1D/2D Hybrid Te/Graphene and Te/MoS2: Multifaceted Broadband Photonics and Green-Energy Applications.

We highlight the enhanced electronic and optical functionalization in the hybrid heterojunction of one-dimensional (1D) tellurene with a two-dimensional (2D) monolayer of graphene and MoS2 in both lateral and vertical geometries. The structural configurations of these assemblies are optimized with a comparative analysis of the energetics for different positional placements of the 1D system with respect to the hexagonal 2D substrate. The 1D/2D coupling of the electronic structure in this unique assembly enables the realization of the three different types of heterojunctions, viz. type I, type II, and Z-scheme. The interaction with 1D tellurene enables the opening of a band gap of the order of hundreds of meV in 2D graphene for both lateral and vertical geometries. With both static and time-dependent first-principles analysis, we indicate their potential applications in broadband photodetection and absorption, covering a wide range of visible to infrared (near-IR to mid-IR) spectrum from 380 to 10 000 nm. We indicate that this 1D/2D assembly also has bright prospects in green-energy harvesting.

Interaction of a Jaundice Marker Molecule with a Redox-Modulatory Nano-Hybrid: A Combined Electrochemical and Spectroscopic Study toward the Development of a Theranostic Tool.

This study explores a combined electrochemical and spectroscopic approach to investigate the degradation of bilirubin, a molecular marker of jaundice in humans using a biocompatible nanohybrid (citrate-functionalized Mn3 O4 nanohybrid; C-Mn3 O4 NH). The approach is aimed at the development of a facile theranostic tool for treatment, detection, and prognosis of jaundice. Linear sweep voltammetry (LSV) studies on bilirubin, C-Mn3 O4 NH, a model carrier protein, and its complex with bilirubin reveal the efficacy of the nanohybrid for both degradation and detection of bilirubin. Furthermore, spectroscopic studies depict that distal electron transfer to be the probable mechanism behind the observed bilirubin degradation in physiological milieu.

Anisotropic nonlinear optical response in a graphene oxide-gold nanohybrid.

In this Letter, we report for the first time, to the best of our knowledge, the anisotropic optical response in a graphene oxide (GO)-gold (Au) nanohybrid. Polarization-sensitive nonlinear optical absorption measurements revealed that nanohybrids are highly anisotropic, (ß⊥-ß‖)≈28cm/GW, which is more than one order of magnitude higher than that of control GO (2 cm/GW). The first-principle analysis of absorbance at nanohybrid interfaces with varying functional ligand concentrations corroborates with the experimentally observed intrinsic linear anisotropy. Thus, this Letter enables new routes to realize smart and high-performing nonlinear optical systems selectively and directionally such as tunable optical limiters and optical data processing devices.

Broken symmetries and the related interface-induced effects at Weyl-system TaAs in proximity of noble metals.

Weyl semimetal TaAs, congenially accommodating the massless Weyl fermions, furnishes a platform to observe a spontaneous breaking of either the time-reversal or the inversion symmetry and the concurrent genesis of pairs of Weyl nodes with significant topological durability. Former experimental analysis, which reveals that the near-zero spin-polarization of bulk TaAs, experiences a boost in proximity of point-contacts of non-magnetic metals along with the associated tip-induced superconductivity, provides the impetus to study the large-area stacked interfaces of TaAs with noble metals like Au and Ag. The primary outcomes of the present work can be listed as follows: (1) First-principles calculations on the interfacial systems have manifested an increment of the interface-induced spin-polarization and contact-induced transport spin-polarization of TaAs in proximity of noble metals; (2) In contrast to the single interface, for vertically stacked cases, the broken inversion symmetry of the system introduces a z-directional band-dispersion, resulting in an energetically separated series of non-degenerate band crossings. The simultaneous presence of such band-crossings and spin-polarization indicated the coexistence of both broken time reversal and inversion symmetries for metal-semimetal stacked interfaces; (3) quantum transport calculations on different device geometries reveal the importance of contact geometry for spin-transport in TaAs devices. Lateral contacts are found to be more effective in obtaining a uniform spin transport and larger transport spin polarization; (4) the phonon dispersion behaviour of TaAs displays a closure of band-gap with the associated increase of phonon-density of states for the acoustic modes in proximity of lateral contacts of noble metals.

Combinatorial Large-Area MoS2/Anatase-TiO2 Interface: A Pathway to Emergent Optical and Optoelectronic Functionalities.

The interface of transition-metal dichalcogenides (TMDCs) and high-k dielectric transition-metal oxides (TMOs) had triggered umpteen discourses because of the indubitable impact of TMOs in reducing the contact resistances and restraining the Fermi-level pinning for the metal-TMDC contacts. In the present work, we focus on the unresolved tumults of large-area TMDC/TMO interfaces, grown by adopting different techniques. Here, on a pulsed laser-deposited MoS2 thin film, a layer of TiO2 is grown by atomic layer deposition (ALD) and pulsed laser deposition (PLD). These two different techniques emanate the layer of TiO2 with different crystallinities, thicknesses, and interfacial morphologies, subsequently influencing the electronic and optical properties of the interfaces. Contrasting the earlier reports of n-type doping at the exfoliated MoS2/TiO2 interfaces, the large-area MoS2/anatase-TiO2 films had realized a p-type doping of the underneath MoS2, manifesting a boost in the extent of p-type doping with increasing thickness of TiO2, as emerged from the X-ray photoelectron spectra. Density functional analysis of the MoS2/anatase-TiO2 interfaces, with pristine and interfacial defect configurations, could correlate the interdependence of doping and the terminating atomic surface of TiO2 on MoS2. The optical properties of the interface, encompassing photoluminescence, transient absorption and z-scan two-photon absorption, indicate the presence of defect-induced localized midgap levels in MoS2/TiO2 (PLD) and a relatively defect-free interface in MoS2/TiO2 (ALD), corroborating nicely with the corresponding theoretical analysis. From the investigation of optical properties, we indicate that the MoS2/TiO2 (PLD) interface may act as a promising saturable absorber, having a significant nonlinear response for the sub-band-gap excitations. Moreover, the MoS2/TiO2 (PLD) interface had exemplified better phototransport properties. A potential application of MoS2/TiO2 (PLD) is demonstrated by the fabrication of a p-type phototransistor with the ionic-gel top gate. This endeavor to analyze and perceive the MoS2/TiO2 interface establishes the prospectives of large-area interfaces in the field of optics and optoelectronics.

Intriguing electronic and optical prospects of FCC bimetallic two-dimensional heterostructures: epsilon near-zero behavior in UV-Vis range.

A higher superconducting critical temperature and large-area epsilon-near-zero systems are two long-standing goals of the scientific community, having an explicit relationship with the correlated electrons in localized orbitals. Motivated by the recent experimental findings of the strongly correlated phenomena in nanostructures of simple Drude metallic systems, we have theoretically investigated some potential bimetallic FCC combinations having close resemblance with the experimental systems. The explored systems include the large-area interface to the embedded and doped two-dimensional (2D) combinatorial nanostructures. Using different effective single-particle first-principles approaches encompassing density functional theory (DFT), time-dependent DFT (TDDFT), phonon and DFT-coupled quantum transport, we propose some interesting correlated prospects of potential bimetallic nanostructures like Au/Ag and Pt/Pd. For the 2D doped and embedded nanostructures of these systems, the DFT-calculated non-trivial band-structures indicate the interfacial morphology-induced band localization. The calculated Fermi-surface topology of the nanostructures and the corresponding nesting behavior may be emblematic to the presence of instabilities, such as charge density waves. The optical attributes extracted from the TDDFT calculations result in near-zero behavior of both real and imaginary parts of the dynamical dielectric response in the ultra-violet to visible (UV-Vis) optical range. In addition, low-energy intra-band plasmonic oscillations, as present for individual metallic surfaces, are completely suppressed for the embedded and doped nanostructures. The TDDFT-derived electron-energy loss spectra manifest the survival of only inter-band transitions. The presence of soft phonons and dynamic instabilities is observed from the phonon-dispersion of the nanostructured systems. Quantum transport calculations on the simplest possible device made out of these bimetallic systems reveal the generation of highly transmitting pockets over the cross-sectional area for some selected device geometry. We envisage that, if scrutinized experimentally, such systems may unveil many fascinating interdisciplinary aspects of orbital chemistry, physics and optics, promoting their relevant applications in many diverse fields.

A combined spectroscopic and ab initio study of the transmetalation of a polyphenol as a potential purification strategy for food additives.

Recently, metal exchange (transmetalation) techniques have become popular for the post-synthesis modification of metal organic complexes (MOCs). Here, we have explored the possibility of toxic metal ion (mercury (Hg)) exchange from a model polyphenol, curcumin, which is a very important food additive, using a much less toxic counterpart (copper). While the attachment of different metals on the polyphenol was confirmed using a picosecond resolved fluorescence technique, the surface plasmon resonance (SPR) band of the Ag nanoparticle (NP) was employed as a tool to detect uncoupled Hg ions in aqueous media. Furthermore, a microscopic understanding of the experimental observations was achieved through density functional theory (DFT) based theoretical studies. The presence of Cu ions in the vicinity of Hg-curcumin, upon ground state optimization, was observed to extrude most of the Hg from the curcumin complex and replace its position in the complex. The study may find relevance in the development of a purification strategy for food additives heavily contaminated with toxic metals.

Wide bandgap semiconductor-based novel nanohybrid for potential antibacterial activity: ultrafast spectroscopy and computational studies.

The properties of nanomaterials generated by external stimuli are considered an innovative and promising replacement for the annihilation of bacterial infectious diseases. The present study demonstrates the possibility of getting the antibiotic-like drug action from our newly synthesized nanohybrid (NH), which consists of norfloxacin (NF) as the photosensitive material covalently attached to the ZnO nanoparticle (NP). The synthesized NH has been characterized using various microscopic and spectroscopic techniques. Steady state fluorescence and time-correlated single photon counting (TCSPC)-based spectroscopic studies demonstrate the efficient electron transfer from NF to ZnO. This enhances the reactive oxygen species (ROS) production capability of the system. First principles density functional theory has been calculated to gain insight into the charge separation mechanism. To explore the electron densities of the occupied and unoccupied levels of NH, we have verified the nature of the electronic structure. It is observed that there is a very high possibility of electron transfer from NF to ZnO in the NH system, which validates the experimental findings. Finally, the efficacy of NH compared to NF and ZnO has been estimated on the in vitro culture of E. coli bacteria. We have obtained a significant reduction in the bacterial viability by NH with respect to control in the presence of light. These results suggest that the synthesized NH could be a potential candidate in the new generation alternative antibacterial drugs. Overall, the study depicts a detailed physical insight for nanohybrid systems that can be beneficial for manifold application purposes.

Sensitized ZnO nanorod assemblies to detect heavy metal contaminated phytomedicines: spectroscopic and simulation studies.

The immense pharmacological relevance of the herbal medicine curcumin including anti-cancer and anti-Alzheimer effects, suggests it to be a superior alternative to synthesised drugs. The diverse functionalities with minimal side effects intensify the use of curcumin not only as a dietary supplement but also as a therapeutic agent. Besides all this effectiveness, some recent literature reported the presence of deleterious heavy metal contaminants from various sources in curcumin leading to potential health hazards. In this regard, we attempt to fabricate ZnO based nanoprobes to detect metal conjugated curcumin. We have synthesized and structurally characterized the ZnO nanorods (NR). Three samples namely curcumin (pure), Zn-curcumin (non-toxic metal attached to curcumin) and Hg-curcumin (toxic heavy metal attached to curcumin) were prepared for consideration. The samples were electrochemically deposited onto ZnO surfaces and the attachment was confirmed by cyclic voltammetry experiments. Moreover, to confirm a molecular level interaction picosecond-resolved PL-quenching of ZnO NR due to Förster Resonance Energy Transfer (FRET) from donor ZnO NR to the acceptor curcumin moieties was employed. The attachment proximity of ZnO NR and curcumin moieties depends on the size of metals. First principles analysis suggests a variance of attachment sites and heavy metal Hg conjugated curcumin binds through a peripheral hydroxy group to NR. We fabricated a facile photovoltaic device consisting of ZnO NR as the working electrode with Pt counter electrode and iodide-triiodide as the electrolyte. The trend in photocurrent under visible light illumination suggests an enhancement in the case of heavy metal ions due to long range interaction and greater accumulation of charge at the active electrode. Our results provide a detailed physical insight into interfacial processes that are crucial for detecting heavy-metal attached phytomedicines and are thus expected to find vast application as sensors for the detection of selective metal contaminants.

In-Situ Hydrothermal Synthesis of Bi-Bi2O2CO3 Heterojunction Photocatalyst with Enhanced Visible Light Photocatalytic Activity.

Bismuth containing nanomaterials recently received increasing attention with respect to environmental applications because of their low cost, high stability and nontoxicity. In this work, Bi-Bi2O2CO3 heterojunctions were fabricated by in-situ decoration of Bi nanoparticles on Bi2O2CO3 nanosheets via a simple hydrothermal synthesis approach. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) were used to confirm the morphology of the nanosheet-like heterostructure of the Bi-Bi2O2CO3 composite. Detailed ultrafast electronic spectroscopy reveals that the in-situ decoration of Bi nanoparticles on Bi2O2CO3 nanosheets exhibit a dramatically enhanced electron-hole pair separation rate, which results in an extraordinarily high photocatalytic activity for the degradation of a model organic dye, methylene blue (MB) under visible light illumination. Cycling experiments revealed a good photochemical stability of the Bi-Bi2O2CO3 heterojunction under repeated irradiation. Photocurrent measurements further indicated that the heterojunction incredibly enhanced the charge generation and suppressed the charge recombination of photogenerated electron-hole pairs.

A novel nanohybrid for cancer theranostics: folate sensitized Fe2O3 nanoparticles for colorectal cancer diagnosis and photodynamic therapy.

Organic-inorganic nanohybrids are becoming popular for their potential biological applications, including diagnosis and treatment of cancerous cells. The motive of this study is to synthesise a nanohybrid for the diagnosis and therapy of colorectal cancer. Here we have developed a facile and cost-effective synthesis of folic acid (FA) templated Fe2O3 nanoparticles with excellent colloidal stability in water using a hydrothermal method for the theranostics applications. The attachment of FA to Fe2O3 was confirmed using various spectroscopic techniques including FTIR and picosecond resolved fluorescence studies. The nanohybrid (FA-Fe2O3) is a combination of two nontoxic ingredients FA and Fe2O3, showing remarkable photodynamic therapeutic (PDT) activity in human colorectal carcinoma cell lines (HCT 116) via generation of intracellular ROS. The light induced enhanced ROS activity of the nanohybrid causes significant nuclear DNA damage, as confirmed from the comet assay. Assessment of p53, Bax, Bcl2, cytochrome c (cyt c) protein expression and caspase 9/3 activity provides vivid evidence for cell death via an apoptotic pathway. In vitro magnetic resonance imaging (MRI) experiments in folate receptor (FR) overexpressed cancer cells (HCT 116) and FR deficient human embryonic kidney cells (HEK 293) reveal the target specificity of the nanohybrid towards cancer cells, and are thus pronounced MRI contrasting agents for the diagnosis of colorectal cancer.