Biomedical applications of electrospun polycaprolactone fiber mats

Polycaprolactone (PCL) is a biodegradable polyester emerging into biomedical applications because of its biodegradability, biocompatibility, chemical stability, thermal stability and good mechanical properties. Electrospinning is a versatile method using electrostatic forces for fabricating continuous ultrafine fibers that offer various advantages such as high surface area and high porosity. Thus, this method has gained interest for use in many fields, especially biomedical fields. This review focuses on researches and studies in electrospinning, PCL, electrospinning of PCL and also biomedical applications of the electrospun PCL fiber mats. Copyright © 2016 John Wiley & Sons, Ltd.     

A review on electrospun polymeric nanofibers: Production parameters and potential applications

This review deals with electrospun nanofibers and their applications in several fields. Nanofibers have mainly been produced via electrospinning technique due to the simple, cost-effective, and versatile setup. Electrospinning is defined as a process, which produces fibers from its polymer solutions under exposure of high electric field voltage. The technique needs optimization of several parameters such solution, processing and ambient parameters to refine nanofiber morphology, diameter and porosity. The basic technique has been modified to produce composite fibers and to increase production capacity. Nanofiber characterization methods are summarized with examples. The relation between electrospinning and electrospraying is discussed. Nanofibers have the ability to form highly porous mesh with large surface to volume ratio enhancing its performance for various applications such as water filtration, tissue engineering scaffold, wounds, fiber composites, drug release and protective clothes. Single nanofibers could potentially be used as soft microrobots for drug delivery. Finally, results from modeling and simulations are illustrated.     

Electrospinning nanofibers of microbial polyhydroxyalkanoates for applications in medical tissue engineering

Differently to most chemically synthesized medical materials, polyhydroxyalkanoates (PHAs) are intracellular carbon and energy storage granules, which is a family of natural bio-polymers synthesized by microorganism's materials. Due to excellent biocompatibility reasonable biodegradability and versatile material difference, PHAs are well medical biomaterials candidates for applications in tissue engineering and drug delivery, including commercial PHB, PHBV, PHBHHx, PHBVHHx, P34HB and few uncommercial PHAs. Electrospinning nanofibers with the size of 10–10,000 nm can improve the mechanical properties and decrease the crystallinity of PHA, meanwhile simulate the structure and function of native extracellular matrix of cells. Hence, PHAs electrospinning nanofibers as engineered scaffolds have been widely used for tissue engineering scaffolds in cardiovascular, vascular, nerve, bone, cartilage and skin; also, as carriers for application in drug delivery system. In this review, we highlight the extraction and properties of medical PHAs from natural or engineered microorganism, and microstructure, current manufacturing techniques and medical applications of electrospinning nanofibers of PHAs. Moreover, the current challenges and prospects of PHAs electrospinning nanofibers are discussed rationally, providing an insight into developing vibrant fields of PHAs electrospinning nanofibers-based biomedicine.     

Thermal shrinkage of electrospun PVP nanofibers

This paper outlines the shrinkage of electrospun polyvinylpyrrolidone (PVP) fiber mats during thermal treatment. The thermal behavior and phase changes within the fibers were investigated by DSC and TGA/DTA. Five precursors with different PVP loading in ethanol were electrospun. The mats shrinkage as function of temperature was measured in the RT–200 °C range. Shrinkage rate drastically increased above the polymer glass transition point, T_g (150–180 °C), due to increase in polymer chain mobility. Mats shrinkage at 200 °C as function of PVP concentration showed a minimum at ∼10%wt. Below 10% PVP the mats morphology is non‐uniform, consisting of beads and fibers. Above 10% PVP, only flat and uniform fibers were observed. This paper outlines the dominant mechanism governing the mats shrinkage during heating. In addition, the effect of PVP concentration on the expansion of fibers diameter was investigated and found to be consistent with the linear shrinkage observing a minimum at ∼10% PVP. The effect of applied voltage on mat shrinkage was investigated, and showed a minimum at 12 kV. Understanding the interplay between fibers morphology and thermal shrinkage allows precursor composition and system optimization needed for minimizing shrinkage negative effects on the structure and properties of electrospun fiber mats. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 248–254     

Electrospun nanofibers for drug delivery applications: Methods and mechanism

Electrospinning procedures such as blend electrospinning, coaxial electrospinning, and emulsion electrospinning have been used for the fabrication of electrospun nanofibers (ENFs) for biomedical applications. These ENFs are attracted great interest especially in drug delivery applications due to their small size, high surface area-to-volume, and porosity. The aim of this review is to focus on the controlled release mechanism among the different electrospinning methods, and the selectivity of hydrophilic, water-soluble polymers as a carrier for drug. The mechanism for the drug delivery depends mainly on the method of drug loading, polymeric interactions, and the nature of polymer swelling, erosion, or degradation. This review compressed on the literature survey about the fabrication of nanofibers by different electrospinning methods, factors affecting the nanofiber morphologies, selectivity of polymeric blends for successful controlled release behavior, and the mechanism involved in the drug release steps.     

Recent progress in electrospun nanofibers: Reinforcement effect and mechanical performance

Composite materials are becoming increasingly important as structural materials for aeronautical and space engineering, naval, automotive, and civil engineering, sporting goods, and other consumer products. Fiber‐based reinforcement represents one of the most effective manufacturing strategies for enhancing the mechanical strength and other properties of composite materials. Electrospinning has gained widespread interest in the last two decades because of its ability to fabricate continuous ultrafine nanofibers with unique characteristics. The impact of electrospinning on fiber synthesis and processing, characterization, and applications in drug delivery, nanofiltration, tissue scaffolding, and electronics has been extensively studied in the past. In this article, the authors have focused on a comprehensive review of the mechanical performance and properties of electrospun nanofibers as potential reinforcements as well as their advanced nanocomposites. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1171–1212     

Phosphorylated polyacrylonitrile‐based electrospun nanofibers for removal of heavy metal ions from aqueous solution

The phosphorylated polyacrylonitrile‐based (P‐PAN) nanofibers were prepared by electrospinning technique and used for removal of Cu²⁺, Ni²⁺, Cd²⁺, and Ag⁺ from aqueous solution. The morphological and structural properties of P‐PAN nanofibers were characterized by scanning electron microscope and Fourie transform infrared spectra. The P‐PAN nanofibers were evaluated for the adsorption capacity at various pH, contact time, and reaction temperature in a batch system. The reusability of P‐PAN nanofibers for the removal of heavy metal ions was also determined. Adsorption isotherms and adsorption kinetics were also used to examine the fundamental adsorption properties. It is found that the P‐PAN nanofibers show high efficiency, and the maximal adsorption capacities of metal ions as calculated from the Langmuir model were 92.1, 68.3, 14.8, and 51.7 mg/g, respectively. The kinetics of the heavy metal ions adsorption were found to follow pseudo‐second‐order rate equation, suggesting chemical adsorption can be regarded as the major factor in the adsorption process. Sorption/desorption results reveal that the obtained P‐PAN nanofibers can remain high removal efficiency after four cycles.     

Enhanced conductivity composites for aircraft applications: carbon nanotube inclusion both in epoxy matrix and in carbonized electrospun nanofibers

The potential of carbonized electrospun nanofiber mats to render epoxy resin composites for aircraft applications electrically and thermally more conductive was investigated. The effect of carbon nanotube inclusion both inside the carbon nanofiber and in the epoxy resin matrix material was studied, in order to reveal any synergistic effects of multilevel presence of nanosized reinforcements on the conductivity and mechanical properties. The carbon nanotube inclusion into the carbonized nanofibers increased the electrical conductivity of the samples by 20–50% and the thermal conductivity by approximately three times leading to a higher value than that of the conventional composites. The preparation of layered composites with a conductive upper layer containing nonwoven carbon nanofabric and a load bearing lower layer with conventional unidirectional carbon fiber reinforcement can offer a cost‐effective and weight‐saving solution for the replacement of metal meshes in structural aircraft composites. Copyright © 2014 John Wiley & Sons, Ltd.     

Different types of electrospun nanofibers and their effect on microfluidic‐based immunoassay

Protein capturing on polymeric substrate of microfluidic devices is a key factor for the fabrication of immunoassay with high sensitivity. In this work, simple and versatile technique of electrospinning was used to produce electrospun nanofibrous membranes (e.NFMs) with high surface area as a substrate for microfluidic‐based immunoassay to increase sensitivity. It was found that the simultaneous use of e.NFM and 1‐Ethylethyl‐3‐(3‐dimethylaminopropyl)‐carbodiimide/N‐Hydroxysuccinimide hydroxysuccinimide as coupling agent has synergic effect on antigen immobilization onto the microchannels. It was found that the oxygen plasma technique for the creation of oxygen containing functional group like carboxyl and hydroxyl causes extreme leakage of solution through the microchannels. Thus, due to capillary effect, it is impossible to use hydrophilic substrate to modify microchannels. In order to compensate this problem, it is propose to utilize other type of polymer for the fabrication of nanofiber to answer this important question that if it is possible to enhance the sensitivity of immunoassay just by changing the polymer type? For this purpose, four different polymers, namely, polycaprolactone, poly lactic‐co‐glycolic acid, poly L‐lactic acid, and polyethersolfone were used as the based material for e.NFM fabrication. Results showed that compared with plain poly (dimethylsiloxane) surface of microchannels, poly lactic‐co‐glycolic acidand poly L‐lactic acid, which inherently contain end‐group of carboxyl in their chemical structure, can improve the protein immobilization, which leads to immunoassay signal enhancement through 1‐ethyl‐3‐(3‐dimethylaminopropyl)‐carbodiimide/N‐hydroxysuccinimide coupling chemistry, significantly.     

Gallic acid‐loaded electrospun cellulose acetate nanofibers as potential wound dressing materials

Gallic acid (GA)–loaded cellulose acetate (CA) nanofiber mats with 10 to 40 wt.% GA contents (based on the weight of CA) were fabricated by electrospinning. The effects of GA contents and applied potential on the morphology and the average diameters of fibers were studied. The electrospun fiber mats containing 20 and 40 wt.% GA were investigated for their potential use as carrier of GA in wound dressing application. The GA‐loaded CA films were prepared by solvent casting technique for use in comparative studies. Determination of the release characteristics of GA from the GA‐loaded fiber mats and films was carried out by the total immersion and the transdermal diffusion through a pig skin method in acetate buffer solution (pH 5.5) or normal saline (pH 7.0) at either 32 or 37°C, respectively. In the total immersion method, the maximum amounts of the GA released from the fiber mats containing 20 and 40 wt.% GA in the acetate buffer were approximately 97% and 71% (based on the weight of initial GA), while those of the GA released into the normal saline were approximately 96% and 81%, respectively. Lower values were observed in the experiments of the transdermal diffusion through a pig skin method. The corresponding GA‐loaded CA films showed the lower amounts of GA released into media. The as‐loaded and the as‐released GA remained its antioxidant activity as investigated by 1,1‐diphenyl‐2‐picrylhydrazyl (DPPH) assay. Lastly, the GA‐loaded CA fiber mats exhibited antibacterial activity against Staphylococcus aureus, which showed the potential for use as wound dressing materials.     

Bioconjugation of alkaline phosphatase to mechanically processed, aqueous suspendible electrospun polymer nanofibers for use in chemiluminescent detection assays

Aqueous suspendible polymer nanostructures were prepared by simple microtome processing of electrospun nylon 6 nanofibers and were used to immobilize calf intestinal alkaline phosphatase (ALP) by either covalent or noncovalent bioconjugation chemistries. It was found that noncovalent immobilization of ALP to the mechanically cut nanofibers (mean length approximately 4 microm; mean diameter approximately 80 nm) using a multi-stacked, layer-by-layer (LBL) approach with the cationic polymer Sapphire II resulted in the highest enzyme loading (48.1 +/- 0.4 microg . mg(-1) nanofiber) when compared to other covalent immobilization methods based on glutaraldehyde crosslinking. The biofunctionalized nanofibers were also characterized for their chemiluminescent activity with the dioxetane substrate, CSPD. The results indicate that the kinetic parameters, K(m) and V(max), for the catalytic activity of the nanostructure-bound ALP enzyme were influenced by the particular types of immobilization methods employed. In terms of the overall catalytic performance of the various immobilized ALP systems, a single-stacked LBL assembly approach resulted in the highest level of enzymatic activity per unit mass of nanofiber support. To the best of our knowledge, this study represents the first report examining the preparation of mechanically shortened, aqueous dispersed electrospun polymer nanofibers for potential application as enzyme scaffolds in chemiluminescent-based assay systems.     

Tensile deformation of electrospun nylon‐6,6 nanofibers

Nylon‐6,6 nanofibers were electrospun at an elongation rate of the order of 1000 s^?1 and a cross‐sectional area reduction of the order of 0.33 × 10⁵. The influence of these process peculiarities on the intrinsic structure and mechanical properties of the electrospun nanofibers is studied in the present work. Individual electrospun nanofibers with an average diameter of 550 nm were collected at take‐up velocities of 5 and 20 m/s and subsequently tested to assess their overall stress–strain characteristics; the testing included an evaluation of Young's modulus and the nanofibers' mechanical strength. The results for the as‐spun nanofibers were compared to the stress–strain characteristics of the melt‐extruded microfibers, which underwent postprocessing. For the nanofibers that were collected at 5 m/s the average elongation‐at‐break was 66%, the mechanical strength was 110 MPa, and Young's modulus was 453 MPa, for take‐up velocity of 20 m/s—61%, 150 and 950 MPa, respectively. The nanofibers displayed α‐crystalline phase (with triclinic cell structure). © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1482–1489, 2006     

Fabrication and characterization of chitosan-gelatin/single-walled carbon nanotubes electrospun composite scaffolds for cartilage tissue engineering applications

Cartilage is a connective tissue with a slow healing rate due to lack in blood circulation and slow metabolism. Designing tissue engineering scaffolds modified based on its specific features can assist its natural regeneration process. In this study, the chitosan-gelatin/single-walled carbon nanotubes functionalized by COOH (SWNTs-COOH) nanocomposite scaffolds were fabricated through electrospinning. The effect of each component and different duration of cross-linking were assessed in terms of morphology, porosity, chemical structure, thermal behavior, mechanical properties, wettability, biodegradability, and in vitro cell culture study. Adding SWNTs-COOH decreased fiber diameter, water contact angle and degradation rate while increased tensile strength, hydrophilicity, stability and cell viability, due to their high intrinsic electrical conductivity, and mechanical properties and the presence of COOH functional groups in its structure. All the sample presented a porosity percentage of more than 80%, which is essential for tissue engineering scaffolds. The presence SWNTs-COOH did not have any adverse effect on cytocompatibility. The optimal cross-linking time increased the stability of the scaffolds in PBS. It can be concluded that the chitosan-gelatin/1wt% SWNTs-COOH scaffold can be appropriate for cartilage tissue engineering applications.     

ZIF-8/改性聚丙烯腈电纺纳米纤维的制备及其高效去除水中孔雀石绿

通过原位生长方法,将最常见的金属有机骨架（MOFs）——沸石咪唑酯骨架材料（ZIF‐8）固定到羧甲基化聚丙烯腈静电纺丝纳米纤维（PAN‐COOH NFs）表面,得到ZIF‐8/PAN‐COOH NFs。通过扫描电子显微镜（SEM）、能量色散光谱（EDS）、X射线粉末衍射（XRD）和傅里叶变换红外光谱（FTIR）对合成的ZIF‐8/PAN‐COOH NFs形貌和结构进行表征,并深入研究ZIF‐8/PAN‐COOHNFs从废水中去除孔雀石绿（MG）的性能。研究发现： ZIF‐8/PAN‐COOH NFs对MG的吸附符合拟二级动力学方程,吸附过程可采用Langmuir等温线模型拟合,其对MG的最大吸附容量可达3 604 mg·g^-1。此外,ZIF‐8/PAN‐COOH NFs在染料吸附实验中表现出良好的分离功能和重复利用性。     

Dual-syringe reactive electrospinning of cross-linked hyaluronic acid hydrogel nanofibers for tissue engineering applications

A facile fabrication of a cross-linked hyaluronic acid (HA) hydrogel nanofibers by a reactive electrospinning method is described. A thiolated HA derivative, 3,3'-dithiobis(propanoic dihydrazide)-modified HA (HA-DTPH), and poly(ethylene glycol) diacrylate (PEGDA) are selected as the cross-linking system. The cross-linking reaction occurs simultaneously during the electrospinning process using a dual-syringe mixing technique. Poly(ethylene oxide) (PEO) is added into the spinning solution as a viscosity modifier to facilitate the fiber formation and is selectively removed with water after the electrospinning process. The nanofibrous structure of the electrospun HA scaffold is well preserved after hydration with an average fiber diameter of 110 nm. A cell morphology study on fibronectin (FN)-adsorbed HA nanofibrous scaffolds shows that the NIH 3T3 fibroblasts migrate into the scaffold through the nanofibrous network, and demonstrate an elaborate three-dimensional dendritic morphology within the scaffold, which reflects the dimensions of the electrospun HA nanofibers. These results suggest the application of electrospun HA nanofibrous scaffolds as a potential material for wound healing and tissue regeneration. [image: see text] Laser scanning confocal microscopy demonstrates that the NIH3T3 fibroblast develops an extended 3D dendritic morphology within the fibronectin-adsorbed electrospun HA nanofibrous scaffold.     

ZIF-8/改性聚丙烯腈电纺纳米纤维的制备及其高效去除水中孔雀石绿

通过原位生长方法,将最常见的金属有机骨架(MOFs)——沸石咪唑酯骨架材料(ZIF-8)固定到羧甲基化聚丙烯腈静电纺丝纳米纤维(PAN-COOH NFs)表面,得到ZIF-8/PAN-COOH NFs。通过扫描电子显微镜(SEM)、能量色散光谱(EDS)、X射线粉末衍射(XRD)和傅里叶变换红外光谱(FTIR)对合成的ZIF-8/PAN-COOH NFs形貌和结构进行表征,并深入研究ZIF-8/PAN-COOHNFs从废水中去除孔雀石绿(MG)的性能。研究发现： ZIF-8/PAN-COOH NFs对MG的吸附符合拟二级动力学方程,吸附过程可采用Langmuir等温线模型拟合,其对MG的最大吸附容量可达3 604 mg·g^-1。此外,ZIF-8/PAN-COOH NFs在染料吸附实验中表现出良好的分离功能和重复利用性。     

Nanogel engineering for new nanobiomaterials: from chaperoning engineering to biomedical applications

Nanosize hydrogels (nanogels) are polymer nanoparticles with three‐dimensional networks, formed by chemical and/or physical cross‐linking of polymer chains. Recently, various nanogels have been designed, with a particular focus on biomedical applications. In this review, we describe recent progress in the synthesis of nanogels and nanogel‐integrated hydrogels (nanogel cross‐linked gels) for drug‐delivery systems (DDS), regenerative medicine, and bioimaging. We also discuss chaperone‐like functions of physical cross‐linking nanogel (chaperoning engineering) and organic‐inorganic hybrid nanogels. © 2010 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.201000008     

Hard‐block degradable thermoplastic urethane‐elastomers for electrospun vascular prostheses

Thermoplastic polyurethane (TPU) elastomers with biodegradable chain extenders were synthesized and tested for mechanical performance and biocompatibility. The design of the TPUs was based on structural modification of a mechanically appropriate aromatic isocyanate‐based TPU. As the aromatic isocyanate was substituted with a less toxic but also less “hard” aliphatic isocyanate, the chain extender plays an important role on the mechanical properties. Here, the terephthalate ester chain extender was found to work better than hydroxyl ethyl lactate in providing polymers with mechanical properties similar to commercial aromatic isocyanate‐based TPUs. The polymers were degraded in aqueous solutions at elevated temperatures and compared to polylactic acid (PLA) to partially simulate biodegradation. The lactate‐based TPUs degraded about twice as fast as PLA while the terephthalate‐based TPU degraded much more slowly. The latter material was processed by electrospinning to give a tubular graft approximately the size of a large rat blood vessel. Initial results from implantation of these TPUs into rats are promising and indicate that biodegradation occurs and is likely beneficial to cell proliferation. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Human Albumin-Based Hydrogels for Their Potential Xeno-Free Microneedle Applications

Nowadays, hydrogels-based microneedles (MNs) have attracted a great interest owing to their outstanding qualities for biomedical applications. For the fabrication of hydrogels-based microneedles as tissue engineering scaffolds and drug delivery carriers, various biomaterials have been tested. They are required to feature tunable physiochemical properties, biodegradability, biocompatibility, nonimmunogenicity, high drug loading capacity, and sustained drug release. Among biomaterials, human proteins are the most ideal biomaterials for fabrication of hydrogels-based MNs; however, they are mechanically weak and poorly processible. To the best of the knowledge, there are no reports of xeno-free human protein-based MNs so far. Here, human albumin-based hydrogels and microneedles for tissue engineering and drug delivery by using relatively new processible human serum albumin methacryloyl (HSAMA) are engineered. The resultant HSAMA hydrogels display tunable mechanical properties, biodegradability, and good biocompatibility. Moreover, the xeno-free HSAMA microneedles display a sustained drug release profile and significant mechanical strength to penetrate the model skin. In vitro, they also show good biocompatibility and anticancer efficacy. Sustainable processible human albumin-based biomaterials may be employed as a xeno-free platform in vivo for tissue engineering and drug delivery in clinical trials in the future.     

Electrospun aligned nanofibers: A review

Electrospinning (e-spinning) is famous for the construction and production of ultrafine and continuous micro-/nanofibers. Then, the alignment of electrospun (e-spun) nanofibers becomes one of the most valuable research topics. Because aligned fibers have more advantages over random fibers, such as better mechanical properties, faster charge transport, more regular spatial structure, etc. This review summarizes various electrospinning techniques of fabricating aligned e-spun nanofibers, such as early conventional methods, near-field e-spinning, and three-dimensional (3D) printing e-spinning. Among them, four auxiliary preparation methods (e.g., auxiliary solid template, auxiliary liquid, auxiliary electromagnetic field and auxiliary airflow), two collection modes (static and dynamic collection), and the controllability of near-field e-spinning and 3D printing e-spinning are highlighted. The representative applications depending on aligned nanofibers are classified and briefly introduced, emphasizing in the fields of 1D applications (e.g., field-effect transistor, nanochannel and guidance carrier), 2D applications (e.g., platform for gas detection, filter, and electrode materials storage), and 3D applications (e.g., bioengineering, supercapacitor, and nanogenerator). At last, the challenges and prospects are addressed.