Crowder-directed interactions and conformational dynamics in multistimuli-responsive intrinsically disordered protein.

The consequences of crowding on the dynamic conformational ensembles of intrinsically disordered proteins (IDPs) remain unresolved because of their ultrafast motion. Here, we report crowder-induced interactions and conformational dynamics of a prototypical multistimuli-responsive IDP, Rec1-resilin. The effects of a range of crowders of varying sizes, forms, topologies, and concentrations were examined using spectroscopic, spectrofluorimetric, and contrast-matching small- and ultrasmall-angle neutron scattering investigation. To achieve sufficient neutron contrast against the crowders, deuterium-labeled Rec1-resilin was biosynthesized successfully. Moreover, the ab initio "shape reconstruction" approach was used to obtain three-dimensional models of the conformational assemblies. The IDP revealed crowder-specific systematic extension and compaction with the level of macromolecular crowding. Last, a robust extension-contraction model has been postulated to capture the fundamental phenomena governing the observed behavior of IDPs. The study provides insights and fresh perspectives for understanding the interactions and structural dynamics of IDPs in crowded states.

Plastic Waste Upcycling: A Sustainable Solution for Waste Management, Product Development, and Circular Economy.

Plastic waste pollution, including non-biodegradable landfills, leaching of toxic chemicals into soil and waterways, and emission of toxic gases into the atmosphere, is significantly affecting our environment. Conventional plastic waste recycling approaches generally produce lower value materials compared to the original plastic or recover inefficient heat energy. Lately, upcycling or the valorization approach has emerged as a sustainable solution to transform plastic waste into value-added products. In this review, we present an overview of recent advancements in plastic waste upcycling, such as vitrimerization, nanocomposite fabrication, additive manufacturing, catalytic transformation, and industrial biotechnology, envisaged with technical challenges, future developments, and new circular economy opportunities.

4D Printing of Hydrogels: Innovation in Material Design and Emerging Smart Systems for Drug Delivery.

Advancements in the material design of smart hydrogels have transformed the way therapeutic agents are encapsulated and released in biological environments. On the other hand, the expeditious development of 3D printing technologies has revolutionized the fabrication of hydrogel systems for biomedical applications. By combining these two aspects, 4D printing (i.e., 3D printing of smart hydrogels) has emerged as a new promising platform for the development of novel controlled drug delivery systems that can adapt and mimic natural physio-mechanical changes over time. This allows printed objects to transform from static to dynamic in response to various physiological and chemical interactions, meeting the needs of the healthcare industry. In this review, we provide an overview of innovation in material design for smart hydrogel systems, current technical approaches toward 4D printing, and emerging 4D printed novel structures for drug delivery applications. Finally, we discuss the existing challenges in 4D printing hydrogels for drug delivery and their prospects.

Electrospun Composite Nanofiltration Membranes for Arsenic Removal.

In recent years, significant attention has been paid towards the study and application of mixed matrix nanofibrous membranes for water treatment. The focus of this study is to develop and characterize functional polysulfone (PSf)-based composite nanofiltration (NF) membranes comprising two different oxides, such as graphene oxide (GO) and zinc oxide (ZnO) for arsenic removal from water. PSf/GO- and PSf/ZnO-mixed matrix NF membranes were fabricated using the electrospinning technique, and subsequently examined for their physicochemical properties and evaluated for their performance for arsenite-As(III) and arsenate-As(V) rejection. The effect of GO and ZnO on the morphology, hierarchical structure, and hydrophilicity of fabricated membranes was studied using a scanning electron microscope (SEM), small and ultra-small angle neutron scattering (USANS and SANS), contact angle, zeta potential, and BET (Brunauer, Emmett and Teller) surface area analysis. Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) were used to study the elemental compositions and polymer-oxide interaction in the membranes. The incorporation of GO and ZnO in PSf matrix reduced the fiber diameter but increased the porosity, hydrophilicity, and surface negative charge of the membranes. Among five membrane systems, PSf with 1% ZnO has the highest water permeability of 13, 13 and 11 L h-1 m-2 bar-1 for pure water, As(III), and As(V)-contaminated water, respectively. The composite NF membranes of PSf and ZnO exhibited enhanced (more than twice) arsenite removal (at 5 bar pressure) of 71% as compared to pristine PSf membranes, at 43%, whereas both membranes showed only a 27% removal for arsenate.

Additive Manufacturing of Polymer Materials: Progress, Promise and Challenges.

The use of additive manufacturing (AM) has moved well beyond prototyping and has been established as a highly versatile manufacturing method with demonstrated potential to completely transform traditional manufacturing in the future. In this paper, a comprehensive review and critical analyses of the recent advances and achievements in the field of different AM processes for polymers, their composites and nanocomposites, elastomers and multi materials, shape memory polymers and thermo-responsive materials are presented. Moreover, their applications in different fields such as bio-medical, electronics, textiles, and aerospace industries are also discussed. We conclude the article with an account of further research needs and future perspectives of AM process with polymeric materials.

3D Printable Electrically Conductive Hydrogel Scaffolds for Biomedical Applications: A Review.

Electrically conductive hydrogels (ECHs), an emerging class of biomaterials, have garnered tremendous attention due to their potential for a wide variety of biomedical applications, from tissue-engineered scaffolds to smart bioelectronics. Along with the development of new hydrogel systems, 3D printing of such ECHs is one of the most advanced approaches towards rapid fabrication of future biomedical implants and devices with versatile designs and tuneable functionalities. In this review, an overview of the state-of-the-art 3D printed ECHs comprising conductive polymers (polythiophene, polyaniline and polypyrrole) and/or conductive fillers (graphene, MXenes and liquid metals) is provided, with an insight into mechanisms of electrical conductivity and design considerations for tuneable physiochemical properties and biocompatibility. Recent advances in the formulation of 3D printable bioinks and their practical applications are discussed; current challenges and limitations of 3D printing of ECHs are identified; new 3D printing-based hybrid methods for selective deposition and fabrication of controlled nanostructures are highlighted; and finally, future directions are proposed.

Nanofiltration for Arsenic Removal: Challenges, Recent Developments, and Perspectives.

Arsenic (As) removal is of major significance because inorganic arsenic is highly toxic to all life forms, is a confirmed carcinogen, and is of significant environmental concern. As contamination in drinking water alone threatens more than 150 million people all over the world. Therefore, several conventional methods such as oxidation, coagulation, adsorption, etc., have been implemented for As removal, but due to their cost-maintenance limitations; there is a drive for advanced, low cost nanofiltration membrane-based technology. Thus, in order to address the increasing demand of fresh and drinking water, this review focuses on advanced nanofiltration (NF) strategy for As removal to safeguard water security. The review concentrates on different types of NF membranes, membrane fabrication processes, and their mechanism and efficiency of performance for removing As from contaminated water. The article provides an overview of the current status of polymer-, polymer composite-, and polymer nanocomposite-based NF membranes, to assess the status of nanomaterial-facilitated NF membranes and to incite progress in this area. Finally, future perspectives and future trends are highlighted.

Magnesium Alloys With Tunable Interfaces as Bone Implant Materials.

Magnesium (Mg) based biodegradable materials are a new generation orthopedic implant materials that are intended to possess same mechanical properties as that of bone. Mg alloys are considered as promising substitutes to permanent implants due to their biodegradability in the physiological environment. However, rapid corrosion rate is one of the major constraints of using Mg alloys in clinical applications in spite of their excellent biocompatibility. Approaches to overcome the limitations include the selection of adequate alloying elements, proper surface treatment, surface modification with coating to control the degradation rate. This review focuses on current advances on surface engineering of Mg based biomaterials for biomedical applications. The review begins with a description of corrosion mechanism of Mg alloy, the requirement for appropriate surface functionalization/coatings, their structure-property-performance relationship, and suitability for biomedical applications. The control of physico-chemical properties such as wettability, surface morphology, surface chemistry, and surface functional groups of the coating tailored by various approaches forms the pivotal part of the review. Chemical surface treatment offers initial protection from corrosion and inorganic coating like hydroxyapatite (HA) improves the biocompatibility of the substrate. Considering the demand of ideal implant materials, multilayer hybrid coatings on Mg alloy in combination with chemical pretreatment or inorganic HA coating, and protein-based polymer coating could be a promising technique to improve corrosion resistance and promote biocompatibility of Mg-based alloys.

3D Bioprinted Nanocellulose-Based Hydrogels for Tissue Engineering Applications: A Brief Review.

Nanocellulosic materials, such as cellulose nanocrystals, cellulose nanofibers, and bacterial nanocellulose, that display high surface area, mechanical strength, biodegradability, and tunable surface chemistry have attracted great attention over the last decade for biomedical applications. Simultaneously, 3D printing is revolutionizing the field of biomedical engineering, which enables the fast and on-demand printing of customizable scaffolds, tissues, and organs. Nanocellulosic materials hold tremendous potential for 3D bioprinting due to their printability, their shear thinning behavior, their ability to live cell support and owing to their excellent biocompatibility. The amalgamation of nanocellulose-based feedstocks and 3D bioprinting is therefore of critical interest for the development of advanced functional 3D hydrogels. In this context, this review briefly discusses the most recent key developments and challenges in 3D bioprinting nanocellulose-based hydrogel constructs that have been successfully tested for mammalian cell viability and used in tissue engineering applications.

Graphene-Based Inks for Printing of Planar Micro-Supercapacitors: A Review.

Micro-supercapacitors have recently emerged as promising microscale power sources for portable and wearable microelectronics. However, most reported planar micro-supercapacitors suffer from low energy density and the complexity of fabrication, which calls for their further development. In recent years, the fortification of graphene has enabled the dramatic improvement of planar micro-supercapacitors by taking full advantage of in-plane interdigital architecture and the unique features of graphene. The development of viable printing technologies has also provided better means for manufacturing, bringing micro-supercapacitors closer to practical applications. This review summarizes the latest advances in graphene-based planar micro-supercapacitors, with specific emphasis placed on formulation of graphene-based inks and their fabrication routes onto interdigital electrodes. Prospects and challenges in this field are also discussed towards the realization of graphene-based planar micro-supercapacitors in the world of microelectronics.

Structural evolution of photocrosslinked silk fibroin and silk fibroin-based hybrid hydrogels: A small angle and ultra-small angle scattering investigation.

Regenerated Bombyx mori silk fibroin (RSF) is a widely recognized protein for biomedical applications; however, its hierarchical gel structure is poorly understood. In this paper, the hierarchical structure of photocrosslinked RSF and RSF-based hybrid hydrogel systems: (i) RSF/Rec1-resilin and (ii) RSF/poly(N-vinylcaprolactam (PVCL) is reported for the first time using small-angle scattering (SAS) techniques. The structure of RSF in dilute to concentrated solution to fabricated hydrogels were characterized using small angle X-ray scattering (SAXS), small angle neutron scattering (SANS) and ultra-small angle neutron scattering (USANS) techniques. The RSF hydrogel exhibited three distinctive structural characteristics: (i) a Porod region in the length scale of 2 to 3nm due to hydrophobic domains (containing ß-sheets) which exhibits sharp interfaces with the amorphous matrix of the hydrogel and the solvent, (ii) a Guinier region in the length scale of 4 to 20nm due to hydrophilic domains (containing turns and random coil), and (iii) a Porod-like region in the length scale of few micrometers due to water pores/channels exhibiting fractal-like characteristics. Addition of Rec1-resilin or PVCL to RSF and subsequent crosslinking systematically increased the nanoscale size of hydrophobic and hydrophilic domains, whereas decreased the homogeneity of pore size distribution in the microscale. The presented results have implications on the fundamental understanding of the structure-property relationship of RSF-based hydrogels.

Fabrication and characterisation of an electrospun tubular 3D scaffold platform of poly(vinylidene fluoride-co-hexafluoropropylene) for small-diameter blood vessel application.

In this research, nanofibrous 3D tubular (~4-mm-diameter tube) scaffolds of poly (vinylidene fluoride-co-hexafluoropropylene) were fabricated by electrospinning. The role of surface charge in the success of these scaffolds for potential small-diameter artificial vascular grafts has been investigated using streaming potential study. Prior to endothelial cell culture, surface properties such as wettability and the surface charge of these tubular scaffolds were evaluated using unmodified and fibrinogen-adsorbed surfaces to understand their interaction with surrounding environment. The tubular scaffolds constructed using electrospinning show similar mechanical properties such as tensile strength and elastic modulus as those of native vessels. Whilst endothelial cell proliferation on unmodified tubes, as analysed by scanning electron microscopy, was found to be moderate, a simple process of dynamic fibrinogen adsorption was seen to enhance the endothelialisation of these tubular grafts. The high negative zeta potential values, high strength, robustness and structural reliability of the scaffolds represent them to be promising biomaterials for vascular graft applications.