We report on the oxygen vacancy induced ferromagnetism (FM) at and above room temperature in undoped TiO2 nanoporous nanoribbons synthesized by a solvothermal route. The origin of FM in ...as-synthesized and vacuum annealed undoped nanoribbons grown for different reaction durations followed by calcinations was investigated by several experimental tools. X-Ray diffraction pattern and micro-Raman studies reveal the TiO2(B), TiO2(B)-anatase, and anatase-rutile mixed phases of TiO2 structure. Field emission scanning electron microscopy and transmission electron microscopy observations reveal nanoribbons with uniform pore distribution and nanopits/nanobricks formed on the surface. These samples exhibit strong visible photoluminescence associated with oxygen vacancies and a clear ferromagnetic hysteresis loop, both of which dramatically enhanced after vacuum annealing. Direct evidence of oxygen vacancies and related Ti(3+) in the as-prepared and vacuum annealed TiO2 samples are provided through X-ray photoelectron spectroscopy analysis. Micro-Raman, infrared absorption and optical absorption spectroscopic analyses further support our conclusion. The observed room temperature FM in undoped TiO2 nanoribbons is quantitatively analyzed and explained through a model involving bound magnetic polarons (BMP), which include an electron locally trapped by an oxygen vacancy with the trapped electron occupying an orbital overlapping with the unpaired electron (3d(1)) of Ti(3+) ion. Our analysis interestingly shows that the calculated BMP concentration scales linearly with concentration of oxygen vacancies and provides a stronger footing for exploiting defect engineered ferromagnetism in undoped TiO2 nanostructures. The development of such highly porous TiO2 nanoribbons constitutes an important step towards realizing improved visible light photocatalytic and photovoltaic applications of this novel material.
The formation of a heterostructure with plasmonic nanoparticles drastically alters the optoelectronic properties of graphene quantum dots (GQDs), resulting in exceptional properties. In the present ...work, we prepare nitrogen-doped GQDs decorated on gold nanoparticles (Au@N-GQDs) by a one-step green reduction method and study its extraordinary fluorescence and photoresponse characteristics. The as-prepared Au@N-GQDs show more than one order of magnitude enhancement in the fluorescence intensity as compared to the bare N-GQDs, which is attributed to hot electron generation and improved absorption in N-GQDs by local field enhancement and the modification of the edge functional groups. Because of the selective coordination to Fe3+ ions, the Au@N-GQDs exhibit extraordinary quenching of fluorescence, with ultrahigh sensitivity for the detection of Fe3+ (<1 nM). A new model for the charge-transfer dynamics is developed involving the Langmuir’s law of adsorption to explain the unusual quenching, which strongly deviates from the known models of static/dynamic quenching. The proposed sensor is successfully implemented for the ultrasensitive detection of Fe3+ ions in human serum and Brahmaputra river water samples, representing its high potential applications in clinical as well as environmental diagnosis. Additionally, because of its high absorption in the UV–vis–NIR region and high charge density with long life excitons, the Au@N-GQDs are utilized as photodetectors with ∼104 times faster response than that of bare N-GQDs. The Au@N-GQD-based photodetector possesses a high responsivity of ∼1.36 A/W and a remarkably high external quantum efficiency of ∼292.2%, which is much superior to the GQD-based photodetectors reported till date. The underlying mechanism of ultrafast photoresponse is ascribed to the transfer of hot electrons along with the tunneling of the electrons from Au NPs to N-GQDs as well as the defect reduction of N-GQDs by the incorporation of Au NPs. Without the use of any charge transporting layer, the outstanding performance of N-GQD-based plasmonic photodetector opens up unique opportunities for future high-speed optoelectronic devices.
Precise control of the thickness of large-area two-dimensional (2D) organometal halide perovskite layers is extremely challenging owing to the inherent instability of the organic component. Herein, a ...novel, highly reproducible, and facile solvothermal route is reported to synthesize and tailor the thickness and optical band gap of the organic–inorganic halide perovskite nanosheets (NSs). Our study reveals that self-assembly of randomly oriented perovskite nanorods leads to the growth of multilayered perovskite NSs at ∼100 °C, while at higher temperature, large-area few-layer to bilayer 2D NSs (CH3NH3PbBr3) are obtained through lattice expansion and layer separation depending precisely on the temperature. Interestingly, the thickness of the 2D NSs shows a linear dependence on the reaction temperature and thus enables precise tuning of the thickness from 14 layers to 2 layers, giving rise to a systematic increase in the band gap and appearance of excitonic absorption bands. Quantitative analysis of the change in the band gap with thickness revealed a strong quantum confinement effect in the 2D layers. The perovskite 2D NSs exhibit tunable color and a high photoluminescence (PL) quantum yield (QY) up to 84%. Through a careful analysis of the steady-state and time-resolved PL spectra, the origin of the lower PL QY in thinner NSs is traced to surface defects in the 2D layers, for the first time. A white light converter was fabricated using the composition-tuned 2D CH3NH3PbBrI2 NS on a blue light-emitting diode chip. The 2D perovskite photodetector exhibits a stable and very fast rise/fall time (24 μs/103 μs) along with high responsivity and detectivity of ∼1.93 A/W and 1.04 × 1012 Jones, respectively. Storage, operational, and temperature-dependent stability studies reveal high stability of the 2D perovskite NSs under the ambient condition with high humidity. The reported method is highly promising for the development of large-area stable 2D perovskite layers for various cutting-edge optoelectronic applications.
Heterogeneous photocatalysis is of overriding significance for emerging energy and environment applications. Nanosized metal–semiconductor heterostructures (HSs) allow extraordinarily tuned and ...intense absorption of light, making it very promising for efficient solar energy harvesting in photovoltaic and photocatalytic applications. Here we report on the ultrahigh rate of photodegradation of organic dye, Rhodamine-B, with two distinct sequential degradation rate processes under visible light illumination on Ag nanoparticle (NP) decorated anatase TiO2 nanorods (NRs) grown by a solvothermal route. HRTEM analysis reveals the uniform decoration of Ag NPs (∼17 nm) over the TiO2 NRs surface for the optimized Ag@TiO2 HS. The defect rich Ag@TiO2 NR HSs grown with an optimal weight ratio Ag:TiO2 = 3:2 (TA32) exhibit very strong optical absorption due to the localized surface plasmon resonance (LSPR) effect over the entire visible region, having an absorption peak at ∼520 nm. The effective band gap of TA32 has been significantly reduced to 2.71 eV from the pure TiO2 band gap of 3.2 eV. Studies on photocatalysis of Rhodamine-B show a very high degradation rate for the HSs due to the LSPR effect in the noble Ag NPs and fast charge transfer at the Ag@TiO2 interface. The optimized heterostructure (TA32) exhibits nearly double plasmonic absorbance than the other HSs, and it shows the highest degradation rate under visible light irradiation. In contrast to the available models, in the present case the degradation kinetics follows a sequential rate process with two distinct exponential decay functions/rate constants. For the optimized HS (TA32), the degradation rate constants are found to be 0.083 (k 2) and 0.033 min–1 (k 1) in the second and first stages of degradation, respectively. The pseudo first order rate constant was >4 times higher in the first stage and ∼10 times stronger in the second stage of degradation for TA32 HS in comparison to the bare TiO2 NRs as well as commercial P25. Our results demonstrate the long-term stability and superiority of the Ag@TiO2 HS over the bare TiO2 NRs and other TiO2 based photocatalysts for detoxification of air/water. This study offers new insights in understanding the mechanism of advanced photocatalysis with multi rate constants by oxygen vacancy enriched Ag@TiO2 nanoheterostructures.
Phytochemicals belonging to the group of alkaloids are signature specialized metabolites endowed with countless biological activities. Plants are armored with these naturally produced nitrogenous ...compounds to combat numerous challenging environmental stress conditions. Traditional and modern healthcare systems have harnessed the potential of these organic compounds for the treatment of many ailments. Various chemical entities (functional groups) attached to the central moiety are responsible for their diverse range of biological properties. The development of the characterization of these plant metabolites and the enzymes involved in their biosynthesis is of an utmost priority to deliver enhanced advantages in terms of biological properties and productivity. Further, the incorporation of whole/partial metabolic pathways in the heterologous system and/or the overexpression of biosynthetic steps in homologous systems have both become alternative and lucrative methods over chemical synthesis in recent times. Moreover, in-depth research on alkaloid biosynthetic pathways has revealed numerous chemical modifications that occur during alkaloidal conversions. These chemical reactions involve glycosylation, acylation, reduction, oxidation, and methylation steps, and they are usually responsible for conferring the biological activities possessed by alkaloids. In this review, we aim to discuss the alkaloidal group of plant specialized metabolites and their brief classification covering major categories. We also emphasize the diversity in the basic structures of plant alkaloids arising through enzymatically catalyzed structural modifications in certain plant species, as well as their emerging diverse biological activities. The role of alkaloids in plant defense and their mechanisms of action are also briefly discussed. Moreover, the commercial utilization of plant alkaloids in the marketplace displaying various applications has been enumerated.
•3% and 5% Ni doped ZnO nanoparticles are grown by a ball milling technique.•3% doped ZnO nanoparticles exhibit room temperature high magnetic moment that changes with milling time.•Optical and ...magnetic properties of doped ZnO nanoparticles are correlated well.•Mechanism of the magnetic interaction is quantitatively analyzed using a bound magnetic polar model.•Direct correlation between the defects in doped ZnO and magnetic moment is demonstrated.
We report on the room temperature ferromagnetism in the Zn1−xNixO (x=0, 0.03 and 0.05) nanoparticles (NPs) synthesized by a ball milling technique. X-ray diffraction analysis confirms the single crystalline, wurtzite ZnO structure for the 3% Ni doped ZnO NPs for higher milling time. HRTEM lattice image and SAED pattern show that the doped NPs are single crystalline with a d-spacing of 2.47Å corresponding to the (101) plane. Energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy confirm the presence of Ni ions inside the ZnO matrix with 2+ valance state. Room temperature magnetic measurements exhibit the hysteresis loop with saturation magnetization (Ms) of 1.6–2.56 (emu/g) and coercive field (Hc) of 260Oe. Micro-Raman studies illustrate doping/disorder induced additional Raman modes at ∼547, 574cm−1 in addition to 437cm−1 peak of pure ZnO. Photoluminescence (PL) spectra and UV–vis absorption measurements demonstrate some modification in the band edge emission and absorption characteristics, respectively. PL spectra also show defect related strong visible emission, which is believed to play a significant role in the FM ordering. These observations highlight the effect of changing defect density on the observed ferromagnetic moment values for the as synthesized Zn1−xNixO NPs. Magnetic interaction is quantitatively analyzed and explained using a bound magnetic polaron model and expected to arise from the intrinsic exchange interaction of Ni ions and OV, Zni defects. Systemic studies on the structural, magnetic, and optical properties reveal that both the nature of the defects as well as Ni2+ ions are significant ingredients behind attaining high moment as well as high ordering temperature in Ni doped ZnO NPs.
Phenylpropanoid pathway provides precursors for numerous secondary metabolites in plants. In this pathway, 4-coumarate-CoA ligase (EC 6.2.1.12, 4CL) is the main branch point enzyme which generates ...activated thioesters. Being the last enzyme of three shared common steps in general phenylpropanoid pathway, it contributes to channelize precursors for different phenylpropanoids. In plants, 4CL enzymes are present in multiple isoforms and encoded by small gene family. It belongs to adenylate-forming enzyme family and catalyzes the reaction that converts hydroxy or methoxy cinnamic acid derivatives to corresponding thioesters. These thioesters are further utilized for biosynthesis of phenylpropanoids, which are known for having numerous nutritional and medicinal applications. In addition, the 4CL enzymes have been characterized from various plants for their role in plant physiology or in biotic and abiotic stresses. Furthermore, specific isoforms are differentially regulated upon exposure to diverse stimuli leading to flux diversion toward the particular metabolite biosynthesis. Evolutionary studies showed that 4CL separately evolved after monocot and dicot segregation. Here, we provide a comprehensive review on 4CL, which includes evolution, function, gene/protein structure, role in metabolite biosynthesis and cellular partition, and their regulation. Based on the available data, we have explored the scope for pathway engineering by utilizing 4CL enzymes.
This study presents a comprehensive analysis of the strong cathodoluminescence (CL), photoluminescence (PL), and photoresponse characteristics of CH3NH3PbBr3 nanoparticles (NPs) embedded in a ...mesoporous nanowire (NW) template. Our study revealed a direct correlation between the CL and PL emissions from the perovskite NPs (Per NPs), for the first time. Per NPs are fabricated by a simple spin-coating of a perovskite precursor on the surface of metal-assisted chemically etched mesoporous Si NW arrays. The Per NPs confined in the mesopores show blue-shifted and enhanced CL emission as compared to the bare perovskite film, while the PL intensity of Per NPs is dramatically high compared to that of their bulk counterpart. A systematic analysis of the CL/PL spectra reveals that the quantum confinement effect and ultralow defects in Per NPs are mainly responsible for the enhanced CL and PL emissions. Low-temperature PL and time-resolved PL analysis confirm the high exciton binding energy and radiative recombination in Per NPs. The room temperature PL quantum yield of the Per NP film on the NW template was found to be 40.5%, while that of Per film was 2.8%. The Per NPs show improved ambient air stability than the bare film due to the protection provided by the dense NW array, since a dense NW array can slow down the lateral diffusion of oxygen and water molecules in Per NPs. Interestingly, the Si NW/Per NP junction shows superior visible light photodetection and the prototype photodetector shows a high responsivity (0.223 A/W) with response speeds of 0.32 and 0.28 s of growth and decay in photocurrent, respectively, at 2 V applied bias, which is significantly better than the reported photodetectors based on CH3NH3PbBr3 nanostructures. This work demonstrates a low-cost fabrication of CH3NH3PbBr3 NPs on a novel porous NW template, which shows excellent photophysical and optoelectronic properties with superior ambient stability.
Sleep plays an important role in the consolidation of recent memories. However, the cellular and synaptic mechanisms of consolidation during sleep remain poorly understood. In this study, using a ...realistic computational model of the thalamocortical network, we tested the role of Non-Rapid Eye Movement (NREM) sleep in memory consolidation. We found that sleep spindles (the hallmark of N2 stage sleep) and slow oscillations (the hallmark of N3 stage sleep) both promote replay of the spike sequences learned in the awake state and replay was localized at the trained network locations. Memory performance improved after a period of NREM sleep but not after the same time period in awake. When multiple memories were trained, the local nature of the spike sequence replay during spindles allowed replay of the distinct memory traces independently, while slow oscillations promoted competition that could prevent replay of the weak memories in a presence of the stronger memory traces. This could lead to extinction of the weak memories unless when sleep spindles (N2 sleep) preceded slow oscillations (N3 sleep), as observed during the natural sleep cycle. Our study presents a mechanistic explanation for the role of sleep rhythms in memory consolidation and proposes a testable hypothesis how the natural structure of sleep stages provides an optimal environment to consolidate memories.
This paper presents a distributed, guidance and control algorithm for reconfiguring swarms composed of hundreds to thousands of agents with limited communication and computation capabilities. This ...algorithm solves both the optimal assignment and collision-free trajectory generation for robotic swarms, in an integrated manner, when given the desired shape of the swarm (without pre-assigned terminal positions). The optimal assignment problem is solved using a distributed auction assignment that can vary the number of target positions in the assignment, and the collision-free trajectories are generated using sequential convex programming. Finally, model predictive control is used to solve the assignment and trajectory generation in real time using a receding horizon. The model predictive control formulation uses current state measurements to resolve for the optimal assignment and trajectory. The implementation of the distributed auction algorithm and sequential convex programming using model predictive control produces the swarm assignment and trajectory optimization (SATO) algorithm that transfers a swarm of robots or vehicles to a desired shape in a distributed fashion. Once the desired shape is uploaded to the swarm, the algorithm determines where each robot goes and how it should get there in a fuel-efficient, collision-free manner. Results of flight experiments using multiple quadcopters show the effectiveness of the proposed SATO algorithm.
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