Poly(butylene adipate-co-terephthalate)/Polylactic Acid/Tetrapod-Zinc Oxide Whisker Composite Films with Antibacterial Properties.

Biodegradable composite films comprising of poly(butylene adipate-co-terephthalate) (PBAT), polylactic acid (PLA), and tetrapod-zinc oxide (T-ZnO) whisker were prepared by a melt-extrusion and blow molding process. The effect of the incorporation of the T-ZnO whisker (1 to 7 wt.%) in the PBAT/PLA blend film was studied systematically. The composite films with an optimal T-ZnO whisker concentration of 3 wt.% exhibited the highest mechanical (tensile strength ~32 MPa), rheological (complex viscosity~1200 Pa.s at 1 rad/s angular frequency), and gas barrier (oxygen permeability~20 cc/m2·day) properties, whereas the composite films with 7 wt.% T-ZnO whiskers exhibited the highest antibacterial properties. The developed composite films can find potential application as antibacterial food packaging materials.

3D-Printable Sustainable Bioplastics from Gluten and Keratin.

Bioplastic films comprising both plant- and animal-derived proteins have the potential to integrate the optimal characteristics inherent to the specific domain, which offers enormous potential to develop polymer alternatives to petroleum-based plastic. Herein, we present a facile strategy to develop hybrid films comprised of both wheat gluten and wool keratin proteins for the first time, employing a ruthenium-based photocrosslinking strategy. This approach addresses the demand for sustainable materials, reducing the environmental impact by using proteins from renewable and biodegradable sources. Gluten film was fabricated from an alcohol-water mixture soluble fraction, largely comprised of gliadin proteins. Co-crosslinking hydrolyzed low-molecular-weight keratin with gluten enhanced its hydrophilic properties and enabled the tuning of its physicochemical properties. Furthermore, the hierarchical structure of the fabricated films was studied using neutron scattering techniques, which revealed the presence of both hydrophobic and hydrophilic nanodomains, gliadin nanoclusters, and interconnected micropores in the matrix. The films exhibited a largely (>40%) ß-sheet secondary structure, with diminishing gliadin aggregate intensity and increasing micropore size (from 1.2 to 2.2 µm) with an increase in keratin content. The hybrid films displayed improved molecular chain mobility, as evidenced by the decrease in the glass-transition temperature from ~179.7 °C to ~173.5 °C. Amongst the fabricated films, the G14K6 hybrid sample showed superior water uptake (6.80% after 30 days) compared to the pristine G20 sample (1.04%). The suitability of the developed system for multilayer 3D printing has also been demonstrated, with the 10-layer 3D-printed film exhibiting >92% accuracy, which has the potential for use in packaging, agricultural, and biomedical applications.

Stimuli-Responsive Ion Adsorbents for Sustainable Separation Applications.

Stimuli-responsive ion absorbents (SRIAs) with reversible ion adsorption and desorption properties have recently attracted immense attention due to their outstanding functionalities for sustainable separation applications. Over the past decade, a series of SRIAs that respond to single or multiple external stimuli (e.g., pH, gas, temperature, light, magnetic, and voltage) have been reported to achieve excellent ion adsorption capacity and selectivity while simultaneously allowing for their reusability. In contrast to traditional adsorbents that are mainly regenerated through chemical additives, SRIAs allow for reduced chemical and even chemical-free regeneration capacities, thereby enabling environmentally friendly and energy-efficient separation technologies. In this review, we systematically summarize the materials and strategies reported to date for synthesizing single-, dual-, and multiresponsive ion adsorbents. Following a discourse on the fundamental mechanisms that govern their adsorption and desorption under various external stimuli, we provide a concise discussion of the regeneration capacity and application of these responsive ion adsorbents for sustainable water desalination, toxic ion removal, and valuable ion extract and recovery. Finally, we discuss the challenges in developing and deploying these promising multifunctional responsive ion adsorbents together with strategies to overcome these limitations and provide prospects for their future.

Antifouling and Antimicrobial Study of Nanostructured Mixed-Matrix Membranes for Arsenic Filtration.

Membrane fouling is a major drawback in the membrane filtration industry for water treatment. Mixed-matrix membranes (MMMs) are well known for their enhanced antifouling and antibacterial properties, which could offer potential benefits for membrane filtration processes in the water treatment field. In this work, three electrospun nanofibrous MMMs (P, CP, and MCP, which were, respectively, the pristine polysulfone membrane and mixed-matrix membranes (MMMs) consisting of GO-ZnO and GO-ZnO-iron oxides) were studied for antifouling and antibacterial properties with respect to the arsenic nanofiltration process. The effects of these composites on the antifouling behaviour of the membranes were studied by characterising the bovine serum albumin (BSA) protein adsorption on the membranes and subsequent analysis using microscopic (morphology via scanning electron microscopy) and Brunauer-Emmett-Teller (BET) analyses. The antibacterial properties of these membranes were also studied against Gram-positive Staphylococcus aureus (S. aureus) and Gram-negative Escherichia coli (E. coli). The composite nanoparticle-incorporated membranes showed improved antifouling properties in comparison with the pristine polysulfone (PSF) membrane. The excellent antimicrobial properties of these membranes make them appropriate candidates to contribute to or overcome biofouling issues in water or wastewater treatment applications.

Polyelectrolyte Gels: Fundamentals, Fabrication and Applications.

Polyelectrolyte gels are an important class of polymer gels and a versatile platform with charged polymer networks with ionisable groups. They have drawn significant recent attention as a class of smart material and have demonstrated potential for a variety of applications. This review begins with the fundamentals of polyelectrolyte gels, which encompass various classifications (i.e., origin, charge, shape) and crucial aspects (ionic conductivity and stimuli responsiveness). It further centralises recent developments of polyelectrolyte gels, emphasising their synthesis, structure-property relationships and responsive properties. Sequentially, this review demonstrates how polyelectrolyte gels' flourishing properties create attractiveness to a range of applications including tissue engineering, drug delivery, actuators and bioelectronics. Finally, the review outlines the indisputable appeal, further improvements and emerging trends in polyelectrolyte gels.

Emerging bioadhesives: from traditional bioactive and bioinert to a new biomimetic protein-based approach.

Bioadhesives have reached significant milestones over the past two decades. Research has shown not only to produce adhesives capable of adhering to dry tissue but recently wet tissue as well. However, most bioadhesives developed have exhibited high adhesion strength yet lack other properties required for versatility in application, such as elasticity, biocompatibility and biodegradability. Adapting from limitations met from early bioadhesives and meeting the current demand allows novel bioadhesives to reach new milestones for the future. In this review, we overview the progression and variations of bioadhesives, current trends, characterisation techniques and conclude with future perspectives for bioadhesives for tissue engineering applications.

3D Printable Soy/Silk Hybrid Hydrogels for Tissue Engineering Applications.

The development of protein-based 3D printable hydrogel systems with tunable structure and properties is a critical challenge in contemporary biomedicine. Particularly, 3D printing of modular hydrogels comprising different types of protein tertiary structure, such as globular and fibrous, has not yet been achieved. Here we report the extrusion-based 3D printing of hybrid hydrogels photochemically co-cross-linked between globular soy protein isolate (SPI) and fibrous silk fibroin (SF) for the first time. The hierarchical structure and organization of pristine SPI and SF, and 1:3 (SPI/SF) hybrid inks under various shear stress were investigated using in situ rheology combined with small-/ultra-small-angle neutron scattering (Rheo-SANS/USANS). The hybrid ink exhibited an isotropic mass fractal structure that was stable between tested shear rates of 0.1 and 100 s-1 (near printing shear). The kinetics of sol-gel transition during the photo-cross-linking reaction and the micromechanical properties of fabricated hydrogels were investigated using photorheology and atomic force microscopy, where the hybrid hydrogels exhibited tunable storage and Young's moduli in the range of 13-29 and 214-811 kPa, respectively. The cross-link density and printing accuracy of hybrid hydrogels and inks were observed to increase with the increase in SF content. The 3D printed hybrid hydrogels exhibited a micropore size larger than that of solution casted hydrogels; where the 3D printed 1:3 (SPI/SF) hybrid hydrogel showed a pore size about 7.6 times higher than that of the casted hydrogel. Moreover, the fabricated hybrid hydrogels exhibit good mouse fibroblast cell attachment, viability, and proliferation, demonstrating their potential for tissue engineering applications.

Mixed-Matrix Membrane Fabrication for Water Treatment.

In recent years, technology for the fabrication of mixed-matrix membranes has received significant research interest due to the widespread use of mixed-matrix membranes (MMMs) for various separation processes, as well as biomedical applications. MMMs possess a wide range of properties, including selectivity, good permeability of desired liquid or gas, antifouling behavior, and desired mechanical strength, which makes them preferable for research nowadays. However, these properties of MMMs are due to their tailored and designed structure, which is possible due to a fabrication process with controlled fabrication parameters and a choice of appropriate materials, such as a polymer matrix with dispersed nanoparticulates based on a typical application. Therefore, several conventional fabrication methods such as a phase-inversion process, interfacial polymerization, co-casting, coating, electrospinning, etc., have been implemented for MMM preparation, and there is a drive for continuous modification of advanced, easy, and economic MMM fabrication technology for industrial-, small-, and bulk-scale production. This review focuses on different MMM fabrication processes and the importance of various parameter controls and membrane efficiency, as well as tackling membrane fouling with the use of nanomaterials in MMMs. Finally, future challenges and outlooks are highlighted.

Perspective on Constructing Cellulose-Hydrogel-Based Gut-Like Bioreactors for Growth and Delivery of Multiple-Strain Probiotic Bacteria.

The current perspective presents an outlook on developing gut-like bioreactors with immobilized probiotic bacteria using cellulose hydrogels. The innovative concept of using hydrogels to simulate the human gut environment by generating and maintaining pH and oxygen gradients in the gut-like bioreactors is discussed. Fundamentally, this approach presents novel methods of production as well as delivery of multiple strains of probiotics using bioreactors. The relevant existing synthesis methods of cellulose hydrogels are discussed for producing porous hydrogels. Harvesting methods of multiple strains are discussed in the context of encapsulation of probiotic bacteria immobilized on cellulose hydrogels. Furthermore, we also discuss recent advances in using cellulose hydrogels for encapsulation of probiotic bacteria. This perspective also highlights the mechanism of probiotic protection by cellulose hydrogels. Such novel gut-like hydrogel bioreactors will have the potential to simulate the human gut ecosystem in the laboratory and stimulate new research on gut microbiota.

Microroughness induced biomimetic coating for biodegradation control of magnesium.

Herein we explore a combination of anodization induced micro-roughness and biomimetic coating on pure magnesium (Mg) metal at different applied voltages to control adhesion, biodegradation, and corrosion performance in simulated body fluid solution. The anodic film was fabricated using two different potentials, 3 and 5 V, respectively, to create microroughness on the Mg surface. The microroughened Mg surface was subsequently coated with a biomimetic silk thin film; and the characteristics of the treated Mg-substrates were evaluated using various spectroscopic, microscopic, immersion, and electrochemical techniques. A number of independent measurements, including hydrogen evolution, weight loss and electrochemical methods were employed to assess the corrosion characteristics. The silk-coated anodized samples revealed dramatically reduced degradation rate in terms of volume of hydrogen gas generation and weight loss compared to the respective anodized but uncoated, which revealed that optimized biomimetic silk-coated Mg surface (anodized at 5 V and subsequently biomimetic silk-coated ANMg5V) exhibited the best corrosion performance among all other tested samples. The ANMg5V Silk showed the highest polarization resistance (46.12 kΩ·cm2), protection efficiency (>0.99) and lowest corrosion rate (only 0.017 mm/year) relative to untreated Mg (8.457 mm/year), and anodized Mg (1.039 for anodized at 3 V and 0.986 for anodized at 5 V) surface due to the formation of a pore-free dense biomimetic protective film over Mg surface. The results of the cytotoxicity test confirm that silk-coated samples are significantly less cytotoxic compared to bare and anodized Mg samples. With enhanced corrosion resistance and cytocompatibility, silk-coated Mg could be a potential material for clinical applications.

Resilin-mimetics as a smart biomaterial platform for biomedical applications.

Intrinsically disordered proteins have dramatically changed the structure-function paradigm of proteins in the 21st century. Resilin is a native elastic insect protein, which features intrinsically disordered structure, unusual multi-stimuli responsiveness and outstanding resilience. Advances in computational techniques, polypeptide synthesis methods and modular protein engineering routines have led to the development of novel resilin-like polypeptides (RLPs) including modular RLPs, expanding their applications in tissue engineering, drug delivery, bioimaging, biosensors, catalysis and bioelectronics. However, how the responsive behaviour of RLPs is encoded in the amino acid sequence level remains elusive. This review summarises the milestones of RLPs, and discusses the development of modular RLP-based biomaterials, their current applications, challenges and future perspectives. A perspective of future research is that sequence and responsiveness profiling of RLPs can provide a new platform for the design and development of new modular RLP-based biomaterials with programmable structure, properties and functions.

Engineering a Bioactive Hybrid Coating for In Vitro Corrosion Control of Magnesium and Its Alloy.

Magnesium (Mg) and its alloys are promising biodegradable metallic implant materials. However, their clinical applications are limited by their fast corrosion rate in the biological environment. In this work, with an outlook to improve the in vitro corrosion resistance of Mg and WE43 Mg alloy, a layer-by-layer interfacially engineered anticorrosive and bioactive coating consisting of a natural oxide lower layer, hydroxyapatite (HA) middle layer, and silk fibroin (SF) top layer was fabricated and investigated. Anodization was used to create natural oxide layer induced microroughness on substrates. The electrochemically deposited HA layer improved the surface microroughness and microhardness but significantly decreased Mg ion release, hydrogen gas evolution, and weight loss in simulated body fluid. The spin-coated SF layer further decreased hydrophilicity, in vitro degradation, and corrosion rate. The nonspecific and specific intermolecular interactions between fabricated layers along with their mechanical interlocking interface contributed to improved adhesion strength and integrity of the coating. The SF+HA-coated samples showed enhanced degradation and corrosion resistance due to a synergistic effect of the underlying HA layer, hindering the ingress of aggressive ions and the top hydrophobic SF layer, preventing the ingress of corrosive solution. The SF+HA-coated Mg and WE43 Mg alloy samples exhibited 50 and 26 times decreased corrosion rate, respectively, compared to uncoated samples. Moreover, in vitro cytotoxicity and cell culture studies using a mouse fibroblast cell showed that the SF+HA hybrid coating improved the cell viability, attachment, and proliferation, with cells exhibiting elongated morphology on coated samples as compared to a round shape on uncoated samples.

Bioprintable tough hydrogels for tissue engineering applications.

Bioprinting is an advanced fabrication approach to engineer complex living structures as the conventional fabrication methods are incapable of integrating structural and biological complexities. It offers the versatility of printing different cell incorporated hydrogels (bioink) layer by layer; offering control over spatial resolution and cell distribution to mimic native tissue architectures. However, the bioprinting of tough hydrogels involve additional complexities, such as employing complex crosslinking or reinforcing mechanisms during printing and pre/post printing cellular activities. Solving this complexity requires attention from engineering, material science and cell biology perspectives. In this review, we discuss different types of bioprinting techniques with focus on current state-of-the-art in bioink formulations and pivotal characteristics of bioinks for tough hydrogel printing. We discuss the scope of transition from 3D to 4D bioprinting and some of the advanced characterization techniques for in-depth understanding of the 3D printing process from the microstructural perspective, along with few specific applications and conclude with the future perspectives in biofabrication of hydrogels for tissue engineering applications.

Silk fibroins in multiscale dimensions for diverse applications.

Silk biomaterials in different forms such as particles, coatings and their assemblies, represent unique type of materials in multiple scales and dimensions. Herein, we provide an overview of multi-scale silk fibroin materials including silk particles, silk coatings and silk assemblies, each of which represents a unique type of material with wide range of applications. They feature tunable structures and mechanical properties with excellent biocompatibility, which are essentially required for various biomedical and drug delivery applications. The review focuses on bringing a new perspective on the utilization of regenerated silk fibroins in modern biomedicine by beginning with the fabrication of silk in multiscale dimensions and their state-of-the-art applications in various biomedical and bioelectronic fields. It covers the fundamentals of processing silk fibroins in multi-dimensions (sizes and shapes) with a specific emphasis on its structural tunability at various length scales (nano-micro) by using the latest fabrication methods/mechanisms and advanced fabrication technologies, followed by their recent applications in diverse fields of biomedicine.

Evolution of the Interfacial Structure of a Catalyst Ink with the Quality of the Dispersing Solvent: A Contrast Variation Small-Angle and Ultrasmall-Angle Neutron Scattering Investigation.

The electrocatalyst layer (ECL) of the proton-exchange membrane fuel cell (PEMFC) is commonly fabricated from colloidal catalyst ink containing carbon-supported catalyst nanoparticles (NPs), ionomer stabilizer, and dispersion medium (DM). The structure, stability, and aggregate size distribution of fuel cell catalyst ink are critically dependent on the quality of DM. However, understanding of the influence of the quality of DM on the hierarchical structure of the ECL is lacking. This work presents a systematic investigation of the effects of reducing alcohol content in isopropyl alcohol/water (IPA/H2O) binary mixtures as DM on the structural evolution of water-rich (green) catalyst ink using contrast-variation small-angle and ultrasmall-angle neutron scattering techniques. Both qualitative and quantitative information are extracted from the data to obtain information about the size, structure, and organization of the catalyst ink using different model functions fit to the experimental data. The catalyst ink prepared using 70% IPA (commonly employed in industry and extensively reported in the literature) is shown to consist of randomly distributed globular carbon aggregates (mean radius of gyration of ∼178.9 nm) stabilized by an ionomer mass fractal shell (thickness of ∼13.0 nm), which is dispersed in the matrix of rodlike (∼1.3 nm radius and ∼35.0 nm length) negatively surface-charged ionomer NPs. These well characterized baseline data are then compared and contrasted with DM formulations of lower IPA content. A sequential reduction in IPA content of DM shows a progressive increase in the ionomer NP radius and electrostatic repulsion, concomitantly with the decrease in the carbon aggregate size and ionomer shell thickness of the catalyst ink. Therefore, the changes in the interfacial structure via adjustments of the DM composition can be used as a controlling parameter to tailor the hierarchical structure of the colloidal fuel cell catalyst ink and to further optimize the performance of the ECL.

Sulfonated Thiophene Derivative Stabilized Aqueous Poly(3-hexylthiophene):Phenyl-C61-butyric Acid Methyl Ester Nanoparticle Dispersion for Organic Solar Cell Applications.

Aqueous dispersions of poly(3-hexylthiophene):phenyl-C61-butyric acid methyl ester (P3HT:PCBM) nanoparticles (NPs) have been fabricated using a thiophene-based surfactant 2-(3-thienyl)ethyloxybutylsulfonate sodium salt (TEBS) for the first time via the mini-emulsion process. The use of TEBS resulted in a stable colloidal dispersion of P3HT:PCBM NPs, of which the effect of various fabrication parameters is investigated. The fabricated NPs were characterized by dynamic light scattering, scanning electron microscopy, UV-visible spectroscopy, contrast-variation small and ultra-small angle neutron scattering, and cyclic voltammetry. The internal structure and electrochemical performance of TEBS-stabilized P3HT:PCBM NPs were compared to those of sodium dodecyl sulfate-stabilized core-shell (PCBM-P3HT) NPs at the same surfactant concentration. Neutron scattering and cyclic voltammetry results reveal a homogeneous distribution of small de-mixed P3HT and PCBM domains in the internal structure of TEBS-stabilized P3HT:PCBM NPs, reminiscent of cast film. Moreover, electron microscopy images show evidence of diffused NP surface/interface upon drying (without annealing), which indicates that the thiophene-containing TEBS may improve compatibility and film-forming properties of fabricated P3HT:PCBM NPs, and consequently be more suited for conventional film-processing methods for organic solar cell applications.

Graphene inks for printed flexible electronics: Graphene dispersions, ink formulations, printing techniques and applications.

Graphene inks have recently enabled the dramatic improvement of printed flexible electronics due to their low cost, ease of processability, higher conductivity and flexibility. In this review, we discuss the state-of-the-art of the fundamental formulation of graphene inks and the current printing techniques used for inks deposition, followed by recent practical applications for printed flexible electronics. The progression of science and technology for the dispersion of graphene using variety of solvents and the characteristics of the resulting conductive inks have been highlighted, with specific emphasis focused on the challenges to be resolved. The printing techniques discussed here include screen printing, gravure printing, inkjet printing and other emerging printing technologies. Each approach's pros and cons are discussed in correlation with the ink formulations and the operating principles. We also discuss the challenges and outlook of graphene ink for its future development in the world of printed flexible devices.

Tough Photocrosslinked Silk Fibroin/Graphene Oxide Nanocomposite Hydrogels.

The development of protein-based hydrogels for tissue engineering applications is often limited by their mechanical properties. Herein, we present the facile fabrication of tough regenerated silk fibroin (RSF)/graphene oxide (GO) nanocomposite hydrogels by a photochemical cross-linking method. The RSF/GO composite hydrogels demonstrated soft and adhesive properties during initial stages of photocrosslinking (<2 min), which is not observed for the pristine RSF hydrogel, and rendered a tough and nonadhesive hydrogel upon complete cross-linking (10 min). The composite hydrogels exhibited superior tensile mechanical properties, increased ß-sheet content, and decreased chain mobility compared to that of the pristine RSF hydrogels. The composite hydrogels demonstrated Young's modulus as high as ∼8 MPa, which is significantly higher than native cartilage (∼1.5 MPa), and tensile toughness as high as ∼2.4 MJ/m3, which is greater than that of electroactive polymer muscles and at par with RSF/GO composite membranes fabricated by layer-by-layer assembly. Small-angle scattering study reveals the hierarchical structure of photocrosslinked RSF hydrogels to comprise randomly distributed water-poor (hydrophobic) and water-rich (hydrophilic) regions at the nanoscale, whereas water pores and channels exhibiting fractal-like characteristics at the microscale. The size of hydrophobic domain (containing ß-sheets) was observed to increase slightly with GO incorporation and/or alcohol post-treatment, whereas the size of the hydrophilic domain (intersheet distance containing random coils) was observed to increase significantly, which influences/affects water uptake capacity, cross-link density, and mechanical properties of hydrogels. The presented results have implications for both fundamental understanding of the structure-property relationship of RSF-based hydrogels and their technological applications.

Water-Reprocessable, Reformable, and Ecofriendly Sustainable Material Based on Disulfide-Cross-Linked Polyethyleneimine.

A reformable polymer gel material has been developed based on the disulfide cross-linking of low-molecular-weight polyethylenimine (PEI) that can be synthesized through a facile thiolation method and reprocessed through an aqueous method without the use of solvents or additional chemicals. Despite being made with water-soluble PEI, the cross-linked gel shows good mechanical integrity and its properties can be controlled through the fabrication parameters, maintaining the hydrophilic nature of PEI while being sufficiently robust to form a free-standing film that does not dissolve in water. The properties of the gel have been characterized by Fourier transform infrared spectroscopy, thermogravimetry, and dynamic mechanical analyses, showing the effect of parameters such as the degree of thiolation and thermal curing. The reformability of the gel comes from the disulfide cross-links, which can be disrupted and reformed through a simple, aqueous processing method utilizing ultrasonication, creating an aqueous dispersion, which can be recast multiple times with minimal loss in physical properties.

Bulk heterojunction organic photovoltaics from water-processable nanomaterials and their facile fabrication approaches.

Organic thin film photovoltaics based on bulk-heterojunction donor-acceptor combinations have received significant interest due to their potential for low-cost, large-scale solution processing. However, current state-of-the-art cells utilise materials soluble mainly in halogenated solvents which pose processing challenges due to their toxicity and thus environmental hazards. In this contribution, we look at various nanomaterials, and alternative processing of these solar cells using environmentally friendly solvents, and review recently reported different strategies and approaches that are making inroads in this field. Specifically, we focus on the use of water-dispersible donors and acceptors, use of aqueous solvents for fabrication and discuss the merits of the two main approaches of water-processable solar cells; namely, through the use of water-soluble materials and the use of aqueous dispersion rather than a solution, as well as review some of the recent advances in alternative fabrication techniques.