Zeynep Aytac

Surface modification of electrospun polyester nanofibers with cyclodextrin polymer for the removal of phenanthrene from aqueous solution.

Surface modified electrospun polyester (PET) nanofibers with cyclodextrin polymer (CDP) were produced (PET/CDP). CDP formation onto electrospun PET nanofibers was achieved by polymerization between citric acid (CTR, crosslinking agent) and cyclodextrin (CD). Three different types of native CD (α-CD, β-CD and γ-CD) were used to form CDP. Water-insoluble crosslinked CDP coating was permanently adhered onto the PET nanofibers. SEM imaging indicated that the nanofibrous structure of PET mats was preserved after CDP surface modification process. PET/CDP nanofibers have shown rougher/irregular surface and larger fiber diameter when compared to untreated PET nanofibers. The surface analyses of PET/CDP nanofibers by XPS elucidated that CDP was present on the fiber surface. DMA analyses revealed the enhanced mechanical properties for PET/CDP where PET/CDP nanofibers have shown higher storage modulus and higher glass transition temperature compared to untreated PET nanofibers. The surface area of the PET/CDP nanofibers investigated by BET measurements showed slight decrease due to the presence of CDP coating compared to pristine PET nanofibers. Yet, it was observed that PET/CDP nanofibers were more efficient for the removal of phenanthrene as a model polycyclic aromatic hydrocarbon (PAH) from aqueous solution when compared to pristine PET nanofibers. Our findings suggested that PET/CDP nanofibers can be a very good candidate as a filter material for water purification and waste treatment owing to their very large surface area as well as inclusion complexation capability of surface associated CDP.

Release and antibacterial activity of allyl isothiocyanate/β-cyclodextrin complex encapsulated in electrospun nanofibers.

Allyl isothiocyanate (AITC) is known as an efficient antibacterial agent but it has a very high volatility. Herein, AITC and AITC/β-cyclodextrin (CD)-inclusion complex (IC) incorporated in polyvinyl alcohol (PVA) nanofibers were produced via electrospinning. SEM images elucidated that incorporation of AITC and AITC/β-CD-IC into polymer matrix did not affect the bead-free fiber morphology of PVA nanofibers. (1)H-NMR and headspace GC-MS analyses revealed that very low amount of AITC was remained in PVA/AITC-NF because of the rapid evaporation of AITC during the electrospinning process. Nevertheless, much higher amount of AITC was preserved in the PVA/AITC/β-CD-IC-NF due to the CD inclusion complexation. The sustained release of AITC from nanofibers was evaluated at 30°C, 50°C and 75°C via headspace GC-MS. When compared to PVA/AITC-NF, PVA/AITC/β-CD-IC-NF has shown higher antibacterial activity against Escherichia coli and Staphylococcus aureus due to the presence of higher amount of AITC in this sample which was preserved by CD-IC.

One-step synthesis of size-tunable Ag nanoparticles incorporated in electrospun PVA/cyclodextrin nanofibers

One-step synthesis of size-tunable silver nanoparticles (Ag-NP) incorporated into electrospun nanofibers was achieved. Initially, in situ reduction of silver salt (AgNO3) to Ag-NP was carried out in aqueous solution of polyvinyl alcohol (PVA). Here, PVA was used as reducing agent and stabilizing polymer as well as electrospinning polymeric matrix for the fabrication of PVA/Ag-NP nanofibers. Afterwards, hydroxypropyl-beta-cyclodextrin (HPβCD) was used as an additional reducing and stabilizing agent in order to control size and uniform dispersion of Ag-NP. The size of Ag-NP was ∼8 nm and some Ag-NP aggregates were observed for PVA/Ag-NP nanofibers, conversely, the size of Ag-NP decreased from ∼8 nm down to ∼2 nm within the fiber matrix without aggregation were attained for PVA/HPβCD nanofibers. The PVA/Ag-NP and PVA/HPβCD/Ag-NP nanofibers exhibited surface enhanced Raman scattering (SERS) effect. Moreover, antibacterial properties of PVA/Ag-NP and PVA/HPβCD/Ag-NP nanofibrous mats were tested against Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) bacteria.

Sulfisoxazole/cyclodextrin inclusion complex incorporated in electrospun hydroxypropyl cellulose nanofibers as drug delivery system

Herein, hydroxypropyl-beta-cyclodextrin (HPβCD) inclusion complex (IC) of a hydrophobic drug, sulfisoxazole (SFS) was incorporated in hydroxypropyl cellulose (HPC) nanofibers (HPC/SFS/HPβCD-IC-NF) via electrospinning. SFS/HPβCD-IC was characterized by DSC to investigate the formation of inclusion complex and the stoichiometry of the complex was determined by Jobs plot. Modeling studies were also performed on SFS/HPβCD-IC using ab initio technique. SEM images depicted the defect free uniform fibers and confirmed the incorporation of SFS/HPβCD-IC in nanofibers did not alter the fiber morphology. XRD analyses showed amorphous distribution of SFS/HPβCD-IC in the fiber mat. Release studies were performed in phosphate buffered saline (PBS). The results suggest higher amount of SFS released from HPC/SFS/HPβCD-IC-NF when compared to free SFS containing HPC nanofibers (HPC/SFS-NF). This was attributed to the increased solubility of SFS by inclusion complexation. Sandwich configurations were prepared by placing HPC/SFS/HPβCD-IC-NF between electrospun PCL nanofibrous mat (PCL-HPC/SFS/HPβCD-IC-NF). Consequently, PCL-HPC/SFS/HPβCD-IC-NF exhibited slower release of SFS as compared with HPC/SFS/HPβCD-IC-NF. This study may provide more efficient future strategies for developing delivery systems of hydrophobic drugs.

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.

Encapsulation of gallic acid/cyclodextrin inclusion complex in electrospun polylactic acid nanofibers: Release behavior and antioxidant activity of gallic acid.

Cyclodextrin-inclusion complexes (CD-ICs) possess great prominence in food and pharmaceutical industries due to their enhanced ability for stabilization of active compounds during processing, storage and usage. Here, CD-IC of gallic acid (GA) with hydroxypropyl-beta-cyclodextrin (GA/HPβCD-IC) was prepared and then incorporated into polylactic acid (PLA) nanofibers (PLA/GA/HPβCD-IC-NF) using electrospinning technique to observe the effect of CD-ICs in the release behavior of GA into three different mediums (water, 10% ethanol and 95% ethanol). The GA incorporated PLA nanofibers (PLA/GA-NFs) were served as control. Phase solubility studies showed an enhanced solubility of GA with increasing amount of HPβCD. The detailed characterization techniques (XRD, TGA and (1)H-NMR) confirmed the formation of inclusion complex between GA and HPβCD. Computational modeling studies indicated that the GA made an efficient complex with HPβCD at 1:1 either in vacuum or aqueous system. SEM images revealed the bead-free and uniform morphology of PLA/GA/HPβCD-IC-NF. The release studies of GA from PLA/GA/HPβCD-IC-NF and PLA/GA-NF were carried out in water, 10% ethanol and 95% ethanol, and the findings revealed that PLA/GA/HPβCD-IC-NF has released much more amount of GA in water and 10% ethanol system when compared to PLA/GA-NF. In addition, GA was released slowly from PLA/GA/HPβCD-IC-NF into 95% ethanol when compared to PLA/GA-NF. It was also observed that electrospinning process had no negative effect on the antioxidant activity of GA when GA was incorporated in PLA nanofibers.

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.

Antibacterial electrospun zein nanofibrous web encapsulating thymol/cyclodextrin-inclusion complex for food packaging

Thymol (THY)/γ-Cyclodextrin(γ-CD) inclusion complex (IC) encapsulated electrospun zein nanofibrous webs (zein-THY/γ-CD-IC-NF) were fabricated as a food packaging material. The formation of THY/γ-CD-IC (1:1 and 2:1) was proved by experimental (X-ray diffraction (XRD), thermal gravimetric analysis (TGA), 1H NMR) and computational techniques. THY/γ-CD-IC (2:1) exhibited higher preservation rate and stability than THY/γ-CD-IC (1:1). It is worth mentioning that zein-THY/γ-CD-IC-NF (2:1) preserved much more THY as observed in TGA and stability of THY/γ-CD-IC (2:1) was higher, as shown by a modelling study. Therefore, much more THY was released from zein-THY/γ-CD-IC-NF (2:1) than zein-THY-NF and zein-THY/γ-CD-IC-NF (1:1). Similarly, antibacterial activity of zein-THY/γ-CD-IC-NF (2:1) was higher than zein-THY-NF and zein-THY/γ-CD-IC-NF (1:1). It was demonstrated that zein-THY/γ-CD-IC-NF (2:1) was most effective in inhibiting the growth of bacteria on meat samples. These webs show potential application as an antibacterial food packaging material.

Electrospinning of polymer-free cyclodextrin/geraniol–inclusion complex nanofibers: enhanced shelf-life of geraniol with antibacterial and antioxidant properties

Free-standing nanofibrous webs of cyclodextrin/geraniol–inclusion complex (CD/geraniol–IC-NF) showing antibacterial, antioxidant activity and slow release of geraniol were developed as flavour/fragrance releasing materials via electrospinning. The electrospinning of CD/geraniol–IC-NFs with uniform and bead-free morphology was achieved without using a polymer matrix. Three types of CDs modified with hydroxypropyl and methyl groups (HPβCD, MβCD, and HPγCD) were used to obtain CD/geraniol–IC-NFs. The polymer-free CD/geraniol–IC-NFs allow us to attain much higher geraniol loading (∼11%, w/w) when compared to electrospun polymeric nanofibers containing CD/geraniol–IC (∼5%, w/w). Geraniol has a volatile nature, yet, a significant amount of geraniol (∼60–90%) was preserved in CD/geraniol–IC-NFs due to the complexation, whereas evaporation of geraniol was unavoidable for polymeric nanofibers incorporating geraniol without cyclodextrin. Short-term (3 h) temperature dependent release (37 °C, 50 °C, and 75 °C) and long-term open air (50 days, at RT) release tests revealed that MβCD/geraniol–IC-NF released less geraniol compared to HPβCD/geraniol–IC-NF and HPγCD/geraniol–IC-NF, indicating that much stronger inclusion complexation was formed between MβCD and geraniol. The release of geraniol from CD/geraniol–IC-NFs prevented the colonization of Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) bacteria to a great extent, as observed in the antibacterial activity results. It was observed that CD/geraniol–IC-NFs had higher antioxidant activity compared to pure geraniol due to the solubility increase. In brief, the results reported here may open a new door to enhance the performance of essential oils and flavour/fragrances, to preserve volatile compounds from evaporation and to better understand the potential of CD/IC-NFs as carrier systems for guest compounds in the food, cosmetic and household cleaning industries.

pH-responsive nanofibers with controlled drug release properties

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.