Sonia Maria Cabral de Menezes

Further conventions for NMR shielding and chemical shifts (IUPAC Recommendations 2008)

IUPAC has published a number of recommendations regarding the reporting of nuclear magnetic resonance (NMR) data, especially chemical shifts. The most recent publication [Pure Appl. Chem.73, 1795 (2001)] recommended that tetramethylsilane (TMS) serve as a universal reference for reporting the shifts of all nuclides, but it deferred recommendations for several aspects of this subject. This document first examines the extent to which the 1H shielding in TMS itself is subject to change by variation in temperature, concentration, and solvent. On the basis of recently published results, it has been established that the shielding of TMS in solution [along with that of sodium-3-(trimethylsilyl)propanesulfonate, DSS, often used as a reference for aqueous solutions] varies only slightly with temperature but is subject to solvent perturbations of a few tenths of a parts per million (ppm). Recommendations are given for reporting chemical shifts under most routine experimental conditions and for quantifying effects of temperature and solvent variation, including the use of magnetic susceptibility corrections and of magic-angle spinning (MAS). This document provides the first IUPAC recommendations for referencing and reporting chemical shifts in solids, based on high-resolution MAS studies. Procedures are given for relating 13C NMR chemical shifts in solids to the scales used for high-resolution studies in the liquid phase. The notation and terminology used for describing chemical shift and shielding tensors in solids is reviewed in some detail, and recommendations are given for best practice.

Further conventions for NMR shielding and chemical shifts (IUPAC Recommendations 2008).

IUPAC has published a number of recommendations regarding the reporting of nuclear magnetic resonance (NMR) data, especially chemical shifts. The most recent publication [Pure Appl. Chem. 73, 1795 (2001)] recommended that tetramethylsilane (TMS) serve as a universal reference for reporting the shifts of all nuclides, but it deferred recommendations for several aspects of this subject. This document first examines the extent to which the 1H shielding in TMS itself is subject to change by variation in temperature, concentration, and solvent. On the basis of recently published results, it has been established that the shielding of TMS in solution [along with that of sodium‐3‐(trimethylsilyl)propanesulfonate, DSS, often used as a reference for aqueous solutions] varies only slightly with temperature but is subject to solvent perturbations of a few tenths of a part per million (ppm). Recommendations are given for reporting chemical shifts under most routine experimental conditions and for quantifying effects of temperature and solvent variation, including the use of magnetic susceptibility corrections and of magic‐angle spinning (MAS).

Further conventions for NMR shielding and chemical shifts IUPAC recommendations 2008.

IUPAC has published a number of recommendations regarding the reporting of nuclear magnetic resonance (NMR) data, especially chemical shifts. The most recent publication [Pure Appl. Chem. 73, 1795 (2001)] recommended that tetramethylsilane (TMS) serve as a universal reference for reporting the shifts of all nuclides, but it deferred recommendations for several aspects of this subject. This document first examines the extent to which the (1)H shielding in TMS itself is subject to change by variation in temperature, concentration, and solvent. On the basis of recently published results, it has been established that the shielding of TMS in solution [along with that of sodium-3-(trimethylsilyl)propanesulfonate, DSS, often used as a reference for aqueous solutions] varies only slightly with temperature but is subject to solvent perturbations of a few tenths of a part per million (ppm). Recommendations are given for reporting chemical shifts under most routine experimental conditions and for quantifying effects of temperature and solvent variation, including the use of magnetic susceptibility corrections and of magic-angle spinning (MAS). This document provides the first IUPAC recommendations for referencing and reporting chemical shifts in solids, based on high-resolution MAS studies. Procedures are given for relating (13)C NMR chemical shifts in solids to the scales used for high-resolution studies in the liquid phase. The notation and terminology used for describing chemical shift and shielding tensors in solids are reviewed in some detail, and recommendations are given for best practice.

Solvation of Carbon Dioxide in [C4mim][BF4] and [C4mim][PF6] Ionic Liquids Revealed by High-Pressure NMR Spectroscopy†

Where is CO2 ? The intermolecular interactions of [C4 mim]BF4 and [C4 mim]PF6 ionic liquids and CO2 have been determined by high-pressure NMR spectroscopy in combination with molecular dynamic simulations. The anion and the cation are both engaged in interactions with CO2 . A detailed picture of CO2 solvation in these ILs is provided. CO2 solubility is essentially determined by the microscopic structure of the IL.

Estoque e qualidade da matéria orgânica de um solo cultivado com cana-de-açúcar por longo tempo

The aim of this study was to evaluate the stocks, and quality of the soil organic matter (SOM) through the use of solid state 13C nuclear magnetic resonance (13C NMR), electronic paramagnetic resonance (EPR) and fluorescence spectroscopy of a fine clay fluventic Eutrichrept after long-term sugarcane cultivation. In one area, sugarcane has been grown for 55 years no field burning before harvest. In another area managed under the traditional system the crop field has been burned before harvest for 35 years; vinasse has been applied on one part (at a rate of 120 m3 ha-1 yr -1), but not on another. The increases of 157 and 57 % in C stocks of humic acids in the area cultivated without field burning for 55 years were related with the increase in the aromaticity degree as well as lower acidity of the SOM, as shown by 13C NMR spectroscopy. The semiquinone-type free radical concentration, as observed by EPR, and intensity of fluorescence emission were higher in the humic acid extracted from soils under management system without field burning before harvest. Significant changes in the humification process were observed in the areas with crop trash preservation. However, in areas where sugar-cane fields were burnt at harvest, vinasse application for 35 years resulted in only minor changes in the organic matter quality and C stocks. These data indicate a rapid evolution of the soluble organic matter added to the soil through vinasse application.

A Rational Approach to CO2 Capture by Imidazolium Ionic Liquids: Tuning CO2 Solubility by Cation Alkyl Branching

Branching at the alkyl side chain of the imidazolium cation in ionic liquids (ILs) was evaluated towards its effect on carbon dioxide (CO2 ) solubilization at 10 and 80 bar (1 bar=1×10(5)  Pa). By combining high-pressure NMR spectroscopy measurements with molecular dynamics simulations, a full description of the molecular interactions that take place in the IL-CO2 mixtures can be obtained. The introduction of a methyl group has a significant effect on CO2 solubility in comparison with linear or fluorinated analogues. The differences in CO2 solubility arise from differences in liquid organization caused by structural changes in the cation. ILs with branched cations have similar short-range cation-anion orientations as those in ILs with linear side chains, but present differences in the long-range order. The introduction of CO2 does not cause perturbations in the former and benefits from the differences in the latter. Branching at the cation results in sponge-like ILs with enhanced capabilities for CO2 capture.

Syntheses and characterization of new poly(ionic liquid)s designed for CO2 capture

A series of new poly(ionic liquid)s-p(IL)s based on polyurethane structures were synthesized and characterized and their behavior evaluated in CO2 sorption tests under different pressures. The synthesized materials were characterized according to structure, composition, and thermal stability, by techniques such as FTIR, 1H-NMR, TGA and DSC. The CO2 sorption measurements were carried out in a Magnetic Suspension Balance-PTGA and proved that the change of the components of the polymer chain directly indicates the sorption behavior. The best performance for CO2 sorption (75.7 mol% at 20 bar) was achieved with the p(IL) PUA-02a obtained from HDI and PTMG-2000 with [bmim]+ as a counter-ion. The synthesized p(IL)s presenting nitrogenated and polyether structures into the backbone allied to imidazolium counter-cations proved to be worthy of note in the CO2 sorption besides being based on poly(urethane) a versatile and low-cost material. The results also highlighted the good performance of PUA-02 when compared with traditional solvents used in pre-combustion process, as well as the p(IL)s described in the literature.

NMR and acidity studies of dealuminated metakaolin and their correlation with cumene cracking

Abstract Metakaolin is obtained by dehydroxylation of kaolin; its dealumination is carried out with sulfuric acid. 29 Si MAS NMR studies show that a three-dimensional framework of SiO 4 is formed with an increase in kaolin calcination temperature. On the other hand, 27 Al MAS NMR shows that calcination temperatures up to 850°C bring on a decrease of the hexa-coordinated aluminum nuclei, while tetra- and penta-coordinated aluminum nuclei are being formed. In the range of temperatures studied, the amount of Bronsted sites are not constant and decrease up to 850°C, probably because the metakaolin structure undergoes less collapse during acid attack. A synergism between Lewis and Bronsted sites is suspected. Thus, it is suggested that penta-coordinated aluminum nuclei, which are strong Lewis sites, increase the strength of Bronsted sites. Consequently, cumene cracking activity increases.

Characterization of a brazilian smectite by solid state NMR and X-ray diffraction techniques

X-ray diffraction (XRD), differential thermal analysis (DTA) and 27Al and 29Si solid state MAS-NMR techniques were used to monitor the fractionation steps of a brazilian smectite, previously crushed, from Campina Grande, Paraiba. The sand, silt and clay fractions were obtained by physical and chemical treatments. The XRD analysis of sand and silt fractions showed that both fractions had predominant quartz and feldspar, respectively. The XRD results of the K+ saturated and heated clay fraction confirmed that the natural clay belongs to the 2:1 clay-mineral group, whereas the analysis of the Mg2+ saturated and glycolated clay fraction confirmed the presence of a smectite group clay. The MAS-NMR results of 27Al and 29Si showed that the sand fraction contains 79% of quartz and the silt fraction contains 55% of quartz, while the clay fraction is rich in smectite with low isomorphic replacement of Si by Al, and contains 38 % of quartz.

SOLID-STATE 13C NMR QUANTITATIVE STUDY OF EUCALYPTUS TAR PITCHES

Solid-state 13C NMR has been important to overcome analysis difficulties arising from the low solubility of carbonaceous materials. Its use provides accurate information about these materials. In this work, resonance techniques involving magic angle spinning with cross-polarisation (CP/MAS) or single pulse (SP/MAS) are used in conjunction with other analysis tools to quantitatively characterise Eucalyptus tar pitches and to follow their polymerisation reactions. The results showed that SP/MAS technique is more suitable for quantitative analyses, and that the pitches have a high content of aliphatic and oxygenated carbons. Moreover, they underwent thermal polymerisation, and the presence of AlCl3 or formaldehyde permitted the use of lower treatment temperatures. The polymerisation reactions were followed by aromaticity enhancements, giving rise to higher coke yields.