ABSTRACT
Despite a few recent reports on Rashba effects in two-dimensional (2D) Ruddlesden-Popper (RP) hybrid perovskites, the precise role of organic spacer cations in influencing Rashba band splitting remains unclear. Here, using a combination of temperature-dependent two-photon photoluminescence (2PPL) and time-resolved photoluminescence spectroscopy, alongside density functional theory (DFT) calculations, we contribute to significant insights into the Rashba band splitting found for 2D RP hybrid perovskites. The results demonstrate that the polarity of the organic spacer cation is crucial in inducing structural distortions that lead to Rashba-type band splitting. Our investigations show that the intricate details of the Rashba band splitting occur for organic cations with low polarity but not for more polar ones. Furthermore, we have observed stronger exciton-phonon interactions due to the Rashba-type band splitting effect. These findings clarify the importance of selecting appropriate organic spacer cations to manipulate the electronic properties of 2D perovskites.
ABSTRACT
Selectively focusing on a behaviorally relevant stimulus while ignoring irrelevant stimuli improves perception. Enhanced neuronal response gain is thought to support attention-related improvements in detection and discrimination. However, understanding of the neuronal pathways regulating perceptual sensitivity remains limited. Here, we report that responses of norepinephrine (NE) neurons in the locus coeruleus (LC) of non-human primates to behaviorally relevant sensory stimuli promote visual discrimination in a spatially selective way. LC-NE neurons spike in response to a visual stimulus appearing in the contralateral hemifield only when that stimulus is attended. This spiking is associated with enhanced behavioral sensitivity, is independent of motor control, and is absent on error trials. Furthermore, optogenetically activating LC-NE neurons selectively improves monkeys' contralateral stimulus detection without affecting motor criteria, supporting NE's causal role in granular cognitive control of selective attention at a cellular level, beyond its known diffuse and non-selective functions.
Subject(s)
Attention , Locus Coeruleus , Macaca mulatta , Norepinephrine , Visual Perception , Locus Coeruleus/physiology , Animals , Attention/physiology , Norepinephrine/metabolism , Visual Perception/physiology , Male , Photic Stimulation/methods , Optogenetics , Neurons/physiology , Neurons/metabolism , Space Perception/physiologyABSTRACT
The presence of a companion can reduce fear, but the neural mechanisms underlying this social buffering of fear are incompletely known. We studied social buffering of fear in male and female, and its encoding in the amygdala of male, auditory fear-conditioned rats. Pharmacological, opto,- and/or chemogenetic interventions showed that oxytocin signaling from hypothalamus-to-central amygdala projections underlied fear reduction acutely with a companion and social buffering retention 24 h later without a companion. Single-unit recordings with optetrodes in the central amygdala revealed fear-encoding neurons (showing increased conditioned stimulus-responses after fear conditioning) inhibited by social buffering and blue light-stimulated oxytocinergic hypothalamic projections. Other central amygdala neurons showed baseline activity enhanced by blue light and companion exposure, with increased conditioned stimulus responses that persisted without the companion. Social buffering of fear thus switches the conditioned stimulus from encoding "fear" to "safety" by oxytocin-mediated recruitment of a distinct group of central amygdala "buffer neurons".
Subject(s)
Central Amygdaloid Nucleus , Conditioning, Psychological , Rats , Male , Female , Animals , Conditioning, Psychological/physiology , Oxytocin , Rats, Wistar , Fear/physiology , NeuronsABSTRACT
The dynamics of excited electronic states in self-assembled structures formed between silver(I) ions and cytosine-containing DNA strands or monomeric cytosine derivatives were investigated by time-resolved infrared (TRIR) spectroscopy and quantum mechanical calculations. The steady-state and time-resolved spectra depend sensitively on the underlying structures, which change with pH and the nucleobase and silver ion concentrations. At pH â¼ 4 and low dC20 strand concentration, an intramolecularly folded i-motif is observed, in which protons, and not silver ions, mediate C-C base pairing. However, at the higher strand concentrations used in the TRIR measurements, dC20 strands associate pairwise to yield duplex structures containing C-Ag+-C base pairs with a high degree of propeller twisting. UV excitation of the silver ion-mediated duplex produces a long-lived excited state, which we assign to a triplet excimer state localized on a pair of stacked cytosines. The computational results indicate that the propeller-twisted motifs induced by metal-ion binding are responsible for the enhanced intersystem crossing that populates the triplet state and not a generic heavy atom effect. Although triplet excimer states have been discussed frequently as intermediates in the formation of cyclobutane pyrimidine dimers, we find neither computational nor experimental evidence for cytosine-cytosine photoproduct formation in the systems studied. These findings provide a rare demonstration of a long-lived triplet excited state that is formed in a significant yield in a DNA duplex, demonstrating that supramolecular structural changes induced by metal ion binding profoundly affect DNA photophysics.
Subject(s)
DNA , Silver , Base Pairing , Silver/chemistry , DNA/chemistry , Cytosine/chemistry , ProtonsABSTRACT
To swim through a viscous fluid, a flagellated bacterium must overcome the fluid drag on its body by rotating a flagellum or a bundle of multiple flagella. Because the drag increases with the size of bacteria, it is expected theoretically that the swimming speed of a bacterium inversely correlates with its body length. Nevertheless, despite extensive research, the fundamental size-speed relation of flagellated bacteria remains unclear with different experiments reporting conflicting results. Here, by critically reviewing the existing evidence and synergizing our own experiments of large sample sizes, hydrodynamic modeling, and simulations, we demonstrate that the average swimming speed of Escherichia coli, a premier model of peritrichous bacteria, is independent of their body length. Our quantitative analysis shows that such a counterintuitive relation is the consequence of the collective flagellar dynamics dictated by the linear correlation between the body length and the number of flagella of bacteria. Notably, our study reveals how bacteria utilize the increasing number of flagella to regulate the flagellar motor load. The collective load sharing among multiple flagella results in a lower load on each flagellar motor and therefore faster flagellar rotation, which compensates for the higher fluid drag on the longer bodies of bacteria. Without this balancing mechanism, the swimming speed of monotrichous bacteria generically decreases with increasing body length, a feature limiting the size variation of the bacteria. Altogether, our study resolves a long-standing controversy over the size-speed relation of flagellated bacteria and provides insights into the functional benefit of multiflagellarity in bacteria.
Subject(s)
Movement , Swimming , Movement/physiology , Flagella/physiology , Rotation , Escherichia coli/physiologyABSTRACT
A novel approach to studying attention in mice reveals processes similar to those in humans and lays out an efficient way to explore its neuronal correlates in a genetically tractable animal model.
Subject(s)
Attention , Models, Animal , Animals , Humans , MiceABSTRACT
In recent years, there has been an impressively fast technological progress in the development of highly efficient lead halide perovskite solar cells. Nonetheless, the stability of perovskite films and associated solar cells remains a source of uncertainty and necessitates sophisticated characterization techniques. Here, we report low- to mid-frequency resonant Raman spectra of formamidinium-based lead mixed-halide perovskites. The assignment of the different Raman lines in the measured spectra is assisted by DFT simulations of the Raman spectra of suitable periodic model systems. An important result of this work is that both experiment and theory point to an increase of the stability of the perovskite structure with increasing chloride doping concentration. In the Raman spectra, this is reflected by the appearance of new lines due to the formation of hydrogen bonds. Thus, higher chloride doping results in less torsional motion and lower asymmetric bending contributing to higher stability. This study yields a solid basis for the interpretation of the Raman spectra of formamidinium-based mixed-halide perovskites, furthering the understanding of the properties of these materials, which is essential for their full exploitation in solar cells.
ABSTRACT
Over the past two decades, intensive research efforts have been devoted to suppressions of Auger recombination in metal-chalcogenide and perovskite nanocrystals (PNCs) for the application of photovoltaics and light emitting devices (LEDs). Here, we have explored dodecahedron cesium lead bromide perovskite nanocrystals (DNCs), which show slower Auger recombination time compared to hexahedron nanocrystals (HNCs). We investigate many-body interactions that are manifested under high excitation flux density in both NCs using ultrafast spectroscopic pump-probe measurements. We demonstrate that the Auger recombination rate due to multiexciton recombinations are lower in DNCs than in HNCs. At low and intermediate excitation density, the majority of carriers recombine through biexcitonic recombination. However, at high excitation density (>1018 cm-3) a higher number of many-body Auger process dominates over biexcitonic recombination. Compared to HNCs, high PLQY and slower Auger recombinations in DNCs are likely to be significant for the fabrication of highly efficient perovskite-based photonics and LEDs.
ABSTRACT
Cobalt oxides have long been understood to display intriguing phenomena known as spin-state crossovers, where the cobalt ion spin changes vs. temperature, pressure, etc. A very different situation was recently uncovered in praseodymium-containing cobalt oxides, where a first-order coupled spin-state/structural/metal-insulator transition occurs, driven by a remarkable praseodymium valence transition. Such valence transitions, particularly when triggering spin-state and metal-insulator transitions, offer highly appealing functionality, but have thus far been confined to cryogenic temperatures in bulk materials (e.g., 90 K in Pr1-xCaxCoO3). Here, we show that in thin films of the complex perovskite (Pr1-yYy)1-xCaxCoO3-δ, heteroepitaxial strain tuning enables stabilization of valence-driven spin-state/structural/metal-insulator transitions to at least 291 K, i.e., around room temperature. The technological implications of this result are accompanied by fundamental prospects, as complete strain control of the electronic ground state is demonstrated, from ferromagnetic metal under tension to nonmagnetic insulator under compression, thereby exposing a potential novel quantum critical point.
ABSTRACT
Task demands can differentially engage two fundamental attention components: selectivity (spatial bias) and effort (total nonselective attentional intensity). The relative contributions and interactions of these components in modulating neuronal signals remain unknown. We recorded V4 neurons while monkeys' spatially selective attention and effort were independently controlled by adjusting either task difficulty or reward size at two locations. Neurons were robustly modulated by either selective attention or effort. Notably, increasing overall effort to improve performance at a distant site reduced neuronal responses even when performance was unchanged for receptive field stimuli. This interaction between attentional selectivity and effort was evident in single-trial spiking and can be explained by divisive normalization of spatially distributed behavioral performance at the single-neuron level. Changing motivation using task difficulty or reward produced indistinguishable effects. These results provide a cellular-level mechanism of how attention components integrate to modulate sensory processing in different motivational contexts.
Subject(s)
Motivation , Visual Cortex , Animals , Attention/physiology , Macaca mulatta , Neurons/physiology , Photic Stimulation/methods , Visual Cortex/physiologyABSTRACT
The rapid discovery of two-dimensional (2D) van der Waals (vdW) quantum materials has led to heterostructures that integrate diverse quantum functionalities such as topological phases, magnetism, and superconductivity. In this context, the epitaxial synthesis of vdW heterostructures with well-controlled interfaces is an attractive route towards wafer-scale platforms for systematically exploring fundamental properties and fashioning proof-of-concept devices. Here, we use molecular beam epitaxy to synthesize a vdW heterostructure that interfaces two material systems of contemporary interest: a 2D ferromagnet (1T-CrTe2) and a topological semimetal (ZrTe2). We find that one unit-cell (u.c.) thick 1T-CrTe2 grown epitaxially on ZrTe2 is a 2D ferromagnet with a clear anomalous Hall effect. In thicker samples (12 u.c. thick CrTe2), the anomalous Hall effect has characteristics that may arise from real-space Berry curvature. Finally, in ultrathin CrTe2 (3 u.c. thickness), we demonstrate current-driven magnetization switching in a full vdW topological semimetal/2D ferromagnet heterostructure device.
ABSTRACT
Zeolite nanosheets can be used for the fabrication of low-defect-density, thin, and oriented zeolite separation membranes. However, methods for manipulating their morphology are limited, hindering progress toward improved performance. We report the direct synthesis (i.e., without using exfoliation, etching, or other top-down processing) of thin, flat MFI nanosheets and demonstrate their use as high-performance membranes for xylene isomer separations. Our MFI nanosheets were synthesized using nanosheet fragments as seeds instead of the previously used MFI nanoparticles. The obtained MFI nanosheets exhibit improved thickness uniformity and are free of rotational and MEL intergrowths as shown by transmission electron microscopy (TEM) imaging. The nanosheets can form well-packed nanosheet coatings. Upon gel-free secondary growth, the obtained zeolite MFI membranes show high separation performance for xylene isomers at elevated temperature (e.g., p-xylene flux up to 1.5 × 10-3 mol m-2 s-1 and p-/o-xylene separation factor of ~600 at 250°C).
ABSTRACT
Here, we quantify the effect of an external magnetic field (ß) on the oxygen evolution reaction (OER) for a cobalt oxide|fluorine-doped tin oxide coated glass (CoOx|FTO) anode. A bespoke apparatus enables us to precisely determine the relationship between magnetic flux density (ß) and OER activity at the surface of a CoOx|FTO anode. The apparatus includes a strong NdFeB magnet (ßmax = 450 ± 1 mT) capable of producing a magnetic field of 371 ± 1 mT at the surface of the anode. The distance between the magnet and the anode surface is controlled by a linear actuator, enabling submillimeter distance positioning of the magnet relative to the anode surface. We couple this apparatus with a finite element analysis magnetic model that was validated by Hall probe measurements to determine the value of ß at the anode surface. At the largest tested magnetic field strength of ß = 371 ± 1 mT, a 4.7% increase in current at 1.5 V vs the normal hydrogen electrode (NHE) and a change in the Tafel slope of 14.5 mV/dec were observed. We demonstrate through a series of OER measurements at sequential values of ß that the enhancement consists of two distinct regions. The possible use of this effect to improve the energy efficiency of commercial water electrolyzers is discussed, and major challenges pertaining to the accurate measurement of the phenomenon are demonstrated.
ABSTRACT
The present study aimed to systematically investigate the particle size effects of copper (II) oxide [CuO nanoparticles (<50 nm) and CuO bulk particles (<10 µm)] on maize (Zea mays L.). Bioaccumulation of Cu, in vivo ROS generation, membrane damage, transcriptional modulation of antioxidant genes, cellular redox status of glutathione and ascorbate pool, expression patterns of COPPER TRANSPORTER 4 and stress responsive miRNAs (miR398a, miR171b, miR159f-3p) with their targets were investigated for better understanding of the underlying mechanisms and the extent of CuO nanoparticles and CuO bulk particles induced oxidative stress damages. More restricted seedling growth, comparatively higher membrane injury, marked decline in the levels of chlorophylls and carotenoids and severe oxidative burst were evident in CuO bulk particles challenged leaves. Dihydroethidium and CM-H2DCFDA staining further supported elevated reactive oxygen species generation in CuO bulk particles stressed roots. CuO bulk particles exposed seedlings accumulated much higher amount of Cu in roots as compared to CuO nanoparticles stressed plants with low root-to-shoot Cu translocation. Moderately high GR expression with maintenance of a steady GSH-GSSG ratio in CuO nanoparticles challenged leaves might be accountable for their rather improved performance under stressed condition. miR171b-mediated enhanced expression of SCARECROW 6 might participate in the marked decline of chlorophyll content in CuO bulk particles exposed leaves. Ineffective recycling of AsA pool is another decisive feature of inadequate performance of CuO bulk particles stressed seedlings in combating oxidative stress damages. Taken together, our findings revealed that toxicity of CuO bulk particles was higher than CuO nanoparticles and the adverse effects of CuO bulk particles on maize seedlings might be due to higher Cu ions dissolution.
Subject(s)
Metal Nanoparticles , Nanoparticles , Antioxidants , Copper , Metal Nanoparticles/toxicity , Nanoparticles/toxicity , Oxidative Stress , Zea mays/geneticsABSTRACT
Synthesis of a pentasil-type zeolite with ultra-small few-unit-cell crystalline domains, which we call FDP (few-unit-cell crystalline domain pentasil), is reported. FDP is made using bis-1,5(tributyl ammonium) pentamethylene cations as structure directing agent (SDA). This di-quaternary ammonium SDA combines butyl ammonium, in place of the one commonly used for MFI synthesis, propyl ammonium, and a five-carbon nitrogen-connecting chain, in place of the six-carbon connecting chain SDAs that are known to fit well within the MFI pores. X-ray diffraction analysis and electron microscopy imaging of FDP indicate ca. 10â nm crystalline domains organized in hierarchical micro-/meso-porous aggregates exhibiting mesoscopic order with an aggregate particle size up to ca. 5â µm. Al and Sn can be incorporated into the FDP zeolite framework to produce active and selective methanol-to-hydrocarbon and glucose isomerization catalysts, respectively.
ABSTRACT
Understanding how activity of visual neurons represents distinct components of attention and their dynamics that account for improved visual performance remains elusive because single-unit experiments have not isolated the intensive aspect of attention from attentional selectivity. We isolated attentional intensity and its single trial dynamics as determined by spatially non-selective attentional performance in an orientation discrimination task while recording from neurons in monkey visual area V4. We found that attentional intensity is a distinct cognitive signal that can be distinguished from spatial selectivity, reward expectations and motor actions. V4 spiking on single trials encodes a combination of sensory and cognitive signals on different time scales. Attentional intensity and the detection of behaviorally relevant sensory signals are well represented, but immediate reward expectation and behavioral choices are poorly represented in V4 spiking. These results provide a detailed representation of perceptual and cognitive signals in V4 that are crucial for attentional performance.
Subject(s)
Algorithms , Attention/physiology , Macaca mulatta/physiology , Neurons/physiology , Visual Cortex/physiology , Visual Perception/physiology , Animals , Electrophysiological Phenomena , Linear Models , Male , Photic Stimulation/methods , Pupil/physiology , Visual Cortex/cytologyABSTRACT
Quasi two-dimensional perovskites have attracted great attention for applications in light-emitting devices and photovoltaics due to their robustness and tunable highly efficient photoluminescence (PL). However, the mechanism of intrinsic PL in these materials is still not fully understood. In this work, we have analysed the nature of the different emissive states and the impact of temperature on the emissions in quasi two-dimensional methyl ammonium lead bromide perovskite (q-MPB) and cesium lead bromide perovskite (q-CPB). We have used spatially resolved phase-modulated two-photon photoluminescence (2PPL) and temperature-dependent 2PPL to characterize the emissions. Our results show that at room temperature, the PL from q-MPB is due to the recombination of excitons and free carriers while the PL from q-CPB is due to the recombination of excitons only. Temperature-dependent measurements show that in both materials the linewidth broadening is due to the interactions between the excitons and optical phonons at high temperatures. Comparing the characteristics of the emissions in the two systems, we conclude that q-CPB is better suited for light emitting devices. With a further optimization to reduce the impact on the environment, q-CPB-based LEDs could perform as well as OLEDs.
ABSTRACT
Most of the heavy metals (HMs), and metals/metalloids are released into the nature either by natural phenomenon or anthropogenic activities. Being sessile organisms, plants are constantly exposed to HMs in the environment. The metal non-hyperaccumulating plants are susceptible to excess metal concentrations. They tend to sequester metals in their root vacuoles by forming complexes with metal ligands, as a detoxification strategy. In contrast, the metal-hyperaccumulating plants have adaptive intrinsic regulatory mechanisms to hyperaccumulate or sequester excess amounts of HMs into their above-ground tissues rather than accumulating them in roots. They have unique abilities to successfully carry out normal physiological functions without showing any visible stress symptoms unlike metal non-hyperaccumulators. The unique abilities of accumulating excess metals in hyperaccumulators partly owes to constitutive overexpression of metal transporters and ability to quickly translocate HMs from root to shoot. Various metal ligands also play key roles in metal hyperaccumulating plants. These metal hyperaccumulating plants can be used in metal contaminated sites to clean-up soils. Exploiting the knowledge of natural populations of metal hyperaccumulators complemented with cutting-edge biotechnological tools can be useful in the future. The present review highlights the recent developments in physiological and molecular mechanisms of metal accumulation of hyperaccumulator plants in the lights of metal ligands and transporters. The contrasting mechanisms of metal accumulation between hyperaccumulators and non-hyperaccumulators are thoroughly compared. Moreover, uses of different metal hyperaccumulators for phytoremediation purposes are also discussed in detail.
Subject(s)
Metals, Heavy , Soil Pollutants , Biodegradation, Environmental , Plants/genetics , VacuolesABSTRACT
Optogenetics has revolutionized neuroscience in small laboratory animals, but its effect on animal models more closely related to humans, such as non-human primates (NHPs), has been mixed. To make evidence-based decisions in primate optogenetics, the scientific community would benefit from a centralized database listing all attempts, successful and unsuccessful, of using optogenetics in the primate brain. We contacted members of the community to ask for their contributions to an open science initiative. As of this writing, 45 laboratories around the world contributed more than 1,000 injection experiments, including precise details regarding their methods and outcomes. Of those entries, more than half had not been published. The resource is free for everyone to consult and contribute to on the Open Science Framework website. Here we review some of the insights from this initial release of the database and discuss methodological considerations to improve the success of optogenetic experiments in NHPs.