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Advanced Science (Weinheim,... Jul 2024The phenomenon of flexoelectricity, wherein mechanical deformation induces alterations in the electron configuration of metal oxides, has emerged as a promising avenue...
The phenomenon of flexoelectricity, wherein mechanical deformation induces alterations in the electron configuration of metal oxides, has emerged as a promising avenue for regulating electron transport. Leveraging this mechanism, stress sensing can be optimized through precise modulation of electron transport. In this study, the electron transport in 2D ultra-smooth InO crystals is modulated via flexoelectricity. By subjecting cubic InO (c-InO) crystals to significant strain gradients using an atomic force microscope (AFM) tip, the crystal symmetry is broken, resulting in the separation of positive and negative charge centers. Upon applying nano-scale stress up to 100 nN, the output voltage and power values reach their maximum, e.g. 2.2 mV and 0.2 pW, respectively. The flexoelectric coefficient and flexocoupling coefficient of c-InO are determined as ≈0.49 nC m and 0.4 V, respectively. More importantly, the sensitivity of the nano-stress sensor upon c-InO flexoelectric effect reaches 20 nN, which is four to six orders smaller than that fabricated with other low dimensional materials based on the piezoresistive, capacitive, and piezoelectric effect. Such a deformation-induced polarization modulates the band structure of c-InO, significantly reducing the Schottky barrier height (SBH), thereby regulating its electron transport. This finding highlights the potential of flexoelectricity in enabling high-performance nano-stress sensing through precise control of electron transport.
PubMed: 38953411
DOI: 10.1002/advs.202404272 -
Small (Weinheim An Der Bergstrasse,... Jul 2024Asymmetric electronic environments based on microscopic-scale perspective have injected infinite vitality in understanding the intrinsic mechanism of polarization loss...
Asymmetric electronic environments based on microscopic-scale perspective have injected infinite vitality in understanding the intrinsic mechanism of polarization loss for electromagnetic (EM) wave absorption, but still exists a significant challenge. Herein, Zn single-atoms (SAs), structural defects, and Co nanoclusters are simultaneously implanted into bimetallic metal-organic framework derivatives via the two-step dual coordination-pyrolysis process. Theoretical simulations and experimental results reveal that the electronic coupling interactions between Zn SAs and structural defects delocalize the symmetric electronic environments and generate additional dipole polarization without sacrificing conduction loss owing to the compensation of carbon nanotubes. Moreover, Co nanoclusters with large nanocurvatures induce a strong interfacial electric field, activate the superiority of heterointerfaces and promote interfacial polarization. Benefiting from the aforementioned merits, the resultant derivatives deliver an optimal reflection loss of -58.9 dB and the effective absorption bandwidth is 5.2 GHz. These findings provide an innovative insight into clarifying the microscopic loss mechanism from the asymmetric electron environments viewpoint and inspire the generalized electronic modulation engineering in optimizing EM wave absorption.
PubMed: 38953301
DOI: 10.1002/smll.202403903 -
Nanoscale Jul 2024Liquid crystalline materials have attracted significant attention in chiroptical research due to their ability to form long range ordered helical superstructures....
Liquid crystalline materials have attracted significant attention in chiroptical research due to their ability to form long range ordered helical superstructures. Research focus has been on exploiting the unique properties of liquid crystalline materials to demonstrate highly dissymmetric circularly polarised luminescent (CPL) systems. In this study, we present a thermally driven, facile approach to fabricate CPL-active materials utilizing cholesteryl benzoate as the active substrate. Cholesteryl benzoate, a well-known thermotropic liquid crystal, has been found to manifest intriguing optical characteristics upon subjecting to repeated heating-cooling cycles. Despite the absence of conventional fluorescent moieties, the material exhibited luminescence through aggregation induced clustering triggered emission mechanism. Systematic investigations revealed excitation-dependent CPL for solid cholesteryl benzoate films when subjected to multiple thermal cycles. The excited state chiroptical investigation performed after multiple thermal cycles showed a luminescence anisotropy () of 8 × 10, which is a high value for simple organic molecules. Moreover, upon co-assembly with lanthanide-based upconversion nanophosphors (UCNPs), the hybrid system demonstrated upconverted circularly polarised luminescence (UC-CPL). Benefiting from the ability to endow upconversion nanoparticles of various sizes, fabrication of UCNP-ChB hybrid nanocomposites exhibiting multicoloured upconversion CPL was demonstrated. These findings highlight the potential of liquid crystalline materials for diverse applications, including 3D optical displays and anticounterfeiting technologies.
PubMed: 38953233
DOI: 10.1039/d4nr00865k -
Angewandte Chemie (International Ed. in... Jul 2024Fluorescent molecular systems are important for various applications such as sensing of analytes, probes for biologically relevant processes and as optoelectronic...
Fluorescent molecular systems are important for various applications such as sensing of analytes, probes for biologically relevant processes and as optoelectronic materials. Achieving high fluorescence quantum yield across the spectrum of solvent polarity and in solid-state is challenging in molecular materials. Herein, we present a strategy to achieve strongly fluorescent molecular materials based on weak intramolecular charge-transfer (ICT) in a family of unsymmetrical donor-thiazolo[5,4-d]thiazoles-acceptor systems (both neutral and cationic). Detailed photophysical studies reveal that the delicate balance between the donor and acceptor result in high solution-state fluorescence quantum yield (> 80%) in both polar protic and apolar solvents. Quantum chemical computations uncover a hitherto unappreciated insight that the extent of ICT is aptly represented by the change in Mulliken charges between the ground and excited-state for different fragments rather than the classical approach of monitoring the change in dipole moment for the entire molecule. This insight rationalizes the observed photophysical properties and can have implications in the design of tuneable donor-π-acceptor systems.
PubMed: 38953140
DOI: 10.1002/anie.202409725 -
The Analyst Jul 2024Mass spectrometry imaging (MSI) is used for visualizing the distribution of components in solid samples, such as biological tissues, and requires a technique to ionize...
Mass spectrometry imaging (MSI) is used for visualizing the distribution of components in solid samples, such as biological tissues, and requires a technique to ionize the components from local areas of the sample. Tapping-mode scanning probe electrospray ionization (t-SPESI) uses an oscillating capillary probe to extract components from a local area of a sample with a small volume of solvent and to perform electrospray ionization of those components at high speed. MSI can be conducted by scanning the sample surface with a capillary probe. To ensure stable extraction and ionization for MSI, the probe oscillation during measurements must be understood. In this study, we examined the changes in oscillation amplitude and phase due to the interaction between the oscillating probe and the brain tissue section when the probe tip was dynamically brought close to the sample surface. The changes in the probe oscillation depended on the oscillation frequency and polarity of the bias voltage applied to the solvent because an electrostatic force shifted the frequency of the probe oscillation. These findings suggest that controlling the probe oscillation frequency is important for stabilizing MSI by t-SPESI.
PubMed: 38953117
DOI: 10.1039/d4an00712c -
RSC Advances Jun 2024The search for novel intrinsic two-dimensional (2D) magnetic materials is crucial to understand the fundamentals of 2D magnetism and realize next-generation...
The search for novel intrinsic two-dimensional (2D) magnetic materials is crucial to understand the fundamentals of 2D magnetism and realize next-generation magneto-electric and magneto-optical systems. Using the rigorous framework of spin-polarized density functional theory (SPDFT)-based calculations, this investigation systematically investigates the effects of a stepwise change in the Fe composition () on the structural, electro-magnetic and optical properties of the ordered SrS based single-layer alloys, with encompassing values from 0 to 1. Our comprehensive analysis revealed that the calculated formation energies, cohesive energies, phonon dispersions, molecular dynamics, and elastic constants of both bare SrS and FeS monolayers indicate their thermodynamic, dynamic, thermal, and mechanical stability in hexagonal and square structures, respectively. Significantly, the introduction of magnetic Fe dopants into the non-magnetic SrS semiconductor enabled the creation of an intrinsic magnetic (FM) state characterized by spin-polarized charge carriers at the Fermi level ( ). As doping increases, the electronic structure shows a noticeable dependence on the chemical composition. It is noteworthy that the systems doped with 0.750 and 1 Fe exhibit metallic-magnetic and metallic non-magnetic properties, respectively, and the rest are half-semiconductors (HSC) according to the GGA approximation. Conversely, the HSE approach shows a transition to HSC for a doping level of 0.750, while others maintain the same behavior. The study of the optical properties shows improvements compared to the bare SrS monolayer through the incorporation of Fe dopants. The bare SrS has light absorption in the ultraviolet region, while the absorption band edges for HSC compounds change from the infrared to visible regions. This study proposes a practical method to tune the properties of the SrS single-layer by selectively adjusting the dopant concentration. Such control is promising for applications in spintronics and optical based nanodevices.
PubMed: 38952946
DOI: 10.1039/d4ra04352a -
Temporal patterns in multiple stressors shape the vulnerability of overwintering Arctic zooplankton.Ecology and Evolution Jul 2024The Arctic polar nights bring extreme environmental conditions characterised by cold and darkness, which challenge the survival of organisms in the Arctic. Additionally,...
The Arctic polar nights bring extreme environmental conditions characterised by cold and darkness, which challenge the survival of organisms in the Arctic. Additionally, multiple anthropogenic stressors can amplify the pressure on the fragile Arctic ecosystems during this period. Determining how multiple anthropogenic stressors may affect the survival of Arctic life is crucial for ecological risk assessments and management, but this topic is understudied. For the first time, our study investigates the complex interactions of multiple stressors, exploring stressor temporal dynamics and exposure duration on a key Arctic copepod during the polar nights. We conducted experiments with pulse (intermittent) and press (continuous) exposure scenarios, involving microplastics, pyrene and warming in a fully factorial design. We observed significant effects on copepod survival, with pronounced impacts during later stressor phases. We also detected two-way interactions between microplastics and pyrene, as well as pyrene and warming, further intensified with the presence of a third stressor. Continuous stressor exposure for 9 days (press-temporal scenario) led to greater reductions in copepod survival compared to the pulse-temporal scenario, characterised by two 3-day stressor exposure phases. Notably, the inclusion of recovery phases, free from stressor exposure, positively influenced copepod survival, highlighting the importance of temporal exposure dynamics. We did not find behaviour to be affected by the different treatments. Our findings underscore the intricate interactions amongst multiple stressors and their temporal patterns in shaping the vulnerability of overwintering Arctic copepods with crucial implications for managing Arctic aquatic ecosystems under the fastest rate of ongoing climate change on earth.
PubMed: 38952656
DOI: 10.1002/ece3.11673 -
Environmental Science & Technology Jul 2024Advanced oxidation processes (AOPs) are the most efficient water cleaning technologies, but their applications face critical challenges in terms of mass/electron...
Advanced oxidation processes (AOPs) are the most efficient water cleaning technologies, but their applications face critical challenges in terms of mass/electron transfer limitations and catalyst loss/deactivation. Bipolar electrochemistry (BPE) is a wireless technique that is promising for energy and environmental applications. However, the synergy between AOPs and BPE has not been explored. In this study, by combining BPE with AOPs, we develop a general approach of using carbon nanotubes (CNTs) as electric-field-induced bipolar electrodes to control electron transfer for efficient water purification. This approach can be used for permanganate and peroxide activation, with superior performances in the degradation of refractory organic pollutants and excellent durability in recycling and scale-up experiments. Theoretical calculations, in situ measurements, and physical experiments showed that an electric field could substantially reduce the energy barrier of electron transfer over CNTs and induce them to produce bipolar electrodes via electrochemical polarization or to form monopolar electrodes through a single particle collision effect with feeding electrodes. This approach can continuously provide activated electrons from one pole of bipolar electrodes and simultaneously achieve "self-cleaning" of catalysts through CNT-mediated direct oxidation from another pole of bipolar electrodes. This study provides a fundamental scientific understanding of BPE, expands its scope in the environmental field, and offers a general methodology for water purification.
Topics: Nanotubes, Carbon; Electrodes; Water Purification; Oxidation-Reduction; Catalysis
PubMed: 38952299
DOI: 10.1021/acs.est.4c03218 -
ACS Nano Jul 2024Ferroelectric materials display exotic polarization textures at the nanoscale that could be used to improve the energetic efficiency of electronic components. The vast...
Ferroelectric materials display exotic polarization textures at the nanoscale that could be used to improve the energetic efficiency of electronic components. The vast majority of studies were conducted in two dimensions on thin films that can be further nanostructured, but very few studies address the situation of individual isolated nanocrystals (NCs) synthesized in solution, while such structures could have other fields of applications. In this work, we experimentally and theoretically studied the polarization texture of ferroelectric barium titanate (BaTiO, BTO) NCs attached to a conductive substrate and surrounded by air. We synthesized NCs of well-defined quasicubic shape and 160 nm average size that conserve the tetragonal structure of BTO at room temperature. We then investigated the inverse piezoelectric properties of such pristine individual NCs by vector piezoresponse force microscopy (PFM), taking particular care to suppress electrostatic artifacts. In all of the NCs studied, we could not detect any vertical PFM signal, and the maps of the lateral response all displayed larger displacement amplitude on the edges with deformations converging toward the center. Using field phase simulations dedicated to ferroelectric nanostructures, we were able to predict the equilibrium polarization texture. These simulations revealed that the NC core is composed of 180° up and down domains defining the polar axis that rotate by 90° in the two facets orthogonal to this axis, eventually lying within these planes forming a layer of about 10 nm thickness mainly composed of 180° domains along an edge. From this polarization distribution, we predicted the lateral PFM response, which was revealed to be in very good qualitative agreement with the experimental observations. This work positions PFM as a relevant tool to evaluate the potential of complex ferroelectric nanostructures to be used as sensors.
PubMed: 38952163
DOI: 10.1021/acsnano.4c02291 -
Advanced Science (Weinheim,... Jul 2024Traditional artificial vision systems built using separate sensing, computing, and storage units have problems with high power consumption and latency caused by frequent...
Traditional artificial vision systems built using separate sensing, computing, and storage units have problems with high power consumption and latency caused by frequent data transmission between functional units. An effective approach is to transfer some memory and computing tasks to the sensor, enabling the simultaneous perception-storage-processing of light signals. Here, an optical-electrical coordinately modulated memristor is proposed, which controls the conductivity by means of polarization of the 2D ferroelectric Ruddlesden-Popper perovskite film at room temperature. The residual polarization shows no significant decay after 10-cycle polarization reversals, indicating that the device has high durability. By adjusting the pulse parameters, the device can simulate the bio-synaptic long/short-term plasticity, which enables the control of conductivity with a high linearity of ≈0.997. Based on the device, a two-layer feedforward neural network is built to recognize handwritten digits, and the recognition accuracy is as high as 97.150%. Meanwhile, building optical-electrical reserve pool system can improve 14.550% for face recognition accuracy, further demonstrating its potential for the field of neural morphological visual systems, with high density and low energy loss.
PubMed: 38952052
DOI: 10.1002/advs.202403150