Review of methodological decisions in life cycle assessment (LCA) of biorefinery systems across feedstock categories.

The application of life cycle assessment (LCA) to biorefineries is a necessary step to estimate their environmental sustainability. This review explores contemporary LCA biorefinery studies, across different feedstock categories, to understand approaches in dealing with key methodological decisions which arise, including system boundaries, consequential or attributional approach, allocation, inventory data, land use changes, product end-of-life (EOL), biogenic carbon storage, impact assessment and use of uncertainty analysis. From an initial collection of 81 studies, 59 were included within the final analysis, comprising 22 studies which involved dedicated feedstocks, 34 which involved residue feedstocks (including by-products and wastes), and a further 3 studies which involved multiple feedstocks derived from both dedicated and secondary sources. Many studies do not provide a comprehensive LCA assessment, often lacking detail on decisions taken, omitting key parts of the value chain, using generic data without uncertainty analyses, or omitting important impact categories. Only 28% of studies included some level of primary data, while 39% of studies did not undertake an uncertainty or sensitivity analysis. Just 8% of studies included data related to dLUC with a further 8% including iLUC, and only 14% of studies considering product end of life within their scope. The authors recommend more transparency in biorefinery LCA, with justification of key methodological decisions. A full value-chain approach should be adopted, to fully assess burdens and opportunities for biogenic carbon storage. We also propose a more prospective approach, taking into account future use of renewable energy sources, and opportunities for increasing circularity within bio-based value chains.

Facile Tailoring of Structures for Controlled Release of Paracetamol from Sustainable Lignin Derived Platforms.

Nowadays, sustainable materials are receiving significant attention due to the fact that they will be crucial for the development of the next generation of products and devices. In the present work, hydrogels have been successfully synthesized using lignin which is non-valorized biopolymer from the paper industry. Hydrogels were prepared via crosslinking with Poly(ethylene) glycol diglycidyl ether (PEGDGE). Different crosslinker ratios were used to determine their influence on the structural and chemical properties of the resulting hydrogels. It has been found that pore size was reduced by increasing crosslinker amount. The greater crosslinking density increased the swelling capacity of the hydrogels due to the presence of more hydrophilic groups in the hydrogel network. Paracetamol release test showed higher drug diffusion for hydrogels produced with a ratio lignin:PEGDGE 1:1. The obtained results demonstrate that the proposed approach is a promising route to utilize lignocellulose waste for producing porous materials for advanced biomedical applications in the pharmacy industry.

The Meniscus in Normal and Osteoarthritic Tissues: Facing the Structure Property Challenges and Current Treatment Trends.

The treatment of meniscus injuries has recently been facing a paradigm shift toward the field of tissue engineering, with the aim of regenerating damaged and diseased menisci as opposed to current treatment techniques. This review focuses on the structure and mechanics associated with the meniscus. The meniscus is defined in terms of its biological structure and composition. Biomechanics of the meniscus are discussed in detail, as an understanding of the mechanics is fundamental for the development of new meniscal treatment strategies. Key meniscal characteristics such as biological function, damage (tears), and disease are critically analyzed. The latest technologies behind meniscal repair and regeneration are assessed.

Controlled solvent vapor annealing of a high χ block copolymer thin film.

Molecular self-assembling block copolymers (BCPs) have shown promise as a next generation bottom-up lithography technology. However, a critical step in advancing this approach is the elimination of polymer dewetting due to bulk solvent nucleation and thermodynamically driven film rupture that can occur during the solvent vapor annealing process. We report on the pattern formation via phase segregation of spin coated diblock copolymer films through the investigation of annealing parameters in the limit of high solvent vapor saturation conditions that results in wafer-scale patterning without observing polymer dewetting defects. Specifically, the work addresses polymer dewetting in diblock copolymer nanodot templates through the use of a "neutral" functionalization layer and the development of a custom-built solvent vapor annealing chamber to precisely control saturation conditions. Furthermore, the long anneal times (4 h) using a standard static solvent vapor annealing procedure were reduced to ∼15-30 minutes with our dynamic solvent vapor annealing system for the high χ, cylindrical forming poly(styrene)-block-poly(4-vinyl-pyridine) [PS-b-P4VP] diblock copolymer system. We discuss the kinetic mechanism governing the phase segregation process that highlights the small processing window bounded by long phase segregation timescales (≳1 min) on one side and the initiation of polymer film dewetting on the other. These results demonstrate a key step towards realizing a high fidelity, low cost BCP patterning technique for large-scale "bottom-up" feature definition at nanometer length scales.

Development of 3D Printable Gelatin Methacryloyl/Chondroitin Sulfate/Hyaluronic Acid Hydrogels as Implantable Scaffolds.

The development of biomaterials tailored for various tissue engineering applications has been increasingly researched in recent years; however, stimulating cells to synthesise the extracellular matrix (ECM) is still a significant challenge. In this study, we investigate the use of ECM-like hydrogel materials composed of Gelatin methacryloyl (GelMA) and glycosaminoglycans (GAG), such as hyaluronic acid (HA) and chondroitin sulphate (CS), to provide a biomimetic environment for tissue repair. These hydrogels are fully characterised in terms of physico-chemical properties, including compression, swelling behaviour, rheological behaviour and via 3D printing trials. Furthermore, porous scaffolds were developed through freeze drying, producing a scaffold morphology that better promotes cell proliferation, as shown by in vitro analysis with fibroblast cells. We show that after cell seeding, freeze-dried hydrogels resulted in significantly greater amounts of DNA by day 7 compared to the GelMA hydrogel. Furthermore, freeze-dried constructs containing HA or HA/CS were found to have a significantly higher metabolic activity than GelMA alone.

On the design of lignin reinforced acrylic acid/hyaluronic acid adhesive hydrogels with conductive PEDOT:HA nanoparticles.

Hydrogels are of great importance in biomedical engineering. They possess the ability to mimic bodily soft tissues, and this allows exciting possibilities for applications such as tissue engineering, drug delivery and wound healing, however much work remains on stability and mechanical robustness to allow for translation to clinical applications. The work herein describes the synthesis and analysis of a biocompatible, versatile hydrogel that has tailorable swelling, high stability when swollen and thermal stability. The synthesis methods used produce a hydrogel with high elasticity, good mechanical properties and rapid crosslinking whilst displaying biocompatibility, adhesion, and conductivity. It has been shown that cell viability in the samples is above 80 % in all cases, a Young's Modulus of up to 85 kPa and high swelling degrees were achieved. These materials show potential for use in numerous applications such as adhesive sensors, skin grafts and drug delivery systems.

Polymorph selection of pharmaceutical cocrystals via bench-top and continuous production techniques.

Polymorphism can be a valuable tool as well as an impediment in the development and approval of pharmaceuticals, providing an opportunity to tune active pharmaceutical ingredient (API) physicochemical properties. The control of polymorphism in cocrystalline systems and other multicomponent forms remains underexplored. The study herein aims to investigate the potential of several techniques, liquid-assisted grinding (LAG), solvent evaporation (SE), supercritical enhanced atomization (SEA) and electrospraying, to control the cocrystal polymorphic outcome of three cocrystals: isonicotinamide-citric acid (IsoCa), ethenzamide-saccharin (EthSac) and ethenzamide-gentisic acid (EthGa). Solvent selection employing LAG and SE showed little effect on polymorphic outcome. Electrospraying and SEA primarily produced the α form of IsoCa, with process parameter variations leading to the ß form during SEA, and a mixture of α and γ from electrospraying. Electrospraying led to the stable form I of EthSac, while SEA could produce pure form II, and a mixture. Electrospraying produced the form I of EthGa while SEA could produce form II, with an unknown polymorphic impurity. Density functional theory (DFT) computed electron density (ED) maps of cocrystal polymorph binary systems further rationalised the polymorphic predominance observed through the electrospraying. Ultimately this study provides a general road map for polymorph selection via atomization-based methodologies.

Hydrothermal processing of Sarcopeltis skottsbergii and study of the potential of its carrageenan for tissue engineering.

The red macroalga Sarcopeltis skottsbergii was subjected to hydrothermal processing to maximize the solubilization and recovery of carrageenan. Once isolated by ethanol precipitation, the carrageenan was further chemically (oligosaccharides composition), and structurally (TGA/DTG, DSC, HPSEC, FTIR-ATR, 1H NMR, SEM, etc.) characterized, as well as employed as source for the synthesis of hydrogels. The rheological properties of the carrageenan showed promising results as biopolymer for food applications due to the high molecular weight (500 kDa) presenting higher cell viability than 70 %. The evaluation of immune activation using ELISA test reflected a lower inflammatory response for concentrations of 0.025 % of carrageenan. Conversely, the cell viability of the synthesized hydrogels did not surpass 50 %. This work represents a considerable step forward to obtain a biopolymer from natural sources and a thorough study of their chemical, structural and biological properties.

Synthesis of Sustainable Lignin Precursors for Hierarchical Porous Carbons and Their Efficient Performance in Energy Storage Applications.

Lignin-derived porous carbons have great potential for energy storage applications. However, their traditional synthesis requires highly corrosive activating agents in order to produce porous structures. In this work, an environmentally friendly and unique method has been developed for preparing lignin-based 3D spherical porous carbons (LSPCs). Dropwise injection of a lignin solution containing PVA sacrificial templates into liquid nitrogen produces tiny spheres that are lyophilized and carbonized to produce LSPCs. Most of the synthesized samples possess excellent specific surface areas (426.6-790.5 m2/g) along with hierarchical micro- and mesoporous morphologies. When tested in supercapacitor applications, LSPC-28 demonstrates a superior specific capacitance of 102.3 F/g at 0.5 A/g, excellent rate capability with 70.3% capacitance retention at 20 A/g, and a commendable energy density of 2.1 Wh/kg at 250 W/kg. These materials (LSPC-46) also show promising performance as an anode material in sodium-ion batteries with high reversible capacity (110 mAh g-1 at 100 mA g-1), high Coulombic efficiency, and excellent cycling stability. This novel and green technique is anticipated to facilitate the scalability of lignin-based porous carbons and open a range of research opportunities for energy storage applications.

Recent advances in ionic thermoelectric systems and theoretical modelling.

Converting waste heat from solar radiation and industrial processes into useable electricity remains a challenge due to limitations of traditional thermoelectrics. Ionic thermoelectric (i-TE) materials offer a compelling alternative to traditional thermoelectrics due to their excellent ionic thermopower, low thermal conductivity, and abundant material options. This review categorizes i-TE materials into thermally diffusive and thermogalvanic types, with an emphasis on the former due to its superior thermopower. This review also highlights the i-TE materials for creating ionic thermoelectric supercapacitors (ITESCs) that can generate significantly higher voltages from low-grade heat sources compared to conventional technologies. Additionally, it explores thermogalvanic cells and combined devices, discussing key optimization parameters and theoretical modeling approaches for maximizing material and device performance. Future directions aim to enhance i-TE material performance and address low energy density challenges for flexible and wearable applications. Herein, the cutting-edge of i-TE materials are comprehensively outlined, empowering researchers to develop next-generation waste heat harvesting technologies for a more sustainable future.

Assessing the environmental footprint of alternative green biorefinery protein extraction techniques from grasses and legumes.

The significant grasslands of Europe and its member states represents a significant feedstock opportunity for circular bioeconomy development. The development of green biorefineries (GBR), to supply protein for the feed industry from grass, could help many European member states to address significant deficits in protein availability and reduce imports. The current study assesses the environmental footprint of alternative GBR protein extraction techniques from grasses and legumes using life cycle assessment. The focus is on comparing feedstock and technology pathways that could displace soya bean imports. The study finds that leaf protein concentrate (LPC) produced from grass had an improved environmental performance when compared to soya bean meal (SBM), across the assessed feedstock (perennial ryegrass or grass-clover mixtures) and technology pathways (one-stage maceration versus multi-stage maceration). For example, in the case of Climate Change the emission intensity for LPC was 57-85 % lower per tonne of crude protein (CP) compared with SBM. Acidification burdens were 54-88 % lower, and Eutrophication: Freshwater burdens were 74-89 % lower. Some scenarios of GBR produced LPC with a larger Energy Resources: Non-Renewable burden than SBM, though this could be mitigated with higher renewable energy (biogas and wind energy) integration within the scenario. Grass-clover scenarios generally achieved a lower intensity of emissions compared to ryegrass scenarios, particularly in the category of Climate Change, where feedstock cultivation represented a significant contributor to impacts. Overall, GBR can produce high quality protein with a lower environmental burden than SBM, but choice of feedstock and system design are critical factors for overall environmental performance.

Synthesis of high-efficient low-cost fertilizer carriers based on biodegradable lignin hydrogels.

Conventional fertilizers face environmental and economic challenges due to their high solubility, leading to significant losses via runoff and leachate. This study presents a biodegradable hydrogel, synthesized from lignin and polyvinyl alcohol (PVA), designed as an eco-friendly carrier for struvite (fertilizer) with controlled phosphate release. The hydrogel was analysed through scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), Thermogravimetric analysis (TGA) and Differential scanning calorimetry (DSC). Furthermore, the prepared hydrogels demonstrated high water absorption capacities (963.4 %, 706.4 %, and 410 % for LH4, LH8, and LH12, respectively) and exhibited Fickian diffusion behaviour. Phosphate release studies showed a gradual release over 6-8 h with concentrations of 20.5 ppm, 19.45 ppm, and 17.85 ppm for St-LH4, St-LH8, and St-LH12. These lignin-based hydrogels offer a promising, cost-effective solution for slow-release fertilizers with high efficiency.

Synthesis and evaluation of alginate, gelatin, and hyaluronic acid hybrid hydrogels for tissue engineering applications.

Tissue engineering (TE) has been proposed extensively as a potential solution to the worldwide shortages of donor organs needed for transplantation. Over the years, numerous hydrogel formulations have been studied for various TE endeavours, including bone, cardiac or neural TE treatment strategies. Amongst the materials used, organic and biocompatible materials which aim to mimic the natural extracellular matrix of the native tissue have been investigated to create biomimicry regenerative environments. As such, the comparison between studies using the same materials is often difficult to accomplish due to varying material concentrations, preparation strategies, and laboratory settings, and as such these variables have a huge impact on the physio-chemical properties of the hydrogel systems. The purpose of the current study is to investigate popular biomaterials such as alginate, hyaluronic acid and gelatin in a variety of concentrations and hydrogel formulations. This aims to provide a clear and comprehensive understanding of their behaviours and provide a rational approach as to the appropriate selection of natural polysaccharides in specific targeted TE strategies.

Hyaluronic acid association with bacterial, fungal and viral infections: Can hyaluronic acid be used as an antimicrobial polymer for biomedical and pharmaceutical applications?

The relationships between hyaluronic acid (HA) and pathological microorganisms incite new understandings on microbial infection, tissue penetration, disease progression and lastly, potential treatments. These understandings are important for the advancement of next generation antimicrobial therapeutical strategies for the control of healthcare-associated infections. Herein, this review will focus on the interplay between HA, bacteria, fungi, and viruses. This review will also comprehensively detail and discuss the antimicrobial activity displayed by various HA molecular weights for a variety of biomedical and pharmaceutical applications, including microbiology, pharmaceutics, and tissue engineering.

Design and characterization of functional TiO2-lignin fillers used in rotational molded polyethylene containers.

In this study, new TiO2-lignin hybrid systems were synthesized and characterized by various methods, including non-invasive backscattering (NIBS), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), elemental analysis (EA) and zeta potential analysis (ZP). The weak hydrogen bonds between the components, as shown on FTIR spectra, proved the production of class I hybrid systems. TiO2-lignin systems were found to display good thermal stability and relatively good homogeneity. These newly designed hybrid materials were used to produce functional composites via rotational molding in a linear low-density polyethylene (LLDPE) matrix at 2.5 % and 5.0 % loading by weight of the fillers, namely, TiO2, TiO2-lignin (5:1 wt./wt.), TiO2-lignin (1:1 wt./wt.), TiO2-lignin (1:5 wt./wt.) and pristine lignin, creating rectangular specimens. The mechanical properties of the specimens were measured via compression testing and by low-energy impact damage testing (the drop test). The results showed that the system containing 5.0 % by weight of TiO2-lignin (1:1 wt./wt.) had the most positive effect on the container's compression strength, while the LLDPE filled with 5.0 % by weight of TiO2-lignin (5:1 wt./wt.) demonstrated the best impact resistance among all the tested composites.

The impact of varying dextran oxidation levels on the inhibitory activity of a bacteriocin loaded injectable hydrogel.

In the design of injectable antimicrobial dextran-alginate hydrogels, the impact of dextran oxidation and its subsequent changes in molecular weight and the incorporation of glycol chitosan on (i) gel mechanical strength and (ii) the inhibitory profile of an encapsulated bacteriocin, nisin A, are explored. As the degree of oxidation increases, the weight average molecular mass of the dextran decreases, resulting in a reduction in elastic modulus of the gels made. Upon encapsulation of the bacteriocin nisin into the gels, varying the dextran mass/oxidation level allowed the antimicrobial activity against S. aureus to be controlled. Gels made with a higher molecular weight (less oxidised) dextran show a higher initial degree of inhibition while those made with a lower molecular weight (more oxidised) dextran exhibit a more sustained inhibition. Incorporating glycol chitosan into gels composed of dextran with higher masses significantly increased their storage modulus and the gels' initial degree of inhibition.

Synthesis and characterization of gelatin/lignin hydrogels as quick release drug carriers for Ribavirin.

In this study, hydrogels based on gelatin and lignin were fabricated as efficient drug carriers for Ribavirin. The obtained hydrogels were characterized by scanning electron microscopy (SEM), ATR-FTIR spectroscopy, differential scanning calorimetry (DSC), mechanical compression and rheometry. Results showed that the pore structure, viscoelastic behavior and swelling ability significantly influenced by varying lignin content and crosslinker ratio. By increasing the crosslinker N-(3-Dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC) content, the pore size became smaller, while increasing the lignin content resulted in larger pores. In addition, all hydrogels show strong shear thinning behavior. Ribavirin was used as a drug model, and its release rate was enhanced by increasing lignin content in the binary hydrogel structure. A higher Ribavirin cumulative release was observed for gelatin/lignin with higher lignin content (3 %) hydrogel. These findings emphasize the chemical composition on the structure and the release behavior of lignin-containing hydrogels.

Tailoring TiO2-lignin hybrid materials as a bio-filler for the synthesis of composites based on epoxy resin.

In this publication, the functional TiO2-lignin hybrid materials were designed and characterized. Based on elemental analysis and Fourier transform infrared spectroscopy, the efficiency of the mechanical method used to obtain systems was confirmed. Hybrid materials were also characterized by good electrokinetic stability, in particular in the inert and alkaline environments. The addition of TiO2 improves thermal stability in the entire analyzed range of temperatures. Similarly, as the content of inorganic component increases, the homogeneity of the system and the occurrence of smaller nanometric particles increase. In addition, a novel synthesis method of cross-linked polymer composites based on a commercial epoxy resin and an amine cross-linker was described as a part of the article, where additionally newly designed hybrids were also used. Subsequently, the obtained composites were subjected to simulated tests of accelerated UV-aging, and then their properties were studied, including changes in wettability (using water, ethylene glycol, and diiodomethane as measurement liquids) and surface free energy by the Owens-Wendt-Eabel-Kealble method. Changes in the chemical structure of the composites were monitored by FTIR spectroscopy due to aging. Microscopic studies of surfaces were also carried out as well as measurements in the field of changes in color parameters in the CIE-Lab system.

Cellulose: Characteristics and applications for rechargeable batteries.

Cellulose, an abundant natural polymer, has promising potential to be used for energy storage systems because of its excellent mechanical, structural, and physical characteristics. This review discusses the structural features of cellulose and describes its potential application as an electrode, separator, and binder, in various types of high-performing batteries. Various surface and structural characteristics of cellulose (e.g., fiber size, surface functional groups, the hierarchy of pores, and porosity levels) that contribute to its electrochemical performance are discussed. Cellulose structure/property/processing/function relationships are further focused and elucidated in terms of the latest developments in the emerging field of sustainable materials in Li-Ion, Na-Ion, and LiS batteries.

Sustainable lignin precursors for tailored porous carbon-based supercapacitor electrodes.

Sustainable materials are attracting a lot of attention since they will be critical in the creation of the next generation of products and devices. In this study, hydrogels were effectively synthesized utilizing lignin, a non-valorised biopolymer from the paper industry. This study proposes a method based on utilizing lignin to create highly swollen hydrogels using poly(ethylene) glycol diglycidyl ether (PEGDGE) as a crosslinking agent. The influence of different crosslinker ratios on the structural and chemical properties of the resultant hydrogels was investigated. Pore size was observed to be lowered when the amount of crosslinker was increased. The inclusion of additional hydrophilic groups in the hydrogel network decreased the swelling capacity of the hydrogels as the crosslinking density increases. These precursor materials were carbonised and electrochemically tested for application as electrodes for supercapacitors with capacitance characterized as a function of crosslinker ratio.