Development and Application of a Lignin-Based Polyol for Sustainable Reactive Polyurethane Adhesives Synthesis.

In response to the environmental impacts of conventional polyurethane adhesives derived from fossil fuels, this study introduces a sustainable alternative utilizing lignin-based polyols extracted from rice straw through a process developed at INESCOP. This research explores the partial substitution of traditional polyols with lignin-based equivalents in the synthesis of reactive hot melt polyurethane adhesives (HMPUR) for the footwear industry. The performance of these eco-friendly adhesives was rigorously assessed through Thermogravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC), rheological analysis, and T-peel tests to ensure their compliance with relevant industry standards. Preliminary results demonstrate that lignin-based polyols can effectively replace a significant portion of fossil-derived polyols, maintaining essential adhesive properties and marking a significant step towards more sustainable adhesive solutions. This study not only highlights the potential of lignin in the realm of sustainable adhesive production but also emphasises the valorisation of agricultural by-products, thus aligning with the principles of green chemistry and sustainability objectives in the polymer industry.

Restoring a balanced pool of host-derived and microbiota-derived ligands of the aryl hydrocarbon receptor is beneficial after stroke.

Background: Stroke is a major cause of morbidity and mortality, and its incidence increases with age. While acute therapies for stroke are currently limited to intravenous thrombolytics and endovascular thrombectomy, recent studies have implicated an important role for the gut microbiome in post-stroke neuroinflammation. After stroke, several immuno-regulatory pathways, including the aryl hydrocarbon receptor (AHR) pathway, become activated. AHR is a master regulatory pathway that mediates neuroinflammation. Among various cell types, microglia (MG), as the resident immune cells of the brain, play a vital role in regulating post-stroke neuroinflammation and antigen presentation. Activation of AHR is dependent on a dynamic balance between host-derived and microbiota-derived ligands. While previous studies have shown that activation of MG AHR by host-derived ligands, such as kynurenine, is detrimental after stroke, the effects of post-stroke changes in microbiota-derived ligands of AHR, such as indoles, is unknown. Our study builds on the concept that differential activation of MG AHR by host-derived versus microbiome-derived metabolites affects outcomes after ischemic stroke. We examined the link between stroke-induced dysbiosis and loss of essential microbiota-derived AHR ligands. We hypothesize that restoring the balance between host-derived (kynurenine) and microbiota-derived (indoles) ligands of AHR is beneficial after stroke, offering a new potential avenue for therapeutic intervention in post-stroke neuroinflammation. Method: We performed immunohistochemical analysis of brain samples from stroke patients to assess MG AHR expression after stroke. We used metabolomics analysis of plasma samples from stroke and non-stroke control patients with matched comorbidities to determine the levels of indole-based AHR ligands after stroke. We performed transient middle cerebral artery occlusion (MCAO) in aged (18 months) wild-type (WT) and germ-free (GF) mice to investigate the effects of post-stroke treatment with microbiota-derived indoles on outcome. To generate our results, we employed a range of methodologies, including flow cytometry, metabolomics, and 16S microbiome sequencing. Results: We found that MG AHR expression is increased in human brain after stroke and after ex vivo oxygen-glucose deprivation and reperfusion (OGD/R). Microbiota-derived ligands of AHR are decreased in the human plasma at 24 hours after ischemic stroke. Kynurenine and indoles exhibited differential effects on aged WT MG survival after ex vivoOGD/R. We found that specific indole-based ligands of AHR (indole-3-propionic acid and indole-3-aldehyde) were absent in GF mice, thus their production depends on the presence of a functional gut microbiota. Additionally, a time-dependent decrease in the concentration of these indole-based AHR ligands occurred in the brain within the first 24 hours after stroke in aged WT mice. Post-stroke treatment of GF mice with a cocktail of microbiota-derived indole-based ligands of AHR regulated MG-mediated neuroinflammation and molecules involved in antigen presentation (increased CD80, MHC-II, and CD11b). Post-stroke treatment of aged WT mice with microbiota-derived indole-based ligands of AHR reduced both infarct volume and neurological deficits at 24 hours. Conclusion: Our novel findings provide compelling evidence that the restoration of a well-balanced pool of host-derived kynurenine-based and microbiota-derived indole-based ligands of AHR holds considerable therapeutic potential for the treatment of ischemic stroke.

Polyurethane Adhesives with Chemically Debondable Properties via Diels-Alder Bonds.

Covalent adaptable networks (CANs) represent a pioneering advance in polymer science, offering unprecedented versatility in materials design. Unlike conventional adhesives with irreversible bonds, CAN-based polyurethane adhesives have the unique ability to undergo chemical restructuring through reversible bonds. One of the strategies for incorporating these types of reactions in polyurethanes is by functionalisation with Diels-Alder (DA) adducts. By taking advantage of the reversible nature of the DA chemistry, the adhesive undergoes controlled crosslinking and decrosslinking processes, allowing for precise modulation of bond strength. This adaptability is critical in applications requiring reworkability or recyclability, as it allows for easy disassembly and reassembly of bonded components without compromising the integrity of the material. This study focuses on the sustainable synthesis and characterisation of a solvent-based polyurethane adhesive, obtained by functionalising a polyurethane prepolymer with DA diene and dienophiles. The characterisation of the adhesives was carried out using different experimental techniques: nuclear magnetic resonance spectroscopy (NMR), Brookfield viscosity, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and T-peel strength testing of leather/adhesive/rubber joints to determine the adhesive properties, both before and after the application of external stimuli. The conversion of both the DA and retro-Diels-Alder (r-DA) reactions was confirmed by 1H-NMR. The adhesive properties were not altered by the functionalisation of the adhesive prepolymer, showing similar thermal resistance and good rheological and adhesive properties, even exceeding the most demanding technical requirements for upper-to-sole joints in footwear. After the application of an external thermal stimuli, the bonded materials separated without difficulty and without damage, thus facilitating their separation, recovery and recycling.

Organosilicon-Based Plasma Nanocoating on Crust Leather for Water-Repellent Footwear.

In this study, functional nanocoatings for water-repellent footwear leather materials were investigated by chemical plasma polymerisation by implanting and depositing the organosilicon compound hexamethyldisiloxane (HMDSO) using a low-pressure plasma system. To this end, the effect of monomers on leather plasma deposition time was evaluated and both the resulting plasma polymers and the deposited leather samples were characterised using different experimental techniques, such as: Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). In addition, leather samples were tested by standard tests for color change, water resistance, surface wetting resistance and dynamic water contact angle (DWCA). The resulting polysiloxane polymers exhibited hydrophobic properties on leather. Furthermore, these chemical surface modifications created on the substrate can produce water repellent effects without altering the visual leather appearance and physical properties. Both plasma coating treatments and nanocoatings with developed water-repellency properties can be considered as a more sustainable, automated and less polluting alternative to chemical conventional processing that can be introduced into product-finishing processes in the footwear industry.

Sustainable Reactive Polyurethane Hot Melt Adhesives Based on Vegetable Polyols for Footwear Industry.

The aim of this work is to develop sustainable reactive polyurethane hot melt adhesives (HMPUR) for footwear applications based on biobased polyols as renewable resources, where ma-croglycol mixtures of polyadipate of 1,4-butanediol, polypropylene and different biobased polyols were employed and further reacted with 4-4'-diphenylmethane diisocyanate. The different reactive polyurethane hot melt adhesives obtained were characterized with different experimental techniques, such as Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), softening temperature and melting viscosity. Finally, their adhesion properties were measured from T-peel tests on leather/HMPUR adhesives/SBR rubber joints in order to establish the viability of the used biobased polyols and the amount of these polyols that could be added to reactive polyurethane hot melt adhesives satisfactorily to meet the quality requirements of footwear joints. All biobased polyols and percentages added to the polyurethane adhesive formulations successfully met the quality requirements of footwear, being comparable to traditional adhesives currently used in footwear joints in terms of final strength. Therefore, these new sustainable polyurethane adhesives can be considered as suitable and sustainable alternatives to the adhesives commonly used in footwear joints.

Hydrophobic Leather Coating for Footwear Applications by a Low-Pressure Plasma Polymerisation Process.

The aim of this work is to develop hydrophobic coatings on leather materials by plasma polymerisation with a low-pressure plasma system using an organosilicon compound, such as hexamethyldisiloxane (HMDSO), as chemical precursor. The hydrophobic coatings obtained by this plasma process were evaluated with different experimental techniques such as Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and standardised tests including colour measurements of the samples, surface coating thickness and water contact angle (WCA) measurements. The results obtained indicated that the monomer had polymerised correctly and completely on the leather surface creating an ultra-thin layer based on polysiloxane. The surface modification produced a water repellent effect on the leather that does not alter the visual appearance and haptic properties. Therefore, the application of the plasma deposition process showed promising results that makes it a more sustainable alternative to conventional functional coatings, thus helping to reduce the use of hazardous chemicals in the finishing process of footwear manufacturing.

Age-dependent involvement of gut mast cells and histamine in post-stroke inflammation.

BACKGROUND: Risk of stroke-related morbidity and mortality increases significantly with age. Aging is associated with chronic, low-grade inflammation, which is thought to contribute to the poorer outcomes after stroke seen in the elderly. Histamine (HA) is a major molecular mediator of inflammation, and mast cells residing in the gut are a primary source of histamine. METHODS: Stroke was induced in male C57BL/6 J mice at 3 months (young) and 20 months (aged) of age. Role of histamine after stroke was examined using young (Yg) and aged (Ag) mice; mice underwent MCAO surgery and were euthanized at 6 h, 24 h, and 7 days post-ischemia; sham mice received the same surgery but no MCAO. In this work, we evaluated whether worsened outcomes after experimental stroke in aged mice were associated with age-related changes in mast cells, histamine levels, and histamine receptor expression in the gut, brain, and plasma. RESULTS: We found increased numbers of mast cells in the gut and the brain with aging. Using the middle cerebral artery occlusion (MCAO) model of ischemic stroke, we demonstrate that stroke leads to increased numbers of gut mast cells and gut histamine receptor expression levels. These gut-centric changes are associated with elevated levels of HA and other pro-inflammatory cytokines including IL-6, G-CSF, TNF-α, and IFN-γ in the peripheral circulation. Our data also shows that post-stroke gut inflammation led to a significant reduction of mucin-producing goblet cells and a loss of gut barrier integrity. Lastly, gut inflammation after stroke is associated with changes in the composition of the gut microbiota as early as 24-h post-stroke. CONCLUSION: An important theme emerging from our results is that acute inflammatory events following ischemic insults in the brain persist longer in the aged mice when compared to younger animals. Taken together, our findings implicate mast cell activation and histamine signaling as a part of peripheral inflammatory response after ischemic stroke, which are profound in aged animals. Interfering with histamine signaling orally might provide translational value to improve stroke outcome.