13C Cross-polarization Magic Angle Spinning Research Articles

Dehydration of fructose over thiol– and sulfonic– modified alumina in a continuous reactor for 5–HMF production: Study of catalyst stability by NMR

In the present study, the synthesis of an organic group–modified alumina by the sol–gel method is proposed. This material has shown to have an enhanced catalytic performance with grafted organic groups and showed an improved stability. The prepared material has shown to have several OH groups and an enhanced surface acidity. The alumina acidity was improved by incorporating thiol groups by grafting method, which promotes the tautomerization of fructose to its furanose form. Furthermore, the grafting of sulfonic groups catalyzes its dehydration. The modified alumina was thermally treated up to 200 °C to improve the functional groups stability. After, this modified material was packed into a continuous reactor system, designed and built by this group, to obtain 5–hydroxymethylfurfural (5–HMF) from fructose dissolved in a single–phase solution of tetrahydrofuran (THF) and H2O (4:1 w/w). The catalytic activity of this material was evaluated by the reaction of fructose dehydration at different reaction temperatures (60, 70, 80 and 90 °C). Fructose conversion and selectivity towards 5–HMF were determined by high performance liquid chromatography (HPLC), obtaining 95% and 73% respectively for the highest temperature. The catalyst showed an efficient stability after 24 h in continuous flow at 70 °C. The loss of sulfur content was 15%, but the fructose conversion yield and the selectivity to 5–HMF after 24 h of continuous reaction did not undergo significant changes (less than 5%). The nuclear magnetic resonance (NMR) tests confirmed the presence of the thiol and sulfonic groups before and after 24 h of reaction, as well as the conservation of the same structure, demonstrating the efficient catalytic performance of the material. The catalysts were characterized by nitrogen adsorption/desorption, X–ray diffraction and infrared (IR) spectroscopy. Also, before and after use by utilizing elemental analysis and 1H–13C cross–polarization magic–angle spinning (CPMAS) and dynamic–nuclear polarization (DNP)–enhanced 1H–13C and 1H–29Si CPMAS as well as directly excited 29Si magic–angle spinning (MAS) NMR methods in solid–state.

Elucidating the internal structure and dynamics of [formula omitted]chitin by 2DPASS-MAS-NMR and spin-lattice relaxation measurements

The structure and dynamics of the second most abundant biopolymer α−chitin were studied by high resolution solid state 13C cross-polarization magic angle spinning nuclear magnetic resonance (CP-MAS-NMR) spectral analysis, 13C relaxation measurements at eight chemically different carbon sites and chemical shift anisotropy measurement by two-dimensional phase-adjusted spinning sidebands (2DPASS) magic angle spinning (MAS) solid state NMR method.13C spin-lattice relaxation time was measured by high resolution Torchia CP method. Spin-lattice relaxation rate (1/T1) of side chain carbon nuclei were remarkably high, because those nuclei possess higher degree of motional freedom. Chemical shift anisotropy parameters of eight chemically different carbon nuclei were determined by 2DPASS-MAS-NMR experiment. Large value of chemical shift anisotropy was observed for carbonyl group carbon (C7) nuclei, because of electrostatic effect, hydrogen bonding and molecular magnetic susceptibility. 13C relaxation mechanism is mainly governed by chemical shift anisotropy interaction, especially at high value of external magnetic field (11.74 T). Thus, the correlation time at different carbon sites were also calculated by using the spin-lattice relaxation times and chemical shift anisotropy values. The correlation time of side chain carbon (C8) was two orders of magnitude less than the carbonyl group carbon. These types of investigations would enlighten the correlation between the structure and dynamics of long polysaccharide chain compound.

Protaetia brevitarsis larvae can efficiently convert herbaceous and ligneous plant residues to humic acids

Utilization of the organic residues produced after crop harvesting is currently an important issue across the world. The edible insect Protaetia brevitarsis larvae can feed various organic matters. In this paper, we investigated the potential to utilize the insect to convert herbaceous and ligneous plant residues. We feed the insect larvae with maize straw and sawdust and analyzed the produced insect manure. P. brevitarsis larval was found to be able to digest both herbaceous and ligneous straw and insect manure extract shown no phytotoxicity. The mass fractions of humic acids (HAs) in the insect manure derived from maize straw and sawdust digestion were 24.37% and 14.46%, respectively. The 13C cross-polarization magic-angle spinning nuclear magnetic resonance (CP–MAS NMR) spectra data indicated that the HAs in the insect manure were similar to those found in the soil. These data suggested that P. brevitarsis larvae can be used to convert agricultural residues and produce organic fertilizers.

Chemical nature of soil organic carbon under different long-term fertilization regimes is coupled with changes in the bacterial community composition in a Calcaric Fluvisol

Fertilization is an important factor influencing the chemical structure of soil organic carbon (SOC) and soil microbial communities; however, whether any connection exists between the two under different fertilization regimes remains unclear. Soils from a 27-year field experiment were used to explore potential associations between SOC functional groups and specific bacterial taxa, using quantitative multiple cross-polarization magic-angle spinning 13C nuclear magnetic resonance and 16S rRNA gene sequencing. Treatments included balanced fertilization with organic materials (OM) and with nitrogen (N), phosphorus (P), and potassium (K) mineral fertilizers (NPK); unbalanced fertilization without one of the major elements (NP, PK, or NK); and an unamended control. These treatments were divided into four distinct groups, namely OM, NPK, NP plus PK, and NK plus control, according to their bacterial community composition and SOC chemical structure. Soil total P, available P, and SOC contents were the major determinants of bacterial community composition after long-term fertilization. Compared to NPK, the OM treatment generated a higher aromatic C–O and OCH3 and lower alkyl C and OCH abundance, which were associated with the enhanced abundance of members of the Acidobacteria subgroups 6 and 5, Cytophagaceae, Chitinophagaceae, and Bacillus sp.; NP plus PK treatments resulted in a higher OCH and lower aromatic C–C abundance, which showed a close association with the enrichment of unclassified Chloracidobacteria, Syntrophobacteraceae, and Anaerolineae and depletion of Bacillales; and NK plus control treatments resulted in a higher abundance of aromatic C–C, which was associated with the enhanced abundance of Bacillales. Our results indicate that different fertilization regimes changed the SOC chemical structure and bacterial community composition in different patterns. The results also suggest that fertilization-induced variations in SOC chemical structure were strongly associated with shifts in specific microbial taxa which, in turn, may be affected by changes in soil properties.

Template-free synthesis of tunable hollow microspheres of aniline and aminocarbazole copolymers emitting colorful fluorescence for ultrasensitive sensors

Conductive and fluorescent hollow micro/nanospheres have attracted great attention owing to their potential applications such as environmental clean-up, energy storage, sensors, and medical diagnosis. We report novel, tunable, and uniform hollow microspheres of conjugated poly(aniline-co-3-amino-9-ethyl-carbazole) (PAC) copolymer synthesized by a template-free method, namely a simple chemical oxidative copolymerization of aniline and 3-amino-9-ethyl-carbazole. The molecular structure of the copolymers has been systematically characterized by UV–vis, ATR-IR, Raman, and solid-state 13C cross-polarization magic angle spinning NMR spectroscopies. The particle size and properties including dispersibility, thermostability, electrical conductivity, fluorescence emission and its sensitive quenching of PAC hollow microspheres can be significantly controlled by simply optimizing feed comonomer ratios and reaction parameters such as acidic media and oxidants used. The formation mechanism of PAC hollow microspheres and their sensitively and selectively sensing properties toward nitro-based explosives and Cu(II) ions with the limit of detection down to 5 μM and 5 nM are demonstrated, respectively. In particular, the limit of detection for Cu2+ is superior as compared to literature reports.

Millimeter-Size Spherical Polyurea Aerogel Beads with Narrow Size Distribution.

We report the room temperature synthesis of spherical millimeter-size polyurea (PUA) aerogel beads. Wet-gels of said beads were obtained by dripping a propylene carbonate solution of an aliphatic triisocyanate based on isocyanurate nodes into a mixture of ethylenediamine and heavy mineral oil. Drying the resulting wet spherical gels with supercritical fluid (SCF) CO2 afforded spherical aerogel beads with a mean diameter of 2.7 mm, and a narrow size distribution (full width at half maximum: 0.4 mm). Spherical PUA aerogel beads had low density (0.166 ± 0.001 g cm–3), high porosity (87% v/v) and high surface area (197 m2 g–1). IR, 1H magic angle spinning (MAS) and 13C cross-polarization magic angle spinning (CPMAS) NMR showed the characteristic peaks of urea and the isocyanurate ring. Scanning electron microscopy (SEM) showed the presence of a thin, yet porous skin on the surface of the beads with a different (denser) morphology than their interior. The synthetic method shown here is simple, cost-efficient and suitable for large-scale production of PUA aerogel beads.

Synthesis of Nitrogen-Rich Polymers by Click Polymerization Reaction and Gas Sorption Property.

Microporous organic polymers (MOPs) are promising materials for gas sorption because of their intrinsic and permanent porosity, designable framework, and low density. The introduction of nitrogen-rich building block in MOPs will greatly enhance the gas sorption capacity. Here, we report the synthesis of MOPs from the 2,4,6-tris(4-ethynylphenyl)-1,3,5-triazine unit and aromatic azides linkers by click polymerization reaction. Fourier transform infrared (FTIR) and solid-state 13C CP-MAS (Cross Polarization-Magic Angle Spinning) NMR confirm the formation of the polymers. CMOP-1 and CMOP-2 exhibit microporous networks with a BET (Brunauer–Emmett–Teller) surface area of 431 m2·g−1 and 406 m2·g−1 and a narrow pore size distribution under 1.2 nm. Gas sorption isotherms including CO2 and H2 were measured. CMOP-1 stores a superior CO2 level of 1.85 mmol·g−1 at 273 K/1.0 bar, and an H2 uptake of up to 2.94 mmol·g−1 at 77 K/1.0 bar, while CMOP-2, with its smaller surface area, shows a lower CO2 adsorption capacity of 1.64 mmol·g−1 and an H2 uptake of 2.48 mmol·g−1. In addition, I2 vapor adsorption was tested at 353 K. CMOP-1 shows a higher gravimetric load of 160 wt%. Despite the moderate surface area, the CMOPs display excellent sorption ability for CO2 and I2 due to the nitrogen-rich content in the polymers.

Fungistatic Activity of Multiorigin Humic Acids in Relation to Their Chemical Structure.

Humic acid (HA) has an inhibitory effect on phytopathogenic fungi, but the structure-activity relationship remains unclear. HAs were extracted from 14 different materials, and their fungistatic activities and elemental C, N, S, and O contents were measured. Cross-polarization magic-angle spinning 13C nuclear magnetic resonance (CPMAS 13C NMR) was used to measure the organic carbon composition. The results showed that all HAs suppressed phytopathogenic fungi growth, with Yunnan lignite HAs showing the highest inhibition (85.3%) against Physalospora piricola. The soil and compost HA aromaticity (ARO) was <50%, except for black soil HAs, while the ARO of all coal HAs was >60%. The ARO of meadow and moss peat HAs was <50%, while the ARO of woody peat HAs was 50.61%. Mantel test and redundancy analysis (RDA) were applied to evaluate the structure-activity relationship. The Mantel test revealed that the N, S, O, N/O, carbonyl C, aromatic C-O, and anomeric C contents were significantly correlated with fungistatic activity. The RDA analysis showed that the S content was positively correlated with fungistatic activity, while the O content was negatively correlated. The carbonyl C content had a positive correlation with fungistatic activity, while the anomeric C and aromatic C-O content had a negative correlation. A high S content and an active composition (carbonyl C) in HAs would lead to a high degree of fungistatic activity. Phytotoxicity test indicated all HAs were beneficial to plant growth. This work identified the basic properties of HAs from various raw materials that control their fungistatic activities.

Facile preparation of an alternating copolymer-based high molecular shape-selective organic phase for reversed-phase liquid chromatography

The synthesis of a new alternating copolymer-grafted silica phase is described for the separation of shape-constrained isomers of polycyclic aromatic hydrocarbons (PAHs) and tocopherols in reversed-phase high-performance liquid chromatography (RP-HPLC). Telomerization of the monomers (octadecyl acrylate and N-methylmaleimide) was carried out with a silane coupling agent; 3-mercaptopropyltrimethoxysilane (MPS), and the telomer (T) was grafted onto porous silica surface to prepare the alternating copolymer-grafted silica phase (Sil-alt-T). The new hybrid material was characterized by elemental analyses, diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, and solid-state 13C and 29Si cross-polarization magic-angle spinning (CP/MAS) NMR spectroscopy. The results of 13C CP/MAS NMR demonstrated that the alkyl chains of the grafted polymers in Sil-alt-T remained disordered, amorphous, and mobile represented by gauche conformational form. Separation abilities and molecular-shape selectivities of the prepared organic phase were evaluated by the separation of PAHs isomers and Standard Reference Material 869b, Column Selectivity Test Mixture for Liquid Chromatography, respectively and compared with commercially available octadecylsilylated silica (ODS) and C30 columns as well as previously reported alternating copolymer-based column. The effectiveness of this phase is also demonstrated by the separation of tocopherol isomers. Oriented functional groups along the polymer main chains and cavity formations are investigated to be the driving force for better separation with multiple-interactions with the solutes. One of the advantages of the Sil-alt-T phase to that of the previously reported phase is the synthesis of the telomer first and then immobilized onto silica surface. In this case, the telomer was characterized easily with simple spectroscopic techniques and the molecular mass and polydispersity index of the telomer were determined by size exclusion chromatography (SEC) before grafting onto silica surface. Moreover, both of the monomers were commercially available. Therefore, the technique of preparation was very facile and better separation was achieved with the Sil-alt-T phase compared to the ODS, C30 and other previously reported alternating copolymer-based columns.

Structural Elucidation of Amorphous Photocatalytic Polymers from Dynamic Nuclear Polarization Enhanced Solid State NMR

Dynamic nuclear polarization (DNP) solid-state nuclear magnetic resonance (NMR) offers a recent approach to dramatically enhance NMR signals and has enabled detailed structural information to be obtained in a series of amorphous photocatalytic copolymers of alternating pyrene and benzene monomer units, the structures of which cannot be reliably established by other spectroscopic or analytical techniques. Large 13C cross-polarization (CP) magic angle spinning (MAS) signal enhancements were obtained at high magnetic fields (9.4–14.1 T) and low temperature (110–120 K), permitting the acquisition of a 13C INADEQUATE spectrum at natural abundance and facilitating complete spectral assignments, including when small amounts of specific monomers are present. The high 13C signal-to-noise ratios obtained are harnessed to record quantitative multiple contact CP NMR data, used to determine the polymers’ composition. This correlates well with the putative pyrene:benzene stoichiometry from the monomer feed ratio, enabl...

Silane-based hyper-cross-linked porous polymers and their applications in gas storage and water treatment

A series of novel silane-based hyper-cross-linked porous polymers was prepared through the Friedel–Crafts alkylation reaction of dimethyldiphenylsilane as the monomer and formaldehyde dimethyl acetal as the external cross-linker. The structures of the polymers were confirmed by FTIR and solid-state cross-polarization magic-angle spinning 13C NMR. We investigated the porous polymers with different ratios of dimethyldiphenylsilane to formaldehyde dimethyl acetal. Porous properties were determined by nitrogen, carbon dioxide and hydrogen adsorptions. The results revealed that the porous materials possessed surface areas from 742 to 1205 m2 g−1 with the increasing amount of formaldehyde dimethyl acetal. Moreover, this material exhibited high thermal stabilities, good CO2 capture, and H2 storage capacities. The material was also used as adsorbent for organic dyes in aqueous solution and showed an excellent adsorption capacity of 952 mg g−1 for Congo red dye. These results suggest that the silane-based hyper-cross-linked porous polymers are promising materials for CO2 capture, H2 storage, and water treatment.

Hydrophobic Calcium Carbonate for Cement Surface

This report describes a novel way to generate a highly effective hydrophobic cement surface via a carbonation route using sodium stearate. Carbonation reaction was carried out at different temperatures to investigate the hydrophobicity and morphology of the calcium carbonate formed with this process. With increasing temperatures, the particles changed from irregular shapes to more uniform rod-like structures and then aggregated to form a plate-like formation. The contact angle against water was found to increase with increasing temperature; after 90 °C there was no further increase. The maximum contact angle of 129° was obtained at the temperature of 60 °C. It was also found that carbonation increased the micro hardness of the cement material. The micro hardness was found to be dependent on the morphology of the CaCO3 particles. The rod like structures which caused increased mineral filler produced a material with enhanced strength. The 13C cross polarization magic-angle spinning NMR spectra gave plausible explanation of the interaction of organic-inorganic moieties.

Aerosol Cross-Linked Crown Ether Diols Melded with Poly(vinyl alcohol) as Specialized Microfibrous Li+ Adsorbents.

Crown ether (CE)-based Li+ adsorbent microfibers (MFs) were successfully fabricated through a combined use of CE diols, electrospinning, and aerosol cross-linking. The 14- to 16-membered CEs, with varied ring subunits and cavity dimensions, have two hydroxyl groups for covalent attachments to poly(vinyl alcohol) (PVA) as the chosen matrix. The CE diols were blended with PVA and transformed into microfibers via electrospinning, a highly effective technique in minimizing CE loss during MF fabrication. Subsequent aerosol glutaraldehyde (GA) cross-linking of the electrospun CE/PVA MFs stabilized the adsorbents in water. The aerosol technique is highly effective in cross-linking the MFs at short time (5 h) with minimal volume requirement of GA solution (2.4 mL g-1 MF). GA cross-linking alleviated CE leakage from the fibers as the CEs were securely attached with PVA through covalent CE-GA-PVA linkages. Three types of CE/PVA MFs were fabricated and characterized through Fourier transform infrared-attenuated total reflection, 13C cross-polarization magic angle spinning NMR, field emission scanning electron microscope, N2 adsorption/desorption, and universal testing machine. The MFs exhibited pseudo-second-order rate and Langmuir-type Li+ adsorption. At their saturated states, the MFs were able to use 90-99% CEs for 1:1 Li+ complexation, suggesting favorability of their microfibrous structures for CE accessibility to Li+. The MFs were highly Li+-selective in seawater. Neopentyl-bearing CE was most effective in blocking larger monovalents Na+ and K+, whereas the dibenzo CE was best in discriminating divalents Mg2+ and Ca2+. Experimental selectivity trends concur with the reaction enthalpies from density functional theory calculations, confirming the influence of CE structures and cavity dimensions in their "size-match" Li+ selectivity.

Experimental nuclear magnetic resonance spectral assignments, 1H/13C GIAO calculations, molecular structure and molecular resonance states of 4-Methyl-1H-Indazole-5-Boronic acid

Some molecules such as 4-Methyl-1H-Indazole-5-Boronic Acid (4M1HI5BA) have different resonance states under different temperatures. Henceforth, it is difficult to characterize these type of molecules. Since, in general one or more hydrogen atoms move through the molecule and molecular symmetry changes. The possible 3 different resonance forms and molecular structure of 4-Methyl-1H-Indazole-5-Boronic Acid (4M1HI5BA) molecule have been studied experimentally using nuclear magnetic resonance (NMR) spectroscopy. 13C cross-polarization magic-angle spinning, 11B, 1H, 13C, COSY, HMBC, NOESY, T1 relaxation time NMR spectra of 4M1HI5BA molecule have been reported. Moreover, 1H NMR spectra were obtained in different solvents and under variable temperatures. Results from experimental datas showed that title molecule has three different resonance states and these resonance states change with different temperature. In addition, 1H and 13C chemical shift values were calculated by GIAO method and computed values were compared with experimentally obtained values. There are good agreement between experimental and theoretical chemical shift values.

Racemic crystals of trolox derivatives compared to their chiral counterparts: Structural studies using solid-state NMR, DFT calculations and X-ray diffraction

Trolox C (6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid) is a water-soluble vitamin E analogue that is available in enantiomeric forms R or S. Enantiomerically pure Trolox 1, its derivatives 2, 3 (R and S enantiomers) and racemic forms 1–3 were studied using solid-state 13C cross-polarisation (CP) magic angle spinning (MAS) NMR (13C CPMAS NMR). Gauge-including projector-augmented wave density functional theory (GIPAW DFT) calculations of the shielding constants supported the assignment of 13C resonances in the solid-state NMR spectra. For the 13C CPMAS NMR spectra of 1, resonances of pure enantiomers were significantly broader than those of the racemic R/S form. In order to explain these effects, five of the available crystal structures were analysed (1R/S, 3R/S, 2S and the newly measured 2R/S and 3S). Cyclic dimers with one R and one S enantiomer linked by two OHOC2b hydrogen bonds were formed in 1R/S. Similar hydrogen-bonded dimers were present in 3S but not in 3R/S, in which interactions are water-mediated. A comparison of X-ray diffraction, CPMAS NMR data and the DFT GIPAW calculations of racemic forms and pure enantiomers was conducted for the first time. Our results, particularly the solid-state NMR data, were discussed in relation to Wallach's rule, that the racemic crystal appears as more ordered than its chiral counterpart.

Preparation of ibuprofen/hydroxypropyl-γ-cyclodextrin inclusion complexes using supercritical CO2-assisted spray drying

Herein we report the formation of dry powder complexes of ibuprofen (IBU) and hydroxypropyl-γ-cyclodextrin (HP-γ-CyD) by supercritical CO2-assisted spray-drying (SASD). SASD of HP-γ-CyD alone, IBU/HP-γ-CyD, as well as the physical mixture were prepared and characterized using attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), X-ray diffraction (XRD), ultra-violet spectroscopy (UV), 13C cross-polarization magic angle spinning nuclear magnetic resonance (13C CP/MAS NMR), differential scanning calorimetry (DSC) and morphological studies. Results indicate the successful formation of amorphous inclusion complexes. SASD is a clean technology, suitable for processing thermolabile APIs, thus an interesting alternative to conventional spray drying and other methods of CyD solid complex formation.

Highly Efficient and Selective Recovery of Rare Earth Elements Using Mesoporous Silica Functionalized by Preorganized Chelating Ligands.

Separating the rare earth elements (REEs) in an economically and environmentally sustainable manner is one of the most pressing technological issues of our time. Herein, a series of preorganized bidentate phthaloyl diamide (PA) ligands was synthesized and grafted on large-pore 3-dimensional (3-D) KIT-6 mesoporous silica. The synthesized sorbents were fully characterized by N2 physisorption, FT-IR, 13C cross-polarization (CP) and 29Si magic-angle spinning (MAS) NMR, thermogravimetric analysis-differential thermal analysis (TGA-DTA), and elemental analysis. Overall, the grafting of PA-type ligands was found to have significantly improved the extraction performance of the sorbents toward REEs compared to the homogeneous analogues. Specifically, the sorbent modified with the 1,2-phtaloyl ligand shows high preference over lanthanides with smaller size, whereas the 1,3-phtaloyl ligand exhibits selectivity toward elements with larger ion radius. This selectivity drastically changes from the homogeneous models that do not exhibit any selectivity. The possibility of regenerating the mesoporous sorbents through simple stripping using oxalate salt is demonstrated over up to 10 cycles with no significant loss in REEs extraction capacity, suggesting adequate chemical and structural stability of the new sorbent materials. Despite the complex ion matrix and high ionic composition, the exposure of industrial mining deposits containing REEs to the sorbents results in selective recovery of target REEs.

Structure of melanins from the fungi Ochroconis lascauxensis and Ochroconis anomala contaminating rock art in the Lascaux Cave

Two novel species of the fungal genus Ochroconis, O. lascauxensis and O. anomala have been isolated from the walls of the Lascaux Cave, France. The interest in these fungi and their melanins lies in the formation of black stains on the walls and rock art which threatens the integrity of the paintings. Here we report solid-state cross polarization magic-angle spinning 13C and 15N nuclear magnetic resonance (NMR) spectroscopy and surface-enhanced Raman spectroscopy (SERS) of the melanins extracted from the mycelia of O. lascauxensis and O. anomala in order to known their chemical structure. The melanins from these two species were compared with those from other fungi. The melanins from the Ochroconis species have similar SERS and 13C and 15N NMR spectra. Their chemical structures as suggested by the data are not related to 3,4-dihydroxyphenylalanine, 5,6-dihydroxyindole or 1,8-dihydroxynaphthalene precursors and likely the building blocks from the melanins have to be based on other phenols that react with the N-terminal amino acid of proteins. The analytical pyrolysis of the acid hydrolysed melanin from O. lascauxensis supports this assumption.

Instrumental analyses of nanostructures and interactions with water molecules of biomass constituents of Japanese cypress

Nanostructures consisting of the biomass constituents of the denatured Japanese cypress (Chamaecyparis obtusa) were examined by instrumental analyses at multiple hierarchical levels. Delignification with NaClO2 solution smoothly proceeded to reveal a distorted cell by scanning electron microscopy; however, a trace amount of lignin still remained in the delignified sample according to attenuated total reflection infrared spectra (ATR-IR). Although hemicellulose could be removed by a treatment with NaOH solution, thermogravimetric analysis and 13C cross-polarization/magic angle spinning (CP-MAS) NMR showed a certain amount of hemicellulose remaining. Reaction of the delignified sample with NaOH solution produced a shrunken cell wall that consisted of cellulose with small amounts of lignin and hemicellulose, which were detected by ATR-IR and 13C CP-MAS NMR, respectively. These samples from which lignin and/or hemicellulose had been removed easily released water molecules, producing a decrease in the 1H signal intensity and longer 1H spin–lattice relaxation time (T1H) values in variable temperature 1H MAS NMR. The T1H values provided information about nano-scale molecular interaction difficult to obtain by other instrumental analyses and they greatly changed depending on the water content and ratio of the biomass constituents. The spin–lattice relaxation of all samples occurred via water molecules under humid conditions that provided sufficient water. Under heat-dried conditions, the spin–lattice relaxation mainly occurred via lignin for the samples with lignin remaining while it occurred via cellulose/hemicellulose for the samples without lignin. The variable temperature T1H analysis indicated that predominant spin–lattice relaxation route via lignin was caused by higher molecular mobility of lignin-containing samples compared with lignin-free samples.

Comparative Structural Characterization of Spiral Dextrin Inclusion Complexes with Vitamin E or Soy Isoflavone

In this study, the preparation and structural properties of spiral dextrin (SD)/vitamin E and SD/soy isoflavone inclusion complexes were studied. SD was obtained from debranched normal maize starch using isoamylases. After fractionation using a novel method of gradient ethanol precipitation, SD was separated into different fractions, among which SD-40 was found to be the optimal host molecule to prepare SD inclusion complexes with vitamin E or soy isoflavone. X-ray diffraction (XRD) and 13C cross-polarization magic angle spinning nuclear magnetic resonance (NMR) suggested that the crystalline structures of SD-40/vitamin E and SD-40/soy isoflavone were V6II and V6III types, respectively. Small-angle X-ray scattering revealed that the SD-40/vitamin E inclusion complex formed a tighter and more compact crystallite than the SD-40/soy isoflavone inclusion complex. Furthermore, the connection structures of inclusion complexes were investigated by two-dimensional nuclear Overhauser effect spectroscopy NMR, indicating that part of vitamin E with an alkyl chain was encapsulated in the helix cavity of SD-40, whereas the aromatic ring B of the soy isoflavone molecule was complexed by the helix cavity and screw of SD.