13C 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.

Synthesis and application of cationised cellulose for removal of Cr(VI) from acid mine-drainage contaminated water

Background: Acid mine drainage (AMD) leads to contamination of surface and ground water by high levels of toxic metals including chromium. In many cases, these waters are sources of drinking water for communities, and treatment is therefore required before consumption to prevent negative health effects. Methods: Cationised hemp cellulose was prepared by etherification with two quaternary ammonium salts: 3-chloro-2-hydroxypropyl trimethyl ammonium chloride (CHPTAC) and glycidyltrimethylammonium chloride (GTMAC) and examined for (i) the efficiency of Cr(VI) removal under acid mine-drainage (AMD) conditions, and (ii) antibacterial activity. Adsorbents were characterised by electron microscopy, Fourier transform infrared (FTIR), CP-MAS 13C nuclear magnetic resonance (NMR) spectroscopy, elemental composition and surface charge. Results: FTIR and solid state 13C NMR confirmed the introduction of quaternary ammonium moieties on cellulose. 13C NMR also showed that cationisation decreased the degree of crystallisation and lateral dimensions of cellulose fibrils. Nevertheless, 47 % - 72 % of Cr(VI) ions were removed from solutions at pH 4, by 0.1 g of CHPTAC and GTMAC-cationised cellulose, respectively. Adsorption kinetics followed the pseudo-second order model and isotherms were best described by the Freundlich and Dubinin-Radushkevich models. When GTMAC-modified cellulose was applied to AMD contaminated water (pH 2.7); however, Cr(VI) removal decreased to 22% likely due to competition from Al and Fe ions. Cationised materials displayed considerable antibacterial effects, reducing the viability of Escherichia coli by up to 45 % after just 3 hours of exposure. Conclusions: Together, these results suggest that cationised cellulose can be applied in the treatment of Cr(VI)-contaminated mine water particularly if pre-treatments to reduce Fe and Al concentrations are applied.

Synthesis and application of cationised cellulose for removal of Cr(VI) from acid mine-drainage contaminated water.

Background: Acid mine drainage (AMD) leads to contamination of surface and ground water by high levels of toxic metals including chromium. In many cases, these waters are sources of drinking water for communities, and treatment is therefore required before consumption to prevent negative health effects. Methods: Cationised hemp cellulose was prepared by etherification with two quaternary ammonium salts: 3-chloro-2-hydroxypropyl trimethyl ammonium chloride (CHPTAC) and glycidyltrimethylammonium chloride (GTMAC) and examined for (i) the efficiency of Cr(VI) removal under acid mine-drainage (AMD) conditions, and (ii) antibacterial activity. Adsorbents were characterised by electron microscopy, Fourier transform infrared (FTIR), CP-MAS 13C nuclear magnetic resonance (NMR) spectroscopy, elemental composition and surface charge. Results: FTIR and solid state 13C NMR confirmed the introduction of quaternary ammonium moieties on cellulose. 13C NMR also showed that cationisation decreased the degree of crystallisation and lateral dimensions of cellulose fibrils. Nevertheless, 47 % - 72 % of Cr(VI) ions were removed from solutions at pH 4, by 0.1 g of CHPTAC and GTMAC-cationised cellulose, respectively. Adsorption kinetics followed the pseudo-second order model and isotherms were best described by the Freundlich and Dubinin-Radushkevich models. When GTMAC-modified cellulose was applied to AMD contaminated water (pH 2.7); however, Cr(VI) removal decreased to 22% likely due to competition from Al and Fe ions. Cationised materials displayed considerable antibacterial effects, reducing the viability of Escherichia coli by up to 45 % after just 3 hours of exposure. Conclusions: Together, these results suggest that cationised cellulose can be applied in the treatment of Cr(VI)-contaminated mine water particularly if pre-treatments to reduce Fe and Al concentrations are applied.

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.

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.

Comparison of soil organic carbon speciation using C NEXAFS and CPMAS 13C NMR spectroscopy

We compared synchrotron-based C near-edge X-ray absorption fine structure (NEXAFS) and CPMAS 13C nuclear magnetic resonance (NMR) spectroscopy with respect to their precision and accuracy to quantify different organic carbon (OC) species in defined mixtures of soil organic matter source compounds. We also used both methods to quantify different OC species in organic surface horizons of a Histic Leptosol as well as in mineral topsoil and subsoil horizons of two soils with different parent material, stage of pedogenesis, and OC content (Cambisol: 15–30 OC mgg−1, Podzol: 0.9–7 OC mgg−1). CPMAS 13C NMR spectroscopy was more accurate and precise (mean recovery of different C functional groups 96–103%) than C NEXAFS spectroscopy (mean recovery 92–113%). For organic surface and topsoil samples, NMR spectroscopy consistently yielded larger O-alkyl C percentages and smaller alkyl C percentages than C NEXAFS spectroscopy. For the Cambisol subsoil samples both methods performed well and showed similar C speciation results. NEXAFS spectroscopy yielded excellent spectra with a high signal-to-noise ratio also for OC-poor Podzol subsoil samples, whereas this was not the case for CPMAS 13C NMR spectroscopy even after sample treatment with HF. Our results confirm the analytical power of CPMAS 13C NMR spectroscopy for a reliable quantitative OC speciation in soils with >10mgOCg−1. Moreover, they highlight the potential of synchrotron-based C NEXAFS spectroscopy as fast, non-invasive method to semi-quantify different C functional groups in soils with low C content (0.9–10mgg−1).

Aggregation controls the stability of lignin and lipids in clay-sized particulate and mineral associated organic matter

Physical separation of soil into different soil organic matter (SOM) fractions is widely used to identify organic carbon pools that are differently stabilized and have distinct chemical composition. However, the mechanisms underlying these differences in stability and chemical composition are only partly understood. To provide new insights into the stabilization of different chemical compound classes in physically-separated SOM fractions, we assessed shifts in the biomolecular composition of bulk soils and individual particle size fractions that were incubated in the laboratory for 345 days. After the incubation, also the incubated bulk soil was fractionated. The chemical composition of organic matter in bulk soils and fractions was characterized by 13C-CPMAS nuclear magnetic resonance spectroscopy and sequential chemical extraction followed by GC/MS measurements. Plant-derived lipids and lignin were abundant in particulate organic matter (POM) fractions of sand-, silt-, and clay-size and the mineral-bound, clay-sized organic matter. These results indicate that recent conceptualizations of SOM stabilization probably understate the contribution of plant-derived organic matter to stable SOM pools. Although our data indicate that inherent recalcitrance could be important in soils with limited aggregation, organo-mineral interactions and aggregation were responsible for long-term SOM stabilization. In particular, we observed consistently higher concentrations of plant-derived lipids in POM fractions that were incubated individually, where aggregates were disrupted, as compared to those incubated as bulk soil, where aggregates stayed intact. This finding emphasizes the importance of aggregation for the stabilization of less ‘recalcitrant’ biomolecules in the POM fractions. Because also the abundance of lipids and lignin in clay-sized, mineral-associated SOM was substantially influenced by aggregation, the bioavailability of mineral-associated SOM likely increases after the destruction of intact soil structures.

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.

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.

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.

Humic acids as proxies for assessing different Mediterranean forest soils signatures using solid-state CPMAS 13C NMR spectroscopy

Humic acids (HAs) of four representative forest soils profiles from Central Spain (two with different vegetation – pine and oak – but same parent material – granitie, and two with same vegetation – holm oak – but different parent material – granite and limestone) were investigated by solid-state cross polarization with magic angle spinning 13C nuclear magnetic resonance (NMR) spectroscopy. The objectives included the investigation of the impact of different forest properties on HA composition, assessing how the structural characteristics of the HA vary with soil depth, and evaluating the role of HA as surrogates for mapping the different forest soils signatures using structural data derived from 13C NMR spectroscopy. On average, alkyl C is the dominant C constituent (38–48% of the total NMR peak area) in all HA samples, followed by aromatic (12–22%) and O-alkyl C (12–19%), and finally carboxyl C (7.0–10%). The NMR data also indicated that HA composition is likely to be differently affected by the soil physico-chemical properties and type of forest vegetation. The structural characteristics of the HA from soil under oak did not differ broadly downward in the profile, whereas soil HA under pine forest exhibits a somewhat higher recalcitrant nature as a consequence of a higher degree of decomposition. The soil HA from holm oak forests differed from the other two forest soils, exhibiting a progressive decomposition of the alkyl C structures with increasing depth, while the carbohydrate-like indicator (O-alkyl C) is apparently being protected from mineralization in the horizons below the ground level. Overall, these differences in soil HA NMR signatures are an important diagnostic tool for understanding the role of different soil environmental factors on the structural composition of HA from Mediterranean forest soils.

Terephthalaldehyde- and isophthalaldehyde-based polyspiroacetals

Condensations of polyhydroxyl monomers with terephthalaldehyde or isophthalaldehyde give the corresponding polyspiroacetals. The effects of various dialdehydes and multihydroxy monomers on the properties of the resulting polymer have been examined. Model compounds were synthesized by the condensation of multihydroxy monomers with benzaldehyde. The model compounds and polymers were characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance (NMR), thermogravimetric analysis and differential scanning calorimetry. The proposed polymer structure is supported by the solid-state CPMAS 13C NMR spectrum of the model compound. The synthesized polyspiroacetals are thermally stable, have a high degree of chemical stability and are soluble in hexafluoroisopropanol. Condensations of polyhydroxyl monomers with terephthalaldehyde and isophthalaldehyde in the presence of acid catalyst give polyspiroacetals. Model compounds have been synthesized by the condensation of multihydroxyl monomers with benzaldehyde. The effects of different dialdehyde and multihydroxy monomer on polymer properties have been examined. These polymers are found to be chemically and thermally stable.

Spectroscopic characterization of the exopolysaccharide of Xanthomonas axonopodis pv. citri in Cu2+ resistance mechanism

We analyzed the role of exopolysaccharide in the Xanthomonas axonopodis pv. citri (Xac) Cu2+ resistance mechanism by Fourier transform infrared (FTIR), electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) spectroscopies. The FTIR data show that cells cultivated in the presence of 0.2 mmol L-1 of CuSO4 produce larger amounts of pyruvated exopolissacharide (EPS) than the ones cultivated in its absence. The EPR data indicate that the amount of Cu2+ decreases with cultivation time. The 13C-CPMAS NMR data also show the complexation of Cu2+ ions to the EPS. The results demonstrate that EPS plays an important role in Xac Cu2+ protection. Both capsular and slime EPS act as an initial protection mechanism, binding free Cu2+ ions, reducing their diffusion and their active transport to the cytoplasm. Cu2+ also induces the production of a highly pyruvated negative EPS, increasing its capture and binding capacity.

Synthesis and solid-state NMR characterization of cubic mesoporous silica SBA-1 functionalized with sulfonic acid groups

Well-ordered cubic mesoporous silicas SBA-1 functionalized with sulfonic acid groups have been synthesized through in situ oxidation of mercaptopropyl groups with H2O2 via co-condensation of tetraethoxysilane (TEOS) and 3-mercaptopropyltrimethoxysilane (MPTMS) templated by cetyltriethylammonium bromide (CTEABr) under strong acidic conditions. Various synthesis parameters such as the amounts of H2O2 and MPTMS on the structural ordering of the resultant materials were systematically investigated. The materials thus obtained were characterized by a variety of techniques including powder X-ray diffraction (XRD), multinuclear solid-state Nuclear Magnetic Resonance (NMR) spectroscopy, 29Si{1H} 2D HETCOR (heteronuclear correlation) NMR spectroscopy, thermogravimetric analysis (TGA), and nitrogen sorption measurements. By using 13C CPMAS NMR technique, the status of the incorporated thiol groups and their transformation to sulfonic acid groups can be monitored and, as an extension, to define the optimum conditions to be used for the oxidation reaction to be quantitative. In particular, 29Si{1H} 2D HETCOR NMR revealed that the protons in sulfonic acid groups are in close proximity to the silanol Q3 species, but not close enough to form a hydrogen bond.

Biomimetic Apatite Mineralization Mechanisms of Mesoporous Bioactive Glasses as Probed by Multinuclear 31P, 29Si, 23Na and 13C Solid-State NMR

An array of magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy experiments is applied to explore the surface reactions of a mesoporous bioactive glass (MBG) of composition Ca0.10Si0.85P0.04O1.90 when subjected to a simulated body fluid (SBF) for variable intervals. Powder X-ray diffraction and 31P NMR techniques are employed to quantitatively monitor the formation of an initially amorphous calcium phosphate surface layer and its subsequent crystallization into hydroxycarbonate apatite (HCA). Prior to the onset of HCA formation, 1H → 29Si cross-polarization (CP) NMR evidence dissolution of calcium ions; a slightly increased connectivity of the speciation of silicate ions is observed at the MBG surface over 1 week of SBF exposure. The incorporation of carbonate and sodium ions into the bioactive orthophosphate surface layer is explored by 1H → 13C CPMAS and 23Na NMR, respectively. We discuss similarities and distinctions in composition−bioactivity relationships established for traditio...

Characterization of Acacia mangium polyflavonoid tannins by MALDI-TOF mass spectrometry and CP-MAS 13C NMR

The MALDI-TOF mass spectrometry (MS) and solid state CP-MAS 13C Nuclear Magnetic Resonance (NMR) spectroscopic technique were introduced to characterize Acacia mangium tannin (condensed tannins). The MALDI-TOF MS illustrated a series of peaks corresponding to oligomers of condensed tannins of up to 11 flavonoid units (3200 Da). A. mangium condensed tannins were found to consist predominantly of prorobinetinidin combined with profisetinidin and prodelphinidin. Both the MALDI-TOF mass spectra and the solid state CP-MAS 13C NMR indicated that the A. mangium tannins obtained from Kudat, had an almost completely linear structure; In addition, Lembah Beringin, consist of “angular” polymer structure; and Tawau, has included “twice-angular” polymer structures present in oligomers type of up to 7 flavonoid units. The high degree of polymerization of linear, angular type, twice-angular structures and longer oligomer (3200 Da) chains have not been observed in previous studies of condensed tannins. The spectra also indicated that A. mangium tannins are more heavily branched and have higher degree of polymerization (>7.0) compared to commercial mimosa (A. mearnsii) tannin (4.9). Because tannins are phenolic, it was expected that they can be used to replace phenol–formaldehyde (PF) adhesives.