Upcycling of industrial footwear waste into nonwoven fibrous structures with thermal and acoustic insulation properties.

The footwear industry significantly impacts the environment, from raw material extraction to waste disposal. Transforming waste into new products is a viable option to mitigate the environmental consequences, reducing the reliance on virgin raw materials. This work aims to develop thermal and acoustic insulation materials using polyester waste from footwear industry. Two nonwoven and two compressed nonwoven structures, comprising 80% polyester waste and 20% commercial recycled polyester (matrix), were produced. The materials were created through needle-punching and compression molding techniques. The study included the production of sandwich and monolayer nonwoven structures, which were evaluated considering area weight, thickness, air permeability, mechanical properties, morphology using field emission scanning electron microscopy, and thermal and acoustic properties. The nonwoven samples presented high tensile strength (893 kPa and 629 kPa) and the highest strain (79.7% and 73.3%) and compressed nonwoven structures showed higher tensile strength (2700 kPa and 1291 kPa) but reduced strain (25.8% and 40.8%). Nonwoven samples showed thermal conductivity of 0.041 W/K.m and 0.037 W/K.m. Compressed nonwoven samples had higher values at 0.060 W/K.m and 0.070 W/K.m. While the sample with the highest conductivity exceeds typical insulation levels, other samples are suitable for thermal insulation. Nonwoven structures exhibited good absorption coefficients (0.640-0.644), suitable for acoustic insulation. Compressed nonwoven structures had lower values (0.291-0.536), unsuitable for this purpose. In summary, this study underscores the potential of 100% recycled polyester structures derived from footwear and textile industry waste, showcasing remarkable acoustic and thermal insulation properties ideal for the construction sector.

Localized Therapeutic Approaches Based on Micro/Nanofibers for Cancer Treatment.

Cancer remains one of the most challenging health problems worldwide, and localized therapeutic approaches based on micro/nanofibers have shown potential for its treatment. Micro/nanofibers offer several advantages as a drug delivery system, such as high surface area, tunable pore size, and sustained release properties, which can improve drug efficacy and reduce side effects. In addition, functionalization of these fibers with nanoparticles can enhance their targeting and therapeutic capabilities. Localized delivery of drugs and/or other therapeutic agents via micro/nanofibers can also help to overcome the limitations of systemic administration, such as poor bioavailability and off-target effects. Several studies have shown promising results in preclinical models of cancer, including inhibition of tumor growth and improved survival rates. However, more research is needed to overcome technical and regulatory challenges to bring these approaches to clinical use. Localized therapeutic approaches based on micro/nanofibers hold great promise for the future of cancer treatment, providing a targeted, effective, and minimally invasive alternative to traditional treatments. The main focus of this review is to explore the current treatments utilizing micro/nanofibers, as well as localized drug delivery systems that rely on fibrous structures to deliver and release drugs for the treatment of cancer in a specific area.

Extraction, characterization and properties evaluation of pineapple leaf fibers from Azores pineapple.

Pineapple leaves can provide competitive and high-quality fibers for textile purposes. Despite pineapple being cultivated in the Portugues islands there is still a technology gap for the extraction and treatment of Pineapple Leaf Fibers (PALF) in Europe. Since Azorean Pineapple differs significantly from other plants in the bromeliad family, the properties and characterization of its leaf fibers were explored for the first time. Long fibers have been extracted by hand scraping and compared to biological retting at 25 °C for different time periods. It was explored the properties of PALF from plants of different ages (11- and 18-months) and from different zones of the leaves (beginning, middle, and tip). Physical-mechanical properties of Azores PALF were determined, including diameter, linear density, strength, Young's modulus, and elongation at break and characterized by ATR-FTIR, XRD, TGA/DTG, and FESEM to understand their chemical and morphological characteristics. While slight differences were observed between different ages, variations in physical-mechanical properties were notable among fibers extracted from different leaf positions. Extraction of Azores PALF through 25 °C biological retting for 14 days effectively eliminated non-fibrous matter and produced the thinnest and strongest fibers. These fibers ranged between 34.9 and 168.3 µm in diameter, 1.39 and 7.07 tex in linear mass density, 37-993 MPa in tensile strength, 1.0-3.9 % in elongation at break, and 2.4-21.8 GPa in Young's modulus.

The Potential of Electrospun Membranes in the Treatment of Textile Wastewater: A Review.

Water security and industrial wastewater treatment are significant global concerns. One of the main issues with environmental contamination has been the discharge of dye wastewater from the textile and dye industries, contributing to an ever-growing problem with water pollution, poisoning water supplies, and harming the ecosystem. The traditional approach to wastewater treatment has been found to be inefficient, and biosorption techniques and mechanisms have been proven to be a successful replacement for conventional methods. Recent developments have led to the recognition of fibrous materials as an environmentally friendly option with broad application in several industries, including wastewater treatment. This review explores the potential of fibrous materials produced by the electrospinning technique as adsorbents for wastewater treatment, while at the same time, for the removal of adsorbates such as oil, dyes, heavy metals, and other substances, as reported in the literature. Textile wastewater filtering structures, produced by electrospinning, are summarized and the use of synthetic and natural polymers for this purpose is discussed. The limitations of electrospun textile wastewater filtering structures are also mentioned. Electrospun nanofibrous membranes appear to be a very promising route to filter textile wastewater and therefore contribute to water reuse and to reducing the contamination of water courses.

Photochemistry and Cytotoxicity Evaluation of Heptamethinecyanine Near Infrared (NIR) Dyes.

The present study investigates the photochemical properties of potential photosensitizers for photodynamic therapy, namely four commercial heptamethinecyanine dyes (IR125, IR780, IR813, IR820). Spectroscopic studies were made by means of laser induced fluorescence and laser flash photolysis in order to obtain fluorescence quantum yields and transient absorption spectra. Fluorescence lifetimes were also determined. The differences encountered were essentially related with the interaction of the sulfonate groups with the solvent, and also regarding the rigidification of the central bridge connecting the two nitrogen-containing heterocyclic groups. Transient absorption studies were performed both in aerated and oxygen free samples, to conclude about the formation of photoisomers and triplet state. For the four dyes under study, a cytotoxic evaluation in the dark and after irradiation was performed using HeLa cells as the model cell line, which revealed significant changes after irradiation mainly in IR125 and IR813 dyes. Confocal microscopy analysis showed that these dyes tend to enter to the intracellular space.

Photophysical studies of a new water soluble indocarbocyanine dye adsorbed onto microcrystalline cellulose and ß-cyclodextrin.

A water-soluble indocarbocyanine dye was synthesized and its photophysics were studied for the first time on two solid hosts, microcrystalline cellulose and b-cyclodextrin, as well as in homogeneous media. The inclusion of the indocarbocyanine moiety onto microcrystalline cellulose increased the dye aggregation with both H and J aggregates being formed. Adsorption on b-cyclodextrin enhanced aggregation in a similar way. The fluorescence quantum yields were determined for the powdered samples of the cyanine dye on the two hosts and a significant increase was observed relative to homogeneous solution. A remarkable concentration dependence was also detected in both cases. A lifetime distribution analysis has shown that the indocarbocyanine dye mainly occupies the amorphous part of cellulose and is not entrapped in the crystalline part of this host. In the b-CD case, the adsorption occurs outside the host cavity. In both hosts a strong concentration quenching effect is observed and only monomers emit. Both adsorptions may be explained by stereochemical constraints imposed by the two long sulphoethyl tails linked to nitrogen atoms of the indocarbocyanine dye.

Synthesis and spectral evaluation of some unsymmetrical mesoporphyrinic complexes.

Synthesis and spectral evaluation of new zinc and copper unsymmetrical mesoporphyrinic complexes are reported. Zn(II)-5-(4-acetoxy-3-methoxyphenyl)-10,15,20- tris-(4-carboxymethylphenyl)porphyrin, Zn(II)-5-[(3,4-methylenedioxy)phenyl]-10,15,20- tris-(4-carboxymethylphenyl)porphyrin, Cu(II)-5-(4-acetoxy-3-methoxyphenyl)-10,15,20- tris-(4-carboxymethylphenyl)porphyrin and Cu(II)-5-[(3,4-methylenedioxy)phenyl]-10,15,20- tris-(4-carboxymethylphenyl)porphyrin were synthesized using microwave-assisted synthesis. The complexes were characterized by elemental analysis, FT-IR, UV-Vis, EPR and NMR spectroscopy, which fully confirmed their structure. The spectral absorption properties of the porphyrinic complexes were studied in solvents with different polarities. Fluorescence emission and singlet oxygen formation quantum yields were evaluated for the compounds under study, revealing high yields for the zinc derivatives. The copper complexes are not emissive and only display residual capacity for singlet oxygen formation.

Surface photochemistry: 3,3'-dialkylthia and selenocarbocyanine dyes adsorbed onto microcrystalline cellulose.

In this work, thia and selenocarbocyanines with n-alkyl chains of different length, namely with methyl, ethyl, propyl, hexyl and decyl substituents, were studied in homogeneous and heterogeneous media for comparison purposes. For both carbocyanine dyes adsorbed onto microcrystalline cellulose, a remarkable increase in the fluorescence quantum yields and lifetimes were detected, when compared with solution. Contrary to the solution behaviour, where the increase in the n-alkyl chains length increases to a certain extent the fluorescence emission Φ(F) and τ(F), on powdered solid samples a decrease of Φ(F) and τ(F) was observed. The use of an integrating sphere enabled us to obtain absolute Φ(F)'s for all the powdered samples. The main difference for liquid homogeneous samples is that the increase of the alkyl chain strongly decreases the Φ(F) values, both for thiacarbocyanines and selenocarbocyanines. A lifetime distribution analysis for the fluorescence of these dyes adsorbed onto microcrystalline cellulose, evidenced location on the ordered and crystalline part of the substrate, as well as on the more disordered region where the lifetime is smaller. The increase of the n-alkyl chains length decreases the photoisomer emission for the dyes adsorbed onto microcrystalline cellulose, as detected for high fluences of the laser excitation, for most samples.

Phloxine B as a probe for entrapment in microcrystalline cellulose.

The photophysical behaviour of phloxine B adsorbed onto microcrystalline cellulose was evaluated by reflectance spectroscopy and laser induced time-resolved luminescence in the picosecond-nanosecond and microsecond-millisecond ranges. Analysis of the absorption spectral changes with concentration points to a small tendency of the dye to aggregate in the range of concentrations under study. Prompt fluorescence, phosphorescence and delayed fluorescence spectral decays were measured at room temperature and 77 K, without the need of sample degassing because cellulose protects triplet states from oxygen quenching. In all cases, spectral changes with time and lifetime distribution analysis were consistent with the dye coexisting in two different environments: dyes tightly entrapped between polymer chains in crystalline regions of cellulose showed longer fluorescence and phosphorescence lifetimes and more energetic triplet states, while dyes adsorbed in more amorphous regions of the support showed shorter lifetimes and less energetic triplet states. This behaviour is discussed in terms of the different dye-support interactions in both kinds of adsorption sites.

Drug Delivery Systems for Photodynamic Therapy: The Potentiality and Versatility of Electrospun Nanofibers.

Recently, photodynamic therapy (PDT) has become a promising approach for the treatment of a broad range of diseases, including oncological and infectious diseases. This minimally invasive and localized therapy is based on the production of reactive oxygen species able to destroy cancer cells and inactivate pathogens by combining the use of photosensitizers (PSs), light, and molecular oxygen. To overcome the drawbacks of drug systemic administration, drug delivery systems (DDS) can be used to carrier the PSs, allowing higher therapeutic efficacy and minimal toxicological effects. Polymeric nanofibers produced by electrospinning emerged as powerful platforms for drug delivery applications. Electrospun nanofibers exhibit outstanding characteristics, such as large surface-area-to-volume ratio associated with high drug loading, high porosity, flexibility, ability to incorporate and release a wide variety of therapeutic agents, biocompatibility, and biodegradability. Due to the versatility of this technique, fibers with different morphologies and functionalities, including drug release profile can be produced. The possibility of scalability makes electrospinning even more attractive for the development of DDS. This review aims to explore and show an up to date of the huge potential of electrospun nanofibers as DDS for different PDT applications and discuss the opportunities and challenges in this field.

Wetspun Polymeric Fibrous Systems as Potential Scaffolds for Tendon and Ligament Repair, Healing and Regeneration.

Tendon and ligament traumatic injuries are among the most common diagnosed musculoskeletal problems. Such injuries limit joint mobility, reduce musculoskeletal performance, and most importantly, lower people's comfort. Currently, there are various treatments that are used to treat this type of injury, from surgical to conservative treatments. However, they're not entirely effective, as reinjures are frequent and, in some cases, fail to re-establish the lost functionality. Tissue engineering (TE) approaches aim to overcome these disadvantages by stimulating the regeneration and formation of artificial structures that resemble the original tissue. Fabrication and design of artificial fibrous scaffolds with tailored mechanical properties are crucial for restoring the mechanical function of the tissues. Recently, polymeric nanofibers produced by wetspinning have been largely investigated to mimic, repair, and replace the damaged tissue. Wetspun fibrous structures are extensively used due to their exceptional properties, such as the ability to mimic the native tissue, their biodegradability and biocompatibility, and good mechanical properties. In this review, the tendon and ligament structure and biomechanics are presented. Then, promising wetspun multifunctional fibrous structures based on biopolymers, more specifically polyhydroxyalkanoates (PHA), polycaprolactone (PCL), and polyethylenes, will be discussed, as well as reinforcing agents such as cellulose nanocrystals (CNC), nanoparticles, and growth factors.

Antibacterial and hemostatic capacities of cellulose nanocrystalline-reinforced poly(vinyl alcohol) electrospun mats doped with Tiger 17 and pexiganan peptides for prospective wound healing applications.

Infection is a major issue in chronic wound care. Different dressings have been developed to prevent microbial propagation, but an effective, all-in-one (cytocompatible, antimicrobial and promoter of healing) solution is still to be uncovered. In this research, polyvinyl alcohol (PVA) nanofibrous mats reinforced with cellulose nanocrystal (CNC), at 10 and 20% v/v ratios, were produced by electrospinning, crosslinked with glutaraldehyde vapor and doped with specialized peptides. Crosslinking increased the mats' fiber diameters but maintained their bead-free morphology. Miscibility between polymers was confirmed by Fourier-transform infrared spectroscopy and thermal evaluations. Despite the incorporation of CNC having reduced the mats' mechanical performance, it improved the mats' surface energy and its structural stability over time. Pexiganan with an extra cysteine group was functionalized onto the mats via hydroxyl- polyethylene glycol 2-maleimide, while Tiger 17 was physisorbed to preserve its cyclic conformation. Antimicrobial assessments demonstrated the peptide-doped mat's effectiveness against Staphylococcus aureus and Pseudomonas aeruginosa; pexiganan contributed mostly for such outcome. Tiger 17 showed excellent capacity in accelerating clotting. Cytocompatibility evaluations attested to these mats' safety. C90/10 PVA/CNC mats were deemed the most effective from the tested group and, thus, a potentially effective option for chronic wound treatments.

Protective Multifunctional Fibrous Systems Based on Natural Fibers and Metal Oxide Nanoparticles.

In recent years, an unprecedented increase in the development of products and technologies to protect the human being has been observed. Now, more than ever, the world population is exposed to several threats, harmful to their well-being and health. Chemical and biological hazardous agents stand out as one of the biggest threats, not only for the military forces, but also for the civilians. Consequently, it's essential to develop personal protective systems that are able to protect their user, not only passively, but actively, being able to detect, adsorb, degrade and decontaminate pesticides, pollutants, microorganisms and most importantly: chemical/biological warfare agents. One recent strategy for the development of active fibrous structures with improved functions and new properties is their functionalization with nanoparticles (NPs), especially metal oxides. Although their known effectiveness in the decomposition of harmful agents, the NPs could also include other functionalities in the same structure using low quantities of material, without adding extra weight, which is of huge importance for a soldier in the battlefield. The use of natural fibers as the substrate is also very interesting, since this material is a much sustainable alternative when compared to synthetic ones, also providing excellent properties.

Active natural-based films for food packaging applications: The combined effect of chitosan and nanocellulose.

This work aimed to evaluate the potential of chitosan/cellulose nanocrystals (CNC) films to be used as active pads for meat packages to prolong its shelf-life and preserve its properties over time. Several CNC concentrations (5, 10, 25, and 50 wt%) were tested and the films were produced by solvent casting. The developed samples were characterized by ATR-FTIR, TGA, FESEM, and XRD. The transparency, antimicrobial, barrier and mechanical properties were also assessed. Finally, the films' ability to prolong food shelf-life was studied in real conditions using chicken meat. CNC incorporation improved the thermal stability and the oxygen barrier while the water vapor permeability was maintained. An enhancement of mechanical properties was also observed by the increase in tensile strength and Young's modulus in chitosan/CNC films. These films demonstrated bactericidal effect against Gram-positive and Gram-negative bacteria and fungicidal activity against Candida albicans. Lastly, chitosan-based films decreased the growth of Pseudomonas and Enterobacteriaceae bacteria in meat during the first days of storage compared to commercial membranes, while chitosan/CNC films reduced the total volatile basic nitrogen (TVB-N), indicating their efficiency in retarding meat's spoilage under refrigeration conditions. This work highlights the great potential of natural-based films to act as green alternatives for food preservation.

The Potential of Graphene Nanoplatelets in the Development of Smart and Multifunctional Ecocomposites.

Graphene and its derivatives have shown outstanding potential in many fields and textile/composites industry are not an exception. Giving their extraordinary properties, Graphene Nanoplatelets (GNPs) are excellent candidates for providing new functionalities to fibers and composites. In this work, natural fabrics (flax) were functionalized with chitosan (CS) based polymeric formulations of GNPs to develop fibrous systems with electrical properties as well as other functionalities. One of the greatest disadvantages of using carbon-based materials for fabrics' impregnation is their difficult dispersion. Therefore, several polymers were used as matrices, binding and dispersive agents including chitosan, polyethylene glycol (PEG), and glycerol. All the systems were characterized using several techniques that demonstrated the presence and incorporation of the GNPs onto the composites. Besides their characterization, considering their use as smart materials for monitoring and sensing applications, electrical properties were also evaluated. The highest value obtained for electrical conductivity was 0.04 S m-1 using 2% of GNPs. Furthermore, piezoresistive behavior was observed with Gauge Factor (GF) of 1.89 using 0.5% GNPs. Additionally, UV (ultraviolet) protection ability and hydrophobicity were analyzed, confirming the multifunctional behavior of the developed systems extending their potential of application in several areas.

Searching for Natural Conductive Fibrous Structures via a Green Sustainable Approach Based on Jute Fibers and Silver Nanoparticles.

This paper provides new insights regarding jute fibers functionalization with silver nanoparticles (Ag NPs) with improved conductivity values and highlights the sustainability of the processes involved. These NPs were applied onto jute fabrics by two different sustainable methods: ultraviolet (UV) photoreduction and by using polyethylene glycol (PEG) as a reducing agent and stabilizer. Field Emission Scanning Electron Microscopy (FESEM) images demonstrated that the Ag NPs were incorporated on the jute fibers surface by the two different approaches, with sizes ranging from 70 to 100 nm. Diffuse reflectance spectra revealed the plasmon absorption band, corresponding to the formation of metallic Ag NPs, in all samples under study. Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR) was used to characterize the obtained samples, demonstrating NPs adsorption to the surface of the fibers. The resistivity value obtained by the two-point probe method of the jute fabric without functionalization is about 1.5 × 107 Ω·m, whereas, after NPs functionalization, it decreased almost 15,000 times, reaching a value of 1.0 × 10³ Ω·m. Further research work is being undertaken for improving these values, however, 1000 Ω·m of resistivity (conductivity = 0.001 S/m) is already a very reasonable value when compared with those obtained with other developed systems based on natural fibers. In summary, this work shows that the use of very simple methodologies enabled the functionalization of jute fibers with reasonable values of conductivity. This achievement has a huge potential for use in smart textile composites.

Multifunctional Flax Fibres Based on the Combined Effect of Silver and Zinc Oxide (Ag/ZnO) Nanostructures.

Cellulosic fibre-based smart materials exhibiting multiple capabilities are getting tremendous attention due to their wide application areas. In this work, multifunctional flax fabrics with piezoresistive response were developed through the combined functionalization with silver (Ag) and zinc oxide (ZnO) nanoparticles (NPs). Biodegradable polyethylene glycol (PEG) was used to produce AgNPs, whereas ZnONPs were synthetized via a simple and low-cost method. Flax fabrics with and without NPs were characterized by Ground State Diffuse Reflectance (GSDR), Field Emission Scanning Electron Microscopy (FESEM), Energy Dispersive Spectroscopy (EDS), X-ray Diffraction (XRD), Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR), and Thermogravimetric analysis (TGA). After creating a conductive surface by flax functionalization with AgNPs, ZnONPs were synthetized onto these fabrics. The developed fibrous systems exhibited piezoresistive response and the sensor sensitivity increased with the use of higher ZnO precursor concentrations (0.4 M). Functionalized fabrics exhibited excellent antibacterial activity against Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) bacteria, higher hydrophobicity (WCA changed from 0° to >100°), UV radiation resistance, and wash durability. Overall, this work provides new insights regarding the bifunctionalization of flax fabrics with Ag/ZnO nanostructures and brings new findings about the combined effect of both NPs for the development of piezoresistive textile sensors with multifunctional properties.

Characterization of a Squaraine/Chitosan System for Photodynamic Therapy of Cancer.

In this work, a squaraine dye CS5 was characterized and evaluated for its potential in photodynamic therapy. The studies were performed in ethanol and also in a powdered biopolymer, in this case chitosan. Ground state absorption, absolute fluorescence quantum yields, fluorescence lifetimes, and transient absorption were determined in order to evaluate the advantage of adsorbing the dye onto a biopolymer. Several concentrations of the dye, adsorbed onto chitosan, were prepared in order to evaluate the concentration effect on the photophysical parameters under study. A remarkable increase in the fluorescence quantum yield and lifetimes was detected when compared with the dye in solution. Also, a very clear dependence of the fluorescence quantum yield on the concentration range was found. A lifetime distribution analysis of these systems fluorescence evidenced the entrapment of the dye onto the chitosan environment with a monoexponential decay which corresponds to the monomer emission in slightly different environments. The transient absorption spectrum was obtained without sensitization indicating the existence of a triplet state which takes special importance in the generation of phototoxic species namely singlet oxygen. The subcellular localization of a photosensitizer is critical for efficient photoinduced cell death, in this way, colocalization studies were performed within HeLa cell line (human cervical carcinoma) through confocal microscopy. Toxicity in the dark and phototoxicity of CS5 were also evaluated for the same cellular model.