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Crustacean shells, waste from the seafood industry, have been identified as a potential sustainable material for the adsorption of lead, a potent heavy metal found in the discharge of industrial processes. The dynamics and kinetics of its performance were evaluated in batch experiments under pH, temperature, time, and initial concentration. A unique and non-intuitive key finding was that among the native components of the crab shell matrix, i.e., chitin, protein, and calcium carbonate, calcium carbonate was instrumental in sequestration. The role of protein was minimal, whereas the efficiency of chitin in lead complexation was linked to the lead atomic radius, which, of the crab shell components, we determined was very prone to interacting with chitin. [ABSTRACT FROM AUTHOR]

Every year, over 8 million tons of crustacean shells are discarded. However, there exists an opportunity for valorizing the chitin and calcium carbonate part of the composition of the shells. Our study revealed crustacean chitin reduces self-aggregation effects. It was shown that crustacean-based nanofibers alone or added to cellulose offer unprecedented reductions in viscosity even after drying to produce foams impossible for cellulose. Polysaccharide nanofibers suffer from increased viscosity from strong hydrogen bonding addressed by the incorporation of crustacean-based nanofibers. The ability of the nanocomposite to overcome self-aggregation and collapse was attributed to organized chitin nanofiber morphology in the crustacean matrix. As a result of enhanced surface area from reduced fiber aggregation, the chitin/crustacean-cellulose blend was tested for a biomedical application requiring a high surface area: coagulation. Preliminary experiments showed the crustacean matrices, especially those containing calcium carbonate, induced blood clotting when 35 s. A materials platform is proposed for bio-based nanofiber production overcoming intractable and difficult-to-address self-aggregation effects associated with polysaccharides. [ABSTRACT FROM AUTHOR]

Anewfunctional biopolymerwas synthesized through an ionic liquid-mediated homogeneous grafting of cinnamic anhydride to xylans. The ionic liquid used was 1-allyl-3-methylimidazolium chloride (AMIMCl) ionic liquid. Xylans with degrees of substitution (DS) between 0.11 and 0.57 were accessible in a completely homogeneous system by changing catalysts (NaOH, KOH and LiOH), time, reaction temperature, and cinnamic anhydride/xylan molar ratio. The chemical structure and the thermal stability of the derivatives were characterized by Fourier transform infrared spectroscopy (FT-IR), 13C-NMR spectroscopy, and thermogravimetry. The thermal stability of the derivatives was reduced compared with the original xylan. Possible applications of the cinnamic anhydride-acylated xylan derivatives include wet-end papermaking, organic-inorganic composite films, and hydrogels. [ABSTRACT FROM AUTHOR]

Deep eutectic solvents (DESs) are a potentially high-value lignin extraction methodology. DESs prepared from choline chloride (ChCl) and three hydrogen-bond donors (HBD)--lactic acid (Lac), glycerol, and urea--were evaluated for isolation of willow (Salix matsudana cv. Zhuliu) lignin. DESs types, mole ratio of ChCl to HBD, extraction temperature, and time on the fractionated DES-lignin yield demonstrated that the optimal DES-lignin yield (91.8 wt % based on the initial lignin in willow) with high purity of 94.5% can be reached at a ChCl-to-Lac molar ratio of 1:10, extraction temperature of 120 ¯C, and time of 12 h. Fourier transform infrared spectroscopy (FT-IR) , 13C-NMR, and 31P-NMR showed that willow lignin extracted by ChCl-Lac was mainly composed of syringyl and guaiacyl units. Serendipitously, a majority of the glucan in willow was preserved after ChCl-Lac treatment. [ABSTRACT FROM AUTHOR]

Lignin has shown a great potential to produce fuels, value-added chemicals, and functional materials due to its high-energy density and intrinsic aromatic-based structure. Yet, the lignin precipitation of different biomasses needs investigation because most of the work has been performed on softwood and much less is known about hardwoods. In fact, the lignin from these two wooden biomasses vary in composition and pulping performance, which can reflect on lignin precipitation. Therefore, the present study investigated the precipitation and composition of 40 distinct kraft lignins obtained from pine, acacia, sweetgum, and eucalyptus black liquors. Two lignin fractions were precipitated at different pHs, according to known industrial lignin separation practices (pH = 9.5 and 2.5) from black liquors taken at different levels of pulping. Overall, lignin recovery increased with increasing lignin concentration in the black liquor, i.e., higher amounts of lignin were obtained at higher levels of delignification. In addition, pine lignins showed superior yields than the hardwoods and were around five times purer. Among the hardwoods, lignin recovery increased with the S–G ratio of the native lignin, and eucalyptus showed the best performance by achieving the highest yields and purities. Finally, the present work compared the lignin recovery yield and the purity of softwood and different hardwood lignins in a systematic way, which will increase awareness of this underutilized green material and could potentially increase the interest in establishing new lignin plants across the globe. [ABSTRACT FROM AUTHOR]

Herein, we synthesized 2,3-diaminophenazine (DAP) from o-phenylenediamine (OP) using fungal laccase as a biocatalyst. The conversion ratio of OP monomer was 85% and the yield of the final purified product, DAP, was 63%. The structure of the main product, DAP, was confirmed by using several spectroscopy techniques (UV-VIS, IR, 2D-NMR, and MS). [ABSTRACT FROM AUTHOR]

A deep eutectic solvent (DES) composed of sulfamic acid and glycerol allowed for the sustainable preparation of cellulose nanofibrils (CNF) with simultaneous sulfation. The reaction time and the levels of sulfamic acid demonstrated that fibers could be swelled and sulfated simultaneously by a sulfamic acid-glycerol-based DES and swelling also promoted sulfation with a high degree of substitution (0.12). The DES-pretreated fibers were further nanofibrillated by a grinder producing CNF with diameters from 10 nm to 25 nm. The crystallinity ranged from 53–62%, and CNF maintained the original crystal structure. DES pretreatment facilitated cellulose nano-fibrillation and reduced the energy consumption with a maximum reduction of 35%. The films prepared from polyvinyl alcohol (PVA) and CNF showed good UV resistance ability and mechanical properties. This facile and efficient method provided a more sustainable strategy for the swelling, functionalization and nano-fibrillation of cellulose, expanding its application to UV-blocking materials and related fields. [ABSTRACT FROM AUTHOR]

Lignin is an abundant, renewable, and relatively cheap biobased feedstock that has potential in energy, chemicals, and materials. Kraft lignin, more specifically, has been used for more than 100 years as a self-sustaining energy feedstock for industry after which it has finally reached more widespread commercial appeal. Unfortunately, hardwood kraft lignin (HWKL) has been neglected over these years when compared to softwood kraft lignin (SWKL). Therefore, the present work summarizes and critically reviews the research and development (R&D) dealing specifically with HWKL. It will also cover methods for HWKL extraction from black liquor, as well as its structure, properties, fractionation, and modification. Finally, it will reveal several interesting opportunities for HWKL that include dispersants, adsorbents, antioxidants, aromatic compounds (chemicals), and additives in briquettes, pellets, hydrogels, carbon fibers and polymer blends and composites. HWKL shows great potential for all these applications, however more R&D is needed to make its utilization economically feasible and reach the levels in the commercial lignin market commensurate with SWKL. The motivation for this critical review is to galvanize further studies, especially increased understandings in the field of HWKL, and hence amplify much greater utilization. [ABSTRACT FROM AUTHOR]

A novel choline-based deep eutectic solvent (DES) with low halogen content—namely choline lactate-lactic acid (CLL)—was synthesized by replacing the chloride anion with lactate anion in choline chloride-lactic acid (CCL). CLL and CCL treatments were conducted at 140 °C for 12 h with hydrogen bond acceptor/hydrogen bond donor =1/10, thereafter composition analysis and characterizations of the lignin extracted by DES treatment (DES lignin) and the solid residue were carried out. The proposed low halogen content DES presented an improved lignin extraction efficiency. The CLL treatment extracted 90.13% of initial lignin from poplar, while CCL extracted 86.02%. In addition, the CLL treatment also provided DES lignin with an improved purity (91.17%), lower molecular weight (Mw/Mn=1805/971 g/mol) and more concentrated distribution (polydispersity index=1.86). The efficient lignin extraction was mainly ascribed to the cleavage of β-O-4 bonds in lignin macromolecule, especially in the guaiacyl units, thereby breaking them into smaller molecules, facilitating the lignin extraction. The replacement of chloride anion allowed CLL acting as a more efficient DES to interact with lignin macromolecules, thus providing lignin with higher uniformity and suitable molecular weight. The low halogen content DES system proposed in present work could benefit the fractionation of biomass, improve the valorization of lignin compounds and facilitate industrial process in the downstream. [ABSTRACT FROM AUTHOR]

Citric acid (CA) was used for the hydrothermal carbonization (HTC) of cellulose nanofiber and found to exert remarkable effects on the chemistry and physical aspects of the product distribution. More specifically, the morphology, yield, elemental and proximate composition, chemical functional groups, thermal properties and surface properties of the resultant hydrochars were studied extensively. The morphological properties of the final char were the singularly most surprising and unique finding of this study. The cellulose nanofiber hydrochars were contrasted to hydrochars from bleached softwood pulp, having a similar composition with the former, to pinpoint the role of nano-dimensions. Without the presence of CA, the pulp hydrochar lacked several of the spherical dimensions shown in the nanocellulose; however, and unexpectedly, the presence of CA caused a homogenization of the final product distribution for both samples. Finally, thermally stable and high surface area hydrochars were obtained when the hydrochar was rinsed with acetone. [ABSTRACT FROM AUTHOR]

Purity, morphology, and structural characterization of synthesized deep eutectic solvent (DES)-lignins (D6h, D9h, D12h, D18h, D24h) extracted from willow (Salix matsudana cv. Zhuliu) after treatment with a 1:10 molar ratio of choline chloride and lactic acid at 120 °C for 6, 9, 12, 18, and 24 h were carried out. The purity of DES-lignin was ~95.4%. The proportion of hydrogen (H) in DES-lignin samples increased from 4.22% to 6.90% with lignin extraction time. The DES-lignin samples had low number/weight average molecular weights (1348.1/1806.7 to 920.2/1042.5 g/mol, from D6h to D24h) and low particle sizes (702–400 nm). Atomic force microscopy (AFM) analysis demonstrated that DES-lignin nanoparticles had smooth surfaces and diameters of 200–420 nm. Syringyl (S) units were dominant, and total phenolic hydroxyl content and total hydroxyl content reached their highest values of 2.05 and 3.42 mmol·g−1 in D12h and D6h, respectively. β-Aryl ether (β-O-4) linkages were eliminated during DES treatment. [ABSTRACT FROM AUTHOR]

A new functional biopolymer was synthesized through an ionic liquid-mediated homogeneous grafting of cinnamic anhydride to xylans. The ionic liquid used was 1-allyl-3-methylimidazolium chloride (AMIMCl) ionic liquid. Xylans with degrees of substitution (DS) between 0.11 and 0.57 were accessible in a completely homogeneous system by changing catalysts (NaOH, KOH and LiOH), time, reaction temperature, and cinnamic anhydride/xylan molar ratio. The chemical structure and the thermal stability of the derivatives were characterized by Fourier transform infrared spectroscopy (FT-IR), 13 C-NMR spectroscopy, and thermogravimetry. The thermal stability of the derivatives was reduced compared with the original xylan. Possible applications of the cinnamic anhydride-acylated xylan derivatives include wet-end papermaking, organic-inorganic composite films, and hydrogels., Competing Interests: The authors declare no conflict of interest.

Deep eutectic solvents (DESs) are a potentially high-value lignin extraction methodology. DESs prepared from choline chloride (ChCl) and three hydrogen-bond donors (HBD)-lactic acid (Lac), glycerol, and urea-were evaluated for isolation of willow ( Salix matsudana cv. Zhuliu ) lignin. DESs types, mole ratio of ChCl to HBD, extraction temperature, and time on the fractionated DES-lignin yield demonstrated that the optimal DES-lignin yield (91.8 wt % based on the initial lignin in willow) with high purity of 94.5% can be reached at a ChCl-to-Lac molar ratio of 1:10, extraction temperature of 120 °C, and time of 12 h. Fourier transform infrared spectroscopy (FT-IR) , 13 C-NMR, and 31 P-NMR showed that willow lignin extracted by ChCl-Lac was mainly composed of syringyl and guaiacyl units. Serendipitously, a majority of the glucan in willow was preserved after ChCl-Lac treatment., Competing Interests: The authors declare no conflict of interest.