Unique Crystallization Characteristics of Pickering High Internal Phase Emulsion Templated Porous Constructs.

To study the crystallization behavior of polymeric chains under the influence of porosity, the thermal properties of various nonporous and porous poly(ε-caprolactone) (PCL) based constructs were investigated. Porous cross-linked PCL nanocomposite constructs were fabricated utilizing in situ polymerization of CL-based surfactant-free Pickering high internal phase emulsions (HIPEs), stabilized using modified fumed silica nanoparticles (mSiNP) at a minimal concentration of 0.6 wt %. The corresponding nanocomposite constructs exhibited polyhedral pore morphology with significant pore roughness due to the presence of mSiNP. DSC thermograms of nonporous constructs illustrated diminished crystallization temperature and kinetics upon cross-linking and inclusion of mSiNP which confirmed suppressed mobility of polymer chains. Further introduction of porosity led to substantial supercooling, resulting in crystallization temperatures as low as -24 °C. Changes in the crystal structure of various nonporous and porous constructs were also studied using XRD. The crystallization behavior of porous constructs was finally evaluated using Jeziorny, Ozawa, and Mo theories under nonisothermal conditions. Significant deviation from the theoretical model, as observed in the case of porous constructs, implied a complex crystallization mechanism that eventually was not only controlled by the chain immobility due to cross-linking but also heterogeneity present in the wall thickness of the constructs. The unique melting-crystallization phenomenon observed in such constructs may further be expanded to other systems of high heat capacity for utilization as energy storage materials.

Solid Polymer Electrolytes with Dual Anion Synergy and Twofold Reinforcement Effect for All-Solid-State Lithium Batteries.

Solid polymer electrolytes (SPEs) have emerged as a viable alternative to traditional organic liquid-based electrolytes for high energy density and safer lithium batteries. Poly(ethylene oxide) (PEO)-based SPEs are considered one of the mainstream SPE materials with excellent dissociation ability of lithium salts. However, the inferior ionic conductivity at room temperature and poor dimensional stability at high temperature limit their utilization. In this work, a semi-interpenetrating polymer network (semi-IPN) forming a precursor based on an ionic liquid (IL) monomer and linear PEO chains were introduced into an electrospun poly(acrylonitrile) (PAN) fibrous mat with subsequent thermal-initiated cross-linking. 1,4-Diazabicyclo [2.2.2] octane (DABCO) and 4-(chloromethyl) styrene were used to synthesize the styrenic-DABCO-based IL monomer with bis(trifluoromethane sulfonyl)imide (TFSI-) or bis(fluoromethane sulfonyl)imide (FSI-) as the anion, named as SDTFSI and SDFSI, respectively. Together, the FSI- and TFSI- anions demonstrate a synergistic effect in providing ion-conductive LiF and Li3N-rich inorganic SEI layer with enhanced lithium dendrite suppression ability. The twofold reinforcement effect is achieved collectively from the semi-IPN structure and the three-dimensional (3D) PAN network that help to construct highly efficient and uniform ion transport channels with excellent flexibility, further suppressing the lithium dendrite growth. The SPEs were dimensionally stable even at elevated temperatures of 150 °C. Moreover, the SPEs show an ionic conductivity of 4.4 × 10-4 S cm-1 at 25 °C and 1.81 × 10-3 S cm-1 at 55 °C and a lithium-ion transference number of 0.56. The favorable electrochemical performance of the SPEs was verified by operating LiFePO4/Li and NMC/Li cells.

"Biomass to Membrane": Sulfonated Kraft Lignin/PCL Superhydrophilic Electrospun Membrane for Gravity-Driven Oil-in-Water Emulsion Separation.

Biobased membranes made with green solvents have numerous advantages in the water purification industry; however, their long-term use is impeded by severe membrane fouling and low structural stability. Herein, we proposed a facile and green approach to fabricate an eco-friendly and biodegradable electrospun membrane by simply blending polycaprolactone (PCL) with sulfonated kraft lignin (SKL) in a green solvent (i.e., acetic acid) without needing any additional post-treatment. We investigated the influence of SKL content on the surface morphology, chemical composition, and mechanical properties of the electrospun membrane. The SKL-modified membranes (L-5 and L-10) showed superhydrophilicity and underwater superoleophobicity with a water contact angle (WCA) of 0° (<3 s) and an underwater-oil contact angle (UWOCA) over 150° due to the combined effect of surface roughness and hydrophilic chemical functionality. Furthermore, the as-prepared membranes demonstrated excellent pure water flux of 800-900 LMH and an emulsion flux of 170-480 LMH during the gravity-driven filtration of three surfactant-stabilized oil-in-water emulsions, namely, mineral oil/water, gasoline/water, and n-hexadecane/water emulsions. In addition, these membranes exhibited superior antioil-fouling performance with excellent separation efficiency (97-99%) and a high flux recovery ratio (>98%). The 10 wt % SKL-incorporated membrane (L-10) also showed consistent separation performance after 10 cyclic tests, indicating its excellent reusability and recyclability. Furthermore, the stability of the membrane under harsh pH conditions was also evaluated and proved to be robust enough to maintain its wettability in a wide pH range (pH 1-10).

Physics of moderately stretched electrified jets in electrohydrodynamic jet printing.

Electrohydrodynamic (EHD) jet printing involves the deposition of a liquid jet issuing from a needle stretched under the effect of a strong electric field between the needle and a collector plate. Unlike the geometrically independent classical cone-jet observed at low flow rates and high applied electric fields, at a relatively high flow rate and moderate electric field, EHD jets are moderately stretched. Jetting characteristics of such moderately stretched EHD jets differ from the typical cone-jet due to the nonlocalized cone-to-jet transition. Hence, we describe the physics of the moderately stretched EHD jet applicable to the EHD jet printing process through numerical solutions of a quasi-one-dimensional model of the EHD jet and experiments. Through comparison with experimental measurements, we show that our simulations correctly predict the jet shape for varying flow rates and applied potential difference. We present the physical mechanism of inertia-dominated slender EHD jets based on the dominant driving and resisting forces and relevant dimensionless numbers. We show that the slender EHD jet stretches and accelerates primarily due to the balance of driving tangential electric shear and resisting inertia forces in the developed jet region, whereas in the vicinity of the needle, driving charge repulsion and resisting surface tension forces govern the cone shape. The findings of this study can help in operational understanding and better control of the EHD jet printing process.

Block Copolymer-Templated Au@CdSe Core-Satellite Nanostructures with Solvent-Dependent Optical Properties.

In the present work, we report the fabrication and characterization of well-defined core-satellite nanostructures. These nanostructures comprise block copolymer (BCP) micelles, containing a single gold nanoparticle (AuNP) in the core and multiple photoluminescent cadmium selenide (CdSe) quantum dots (QDs) attached to the micelle's coronal chains. The asymmetric polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) BCP was employed to develop these core-satellite nanostructures in a series of P4VP-selective alcoholic solvents. The BCP micelles were first prepared in 1-propanol and subsequently mixed with AuNPs, followed by gradual addition of CdSe QDs. This method resulted in the development of spherical micelles that contained a PS/Au core and a P4VP/CdSe shell. These core-satellite nanostructures, developed in different alcoholic solvents, were further employed for the time-resolved photoluminescence analysis. It was found that solvent-selective swelling of the core-satellite nanostructures tunes the distance between the QDs and AuNPs and modulates their Förster resonance energy transfer (FRET) behavior. The average lifetime of the donor emission varied from 12.3 to 10.3 nanoseconds (ns) with the change in the P4VP-selective solvent within the core-satellite nanostructures. Furthermore, the distances between the donor and acceptor were also calculated using efficiency measurements and corresponding Förster distances. The resulting core-satellite nanostructures hold promising potential in various fields, such as photonics, optoelectronics, and sensors that utilize the FRET process.

Valorised polypropylene waste based reversible sensor for copper ion detection in blood and water.

Heavy metals and plastic pollutants are the two most disastrous challenges to the environment requiring immediate actions. In this work, a techno-commercially feasible approach to address both challenges is presented, where a waste polypropylene (PP) based reversible sensor is produced to selectively detect copper ions (Cu2+) in blood and water from different sources. The waste PP-based sensor was fabricated in the form of an emulsion-templated porous scaffold decorated with benzothiazolinium spiropyran (BTS), which produced a reddish colour upon exposure to Cu2+. The presence of Cu2+ was checked by naked eye, UV-Vis spectroscopy, and DC (Direct Current) probe station by measuring the current where the sensor's performance remained unaffected while analysing blood, water from different sources, and acidic or basic environment. The sensor exhibited 1.3 ppm as the limit of detection value in agreement with the WHO recommendations. The reversible nature of the sensor was determined by cyclic exposure of the sensor towards visible light turning it from coloured to colourless within 5 min and regenerated the sensor for the subsequent analysis. The reversibility of the sensor through exchange between Cu2+- Cu+ was confirmed by XPS analysis. A resettable and multi-readout INHIBIT logic gate was proposed for the sensor using Cu2+ and visible light as the inputs and colour change, reflectance band and current as the output. The cost-effective sensor enabled rapid detection of the presence of Cu2+ in both water and complex biological samples such as blood. While the approach developed in this study provides a unique opportunity to address the environmental burden of plastic waste management, it also allows for the possible valorization of plastics for use in enormous value-added applications.

Dual-functionalized Pickering HIPE templated poly(ɛ-caprolactone) scaffold for maxillofacial implants.

High internal phase emulsion (HIPE) templated poly (ɛ-caprolactone) (PCL) scaffolds have gained widespread attention for large-sized bone defects due to its tuneable 3D architecture and ease of fabricating crosslinked PCL (cPCL) scaffolds. However, extremely high stabilizer (surfactant or nanoparticle) concentration and negligence of microenvironment for regeneration sites like alveolar bones have restrained industrial acceptance of these scaffolds. Herein, we demonstrated the fabrication of nanocomposite cPCL scaffolds within Pickering HIPE templates stabilized using modified silica nanoparticles (mSiNP) concentrations as low as 0.1 to 1.0 wt%. Using an unconventional approach, the mSiNP Pickering stabilizer was added in dispersed phase, contradicting Bancroft's rule. The colloidal stability was attained due to faster drifting of mSiNP towards the interface when it was dispersed in silicone oil. Scaffolds with tuneable properties were fabricated by controlling the mSiNP concentration and ϕd. Further, cPCL scaffolds were functionalized using clove oil (CO) to improve their efficiency in eradicating S. aureus and E. coli by disrupting their cellular integrity. Additionally, formation of biofilm on the surface of the scaffolds was successfully inhibited by the incorporation of CO. CO-functionalized scaffolds demonstrated excellent cytocompatibility towards MG-63 cells allowing their successful adhesion and proliferation on the surface of the scaffolds.

3D Printed Hierarchical Porous Poly(ε-caprolactone) Scaffolds from Pickering High Internal Phase Emulsion Templating.

In the realm of biomaterials, particularly bone tissue engineering, there has been a great increase in interest in scaffolds with hierarchical porosity and customizable multifunctionality. Recently, the three-dimensional (3D) printing of biopolymer-based inks (solutions or emulsions) has gained high popularity for fabricating tissue engineering scaffolds, which optimally satisfies the desired properties and performances. Herein, therefore, we explore the fabrication of 3D printed hierarchical porous scaffolds of poly(ε-caprolactone) (PCL) using the water-in-oil (w/o) Pickering PCL high internal phase emulsions (HIPEs) as the ink in 3D printer. The Pickering PCL HIPEs stabilized using hydrophobically modified nanoclay comprised of aqueous poly(vinyl alcohol) (PVA) as the dispersed phase. Rheological measurements suggested the shear thinning behavior of Pickering HIPEs having a dispersed droplet diameter of 3-25 µm. The pore morphology resembling the natural extracellular matrix and the mechanical properties of scaffolds were customized by tuning the emulsion composition and 3D printing parameters. In vitro biomineralization and drug release studies proved the scaffolds' potential in developing the apatite-rich bioactive interphase and controlled drug delivery, respectively. During in vitro osteoblast (MG63) growth experiments for up to 7 days, good adhesion and proliferation on PCL scaffolds confirmed their cytocompatibility, assessed by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) analysis. This study suggests that the assembly of HIPE templates and 3D printing is a promising approach to creating hierarchical porous scaffolds potentially suitable for bone tissue engineering and can be stretched to other biopolymers as well.

Pickering Emulsion-Templated Nanocomposite Membranes for Excellent Demulsification and Oil-Water Separation.

A worldwide steady increase in oily wastewater, due to oil spillage and various industrial discharges, requires immediate efforts toward development of an effective strategy and materials to preserve the natural water bodies. Designing a superwettable fibrous membrane of robust structure and anti-fouling property for efficient separation of oil-water mixtures and emulsions is therefore highly demanding. The electrospun fibrous membrane, which possesses porosity and flexibility and properties including superwettability and tunable functionality, can be considered as apposite materials for this cause. In this approach, we combined two strategies, viz., Pickering emulsion and near gel resin (nGR) emulsion electrospinning together to produce a fibrous nanocomposite membrane for efficient oil-water separation and demulsification. nGR Pickering emulsions were stabilized using hydrophilic SiO2 nanoparticles and successfully optimized for fabricating the crosslinked core sheath-structured fibrous membrane. The prepared membrane provided twofold functionality due to the core sheath structure of the fibers. The crosslinked polystyrene core offered high oil adsorption capacity, whereas SiO2-functionalized crosslinked polyvinyl alcohol sheath provided a rough, superhydrophilic surface with underwater oleophobic behavior to the membrane. The optimized SiO2-Pickering emulsion-templated nanocomposite membrane demonstrated excellent underwater anti-oil adhesion behavior (UWOCA ∼148°) with efficient oil-water separation capacity of more than 99% and separation flux up to 3346 ± 91 L m-2 h-1. The membrane was evaluated against various oil-water emulsions and found to have a superior separation efficiency. Moreover, excellent anti-oil adhesion property provided the intact membrane, where consistent separation performance was achieved up to 10 separation cycles without any loss. The membrane was used for separation of hot oil-water emulsions and showed no structural disintegration or loss in separation performance when exposed to elevated temperatures. The developed nanocomposite membranes could efficiently be used for separation and demulsification, and their applications can be explored in various other fields including selective sorption, catalysis, and storage in future.

Emulsion templated scaffolds of poly(ε-caprolactone) - a review.

The role of poly(ε-caprolactone) (PCL) and its 3D scaffolds in tissue engineering has already been established due to its ease of processing into long-term degradable implants and approval from the FDA. This review presents the role of high internal phase emulsion (HIPE) templating in the fabrication of PCL scaffolds, and the versatility of the technique along with challenges associated with it. Considering the huge potential of HIPE templating, which so far has mainly been focused on free radical polymerization of aqueous HIPEs, we provide a summary of how the technique has been expanded to non-aqueous HIPEs and other modes of polymerization such as ring-opening. The scope of coupling of HIPE templating with some of the advanced fabrication methods such as 3D printing or electrospinning is also explored.

Synthesis of Lactic Acid-Based Thermosetting Resins and Their Ageing and Biodegradability.

The present work is focused on the synthesis of bio-based thermoset polymers and their thermo-oxidative ageing and biodegradability. Toward this aim, bio-based thermoset resins with different chemical architectures were synthesized from lactic acid by direct condensation with ethylene glycol, glycerol and pentaerythritol. The resulting branched molecules with chain lengths (n) of three were then end-functionalized with methacrylic anhydride. The chemical structures of the synthesized lactic acid derivatives were confirmed by proton nuclear magnetic resonance spectroscopy (1H-NMR) and Fourier transform infrared spectroscopy (FT-IR) before curing. To evaluate the effects of structure on their properties, the samples were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and the tensile testing. The samples went through thermo-oxidative ageing and biodegradation; and their effects were investigated. FT-IR and 1H-NMR results showed that three different bio-based resins were synthesized using polycondensation and end-functionalization. Lactic acid derivatives showed great potential to be used as matrixes in polymer composites. The glass transition temperature of the cured resins ranged between 44 and 52 °C. Pentaerythritol/lactic acid cured resin had the highest tensile modulus and it was the most thermally stable among all three resins. Degradative processes during ageing of the samples lead to the changes in chemical structures and the variations in Young's modulus. Microscopic images showed the macro-scale surface degradation on a soil burial test.

Facile synthesis of templated macrocellular nanocomposite scaffold via emulsifier-free HIPE-ROP.

A macrocellular nanocomposite scaffold of crosslinked poly(ε-caprolactone) was made by conducting a ring-opening polymerization of an emulsifier-free Pickering high internal phase emulsion (HIPE). The Pickering HIPE formulation, stabilized using hydrophobically modified silica nanoparticles (mSiNPs), showed extraordinary stability up to a temperature of polymerization as high as 120 °C. The nanocomposite scaffolds demonstrated high porosity and a liquid uptake capacity of up to ∼23 g g-1. The scaffolds decorated with mSiNPs were mechanically robust and showed high resiliency under cyclic compression tests.

Hydrolytic Degradation of Porous Crosslinked Poly(ε-Caprolactone) Synthesized by High Internal Phase Emulsion Templating.

Porous poly(ε-caprolactone) (PCL) scaffolds were fabricated using the high internal polymerization emulsion (HIPE) technique. Bis(ε-caprolactone-4-yl) (BCY) was utilized as crosslinker. The crosslinking density and the volume fraction of the dispersed phase were varied in order to study the potential effect of these parameters on the hydrolytic degradation at 37 °C and 60 °C. After different hydrolysis times the remaining solid samples were analyzed by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM), while the degradation products in the aqueous aging solutions were analyzed by laser desorption ionization-mass spectrometry (LDI-MS). The effect of temperature on the degradation process and release of degradation products was, as expected, significant. The temperature effect was also shown by FTIR analysis that displayed a pronounced increase in the intensity of the hydroxyl-group absorption band after 70 days of hydrolysis at 60 °C indicating significant cleavage of the polymer chains. LDI-MS analysis proved the release of oligomers ranging from dimers to hexamers. The product patterns were similar, but the relative m/z signal intensities increased with increasing time, temperature and crosslinking density, indicating larger amounts of released products. The latter is probably due to the decreasing degree of crystallinity as a function of amount of crosslinker. The porous structure and morphology of the scaffolds were lost during the aging. The higher the crosslinking density, the longer the scaffolds retained their original porous structure and morphology.

Electrospinning of a Near Gel Resin To Produce Cross-Linked Fibrous Matrices.

Electrospun fibers and matrices have been researched for their utility in various fields; however, because of poor mechanical strength and loss of structural integrity, their commercial viability is limited. A near gel resin (nGR) of polystyrene (PS) was used in the present approach to fabricate cross-linked fibrous matrices of better mechanical strength and oil adsorption while retaining the structural integrity. Electrospinnability of nGR was assessed in bulk (i.e., in styrene monomer) and solution (i.e., in dimethyl formamide) forms with variations in formulation and electrospinning conditions. Ultimately, a uniform cross-linked fibrous matrix of PS was prepared using an oil-in-water emulsion, where the oil phase composed of a monomer (styrene), an initiator (benzoyl peroxide), and a cross-linker (divinylbenzene) was dispersed in a continuous phase of aqueous poly(vinyl alcohol) (PVA). The monomer conversion in the oil phase was carried out below the gel point, and the nGR of PS formed in dispersed droplets was electrospun to fabricate uniform fibrous matrices with the help of a template polymer, that is, PVA. The effect of various material and process parameters on the gelation behavior, electrospinnability, and fiber uniformity was studied and optimized to produce uniform core-sheath fibrous matrices of cross-linked PS. Postelectrospinning heat treatment of matrices was carried out to achieve complete monomer conversion and cross-linking. Fiber formation behavior of the emulsion was assessed using ionic and nonionic surfactants. The cross-link density of the matrices was optimized to achieve the desired structural morphology and dimensional stability. The process of fabrication of emulsion electrospun cross-linked fibers can be further extended to a variety of other monomers in order to enhance the suitability of fibrous matrices for many applications.

Cellulose-Derived Nanographene Oxide Reinforced Macroporous Scaffolds of High Internal Phase Emulsion-Templated Cross-Linked Poly(ε-caprolactone).

Cellulose-derived nanographene oxide (nGO)-type carbon dot reinforced porous scaffolds of poly(ε-caprolactone) (PCL) were developed as templates from high internal phase emulsions (HIPE). The mechanical strength, structural integrity, and reusability of the scaffolds were enhanced via in situ cross-linking. An oil-in-oil (o/o) HIPE of ε-caprolactone monomer (CL) was made for this purpose, and the ring-opening polymerization of a continuous phase comprised of CL, catalyst (Sn(Oct)2), and cross-linker (bis(caprolactone-4-yl)) (BCY) was carried out. The functionalization of scaffolds with nGO was assessed along with its role as an effective Pickering stabilizer of the HIPEs. The pore size and porosity of the scaffolds were governed by HIPE morphology, which in turn was controlled by the amount of nGO and the volume fraction of the dispersed phase. The nGO-functionalized scaffolds of cross-linked PCL thus prepared were characterized for their morphological structure, mechanical strength, and oil sorption capacity. Enhanced oil adsorption of nGO-functionalized scaffolds proved them to be of higher potency compared to those made of neat PCL. Superior compressive strength and reusability of scaffolds for oil adsorption up to 40 times while maintaining the structural integrity for ≥25 sorption-desorption cycles added extra value to such scaffolds. The scaffolds also had excellent cell viability as evaluated by MG63 osteoblast-like cells and some bioactivity in the form of calcium phosphate mineralization on the surface of the scaffolds.

Nano-Graphene Oxide Functionalized Bioactive Poly(lactic acid) and Poly(ε-caprolactone) Nanofibrous Scaffolds.

A versatile and convenient way to produce bioactive poly(lactic acid) (PLA) and poly(ε-caprolactone) (PCL) electrospun nanofibrous scaffolds is described. PLA and PCL are extensively used as biocompatible scaffold materials for tissue engineering. Here, biobased nano graphene oxide dots (nGO) are incorporated in PLA or PCL electrospun scaffolds during the electrospinning process aiming to enhance the mechanical properties and endorse osteo-bioactivity. nGO was found to tightly attach to the fibers through secondary interactions. It also improved the electrospinnability and fiber quality. The prepared nanofibrous scaffolds exhibited enhanced mechanical properties, increased hydrophilicity, good cytocompatibility and osteo-bioactivity. Therefore, immense potential for bone tissue engineering applications is anticipated.

Supramolecular Route for Enhancing Polymer Electrospinnability.

Electrospinning of polymers typically requires high solution concentrations necessitated by the requirement of sufficient chain overlaps to achieve the required viscoelastic properties. Here, we report on a novel supramolecular approach, involving polymer/surfactant complexes, which allows for a significant reduction in the solution concentration of polymer for electrospinning. The approach involved supramolecular complexation of poly(4-vinylpyridine) (P4VP) with a surfactant, dodecylbenzenesulfonic acid (DBSA), via ionic interactions. The supramolecular complexation of P4VP with DBSA led to a significant increase in the solution viscosity even at a DBSA/4VP molar ratio as low as 0.05. Furthermore, the solution viscosity of the P4VP/DBSA complex increased significantly with the DBSA/4VP molar ratio. The increase in the viscosity for the P4VP/DBSA complexes was plausibly due to the formation of physical cross-links between P4VP chains driven by hydrophobic interactions between the surfactant tails. The formation of such physical cross-links led to a significant decrease in the solution concentration needed for the onset of semidilute entangled regime. Thus, the P4VP/DBSA complexes could be electrospun at a much lower concentration. The critical solution concentration to obtain bead-free uniform nanofibers of P4VP/DBSA complexes in dimethylformamide was reduced to 12% (w/v), which was not possible for neat P4VP solution even up to approximately 35% (w/v). Furthermore, small-angle X-ray scattering and polarized optical microscopy results revealed that the electrospun nanofibers of P4VP/DBSA complexes self-assembled in lamellar mesomorphic structures similar to that observed in bulk. However, the electrospun nanofibers exhibited significantly improved lamellar order, which was plausibly facilitated by the preferred orientation of P4VP chains along the fiber axis.

Facile Fabrication of Composite Electrospun Nanofibrous Matrices of Poly(ε-caprolactone)-Silica Based Pickering Emulsion.

Functionalized matrices have been sought for their application in sensors, filtration, energy storage, catalysis, and tissue engineering. We report formation of an inorganic-organic composite matrix based on poly(ε-caprolactone) (PCL) functionalized with hydrophobically modified silica (m-silica) fabricated with reduced organic solvent usage. The matrix was obtained via electrospinning of a water-in-oil emulsion of PCL that was stabilized by judicious choice of m-silica as a Pickering agent resulting into an emulsifier free matrix. Inclusion of m-silica in PCL matrix resulted in enhancing tensile properties and cell proliferation efficiency. The electrospun composite matrix was free from any emulsifier or template polymer; thus any abrupt loss in mechanical properties was prevented when the matrix was subjected to aqueous conditions. The inorganic-organic biodegradable composite matrices thus produced using an emulsifier free emulsion find applications in tissue engineering and may further be evaluated for other areas including selective sorption and separation.

Starch-Derived Nanographene Oxide Paves the Way for Electrospinnable and Bioactive Starch Scaffolds for Bone Tissue Engineering.

A straightforward process that enabled electrospinning of bioactive starch-based nanofiber scaffolds was developed by utilizing starch derived nano graphene oxide (nGO) as a property enhancer and formic acid as a solvent and esterification reagent. The reaction mechanism and process were followed by detailed spectroscopic investigation. Furthermore, the incorporation of nGO as a "green bioactive additive" endorsed starch nanofibrous scaffolds several advantageous functionalities including improved electrospinnability and thermal stability, good cytocompatibility, osteo-bioactivity, and retained biodegradability. The biodegradable starch/nGO nanofibers underwent simultaneous degradation and mineralization process during 1 week of cell culture and mineralization test, thus, mimicking the structure and function of extracellular matrices (ECMs) and indicating promise for bone tissue engineering applications.

Electrospun composite matrices of poly(ε-caprolactone)-montmorillonite made using tenside free Pickering emulsions.

The production of composite electrospun matrices of poly(ε-caprolactone) (PCL) using an emulsifier-free emulsion, made with minimal organic solvent, as precursor is reported. Pickering emulsions of PCL were prepared using modified montmorillonite (MMT) clay as the stabilizer. Hydrophobic tallow group of the modified MMT clay resulted in analogous interaction of clay with oil and aqueous phase and its adsorption at the interface to provide stability to the resultant emulsion. Composite fibrous matrices of PCL and MMT were produced using electrospinning under controlled conditions. The fiber fineness was found to alter with PCL concentration and volume fraction of the aqueous and oil phases. A higher tensile strength and modulus was obtained with inclusion of MMT in PCL electrospun matrix in comparison to a matrix made using neat PCL. The presence of clay in the fibrous matrix did not change the cell proliferation efficiency in comparison to neat PCL matrix. Composite fibrous matrices of PCL/MMT bearing enhanced tensile properties may find applications in areas other than tissue engineering for example food packaging and filtration.