Methacrylate Groups Research Articles

UV-Triggered On-Demand Temperature-Responsive Reversible and Irreversible Gelation of Cellulose Nanocrystals.

We show ionically cross-linked, temperature-responsive reversible or irreversible hydrogels of anionic cellulose nanocrystals (CNCs) and methacrylate terpolymers by mixing them homogeneously in the initially charge-neutral state of the polymer, which was subsequently switched to be cationic by cleaving side groups by UV irradiation. The polymer is a random terpolymer poly(di(ethylene glycol) methyl ether methacrylate)-rnd-poly(oligo(ethylene glycol) methyl ether methacrylate)-rnd-poly(2-((2-nitrobenzyl)oxycarbonyl)aminoethyl methacrylate), that is, PDEGMA-rnd-POEGMA-rnd-PNBOCAEMA. The PDEGMA and POEGMA repeating units lead to a lower critical solution temperature (LCST) behavior. Initially, homogeneous aqueous mixtures are obtained with CNCs, and no gelation is observed even upon heating to 60 °C. However, upon UV irradiation, the NBOCAEMAs are transformed to cationic 2-aminoethyl methacrylate (AEMA) groups, as 2-nitrobenzaldehyde moieties are cleaved. The resulting mixtures of anionic CNC and cationic PDEGMA-rnd-POEGMA-rnd-PAEMA show gelation for sufficiently high polymer fractions upon heating to 60 °C due to the interplay of ionic interactions and LCST. For short heating times, the gelation is thermoreversible, whereas for long enough heating times, irreversible gels can be obtained, indicating importance of kinetic aspects. The ionic nature of the cross-linking is directly shown by adding NaCl, which leads to gel melting. In conclusion, the optical triggering of the polymer ionic interactions in combination with its LCST phase behavior allows a new way for ionic nanocellulose hydrogel assemblies.

Methacrylate Coatings for Titanium Surfaces to Optimize Biocompatibility.

Currently, there are more than 1.5 million knee and hip replacement procedures carried out in the United States. Implants have a 10–15-year lifespan with up to 30% of revision surgeries showing complications with osteomyelitis. Titanium and titanium alloys are the favored implant materials because they are lightweight and have high mechanical strength. However, this increased strength can be associated with decreased bone density around the implant, leading to implant loosening and failure. To avoid this, current strategies include plasma-spraying titanium surfaces and foaming titanium. Both techniques give the titanium a rough and irregular finish that improves biocompatibility. Recently, researchers have also sought to surface-conjugate proteins to titanium to induce osteointegration. Cell adhesion-promoting proteins can be conjugated to methacrylate groups and crosslinked using a variety of methods. Methacrylated proteins can be conjugated to titanium surfaces through atom transfer radical polymerization (ATRP). However, surface conjugation of proteins increases biocompatibility non-specifically to bone cells, adding to the risk of biofouling which may result in osteomyelitis that causes implant failure. In this work, we analyze the factors contributing to biofouling when coating titanium to improve biocompatibility, and design an experimental scheme to evaluate optimal coating parameters.

Hybrid manufacturing strategies for tissue engineering scaffolds using methacrylate functionalised poly(glycerol sebacate).

Poly(glycerol sebacate) is an attractive biomaterial for tissue engineering due to its biocompatibility, elasticity and rapid degradation rate. However, poly(glycerol sebacate) requires harsh processing conditions, involving high temperatures and vacuum for extended periods, to produce an insoluble polymer matrix. These conditions make generating accurate and intricate geometries from poly(glycerol sebacate), such as those required for tissue engineering scaffolds, difficult. Functionalising poly(glycerol sebacate) with methacrylate groups produces a photocurable polymer, poly(glycerol sebacate)-methacrylate, which can be rapidly crosslinked into an insoluble matrix. Capitalising on these improved processing capabilities, here, we present a variety of approaches for fabricating porous tissue engineering scaffolds from poly(glycerol sebacate)-methacrylate using sucrose porogen leaching combined with other manufacturing methods. Mould-based techniques were used to produce porous disk-shaped and tubular scaffolds. Porogen size was shown to influence scaffold porosity and mechanical performance, and the porous poly(glycerol sebacate)-methacrylate scaffolds supported the proliferation of primary fibroblasts in vitro. Additionally, scaffolds with spatially variable mechanical properties were generated by combining variants of poly(glycerol sebacate)-methacrylate with different stiffness. Finally, subtractive and additive manufacturing methods were developed with the capabilities to generate porous poly(glycerol sebacate)-methacrylate scaffolds from digital designs. These hybrid manufacturing strategies offer the ability to produce accurate macroscale poly(glycerol sebacate)-methacrylate scaffolds with tailored microscale porosity and spatially resolved mechanical properties suitable for a broad range of applications across tissue engineering.

Mechanical Recycling of Partially Bio-Based and Recycled Polyethylene Terephthalate Blends by Reactive Extrusion with Poly(styrene-co-glycidyl methacrylate).

In the present study, partially bio-based polyethylene terephthalate (bio-PET) was melt-mixed at 15–45 wt% with recycled polyethylene terephthalate (r-PET) obtained from remnants of the injection blowing process of contaminant-free food-use bottles. The resultant compounded materials were thereafter shaped into pieces by injection molding for characterization. Poly(styrene-co-glycidyl methacrylate) (PS-co-GMA) was added at 1–5 parts per hundred resin (phr) of polyester blend during the extrusion process to counteract the ductility and toughness reduction that occurred in the bio-PET pieces after the incorporation of r-PET. This random copolymer effectively acted as a chain extender in the polyester blend, resulting in injection-molded pieces with slightly higher mechanical resistance properties and nearly the same ductility and toughness than those of neat bio-PET. In particular, for the polyester blend containing 45 wt% of r-PET, elongation at break (εb) increased from 10.8% to 378.8% after the addition of 5 phr of PS-co-GMA, while impact strength also improved from 1.84 kJ·m−2 to 2.52 kJ·m−2. The mechanical enhancement attained was related to the formation of branched and larger macromolecules by a mechanism of chain extension based on the reaction of the multiple glycidyl methacrylate (GMA) groups present in PS-co-GMA with the hydroxyl (–OH) and carboxyl (–COOH) terminal groups of both bio-PET and r-PET. Furthermore, all the polyester blend pieces showed thermal and dimensional stabilities similar to those of neat bio-PET, remaining stable up to more than 400 °C. Therefore, the use low contents of the tested multi-functional copolymer can successfully restore the properties of bio-based but non-biodegradable polyesters during melt reprocessing with their recycled petrochemical counterparts and an effective mechanical recycling is achieved.

Cartilage repair mediated by thermosensitive photocrosslinkable TGFβ1-loaded GM-HPCH via immunomodulating macrophages, recruiting MSCs and promoting chondrogenesis.

Repairing cartilage defects using thermosensitive hydrogels is an attractive treatment strategy, but the poor mechanical properties and limited understanding of the interactions between hydrogels and cells limit their application.Methods: In this study, a thermosensitive hydroxypropyl chitin hydrogel (HPCH) was functionalized with methacrylate groups to synthesize photocrosslinkable glycidyl methacrylate-modified HPCH (GM-HPCH). GM-HPCH could form a gel in situ through a thermosensitive sol-gel transition and its mechanical properties can be improved by UV irradiation. Cell viability, cell adhesion and anti-apoptosis activity of GM-HPCH were evaluated. Transforming growth factor-β1 (TGFβ1) was introduced into the GM-HPCH hydrogel to fabricate the composite hydrogel. The macrophage immunomodulation, MSC recruitment and chondrogenesis of the composite hydrogel were evaluated.Results: With high biocompatibility, GM-HPCH could protect chondrocytes from apoptosis. Both the in vitro and in vivo experiments showed that GM-HPCH + TGFβ1 shifted the recruited macrophages from M1 to M2 and promoted chondrogenic gene expression. Additionally, the composite hydrogel could promote the migration of marrow stromal cells (MSCs) in the Transwell test and increase migrated gene expression. The fluorescent tracking of MSCs confirmed MSC homing in the rat chondral defect with the help of GM-HPCH. The macroscopic evaluation and histological results at 6 weeks and 12 weeks postsurgery showed that GM-HPCH + TGFβ1 can achieve superior cartilage healing.Conclusions: The GM-HPCH + TGFβ1 hydrogel effectively promoted cartilage repair via immunomodulating macrophages, recruiting MSCs and promoting chondrogenesis; thus it is a promising injectable hydrogel for cartilage regeneration.

Improved accumulation of TGF-β by photopolymerized chitosan/silk protein bio-hydrogel matrix to improve differentiations of mesenchymal stem cells in articular cartilage tissue regeneration

Articular cartilage regeneration is a challenging process due to its inadequate ability of self-recovering biological mechanisms. The progresses of cartilage tissue engineering is supported to overwhelmed the repairing difficulties and degenerative diseases. The main goal of the present study is to design biomaterials with suitable physico-chemical, mechanical and biological properties for the carrier of growth factor and improving differentiation of mesenchymal stem cell into damaged cartilage tissues. Herein, TGF-β loaded hydrogel network was prepared through the chemical interactions between vinyl group of natural polymers. Fourier-transform infrared spectroscopy results show the characteristic peaks at 3074 cm−1, 1713 cm−1, and 810 cm−1, which confirm the existence of the vinyl group and successful formation of maleoyl functionalized Chitosan (MCh). The obtained MCh was freely dissolved in the distilled water up to 8% (w/v). X-ray photoelectron spectroscopy survey spectral results show a peak at 289.0 eV which revealed that the OCO and DS were 1.2% and also evidenced the methacryl substitution of Silk fibroin (SF) nanoformulations. The weight loss and mechanical test were analyzed and the results showed that MSF acts as a foremost crosslinking point with MCh through the reaction between the methacrylate groups of MSF and maleoyl groups of MCh which led to enhancing the density and improved the compressive strength. The maximum drug release activity was recorded in the TGF-β loaded MCh@MSF hydrogel compared to bare MCh hydrogel. Further, the TGF-β loaded MCh@ MSF hydrogel exhibited the cell viability percentage nearly at 79–102% for MC3T3-E1 and 88–104% for BMDSCs. Similarly, the TGF-β loaded MCh@MSF exhibited the highest inhibitory activity against E. coli (83%) than S. aureus (67%). Overall, this study concluded the TGF-β loaded MCh@MSF showed better biocompatibility and could be utilized in the field of cartilage tissue engineering.

New Pre-reacted Glass Containing Dental Composites (giomers) with Improved Fluoride Release and Biocompatibility.

The aim of the present work was to prepare a series of novel restorative giomers and investigate the morphology, the physico-chemical properties (residual monomer, fluoride release), and the cytotoxicity of the new materials. The experimental giomers were prepared as light-cured pastes by blending different resin matrices comprising aromatic/aliphatic/urethane (di) methacrylates, with hybrid fillers containing pre-reacted glasses (PRGs), a radiopaque glass, and nano fluorhydroxyapatite. Polyalkenoic acids based on acrylic acid/itaconic acid/N-acryloyl -L-leucine modified or not with methacrylic groups, together with a superficially active glass, were used to prepare the PRGs. The fluoride ion release of the experimental giomers was investigated within a period of 60 days of storage in bidistilled water while using a fluoride ion selective electrode. Beautifil II commercial product was used as a reference. Cell cytotoxicity tests were done in vitro, in accordance with ISO 10993-122012 proceedings. Human dermal fibroblasts and umbilical endothelial vein cultures were used. The values that were obtained for cumulative fluoride release for all experimental giomers were higher than for the Beautifil II product, being more than twice the ones that were obtained for the commercial product after 60 days of storage in bidistilled water. The experimental biomaterials showed similar and/or better results when compared to the commercial one; this effect was maintained in all tested conditions.

The role of conductivity and molecular mobility on the photoanisotropic response of a new azo-polymer containing sulfonic groups

We report the preparation of a new light-responsive side-chain terpolymer containing azobenzenes, as chromophoric components, sulfonic groups, as polar components, and methacrylate groups, as film forming components, and we provide a detailed characterisation of its thermal parameters, photoanisotropic character, dielectric response and optoelectronic properties. The poly[(4-methoxyazobenzene -4′-oxy) methacrylate]-co-poly[2-acrylamido-2-methyl-1-propanesulfonic acid]-co-poly[methyl methacrylate], MeOAzB/AMPS/MMA, was prepared by radical copolymerisation, possesses high thermal stability and is amorphous. Its high glass transition (Tg = 151 °C) is explained by steric effects (induced by the bulky azobenzenes) and hydrogen bonding (promoted by the polar sulfonic groups) near the polymeric backbone, which may also reduce the photoanisotropic efficiency. The transition between the energy levels of the azobenzenes (MeOAzB) in the terpolymer is controlled by p-type conductivity, and can be associated to motions in the side-chains containing the sulfonic groups (AMPS), which are locally activated below the MeOAzB/AMPS/MMA glass transition.

Preparation of chitin-based fluorescent hollow particles by Pickering emulsion polymerization using functional chitin nanofibers

This study investigated the preparation of chitin-based fluorescent hollow particles by Pickering emulsion polymerization of styrene using bifunctional chitin nanofibers (ChNFs) as stabilizer, giving CNF-based composite particles, followed by solubilizing out inner polystyrene. In addition to the introduction of anionic maleyl groups on ChNFs to improve dispersibility in aqueous ammonia, polymerizable methacryl groups were substituted on ChNFs as second functionalization to provide ability in copolymerization with styrene for stabilization of hollow structures. Consequently, after the formation of styrene-in-water Pickering emulsion using the bifunctional ChNFs as stabilizer, radical polymerization was conducted in the presence of potassium persulfate as an initiator to produce the composite particles. The hollow particles were then fabricated by solubilizing out inner polystyrene with toluene, which stably dispersed in water. Encapsulation of a fluorescent dye, pyrene, into the cavity of the hollow particles was achieved by hydrophobic interaction with polystyrene present on the inner walls, which could be released by treatment of the resulting fluorescent hollow particles with surfactant, oleyl alcohol, in water. The same Pickering emulsion polymerization system was also performed in the presence of a pyrene derivative having a polymerizable group to obtain fluorescent composite/hollow particles with pyrene moieties covalently bound to polystyrene.

Immunomodulatory properties of photopolymerizable fucoidan and carrageenans

Innovative approaches to the control of immune response to tissue engineering scaffolds is of high priority. IL-10, an anti-inflammatory cytokine, has traditionally been conjugated to synthetic polymers for local immunomodulation. Marine-sulfated polysaccharides have been reported to possess anti-inflammatory properties. In the present work, it was hypothesized that photopolymerizable fucoidan and carrageenan play similar roles as the IL-10. The polysaccharides were functionalized with methacrylate groups. Their immunomodulatory properties were evaluated and compared relative to IL-10. The polysaccharides were characterized by NMR spectroscopy, revealing 12–13 % functionalization. The data revealed that fucoidan had the same activity as the IL-10 in decreasing LPS- and IFN-γ-stimulated CD86 expression. In addition, fucoidan had a protective role against LPS- and IFN-γ-induced cell growth inhibition. All polysaccharides demonstrated ∼90 % superoxide radical scavenging and they considerably decreased LPS-stimulated nitric oxide production. These results suggest that photopolymerizable fucoidan can be an alternative to IL-10 in the design of immunomodulatory biomaterials.

The Effect of Different Acrylic Monomers Contents on the Properties of Waterborne Polyurethane/Acrylate Hybrids

Waterborne polyurethane/acrylate hybrids with various ratios of acrylic monomers including: butyl acrylate, methyl methacrylate and acrylic acid were prepared using prepolymer route towards emulsion copolymerization. In the first step, after prepolymer synthesis, vinyl groups were incorporated into the prepolymer chain ends through reaction of OH groups of hydroxy ethyl methacrylate (HEMA) and NCO groups of diisocyanate. Next, the chain extension, neutralization and dispersion were carried out. In the second step, hybrids of waterborne polyurethane acrylate were synthesized by emulsion copolymerization of acrylate monomers with synthesized waterborne polyurethane. Different amounts of acrylate monomers were examined to obtain an optimum composition. The structural study and confirmation of the functional groups were performed using ATR-FTIR. The effects of acrylate monomers on thermal stability, mechanical properties, morphology, and particle size were investigated.

Co-curable poly(glycidyl methacrylate)-grafted graphene/epoxy composite for thermal conductivity enhancement

Thermally conductive epoxy composite is prepared by directly incorporated graphene into the matrix. The 3-methacryloyloxypropyltriethoxysilane (MPTES) functionalized reduced graphene oxide (MRGO) is synthesized by a sol-gel reaction followed by chemical reduction, leading to the introduction of methacrylate groups with carbon-carbon double bonds. Then, radical copolymerization is employed to afford poly(glycidyl methacrylate) grafted MRGO, which can react with amine groups in the curing agent, 4.4′-diaminodiphenylmethane. The exothermic peaks were observed for the epoxy composites revealed that p-MRGO is co-cured with the curing agent and incorporated into the matrix. The thermal conductivity of the p-MRGO/epoxy composites reaches 0.75 W m−1 K−1 at p-MRGO content of 7 wt%, corresponding to a thermal conductivity enhancement of 249% Furthermore, the crosslinking density is calculated to confirm the co-curing effect of p-MRGO. Our results demonstrated that the covalent bond between the filler and matrix is an advantageous approach for improving the thermal conductivity of epoxy composites.

Functionalization of silica membranes for CO2 separation

Five organic CO2-philic functional groups were incorporated in silica matrixes for preparation of functionalized silica membranes to explore the CO2 separation performance. Chemical groups including acetate, trifluoromethyl, methacrylate, urea and vinyl groups were anchored in the silica network using the co-condensation method.The information from 29Si solid-state NMR and FTIR analyses indicates the successful formation of a covalent bond between functional groups and the silica network. The thickness of the functionalized silica layers was measured by SEM and the thermal stability of the organic groups was determined by thermogravimetric analysis (TGA).The gas permeance and mixed gas selectivity of CO2/N2 was measured in the temperature range of 253–373 K with a feed pressure of 9 bar. A maximum selectivity of as high as 10 was observed for a trifluoromethyl functionalized silica membrane with a CO2 permeance of 5.5 × 10−7 mol s−1 m−2 Pa−1. Permporometry measurements indicated that the contribution of flow through micropores to the total flow for all the functionalized silica membranes varied between 62 and 82%. All membranes were CO2 selective.

Tough Bonding, On-Demand Debonding, and Facile Rebonding between Hydrogels and Diverse Metal Surfaces.

Hybrid systems of hydrogels and metals with tough bonding may find widespread applications. Here, a simple and universal method to obtain strong adhesion between hydrogels and diverse metal surfaces, such as titanium, steel, nickel, tantalum, argentum, and aluminum, with adhesion energy up to >1000 J m-2 is reported. To achieve such, the metal surfaces are instantly modified with a linker molecule via soaking, dip-coating, or drop-casting. The designed linker molecule has a carboxylic acid group to bind with a metal surface, and a methacrylic group to crosslink with a hydrogel, thus bridging the interface between them. In addition, by introducing a stimulus-responsive disulfide bond into the linker molecule, the on-demand debonding between toughly bonded hydrogel and metal surface, which is enabled by reductive cleavage of the disulfide chemical linkage, is also demonstrated. More interestingly, after the reductive debonding, the resulting metal surface with free thiol groups can be easily rebonded with a second hydrogel without any further surface modification. The strategy may provide unique opportunities in designing hybrid devices that are suitable for complex and dynamic environments.

Cost-effective robust synthesis of methacrylic cellulosic sponge for organoid culture

We previously reported the development of a three-dimensional cellulosic sponge capable of constraining hepatocytes within macropores to support the rapid formation of organoids with preserved hepatocyte functions for hepatotoxicity testing applications. Fabrication of this macroporous sponge involves conjugating allyl groups onto hydroxypropyl cellulose (HPC) to serve as crosslinking sites during gamma irradiation following thermally-induced phase separation. However, this method requires the use of moisture-sensitive reagents and unstable organic solvents which introduces batch-to-batch variability. To address this problem, we developed a cellulosic sponge system which replaces the use of allyl groups as cross-linkers with methacrylic groups to generate methacrylic-HPC (MA-HPC) under fully aqueous conditions. The resulting MA-HPC sponge contains macropores (94 ± 8 μm, 90% porosity) to constrain cells to form organoids, and has an average elastic modulus of 8.5 kPa that is close to the modulus of native rat and human livers. We demonstrate that similar to the allyl-based sponge, the MA-HPC sponge reliably supports human hepatocyte organoid culture and maintains high level cellular functions for at least 1 week in culture, thereby providing a reliable alternative to the existing allyl-based sponge for organoid culture.

Dual Crosslinked Methacrylated Alginate Hydrogel Micron Fibers and Tissue Constructs for Cell Biology.

As an important natural polysaccharide biomaterial from marine organisms, alginate and its derivatives have shown great potential in the fabrication of biomedical materials such as tissue engineering, cell biology, drug delivery, and pharmaceuticals due to their excellent biological activity and controllable physicochemical properties. Ionic crosslinking is the most common method used in the preparation of alginate-based biomaterials, but ionic crosslinked alginate hydrogels are prone to decompose in physiological solution, which hinders their applications in biomedical fields. In this study, dual crosslinked alginate hydrogel microfibers were prepared for the first time. The ionic crosslinked methacrylated alginate (Alg-MA) hydrogel microfibers fabricated by Microfluidic Fabrication (MFF) system were exposed to ultraviolet (UV) light and covalent crosslink between methacrylate groups avoided the fracture of dual crosslinked macromolecular chains in organizational environment. The chemical structures, swelling ratio, mechanical performance, and stability were investigated. Cell-encapsulated dual crosslinked Alg-MA hydrogel microfibers were fabricated to explore the application in tissue engineering for the first time. The hydrogel microfibers provided an excellent 3D distribution and growth conditions for cells. Cell-encapsulated Alg-MA microfibers scaffolds with functional 3D tissue structures were developed which possessed great potential in the production of next-generation scaffolds for tissue engineering and regenerative medicine.

Facile synthesis of poly(trimethylene carbonate) by alkali metal carboxylate-catalyzed ring-opening polymerization

Alkali metal carboxylates, including sodium acetate, sodium benzoate, and sodium sorbate, which are all readily available and widely used as food additives, were found to promote the ring-opening polymerization (ROP) of trimethylene carbonate (TMC) to produce poly(trimethylene carbonate) (PTMC). The sodium acetate-catalyzed ROP of TMC proceeded in the presence of an alcohol initiator under solvent-free conditions at 70 °C, even at very low catalyst loadings of 0.01–0.0001 mol%. The controlled nature of this ROP system enabled the synthesis of PTMCs with predicted molecular weights ranging from 2400 to 11 700 g mol−1 and narrow dispersities (~1.23). Importantly, ROP is initiated by an alcohol initiator, allowing PTMC production with desired functional groups, such as azido, alkyne, and methacrylate groups, at the α-chain end. Furthermore, the poly(l-lactic acid)-b-PTMC-b-poly(l-lactic acid) triblock copolymer, a biodegradable thermoplastic elastomer, was successfully synthesized in one pot via the sodium acetate-catalyzed ring-opening block copolymerization of TMC and l-lactide with a 1,3-propanediol initiator. Alkali metal carboxylates, which are readily available and widely used as food additives, were found to promote the ring-opening polymerization (ROP) of trimethylene carbonate (TMC) to produce poly(trimethylene carbonate) (PTMC). The sodium acetate-catalyzed ROP of TMC proceeded in the presence of an alcohol initiator under solvent-free conditions, even at very low catalyst loadings of 0.01–0.0001 mol%. This ROP system enabled the synthesis of PTMCs with predicted molecular weights ranging from 2400 to 11 700 g mol−1 and narrow dispersities (~1.23).

A thermo-kinetic study on acrylic copolymer nanocomposite particles containing GMA-modified nanosilica prepared via miniemulsion polymerization

Silica/polyacrylic nanocomposite particles are the most attractive hybrid materials due to their outstanding physical and chemical properties. This paper deals with the chemical incorporation of glycidyl methacrylate-modified silica nanoparticles (GMA-modified SNPs) into acrylic copolymer through miniemulsion polymerization with a well dispersion. Fractional conversions and rate of polymerizations were investigated to study the role of GMA-modified SNPs on the polymerization kinetics by probable radical engagement. DSC analyses revealed some enhancement in Tg for the obtained polyacrylic nanocomposite particles because of the occurrence of limited chain flexibility. However, appearance of an exothermic peak above 90 °C in these thermograms was attributed to the possible radical generation by unreacted and trapped methacrylate groups of GMA on the surface of SNPs and their subsequent involvement in the progress of exothermic grafting reactions. Besides, the effect of GMA-modified SNPs on thermal degradation and thermo-oxidative stability of the prepared nanocomposites were evaluated by TGA. Storage modulus in the glassy and rubbery regions before and after thermal treatment were studied by DMTA and the results confirmed the above observations too.

Tethering peptides onto biomimetic and injectable nanofiber microspheres to direct cellular response

Biomimetic and injectable nanofiber microspheres (NMs) could be ideal candidate for minimally invasive tissue repair. Herein, we report a facile approach to fabricate peptide-tethered NMs by combining electrospinning, electrospraying, and surface conjugation techniques. The composition and size of NMs can be tuned by varying the processing parameters during the fabrication. Further, bone morphogenic protein-2 (BMP-2) and vascular endothelial growth factor (VEGF) mimicking peptides have been successfully tethered onto poly(ε-caprolactone) (PCL):gelatin:(gelatin-methacryloyl) (GelMA)(1:0.5:0.5) NMs through photocrosslinking of the methacrylic group in GelMA and octenyl alanine (OCTAL) in the modified peptides. The BMP-2-OCTAL peptide-tethered NMs significantly promote osteogenic differentiation of bone marrow-derived stem cells (BMSCs). Moreover, human umbilical vein endothelial cells (HUVECs) seeded on VEGF mimicking peptide QK-OCTAL-tethered NMs significantly up-regulated vascular-specific proteins, leading to microvascularization. The strategy developed in this work holds great potential in developing a biomimetic and injectable carrier to efficiently direct cellular response (Osteogenesis and Angiogenesis) for tissue repair.

Crosslinked thermoelectric hydro-ionogels: A new class of highly conductive thermoelectric materials

In this work, a new class of highly-conductive chemically cross-linked gel has been synthesized by the confinement of water and IL N, N, N triethyl octyl ammonium bromide ([N2228] Br) in polyethylene glycol dimethacrylate (PEGDMA) matrix, using in situ thermally initiated radical polymerization loaded with 1 wt% free radical initiator azobisisobutyronitrile (AIBN). This novel gel was named as hydro-ionogel (HIG). The thermoelectric properties of HIG such as ionic conductivity, Seebeck coefficient, and thermal conductivity were measured and owing to its high thermoelectric performance, we referred to this as crosslinked thermoelectric hydro-ionogel, henceforth will be denoted by X-TEHIG. For all the measurements, coin cells were fabricated using commercial LIR 2032 stainless steel battery casings with X-TEHIG sandwiched between the two graphene electrodes. The ionic conductivity of X-TEHIG was examined via AC impedance spectroscopy technique by using a Gamry apparatus. Remarkably, the ionic conductivity of X-TEHIG was higher than that of neat [N2228] Br. A linear increase in ionic conductivity of X-TEHIG as a function of temperature was recorded that showed a considerably higher value of 74 mScm−1 at 70 °C. The origin of this high conductivity is attributed to interactions between PEGDMA monomers and cations and anions of the IL and formation of hydrogen bonds between water and Br− anion, OH⋯Br−. X-TEHIG demonstrated a higher Seebeck coefficient of 1.38 mVK−1. The Fourier transform infrared (FTIR) spectroscopy results revealed the successful polymerization of X-TEHIG by the disappearance of CC peak of methacrylate group in the spectrum of PEGDMA. These results suggest that X-TEHIG may be a potential candidate for thermoelectric applications owing to their high values of ionic conductivity and Seebeck coefficient.