When it comes to crystal structure determination, computational approaches such as Crystal Structure Prediction (CSP) have gained more and more attention since they offer some insight on how atoms and molecules are packed in the solid state, starting from only very basic information without diffraction data. Furthermore, it is well known that the coupling of CSP with solid-state NMR (SSNMR) greatly enhances the performance and the accuracy of the predictive method, leading to the so-called CSP-NMR crystallography (CSP-NMRX). In this paper, we present the successful application of CSP-NMRX to determine the crystal structure of three structural isomers of pyridine dicarboxylic acid, namely quinolinic, dipicolinic and dinicotinic acids, which can be in a zwitterionic form, or not, in the solid state. In a first step, mono- and bidimensional SSNMR spectra, i.e., ¹H Magic-Angle Spinning (MAS), ¹³C and ¹⁵N Cross Polarisation Magic-Angle Spinning (CPMAS), ¹H Double Quantum (DQ) MAS, ¹H-¹³C HETeronuclear CORrelation (HETCOR), were used to determine the correct molecular structure (i.e., zwitterionic or not) and the local molecular arrangement; at the end, the RMSEs between experimental and computed ¹H and ¹³C chemical shifts allowed the selection of the correct predicted structure for each system. Interestingly, while quinolinic and dipicolinic acids are zwitterionic and non-zwitterionic, respectively, in the solid state, dinicotinic acid exhibits in its crystal structure a “zwitterionic-non-zwitterionic continuum state” in which the proton is shared between the carboxylic moiety and the pyridinic nitrogen. Very refined SSNMR experiments were carried out, i.e., ¹⁴N-¹H Phase-Modulated (PM) pulse and Rotational-Echo Saturation-Pulse Double-Resonance (RESPDOR), to provide an accurate N–H distance value confirming the hybrid nature of the molecule. The CSP-NMRX method showed a remarkable match between the selected structures and the experimental ones. The correct molecular input provided by SSNMR reduced the number of CSP calculations to be performed, leading to different predicted structures, while RMSEs provided an independent parameter with respect to the computed energy for the selection of the best candidate.

Many staple foods originate from durum wheat and its milling products; because of this, it is very important to know their characteristics. This study investigates elemental contents in these products and if differences exist because of organic farming. The concentrations of 28 elements in the whole seed and in milling products, that is, bran, semolina and flour, of durum wheat, were determined through ICP-OES. The wheats were grown under conventional or organic agronomic practices to verify the possibility of discriminating, using the elemental content, between products coming from one or the other practice. The elements were more abundant in the outer layer of the seed, the bran, but most of them were also present in the others. Traces of Sb were present only in 3% of the samples, while traces of Tl were detected in approximately half of the seed and bran samples but not in other samples. The absence of an element was more characteristic of specific products, e.g., most semolina and flour lacked Co, while other elements showed small differences between products from organic and conventional cultivation or between different milling products, which was the case, for example, for traces of Ag, B, and V. The concentrations of these elements were coupled with multivariate discriminant analysis, specifically PLS-DA, to identify the cultivation provenance of the milled products. A few elements, although different for each product, are sufficient to attain precision and accuracy of classification close to 1; small differences exist for different products. The worst is flour, where the predicted precision and accuracy are 0.92, although using only three elements: B, K, and Se. Semolina attains perfect prediction when also adding to the three previous elements, Ag, Cd, and Cu. Further elements are necessary for bran, while Fe and Mg replace K and Ag to classify seeds. In conclusion, five elements, B, Cd, Cu, K, and Se, are the most important in distinguishing between organic and conventional agriculture; these elements also permit some differentiation among products. The method could help in fraud prevention.

Alkali-activated aluminosilicate matrices are increasingly studied for their ability to stabilize hazardous metal contaminants via alkali activation at room temperature. In this study, metakaolin-based geopolymers were used to immobilize chromium and nickel salts, with systematic variation of key synthesis parameters, Na/Al molar ratio, metal concentration, anion type, and alkaline solution aging time, which have not been previously studied. A Design of Experiments approach was employed to study the effect of factors on metal leaching behavior and to better understand the underlying immobilization mechanisms. The analysis revealed that higher Na/Al ratios significantly enhance geopolymerization and reduce metal release, as supported by FTIR spectral shifts and decreased shoulder intensity. Notably, aging time had an influence on chromium behavior due to its effect on early silicate network formation, which can hinder the incorporation of chromium species. All tested formulations achieved metal immobilization rates of 98.8% or higher for both chromium and nickel. Overall, this study advances our understanding of geopolymer-based heavy metal immobilization.