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Magnetic resonance imaging (MRI) is the method of choice for noninvasive studies of micrometer-scale structures in biological tissues via their effects on the time- and frequency-dependent (restricted) and anisotropic self-diffusion of water. While new designs of time-dependent magnetic field gradient waveforms have enabled disambiguation between different aspects of translational motion that are convolved in traditional MRI methods relying on single pairs of field gradient pulses, data analysis for complex heterogeneous materials remains a challenge. Here, we propose and demonstrate nonparametric distributions of tensor-valued Lorentzian diffusion spectra, or "D(ω) distributions," as a general representation with sufficient flexibility to describe the MRI signal response from a wide range of model systems and biological tissues investigated with modulated gradient waveforms separating and correlating the effects of restricted and anisotropic diffusion.
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Heavy carbon industries produce solid side stream materials that contain inorganic chemicals like Ca, Na, or Mg, and other metals such as Fe or Al. These inorganic compounds usually react efficiently with CO2 to form stable carbonates. Therefore, using these side streams instead of virgin chemicals to capture CO2 is an appealing approach to reduce CO2 emissions. Herein, we performed an experimental study of the mineral carbonation potential of three industrial steel slags via aqueous, direct carbonation. To this end, we studied the absorption capacities, reaction yields, and physicochemical characteristics of the carbonated samples. The absorption capacities and the reaction yields were analyzed through experiments carried out in a reactor specifically designed to work without external stirring. As for the physicochemical characterization, we used solid-state Fourier Transform Infrared Spectroscopy (FTIR), X-ray diffraction (XRD), and scanning electron microscope (SEM). Using this reactor, the absorption capacities were between 5.8 and 35.3 g/L and reaction yields were in the range of 81-211 kg CO2/ton of slag. The physicochemical characterization of the solid products with solid FTIR, XRD and SEM indicated the presence of CaCO3. This suggests that there is potential to use the carbonated products in commercial applications.
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Resíduos Industriais , Aço , Aço/química , Resíduos Industriais/análise , Espectroscopia de Infravermelho com Transformada de Fourier , Microscopia Eletrônica de Varredura , Difração de Raios X , Dióxido de Carbono/químicaRESUMO
[This corrects the article DOI: 10.1039/D3RA03370H.].
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A series of N-methylmorpholinium salts with varying N-alkyl chains and Cl-, OAc- and OH- as counter ions have been synthesized and investigated for their ability to dissolve cellulose, aiming at elucidating solvent structural features affecting cellulose dissolution. Synthesis procedures have been developed to, to a high extent, rely on conversions in water and microwave-assisted reactions employing a reduced number of work-up steps and ion-exchange resins that can be regenerated. Water solutions of morpholinium hydroxides proved capable of dissolving cellulose, with those of them possessing alkyl chains longer than ethyl showing surprising dissolution ability at room-temperature. Morpholinium acetates behaved as ionic liquids, and were also capable of dissolving cellulose when combined with DMSO. The obtained cellulose solutions were characterized according to their chemical and colloidal stability using 13C NMR spectroscopy, size exclusion chromatography and flow sweep measurements, while the ethanol coagulates were investigated in terms of crystallinity using solid state NMR. In contrast, the morpholinium chlorides obtained were hygroscopic with high melting points and low solubility in common organic solvents e.g., acetone, DMSO and DMAc, thus lacking the ability to swell or dissolve cellulose.
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The high potential use of lignin in novel biomaterials and chemicals represents an important opportunity for the valorization of the most abundant natural resource of aromatic molecules. From an environmental perspective, it is highly desirable replacing the hazardous methods currently used to extract lignin from lignocellulosic biomass and develop more sustainable and environmentally friendly approaches. Therefore, in this work, levulinic acid (a "green" solvent obtained from biomass) was successfully used, for the first time, to selectively extract high-quality lignin from pine wood sawdust residues at 200 °C for 6 h (at atmospheric pressure). Moreover, the addition of catalytic concentrations of inorganic acids (i.e., H2SO4 or HCl) was found to substantially reduce the temperature and reaction times needed (i.e., 140 °C, 2 h) for complete lignin extraction without compromising its purity. NMR data suggests that condensed OH structures and acidic groups are present in the lignin following extraction. Levulinic acid can be easily recycled and efficiently reused several times without affecting its performance. Furthermore, excellent solvent reusability and performance of extraction of other wood residues has been successfully demonstrated, thus making the developed levulinic acid-based procedure highly appealing and promising to replace the traditional less sustainable methodologies.
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Ácidos , Lignina , Lignina/química , Solventes/química , Ácidos Levulínicos , BiomassaRESUMO
Carbon dioxide storage is one of the main long-term strategies for reducing carbon dioxide emissions in the atmosphere. A clear example is Norway's Longship project. If these projects should succeed, the transport of huge volumes of carbon dioxide from the emissions source to the injection points may become a complex challenge. In this work, we propose the production of sodium-based organic carbonates that could be transported to storage sites and be reconverted to CO2. Solid carbonates can be transported in considerably lower volumes than gases or pressurized liquids. Sodium-based carbonates are insoluble in most of the organic solvents and will therefore precipitate in contrast to in aqueous solutions. Particularly, here we focus on sodium hydroxide-ethanol mixtures as solvents for precipitating sodium ethyl carbonate and sodium bicarbonate. Previous works on this approach used limited sodium hydroxide concentrations, which are insufficient to prove the effectiveness of the proposed process. In this paper, we studied higher sodium hydroxide concentrations in sodium hydroxide-ethanol mixtures than previously reported in the literature. To this end, we use the following strategy: (1) In-line monitoring of the formation of carbonates using an in-line FTIR; (2) In-line measurements of the weight increase, which correspond directly to the captured carbon dioxide and reveal the absorption capacity; (3) Characterization of the solids with X-ray diffraction and scanning electron microscope. Our FTIR results confirmed that both sodium ethyl carbonate and sodium bicarbonate were formed, which agrees with X-ray diffraction and scanning electron microscope. With this reactor design, the absorption capacities reached approximately 80-93% of the theoretical values (4.8-13.3 g/L respectively). We hypothesize that full conversion is hampered because the gas might take preferential paths due to gel formation during the experiments.
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Research in the field of photochemistry, including photocatalysis and photoelectrocatalysis, has been revitalized due to the potential that photochemical reactions show in the sustainable production of chemicals. Therefore, there is a need for flexible photoreactor equipment that allows for the evaluation of the geometry, light wavelength, and intensity of the vessel, along with the fluid flow in various photochemical reactions. Light emitting diodes (LEDs) have narrow emission spectra and can be either pulsed or run continuously; being flexible, they can be arranged to fit the dimensions of various types of the reactor vessel, depending on the application. This study presents a 3D printed photoreactor with the ability to adjust distances easily and switch between high-power LED light sources. The reactor design utilizes customized printed circuit boards to mount varying numbers and types of LEDs, which enables multiple wavelengths to be used simultaneously. These LED modules, comprised of heat sinks and cooling fans, fulfill the higher heat dissipation requirements of high-power LEDs. The flexibility of the reactor design is useful for optimizing the reaction geometry, flow conditions, wavelength, and intensity of photochemical reactions on a small scale. The estimates for incident light intensity under five possible reactor configurations using ferrioxalate actinometry are reported so that comparisons with other photoreactors can be made. The performance of the photoreactor for differing vessel sizes and distances, in both the flow and batch modes, is given for a photochemical reaction on 2-benzyloxyphenol-a model substance for lignin and applicable in the production of biobased chemicals.
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Convenience food products tend to alter their quality and texture while stored. Texture-giving food components are often starch-rich ingredients, such as pasta or rice. Starch transforms depending on time, temperature and water content, which alters the properties of products. Monitoring these transformations, which are associated with a change in mobility of the starch chain segments, could optimize the quality of food products containing multiple ingredients. In order to do so, we applied a simple and efficient in situ 13 C solid-state magic angle spinning (MAS) NMR approach, based on two different polarization transfer schemes, cross polarization (CP) and insensitive nuclei enhanced by polarization transfer (INEPT). The efficiency of the CP and INEPT transfer depends strongly on the mobility of chain segments-the time scale of reorientation of the CH-bond and the order parameter. Rigid crystalline or amorphous starch chains give rise to CP peaks, whereas mobile gelatinized starch chains appear as INEPT peaks. Comparing 13 C solid-state MAS NMR experiments based on CP and INEPT allows insight into the progress of gelatinization, and other starch transformations, by reporting on both rigid and mobile starch chains simultaneously with atomic resolution by the 13 C chemical shift. In conjunction with 1 H solid-state MAS NMR, complementary information about other food components present at low concentration, such as lipids and protein, can be obtained. We demonstrate our approach on starch-based products and commercial pasta as a function of temperature and storage.
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Imageamento por Ressonância Magnética , Amido , Espectroscopia de Ressonância Magnética , Amido/química , Temperatura , ÁguaRESUMO
The CO2/CO32- chemistry of the cellulose/NaOH(aq) solutions has been recently reported to comprise a CO2 incorporation through formation of a transient cellulose carbonate intermediate along with cellulose - CO32- interactions. This work explores on molecular interactions arising when this chemistry is brought together with urea, the most common stabiliser of these solutions. 1H, 13C and steady-state heteronuclear Overhauser effect NMR studies on the cellulose analogues (methyl-ß-glucopyranoside (ß-MeO-Glcp) and microcrystalline cellulose), combined with pH and ATR-FTIR measurements, reveal concurrent interactions of urea with both CO2 and CO32-- leading to increased uptake of CO2 and a buffering effect. Yet, regardless of the presence of urea, the route of conversion from CO2 to CO32-, whether going through reaction with the carbohydrate alkoxides or OH-, is likely to determine the chemical environment of the formed CO32-. These findings shed a new light on rather overlooked, albeit prominent, interactions in these solutions with the readily absorbed air CO2, essential for further development and implementation, whether towards regenerated and modified cellulose or CO2-capturing concepts.
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To elucidate what properties control and practically limit ion transport in highly concentrated electrolytes (HCEs), the viscosity, ionic conductivity, ionicity, and transport numbers were studied for nine model electrolytes and connected to the rate capability in Li-ion battery (LIB) cells. The electrolytes employed the LiTFSI salt in three molar ratio concentrations; 1 : 2, 1 : 4, and 1 : 16 (LiTFSI:X) vs. solvents (X) with different permittivities; tert-butyl methyl ether (MTBE), tetrahydrofuran (THF) and propylene carbonate (PC). While the low polarity MTBE creates liquid electrolytes, ion-pairing limits the ionic conductivity despite extremely low viscosities. For the less concentrated 1 : 16 LiTFSI:MTBE and 1 : 16 LiTFSI:THF electrolytes the ionic diffusivities decrease with increased temperature, a sign of aggregation, but still their ionic conductivities and LIB performance increase. In general, the low ionic conductivity and high viscosity both limit the use of HCEs in LIBs, and no compensating mechanism seems to be present.
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This paper investigates a strategy to convert hydrophilic cellulose nanofibrils (CNF) into a hydrophobic highly cross-linked network made of cellulose nanofibrils and inorganic nanoparticles. First, the cellulose nanofibrils were chemically modified through an esterification reaction to produce a nanocellulose-based macroinitiator. Barium titanate (BaTiO3, BTO) nanoparticles were surface-modified by introducing a specific monomer on their outer-shell surface. Finally, we studied the ability of the nanocellulose-based macroinitiator to initiate a single electron transfer living radical polymerization of stearyl acrylate (SA) in the presence of the surface-modified nanoparticles. The BTO nanoparticles will transfer new properties to the nanocellulose network and act as a cross-linking agent between the nanocellulose fibrils, while the monomer (SA) directly influences the hydrophilic-lipophilic balance. The pristine CNF and the nanoparticle cross-linked CNF are characterized by FTIR, SEM, and solid-state 13C NMR. Rheological and dynamic mechanical analyses revealed a high dregee of cross-linking.
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Nanofibras , Nanopartículas , Celulose , Interações Hidrofóbicas e Hidrofílicas , PolimerizaçãoRESUMO
Native hemicellulose lacks many of the properties that make fossil fuel-based polymers excellent for use in today's industrial products and processes. The mechanical and thermal properties of the hemicellulose can, however, be modified, and its processability increased. We functionalized galactoglucomannan to lower its glass transition temperature (Tg) and thereby increase its processability. The functionalization was achieved through an etherification reaction with butyl glycidyl ether used at three molar ratios. Films were produced, and their mechanical and thermal properties were evaluated. Thermogravimetric analysis showed that increased substitution increased the degradation temperature and decreased the water content in the sample, implying increased hydrophobicity upon modification. Dynamic mechanical analysis indicated that butyl glycidyl ether functionalization alters the thermal properties of the modified films both in the absolute values of Tg and in the strength of the films. The etherification reaction resulted in a more ductile material than the unmodified galactoglucomannan (GGM).
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Mananas , Picea , Interações Hidrofóbicas e Hidrofílicas , Resistência à TraçãoRESUMO
Carbon dioxide must be removed from biogas or natural gas to obtain compressed or liquefied methane, and adsorption-driven isolation of CO2 could be improved by developing new adsorbents. Zeolite adsorbents can select CO2 over CH4, and the adsorption of CH4 on zeolite |Na12-xKx|-A is significantly lower for samples with a high K+ content, i.e., x > 2. Nevertheless, we show, using 1H NMR experiments, that these zeolites adsorb CH4 after long equilibration times. Pulsed-field gradient NMR experiments indicated that in large crystals of zeolites |Na12-xKx|-A, the long-time diffusion coefficients of CH4 did not vary with x, and the upper limit of the mean-square displacement was about 1.5 µm, irrespective of the diffusion time. Also for zeolite |Na12|-A samples of three different particle sizes (â¼0.44, â¼2.9, and â¼10.6 µm), the upper limit of the mean-square displacement of CH4 was 1.5 µm and largely independent of the diffusion time. This similarity provided further evidence for an intracrystalline diffusion restriction for CH4 within the medium- and large-sized zeolite A crystals and possibly of clustering and close contact among the small zeolite A crystals. The upper limit of the long-time diffusion coefficient of adsorbed CH4 was (at 1 atm and 298 K) about 10-10 m2/s irrespective of the size of the zeolite particle or the studied content of K+ in zeolites |Na12-xKx|-A and |Na12|-A. The T1 relaxation time for adsorbed CH4 on zeolites |Na12-xKx|-A with x > 2 was smaller than for those with x < 2, indicating that the short-time diffusion of CH4 was hindered.
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Nanostructured hydrated vanadium oxides (V2O5·nH2O) are actively being researched for applications in energy storage, catalysis, and gas sensors. Recently, a one-step exfoliation technique for fabricating V2O5·nH2O nanosheets in aqueous media was reported; however, the underlying mechanism of exfoliation has been challenging to study. Herein, we followed the synthesis of V2O5·nH2O nanosheets from the V2O5 and VO2 precursors in real time using solution- and solid-state 51V NMR. Solution-state 51V NMR showed that the aqueous solution contained mostly the decavanadate anion [H2V10O28]4- and the hydrated dioxovanadate cation [VO2·4H2O]+, and during the exfoliation process, decavanadate was formed, while the amount of [VO2·4H2O]+ remained constant. The conversion of the solid precursor V2O5, which was monitored with solid-state 51V NMR, was initiated when VO2 was in its monoclinic forms. The dried V2O5·nH2O nanosheets were weakly paramagnetic because of a minor content of isolated V4+. Its solid-state 51V signal was less than 20% of V2O5 and arose from diamagnetic V4+ or V5+.This study demonstrates the use of real-time NMR techniques as a powerful analysis tool for the exfoliation of bulk materials into nanosheets. A deeper understanding of this process will pave the way to tailor these important materials.
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Polymer films based on mixtures of ethyl cellulose (EC) and hydroxypropyl cellulose (HPC) have been widely used to coat pellets and tablets to modify the release profile of drugs. For three different EC/HPC films we used 1H and 19F MRI in combination with a designed release cell to monitor the drug, polymer and water in 5 dimensional (5D) datasets; three spatial, one diffusion or relaxation and a temporal dimension, in real time. We observed that the water inflow through the films correlated with the initiation of the dissolution of the drug in the tablet beneath the film. Leaching of the pore forming HPC further accelerated water penetration and resulted in a drug release onset after a hydrostatic pressure was generated below the film indicated by positional changes of the film. For the more permeable film, both water ingress and drug egress showed a large variability of release over the film surface indicating the heterogeneity of the system. Furthermore, the 1H diffusion dataset revealed the formation of a gel layer of HPC at the film surface. We conclude that the setup presented provides a significant level of details, which are not achieved with traditional methods.
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Celulose/análogos & derivados , Imageamento por Ressonância Magnética/métodos , Celulose/química , Preparações de Ação Retardada/química , Liberação Controlada de Fármacos , Solubilidade , Água/químicaRESUMO
Hypomineralized enamel may be found in connection with the condition molar incisor hypomineralization (MIH), which has a prevalence of around 15% in most parts of the world. Molar incisor hypomineralization is associated with extensive objective and subjective problems, such as hypersensitivity of the affected teeth, enamel breakdown, and problems with retention of restorations. The etiology behind MIH has not yet been elucidated, but a number of possible factors, which affect the same or different functions of ameloblasts during their different stages of maturation, have been suggested. The aim of this study was to utilize multi-nuclear, solid-state nuclear magnetic resonance (ss-NMR) and time-of-flight secondary ion mass spectroscopy (ToF-SIMS) to elucidate any differences, at a molecular level, between enamel powder prepared from normal, healthy teeth and enamel powder prepared from teeth diagnosed with MIH. 31 P and 23 Na ss-NMR confirmed the presence of HPO42- and two different Na+ sites in hypomineralized enamel, suggesting a heterogeneous chemical composition. The content of organic components was higher in hypomineralized enamel, as shown by both 13 C ss-NMR and ToF-SIMS, indicating the presence of higher numbers of proteins and phospholipids. The interplay between both is necessary for the formation and mineralization of enamel, which might be disturbed or halted in hypomineralized enamel.
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Hipoplasia do Esmalte Dentário , Esmalte Dentário/química , Dente Molar , Ameloblastos , Esmalte Dentário/patologia , Humanos , Espectroscopia de Ressonância Magnética , Espectrometria de Massas , PrevalênciaRESUMO
Measuring temperature and heat flux is important for regulating any physical, chemical, and biological processes. Traditional thermopiles can provide accurate and stable temperature reading but they are based on brittle inorganic materials with low Seebeck coefficient, and are difficult to manufacture over large areas. Recently, polymer electrolytes have been proposed for thermoelectric applications because of their giant ionic Seebeck coefficient, high flexibility and ease of manufacturing. However, the materials reported to date have positive Seebeck coefficients, hampering the design of ultra-sensitive ionic thermopiles. Here we report an "ambipolar" ionic polymer gel with giant negative ionic Seebeck coefficient. The latter can be tuned from negative to positive by adjusting the gel composition. We show that the ion-polymer matrix interaction is crucial to control the sign and magnitude of the ionic Seebeck coefficient. The ambipolar gel can be easily screen printed, enabling large-area device manufacturing at low cost.
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Postsynthetic reactions of metal-organic frameworks (MOFs) are versatile tools for producing functional materials, but the methods of evaluating these reactions are cumbersome and destructive. Here we demonstrate and validate the use of in situ NMR spectroscopy of species in the liquid state to examine solvent-assisted ligand exchange (SALE) and postsynthetic modification (PSM) reactions of metal-organic frameworks. This technique allows functionalization to be monitored over time without decomposing the product for analysis, which simplifies reaction screening. In the case of SALE, both the added ligand and the ligand leaving the framework can be observed. We demonstrate this in situ method by examining SALE and PSM reactions of the robust zirconium MOF UiO-67 as well as SALE with the aluminum MOF DUT-5. In situ NMR spectroscopy provided insights into the reactions studied, and we expect that future studies using this method will permit the examination of a variety of MOF-solute reactions.
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A colloidal dispersion of uniform organosilica nanoparticles could be produced via the disassembly of the non-surfactant-templated organosilica powder nanostructured folate material (NFM-1). This unusual reaction pathway was available because the folate and silica-containing moieties in NFM-1 are held together by noncovalent interactions. No precipitation was observed from the colloidal dispersion after a week, though particle growth occurred at a solvent-dependent rate that could be described by the Lifshitz-Slyozov-Wagner equation. An organosilica film that was prepared from the colloidal dispersion adsorbed folate-binding protein from solution but adsorbed ions from a phosphate-buffered saline solution to a larger degree. To our knowledge, this is the first instance of a colloidal dispersion of organosilica nanoparticles being derived from a macroscopic material rather than from molecular precursors.
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A new class of highly porous organic sorbents called microporous humins is presented. These microporous humins are derived from sustainable and industrially abundant resources, have high heat of CO2 sorption, and could potentially be useful for the separation of carbon dioxide from gas mixtures. Their synthesis involves the polymerization of 5-hydroxymethyl furfural (HMF) in concentrated sulfuric acid and treatment with diethyl ether and heat. In particular, the porosities were tuned by the heat treatment. HMF is a potential platform chemical from biorefineries and a common intermediate in carbohydrate chemistry. A high uptake of CO2 (up to 5.27 mmol/g at 0 °C and 1 bar) and high CO2-over-N2 and CO2-over-CH4 selectivities were observed. The microporous humins were aromatic and structurally amorphous, which was shown in a multipronged approach using 13C nuclear magnetic resonance and Fourier transform infrared spectroscopies, elemental analysis, and wide-angle X-ray scattering.