1. |
- Abdelaziz, Omar Y., et al.
(author)
-
Conceptual Design of a Kraft Lignin Biorefinery for the Production of Valuable Chemicals via Oxidative Depolymerization
- 2020
-
In: ACS Sustainable Chemistry & Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 8:23, s. 8823-8829
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Journal article (peer-reviewed)abstract
- Lignin is the most abundant aromatic biopolymer on Earth, and its aromatic structure makes it a promising platform for the production of biobased chemicals and other valuable building blocks. The valorization of lignin into chemicals currently presents a challenge, and its facilitation is key in the development of viable lignocellulosic biorefinery processes. This study presents a conceptual design for a recently demonstrated process for lignin oxidative depolymerization. Modeling, simulation, and analysis were performed based on experimental data to assess the viability of the process. Mass and energy balances and main design data were determined for a 700 t/y kraft lignin biorefinery. The production capacity of aromatic chemicals, including vanillin, vanillic acid, guaiacol, and acetovanillone, was 0.3 kg aromatics/kg net lignin use. A heat-integrated process design is suggested, and the energy demands and the CO2 emissions are evaluated and compared. Assuming an interest rate of 10% and a plant lifetime of 10 years, the return on investment was calculated to be 14%, indicating that such a biorefinery is viable. A sensitivity analysis was carried out to assess the impact of the vanillin selling price and the cost of lignin on the profitability of the process. A quantitative investigation of process sustainability resulted in an E-factor of ∼1.6 for the entire synthetic route, that is, 38% material efficiency. The findings of this study underline the need for further research to develop efficient lignin conversion technologies with attractive yields in order to increase profitability on an industrial scale.
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2. |
- Abdelaziz, Omar Y., et al.
(author)
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Oxidative Depolymerization of Kraft Lignin for Microbial Conversion
- 2019
-
In: ACS Sustainable Chemistry and Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 7:13, s. 11640-11652
-
Journal article (peer-reviewed)abstract
- The valorization of lignin is being increasingly recognized as crucial to improve the economic viability of integrated biorefineries. Because of its inherent heterogeneity and recalcitrance, lignin has been treated as a waste product in the pulp and paper industry, but new technologies are now being explored to transform lignin into a sustainable resource and enhance its value chain. In the present study, alkaline oxidative depolymerization was investigated as a potential form of pretreatment to enable further biological conversion of LignoBoost kraft lignin (LB). LB lignin oxidation reactions were studied at various temperatures (120-200 °C) and O2 partial pressures (3-15 bar) to identify the optimal conditions for obtaining a biocompatible, oxidatively depolymerized lignin (ODLB) stream. The low molecular weight compounds resulting from this treatment consisted mainly of aromatic monomers and carboxylic acids. The highest yield of aromatic monomers, 3 wt %, was obtained at 160 °C and 3 bar O2. The yield of carboxylic acids increased with both increasing temperature and O2 pressure, exceeding 13% under the harshest conditions investigated. The growth of four aromatic-catabolizing bacterial strains was examined on reaction product mixtures, all of which showed growth on agar plates utilizing ODLB as the sole source of carbon and energy. Rhodococcus opacus and Sphingobium sp. SYK-6 were found to consume most of the aromatic monomers present in the ODLB (e.g., vanillin, vanillate, acetovanillone, and guaiacol). The findings of this study indicate that pretreatment by oxidative depolymerization has potential in the biological valorization of technical lignin streams, for the production of valuable chemicals and materials.
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3. |
- Adolfsson, Karin H., et al.
(author)
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Microwave Assisted Hydrothermal Carbonization and Solid State Postmodification of Carbonized Polypropylene
- 2018
-
In: ACS Sustainable Chemistry and Engineering. - : AMER CHEMICAL SOC. - 2168-0485. ; 6:8, s. 11105-11114
-
Journal article (peer-reviewed)abstract
- Functional carbon materials produced through a hydrothermal treatment of waste products have gained interest. Particularly, the method is considered more facile and green compared to conventional decomposition methods. Here, we demonstrated an upcycling of polypropylene (PP) waste to carbon materials by a microwave assisted hydro thermal treatment. The solid product obtained from the hydrothermal treatment was analyzed by multiple techniques to reveal the structure and the influence of processing conditions on PP degradation and hydrothermal carbonization. Chemical analyses showed the presence of carbonaceous material independent of acid amount (20 and 30 mL), temperature (210 and 250 degrees C), and time (20-80 min). A complete transformation of PP content to amorphous carbon required 60 min at 250 degrees C. The mass yield of the solid product decreased as a function of harsher processing conditions. At the same time, thermogravimetric analysis illustrated products with increasing thermal stability and a larger amount of remaining residue at 600 degrees C. The solid products consisted of irregular fragments and sheet-like structures. A solid state microwave process in air atmosphere was performed on a product with incomplete carbonization. The modification resulted in a decreased C/O ratio, and TGA analysis in nitrogen showed high thermal stability and degree of carbonization as indicated by the remaining residue of 86.4% at 600 degrees C. The new insights provided on the hydrothermal carbonization, and postmodification in air atmosphere, can catalyze effective handling of plastic waste by enabling transformation of low quality waste into functional carbon materials.
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4. |
- Adolfsson, Karin H., et al.
(author)
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Zero-Dimensional and Highly Oxygenated Graphene Oxide for Multifunctional Poly(lactic acid) Bionanocomposites
- 2016
-
In: ACS Sustainable Chemistry and Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 4:10, s. 5618-5631
-
Journal article (peer-reviewed)abstract
- The unique strengths of 2D graphene oxide nanosheets (GONSs) in polymer composites are thwarted by nanosheet agglomeration due to strong intersheet attractions. Here, we reveal that shrinking the planar size to 0D graphene oxide quantum dots (GOQDs), together with the intercalation of rich oxygen functional groups, reduces filler aggregation and enhances interfacial interactions with the host polymer. With poly(lactic acid) (PLA) as a model matrix, atomic force microscopy colloidal probe measurements illustrated that a triple increase in adhesion force to PLA was achieved for GOQDs (234.8 nN) compared to GONSs (80.4 nN), accounting for the excellent exfoliation and dispersion of GOQDs in PLA, in contrast to the notable agglomeration of GONSs. Although present at trace amount (0.05 wt %), GOQDs made a significant contribution to nucleation activity, mechanical strength and ductility, and gas barrier properties of PLA, which contrasted the inferior efficacy of GONSs, accompanied by clear distinction in film transparency (91% and 50%, respectively). Moreover, the GOQDs with higher hydrophilicity accelerated the degradation of PLA by enhancing water erosion, while the GONSs with large sheet surfaces gave a higher hydrolytic resistance. Our findings provide conceptual insights into the importance of the dimensionality and surface chemistry of GO nanostructures in the promising field of bionanocomposites integrating high strength and multifunction (e.g., enhanced transparency, degradation and gas barrier).
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5. |
- Ail, Ujwala, et al.
(author)
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Effect of Sulfonation Level on Lignin/Carbon Composite Electrodes for Large-Scale Organic Batteries
- 2020
-
In: ACS Sustainable Chemistry and Engineering. - : AMER CHEMICAL SOC. - 2168-0485. ; 8:49, s. 17933-17944
-
Journal article (peer-reviewed)abstract
- The key figure-of-merit for materials in stationary energy storage applications, such as large-scale energy storage for buildings and grids, is the cost per kilo per electrochemical cycle, rather than the energy density. In this regard, forest-based biopolymers such as lignin, are attractive, as they are abundant on Earth. Here, we explored lignin as an electroactive battery material, able to store two electrons per hydroquinone aromatic ring, with the targeted operation in aqueous electrolytes. The impact of the sulfonation level of lignin on the performance of its composite electrode with carbon was investigated by considering three lignin derivatives: lignosulfonate (LS), partially desulfonated lignosulfonate (DSLS), and fully desulfonated lignin (KL, lignin produced by the kraft process). Partial desulfonation helped in better stability of the composite in aqueous media, simultaneously favoring its water processability. In this way, a route to promote ionic conductivity within the lignin/carbon composite electrodes was developed, facilitating the access to the entire bulk of the volumetric electrodes. Electrochemical performance of DSLS/C showed highly dominant Faradaic contribution (66%) towards the total capacity, indicating an efficient mixed ionic-electronic transport within the lignin-carbon phase, displaying a capacity of 38 mAh/g at 0.25 A/g and 69% of capacity retention after 2200 cycles at a rate of 1 A/g.
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6. |
- Almenara Perez, Naroa, et al.
(author)
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Lignin–Chitosan Gel Polymer Electrolytes for Stable Zn Electrodeposition
- 2023
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In: ACS Sustainable Chemistry and Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 11:6, s. 2283-2294
-
Journal article (peer-reviewed)abstract
- Electrochemical energy storage technologies offer means to transition toward a decarbonized society and carbon neutrality by 2050. Compared to conventional lithium-ion batteries, aqueous zinc-ion chemistries do not require scarce materials or toxic and flammable organic-based electrolytes to function, making them favorable contenders in the scenario of intensifying climate change and supply chain crisis. However, environmentally benign and bio-based materials are needed to substitute fossil-based battery materials. Accordingly, this work taps into the possibilities of lignin together with chitosan to form gel polymer electrolytes (GPEs) for zinc-ion chemistries. A simple fabrication process enabling free-standing sodium lignosulfonate–chitosan and micellar lignosulfonate–kraft lignin–chitosan GPEs with diameters exceeding 80 mm is developed. The GPEs combine tensile strength with ductility, reaching Young’s moduli of 55 ± 4 to 940 ± 63 MPa and elongations at break of 14.1 ± 0.2 to 43.9 ± 21.1%. Competitive ionic conductivities ranging from 3.8 to 18.6 mS cm–1 and electrochemical stability windows of up to +2.2 V vs Zn2+/Zn were observed. Given the improved interfacial adhesion of the GPEs with metallic Zn promoted by the anionic groups of the lignosulfonate, a stable cycling of the Zn anode is obtained. As a result, GPEs can operate at 5000 μA cm–2 with no short-circuit and Coulombic efficiencies above 99.7%, outperforming conventional separator–liquid electrolyte configurations such as the glass microfiber separator soaked into 2 M ZnSO4 aqueous electrolyte, which short-circuits after 100 μA cm–2. This work demonstrates the potential of underutilized biorefinery side-streams and marine waste as electrolytes in the battery field, opening new alternatives in the sustainable energy storage landscape beyond LIBs.
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7. |
- Almqvist, Henrik, et al.
(author)
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Muconic Acid Production Using Engineered Pseudomonas putida KT2440 and a Guaiacol-Rich Fraction Derived from Kraft Lignin
- 2021
-
In: ACS Sustainable Chemistry and Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 9:24, s. 8097-8106
-
Journal article (peer-reviewed)abstract
- Industrial lignin such as kraft lignin is an abundant feedstock for renewable chemicals and materials. In this study, a process was developed for depolymerization of kraft lignin followed by an upgrading separation step and further bioconversion of the obtained monoaromatic compounds to muconic acid. First, industrial kraft lignin, Indulin AT, was processed into a guaiacol-rich stream using base-catalyzed depolymerization. This stream was subsequently upgraded using liquid-liquid extraction and evaporation to yield a more concentrated and less inhibitory stream, adapted for bioconversion. Finally, guaiacol was quantitatively converted to muconic acid through bioconversion using an engineered Pseudomonas putida strain containing cytochrome P450 and ferredoxin reductase for guaiacol assimilation and deletion of the native catBC genes for muconic acid production. Isomerization of muconic acid in a fermentation medium depending on pH was also studied.
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8. |
- Antonio, Capezza, et al.
(author)
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Advances in the use of protein-based materials: towards sustainable naturally sourced absorbent materials
- 2019
-
In: American Chemical Society Symposium Series (ACS). - : American Chemical Society (ACS). - 0097-6156 .- 1947-5918. ; 7:5
-
Journal article (peer-reviewed)abstract
- Superabsorbent polymers (SAPs) are important in the health-care and personal care industries. Products like bed pads and diapers improve the comfort and sanitary conditions for people all over the world, with SAPs reaching yearly production volumes of ca. 2 million tons. However, recent sustainability issues have questioned the high negative footprint of polymers from nonrenewable resources. Biomacromolecules, especially when functionalized, have properties that make them an attractive alternative for the production of biobased SAPs. Proteins are a particularly interesting alternative due to their high variability and because of their relatively low price, being available as side streams from the agricultural industries. Due to the harsh extraction conditions, these side stream proteins are not competing with the food industry and alternative source-effective uses are advantageous in a circular bioeconomy. As the properties of a SAP material come from a combination of neutralized functional groups to promote polar liquid uptake and intermolecular cross-links to prevent dissolution, proteins offer unique opportunities due to their variability in polymerization. An increased understanding of the protein characteristics and how these can be tuned through functionalization is therefore a prerequisite for the successful development of a commercial biobased SAP that utilizes industrial and nontoxic wastes toward more sustainable products. This review focuses on proteins as biomacromolecules with relevant characteristics for superabsorbent functions, and discusses the opportunities that they may offer toward sustainable SAPs utilizing nontoxic chemicals and following the green chemistry principles.
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9. |
- Arias, Veluska, et al.
(author)
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Homocomposites of Polylactide (PLA) with Induced Interfacial Stereocomplex Crystallites
- 2015
-
In: ACS Sustainable Chemistry and Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 3:9, s. 2220-2231
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Journal article (peer-reviewed)abstract
- The demand for “green” degradable composite materials increases with growing environmental awareness. The key challenge is achieving the preferred physical properties and maintaining their eco-attributes in terms of the degradability of the matrix and the filler. Herein, we have designed a series of “green” homocomposites materials based purely on polylactide (PLA) polymers with different structures. Film-extruded homocomposites were prepared by melt-blending PLA matrixes (which had different degrees of crystallinity) with PLLA and PLA stereocomplex (SC) particles. The PLLA and SC particles were spherical and with 300–500 nm size. Interfacial crystalline structures in the form of stereocomplexes were obtained for certain particulate-homocomposite formulations. These SC crystallites were found at the particle/matrix interface when adding PLLA particles to a PLA matrix with d-lactide units, as confirmed by XRD and DSC data analyses. For all homocomposites, the PLLA and SC particles acted as nucleating agents and enhanced the crystallization of the PLA matrixes. The SC particles were more rigid and had a higher Young’s modulus compared with the PLLA particles. The mechanical properties of the homocomposites varied with particle size, rigidity, and the interfacial adhesion between the particles and the matrix. An improved tensile strength in the homocomposites was achieved from the interfacial stereocomplex formation. Hereafter, homocomposites with tunable crystalline arrangements and subsequently physical properties, are promising alternatives in strive for eco-composites and by this, creating materials that are completely degradable and sustainable.
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10. |
- Arias, Veluska, et al.
(author)
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Toward "Green" Hybrid Materials : Core-Shell Particles with Enhanced Impact Energy Absorbing Ability
- 2016
-
In: ACS Sustainable Chemistry and Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 4:7, s. 3757-3765
-
Journal article (peer-reviewed)abstract
- Restrained properties of "green" degradable products drive the creation of materials with innovative structures and retained eco-attributes. Herein, we introduce the creation of impact modifiers in the form of core-shell (CS) particles toward the creation of "green" composite materials. Particles with CS structure constituted of PLA stereocomplex (PLASC) and a rubbery phase of poly(epsilon-caprolactone-co-D,L-lactide) (P[CL-co-LA]) were successfully achieved by spray droplet atomization. A synergistic association of the soft P[CL-co-LA] and hard PLASC domains in the core-shell structure induced unique thermo-mechanical effects on the PLA-based composites. The core-shell particles enhanced the crystallization of PLA matrices by acting as nucleating agents. The core-shell particles functioned efficiently as impact modifiers with minimal effect on the composites stiffness and strength. These findings provide a new platform for scalable design of polymeric-based structures to be used in the creation of advanced degradable materials.
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11. |
- Arshadi, Mehrdad
(author)
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Supercritical Extraction of Biomass-A Green and Sustainable Method to Control the Pyrolysis Product Distribution
- 2021
-
In: ACS Sustainable Chemistry and Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 9, s. 5278-5287
-
Journal article (peer-reviewed)abstract
- This research demonstrates that supercritical extraction of the biomass has a remarkable and complex influence on Scots pine tree fractions changing the surface concentration of water, lipids, and metals simultaneously. Surprisingly, this surface composition modification makes a considerable impact on the pyrolysis of the bulk biomass mechanism, leading to the alternation of the volatile and inorganic matter composition. The unique combination of time-of-flight secondary-ion mass spectrometry analysis and utilization of pyrolysis gas chromatography-mass spectrometry data on the thermal behavior of woody biomass demonstrates, for the first time, the extraordinary influence of surface adsorbed metals on the composition of pyrolysis products. ScCO2 could extract the surface metals in the form of fatty acid salts, demonstrating a sustainable and environmentally friendly pretreatment method for controlling the pyrolysis products.
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12. |
- Ashour, Radwa, et al.
(author)
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DTPA-Functionalized Silica Nano- and Microparticles for Adsorption and Chromatographic Separation of Rare Earth Elements
- 2018
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In: ACS Sustainable Chemistry and Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 6:5, s. 6889-6900
-
Journal article (peer-reviewed)abstract
- Silica nanoparticles and porous microparticles have been successfully functionalized with a monolayer of DTPA-derived ligands. The ligand grafting is chemically robust and does not appreciably influence the morphology or the structure of the material. The produced particles exhibit quick kinetics and high capacity for REE adsorption. The feasibility of using the DTPA-functionalized microparticles for chromatographic separation of rare earth elements has been investigated for different sample concentrations, elution modes, eluent concentrations, eluent flow rates, and column temperatures. Good separation of the La(III), Ce(III), Pr(III), Nd(III), and Dy(III) ions was achieved using HNO3 as eluent using a linear concentration gradient from 0 to 0.15 M over 55 min. The long-term performance of the functionalized column has been verified, with very little deterioration recorded over more than 50 experiments. The results of this study demonstrate the potential for using DTPA-functionalized silica particles in a chromatographic process for separating these valuable elements from waste sources, as an environmentally preferable alternative to standard solvent-intensive processes.
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13. |
- Avella, Angelica, 1995, et al.
(author)
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Organo-Mediated Ring-Opening Polymerization of Ethylene Brassylate from Cellulose Nanofibrils in Reactive Extrusion
- 2024
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In: ACS Sustainable Chemistry & Engineering. - 2168-0485. ; 12:29, s. 10727-10738
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Journal article (peer-reviewed)abstract
- Ethylene brassylate is a renewable macrolactone from castor oil that can be polymerized via ring-opening polymerization (ROP) to obtain a fully biosourced biodegradable polyester. ROP mediated by organometallic catalysts leads to high molar mass poly(ethylene brassylate) (PEB). However, the use of metal-free organocatalysis has several advantages, such as the reduction of toxic and expensive metals. In this work, a novel cellulose nanofibril (CNF)/PEB nanocomposite fabrication process by organocatalysis and reactive extrusion (REx) is disclosed. Here, ROP was carried out via solvent-free REx in the presence of CNFs using organic 1,5,7-triazabicyclo[4.4.0]dec-5-ene as a catalyst. Neat or lactate-esterified CNFs (LACNF) were used as initiators to investigate the effect of surface topochemistry on the in situ polymerization and the properties of the nanocomposites. A molar mass of 9 kDa was achieved in the presence of both unmodified and LACNFs with high monomer conversion (>98%) after 30 min reaction in a microcompounder at 130 °C. Tensile analysis showed that both nanofibril types reinforce the matrix and increase its elasticity due to the efficient dispersion obtained through the grafting from polymerization achieved during the REx. Mechanical recycling of the neat polymer and the nanocomposites was proven as a circular solution for the materials’ end-of-life and showed that lactate moieties induced some degradation.
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14. |
- Avella, Angelica, 1995, et al.
(author)
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Reusable, Recyclable, and Biodegradable Heat-Shrinkable Melt Cross-Linked Poly(butylene adipate-co-terephthalate)/Pulp Biocomposites for Polyvinyl Chloride Replacement
- 2024
-
In: ACS Sustainable Chemistry & Engineering. - 2168-0485. ; 12:13, s. 5251-5262
-
Journal article (peer-reviewed)abstract
- Heat-shrinkable films are widely used as disposable secondary packaging but are conventionally made from fossil-based and nonbiodegradable polyvinyl chloride or polyethylene. To lower the environmental impact of such products, this work reports the development of recyclable, biodegradable, and partially biosourced heat-shrinkable biocomposites that are cost-competitive with existing shrink wraps. Poly(butylene adipate-co-terephthalate), a growing biodegradable thermoplastic, was simultaneously reinforced with pulp fibers and partially cross-linked in a single-step reactive melt processing. The designed peroxide-initiated reaction led to a 55 wt % cocontinuous insoluble gel incorporating all the pulp fibers into a cross-linked polymer network. In the solid state, the cross-linked biocomposite shows 60% elongation at break with a 200% increase in Young’s modulus, while the only addition of pulp fibers stiffens and embrittles the matrix. Creep tests in the melt state indicated that the cross-linked network induces homogeneous shrinking even during the loading phase, demonstrating the potential use of the biocomposites as heat-shrinkable films. The shrinking also promotes the shape-memory of the biocomposite, which retains its dimensions after four cycles. The circularity of the materials was assessed by mechanical recycling and industrial composting, which have proven feasible end-of-life options for heat-shrinkable biocomposites.
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15. |
- B. Erdal, Nejla, et al.
(author)
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Green Strategy to Reduced Nanographene Oxide through Microwave Assisted Transformation of Cellulose
- 2018
-
In: ACS Sustainable Chemistry and Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 6:1, s. 1245-1255
-
Journal article (peer-reviewed)abstract
- A green strategy for fabrication of biobased reduced nanographene oxide (r-nGO) was developed. Cellulose derived nanographene oxide (nGO) type carbon nanodots were reduced by microwave assisted hydrothermal treatment with superheated water alone or in the presence of caffeic acid (CA), a green reducing agent. The carbon nanodots, r-nGO and r-nGO-CA, obtained through the two different reaction routes without or with the added reducing agent, were characterized by multiple analytical techniques including FTIR, XPS, Raman, XRD, TGA, TEM, AFM, UV-vis, and DLS to confirm and evaluate the efficiency of the reduction reactions. A significant decrease in oxygen content accompanied by increased number of sp2 hybridized functional groups was confirmed in both cases. The synergistic effect of superheated water and reducing agent resulted in the highest C/O ratio and thermal stability, which also supported a more efficient reduction. Interesting optical properties were detected by fluorescence spectroscopy where nGO, r-nGO, and r-nGO-CA all displayed excitation dependent fluorescence behavior. r-nGO-CA and its precursor nGO were evaluated toward osteoblastic cells MG-63 and exhibited nontoxic behavior up to 200 μg mL-1, which gives promise for utilization in biomedical applications.
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16. |
- Bengtsson, Andreas, et al.
(author)
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Carbon Fibers from Lignin-Cellulose Precursors : Effect of Stabilization Conditions
- 2019
-
In: ACS Sustainable Chemistry and Engineering. - : American Chemical Society. - 2168-0485. ; 7:9, s. 8440-8448
-
Journal article (peer-reviewed)abstract
- There is an increasing demand for lightweight composites reinforced with carbon fibers (CFs). Due to its high availability and carbon content, kraft lignin has gained attention as a potential low-cost CF precursor. CFs with promising properties can be made from flexible dry-jet wet spun precursor fibers (PFs) from blends (70:30) of softwood kraft lignin and fully bleached softwood kraft pulp. This study focused on reducing the stabilization time, which is critical in CF manufacturing. The impact of stabilization conditions on chemical structure, yield, and mechanical properties was investigated. It was possible to reduce the oxidative stabilization time of the PFs from about 16 h to less than 2 h, or even omitting the stabilization step, without fusion of fibers. The main reactions involved in the stabilization stage were dehydration and oxidation. The results suggest that the isothermal stabilization at 250 °C override the importance of having a slow heating rate. For CFs with a commercial diameter, stabilization of less than 2 h rendered in tensile modulus 76 GPa and tensile strength 1070 MPa. Impregnation with ammonium dihydrogen phosphate significantly increased the CF yield, from 31-38 to 46-50 wt %, but at the expense of the mechanical properties.
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17. |
- Bengtsson, Andreas, et al.
(author)
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Carbon Fibers from Lignin-Cellulose Precursors : Effect of Carbonization Conditions
- 2020
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In: ACS Sustainable Chemistry and Engineering. - : American Chemical Society. - 2168-0485. ; 8:17, s. 6826-6833
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Journal article (peer-reviewed)abstract
- Carbon fibers (CFs) are gaining increasing importance in lightweight composites, but their high price and reliance on fossil-based raw materials stress the need for renewable and cost-efficient alternatives. Kraft lignin and cellulose are renewable macromolecules available in high quantities, making them interesting candidates for CF production. Dry-jet wet spun precursor fibers (PFs) from a 70/30 w/w blend of softwood kraft lignin (SKL) and fully bleached softwood kraft pulp (KP) were converted into CFs under fixation. The focus was to investigate the effect of carbonization temperature and time on the CF structure and properties. Reducing the carbonization time from 708 to 24 min had no significant impact on the tensile properties. Increasing the carbonization temperature from 600 to 800 °C resulted in a large increase in the carbon content and tensile properties, suggesting that this is a critical region during carbonization of SKL:KP PFs. The highest Young's modulus (77 GPa) was obtained after carbonization at 1600 °C, explained by the gradual transition from amorphous to nanocrystalline graphite observed by Raman spectroscopy. On the other hand, the highest tensile strength (1050 MPa) was achieved at 1000 °C, a decrease being observed thereafter, which may be explained by an increase in radial heterogeneity.
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18. |
- Berglund, Jennie, et al.
(author)
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Acetylation and Sugar Composition Influence the (In)Solubility of Plant beta-Mannans and Their Interaction with Cellulose Surfaces
- 2020
-
In: ACS Sustainable Chemistry and Engineering. - : AMER CHEMICAL SOC. - 2168-0485. ; 8:27, s. 10027-10040
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Journal article (peer-reviewed)abstract
- Plant beta-mannans are complex heteropolysaccharides that represent an abundant resource from lignocellulosic biomass. The influence of the molecular motifs of plant mannans on the backbone flexibility, solubility, and the interaction with cellulose was investigated by computational and experimental approaches. The regioselectivity of the acetyl substitutions at C2 and C3 distinctively influenced backbone flexibility in aqueous media, as revealed by molecular dynamic simulations. The molecular weight and degree of acetylation were tailored for two model seed mannans (galactomannan and glucomannan) and compared to spruce acetylated galactoglucomannan. The thermal stability was enhanced with increasing acetyl substitutions, independently of the type of mannan. Dynamic light scattering and atomic force microscopy revealed that the occurrence of galactosylation and a low degree of acetylation (similar to that of native acetylated galactoglucomannans) enhanced solubility/dispersibility of mannans, whereas the solubility/dispersibility decreased for higher degrees of acetylation. Mannan solubility influenced their interactions with cellulose at water-cellulose interfaces in terms of adsorbed mass and viscoelastic properties of the adsorbed mannan layers. Our results reveal that modulating the molecular motifs of plant beta-mannans influences their macromolecular conformation and physicochemical properties, with fundamental implications for their role in the plant cell wall and the design of wood-based materials.
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19. |
- Berglund, Lars A., 1956-, et al.
(author)
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Eco-friendly high-strength composites based on hot-pressed lignocellulose microfibrils or fibers
- 2021
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In: ACS Sustainable Chemistry and Engineering. - : American Chemical Society. - 2168-0485. ; 9:4, s. 1899-1910
-
Journal article (peer-reviewed)abstract
- Unbleached lignocellulosic wood fiber materials of low porosity are of great interest as eco-friendly load-bearing materials because their yield is much higher than that for “pure” wood cellulosics. The difference between comparable materials based on lignocellulose fibers or nanocellulose is investigated. The structure, surface area, mechanical properties, moisture sorption, and optical properties of films based on fibers or microfibrillated lignocellulose (MFLC) were characterized as a function of lignin content, and the environmental impact was compared. The modulus and tensile strength of comparable fiber and MFLC films (≈25% porosity) increased up to an optimum lignin content (11−17%) and then decreased at a very high lignin content. Hot-pressed MFLC films with little porosity showed excellent properties, 230−260 MPa strength, 17−20 GPa modulus, and 81 MPa wet strength. The mechanical property values of hot-pressed wood fibers with 25% porosity were also as high as 154 MPa strength and 13.2 GPa modulus, which are higher than those of comparable materials reported in the literature. Because hot-pressed lignocellulose fibers can be readily recycled and show low cumulative energy demand, they are candidates for semistructural engineering materials. MFLC is of great interest for coatings, films, adhesives, and as additives or in high-technology applications.
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20. |
- Bermejo-López, Aitor, et al.
(author)
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Selective Synthesis of Imines by Photo-Oxidative Amine Cross-Condensation Catalyzed by PCN-222(Pd)
- 2021
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In: ACS Sustainable Chemistry and Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 9:43, s. 14405-14415
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Journal article (peer-reviewed)abstract
- Palladium-metalated PCN-222 enables the aerobic photo-oxidative cross-condensation of anilines with benzylic amines yielding a series of linear and cyclic imines. The reaction is very efficient under mild conditions, which allows the isolation of simple, yet elusive, intermediates such as 2-(benzylideneamino)-aniline and 2-(benzylideneamino)phenols. Recyclability studies show excellent activity and selectivity after five runs. The methodology was successfully applied for the synthesis of an antitumor agent (PMX-610).
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21. |
- Bhalla, Aditya, et al.
(author)
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Engineered Lignin in Poplar Biomass Facilitates Cu-Catalyzed Alkaline-Oxidative
- 2018
-
In: ACS Sustainable Chemistry and Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 6:3, s. 2932-2941
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Journal article (peer-reviewed)abstract
- Both untransformed poplar and genetically modified “zip-lignin” poplar, in which additional ester bonds were introduced into the lignin backbone, were subjected to mild alkaline and copper-catalyzed alkaline hydrogen peroxide (Cu-AHP) pretreatment. Our hypothesis was that the lignin in zip-lignin poplar would be removed more easily than lignin in untransformed poplar during this alkaline pretreatment, resulting in higher sugar yields following enzymatic hydrolysis. We observed improved glucose and xylose hydrolysis yields for zip-lignin poplar compared to untransformed poplar following both alkaline-only pretreatment (56% glucose yield for untransformed poplar compared to 67% for zip-lignin poplar) and Cu-AHP pretreatment (77% glucose yield for untransformed poplar compared to 85% for zip-lignin poplar). Compositional analysis, glycome profiling, and microscopy all supported the notion that the ester linkages increase delignification and improve sugar yields. Essentially no differences were noted in the molecular weight distributions of solubilized lignins between the zip-lignin poplar and the control line. Significantly, when zip-lignin poplar was utilized as the feedstock, hydrogen peroxide, catalyst, and enzyme loadings could all be substantially reduced while maintaining high sugar yields.
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22. |
- Bhattacharyya, Shubhankar, et al.
(author)
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Ether Functionalized Choline Tethered Amino Acid Ionic Liquids for Enhanced CO2 Capture
- 2016
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In: ACS Sustainable Chemistry and Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 4:10, s. 5441-5449
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Journal article (peer-reviewed)abstract
- Amino acid ionic liquids (ILs) are the most interesting and effective for CO2 capture due to their low toxicity, biodegradability and fast reactivity towards CO2. Ionic nature of amino acid ILs can raise an environmental issue if the cation counterpart becomes toxic to the aquatic ecosystems and can become potential atmospheric pollutant. In this regard, choline based ILs are known to be promising scaffolds for the development of less toxic amino acid ILs. However, the existing choline amino acid ILs are highly viscous limiting their applicability as solvents. Ether functionalized choline based amino acid ILs with novel series of less toxic green ILs were explored with reduced viscosity and high CO2 capture capacity. A simple, economic, clean and environmentally benign method was utilized for the synthesis of novel choline based amino acid ILs using a commercially available and economical starting material 2-(dimethylamino)ethanol (deanol, a human dietary food supplement). Reported ILs have low viscosity with high CO2 capture capacity (1.62 mol of CO2 /mol of IL, 4.31 mol of CO2/kg of IL, 19.02 wt.% of CO2). Mechanism of [N1,1,6,2O4][Lys]+CO2 reaction and adduct structure was proposed by means of DFT and NMR.
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23. |
- Björnerbäck, Fredrik, et al.
(author)
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Microporous Humins Prepared from Sugars and Bio-Based Polymers in Concentrated Sulfuric Acid
- 2019
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In: ACS Sustainable Chemistry and Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 7:1, s. 1018-1027
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Journal article (peer-reviewed)abstract
- Highly microporous humins were synthesized from readily available sugars and bio-based polymers (monosaccharides, disaccharides, and polysaccharides) in sulfuric acid followed by a diethyl ether wash and heat treatment at 400 degrees C. The relative sustainability, costs of production, and availability of the starting materials were improved significantly as compared with the 5-hydroxymethyl-furfural-based microporous humins recently studied by us. A multipronged approach was used to study the detailed characteristics of the adsorbents. Results from H-1 NMR, C-13 NMR, FTIR, WAXS, and elemental analysis were combined and showed that the adsorbents predominantly consisted of amorphous and aromatic carbon structures being rich in oxygen. They were highly porous, and the micropore volumes varied among the compositions as could be observed by analyzing CO2 and N-2 gas adsorption data. Comparably high CO2 uptakes of 4.25 and 1.94 mmol/g at 0 degrees C and 1 and 0.15 bar were observed. With the synthesis of microporous humins with varying porosities, the domain of potential applications of this class of materials could be expanded.
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24. |
- Blaschek, Leonard, et al.
(author)
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Determining the Genetic Regulation and Coordination of Lignification in Stem Tissues of Arabidopsis Using Semiquantitative Raman Microspectroscopy
- 2020
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In: ACS Sustainable Chemistry and Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 8:12, s. 4900-4909
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Journal article (peer-reviewed)abstract
- Lignin is a phenolic polymer accumulatig in the cell walls of specific plant cell types to confer unique properties such as hydrophobicity, mechanical strengthening, and resistance to degradation. Different cell types accumulate lignin with specific concentration and composition to support their specific roles in the different plant tissues. Yet the genetic mechanisms controlling lignin quantity and composition differently between the different lignified cell types and tissues still remain poorly understood. To investigate this tissue-specific genetic regulation, we validated both the target molecular structures as well as the linear semi-quantitative capacity of Raman microspectroscopy to characterize the total lignin amount, S/G ratio, and coniferyl alcohol content in situ directly in plant biopsies. Using the optimized method on stems of multiple lignin biosynthesis loss-of-function mutants revealed that the genetic regulation of lignin is tissue specific, with distinct genes establishing nonredundant check-points to trigger specific compensatory adjustments affecting either lignin composition and/or cell wall polymer concentrations.
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25. |
- Bonjour, Olivier, et al.
(author)
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Lignin-Inspired Polymers with High Glass Transition Temperature and Solvent Resistance from 4-Hydroxybenzonitrile, Vanillonitrile, and Syringonitrile Methacrylates
- 2021
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In: ACS Sustainable Chemistry & Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 9:50, s. 16874-16880
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Journal article (peer-reviewed)abstract
- We here report on the synthesis and polymerization of nitrile-containing methacrylate monomers, prepared via straightforward nitrilation of the corresponding lignin-inspired aldehyde. The polymethacrylates reached exceptionally high glass transition temperatures (Tg values), i.e., 150, 164, and 238 °C for the 4-hydroxybenzonitrile, vanillonitrile, and syringonitrile derivatives, respectively, and were thermally stable up to above 300 °C. Copolymerizations of the nitrile monomers with styrene and methyl methacrylate, respectively, gave potentially melt processable materials with tunable Tg values and enhanced solvent resistance. The use of lignin-derived nitrile-containing monomers represents an efficient strategy toward well-defined biobased high Tg polymer materials.
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