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Tannin-based foams have gained attention as a potential bio-based alternative to conventional synthetic foams. Traditionally, namely condensed tannins (CT) have been used, leaving the potential of hydrolysable tannins (HT) largely unexplored. This study compared the performance of chestnut (HT) and quebracho (CT) in tannin–protein-based foams at different tannin ratios. Using soy protein isolate (SPI) and hexamine under acidic conditions, a series of tannin foams were produced through a mechanical foaming method and analyzed for cell structure, compression strength, thermal conductivity, and chemical stability. Results show that chestnut tannin is viable in hexamine SPI formulations but is harder to process due to lower reactivity, further resulting in higher material densities compared to quebracho. Foams with higher quebracho content featured smaller, more interconnected cells, while increasing chestnut content led to larger, less interconnected cells. Compression strength decreased with higher chestnut content, while fire resistance and thermal conductivity were influenced by material density rather than tannin type. The 13C-NMR analysis revealed covalent bonding of hexamine with both tannins, but potential covalent bonds with SPI were undetectable. Overall, chestnut tannin can substitute quebracho tannin in hexamine-SPI foams, though with compromises in terms of specific material properties and processability. [ABSTRACT FROM AUTHOR]

To investigate the molecular structure characteristics and chemical reaction mechanisms of gas coal from the Hong II coal mine of the Ningxia Hongdunzi Coal Industry, this study explores its elemental composition, structural features, and methods for constructing and optimizing molecular models. The basic properties of the coal were determined through proximate and elemental analyses. The carbon structure was characterized using 13C-NMR nuclear magnetic resonance, the N and S chemical states were analyzed with XPS, and the distribution of hydroxyl, aliphatic hydrocarbons, aromatic rings, and oxygen-containing functional groups was characterized by FT-IR. Based on the analysis results, a molecular structure model of Hongdunzi gas coal was constructed with the molecular formula C204H117O17NS, and the calculated results of the model showed high consistency with the experimental spectra of 13C-NMR. The macromolecular model of gas coal was constructed using the Materials Studio 2020 software, and its structure was optimized through geometric optimization and dynamic simulations. After optimization, the total energy of the model was significantly reduced from 8525.12 kcal·mol−1 to 3966.16 kcal·mol−1, highlighting the enhanced stability of the coal molecular structure. This optimization indicates that torsional energy plays a dominant role in molecular stability, while van der Waals forces and electrostatic interactions were significantly improved during the optimization process. [ABSTRACT FROM AUTHOR]

A root factor for the accuracy of all quantum chemical calculations of nuclear magnetic resonance (NMR) chemical shifts is the quality of the molecular equilibrium geometry used. In turn, this quality depends largely on the basis set employed at the geometry optimization stage. This parameter represents the main subject of the present study, which is a continuation of our recent work, where new pecG-n (n = 1, 2) basis sets for the geometry optimization were introduced. A goal of this study was to compare the performance of our geometry-oriented pecG-n (n = 1, 2) basis sets against the other basis sets in massive calculations of 13C NMR shielding constants/chemical shifts in terms of their efficacy in reducing geometry factor errors. The testing was carried out with both large-sized biologically active natural products and medium-sized compounds with complicated electronic structures. The former were treated using the computation protocol based on the density functional theory (DFT) and considered in the theoretical benchmarking, while the latter were treated using the computational scheme based on the upper-hierarchy coupled cluster (CC) methods and were used in the practical benchmarking involving the comparison with experimental NMR data. Both the theoretical and practical analyses showed that the pecG-1 and pecG-2 basis sets resulted in substantially reduced geometry factor errors in the calculated 13C NMR chemical shifts/shielding constants compared to their commensurate analogs, with the pecG-2 basis set being the best of all the considered basis sets. [ABSTRACT FROM AUTHOR]

The control of metabolic networks is incompletely understood, even for glycolysis in highly studied model organisms. Direct real-time observations of metabolic pathways can be achieved in cellular systems with 13C NMR using dissolution Dynamic Nuclear Polarization (dDNP NMR). The method relies on a short-lived boost of NMR sensitivity using a redistribution of nuclear spin states to increase the alignment of the magnetic moments by more than four orders of magnitude. This temporary boost in sensitivity allows detection of metabolism with sub-second time resolution. Here, we hypothesized that dDNP NMR would be able to investigate molecular phenotypes that are not easily accessible with more conventional methods. The use of dDNP NMR allows real-time insight into carbohydrate metabolism in a Gram-positive bacterium (Lactoccocus lactis), and comparison to other bacterial, yeast and mammalian cells shows differences in the kinetic barriers of glycolysis across the kingdoms of life. Nevertheless, the accumulation of non-toxic precursors for biomass at kinetic barriers is found to be shared across the kingdoms of life. We further find that the visualization of glycolysis using dDNP NMR reveals kinetic characteristics in transgenic strains that are not evident when monitoring the overall glycolytic rate only. Finally, dDNP NMR reveals that resting Lactococcus lactis cells use the influx of carbohydrate substrate to produce acetoin rather than lactate during the start of glycolysis. This metabolic regime can be emulated using suitably designed substrate mixtures to enhance the formation of the C4 product acetoin more than 400-fold. Overall, we find that dDNP NMR provides analytical capabilities that may help to clarify the intertwined mechanistic determinants of metabolism and the optimal usage of biotechnologically important bacteria. [ABSTRACT FROM AUTHOR]

Early NMR studies of several heterohelicenes containing an annular nitrogen atom and a thiophene ring in their structure suggested the possibility of the lengthening of the carbon–carbon bonds in the interior of the helical turn of the molecule based on the progressive upfield shift of 13C resonances toward the center of the helical turn. We now report a comprehensive analysis of the optimized geometry and a comparison of the calculated vs. observed 1H and 13C NMR chemical shifts of nineteen representative benzothienoquinoline heterohelicenes. As was initially hypothesized on the basis of the progressive upfield shift of carbon resonances toward the center of the interior helical turn, the present computational study has demonstrated that carbon–carbon bonds indeed have more sp3 character and are longer than normal sp2 bonds to accommodate the helical twist of the molecule, as expected. [ABSTRACT FROM AUTHOR]

Mefloquine (MQ) is an antimalarial medication prescribed to treat or malaria prevention.. When taken by children, vomiting usually occurs, and new doses of medication frequently need to be taken. So, developing pediatric medicines using taste-masked antimalarial drug complexes is mandatory for the success of mefloquine administration. The hypothesis that binding mefloquine to an ion-exchange resin (R) could circumvent the drug's bitter taste problem was proposed, and solid-state 13C cross-polarization magic angle spinning (CPMAS) NMR was able to follow MQ–R mixtures through chemical shift and relaxation measurements. The nature of MQ–R complex formation could then be determined. Impedimetric electronic tongue equipment also verified the resinate taste-masking efficiency in vitro. Variations in chemical shifts and structure dynamics measured by proton relaxation properties (e.g., T1ρH) were used as probes to follow the extension of mixing and specific interactions that would be present in MQ–R. A significant decrease in T1ρH values was observed for MQ carbons in MQ–R complexes, compared to the ones in MQ (from 100–200 ms in MQ to 20–50 ms in an MQ–R complex). The results evidenced that the cationic resin interacts strongly with mefloquine molecules in the formulation of a 1:1 ratio complex. Thus, 13C CPMAS NMR allowed the confirmation of the presence of a binding between mefloquine and polacrilin in the MQ–R formulation studied. [ABSTRACT FROM AUTHOR]

Chitin, a ubiquitous biopolymer, holds paramount scientific and economic significance. Historically, it has been primarily isolated from marine crustaceans. However, the surge in demand for chitin and the burgeoning interest in biopolymers have necessitated the exploration of alternative sources. Among these methods, the mulberry silkworm (Bombyx mori) has emerged as a particularly intriguing prospect. To isolate chitin from Bombyx mori, a chemical extraction methodology was employed. This process involved a series of meticulously orchestrated steps, including Folch extraction, demineralization, deproteinization, and decolorization. The resultant chitin was subjected to comprehensive analysis utilizing techniques such as attenuated total reflectance–Fourier transform infrared spectroscopy (ATR-FTIR), 13C nuclear magnetic resonance (NMR) spectroscopy, and wide-angle X-ray scattering (WAXS). The obtained results allow us to conclude that the Bombyx mori represents an attractive alternative source of α-chitin. [ABSTRACT FROM AUTHOR]

Chicken feathers represent a viable material for producing biochar adsorbents. Traditional slow pyrolysis methods often result in sulfur element losses from chicken feathers, whereas hydrothermal reactions generate substantial amounts of nutrient-rich hydrothermal liquor. Magnesium-modified high-sulfur hydrochar MWF was synthesized through magnesium modification, achieving a S content of 3.68%. The maximum equilibrium adsorption amounts of MWF for Cd2+ and Pb2+ were 25.12 mg·g−1 and 70.41 mg·g−1, respectively, representing 4.00 times and 2.75 times of WF. Magnesium modification elevated the sulfur content, pH, ash content, and electronegativity of MWF. The primary mechanisms behind MWF's adsorption of Cd2+ and Pb2+ involve magnesium ion exchange and complexation with C=O/O=C–O, quaternary N, and S functional groups. MWF maintains robust stability and antioxidative properties, even with low aromaticity levels. Given the lower energy consumption during hydrochar production, MWF offers notable carbon sequestration benefits. The hydrothermal solution derived from MWF is nutrient-rich. Following supplementation with inorganic fertilizer, the hydrothermal solution of MWF significantly enhanced bok choy growth compared to the control group. In general, adopting magnesium-modified hydrothermal reactions to produce hydrochar and converting the resultant hydrothermal solution into water-soluble fertilizer proves a viable strategy for the eco-friendly utilization of chicken feathers. This approach carries substantial value for heavy metal remediation and agricultural practices. [ABSTRACT FROM AUTHOR]

Since the discovery of the first ferroelectric liquid crystal (FLC) in the chiral smectic C (SmC*) phase, ferroelectricity in liquid crystals has attracted much attention due to not only the fundamental interest but also the applications. This review focuses on the evolution of the design concept for ferroelectric smectic liquid crystals. It progresses from considering macroscopic phase symmetry to designing intermolecular interactions. For the purpose of understanding the molecular organization in smectic phases, we propose a dynamic model of constituent molecules in the smectic A (SmA) and SmC* phases based on 13C NMR studies. Then, we follow the structure–property relationship in ferroelectric SmC* liquid crystals for FLC displays. We reconsider de Vries-like materials that can provide defect-free alignment. We pay attention to the electro-optical switching in the chiral de Vries smectic A phase. Finally, we show several liquid crystals exhibiting polar smectic A phases and discuss how the polar order occurs in the highest symmetric smectic A phase. [ABSTRACT FROM AUTHOR]

The object of the study is lignite. Analytical testing techniques, such as elemental analysis, 13C nuclear magnetic resonance (13C NMR) spectroscopy, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and high-resolution transmission electron microscopy (HRTEM), were used to acquire information on the structural parameters of lignite. The aromaticity of Xianfeng lignite is 43.57%, and the aromatic carbon structure is mainly naphthalene and anthracene/phenanthrene. The aliphatic carbon structure is dominated by cycloalkanes, alkyl side chains, and hydrogenated aromatics. Oxygen is mainly present in ether oxygen, carboxyl, and carbonyl groups. Nitrogen is mainly in the form of pyrrole nitrogen and quaternary nitrogen. Sulfur is mainly thiophene sulfur. According to the analysis results, the molecular structure model of XF lignite was constructed. The molecular formula is C184H172O39N6S2. The 2D structure was converted to a 3D structure using computer simulation software and optimized. The optimized model has a remarkable stereoconfiguration, and the aromatic lamellae are irregularly arranged in space. The aromatic rings were mainly connected by methylene, hypomethylene, methoxy, and aliphatic rings. In addition, the simulated 13C NMR spectra are in good agreement with the experimental spectra. This shows the rationality of the 3D chemical structure model. [ABSTRACT FROM AUTHOR]

There were some ecological and environmental problems in limestone soil in the karst peak-cluster depression in Pingguo City of Guangxi, such as the destruction of soil structure, soil acidification and soil fertility decline, and these problems were closely related to soil organic matter. The soil in this site was classified as Cambisols. Therefore, this project took soil under five major land uses (grassland, afforestation, sugarcane field, corn field and pitaya field) in the karst area of Guangxi as the research object. The contents and molecular structure properties of humic acids, fulvic acids and humins in soils were studied by solid-state 13C nuclear magnetic resonance spectroscopy and elemental composition. From the perspective of the chemical structure of humic substances, the differences in the quantity and structural characteristics of humic acids, fulvic acids and humins in different land uses were revealed. The results showed that the organic carbon content of both afforestation (34.83 g kg−1) and natural restored grassland (31.67 g kg−1) were significantly higher than that of sugarcane field (17.60 g kg−1), corn field (16.35 g kg−1) and pitaya field (14.31 g kg−1) (p < 0.05). The contents of three humic fractions in grassland were relatively high, and the contents of three humic fractions in sugarcane field were relatively low (p < 0.05). The structural characteristics of humic substances showed that the protein components of the three humic fractions in the afforestation were high, indicating that the humic substances in the afforestation contained more unstable components. The Alkyl C/O-alkyl C and Hydrophobic C/hydrophilic C ratios of the three humic fractions of corn field were high, indicating high stability and maturity in humic substances in corn field. [ABSTRACT FROM AUTHOR]

The basis set issue has always been one of the most important factors of accuracy in the quantum chemical calculations of NMR chemical shifts. In a previous paper, we developed new pecS-n (n = 1, 2) basis sets purposed for the calculations of the NMR chemical shifts of the nuclei of the most popular NMR-active isotopes of 1–2 row elements and successfully approbated these on the DFT calculations of chemical shifts in a limited series of small molecules. In this paper, we demonstrate the performance of the pecS-n (n = 1, 2) basis sets on the calculations of as much as 713 1H and 767 13C chemical shifts of 23 biologically active natural products with complicated stereochemical structures, carried out using the GIAO-DFT(PBE0) approach. We also proposed new alternative contraction schemes for our basis sets characterized by less contraction depth of the p-shell. New contraction coefficients have been optimized with the property-energy consistent (PEC) method. The accuracies of the pecS-n (n = 1, 2) basis sets of both the original and newly contracted forms were assessed on massive benchmark calculations of proton and carbon chemical shifts of a vast variety of natural products. It was found that less contracted pecS-n (n = 1, 2) basis sets provide no noticeable improvement in accuracy. These calculations represent the most austere test of our basis sets as applied to routine calculations of the NMR chemical shifts of real-life compounds. [ABSTRACT FROM AUTHOR]

Composting is described as a sustainable alternative to organic waste reuse from the agricultural and household sectors. The organic matter degradation and stabilization product presents great variability due to the waste composition used. Thus, the use of techniques that allow the monitoring of the decomposition process is necessary to determine the quality of the final product. Therefore, this review critically analyzes and updates the chemical spectroscopy methods described for the evaluation of the organic matter transformation in the composting process to optimize and generate amendments for agricultural use. This review examines spectroscopic techniques such as ultraviolet-visible (UV-Vis), infrared (IR), fluorescence, and 13C NMR reported for the evolution and maturation of carbonate structures in composting. In addition, they are used in the study of indicators for monitoring the degradation of complex structures, such as sugars and proteins, for the formation of precursors that are responsible for the formation of highly stabilized substances such as humic and fulvic compounds. Finally, these parameters may be used to elucidate organic matter degradation and its stabilization process, establish patterns that characterize each stage of composting along with its physicochemical characteristics, and monitor potential phytotoxicity levels. [ABSTRACT FROM AUTHOR]

Agar is a hydrophilic biopolymer extracted from red seaweed. This phycocolloid consists of two components: agarose and agaropectin. In the present work, agar extracted from the invasive red seaweed Agarophyton vermiculophyllum was characterized using physical, chemical, and spectroscopic analyses to investigate the effect of alkaline pretreatment on agar properties. Two extraction conditions, native and alkali-pretreated agars, were comparatively studied. The native yield (28.4 ± 0.9%) was higher than that of the alkaline-pretreated agar (20.4 ± 0.8%). The alkali-pretreated agar showed higher gel strength (763.8 ± 57.0g cm−2), gelling (36.5 ± 0.9 °C), and melting (83.2 ± 0.6 °C) temperatures and increased 3,6-anhydrogalactose (26.2 ± 1.9%) and decreased sulfate contents (6.2 ± 0.8%) compared with native agar (gel strength: 204.8 ± 17.10g cm−2, gelling temperature: 29.5 ± 0.9 °C, melting temperature: 73.4 ± 0.7 °C, 3,6-AG content: 13.8 ± 0.7%, sulfate content: 10.5 ± 0.5%). The alkaline pretreatment improved the agar's gelling properties and significantly influenced its chemical properties. In view of the obtained results, A. vermiculophyllum might potentially be thought of as a viable source for the agar industry in Morocco, serving as a local source of agar. [ABSTRACT FROM AUTHOR]

Pollution of the Arctic Ocean by potentially toxic elements (PTEs) is a current environmental problem. Humic acids (HAs) play an important role in the regulation of PTE mobility in soil and water. The permafrost thaw releases ancient organic matter (OM) with a specific molecular composition into the Arctic watersheds. This could affect the mobility of PTEs in the region. In our study, we isolated HAs from two types of permafrost deposits: the Yedoma ice complex, which contains pristine buried OM, and the alas formed in the course of multiple thaw–refreezing cycles with the most altered OM. We also used peat from the non-permafrost region as the recent environmental endmember for the evolution of Arctic OM. The HAs were characterized using 13C NMR and elemental analysis. Adsorption experiments were conducted to assess the affinity of HAs for binding Cu2+ and Ni2+. It was found that Yedoma HAs were enriched with aliphatic and N-containing structures as compared to the much more aromatic and oxidized alas and peat HAs. The adsorption experiments have revealed that the peat and alas HAs have a higher affinity for binding both ions as compared to the Yedoma HAs. The obtained data suggest that a substantial release of the OM from the Yedoma deposits due to a rapid thaw of the permafrost might increase the mobility of PTEs and their toxicity in the Arctic Ocean because of much lesser "neutralization potential". [ABSTRACT FROM AUTHOR]

Cladanthus mixtus (L.) Chevall., Asteraceae, also known as Moroccan chamomile, is a spontaneous, annual plant growing wild in North-Western Morocco. Economically, the essential oil of C. mixtus is of high interest, Morocco being the only supplier on the international market. Two essential oil samples (EO) were isolated from aerial parts of Cladanthus mixtus (L.) Chevall., and analyzed by a combination of chromatographic and spectroscopic techniques (gas chromatography (GC) in combination with retention indices (RI), gas chromatography-mass spectrometry (GC/MS), and 13C NMR spectroscopy). Computer matching against the in-house 13C NMR library allowed the identification of the eight components at appreciable contents, namely 3,6,6,9-bis-epoxy-farnesa-1,7(14),10-triene, and its 3-epi, 9-epi, and 3,9-diepi epimers, and 6,9-epoxy-farnesa-1,7(14),10-trien-3-ol and its 3-epi, 6-epi, and 3,6-diepi epimers. Our results confirm the tremendous chemical variability of Moroccan C. mixtus essential oil and the usefulness of 13C NMR analysis, in combination with GC(RI), for the identification of uncommon oxygenated sesquiterpenes that induce an original composition. [ABSTRACT FROM AUTHOR]

This study examines the influence of mefenamic acid on the physical and chemical properties of silica aerogels, as well as its effect on the sorption characteristics of the composite material. Solid state magic angle spinning nuclear magnetic resonance (MAS NMR) and high-pressure 13C NMR kinetic studies were conducted to identify the presence of mefenamic acid and measure the kinetic rates of CO2 sorption. Additionally, a high-pressure T1–T2 relaxation-relaxation correlation spectroscopy (RRCOSY) study was conducted to estimate the relative amount of mefenamic acid in the aerogel's pores, and a high-pressure nuclear Overhauser effect spectoscopy (NOESY) study was conducted to investigate the conformational preference of mefenamic acid released from the aerogel. The results indicate that mefenamic acid is affected by the chemical environment of the aerogel, altering the ratio of mefenamic acid conformers from 75% to 25% in its absence to 22% to 78% in the presence of aerogel. [ABSTRACT FROM AUTHOR]

Condensed tannin copolymerized with hyperbranched tris(2-aminoethyl)amine-urea formed by amine-amido deamination yields a particleboard thermosetting adhesive without any aldehydes satisfying the requirements of relevant standards for the particleboard internal bond strength. The tannin–triamine–urea cures well at 180 °C, a relatively low temperature for today's particleboard hot pressing. As aldehydes were not used, the formaldehyde emission was found to be zero, not even in traces due to the heating of wood. The effect is ascribed to the presence of many reactive sites, such as amide, amino, and phenolic groups belonging to the three reagents used. The tannin appears to function as an additional cross-linking agent, almost a nucleating agent, for the triamine–urea hyperbranched oligomers. Chemical analysis by MALDI ToF and 13C NMR has shown that the predominant cross-linking reaction is that of the substitution of the tannin phenolic hydroxyls by the amino groups of the triamine. The reaction of tannin with the still-free amide groups of urea is rather rare, but it may occur with the rarer tannin flavonoid units in which the heterocyclic ring is opened. Due to the temperature gradient between the surfaces and the board core in the particleboard during hot pressing, the type and the relative balance of covalent and ionic bonds in the resin structure may differ in the surfaces and the board core. [ABSTRACT FROM AUTHOR]

The controversial question of whether optical rotation data can be used to distinguish floral from honeydew honey was investigated. Specific optical rotation angles were determined for 41 honey samples, including floral, honeydew, and adulterated honey, indicating that moderate to high positive optical rotation angles were found for all adulterated samples measured. A strong correlation between the sugar profile and the specific optical rotation angle of honey was confirmed, and a method based on 13C NMR metabolomics was proposed to calculate specific optical rotation angles with good correlation with the experimental values. The results indicate that optical rotation is not a reliable method for distinguishing the origin of honey but could indicate adulteration. [ABSTRACT FROM AUTHOR]

Dietary glucose and fructose are both efficiently assimilated by the liver but a comprehensive measurement of this process starting from their conversion to sugar phosphates, involvement of the pentose phosphate pathway (PPP), and conversion to glycogen and lipid storage products, remains incomplete. Mice were fed a chow diet supplemented with 35 g/100 mL drinking water of a 55/45 fructose/glucose mixture for 18 weeks. On the final night, the sugar mixture was enriched with either [U-13C]glucose or [U-13C]fructose, and deuterated water (2H2O) was also administered. 13C-isotopomers representing newly synthesized hepatic glucose-6-phosphate (glucose-6-P), glycerol-3-phosphate, and lipogenic acetyl-CoA were quantified by 2H and 13C NMR analysis of post-mortem liver glycogen and triglyceride. These data were applied to a metabolic model covering glucose-6-P, PPP, triose-P, and de novo lipogenesis (DNL) fluxes. The glucose supplement was converted to glucose-6-P via the direct pathway, while the fructose supplement was metabolized by the liver to gluconeogenic triose-P via fructokinase–aldolase–triokinase. Glucose-6-P from all carbohydrate sources accounted for 40–60% of lipogenic acetyl-CoA and 10–12% was oxidized by the pentose phosphate pathway (PPP). The yield of NADPH from PPP flux accounted for a minority (~30%) of the total DNL requirement. In conclusion, this approach integrates measurements of glucose-6-P, PPP, and DNL fluxes to provide a holistic and informative assessment of hepatic glucose and fructose metabolism. [ABSTRACT FROM AUTHOR]

The hydrazine derivatives are known to possess several biological activities including anticancer, antibacterial and anti-fungal, anticonvulsant, and antioxidant. This communication presents the synthesis, X-ray crystal structure analysis, DFT calculations, cell cytotoxicity, and antioxidant activity of the Schiff base 4,4′-((1E,1′E)-hydrazine-1,2-diylidenebis(ethan-1-yl-1-ylidene))bis(benzene-1,3-diol) (compound 2). We have also isolated the side product compound 1 and characterized it using single X-ray crystallography. The crystal structure of compound 1 depicts that the ensuing C–H···N hydrogen bonding interaction is presented and discussed herein. In addition, the calculations using density functional theory (DFT) approximation supported by experimental 1H and 13C NMR studies on the key compound 2 are reported. The results of theoretical and experimental 1H and 13C NMR were concordant. The antioxidant activity of compound 2 was determined by using 2,2′-azinobis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS•+) radical cation assays and 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical assay. Compound 2 demonstrated excellent antioxidant activity in ABTS assay (IC50 = 4.30 ± 0.21 µM) and DPPH assay (IC50 = 81.06 ± 0.72 µM) with almost no cytotoxicity below 25 µM. [ABSTRACT FROM AUTHOR]

Benzimidazole is an important heterocyclic fragment, present in many biologically active compounds with a great variety of therapeutic purposes. Most of the benzimidazole activities are explained through the existence of 1,3-tautomeric equilibrium. As the binding affinity of each tautomer to a protein target depends on an established bioactive conformation, the effect of tautomers on the ligand protein binding mechanism is determinant. In this work, we searched and analyzed a series of reported 13C-NMR spectra of benzazoles and benzazolidine-2-thiones with the purpose of estimating their tautomeric equilibrium. Herein, several approaches to determine this problem are presented, which makes it a good initial introduction to the non-expert reader. This chemical shift difference and C4/C7 signals of benzimidazolidine-2-thione and 1-methyl-2-thiomethylbenzimidazole as references were used in this work to quantitatively calculate, in solution, the pyrrole–pyridine tautomeric ratio in equilibrium. The analysis will help researchers to correctly assign the chemical shifts of benzimidazoles and to calculate their intracyclic or exocyclic tautomeric ratio as well as mesomeric proportion in benzimidazoles. [ABSTRACT FROM AUTHOR]

The reaction of condensation and cross-linking of desulfurized kraft lignin with triethyl phosphate (TEP) was explored. Catechol, a simple model of the aromatic ring of lignin, and glycerol, a model compound of the aliphatic hydroyl groups of the side chain of lignin, were employed under similar reaction conditions. Solid state cross-polarisation/magic-angle spinning (CP-MAS) 13C NMR and matrix assisted laser desorption ionization time-of-flight (MALDI-TOF) spectroscopy studies showed that polycondensation occurs on phenolic hydroxyl groups of lignin, as well as on aliphatic hydroxyls groups of its side chain. The reactions appear to be favoured by higher temperatures and in the presence of ammonia. Preliminary adhesion tests on wood shown good hydrophobicity properties of the surface treated with lignin-TEP-based resin. Initial application tests carried out at high temperature demonstrated as good performance as metallic coating. [ABSTRACT FROM AUTHOR]

Soil organic matter (SOM) was studied in different types of organo-mineral material (from surface horizons and partially isolated materials—cryoturbated or buried horizons) sampled from the surface horizons, the central parts of the Cryosol profiles, and the lower active layer. We found that the humic acids (HAs) of the cryoturbated and buried horizons showed an increased degree of oxidation and an increment of alkylaromatic and protonized aromatic fraction content. In contrast, the HAs of the surface horizons showed increased values of alkylic carbon components. The content of free radicals was essentially higher in the surface layers than in the cryoturbated and buried layers. While the bulk soil organic matter composition (total organic carbon, total nitrogen, and aromatic/aliphatic values) was not essentially different between surface, cryoturbated, and buried horizons, there were essential differences in elemental composition, carbon species, and free radical content. This indicates that the degree of humification in cryoturbated and buried organo-mineral material is higher than in surface horizons and that partial isolation results in relative stabilization of such material in soil profiles. [ABSTRACT FROM AUTHOR]

The effect of acidic ionic liquid (IL) as a new catalyst on the properties of wood-based panels bonded with urea-glyoxal (UG) resins was investigated. Different levels of N-methyl-2-pyrrolidone hydrogen sulfate ([HNMP] HSO4 (0, 1, 2, 3 wt %)) were added to prepared UG resin. The resin was then used for preparing laboratory particleboard panels. Then, the properties of the prepared panels were evaluated. The structure of the prepared UG resin was studied by 13C NMR, and thermal curing behavior of the resin before and after the addition of IL was measured by DSC. Additionally, the main oligomers formed in the UG reaction were identified by matrix-assisted laser desorption/ionization time-of-flight (MALDI TOF) mass spectroscopy. The results indicated that IL can be used as an efficient catalyst for UG resin. The physicochemical tests indicated that the addition of [HNMP] HSO4 from 0 to 3 wt % decreased the pH value of the glue-mix, and the pH decreased on curing to the same level as urea-formaldehyde resins. The gel accelerated with increasing catalyst content and with the decreasing of the pH in the UG resin. The panels prepared with IL had higher mechanical strength and dimensional stability compared to those made from UG resins containing NH4Cl. Scanning electron microscope (SEM) micrographs showed that the panels prepared with ionic liquid presented low porous. DSC analysis showed that the addition of IL to the UG resin decrease the energy of activation of the curing reaction to render possible cross-linking. The MALDI TOF results indicated a preponderant linearity of the oligomers formed, implying a high energy of activation of curing for UG resins. [ABSTRACT FROM AUTHOR]

To investigate the potential for the utilization of cotton stalk, ammonia hydrothermal treatment was applied to fractionate the samples into aqueous ammonia-soluble and ammonia-insoluble portions. The ammonia-soluble portion was purified to yield lignin fractions. The lignin fractions obtained were characterized by wet chemistry (carbohydrate analysis) and spectroscopy methods (FT-IR, 13C and ¹H-13C HSQC NMR spectroscopy) as well as gel permeation chromatography (GPC). The results showed that the cotton stalk lignin fractions were almost absent of neutral sugars (0.43%-1.29%) and had relatively low average molecular weights (1255-1746 g/mol). The lignin fractions belonged to typical G-S lignin, which was composed predominately of G-type units (59%) and noticeable amounts of S-type units (40%) together with a small amount of H-type units (~1%). Furthermore, the ammonia-extractable lignin fractions were mainly composed of β-O-4' inter-unit linkages (75.6%), and small quantities of β-β' (12.2%), together with lower amounts of β-5' carbon-carbon linkages (7.4%) and p-hydroxycinnamyl alcohol end groups. [ABSTRACT FROM AUTHOR]

Aplysina is the best representative genus of the family Aplysinidae. Halogenated substances are its main class of metabolites. These substances contribute greatly to the chemotaxonomy and characterization of the sponges belonging to this genus. Due to their pharmacological activities, these alkaloids are of special interest. The chemistry of halogenated substances and of the alkaloids has long been extensively studied in terrestrial organisms, while the number of marine organisms studied has just started to increase in the last decades. This review describes 101 halogenated substances from 14 species of Aplysina from different parts of the world. These substances can be divided into the following classes: bromotyramines (A), cavernicolins (B), hydroverongiaquinols (C), bromotyrosineketals (D), bromotyrosine lactone derivatives (E), oxazolidones (F), spiroisoxazolines (G), verongiabenzenoids (H), verongiaquinols (I), and dibromocyclohexadienes (J). A compilation of their 13C NMR data is also part of the review. For this purpose 138 references were consulted. [ABSTRACT FROM AUTHOR]

Isotope labeling is one of the few methods of revealing the in vivo bidirectionality and compartmentalization of metabolic fluxes within metabolic networks. We argue that a shift from steady state to dynamic isotopomer analysis is required to deal with these cellular complexities and provide a review of dynamic studies of compartmentalized energy fluxes in eukaryotic cells including cardiac muscle, plants, and astrocytes. Knowledge of complex metabolic behaviour on a molecular level is prerequisite for the intelligent design of genetically modified organisms able to realize their potential of revolutionizing food, energy, and pharmaceutical production. We describe techniques to explore the bidirectionality and compartmentalization of metabolic fluxes using information contained in the isotopic transient, and discuss the integration of kinetic models with MFA. The flux parameters of an example metabolic network were optimized to examine the compartmentalization of metabolites and and the bidirectionality of fluxes in the TCA cycle of Saccharomyces uvarum for steady-state respiratory growth. [ABSTRACT FROM AUTHOR]

Wildfire induces soil alterations that have a long-term impact on soil organic matter (SOM) quality. We postulated that after different fire severities, the neutral sugars in soils can be used as an indicator of soil organic matter quality after fire. The aim of this study was to determine the contribution of neutral sugar, bulk and occluded particulate organic matter (oPOM) affected by wildfire, at different soil depths in an Araucaria–Nothofagus Forest, four years post-after fire. The concentration and composition of the neutral sugars in the soils clearly comprised the major fraction in the unburned soil. Medium- and high-severity fires caused a drastic reduction in soil sugars in the bulk soil as well as in the oPOM fractions. The 13C-CPMAS NMR spectroscopy analysis revealed a high contribution of recalcitrant carbon to the decomposition such as aryl–C and aryl–O derived from charred material, whereas the abundance of O–alkyl C and alkyl C functional groups were decreased. The neutral sugars (Galactose+Mannose/Xilose+Arabinose) revealed a major microbial origin in fire affected areas as the ratio was >2. Therefore. Therefore, we suggest that the neutral sugar content of soil should be used for monitoring both short- and long-term changes in SOM altered by fires. [ABSTRACT FROM AUTHOR]

Several spectroscopic techniques have been optimized to check extra-virgin olive oil quality and authenticity, as well as to detect eventual adulterations. These methods are usually complementary and can give information about different olive oil chemical components with bioactive and antioxidant properties. In the present work, a well-characterized set of extra-virgin olive oil (cultivar Frantoio) samples from a specific area of Tuscany (Italy) were investigated by combining near UV-Vis absorption spectroscopy, 1H and 13C nuclear magnetic resonance (NMR) to identify and quantify different chemical components, such as pigments, secoiridoids and squalene, related to the nutritional and quality properties of olive oils. Moreover, the pigmentation index of olives, organoleptic and sensory properties, total phenolic compound contents and the lipidic fractions of olive oils were investigated. The results obtained are, finally, compared and discussed in order to correlate several properties of both olives and olive oils with specific features of the cultivation area. [ABSTRACT FROM AUTHOR]

Due to the emissions of air pollutants, acid rain in southern China poses a great threat to terrestrial ecosystems. However, its influences on ecological processes such as litter decomposition and soil organic carbon (SOC) accumulation are still not clear. The aim of this study was to understand the potential mechanisms of carbon sequestration change in response to long-term acid rain in a subtropical forest. A field experiment with simulated acid rain (SAR) treatment was conducted in a monsoon evergreen broadleaf forest in southern China. Four levels of SAR treatment were implemented by irrigating the plots with water of different pH values (4.5 as a control, 4.0, 3.5, and 3.0). The results showed that the concentration of SOC and recalcitrant index for the SAR pH = 3.0 treatment were significantly higher compared to the control. Lignin fractions in litter residue layers were significantly increased, while soil microbial biomass carbon and soil ligninolytic enzyme activities were reduced under the SAR treatment. The concentration of SOC and recalcitrant index had positive relationships with the litter residue lignin fraction, but negative relationships with soil ligninolytic enzyme activity. These findings indicate that soil carbon accumulation could be enhanced with more stable lignin input under prolonged acid rain in forest ecosystems in southern China. [ABSTRACT FROM AUTHOR]

Bio-based thermosetting resins were synthesized from a ternary composition: humins; epoxidized linseed oil (ELO); and an industrial hardener, Capcure3-800 (CAP). Humins are in a focused attention in the last years, as biorefinery by-product, therefore its valorization through materials design is very important. Here we present a structural study of terpolymerization of humins/ ELO/CAP. The reactivity of these systems was highlighted by in situ FT-IR and 1H and 13C NMR. The integration of humins in thermosetting resins gives alternatives to new feedstocks for future bio-based materials. [ABSTRACT FROM AUTHOR]

Investigation of glucose utilization during an infection is central to the study of energy metabolism. The heavy utilization of glucose by the malaria parasite, and the consequences of this process, have been investigated extensively. However, host glucose utilization during early infection has not been explored to date. In a first attempt, this article investigates the changes in the host glucose utilization in Balb/c mice infected with Plasmodium berghei ANKA using 13C-labeled glucose infusion followed by NMR spectroscopy. The results suggested significant alterations of liver, brain and red blood cell (RBC) glucose utilization during early infection when the parasitemia was <1%. At the pathway level, we observed a decrease in the shunt metabolite 2,3-bisphosphoglycerate in the RBCs. Glycolysis and pathways associated with it, along with fatty acid unsaturation, were altered in the liver. Significant changes were observed in the central carbon metabolic pathways in the brain. These results have implications in understanding the host physiology during early infection and pave the way for detailed flux analysis of the proposed perturbed pathways. [ABSTRACT FROM AUTHOR]

Research on the composition and structure of coal is the most important and complex basic research in the coal chemistry field. Various methods have been used to study the structure of coal from different perspectives. However, due to the complexity of coal and the limitations of research methods, research on the macromolecular structure of coal still lacks systematicness. Huainan coalfield is located in eastern China and is the largest coal production and processing base in the region. In this study, conventional proximate analysis and ultimate analysis, as well as advanced instrumental analysis methods, such as Fourier transform infrared spectroscopy (FITR), X-ray diffraction (XRD), 13C-CP/MAS NMR, and other methods (SEM and AFM), were used to analyze the molecular structure of Huainan coal (HNC) and the distribution characteristics of oxygen in different oxygen-containing functional groups (OCFGs) in an in-depth manner. On the basis of SEM observation, it could be concluded that the high-resolution morphology of HNC's surface contains pores and fractures of different sizes. The loose arrangement pattern of HNC's molecular structure could be seen from 3D AFM images. The XRD patterns show that the condensation degree of HNC's aromatic ring is low, and the orientation degree of carbon network lamellae is poor. The calculated ratio of the diameter of aromatic ring lamellae to their stacking height (La/Lc = 1.05) and the effective stacking number of aromatic nuclei (Nave = 7.3) show that the molecular space structure of HNC is a cube formed of seven stacked aromatic lamellae. The FTIR spectra fitting results reveal that the aliphatic chains in HNC's molecular structure are mainly methyne and methylene. Oxygen is mainly –O–, followed by –C=O, and contains a small amount of –OH, the ratio of which is about 8:1:2. The molar fraction of binding elements has the approximate molecular structure C100H76O9N of organic matter in HNC. The results of the 13C NMR experiments show that the form of aromatic carbon atoms in HNC's structure (the average structural size Xb of aromatic nucleus = 0.16) is mainly naphthalene with a condensation degree of 2, and the rest are aromatic rings composed of benzene rings and heteroatoms. In addition, HNC is relatively rich in ≡CH and –CH2– structures. [ABSTRACT FROM AUTHOR]

Ambient temperature self-blowing mimosa tannin-based non-isocyanate polyurethane (NIPU) rigid foam was produced, based on a formulation of tannin-based non-isocyanate polyurethane (NIPU) resin. A citric acid and glutaraldehyde mixture served as a blowing agent used to provide foaming energy and cross-link the tannin-derived products to synthesize the NIPU foams. Series of tannin-based NIPU foams containing a different amount of citric acid and glutaraldehyde were prepared. The reaction mechanism of tannin-based NIPU foams were investigated by Fourier Trasform InfraRed (FT-IR), Matrix Assisted Laser Desorption Ionization (MALDI-TOF) mass spectrometry, and 13C Nuclear Magnetic Resonance (13C NMR). The results indicated that urethane linkages were formed. The Tannin-based NIPU foams morphology including physical and mechanical properties were characterized by mechanical compression, by scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). All the foams prepared showed a similar open-cell morphology. Nevertheless, the number of cell-wall pores decreased with increasing additions of glutaraldehyde, while bigger foam cells were obtained with increasing additions of citric acid. The compressive mechanical properties improved with the higher level of crosslinking at the higher amount of glutaraldehyde. Moreover, the TGA results showed that the tannin-based NIPU foams prepared had similar thermal stability, although one of them (T-Fs-7) presented the highest char production and residual matter, approaching 18.7% at 790 °C. [ABSTRACT FROM AUTHOR]

Ergometrine and methylergometrine are two alkaloids that are used as maleate salts for the prevention and control of postpartum hemorrhage. Although the two molecules have been known for a long time, few and discordant crystallographic and NMR spectroscopic data are available in the literature. With the aim of providing more conclusive data, we performed a careful NMR study for the complete assignment of the 1H, 13C, and 15N NMR signals of ergometrine, methylergometrine, and their maleate salts. This information allowed for a better definition of their conformational equilibria. In addition, the stereochemistry and the intermolecular interactions in the solid state of the two maleate salts were deeply investigated by means of single-crystal X-ray diffraction, showing the capability of these derivatives to act as both hydrogen-bond donors and acceptors, and evidencing a correlation between the number of intermolecular interactions and their different solubility. [ABSTRACT FROM AUTHOR]

Biochar has been shown as a potential mean to enhance carbon sequestration in the soil. In Brazil, approximately 15% of the produced charcoal is discarded as charcoal fines, which are chemically similar to biochar. Therefore, we aimed to test charcoal fines as a strategy to increase soil carbon sequestration. Charcoal fines of hardwood Mimosa scabrella were incorporated into a Cambisol down to 10 cm (T1 = 0 and T4 = 40 Mg ha−1) in Southern Brazil. Soil samples were collected (0–30 cm) 20 months after charcoal amendment. Soil organic matter (SOM) acid extract, humic acid, fulvic acid, and humin fractions were separated. Solid-state 13C nuclear magnetic resonance (NMR) spectra from charcoal and SOM in T1 and T4 were obtained before and after 165 days of incubation under controlled conditions. Charcoal increased soil carbon as fulvic (10–20 cm) and humic acids (10–30 cm) and, especially, as humin (0–5 cm), which probably occurred due to the hydrophobic character of the charcoal. The 13C NMR spectra and mean residence times (MRT) measured from incubation essays indicated that the charred material decomposed relatively fast and MRT of T1 and T4 samples were similar. It follows that the charcoal fines underwent similar decomposition as SOM, despite the high charcoal dose applied to the soil and the high aryl C contribution (78%) to the total 13C intensity of the charcoal NMR spectra. [ABSTRACT FROM AUTHOR]

The reaction of citric acid with wood veneers was studied by Cross Polarization Magic Angle Spinning Nuclear Magnetic Resonance (CP MAS 13C NMR) and matrix assisted laser desorption ionization time of flight (MALDI ToF) mass spectrometry. The analysis showed that reactions of citric acid occurred with both lignin and carbohydrate constituents of wood. The reactions occurring are esterifications between the carboxylic acid functions of citric acid and the numerous aromatic and aliphatic hydroxyl groups of the main wood constituents. Reaction of citric acid with glucose as a simple model compound of carbohydrates hydroxyl groups also yielded reactions leading to linear and branched oligomers by esterification. The result indicate that the reactions of esterification are accompanied in parallel by some internal rearrangements of lignin. The applied results on bonding wide flat wood surfaces such as veneers to obtain LVL panels yielded excellent strength results even if the conditions of pressing were more drastic than what is usual for this application. The applied bonding results have shown that citric acid has great potential to be used as a bio-binder for wood veneers. [ABSTRACT FROM AUTHOR]

An overview of the methodologies to elucidate the microstructure of copolymers of ethylene and cyclic olefins through 13C Nuclear magnetic resonance (NMR) analysis is given. 13C NMR spectra of these copolymers are quite complex because of the presence of stereogenic carbons in the monomer unit and of the fact that chemical shifts of these copolymers do not obey straightforward additive rules. We illustrate how it is possible to assign 13C NMR spectra of cyclic olefin-based copolymers by selecting the proper tools, which include synthesis of copolymers with different comonomer content and by catalysts with different symmetries, the use of one- or two-dimensional NMR techniques. The consideration of conformational characteristics of copolymer chain, as well as the exploitation of all the peak areas of the spectra by accounting for the stoichoimetric requirements of the copolymer chain and the best fitting of a set of linear equation was obtained. The examples presented include the assignments of the complex spectra of poly(ethylene-co-norbornene (E-co-N), poly(propylene-co-norbornene (P-co-N) copolymers, poly(ethylene-co-4-Me-cyclohexane)s, poly(ethylene-co-1-Me-cyclopentane)s, and poly(E-ter-N-ter-1,4-hexadiene) and the elucidation of their microstructures. [ABSTRACT FROM AUTHOR]

In the current study, we employed high-resolution proton and carbon nuclear magnetic resonance spectroscopy (1H and 13C NMR) for quantitative analysis of glycerol in drug injections without any complex pre-treatment or derivatization on samples. The established methods were validated with good specificity, linearity, accuracy, precision, stability, and repeatability. Our results revealed that the contents of glycerol were convenient to calculate directly via the integration ratios of peak areas with an internal standard in 1H NMR spectra, while the integration of peak heights were proper for 13C NMR in combination with an external calibration of glycerol. The developed methods were both successfully applied in drug injections. Quantitative NMR methods showed an extensive prospect for glycerol determination in various liquid samples. [ABSTRACT FROM AUTHOR]

Mostly biosourced non-isocyanate polyurethanes (NIPU) were prepared from mono- and disaccharides, namely glucose and sucrose, reacted with dimethyl carbonate and hexamethylene diamine. The main aim of this research was to show that NIPU can be prepared from mono- and disaccharides, this just being an initial exploratory work and its sole main aim. The oligomers obtained were detected by MALDI-ToF, CP-MAS 13C NMR, and FTIR spectrometries. The glucose-derived NIPU were shown to harden at a markedly lower temperature than the sucrose-derived ones and to be easier to handle and spread. The NIPU obtained were applied as wood and steel surface coatings and tested by the sessile drop test (on wood) and cross-cut test (on steel) with encouraging results. The glucose NIPU gave good surface coating results already at 103 °C, while the sucrose NIPU yielded good results only at a markedly higher temperature of hardening. The NIPU saccharide resins were also tested as thermosetting wood joint adhesives with the glucose NIPU yielding very encouraging results. [ABSTRACT FROM AUTHOR]