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Photocatalytic activity (PCA) on semiconductors is known to be majorly influenced by specific surface area and intrinsic lattice defects of the catalyst. In this report, we tested the efficiencies of 1D ZnO catalysts of varying fiber diameter (80 nm and 650 nm of inner diameter) in two formats, viz. core–shell and hollow nanofibers, where the former is calcined to yield the latter. These nanofibrous catalysts were produced by combining electrospinning and atomic layer deposition processes which were then subjected to thorough characterization including photoluminescence (PL) unveiling the details of intrinsic defects/densities. During the thermal treatment, intrinsic defects are reorganized and as a result a new PL band is observed apart from some significant changes in the intensities of other emissions. The densities of various intrinsic defects from PL are compared for all samples and juxtaposed with the PCA. Careful scrutiny of the various results suggested an anti-correlation between surface area and PCA; i.e., higher surface area does not necessarily imply better PCA. Beyond a limit, the most deterministic factor would be the density of surface defects rather than the specific surface area. The results of this study enable the researchers to fabricate 1D semiconductor photocatalysts while striking the balance between surface area and density of defects.

In this report, we study the evolution of valence band (VB) structure during a controlled amorphous to tetragonal transformation of ZrO2 core shell nanostructures fabricated from electrospun nanofiber template (at 130, 200, and 250 degrees C). Shell-ZrO2 was formed with atomic layer deposition. X-ray diffraction and transmission electron microscopy are employed to unveil the transformation of amorphous to crystalline structure of ZrO2. O is core-level spectra indicated chemisorbed oxygen (O-Ch) of almost invariant fraction for the three samples. Zr 3s level suggested that the sample deposited at 130 degrees C has depicted a peak at relatively higher binding energy. Analyses on Zr 3d spectra indicated the presence of metallic-Zr (Zr+zeta, 0

Hollow cathode plasma-assisted atomic layer deposition (HCPA-ALD) is a promising technique for obtaining III-nitride thin films with low impurity concentrations at low temperatures. Here we report our previous and current efforts on the development of HCPA-ALD processes for III-nitrides together with the properties of resulting thin films and nanostructures. The content further includes nylon 6,6-GaN core-shell nanofibers, proof-of-concept thin film transistors and UV photodetectors fabricated using HCPA-ALD-grown GaN layers, as well as InN thin films deposited by HCPA-ALD using cyclopentadienyl indium and trimethylindium precursors. (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

Here we demonstrate the combination of electrospinning and hollow cathode plasma-assisted atomic layer deposition (HCPA-ALD) processes by fabricating flexible polymer-GaN organic-inorganic core-shell nanofibers at a processing temperature much lower than that needed for the preparation of conventional GaN ceramic nanofibers. Polymer-GaN organic-inorganic core-shell nanofibers fabricated by the HCPA-ALD of GaN on electrospun polymeric (nylon 6,6) nanofibers at 200 °C were characterized in detail using electron microscopy, energy dispersive X-ray analysis, selected area electron diffraction, X-ray diffraction, X-ray photoelectron spectroscopy, photoluminescence measurements, and dynamic mechanical analysis. Although transmission electron microscopy studies indicated that the process parameters should be further optimized for obtaining ultimate uniformity and conformality on these high surface area 3D substrates, the HCPA-ALD process resulted in a ∼28 nm thick polycrystalline wurtzite GaN layer on polymeric nanofibers of an average fiber diameter of ∼70 nm. Having a flexible polymeric core and low processing temperature, these core-shell semiconducting nanofibers might have the potential to substitute brittle ceramic GaN nanofibers, which have already been shown to be high performance materials for various electronic and optoelectronic applications.

The volatility and limited water solubility of linalool is a critical issue to be solved. Here, we demonstrated the electrospinning of polymer-free nanofibrous webs of cyclodextrin/linalool-inclusion complex (CD/linalool-IC-NFs). Three types of modified cyclodextrin (HP beta CD, M beta CD, and HP gamma CD) were used to electrospin CD/linalool-IC-NFs. Free-standing CD/linalool-IC-NFs facilitate maximum loading of linalool up to 12% (w/w). A significant amount of linalool (45-89%) was preserved in CD/linalool-IC-NFs, due to enhancement in the thermal stability of linalool by cyclodextrin inclusion complexation. Remarkably, CD/linalool-IC-NFs have shown fast-dissolving characteristics in which these nanofibrous webs dissolved in water within two seconds. Furthermore, linalool release from CD/linalool-IC-NFs inhibited growth of model Gram-negative (E. coli) and Gram-positive (S. aureus) bacteria to a great extent. Briefly, characteristics of liquid linalool have been preserved in a solid nanofiber form and designed CD/linalool-IC-NFs confer high loading capacity, enhanced shelf life and strong antibacterial activity of linalool. (C) 2017 Elsevier Ltd. All rights reserved.

Cataloged from PDF version of article. We report on the synthesis and photocatalytic activity (PCA) of electrospun poly(acrylonitrile) (PAN) nanofibrous mat decorated with nanoneedles of zinc oxide (ZnO). Apart from a detailed morphological and structural characterization, the PCA has been carefully monitored and the results are discussed elaborately when juxtaposed with the photoluminescence. The present hierarchal homoassembled nanostructures are a combination of two types of ZnO with diverse optical qualities, i.e. (a) controlled deposition of ZnO coating on nanofibers with dominant oxygen vacancies and significant grain boundaries by atomic layer deposition (ALD), and (b) growth of single crystalline ZnO nanoneedles with high optical quality on the ALD seeds via hydrothermal process. The needle structure (similar to 25 nm in diameter with an aspect ratio of similar to 24) also supports the vectorial transport of photo-charge carriers, which is crucial for high catalytic activity. Furthermore, it is shown that enhanced PCA is because of the catalytic activity at surface defects (on ALD seed), valence band, and conduction band (of ZnO nanoneedles). PCA and durability of the PAN/ZnO nanofibrous mat have also been tested with aqueous solution of methylene blue and the results showed almost no decay in the catalytic activity of this material when reused. (C) 2014 Elsevier B.V. All rights reserved.

Polyester (PET) nanofibers incorporating cyclodextrins (CD) were obtained via electrospinning. α-CD, β-CD, and γ-CD were used to functionalize PET nanofibers. Bead-free PET/CD nanofibers were obtained from lower polymer concentration indicating that the incorporation of CD in polymer solution improved the electrospinnability of the PET nanofibers. XRD studies indicated that CD were distributed into nanofiber without forming crystalline aggregates. FTIR peak shift was observed possibly due to interaction between CD and PET. TGA confirmed that initial CD loading (25%, w/w) in the polymer solution was preserved for the PET/CD nanofibers. The presence of most of CD on the surface of PET/CD nanofibers was confirmed by XPS analysis and contact angle measurement. DMA results indicated that incorporation of CD improved the mechanical property of the nanofibers. Our studies showed that PET/CD nanofibers can effectively entrap aniline vapor as a model volatile organic compound (VOC) from surrounding owing to their very large surface area and inclusion complexation capability of CD. The entrapment efficiency of aniline vapor was found to be better for PET/γ-CD nanofibers compared to PET/α-CD and PET/β-CD nanofibers. Our findings suggested that electrospun PET nanofibers functionalized with CD may be used as filtering material for removal of VOC in air filtration. POLYM. ENG. SCI., 54:2970-2978, 2014. © 2014 Society of Plastics Engineers © 2014 Society of Plastics Engineers.

Hafnia (HfO2) hollow nanofibers (HNs) were synthesized by atomic layer deposition (ALD) using electrospun nylon 6,6 nanofibers as templates. HfO2 layers were deposited on polymeric nanofibers at 200 degrees C by alternating reactant exposures of tetrakis(dimethylamido) hafnium and water. Polymeric nanofiber templates were subsequently removed by an ex situ calcination process at 500 degrees C under air ambient. Morphological and structural characterizations of the HN samples were conducted by scanning electron microscopy, transmission electron microscopy and X-ray diffraction. Freestanding network of HfO2 HNs was found to be polycrystalline with a monoclinic crystal structure. Elemental composition and chemical bonding states of the resulting HfO2 HNs were studied by using X-ray photoelectron spectroscopy. The presence of HfO2 was evidenced by high resolution scans of Hf 4f and O 1s with binding energies of 16.3-17.9 and 529.6 eV, respectively. Combination of electrospinning and ALD processes provided an opportunity to precisely control both diameter and wall thickness of the synthesized HfO2 HNs. (C) 2013 Elsevier B. V. All rights reserved.

We have proposed a new strategy for preparing free-standing nanofibrous webs from an inclusion complex (IC) of a well-known flavor/fragrance compound (limonene) with three modified cyclodextrins (HP beta CD, M beta CD, and HP gamma CD) via electrospinning (CD/limonene-IC-NFs) without using a polymeric matrix. The experimental and computational modeling studies proved that the stoichiometry of the complexes was 1:1 for CD/limonene systems. M beta CD/limonene-IC-NF released much more limonene at 37, 50, and 75 degrees C than HP beta CD/limonene-IC-NF and HP gamma CD/limonene-IC-NF because of the greater amount of preserved limonene. Moreover, M beta CD/limonene-IC-NF has released only 25% (w/w) of its limonene, whereas HP beta CD/limonene-IC-NF and HP gamma CD/limonene-IC-NF released 51 and 88% (w/w) of their limonene in 100 days, respectively. CD/limonene-IC-NFs exhibited high antibacterial activity against E. coli and S. aureus. The water solubility of limonene increased significantly and CD/limonene-IC-NFs were dissolved in water in a few seconds. In brief, CD/limonene-IC-NFs with fast dissolving character enhanced the thermal stability and prolonged the shelf life along with antibacterial properties could be quite applicable in food and oral care applications.

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 (HP beta CD, M beta CD, and HP gamma CD) were used to obtain CD/geraniol-IC-NFs. The polymer-free CD/geraniol-IC-NFs allow us to attain much higher geraniol loading (similar to 11%, w/w) when compared to electrospun polymeric nanofibers containing CD/geraniol-IC (similar to 5%, w/w). Geraniol has a volatile nature, yet, a significant amount of geraniol (similar to 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 degrees C, 50 degrees C, and 75 degrees C) and long-term open air (50 days, at RT) release tests revealed that M beta CD/geraniol-IC-NF released less geraniol compared to HP beta CD/geraniol-IC-NF and HP gamma CD/geraniol-IC-NF, indicating that much stronger inclusion complexation was formed between M beta CD 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.

Vanillin/cyclodextrin inclusion complex nanofibers (vanillin/CD-IC NFs) were successfully obtained from three modified CD types (HP beta CD, HP gamma CD and M beta CD) in three different solvent systems (water, DMF and DMAc) via an electrospinning technique without using a carrier polymeric matrix. Vanillin/CD-IC NFs with uniform and bead-free fiber morphology were successfully produced and their free-standing nanofibrous webs were obtained. The polymer-free CD/vanillin-IC-NFs allow us to accomplish a much higher vanillin loading (similar to 12%, w/w) when compared to electrospun polymeric nanofibers containing CD/vanillin-IC (similar to 5%, w/w). Vanillin has a volatile nature yet, after electrospinning, a significant amount of vanillin was preserved due to complex formation depending on the CD types. Maximum preservation of vanillin was observed for vanillin/M beta CD-IC NFs which is up to similar to 85% w/w, besides, a considerable amount of vanillin (similar to 75% w/w) was also preserved for vanillin/HP beta CD-IC NFs and vanillin/HP gamma CD-IC NFs. Phase solubility studies suggested a 1:1 molar complexation tendency between guest vanillin and host CD molecules. Molecular modelling studies and experimental findings revealed that vanillin : CD complexation was strongest for M beta CD when compared to HP beta CD and HP gamma CD in vanillin/CD-IC NFs. For vanillin/CD-IC NFs, water solubility and the antioxidant property of vanillin was improved significantly owing to inclusion complexation. In brief, polymer-free vanillin/CD-IC NFs are capable of incorporating a much higher loading of vanillin and effectively preserve volatile vanillin. Hence, encapsulation of volatile active agents such as flavor, fragrance and essential oils in electrospun polymer-free CD-IC NFs may have potential for food related applications by integrating the particularly large surface area of NFs with the non-toxic nature of CD and inclusion complexation benefits, such as high temperature stability, improved water solubility and an enhanced antioxidant property, etc.

Cataloged from PDF version of article. Aluminum nitride (AlN) hollow nanofibers were synthesized via plasma-enhanced atomic layer deposition using sacrificial electrospun polymeric nanofiber templates having different average fiber diameters (~70, ~330, and ~740 nm). Depositions were carried out at 200°C using trimethylaluminum and ammonia precursors. AlN-coated nanofibers were calcined subsequently at 500°C for 2 h to remove the sacrificial polymeric nanofiber template. SEM studies have shown that there is a critical wall thickness value depending on the template's average fiber diameter for AlN hollow nanofibers to preserve their shapes after the template has been removed by calcination. Best morphologies were observed for AlN hollow nanofibers prepared by depositing 800 cycles (corresponding to ~69 nm) on nanofiber templates having ~330 nm average fiber diameter. TEM images indicated uniform wall thicknesses of ~65 nm along the fiber axes for samples prepared using templates having ~70 and ~330 nm average fiber diameters. Synthesized AlN hollow nanofibers were polycrystalline with a hexagonal crystal structure as determined by high-resolution TEM and selected area electron diffraction. Chemical compositions of coated and calcined samples were studied using X-ray photoelectron spectroscopy (XPS). High-resolution XPS spectra confirmed the presence of AlN. © 2012 The American Ceramic Society

Recent experimental research efforts on developing functional nanostructured III-nitride and metal-oxide materials via low-temperature atomic layer deposition (ALD) will be reviewed. Ultimate conformality, a unique propoerty of ALD process, is utilized to fabricate core-shell and hollow tubular nanostructures on various nano-templates including electrospun nanofibrous polymers, self-assembled peptide nanofibers, metallic nanowires, and multi-wall carbon nanotubes (MWCNTs). III-nitride and metal-oxide coatings were deposited on these nano-templates via thermal and plasma-enhanced ALD processes with thickness values ranging from a few mono-layers to 40 nm. Metal-oxide materials studied include ZnO, TiO2, HfO2, ZrO2, and Al2O3. Standard ALD growth recipes were modified so that precursor molecules have enough time to diffuse and penetrate within the layers/pores of the nano-template material. As a result, uniform and conformal coatings on high-surface area nano-templates were demonstrated. Substrate temperatures were kept below 200C and within the self-limiting ALD window, so that temperature-sensitive template materials preserved their integrity III-nitride coatings were applied to similar nano-templates via plasma-enhanced ALD (PEALD) technique. AlN, GaN, and InN thin-film coating recipes were optimized to achieve self-limiting growth with deposition temperatures as low as 100C. BN growth took place only for >350C, in which precursor decomposition occured and therefore growth proceeded in CVD regime. III-nitride core-shell and hollow tubular single and multi-layered nanostructures were fabricated. The resulting metal-oxide and III-nitride core-shell and hollow nano-tubular structures were used for photocatalysis, dye sensitized solar cell (DSSC), energy storage and chemical sensing applications. Significantly enhanced catalysis, solar efficiency, charge capacity and sensitivity performance are reported. Moreover, core-shell metal-oxide and III-nitride materials showed promise to be used in applications where flexibility is critical like functional membranes, textile and flexible electronic applications.

Functional nylon 6,6 nanofibers incorporating cyclodextrins (CD) were developed via electrospinning. Enhanced thermal stability of the nylon 6,6/CD nanofibers was observed due to interaction between CD and nylon 6,6. X-ray photoelectron spectros- copy and attenuated total reflectance Fourier transform infrared spectroscopy studies indicated the existence of some CD molecules on the surface of the nanofibers. Electrospun nylon 6,6 nanofibers without having CD were ineffective for entrapment of toluene vapor from the environment, whereas nylon 6,6/CD nanofibrous membranes can effectively entrap toluene vapor from the surround- ing by taking advantage of the high surface-volume ratio of nanofibers with the added advantage of inclusion complexation capability of CD presenting on the nanofiber surface. The modeling studies for formation of inclusion complex between CD and toluene were also performed by using ab initio techniques. Our results suggest that nylon 6,6/CD nanofibrous membranes may have potential to be used as air filters for the removal of organic vapor waste from surroundings. V C 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41941.

Here we present an investigation on Zn-Ti-O ternary (zinc titanate) nanostructures which were prepared by a combination of electrospinning and atomic layer deposition. Depending on the ZnO and TiO2 molar ratio, two titanates and one mix phased compound were synthesized by varying the post-annealing temperatures. Specifically Zn2TiO4, ZnTiO3 and ZnO/TiO2 nanostructures were fabricated via thermal treatments (900, 700, 800 degrees C, respectively). Structural studies unveiled the titanate phase of the nanostructures. Furthermore, the ionic states of the titanate nanostructures on the surface are revealed to be Ti3+ and Zn2+. Spin-orbit splitting of Zn2p and Ti2p doublets were, however, not identical for all titanates which vary from 23.09-23.10 eV and 5.67-5.69 eV respectively. Oxygen vacancies were found on the surface of all titanates. The valance band region was analyzed for Zn3d, Ti3p, O2s and O2p and their hybridization, while the edge (below Fermi level) was determined to be at 2.14 eV, 2.00 eV and 1.99 eV for Zn2TiO4, ZnTiO3 and ZnO/TiO2 respectively.

Cataloged from PDF version of article. In this study, solid geraniol/cyclodextrin inclusion complexes (geraniol/CD-IC) were successfully prepared by using three types of native CD (alpha-CD, beta-CD and gamma-CD). The modeling studies for inclusion complexation between CD and geraniol were performed by using ab initio techniques. Both experimentally and theoretically, the cornplexation efficiency between geraniol and gamma-CD was higher; therefore, geraniol/gamma-CD-IC was chosen and then incorporated into polyvinyl alcohol (PVA) nanofibers (NF) via electrospinning. The scanning electron microscopy imaging elucidated that the aggregates of geraniol/gamma-CD-IC crystals were distributed in the PVA NF, whereas bead-free and uniform PVA and PVA/geraniol NF without CD-IC were obtained. Higher thermal stability of geraniol was observed in the electrospun PVA/geraniol/gamma-CD-IC NF, However, geraniol molecules having volatile nature could not be preserved without CD-IC during electrospinning or during storage; therefore, the complete evaporation of geraniol in PVA/geraniol NF was unavoidable even after one day of its production. On the contrary, the loss of geraniol was minimal (similar to 10%) for PVA/geraniol/gamma-CD-IC NF even after storage of these NF for two years owing to inclusion complexation. Our study demonstrated that electrospun NF incorporating CD-IC may be quite applicable in food industry, e.g.: active food packaging or functional foods, due to very high surface area and nanoporous structure of NF; high thermal stability and enhanced durability of active agents and functional food ingredients. (C) 2014 Elsevier Ltd. All rights reserved.

WOS: 000334572800080, PubMed ID: 24660809, The combination of nanomaterials and conducting polymers attracted remarkable attention for development of new immobilization matrices for enzymes. Hereby, an efficient surface design was investigated by modifying the graphite rod electrode surfaces with one-step electrospun nylon 6,6 nanofibers or 4% (w/w) multiwalled carbon nanotubes (MWCNTs) incorporating nylon 6,6 nanofibers (nylon 6,6/4MWCNT). High-resolution transmission electron microscopy study confirmed the successful incorporation of the MWCNTs into the nanofiber matrix for nylon 6,6/4MWCNT sample. Then, these nanofibrous surfaces were coated with a conducting polymer, (poly-4-(4,7-di(thiophen-2-yl)-1H-benzo[d]imidazol-2-yl)benzaldehyde) (PBIBA) to obtain a high electroactive surface area as new functional immobilization matrices. Due to the free aldehyde groups of the polymeric structures, a model enzyme, glucose oxidase was efficiently immobilized to the modified surfaces via covalent binding. Scanning electron microscope images confirmed that the nanofibrous structures were protected after the electrodeposition step of PBIBA and a high amount of protein attachment was successfully achieved by the help of high surface to volume ratio of electroactive nanofiber matrices. The biosensors were characterized in terms of their operational and storage stabilities and kinetic parameters (K-m(app) and I-max). The resulting novel glucose biosensors revealed good stability and promising I-max (10.03 and 16.67 mu A for nylon 6,6/PBIBA and nylon 6,6/4MWCNT/PBIBA modified biosensors, respectively) and long shelf life (32 and 44 days for nylon 6,6/PBIBA and nylon 6,6/4MWCNT/PBIBA modified biosensors, respectively). Finally, the biosensor was tested on beverages for glucose detection., EU FP7-PEOPLE-2009-RG Marie Curie-IRG (NANOWEB)European Union (EU) [PIRG06-GA-2009-256428]; The Turkish Academy of Sciences - Outstanding Young Scientists Award Program (TUBA-GEBIP)Turkish Academy of Sciences; TUBITAK-BIDEBTurkiye Bilimsel ve Teknolojik Arastirma Kurumu (TUBITAK), Dr. T. Uyar acknowledges EU FP7-PEOPLE-2009-RG Marie Curie-IRG (NANOWEB, PIRG06-GA-2009-256428) and The Turkish Academy of Sciences - Outstanding Young Scientists Award Program (TUBA-GEBIP) for partial funding of the research. F. Kayaci acknowledges TUBITAK-BIDEB for National PhD Scholarship.

Oxygen vacancies (VOs) in ZnO are well-known to enhance photocatalytic activity (PCA) despite various other intrinsic crystal defects. In this study, we aim to elucidate the effect of zinc interstitials (Zn i) and VOs on PCA, which has applied as well as fundamental interest. To achieve this, the major hurdle of fabricating ZnO with controlled defect density requires to be overcome, where it is acknowledged that defect level control in ZnO is significantly difficult. In the present context, we fabricated nanostructures and thoroughly characterized their morphological (SEM, TEM), structural (XRD, TEM), chemical (XPS) and optical (photoluminescence, PL) properties. To fabricate the nanostructures, we adopted atomic layer deposition (ALD), which is a powerful bottom-up approach. However, to control defects, we chose polysulfone electrospun nanofibers as a substrate on which the non-uniform adsorption of ALD precursors is inevitable because of the differences in the hydrophilic nature of the functional groups. For the first 100 cycles, Znis were predominant in ZnO quantum dots (QDs), while the presence of VOs was negligible. As the ALD cycle number increased, VOs were introduced, whereas the density of Zni remained unchanged. We employed PL spectra to identify and quantify the density of each defect for all the samples. PCA was performed on all the samples, and the percent change in the decay constant for each sample was juxtaposed with the relative densities of Znis and VOs. A logical comparison of the relative defect densities of Znis and VOs suggested that the former are less efficient than the latter because of the differences in the intrinsic nature and the physical accessibility of the defects. Other reasons for the efficiency differences were elaborated. © 2014 the Partner Organisations.

A hierarchy of nanostructured-ZnO was fabricated on the electrospun nanofibers by atomic layer deposition (ALD) and hydrothermal growth, subsequently. Firstly, we produced poly(acrylonitrile) (PAN) nanofibers via electrospinning, then ALD process provided a highly uniform and conformal coating of polycrystalline ZnO with a precise control on the thickness (50 nm). In the last step, this ZnO coating depicting dominant oxygen vacancies and significant grain boundaries was used as a seed on which single crystalline ZnO nanoneedles (average diameter and length of ∼25 nm and ∼600 nm, respectively) with high optical quality were hydrothermally grown. The detailed morphological and structural studies were performed on the resulting nanofibers, and the photocatalytic activity (PCA) was tested with reference to the degradation of methylene blue. The results of PCA were discussed in conjunction with photoluminescence response. The nanoneedle structures supported the vectorial transport of photo-charge carriers, which is crucial for high catalytic activity. The enhanced PCA, structural stability and reusability of the PAN/ZnO nanoneedles indicated that this hierarchical structure is a potential candidate for waste water treatment.

Heterojunctions are a well-studied material combination in photocatalysis studies, the majority of which aim to improve the efficacy of the catalysts. Developing novel catalysts begs the question of which photo-generated charge carrier is more efficient in the process of catalysis and the associated mechanism. To address this issue we have fabricated core-shell heterojunction (CSHJ) nanofibers from ZnO and TiO2 in two combinations where only the 'shell' part of the heterojunction is exposed to the environment to participate in the photocatalysis. Core and shell structures were fabricated via electrospinning and atomic layer deposition, respectively which were then subjected to calcination. These CSHJs were characterized and studied for photocatalytic activity (PCA). These two combinations expose electrons or holes selectively to the environment. Under suitable illumination of the ZnO-TiO 2 CSHJ, e/h pairs are created mainly in TiO2 and the electrons take part in catalysis (i.e. reduce the organic dye) at the conduction band or oxygen vacancy sites of the 'shell', while holes migrate to the core of the structure. Conversely, holes take part in catalysis and electrons diffuse to the core in the case of a TiO2-ZnO CSHJ. The results further revealed that the TiO2-ZnO CSHJ shows ∼1.6 times faster PCA when compared to the ZnO-TiO2 CSHJ because of efficient hole capture by oxygen vacancies, and the lower mobility of holes. © 2014 the Partner Organisations.

The photoluminescent germanium nanocrystals (Ge-NCs) were successfully incorporated into electrospun polymeric nanofiber matrix in order to develop photoluminescent nanofibrous composite web. In the first step, the synthesis of Ge-NCs was achieved by nanosecond pulsed laser ablation of bulk germanium wafer immersed in organic liquid. The size, the structural and the chemical characteristics of Ge-NCs investigated by TEM, XPS, XRD and Raman spectroscopy revealed that the Ge-NCs were highly pure and highly crystalline having spherical shape within 3-20 nm particle size distribution. In the second step, Ge-NCs were mixed with polyvinyl alcohol (PVA) polymer solution, and then, Ge-NC/PVA nanofibers were obtained via electrospinning technique. The electrospinning of Ge-NCs/PVA nanoweb composite structure was successful and bead-free Ge-NCs/PVA nanofibers having average fiber diameter of 185 +/- 40 nm were obtained. The STEM analysis of the electrospun Ge-NCs/PVA nanofibers elucidated that the Ge-NCs were distributed homogeneously in the polymeric nanofiber matrix. The UV-Vis absorption and photoluminescence spectroscopy studies indicated the quantum confinement effect of Ge-NCs on the optical properties of the electrospun Ge-NCs/PVA nanoweb. (C) 2013 Elsevier Ltd. All rights reserved.

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. © 2013 American Chemical Society.

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 (alpha-CD, beta-CD and gamma-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. (C) 2013 Elsevier B.V. All rights reserved.

We produced functional nanowebs, containing vanillin, having prolonged shelf-life and high temperature stability facilitated by cyclodextrin (CD) inclusion complexation. Polyvinyl alcohol (PVA) nanowebs incorporating vanillin/cyclodextrin inclusion complex (vanillin/CD-IC) were produced via electrospinning technique. The vanillin/CD-IC was prepared with three types of CDs; alpha-CD, beta-CD and gamma-CD to find out the most favourable CD type for the stabilization of vanillin. PVA/vanillin/CD-IC nanofibres, having fibre diameters around similar to 200 nm, were successfully electrospun from aqueous mixture of PVA and vanillin/CD-IC. Our results indicated that vanillin with enhanced durability and high temperature stability was achieved for PVA/vanillin/CD-IC nanowebs due to complexation of vanillin with CD, whereas the PVA nanofibres without CD-IC could not effectively preserve the vanillin. Additionally, we observed that PVA/vanillin/gamma-CD-IC nanoweb was more effective for the stabilization and slow release of vanillin suggesting that the strength of interaction between vanillin and the gamma-CD cavity is stronger when compared to alpha-CD and beta-CD. (C) 2012 Elsevier Ltd. All rights reserved.

Conference name: Materials Research Society Symposium (MRS) Proceedings, 2011 Materials Research Society (MRS) Fall Meeting & Exhibit, Date of Conference: November 28-December 2, 2011 Al 2O 3 and AlN nanotubes were fabricated by depositing conformal thin films via atomic layer deposition (ALD) on electrospun nylon 66 (PA66) nanofiber templates. Depositions were carried out at 200°C, using trimethylaluminum (TMAl), water (H 2O), and ammonia (NH 3) as the aluminum, oxygen, and nitrogen precursors, respectively. Deposition rates of Al 2O 3 and AlN at this temperature were ∼1.05 and 0.86 Å/cycle. After the depositions, Al 2O 3- and AlN-coated nanofibers were calcinated at 500°C for 2 h in order to remove organic components. Nanotubes were characterized by using X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). AlN nanotubes were polycrystalline as determined by high resolution TEM (HR-TEM) and selected area electron diffraction (SAED). TEM images of all the samples reported in this study indicated uniform wall thicknesses. © 2012 Materials Research Society.

Cataloged from PDF version of article. Polymer-inorganic core-shell nanofibers were produced by two-step approach; electrospinning and atomic layer deposition (ALD). First, nylon 6,6 (polymeric core) nanofibers were obtained by electrospinning, and then zinc oxide (ZnO) (inorganic shell) with precise thickness control was deposited onto electrospun nylon 6,6 nanofibers using ALD technique. The bead-free and uniform nylon 6,6 nanofibers having different average fiber diameters (∼80, ∼240 and ∼650 nm) were achieved by using two different solvent systems and polymer concentrations. ZnO layer about 90 nm, having uniform thickness around the fiber structure, was successfully deposited onto the nylon 6,6 nanofibers. Because of the low deposition temperature utilized (200 °C), ALD process did not deform the polymeric fiber structure, and highly conformal ZnO layer with precise thickness and composition over a large scale were accomplished regardless of the differences in fiber diameters. ZnO shell layer was found to have a polycrystalline nature with hexagonal wurtzite structure. The core-shell nylon 6,6-ZnO nanofiber mats were flexible because of the polymeric core component. Photocatalytic activity of the core-shell nylon 6,6-ZnO nanofiber mats were tested by following the photocatalytic decomposition of rhodamine-B dye. The nylon 6,6-ZnO nanofiber mat, having thinner fiber diameter, has shown better photocatalytic efficiency due to higher surface area of this sample. These nylon 6,6-ZnO nanofiber mats have also shown structural stability and kept their photocatalytic activity for the second cycle test. Our findings suggest that core-shell nylon 6,6-ZnO nanofiber mat can be a very good candidate as a filter material for water purification and organic waste treatment because of their photocatalytic properties along with structural flexibility and stability. © 2012 American Chemical Society.

Zein nanofibers containing cyclodextrins (zein/CD) were produced via electrospinning. Three types of CDs (alpha-CD, beta-CD and gamma-CD) having 10%, 25% and 50% (w/w) were individually incorporated into zein nanofibers. SEM imaging elucidated that the morphologies of the electrospun zein/CD nanofibers depended on the CD type and weight percentage. The incorporation of CDs in zein improved the electrospinnability and bead-free nanofibers were obtained at lower zein concentrations. Zein/CD nanofibers having fiber diameters similar to 100-400 nm were obtained depending on the zein concentrations, types and weight percentages of CD. XRD studies revealed that CDs were mostly distributed without forming crystalline aggregates for zein/CD nanofibers containing lower weight percentage of CDs. The surface analyses of zein/CD nanofibers by ATR-FTIR and XPS indicated that some of the CDs were present on the fiber surface. Thermal analyses showed that zein/beta-CD nanofibers have shown higher glass transition temperatures and higher degradation temperature with increasing CD content. (C) 2012 Elsevier Ltd. All rights reserved.

In this study, polymeric nanofibrous composites containing anatase TiO 2 short nanofibers (TiO2-SNF) were successfully produced via electrospinning. The fabrication of the nanofibrous composite structure includes two steps. First, anatase TiO2 nanofibers were obtained by calcination of electrospun PVP/TiO2 nanofibers and then crushed into short nanofibers ranging from few microns in length. Second, these TiO 2-SNF were dispersed into polymer solutions and then electrospun into nanofibrous composites. We obtained nanofibers containing TiO2-SNF from different polymer types including PMMA, PAN, PET and PC. The SEM and TEM imaging indicated that some of the TiO2-SNF were fully covered by the polymeric matrix whereas some TiO2-SNF were partially covered and/or stick on the surface of the fibers. The photocatalytic activity of nanofibrous composites containing TiO2-SNF was evaluated by monitoring the photocatalytic decomposition of a model dye (rhodamine-6G) under UV irradiation. © 2011 Elsevier B.V. All rights reserved.

Cataloged from PDF version of article. Electrospun polymeric nanofibers were either surface-decorated with zinc oxide (ZnO) nanoparticles or coated with a continuous ZnO thin film with a precise thickness (similar to 27 nm) via atomic layer deposition (ALD) for the fabrication of flexible photocatalytic nanofibrous membranes.