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.

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.

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.

Unique case of vascularization: superficial brachial artery and radial persistent median artery.

During a routine cadaveric dissection of a 93-year-old male donor, unique arterial variations were observed in the right upper extremity. This rare arterial branching pattern began at the third part of the axillary artery (AA), where it gave off a large superficial brachial artery (SBA) before bifurcating into the subscapular artery and a common stem. The common stem then gave off a division for the anterior and posterior circumflex humeral arteries, before continuing as a small brachial artery (BA). The BA terminated as a muscular branch to the brachialis muscle. The SBA bifurcated into a large radial artery (RA) and small ulnar artery (UA) in the cubital fossa. The UA branching pattern was atypical, giving off only muscular branches in the forearm and a deep UA before contributing to the superficial palmar arch (SPA). The RA provided the radial recurrent artery and a common trunk (CT) proximally before continuing its course to the hand. The CT from the RA gave off a branch that divided into anterior and posterior ulnar recurrent arteries, as well as muscular branches, before it bifurcated into the persistent median artery (PMA) and the common interosseous artery. The PMA anastomosed with the UA before entering the carpal tunnel and contributed to the SPA. This case presents a unique combination of arterial variations in the upper extremity and is clinically and pathologically relevant.

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.

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.

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.

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.

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.

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.

Electroconductive PEDOT nanoparticle integrated scaffolds for spinal cord tissue repair.

BACKGROUND: Hostile environment around the lesion site following spinal cord injury (SCI) prevents the re-establishment of neuronal tracks, thus significantly limiting the regenerative capability. Electroconductive scaffolds are emerging as a promising option for SCI repair, though currently available conductive polymers such as polymer poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) present poor biofunctionality and biocompatibility, thus limiting their effective use in SCI tissue engineering (TE) treatment strategies. METHODS: PEDOT NPs were synthesized via chemical oxidation polymerization in miniemulsion. The conductive PEDOT NPs were incorporated with gelatin and hyaluronic acid (HA) to create gel:HA:PEDOT-NPs scaffolds. Morphological analysis of both PEDOT NPs and scaffolds was conducted via SEM. Further characterisation included dielectric constant and permittivity variances mapped against morphological changes after crosslinking, Young's modulus, FTIR, DLS, swelling studies, rheology, in-vitro, and in-vivo biocompatibility studies were also conducted. RESULTS: Incorporation of PEDOT NPs increased the conductivity of scaffolds to 8.3 × 10-4 ± 8.1 × 10-5 S/cm. The compressive modulus of the scaffold was tailored to match the native spinal cord at 1.2 ± 0.2 MPa, along with controlled porosity. Rheological studies of the hydrogel showed excellent 3D shear-thinning printing capabilities and shape fidelity post-printing. In-vitro studies showed the scaffolds are cytocompatible and an in-vivo assessment in a rat SCI lesion model shows glial fibrillary acidic protein (GFAP) upregulation not directly in contact with the lesion/implantation site, with diminished astrocyte reactivity. Decreased levels of macrophage and microglia reactivity at the implant site is also observed. This positively influences the re-establishment of signals and initiation of healing mechanisms. Observation of axon migration towards the scaffold can be attributed to immunomodulatory properties of HA in the scaffold caused by a controlled inflammatory response. HA limits astrocyte activation through its CD44 receptors and therefore limits scar formation. This allows for a superior axonal migration and growth towards the targeted implantation site through the provision of a stimulating microenvironment for regeneration. CONCLUSIONS: Based on these results, the incorporation of PEDOT NPs into Gel:HA biomaterial scaffolds enhances not only the conductive capabilities of the material, but also the provision of a healing environment around lesions in SCI. Hence, gel:HA:PEDOT-NPs scaffolds are a promising TE option for stimulating regeneration for SCI.

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.

Curcumin encapsulated polylactic acid nanoparticles embedded in alginate/gelatin bioinks for in situ immunoregulation: Characterization and biological assessment.

Curcumin is a known naturally occurring anti-inflammatory agent derived from turmeric, and it is commonly used as a herbal food supplement. Here, in order to overcome the inherent hydrophobicity of curcumin (Cur), polylactic acid (PLA) nanoparticles (NPs) were synthesised using a solvent evaporation, and an oil-in-water emulsion method used to encapsulate curcumin. Polymeric NPs also offer the ability to control rate of drug release. The newly synthesised NPs were analysed using a scanning electron microscope (SEM), where results show the NPs range from 50 to 250 nm. NPs containing graded amounts of curcumin (0 %, 0.5 %, and 2 %) were added to cultures of NIH3T3 fibroblast cells for cytotoxicity evaluation using the Alamar Blue assay. Then, the curcumin NPs were incorporated into an alginate/gelatin solution, prior to crosslinking using a calcium chloride solution (200 nM). These hydrogels were then characterised with respect to their chemical, mechanical and rheological properties. Following hydrogel optimization, hydrogels loaded with NP containing 2 % curcumin were selected as a candidate as a bioink for three-dimensional (3D) printing. The biological assessment for these bioinks/hydrogels were conducted using THP-1 cells, a human monocytic cell line. Cell viability and immunomodulation were evaluated using lactate dehydrogenase (LHD) and a tumour necrosis factor alpha (TNF-α) enzyme-linked immunosorbent (ELISA) assay, respectively. Results show that the hydrogels were cytocompatible and supressed the production of TNF-α. These bioactive hydrogels are printable, supress immune cell activation and inflammation showing immense potential for the fabrication of tissue engineering constructs.

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.

Towards the Development of a Female Animal Model of T1DM Using Hyaluronic Acid Nanocoated Cell Transplantation: Refinements and Considerations for Future Protocols.

Female mice (Black 6 strain) (C57BL/6) aged 6 weeks were subject to low dose streptozotocin (STZ) treatment for five consecutive days to mimic type 1 diabetes mellitus (T1DM) with insulitis. At two weeks after STZ injections, evaluation of the elevated glucose levels was used to confirm diabetes. The diabetic mice were then subject to the transplantation of pancreatic ß-cells (MIN-6 line). Four groups of mice were studied. The first group was injected with saline-only acting as the placebo surgery control, also known as SHAM group, the second and third groups were injected with MIN-6 single cells and polyethylene glycol-modified dipalmitoyl-glycerol-phosphatidyl ethanolamine (PEG-DPPE) modified MIN-6 single cells (500 µg per 1.106 cells), respectively, while the fourth group was injected with hyaluronic acid (HA)-coated MIN-6 single cells (5 bilayers). At seven- and fourteen-days following transplantation, the mice were euthanised. The renal and pancreatic tissues were then collected and histologically analysed. The induction of diabetes in female mice, through five-consecutive daily STZ injections resulted in inconsistent glycaemic levels. Interestingly, this shows an incomplete diabetes induction in female mice, of which we attribute to sex dimorphism and hormonal interferences. Transplantation failure of free-floating encapsulated cells was unable to decrease blood glucose hyperglycaemia to physiological ranges. The result is attributed to deprived cell-cell interactions, leading to decreased ß-cells functionality. Overall, we highlight the necessity of refining T1DM disease models in female subjects when using multiple low-dose STZ injections together with transplantation protocols. Considerations need to be made regarding the different developmental stages of female mice and oestrogen load interfering with pancreatic ß-cells susceptibility to STZ. The use of pseudo islets, cell aggregates and spheroids are sought to improve transplantation outcome in comparison to free-floating single cells.

Tuning the biomimetic behavior of hybrid scaffolds for bone tissue engineering through surface modifications and drug immobilization.

Bone defects arising from injury and/or disease are a common and debilitating clinical lesion. While the development of tissue microenvironments utilizing biomimetic constructs is an emerging approach for bone tissue engineering. In this context, bioactive glass nanoparticles (BGNPs) were embedded within polycaprolactone (PCL) scaffolds. The scaffolds exhibit an engineered unidirectional pore structure which are surface activated via oxygen plasma to allow immobilization of simvastatin (SIM) on the pore surface. Microscopic observation indicated the surface modification did not disturb the lamellar orientation of the pores improving the biomimetic formation of hydroxyapatite. Mathematically modelled release profiles reveal that the oxygen plasma pre-treatment can be utilized to modulate the release profile of SIM from the scaffolds. With the release mechanism controlled by the balance between the diffusion and erosion mechanisms. Computational modelling shows that Human Serum Albumin and Human α2-macroglobulin can be utilized to increase SIM bioavailability for cells via a molecular docking mechanism. Cellular studies show positive MG-63 cell attachment and viability on optimized scaffolds with alkaline phosphatase activity enhanced along with enhanced expression of osteocalcoin biomarker.

The role of lignin and lignin-based materials in sustainable construction - A comprehensive review.

The construction industry in the 21st century faces numerous global challenges associated with growing concerns for the environment. Therefore, this review focuses on the role of lignin and its derivatives in sustainable construction. Lignin's properties are defined in terms of their structure/property relationships and how structural differences arising from lignin extraction methods influence its application within the construction sector. Lignin and lignin composites allow the partial replacement of petroleum products, making the final materials and the entire construction sector more sustainable. The latest technological developments associated with cement composites, rigid polyurethane foams, paints and coatings, phenolic or epoxy resins, and bitumen replacements are discussed in terms of key engineering parameters. The application of life cycle assessment in construction, which is important from the point of view of estimating the environmental impact of various solutions and materials, is also discussed.

Wood-Derived Hydrogels as a Platform for Drug-Release Systems.

Wood (cellulose and lignin)-based hydrogels were successfully produced as platforms for drug-release systems. Viscoelastic and cross-linking behaviors of precursor solutions were tuned to produce highly porous hydrogel architectures via freeze-drying. Pore sizes in the range of 100-160 µm were obtained. Varying lignin molecular structure played a key role in tailoring swelling and mechanical performance of these gels with organosolv-type lignin showing optimum properties due to its propensity for intermolecular cross-linking, achieving a compressive modulus around 11 kPa. Paracetamol was selected as a standard drug for release tests and its release rate was improved with the presence of lignin (50% more compared to pure cellulose hydrogels). This was attributed to a reduction in molecular interactions between paracetamol and cellulose. These results highlight the potential for the valorization of lignin as a platform for drug-release systems.

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.