotropic’–cubic mesophase behavior, mainly on the dynamic point of view. In particular, the temperature trend of the self-diffusion coefficients measured for both samples allowed us to significantly distinguish between the two isotropic phases, while the temperature dependence of the 1H spin-lattice relaxation time (T1) did not show significant discontinuities at the isotropic–isotropic’ phase transition. A preliminary analysis of the frequency-dependence of 1H T1 at different temperatures gives information about the main motional processes active in the isotropic mesophases

Nuclear Quadrupole Resonance (NQR)

Nuclear Quadrupole Resonance (NQR) spectroscopy has been known for 70 years. It is suitable for the study of measured (poly)crystalline chemical compounds containing quadrupole nuclei (nuclei with spin I ≥ 1) where the characteristic NQR frequencies represent the fingerprints of these compounds. In several cases, $^{14}$N NQR can distinguish between the polymorphic crystalline phases of active pharmaceutical ingredients (APIs). In order to further stimulate $^{14}$N NQR studies, we review here several results of API polymorphism studies obtained in Ljubljana laboratories: (a) In sulfanilamide, a clear distinction between three known polymorphs (α, β, γ) was demonstrated. (b) In famotidine, the full spectra of all seven different nitrogen positions were measuredtwo polymorphs were distinguished. (c) In piroxicam, the $^{14}$N NQR data helped in confirming the new polymorphic form V. (d) The compaction pressure in the tablet production of paracetamol, which is connected with linewidth change, can be used to distinguish between producers of paracetamol. We established that paracetamol in the tablets of six different manufacturers can be identified by $^{14}$N NQR linewidth. (e) Finally, in order to get an extremely sensitive $^{14}$N NQR spectrometer, the optical detection of the $^{14}$N NQR signal is mentioned