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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.

The envisaged shift in the interest of crystal engineering researchers from crystal structure to mechanical property has sown the seeds of analogous understanding and interpretation of the molecula...

This paper investigates the frequency-dependent pile-head impedance characteristics of a model soil-pile foundation system under large amplitude loads, inducing soil yielding. Testing was conducted on a scaled single pile embedded in sand under a 1g condition. A laminar shear box mounted on a unidirectional shaking table was used to house the soil-pile foundation system. Quasi-static loads and dynamic loads were applied to obtain the force–displacement relationships and pile-head impedance functions, respectively, through the pile head connected to a loading actuator providing fixity to the pile head in all directions, except horizontal. In the quasi-static case, loads with three different velocities were applied to study the rate-dependent characteristics of the lateral bearing capacity of the pile. The Stereo-PIV system was employed to measure the surface soil displacement around the pile. The lateral bearing capacity changed with the loading velocity, but the soil near the pile showed a consistent failure pattern despite a significant change in velocity. Lateral pile-head dynamic impedance functions were obtained for low-to-high amplitude harmonic loading for a wide range of frequencies. The dynamic stiffness was seen to converge to that of the secant static stiffness with an increase in the amplitude of the dynamic loading for all the excitation frequencies.

This study endeavoured to explore and fabricate antiviral and antibacterial facemasks using zinc (oligo-lactate) (ZL), developed through a microwave synthesis technique. The prepared nano-fabric layer has excellent antiviral and antibacterial properties against Newcastle Disease Virus (NDV) and E. coli and S. aureus, respectively. Thermogravimetric analysis (TGA) of ZL shows a two-step thermal degradation, which confirms the formation of low molecular weight end group lactyl units with zinc ions. Another investigation using varying ZL concentration and silk nanocrystal (SNC) with poly(lactic acid) (PLA) and electrospinning them into nanofibres led to the fabrication of a facile and sustainable nanofabric that can be utilized as a protective layer for facemasks. Morphological analysis revealed the successful preparation of the nanofabric with proper distribution and uniformity in fibre diameter. Hydrophobicity of the prepared nanofabric confirmed excellent protection from water droplets that may transpire during coughing or sneezing by an infected individual. Breathability and reusability tests confirmed that the prepared facemask could be reused by ethanol washing without compromising its surface properties till 4 cycles. The PLA/ZL nanofabric layer demonstrated 97% antiviral efficacy against NDV in 10 minutes. In conclusion, the electrospun nanofabric layer can be used as a facemask having high hydrophobicity, good breathability, antibacterial, and antiviral properties to control the spread of contagious diseases.

Sulfonylhydrazones are a novel hydrazone-based organic molecular photoswitch. The four derivatives with unsubstituted and o-, m- and p-nitro substituted sulfonylhydrazone (SH-1, SH-2, SH-3, and SH-4, respectively) derived from p-toluenesulfonyl hydrazide and corresponding benzaldehydes were examined with respect to their solution state photoswitching and photomechanical response in the crystalline state. All the compounds displayed UV-induced E → Z isomerization in the solution state, whereas the back conversion was slow. Single crystals of SH-3 displayed rapid and large photomechanical bending, whereas SH-1 and SH-4 crystals underwent slow bending to a comparatively lesser extent. On the contrary, SH-2 crystals did not show any photomechanical effects. The photomechanical deflection of the crystal tip of SH-1 increased linearly; for SH-3, the deflection increased in a sub-linear manner for few seconds, after which it started to revert towards the light source. For SH-4 crystals, the photo-induced tip deflection initially increased in a sub-linear fashion, after which no motion was observed even after continuous exposure to UV light irradiation. The photomechanical behavior of the crystals was also inspected with the aid of velocity-time and acceleration-time plots that unravelled the instantaneous photomechanical motion at various time intervals.

Stable dispersions of pristine graphene in innocuous mediums are highly desired for the use of this 2D material into a variety of practical applications. Here, we report the direct layer-by-layer f...

Tuning the mechanical properties of crystalline materials is alluring and has captivated the interest of material scientists. Here, we have demonstrated a crystal engineering approach to introduce ...

Resilin-like polypeptides (RLPs) are an important class of intrinsically disordered multistimuli-responsive bioelastomers. The nanostructure of RLPs in solution has been extensively studied in the past few years, from dilute to molecular crowding conditions, and with the addition of rigid biopolymers. Modification of the hierarchical network structure of RLP hydrogels using graphene oxide (GO) as an additive is a burgeoning prospect for their application in the bioelectronic and biomedical fields. In this work, we systemically study the influence of incorporating GO into RLP (Rec1) hydrogels for tuning their physicochemical properties and understanding the gel-cell interactions. The nature of GO interaction with the Rec1 hydrogel is deduced from the change in structure and properties. Contrast-matching small-angle and ultra-small-angle neutron-scattering techniques were used to investigate the network structure of the Rec1 hydrogel and how this structure is modified in the presence of GO. Incorporation of GO in the Rec1 hydrogel matrix results in an increase in the micromechanical resilience, equilibrium water swelling ratio, micropore size, cross-linked domain size; with a decrease in the cross-link density, mass fractal cluster size, local compressive elastic modulus, and cell inert characteristics. These property combinations achieved with the addition of GO further open up the available structure-property design window for RLP 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.

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.

4-n-Hexyloxybenzoic acid and the corresponding potassium salt were synthesized and crystallized, and their force-induced mechanical response was studied. 4-n-Hexyloxybenzoic acid is crystallized as large single crystals of the reported monoclinic polymorph, whereas, its potassium salt forms a 2D polymeric structure. When a localized mechanical force is applied, crystals of both materials undergo plastic deformation to the extent that they can be folded to resemble characters of the English alphabet. With few cycles of bending and unbending, the crystals can be exfoliated, and crystalline layers can be separated. In both structures, van der Waals interactions of the hexyl chains contribute toward the formation of slip plane parallel to the wider face of the crystals, which is necessary for their plastic deformability. Reported crystal structures of 4-n-alkoxybenzoic acids with alkyl chain length ranging from C1 to C10 and their inorganic salts were analyzed, and it was found that packing of alkyl chains su...

This study evaluates the aerobic biodegradation of modified Poly(lactic acid) (PLA) based biocomposites under composting condition. Samples of neat PLA (NPLA), PLA/chitosan 5% (modified) (PLA/Chitosan), PLA/CNC SO4 (1%) (PLA/CNC) and PLA/Gum Arabic 5% (modified) (PLA/Gum) were used for evaluation of biodegradation under simulated composting condition without adding any inoculum to the compost and utilizing the thermophilic microflora already present in the compost. Various analytical techniques like molecular weight analysis, differential scanning calorimetry (DSC), contact angle analysis and microbial colony count were used for analysis of biodegradation. Colony formation was analyzed and was found to be 5.12 × 106 cfu/ml in PLA/Chitosan sample. Contact angle measurement was employed for understanding biodegradation over a period of 70 days for the biocomposites. Biodegradation study was also confirmed through decrease in transparency and major peak shift in infra-red (IR) spectroscopy. DSC studies showed increase in crystallinity for all the degraded test samples, which confirms biodegradation. The results confirmed modified PLA films as biodegradable and also confirmed suitability of the test system for studying biopolymer biodegradation.

The advancement of our understanding of stimuli-responsive molecular crystals has led to the realization that they hold great yet unexplored potential as adaptive materials. Although molecular crystals that exhibit a single mechanical response to a single input stimulus are now abundant, crystals that are capable of response to multiple stimuli are rather scarce. Here we report two photoswitchable acylhydrazone derivatives, Ac-1 and Ac-2, which respond to light as well as to mechanical force. Upon application of localized mechanical stress, the anhydrous (Ac-1a) and monohydrate (Ac-1h) crystals of Ac-1 undergo plastic shearing deformation and bending, whereas monohydrate crystals of Ac-2 undergo elastic deformation. When they are exposed to UV light, crystals of Ac-1h and Ac-2 undergo photoinduced bending; on the other hand, crystals of Ac-1a and thicker crystals of Ac-2 exhibit photosalient effect (light-induced leaping). It is demonstrated that the synergistic action of multiple stimuli (UV light and fo...

Herein, we report the sustainable, cost-effective, and greener surface modification strategy of a quantum dot complex (QDC)—comprised of zinc chalcogenide quantum dot (Qdot; for example, undoped ZnS and Mn2+-doped ZnS) and surface zinc quinolate (ZnQ2) complexes—following interaction with bovine serum albumin (BSA) protein. The interaction of BSA with QDC led to an enhancement in their luminescence properties (such as the quantum yield and emission lifetime), solubility, and stability (in water), compared to their bare form. The enhanced luminescence properties of BSA coupled with QDC—also termed herein as the BSA–QDC nanocomposite—are due to the BSA-induced structural rigidity of the ZnQ2 complex (being present on the surface of zinc chalcogenide Qdot). The highly green luminescent nontoxic BSA–QDC nanocomposite—consisting of undoped ZnS and the ZnQ2 complex—showed better imaging capability of HeLa cells in comparison to only QDC and sensing ability of an enzyme (trypsin) with a detection limit of 0.06 μ...

Interface of transition metal dichalcogenide (TMDC) and high-k dielectric transition metal oxides (TMO) had triggerred umpteen discourses due to the indubitable impact of TMO in reducing the contact resistances and restraining the Fermi-level pinning for the metal-TMDC contacts. In the present work, we focus on the unresolved tumults of large-area TMDC/TMO interfaces, grown by adopting different techniques. Here, on a pulsed laser deposited (PLD) MoS2 thin film, a layer of TiO2 is grown by using both atomic layer deposition (ALD) and PLD. These two different techniques emanate TiO2 layers with different crystalline properties, thicknesses and interfacial morphologies, subsequently influencing the electronic and optical properties of the interfaces. In addition, they manifest a boost in the extent of p-type doping with increasing thickness of TiO2, as emerged after analyzing the core-level shifts of the X-ray photoelectron spectra (XPS). Density functional analysis of the MoS2/Anatase-TiO2 interfaces, for pristine and in presence of a wide range of interfacial defects, could explain the interdependence of doping and the terminating atomic-surface of TiO2 on MoS2. The optical properties of the interface, encompassing the photoluminescence, transient absorption and z-scan two-photon absorption indicate the presence of defect-induced localized mid-gap levels in MoS2/TiO2 (PLD), resulting quenched exciton signals. On the contrary, the relatively defect-free interface in MoS2/TiO2 (ALD) demonstrates a clear presence of both A and B excitons of MoS2. From the investigation of optical properties, we indicate that MoS2/TiO2 (PLD) interface may act as a promising saturable absorber. Moreover, MoS2/TiO2 (PLD) interface had resulted a better photo-transport. A potential application of MoS2/TiO2 (PLD) is demonstrated by the fabrication of a p-type photo-transistor with the ionic-gel top gate.

The inclusion of chitosan (CS) nanostructured materials as a constituent of edible food packaging is a potential candidate to be used as an alternative against existing conventional packaging materials for attaining enhanced product life of perishable food products. The several properties such as excellent physicochemical properties, bioactivity, antimicrobial, antifungal, health benefits, and packaging properties are better obtained by the use of CS nanomaterials as a biocomposite or as an individual material. Further, the CS nanostructured materials are generally availed in the forms of nanocrystals, nanofibers, and nanoparticle (NP), which can be fabricated using several processes, where optimization of the processing conditions deliver targeted morphology. The several processes for fabricating CS nanoparticles (CSNPs) include ionotropic gelation, microemulsion, emulsification solvent diffusion, polyelectrolyte complexes, reverse micellar, solvent evaporation, coprecipitation, complex coacervation, and other methods. The chapter discusses the fabrication methods and property analysis of CS-based nanostructured materials for delivering the tailored packaging properties to act as a potential material in developing edible films and coatings. Interestingly, CSNPs-aided composites help to improve the shelf life of food products while maintaining the several quality parameters throughout the storage life. The effect of various sources and molecular weight of CS and their effectiveness to fabricate the edible food packaging will be discussed in the current chapter. Additionally, the use of CSNPs as an edible-coating material further provides a strategical way to improve the functionality and performance of food products in terms of microbiological property, weight stability, texture property, and others, which is detailed in the current chapter.

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. Refereed/Peer-reviewed

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.

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.

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.

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.

The development of novel hydrogels that possess adequate elasticity and toughness to withstand mechanically active environments, along with being biocompatible, remains a significant challenge in the design of materials for tissue engineering applications. In this study, a family of regenerated silk fibroin (RSF) based double network (DN) hydrogels were fabricated for the first time using a rapid one-pot method. The DN hydrogels combine the rigid covalently crosslinked RSF with the softer poly(N-vinylcaprolactam) (PVCL) through strong physical interactions. The formation of these DN hydrogels resulted in an improvement of the water uptake capacity, elasticity and toughness compared to the individual RSF hydrogel. The elasticity of the RSF/PVCL DN hydrogels was closer to that of native cartilage, which makes them promising materials for cartilage regeneration applications. An in vitro study on adhesion, proliferation and differentiation of a mouse pre-chondrocyte cell line (ATDC5) conducted using microscopic analysis, a cell proliferation assay and RT-PCR confirmed the cells cultured on the less stiff hydrogels demonstrated the most favourable chondrogenic response. Thus, this study demonstrates the potential of RSF-based hybrid hydrogels for cartilage tissue engineering 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 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.

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 (

The first example of a smart crystalline material, the 2:1 cocrystal of probenecid and 4,4'-azopyridine, which responds reversibly to multiple external stimuli (heat, UV light, and mechanical pressure) by twisting, bending, and elastic deformation without fracture is reported. This material is also able to self-heal on heating and cooling, thereby overcoming the main setbacks of molecular crystals for future applications as crystal actuators. The photo- and thermomechanical effects and self-healing capabilities of the material are rooted in reversible trans-cis isomerization of the azopyridine unit and crystal-to-crystal phase transition. Fairly isotropic intermolecular interactions and interlocked crisscrossed molecular packing secure high elasticity of the crystals.

Aqueous gels formulated using hydrophilic polymers (hydrogels) along with those based on stimuli responsive polymers (in situ gelling or gel forming systems) continue to attract increasing interest for various eye health-related applications. They allow the incorporation of a variety of ophthalmic pharmaceuticals to achieve therapeutic levels of drugs and bioactives at target ocular sites. The integration of sophisticated drug delivery technologies such as nanotechnology-based ones with intelligent and environment responsive systems can extend current treatment duration to provide more clinically relevant time courses (weeks and months instead of hours and days) which will inevitably reduce dose frequency, increase patient compliance and improve clinical outcomes. Novel applications and design of contact lenses and intracanalicular delivery devices along with the move towards integrating gels into various drug delivery devices like intraocular pumps, injections and implants has the potential to reduce comorbidities caused by glaucoma, corneal keratopathy, cataract, diabetic retinopathies and age-related macular degeneration. This review describes ophthalmic gelling systems with emphasis on mechanism of gel formation and application in ophthalmology. It provides a critical appraisal of the techniques and methods used in the characterization of ophthalmic preformed gels and in situ gelling systems along with a thorough insight into the safety and biocompatibility of these systems. Newly developed ophthalmic gels, hydrogels, preformed gels and in situ gelling systems including the latest in the area of stimuli responsive gels, molecularly imprinted gels, nanogels, 3D printed hydrogels; 3D printed devices comprising ophthalmic gels are covered. Finally, new applications of gels in the production of artificial corneas, corneal wound healing and hydrogel contact lenses are described.

Creating a well-defined nanostructure through de-oxyribo nucleic acid (DNA)-nanotechnology, and specifically the development of metal/inorganic semiconductor junctions on DNA-assembled nanostructures, is an emerging research area. Herein, we investigate the electrical properties of biomolecule DNA-template based one-dimensional nanowires (NWs)-CdS/Au and without-template based nanoparticles (NPs)-CdS/Au devices grown on the Indium Tin Oxide (ITO) glass substrates. More importantly, the NWs-CdS/Au device displays a dramatic augmentation of current flow and also a striking change in threshold voltage (~55 mV) in comparison to NPs (~190 mV) and reported bulk-CdS/Au (~680 mV) devices. Albeit the manifestation of non-linear/asymmetric current-voltage (I–V) characteristic establishes the CdS/Au junction as Schottky device, but captivatingly, the large ideality factor of about 24 found in NWs-CdS/Au device could be due to the DNA-assembled based organic process CdS-semiconductor. Capacitance-voltage (C–V) measurements of the NWs-CdS/Au divulge a remarkable hump-like feature at lower frequency owing to the frequency dispersion effect. In contrast, the effect appears to be enfeebled with increasing frequency. We conjecture that the density of surface/interface traps materialises at the interface of nanostructures-CdS/metal-Au results in the changes in underlying electrical properties. The observation of significant differences in the electrical properties of DNA-assembled NWs-based Schottky junctions could possibly be helpful for the fabrication of more sophisticated and higher multispecificity biosensors for medical applications.

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 3 nm due to hydrophobic domains (containing β-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 20 nm 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. Refereed/Peer-reviewed

The corrosion process is a surface reaction that can be controlled by the addition of corrosion inhibitors, which adsorb on the reacting metal surface. The inhibitors could be applied to a metal surface in many different ways. In this contribution, influence of polymerized ionic liquid (PIL) was examined on inhibition performance of a coating using carbon steel samples. The PIL was loaded in self-assembled nanophase particle (SNAP) coating and the inhibition behaviour was investigated using potentiodynamic polarization, electrochemical impedance spectroscopy and scanning kelvin probe techniques. The inhibition efficiency of the coating increases with the addition of PIL as observed from potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) measurements. In addition, scanning kelvin probe (SKP) measurement provides further understanding on the strong interfacial properties of the modified coating compared to that of the SNAP. Refereed/Peer-reviewed

With the development of nanotechnology, metal oxide nanoparticles have been applied in many industries, increasing their potential exposure level in the environment, yet their environmental safety remains poorly evaluated. Present work demonstrated the effects of ZnO and TiO2 nanoparticles on the germination, morphoanatomical attributes and biochemistry of Cicer arietinum. The nanoparticles are used in three doses, i.e., 100, 500 and 1000 ppm along with control and each dose has three replicates. Results demonstrated that ZnO nanoparticles did not aid in the germination of seed, whereas TiO2 nanoparticles showed positive impact on germination at 48-h observation. But at 72-h observation both the nanoparticle-treated and control seeds showed 100% germination. Morphological parameters revealed that ZnO nanoparticles have drastic negative impact on both root and shoot length, root and shoot fresh and dry biomass. On the other hand, the status of chlorophyll is almost opposite, i.e., ZnO nanoparticle-treated plants showed higher pigment content than TiO2 nanoparticle-treated plants. From the statistical point of view, it is revealed that ZnO nanoparticle-treated plant showed significantly different results than that of TiO2 nanoparticle-treated plants in Chl ‘a’ (p

Solid electrolyte interphase (SEI) plays an important role in determining electrochemical performances of Li-ion batteries. The ideal SEI layer protects the electrolyte from being further reduced on the electrode surface and allows Li-ion diffusion in and out of electrodes without any consumption. However, degradation of the SEI layer over time, which contributes to the thickening of the SEI layer, is a leading pathway for gradual capacity fade. In this study, a hyperpolarized (HP) 129Xe nuclear magnetic resonance (NMR) technique was applied for the first time to probe changes in porosity and connectivity in Si nanoparticle composite electrodes as a result of the SEI formation. Nanopores are present in nanocomposite electrodes as a result of aggregation of the constituting nanoparticles. The connectivity among nanopores greatly affects the ion transport property of the electrode materials, which has a substantial influence on the overall energy output of Li-ion batteries. In this work, information on thic...

Indoor air pollution from burning of solid unprocessed biomass fuel and health risk arising from it are a crucial issue in developing countries. Smoke deposits (black soot) from traditional cooking stoves in the kitchen are characterized, and the health risk of children arising from it is assessed. Five types of wood, sissoo (Dalbergia sissoo), banyan (Ficus benghalensis), eucalyptus (Eucalyptus sp.), palm (Borassus flabellifer) and mixed wood were used by the villagers as their main cooking fuels. Black soots were collected and characterization was done by X-Ray fluorescence spectroscopy, atomic absorption spectroscopy and scanning electron microscopy. The highest concentration of lead was observed in soot from sissoo wood burning among the five types of black soots, followed by mixed wood, palm, banyan and eucalyptus. The quantitative estimation of manganese concentration was found to be very high in all varieties of black soot. Surface morphology study revealed that all the surfaces of black soot were similar in nature. Using metal concentration derived from the five types of black soot, exposure of children to heavy metals was calculated via three types of exposure pathways and it was found that the average daily exposure level of all elements was in the order of hand-to-mouth ingestion > dermal contact > inhalation. It was also noted that the non-carcinogenic hazard indexes and carcinogenic risks of metals in black soots were both well under the safe values.

Current state of the art plastic solar cells utilise halogenated solvents which pose processing challenges due to their toxicity and thus environmental hazards. In this work, we investigate alternative materials which are processable using environmentally friendly solvents. Specifically, we investigate the use of water-soluble materials. Fullerenol, due to the presence of hydroxyl groups, can be functionalised by esterification using reagents such as acid chlorides. In this contribution, we studied the effect of thiophene substituents on the miscibility of fullerenol and P3HT. The chemical modification on fullerene did not alter the electrochemical property of fullerene which makes it suitable for acceptor applications for organic solar cells.

Herein we report the first example of a facile biomineralization process to produce ultra-small-sized highly fluorescent aqueous dispersions of platinum noble metal quantum clusters (Pt-NMQCs) using a multi-stimulus responsive, biomimetic intrinsically disordered protein (IDP), Rec1-resilin. We demonstrate that Rec1-resilin acts concurrently as the host, reducing agent, and stabilizer of the blue-green fluorescent Pt-NMQCs once they are being formed. The photophysical properties, quantum yield, and fluorescence lifetime measurements of the synthesized Pt-NMQCs were examined using UV-Vis and fluorescence spectroscopy. The oxidation state of the Pt-NMQCs was quantitatively analyzed using X-ray photoelectron spectroscopy. Both a small angle X-ray scattering technique and a modeling approach have been attempted to present a detailed understanding of the structure and conformational dynamics of Rec1-resilin as an IDP during the formation of the Pt-NMQCs. It has been demonstrated that the green fluorescent Pt-NMQCs exhibit a high quantum yield of ~7.0% and a lifetime of ~9.5 ns in aqueous media. The change in photoluminescence properties due to the inter-dot interactions between proximal dots and aggregation of the Pt-NMQCs by evaporation was also measured spectroscopically and discussed.

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.

Present work is highlighted on the removal of U(VI) through batch experiment, by varying the parameters such as pH, adsorbent contact time & dose, temperature, initial concentration. The SB@Fe was characterized by X-ray diffraction spectroscopy (XRD), Brunauer Emmett-Teller surface area (BETsurface), Point Zero Charge (ZPC), Field Emission Scanning Electron Microscopy (FESEM), Energy-dispersive X-ray spectroscopy (XEDS), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FT-IR). Adsorption equilibrium were explained through kinetics and isotherm model. The pseudo-second order kinetic and the Langmuir isotherm were comparatively the best fitted, with the highest adsorption capacity at pH 5.5 of 138.88 mg/g. The adsorption mechanism was ascribed by thermodynamics parameters, which recommended the process in terms of exothermic, spontaneous and large available of randomness. Finally, Box-Behnken Design (BBD) was used for optimization of U (VI) removal up to 99.813%. Therefore, the present study indicated that the silicon containing biochar supported iron oxide nanoparticle could be a promising adsorbent for decontamination of U(VI) from underground water.

Higher level of fluoride in underground water is a burning problem in many parts of the world. Continuous ingestion of fluoride containing water leads to fluorosis. In the present work, natural banana (Musa acuminate) peel (NBP), an unconventional adsorbent, has been explored for removal of fluoride from aqueous system. The NBP was characterized by using SEM, FTIR, and point of zero charge. In the batch study, maximum fluoride removal was achieved at the pH 4.0 (pHZPC 5.63), taking about 60 min to attain equilibrium. Kinetics data were fitted with a pseudo-second-order (R 2 = 0.99) and Bahangam models (R 2 = 1.00). The experimental data fitted well to a D-R adsorption isotherm (R 2 = 0.995). Thermodynamic data suggests that the adsorption of fluoride on NBP is an exothermic reaction. Therefore, the results suggest that natural banana peel dust could be a cost-effective, eco-friendly adsorbent for removal of fluoride from aqueous medium.

Water pollution due to contamination of dye containing effluents is a great threat to water body. A study on the biosorption of methylene blue (MB) onto low-cost Lemna major biomass was conducted and the process parameters were optimized by response surface methodology (RSM). A two-level, four-factor central composite design (CCD) has been employed to determine the effect of various process parameters namely initial concentration (600–1000 mg L−1), bioadsorbent dose (0.20–1.50 g/100 mL), pH (5–12) and stirring rate (250–800 rpm) on MB uptake from aqueous solution. By using this design a total of 30 biosorption experimental data were fitted. The regression analysis showed good fit of the experimental data to the second-order polynomial model with coefficient of determination (R2) value of 0.9978 and model F-value of 953.48. The optimum conditions of initial concentration (1000 mg L−1), adsorbent dose (0.2 g), pH (5) and stirring rate (251.51 rpm) were recorded from desirability function. The adsorption isotherm data were best described by both Freundlich and Langmuir models with a maximum adsorption capacity of 488 mg MB g−1 L. major biomass at 30 °C which is higher than that available with adsorbents used by past researchers. Finally the pseudo second order kinetic model described the MB biosorption process with a good fitting (R2 = 0.999). The adsorbent was characterised by scanning electron micrograph (SEM) and Fourier transform infrared spectroscopy (FTIR).

In this contribution, we report the facile preparation of cross-linked polymerizable ionic liquid (PIL)-based nanoparticles via thiol–ene photopolymerization in a miniemulsion. The synthesized PIL nanoparticles with a diameter of about 200 nm were fully characterized with regard to their chemical structures, morphologies, and properties using different techniques, such as Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, and transmission electron microscopy. To gain an in-depth understanding of the physical and morphological structures of the PIL nanoparticles in an emulsion, small-angle neutron scattering and ultra-small-angle neutron scattering were used. Neutron scattering studies revealed valuable information regarding the formation of cylindrical ionic micelles in the spherical nanoparticles, which is a unique property of this system. Furthermore, the PIL nanoparticle emulsion was utilized as an inhibitor in a self-assembled nanophase particle (SNAP) coating. The corrosion protection ability of the resultant coating was examined using potentiodynamic polarization and electrochemical impedance spectroscopy. The results show that the PIL nanoparticle emulsion in the SNAP coating acts as an inhibitor of corrosion and is promising for fabricating advanced coatings with improved barrier function and corrosion protection.

Segregated elements and their diffusion profiles within grain boundaries and interfaces resulting from post deposition heat treatments are revealed using atom probe tomography (APT), scanning transmission electron microscopy (STEM), and electron beam induced current (EBIC) techniques. The results demonstrate how these techniques complement each other to provide conclusive evidence for locations of space charge regions and mechanisms that create them at the nanoscale. Most importantly, a Cl dopant profile that extends ~5 nm into CdTe grains interfacing the CdS is shown using APT and STEM synergy, which has been shown to push the pn-junction into the CdTe layer indicative of a homojunction (revealed by STEM EBIC). In addition, Cu and Cl concentrations within grain boundaries within several nms and µms from the CdS/CdTe interface are compared, Na segregation of

Electronic supplementary information (ESI) available: This includes the NMR data confirming the identity of the silk powder, the full crosslinking reaction schematic, fluorescence and UV-vis spectra of the gels, and the determination of the minimum Ru(II)(bpy)3 2+ concentration required for crosslinking. See DOI: 10.1039/c4tb00698d A facile and rapid ruthenium catalysed photo-crosslinking method was employed to prepare Bombyx mori silk fibroin hydrogels for the first time that may be used for biomedical applications. The gels have been characterised by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), photoacoustic Fourier transform infrared spectroscopy (PA-FTIR), and X-ray diffraction (XRD). We have reported the tuning of the properties of the chemically crosslinked gels through hydration level. DSC and DMA measurements have shown that the molecular chain dynamics and mechanical properties are dependent on the moisture/water content. The structural changes upon gelation were examined through the use of DSC, PA-FTIR and XRD, which confirmed that the gels were less crystalline than the original silk powder. Finally, the biocompatibility and hence, the potential tissue engineering application of the silk fibroin hydrogel was also assessed by culturing chondrocyte progenitor cells for up to one week on the engineered fibroin surfaces. Refereed/Peer-reviewed