pH-responsive nanofibers with controlled drug release properties

Cataloged from PDF version of article.Smart polymers and nanofibers are potentially intriguing materials for controlled release of bioactive agents. This work describes a new class of pH responsive nanofibers for drug delivery systems with controlled release properties. Initially, poly(4-vinylbenzoic acid-co-(ar-vinylbenzyl) trimethylammonium chloride) [poly(VBA-co-VBTAC)] was synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. Then, ciprofloxacin was chosen as the model drug for the release study and encapsulated into pH-responsive polymeric carriers of poly(VBA-co-VBTAC) nanofibers via electrospinning. The morphology of the electrospun nanofibers was examined by scanning electron microscopy (SEM). The structural characteristics of the pH responsive nanofibers were investigated by Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The release measurements of ciprofloxacin from pH responsive nanofibers were also performed by high-performance liquid chromatography (HPLC) analysis. To show the pH sensitivity of these nanofibers, the release profile of ciprofloxacin was examined under acidic, neutral and basic conditions. The results indicate that pH responsive nanofibers can serve as effective drug carriers since the release of ciprofloxacin could be controlled by changing the pH of the environment, and therefore these drug loaded pH-responsive nanofibers might have potential applications in the biomedical field. This journal is © The Royal Society of Chemistry

Antioxidant activity and photostability of α-tocopherol/β-cyclodextrin inclusion complex encapsulated electrospun polycaprolactone nanofibers

Cyclodextrin inclusion complexes (CD-ICs) can be encapsulated into electrospun nanofibers in order to achieve delivery systems having high surface area and highly porous nanofibrous structures. In this study, a well-known antioxidant molecule, α-tocopherol (α-TC) (vitamin E) was chosen as an active agent for inclusion complexation with β-cyclodextrin. Polycaprolactone (PCL) nanofibers encapsulating α-tocopherol/β-cyclodextrin inclusion complex (α-TC/β-CD-IC) which has high antioxidant activity and photostability was produced via electrospinning (PCL/α-TC/β-CD-IC-NF). The formation of α-TC/β-CD-IC was confirmed by XRD. Phase solubility studies showed An-type complex formation between α-TC and β-CD. SEM revealed that bead-free nanofibers were successfully produced from PCL/α-TC/β-CD-IC system. PCL nanofibers encapsulating α-TC without CD-IC was also produced for comparison (PCL/α-TC-NF). Antioxidant test results showed that PCL/α-TC/β-CD-IC-NF had higher antioxidant activity as compared to PCL/α-TC-NF in methanol:water (1:1) system due to the stabilization and solubility increment of α-TC in the cavity of β-CD. PCL/α-TC/β-CD-IC-NF was more stable against UV-light when compared to PCL/α-TC-NF due to the presence of inclusion complexation. In brief, PCL/α-TC/β-CD-IC-NF with the advantages of having nanofibrous structure and encapsulating CD-ICs, may serve as a novel route for administration of α-TC due to its higher antioxidant activity and better UV-light stability. © 2016 Elsevier Ltd. All rights reserved

Core-shell nanofibers of curcumin/cyclodextrin inclusion complex and polylactic acid: Enhanced water solubility and slow release of curcumin

Core-shell nanofibers were designed via electrospinning using inclusion complex (IC) of model hydrophobic drug (curcumin, CUR) with cyclodextrin (CD) in the core and polymer (polylactic acid, PLA) in the shell (cCUR/HPβCD-IC-sPLA-NF). CD-IC of CUR and HPβCD was formed at 1:2 molar ratio. The successful formation of core-shell nanofibers was revealed by TEM and CLSM images. cCUR/HPβCD-IC-sPLA-NF released CUR slowly but much more in total than PLA-CUR-NF at pH 1 and pH 7.4 due to the restriction of CUR in the core of nanofibers and solubility improvement shown in phase solubility diagram, respectively. Improved antioxidant activity of cCUR/HPβCD-IC-sPLA-NF in methanol:water (1:1) is related with the solubility enhancement achieved in water based system. The slow reaction of cCUR/HPβCD-IC-sPLA-NF in methanol is associated with the shell inhibiting the quick release of CUR. On the other hand, cCUR/HPβCD-IC-sPLA-NF exhibited slightly higher rate of antioxidant activity than PLA-CUR-NF in methanol:water (1:1) owing to the enhanced solubility. To conclude, slow release of CUR was achieved by core-shell nanofiber structure and inclusion complexation of CUR with HPβCD provides high solubility. Briefly, electrospinning of core-shell nanofibers with CD-IC core could offer slow release of drugs as well as solubility enhancement for hydrophobic drugs. © 2017 Elsevier B.V

Polylactic acid (PLA)/Silver-NP/VitaminE bionanocomposite electrospun nanofibers with antibacterial and antioxidant activity

Cataloged from PDF version of article.The antibacterial property of silver nanoparticles (Ag-NPs) and the antioxidant activity of Vitamin E have been combined by incorporation of these two active components within polylactic acid (PLA) nanofibers via electrospinning (PLA/Ag-NP/VitaminE nanofibers). The morphological and structural characterizations of PLA/Ag-NP/VitaminE nanofibers were performed by Scanning Electron Microscopy (SEM), Transmission Electron Microscopy and X-ray diffraction. The average fiber diameter was 140 ± 60 nm, and the size of the Ag-NP was 2.7 ± 1.5 nm. PLA/Ag-NP/VitaminE nanofibers inhibited growth of Escherichia coli, Listeria monocytogenes and Salmonella typhymurium up to 100 %. The amount of released Ag ions from the nanofibers immersed in aqueous solution was determined by Inductively Coupled Plasma Mass Spectrometry, and it has been observed that the release of Ag ions was kept approximately constant after 10 days of immersion. The antioxidant activity of PLA/Ag-NP/VitaminE nanofibers was evaluated according to DPPH (2,2-diphenyl-1-picrylhydrazyl) method and determined as 94 %. The results of the tests on fresh apple and apple juice indicated that the PLA/Ag/VitaminE nanofiber membrane actively reduced the polyphenol oxidase activity. The multifunctional electrospun PLA nanofibers incorporating Ag-NP and Vitamin E may be quite applicable in food packaging due to the extremely large surface area of nanofibers along with antibacterial and antioxidant activities. These materials could find application in food industry as a potential preservative packaging for fruits and juices. © 2014, Springer Science+Business Media Dordrecht

Fluorescent Si QD decoration onto a flexible polymeric electrospun nanofibrous mat for the colorimetric sensing of TNT

UV range light was used for the facile, effective and large-scale synthesis of visible light emitting, surface-protected silicon quantum dots (Si QDs) starting from an amine-functionalized alkoxy silane precursor. Within mild and easy hydrolysis/condensation environments, the use of an amine-functionalized precursor together with a reducing agent resulted in a bright visible green light that could be used for fluorescent analytical detection systems. Visible light emitting Si QDs were investigated and it was found that their emission character depends on the illumination time, hydrolysis/condensation conditions and pretreatments for the silane coupling agents. A Nylon 6,6 electrospun nanofibrous mat was selected as a substrate for decoration by the Si QDs in order to fabricate a flexible and free-standing polymeric nanofibrous mat posessing a visible light emitting character so that it could act as a visible colorimetric sensor. The visible light emitting Si QDs were decorated onto the Nylon 6,6 nanofibrous mats via covering the surfaces as a ‘nanodress’ by a simple impregnation/dip-coating and heat-curing methods. The analytical results revealed that the Si QDs decorated flexible polymeric nanofibrous mats could be utilized for colorimetric trinitrotoluene (TNT) detection in low concentrations. © The Royal Society of Chemistry

Superhydrophobic, Hybrid, Electrospun Cellulose Acetate Nanofibrous Mats for Oil/Water Separation by Tailored Surface Modification

Electrospun cellulose acetate nanofibers (CA-NF) have been modified with perfluoro alkoxysilanes (FS/CA-NF) for tailoring their chemical and physical features aiming oil-water separation purposes. Strikingly, hybrid FS/CA-NF showed that perfluoro groups are rigidly positioned on the outer surface of the nanofibers providing superhydrophobic characteristic with a water contact angle of ∼155°. Detailed analysis showed that hydrolysis/condensation reactions led to the modification of the acetylated β(1 → 4) linked d-glucose chains of CA transforming it into a superhydrophobic nanofibrous mat. Analytical data have revealed that CA-NF surfaces can be selectively controlled for fabricating the durable, robust and water resistant hybrid electrospun nanofibrous mat. The -OH groups available on the CA structure allowed the basic sol-gel reactions started by the reactive FS hybrid precursor system which can be monitored by spectroscopic analysis. Since alkoxysilane groups on the perfluoro silane compound are capable of reacting for condensation together with the CA, superhydrophobic nanofibrous mat is obtained via electrospinning. This structural modification led to the facile fabrication of the novel oil/water nanofibrous separator which functions effectively demonstrated by hexane/oil and water separation experiments. Perfluoro groups consequently modified the hydrophilic CA nanofibers into superhydrophobic character and therefore FS/CA-NF could be quite practical for future applications like water/oil separators, as well as self-cleaning or water resistant nanofibrous structures. © 2016 American Chemical Society

Quercetin/β-cyclodextrin inclusion complex embedded nanofibres: Slow release and high solubility

Electrospinning of polyacrylic acid (PAA) nanofibres (NF) incorporating β-cyclodextrin inclusion complex (β-CD-IC) of quercetin (QU) was performed. Here, β-CD was used as not only the crosslinking agent for PAA nanofibres but also as a host molecule for inclusion of QU. The phase solubility test showed enhanced solubility of QU due to the inclusion complexation; in addition, the stoichiometry of QU/β-CD-IC was determined to be 1:1. Computational modelling studies confirmed that 1:1 and 1:2 complex formation are desirable; 1:1 complex formation was chosen to have higher weight loading of QU. SEM images showed that PAA/QU/β-CD-IC-NF were bead-free and uniform. XRD indicated that PAA/QU/β-CD-IC-NF were amorphous in nature without the crystalline peaks of QU. Comparative results revealed that the release profile of QU from PAA/QU/β-CD-IC-NF was much slower but greater in total than from PAA/QU/β-CD-IC-film. Moreover, high antioxidant activity and photostability of QU was achieved in PAA/QU/β-CD-IC-NF. © 2015 Elsevier Ltd

Antioxidant α-tocopherol/γ-cyclodextrin–inclusion complex encapsulated poly(lactic acid) electrospun nanofibrous web for food packaging

α-Tocopherol (α-TC) and α-TC/cyclodextrin (CD)–inclusion complex (IC) incorporated electrospun poly(lactic acid) (PLA) nanofibers (NF) were developed via electrospinning (PLA/α-TC–NF and PLA/α-TC/γ-CD–IC–NF). The release of α-TC into 95% ethanol (fatty food simulant) was much greater from PLA/α-TC/γ-CD–IC–NF than from PLA/α-TC–NF because of the solubility increase in α-TC; this was confirmed by a phase-solubility diagram. 2,2-Diphenyl-1-picrylhydrazyl radical-scavenging assay shows that PLA/α-TC–NF and PLA/α-TC/γ-CD–IC–NF had 97% antioxidant activities; this value was expected to be high enough to inhibit lipid oxidation. PLA/α-TC–NF and PLA/α-TC/γ-CD–IC–NF were tested directly on beef with the thiobarbituric acid reactive substance (TBARS) method, and the nanofibers displayed a lower TBARS content than the unpackaged meat sample. Thus, active packaging significantly enhanced the oxidative stability of the meat samples at 4 °C. In conclusion, PLA/α-TC/γ-CD–IC–NF was shown to be promising as an active food-packaging material for prolonging the shelf life of foods. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44858. © 2017 Wiley Periodicals, Inc

Ultrasensitive electrospun fluorescent nanofibrous membrane for rapid visual colorimetric detection of H2O2

We report herein a flexible fluorescent nanofibrous membrane (FNFM) prepared by decorating the gold nanocluster (AuNC) on electrospun polysulfone nanofibrous membrane for rapid visual colorimetric detection of H2O2. The provision of AuNC coupled to NFM has proven to be advantageous for facile and quick visualization of the obtained results, permitting instant, selective, and on-site detection. We strongly suggest that the fast response time is ascribed to the enhanced probabilities of interaction with AuNC located at the surface of NF. It has been observed that the color change from red to blue is dependent on the concentration, which is exclusively selective for hydrogen peroxide. The detection limit has been found to be 500 nM using confocal laser scanning microscope (CLSM), visually recognizable with good accuracy and stability. A systematic comparison was performed between the sensing performance of FNFM and AuNC solution. The underlying sensing mechanism is demonstrated using UV spectra, transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The corresponding disappearance of the characteristic emissions of gold nanoclusters and the emergence of a localized surface plasmon resonance (LSPR) band, stressing this unique characteristic of gold nanoparticles. Hence, it is evident that the conversion of nanoparticles from nanoclusters has taken place in the presence of H2O2. Our work here has paved a new path for the detection of bioanalytes, highlighting the merits of rapid readout, sensitivity, and user-friendliness. © 2015 Springer-Verlag Berlin Heidelberg

Grain boundary engineering in electrospun ZnO nanostructures as promising photocatalysts

Electrospun ZnO nanofibers (ZNF) have received increased attention as photocatalysts owing to their potential for incredible performance. However, uncertainty still exists in determining the correlation between grain boundaries (GBs) and photocatalytic activity. Therefore, effective thought has been put into engineering the GBs to convert ZNF into a promising photocatalyst. Herein, the obtained electrospun ZnO structures are composed of nanograins, which are connected to each other in an ordered manner. In-depth studies have revealed that the growth of nanograins severely altered the morphology of ZNF and GB areas at higher annealing temperatures ranging from 500 °C to 1000 °C. Based on the morphological features and their structural evolution, the obtained structures are named as ZnO nanofibers-1 (ZNF-1, 500 °C), ZnO hollow tubes (ZHT, 600 °C), ZnO nanofibers-2 (ZNF-2, 700 °C), ZnO bamboo structured fibers (ZBF, 800 °C), ZnO segmented fibers (ZSF, 900 °C) and ZnO nanoparticles (ZNP, 1000 °C). A strong correlation between the inherent emission features of ZNF and their peak positions have been detected with the GB. The comparative degradation efficiency of methylene blue (MB) has been studied and the results showed that the ZNF-1 with highly stacked nanograins containing rich grain boundaries demonstrated ∼6 times higher efficiency than other structures. In addition, it has been shown to have a strong effect towards the degradation of Rhodamine B (Rh B) and 4-nitro-phenol (4-NP). A critical parameter for improving the photocatalytic activity is found to be the GB mediated defects, which are proposed to be oxygen/zinc vacancies at nanograin fusion interfaces, while supposedly maintaining its fibrous structure, wherein no relationship has been drawn implying the direct domination of morphology, surface area and defect. © 2016 The Royal Society of Chemistry