Poly(hexamethylene adipate)‐PEO block copolymers (PHA‐b‐PEO) with different PEO contents were synthesized and processed to aqueous suspensions with high solid contents by a solvent displacement method followed by dialysis. The best suspension displayed a solid content of 16 wt.‐% and an average particle size of 108 nm. This suspension was mixed with a small amount of high molecular weight PEO and Brij78 and electrospun into corresponding nanofibers. After extraction with water, nanofibers of PHA‐b‐PEO were obtained. Electrospinning of aqueous suspensions of biodegradable polyesters alleviates concerns regarding safety, toxicology and environmental problems, which are associated with spinning of such polyesters from harmful organic solvents and thereby offers novel perspectives for applications in medicine, pharmacy and agriculture. Electrospinning of polymers from aqueous suspensions avoiding harmful organic solvents is suggested to be “green electrospinning”.
Different micromechanical models for the prediction of mechanical properties of CNT/polymer composites, taking into consideration filler percolation throughout the matrix, are considered. It is demonstrated that the critical filler volume fraction, where a percolating network of CNTs is forming, marks a “turning point” in the reinforcement efficiency. Expectations for the reinforcing effect of CNTs at concentrations above a percolating threshold with the current technology are in general unrealistic.
Nanofiber scaffolds of collagen have been fabricated via electrospinning using benign solvent systems as a replacement for 1,1,1,3,3,3 hexafluoro‐2‐propanol. Simple binary mixtures of phosphate‐buffered saline and ethanol have been found to be highly effective for electrospinning. FTIR spectra suggest that the triple helical structure of collagen was conserved after dissolution and electrospinning. Crosslinking of the electrospun collagen scaffolds was achieved with standard methods.
Nanofiber‐based non‐wovens can be prepared by electrospinning. The chemical modification of such nanofibers or chemistry using nanofibers opens a multitude of application areas and challenges. A wealth of chemistry has been elaborated in recent years on and with electrospun nanofibers. Known methods as well as new methods have been applied to modify the electrospun nanofibers and thereby generate new materials and new functionalities. This Review summarizes and sorts the chemistry that has been reported in conjunction with electrospun nanofibers. The major focus is on catalysis and nanofibers, enzymes and nanofibers, surface modification for biomedical and specialty applications, coatings of fibers, crosslinking, and bulk modifications. A critical focus is on the question: what could make chemistry on or with nanofibers different from bulk chemistry?
We report the synthesis of a series of block copolymers consisting of a rod‐like semiconducting poly(2,5‐di(2′‐ethylhexyloxy)‐1,4‐phenylenevinylene) (DEH‐PPV) block and a flexible poly(lactic acid) (PLA) block that can be selectively degraded under mild conditions. Such selectively degradable block copolymers are designed as self‐assembling templates for bulk heterojunction donor–acceptor layers in organic solar cells. A lamellar microphase‐separated domain structure was identified for block copolymers with PLA volume fractions between 29 and 79% in bulk and thin films using SAXS, TEM, and AFM. Depending on the ratio of the two blocks we find either lamellae oriented parallel or perpendicular to the substrate in thin films.
Development of peptides as clinically useful drugs is limited by their poor metabolic stability and low bioavailability. Recent progresses in chemical synthesis and design have led to several strategies for producing potent mimetics. This study aims to analyze sequence/structure requirements and composition for antimicrobial peptoid designs, as use of peptoids is one of the most representative approaches to meet the goal of biomimicry. Analysis of the designs showed that for maximum activity and minimum hemolysis, the plane of the aromatic residues should be at an angle between 0 and 90 ° with respect to membranes, cationic residues need not be at the terminal position, and central positions should be uniform in NIle, NLys, and NPhe residues.
Green nanocomposite coatings based on renewable plant oils have been developed. An acid‐catalyzed curing of epoxidized plant oils with 3‐glycidoxypropyltrimethoxysilane produced transparent nanocomposites. The hardness and mechanical strength improved by incorporating the silica network into the organic polymer matrix, and good flexibility was observed in the nanocomposite. The nanocomposites showed high biodegradability.
Electrospinning has been exploited for almost one century to process polymers and related materials into nanofibers with controllable compositions, diameters, porosities, and porous structures for a variety of applications. Owing to its high porosity and large surface area, a non‐woven mat of electrospun nanofibers can serve as an ideal scaffold to mimic the extracellular matrix for cell attachment and nutrient transportation. The nanofiber itself can also be functionalized through encapsulation or attachment of bioactive species such as extracellular matrix proteins, enzymes, and growth factors. In addition, the nanofibers can be further assembled into a variety of arrays or architectures by manipulating their alignment, stacking, or folding. All these attributes make electrospinning a powerful tool for generating nanostructured materials for a range of biomedical applications that include controlled release, drug delivery, and tissue engineering.
Bimodal fiber meshes with fiber diameters differing by one order of magnitude, are electrospun in a simple one‐step process, using a standard single syringe electrospin setup. The nano‐ and microfiber meshes combine the benefits of nanofibers (cell adhesion, proliferation) with those of microfibers (open structure, large pore size) and are therefore interesting as scaffolds for cellular infiltration.
Polyaniline nanostructures (nanosheets, nanofibers, and nanoparticles) can be assembled at the organic/aqueous interface or in solution by controlling the diffusion rate and the polymerization induction time of aniline. The quality of polyaniline nanostructures is determined by the polymerization solution conditions. Polyaniline nanosheets formation mechanism was proposed. Under certain polymerization conditions, polyaniline nanofibers or/and nanoparticles were obtained.
Grafted conjugated polyelectrolytes were synthesized for the first time and characterized. The polymers demonstrated properties of a convenient and efficient protocol for creating Hg2+ sensors. The unique character of the new material comes from an anionic counterion nature with no external cofactors, and imparts high selectivity and fast detection for mercury ion in a fluorescence probe. The concept may be potentially applied to create new sensors for monitoring other ions.
Summary: PANCMPCs containing phospholipid side moieties were electrospun into nanofibers with a mean diameter of 90 nm. Field emission SEM was used to characterize the morphologies of the nanofibers. These phospholipid‐modified nanofibers were explored as supports for enzyme immobilization due to the characteristics of excellent biocompatibility, high surface/volume ratio, and porosity, which were beneficial to the catalytic efficiency and activity of immobilized enzymes. Lipase from Candida rugosa was immobilized on these nanofibers by adsorption. Preliminary results indicated that the properties of the immobilized lipase on these phospholipid‐modified nanofibers were greatly promising.
Schematic representation of the structure and electrostatic properties of phospholipid‐modified nanofibers. 相似文献
Photochromic spiropyran molecules were embedded in electrospun polymer microfibers. Electrospinning of a clear viscous chloroform solution containing a spiropyran and a matrix polymer, such as polystyrene and polyethylene oxide, affords polymer microfibers that are photoswitchable. Photomasked, 365 nm UV irradiation of the microfibers results in the generation of patterned color images owing to the selective transformation of the spiropyran molecules from their ring‐closed SP to ring‐opened MC form. The UV‐irradiated areas display brilliant red fluorescence, which changes to green fluorescence upon prolonged irradiation.
Summary: Magnetic nanoparticles have been prepared by a co‐precipitation method and modified with methacryloxypropyltrimethoxysilane. Magnetic molecularly imprinted polymer particles have been prepared by suspension polymerization in silicone oil. The particles possess a high affinity to the template molecules and are rapidly separated under a magnetic field.
Three‐pole electrospinning devices integrated with a blade‐cage collector were developed to fabricate well‐aligned nano‐fiberous membranes. The proposed three‐pole configuration with a channel electrode can be a powerful tool in aligning nano‐fibers with regular diameter because the generated electric field can be accurately controlled without severe fluctuation in comparison with other methods. The three‐pole electrospinning method is also valid for industrial mass production and accurate diameter control of the aligned nano‐fibers.
Summary: In this paper, unsaturated groups were introduced into poly(lactic acid) (PLA) for fabricating PLA‐based nanospheres with carbon‐carbon double bonds as functional groups. The morphology dependencies on fabrication conditions, including the fabrication time as well as the stirring rate, were also investigated.
SEM‐EDX image of poly(lactic acid) diacrylate nanospheres after exposure to osmium tetroxide vapor for 14 h. 相似文献
This review article describes the preparation of polymer brushes by nitroxide‐mediated radical polymerization using either the ‘grafting to’ or the ‘grafting from’ approach. The use of TEMPO as a classical initiator is intensively described. More sophisticated nitroxides are also included in the discussion. Brush formation on flat surfaces such as wafers and also on particles is reported. Finally, some applications of polymer brushes are presented.
