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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.

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.

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.