Functional polymeric micro-/nanofibers have emerged as promising materials for the construction of structures potentially useful in biomedical fields. Among all kinds of technologies to produce polymer fibers, spinning methods have gained considerable attention. Herein, we provide a recent review on advances in the design of micro-and nanofibrous platforms via spinning techniques for biomedical applications. Specifically, we emphasize electrospinning, solution blow spinning, centrifugal spinning, and microfluidic spinning approaches. We first introduce the fundamentals of these spinning methods and then highlight the potential biomedical applications of such micro-and nanostructured fibers for drug delivery, tissue engineering, regenerative medicine, disease modeling, and sensing/biosensing. Finally, we outline the current challenges and future perspectives of spinning techniques for the practical applications of polymer fibers in the biomedical field.
In this paper, chitosan was reacted with monochloroacetic acid under alkaline conditions to prepare carboxymethyl chitosan. A 2(3) full-factorial central composite design was applied to evaluate the effect of molar ratio sodium hydroxide (NaOH)/Chitosan (Ch), time and molar ratio monochloroacetic acid (MCA)/Chitosan (Ch) on the reaction yield and on the characteristics of carboxymethyl chitosan such as average degree of substitution (DS¯) and solubility. An optimization strategy based on response surface methodology was used together with the desirability function approach to optimize this process. The occurrence of carboxymethylation was evidenced by FTIR and (1)H NMR spectroscopy. The optimum conditions for carboxymethylation process were found to be 12.4, 10.6h and 5 for molar ratio sodium hydroxide (NaOH)/Chitosan (Ch), time and molar ratio monochloroacetic acid (MCA)/Chitosan (Ch), respectively. Under these optimal conditions, it was possible to obtain carboxymethyl chitosan with DS¯ of 1.86 and solubility of 99.6%. X-ray diffraction and thermogravimetry analysis showed that crystallinity and thermal stability of derivatives was lower than chitosan and decreased with increase of DS¯.
Cellulose was extracted from brewer's spent grain (BSG) by alkaline and bleaching treatments. The extracted cellulose was used in the preparation of carboxymethyl cellulose (CMC) by reaction with monochloroacetic acid in alkaline medium with the use of a microwave reactor. A full-factorial 2(3) central composite design was applied in order to evaluate how parameters of carboxymethylation process such as reaction time, amount of monochloroacetic acid and reaction temperature affect the average degree of substitution (DS) of the cellulose derivative. An optimization strategy based on response surface methodology has been used for this process. The optimized conditions to yield CMC with the highest DS of 1.46 follow: 5g of monochloroacetic acid per gram of cellulose, reaction time of 7.5min and temperature of 70°C. This work demonstrated the feasibility of a fast and efficient microwave-assisted method to synthesize carboxymethyl cellulose from cellulose isolated of brewer's spent grain.
Blend solutions of poly(ε-caprolactone) (PCL) and N-(2-hydroxy)-propyl-3-trimethylammonium chitosan chloride (QCh) were successfully electrospun. The weight ratio PCL/QCh ranged in the interval 95/5-70/30 while two QCh samples were used, namely QCh1 (DQ¯ = 47.3%; DPv¯ = 2218) and QCh2 (DQ¯ = 71.1%; DPv¯ = 1427). According to the characteristics of QCh derivative and to the QCh content on the resulting PCL/QCh nonwoven, the nanofibers displayed different average diameter (175 nm-415 nm), and the nonwovens exhibited variable porosity (57.0%-81.6%), swelling capacity (175%-425%) and water vapor transmission rate (1600 g m 24 h-2500 g m 24 h). The surface hydrophilicity of nonwovens increases with increasing QCh content, favoring fibroblast (HDFn) adhesion and spreading. Tensile tests revealed that the nonwovens present a good balance between elasticity and strength under both dry and hydrated state. Results indicate that the PCL/QCh electrospun nonwovens are new nanofibers-based biomaterials potentially useful as wound dressings.
A quaternized derivative of chitosan, namely N-(2-hydroxy)-propyl-3-trimethylammonium chitosan chloride (QCh), was synthesized by reacting glycidyltrimethylammonium chloride (GTMAC) and chitosan (Ch) in acid medium under microwave irradiation. Full-factorial 2(3) central composite design and response surface methodology (RSM) were applied to evaluate the effects of molar ratio GTMAC/Ch, reaction time and temperature on the reaction yield, average degree of quaternization (DQ) and intrinsic viscosity ([η]) of QCh. The molar ratio GTMAC/Ch was the most important factor affecting the response variables and RSM results showed that highly substituted QCh (DQ = 71.1%) was produced at high yield (164%) when the reaction was carried out for 30min. at 85°C by using molar ratio GTMAC/Ch 6/1. Results showed that microwave-assisted synthesis is much faster (≤30min.) as compared to conventional reaction procedures (>4h) carried out in similar conditions except for the use of microwave irradiation.
Herein, we developed honeycomb-like scaffolds by combining poly (d, l-lactic acid) (PDLLA) with a high amount of graphene/multi-walled carbon nanotube oxides (MWCNTO-GO, 50% w/w). From pristine multi-walled carbon nanotubes (MWCNT) powders, we produced MWCNTO-GO via oxygen plasma etching (OPE), which promoted their exfoliation and oxidation. Initially, we evaluated PDLLA and PDLLA/MWCNTO-GO scaffolds for tensile strength tests, cell adhesion and cell viability (with osteoblast-like MG-63 cells), alkaline phosphatase (ALP, a marker of osteoblast differentiation) activity and mineralized nodule formation. In vivo tests were carried out using PDLLA and PDLLA/MWCNTO-GO scaffolds as fillers for critical defects in the tibia of rats. MWCNTO-GO loading was responsible for decreasing the tensile strength and elongation-at-break of PDLLA scaffolds, although the high mechanical performance observed (~600MPa) assures their application in bone tissue regeneration. In vitro results showed that the scaffolds were not cytotoxic and allowed for osteoblast-like cell interactions and the formation of mineralized matrix nodules. Furthermore, MG-63 cells grown on PDLLA/MWCNTO-GO significantly enhanced osteoblast ALP activity compared to controls (cells alone), while the PDLLA group showed similar ALP activity when compared to controls and PDLLA/MWCNTO-GO. Most impressively, in vivo tests suggested that compared to PDLLA scaffolds, PDLLA/MWCNTO-GO had a superior influence on bone cell activity, promoting greater new bone formation. In summary, the results of this study highlighted that this novel scaffold (MWCNTO-GO, 50% w/w) is a promising alternative for bone tissue regeneration and, thus, should be further studied.
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