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Tailoring the blue photoluminescence (PL) in Al-doped ZnO (AZO)/TiO2 heterostructures is demonstrated by a controlled induction of shallow defect centers by 50 keV Ar+-ions. This is established by a combination of temperature dependent PL and electron paramagnetic resonance spectroscopy. The dominant blue-violet PL in an as-grown sample comprises a near band-edge emission, along with a peak associated with a radiative recombination of the electrons in shallow donor levels (Zn interstitials) and the holes from the valence band. However, the evolution of an additional yellow-green PL band at a fluence of 1 × 1015 ions/cm2 is governed by deep donor levels, particularly ionized oxygen vacancies. Irradiation at 1 × 1016 ions/cm2 further leads to the formation of Zn vacancies (shallow acceptors) owing to the development of an O-rich surface. The structural modifications of these samples have been investigated by field-emission scanning electron microscopy , transmission electron microscopy, and Rutherford backscattering. While small micro-cracks are found at a fluence of 2 × 1016 ions/cm2, the formation of graded layers is obtained at the highest fluence of 5 × 1016 ions/cm2 owing to ballistic intermixing and diffusion of the constituents. Detailed investigation suggests that a significant amount of Ti atoms is diffused in AZO by a complete deterioration of the AZO/TiO2 matrix at the highest fluence. [ABSTRACT FROM AUTHOR]

Chaman Saini,1 Praveen Kumar,1,2 Mohd Tarique,1 Alpana Sharma,1 Venkatesh Ramesh3 1Department of Biochemistry, All India Institute of Medical Sciences, New Delhi, India; 2Department of Microbiology, Government Medical College, Kota, India; 3Department of Dermatology, Safdarjung Hospital, New Delhi, India Background: The clinical forms of cutaneous tuberculosis (CTB) consist of a spectrum that reflects the host’s immune response to Mycobacterium tuberculosis; it provides an ideal model to study the immunological dysregulation in humans. IL-17 plays an important role in initial immune response and is involved in both immune-mediated protection and pathology during M. tuberculosis infection. TGF-β producing regulatory T-cells (Tregs) are high in leprosy patients and responsible for immune suppression. However, in CTB, the involvement of Tregs and Th17 remains unevaluated. Objective: To study the role of proinflammatory Th17 and Treg cells in the human CTB. Methods: Blood and skin biopsies of CTB patients and healthy controls (HC) were included in the study. Flow cytometric analysis of IL-17, FOXP3, and TGF-β in blood was done followed by immunohistochemistry on paraffin-embedded skin sections. Expression of IFN-γ, TGF-β, and IL-17 was evaluated by quantitative real-time PCR. Results: We found significant (P

The work function engineering in metal-oxide nanostructures by judicious doping of impurities is not straightforward as it introduces multiple defects in the system. In this regard, understanding the nitrogen (N) doping-induced modulation of Fermi levels in TiO2 nanotubes (TNTs) is challenging for visible-range photocatalytic applications. Here, 50 keV N ions are implanted in TNTs with a fluence range of 1014–1016 ions/cm2. X-ray diffraction and micro-Raman analyses demonstrate the formation of anatase-TiO2 in pristine TNTs, while the crystalline quality is significantly affected by increasing ion fluence. The evolution of Ti3+ is also established by X-ray photoelectron spectroscopy, whereas ultraviolet photoelectron spectroscopy reveals the reduction in work function due to the formation of oxygen vacancies, in good agreement with X-ray absorption spectroscopy and photoluminescence results. The electron paramagnetic resonance study further identifies the evolution of Ti3+/N-substitutional defect centers. Finally, an enhancement in visible-light-assisted methylene blue and Rhodamine B dye degradation is recorded up to a fluence of 1 × 1015 ions/cm2, and it is correlated with the N-ion implantation-induced formation of electrochemically active states near the conduction band minimum and the valence band maximum. The decrease in degradation efficiency beyond a critical fluence of 1015 ions/cm2 is discussed on the ground of ion-beam-mediated amorphization and the subsequent increase in electron–hole recombination in the defect states. [ABSTRACT FROM AUTHOR]

The efficacy of 50 keV Ar+-ion irradiation toward the interfacial and stoichiometric engineering of strained Al-doped ZnO (AZO)/TiO2 heterostructure is systematically investigated using a variety of experimental techniques, notably by cross-sectional transmission electron microscopy. Glancing-angle X-ray diffraction evidences the release of in-plane compressive stress from the as-grown AZO/TiO2 bilayer structure at a critical fluence of 1 × 1016 ions/cm2, and we discuss in the light of microcracks and voids formation combined with the dewetting phenomenon. Ion irradiation also leads to an improvement of stoichiometry in both top AZO and underneath amorphous TiO2 layers, as manifested by depth-dependent energy dispersive X-ray spectroscopy owing to the large diffusion of oxygen toward the AZO/TiO2 interfacial region through the AZO defect sites. Such ion beam induced self-healing in stoichiometry of AZO/TiO2 heterostructure has been attributed to a conjunction of sputtering and diffusion phenomena involving the constituent elements (Zn, Ti, and O). Further increase in ion fluence up to 5 × 1016 ions/cm2 causes a complete deterioration of the heterostructure with the formation of a graded layer via intermixing of these elements, followed by the evolution of voids. [ABSTRACT FROM AUTHOR]

Post-deposition annealing mediated evolution of self-decorated Au nanoparticles (NPs) on chemically etched Si pyramids is presented. A distinct transformation of Si surfaces from hydrophilic to hydrophobic is initially found after chemical texturing, showing an increase in contact angle (CA) from 58° to 98° (±1°). Further improvement of hydrophobicity with CA up to ~118° has been established after annealing a 10 nm thick Au-coated Si pyramids at 400 °C that led to the formation of Au NPs on Si facets along with self-ordering at the pyramid edges. Detailed x-ray diffraction studies suggest the evolution of crystalline Au NPs on strained Si facets. Microstructural studies, however, indicate no mixing of Au and Si atoms at the Au/Si interfaces, instead of forming Au nanocrystals at 400 °C. The improved hydrophobicity of Si pyramids, even with Au NPs can be explained in the light of a decrease in solid fractional surface area according to Wenzel's model. Moreover, a sharp drop in specular reflectance from Si pyramids in the range of 300-800 nm, especially in the ultraviolet region up to ~0.4% is recorded in the presence of Au NPs by ultraviolet-visible spectroscopy, reflecting the possible use in photovoltaic devices with improved antireflection property. [ABSTRACT FROM AUTHOR]

Towards developing next generation scalable TiO2-based resistive switching (RS) memory devices, the efficacy of 50 keV Ar+-ion irradiation to achieve self-organized nano-channel based structures at a threshold fluence of 5×1016 ions/cm2 at ambient temperature is presented. Although x-ray diffraction results suggest the amorphization of as-grown TiO2 layers, detailed transmission electron microscopy study reveals fluence-dependent evolution of voids and eventual formation of selforganized nano-channels between them. Moreover, gradual increase of TiO/Ti2O3 in the near surface region, as monitored by x-ray photoelectron spectroscopy, establishes the upsurge in oxygen deficient centers. The impact of structural and chemical modification on local RS behavior has also been investigated by current-voltage measurements in conductive atomic force microscopy, while memory application is manifested by fabricating Pt/TiO2/Pt/Ti/SiO2/Si devices. Finally, the underlying mechanism of our experimental results has been analyzed and discussed in the light of oxygen vacancy migration through nano-channels. [ABSTRACT FROM AUTHOR]

Al-doped ZnO (AZO) thin films of thicknesses 5,10, 15, 20, and 30 nm were deposited on 500 eV argon ion-beam fabricated nanoscale self-organized rippled-Si substrates at room temperature and are compared with similar films deposited on pristine-Si substrates (without ripples). It is observed that morphology of self-organized AZO films is driven by the underlying substrate morphology. For instance, for pristine-Si substrates, a granular morphology evolves for all AZO films. On the other hand, for rippled-Si substrates, morphologies having chain-like arrangement (anisotropic in nature) are observed up to a thickness of 20 nm, while a granular morphology evolves (isotropic in nature) for 30 nm-thick film. Photoluminescence studies reveal that excitonic peaks corresponding to 5-15 nm-thick AZO films, grown on rippled-Si templates, show a blue shift of 8 nm and 3 nm, respectively, whereas the peak shift is negligible for 20-nm thick film (with respect to their pristine counter parts). The observed blue shifts are substantiated by diffuse reflectance study and attributed to quantum confinement effect, associated with the size of the AZO grains and their spatial arrangements driven by the anisotropic morphology of underlying rippled-Si templates. The present findings will be useful for making tunable AZO-based light-emitting devices. [ABSTRACT FROM AUTHOR]

Room temperature transformation from anatase (A-TiO2) to rutile (R-TiO2) thin films through an intermediate mixed phase on stainless steel driven by a controlled oxygen flow rate (OFR) is investigated. Such OFR dependent phase transition is confirmed by X-ray diffraction and also consistent with X-ray absorption spectroscopy at Ti L and O K-edges, showing a long range ordering in TiO6 octahedral symmetry. X-ray photoelectron spectroscopy reveals a gradual reduction in Ti2O3 and/or TiO intermediate phases with increasing OFR. Finally, an enhanced photocatalytic activity is observed in the mixed phase and discussed in terms of photo-generated charge transport in the type-II staggered band structure between A-TiO2 and R-TiO2 phases. [ABSTRACT FROM AUTHOR]

Oxygen vacancy (OV) controlled hydrophobicity of self-assembled TiO2 nanorods (NRs) on chemically etched Si pyramids is investigated by irradiating with 50 keV Ar+-ions at room temperature. Apparent contact angle (CA) is found to increase from 122° to 141° up to a fluence of 1 × 1015 ions/cm2, followed by a gradual reduction to 130° at 1 × 1017 ions/cm2. However, the drop in apparent CA is found to be associated with the decrease in fractional surface area via transformation of NRs to an amorphous layer above 1 × 1015 ions/cm2, though it is still higher than that of as-grown one. Detailed X-ray photoelectron spectroscopy and electron paramagnetic resonance measurements suggest that the control of hydrophobic behavior is related to the suppression of surface free energy via migration of OVs into the voids in TiOx layers. [ABSTRACT FROM AUTHOR]

The variation of electron density in TiO2-x nanochannels, exhibiting resistive switching phenomenon, produced by Ar+ ion-irradiation at the threshold fluence of 5x1016 ions/cm² is demonstrated by X-ray reflectivity (XRR). The transmission electron microscopy reveals the formation of nanochannels, while the energy dispersive X-ray spectroscopy confirms Ti enrichment near the surface due to ion-irradiation, in consistent with the increase in electron density by XRR measurements. Such a variation in Ti concentration indicates the evolution of oxygen vacancies (OVs) along the TiO2-x nanochannels, and thus paves the way to explain the operation and performance of the Pt/TiO2-x/Pt-based memory devices via OV migration. [ABSTRACT FROM AUTHOR]

Herein, we present the cationic impurity-assisted band offset phenomena in NixCd1-xO (x = 0, 0.02, 0.05, 0.1, 0.2, 0.4, 0.8, and 1) thin films and further discuss them based on orbital hybridization modification. The compositional and structural studies revealed that the cationic substitution of Cd2+ by Ni2+ ions leads to a monotonic shift in the (220) diffraction peak, indicating the suppression of lattice distortion, while the evolution of local strain with an increase in Ni concentration is mainly associated with the mismatch in the electronegativity of the Cd2+ and Ni2+ ions. In fact, Fermi level pinning towards the conduction band minimum takes place with an increase in the Ni concentration at the cost of electronically compensated oxygen vacancies, resulting in the modification of the distribution of carrier concentration, which eventually affects the band edge effective mass of the conduction band electrons and further endorses band gap renormalization. Besides, the appearance of a longitudinal optical (LO) mode at 477 cm-1, as manifested by Raman spectroscopy, also indicates the active involvement of electron-phonon scattering, whereas modification in the local coordination environment, particularly anti-crossing interaction in conjunction with the presence of satellite features and shake-up states with Ni doping, was confirmed by X-ray absorption near-edge and X-ray photoelectron spectroscopy studies. These results manifest the gradual reduction of orbital hybridization upon the incorporation of Ni, leading to a decrement in the band edge effective electron mass. Finally, the molecular dynamics simulation reflected a 13% reduction in the lattice parameter for the NiO thin film compared to the undoped film, while the projected density of states calculation further supports the experimental observation of reduced orbital hybridization with an increase in Ni concentration.

Visceral Leishmaniasis is a deadly parasitic disease caused by Leishmania donovani. Paucity exists in the discovery of novel chemotherapeutics against Leishmaniasis. In this study, we synthesized a natural product inspired Diversity Oriented Synthesis library of L. donovani Trypanothione reductase (LdTR) inhibitor β-carboline-quinazolinone hybrids, which are different in stereochemical architecture and diverse in the bioactive chemical space. It is noteworthy that chirality affects drug-to-protein binding affinity since proteins in any living system are present only in one of the chiral forms. Upon evaluation of the hybrids, one of the chiral forms i.e. Compound 1 showed profound cytotoxic effect in micromolar range as compared to its other chiral form i.e. Compound 2. In-silico docking studies confirmed high binding efficiency of Compound 1 with the catalytic pocket of LdTR. Treatment of L. donovani parasites with Compound 1 inhibits LdTR activity, induces imbalance in redox homeostasis by enhancing ROS, disrupts the mitochondrial membrane potential, modifies actin polymerization and alters the surface topology and architecture. All these cellular modifications eventually led to apoptosis-like death of promastigotes. Furthermore, we synthesized the analogues of Compound 1 and found that these compounds show profound antileishmanial activity in the nanomolar range both in promastigotes and intracellular amastigotes. The enhanced inhibitory potential of these compounds was further supported by in-silico analysis of protein-ligand interactions which revealed high binding efficiency towards the catalytic pocket of LdTR. Taken together, this study reports the serendipitous discovery of β-carboline-quinazolinone hybrids with enhanced antileishmanial activity along with the in-depth structure-activity relationships and mechanism of action of these analogues., (Copyright © 2016 Elsevier Inc. All rights reserved.)