Cross-Polarization Magic Angle Spinning Carbon-13 Research Articles

Direct oxidation of alcohols to carboxylic acids using simple and economical Pd@Glu-HTC catalyst: Practical and scalable approach towards biomass based value added chemicals

Sustainable catalytic transformation of bio-based alcohols to high value-added fine chemicals is an important topic of research. This work described preparation of simple and economical Pd@Glu-HTC catalyst from biomass derived low cost d-glucose. Hydrothermal carbonization of glucose was carried out in first step to synthesize Glu-HTC support in a simpler, greener, economical and efficient manner followed by incorporation of palladium metal on surface of the catalyst in second step. The catalyst was characterized using techniques such as Fourier Transform Infrared Spectroscopy (FT-IR), Solid-state Cross-Polarization Magic Angle Spinning Carbon-13 (13C CPMAS), Energy-dispersive X-ray spectroscopy (EDAX), Powder X-ray diffraction (P-XRD), X-ray photoelectron spectroscopy (XPS), Thermogravimetric/Differential Thermal Analyzer (TG-DTA), Field emission scanning electron microscopy (FE-SEM) and High-resolution transmission electron microscopy (HR-TEM). The catalyst was evaluated for direct oxidation of alcohols to yield carboxylic acids and exhibited very good catalytic activity for wider substrate scope. Oxidation of alcohols was carried out using milder base, molecular oxygen and water as a solvent to achieve 92–99 % excellent yields. The practical utility of current strategy was also studied for gram scale synthesis of bio-based value added industrially important chemicals such as furoic acid (flavouring agent and preservative in industry), 2, 5-furan-dicarboxylic acid (monomer to 100 % fossil-free, recyclable polymer polyethylene furanoate (PEF), tetrahydro-2-furoic acid (production of many drugs) and vanillin (important product of flavor and fragrance industry). Pd@Glu-HTC catalyst was found to be reusable for four recycles and the catalytic performance was retained without any loss in its activity after four cycles.

Multi-components reactions on construction carboxylic-rich conjugated polymeric crown ethers as sustainable materials for CO2-fixation and iodine vapor adsorption: Experimental and kinetics

Carbon dioxide, as an industrial waste gas, has a severe impact on the climate. Thus, efficient catalytic conversion of CO2 has attracted considerable attention worldwide. In this study, a series of crown ether-conjugated microporous polymer materials containing carboxylic groups (CCMPs) were synthesized through multi-components reactions in one pot. This synthesis involved the reaction of dialdehydebenzo-18-crown-6 with different monomers of amino and pyruvate in the presence of DDQ. Fourier transform infrared spectroscopy, carbon-13 cross-polarization magic angle spinning nuclear magnetic resonance, scanning electron microscopy, thermogravimetric analysis, and X-ray photoelectron spectroscopy were used to characterize the CCMPs. Then, CCMPs were used in CO2 fixation and iodine vapor adsorption. The co-catalyst KI and CCMP-4 exhibited excellent activity in mild conditions, resulting in a 94% yield. The catalytic activity of the CCMP-4 was maintained after the five cycles. The kinetics of CCMP-4 was studied, and a potential reaction mechanism was proposed. The iodine adsorption experiments were conducted on CCMPs. The results showed that CCMPs exhibited excellent adsorption effects at 75 °C. The adsorption capacities of CCMP-1, CCMP-2, CCMP-3 and CCMP-4 were 3.02, 2.68, 2.72 and 3.21 g·g−1, respectively. The experimental results showed that CCMPs effectively absorbed iodine vapor and exhibited an excellent catalytic effect on CO2 cycloaddition under mild conditions, which is proved by density functional theory calculations further.

Microbiota modulation of allelopathy depends on litter chemistry: Mitigation or exacerbation?

Having a pivotal role in biogeochemical cycles, litter decomposition affects plant growth and regeneration by inducing the release of allelochemicals. The aim of this study was to assess the role of the microbiota in modulating the allelopathic effects of freshly fallen and decomposed leaf litter. To disentangle the chemical and microbial effects, bioassays were carried out on four target plants in sterile and non-sterile conditions. All litter types were characterized by carbon-13 cross polarization magic-angle spinning nuclear magnetic resonance (13C-CPMAS NMR) spectroscopy, and the associated fungal and bacterial microbiota were described by next-generation sequencing. When the litter extract was sterilized, freshly fallen litter severely inhibited the plant root growth, but during decomposition, the allelopathic effect rapidly decreased. Root growth was negatively correlated with extractable carbon and positively correlated with parameters associated with tissue lignification. In non-sterile conditions, the living microbiota modulated the leaf litter allelopathic effects of mitigation (26.5% of cases) and exacerbation (26.6% of cases). The mitigation effect was more frequent and intense in stressful conditions, i.e., highly phytotoxic freshly fallen litter, than in benign environments, i.e., decomposed litter. Finally, we identified specific bacterial and fungal operational taxonomic units (OTUs) that could be involved in the mediation of the litter allelopathic effect. This study highlights the importance of studying allelopathy in both sterile conditions and in the presence of a living microbiota to assess the role of litter chemistry and the potential impact of plant detritus on the agro-ecosystem and natural plant communities.

Decomposition of woody debris in Mediterranean ecosystems: the role of wood chemical and anatomical traits

Data about woody debris (WD) decomposition are very scarce for the Mediterranean basin. The specific aim of this work is to explore the relationships between WD traits with the decay rate. We carried out a three-year litterbag decomposition experiment using ten WD types incubated in two plant communities (i.e. shrubland and woodland) and in laboratory conditions. WD was characterized for 31 chemical and anatomical traits, including macro- and micronutrients, lignin, and cellulose as well as organic chemistry by Solid-state Cross-Polarization Magic Angle Spinning Carbon-13 Nuclear Magnetic Resonance (13C CPMAS NMR) and Fourier transform infrared spectroscopy/ Attenuated Total Reflection (FT-IR/ATR spectroscopy). WD decay rate was negatively associated with di-O-alkyl, lignin/N and C/N ratios, but positively with N concentration. Less consistent but positive correlations were recored for K, Mn, and Na concentration. The alkyl C and carboxylic C regions, associated with aliphatic and amide compounds, was positively correlated with WD decomposition. Conversely, di-O-alkyl C and O-alkyl C fractions, largely associated with cellulose and hemicellulose, were negatively correlated with WD decay rate. Finally, the positive correlation between Na concentration and WD mass loss in field conditions suggest a role of this neglected micronutrient for wood decomposition. WD specific density and anatomical features, have a minor capability to explain decomposition rate. Our findings demonstrate a major role of WD chemical traits in explaining the variability of decomposition in Mediterranean ecosystems.

13C CP/MAS NMR Can Discriminate Genetic Backgrounds of Rice Starch

Solid-state cross-polarization magic-angle spinning carbon-13 nuclear magnetic resonance (13C CP/MAS NMR) spectroscopy is used to analyze starch derived from plants including wheat, maize, and potato, but few reports have described its application to rice starch. Here, we combined 13C CP/MAS NMR with deconvolution and subtraction methods to analyze rice lines including mutants that are deficient in at least one enzyme involved in amylose and/or amylopectin biosynthesis. We found that differences in the content of ordered structures between rice lines could be evaluated using C1 signal deconvolution and subtraction. The content of the V-type ordered structure increased with increasing amylose content. Furthermore, starch derived from a starch synthase (SS) IIIa/starch branching enzyme (BE) IIb-deficient mutant formed B- and V-type ordered structures and significantly more nonordered structures than the other rice lines. These data indicate that 13C CP/MAS NMR analysis is useful for discriminating the genetic backgrounds of starch derived from different rice cultivars.

Preparation and Characterization of Regenerated Cellulose Film from a Solution in Lithium Bromide Molten Salt Hydrate.

In this study, the molten salt hydrate of lithium bromide (LiBr) was utilized as a non-derivatizing cellulose dissolution solvent to prepare regenerated cellulose films for kraft pulp. The effects of LiBr concentrations (60, 62, and 65 wt %) and dissolving time (from 5 to 40 min with the interval of 5 min) on the structures and the properties of the films were investigated. Fourier transform infrared (FT-IR) and cross-polarization magic-angle spinning carbon-13 nuclear magnetic resonance (CP/MAS 13C NMR) characterizations verified the breakage of inter- and intra-cellulose hydrogen bonds during the regeneration, resulting in the disruption of the crystalline structure of cellulose. X-ray diffraction (XRD) data indicated that the regeneration converted the polymorphism of cellulose from I to II as well as decreased its crystallinity. Ultraviolet-visible spectra (UV-Vis) and scanning electron microscopy (SEM) analyses revealed the excellent optical transparency of the films to visible light due to the complete dissolution of cellulose fibers as well as the sufficient breaking of the inter- and intra-cellulose hydrogen bonds. In terms of tensile testing, tuning LiBr concentrations and dissolving time could increase the elongation at break and tensile strength of the films. The maximum elongation at break of 26% and tensile strength of 67 MPa were achieved when the films prepared in 65 wt % LiBr for 10 and 15 min, respectively. These results indicated the great potential of the cellulose films for packaging use.

Enhanced Enzymatic Hydrolysis and Structural Features of Corn Stover by NaOH and Ozone Combined Pretreatment.

A two-step pretreatment using NaOH and ozone was performed to improve the enzymatic hydrolysis, compositions and structural characteristics of corn stover. Comparison between the unpretreated and pretreated corn stover was also made to illustrate the mechanism of the combined pretreatment. A pretreatment with 2% (w/w) NaOH at 80 °C for 2 h followed by ozone treatment for 25 min with an initial pH 9 was found to be the optimal procedure and the maximum efficiency (91.73%) of cellulose enzymatic hydrolysis was achieved. Furthermore, microscopic observation of changes in the surface structure of the samples showed that holes were formed and lignin and hemicellulose were partially dissolved and removed. X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR) and Cross-Polarization Magic Angle Spinning Carbon-13 Nuclear Magnetic Resonance (CP/MAS 13C-NMR) were also used to characterize the chemical structural changes after the combined pretreatment. The results were as follows: part of the cellulose I structure was destroyed and then reformed into cellulose III, the cellulose crystal indices were also changed; a wider space between the crystal layer was observed; disruption of hydrogen bonds in cellulose and disruption of ester bonds in hemicellulose; cleavage of bonds linkage in lignin-carbohydrate complexes; removal of methoxy in lignin and hemicellulose. As a result, all these changes effectively reduced recalcitrance of corn stover and promoted subsequent enzymatic hydrolysis of cellulose.

Spectroscopic-Chemical Fingerprint and Biostimulant Activity of a Protein-Based Product in Solid Form.

A solid biostimulant (AA309) obtained through thermobaric hydrolysis applied on trimmings and shavings of bovine hides tanned with wet-blue technology was chemically characterized, and its effects in maize (Zea mays L.) were evaluated. AA309 contained 13.60% total nitrogen (N), mainly in organic forms (13.40%), and several amino acids, especially lysine, phenylalanine, glycine, aspartate, and isoleucine. AA309 was further analyzed using Fourier Transform Infrared (FT-IR) spectroscopy, which revealed the presence of amide I and amide II bands, indicative of peptide structures. When supplied to maize plants for 15 days at two N dosages (2.1 or 4.2 mg/kg), AA309 induced positive physiological responses, likely because of its content in amino acids functioning as signaling molecules. The low dosage was the most effective in improving leaf (+24%) and root (+98%) dry weight, photosynthetic activity (+70%), and accumulation of N (+80%), proteins (+65–75%) and antioxidants (+60%). Spectroscopic analyses (Solid-state Cross-Polarization Magic Angle Spinning Carbon-13 Nuclear Magnetic Resonance, CP/MAS 13C–NMR, and High resolution-magic angle spinning nuclear magnetic resonance, HR-MAS NMR) on plant tissues revealed the increase in proteins, lignin structures and cutin in AA309-treated plants compared to untreated plants. Our results indicate that AA309 could be used as a valuable biostimulant in agriculture.

Carbohydrate gel beads as model probes for quantifying non-ionic and ionic contributions behind the swelling of delignified plant fibers

Macroscopic beads of water-based gels consisting of uncharged and partially charged β-(1,4)-d-glucan polymers were developed to be used as a novel model material for studying the water induced swelling of the delignified plant fiber walls. The gel beads were prepared by drop-wise precipitation of solutions of dissolving grade fibers carboxymethylated to different degrees. The internal structure was analyzed using Solid State Cross-Polarization Magic Angle Spinning Carbon-13 Nuclear Magnetic Resonance and Small Angle X-ray Scattering showing that the internal structure could be considered a homogeneous, non-crystalline and molecularly dispersed polymer network. When beads with different charge densities were equilibrated with aqueous solutions of different ionic strengths and/or pH, the change in water uptake followed the trends expected for weak polyelectrolyte gels and the trends found for cellulose-rich fibers. When dried and subsequently immersed in water the beads also showed an irreversible loss of swelling depending on the charge and type of counter-ion which is commonly also found for cellulose-rich fibers. Taken all these results together it is clear that the model cellulose-based beads constitute an excellent tool for studying the fundamentals of swelling of cellulose rich plant fibers, aiding in the elucidation of the different molecular and supramolecular contributions to the swelling.

Reactions of Antitumor Active Dirhodium(II) Tetraacetate Rh2(CH3COO)4 with Cysteine and Its Derivatives.

We have combined results from several spectroscopic techniques to investigate the aerobic reactions of Rh2(AcO)4 (AcO– = CH3COO–) with l-cysteine (H2Cys) and its derivatives d-penicillamine (3,3′-dimethylcysteine, H2Pen), with steric hindrance at the thiol group, and N-acetyl-l-cysteine (H2NAC), with its amino group blocked. Previous investigations have shown that antitumor active dirhodium(II) carboxylates may irreversibly inhibit enzymes containing a thiol group at or near their active sites. Also, cysteine, the only thiol-containing proteinogenic amino acid, interacts in vivo with this class of antitumor compounds, but structural information on the products of such reactions is lacking. In the present study, the reactions of Rh2(AcO)4 and H2L were carried out in aqueous solutions at the pH of mixing (acidic) and at physiological pH, using the different mole ratios 1:2, 1:4, and 1:6, which resulted in the same products in increasing yields. Electrospray ionization mass spectrometry (ESI-MS) indicates formation of dimeric [RhIII2Pen4]2– or oligomeric {RhIII2L4}n (L = Cys, NAC) complexes with bridging thiolate groups. Analyses of Rh K edge extended X-ray absorption fine structure (EXAFS) data reveal 3–4 Rh–S and 2–3 Rh–(N/O) bonds around six-coordinated Rh(III) ions at mean distances of 2.33 ± 0.02 and 2.09 ± 0.02 Å, respectively. In the N-acetyl-l-cysteine compound, the RhIII···RhIII distance 3.10 ± 0.02 Å obtained from the EXAFS spectrum supports trithiolate bridges between the Rh(III) ions, as was also found when using glutathione as ligand. In the cysteine and penicillamine complexes, double thiolate bridges join the Rh(III) ions, with the nonbridging Cys2– and Pen2– ligands in tridentate chelating (S,N,O) mode, which is consistent with the ΔδC = 7.3–8.4 ppm shift of the COO– signal in their carbon-13 cross polarization magic angle spinning (CPMAS) NMR spectra. For the penicillamine complex, the 2475.6 eV peak in its S K edge X-ray absorption near edge structure (XANES) spectrum shows partial oxidation, probably caused by peroxide generated from reduction of dissolved O2, of thiolato to sulfenato (S=O) groups, which were also identified by ESI-MS for all three {RhIII2L4}n compounds.

Effects of Different Deinking Processes on Fiber Morphology, Hydrogen Bond Models, and Cellulose Supramolecular Structure

Deinked pulp fibers produced by three kinds of deinking processes, alkaline deinking, neutral deinking, and enzymatic deinking, were studied by Scanning Electron Microscope (SEM), Fourier Transform Infrared Spectrometer (FTIR), X-ray Diffraction (XRD), and Cross-Polarization Magic Angle Spinning Carbon-13 Nuclear Magnetic Resonance (CP/MAS 13C-NMR). There were remarkable differences in both macroscopic and microscopic structure between the samples. SEM images showed that the effects of deinking processes on fiber morphology were obvious and the influences of alkaline deinking were the most apparent. FTIR analysis indicated that the content of intermolecular hydrogen bonds increased by 22.63%, 9.42%, and 14.40% after the alkaline deinking process, neutral deinking process, and enzymatic deinking process, respectively. XRD revealed that the average width of crystallite size in the (002) lattice plane was decreased after different deinking processes, in accordance with the change tendency of cellulose crystallinity. CP/MAS 13C NMR combined with spectral fitting demonstrated that the content of different cellulose polymorphs changed during deinking processes. The increase of WRV was attributed to changes in the hydrogen bonding patterns and cellulose supramolecular structure.

The Content of Different Hydrogen Bond Models and Crystal Structure of Eucalyptus Fibers during Beating

Different hydrogen bond and crystalline cellulose structure models of eucalyptus fibers were studied by Fourier transform infrared spectrometer (FTIR), X-ray diffraction (XRD), and Cross-Polarization Magic Angle Spinning Carbon-13 Nuclear Magnetic Resonance (CP/MAS 13C NMR). It was shown that when the beating time was increased from 5 to 15 min., the content of inter-molecular hydrogen bonds, O(6)H···O3′, increased by 11.2% as measured by FTIR. However, the content of the inter-molecular hydrogen bonds decreased quickly as the beating time was increased from 15 to 25 min. Meanwhile, the contents of the intra-molecular hydrogen bond, O(2)H···O(6) and O(3)H···O(5), changed from 8.25% to 8.18% and from 39.33% to 31.27%, respectively, when the beating time increased from 5 to 15 min. The content of the intra-molecular hydrogen bonds increased quickly with the further increase in the beating time. It was shown by XRD that there was a little difference in the average width of crystallite size in the (002) lattice plane when the beaten time was between 5 to 25 min. Non-linear fitting of the cellulose C4 region of the 13C CP/MAS NMR showed that the average lateral fibril aggregate dimensions and the content of different cellulose polymorphs changed during beating.

Effects of hemicellulose removal on cellulose fiber structure and recycling characteristics of eucalyptus pulp

Eucalyptus pulp fibers with large differences in cellulose and hemicellulose proportions but similar lignin contents were produced by partial removal of the hemicellulose and studied using Cross-Polarization Magic Angle Spinning Carbon-13 Nuclear Magnetic Resonance (CP/MAS 13C NMR) in combination with spectral fitting, Atomic Force Microscopy (AFM), X-ray Diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FTIR). There were remarkable differences in both cellulose fibril structure, pore structure and cellulose supermolecular structure between the samples. CP/MAS 13C NMR combined with spectral fitting demonstrated an increase in average fibril aggregate size (17.9–22.2nm) with decreasing hemicellulose content. AFM observations revealed that when the hemicellulose content decreased from 27.62% to 19.80%, the average diameters of pores decreased by 12.53%, but increased by 13.55% when the hemicellulose content decreased from 19.80% to 9.09%. XRD and FTIR analysis indicated that cellulose crystallinity increased with decreasing hemicellulose content. The low and high hemicellulose-containing pulps had very different recycling characteristics, which may be explained by the changes observed at cellulose fiber structure level. Fibrils appear to aggregate and form a more compact structure when the hemicellulose is removed, which was caused by a coalescence of the cellulose microfibrils. The removal of hemicellulose had disadvantageous influence on the accessibility of fibers and enhanced fiber flattening during drying, leading to increased sheet density and increased hornification.

Carbon-13 CP MAS NMR Study on Structures of Octadecyl Chains Influenced by Co-Presence of 3-Aminopropyl Chains on SBA-15

Functionalized SAB-15 samples by octadecyltrimethoxysilane (OTC) were studied by 13C magic angle spinning (MAS) cross polarization (CP) nuclear magnetic resonance (NMR) spectroscopy. In the SBA-15 sample fully functionalized by 3-aminopropyltrimethoxysilane (APS) and OTC in 1:1 molar ratio, octadecyl chains were observed to have, on average, more trans conformation than those in the SBA-15 samples fully modified by OTC only. Our results confirm that long chain molecules tend to organize themselves better in the co-presence of short chain molecules on the surface of mesoporous materials by packing of the different length chains in an interdigitized fashion even when the short chains are long enough to have three carbons and a functional group at the ends. In addition, our results indicate that solid-state 13C CP MAS NMR spectroscopy is a simple and non-destructive method to probe the molecular structures of the domains composed of long alkyl chains.

Investigation of the hygroscopic growth of self-assembled layers of N-alkyl-N-methylpyrrolidinium bromides at the interface between air and organic salt

We report on the hygroscopic growth of self-assembled lamellae, composed of N-alkyl-N-methylpyrrolidinium bromide (CnMPB; n = 10, 12, 14, 16, 18) surfactant molecules, spontaneously formed at the interface between ambient air and the low-melting organic salt tetrabutylammonium acetate (TBAAc). The organization process to form well-defined hygroscopic bilayer patterns at the air/TBAAc interface was investigated using a combination of time-dependent X-ray diffraction (XRD) and carbon-13 cross-polarization magic angle spinning nuclear magnetic resonance (13C CP/MAS NMR) spectroscopy. CnMPB surfactants containing the highest alkyl chain lengths studied (n = 16, 18) formed highly ordered, fully interdigitated bilayer patterns with an all-trans conformation of interior methylene carbons. In contrast, CnMPB surfactants with shorter alkane chains (n = 10, 12, 14) in this series formed less-ordered bilayer arrangements with mixed trans/gauche aliphatic character. The lamellar patterns became increasingly ordered with longer exposure to humid air at the air/salt interface.

Chemical and carbon-13 cross-polarization magic-angle spinning nuclear magnetic resonance characterization of logyard fines from British Columbia.

Phasing out beehive burners and rising costs for landfilling have increased the need to widen options for utilization of the smaller size fractions of woody wastes generated during log handling and sawmilling in British Columbia. We characterized several size classes of logyard fines up to 16 mm sampled from coastal and interior operations. Total C, total N, ash, and condensed tannin concentrations were consistent with properties derived largely from wood, with varying proportions of bark and mixing with mineral soil. Especially for < 3-mm fractions, the latter resulted in high ash contents that would make them unsuitable for fuel. Solid-state 13C cross-polarization magic-angle spinning (CPMAS) nuclear magnetic resonance (NMR) spectra were consistent with the chemical data, with high O-alkyl intensity and similarity to naturally occurring woody forest floor; no samples were high in aromatic or phenolic C. Aqueous extracts of two < 16-mm fines, which accounted for only a small proportion of the total C, were enriched in alkyl C and had low or undetectable tannins. Application to forest sites might cause short-term immobilization of N, but also might include possible longer-term benefits from reduction of N loss after harvesting and restoration of soil organic matter in degraded sites.

Chemical and Carbon-13 Cross-Polarization Magic-Angle Spinning Nuclear Magnetic Resonance Characterization of Logyard Fines from British Columbia

Chemical and Carbon-13 Cross-Polarization Magic-Angle Spinning Nuclear Magnetic Resonance Characterization of Logyard Fines from British Columbia

Carbon-13 NMR spectroscopic studies on chemically modified and unmodified synthetic and natural humic acids

Carbon-13 cross-polarization magic-angle spinning nuclear magnetic resonance spectroscopy ( 13C-CP/MAS-NMR) was applied to study the chemical modification process of humic acids (HA) with diazomethane and the subsequent alkaline hydrolysis of the methylated HA. This modification process results in HA with selectively blocked phenolic OH groups, which can be used for metal ion binding studies with humic substances. Different chemically modified and unmodified natural and synthetic HA with carbon-13 of natural abundance were investigated. In addition, carbon-13 labeled modified synthetic HA, that were synthesized with [ 13C]diazomethane as methylation reagent, were studied to confirm the assumed modification process and to determine the type of functional groups that have the highest affinity for methylation with diazomethane. The results of the NMR studies with carbon-13 labeled modified HA show that predominantly carboxyl and phenolic OH groups are methylated with diazomethane resulting in methyl ester and methyl ether groups, respectively. Due to the alkaline treatment of the methylated HA, the methyl esters of carboxyl groups are hydrolyzed, whereas methyl ethers of phenolic OH groups remain unchanged, which results in modified HA with blocked phenolic OH groups. From the spectra of the modified and unmodified HA with carbon-13 of natural abundance it can be concluded that the applied preparative modification procedure causes only the desired structural changes in HA.

CP/MAS [formula omitted]-NMR spectroscopy applied to structure and interaction studies on cellulose I

Solid-state Cross-Polarization Magic Angle Spinning Carbon-13 Nuclear Magnetic Resonance (CP/MAS 13 C -NMR) has been used to investigate the structure and interactions of cellulose I. The use of spectral fitting for the extraction of information from CP/MAS 13 C -NMR spectra is reviewed and results obtained are discussed. Examples are shown where the method has been used to monitor the structural changes occurring in wood cellulose during kraft pulping. The effects observed on the cellulose and hemicelluloses are further investigated using a model system. Assignments of signal intensities originating from xylan–cellulose interactions are made.

Analysis of carboxyl content in oxidized celluloses by solid-state 13C CP/MAS NMR spectroscopy

A noninvasive method to determine the carboxyl content in oxidized celluloses, using solid-state carbon-13 cross-polarization–magic angle spinning nuclear magnetic resonance ( 13C CP/MAS NMR) spectroscopy, has been developed. Standard samples containing 0, 4, 8, 12, 16, and 20% carboxyl content were prepared by mixing appropriate amounts of powdered cellulose, a non-oxidized cellulose standard prepared from cotton linter by ball-milling for 96 h, and a commercial oxidized cellulose sample that had a 20% carboxyl content. Standard curves were constructed by plotting the percent carboxyl content against the peak area at 171 ppm, normalized with (i) a peak area at 104 ppm and (ii) the sum of peak areas at 171, 62, and 65 ppm. The regression analysis of the curves yielded a linear relationship with correlation coefficient ( R 2) values of 0.9868 and 0.9863, respectively. To validate the methods, five new samples of oxidized cellulose were prepared and analyzed. The values obtained were comparable to those determined by the calcium acetate method described in the United States Pharmacopoeia (USP), indicating that the solid-state 13C CP/MAS NMR can be used to analyze carboxyl content in oxidized celluloses.