Shape memory polyester-based nanomaterials: cutting-edge advancements

ABSTRACT

Shape memory polymers have gained immense importance across technical industries ranging from aerospace and electronics to biomedical fields. This article presents state-of-the-art overview of versatile shape memory polyesters and derived nanocomposites. Shape memory polyesters such as polylactic acid, polyhydroxyalkanoate, polycarbonate, and polyester blends have been identified. Shape memory polyesters have also been reinforced with nanoreinforcements including fullerene, graphene, carbon nanotube, and polyhedral oligomeric silsesquioxane (POSS). Consequently, different groups of stimuli-responsive polyester nanocomposites have been discussed such as polyester/graphene, polyester/carbon nanotube, polyester/fullerene, and polyester/POSS. Future development of shape memory polyesters may reveal superior electrical, mechanical, and thermal performance for technical applications.     

Smart Poly (N-Isopropylacrylamide)-block-Poly (L-Lactide) Nanoparticles for Prolonged Release of Naltrexone

The authors synthesized core-shell smart nanoparticles composed of poly (N-isopropylacrylamide)-b-poly (L-lactide) (PNIPAAm–b-PLA) and developed for narcotic antagonists’ drug-delivery purpose. Micelle structure was verified by ¹H-NMR, FT-IR, and TEM. Effect of drug loading, polymer composition, and temperature on micelles morphology and diameter was investigated. Stimuli-responsive behaviors of these nanoparticles were determined using a three-factor full factorial experiment. Naltrexone was successfully incorporated into the PLA cores. By varying the PLA to PNIPAAm ratio, drug loading content, and release time were changed. Results suggest that smart micelles can be suitable for preparation of sustained release systems.     

Fluorescent Hydrogel–Textile Composite Material Synthesized by Photopolymerization

A fluorescent textile sensor and its capacities to detect pH changes in aqueous solutions have been reported. A new hydrogel-cotton fabric was obtained via surface initiated photopolymerization of 2-aminoethylmethacrylate hydrochloride, with N,N′-methylene-bis-acrylamide as a crosslinker, and fluorophore and modified eosin Y and N-methyldiethanolamine as photoinitiators. The synthesis of the modified eosin Y and a new 1,8-naphtalimide used as signal units in the hydrogel composite have been described. It has been found that the concentration of the photoinitiator affects the functional properties of the composite. pH variations influence the gel structure and this is transduced into fluorescence and color changes of the material.     

Synergistic Effect of PVDF-Coated PCL-TCP Scaffolds and Pulsed Electromagnetic Field on Osteogenesis

Bone exhibits piezoelectric properties. Thus, electrical stimulations such as pulsed electromagnetic fields (PEMFs) and stimuli-responsive piezoelectric properties of scaffolds have been investigated separately to evaluate their efficacy in supporting osteogenesis. However, current understanding of cells responding under the combined influence of PEMF and piezoelectric properties in scaffolds is still lacking. Therefore, in this study, we fabricated piezoelectric scaffolds by functionalization of polycaprolactone-tricalcium phosphate (PCL-TCP) films with a polyvinylidene fluoride (PVDF) coating that is self-polarized by a modified breath-figure technique. The osteoinductive properties of these PVDF-coated PCL-TCP films on MC3T3-E1 cells were studied under the stimulation of PEMF. Piezoelectric and ferroelectric characterization demonstrated that scaffolds with piezoelectric coefficient d₃₃ = −1.2 pC/N were obtained at a powder dissolution temperature of 100 °C and coating relative humidity (RH) of 56%. DNA quantification showed that cell proliferation was significantly enhanced by PEMF as low as 0.6 mT and 50 Hz. Hydroxyapatite staining showed that cell mineralization was significantly enhanced by incorporation of PVDF coating. Gene expression study showed that the combination of PEMF and PVDF coating promoted late osteogenic gene expression marker most significantly. Collectively, our results suggest that the synergistic effects of PEMF and piezoelectric scaffolds on osteogenesis provide a promising alternative strategy for electrically augmented osteoinduction. The piezoelectric response of PVDF by PEMF, which could provide mechanical strain, is particularly interesting as it could deliver local mechanical stimulation to osteogenic cells using PEMF.     

层层自组装多糖微胶囊的制备及其缓释型纯棉织物修饰应用

为制备生物相容性功能纺织材料,采用层层自组装技术将带有不同电荷的海藻酸钠(Alg)、壳聚糖(Chi)、透明质酸(HA)组装到碳酸钙模板上,利用乙二胺四乙酸(EDTA)去除模板,得到Alg/ Chi/ HA生物多糖微胶囊;利用超景深三维显微镜、扫描电子显微镜、红外光谱、综合热分析仪研究了微胶囊的形貌结构及热稳定性。结果表明:Alg/Chi/HA多糖微胶囊具有很好的中空结构及较强的稳定性;考察了多糖微胶囊吸附释放行为及其随pH值的变化规律,发现Alg/Chi/HA多糖微胶囊具有良好的pH值响应性;进一步将Alg/Chi/HA多糖微胶囊整理至棉纤维上,以制备缓释型功能纺织材料,为功能纺织品开发提供有益的实践经验与技术储备。     

Growth factor delivery-based tissue engineering: general approaches and a review of recent developments

The identification and production of recombinant morphogens and growth factors that play key roles in tissue regeneration have generated much enthusiasm and numerous clinical trials, but the results of many of these trials have been largely disappointing. Interestingly, the trials that have shown benefit all contain a common denominator, the presence of a material carrier, suggesting strongly that spatio-temporal control over the location and bioactivity of factors after introduction into the body is crucial to achieve tangible therapeutic effect. Sophisticated materials systems that regulate the biological presentation of growth factors represent an attractive new generation of therapeutic agents for the treatment of a wide variety of diseases. This review provides an overview of growth factor delivery in tissue engineering. Certain fundamental issues and design strategies relevant to the material carriers that are being actively pursued to address specific technical objectives are discussed. Recent progress highlights the importance of materials science and engineering in growth factor delivery approaches to regenerative medicine.     

Enzyme-Responsive Hydrogels as Potential Drug Delivery Systems—State of Knowledge and Future Prospects

Fast advances in polymer science have provided new hydrogels for applications in drug delivery. Among modern drug formulations, polymeric type stimuli-responsive hydrogels (SRHs), also called smart hydrogels, deserve special attention as they revealed to be a promising tool useful for a variety of pharmaceutical and biomedical applications. In fact, the basic feature of these systems is the ability to change their mechanical properties, swelling ability, hydrophilicity, or bioactive molecules permeability, which are influenced by various stimuli, particularly enzymes. Indeed, among a great number of SHRs, enzyme-responsive hydrogels (ERHs) gain much interest as they possess several potential biomedical applications (e.g., in controlled release, drug delivery, etc.). Such a new type of SHRs directly respond to many different enzymes even under mild conditions. Therefore, they show either reversible or irreversible enzyme-induced changes both in chemical and physical properties. This article reviews the state-of-the art in ERHs designed for controlled drug delivery systems (DDSs). Principal enzymes used for biomedical hydrogel preparation were presented and different ERHs were further characterized focusing mainly on glucose oxidase-, β-galactosidase- and metalloproteinases-based catalyzed reactions. Additionally, strategies employed to produce ERHs were described. The current state of knowledge and the discussion were made on successful applications and prospects for further development of effective methods used to obtain ERH as DDSs.     

Comonomer effect: Switching the lower critical solution temperature to upper critical solution temperature in thermo-pH sensitive binary graft copolymers

Hydrophilic biocompatible surfaces can be obtained by grafting stimuli-sensitive polymers onto commercially available medical devices. Thermo and pH-responsive polymers are two of the most studied materials due to their potential application as drug delivery systems. Poly(N-vinylcaprolactam) has a lower critical solution temperature (LCST) near to physiological temperature. However, when it is grafted with pH-sensitive moieties its LCST it is affected undergoing remarkable displacements. We studied the effect of acrylic acid (AAc), 4-vinylpyridine (4VP), and 1-vinylimidazole (Vim) on the LCST of N-vinylcaprolactam (NVCL) grafted onto silicone rubber (SR), and SR-g-NVCL (32.5 °C). The binary graft copolymers were obtained by ionizing grafting radiation using the simultaneous technique; the samples were characterized by Fourier transform infrared attenuated total reflectance (FTIR-ATR), cross-polarization magic angle spinning nuclear magnetic resonance (CP/MAS ¹³C-NMR), and thermogravimetrical analysis (TGA). LCST value was dramatically affected by the comonomer content; even it was observed the switching from LCST to upper critical solution temperature (UCST) for (SR-g-NVCL)-g-AAc and (SR-g-NVCL)-g-4VP samples. The observed behavior is rarely reported for binary graft copolymers. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48170.     

光定域化蓝相软晶格结构的光学应用

实验利用表面光取向技术控制蓝相晶格的有序生长,将光定域化取向与分子自组装相结合。通过对基板表面进行交替的取向/非取向控制,平面内获得周期排列的微结构,使蓝相图形化结构的反射光强度在空间上形成周期性调制,同时设计制备了振幅型衍射器件;通过对基板表面做正交取向方向交替排列的微结构,使蓝相图形化结构的反射光相位在空间上形成周期性调制,设计制备了相位型衍射器件。这两类衍射器件均具有对入射光的波段选择性,即只有当入射光的波长局域在蓝相的反射带时才会呈现衍射效应。蓝相液晶软物质的特性又赋予它在电场下可调谐的波段选择性,即反射带位置随电场的增加发生红移从532nm到610nm,电场撤除则回复到初始状态。同时,借助于光取向材料的光可擦写特性,蓝相晶格的取向微结构能够重复的擦写与重构,从而实现不同衍射器件乃至不同衍射调制方式的转换。