Flexible Conductive Decellularized Fish Skin Matrix as a Functional Scaffold for Myocardial Infarction Repair

Engineering cardiac patches are proven to be effective in myocardial infarction (MI) repair, but it is still a tricky problem in tissue engineering to construct a scaffold with good biocompatibility, suitable mechanical properties, and solid structure. Herein, decellularized fish skin matrix is utilized with good biocompatibility to prepare a flexible conductive cardiac patch through polymerization of polydopamine (PDA) and polypyrrole (PPy). Compared with single modification, the double modification strategy facilitated the efficiency of pyrrole polymerization, so that the patch conductivity is improved. According to the results of experiments in vivo and in vitro, the scaffold can promote the maturation and functionalization of cardiomyocytes (CMs). It can also reduce the inflammatory response, increase local microcirculation, and reconstruct the conductive microenvironment in infarcted myocardia, thus improving the cardiac function of MI rats. In addition, the excellent flexibility of the scaffold, which enables it to be implanted in vivo through “folding-delivering-re-stretehing” pathway, provides the possibility of microoperation under endoscope, which avoids the secondary damage to myocardium by traditional thoracotomy for implantation surgery.     

Elucidating Electrocatalytic Oxygen Reduction Kinetics via Intermediates by Time-Dependent Electrochemiluminescence

Facile evaluation of oxygen reduction reaction (ORR) kinetics for electrocatalysts is critical for sustainable fuel-cell development and industrial H₂O₂ production. Despite great success in ORR studies using mainstream strategies, such as the membrane electrode assembly, rotation electrodes, and advanced surface-sensitive spectroscopy, the time and spatial distribution of reactive oxygen species (ROS) intermediates in the diffusion layer remain unknown. Using time-dependent electrochemiluminescence (Td-ECL), we report an intermediate-oriented method for ORR kinetics analysis. Owing to multiple ultrasensitive stoichiometric reactions between ROS and the ECL emitter, except for electron transfer numbers and rate constants, the potential-dependent time and spatial distribution of ROS were successfully obtained for the first time. Such exclusively uncovered information would guide the development of electrocatalysts for fuel cells and H₂O₂ production with maximized activity and durability.     

Co-Intercalation of Dual Charge Carriers in Metal-Ion-Confining Layered Vanadium Oxide Nanobelts for Aqueous Zinc-Ion Batteries

Vanadium-based oxides with high theoretical specific capacities and open crystal structures are promising cathodes for aqueous zinc-ion batteries (AZIBs). In this work, the confined synthesis can insert metal ions into the interlayer spacing of layered vanadium oxide nanobelts without changing the original morphology. Furthermore, we obtain a series of nanomaterials based on metal-confined nanobelts, and describe the effect of interlayer spacing on the electrochemical performance. The electrochemical properties of the obtained Al_2.65V₆O₁₃ ⋅ 2.07H₂O as cathodes for AZIBs are remarkably improved with a high initial capacity of 571.7 mAh ⋅ g⁻¹ at 1.0 A g⁻¹. Even at a high current density of 5.0 A g⁻¹, the initial capacity can still reach 205.7 mAh g⁻¹, with a high capacity retention of 89.2 % after 2000 cycles. This study demonstrates that nanobelts confined with metal ions can significantly improve energy storage applications, revealing new avenues for enhancing the electrochemical performance of AZIBs.     

Ordered Mesoporous Intermetallic Ga-Pt Nanoparticles: Phase-Controlled Synthesis and Performance in Oxygen Reduction Electrocatalysis

The intermetallic phase control is a promising strategy to optimize the physicochemical properties of ordered intermetallic compounds and engineer their performance in various (electro)catalytic reactions. However, the intermetallic phase-dependent catalytic performance is still rarely reported because of the difficulty in synthesizing ordered intermetallics with precisely controlled phase structures at atomic level, especially having ordered mesoscopic structure/morphology. Here, we successfully reported a precise synthesis of two phase-pure mesoporous intermetallic gallium-platinum (meso-i-Ga-Pt) nanoparticles, including meso-i-Ga₃Pt₅ with an orthorhombic space group and meso-i-Ga₁Pt₁ with a non-symmorphic chiral cubic space group. The intermetallic phase control of ordered meso-i-Ga-Pt nanoparticles was realized by carefully tuning the induced Ga salts with different anions that optimized the free energies during the synthesis. The intermetallic phase-dependent catalytic performance of ordered meso-i-Ga-Pt was systematically evaluated for oxygen reduction reaction (ORR) electrocatalysis, with completely opposite catalytic performance in alkaline media. Interestingly, ordered meso-i-Ga₁Pt₁ catalyst with chiral atomic arrangements disclosed unexpected high ORR activity and stability with 5.9 and 3.2 enhancement factors in mass activity compared to those of meso-i-Ga₃Pt₅ and commercial Pt/C.     

Back Cover: Illustrating the Fate of Methyl Radical in Photocatalytic Methane Oxidation over Ag−ZnO by in situ Synchrotron Radiation Photoionization Mass Spectrometry (Angew. Chem. Int. Ed. 32/2023)

Photocatalysis has emerged as an ideal method for the direct activation and conversion of methane under mild conditions. In this reaction, methyl radical (⋅CH₃) was deemed a key intermediate that affected the yields and selectivity of the products. However, direct observation of ⋅CH₃ and other intermediates is still challenging. Here, a rectangular photocatalytic reactor coupled with in situ synchrotron radiation photoionization mass spectrometry (SR-PIMS) was developed to detect reactive intermediates within several hundred microseconds during photocatalytic methane oxidation over Ag−ZnO. Gas phase ⋅CH₃ generated by photogenerated holes (O⁻) was directly observed, and its formation was demonstrated to be significantly enhanced by coadsorbed oxygen molecules. Methoxy radical (CH₃O⋅) and formaldehyde (HCHO) were confirmed to be key C1 intermediates in photocatalytic methane overoxidation to CO₂. The gas-phase self-coupling reaction of ⋅CH₃ contributes to the formation of ethane, which indicates the key role of ⋅CH₃ desorption in the highly selective synthesis of ethane. Based on the observed intermediates, the reaction network initiated from ⋅CH₃ of photocatalytic methane oxidation could be clearly illustrated, which is helpful for studying the photocatalytic methane conversion processes.     

Unlocking the Transition of Electrochemical Water Oxidation Mechanism Induced by Heteroatom Doping

Heteroatom doping has emerged as a highly effective strategy to enhance the activity of metal-based electrocatalysts toward the oxygen evolution reaction (OER). It is widely accepted that the doping does not switch the OER mechanism from the adsorbate evolution mechanism (AEM) to the lattice-oxygen-mediated mechanism (LOM), and the enhanced activity is attributed to the optimized binding energies toward oxygen intermediates. However, this seems inconsistent with the fact that the overpotential of doped OER electrocatalysts (<300 mV) is considerably smaller than the limit of AEM (>370 mV). To determine the origin of this inconsistency, we select phosphorus (P)-doped nickel-iron mixed oxides as the model electrocatalysts and observe that the doping enhances the covalency of the metal-oxygen bonds to drive the OER pathway transition from the AEM to the LOM, thereby breaking the adsorption linear relation between *OH and *OOH in the AEM. Consequently, the obtained P-doped oxides display a small overpotential of 237 mV at 10 mA cm⁻². Beyond P, the similar pathway transition is also observed on the sulfur doping. These findings offer new insights into the substantially enhanced OER activity originating from heteroatom doping.     

Supported Metal Sulfate Catalysts FexZny/SiO2 for Selective Dimerization of Isobutene in Mixed C4 to Isooctenes

Isobutene dimerization is an important route to properly utilize mixed C₄ and further produce isooctane with a high-octane number to replace MTBE in gasoline. A highly selective catalyst, which is effective for isobutene dimerization but ineffective for other olefins in the C₄ mixture, is necessary for industrial implementation. In this work, a series of supported metal sulfate catalysts Fe_xZn_y/SiO₂ were prepared and characterized by XRD, SEM, N₂ physical adsorption-desorption, NH₃-TPD, Py-FTIR, and XPS. Fe_0.2Zn_1.8/SiO₂ can achieve isobutene conversion up to 89 % with 0 % conversion of n-butene, and the selectivity of isooctenes (C₈⁼) product is 57 % (10 h on stream). Furthermore, isobutene conversion can sustain above 80 % after 50 h. It is found that these supported catalysts contain Zn²⁺, Zn⁺, Fe³⁺, and Fe²⁺ species, and there is a synergetic effect between Zn²⁺ and Fe²⁺. Zn²⁺ is beneficial to improve the conversion of isobutene, and Fe²⁺ facilitates the formation of C₈⁼, resulting in a high C₈⁼ yield.     

A novel method for preparation of exfoliated UV-curable polymer/clay nanocomposites

The half adduct of isophorone diisocyanate and 2-hydroxyethyl acrylate (IPDI-HEA), as a reactive organic modifier, was used to functionalize Na-montmorillonite (Na-MMT) clay. Unlike the electronic interaction in the conventional cation-exchange method, the driving force for the organic modification came from the chemical reaction between IPDI-HEA and framework hydroxyl groups on the surface of clay. With high degree of organic modification (48%), the d-spacing of clay layer was greatly enlarged to 3.32 nm, and the clay became more organophilic. After in situ photopolymerization among the IPDI-HEA grafted MMT clay, monomers and oligomers, the exfoliated polymer/clay nanocomposites were obtained. X-ray diffraction and transmission electron microscopy were used to detect the structure and morphology of the clay dispersed in the polymer matrix. Compared with the pure polymer materials, the exfoliated polymer/clay nanocomposites exhibited enhancements in mechanical and thermal properties.     

Magnetic structure and orbital ordering in tetragonal and monoclinic KCrF(3) from first-principles calculations

KCrF(3) has been systematically investigated by using the full-potential linearized augmented plane wave plus local orbital method within the generalized gradient approximation and the local spin density approximation plus the on-site Coulomb repulsion approach. The total energies for ferromagnetic and three different antiferromagnetic configurations are calculated in the high-temperature tetragonal and low-temperature monoclinic phases, respectively. It reveals that the ground state is the A-type antiferromagnetic in both phases. Furthermore, the ground states of the two phases are found to be Mott-Hubbard insulators with the G-type orbital ordering pattern. In addition, our calculations show the staggered orbital ordering of the 3d(x(2) ) and 3d(y(2) ) orbitals for the tetragonal phase and the 3d(z(2) ) and 3d(x(2) ) orbitals for the monoclinic phase, which is in agreement with the available data. More importantly, the relationship between magnetic structure and orbital ordering as well as the origin of the orbital ordering are analyzed in detail.     

Robust estimation for varying index coefficient models

Varying index coefficient models (VICMs) proposed by Ma and Song (J Am Stat Assoc, 2014. doi: 10.1080/01621459.2014.903185) are a new class of semiparametric models, which encompass most of the existing semiparametric models. So far, only the profile least squares method and local linear fitting were developed for the VICM, which are very sensitive to the outliers and will lose efficiency for the heavy tailed error distributions. In this paper, we propose an efficient and robust estimation procedure for the VICM based on modal regression which depends on a bandwidth. We establish the consistency and asymptotic normality of proposed estimators for index coefficients by utilizing profile spline modal regression method. The oracle property of estimators for the nonparametric functions is also established by utilizing a two-step spline backfitted local linear modal regression approach. In addition, we discuss the bandwidth selection for achieving better robustness and efficiency and propose a modified expectation–maximization-type algorithm for the proposed estimation procedure. Finally, simulation studies and a real data analysis are carried out to assess the finite sample performance of the proposed method.