Tuning the Properties of Shape-Memory Polyurethanes via the Nature of the Polyester Switching Segment

Shape-memory polymers that contain semicrystalline domains with a melting temperature (T_m) above and a crystallization temperature (T_c) below physiological temperature as fixing elements are useful to create medical devices or implants that can be custom-shaped inside or around the body. With the goal to expand the palette of materials that exhibit such properties, a series of segmented polyurethanes (PUs) containing different crystallizable polyester segments is investigated. The nature of the polyester, its molecular weight, and the ratio of hard to soft segments are systematically varied and the effect on the mechanical, thermal, and shape-memory properties of the various PUs is studied. Poly(1,12-dodecylene dodecanoate), poly(1,6-hexylene dodecanoate), and poly(ethylene sebacate) (PES) are selected as crystallizable polyester segments. The PES-based PUs display T_c values of 25–35 °C and a T_m of 60–63 °C, and allow good shape fixing at 37 °C.     

Biomedical Applications of Magnetically Functionalized Organic/Inorganic Hybrid Nanofibers

Nanofibers are one-dimensional nanomaterial in fiber form with diameter less than 1 µm and an aspect ratio (length/diameter) larger than 100:1. Among the different types of nanoparticle-loaded nanofiber systems, nanofibers loaded with magnetic nanoparticles have gained much attention from biomedical scientists due to a synergistic effect obtained from the unique properties of both the nanofibers and magnetic nanoparticles. These magnetic nanoparticle-encapsulated or -embedded nanofiber systems can be used not only for imaging purposes but also for therapy. In this review, we focused on recent advances in nanofibers loaded with magnetic nanoparticles, their biomedical applications, and future trends in the application of these nanofibers.     

Electrospun Nanofibers: Materials,Synthesis Parameters,and Their Role in Sensing Applications

Since the last decade, electrospinning is garnering more attention in the scientific research community, industries, applications like sensing (glucose, H₂O₂, dopamine, ascorbic acid, uric acid, neurotransmitter, etc.), biomedical applications (wound dressing, wound healing, skin, nerve, bone tissue engineering, and drug delivery systems), water treatment, energy harvesting, and storage applications. This review paper provides a brief overview of the electrospinning method, history of the electrospinning, factors affecting the electrospun nanofibers, and their morphology with different materials and composites (metals, metal oxides, 2D material, polymers and copolymers, carbon-based materials, etc.) used in the electrospinning technique with optical spinning parameters. Moreover, this paper deliberates the application of electrospun nanofibers and fibrous mats for sensing (electrochemical, optical, fluorescence, colorimetric, mechanical, photoelectric, mass sensitive change, resistive, ultrasensitive, etc.) in most illustrative representations. In the end, the challenges, opportunities of the electrospun nanofibers, and new direction for future progress are also discussed.     

静电纺再生丝素纳米纤维的结构与性能

静电纺丝获得的丝素纳米级纤维可作为细胞培养支架,用于纺丝工艺及后处理能改变丝素微细结构,影响其水溶性和力学性能。本文采用XRD、FTIR、固态13CNMR和DSC研究了不同工艺下丝素纳米纤维及经甲醇处理后的微细结构,比较了不同微细结构下的水溶性和力学性能。结果表明,电纺丝的微细结构受纺丝工艺影响,高电压、纺丝液中丝素质量分数大时纺得的电纺丝结晶度高,经甲醇处理后,β化程度提高;w(丝素)=11%、15%时制备的电纺丝断裂强度分别为8.5、11.9 cN/mm;w(丝素)=11%、19%,水溶性由51.2%下降到43.3%;w(丝素)=19%、电压32 kV制得的电纺丝甲醇处理前后水溶性从43.3%下降到6.6%,说明丝素纳米纤维结晶度提高,强度增加、水溶性下降,满足了细胞支架的要求。     

Thiol-ene Reaction as Reversible Covalent Bond for the Design of Shape-Memory Polymers

Besides a stable phase, shape-memory polymers require an additional switchable moiety. In addition to thermal transitions and supramolecular interactions, these units can also be based on covalent bonds. Herein, the use of the reversible thiol-ene reaction as reversible cross-linker for the design of shape-memory polymers is demonstrated. A facile route to polymer networks with a thiol-ene acceptor and a comonomer (butyl methacrylate or 2-ethylhexyl methacrylate) cross-linked by dithiols is introduced. The thermal and mechanical properties of the resulting polymers are characterized in detail. Hereby, the polymers feature excellent shape-memory behavior with fixity and recovery rates above 90%. This study shows that the thiol-ene cross-linker can function as both, the stable and the switchable structural moiety rendering the usage of a covalent cross-linker unnecessary. This partial reversibility can also be proven by temperature-depending Raman spectroscopy.     

生物降解性形状记忆聚合物及其在生物医学工程方面的应用

综述了生物降解性形状记忆聚合物如聚乳酸、聚己内酯、聚氨酯等的最新研究进展及其形状记忆机理。聚乳酸、聚己内酯和聚氨酯分别是通过相态转化、物理或化学交联以及相分离来实现形状记忆特性的。着重讨论了生物降解性形状记忆聚合物在生物医学工程领域的应用研究现状,详述了其在药物缓释、医疗器械、骨组织以及手术缝合线方面的医学应用,并展望了生物降解性形状记忆聚合物今后的发展前景。     

NVCL-Based Hydrogels and Composites for Biomedical Applications: Progress in the Last Ten Years

Hydrogels consist of three-dimensionally crosslinked polymeric chains, are hydrophilic, have the ability to absorb other molecules in their structure and are relatively easy to obtain. However, in order to improve some of their properties, usually mechanical, or to provide them with some physical, chemical or biological characteristics, hydrogels have been synthesized combined with other synthetic or natural polymers, filled with inorganic nanoparticles, metals, and even polymeric nanoparticles, giving rise to composite hydrogels. In general, different types of hydrogels have been synthesized; however, in this review, we refer to those obtained from the thermosensitive polymer poly(N-vinylcaprolactam) (PNVCL) and we focus on the definition, properties, synthesis techniques, nanomaterials used as fillers in composites and mainly applications of PNVCL-based hydrogels in the biomedical area. This type of material has great potential in biomedical applications such as drug delivery systems, tissue engineering, as antimicrobials and in diagnostic and bioimaging.     

Fabrication of Zein-Based Fibrous Scaffolds for Biomedical Applications—A Review

Zein, which accounts for around 80% of the total protein composition in corn, is a biocompatible and biodegradable substance derived from renewable sources. Although insoluble in water, its amphiphilic characteristics are utilized to generate nanoparticles, nanofibers, microparticles, and even films. Numerous recent studies have demonstrated the potential of zein as a prospective biomaterial to develop fibrous scaffolds for biomedical functions owing to its biocompatibility, fibrous formation, and encapsulating qualities. Fabrication of zein-based fibrous scaffolds for biomedical applications is achieved by a wide variety of techniques, including electrospinning, wet spinning, freeze drying, and additive manufacturing. This article overviews current advancements in manufacturing techniques for zein-based fibrous scaffolds. In addition, it summarizes the most recent biomedical applications and research activities utilizing zein-based fibrous scaffolds. Overall, zein is proposed as a potential biomaterial for the production of fibrous scaffolds that stimulate cell adhesion and proliferation in a number of exciting biomedical applications due to its biodegradability, biocompatibility, and other unique features related to its structure.     

Biological,Chemical, and Electronic Applications of Nanofibers

With their high‐surface‐to‐volume ratio, nanofibers have been postulated to increase interactions between nanofibrous materials and targeted substrates, which are helpful to overcome many obstacles and enhance the efficiency in a diverse number of applications. Over the past decade, many studies have been published on the fabrication of nanofibers and their applications in various fields. In this review, novel biological, chemical, and electrical characteristics of nanofibers as well as their recent status and achievements in medicine, chemistry, and electronics are analyzed. It is found that nanofibers can induce fast regeneration of many tissues/organs in medical applications and improve the efficiency of many chemical and electronics applications.

     

静电纺丝聚合物加工技术及其应用

电纺丝是一种使带电荷的聚合物溶液或熔体在静电场中射流来制备聚合物超细纤维的加工方法。电纺纤维织物的空隙率高、比表面积大、构架织物的直径处于纳米级别。综述了电纺丝技术的发展以及过程参数对电纺丝织物的影响。介绍了最新研究的许多新颖纤维品种、它们的微观形貌、制备方法以及不同纳米纤维在不同领域中的应用。     

Anisotropy Effects in the Shape-Memory Performance of Polymer Foams

Isotropic and anisotropic shape-memory polymer foams are prepared by supercritical carbon dioxide foaming from a multiblock copolymer (PDLCL) consisting of poly(ω-pentadecalactone) and poly(ε-caprolactone) segments. Analysis by micro-computed tomography reveals for the anisotropic PDLCL foam cells a high shape anisotropy ratio of R = 1.72 ± 0.62 with a corresponding Young's compression moduli ratio between longitudinal and transversal direction of 4.3. The experimental compression data in the linear elastic range can be well described by the anisotropic open foam model of Gibson and Ashby. A micro-morphological analysis for single pores using scanning electron microscopy images permits the correlation between the macroscopic stress-compression behavior and microscale structural changes.     

钒掺杂TiO2纳米纤维的制备及其光催化性能

以体积比为1∶2的N,N-二甲基甲酰胺和丙酮为溶剂、钛酸四丁酯[Ti(OiPr)4]和氯化钒[VC13]为前驱体、醋酸纤维素(CA)为模板,采用静电纺丝法制备了V-TiO2/醋酸纤维素纳米纤维.将V-TiO2/醋酸纤维素纳米纤维用0.1 mol/L NaOH/乙醇溶液水解得到V-TiO2/纤维素纳米纤维.在500℃煅烧V-TiO2/纤维素纳米纤维5h,得到直径为(200±53)nm的V-TiO2纳米纤维.利用扫描电子显微镜、X射线粉末衍射仪和紫外-可见漫反射光谱对纤维形貌、物相和结构进行了表征.以染料罗丹明B为目标降解物考察了纤维的光催化活性.结果表明:掺杂少量V后,TiO2对紫外光的最大吸收峰和吸收带边发生了红移,说明V-TiO2对光响应更宽、光利用率更高.TiO2和V-TiO2纳米纤维在20min内对罗丹明B的降解率分别为67％和77％.     

Design and characterization of pH stimuli-responsive nanofiber drug delivery system: The promising targeted carriers for tumor therapy

New carrier platforms have been designed for an electrospun pyridinium calixarene nanofiber for controlled drug delivery. First, 5,11,17,23-tetra-tert-butyl-25,27-bis(3-aminomethyl-pyridineamido)-26,28-dihydroxycalix[4]arene (3-AMP) scaffold was produced by electrospinning. AMP scaffold was modified by human serum albumin (HSA), folic acid (FA), and glutathione (GSH). Doxorubicin (DOX) was loaded to surfaces of the AMP, AMP-HSA, AMP-HSA-FA, and AMP-HSA-GSH nanofibers by using DOX solution in different buffers with, 2.2, 4.0, 6.0, and 7.4 pH. The release studies DOX from four different nanofibers was also done in a various amount microenviroments by changing pH values. The loading and release amount of DOX was estimated from the calibration curve drawn at 480 and 560 nm of excitation and emission wavelengths by using a fluorescence spectrophotometer. The loading studies were confirmed by Fourier transforms infrared, atomic force microscopy, transmission electron microscopy, scanning electron microscope, and energy-dispersive X-ray (EDX) analysis.     

高分子纳米纤维表面压痕及其分形特征研究

采用静电纺丝法制备了纳米级高分子聚己酸内酯(PCL)纤维,通过扫描电子显微镜和原子力显微镜观察了聚己酸内酯纳米纤维的表面结构和微观特征,并通过原子力显微镜对纤维表面进行纳米压痕实验。实验发现随着压痕深度的变小,纤维的弹性模量呈现增大的趋势。利用统计分形理论对高分子纤维表面压痕过程进行建模,通过拟合实验曲线得到了材料的分形参数,该模型可以很好的模拟高分子纤维材料在纳米压痕实验中的尺寸效应。     

Engineering of Vaginal Lactobacilli to Express Fluorescent Proteins Enables the Analysis of Their Mixture in Nanofibers

Lactobacilli are a promising natural tool against vaginal dysbiosis and infections. However, new local delivery systems and additional knowledge about their distribution and mechanism of action would contribute to the development of effective medicine. This will be facilitated by the introduction of the techniques for effective, inexpensive, and real-time tracking of these probiotics following their release. Here, we engineered three model vaginal lactobacilli (Lactobacillus crispatus ATCC 33820, Lactobacillus gasseri ATCC 33323, and Lactobacillus jensenii ATCC 25258) and a control Lactobacillus plantarum ATCC 8014 to express fluorescent proteins with different spectral properties, including infrared fluorescent protein (IRFP), green fluorescent protein (GFP), red fluorescent protein (mCherry), and blue fluorescent protein (mTagBFP2). The expression of these fluorescent proteins differed between the Lactobacillus species and enabled quantification and discrimination between lactobacilli, with the longer wavelength fluorescent proteins showing superior resolving power. Each Lactobacillus strain was labeled with an individual fluorescent protein and incorporated into poly (ethylene oxide) nanofibers using electrospinning, as confirmed by fluorescence and scanning electron microscopy. The lactobacilli retained their fluorescence in nanofibers, as well as after nanofiber dissolution. To summarize, vaginal lactobacilli were incorporated into electrospun nanofibers to provide a potential solid vaginal delivery system, and the fluorescent proteins were introduced to distinguish between them and allow their tracking in the future probiotic-delivery studies.     

Enhancement of β‐Phase Crystalline Structure and Piezoelectric Properties of Flexible PVDF/Ionic Liquid Surfactant Composite Nanofibers for Potential Application in Sensing and Self‐Powering

Polyvinylidene fluoride (PVDF) is a piezo‐polymer which among its crystalline phases, the β‐phase has been researched for the improvement of piezoelectric properties. In this study, to improve the β‐phase contents and thereby the piezoelectric response of the polymer, the effect of adding self‐synthesized ionic liquid surfactant (ILS) in PVDF nanofibers is studied. This material is added in different weight percentages into the PVDF solution and the nanofibers are produced by electrospinning to prepare active piezoelectric thin layers. SEM, XRD, FTIR, and piezo‐tests are employed for assessing the effect of the ILS on the enhancement of β‐phase in electrospun nanofibers and their piezoelectric performance. The results indicate ≈98.6% β‐phase formation in the sample containing 4 wt% ILS and in comparison with the pure nanofibers, the output voltage and its power density are improved 186.9% and 275%, respectively. Considering the results, it is suggested that the ILS can improve the piezoelectric response of the polymer in the fabricated structure by simple mixing in solution compared to other additives.     

Green fabrication route of robust,biodegradable silk sericin and poly(vinyl alcohol) nanofibrous scaffolds

Silk sericin (SS) has been extensively used to fabricate scaffolds for tissue engineering. However, due to its inferior mechanical properties, it has been found to be a poor choice of material when being electrospun into nanofibrous scaffolds. Here, SS has been combined with poly(vinyl alcohol) (PVA) and electrospun to create scaffolds with enhanced physical properties. Crucially, these SS/PVA nanofibrous scaffolds were created using only distilled water as a solvent with no added crosslinker in an environmentally friendly process. Temperature has been shown to have a marked effect on the formation of the SS sol–gel transition and thus influence the final formation of fibers. Heating the spinning solutions to 70 °C delivered nanofibers with enhanced morphology, water stability and mechanical properties. This is due to the transition of SS from β‐sheets into random coils that enables enhanced molecular interactions between SS and PVA. The most applicable SS/PVA weight ratios for the formation of nanofibers with the desired properties were found to be 7.5/1.5 and 10.0/1.5. The fibers had diameters ranging from 60 to 500 nm, where higher PVA and SS concentrations promoted larger diameters. The crystallinity within the fibers could be controlled by manipulation of the balance between PVA and SS loadings. In vitro degradation (in phosphate buffer solution, pH 7.4 at 37 °C) was 30–50% within 42 days and fibers were shown to be nontoxic to skin fibroblast cells. This work demonstrates a new green route for incorporating SS into nanofibrous fabrics, with potential use in biomedical applications. © 2019 Society of Chemical Industry     

Role of rheology on the formation of Nanofibers from pectin and polyethylene oxide blends

Characterizing the parameters critical to the prediction of a successful electrospinning process from solution properties is essential, yet, not easy in the case of biopolymers. In this study, we attempted to present a broad perspective by simultaneously evaluating the effect of eight different parameters, namely zero shear viscosity, tip viscosity, elastic modulus, phase angle, cohesive energy, pH, conductivity, and surface tension, on the formation of smooth pectin nanofibers. Our results showed that (1) the viscosity of the solution is not an indication of jet formation, but once the jet is formed, high zero shear viscosity and high tip viscosity are required to maintain a dominant whipping instability for smooth nanofiber formation and (2) while evaluating the elasticity of the spinning solutions, comparing only the elastic modulus values would be misleading, since low phase angle values are also necessary for pectin solutions to be electrospun into nonbeaded fibers. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48294.     

静电纺丝制备苯乙烯马来酸酐共聚物纳米纤维及其固定化b-D-半乳糖苷酶

采用静电纺丝技术制备苯乙烯-马来酸酐共聚物纳米纤维,最佳电纺条件为：聚合物浓度0.35 g/mL、针尖到接收板距离25 cm、电纺液流量250 mL/h、电压21 kV. 该条件下获得了直径约300 nm且分布均一的纳米纤维. 利用该纳米纤维固定b-D-半乳糖苷酶,固定化反应的最适pH值为4.0,此时酶负载量为(15.1±0.5) mg/g. 固定化酶催化2-硝基苯酚-b-D-半乳吡喃糖苷水解反应的米氏常数Km=2.7 mmol/L,略大于游离酶的Km值(2.2 mmol/L);最大反应速率Vmax为97.2 mmol/(min×mg),为游离酶的47.8%. 固定化酶在37℃下重复操作21次后活性损失仅为15%. 在连续搅拌式反应器中将固定化酶用于催化乳糖的水解反应,连续使用17 d仍能稳定运行.     

Fabrication and Thermal Dissipation Properties of Carbon Nanofibers Derived from Electrospun Poly(Amic Acid) Carboxylate Salt Nanofibers

Polyimides (PIs) possess excellent mechanical properties, thermal stability, and chemical resistance and can be converted to carbon materials by thermal carbonization. The preparation of carbon nanomaterials by carbonizing PI‐based nanomaterials, however, has been less studied. In this work, the fabrication of PI nanofibers is investigated using electrospinning and their transformation to carbon nanofibers. Poly(amic acid) carboxylate salts (PAASs) solutions are first electrospun to form PAAS nanofibers. After the imidization and carbonization processes, PI and carbon nanofibers can then be obtained, respectively. The Raman spectra reveal that the carbon nanofibers are partially graphitized by the carbonization process. The diameters of the PI nanofibers are observed to be smaller than those of the PAAS nanofibers because of the formation of the more densely packed structures after the imidization processes; the diameters of the carbon nanofibers remain similar to those of the PI nanofibers after the carbonization process. The thermal dissipation behaviors of the PI and carbon nanofibers are also examined. The infrared images indicate that the transfer rates of thermal energy for the carbon nanofibers are higher than those for the PI nanofibers, due to the better thermal conductivity of carbon caused by the covalent sp² bonding between carbon atoms.