Polymer-in-ionic-liquid electrolytes

In order to achieve high conductivity in a polymer electrolyte, polymer-in-ionic-liquid electrolytes have been explored. It is found in this study that poly[vinylpyrrolidone-co-(vinyl acetate)] (P(VP-c-VA)) in 1-ethyl-3-methylimidazolium bis(trifluoromethyl sulfonyl) amide (EtMeIm+Tf2N−) and poly(N,N-dimethyl acrylamide) (PDMAA) in trimethyl butyl ammonium bis(trifluoromethane sulfonyl) amide (N1114+Tf2N−) produce ion-conducting liquids and gels. The P(VP-c-VA)/ EtMeIm+Tf2N− mixture has a conductivity around 10−3 S · cm−1 at 22 °C, for copolymer concentrations up to 30 wt.-%. Thermal analysis shows that the Tg of the P(VP-c-VA)/ EtMeIm+Tf2N− system is well described by the Fox equation as a function of polymer content. Poly(methyl methacrylate) (PMMA)/ EtMeIm+Tf2N− gel electrolytes were prepared by in-situ polymerisation of the monomer in the ionic liquid. In the presence of 0.5–2.0 wt.-% of a crosslinking agent, these PMMA-based electrolytes displayed elastomeric properties and high conductivity (ca. 10−3 S · cm−1) at room temperature.

Shear-enhanced solution precipitation : a simple process to produce short polymeric nanofibers

The growing interest in polymeric nanofibers has been increasing the push for the development of simple and efficient nanofiber-preparation techniques. We herein describe how a conventional solution process is readapted to suit the needs for fast and efficient production of short polymeric nanofibers. Poly(ethylene-co-acrylic acid) (PEAA), a semi-crystalline polymer, was used as model. When a PEAA solution was injected into an alcoholic non-solvent while simultaneously applying high shear to the non-solvent system, PEAA nanofibers were obtained with average diameter as thin as 113 nm and length as short as 4.5 _m. The fiber diameter and length were also adjustable by varying the operating parameters. This one-step technique advances the currently available nanofabrication tools by adjusting a widely accepted concept to the nano-scale. It may constitute a viable method for large-scale production of short polymeric nanofibers.

Enzymatic synthesis of isopropyl myristate using immobilized lipase from Bacillus cereus MTCC 8372

A purified alkaline thermo-tolerant bacterial lipase from Bacillus cereus MTCC 8372 was immobilized on a Poly (MAc- co -DMA- cl -MBAm) hydrogel. The hydrogel showed approximately 94% binding capacity for lipase. The immobilized lipase (2.36 IU) was used to achieve esterification of myristic acid and isopropanol in n -heptane at 65 °C under continuous shaking. The myristic acid and isopropanol when used at a concentration of 100 mM each in n -heptane resulted in formation of isopropyl myristate (66.0 ± 0.3 mM) in 15 h. The reaction temperature below or higher than 65°C markedly reduced the formation of isopropyl myristate. Addition of a molecular sieve (3 Å × 1.5 mm) to the reaction mixture drastically reduced the ester formation. The hydrogel bound lipase when repetitively used to perform esterification under optimized conditions resulted in 38.0 ± 0.2 mM isopropyl myristate after the 3 ^rd cycle of esterification.

Synthesis of ethyl oleate employing synthetic hydrogel-immobilized lipase of Bacillus coagulans MTCC-6375

Ten polymeric hydrogels were chemically synthesized by varying the concentrations of copolymer (DMA) and cross-linker (MBAm) molecules. An alkaline lipase of Bacillus coagulans MTCC-6375 was immobilized onto a poly (MAc-co-DMA-cl-MBAm)-hydrogel support at pH 8.5 and temperature 55ºC in 16 h. The bound lipase possessed 7.6 U.g⁻¹ (matrix) lipase activity with a specific activity of 18 U.mg⁻¹ protein. Hydrogel bound-lipase catalyzed esterification of oleic acid and ethanol to synthesize ethyl oleate in n-nonane. Various kinetic parameters were optimized to produce ethyl oleate using immobilized lipase. The optimal parameters were bound enzyme/substrate (E/S) ratio 0.62 mg/mM, ethanol/oleic acid 100 mM:75 mM or 100 mM:100 mM, incubation time 18 h and reaction temperature 55ºC that resulted in approximately 53% conversion of reactants into ethyl oleate in n-nonane. However, addition of a molecular sieve to the reaction mixture promoted the conversion to 58% in 18 h in n-nonane, which was equivalent to 55 mM of ethyl oleate produced.

Synthesis of ethyl laurate by hydrogel immobilized lipase of Bacillus coagulans MTCC-6375

An alkaline thermo-tolerant lipase from Bacillus coagulans MTCC-6375 was purified and efficiently immobilized onto a synthetic hydrophobic poly (MAc-co-DMA-cl-MBAm)-hydrogel at pH 8.5 and temperature 55°C in 16 h. The hydrogel bound matrix possessed 7.6 IU g -1 matrix lipase activity with a specific activity of 18 IU mg -1 protein. Immobilized lipase was used to catalyze the esterification of lauric acid and ethanol to produce ethyl laurate in n-nonane. The reaction conditions that were optimized to produce ethyl laurate in n-nonane included enzyme/substrate (E/S) ratio, substrate concentration, reaction time and reaction temperature. The optimized parameters were E/S ratio of 0.5 mg mM -1, ethanol:lauric acid in ratio of 100 mM:100 mM and reaction time of 15 h at 65°C under continuous shaking (200 rpm). Optimized conditions resulted in 66% conversion of reactants into ethyl laurate in n-nonane in the presence of 300 mg molecular sieve mL -1 reaction mixture.

Nanofibrillar micelles and entrapped vesicles from biodegradable block copolymer/polyelectrolyte complexes in aqueous media

Here we report a viable route to fibrillar micelles and entrapped vesicles in aqueous solutions. Nanofibrillar micelles and entrapped vesicles were prepared from complexes of a biodegradable block copolymer poly(ethylene oxide)-block-poly(lactide) (PEO-b-PLA) and a polyelectrolyte poly(acrylic acid) (PAA) in aqueous media and directly visualized using cryogenic transmission electron microscopy (cryo-TEM). The self-assembly and the morphological changes in the complexes were induced by the addition of PAA/water solution into the PEO-b-PLA in tetrahydrofuran followed by dialysis against water. A variety of morphologies including spherical wormlike and fibrillar micelles, and both unilamellar and entrapped vesicles, were observed, depending on the composition, complementary binding sites of PAA and PEO, and the change in the interfacial energy. Increasing the water content in each [AA]/[EO] ratio led to a morphological transition from spheres to vesicles, displaying both the composition- and dilution-dependent micellar-to-vesicular morphological transitions.

Toughening epoxy thermosets with block ionomers : the role of phase domain size

Herein we report a novel approach to toughen epoxy thermosets using a block ionomer, i.e., sulfonated polystyrene-block-poly(ethylene-co-butylene)-block- polystyrene (SSEBS). SSEBS was synthesized by sulfonation of SEBS with 67 wt % polystyrene (PS). Phase morphology of the epoxy/SSEBS blends can be controlled at either nanometer or micrometer scale by simply adjusting the sulfonation degree of SSEBS. It has been found that there exists a critical degree of sulfonation (10.8 mol %) forming nanostructures in these epoxy/SSEBS blends. Above this critical value, macrophase separation can be avoided and only microphase separation occurs, yielding transparent nanostructured blends. All epoxy/SSEBS blends display increased fracture toughness compared to neat epoxy. But the toughening efficiency varies with the phase domain size, and their correlation has been established over a broad range of length scales from nanometers to a few micrometers. In the nanostructured blends with SSEBS of high sulfonation degrees, the fracture toughness decreases with decreasing size of the phase domains. In the macrophase-separated blends, only a slight improvement in toughness can be obtained with SSEBS of low sulfonation degrees. The epoxy blend with submicrometer phase domains in the range 0.05-1.0 μm containing SSEBS of a moderate degree of sulfonation (5.8 mol %) displays the maximum toughness. This study has clearly clarified the role of phase domain size on toughening efficiency in epoxy thermosets.

Engineering a multimodal nerve conduit for repair of injured peripheral nerve

Injury to nerve tissue in the peripheral nervous system (PNS) results in long-term impairment of limb function, dysaesthesia and pain, often with associated psychological effects. Whilst minor injuries can be left to regenerate without intervention and short gaps up to 2 cm can be sutured, larger or more severe injuries commonly require autogenous nerve grafts harvested from elsewhere in the body (usually sensory nerves). Functional recovery is often suboptimal and associated with loss of sensation from the tissue innervated by the harvested nerve. The challenges that persist with nerve repair have resulted in development of nerve guides or conduits from non-neural biological tissues and various polymers to improve the prognosis for the repair of damaged nerves in the PNS. This study describes the design and fabrication of a multimodal controlled pore size nerve regeneration conduit using polylactic acid (PLA) and (PLA):poly(lactic-co-glycolic) acid (PLGA) fibers within a neurotrophin-enriched alginate hydrogel. The nerve repair conduit design consists of two types of PLGA fibers selected specifically for promotion of axonal outgrowth and Schwann cell growth (75:25 for axons; 85:15 for Schwann cells). These aligned fibers are contained within the lumen of a knitted PLA sheath coated with electrospun PLA nanofibers to control pore size. The PLGA guidance fibers within the nerve repair conduit lumen are supported within an alginate hydrogel impregnated with neurotrophic factors (NT-3 or BDNF with LIF, SMDF and MGF-1) to provide neuroprotection, stimulation of axonal growth and Schwann cell migration. The conduit was used to promote repair of transected sciatic nerve in rats over a period of 4 weeks. Over this period, it was observed that over-grooming and self-mutilation (autotomy) of the limb implanted with the conduit was significantly reduced in rats implanted with the full-configuration conduit compared to rats implanted with conduits containing only an alginate hydrogel. This indicates return of some feeling to the limb via the fully-configured conduit. Immunohistochemical analysis of the implanted conduits removed from the rats after the four-week implantation period confirmed the presence of myelinated axons within the conduit and distal to the site of implantation, further supporting that the conduit promoted nerve repair over this period of time. This study describes the design considerations and fabrication of a novel multicomponent, multimodal bio-engineered synthetic conduit for peripheral nerve repair.

Electrosprayed PLGA smart containers for active anti-corrosion coating on magnesium alloy Amlite

A novel self-healing system, consisting of poly(lactic-co-glycolic) acid (PLGA) porous particles loaded with a corrosion inhibitor, i.e. benzotriazole (BTA), has been successfully achieved via direct electro-spray deposition and subsequent epoxy spraying upon magnesium (Mg) alloy AMlite. The two-step process greatly simplified the multi-step fabrication of smart coatings reported previously. The PLGA particles demonstrate rapid response to both water and pH increase incurred by corrosion of Mg, ensuring instant and ongoing release of BTA to self-heal the protective functionality and retard further corrosion. Furthermore, nanopores in the PLGA–BTA microparticles, formed by the fast evaporation of dichloromethane during the electrospray process, also contribute to the fast release of BTA. Using Mg alloy AMlite as a model substrate which requires corrosion protection, potentiodynamic polarisation characterisation and scratch testing were adopted to reveal the anti-corrosion capability of the active coating.

Nanoformulated cell-penetrating survivin mutant and its dual actions

In this study, we investigated the differential actions of a dominant-negative survivin mutant (SurR9-C84A) against cancerous SK-N-SH neuroblastoma cell lines and differentiated SK-N-SH neurons. In both the cases, the mutant protein displayed dual actions, where its effects were cytotoxic toward cancerous cells and proliferative toward the differentiated neurons. This can be explained by the fact that tumorous (undifferentiated SK-N-SH) cells have a high endogenous survivin pool and upon treatment with mutant SuR9-C84A causes forceful survivin expression. These events significantly lowered the microtubule dynamics and stability, eventually leading to apoptosis. In the case of differentiated SK-N-SH neurons that express negligible levels of wild-type survivin, the mutant indistinguishably behaved in a wild-type fashion. It also favored cell-cycle progression, forming the chromosome-passenger complex, and stabilized the microtubule-organizing center. Therefore, mutant SurR9-C84A represents a novel therapeutic with its dual actions (cytotoxic toward tumor cells and protective and proliferative toward neuronal cells), and hence finds potential applications against a variety of neurological disorders. In this study, we also developed a novel poly(lactic-co-glycolic acid) nanoparticulate formulation to surmount the hurdles associated with the delivery of SurR9-C84A, thus enhancing its effective therapeutic outcome.

Brain targeted PLGA nanocarriers alleviating amyloid-Β expression and preserving basal survivin in degenerating mice model

The chronic systemic administration of d-Galactose in C57BL/6J mice showed a relatively high oxidative stress, amyloid-β expression and neuronal cell death. Enhanced expression of pyknotic nuclei, caspase-3 and reduced expression of neuronal integrity markers further confirmed the aforesaid insults. However, concomitant treatment with the recombinant protein (SurR9-C84A) and the anti-transferrin receptor antibody conjugated SurR9-C84A (SurR9+TFN) nanocarriers showed a significant improvement in the disease status and neuronal health. The beauty of this study is that the biodegradable Food and Drug Administration (FDA) approved poly(lactic-co-glycolic acid) (PLGA) nanocarriers enhanced the biological half-life and the efficacy of the treatments. The nanocarriers were effective in lowering the amyloid-β expression, enhancing the neuronal integrity markers and maintaining the basal levels of endogenous survivin that is essential for evading the caspase activation and apoptosis. The current study herein reports for the first time that the brain targeted SurR9-C84A nanocarriers alleviated the d-Galactose induced neuronal insults and has potential for future brain targeted nanomedicine application.

Nanoformulated mutant SurR9-C84A: a possible key for alzheimer's and its associated inflammation

PURPOSE: Alzheimer's disease (AD) is one of the untreatable neurodegenerative diseases characterised by the pathologic amyloid plaque deposition and inflammation. The aim of this study is to evaluate the neuroprotective effects of nanoformulated SurR9-C84A, a survivin mutant belonging to the inhibitors of the apoptosis (IAP) protein family. The effect of SurR9-C84A was studied against the β-amyloid toxicity and various inflammatory insults in the differentiated SK-N-SH neurons. METHOD: SurR9-C84A loaded poly(lactic-co-glycolic acid) nanoparticles were prepared following the modified double emulsion technique. The neuroprotective effect of SurR9-C84A was evaluated against the amyloid-β (Aβ) peptide fragment, N-methyl-D-aspartate (NMDA) toxicity and the inflammatory assaults. To mimic the in vivo situation, a co-culture of neurons and microglia was also studied to validate these results. RESULTS: SurR9-C84A treatments showed improved neuronal health following Aβ, and NMDA toxicity in addition to inflammatory insults induced in mono and co-cultures. The neuroprotective effect was evident with the reduced neuronal death, accelerated expression of neuronal integrity markers (neurofilaments, beta-tubulin III etc.,) and the neuroprotective ERK/MAPK signalling. CONCLUSION: The current results demonstrated that the SurR9-C84A nanoformulation was very effective in rescuing the neurons and holds a potential future application against AD.

High-performance multifunctional graphene-PLGA fibers: toward biomimetic and conducting 3D scaffolds

The development of electrically conducting fibers based on known cytocompatible materials is of interest to those engaged in tissue regeneration using electrical stimulation. Herein, it is demonstrated that with the aid of rheological insights, optimized formulations of graphene containing spinnable poly(lactic-co-glycolic acid) (PLGA) dopes can be made possible. This helps extend the general understanding of the mechanics involved in order to deliberately translate the intrinsic superior electrical and mechanical properties of solution-processed graphene into the design process and practical fiber architectural engineering. The as-produced fibers are found to exhibit excellent electrical conductivity and electrochemical performance, good mechanical properties, and cellular affinity. At the highest loading of graphene (24.3 wt%), the conductivity of as-prepared fibers is as high as 150 S m-1 (more than two orders of magnitude higher than the highest conductivity achieved for any type of nanocarbon-PLGA composite fibers) reported previously. Moreover, the Young's modulus and tensile strength of the base fiber are enhanced 647- and 59-folds, respectively, through addition of graphene.

Miscibility, UV resistance, thermal degradation, and mechanical properties of PMMA/SAN blends and their composites with MWCNTs

Poly(methyl methacrylate)/poly(styrene-co-acrylonitrile) (PMMA/SAN) blends, with varying concentrations, were prepared by melt-mixing technique. The miscibility is ensured by fixing the acrylonitrile (AN) content of styrene acrylonitrile (SAN) as 25% by weight. The blends were transparent as well. The Fourier transform infrared spectroscopic (FTIR) studies did not reveal any specific interactions, supporting the well accepted 'copolymer repulsion effect' as the driving mechanism for miscibility. Addition of SAN increased the stability of PMMA towards ultraviolet (UV) radiations and thermal degradation. Incorporation of even 0.05% by weight of multi-walled carbon nanotubes (MWCNTs) significantly improved the UV absorbance and thermal stability. Moreover, the composites exhibited good strength and modulus. However, at higher concentrations of MWCNTs (0.5 and 1% by weight) the thermo-mechanical properties experienced deterioration, mainly due to the agglomeration of MWCNTs. It was observed that composites with 0.05% by weight of finely dispersed and well distributed MWCNTs provided excellent protection in most extreme climatic conditions. Thus, PMMA/SAN/MWCNTs composites can act as excellent light screens and may be useful, as cost-effective UV absorbers, in the outdoor applications.

Conjugation of bioactive groups to poly(lactic acid) and poly[(lactic acid)-co-(glycolic acid)] films

A novel PLA-based polymer containing reactive pendent ketone or hydroxyl groups was synthesized by the copolymerization of L-lactide with epsilon-caprolactone-based monomers. The polymer was activated with NPC, resulting in an amine-reactive polymer which was then cast into thin polymeric films, either alone or as part of a blend with PLGA, before immersion into a solution of the cell adhesion peptide GRGDS in PBS buffer allowed for conjugation of GRGDS to the film surfaces. Subsequent 3T3 fibroblast cell adhesion studies demonstrated an increase in cellular adhesion and spreading over films cast from unmodified PLGA. Hence the new polymer can be used to obtain covalent linkage of amine-containing molecules to polymer surfaces.