Differences in the chemical structure of the lignins from sugarcane bagasse and straw

Two major residues are produced by the sugarcane industry, the fibrous fraction following juice extraction (bagasse), and the harvest residue (straw). The structures of the lignins from these residues were studied by pyrolysis coupled to gas chromatography-mass spectrometry (Py-GC/MS), nuclear magnetic resonance (NMR), and derivatization followed by reductive cleavage (DFRC). Whereas the lignin from bagasse has a syringyl-rich p-hydroxyphenyl:guaiacyl:syringyl (H:G:S) molar composition of 2:38:60, the lignin from straw is guaiacyl-rich (H:G:S of 4:68:28). The compositional differences were also reflected in the relative abundances of the different interunit linkages. Bagasse lignin was primarily β–O–4′ alkyl-aryl ether substructures (representing 83% of NMR-measurable linkages), followed by minor amounts of β–5′ (phenylcoumarans, 6%) and other condensed substructures. The lignin from straw has lower levels of β-ethers (75%) but higher relative levels of phenylcoumarans (β–5′, 15%) and dibenzodioxocins (5–5/4–O–β, 3%), consistent with a lignin enriched in G-units. Both lignins are extensively acylated at the γ-hydroxyl of the lignin side-chain (42% and 36% acylation in bagasse and straw), predominantly with p-coumarates (preferentially on S-units) but also with acetates (preferentially on G-units) to a minor extent. Tetrahydrofuran structures diagnostically arising from β–β-coupling (dehydrodimerization) of sinapyl p-coumarate or its cross-coupling with sinapyl alcohol were found in both lignins, indicating that sinapyl p-coumarate acts as a monomer participating in lignification. The flavone tricin was also found in the lignins from sugarcane, as also occurs in other grasses.     

Insights into the development of crystallinity in liquid urea-formaldehyde resins

Differently from most thermoset materials, urea-formaldehyde (UF) resins display the appearance of crystalline domains. In the effort of understanding the mechanism of formation of such crystals, wide angle X-ray diffraction (WAXD), infrared spectroscopy and transmission electron microscopy (TEM) were applied. Liquid UF resins with two different F/U mole ratios (i.e. 1.6 and 1.0) were investigated as a function of hardener level and curing times at room temperature. The WAXD results showed that the liquid UF resin with a low F/U mole ratio had a greater crystallinity than the one with a high F/U mole ratio. An advance in crystal formation in the low F/U mole UF resins was visible, especially in the first phases of curing. However, there were no significant differences in the degree of crystallinity as a function of hardener level. IR spectroscopy highlighted the important role of methylolated species in the formation of crystals. TEM results also confirmed the presence of crystals in all the considered liquid UF resins. The concentration of the hardener and the curing time were critical in shaping morphology and particle dispersion. As a function of the curing conditions, the globular structures present in the samples can aggregate into different morphologies, which can be fibrillar and also lamellar. The obtained results stress the importance of controlling the subtle interplay between crosslinking and formulation for the obtainment and control of the size, quantity and morphology of crystals in UF resins, and therefore for an effective tuning of their properties.     

Functionalized galactoglucomannan‐based hydrogels for the removal of metal cations from aqueous solutions

New types of hydrogels derived from O‐acetyl galactoglucomannan (AcGGM) hemicellulose have been synthesized and characterized. The objective of this work was to analyze the sorption capacity (S) of three types of hydrogels containing AcGGM derivatives incorporated into the carboxylic groups of the polymer chain in the AA hydrogel, sulfonic groups in the APA hydrogel, and amide groups in the acrylamide (Aam) hydrogel. These hydrogels are capable of interacting and removing ions such as cadmium [Cd(II)], copper [Cu(II)], lead [Pb(II)], nickel [Ni(II)], and zinc [Zn(II)]. The results show that AA and Aam hydrogels had a lower sorption capacity of ions compared to the APA hydrogel, which had a high sorption capacity. The maximal sorption capacity was determined by the successive enrichment method, obtaining Pb(II) amount of 48.3 mg/g of AA hydrogel, 65.8 mg/g of APA hydrogel, and 40.8 mg/g of Aam hydrogel. Hence, Pb(II) ions are greatly retained by the three hydrogels. These results are promising for the development of new materials with potential applications in metal ion removal. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44093.     

Catalyst development for the selective oxidation of ethoxylates to their corresponding ether carboxylic acids

The aerobic selective oxidation of polyethoxylates to their corresponding carboxylic acids was investigated using supported Au-based catalysts in aqueous alkaline solution. Introduction of Pt as secondary metal to the titania supported Au catalyst led to a significant boost in activity while maintaining total selectivity. A screening of different preparation methods and metal ratios led to a titania supported AuPt catalyst with a substantially reduced intermediate leaching of the catalytically active metals. A long-term stability study showed no noble metal loss of this particular catalyst after a set of repeated batches, but still revealed a distinct loss in activity due sintering of the metal nanoparticles. By switching from titania to ceria as support material, intermediate metal leaching could be prevented completely while maintaining total selectivity and further enhancing the activity.     

Chemical composition of degrading mangrove leaf litter and changes produced after consumption by mangrove crabNeosarmatium smithi (Crustacea: Decapoda: Sesarmidae)

The leaves of the mangroveCeriops tagal contained 3.2–4.1% (all percentages relate to dry weight) ofd-1-O-methyl-muco-inositol previously unreported in mangroves. They consisted of 37% aqueous acetone-water-soluble material, 18% water-insoluble polysaccharides, and ca. 50% polyphenols, which include soluble and insoluble tannins and lignin. The polysaccharide component sugars were glucose, arabinose, uronic acids, mannose, xylose, galactose, and rhamnose in the proportions 28262210752, respectively. The leaves were pectate rich, and the low level of glucan was presumed to consist mainly of cellulose. After four weeks of biodegradation, ca. 60% of the acetone-water-soluble material was lost from the leaves. Degradation processes greatly altered the polysaccharide components in the leaves. Pectates were rapidly degraded, while other polysaccharides, although reduced proportionately, resisted degradation at about the same level, and all component sugars were found in the 8-week-old leaves. Apparent lignin contents increased from 15 to >30% during biodegradation up to eight weeks. The yields of the major fractions in corresponding fecal material fromNeosarmatium smithi showed a similar trend to the diets. An enrichment of the insoluble residue was noticeable due to the digestion of dialyzable material. The fecal carbohydrate content was greatly reduced (7–11%) and the apparent lignin increased (27–39%) due to its resistance to degradation. All dietary polysaccharide component sugars were found in the fecal residues, including some uronic acids. The leaves also contained a readily water-soluble fraction (15%) which consisted of pectates strongly complexed with proanthocyanidins.     

Lipophilic Extractives in Populus × euramericana “Guariento” Stemwood and Bark

Abstract

The lipophilic extractives in stemwood and bark from three different heights of Populus × euramericana “Guariento” were analyzed. The bark samples, especially from 4 and 8 meters height, contained much more extractives than the stemwood samples. The lipophilic extractives identified by Gas Chromatography–Mass Spectroscopy (GC-MS) were composed of five component groups (i.e. triglycerides, steryl esters, free fatty acids, sterols, and free fatty alcohols both in the stemwood and bark). Besides ferulic acid esters, α-amyrin and its esters, 4-hydroxycinnamic acid esters of fatty alcohols were also identified in the stemwood and bark. Small amounts of alkanes and oligomeric or polymeric material with higher molar mass than triglycerides were present only in the bark. Glycerides, mainly triglycerides, were the largest component group of the lipophilic extractives. The high proportion of short-chain fatty acids released after alkaline hydrolysis are beneficial when removing pitch particles or fatty acid soaps by dispersing and washing during pulping and papermaking.     

Lignin and Other Aromatic Substances Released from Spruce Wood During Pressurized Hot-Water Extraction,Part 2: Structural Characterization

Extraction of ground spruce sapwood with pressurized hot water in an accelerated solvent extractor (ASE) at 170°C during 20, 60, and 100 min resulted in isolation of galactoglucomannans and aromatic substances, including lignin. The isolated lignin preparations were characterized by spectrometric (UV, FT-IR, ¹H NMR, liquid and solid-state ¹³C NMR), chromatographic (RP-HPLC, HP-SEC, GC-FID, and GC-MS), conventional pyrolysis, thermally assisted hydrolysis, and methylation techniques in tandem with GC-MS, and classical wet chemistry (methoxyl groups, total and phenolic hydroxyl groups, derivatization followed by reductive cleavage—DFRC). The content of β-O-4 bonds in isolated lignins was similar to that in MWL and their proportion decreased with extraction time. The oxidation of isolated lignins and content of total hydroxyl groups were significantly increased with extraction time. The lignin structure underwent condensation and demethylation reactions during hot-water extraction. The induction of new phenylcoumaran substructures was proposed in isolated lignins.     

Hydrogenolysis of Hydroxymatairesinol Over Carbon-Supported Palladium Catalysts

The natural lignan hydroxymatairesinol was hydrogenolysed to a potential anticarcinogenic substance matairesinol over different carbon-supported palladium catalysts. The reaction was conducted in 2-propanol at 70 °C under hydrogen flow in a stirred glass reactor. The catalysts were characterised by N₂-physisorption, CO pulse chemisorption and pH measurement of aqueous catalyst slurries. The most active catalyst (Degussa-Hüls) gave yields of matairesinol over 90% in 4 h. It was concluded that the acidity of the catalyst had a profound influence on the reaction rate.     

Allyloxy-modified starch with low degree of substitution for fiber reinforced thermoset starch composites

In the present work dough moulding compound premixes of allyl glycidyl ether modified (AGE)-potato starch, (DS) = 0.2, has been prepared and tested for its fiber reinforced composite properties. The AGE-starch was hydrolyzed with α-amylase under neutral condition for 6 h at 45 °C for improved process ability. The grafting and hydrolytic scission was confirmed by nuclear magnetic resonance (NMR) and size exclusion chromatography (SEC), respectively. Homogeneous composite premixes of AGE-starch, wood fibers, various amount of glycerol and ethylene glycol dimethacrylate were successfully mixed with a Brabender-kneader at 55 °C and cured by compression molding at 150 °C using 2 wt% of dibenzoyl peroxide. Adding 5 wt% of glycerol did not reduce the ultimate strength of the composites; 10% glycerol reduced the strength from 60 MPa to 40 MPa, and 16% glycerol to 14 MPa. The results with 5 wt% glycerol are comparable with earlier achieved results. The water absorption rate increased with increased glycerol content and the mechanical strength of the composites was lost completely when the moisture uptake reached 15 wt%.