Polyvinyl alcohol (PVA) nanofibers encapsulating eugenol (EG)/cyclodextrin (CD) inclusion complexes (IC) (EG/CD-IC) were produced via electrospinning technique in order to achieve high thermal stability and slow release of EG. In order to find out the most favorable CD type for the stabilization of EG, three types of native cyclodextrins (α-CD, β-CD, and γ-CD) were used for the formation of EG/CD-IC. In the case of PVA/EG/α-CD nanofibers, uncomplexed EG was detected indicating that α-CD is not a proper host for EG/CD-IC formation. However, for PVA/EG/β-CD-IC and PVA/EG/γ-CD-IC nanofibers, enhanced durability and high thermal stability for EG were achieved due to the inclusion complexation. The electrospun nanofibers encapsulating CD-IC of active compounds such as eugenol may be quite useful in the food industry due to the extremely large surface area of nanofibers along with specific functionality, enhanced thermal stability, and slow release of the active compounds by CD inclusion complexation.

Herein, polybenzoxazine based cross-linked cellulose acetate nanofibrous membrane exhibiting enhanced thermal/mechanical properties and improved adsorption efficiency was successfully produced via electrospinning and thermal curing. Initially, suitable solution composition was determined by varying the amount of the benzoxazine (BA-a) resin, cellulose acetate (CA) and citric acid (CTR) to obtain uniform nanofibrous membrane via electrospinning. Subsequently, thermal curing was performed by step-wise at 150, 175, 200 and 225°C to obtain cross-linked composite nanofibrous membranes. SEM images and solubility experiments demonstrated that most favorable result was obtained from the 10% (w/v) CA, 5% (w/v) BA-a and 1% (w/v) CTR composition and cross-linked nanofibrous membrane (CA10/PolyBA-a5/CTR1) was obtained after the thermal curing. Chemical structural changes (ring opening) occurred by thermal curing revealed successful cross-linking of BA-a in the composite nanofibrous membrane. Thermal, mechanical and adsorption performance of pristine CA and CA10/PolyBA-a5/CTR1 nanofibrous membranes were studied. Char yield of the pristine CA nanofibrous membrane has increased notably from 12 to 24.7% for composite CA10/PolyBA-a5/CTR1 membrane. When compared to pristine CA membrane, CA10/PolyBA-a5/CTR1 nanofibrous membrane has shown superior mechanical properties having tensile strength and Young's modulus of 8.64±0.63MPa and 213.87±30.79MPa, respectively. Finally, adsorption performance of pristine CA and CA10/PolyBA-a5/CTR1 nanofibrous membranes was examined by a model polycyclic aromatic hydrocarbon (PAH) compound (i.e. phenanthrene) in aqueous solution, in which CA10/PolyBA-a5/CTR1 nanofibrous membrane has shown better removal efficiency (98.5%) and adsorption capacity (592μg/g).

We report on phase sensitive surface states of CdS quantum dots (QDs), where it is noticed that a simple phase change from dispersion to solid has shown significant influence on the emission spectrum. As the solvent evaporates from the dispersion, apparently yellow dispersion transforms into a white light emitter because of the conformal changes in the polymer that surrounds the QDs. In turn, these changes catalyze the emission from three specific wavelengths in the blue region of the spectrum, shifting the surface defects closer to the conduction band of CdS. In the phase change from dispersion to solid, flexible and dangling polymer chains are transformed into rigid moieties that can be treated as a modified chemical environment. Furthermore, to ascertain the origin of the new emission lines, we have studied a dipole interaction-based passivation mechanism between QDs and the polymer. The proposed mechanism may be valuable for designing future QD-based fluorophores and explains the sensitivity of the surface states in the case of CdS.

We report on the effects of ionic interaction on the electronic structure of PEDOT:PSS where the oxidation state of PEDOT is an import aspect for various applications. Additional ionic interactions are introduced and controlled by varying the fraction of poly(ethylene oxide) (PEO). These interactions are balanced against the inherent cohesive forces within each of the polymers constituting intertwined networks. Raman spectra evidenced a peak-shift as high as ∼14 cm −1 for C C vibrational region which suggested increasing degree of oxidation of PEDOT for higher PEO fractions. Changes to the single and bipolaronic absorption bands support the results from the Raman spectra. For highest PEO fraction neutral-PEDOT and lowered bipolaron density is attributed to localization of PEDOT chains within PEO matrix. Interestingly, for higher PEO fractions the electronic density of states (DOS) of HOMO and core-levels (S2p, C1s and O1s) suggested increased degree of oxidation and electron localization on PEDOT. Near and below (∼12 eV) Fermi level, contribution to the O2p and C2p atomic orbitals depicted significantly different DOS. Also we note energetic shift for O2s/C2s and bonding CC atomic and molecular DOS, respectively. The correlation between some surface and bulk-related properties suggests the uniformity of the blend material which might be vital for the application in electrochemical devices.

In this study, for the first time cross-linking of linear aliphatic diamine-based main-chain polybenzoxazine (MCPBz) electrospun nanofibers were accomplished by two-step approach consisting of photo and thermal curing. Initially, two novel MCPBz resins which comprise of a benzophenone unit in the polymer main-chain were synthesized and uniform MCPBz nanofibers were produced by electrospinning. At first step, photo curing was performed by free radical polymerization initiated by UV-light and thermal stability of nanofibers was enhanced. At second step, thermal curing was carried out at different temperatures (150e225 C) and ring opening and cross-linking of benzoxazine groups in the fiber structure were achieved. After two-step curing, cross-linked MCPBz nanofibers were obtained as free-standing material with good mechanical properties. Moreover, it was shown that these two crosslinked MCPBz nanofibers were structurally stable and maintained their fibrous morphology at high temperatures (400 C), in good solvents (chloroform, DMF, 1,4-dioxane, DMAc, THF) and highly concentrated strong acids (HCl, HNO 3 , H 2 SO 4).

a b s t r a c tHere we report the successful production of nanofibers from main-chain polybenzoxazines (MCPBz) via electrospinning without using any other carrier polymer matrix. Two different types of MCPBz (PBA-ad6 and PBA-ad12) were synthesized by using two types of difunctional amine (1,6-diaminohexane and 1,12-diaminododecane), bisphenol-A, and paraformaldehyde as starting materials through a Mannich reaction.1 H NMR and FTIR spectroscopy studies have confirmed the chemical structures of the two MCPBz.We were able to obtain highly concentrated homogeneous solutions of the two MCPBz in chloroform/ N,N-dimethylformamide (DMF) (4:1, v/v) solvent system. The electrospinning conditions were optimized in order to produce bead-free, uniform and continuous nanofibers from these two MCPBz by varying the concentrations of PBA-ad6 (30e45%, w/v) and PBA-ad12 (15e20%, w/v) in chloroform/DMF (4:1, v/v). The bead-free fiber morphology was evidenced under SEM imaging when PBA-ad6 and PBAad12 were electrospun at solution concentration of 40% and 18% (w/v), respectively. The nanofibrous mats of MCPBz were obtained as free-standing material, yet, PBA-ad12 mat was more flexible than and PBA-ad6 mat. Furthermore, the curing studies of these MCPBz nanofibrous mats were performed to obtain cross-linked materials.

Integrated structure of titanate nanotubes and nanosheets is investigated for their optical, electronic and optoelectronic properties when combined with HCl doped polyaniline (PANI). HR-TEM, SEM and XRD were employed for detailed morphological and microstructural understanding of the orthorhombic titanate nanostructure. Chemisorbed oxygeneous groups are probed with Raman spectroscopy which are found to desorb under UV-Vis treatment. We note a blue shift of Ti-O-Ti Raman frequency in contrast to Na-O-Ti stretching. Valence band region of titanate is analyzed for contribution of O2p, O2s, Na2p and Ti3p. Photoluminescence with different excitation energies revealed the presence of oxygen vacancy related defects in titanate. The highly occupied electronic states of PANI were also analyzed until 40 eV below the Fermi energy. XPS core-level analyses revealed~25 % doping density in PANI. Edges of valence band and HOMO are determined to be at 2.45 eV and 2.54 eV below Fermi energy for titanate and PANI, respectively. ITO/PANI/ITO has depicted negative photoresponse and the magnitude of which is reduced~4 times after combining with titanate nanostructure. Essentially the nanoscale architecture separates the emeraldine base and salt regions of PANI. This separation channelizes the charge carriers before trapping which reduces the magnitude of the negative photoresponse.

Poly(vinyl acetate) (PVAc)/TiO2 nanofibers, PVAc/SnO2 nanoribbons and PVAc/SnO2-TiO2 nanoribbons were produced via electrospinning. TiO2 nanofibers and SnO2 nanoribbons were obtained by removal of the polymeric matrix (PVAc) after calcination at 450 °C. Interestingly, PVAc/SnO2-TiO2 nanoribbons were transformed into SnO2-TiO2 nanofibers after calcination under the similar conditions. Fiber morphology and elemental mapping confirmed through SEM and TEM microscope techniques respectively. The X-ray diffraction measurements suggested the presence of anatase TiO2 and rutile SnO2 and both were present in the SnO2-TiO2 mixed system. Systematic photoluminescence studies were performed on the electrospun nanostructures at different excitation wavelengths (λex1 = 325, λex2 = 330, λex3 = 350, λex4 = 397 and λex5 = 540 nm). We emphasize that the defects in the SnO2-TiO2 based on the defect levels present in TiO2 and SnO2 and anticipate that these defect levels may have great potential in understanding and characterizing various semiconducting nanostructures. © The Royal Society of Chemistry