Evaluation of the surface affinity of water in three biochars using fast field cycling NMR relaxometry.

Many soil functions depend on the interaction of water with soil. The affinity of water for soils can be altered by applying soil amendments like stone meal, manure, or biochar (a carbonaceous material obtained by pyrolysis of biomasses). In fact, the addition of hydrophobic biochar to soil may increase soil repellency, reduce water-adsorbing capacity, inhibit microbial activity, alter soil filter, buffer, storage, and transformation functions. For this reason, it is of paramount importance to monitor water affinity for biochar surface (also referred to as 'wettability') in order to better address its applications in soil systems. In this study, we propose the use of fast field cycling NMR relaxometry technique with the application of a new mathematical model for data interpretation, as a valid alternative to the traditional contact angle (CA) measurements for biochar wettability evaluation. Either NMR or CA results revealed the same wettability trend for the biochars studied here. The advantage of NMR relaxometry over CA measurements lies in the possibility to obtain at the microscopic level a variety of different information in only one shot. In fact, while CA provides only wettability evaluation, NMR relaxometry also allows achievement of the mechanisms for water molecular dynamics on biochar surface, thereby leading to the possibility to understand better, in future research, the role of biochar in increasing soil quality and plant nutrition.

New applications and perspectives of fast field cycling NMR relaxometry.

The field cycling NMR relaxometry method (also known as fast field cycling (FFC) when instruments employing fast electrical switching of the magnetic field are used) allows determination of the spin-lattice relaxation time (T1 ) continuously over five decades of Larmor frequency. The method can be exploited to observe the T1 frequency dependence of protons, as well as any other NMR-sensitive nuclei, such as (2) H, (13) C, (31) P, and (19) F in a wide range of substances and materials. The information obtained is directly correlated with the physical/chemical properties of the compound and can be represented as a 'nuclear magnetic resonance dispersion' curve. We present some recent academic and industrial applications showing the relevance of exploiting FFC NMR relaxometry in complex materials to study the molecular dynamics or, simply, for fingerprinting or quality control purposes. The basic nuclear magnetic resonance dispersion features are outlined in representative examples of magnetic resonance imaging (MRI) contrast agents, porous media, proteins, and food stuffs. We will focus on the new directions and perspectives for the FFC technique. For instance, the introduction of the latest Wide Bore FFC NMR relaxometers allows probing, for the first time, of the dynamics of confined surface water contained in the macro-pores of carbonate rock cores. We also evidence the use of the latest field cycling technology with a new cryogen-free variable-field electromagnet, which enhances the range of available frequencies in the 2D T1 -T2 correlation spectrum for separating oil and water in crude oil. Copyright © 2015 John Wiley & Sons, Ltd.

NMR methodologies in the analysis of blueberries.

An NMR analytical protocol based on complementary high and low field measurements is proposed for blueberry characterization. Untargeted NMR metabolite profiling of blueberries aqueous and organic extracts as well as targeted NMR analysis focused on anthocyanins and other phenols are reported. Bligh-Dyer and microwave-assisted extractions were carried out and compared showing a better recovery of lipidic fraction in the case of microwave procedure. Water-soluble metabolites belonging to different classes such as sugars, amino acids, organic acids, and phenolic compounds, as well as metabolites soluble in organic solvent such as triglycerides, sterols, and fatty acids, were identified. Five anthocyanins (malvidin-3-glucoside, malvidin-3-galactoside, delphinidin-3-glucoside, delphinidin-3-galactoside, and petunidin-3-glucoside) and 3-O-α-l-rhamnopyranosyl quercetin were identified in solid phase extract. The water status of fresh and withered blueberries was monitored by portable NMR and fast-field cycling NMR. (1) H depth profiles, T2 transverse relaxation times and dispersion profiles were found to be sensitive to the withering.

Dynamics of pistachio oils by proton nuclear magnetic resonance relaxation dispersion.

A number of pistachio oils were selected in order to test the efficacy of nuclear magnetic resonance relaxation dispersion (NMRD) technique in the evaluation of differences among oils (1) obtained from seeds subjected to different thermal desiccation processes, (2) retrieved from seeds belonging to the same cultivar grown in different geographical areas and (3) produced by using seed cultivars sampled in the same geographical region. NMRD measures relaxation rate values which are related to the dynamics of the chemical components of complex food systems. Results not only allowed to relate kinematic viscosity to relaxometry parameters but also were successful in the differentiation among the aforementioned oils. In fact, from the one hand, the larger the kinematic viscosity, the faster the rotational motions appeared as compared to the translational ones. On the other hand, relaxation rate curves (NMRD) varied according to the oxidative stresses and chemical composition of each sample. The present study showed for the first time that NMRD is a very promising technique for quick evaluations of pistachio oil quality without the need for time-consuming chemical manipulations.

Dissolution mechanism of crystalline cellulose in H3PO4 as assessed by high-field NMR spectroscopy and fast field cycling NMR relaxometry.

Many processes have been proposed to produce glucose as a substrate for bacterial fermentation to obtain bioethanol. Among others, cellulose degradation appears as the most convenient way to achieve reliable amounts of glucose units. In fact, cellulose is the most widespread biopolymer, and it is considered also as a renewable resource. Due to extended intra- and interchain hydrogen bonds that provide a very efficient packing structure, however, cellulose is also a very stable polymer, the degradation of which is not easily achievable. In the past decade, researchers enhanced cellulose reactivity by increasing its solubility in many solvents, among which concentrated phosphoric acid (H(3)PO(4)) played the major role because of its low volatility and nontoxicity. In the present study, the solubilization mechanism of crystalline cellulose in H(3)PO(4) has been elucidated by using high- and low-field NMR spectroscopy. In particular, high-field NMR spectra showed formation of direct bonding between phosphoric acid and dissolved cellulose. On the other hand, molecular dynamics studies by low-field NMR with a fast field cycling (FFC) setup revealed two different H(3)PO(4) relaxing components. The first component, described by the fastest longitudinal relaxation rate (R(1)), was assigned to the H(3)PO(4) molecules bound to the biopolymer. Conversely, the second component, characterized by the slowest R(1), was attributed to the bulk solvent. The understanding of cellulose dissolution in H(3)PO(4) represents a very important issue because comprehension of chemical mechanisms is fundamental for process ameliorations to produce bioenergy from biomasses.