A critical review on emerging industrial applications of chars from thermal treatment of biosolids.

Thermochemical treatment is rapidly emerging as an alternative method for the management of stabilised sewage sludges (biosolids) to effectively reduce waste volume, degrade contaminants, and generate valuable products, particularly biochar and hydrochar. Biosolids-derived char has a relatively high concentration of heavy metals compared with agricultural chars but is still applied to land due to its beneficial properties and ability to retain metals. However, non-agricultural applications can provide additional economic and environmental benefits, promote sustainability and support a circular economy. This review identifies extensive non-agricultural opportunity for biosolids biochar, including adsorption, catalysis, energy storage systems, biological process enhancement, and as additives for rubber compounding and construction. Biosolids chars have received limited attention vs agricultural char, and we draw on both areas of literature, as well as evaluating differences between agricultural and biosolids chars. A key opportunity for biosolids biochar in comparison with other materials and agricultural chars is its sustainable and low-cost nature, relatively high metals content, improving catalyst properties, and ability to modify in various stages to tune it to specific applications. The specific opportunities for hydrochar have only received limited attention. Research needs to include better understanding of the benefits and limitations for specific applications, as well as adjacent drivers, including society, regulation, and market and economics.

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.

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.

Engineering Stent Based Delivery System for Esophageal Cancer Using Docetaxel.

Esophageal cancer patients are often diagnosed as "advanced" cases. These patients are subjected to palliative stenting using self-expanding metallic stents (SEMS) to maintain oral alimentation. Unfortunately, SEMS get reoccluded due to tumor growth, in and over the stent struts. To investigate potential solutions to this problem, docetaxel (DTX) delivery films were prepared using PurSil AL 20 (PUS), which can be used as a covering material for the SEMS. Drug-polymer miscibility and interactions were studied. Bilayer films were prepared by adhering the blank film to the DTX loaded film in order to maintain the unidirectional delivery to the esophagus. In vitro release and the local DTX delivery were studied using in vitro permeation experiments. It was found that DTX and PUS were physically and chemically compatible. The bilayer films exhibited sustained release (>30 days) and minimal DTX permeation through esophageal tissues in vitro. The rate-determining step for the DTX delivery was calculated. It was found that >0.9 fraction of rate control lies with the esophageal tissues, suggesting that DTX delivery can be sustained for longer periods compared to the in vitro release observed. Thus, the bilayer films can be developed as a localized sustained delivery system in combination with the stent.

Tunable Thermoresponsiveness of Resilin via Coassembly with Rigid Biopolymers.

The ability to tune the thermoresponsiveness of recombinant resilin protein, Rec1-resilin, through a facile coassembly system was investigated in this study. The effects of change in conformation and morphology with time and the responsive behavior of Rec1-resilin in solution were studied in response to the addition of a rigid model polypeptide (poly-l-proline) or a hydrophobic rigid protein (Bombyx mori silk fibroin). It was observed that by inducing more ordered conformations and increasing the hydrophobicity the lower critical solution temperature (LCST) of the system was tuned to lower values. Time and temperature were found to be critical parameters in controlling the coassembly behavior of Rec1-resilin in both the model polypeptide and more complex protein systems. Such unique properties are useful for a wide range of applications, including drug delivery and soft tissue engineering applications.

Engineering interaction between bone marrow derived endothelial cells and electrospun surfaces for artificial vascular graft applications.

The aim of this investigation was to understand and engineer the interactions between endothelial cells and the electrospun (ES) polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP) nanofiber surfaces and evaluate their potential for endothelialization. Elastomeric PVDF-HFP samples were electrospun to evaluate their potential use as small diameter artificial vascular graft scaffold (SDAVG) and compared with solvent cast (SC) PVDF-HFP films. We examined the consequences of fibrinogen adsorption onto the ES and SC samples for endothelialisation. Bone marrow derived endothelial cells (BMEC) of human origin were incubated with the test and control samples and their attachment, proliferation, and viability were examined. The nature of interaction of fibrinogen with SC and ES samples was investigated in detail using ELISA, XPS, and FTIR techniques. The pristine SC and ES PVDF-HFP samples displayed hydrophobic and ultrahydrophobic behavior and accordingly, exhibited minimal BMEC growth. Fibrinogen adsorbed SC samples did not significantly enhance endothelial cell binding or proliferation. In contrast, the fibrinogen adsorbed electrospun surfaces showed a clear ability to modulate endothelial cell behavior. This system also represents an ideal model system that enables us to understand the natural interaction between cells and their extracellular environment. The research reported shows potential of ES surfaces for artificial vascular graft applications.

Interaction of platelets with poly(vinylidene fluoride-co-hexafluoropropylene) electrospun surfaces.

Platelets are the major contributors in the process of thrombosis and in the failure of biomedical implants. A number of factors influence the platelet interaction with foreign surfaces such as surface morphology, surface chemistry, and adsorbed proteins. This study examined the effect of surface topography and chemistry of pristine and fibrinogen-adsorbed solvent cast (SC) and electrospun (ES) samples of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) on platelet adhesion, activation, and aggregation. Qualitative and quantitative studies of fibrinogen adsorption were performed using time-of-flight secondary ion mass spectrometry (ToF-SIMS), while SEM, aggregometry, and liquid scintillation analyses were performed to evaluate platelet adhesion, aggregation, and serotonin release. While little or no platelet adhesion was observed on pristine ES surfaces, considerable adhesion, and measurable aggregation and serotonin release were observed on pristine SC surfaces. Notably, increased adhesion of platelets was observed following fibrinogen adsorption on SC surface with considerable aggregation and serotonin release compared with ES samples, where limited aggregation and platelet adhesion was observed. A further comparison of platelet adhesion, aggregation, and serotonin release was performed with plasma-adsorbed SC and ES surfaces. SC surfaces showed enhanced platelet adhesion, aggregation, and serotonin release compared to ES surfaces. This study shows that the morphology of samples plays a critical role on the biocompatibility of samples by altering the adsorption and adhesion of biomolecules and cells. The low level of adhesion, low aggregation, and serotonin release of platelets, even in the presence of fibrinogen and plasma-derived proteins, suggested that ES samples have the least thrombogenicity.

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.

Near superhydrophobic fibrous scaffold for endothelialization: fabrication, characterization and cellular activities.

In this work, we have applied an electrospinning method to control wettability and further hydrophobic modification of a hydrophobic polymer mat of poly(vinylidene fluoride-co-hexafluoropropylene). A correlation between the processing parameters, rheological properties of polymer solutions, and electrospinning ability was made using the polymer's critical entanglement concentration, the boundary between the semidilute unentangled regime and the semidilute entangled regime. The wetting behavior, structural and thermal characteristics of electrospun (ES) mats were evaluated and compared with solvent cast sample using advancing and receding contact angle analyses, differential scanning calorimetry, and small-angle X-ray scattering. To demonstrate the feasibility, the best optimized ES samples were examined for their potential and ability to support bone marrow derived endothelial cell seeding efficiency, adhesion and proliferation. Our studies show that, while different processing techniques can effectively modulate physical and morphological changes such as porosity and hydrophobicity, the cellular adhesion and proliferation are highly time-dependent and controlled by chemical factors. As such, these results suggest that it is the interplay of both physical and chemical factors that determine the endothelialization of porous near superhydrophobic scaffolds. The developed electrospun samples demonstrate their feasibility for endothelialization.

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.

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.

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.

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.

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.

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.

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.

Nanostructure evolution in high-temperature perfluorosulfonic acid ionomer membrane by small-angle X-ray scattering.

The high-temperature morphology of supported liquid membranes (SLMs) prepared from perfluorinated membranes such as Nafion and Hyflon and hydrophobic ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMI-TFSI) has been investigated by small-angle X-ray scattering (SAXS). Proton conductivity results of SLMs before and after leaching show an increase in conductivity with temperature up to 160 °C in an anhydrous environment. DSC results show that crystallites within perfluorinated membranes are thermally stable up to 196 °C. High-temperature SAXS results have been used to correlate structure and morphology of supported liquid membranes with high-temperature conductivity data. The ionic liquid essentially acts as a proton solvent in a similar way to water in hydrated Nafion membranes and increases size of clusters, which allow percolation to be achieved more easily. The cation of the ionic liquid interacts with sulfonate groups within ionic domains through electrostatic interactions and displaces protons. Protons can associate with free anions of the ionic liquid, which are loosely associated with cations and can transport by hopping from anion sites within the membrane. The ionic liquid contributes to proton conductivity at high temperature through achievement of long-range ordering and subsequent percolation.