Solid-state 13C Nuclear Magnetic Resonance Research Articles

Divergent accumulation of microbial necromass and plant lignin phenol induced by adding maize straw to fertilized soils

Plant carbon (C) inputs and their subsequent microbial transformation affect the build-up process of soil organic C (SOC) pool. Nevertheless, there are knowledge gaps on how crop straw addition modifies SOC composition at molecular-level, especially in soils with different fertilization practices. Here, long-term fertilized Mollisols (unfertilized control, NF; inorganic fertilization, IF; inorganic fertilization plus manure, IFM) were incubated with or without maize straw addition in a 900-day field mesocosm experiment. The microbial necromass and plant lignin components contents were synchronously quantified based on amino sugar and lignin phenol biomarkers, respectively. And changes in SOC chemical composition were examined using solid-state 13C nuclear magnetic resonance spectroscopy. Relative to the NF treatment, long-term fertilization increased amino sugar and lignin phenol contents, and manure application enhanced the accumulation of plant lignin components more than that of microbial necromass. Compared with the NF treatment, the IF treatment decreased the relative proportion of alkyl C and SOC content, suggesting that changes in microbial necromass and lignin phenol were not always consistent with changes in SOC. For the NF and IF treatments, maize straw incorporation increased both amino sugar content and its contribution to SOC, indicating that microbial anabolism was important for SOC accumulation after adding maize straw in C-poor soils. For the IFM treatment, maize straw addition decreased lignin phenol content (27 %) and its contribution to SOC but increased the contribution of amino sugar to SOC, reflecting an enlarged contribution of microbial necromass to soil C pool formation under manure application after maize straw addition. The contribution of lignin phenol to SOC was decreased from days 360–900, whereas fungal necromass C content and the contribution of amino sugar to SOC were increased from days 360–900 under the IFM soil with maize straw addition, indicating that plant lignin components might be converted into fungal biomass and its necromass with increasing maize straw decomposition under manure application. Overall, we concluded that maize straw addition favored microbial immobilization in all fertilization treatments.

Study on the swelling of macromolecular geological organic matter with hydrocarbons and heteroatomic compounds

In this study, we conducted swelling experiments on eleven macromolecular geological organic materials using five types of organic solvents. Our primary objective was to investigate the absorption capacity of different solid organic materials in organic fluids and analyze the influence of their chemical structures. The samples utilized in this research included solid bitumen, kerogen, and coal samples from various basins. The chemical structure of the samples was assessed using solid-state 13C nuclear magnetic resonance (NMR), while X-ray diffraction (XRD) was employed to monitor any detect the structural changes during the swelling process. Our findings reveal that macromolecular geological organic compounds demonstrate a preferential expulsion of saturated hydrocarbons, followed by polycyclic aromatic hydrocarbons, upon interaction with liquid organic matter. The sulfur-containing compounds in solid organic matter demonstrated higher solubility than hydrocarbon compounds, while the solubility of oxygen-containing compounds varied based on the structure of the aliphatic chain and the proportion of oxygen atoms. This research, introduces LA [= Lac × Aac] as a new parameter to assess the combination of aliphatic chain length [Lac] and [Aac] abundance in solid organic matter. Furthermore, XRD testing revealed that the chemical structure unit of heteroatom compounds in solid organic matter consists of amorphous carbon, primarily composed of aliphatic chains. In this study, we evaluated the retention capacity of various macromolecular geological organic matter for both hydrocarbons and heteroatomic compounds. Additionally, the extent of swelling was investigated, providing theoretical support to diverse fields including organic petrology, petroleum geology, coal geology, and organic geochemistry.

Cellulose nanocrystals isolated from sugarcane bagasse using the formic/peroxyformic acid process: Structural, chemical, and thermal properties

Sugarcane bagasse (SCB) is a renewable biomass source for cellulose extraction. In the pretreatment, SCB is processed to break down the cellulose-lignin-hemicellulose matrix and isolate components. This work proposes a formic/peroxyformic acid process for extracting cellulose nanocrystals (CNCs) from SCB. Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and solid-state 13C nuclear magnetic resonance (ss- 13C NMR) were employed to evidence the removal of wax, hemicellulose, and lignin from the raw SCB. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA) were used for analyzing crystallinity, morphology, and thermal properties. SEM results showed that after lignin removal, the size of purified cellulose fibrils decreased significantly, and the structure of cellulose microfibers became smoother and more apparent. After acid hydrolysis of bleached cellulose microfibers, XRD analysis showed CNCs had the highest crystallinity (70.8 %). In TEM images, rod-like structures of CNCs were measured to be 23 ± 2.7 nm wide and 610 ± 18 nm long. The eco-friendly formic/peroxyformic acid procedure with a chlorine-free bleaching stage produced a white, cellulose-rich solid powder of CNCs.

Changes in soil organic carbon components and microbial community following spent mushroom substrate application.

While spent mushroom substrate (SMS) has shown promise in increasing soil organic carbon (SOC) and improving soil quality, research on the interplay between SOC components and microbial community following the application of diverse SMS types remains scant. A laboratory soil incubation experiment was conducted with application of two types of SMSs from cultivation of Pleurotus eryngii (PE) and Agaricus bisporus (AB), each at three application rates (3, 5.5, and 8%). Advanced techniques, including solid-state 13C nuclear magnetic resonance (NMR) and high-throughput sequencing, were employed to investigate on SOC fractions and chemical structure, microbial community composition and functionality. Compared to SMS-AB, SMS-PE application increased the relative abundances of carbohydrate carbon and O-alkyl C in SOC. In addition, SMS-PE application increased the relative abundance of the bacterial phylum Proteobacteria and those of the fungal phyla Basidiomycota and Ascomycota. The relative abundances of cellulose-degrading bacterial (e.g., Flavisolibacter and Agromyces) and fungal genera (e.g., Myceliophthora, Thermomyces, and Conocybe) were increased as well. The application of SMS-AB increased the aromaticity index of SOC, the relative abundance of aromatic C, and the contents of humic acid and heavy fraction organic carbon. In addition, SMS-AB application significantly increased the relative abundances of the bacterial phyla Firmicutes and Actinobacteria. Notably, the genera Actinomadura, Ilumatobacter, and Bacillus, which were positively correlated with humic acid, experienced an increase in relative abundance. Functional prediction revealed that SMS-PE application elevated carbohydrate metabolism and reduced the prevalence of fungal pathogens, particularly Fusarium. The application of high-rate SMS-AB (8%) enhanced bacterial amino acid metabolism and the relative abundances of plant pathogenic fungi. Our research provides strategies for utilizing SMS to enrich soil organic carbon and fortify soil health, facilitating the achievement of sustainable soil management.

Vinyl and methyl-ester groups in the insoluble polymer drug patiromer identified and quantified by solid-state NMR

Patiromer (Veltassa®) is a crosslinked, insoluble co-polymer drug used as a nonabsorbent potassium binder, approved for treatment of hyperkalemia. Quantitative solid-state 13C nuclear magnetic resonance (NMR) analysis with comprehensive peak assignment, component quantification, and calculation of mole and weight fractions of monomer units was performed on three doses of patiromer. The workflow is documented in detail. Spectrally edited solid-state 13C NMR spectra of patiromer show =CHn peaks of matching intensity at 116 and 141 ppm, characteristic of -CH=CH2 vinyl groups. Similar spectral features can be observed in earlier studies but were previously ignored. In this study, the vinyl signals are well-resolved in a 2-s direct polarization (DP) spectrum without and with dipolar dephasing, which confirms that these sp2-hybridized carbons are bonded to hydrogen and partially mobile, consistent with vinyl side groups from incompletely reacted divinyl crosslinkers. The vinyl groups account for 1.6% of all carbon, 3% of the monomer units, and nearly 1/3 of the crosslinkers. Furthermore, an unexpected OCH3 moiety accounting for ∼1.2% of all carbons was identified by spectral editing; its chemical shift of 54 ppm is more consistent with a methyl ester than with a methyl ether. It can originate from incomplete hydrolysis of ∼6% of methyl-2-fluoroacrylate, the main monomer of patiromer. Characteristic cross peaks in two-dimensional 1H–13C heteronuclear correlation NMR confirm the presence of the vinyl and OCH3 groups. Trace amounts of xanthan gum are also detected. The quantitative 13C NMR spectrum of patiromer has been matched in a simulation using a model with five monomer units.

Molecular structure and selective theophylline complexation by conformational change of diethyl N,N'-(1,3-phenylene)dicarbamate.

The receptor ability of diethyl N,N'-(1,3-phenylene)dicarbamate (1) to form host-guest complexes with theophylline (TEO) and caffeine (CAF) by mechanochemistry was evaluated. The formation of the 1-TEO complex (C12H16N2O4·C7H8N4O2) was preferred and involves the conformational change of one of the ethyl carbamate groups of 1 from the endo conformation to the exo conformation to allow the formation of intermolecular interactions. The formation of an N-H...O=C hydrogen bond between 1 and TEO triggers the conformational change of 1. CAF molecules are unable to form an N-H...O=C hydrogen bond with 1, making the conformational change and, therefore, the formation of the complex impossible. Conformational change and selective binding were monitored by IR spectroscopy, solid-state 13C nuclear magnetic resonance and single-crystal X-ray diffraction. The 1-TEO complex was characterized by IR spectroscopy, solid-state 13C nuclear magnetic resonance, powder X-ray diffraction and single-crystal X-ray diffraction.

Continuous straw returning enhances the carbon sequestration potential of soil aggregates by altering the quality and stability of organic carbon

Soil structure plays an important role in organic carbon (OC) sequestration, thereby influencing soil fertility and changes in global climate. However, aggregate OC chemical structure changes due to long-term return of straw in oasis farmland of arid northwest China remains unclear. This study conducted 0-, 5-, 10-, 15-, and 20-year straw returning experiments during which three soil components where measured: (1) the functional carbon (C) pool and macroaggregates; (2) microaggregates and silt + clay; (3) the chemical structure of soil OC (SOC). The results demonstrated that in comparison with the control, straw return increased SOC, particulate OC (POC), and mineral-associated OC (MAOC) by 21.90%–63.51%, 5.00%–31.00%, and 46.00%–226.00%, respectively. With increasing duration of straw return, microaggregates transitioned to macroaggregates, and percentages of soil macroaggregates under 10-year straw return increased by 20.26%, 3.39%, 4.40%, and 11.12% compared with that under 0-, 5-, 15- and 20-year straw return, respectively. Soil geometric mean diameter (GMD) and mean weight diameter (MWD) first increased and then decreased, with maximum values after 10-year straw return at 1.20 mm and 1.63 mm, respectively. Solid state 13C NMR (Nuclear Magnetic Resonance) indicated O-alkyl C to be the dominant chemical component of soil OC over different years of straw return. There were increases in aromatic C, aromaticity, and hydrophobicity up to 10-year straw return, after which they decreased. A mantel test confirmed positive correlations of the distributions of macroaggregates, microaggregates, OC of macroaggregates, and silt + clay with MWD and GMD, whereas the OC content of aggregates was positively correlated with O-OA and hydrophobicity. Long-term straw returns improved soil structure and stabilized soil OC, thereby facilitating soil sequestration of OC.

The immobilization of cadmium by rape straw derived biochar in alkaline conditions: Sorption isotherm, molecular binding mechanism, and in-situ remediation of Cd-contaminated soil

The issue of cadmium (Cd) contamination in alkaline soils is escalating, necessitating the prompt implementation of effective passivation strategies. Biochar has gained significant attention for its potential in immobilizing heavy metals; however, the suitability of biochar as a remediation material and its micro-scale interaction mechanisms with Cd under alkaline conditions remain unclear. Rape straw (RS) were pyrolyzed at 400 °C (RB400) and 700 °C (RB700) to produce biochar. Adsorption and soil incubation experiments were carried out to assess the feasibility of using rape straw derived biochar pyrolyze at different temperatures and understanding their remediation mechanisms in alkaline environments. The sorption capacity for Cd immobilization was evaluated using sorption isotherms, revealing that RB700 exhibited enhanced Cd sorption performance with a maximum sorption capacity of 119.33 mg g−1 calculated from the Langmuir isotherm equation at pH 8. Cd L3-edge X-ray absorption near-edge structure (XANES) spectroscopy analysis confirmed that the dominant sorption species of Cd were organic Cd in RB400, with CdCO3 precipitation increased to 73.9% in RB700. Solid-state 13C nuclear magnetic resonance (13C-NMR) spectroscopy demonstrated that aromatic and carboxyl C functional groups are involved in the organic sorption of Cd through complexation and Cd2+-π interactions in alkaline solutions. The precipitation of CdCO3 in RB700 may resulted in a more effective passivation effect compared to RB400, leading to a significant 15.54% reduction in the DTPA-Cd content in Cd-contaminated soil. These findings highlight the effective Cd passivation Cd in alkaline environments by rape straw derived biochar, providing new molecular insights into the Cd retention mechanism of biochar. Furthermore, it presents novel ideas for improving remediation approaches for alkaline Cd-contaminated soils.

Preparation and characterization of double-shell phase change material microcapsules with flame retardancy and temperature regulation capability as low-emission building fillers

The building application of phase change materials (PCMs) has attracted widespread attention due to energy conservation and emission reduction. In this study, designed and prepared by two-step polymerization poly melamine tetramethylene phosphonium sulfate (PMTMPS) coating the raw phase change materials microcapsules (MPCMs), which were novel double-shell microcapsules (D-MPCMs). D-MPCMs further achieved low smoke and low toxicity in the fire based on enhancing the temperature regulation performance of MPCMs. The chemical structure of D-MPCMs was characterized by Fourier transform infrared (FTIR) spectroscopy, and 13C solid-state nuclear magnetic resonance (NMR). Transmission electron microscope (TEM) confirmed that D-MPCMs were successfully prepared, whose shapes were regular spherical. The results of differential scanning calorimetry (DSC) showed that D-MPCMs revealed excellent phase transition enthalpy (80.51 J/g). Then, the resultant D-MPCMs had good thermal reliability and stability from the thermogravimetric analysis (TGA), characterized by a residual mass of D-MPCMs was 17 % more than that of MPCMs. In the cone calorimeter test (CCT), we confirmed that the coated PMTMPS significantly reduced the fire risk parameters of the rigid polyurethane foam (RPUF) containing D-MPCMs (D-MPCM/RPUF) referring to the heat release rate (HRR), total heat release (THR), and total smoke production (TSP). D-MPCM/RPUF exhibited the lowest peak values of HRR and TSP, which were 400.115 kW/m2 and 10.512 m2, respectively. In addition, the PMTMPS shell significantly enhanced the solar photo-thermal conversion performance of the D-MPCMs. To sum up, D-MPCMs have great potential to improve flame retardancy, environmental protection, and temperature regulation capability for building thermal insulation materials.

Construction of a food waste biochar model and determination of contaminant adsorption sites: Combining experimental characterisation with quantum chemical calculations

Increasing urbanization has made it a serious challenge to deal with food waste (FW) from people and wastewater with pollutants from industry. Biochar from FW pyrolysis(FWB) can be used as an adsorbent to adsorb pollutants from wastewater, but its molecular structure is still unknown, limiting the understanding of its adsorption mechanism and its application in industry. In this paper, a series of combined methods of experimental characterization and quantum chemical calculations, such as solid-state 13C nuclear magnetic resonance spectroscopy (13C NMR), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS) were used to investigate and successfully construct a model of the molecular structural features of FWB under the optimal contaminant adsorption preparation conditions. Based on the electrostatic potential distribution and adsorption experiments, the adsorption sites of the pollutants were elucidated. The results showed that the FWB prepared at different temperatures, 450 °C had a variety of oxygen-containing functional groups and polarity favorable for adsorption. In the molecular structure of FWB with the molecular formula C60H49N7O8, oxygen is present in the form of carboxyl, carbonyl, ether, alcohol hydroxyl, and phenol hydroxyl groups with numbers 1, 1, 1, 1, 2, 1, 2. Nitrogen is present in the form of pyridinyl nitrogen, pyrrolidinyl nitrogen, and primary amines with numbers 1, 1, and 5, respectively. In addition, nitrogen-containing and oxygen-containing functional groups are possible adsorption sites for pollutants on FWB, and alcohol hydroxyl and amino groups can bind better to Cu2+, which provides scientific guidance for improving the adsorption performance of biochar. This provides a solid foundation for the study of the microscopic adsorption mechanism of FWB and a method for the modeling of biochar from other biomasses.

Analysis of natural organic matter chemistry in bentonite clay under compaction using different dry densities and duration

The Nuclear Waste Management Organization of Canada has adopted an adaptive phased management plan for the long-term storage of used nuclear fuel in a Deep Geological Repository (DGR). The DGR barrier system employs copper-coated used fuel containers (UFCs) surrounded by buffer material which is composed of highly compacted bentonite clay. The natural organic matter (NOM) composition of the compacted bentonite is of practical importance for the safety assessment as it regulates the biogeochemical processes at the interface between the UFCs and the buffer layer. However, insufficient investigations on NOM constituents limits the understanding of biogeochemical dynamics in bentonites compacted under different dry densities. This study analyzed the carbon content and NOM composition using targeted compound analysis and solid-state 13C nuclear magnetic resonance (NMR) spectroscopy with bentonites compacted at 1.1, 1.4 or 1.6 g/cm3 dry density for 1, 3, 6, 12 or 18 months. Organic carbon contents were similar across bentonites with different compaction densities at various durations as compared to the reference clay (powdered bentonite sample before compaction). The overall NOM composition measured by solid-state 13C NMR suggested a predominance of alkyl and aromatic carbon in bentonite samples. No marked variations were observed for the NOM components (i.e., alkyl, O-alkyl and aromatic carbon) between the compacted bentonites and the reference clay. Targeted compound analysis revealed that the extractable lipid concentrations in the compacted clays did not significantly vary from the reference bentonite with only some compounds exhibiting nano-gram level differences. Bentonites with relatively lower dry densities (1.1 and 1.4 g/cm3) demonstrated slightly higher extractable compound concentrations, but these differences were not statistically significant. In contrast, the compound concentrations of bentonites compacted to 1.6 g/cm3 were similar or slightly lower compared with the reference bentonite, likely associated with limited microbial growth under high dry compaction density. Taken together, these results suggested that NOM composition and quantity did not significantly alter in bentonites under various pressures nor with longer experimental durations. These findings highlight that compacted bentonite exhibited geochemical stability under the simulated repository environments, which provides critical insight for design and performance of engineered barrier system in a DGR concept.

Controlled Sublimation Rate of Guest Drug from Polymorphic Forms of a Cyclodextrin-Based Polypseudorotaxane Complex and Its Correlation with Molecular Dynamics as Probed by Solid-State NMR.

Encapsulation of active pharmaceutical ingredients (APIs) in confined spaces has been extensively explored as it dramatically alters the molecular dynamics and physical properties of the API. Herein, we explored the effect of encapsulation on the molecular dynamics and physical stability of a guest drug, salicylic acid (SA), confined in the intermolecular spaces of γ-cyclodextrin (γ-CD) and poly(ethylene glycol) (PEG)-based polypseudorotaxane (PPRX) structure. The sublimation tendency of SA encapsulated in three polymorphic forms of the γ-CD/PEG-based PPRX complex, monoclinic columnar (MC), hexagonal columnar (HC), and tetragonal columnar (TC), was investigated. The SA sublimation rate was decreased by 3.0-6.6-fold and varied in the order of MC form > HC form > TC form complex. The 13C and 1H magic-angle spinning (MAS) solid-state nuclear magnetic resonance (NMR) spectra and 13C spin-lattice relaxation time (T1) indicated that the encapsulated SA molecules existed as the monomeric form, and its molecular mobility increased in the order of MC form > HC form > TC form complex. In the complexes, a rapid chemical exchange between two dynamic states of SA (free and bound) was suggested, with varying adsorption/desorption rates accounting for its distinct molecular mobility. This adsorption/desorption process was influenced by proton exchange at the interaction site and interaction strength of SA in the complexes, as evidenced by 1H MAS spectra and temperature dependency of the 13C carbonyl chemical shift. A positive correlation between the molecular mobility of SA and its sublimation rate was established. Moreover, the molecular mobility of γ-CD and PEG in the complexes coincided with that of SA, which can be explained by fast guest-driven dynamics. This is the first report on the stability improvement of an API through complexation in polymorphic supramolecular host structures. The relationship between the molecular dynamics and physical properties of encapsulated API will aid in the rational design of drug delivery systems.

Water-Enhanced Direct Air Capture of Carbon Dioxide in Metal-Organic Frameworks.

We have developed two series of amine-functionalized zirconium (Zr) metal-organic framework-808 (MOF-808), which were produced by postsynthetic modifications to have either amino acids coordinated to Zr ions (MOF-808-AAs) or polyamines covalently bound to the chloro-functionalized structure (MOF-808-PAs). These MOF variants were comprehensively characterized by liquid-state 1H nuclear magnetic resonance (NMR) measurements and potentiometric acid-base titration to determine the amounts of amines, energy-dispersive X-ray spectroscopy to assess the extent of covalent substitution by polyamines, powder X-ray diffraction analysis to verify the maintenance of the MOF crystallinity and structure after postsynthetic modifications, nitrogen sorption isotherm measurements to confirm retention of the porosity, and water sorption isotherm measurements to find the water uptake in the pores of each member of the series. Evaluation and testing of these compounds in direct air capture (DAC) of CO2 showed improved CO2 capture performance for the functionalized forms, especially under humid conditions: In dry conditions, the l-lysine- and tris(3-aminopropyl)amine-functionalized variants, termed as MOF-808-Lys and MOF-808-TAPA, exhibited the highest CO2 uptakes at 400 ppm, measuring 0.612 and 0.498 mmol g-1, and further capacity enhancement was achieved by introducing 50% relative humidity, resulting in remarkable uptakes of 1.205 and 0.872 mmol g-1 corresponding to 97 and 75% increase compared to the dry uptakes, respectively. The mechanism underlying the enhanced uptake efficiency was revealed by 13C solid-state NMR and temperature-programmed desorption measurements, indicating the formation of bicarbonate species, and therefore a stoichiometry of 1:1 CO2 to each amine site.

Chemical composition of soil carbon is governed by microbial diversity during understory fern removal in subtropical pine forests

Understory vegetation has an important impact on soil organic carbon (SOC) accumulation. However, little is known about how understory vegetation alters soil microbial community composition and how microbial diversity contributes to SOC chemical composition and persistence during subtropical forest restoration. In this study, removal treatments of an understory fern (Dicranopteris dichotoma) were carried out within pine (Pinus massoniana) plantations restored in different years in subtropical China. Soil microbial community composition and microbial diversity were measured using phospholipid fatty acids (PLFAs) biomarkers and high-throughput sequencing, respectively. The chemical composition of SOC was also measured via solid-state 13C nuclear magnetic resonance (13C NMR). Our results showed that fern removal decreased alkyl C by 4.2 % but increased O-alkyl C by 15.6 % on average, leading to a decline of alkyl C/O-alkyl C ratio, suggesting altered chemical composition of SOC and lowered SOC recalcitrance without fern. Fern removal significantly lowered the fungi-to-bacteria ratio, and it also reduced fungal and bacterial diversity. Partial correlation analysis revealed that soil nitrogen availability was a key factor influencing microbial diversity. Bacterial diversity showed a close relationship with the Alkyl C/O-alkyl C ratio following fern removal. Furthermore, the microbial community structure and bacterial diversity were responsible for 18 % and 55 % of the explained variance in the chemical composition of SOC, respectively. Taken together, these analyses jointly suggest that bacterial diversity exerts a greater role than microbial community structure in supporting SOC persistence during understory fern removal. Our study emphasizes the significance of understory ferns in supporting microbial abundance and diversity as a means of altering SOC persistence during subtropical forest restoration.

Effects of cage topology on ethylene adsorption mechanism in silver exchanged CHA and RHO zeolites: An Inelastic Neutron Scattering and Density Functional study

Zeolite-based adsorbents have been successfully used for many challenging separations due to their tunable properties. A particularly notable application involves the separation of light olefins from paraffins, wherein the molecular sieving properties of zeolites play a pivotal role. Additionally, the selective interaction of alkenes with transition metal cations, positioned within the channels and cavities of microporous zeolites, further enhances separation capabilities.This study aims to comprehensively characterize the interactions between ethylene and Ag+ exchanged zeolites, employing a multidisciplinary approach, combining Inelastic Neutron Scattering (INS), Infrared (IR) spectroscopy, Nuclear Magnetic Resonance (NMR), UV–Vis and Density Functional Theory (DFT) calculations. CHA and RHO, zeolites largely applied in gas separation processes, were chosen due to their similar small pore sizes and pore volume, but different cavity shapes and flexibilities.The interpretation of derived DFT Electron Density Difference, experimentally supported by 13C Solid State NMR results, provide an understanding of each framework’s role during the charge transfer mechanisms between ethylene and transition metal species. Specific deformations in the flexible framework of zeolite RHO explain a blueshift of the band at 400 cm−1 in the librational region of INS spectra compared to CHA. This structural change in RHO, represented by the conic shape of the cage 8-ring side pockets, increases steric effects over the adsorbate while rendering the metallic adsorption center less exposed within the zeolite’s cavity, finally leading to a weaker adsorption energy. The redshift of C=C stretching frequencies observed by IR spectroscopy and DFT calculations, as well as C=C and C-H bond lengthening of ethylene confirm the formation of π-complexes on silver in both zeolites and allowed a further evaluation of the effects of the different frameworks cages on the aforementioned interaction.

Mechanochemical formation of highly stable amorphous calcium carbonate in calcium silicates: Potential long-term storage of CO2 in cement

We have investigated mechanochemical reactions with the calcium silicate wollastonite to probe potential mechanisms of sequestration and long-term storage of CO2 as mineral carbonates in cement pastes. Wollastonite, CaSiO3, was milled under ambient and 13C enriched CO2 atmospheres. Milling induced a structure change from monoclinic wollastonite−2M to triclinic−1T, consistent with high pressure treatment. The results from solid-state 13C nuclear magnetic resonance (NMR) spectroscopy shows this process forms an extraordinarily stable amorphous calcium carbonate (ACC) phase that remains despite a high temperature dehydration treatment (130 °C) and persists in the same form after 3 yrs. of storage at ambient conditions. Thermogravimetric analysis (TGA) of these samples indicates that ACC is produced at the similar solid concentrations in both CO2-enriched and ambient atmospheres. The observation of meta-stable ACC due to wollastonite carbonation may play an important role in further exploration and optimization of mineral carbonation reactions for CO2 capturing cement formulations.

Cellulose fibers and ellagitannin-rich extractives from rambutan (Nephelium Lappaceum L.) peel by an eco-friendly approach

This study assesses the viability of an accelerated solvent extraction technique employing environmentally friendly solvents to extract ellagitannins while producing cellulose-rich fibers from rambutan peel. Two sequential extraction protocols were investigated: 1) water followed by acetone/water (4:1, v:v), and 2) acetone followed by acetone/water (4:1, v:v), both performed at 50 °C. The first protocol had a higher extraction yield of 51 %, and the obtained extractives featured a higher total phenolic (531.4 ± 22.0 mg-GAE/g) and flavonoid (487.3 ± 16.9 mg-QE/g) than the second protocol (495.4 ± 32.8 mg-GAE/g and 310.6 ± 31.4 mg-QE/g, respectively). The remaining extractive-free fibers were processed by bleaching using either 2 wt% sodium hydroxide with 3 wt% hydrogen peroxide or 4–5 wt% peracetic acid. Considering bleaching efficiency, yield, and process sustainability, the single bleaching treatment with 5 wt% of peracetic acid was selected as the most promising approach to yield cellulose-rich fibers. The samples were analyzed by methanolysis to determine the amount and type of poly- and oligosaccharides and studied by 13C solid-state nuclear magnetic resonance spectroscopy and thermal gravimetric analysis. The products obtained from the peels demonstrate significant potential for use in various sectors, including food, nutraceuticals, cosmetics, and paper production.

Internal Vibrations of Pyridinium Cation in One-Dimensional Halide Perovskites and the Corresponding Halide Salts.

We investigate vibrations of the pyridinium cation PyH+ = C5H5NH+ in one-dimensional lead halide perovskites PyPbX3 and pyridinium halide salts PyHX (X- = I-, Br-), combining infrared absorption and Raman scattering methods at room temperature. Internal vibrations of the cation were assigned based on density functional theory modeling. Some of the vibrational bands are sensitive to perovskite or the salt environment in the solid state, while halide substitution has only a minor effect on them. These findings have been confirmed by 1H, 13C and 207Pb solid-state nuclear magnetic resonance (NMR) experiments. Narrower vibrational bands in perovskites indicate less disorder in these materials. The splitting of NH-group vibrational bands in perovskites can be rationalized the presence of nonequivalent crystal sites for cations or by more exotic phenomena such as quantum tunneling transition between two molecular orientations. We have shown how organic cations in hybrid organic-inorganic crystals could be used as spectators of the crystalline environment that affects their internal vibrations.

Solid-State 13C Nuclear Magnetic Resonance Study of Soluble and Insoluble β-Glucans Extracted from Candida lusitaniae.

β-glucans are widely known for their biological activities. However, the choice of extraction method can significantly influence their structural characteristics, thereby potentially impacting their biological functions. In this paper, three fractions of β-glucans were obtained from Candida lusitaniae yeast via alkali and hot-water extraction methods and were analyzed using solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. Solid-state NMR spectroscopy was used as a nondestructive technique that preserves the structure of the analyzed molecules. The results suggest that differences in the β-glucan structure are affected by the choice of extraction method. The main difference occurred in the 82-92 ppm region with signal presence suggesting that β-glucans have a linear structure when hot-water-extracted, which is absent in alkali-extracted fractions resulting in the acquisition of β-glucans with an ordered, possibly helical structure. A hot-water extracted water-insoluble (HWN) fraction consists of linear β-1,3-glucans with other signals indicating the presence of β-1,6-linked side chains, chitin and small amounts of α-glucan impurities. For those that are alkali-extracted, alkali-insoluble (AN) and water-soluble (AWS) fractions are structurally similar and consist of an ordered β-1,3-glucan structure with β-1,6-linked side chains and a significant amount of α-glucan and chitin in both fractions.

Effect of long-term land use change on soil organic carbon fractions and functional groups

Soil organic matter (SOM) fractions and functional groups can be used to study the short-term as well as the long-term effects of land use change on soil organic carbon (SOC) dynamics. In this study, soil samples of grassland (native vegetation), planted forest and cropland (both converted from grassland) were collected from three soil pedogenetic horizons of A-horizon, AB-horizon and Bk-horizon in a semiarid area of Northeast China. The amounts of SOC, particulate organic carbon (POC), and mineral-associated organic carbon (MOC) were evaluated. After grassland conversion into planted forest and cropland, the amount of SOC decreased by 5.71 and 13.59%, POC decreased by 17.39 and 34.72%, and MOC decreased by 2.84 and 8.36%. Based on the analysis of MOC composition, the average content of humic extract-C decreased by 2.19% and humin-C decreased by 3.08% for planted forest, meanwhile humic extract-C decreased by 14.14% and humin-C decreased by 6.24% for cropland, compared to grassland. This result suggested that labile SOC fractions were more affected by land use change. Solid-state 13C nuclear magnetic resonance (NMR) spectra of bulk soil showed that native grassland SOC had a higher proportion of alkoxy C but a lower proportion of aromatic C, and the aromaticity was less than that of planted forest and cropland. Our results suggested that although the chemical structure of SOM tend to be stable, SOM fraction levels were not enough to recover. Reasonable grassland management measures should be formulated to prevent the continued conversion of native grassland.