TiO2/ZnO core/shell nano-heterostructure arrays as photo-electrodes with enhanced visible light photoelectrochemical performance

The present article reports a facile method for preparing the vertically-aligned 1D arrays of a new type of type II n-n TiO2/ZnO core/shell nano-heterostructures by growing the nano-shell of ZnO on the electrochemically fabricated TiO2 nanotubes core for visible light driven photoelectrochemical applications. The strong interfacial interaction at the type II heterojunction leads to an effective interfacial charge separation and charge transport. The presence of various defects such as surface states, interface states and other defects in the nano-heterostructure enable it for improved visible light photoelectrochemical performance. The presence of such defects has also been confirmed by the UV-vis absorption, cathodoluminescence, and crystallographic studies. The TiO2/ZnO core/shell nano-heterostructures exhibit strong green luminescence due to the defect transitions. The TiO2/ZnO core/shell nano-heterostructures photo-electrode show significant enhancement of visible light absorption and it provides a photocurrent density of 0.7 mA cm(-2) at 1 V vs. Ag/AgCl, which is almost 2.7 times that of the TiO2/ZnO core/shell nano-heterostructures under dark conditions. The electrochemical impedance spectroscopy results demonstrate that the substantially improved photoelectrochemical and photo-switching performance of the nano-heterostructures photo-anode is because of the enhancement of interfacial charge transfer and the increase in the charge carrier density caused by the incorporation of the ZnO nano-shell on TiO2 nanotube core.

Dissociation Constants of Weak Acids from ab Initio Molecular Dynamics Using Metadynamics: Influence of the Inductive Effect and Hydrogen Bonding on pK(a) Values

The theoretical estimation of the dissociation constant, or pK(a), of weak acids continues to be a challenging field. Here, we show that ab initio CarParrinello molecular dynamics simulations in conjunction with metadynamics calculations of the free-energy profile of the dissociation reaction provide reasonable estimates of the pK(a) value. Water molecules, sufficient to complete the three hydration shells surrounding the acid molecule, were included explicitly in the computation procedure. The free-energy profiles exhibit two distinct minima corresponding to the dissociated and neutral states of the acid, and the difference in their values provides the estimate for pK(a). We show for a series of organic acids that CPMD simulations in conjunction with metadynamics can provide reasonable estimates of pK(a) values. The acids investigated were aliphatic carboxylic acids, chlorine-substituted carboxylic acids, cis- and trans-butenedioic acid, and the isomers of hydroxybenzoic acid. These systems were chosen to highlight that the procedure could correctly account for the influence of the inductive effect as well as hydrogen bonding on pK(a) values of weak organic acids. In both situations, the CPMD metadynamics procedure faithfully reproduces the experimentally observed trend and the magnitudes of the pK(a) values.

Herringbone to cofacial solid state packing via H-bonding in diketopyrrolopyrrole (DPP) based molecular crystals: influence on charge transport

Themono-alkylation of DPP derivatives leads to cofacial pi-pi stacking via H-bonding unlike their di-alkylated counterparts, which exhibit a classical herringbone packing pattern. Single crystal organic field-effect transistor (OFET) measurements reveal a significant enhancement of charge carrier mobility for mono-hexyl DPP derivatives.

MRT Letter: Two-Photon Excitation-Based 2pi Light-Sheet System for Nano-Lithography

We propose two-photon excitation-based light-sheet technique for nano-lithography. The system consists of 2 -configured cylindrical lens system with a common geometrical focus. Upon superposition, the phase-matched counter-propagating light-sheets result in the generation of identical and equi spaced nano-bump pattern. Study shows a feature size of as small as few tens of nanometers with a inter-bump distance of few hundred nanometers. This technique overcomes some of the limitations of existing nano-lithography techniques, thereby, may pave the way for mass-production of nano-structures. Potential applications can also be found in optical microscopy, plasmonics, and nano-electronics. Microsc. Res. Tech. 78:1-7, 2015. (c) 2014 Wiley Periodicals, Inc.

Experimental validation of `pnicogen bonding' in nitrogen by charge density analysis

The participation of a nitrogen atom acting as an electrophile in pnicogen bonding, a hitherto unexplored interaction has been established by experimental charge density analysis. QTAIM and NBO analyses ratify this observation.

Ionic Bonding between Artificial Atoms

Conventional solids are prepared from building blocks that are conceptually no larger than a hundred atoms. While van der Waals and dipole-dipole interactions also influence the formation of these materials, stronger interactions, referred to as chemical bonds, play a more decisive role in determining the structures of most solids. Chemical bonds that hold such materials together are said to be ionic, covalent, metallic, dative, or otherwise a combination of these. Solids that utilize semiconductor nanocrystal quantum dots as building units have been demonstrated to exist; however, the interparticle forces in such materials are decidedly not chemical. Here we demonstrate the formation of charge transfer states in a binary quantum dot mixture. Charge is observed to reside in quantum confined states of one of the participating quantum dots. These interactions lead to materials that may be regarded as the nanoscale analog of an ionic solid. The process by which these materials form has interesting parallels to chemical reactions in conventional chemistry.

Facile synthesis of PbWO4: Applications in photoluminescence and photocatalytic degradation of organic dyes under visible light

Stolzite polymorph of PbWO4 catalyst was prepared by the facile room temperature precipitation method. Structural parameters were refined by the Rietveld analysis using powder X-ray data. PbWO4 was crystallized in the scheelite-type tetragonal structure with space group I4(1)/a (No. 88). Field emission scanning electron microscopy revealed leaf like morphology. Photoluminescence spectra exhibit broad blue emission (425 nm) under the excitation of 356 nm. The photocatalytic degradation of Methylene blue, Rhodamine B and Methyl orange dyes were measured under visible illumination. The 100% dye degradation was observed for MB and RhB dyes within 60 and 105 min. The rate constant was found to be in the decreasing order of MB > RhB > MO which followed the 1st order kinetic mechanism. Therefore, PbWO4 can be a potential candidate for blue component in white LEDs and also acts as a catalyst for the treatment of toxic and non-biodegradable organic pollutants in water. (C) 2014 Elsevier B.V. All rights reserved.

Visible light assisted photocatalytic degradation of organic dyes on TiO2-CNT nanocomposites

Carbon nanotubes (CNTs) uniformly decorated with nano-anatase TiO2 particles corresponding to different TiO2-CNT weight ratios (up to 90 % TiO2:10 % CNT) were prepared by employing sol-gel process. The nanocomposites were characterized by X-ray diffraction, IR, Raman, Scanning electron microscopy, Transmission electron microscopy, Photoluminescence, BET surface area and diffuse reflectance measurements. The composites show visible light assisted photocatalytic property, for example, the 90 % TiO2-10 % CNT composite completely degrades Indigo Carmine dye within 1 h of exposure to visible light. Similarly, Orange G and Congo Red dyes were decomposed within 2 h under visible light irradiation. The excellent visible light photocatalytic property of the composite is attributed to the synergetic effect of photoexcitation and photosensitization. This is due to the special nanoarchitecture wherein TiO2 nanoparticles are anchored to CNT surface that provides high specific interfacial area for photon absorption and electron trapping. Visible light assisted degradation profile of Indigo Carmine in the presence of TiO2-CNT nanocomposite and TEM image of the TiO2-CNT nanocomposite.

Halogen Bonding Controls the Regioselectivity of the Deiodination of Thyroid Hormones and their Sulfate Analogues

The type1 iodothyronine deiodinase (1D-1) in liver and kidney converts the L-thyroxine (T4), a prohormone, by outer-ring (5) deiodination to biologically active 3,3,5-triiodothyronine (T3) or by inner-ring (5) deiodination to inactive 3,3,5-triiodothronine (rT3). Sulfate conjugation is an important step in the irreversible inactivation of thyroid hormones. While sulfate conjugation of the phenolic hydroxyl group stimulates the 5-deiodination of T4 and T3, it blocks the 5-deiodination of T4. We show that thyroxine sulfate (T4S) undergoes faster deiodination as compared to the parent thyroid hormone T4 by synthetic selenium compounds. It is also shown that ID-3 mimics, which are remarkably selective to the inner-ring deiodination of T4 and T3, changes the selectivity completely when T4S is used as a substrate. From the theoretical investigations, it is observed that the strength of halogen bonding increases upon sulfate conjugation, which leads to a change in the regioselectivity of ID-3 mimics towards the deiodination of T4S. It has been shown that these mimics perform both the 5- and 5-ring deiodinations by an identical mechanism.

Electronic Structure of CH3NH3PbX3 Perovskites: Dependence on the Halide Moiety

A combination of measurements using photoelectron spectroscopy and calculations using density functional theory (DFT) was applied to compare the detailed electronic structure of the organolead halide perovskites CH3NH3PbI3 and CH3NH3PbBr3. These perovskite materials are used to absorb light in mesoscopic and planar heterojunction solar cells. The Pb 4f core level is investigated to get insight into the chemistry of the two materials. Valence level measurments are also included showing a shift of the valence band edges where there is a higher binding energy of the edge for the CH3NH3PbBr3 perovskite. These changes are supported by the theoretical calculations which indicate that the differences in electronic structure are mainly caused by the nature of the halide ion rather than structural differences. The combination of photoelectron spectroscopy measurements and electronic structure calculations is essential to disentangle how the valence band edge in organolead halide perovskites is governed by the intrinsic difference in energy levels of the halide ions from the influence of chemical bonding.

Remarkable Selectivity and Photo-Cytotoxicity of an Oxidovanadium(IV) Complex of Curcumin in Visible Light

Oxidovanadium(IV) complexes of 2-(2'-pyridyl)-1,10-phenanthroline (pyphen), viz. VO(pyphen)(acac)](ClO4) (1), VO(pyphen)(anacac)](ClO4) (2) and VO(pyphen)(cur)](ClO4) (3), where acac is acetylacetonate (in 1), anacac is anthracenylacetylacetonate (in 2) and cur is curcumin monoanion (in 3) were synthesized, characterized and their photo-induced DNA cleavage activities and photo-cytotoxicities studied. The complexes are 1: 1 electrolytes in DMF. The one-electron paramagnetic complexes show a d-d band near 760 nm in DMF. Complexes 2 and 3 are blue and green emissive, respectively, in DMSO. The complexes exhibit irreversible V-IV/V-III reductive responses near -1.1 V and V-V/V-IV oxidative responses near 0.85 V vs. SCE in DMF-0.1 M TBAP. Complexes 2 and 3 display significant and selective photo-cytotoxicity upon irradiation with visible light giving an IC50 value of about 5 mu M against HeLa and MCF-7 cancer cells; they are significantly less-toxic against normal 3T3 control cells and in the absence of light. Complex 1 was used as a control. Both cytosolic and nuclear localization of the complexes were observed on the basis of fluorescence imaging. The complexes, avid binders to calf thymus (ct) DNA, were found to photocleave supercoiled pUC19 DNA upon irradiation with near-IR light (785 nm) by generating hydroxyl radical (OH) as the reactive oxygen species (ROS). Cell death events noted with HeLa and MCF-7 cell lines likely are attributable to apoptotic pathways involving light-assisted generation of intracellular ROS.

Remarkable visible light-triggered cytotoxicity of mitochondria targeting mixed-ligand cobalt(III) complexes of curcumin and phenanthroline bases binding to human serum albumin

Six new mixed-ligand cobalt(III) complexes of formulation Co(N-N)(2)(O-O)](ClO4)(2) (1-6), where N-N is a N,N-donor phenanthroline base, namely, 1,10-phenanthroline (phen in 1, 2), dipyrido3,2-d:2',3'-f] quinoxaline (dpq in 3, 4), and dipyrido3,2-a:2',3'-c]phenazine (dppz in 5, 6), O-O is acetylacetonate (acac in 1, 3, 5) or curcumin (bis(4-hydroxy-3-methoxyphenyl)-1,6-diene-3,5-dione, cur in 2, 4, 6), have been synthesized and characterized. The X-ray crystal structures of complex 1 (as PF6- salt, 1a) and 3 show distorted octahedral geometries formed by the CoN4O2 core. The complexes 1, 3 and 5 having the simple acac ligand are prepared as control species to understand the role of curcumin. The optimized geometries and the frontier orbitals of the curcumin complexes 2, 4, and 6 are obtained from the DFT calculations. The complexes 2, 4, and 6 having the photoactive curcumin moiety display an absorption band in the visible region near 420 nm and show remarkable photocytotoxicity in HeLa cancer cells with respective IC50 values of 7.4 mu M, 5.1 mu M and 1.6 mu M while being much less toxic in dark. MTT assay using complex 6 shows that it is not significantly photocytotoxic to MCF-10A normal cells. The control complexes having the acac ligand are non-toxic both in the presence and absence of light. The cell death is apoptotic in nature and triggered by the photogeneration of reactive oxygen species. Fluorescence imaging experiments on HeLa cells reveals that complex 6 accumulated primarily inside the mitochondria. Human serum albumin (HSA) binding experiments show that the complexes bind HSA with good affinity, but 6 binds with the highest affinity, with a K-b value of 9.8 x 10(5) M-1. Thus, complex 6 with its negligible toxicity in the dark and in normal cells but remarkable toxicity in visible light holds significant photochemotherapeutic potential.

Efficient Solid-State Light-Emitting CuCdS Nanocrystals Synthesized in Air

Semiconductor nanocrystals (NCs) possess high photoluminescence (PL) typically in the solution phase. In contrary, PL rapidly quenches in the solid state. Efficient solid state luminescence can be achieved by inducing a large Stokes shift. Here we report on a novel synthesis of compositionally controlled CuCdS NCs in air avoiding the usual complexity of using inert atmosphere. These NCs show long-range color tunability over the entire visible range with a remarkable Stokes shift up to about 1.25eV. Overcoating the NCs leads to a high solid-state PL quantum yield (QY) of ca. 55% measured by using an integrating sphere. Unique charge carrier recombination mechanisms have been recognized from the NCs, which are correlated to the internal NC structure probed by using extended X-ray absorption fine structure (EXAFS) spectroscopy. EXAFS measurements show a Cu-rich surface and Cd-rich interior with 46% Cu-I being randomly distributed within 84% of the NC volume creating additional transition states for PL. Color-tunable solid-state luminescence remains stable in air enabling fabrication of light-emitting diodes (LEDs).

Fabrication of novel Ag3PO4/BiOBr heterojunction with high stability and enhanced visible-light-driven photocatalytic activity

Herein, we report a facile and effective method to enhance the photocatalytic activity of bismuth oxybromide (BiOBr) semiconductor through the fabrication of heterojunction with Ag3PO4. The as synthesized Ag3PO4/BiOBr microspheres were characterized with transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), X-ray diffraction (XRD) and UV-vis diffuse reflectance spectroscopy (DRS). The new Ag3PO4/BiOBr heterojunctions exhibited wide absorption in the visible-light region and compared to pure BiOBr and Ag3PO4 samples displayed exceptionally high photocatalytic activity for the degradation of typical organic pollutants such as Rhodamine B (RhB) and phenol. The optimal Ag/Bi weight ratio in Ag3PO4/BiOBr microsphere (AB7) was found to be 0.7. The enhanced photocatalytic activity was related to the efficient separation of electron-hole pairs derived from matching band potentials between BiOBr and Ag3PO4 which results into the generation of natural energy bias at heterojunction and subsequent transfer of photoinduced charge carriers. Moreover, the synthesized samples exhibited almost no loss of activity even after 6 recycling runs indicating their high photocatalytic stability. Considering the facile and environment friendly route for the synthesis of Ag3PO4/BiOBr hybrids with enhanced visible-light induced photocatalytic activity, it is possible to widely apply these hybrids in various fields such as waste water treatment. (C) 2015 Elsevier B.V. All rights reserved.

Spatial filter based light-sheet laser interference technique for three-dimensional nanolithography

We propose a laser interference technique for the fabrication of 3D nano-structures. This is possible with the introduction of specialized spatial filter in a 2 pi cylindrical lens system (consists of two opposing cylindrical lens sharing a common geometrical focus). The spatial filter at the back-aperture of a cylindrical lens gives rise to multiple light-sheet patterns. Two such interfering counter-propagating light-sheet pattern result in periodic 3D nano-pillar structure. This technique overcomes the existing slow point-by-point scanning, and has the ability to pattern selectively over a large volume. The proposed technique allows large-scale fabrication of periodic structures. Computational study shows a field-of-view (patterning volume) of approximately 12: 2mm(3) with the pillar-size of 80 nm and inter-pillar separation of 180 nm. Applications are in nano-waveguides, 3D nano-electronics, photonic crystals, and optical microscopy. (C) 2015 AIP Publishing LLC.