Use of NMR as an online sensor in industrial processes

Nuclear magnetic resonance (NMR) is one of the most versatile analytical techniques for chemical, biochemical and medical applications. Despite this great success, NMR is seldom used as a tool in industrial applications. The first application of NMR in flowing samples was published in 1951. However, only in the last ten years Flow NMR has gained momentum and new and potential applications have been proposed. In this review we present the historical evolution of flow or online NMR spectroscopy and imaging, and current developments for use in the automation of industrial processes

Fluorescência induzida por laser da matéria orgânica de um Latossolo brasileiro tratado com lodo de esgoto

A aplicação do lodo de esgoto é utilizada como alternativa de conservação e manutenção da fertilidade dos solos sem prejudicar o ecossistema. O objetivo do presente trabalho foi avaliar a influência da aplicação de lodo de esgoto sobre a matéria orgânica (MO) de um Latossolo vermelho amarelo brasileiro, através da fluorescência induzida por laser (LIF). A LIF foi utilizada para analisar a fluorescência do solo intacto e suas frações químicas e físicas. Houve grande contribuição da fração humina à fluorescência do solo intacto, remarcando a importância de estudar a matéria orgânica (MO) associada à matriz mineral do solo. Para cada fração granulométrica foram obtidos espectros com diferentes perfis, indicando diferenças nos compostos orgânicos a elas ligados. A fração 2-20 µm, que apresentou maior conteúdo de carbono (~5%), representa somente 10% do solo mas acumula 34-39 % do conteúdo total de carbono do mesmo e mostrou a maior intensidade de fluorescência. O espectro desta fração mostra sua heterogeneidade e alta concentração de compostos cuja fluorescência é centrada nos 510 nm, o que indica alta concentração de sistemas com ligações insaturadas, com alto grau de ressonância e maior conjugação do sistema de eletrons pi, indicando maior aromaticidade quando comparado as outras frações. Não foram observadas diferenças significativas entre os tratamentos de lodo de esgoto. A LIF é uma técnica promissora para caraterizar a MO de solos intatos, permitindo estudar sua distribuição na matriz mineral do solo, inclusive nos Latossolos.Sludge applications have been used to maintain fertility of agricultural soils without damaging the natural ecosystem. The aim of this study was evaluating the influence of sewage-sludge addition on the quality of organic matter (OM) of a Brazilian Oxisol by Laser Induced Fluorescence (LIF). LIF was used to analyze OM of whole soil and different soil fractions separated by chemical and physical methods. The high fluorescence contribution of humin fraction to the fluorescence of whole soils was shown, stressing the importance of studying OM associated to mineral matrix of soil. Spectra with different shapes were obtained for every particle size fraction, indicating differences in organic compounds bounded to them. The fraction with the higher carbon content was the 2-20 µm, that contains ~5% C and represents only 10% in soil, but stores 34-39 % of total C and shows the highest fluorescence intensity. The spectrum of this fraction shows its heterogeneity and a higher concentration of compounds which fluorescence is centered at 510 nm. This indicates a higher concentration of unsaturated bond systems capable of high degree of resonance, increased conjugation of the electron pi system, and higher aromaticity comparing with other fractions. No differences were detected for treatments of sewage-sludge applications. LIF spectroscopy is a promising technique for OM studies in whole soils, allowing to study spatial distribution of OM within the soil's mineral matrix, including Oxisols

Use of the Relaxometry Technique for Quantification of Paramagnetic Ions in Aqueous Solutions and a Comparison with Other Analytical Methods

We have demonstrated that the relaxometry technique is very efficient to quantify paramagnetic ions during in situ electrolysis measurements. Therefore, the goal of this work was to validate the relaxometry technique in the determination of the concentration of the ions contained in electrolytic solutions, Cu2+, Ni2+, Cr3+, and Mn2+, and compare it with other analytical methods. Two different NMR spectrometers were used: a commercial spectrometer with a homogeneous magnetic field and a home-built unilateral sensor with an inhomogeneous magnetic field. Without pretreatment, manganese ions do not have absorption bands in the UV-Visible region, but it is possible to quantify them using relaxometry (the limit of quantification is close to 10−5 mol L−1). Therefore, since the technique does not require chemical indicators and is a cheap and robust method, it can be used as a replacement for some conventional quantification techniques. The relaxometry technique could be applied to evaluate the corrosion of metallic surfaces

NMR-based plant metabolomics protocols: a step-by-step guide.

Metabolomics is one of the “omics” sciences that can reveal the metabolic phenotype of organisms. This capability makes it a valuable tool for plant investigation, as plants present a vast chemical diversity. From the analytical point of view, two main techniques are frequently used in metabolomics and are often complementary: Mass spectrometry (MS) and Nuclear Magnetic Resonance (NMR) spectroscopy. Here, we describe NMR and its applications in plant metabolomics. We start by contextualizing the research field to then explore study design, sample collection, sample preparation, NMR data acquisition, and data analysis, showing the key features for achieving quality and relevant results. Within these topics, the most common databases used for plant metabolites identification and assignments are listed, as these help to shorten the laborious task of metabolomics investigation of natural products. Concerning NMR parameters, we discuss the key pulse sequences, recommend acquisition parameters, and examine the data each sequence can provide. Similarly, we delve into data analysis, highlighting the most commonly used chemometric methods and how to achieve high-quality results. Therefore, this review aims to provide a comprehensive guide for NMR-based metabolomics analysis of plants

Use of time domain nuclear magnetic resonance relaxometry to monitor the effect of magnetic field on the copper corrosion rate in real time

The corrosion of metals is a major problem of modern societies, demanding new technologies and studies to understand and minimize it. Here we evaluated the effect of a magnetic field (B) on the corrosion of copper in aqueous HCl solution under open circuit potential. The corrosion product, Cu2+, is a paramagnetic ion and its concentration in the solution was determined in real time in the corrosion cell by time-domain NMR relaxometry. The results show that the magnetic field (B = 0.23 T) of the time-domain NMR instrument reduces the corrosion rate by almost 50%, in comparison to when the corrosion reaction is performed in the absence of B. Atomic force microscopy and X-ray diffraction results of the analysis of the corroded surfaces reveal a detectable CuCl phase and an altered morphology when B is present. The protective effect of B was explained by magnetic forces that maintain the Cu2+ in the solution/metal interface for a longer time, hindering the arrival of the new corrosive agents, and leading to the formation of a CuCl phase, which may contribute to the rougher surface. The time-domain NMR method proved to be useful to study the effect of B in the corrosion of other metals or other corrosive liquid media when the reactions produce or consume paramagnetic ions

Processing of high resolution magic angle spinning spectra of breast cancer cells by the filter diagonalization method

Proton nuclear magnetic resonance (H-1 NMR) spectroscopy for detection of biochemical changes in biological samples is a successful technique. However, the achieved NMR resolution is not sufficiently high when the analysis is performed with intact cells. To improve spectral resolution, high resolution magic angle spinning (HR-MAS) is used and the broad signals are separated by a T-2 filter based on the CPMG pulse sequence. Additionally, HR-MAS experiments with a T-2 filter are preceded by a water suppression procedure. The goal of this work is to demonstrate that the experimental procedures of water suppression and T-2 or diffusing filters are unnecessary steps when the filter diagonalization method (FDM) is used to process the time domain HR-MAS signals. Manipulation of the FDM results, represented as a tabular list of peak positions, widths, amplitudes and phases, allows the removal of water signals without the disturbing overlapping or nearby signals. Additionally, the FDM can also be used for phase correction and noise suppression, and to discriminate between sharp and broad lines. Results demonstrate the applicability of the FDM post-acquisition processing to obtain high quality HR-MAS spectra of heterogeneous biological materials.FAPESPFAPESPFINEPFINEPCNPqCNP

Comparative untargeted metabolome analysis of ruminal fuid and feces of Nelore steers (Bos indicus).

We conducted a study to identify the fecal metabolite profle and its proximity to the ruminal metabolism of Nelore steers based on an untargeted metabolomic approach. Twenty-six Nelore were feedlot with same diet during 105 d. Feces and rumen fuid were collected before and at slaughter, respectively. The metabolomics analysis indicated 49 common polar metabolites in the rumen and feces. Acetate, propionate, and butyrate were the most abundant polar metabolites in both bio-samples. The rumen presented signifcantly higher concentrations of the polar compounds when compared to feces (P< 0.05); even though, fecal metabolites presented an accentuated representability of the ruminal fuid metabolites. All fatty acids present in the ruminal fuid were also observed in the feces, except for C20:2n6 and C20:4n6. The identifed metabolites ofer information on the main metabolic pathways (higher impact factor and P< 0.05), as synthesis and degradation of ketone bodies; the alanine, aspartate and glutamate metabolisms, the glycine, serine; and threonine metabolism and the pyruvate metabolism. The fndings reported herein on the close relationship between the ruminal fuid and feces metabolic profles may ofer new metabolic information, in addition to facilitating the sampling for metabolism investigation in animal production and health routines

Magnetic Resonance and Vibrational Spectroscopy and Imaging in Food Analysis

In the past two decades, there have been remarkable changes in the way we analyze the physical, chemical, and sensory properties of fresh and processed food products, with the progressive replacement of traditional wet analytical methods (destructive, laborious, time-consuming, and requiring the use of hazardous chemicals) with new, fast, non-destructive physical methods where the analysis is performed in a single step, after validation, and without the use of chemical reagents [...

SIMULATION OF NMR SIGNALS THROUGH THE BLOCH EQUATIONS

The aim of this paper was to present a simple and fast way of simulating Nuclear Magnetic Resonance signals using the Bloch equations. These phenomenological equations describe the classical behavior of macroscopic magnetization and are easily simulated using rotation matrices. Many NMR pulse sequences can be simulated with this formalism, allowing a quantitative description of the influence of many experimental parameters. Finally, the paper presents simulations of conventional sequences such as Single Pulse, Inversion Recovery, Spin Echo and CPMG