bluuebunny/crossref_metadata_2025 huggingface dataset:
Preliminary Mechanism of Glial Maturation Factor β on Pulmonary Vascular Remodeling in Pulmonary Arterial Hypertension
Authors: Li Jie , Shi Si , Yan Wenwen , Shen Yuqin , Liu Caiying , Xu Jinyuan , Xu Guotong , Lu Lixia , Song Haoming
Published: April 2024

Recent evidence suggests that glia maturation factor β (GMFβ) is important in the pathogenesis of pulmonary arterial hpertension (PAH), but the underlying mechanism is unknown. To clarify whether GMFβ can be involved in pulmonary vascular remodeling and to explore the role of the IL‐6‐STAT3 pathway in this process, the expression of GMFβ in PAH rats is examined and the expression of downstream molecules including periostin (POSTN) and interleukin‐6 (IL‐6) is measured using real‐time quantitative polymerase chain reaction (RT‐qPCR) and western blot analysis. The location and expression of POSTN is also tested in PAH rats using immunofluorescence. It is proved that GMFβ is upregulated in the lungs of PAH rats. Knockout GMFβ alleviated the MCT‐PAH by reducing right ventricular systolic pressure (RVSP), mean pulmonary arterial pressure (mPAP), and pulmonary vascular remodeling. Moreover, the inflammation of the pulmonary vasculature is ameliorated in PAH rats with GMFβ absent. In addition, the IL‐6‐STAT3 signaling pathway is activated in PAH; knockout GMFβ reduced POSTN and IL‐6 production by inhibiting the IL‐6‐STAT3 signaling pathway. Taken together, these findings suggest that knockout GMFβ ameliorates PAH in rats by inhibiting the IL‐6‐STAT3 signaling pathway.
A Non‐Apoptotic Pattern of Caspase‐9/Caspase‐3 Activation During Differentiation of Human Embryonic Stem Cells into Cardiomyocytes
Authors: Ghorbani Negar , Shiri Mahshad , Alian Maedeh , Yaghubi Roham , Shafaghi Mojtaba , Hojjat Hamidreza , Pahlavan Sara , Davoodi Jamshid
Published: April 2024

In vitro studies have demonstrated that the differentiation of embryonic stem cells (ESCs) into cardiomyocytes requires activation of caspases through the mitochondrial pathway. These studies have relied on synthetic substrates for activity measurements, which can be misleading due to potential none‐specific hydrolysis of these substrates by proteases other than caspases. Hence, caspase‐9 and caspase‐3 activation are investigated during the differentiation of human ESCs (hESCs) by directly assessing caspase‐9 and ‐3 cleavage. Western blot reveals the presence of the cleaved caspase‐9 prior to and during the differentiation of human ESCs (hESCs) into cardiomyocytes at early stages, which diminishes as the differentiation progresses, without cleavage and activation of endogenous procaspase‐3. Activation of exogenous procaspase‐3 by endogenous caspase‐9 and subsequent cleavage of chromogenic caspase‐3 substrate i.e. DEVD‐pNA during the course of differentiation confirmes that endogenous caspase‐9 has the potency to recognize and activate procaspase‐3, but for reasons that are unknown to us fails to do so. These observations suggest the existence of distinct mechanisms of caspase regulation in differentiation as compared to apoptosis. Bioinformatics analysis suggests the presence of caspase‐9 regulators, which may influence proteolytic function under specific conditions.
Enhancement of Damping Characteristics through Hybridization: Investigating the Synergistic Effects of Triply Periodic Minimal Surface Additive Metals and Silicone Polymers
Authors: Ozden Murat Can , Simsek Ugur , Ozdemir Mirhan , Gayir Cemal Efe , Sendur Polat
Published: April 2024

Using triply periodic minimal surface (TPMS) metal parts with added silicone polymer can lead to the development of hybrid materials with enhanced damping characteristics. This study aims to develop composite structures by hybridizing additively manufactured TPMS metal parts with added silicone polymers for vibration applications. Central to this investigation is the quest to ascertain the most efficacious damping mechanism. In this context, the finite element method (FEM)‐based model of the primitive TPMS structure, consisting of cobalt–chrome (CoCr) and the concomitant hybrid structure integrated with silicone polymer, is meticulously developed. The damping characteristics of the FEM‐based models are obtained by modal analysis. The models are also validated using experimental modal tests. The findings show a significant improvement in damping characteristics thanks to the hybrid TPMS structure. Specifically, the damping ratios derived from the hybrid TPMS structure exhibit a sixfold increase in time‐domain damping and up to a 30‐fold increase in frequency‐based analysis across two distinct damping calculation methodologies. Overall, this study highlights the potential of additively fabricated primitive TPMS metal parts with added silicone polymer as a promising structure for improving damping properties in various engineering applications.
Keep it Simple: Ceramic Kelvin Cells via Liquid Crystal Display‐Stereolithography Printing
Authors: Simon Swantje , Hoffmann Patrizia , Stötzel Tim , Weber Jonas , Fey Tobias
Published: April 2024

Additive manufacturing is the state‐of‐the‐art method for producing complex ceramic parts. For cellular materials, the freedom of design is particularly advantageous, as pore networks and shapes can be tailored. Herein, the direct printing of complex parts with high porosity using the cost‐effective manufacturing method of Liquid Crystal Display‐based stereolithography on low‐cost printers is determined. It is investigated how the architecture of the alumina Kelvin cells topology, their fabrication process, the printing parameters, and the microstructure affect the accuracy and mechanical properties of the printed samples. A notable reduction to a strut thickness of Kelvin cells down to 0.20 mm is achieved corresponding to a reduction of 1.5 compared with the state‐of‐the‐art literature (min. 0.35 mm). Ultrahigh porosities between 89.5% and 97.2% and a maximum compressive strength of 1.84 ± 0.17 MPa are reached due to the dense struts of the structure. Low‐cost and simple vat ceramic photopolymerization with high accuracy printing proves to be a promising candidate for the rapid and cost‐effective fabrication of highly porous and complex ceramic structures.
Highly Stable and Sensitive (PEA)2PbBr4/CsPbBr3 Single‐Crystal Heterojunction X‐Ray Detector with Ultra‐Low Detection Limit
Authors: Xu Zhuangjie , Xi He , Sun Xue , Liu Hongjie , Liu Jiaxin , Ba Yanshuang , Chen Dandan , Zhang Guodong , Zhang Chunfu , Ma Xiaohua , Hao Yue
Published: April 2024

Metal halide perovskite (MHP) single crystals have shown great potential for high‐performance X‐ray detection due to their excellent carrier transport properties, tunable optical bandgap, and low‐temperature fabrication process. However, 3D perovskite single crystals suffer from severe ion migration, limiting the stability and sensitivity of X‐ray detectors. Herein, a lowing temperature crystallization (LTC) method for liquid‐phase epitaxial growth of 2D (PEA)2PbBr4 single‐crystal (SC) film on 3D CsPbBr3 substrate is demonstratedand a 2D/3D (PEA)2PbBr4/CsPbBr3 SC heterojunction is successfully constructed. The epitaxial (PEA)2PbBr4 layer shows a pronounced passivation effect on CsPbBr3 SC with a low trap density of 2.27 × 1010 cm−3. As such, the prepared 2D/3D heterojunction X‐ray detector achieves a record‐low detectable dose rate of 3.05 nGyair s−1 and high sensitivity of 34496 µC Gyair−1 cm−2 in 120 keV hard X‐ray detection, with a largely suppressed dark current drift of 2.49 × 10−4 nA cm−1 s−1 V−1. In addition, the heterojunction detector exhibits a self‐driven sensitivity of 44 µC Gyair−1 cm−2 due to its built‐in electric field. This work provides a simple strategy to controllable construct 2D/3D MHP SC heterojunction with excellent optoelectronic characteristic, which is conducive to promoting the development of MHP SC X‐ray detectors and other optoelectronic devices.
Constructing Crown Ether‐Based Supramolecular Adhesives with Ambient‐Temperature Applicable and Durable Adhesion
Authors: Ju Hao , Yin Zhaoliang , Demchuk Zoriana , Bocharova Vera , Gainaru Catalin , Laub Jeffrey A. , Vogiatzis Konstantinos , Advincula Rigoberto , Chen Jiayao , Cao Peng‐Fei
Published: April 2024

Supramolecular adhesives are attracting considerable attentions owing to their dynamic and reversible bonding, while the complex curing conditions and poor performance under extreme conditions severely restrict their applicability. Herein, a series of tetra‐crown ether‐terminated polyethylene glycol (TCE‐PEG) adhesives are presented in which plenty of supramolecular interactions, including Van der Waals, hydrogen bonding, π–π staking, metal coordination, and electrostatic ones, provide strong adhesion on multiple types of substrates. Highly relevant for practical applications, ultra‐strong adhesivity of TCE‐PEG can be achieved without requiring additional ultraviolet radiation, heat, or chemical treatment at ambient temperature. It also exhibits durable adhesive behavior, excellent underwater stability, and low‐temperature tolerance. Especially, by incorporating ionic polymer fragments of polyethyleneimine hydrochloride, additional hydrogen bonding between secondary amines and crown ether rings can be induced to enhance the lap‐shear strength to 7.21 MPa due to the formation of supramolecular cross‐linked network. This work pioneers a rather unique supramolecular approach for easily formed, ultra‐strong crown‐ether‐based adhesives bearing great potential for applications in critical environments of limited heat source and unallowed solvent usage.
Construction of a Pt‐CeOx Interface for the Electrocatalytic Hydrogen Evolution Reaction
Authors: Yu Shen‐Wei , Kwon Soonho , Chen Yizhen , Xie Zhenhua , Lu Xiner , He Kai , Hwang Sooyeon , Chen Jingguang G. , Goddard William A. , Zhang Sen
Published: April 2024

The creation of metal‐metal oxide interfaces is an important approach to fine‐tuning catalyst properties through strong interfacial interactions. This article presents the work on developing interfaces between Pt and CeOx that improve Pt surface energetics for the hydrogen evolution reaction (HER) within an alkaline electrolyte. The Pt‐CeOx interfaces are formed by depositing size‐controlled Pt nanoparticles onto a carbon support already coated with ultrathin CeOx nanosheets. This interface structure facilitates substantial electron transfer from Pt to CeOx, resulting in decreased hydrogen binding energies on Pt surfaces, and water dissociation for the HER, as predicted by the density functional theory (DFT) calculations. Electrochemical testing indicates that both Pt specific activity and mass activity are improved by a factor of 2 to 3 following the formation of Pt‐CeOx interfaces. This study underscores the significance and potential of harnessing robust interfacial effects to enhance electrocatalytic reactions.
Li‐Site Defects Induce Formation of Li‐Rich Impurity Phases: Implications for Charge Distribution and Performance of LiNi0.5−xMxMn1.5O4 Cathodes (M = Fe and Mg; x = 0.05–0.2)
Authors: Murdock Beth E. , Cen Jiayi , Squires Alexander G. , Kavanagh Seán R. , Scanlon David O. , Zhang Li , Tapia‐Ruiz Nuria
Published: April 2024

An understanding of the structural properties that allow for optimal cathode performance, and their origin, is necessary for devising advanced cathode design strategies and accelerating the commercialization of next‐generation cathodes. High‐voltage, Fe‐ and Mg‐substituted LiNi0.5Mn1.5O4 cathodes offer a low‐cost, cobalt‐free, yet energy‐dense alternative to commercial cathodes. In this work, the effect of substitution on several important structure properties is explored, including Ni/Mn ordering, charge distribution, and extrinsic defects. In the cation‐disordered samples studied, a correlation is observed between increased Fe/Mg substitution, Li‐site defects, and Li‐rich impurity phase formation—the concentrations of which are greater for Mg‐substituted samples. This is attributed to the lower formation energy of MgLi defects when compared to FeLi defects. Li‐site defect‐induced impurity phases consequently alter the charge distribution of the system, resulting in increased [Mn3+] with Fe/Mg substitution. In addition to impurity phases, other charge compensators are also investigated to explain the origin of Mn3+ (extrinsic defects, [Ni3+], oxygen vacancies and intrinsic off‐stoichiometry), although their effects are found to be negligible.
Interfacial Electronic and Magnetic Reconstructions in Manganite/Titanate Superlattices
Authors: Lan Da , Yao Bingqing , Swamynadhan M. J. , Li Ning , Cao Jing , Shi Shu , Yu Xiaojiang , Yang Ping , Wu Xiaohan , Liu Chao , Chen Pingfan , Chen Jingsheng , Ghosh Saurabh , He Qian
Published: April 2024

Complex oxide heterointerfaces provide a spacious arena for creating emergent phenomena that are unattainable in the constituent bulk counterparts. Herein, The BaTiO3/La1‐xSrxMnO3 [BTO/LSMO (x)] superlattice (SL) as a model system to investigate the intimately coupled interfacial effects and their resultant phenomena is focused on. The experimental and Density Functional Theory (DFT) calculations reveal that the induced magnetism on Ti originates from both the charge transfer process between Mn and Ti at the titanate/manganite heterointerfaces and the cation intermixing, both contributing comparably to the overall magnetic effect. Upon changing x, the orbital reconstruction of the Mn 3d electrons, tailored by the strain state of the LSMO (x) layers, efficiently modifies the magnetic exchange coupling between Mn–Ti and Mn–Mn at the interfaces, which are proved to account for the modulations of the macroscopic magnetism of the SLs. This work demonstrates the significance of interfacial reconstructions for magnetism, paving a new pathway to manipulate the magnetic properties of artificial oxide heterostructures.
Deactivation of Partially (dis)Charged LNMO in Contact with Water by Electrochemical Protonation of Li(1 − x)Ni0.5Mn1.5O4
Authors: Pitillas Andrea I. , De Taeye Louis L. , Vereecken Philippe M.
Published: April 2024

The development of water‐based composite cathode slurries for Li‐ion batteries is hindered by adverse interactions between the battery active material and water. Insights into interactions between H2O and LiNi0.5Mn1.5O4 (LNMO) are studied using a thin‐film model system. The reactivity of this active material with H2O is evaluated at different lithiation states, showing that protonation of the active material in aqueous environments is electrochemically driven, rather than a chemical Li+/H+ ion exchange reaction. The electrochemically driven mechanism describing the protonation of LNMO is only present when the material is in its partially delithiated form. These findings suggest it is possible to cast this material from an aqueous precursor when lithiated, as long as there are no traces of it when the electrochemical delithiation (cell charging) is carried out.
Visible TADF and NIR Quenching Emission of Chromium Activated Zirconium‐Halide Perovskite Toward Ultra‐High‐Sensitive Ratiometric Fluorescent Thermometer
Authors: Zhao Suxin , Sang Kaihang , Yang Ye , Zhang Junfang , Hu Yangxiang , Chen Mianhong , Zhang Xinguo , Pang Qi , Zhou Liya , Chen Peican
Published: April 2024

With the development of science and technology, the measurement of temperature is receiving more and more attention. However, ratiometric fluorescent thermometers based on thermally coupled energy levels remain challenging because of their low relative sensitivity (Sr). In this work, chromium activated zirconium‐halide perovskite Cs2ZrCl6 microcrystals are successfully synthesized via a simple co‐precipitation method at room temperature. Interestingly, the host Cs2ZrCl6 exhibits reverse thermal quenching due to its thermal‐activated delayed fluorescence (TADF) behavior, while the Cr3+ dopant shows normal thermal quenching. Leveraging the difference in their temperature‐dependent luminescent properties, a ratiometric fluorescent thermometer is ingeniously developed, whose Sr reaches a maximum of 4.23% K−1. Besides, the as‐synthesized thermometer is demonstrated for mobile phone remote temperature measurement. This finding offers a new approach for the design of high‐sensitivity ratiometric fluorescent temperature sensors.
Magnetophotoluminescence Response Triggered by the Triplet State in Metallofullerene
Authors: Zheng Chaofeng , Li Guixian , Liang Jiayi , Yu Lu , Li Wang , Han Yibo , Wang Chunru , Wang Taishan
Published: April 2024

This paper reports the discovery of a magnetophotoluminescence response in metallofullerene Y3N@C80 triggered by the triplet excited state. In experiments, Y3N@C80 exhibits magnetic field‐dependent (0→±42 T) phosphorescence emission at 4.2 K. Crucially, with increasing magnetic field, the phosphorescence peaks shift to longer wavelengths owing to the Zeeman effect. Further, a nanoring of [9]CPPH is employed to modulate the magnetophotoluminescence response of Y3N@C80 through host−guest interaction. The circularly polarized phosphorescence spectra of Y3N@C80 and Y3N@C80⊂[9]CPPH are investigated to further reveal their magnetophotoluminescence properties using the technique of field‐induced circular polarization (FICPO). These results show that metallofullerene Y3N@C80 with magnetophotoluminescence response has potential applications in spin‐related optical devices and quantum technology.
High Rejection‐Ratio IGZO Ultraviolet Phototransistor via Additional Solution Processed ZnO Absorption Layer
Authors: Ma Jin Hyun , Jeong Jun Hyung , Kang Seong Jae , Park Min Ho , Ha Hyoun Ji , Kim Eojin , You Seungyun , Kim Wonsik , Park Soohyung , Kang Seong Jun
Published: April 2024

The depletion of the ozone layer over the last four decades has increased Earth's exposure to ultraviolet (UV) radiation, posing significant health risks. Indium‐Gallium‐Zinc‐Oxide (IGZO) phototransistors have emerged as promising UV detection candidates, boasting a wide bandgap (>3 eV), low off‐current, high on‐current, and stability. However, previous efforts to enhance the photoresponse of IGZO phototransistors focused on visible light absorption layers, neglecting UV detection. Here, zinc oxide (ZnO) nanoparticles (NPs) as an absorption layer in IGZO TFTs for UV phototransistors are introduced. IGZO/ZnO TFTs exhibit robust photoresponsivity for UV light below 360 nm, showcasing rejection ratios (Ruv / Rvis) of 20 258, 62 261, 193 649, and 401 582 for wavelengths of 360, 340, 320, and 300 nm, respectively. The combination of IGZO's wide bandgap with ZnO NPs proves effective for detecting UV light below 360 nm, even at low incident light intensities (15 µW cm−2). Enhanced photoresponse characteristics are confirmed via ultraviolet photoelectron spectroscopy. This research highlights the potential of IGZO materials for UV phototransistors and introduces a novel perspective on the utilization of an additional absorption layer traditionally employed for the conventional extension into the visible light range.
H3K4me3‐Mediated FOXJ2/SLAMF8 Axis Aggravates Thrombosis and Inflammation in β2GPI/Anti‐β2GPI‐Treated Monocytes
Authors: Tan Yuan , Qiao Jiao , Yang Shuo , Liu Hongchao , Wang Qingchen , Liu Qi , Feng Weimin , Cui Liyan
Published: April 2024

Antiphospholipid syndrome (APS) is characterized by thrombus formation, poor pregnancy outcomes, and a proinflammatory response. H3K4me3‐related monocytes activation are key regulators of APS pathogenesis. Therefore, H3K4me3 CUT&Tag and ATAC‐seq are performed to examine the epigenetic profiles. The results indicate that the H3K4me3 signal and chromatin accessibility at the FOXJ2 promoter are enhanced in an in vitro monocyte model by stimulation with β2GPI/anti‐β2GPI, which mimics APS, and decreases after OICR‐9429 administration. Furthermore, FOXJ2 is highly expressed in patients with primary APS (PAPS) and is the highest in patients with triple‐positive antiphospholipid antibodies (aPLs). Mechanistically, FOXJ2 directly binds to the SLAMF8 promoter and activates SLAMF8 transcription. SLAMF8 further interacts with TREM1 to stimulate TLR4/NF‐κB signaling and prohibit autophagy. Knockdown of FOXJ2, SLAMF8, or TREM1 blocks TLR4/NF‐κB and provokes autophagy, subsequently inhibiting the release of inflammatory and thrombotic indicators. A mouse model of vascular APS is established via β2GPI intraperitoneal injection, and the results suggest that OICR‐9429 administration attenuates the inflammatory response and thrombus formation by inactivating FOXJ2/SLAMF8/TREM1 signaling. These findings highlight the overexpression of H3K4me3‐mediated FOXJ2 in APS, which consequently accelerates APS pathogenesis by triggering inflammation and thrombosis via boosting the SLAMF8/TREM1 axis. Therefore, OICR‐9429 is a promising candidate drug for APS therapy.
M2 Tumor‐Associated Macrophages‐Derived Exosomal MALAT1 Promotes Glycolysis and Gastric Cancer Progression
Authors: Wang Yanzheng , Zhang Jiahui , Shi Hui , Wang Maoye , Yu Dan , Fu Min , Qian Yu , Zhang Xiaoxin , Ji Runbi , Wang Shouyu , Gu Jianmei , Zhang Xu
Published: April 2024

M2‐polarized tumor‐associated macrophages (M2 TAMs) promote cancer progression. Exosomes mediate cellular communication in the tumor microenvironment (TME). However, the roles of exosomes from M2 TAMs in gastric cancer progression are unclear. Herein, it is reported that M2 TAMs‐derived exosomes induced aerobic glycolysis in gastric cancer cells and enhanced their proliferation, metastasis, and chemoresistance in a glycolysis‐dependent manner. It is identified that MALAT1 (metastasis‐associated lung adenocarcinoma transcript 1) is enriched in M2 TAM exosomes and confirmed that MALAT1 transfer from M2 TAMs to gastric cancer cells via exosomes mediates this effect. Mechanistically, MALAT1 interacted with the δ‐catenin protein and suppressed its ubiquitination and degradation by β‐TRCP. In addition, MALAT1 upregulated HIF‐1α expression by acting as a sponge for miR‐217‐5p. The activation of β‐catenin and HIF‐1α signaling pathways by M2 TAM exosomes collectively led to enhanced aerobic glycolysis in gastric cancer cells. Finally, a dual‐targeted inhibition of MALAT1 in both gastric cancer cells and macrophages by exosome‐mediated delivery of siRNA remarkably suppressed gastric cancer growth and improved chemosensitivity in mouse tumor models. Taken together, these results suggest that M2 TAMs‐derived exosomes promote gastric cancer progression via MALAT1‐mediated regulation of glycolysis. The findings offer a potential target for gastric cancer therapy.
Mesenchymal Stromal Cells Increase the Natural Killer Resistance of Circulating Tumor Cells via Intercellular Signaling of cGAS‐STING‐IFNβ‐HLA
Authors: Yi Ye , Qin Guihui , Yang Hongmei , Jia Hao , Zeng Qibing , Zheng Dejin , Ye Sen , Zhang Zhiming , Liu Tzu‐Ming , Luo Kathy Qian , Deng Chu‐Xia , Xu Ren‐He
Published: April 2024

Circulating tumor cells (CTCs) shed from primary tumors must overcome the cytotoxicity of immune cells, particularly natural killer (NK) cells, to cause metastasis. The tumor microenvironment (TME) protects tumor cells from the cytotoxicity of immune cells, which is partially executed by cancer‐associated mesenchymal stromal cells (MSCs). However, the mechanisms by which MSCs influence the NK resistance of CTCs remain poorly understood. This study demonstrates that MSCs enhance the NK resistance of cancer cells in a gap junction‐dependent manner, thereby promoting the survival and metastatic seeding of CTCs in immunocompromised mice. Tumor cells crosstalk with MSCs through an intercellular cGAS‐cGAMP‐STING signaling loop, leading to increased production of interferon‐β (IFNβ) by MSCs. IFNβ reversely enhances the type I IFN (IFN‐I) signaling in tumor cells and hence the expression of human leukocyte antigen class I (HLA‐I) on the cell surface, protecting the tumor cells from NK cytotoxicity. Disruption of this loop reverses NK sensitivity in tumor cells and decreases tumor metastasis. Moreover, there are positive correlations between IFN‐I signaling, HLA‐I expression, and NK tolerance in human tumor samples. Thus, the NK‐resistant signaling loop between tumor cells and MSCs may serve as a novel therapeutic target.
Household food security responses for SNAP participants and nonparticipants
Authors: Wilde Parke E. , Arteaga Irma
Published: April 2024

We investigate the distinct associations between Supplemental Nutrition Assistance Program (SNAP) participation and different experiences of food‐related hardship. Using a generalization of the Rasch model with USDA Economic Research Service 2022 data for 10 adult‐referenced food security survey items, we find evidence of uniform differential item function. The gap in odds of response between the first item (food‐related worry) and the third item (difficulty acquiring balanced meals) was larger for SNAP households than for non‐SNAP households. Similar differences were observed for other survey items. We consider whether SNAP policy or program changes could increase beneficial impacts differentially for particular food‐related hardships.
Linker Mediated Electronic‐State Manipulation of Conjugated Organic Polymers Enabling Highly Efficient Oxygen Reduction
Authors: Ma Rui , Tang Chenglong , Wang Yonglin , Xu Xiaoxue , Wu Mingjie , Cui Xun , Yang Yingkui
Published: April 2024

Conjugated polymers with tailorable composition and microarchitecture are propitious for modulating catalytic properties and deciphering inherent structure‐performance relationships. Herein, we report a facile linker engineering strategy to manipulate the electronic states of metallophthalocyanine conjugated polymers and uncover the vital role of organic linkers in facilitating electrocatalytic oxygen reduction reaction (ORR). Specifically, a set of cobalt phthalocyanine conjugated polymers (CoPc‐CPs) wrapped onto carbon nanotubes (denoted CNTs@CoPc‐CPs) are judiciously crafted via in situ assembling square‐planar cobalt tetraaminophthalocyanine (CoPc(NH2)4) with different linear aromatic dialdehyde‐based organic linkers in the presence of CNTs. Intriguingly, upon varying the electronic characteristic of organic linkers from terephthalaldehyde (TA) to 2,5‐thiophenedicarboxaldehyde (TDA) and then to thieno/thiophene‐2,5‐dicarboxaldehyde (bTDA), their corresponding CNTs@CoPc‐CPs exhibit gradually improved electrocatalytic ORR performance. More importantly, theoretical calculations reveal that the charge transfer from CoPc units to electron‐withdrawing linkers (i.e., TDA and bTDA) drives the delocalization of Co d‐orbital electrons, thereby downshifting the Co d‐band energy level. Accordingly, the active Co centers with more positive valence state exhibit optimized binding energy toward ORR‐relevant intermediates and thus a balanced adsorption/desorption pathway that endows significant enhancement in electrocatalytic ORR. This work demonstrates a molecular‐level engineering route for rationally designing efficient polymer catalysts and gaining insightful understanding of electrocatalytic mechanisms.
Ratiometric Afterglow Luminescent Imaging of Matrix Metalloproteinase‐2 Activity via an Energy Diversion Process
Authors: Huang Weijing , Zeng Wenhui , Huang Zheng , Fang Daqing , Liu Hong , Feng Min , Mao Liang , Ye Deju
Published: April 2024

Ratiometric afterglow luminescent (AGL) probes are attractive for in vivo imaging due to their high sensitivity and signal self‐calibration function. However, there are currently few ratiometric AGL probes available for imaging enzymatic activity in living organisms. Here, we present an energy diversion (ED) strategy that enables the design of an enzyme‐activated ratiometric AGL probe (RAG‐RGD) for in vivo afterglow imaging. The ED process provides RAG‐RGD with a radiative transition for an ‘always on’ 520‐nm AGL signal (AGL520) and a cascade three‐step energy transfer (ET) process for an ‘off‐on’ 710‐nm AGL signal (AGL710) in response to a specific enzyme. Using matrix metalloproteinase‐2 (MMP‐2) as an example, RAG‐RGD shows a significant ~11‐fold increase in AGL710/AGL520 toward MMP‐2. This can sensitively detect U87MG brain tumors through ratiometric afterglow imaging of MMP‐2 activity, with a high signal‐to‐background ratio and deep imaging depth. Furthermore, by utilizing the self‐calibration effect of ratiometric imaging, RAG‐RGD demonstrated a strong negative correlation between the AGL710/AGL520 value and the size of orthotopic U87MG tumor, enabling accurate monitoring of orthotopic glioma growth in vivo. This ED process may be applied for the design of other enzyme‐activated ratiometric afterglow probes for sensitive afterglow imaging.
Synthesis and catalytic applications of highly stable copper‐based metal–organic framework as an efficient heterogeneous nanocatalyst for solvent‐free Suzuki–Miyaura cross‐coupling reaction
Authors: Sanati‐Tirgan Parvin , Eshghi Hossein , Mohammadinezhad Arezou
Published: April 2024

The most prominent factors determining the properties and applications of metal–organic frameworks (MOFs) are their structural, morphological, and stability features under harsh conditions. Therefore, it is important to design the new methods to synthesize MOFs with modified structure and morphology and as a result more stability for the expansion of well‐organized MOFs. Herein, we reported the new synthetic strategy for the preparation of copper‐aurin tricarboxylate metal–organic framework (CuATC‐MOF) using a mixed solvent system. Comprehensive monitoring of the new synthetic strategy revealed the mixed solvent system (DMF/EtOH) is a key factor on particle size, morphology, and chemical stability of CuATC‐MOF. Then, the as‐prepared CuATC‐MOF with an acceptable specific surface area (62.655 m2/g), the particle size of 40–90 nm, and mesoporous structure exhibited superior catalytic activity and stability for the catalytic formation of a C‐C bond through a Suzuki‐Miyaura cross‐coupling reaction (SMCR). FT‐IR, PXRD, BET, FE‐SEM, TEM, EDX, EDX‐mapping, TGA, and ICP‐OES are impressive techniques that assisted us to well identified the structure of CuATC‐MOF. Additionally, CuATC‐MOF displayed excellent recyclability, during the six consecutive cycles, without significant reduction in its catalytic efficiency.
An exhaustive ADDIS principle for online FWER control
Authors: Fischer Lasse , Roig Marta Bofill , Brannath Werner
Published: April 2024

In this paper, we consider online multiple testing with familywise error rate (FWER) control, where the probability of committing at least one type I error will remain under control while testing a possibly infinite sequence of hypotheses over time. Currently, adaptive‐discard (ADDIS) procedures seem to be the most promising online procedures with FWER control in terms of power. Now, our main contribution is a uniform improvement of the ADDIS principle and thus of all ADDIS procedures. This means, the methods we propose reject as least as much hypotheses as ADDIS procedures and in some cases even more, while maintaining FWER control. In addition, we show that there is no other FWER controlling procedure that enlarges the event of rejecting any hypothesis. Finally, we apply the new principle to derive uniform improvements of the ADDIS‐Spending and ADDIS‐Graph.
Nervogenic Acid Derivatives and Phenanthrenes from Liparis nervosa and Their Antimicrobial and Immunosuppressive Activities
Authors: Jiang Hong , Liu Yang , Ren Bo , Lai Yi , Chen Hu‐Lan , Li Li‐Mei
Published: April 2024

Two new nervogenic acid derivatives liparisnervosides Q (1) and R (5), as well as five known nervogenic acid derivatives (2–4, 6, 7) and four phenanthrenes (8–11) were isolated from the whole plant of Liparis nervosa (Thunb. ex A. Murray) Lindl.. Their structures were detremined using extensive spectroscopic techniques, including 1D, 2D NMR, and HR‐ESI‐MS, and acid hydrolysis. Furthermore, their antimicrobial and immunosuppressive activities were evaluated. Nervosine VII (3) exhibited antimicrobial activity against Staphylococcus aureus with an MIC of 62.5 μg/mL and inhibited the proliferation of human T cells with an IC50 value of 9.67±0.96 μM. These findings contribute to our understanding of the potential pharmacological properties of these compounds.
Combined transcatheter aortic valve and tricuspid valve‐in‐valve implantation in a patient with a mitral mechanical prosthesis
Authors: Lima Maria Rita , Brito João , Almeida Manuel , Teles Rui Campante
Published: April 2024

Despite progressively uncommon in Western countries, rheumatic heart disease still portrays a significant global burden. In elderly or high‐surgical risk patients, plurivalvular disease may require a complex percutaneous approach. Transcatheter aortic valve implantation (TAVI) in patients with previous monoleaflet mitral prosthesis is challenging due to interference between the aortic valve and the rigid mitral mechanical prosthesis “ring.” Prior cases report the use of CoreValve or Edwards Sapien aortic valves in patients with adequate mitro‐aortic distance. Performing a second major procedure, such as tricuspid valve‐in‐valve (TVIV), sequentially during a single percutaneous intervention, increases treatment complexity. An 83‐year‐old woman with rheumatic heart disease, with previous implantation of a Bjork–Shiley monoleaflet mitral prosthesis, and Carpentier‐Edwards 29 tricuspid bioprosthesis presented with decompensated heart failure due to severe aortic stenosis and tricuspid bioprosthesis stenosis. After HeartTeam discussion, the patient was deemed as inoperable due to a prohibitive surgical risk. As an alternative, a TAVI (Navitor FlexNav) and a transcatheter TVIV replacement (Edwards Sapiens 3 Ultra) were discussed and proposed, with both techniques being performed sequentially in a single procedure. TAVI in a patient with a previous monoleaflet mitral mechanical prosthesis and TVIV may be a feasible approach in inoperable patients with plurivalvular disease.
Calcium‐Based Metal‐Organic Framework: Detection and Idiosyncratic Removal of Copper by Nano‐Particle Deposition
Authors: Mondal Pallav , Brahma Bhaskar K. , Vali Dudekula Khasim , Ray Joydeep , Kasu Jyothirlatha V. N. , Gangopadhyay Avishek , Laha Sourav , Adhikari Utpal
Published: April 2024

A novel calcium‐based metal‐organic framework (CaMOF@LSB) was designed and synthesized, exhibiting dual functionality for both selective detection and removal of Cu2+ ions from aqueous solutions. The framework‘s stability, including solvent and pH variations, was established with notable thermal resilience. Colorimetric Cu2+ detection (≥5 ppm) with a high capture capacity of 484.2 mg g−1 by CaMOF@LSB places this material among the few that ensure efficient colorimetric detection and high removal capabilities of Cu2+ ions. Batch adsorption experiments revealed pH‐dependent behavior and competitive interactions. Langmuir and pseudo‐second‐order kinetics models aptly described adsorption isotherms and kinetics, respectively. Thermodynamic assessments confirmed spontaneous and endothermic adsorption. Mechanistically, nanoparticle deposition contributes to the Cu2+ uptake. CaMOF@LSB also exhibited one of the best removal behaviour of Cu2+ by means of oxide formation on the surface. Regeneration of CaMOF@LSB was achieved by simple sonication in 0.1 M aqueous NaOH solution. The recyclability was also tested up to 5 cycles, and it exhibited a small decrease in adsorption capacity observed across the cycles. This research presents a promising avenue for addressing heavy metal pollution using metal‐organic frameworks, thereby offering potential applications in water purification and environmental pollution monitoring and remediation.
Exploration of Vitamin B6‐Based Redox‐Active Pyridinium Salts Towards the Application in Aqueous Organic Flow Batteries
Authors: Nechaev Anton A. , Gonzalez Gabriel , Verma Prachi , Peshkov Vsevolod A. , Bannykh Anton , Hashemi Arsalan , Hannonen Jenna , Hamza Andrea , Pápai Imre , Laasonen Kari , Peljo Pekka , Pihko Petri M.
Published: April 2024

Pyridoxal hydrochloride, a vitamin B6 vitamer, was synthetically converted to a series of diverse redox‐active benzoyl pyridinium salts. Cyclic voltammetry studies demonstrated redox reversibility under basic conditions, and two of the most promising salts were subjected to laboratory‐scale flow battery tests involving galvanostatic cycling at 10 mM in 0.1 M NaOH. In these tests, the battery was charged completely, corresponding to the transfer of two electrons to the electrolyte, but no discharge was observed. Both CV analysis and electrochemical simulations confirmed that the redox wave observed in the experimental voltammograms corresponds to a two‐electron process. To explain the irreversibility in the battery tests, we conducted bulk electrolysis with the benzoyl pyridinium salts, affording the corresponding benzylic secondary alcohols. Computational studies suggest that the reduction proceeds in three consecutive steps: first electron transfer (ET), then proton‐coupled electron transfer (PCET) and finally proton transfer (PT) to give the secondary alcohol. 1H NMR deuterium exchange studies indicated that the last PT step is not reversible in 0.1 M NaOH, rendering the entire redox process irreversible. The apparent reversibility observed in CV at the basic media likely arises from the slow rate of the PT step at the timescale of the measurement.
Benzoselenadiazole‐Functionalized H‐Bonded Arylamide Foldamers: Solvent‐Responsive Properties and Helix Self‐Assembly Directed by Chalcogen Bonding in Solid State
Authors: Liu Chuan‐Zhi , Zhang Chi , Li Chang‐Gen , Chen Hui‐Bin , Yang Wen , Li Zhong‐Yi , Hu Zhi‐Yuan , Xu Liang , Zhai Bin , Li Zhan‐Ting
Published: April 2024

In this study, a series of H‐bonded arylamide foldamers bearing benzoselenadiazole ends with solvent‐responsive properties have been synthesized. In dichloromethane or dimethyl sulfoxide solvents, the molecules exhibit meniscus or linear structures, respectively, which can be attributed to the unique intramolecular hydrogen bonding behavior evidenced by 1D 1H NMR and 2D NOESY spectra. UV‐vis spectroscopy experiments show that the absorption wavelength of H‐bonded arylamide foldamers are significantly red‐shifted due to the presence of benzoselenadiazole group. In addition, the crystal structures reveal that effective intermolecular dual Se ⋅ ⋅ ⋅ N interactions between benzoselenadiazole groups induce further assembly of the monomers. Remarkably, supramolecular linear and double helices structures are constructed under the synergistic induction of intramolecular hydrogen bonding and intermolecular chalcogen bonding. Additionally, 2D DOSY diffusion spectra and theoretical modelling based on density functional theory (DFT) are performed to explore the persistence of intermolecular Se ⋅ ⋅ ⋅ N interactions beyond the crystalline state.
The threshold energy of low temperature Langevin dynamics for pure spherical spin glasses
Authors: Sellke Mark
Published: April 2024

We study the Langevin dynamics for spherical ‐spin models, focusing on the short time regime described by the Cugliandolo–Kurchan equations. Confirming a prediction of Cugliandolo and Kurchan, we show the asymptotic energy achieved is exactly in the low temperature limit. The upper bound uses hardness results for Lipschitz optimization algorithms and applies for all temperatures. For the lower bound, we prove the dynamics reaches and stays above the lowest energy of any approximate local maximum. In fact the latter behavior holds for any Hamiltonian obeying natural smoothness estimates, even with disorder‐dependent initialization and on exponential time‐scales.
Detection of algal tiny objects based on morphological features
Authors: Yuan Shuai , Peng Ningkang , Shi Ziyan , Zhao Sichuan , Li Runcheng , Gu Yanhui , He Huan
Published: April 2024

The dense and toxic blooms formed by cyanobacteria in aquatic environments pose significant threats to public health and aquatic ecosystems. Timely monitoring and prevention of cyanobacterial blooms in freshwater bodies are thus imperative. Although object detection methods have been applied in the field of algae identification, existing research faces several challenges. A primary issue is the overly idealistic setting of training sets, which are disconnected from the actual water quality environments, impeding practical algae identification and water quality monitoring. In this paper, we collect 2024 microscopic images of algae from a reservoir in Southern China, forming a comprehensive and diverse dataset for object detection. Addressing the aforementioned challenges, we propose an attention‐based strategy for the detection of tiny algal objects, which effectively samples and extracts features from algal targets. Our model uniquely leverages the morphable characteristics of algae, enhancing the accuracy and efficiency of identification. The training and improvement results of this model presented in our study are expected to aid in establishing a future system for real‐time algae monitoring and water quality assessment.
Cross‐Polarization Solid‐State NMR Quantification of Species within Pores of Metal‐Organic Frameworks: A Case Study of α‐Mg3(HCOO)6
Authors: Wu Changzong , Xu Jun
Published: April 2024

The quantitative measurement of adsorbed guest species within metal‐organic framework (MOF) pores is of fundamental importance for evaluating the adsorption performance of MOFs. However, routine analytic techniques such as thermogravimetric analysis cannot distinguish the contribution from species adsorbed within pores, species adsorbed on the surface, and gas phase or liquid phase encapsulated in the inter‐crystalline space. Herein, we developed a new quantification method based on the cross‐polarization (CP) solid‐state nuclear magnetic resonance (ssNMR) technique, in which only the species within MOF pores are selectively probed due to the dramatically reduced mobility. Using the commercialized MOF α‐Mg3(HCOO)6 as an example, a good linear correlation between Areaguest/Areaframework (i. e., the integrated area of guest and framework 13C NMR signals) and guest loading can be observed for several representative molecules such as benzene, tetrahydrofuran (THF), and 1,4‐dioxane, clearly revealing the feasibility of CP quantification approach. The effects of guest molecule and corresponding residual mobility on the CP quantification are further discussed by varying the geometry and size of guest molecules. This methodology thus provides an effective and irreplaceable route to evaluate the adsorption performance of porous materials in‐depth, especially for liquid‐phase adsorption and gas‐phase adsorption in which the capillary condensation is not negligible.
The Transition from Alchemical to Modern Chemical Symbolism: from Bergman and Guiton de Morveau to Hassenfratz and Adet, Higgins, Richter, Dalton, and Berzelius
Authors: Wentrup Curt
Published: April 2024

The alchemical concepts of chemical symbolism, nomenclature, and affinity underwent fundamental changes between the 1770s and the 1820s, roughly simultaneously with the Chemical Revolution (ca. 1772–89), i. e. the replacement of the phlogiston theory with Lavoisier's New Chemistry. Using the old, alchemical symbols, Bergman devised a system of formulas to describe virtually all known inorganic chemistry, and he influenced Guiton de Morveau's Mémoire sur les Dénominations Chimiques, and the subsequent Méthode de nomenclature. Hassenfratz and Adet devised a new artificial sign language which, however, was too complicated and unintuitive to gain widespread acceptance. Bergman refined the concept of affinity, but his belief in phlogiston rapidly made the system obsolete. Wenzel realized that the dissolution of metals in acids is not just a question of affinity but rather of concentration, and he and Berthollet separately formulated early versions of the Law of Mass Action thereby making attempts to quantify affinity redundant. Richter formulated a principle that became known as the Law of Equivalent Proportions, describing acid‐base reactions and double decompositions of salts, but continuing to use Bergman‐style alchemical formulas. Only John Dalton's atomic theory with little globules denoting atoms and their combination into molecules made a definite break with the alchemical symbols.
DNA metabarcoding reveals the seasonal variation of dietary composition of Taihangshan macaque (Macaca mulatta tcheliensis), Jiyuan, north China
Authors: Zhou Yanyan , Liu Chunbo , Tian Jundong , Shao Qi , Lu Jiqi
Published: April 2024

Dietary analysis in wildlife is fundamental for understanding their flexible response to seasonal changes and developing effective conservation management measures. Taihangshan macaque (Macaca mulatta tcheliensis) is the northernmost population of rhesus macaque, currently only distributed in the southern Mt. Taihangshan area. This area belongs to a semi‐arid region resulting in limited plant food availability for Taihangshan macaques, with seasonal variation. Herein, we used a chloroplast trnL DNA metabarcoding approach to identify the plant diet diversity and composition from 100 fecal samples of Taihangshan macaque in four seasons (spring, summer, autumn, and winter) from 2020 to 2021. The results revealed that (1) a total of 48 distinct families, 88 genera, and 52 species within the 105 food items that were consumed by Taihangshan macaques throughout the year; (2) the diversity of food items exhibited significant differences across the four seasons; (3) Rosaceae, Rhamnaceae, Fagaceae, and Poaceae are the preferential food items for Taihangshan macaques and have different relative abundances, fluctuating with seasonal variation. DNA metabarcoding can expand our understanding of the repertoire of food items consumed by Taihangshan macaques by detecting some consumed food items in this population that were not yet discovered using traditional methods. Therefore, the integrative results from traditional methods and DNA metabarcoding can provide a fundamental understanding of dietary composition to guide the conservation management of Taihangshan macaques.
Inhibition of gut digestive proteases by cyanobacterial diets decreases infection in a Daphnia host–parasite system
Authors: Sánchez Kristel F. , von Elert Eric , Monell Kira , Calhoun Siobhan , Maisha Aniqa , McCreadie Paige , Duffy Meghan A.
Published: April 2024

Secondary metabolites produced by primary producers have a wide range of functions as well as indirect effects outside the scope of their direct target. Research suggests that protease inhibitors produced by cyanobacteria influence grazing by herbivores and may also protect against parasites of cyanobacteria. In this study, we asked whether those same protease inhibitors produced by cyanobacteria could also influence the interactions of herbivores with their parasites. We used the Daphnia‐Metschnikowia zooplankton host‐fungal parasite system to address this question because it is well documented that cyanobacteria protease inhibitors suppress trypsin and chymotrypsin in the gut of Daphnia, and because it is known that Metschnikowia infects via the gut. We tested the hypothesis that Daphnia gut proteases are necessary for Metschnikowia spores to be released from their asci. We then also tested whether diets that decrease trypsin and chymotrypsin activity in the guts of Daphnia lead to lower levels of infection. Our results show that chymotrypsin promotes the release of the fungal spores from their asci. Moreover, a diet that strongly inhibited chymotrypsin activity in Daphnia decreased infection levels, particularly in the most susceptible Daphnia clones. Our results support the growing literature that cyanobacterial diets can be beneficial to zooplankton hosts when challenged by parasites and uncover a mechanism that contributes to the protective effect of cyanobacterial diets. Specifically, we demonstrate that host chymotrypsin enzymes promote the dehiscence of Metschnikowia spores; when cyanobacteria inhibit the activity of chymotrypsin in hosts, this most likely traps the spore inside the ascus, preventing the parasite from puncturing the gut and beginning the infection process. This study illustrates how secondary metabolites of phytoplankton can protect herbivores against their own enemies.