Reaction environment self-modification on low-coordination Ni2+ octahedra atomic interface for superior electrocatalytic overall water splitting

Large scale synthesis of high-efficiency bifunctional electrocatalyst based on cost-effective and earth-abundant transition metal for overall water splitting in the alkaline environment is indispensable for renewable energy conversion. In this regard, meticulous design of active sites and probing their catalytic mechanism on both cathode and anode with different reaction environment at molecular-scale are vitally necessary. Herein, a coordination environment inheriting strategy is presented for designing low-coordination Ni²⁺ octahedra (L-Ni-8) atomic interface at a high concentration (4.6 at.%). Advanced spectroscopic techniques and theoretical calculations reveal that the self-matching electron delocalization and localization state at L-Ni-8 atomic interface enable an ideal reaction environment at both cathode and anode. To improve the efficiency of using the self-modification reaction environment at L-Ni-8, all of the structural features, including high atom economy, mass transfer, and electron transfer, are integrated together from atomic-scale to macro-scale. At high current density of 500 mA/cm², the samples synthesized at gram-scale can deliver low hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) overpotentials of 262 and 348 mV, respectively.

     

A Versatile Theranostic Nanoemulsion for Architecture‐Dependent Multimodal Imaging and Dually Augmented Photodynamic Therapy

To design a clinically translatable nanomedicine for photodynamic theranostics, the ingredients should be carefully considered. A high content of nanocarriers may cause extra toxicity in metabolism, and multiple theranostic agents would complicate the preparation process. These issues would be of less concern if the nanocarrier itself has most of the theranostic functions. In this work, a poly(ethylene glycol)‐boron dipyrromethene amphiphile (PEG‐F₅₄‐BODIPY) with 54 fluorine‐19 (¹⁹F) is synthesized and employed to emulsify perfluorohexane (PFH) into a theranostic nanoemulsion (PFH@PEG‐F₅₄‐BODIPY). The as‐prepared PFH@PEG‐F₅₄‐BODIPY can perform architecture‐dependent fluorescence/photoacoustic/¹⁹F magnetic resonance multimodal imaging, providing more information about the in vivo structure evolution of nanomedicine. Importantly, this nanoemulsion significantly enhances the therapeutic effect of BODIPY through both the high oxygen dissolving capability and less self‐quenching of BODIPY molecules. More interestingly, PFH@PEG‐F₅₄‐BODIPY shows high level of tumor accumulation and long tumor retention time, allowing a repeated light irradiation after a single‐dose intravenous injection. The “all‐in‐one” photodynamic theranostic nanoemulsion has simple composition, remarkable theranostic efficacy, and novel treatment pattern, and thus presents an intriguing avenue to developing clinically translatable theranostic agents.     

Chemical bond characteristics and infrared reflectivity spectrum of a novel microwave dielectric ceramic CaIn2O4 with near-zero τf

Orthorhombic-structured CaIn₂O₄ ceramics with a space group Pca2₁ were synthesized via a solid-state reaction method. A high relative density (95.6 %) and excellent microwave dielectric properties (ε_r ～11.28, Qf = 74,200 GHz, τ_f ～ ?4.6 ppm/°C) were obtained when the ceramics were sintered at 1375 °C for 6 h. The dielectric properties were investigated on the basis of the Phillips–Van Vechten–Levine chemical bond theory. Results indicated that the dielectric properties were mainly determined by the InO bonds in the CaIn₂O₄ ceramics. These bonds contributed more (74.65 %) to the dielectric constant than the CaO bonds (25.35 %). Furthermore, the intrinsic dielectric properties of the CaIn₂O₄ ceramics were investigated via infrared reflectivity spectroscopy. The extrapolated microwave dielectric properties were ε_r ～10.12 and Qf = 112,200 GHz. Results indicated that ion polarization is the main contributor to the dielectric constant in microwave frequency ranges.     

Bioengineered magnetoferritin nanozymes for pathological identification of high-risk and ruptured atherosclerotic plaques in humans

Atherosclerotic plaque rupture results in thrombus formation and vessel occlusion, and is the leading cause of death worldwide. There is a pressing need to identify plaque vulnerability for the treatment of carotid and coronary artery diseases. Nanomaterials with enzyme-like properties have attracted significant interest by providing biological, diagnostic and prognostic information about the diseases. Here we showed that bioengineered magnetoferritin nanoparticles (M-HFn NPs) functionally mimic peroxidase enzyme and can intrinsically recognize plaque-infiltrated active macrophages, which drive atherosclerotic plaque progression and rupture and are significantly associated with the plaque vulnerability. The M-HFn nanozymes catalyze the oxidation of colorimetric substrates to give a color reaction that visualizes the recognized active macrophages for one-step pathological identification of plaque vulnerability. We examined 50 carotid endarterectomy specimens from patients with symptomatic carotid disease and demonstrated that the M-HFn nanozymes could distinguish active macrophage infiltration in ruptured and high-risk plaque tissues, and M-HFn staining displayed a significant correlation with plaque vulnerability (r = 0.89, P < 0.0001).

     

An enhanced state estimation for linear parabolic PDE systems with mobile sensors

This paper studies an enhanced state estimation problem of distributed parameter processes modeled by a linear parabolic partial differential equation using mobile sensors. The proposed estimation scheme contains a state estimator and the guidance of mobile sensors, where the spatial domain is decomposed into multiple subdomains according to the number of sensors and each sensor is capable of moving within the respective subdomain. The state estimator is desired to make the state estimation error system exponentially stable while providing an performance bound. The mobile sensor guidance is used to enhance the transient performance of the error system. By the Lyapunov direct technique, an integrated design of state estimator and mobile sensor guidance laws is developed in the form of bilinear matrix inequalities (BMIs) to meet the desired design objectives. Moreover, to make the performance bound as small as possible, a suboptimal enhanced state estimation problem is formulated as a BMI optimization one, which can be solved via an iterative linear matrix inequality algorithm. Finally, numerical simulations are given to show the effectiveness of the proposed method.     

Corrosion behaviour and mechanism of 6082 aluminium alloy in NaCl and Na2SO4 etchants

The corrosion behaviour of 6082 aluminium alloy was studied by measuring the electrochemical impedance spectra and electrode polarization curves. After the electrochemical tests, a microstructural analysis of the samples was conducted by using optical microscopy and electron scanning microscopy techniques to determine the corrosion mechanism. The results show that the Nyquist plot of the electrochemical impedance data in the NaCl solution consists of high- and low-frequency capacitive impedance loops. When ions are added to the NaCl etchant, the Nyquist plots of the electrochemical impedance data are composed of two different curves: a high-frequency capacitive impedance loop and a low-frequency inductive impedance loop. The corrosion current density increases with increasing concentration, and as a result, the corrosion resistance of the aluminium alloy decreases. The microstructures of 6082 aluminium alloy consist of Mg₂Si secondary particles in a large α-Al matrix. Pitting corrosion initially occurs at the boundary between the matrix and secondary particles because the electrode potentials of the matrix and secondary particles are different. Then, corrosion paths develop along the network-like grain boundaries, and finally, massive network-like corrosion occurs throughout the entire alloy.     

Effects of Sr2+ substitution on the crystal structure,Raman spectra,bond valence and microwave dielectric properties of Ba3-xSrx(VO4)2 solid solutions

The effects of Sr²⁺ substitution for Ba²⁺ on microwave dielectric properties and crystal structure of Ba_3-xSr_x(VO₄)₂ (0 ≤ x ≤ 3, BSVO) solid solution were investigated. Such Sr²⁺ substitution contributes to significant reduction in sintering temperature from 1400 °C to 1150 °C. Both permittivity (∑_r) and quality factor (Q × f) values decreased with increasing x value, which was determined to be related with the descending values of average polarizability and packing fraction, whereas the increase in τ_f value was explained by the decreased average VO bond length, A-site bond valence. BSVO ceramics possessed encouraging dielectric performances with ∑_r = 12.2–15.6 ± 0.1, Q × f = 44,340 - 62,000 ± 800 GHz, and τ_f = 24.5–64.5 ± 0.2 ppm/°C. Low-temperature sintering was manipulated by adding B₂O₃ as sintering additive for the representative Sr₃V₂O₈ (SVO) ceramic and only 1 wt.% B₂O₃ addition successfully contributed to a 21.7% decrease in sintering temperature to 900 °C, showing good chemical compatibility with silver electrodes, which render BSVO series and SVO ceramics potential candidates in multilayer electronic devices fabrication.     

Some q-rung orthopair uncertain linguistic aggregation operators and their application to multiple attribute group decision making

q-Rung orthopair fuzzy sets (q-ROFSs), originally presented by Yager, are a powerful fuzzy information representation model, which generalize the classical intuitionistic fuzzy sets and Pythagorean fuzzy sets and provide more freedom and choice for decision makers (DMs) by allowing the sum of the $q\mathrm{t}\mathrm{h}$ power of the membership and the $q\mathrm{t}\mathrm{h}$ power of the nonmembership to be less than or equal to 1. In this paper, a new class of fuzzy sets called q-rung orthopair uncertain linguistic sets (q-ROULSs) based on the q-ROFSs and uncertain linguistic variables (ULVs) is proposed, and this can describe the qualitative assessment of DMs and provide them more freedom in reflecting their belief about allowable membership grades. On the basis of the proposed operational rules and comparison method of q-ROULSs, several q-rung orthopair uncertain linguistic aggregation operators are developed, including the q-rung orthopair uncertain linguistic weighted arithmetic average operator, the q-rung orthopair uncertain linguistic ordered weighted average operator, the q-rung orthopair uncertain linguistic hybrid weighted average operator, the q-rung orthopair uncertain linguistic weighted geometric average operator, the q-rung orthopair uncertain linguistic ordered weighted geometric operator, and the q-rung orthopair uncertain linguistic hybrid weighted geometric operator. Then, some desirable properties and special cases of these new operators are also investigated and studied, in particular, some existing intuitionistic fuzzy aggregation operators and Pythagorean fuzzy aggregation operators are proved to be special cases of these new operators. Furthermore, based on these proposed operators, we develop an approach to solve the multiple attribute group decision making problems, in which the evaluation information is expressed as q-rung orthopair ULVs. Finally, we provide several examples to illustrate the specific decision-making steps and explain the validity and feasibility of two methods by comparing with other methods.     

Study of equivalent efficiency calibration method for radioactive gas source measured on HPGe detectors

ABSTRACT

In view of the complexity of current detection efficiency calibration of radioactive gas sources, a method using solid planar sources to be equivalent to gas sources was studied. For the 50 mL gas source box, an optimal equivalent scheme was selected by Monte Carlo Simulations. Then, the full-energy-peak efficiency curve of gas sources at the measurement position of 25 cm, with source-to-detector distance of 25 cm, was fitted by measuring solid planar sources with known activity. To verify the accuracy of the efficiency curve, ⁴¹Ar, ¹³³Xe and ⁸⁷Kr gases were produced and determined by length-compensated method. Then, their full-energy-peak efficiencies at 25 cm position away from the detector were directly calibrated. The percentage efficiency deviations between interpolation from the efficiency curve and direct calibration are all less than 2.5%, which proves the accuracy of the equivalent method. This calibration method is a general one and can be also used for some other radioactive sample measurements, such as non-destructive analysis of gaseous fission product samples with a suitable source-to-detector distance.