A Mini Review: Electrospun Hierarchical Nanofibers

Electrospinning is a technique that allows the fabrication of continuous fibers with diameters down to a few nanometers. This technique provides a convenient and versatile method for preparing hierarchical nanofibers from a rich variety of materials that include almost all soluble or fusible polymers. The polymers can be chemically modified and can also be tailored with additives. The method provides access to entirely new materials. Until now, electrospinning is also widely being applied in laboratory and industry.     

Polymer nanofibers assembled by electrospinning

Electrospinning is a process by which polymer nanofibers (with diameter lower than 100 nm and lengths up to kilometres) can be produced using an electrostatically driven jet of polymer solution (or polymer melt). Simple alignment of electrospun nanofibers constructs unique functional nanostructures such as nanotubes and nanowires. Significant progress has been made in this area throughout the past few years and this technology has been exploited to a wide range of applications. Most of the recent work on electrospinning has focused either on trying to understand deeper the fundamental aspects of the process in order to gain control of nanofiber morphology, structure, surface functionality, and strategies for assembling them or on determining appropriate conditions for electrospinning of various polymers and biopolymers.     

电纺法制备聚合物纳米纤维的研究进展

电纺技术是一种制备聚合物纳米纤维的新方法,它可制备出直径为纳米级的超细纤维,最小直径可至1nm.电纺法制备聚合物纳米纤维具有设备简单、操作容易以及高效等优点,它是目前能直接、连续制备聚合物纳米纤维的有效方法.本文介绍了电纺过程、原理及影响纤维性能的主要因素,综述了电纺技术在生物医学材料,复合增强纤维,无机纳米纤维,导电纳米纤维等方面的应用进展,最后对电纺技术在制备聚合物纳米纤维方面的发展前景作出了展望.     

Biomedical application of responsive ‘smart’ electrospun nanofibers in drug delivery system: A minireview

Electrospinning is a versatile method for producing continuous nanofibers. It has since become an easy and cost-effective technique in the manufacturing process and drawn keen interests in most biomedical field applications. Nanofibers have garnered great attention in nanomedicine due to their resemblance with the extracellular matrix (ECM). Like nanoparticles, its unique characteristics of higher surface-to-volume ratio and the tunability of the polymers utilizing nanofiber have increased the efficiency in encapsulation and drug-loading capabilities. Smart or “stimuli-responsive” polymers have shown particular fascination in controlled release, where their ability to react to minor changes in the environment, such as temperature, pH, electric field, light, or magnetic field, distinguishes them as intelligent. Polymers are a popular material for the design of drug delivery carriers; consequently, various types of drugs, including antiviral, proteins, antibiotics, DNA and RNA, are successfully encapsulated in the pH-dependent nanofibers with smart polymers which is a polymer that can respond to change such as pH change, temperature. In this minireview, we discuss applications of smart electrospun pH-responsive nanofibers in the emerging biomedical developments which includes cancer drug targeting, oral controlled release, wound healing and vaginal drug delivery.     

Annealing Effect on Electrospun Polymer Fibers and Their Transformation into Polymer Microspheres

Electrospinning is a simple and convenient technique to produce polymer fibers with diameters ranging from several nanometers to a few micrometers. Different types of polymer fibers have been prepared by electrospinning for various applications. Among different post‐treatment methods of electrospun polymer fibers, the annealing process plays a critical role in controlling the fiber properties. The morphology changes of electrospun polymer fibers under annealing, however, have been little studied. Here we investigate the annealing effect of electrospun poly(methyl methacrylate) (PMMA) fibers and their transformation into PMMA microspheres. PMMA fibers with an average size of 2.39 μm are first prepared by electrospinning a 35 wt% PMMA solution in dimethylformamide. After the electrospun fibers are thermally annealed in ethylene glycol, a non‐solvent for PMMA, the surfaces of the fibers undulate and transform into microspheres driven by the Rayleigh instability. The driving force of the transformation process is the minimization of the interfacial energy between the polymer fibers and ethylene glycol. The sizes of the microspheres fit well with the theoretical predictions. Longer annealing times are found to be required at lower temperatures to obtain the microspheres.     

Electrospinning through the prism of time

Electrospinning is a versatile and flexible technique for the preparation of ultrafine fibers. The present study aims to provide a comprehensive overview of electrospinning, as a complex technique, its evolution toward the high-throughput techniques, including the basic principles, parameters influencing the fibers production process, methods applied to solve the alignment difficulties, commonly used polymers and solvents, and the applications of the electrospun materials. We begin with an insight into the history of electrospinning, followed by its theoretical background and typical apparatus. Then, its renaissance over the past two decades as a powerful technology for the production of nanofibers suitable for industrial scale is presented. Afterward, we briefly discuss the applications of electrospun fibers, including use in different fields of industry, energy harvesting/conversion/storage, photonic and electronic devices, as well as biomedical applications. In the end, we also offer perspectives on the challenges and new directions for developments in electrospinning.     

将源药包覆到聚己内酯超细纤维的芯部

采用同轴共纺技术,分别将白藜芦醇(Resveratrol,RT)和硫酸庆大霉素(Gentamycin Sulfate,GS)源药包覆在生物可降解的聚己内酯(PCL)超细(直径为几百纳米)纤维芯部.研究了这种纤维的制备过程以及它们的微观结构.这种复合纳米纤维可在医疗新产品开发中发挥作用,如用于制备新的羊肠线(体内手术伤口缝合线)或伤口敷布.     

Surface morphology and mechanical response of randomly oriented electrospun nanofibrous membrane

Electrospinning for the fabrication of fibrous membranes has received great attention due to the simplicity of the technique, ability to effectively control the process and potential for production scale-up. While the optimization of electrospinning parameters for various polymers is widely investigated, the mechanical characterization and modeling of the mechanical response of electrospun membranes remain a major challenge. The present work focuses on the mechanical characterization of electrospun nanofibrous membrane under simple and complex loading conditions. For this purpose, polyvinylidene fluoride (PVDF) is considered for the membrane material. Three types of uniaxial mechanical tests are conducted: monotonic tensile test, cyclic loading test with increasing maximum strain and cyclic-relaxation test. The evolution of fiber re-orientation with deformation is also investigated. Results show that the membrane is initially isotropic in the plane. Moreover, the evolution of membrane Young’s modulus with increasing maximum strain suggests that mechanical deformation induces two interacting phenomena: fiber re-orientation and inter-fiber bond damage.     

How to Polymerize Ethylene in a Highly Controlled Fashion?

Very fast, reversible, polyethylene (PE) chain transfer or complex-catalysed "Aufbaureaktion" describes a "living" chain-growing process on a main-group metal or zinc atom; this process is catalysed by an organo-transition-metal or lanthanide complex. PE chains are transferred very fast between the two metal sites and chain growth takes place through ethylene insertion into the transition-metal- or lanthanide-carbon bond-coordinative chain-transfer polymerisation (CCTP). The transferred chains "rest" at the main-group or zinc centre, at which chain-termination processes like beta-H transfer/elimination are of low significance. Such protocols can be used to synthesise very narrowly distributed PE materials (M(w)/M(n)<1.1 up to a molecular weight of about 4000 g mol(-1)) with differently functionalised end groups. Higher molecular-weight polymers can be obtained with a slightly increased M(w)/M(n), since diffusion control and precipitation of the polymers influences the chain-transfer process. Recently, a few transition-metal- or lanthanide-based catalyst systems that catalyse such a highly reversible chain-growing process have been described. They are summarised and compared within this contribution.     

Size-exclusion chromatography (SEC) of branched polymers and polysaccharides

Branched polymers are among the most important polymers, ranging from polyolefins to polysaccharides. Branching plays a key role in the chain dynamics. It is thus very important for application properties such as mechanical and adhesive properties and digestibility. It also plays a key role in viscous properties, and thus in the mechanism of the separation of these polymers in size-exclusion chromatography (SEC). Critically reviewing the literature, particularly on SEC of polyolefins, polyacrylates and starch, we discuss common pitfalls but also highlight some unexplored possibilities to characterize branched polymers. The presence of a few long-chain branches has been shown to lead to a poor separation in SEC, as evidenced by multiple-detection SEC or multidimensional liquid chromatography. The local dispersity can be large in that case, and the accuracy of molecular weight determination achieved by current methods is poor, although hydrodynamic volume distributions offer alternatives. In contrast, highly branched polymers do not suffer from this extensive incomplete separation in terms of molecular weight.     

Single-step process to produce surface-functionalized polymeric nanoparticles

Nanoparticles (NPs) are a versatile medium for the localization of therapeutics to tumors and for cellular and tissue imaging. The ability to impart targeting capability or enhance cellular uptake is dependent in part on the presentation of relevant surface functionality, among other design parameters. Currently, the production of functionalized polymeric NPs requires the a priori synthesis of polymers bearing such functionality. Here we describe a process to produce functionalized polymeric NPs derived from nonfunctional polymers in a single step. This was achieved by tailoring the solvation of the polymer using a binary solvent system such that the addition of an aqueous phase rich in water-soluble polymer or polyelectrolytes results in the formation of NPs with the concomitant functionalization of NP surfaces with the polymeric moieties introduced into the aqueous phase. This strategy also allows for easy control over NP size independent of surface functionality. We have demonstrated that poly(lactic-co-glycolic acid) (PLGA) NPs bearing surface functionality as diverse as biological polysaccharides such as heparin, water-soluble ionic polymers, and poly(ethylene glycol) can be prepared under identical conditions in a single step, with surface coverage (mass %) ranging from 3 to >70%. We expect this novel process to enable complex surface engineering of NP chemistry that hitherto was impossible using existing approaches.     

静电纺丝理论模型的研究进展

静电纺丝技术是制备纳米纤维最直接、最有效的方法之一,其生产过程简单经济从而成为世界研究的热点。但是由于静电纺丝过程的复杂性,导致其研究一直处于实验阶段。如何完善数学、力学等理论模型是静电纺丝研究的基础问题,对静电纺丝工艺参数和设备制造有着重要的意义。本文论述了国内外静电纺丝理论模型的研究现状和进展,重点介绍了静电纺丝射流理论模型的研究及需要解决的理论问题,展望了静电纺丝理论模型研究的发展前景。     

Biopolymer microparticle and nanoparticle formation within a microfluidic device

This paper reports a novel microfluidic method for the production of cross-linked alginate microparticles and nanoparticles. We describe a continuous process relying on both thermodynamic and hydrodynamic factors to form microdroplets. A rapid cross-linking reaction thereafter allows solidification of the polymer droplets either within the microfluidic device or "off-chip" to form alginate micro- and nanoparticles. Monodisperse droplets are generated by extruding an aqueous alginate solution using an axisymmetric flow-focusing design. As they flow downstream in the channel, due to water and the continuous phase being partially miscible, the water diffuses very slowly out of the polymeric droplets into the transport fluid, which causes the shrinkage of the drops and the condensation of the polymer phase. The resulting size of the solid particles depends on the polymer concentration and the ensuing balance between the kinetics of the cross-linking reaction and the volume loss due to solvent diffusion. This work details both a single-step microfluidic technique for the formation of alginate microparticles of sizes ranging from 1 to 50 microm via near-equilibrium solvent diffusion within a microfluidic device and thereafter a two-step method, which was shown to generate biopolymer nanoparticles of sizes ranging from 10 to 300 nm. These novel methodologies are extremely flexible and can be extended to the preparation of micro- and nanoparticles from a wide range of single or mixed synthetic and biologically derived polymers.     

Comments on the Status and Future of Interfacial Polycondensation

Abstract

Interfacial polycondensation came into prominence in the 1950′s with the work of Schnell on polycarbonates, Conix on polyesters, and Wittbecker, Morgan and co-workers on polyurethanes, polyamides and other polymer classes. There were a few earlier patent references. The method has several variations and is a highly effective procedure for the rapid preparation of many polymers on a small scale. It is particularly appropriate for polymers which are thermally unstable or unmeltable, for use with volatile or unstable intermediates and for polymers with reactive functional groups. Literally thousands of polymers have been made by this process. There are a number of short-comings to the process, most of which can be overcome by adjustment of the polymerization conditions. Polycarbonates and aromatic polyamides are reported to be prepared commercially by stirred interfacial processes. Another application is the encapsulation of pesticides, inks, and other materials. As to the future, the processes are a basic part of the chemist's tool kit and will continue to be used in the laboratory for rapid syntheses and for those polymers which are not obtained as readily by other means. The basic tests of commercial use of these processes, as with any other process, will be attainment of results not available by other routes, economic considerations, and safety and environmental factors.     

The chemistry and complexes of small cyano anions

The chemistry of the anions dicyanamide and tricyanomethanide (dca and tcm, respectively) has produced a plethora of discoveries over the past few decades, particularly in relation to transition-metal coordination polymers with magnetic coupling. Over recent years there have been an increasing number of reports of heterofunctionalised cyano-containing anions, typically derivatives of dicyanomethanide. Our own group has been particularly concerned with the amide- and nitroso-functionalised anions carbamoyldicyanomethanide (cdm) and dicyanonitrosomethanide (dcnm), respectively. This feature article examines the fascinating diversity of materials and complexes that can be obtained using small cyano anions, ranging from coordination polymers to heterometallic clusters and hydrogen bonding networks. In particular, we focus on results from our own laboratories in the past few years. The magnetic properties of these materials are briefly discussed.     

Development and optimisation of a novel three‐way extraction technique based on a combination of Soxhlet extraction,membrane assisted solvent extraction and a molecularly imprinted polymer using sludge polycyclic aromatic hydrocarbons as model compounds

A novel technique that integrates extraction and clean‐up into a single step format is reported as part of the search for new sample preparation techniques in the analysis of persistent organic pollutants from complex samples. This was achieved by combining the extraction efficiency of the Soxhlet extractor, the selectivity of a size exclusion membrane and the specificity of a molecularly imprinted polymer for the extraction of polycyclic aromatic hydrocarbons from wastewater sludge followed by quantitation using gas chromatography with time‐of‐flight mass spectrometry. The approach is described as the Soxhlet extraction membrane‐assisted solvent extraction molecularly imprinted polymer technique. This technique was optimised for various parameters such as extraction solvent, reflux time and membrane acceptor phase. The applicability of the developed technique was optimised using a wastewater sludge certified reference material and then tested on real wastewater sludge samples. The method detection limits ranged from 0.14 to 12.86 ng/g with relative standard deviation values for the extraction of the 16 US‐EPA priority polycyclic aromatic hydrocarbons from wastewater sludge samples ranging from 0.78 to 18%. The extraction process was therefore reproducible and showed remarkable selectivity. The developed technique is a promising prospect that can be applied in the analysis of organic pollutants from complex solid samples.     

Controlling electrospun nanofiber morphology and mechanical properties using humidity

Electrospinning is a fiber spinning technique used to produce nanoscale polymeric fibers with superior interconnectivity and specific surface area. The fiber diameter, surface morphology, and mechanical strength are important properties of electrospun fibers that can be tuned for diverse applications. In this study, the authors investigate how the humidity during electrospinning influences these specific properties of the fiber mat. Using two previously uninvestigated polymers, poly(acrylonitrile) (PAN) and polysulfone (PSU) dissolved in N,N‐Dimethylformamide (DMF), experimental results show that increasing humidity during spinning causes an increase in fiber diameter and a decrease in mechanical strength. Moreover, surface features such as roughness or pores become evident when electrospinning in an atmosphere with high relative humidity (RH). However, PAN and PSU fibers are affected differently. PAN has a narrower distribution of fiber diameter regardless of the RH, whereas PSU has a wider and more bimodal distribution under high RH. In addition, PSU fibers spun at high humidity exhibit surface pores and higher specific surface area whereas PAN fibers exhibit an increased surface roughness but no visible pores. These fiber morphologies are caused by a complex interaction between the nonsolvent (water), the hygroscopic solvent (DMF), and the polymer. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Grafting from surfaces for "everyone": ARGET ATRP in the presence of air

Atom-transfer radical polymerization (ATRP) is one of the controlled/living radical polymerizations yielding well-defined (co)polymers, nanocomposites, molecular hybrids, and bioconjugates. ATRP, as in any radical process, has to be carried out in rigorously deoxygenated systems to prevent trapping of propagating radicals by oxygen. Herein, we report that ATRP can be performed in the presence of limited amount of air and with a very small (typically ppm) amount of copper catalyst together with an appropriate reducing agent. This technique has been successfully applied to the preparation of densely grafted polymer brushes, poly(n-butyl acrylate) homopolymer, and poly(n-butyl acrylate)-block-polystyrene copolymer from silicon wafers (0.4 chains/nm2). This simple new method of grafting well-defined polymers does not require any special equipment and can be carried out in vials or jars without deoxygenation. The grafting for "everyone" technique is especially useful for wafers and other large objects and may be also applied for molecular hybrids and bioconjugates.     

Separation and quantification of viral double-stranded RNA fragments by capillary electrophoresis in hydroxyethylcellulose polymer solutions

Capillary electrophoresis (CE) is an analytical technique widely utilized to resolve complex mixtures of nucleic acids. CE uses a variety of polymers in solution that act as a molecular sieve to separate nucleic acid fragments according to size. It has been shown previously that purified dsDNA can be resolved efficiently by solutions of hydroxyethylcellulose (HEC) polymer, providing a rapid and high resolution method of separation. We have applied this separation technique to viral double-stranded (ds) RNA segments derived from rotavirus process samples. HEC polymers of various molecular masses and concentrations were identified and compared for their ability to separate dsRNA based on the extent of expected polymer network formation. The HEC polymer exhibiting the most desirable separation characteristics was then used for subsequent optimization of various method parameters, such as, injection time, electric field strength, dye concentration and capillary equilibration. The optimized method was then applied to the quantification of genome concentration based on a representative segment of the rotavirus genome. This study demonstrated that purified viral dsRNA material of known concentration could be used to generate an external standard curve relating concentration to peak area. This standard curve was used to determine the concentration of unknown samples by interpolation. This novel RNA quantification assay is likely to be applicable to other types of virus, including those containing dsDNA.     

Hard X-ray phase imaging and tomography using a grating interferometer

An interferometric technique for hard X-rays is presented. It is based on two transmission gratings and a phase-stepping technique, and it provides separate radiographs of the phase and absorption profiles of bulk samples. Tomographic reconstruction yields quantitative three-dimensional maps of the X-ray refractive index and of the attenuation coefficient, with a spatial resolution down to a few microns. The method is mechanically robust, it requires little monochromaticity, and can be scaled up to large fields of view. These are important prerequisites for use with laboratory X-ray sources. Numerous applications ranging from wave front sensing to medical radiography are presently under investigation.