Biocomposite Cryogels for Photothermal Decontamination of Water.

An effective and sustainable approach to deal with the scarcity of freshwater is interfacial solar-driven evaporation. Nonetheless, some serious challenges for photothermal materials still need to be considered, such as long-term stability in harsh environments, eco-friendly materials, and cost-effective and simple fabrication processes. Keeping these points in mind, we present a multifunctional silver-coated vegetable waste biocomposite cryogel that not only exhibits high porosity and enhanced wettability and stability but also possesses high light absorption and low thermal conductivity favorable for heat localization, solar steam generation, and efficient photothermal conversion efficiency. The achieved solar evaporation rate is 1.17 kg m-2 h-1 with a solar-to-vapor conversion efficiency of 81.11% under 1 Sun irradiation. The developed material is able to effectively desalinate artificial seawater and decontaminate synthetic wastewater (e.g., water containing dye molecules and mercury ions) with an efficiency of >99%. Most importantly, the composite cryogel presents antifouling properties, and in particular, salt antifouling ability and anti-biofouling properties. Thus, the numerous functionalities of the biocomposite cryogel make it a cost-effective promising device for prolonged water decontamination processes.

Functional Polymeric Membranes with Antioxidant Properties for the Colorimetric Detection of Amines.

Herein, the ability of highly porous colorimetric indicators to sense volatile and biogenic amine vapors in real time is presented. Curcumin-loaded polycaprolactone porous fiber mats are exposed to various concentrations of off-flavor compounds such as the volatile amine trimethylamine, and the biogenic amines cadaverine, putrescine, spermidine, and histamine, in order to investigate their colorimetric response. CIELAB color space analysis demonstrates that the porous fiber mats can detect the amine vapors, showing a distinct color change in the presence of down to 2.1 ppm of trimethylamine and ca. 11.0 ppm of biogenic amines, surpassing the limit of visual perception in just a few seconds. Moreover, the color changes are reversible either spontaneously, in the case of the volatile amines, or in an assisted way, through interactions with an acidic environment, in the case of the biogenic amines, enabling the use of the same indicator several times. Finally, yet importantly, the strong antioxidant activity of the curcumin-loaded fibers is successfully demonstrated through DPPH● and ABTS● radical scavenging assays. Through such a detailed study, we prove that the developed porous mats can be successfully established as a reusable smart system in applications where the rapid detection of alkaline vapors and/or the antioxidant activity are essential, such as food packaging, biomedicine, and environmental protection.

Silk fibroin microgels as a platform for cell microencapsulation.

Cell microencapsulation has been utilized for years as a means of cell shielding from the external environment while facilitating the transport of gases, general metabolites, and secretory bioactive molecules at once. In this light, hydrogels may support the structural integrity and functionality of encapsulated biologics whereas ensuring cell viability and function and releasing potential therapeutic factors once in situ. In this work, we describe a straightforward strategy to fabricate silk fibroin (SF) microgels (µgels) and encapsulate cells into them. SF µgels (size ≈ 200 µm) were obtained through ultrasonication-induced gelation of SF in a water-oil emulsion phase. A thorough physicochemical (SEM analysis, and FT-IR) and mechanical (microindentation tests) characterization of SF µgels were carried out to assess their nanostructure, porosity, and stiffness. SF µgels were used to encapsulate and culture L929 and primary myoblasts. Interestingly, SF µgels showed a selective release of relatively small proteins (e.g., VEGF, molecular weight, MW = 40 kDa) by the encapsulated primary myoblasts, while bigger (macro)molecules (MW = 160 kDa) were hampered to diffusing through the µgels. This article provided the groundwork to expand the use of SF hydrogels into a versatile platform for encapsulating relevant cells able to release paracrine factors potentially regulating tissue and/or organ functions, thus promoting their regeneration.

Multifunctional Bioplastics Inspired by Wood Composition: Effect of Hydrolyzed Lignin Addition to Xylan-Cellulose Matrices.

Multifunctional bioplastics have been prepared by amorphous reassembly of cellulose, hemicelluloses (xylan), and hydrolyzed lignin. For this, the biopolymers were dissolved in a trifluoroacetic acid-trifluoroacetic anhydride mixture and blended in different percentages, simulating those found in natural woods. Free-standing and flexible films were obtained after the complete evaporation of the solvents. By varying xylan and hydrolyzed lignin contents, the physical properties were easily tuned. In particular, higher proportions of hydrolyzed lignin improved hydrodynamics, oxygen barrier, grease resistance, antioxidant, and antibacterial properties, whereas a higher xylan content was related to more ductile mechanical behavior, comparable to synthetic and bio-based polymers commonly used for packaging applications. In addition, these bioplastics showed high biodegradation rates in seawater. Such new polymeric materials are presented as alternatives to common man-made petroleum-based plastics used for food packaging.

Plant cuticle under global change: Biophysical implications.

Climatic stressors due to global change induce important modifications to the chemical composition of plant cuticles and their biophysical properties. In particular, plant cuticles can become heavier, stiffer and more inert, improving plant protection.

Surface modification of polymeric foams for oil spills remediation.

In the last decade, a continuous increasing research activity is focused on the surface functionalization of polymeric porous materials for the efficient removal of oil contaminants from water. This work reviews the most significant recent studies on the functionalization of polyurethane and melamine foams, materials commonly reported for oil-water separation applications. After the identification of the key features of the foams required to optimize their oil removal performance, a wide variety of physicochemical treatments are described together with their effect on the oil absorption selectivity and oil absorption capacity, both critical parameters for the application of the foams in the remediation of oil spills. The efficiencies of the different functionalization processes on the same type of foams are compared, determining the main advantages and potentialities of each treatment and remediation procedure.

Cutin from agro-waste as a raw material for the production of bioplastics.

Cutin is the main component of plant cuticles constituting the framework that supports the rest of the cuticle components. This biopolymer is composed of esterified bi- and trifunctional fatty acids. Despite its ubiquity in terrestrial plants, it has been underutilized as raw material due to its insolubility and lack of melting point. However, in recent years, a few technologies have been developed to obtain cutin monomers from several agro-wastes at an industrial scale. This review is focused on the description of cutin properties, biodegradability, chemical composition, processability, abundance, and the state of art of the fabrication of cutin-based materials in order to evaluate whether this biopolymer can be considered a source for the production of renewable materials.

One-Pot Hybrid SnO2 /Poly(methyl methacrylate) Nanocomposite Formation through Pulsed Laser Irradiation.

The localized in situ formation of tin dioxide (SnO2 ) nanoparticles embedded in poly(methyl methacrylate) (PMMA) films is presented. This is achieved by the photoinduced conversion of the tin acetate precursor included in polymeric films, through controlled UV or visible pulsed laser irradiation at λ=355 and 532 nm, respectively. The evolution of the formation of nanoparticles is followed by UV/Vis spectroscopy and shows that their growth is affected in different ways by the laser pulses at the two applied wavelengths. This, in combination with electron microscopy analysis, reveals that, depending on the irradiation wavelength, the size of the nanoparticles in the final nanocomposites differs. This difference is attributed to distinct mechanistic pathways that lead to the synthesis of small nanoparticles (from 1.5 to 4.5 nm) at λ=355 nm, whereas bigger ones (from 5 to 16 nm) are formed at λ=532 nm. At the same time, structural studies with both X-ray and electron diffraction measurements demonstrate the crystallinity of SnO2 nanoparticles in both cases, whereas XPS analysis confirms the light-induced oxidation of tin acetate into SnO2 . Taken all together, it is demonstrated that the pulsed laser irradiation at λ=355 and 532 nm leads to the formation of SnO2 nanoparticles with defined features highly dispersed in PMMA solid matrices.

Controlled formation of gold nanostructures on biopolymer films upon electromagnetic radiation.

The localized formation of gold nanostructures with controlled size and shape on chitosan films doped with gold precursor upon electromagnetic irradiation of various types is demonstrated here. Such controlled formation is achieved by tuning the wavelength, the energy and the interaction time of the radiation with the composite films. In particular, the use of a single UV nanosecond laser pulse results in the formation of gold sub-micron platelets with specific crystal structure, while increasing the number of pulses, further precursor reduction and photofragmentation induce the formation of gold nanoparticles. Using x-ray radiation as an alternative energy source, the reduction of the gold precursor and the subsequent formation of particles follow a different pathway. Specifically, x-ray-induced photo-reduction triggers the selective formation of gold sub-micron platelets with a very well defined {111} crystal phase. In this case, the density of crystal platelets increases by increasing the irradiation time of the films, while no photofragmentation process is observed. The gold structures pre-formed by x-ray radiation can be fragmented by subsequent pulsed UV laser irradiation forming nanoparticles with much narrower size distribution compared to that obtained via exclusive UV irradiation. Thanks to the perfect coupling between the natural polymeric matrix and gold nanostructures, the bionanocomposite systems developed could find various applications in biomaterial science and in biosensors field.

Tunable Friction Behavior of Photochromic Fibrillar Surfaces.

Grasslike compliant micro/nano crystals made of diarylethene (DAE) photochromic molecules are spontaneously formed on elastomer films after dipping them in a solution containing the photochromic molecules. The frictional forces of such micro- and nanofibrillar surfaces are reversibly tuned upon ultraviolet (UV) irradiation and dark storage cycles. This behavior is attributed to the Young's modulus variation of the single fibrils due to the photoisomerization process of the DAE molecules, as measured by advanced atomic force microscopy (AFM) techniques. In fact, a significant yet reversible decrease of the stiffness of the outer part of the fibrils in response to the UV light irradiation is demonstrated. The modification of the molecular structure of the fibrils influences their mechanical properties and affects the frictional behavior of the overall fibrillar surfaces. These findings provide the possibility to develop a system that controllably and accurately generates both low and high friction forces.

Alginate nanofibrous mats with adjustable degradation rate for regenerative medicine.

The broad utilization of electrospun scaffolds of sodium alginate in tissue engineering is strongly limited by their high solubility in aqueous environments and by the difficulty to adjust their degradation dynamics. Here, an alternative strategy to enhance the stability and to control the degradability of alginate nanofibers is described by treating them with trifluoroacetic acid for specific time intervals. It is demonstrated that, by increasing the duration of the acid treatment procedure, a lower degradation rate of the resulting fibers in buffer solutions can be achieved. Furthermore, the produced mats are free from cytotoxic compounds and are highly biocompatible. The properties conferred to the alginate nanofibrous mats by the proposed method are extremely attractive in the production of innovative biomedical devices.

Spontaneous formation of photochromic coatings made of reversible microfibrils and nanofibrils on an elastomer substrate.

We report the spontaneous formation of photochromic microcrystalline and nanocrystalline fibrils forming dense coatings of cactuslike supramolecular structures on the surface of a soft poly(dimethylsiloxane) (PDMS) elastomer. The initial deposition of the photochromic molecules of diarylethenes on the elastomer is done by dip adsorption, a process that permits the homogeneous distribution of the molecules not only on the surface but also in the inner part of the polymer. Detailed thermal and microscopy studies reveal that the growth process of the fibrils is initiated by the formation of crystal seeds of the diarylethene in the proximity of the elastomer's surface empty voids and progresses toward the elastomer-air interface as a result of the high mobility of the molecules at room temperature. Fibril formation is possible only when the molecules are in the open form because the UV irradiation responsible for their transformation to the close isomeric form immediately after deposition totally prohibits the crystals' formation. Furthermore, the UV irradiation of the grown supramolecular assemblies provokes their destruction, but when the irradiated samples are left to recover under ambient conditions, they form new assemblies of fibrils in a faster and more efficient way. The resulting systems exhibit superhydrophobic to slightly hydrophobic properties with differences of almost 80° in water contact angles upon dark storage-UV irradiation cycles. The proposed systems can be an alternative to the facile formation of reversible photochromic fibrils on soft polymer surfaces for utilization on diverse soft devices, where controlled surface morphology and wettability are desired.

Biomimetic approach for liquid encapsulation with nanofibrillar cloaks.

Technologies that are able to handle microvolumes of liquids, such as microfluidics and liquid marbles, are attractive for applications that include miniaturized biological and chemical reactors, sensors, microactuators, and drug delivery systems. Inspired from natural fibrous envelopes, here, we present an innovative approach for liquid encapsulation and manipulation using electrospun nanofibers. We demonstrated the realization of non-wetting soft solids consisting of a liquid core wrapped in a hydrophobic fibrillar cloak of a fluoroacrylic copolymer and cellulose acetate. By properly controlling the wetting and mechanical properties of the fibers, we created final architectures with tunable mechanical robustness that were stable on a wide range of substrates (from paper to glass) and floated on liquid surfaces. Remarkably, the realized fiber-coated drops endured vortex mixing in a continuous oil phase at high stirring speed without bursting or water losses, favoring mixing processes inside the entrapped liquid volume. Moreover, the produced cloak can be easily functionalized by incorporating functional particles, active molecules, or drugs inside the nanofibers.

Data on antimicrobial, barrier, and mechanical properties of biocomposites prepared from carrot pomace and wheat gluten with varied eugenol content.

This article presents analyzed data on the antimicrobial, barrier, and mechanical properties inherent to films created by blending carrot pomace with wheat gluten and polyglycerol-3 plasticizer and combined with varying contents (0 wt.%, 3 wt.%, and 5 wt.%) of eugenol, a natural antimicrobial compound derived from essential oils. The integration of carrot pomace, wheat gluten, plasticizer, and eugenol involved meticulous mortar and pestle processing, ensuring a homogenous blend. Subsequently, the mixture was compression-molded in a hydraulic press to fabricate the films. Standard bacteria strains-Escherichia coli ATCC 25922 and Staphylococcus aureus ATCC 6538-are used in the antimicrobial evaluation, and antimicrobial efficacy is measured using OD600 measurements. Water vapor permeability (WVP) measurement effectively defines the films' potential to prevent water vapor infiltration. Mechanical properties are assessed by determining elastic modulus, tensile strength, and elongation at break, which together reveal the films' adaptive flexibility and durability. The dataset presented herein holds substantial promise for food packaging applications. Researchers in the food packaging industry can leverage the antimicrobial and barrier property data to design novel packaging materials, potentially enhancing shelf-life and food safety. Engineers and material scientists can utilize the mechanical properties data to develop structurally robust and flexible materials.

Electrosprayed zein nanoparticles as antibacterial and anti-thrombotic coatings for ureteral stents.

Ureteral stents are among the most frequently used human implants, with urothelium trauma, blood clots, and bacterial colonization being their main reasons for failure. In this study, berberine-loaded zein (ZB) nanoparticles with high drug encapsulation efficiency (>90 %) were fabricated via electrospray on flat and 3D stainless steel structures. Physico-chemical characterization revealed that the ZB nanoparticles created a highly hydrophilic, antioxidant, and scratch-resistant continuous coating over the metal structure. Results showed that the drug release rate was faster at neutral pH (i.e., PBS pH 7.4) than in an artificial urine medium (pH 5.3) due to the different swelling behavior of the zein polymeric matrix. In vitro evaluation of ZB particles onto human dermal fibroblasts and blood cells demonstrated good cell proliferation and enhanced anti-thrombotic properties compared to bare stainless steel. The ability of the electrosprayed zein particles to resist bacterial adherence and proliferation was evaluated with Gram-negative (Escherichia coli) bacteria, showing high inhibition rates (-29 % and -46 % for empty and berberine-loaded particles, respectively) compared to the medical-grade metal substrates. Overall, the proposed composite coating fulfilled the requirements for ureteral applications, and can advance the development of innovative biocompatible, biodegradable, and antibacterial coatings for drug-eluting stents.

Combining Alginate/PVPI-Based Film with Frequency Rhythmic Electrical Modulation System (FREMS) Technology as an Advanced Strategy for Diabetic Wounds.

Diabetes is rising as one of the most diffused diseases of the century with the related urgent necessity to face its systemic and local effects on the patients, such as cardiovascular problems, degeneration of limbs, and dysfunction of the wound healing process. The diffusion of leg ulcers has been estimated to be 1.51 for 1000 population, and these non-resolved wounds can produce several social, economic, and mental health issues in diabetic patients. At the same time, these people experience neuropathic pain that causes morbidity and a further decrease in their quality of life. Here, a new study is presented where asodium alginate/Polyvinylpyrrolidone-Iodine complex (PVPI)-based wound dressing is combined with the Frequency Rhythmic Electrical Modulation System (FREMS) technology, an established medical device for the treatment of neuropathic pain and diabetic ulcers. The produced Alginate/PVPI-based films are characterized in terms of morphology, chemistry, wettability, bio-/hemo-compatibility, and clotting capacity. Next, the Alginate/PVPI-based films are used together with FREMS technology in diabetic mice models, and synergism of their action in the wound closure rate and anti-inflammatory properties is found. Hence, how the combination of electrical neurostimulation devices and advanced wound dressings can be a new approach to improve chronic wound treatment is demonstrated.

On a Biobased Epoxy Vitrimer from a Cardanol Derivative Prepared by a Simple Thiol-Epoxy "Click" Reaction.

The development of this work lies in the relevant interest in epoxy resins, which, despite their wide use, do not meet the requirements for sustainable materials. Therefore, the proposed approach considers the need to develop environmentally friendly systems, in terms of both the starting material and the synthetic method applied as well as in terms of end-of-life. The above issues were taken into account by (i) using a monomer from renewable sources, (ii) promoting the formation of dynamic covalent bonds, allowing for material reprocessing, and (iii) evaluating the degradability of the material. Indeed, an epoxy derived from cardanol was used, which, for the first time, was applied in the development of a vitrimer system. The exploitation of a diboronic ester dithiol ([2,2'-(1,4-phenylene)-bis[4-mercaptan-1,3,2-dioxaborolane], DBEDT) as a cross-linker allowed the cross-linking reaction to be carried out without the use of solvents and catalysts through a thiol-epoxy "click" mechanism. The dynamicity of the network was demonstrated by gel fraction experiments and rheological and DMA measurements. In particular, the formation of a vitrimer was highlighted, characterized by low relaxation times (around 4 s at 70 °C) and an activation energy of ca. 48 kJ/mol. Moreover, the developed material, which is easily biodegradable in seawater, was found to show promising flame reaction behavior. Preliminary experiments demonstrated that, unlike an epoxy resin prepared from the same monomer and using a classical cross-linker, our boron-containing material exhibited no dripping under combustion conditions, a phenomenon that will allow this novel biobased system to be widely used.

Transparent, plasticized cellulose-glycerol bioplastics for food packaging applications.

Free-standing films have been obtained by drop-casting cellulose-glycerol mixtures (up to 50 wt% glycerol) dissolved in trifluoroacetic acid and trifluoroacetic anhydride (TFA:TFAA, 2:1, v:v). A comprehensive examination of the optical, structural, mechanical, thermal, hydrodynamic, barrier, migration, greaseproof, and biodegradation characteristics of the films was conducted. The resulting cellulose-glycerol blends exhibited an amorphous molecular structure and a reinforced H-bond network, as evidenced by X-ray diffraction analysis and infrared spectroscopy, respectively. The inclusion of glycerol exerted a plasticizing influence on the mechanical properties of the films, while keeping their transparency. Hydrodynamic and barrier properties were assessed through water uptake and water vapor/oxygen transmission rates, respectively, and obtained values were consistent with those of other cellulose-based materials. Furthermore, overall migration levels were below European regulation limits, as stated by using Tenax® as a dry food simulant. In addition, these bioplastics demonstrated good greaseproof performance, particularly at high glycerol content, and potential as packaging materials for bakery products. Biodegradability assessments were carried out by measuring the biological oxygen demand in seawater and high biodegradation rates induced by glycerol were observed.

Biodegradable polylactic acid emulsion ink based on carbon nanotubes and silver for printed pressure sensors.

Investigating biodegradable and biocompatible materials for electronic applications can lead to tangible outcomes such as developing green-electronic devices and reducing the amount of e-waste. The proposed emulsion-based conducting ink formulation takes into consideration circular economy and green principles throughout the entire process, from the selection of materials to the production process. The ink is formulated using the biopolymer polylactic acid dissolved in a sustainable solvent mixed with water, along with conductive carbon nanotubes (CNTs) and silver flakes as fillers. Hybrid conductive fillers can lower the percolation threshold of the ink and the production costs, while maintaining excellent electrical properties. The coating formed after the deposition of the ink, undergoes isothermal treatment at different temperatures and durations to improve its adhesion and electrical properties. The coating's performance was evaluated by creating an eight-finger interdigitated sensor using a Voltera PCB printer. The sensor demonstrates exceptional performance when exposed to various loading and unloading pressures within the 0.2-500.0 kPa range. The results show a consistent correlation between the change in electrical resistance and the stress caused by the applied load. The ink is biodegradable in marine environments, which helps avoiding its accumulation in the ecosystem over time.

Modified Carbon Nanotubes Favor Fibroblast Growth by Tuning the Cell Membrane Potential.

As is known, carbon nanotubes favor cell growth in vitro, although the underlying mechanisms are not yet fully elucidated. In this study, we explore the hypothesis that electrostatic fields generated at the interface between nonexcitable cells and appropriate scaffold might favor cell growth by tuning their membrane potential. We focused on primary human fibroblasts grown on electrospun polymer fibers (poly(lactic acid)─PLA) with embedded multiwall carbon nanotubes (MWCNTs). The MWCNTs were functionalized with either the p-methoxyphenyl (PhOME) or the p-acetylphenyl (PhCOMe) moiety, both of which allowed uniform dispersion in a solvent, good mixing with PLA and the consequent smooth and homogeneous electrospinning process. The inclusion of the electrically conductive MWCNTs in the insulating PLA matrix resulted in differences in the surface potential of the fibers. Both PLA and PLA/MWCNT fiber samples were found to be biocompatible. The main features of fibroblasts cultured on different substrates were characterized by scanning electron microscopy, immunocytochemistry, Rt-qPCR, and electrophysiology revealing that fibroblasts grown on PLA/MWCNT reached a healthier state as compared to pure PLA. In particular, we observed physiological spreading, attachment, and Vmem of fibroblasts on PLA/MWCNT. Interestingly, the electrical functionalization of the scaffold resulted in a more suitable extracellular environment for the correct biofunctionality of these nonexcitable cells. Finally, numerical simulations were also performed in order to understand the mechanism behind the different cell behavior when grown either on PLA or PLA/MWCNT samples. The results show a clear effect on the cell membrane potential, depending on the underlying substrate.