CPMAS Nuclear Magnetic Resonance Research Articles

Real-Time Monitoring of the Structural Transition of Bombyx mori Liquid Silk under Pressure by Solid-State NMR.

Silk fibroin is stored in the silk glands of Bombyx mori silkworms as a condensed aqueous solution called liquid silk. It is converted into silk fibers at the silkworm's spinnerets under mechanical forces including shear stress and pressure. However, the detailed mechanism of the structural transition of liquid silk to silk fibers under pressure is not well understood. Magic angle spinning (MAS) in solid-state nuclear magnetic resonance (NMR) can exert pressure on liquid samples in a quantitative manner. In this study, solid-state NMR was used to quantitatively analyze the impact of pressure on the structural transition of liquid silk. A combination of 13C DD-MAS and CP-MAS NMR measurements enabled the conformation and dynamics of the crystalline region of the silk fibroin (both before (Silk Ip) and after (Silk IIp) the structural transition) to be detected in real time with atomic resolution. Spectral analyses proposed that the pressure-induced structural transition from Silk Ip to Silk IIp proceeds by a two-step autocatalytic reaction mechanism. The first reaction step is a nucleation step in which Silk Ip transforms to single lamellar Silk IIp, and the second is a growth step in which the single lamellar Silk IIp acts as a catalyst that reacts with Silk Ip molecules to further form Silk IIp molecules, resulting in stacked lamellar Silk IIp. Furthermore, the rate constant in the second step shows a significant pressure dependence, with an increase in pressure accelerating the formation of large stacked lamellar Silk IIp.

Solid-state MAS NMR at ultra low temperature of hydrated alanine doped with DNP radicals

Magic angle spinning (MAS) nuclear magnetic resonance (NMR) experiments at ultra low temperature (ULT) (≪ 100 K) have demonstrated clear benefits for obtaining large signal sensitivity gain and probing spin dynamics phenomena at ULT. ULT NMR is furthermore a highly promising platform for solid-state dynamic nuclear polarization (DNP). However, ULT NMR is not widely used, given limited availability of such instrumentation from commercial sources. In this paper, we present a comprehensive study of hydrated [U-13C]alanine, a standard bio-solid sample, from the first commercial 14.1 Tesla NMR spectrometer equipped with a closed-cycle helium ULT-MAS system. The closed-cycle helium MAS system provides precise temperature control from 25 K to 100 K and stable MAS from 1.5 kHz to 12 kHz. The 13C CP-MAS NMR of [U-13C]alanine showed 400% signal gain at 28 K compared with at 100 K. The large sensitivity gain results from the Boltzmann factor, radio frequency circuitry quality factor improvement, and the suppression of its methyl group rotation at ULT. We further observed that the addition of organic biradicals widely used for solid-state DNP significantly shortens the 1H T1 spin lattice relaxation time at ULT, without further broadening the 13C spectral linewidth compared to at 90 K. The mechanism of 1H T1 shortening is dominated by the two-electron-one-nucleus triple flip transition underlying the Cross Effect mechanism, widely relied upon to drive solid-state DNP. Our experimental observations suggest that the prospects of MAS NMR and DNP under ULT conditions established with a closed-cycle helium MAS system are bright.

Newly Designed Mesoporous Silica and Organosilica Nanostructures Based on Pentablock Copolymer Templates in Weakly Acidic Media.

We developed a new category of porous silica and organosilicas nanostructures in a facile method based on weakly acidic aqueous-ethanol media by utilizing two different pentablock copolymer templates of type PLGA-PEO-PPO-PEO-PLGA. Pluronic block templates were used mainly to prepare these pentablock copolymers with different molecular weights and volume ratios. Silica precursor tetraethyl orthosilicate and organosilicas precursor 1,4-bis(triethoxysilyl)benzene have been used as main source for synthesizing the silica and organosilicas samples. Weak Lewis acids iron(III) chloride hexahydrate, aluminum(III) chloride hexahydrate, and boric acid were utilized as catalyst instead of any strong inorganic acids and the molar ratio of catalyst/precursor has been optimized to 1–2 for preparation of ordered mesostructures. Reaction temperatures have been optimized to 25 °C for pure silica and both 25 °C as well as 40 °C for organosilicas to get the best result for mesostructures. A detailed analysis by using various analytical techniques like synchrotron small angle X-ray scattering, nitrogen sorption, transmission electron microscopy, scanning electron microscope, solid-state 29Si CP-MAS nuclear magnetic resonance (NMR), and so on has revealed well developed mesostructures with surface area of 388–836 m2/g for silica and 210–691 m2/g for organosilica samples, respectively. Furthermore, bimodal typepores have been observed from pore size distribution plot of the samples. Thermal stability of the materials was up to 400 °C as analyzed by thermogravimetric analysis.

Dynamics of soil aggregate-associated organic carbon based on diversity and high biomass-C input under conservation agriculture in a savanna ecosystem in Cambodia

No-till (NT) cropping systems have the potential to enhance soil aggregation, providing physical protection and soil C sequestration. The existence of discrepancies in the impact of tillage on soil aggregation and soil C sequestration warrants further studies, particularly for different crop rotations. We hypothesized the following: a) NT biannual crop rotations tend to be more effective in restoring large macroaggregation and the concentrations of soil organic C (SOC), total N and permanganate oxidizable C (POXC) associated with macroaggregates than NT systems with a one-year frequency pattern and conventional tillage (CT); b) the continuous biomass-C inputs via crop residues in large macroaggregates under NT tend to increase the proportion of aliphatic C than those under CT. Therefore, the objectives of this study were: (i) to assess changes in the aggregate size distribution and levels of aggregate-associated total SOC, total N and POXC and (ii) to characterize humic acid (HA) using 13C CP-MAS nuclear magnetic resonance (NMR) spectra of 8- to 19-mm soil aggregate size class in a reference vegetation (RV) and in rice-, soybean- and cassava-based cropping systems (RcCS, SbCS and CsCS, respectively) in a clayed Oxisol after tillage and crop rotation management. We evaluated four treatments in each cropping system: 1) CT, and 2) three NT systems in a randomized complete block design with three replicates. Soil aggregate samples were collected at depths of 0–5, 5–10 and 10–20 cm. The conversion of RV to agricultural land influenced the distribution of aggregate size classes, soil aggregation indices and aggregate-associated SOC, total N and POXC in the two surface layers. The formation of large macroaggregates (8–19 mm) dominated the aggregate size distribution with a relatively higher proportion under RV and NT than under CT. Across all soil depths, the proportions of the 8- to 19-mm aggregate size fraction were 59% (NV), 43% and 47% (RcCS), 45% and 53% (SbCS) and 34% and 37% (CsCS) for the CT and NT systems, respectively. Among the three NT systems, the biannual crop rotations in the three cropping systems (NT2-Rice, NT2-Soybean, NT2-Cassava; NT3-Rice, NT3-Soybean and NT3-Cassava) indicated better performance than the one-year frequency pattern in restoring large macroaggregation and the concentrations of SOC, total N and POXC associated with large macroaggregates. Additionally, in the surface (0–5 cm) and subsurface (10–20 cm) soil layers, the SbCS with a high rate (7.32 Mg C ha−1 year−1) and diversity [Pennisetum typhoides) (Pearl millet)/maize + Brachiaria ruziziensis (Brz), Stylosanthes guianensis (St)] of biomass-C inputs reached the highest levels of lability of SOC and POXC in the macroaggregate size classes of 0.25–0.5 and 8–19 mm, respectively. The CP-MAS 13C NMR measurement suggests that the continuous and high biomass-C inputs with diverse crop residues under NT, such as millet, maize, Brz, St and Crotalaria juncea, tended to increase the proportion of aliphatic C than under CT; an opposite trend was observed for aromatic C. 13C NMR revealed an advance caused by the association between the quantity and quality of C addition via cultural residues in the discrimination of the composition of C in the macroaggregation in the tropical region.

Aqueous adsorption of bisphenol A over a porphyrinic porous organic polymer

A new porphyrinic porous organic polymer (PPOP) with high stability and excellent textural properties (929 m2/g surface area with 0.73 cm3/g pore volume) was made via the Friedel-Crafts reaction and applied for bisphenol A (BPA) adsorption in water. The material was examined by X-ray diffraction, N2 adsorption-desorption isotherms, scanning electron microscopy, infrared spectroscopy, X-ray photoelectron spectroscopy, and solid-state 13C CP-MAS nuclear magnetic resonance spectroscopy. PPOP was proven highly effective for capturing BPA among the many adsorbent materials investigated. The Langmuir model could closely match the adsorption isotherm data with a high adsorption amount of ca. 653 mg/g at 25 °C. Approximately 95% of BPA was adsorbed in 50 min, and the pseudo-second-order kinetic model satisfactorily described the adsorption behavior. This adsorption process was exothermic (ΔH° = −39.10 kJ/mol), and the capacity gradually decreased with increasing pH. Spectroscopic analyses indicated that the BPA adsorption on PPOP was affected by (1) π-π interaction between BPA and the aromatic constituents of PPOP, (2) hydrogen bonding between the N sites of porphyrin units in PPOP and the hydroxyl group of BPA and, and (3) hydrophobic interactions. PPOP was easily regenerated after acetone washing, and >98% efficiency was observed throughout the five repeated adsorption-desorption cycles.

Chemical, Biological and Mechanical Characterization of Wood Treated with Propolis Extract and Silicon Compounds

The development of new bio-friendly alternatives for wood conservation is of great interest and necessary for environmental protection. In this paper, the preparations based on the propolis extract and silicon compounds were used as green wood preservatives. The wood was treated with 15% propolis extract (EEP) and two propolis-silane preparations, namely, EEP-VTMOS/TEOS (EEP with vinyltrimethoxysilane and tetraethyl orthosilicate) and EEP-MPTMOS/TEOS (EEP with 3-(trimethoxysilyl) propyl methacrylate and tetraethyl orthosilicate). The aim of the research was to determine the properties of treated wood, which was characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), atomic absorption spectroscopy (AAS), X-ray fluorescence (XRF), and scanning electron microscopy (SEM). Moreover, the resistance against brown-rot fungus Coniophora puteana and the mechanical properties of treated wood were also determined. The analysis of phenolic compounds concentration in treated wood indicated that phenols were in greater extent leached from wood treated with the propolis extract than from wood impregnated with the propolis-silane preparations. The presence of silicon in treated wood both before and after leaching was confirmed by CP MAS NMR measurements. In turn, AAS and XRF analyses indicated that the degree of Si leaching from wood impregnated with EEP-VTMOS/TEOS was approximately two times lower than from EEP-MPTMOS/TEOS treated wood. The results of chemical analyses confirmed that the constituents of the propolis-silane preparations formed permanent bonds with wood. In turn, the results of the antifungal efficacy against C. puteana showed that the propolis extract and the propolis-silane preparations limited the fungus activity, even the wood was subjected to leaching procedure. The treated wood showed an increase in bending strength and a decrease in the modulus of elasticity compared to untreated wood. The obtained results indicate that the propolis-silane preparations can be promising green wood preservatives, harmless for the natural environment.

13 C solid-state NMR complemented by ATR-FTIR and micro-DSC to study modern collagen-based material and historical leather.

Ancient vegetable tanned leathers and parchments are very complex materials in which both different manufacturing and deterioration processes make their study and chemical characterisation difficult. In this research, solid-state nuclear magnetic resonance (NMR) spectroscopy was applied to identify different tannin families (condensed and hydrolysable) in historical leather objects such as bookbindings, wall upholsters, footwear and accessories, and military apparel. Furthermore, leather deterioration with special focus on collagen gelatinisation was investigated. A comparison with Fourier transform infrared (FTIR) spectroscopy and micro-differential scanning calorimetry (micro-DSC) was also performed to support the 13 C CP-MAS NMR findings and to point out the advantages and limitations of solid-state NMR in analysing historical and archaeological leathers. A wide database of NMR and FTIR spectra of commercial tannins compounds was also collected in order to characterise historical and archaeological leathers.

Effect of land use on organic matter composition in density fractions of contrasting soils: A comparative study using 13C NMR and DRIFT spectroscopy

13C CP-MAS nuclear magnetic resonance (NMR) and diffuse reflectance infrared Fourier transform (DRIFT) spectroscopies were compared for evaluating their potential to characterise the influence of land use change on organic carbon (OC) chemistry of particulate organic matter (POM) and mineral associated OM (MOM) fractions of different soil types. Surface soil samples of Ferralsol, Luvisol, Vertisol and Solonetz were collected from native and crop lands and isolated into different density fractions. NMR and DRIFT showed distinct OC composition for all the soil fractions of two land uses. In NMR spectra, greater proportion of carbohydrate and aromatic C was observed in POM, while MOM fractions were rich in carbohydrate, amino groups and aliphatic C. DRIFT spectra showed greater carboxylic, aromatic C and amide N in MOM than corresponding POM. NMR spectroscopy detected charred aromatic C in both fractions, which was not feasible with DRIFT. The overall effect of land use in both techniques appeared similar on the composition of POM- OC, i.e., increased aromaticity and decreased alkyl C:O-alkyl C ratio. However, differences of land use impact were observed in MOM-OC, e.g., overall decreased aromaticity and increased alkyl C:O-alkyl C for all soils in NMR, and in DRIFT, it varied with soil type (aromaticity: Ferralsol, Vertisol > Luvisol, Solonetz). However, these trends were inconsistent and indistinct among fractions of four soils. Discrepancy in NMR and DRIFT results was ascribed to the sensitivity limitations of the two techniques in characterising soil OM in mineral rich fractions, and sample pre-treatment effect in NMR. We conclude that combination of NMR and DRIFT spectroscopy, preferably supplemented by other techniques e.g., mass spectroscopy and XPS, would improve the proficiency in elucidating small changes in soil OM composition with land use conversion.

Phosphate glass matrix composites incorporating trisilanol phenyl polyhedral oligomeric silsesquioxane prepared by viscous flow sintering method with enhanced benefits

The effect of mixing and sintering processes to prepare tin fluorophosphate glass (Pglass) matrix composites incorporating trisilanol phenyl polyhedral oligomeric silsesquioxane (TSP-POSS) was investigated by comparing manual and suspension mixing, one-step and stepwise sintering processes to explore the structure dynamics and physical properties in the composites as a function of the different process conditions used. Energy Dispersive X-ray analysis confirmed optimal homogeneous dispersion of the TSP-POSS molecules in the composites prepared by the suspension method. The observed increase of glass transition temperature and the reduction of non-bridging bonds in the composites are believed to be the reason for the effective dispersion of TSP-POSS molecules in the composites. The chemical reaction between the TSP-POSS and Pglass was strongly influenced by the mixing/dispersion and sintering processes investigated. 13C cross polarized magic angle spinning (CP MAS) solid state nuclear magnetic resonance (NMR) spectroscopy confirmed the chemical stability of the TSP-POSS during the sintering process at elevated temperatures. In addition, a chemical reaction between the TSP-POSS and Pglass was evidenced by 29Si CP MAS NMR analysis. This study will provide a better fundamental understanding of the effective dispersion mechanism of the TSP-POSS molecules in the Pglass matrix that will facilitate tailoring the physicochemical properties of the composites with addition of various small concentrations of TSP-POSS for a number of applications where the pure Pglass is not applicable due to the intrinsic properties of the Pglass.

Star PEG-based amphiphilic polymers: synthesis, characterization and swelling behaviors

This paper describes the preparation, characterization and application of pentaerythritol ethoxylate-based crosslinked polymers as sorbent materials for a variety of liquids. A bulk polymerization method has been employed to produce amphiphilic polymeric sorbents in a solvent-free medium at moderately high temperature that does not require any initiator, catalyst or an activator. The morphological, structural and thermal properties of amphiphilic polymeric sorbents were determined by means of Fourier transform infrared spectroscopy, 13C and 29Si CPMAS nuclear magnetic resonance, scanning electron microscope and thermal gravimetric analysis. Having hydrophobic and hydrophilic portions in the polymeric structure, the obtained sorbents have affinity toward both water and organic liquids. The effect of molecular weight of monomers on absorption ability was examined via swelling test. The swelling ability in binary mixtures was also studied to determine the absorption capacity of polymers in organic solvent–water mixtures. Absorption studies, absorption–desorption kinetics and reusability tests were also operated, and the experimental outcomes showed that the obtained polymers have high and quick absorption abilities and also can be reusable with no capacity loss in oils.

Oil loving hydrophobic gels made from glycerol propoxylate: Efficient and reusable sorbents for oil spill clean-up

Glycerol propoxylate based oil loving sorbents were prepared through bulk polymerization, without using of an activator, initiator, or catalyst. Fourier transform infrared spectroscopy (FTIR), 13C and 29Si CPMAS nuclear magnetic resonance (NMR), as well as elemental analysis and thermal gravimetric analysis (TGA) were operated in order to identify the structural and thermal features of sorbents. The synthesized gels were employed as absorbents for various organic solvents and oils. The swelling capacity, absorption-desorption kinetics, reusability, and selective removal from an oil/water mixture were also examined. To explore the effects of a crosslinker's concentration on oil absorption capacity, star type propoxylate monomers were reacted at different concentration of tris[3-(trimethoxysilyl)propyl]isocyanurate (ICS) crosslinker; swelling capacity was calculated using dichloromethane as an organic solvent. Oil removal ability from the water surface is another important section contained within this article.

Synthesis of RGD-peptide modified poly(ester-urethane) urea electrospun nanofibers as a potential application for vascular tissue engineering

The development of a biomimetic surface which is able to promote endothelialization is fundamental in the research for blood vessel substitutes to overcome the formation of thrombi or hyperplasia. In the present work, the fabrication of acrylamide-terminated glycine-arginine-glycine-aspartic peptides (Ac-GRGD) modified poly(ester-urethane) urea (PEUU) nanofibrous mats via electrospinning technique followed by covalent immobilizing method for improving its endothelialization was successfully achieved. Series of PEUU based polymers including PEUU, PEUU with t-butoxycarbonyl group (PEUU-Boc), and PEUU-amino group (PEUU-NH2) were synthesized by a two-step solution polymerization and a de-protection process. The PEUU-RGD as-prepared nanofibrous mat was characterized using different techniques, such as, scanning electron microscopy, solide-state 13C CP-MAS nuclear magnetic resonance, and stress-strain test. In addition, to motivate cell adhesion and proliferation, PEUU nanofibers mat was immobilized by coupling of Ac-GRGD. The results present that incorporation of Ac-GRGD peptide improved the mechanical properties and does not have negative effect on the morphology and the structure of PEUU nanofibers. From cell viability and cell morphology results, the prepared PEUU-RGD nanofiber mats are cytocompatible. Interestingly, the immobilized PEUU-RGD nanofibers possess lower hemolysis rate and an improved inhibition of platelet adhesion. Overall, Ac-GRGD peptides immobilized PEUU nanofibrous mats may have a potential application for vascular tissue engineering.

Solid-state NMR study on changes of phosphate and proton species in metal pyrophosphate composite (MP2 O7 -MO2 ) ceramics.

In order to investigate the effects of composite production and the role of the counter cation for metal phosphate conductors, changes in the solid-state nuclear magnetic resonance (NMR) spectra and magnetic relaxation times caused by the removal of volatile products and water washing were examined for various metal pyrophosphate (MP2 O7 -MO2 ; M = Sn, Si, Ti, and Zr). Acidic species could be detected by 1 H MAS NMR spectra for all the composites except ZrP2 O7 -ZrO2 that had the lowest conductivity. The 31 P DD-MAS NMR spectra for MP2 O7 -MO2 composites showed different signal patterns depending on the counter cations participating in the ion exchange as a result of different microstructures. Combinational analysis of 31 P DD-MAS and 31 P CP-MAS NMR spectra of the composites indicated that protonic bulk phosphates were observed at slightly lower fields than non-protonic bulk phosphates in all of the MP2 O7 -MO2 composites. After water washing, the acidic species and the protonic bulk phosphates of MP2 O7 -MO2 composites disappeared or were reduced to trace amounts. The T1 H values of the water-washed composites lengthened because of removal of orthophosphoric acid, although the T1 P values remained almost unchanged. The results of the solid-state NMR studies suggest that the protonic bulk phosphates of MP2 O7 -MO2 composites do not generally distribute in the bulk but exist in the interface between excess H3 PO4 and the bulk. Copyright © 2016 John Wiley & Sons, Ltd.

Pregnancy-Induced Dynamical and Structural Changes of Reproductive Tract Collagen

The tissues and organs of the female reproductive tract and pelvic floor undergo significant remodeling and alterations to allow for fetal growth and birth. In this work, we report on a study of the alterations of murine reproductive tract collagen resulting from pregnancy and parturition by spectrophotometry, histology, and 13C, 2H nuclear magnetic resonance (NMR). Four different cohorts of rats were investigated that included virgin, multiparous, two- and fourteen-day postpartum primiparous rats. 13C CPMAS NMR revealed small chemical shift differences across the cohorts. The measured H-C internuclear correlation times indicated differences in dynamics of some motifs. However, the dynamics of the major amino acids, e.g., Gly, remained unaltered with respect to parity. 2H NMR relaxation measurements revealed an additional water reservoir in the postpartum and multiparous cohorts pointing to redistribution of water due to pregnancy and/or parturition. Spectrophotometric measurements indicated that the collagen content in virgin rats was highest. Histological analysis of the upper vaginal wall indicated a signature of collagen fiber dissociation with smooth muscle and a change in the density of collagen fibers in multiparous rats.

Solution and Solid State Nuclear Magnetic Resonance Spectroscopic Characterization of Efavirenz

Samples of efavirenz (EFZ) were evaluated to investigate the influence of the micronization process on EFZ stability. A combination of X-ray diffraction, thermal analysis, FTIR, observations of isotropic chemical shifts of 1H in distinct solvents, their temperature dependence and spin-lattice relaxation time constants (T1), solution (1D and 2D) 13C nuclear magnetic resonance (NMR), and solid-state 13C NMR (CPMAS NMR) provides valuable structural information and structural elucidation of micronized EFZ and heptane-recrystallized polymorphs (EFZ/HEPT). This study revealed that the micronization process did not affect the EFZ crystalline structure. It was observed that the structure of EFZ/HEPT is in the same form as that obtained from ethyl acetate/hexane, as shown in the literature. A comparison of the solid-state NMR spectra revealed discrepancies regarding the assignments of some carbons published in the literature that have been resolved.

Membranes of chitosan grafted onto poly(3-hydroxybutyrate): new insights into their applicability as scaffolds

Chitosan was grafted onto poly(3-hydroxybutyrate) (P(3HB)) as in our earlier work by using gamma radiation-induced polymerization reaction. We now provide structural and surface characteristics of the graft copolymer in view of potential applications. The modified P(3HB) was characterized by 1H/solid-state 13C CP-MAS nuclear magnetic resonance, Fourier transform infrared spectroscopy, thermogravimetric analysis, atomic force microscopy, contact angles and scratch resistance determination. Copolymer surfaces resemble those of neat P(3HB) and are unsuitable for membranes. However, a novel composite based on grafting copolymer and polyurethane was developed. It displays good properties for the preparation of 3D-scaffolds with potential uses in tissue engineering.

The impact of charcoal and soil mixtures on decomposition and soil microbial communities in boreal forest

Fire is a natural disturbance that operates as a major ecological driver in many ecosystems worldwide, and it produces charcoal which is incorporated into soil in significant quantities. Charcoal can serve as a long-term carbon (C) sink, but it is not inert, and could potentially impact native soil organic matter and decomposer micro-organisms. However, studies have shown contrasting results for how charcoal impacts the belowground subsystem, and the mechanisms involved are poorly understood, especially in pyrogenic ecosystems. We performed a laboratory experiment in which six contrasting boreal forest soil types and nine charcoal types (each from different woody plant species) were incubated for 9.5 months, both by themselves and in 50:50 mixtures for all possible soil–charcoal combinations. At harvest we measured mass loss, and for several charcoal-soil combinations, we measured microbial properties, and composition of C compounds using 13C CP-MAS nuclear magnetic resonance (NMR) spectroscopy. Overall, mixtures of charcoal and soil lost more mass than expected based on when the components were incubated separately. The magnitude of increased soil mass loss in mixtures did not differ among charcoal types, but varied among soil types, because greater mass loss occurred when soil from a site dominated with herbaceous vegetation was used, relative to other soil types. The use of NMR spectroscopy showed that enhanced mass loss in mixtures was due mainly to mass loss of soil organic matter rather than charcoal. However, mixing of charcoal and soil did not influence key decomposer microbial groups compared with expected values derived from when components were incubated alone, irrespective of charcoal and soil type. This study shows that when charcoal is incorporated into boreal forest soil (e.g., after wildfire), there is enhanced loss of total C (arising primarily from mass loss of soil organic matter), with this effect being relatively consistent across contrasting charcoal and soil types. This effect, in combination with recently documented impacts of charcoal on aboveground processes, reveals important but largely overlooked legacy effects of charcoal on forest processes that contribute to ecosystem C balance and ecosystem functioning.

In situ oligomerization of 2-(thiophen-3-yl)acetate intercalated into Zn2Al layered double hydroxide

A layered double hydroxide (LDH) with cation composition Zn2Al was intercalated with 2-(thiophen-3-yl)acetate (3-TA) monomers. To achieve in situ polymerization and/or oligomerization of the intercalated monomers, soft thermal treatments were carried out, and subsequent hybrid LDH materials were analyzed by means of several characterization techniques using powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), 13C CP–MAS nuclear magnetic resonance (NMR), electron spin resonance (EPR), scanning electron microscopy (SEM), and transmission electron microscopy (TEM), inductively coupled plasma optical emission spectroscopy (ICP–OES), and elemental analysis. PXRD analysis suggested that the intercalated monomers formed a bilayer. Thermal treatment of the hybrid LDH assembly above 120°C provokes partially the breakdown of the layered structure, generating the phase zincite. EPR results indicated that vicinal monomers (oligomerization) were bound to each other after hydrothermal or thermal treatment, leading to a polaron response characteristic of electron conductivity localized on a restricted number of thiophene-based monomer segments. Localized unpaired electrons exist in the material and interact with the 27Al nuclei of the LDH layers by superhyperfine coupling. These unpaired electrons also interact with the surface of ZnO (O2− vacancies), formed during the thermal treatments.

Solid-state NMR examination of alteration layers on nuclear waste glasses

Solid-state nuclear magnetic resonance (NMR) is a powerful tool for probing the role and significance of alteration layers in determining the kinetics for the corrosion of nuclear waste glass. NMR methods are used to probe the chemical structure of the alteration layers to elucidate information about their chemical complexity, leading to increased insight into the mechanism of altered layer formation. Two glass compositions were examined in this study: a glass preliminarily designed for nuclear waste immobilization (called AFCI) and a simplified version of this AFCI glass (which we call SA1R). Powdered glasses with controlled and known particle sizes were corroded in ASTM type I water at 90°C for periods of one and five months with a glass surface-area to solution-volume ratio of 100,000m−1. 1H–29Si cross-polarization Carr-Purcell-Meiboom-Gill (CP-CPMG) magic angle spinning (MAS) NMR, 1H–27Al CP-MAS NMR, 1H–11B CP-MAS NMR, and 1H–23Na CP-MAS NMR experiments provided isolated structural information about the alteration layers, which differ in structure from that of the pristine glass. Both glasses studied here develop alteration layers composed primarily of [IV]Si species. Aluminum is also retained in the alteration layers, perhaps facilitated by the observed increase in coordination from [IV]Al to [VI]Al, which correlates with a loss of charge balancing cations. The mechanism of increasing coordination appears to occur through an unstable [V]Al intermediate. 1H–11B CP-MAS NMR observations indicated a retention of boron in the hydrated glass layers, which has not been characterized by previous work. For the AFCI glass, secondary phase formation begins during the corrosion times considered here, and these new phases are detected within the alteration layers. We identify new phases (termed as precursor phases) as crystalline sodium metasilicates. An important finding is that simple glass compositions, while providing general trends about the formation of alteration layers, do not account for all of the various reaction products that occur in the corrosion of more complex nuclear waste glass compositions.

Organically and Silylation of Synthesis Nano- Clay-Magadiite

This paper is an investigation of the properties of covalently bonded magadiite/polyimide nanocomposites synthesized with magadiite and polyimide（PI）. Synthesized magadiite was organically modified by n-hexadecyl trimethyl-ammonium bromide (CTAB) and then grafted by γ-aminopropyltriethoxysilane (APTS) γ-glycidoxypropyltrimethoxysilane( GPS ) or γ-methacryloxy-propyltrimethoxysilane ( MPS ). XRD confirmed the formation of the CTAB-magadiite and showed that the basal spacing increased from 1.54 to 2.46 nm. Three silylating reagents, APTS ,GPS and MPS, were reacted with the CTAB- exchanged magadiite. The subsequent formation of the organic derivatives was confirmed by XRD (X-ray diffractometer), FTIR (Fourier transform infrared spectrometer), and 29Si CP-MAS NMR (Solid-state nuclear magnetic resonance ) spectra. The copolymerization of the APTS- GPS- and MPS- modified magadiite produced new layered silicate-organic compounds and each one contained covalent bonds between the interlayer spaces. This structure is dissimilar to that produced using conventional clay polymer systems in which the ionic interactions between silicates and organic modifiers are dominant.