One major challenge of biomaterial engineering is to mimic the mechanical properties of anisotropic, multifunctional natural soft tissues. Existing solutions toward controlled anisotropy include the use of oriented reinforcing fillers, with complicated interface issues, or UV‐curing processing through patterned masks, that makes use of harmful photosensitive molecules. Here, a versatile process to manufacture biocompatible silicone elastomer membranes by light degradation of the platinum catalyst prior to thermal cross‐linking is presented. The spatial control of network density is demonstrated by experimental and theoretical characterizations of the mechanical responses of patterned cross‐linked membranes, with a view to mimic advanced implantable materials.
In this study, a facile method about generating porous poly (l ‐lactide) (PLLA) materials with uniform morphology by gradual precipitation is reported. By adjusting the solvents, concentrations of polymer solution, and drying process, petal‐like PLLA nanosheets can be conveniently obtained, which can further form porous materials with tunable porosities (85–92%). X‐ray diffraction affirms that α‐form crystals of PLLA with high crystallinity (51.66% according to differential scanning calorimetry) can be obtained. Mechanical test shows that the compression modulus is tunable with values ranging from 1.76 to 19.98 MPa. Notably, because of its high porosity, interconnected pore structure, and tunable mechanical properties, these versatile porous materials are especially fit for being utilized in polymer scaffold field.
The introduction of nanodiamond particles (NDs) in silane‐crosslinked polyethylene is found to lead to a notable and systematic deformation of the polymer unit cell. X‐ray diffraction evidence of the existence of a modified crystalline structure in the bulk of the polymer due to the presence of NDs is reported here for the first time. The covalent bonding between NDs and the surrounding macromolecular chains may support that the excessive local stress field ultimately distorts the polymer conformation, yielding a new distorted but still crystalline interface. Supporting data from solid‐state NMR experiments confirm the existence of a modified crystalline interface of about 1–2 nm in all the nanocomposite materials.
This article deals with the amine blush phenomenon in epoxy coatings. Amine blush is due to amine carbonation and weakens the visual aspect of room temperature epoxy coatings. This paper describes a way to avoid the carbonation by preparing aminotelechelic prepolymers is described. For the first time, the amine‐adduct impact over amine carbonation, as well as the amine decarbonation with temperature, has been investigated by infrared spectroscopy. Moreover, a range of epoxy materials displaying various Tg are synthesized from amine‐adducts and compared to polyurethane references generally used for transparent coating applications. Mechanical and thermal properties are also investigated.
We herein report on an iontronic device to drive and control Aβ1‐40 and Aβ1‐42 fibril formation. This system allows kinetic control of Aβ aggregation by regulation of H+ flows. The formed aggregates show both nanometer‐sized fibril structure and microscopic growth, thus mimicking senile plaques, at the H+‐outlet. Mechanistically we observed initial accumulation of Aβ1‐40 likely driven by electrophoretic migration which preceded nucleation of amyloid structures in the accumulated peptide cluster.
A new facile approach for the fabrication of polymer‐Ag honeycomb film is reported. A polymer‐Ag+ honeycomb thin film is obtained by casting a CHCl3 solution of a functional graft copolymer on aqueous silver nitrate solution, leading to metal complexation induced phase separation at the air/water interface. The film is reduced by UV irradiation to give a polymer‐Ag honeycomb film with regular morphology. Pyrolysis of the film gives a translucent Ag honeycomb film.
A gas‐permeable cellulose template for microimprint lithography has been synthesized and characterized for the reduction of template damage and gas trapping caused by solvents and oxygen generated from cross‐linked materials. The 5 μm line‐pattern failure of the microimprinted UV cross‐linked liquid materials with 4.7 wt% acetone as a volatile solvent is solved by using the gas‐permeable cellulose template because of its increased oxygen permeability. The gas‐permeable cellulose template also allows the use of volatile solvents with high coating property and solubility into the microimprinted materials instead of the compounds and plastic resins conventionally used in mold injection.
Hydrophobic and super‐hydrophobic materials have many important applications, but most of the artificially hydrophobic and super‐hydrophobic surfaces suffer from poor durability. Herein, a facile method is reported to fabricate robust hydrophobic and super‐hydrophobic polymer films through backfilling the silica colloidal crystal templates with the mixture of fluoropolymer, thermoset hydroxyl acrylate resins, and curing agent. After removal of the template, 3D ordered porous structures are obtained. The obtained polymer films have not only excellent hydrophobic or super‐hydrophobic properties but also good stability against temperatures, acids, and alkalis. Dual ordered porous structure can obviously enhance the hydrophobicity of polymer films compared to unitary one.
The previously introduced process for enzyme‐mediated in situ synthesis and deposition of eumelanin is investigated with covalent immobilization of the tyrosinase. It results in a monolayer structure of non‐coalesced melanin particles, with a film thickness of 5–8 nm. The reaction is self‐terminating due to overlay of the enzymes with particles. The melanin particles are rodlike with lengths down to 6 nm. Isolated melanin structures of such small size have not been observed before and might be a kind of protoparticle in the supramolecular buildup of melanin oligomers. Utilization of melanin particles with such small size can enable nanotechnological applications in the areas of bioelectronics and biosensors.
Thermal induced solid phase polymer reactions between bisphenol‐A‐based polycarbonate (PC) and polyvinylamine (PVAm) are used to form permanent composite material. The PC–PVAm interface is characterized by infrared (IR) spectroscopy. IR spectra of synthesized reference substances which can be expected after PC–PVAm reaction are recorded and used to identify amidation product structures within the PC–PVAm interphase. Curve fit analysis is performed to isolated sub‐bands. The spectral position of the carbonyl absorption band is a suitable marker for the identification of different amidation products. While the formation of urethane and cyclic Allophanate points to the formation of a co‐polymer cyclic Urea indicates a PC chain scission without binding between both polymer materials.
Suitable membranes for blood‐contacting medical applications need to be resistant in confrontation with blood proteins and cells, while possessing high blood compatibility and permeability at the same time. Herein, an overview of the recent advances and strategies that have been used to enhance the hemocompatibility of polymeric membranes is provided. The review focuses on two modification strategies: (i) physical modifications and (ii) chemical modifications. It also highlights the current progress in the design of hemocompatible‐functionalized membranes for biomedical applications. Subsequently, the commonly applied biocompatibility tests are also discussed and finally the future perspectives of the application of polymeric membranes in the biomedical field are presented.
The fabrication of asymmetric polymer membranes via vapor phase deposition is demonstrated. In this solventless process, the dense layer is deposited first and then the porous layer is subsequently deposited onto the dense layer. A variety of functional polymer membranes can be produced by varying the precursor molecules. The functionality of the dense and porous layers can be independently tailored to be either hydrophobic or hydrophilic, resulting in membranes that are fully hydrophilic, fully hydrophobic, or asymmetric in both structure and chemical functionality. The thickness of both the porous and dense layers can be separately tuned by controlling the deposition time.
This study describes novel and simple conditions for the fabrication of collagen microfibers with specific physical and mechanical properties, which can then be potentially applied as cell‐based matrices. The microfibers are fabricated from collagen hydrogels, using various concentrations of ethanol, in ethanol–water solvents. At higher ethanol concentration, fibers exhibited increased uniformity of surface morphology, decreased diameter, and increased tensile strength. The morphology of cells on microfibers varies due to the surface morphology of microfibers but the microfibers fabricated under all conditions investigated show similar number of attached cells on the surface of fibers, and cells sustain their viability for 90 h.
Preparation of novel nanocomposite hydrogels opens up new avenues to next generation of biocompatible materials to be used in bioengineering and drug delivery. Toward this goal, chitosan nanocomposite hydrogels using click chemistry inspired cross‐linking are prepared. To enable this, Diels–Alder reaction of furan‐containing chitosan and maleimide‐coated gold nanoparticles is employed. The viscoelastic properties of the obtained nanocomposites as well as the effect of the nanoparticles as cross‐linkers are studied, indicating that they play significant role in hydrogel formation and stability. Nanoparticle‐enriched hydrogels are also found to demonstrate pH‐sensitivity therefore showing their potential for future biosensing applications.
A conjugated polymer, poly(9,9‐bis(6‐bromohexyl)‐9H‐fluorene‐alt‐1,4‐phenylene), is synthesized, converted to nanoparticles via a nanoprecipitation process, and utilized to fabricate thin films including conjugated polymer nanoparticles. The nanoparticles with surface bromides can be conjugated with an amine‐functionalized dendrimer via a nucleophilic coupling reaction. Thus, when microliter solutions of the particulates are dragged at a constant velocity on substrates alternately in a layer‐by‐layer manner, thin films composed of the nanoparticles and dendrimers can be successfully built up on the substrates. Our results suggest a methodology to control the deposition of thin films bearing conjugated polymer nanoparticles while minimizing processing time and decreasing material consumption.
Silicone materials are widely used in many fields such as electrical or food industries and their consumption is constantly growing. They are generally cured by vulcanization reaction for long time at high temperatures which requires high energy consumption. The possibility to achieve the polymerization of silicone rubbers by UV‐activation promotes the reduction of both time and temperature leading to an impressive energy saving. Indeed, this process is more than 30 times faster than the thermal one. Moreover, the properties of the two resulting materials are comparable, indicating that the low time of UV‐activated hydrosilation reaction is suitable for the formation of crosslinked silicone polymers.
Micellar radical polymerization of a short‐chain polyester macromonomer, polycaprolactone choline iodide ester methacrylate (PCLnChMA), is used to produce a new cationic flocculant that becomes more hydrophobic in response to hydrolytic degradation. The cationic tips of the comb‐like poly(PCL3ChMA) accelerate the settling rate of oil sands tailings, while partial hydrolysis of the polyester grafts reveals the hydrophobic segments that reduce capillary suction time by 30%. This technology combines the material properties of polyesters with the productivity of radical polymerization to make dual functional flocculants with characteristics that can be easily tuned to control flocculation performance, such as polymeric cation density, hydrophobic content, and polymer architecture.
A versatile approach to synthesis of hydrophobic polymeric cryogels is proposed using acetic acid crystals instead of ice crystals as porogen through cryo‐polymerization. In the range of 60 to 90 vol% of acetic acid, polymerization at ambient temperature gives rise to particulate polymers in beaded or amorphous shape, while polymerization at 4 °C, lower than the melting point of acetic acid (16.6 °C), leads to the formation of cryogel‐like monoliths with supermacroporous structure, which is mainly ascribed to cryo‐concentration effect. According to the measurements by scanning electron microscopy and mercury intrusion porosimetry, the dried samples are supermacroporous with pore size mainly ranging from several micrometers to several hundred micrometers, which can be feasible for rapid mass transfer. The forming cryogels display a superfast responsiveness to organic solvents, possibly stemming from their supermacroporosity and distinctive hydrophobicity.
The molecular anisotropy that is developed in microscale, centrifugally spun atactic‐polystyrene fibers prepared from the solution state is examined. Small angle neutron scattering is utilised to examine the molecular orientation of the polymer chain conformation in centrifugally spun fiber samples and comparisons are made to anisotropy developed in electrospun fiber samples. The average values of molecular anisotropy developed in the centrifugally spun fibers measured a ratio of the radius of gyration parallel to‐/perpendicular to‐ the fiber axis as 1.02, lower than the average of 1.05 observed for the electrospinning process. The highest level of anisotropy observed for the centrifugally spun fiber samples is ≈1.04, compared with a value of 1.063 for electrospinning. A model of chain anisotropy development in the centrifugal spinning process relating to the tangential speed and solvent evaporation is described.
The effect of varying electrospinning parameters is reported for the production of collagen nanofibers from acetic acid with controlled fiber diameter, orientation, and mechanical properties. Nanofibers with a range of diameters of 175–400 nm are obtained by varying either the voltage or the flow rate. An increase in nanofiber alignment is observed by increasing injection flow rate. Mechanical testing of these fibers reveals that the elasticity modulus can be tuned in the range of 2.7–4.1 MPa by the selection of the crosslinking method. Fourier transform infrared spectroscopy reveals that the secondary structure of collagen is preserved after electrospinning and crosslinking. Lastly, in vitro testing reveals that a high number of fibroblasts attach to the collagen matrices indicating, that they are suitable for mammalian cell culture.
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