bluuebunny/crossref_metadata_2025 huggingface dataset:
Large‐Area Self‐Assembled Hexagonal Boron Nitride Nanosheet Films for Ultralow Dark Current Vacuum‐Ultraviolet Photodetectors
Authors: Zhang Qifan , Li Qiang , Chen Ransheng , Zhang Mingyin , Fang Wannian , Li Jiaxing , Wang Mingdi , Yun Feng , Wang Tao , Hao Yue
Published: March 2024

Hexagonal boron nitride (hBN) is one of the most promising candidates for vacuum‐ultraviolet photodetectors (VUV PDs). However, the efficient and low‐cost fabrication of large‐area hBN‐PDs still encounters challenges. Herein, a cost‐effective route is proposed for fast and scalable fabrication of high‐performance VUV PDs via hBN nanosheet (BNNS) films. BNNSs are peeled from bulk hBN and self‐assembled into large‐area ordered films. In such PDs, junction barriers are present at the contact interfaces of BNNSs and give the PDs a “light‐induced reduction of junction barrier height” working mechanism. The number of junction barriers are qualitatively adjusted by designing the size of BNNSs to optimize the performance of the devices. The performance of ultralow dark current (0.27 pA@80 V), high detectivity (3.42 × 1011 Jones), and fast response speed (20.97/17.69 ms) for 185 nm VUV light is achieved by a fabricated PD. Analysis based on the Schottky contact model proves that the large photoresponse is mainly attributed to the reduction of the barriers and series resistance on illumination. Meanwhile, a physical model is established to describe the working process of such PDs, of which conductivity is dominated by the junction barriers. Besides, a flexible PD is also fabricated, depicting excellent stability, and robustness.
A Strain‐Temperature Integrated Polymer‐Derived SiCN Ceramic High Temperature Sensor with Wide‐Range and Ultra‐Short Response Time
Authors: Yang Mengmeng , Ma Chao , Hu Yibo , Wang Kang , Zhao Rui , Liang Yi , Han Daoyang , Wang Hailong , Zhang Rui , Shao Gang
Published: March 2024

Fabricating strain sensors with high response in a wide temperature and strain range is still a challenge, especially in high temperature harsh environments. Herein, a dual‐functional sensor with cantilever beam structure is fabricated using polymer‐derived SiCN ceramics, which can be applied for temperature and stain monitor. The performance of the integrated sensor is evaluated from room temperature to 1000 °C and the related sensing mechanism is analyzed. The prepared strain sensor has ultrafast response of 60 ms in the strain range of 0–3500 µε and the maximum strain rate can reach 46 200 µε s−1. Moreover, the sensor has excellent stability and ultra‐high sensitivity under high temperature environments. Additionally, the temperature can be detected separately up to 1000 °C without any disturbance. This attractive integration sensor with competitive sensitivity, excellent stability, ultrafast response speed, and broad range, has great potential to detect temperature and strain signals for practical application in high temperature extreme environments.
Enhanced Cellular Uptake through Nanotopography‐Induced Macropinocytosis
Authors: Aramesh Morteza , Yu Di , Essand Magnus , Persson Cecilia
Published: March 2024

Efficient cellular uptake of biomolecules, including genetic material, mRNA, proteins, and nanoparticles, requires novel approaches to overcome inherent cellular barriers. Here, the study investigates how nanotopographical cues from nanoporous surfaces impact the uptake efficiency by cells. The results demonstrate notable enhancements in cellular uptake efficiency across a range of vectors when cells are exposed to nanoporous surfaces. The uptake process is found to be dependent on the size and morphology of the nanopores, reaching a peak efficacy with blind pores of 400 nm in size. Enhanced genetic transduction on nanoporous surfaces are observed for multiple vectors, including lentiviruses, baculoviruses, and mRNA molecules. The versatile nature of this approach allows co‐transfection of cells with multiple mRNA vectors. Moreover, the nanoporous platform is used for efficient and fast manufacturing of Chimeric Antigen Receptor (CAR)‐T cells through lentiviral transduction. Furthermore, the study pinpoints macropinocytosis as the predominant mechanism driving increased cellular uptake induced by the nanoporous surfaces. The introduced method for enhancing genetic transduction of cells has applications in immunotherapy research, drug delivery, and cell engineering.
Conjugated Polythiophene Frameworks as a Hole‐Selective Layer on Ta3N5 Photoanode for High‐Performance Solar Water Oxidation
Authors: Yang Jin Wook , Kwon Hee Ryeong , Ji Su Geun , Kim Jaehyun , Lee Sol A , Lee Tae Hyung , Choi Sungkyun , Cheon Woo Seok , Kim Younhwa , Park Jungwon , Kim Jin Young , Jang Ho Won
Published: March 2024

Discovering a competent charge transport layer promoting charge separation in photoelectrodes is a perpetual pursuit in photoelectrochemical (PEC) water splitting to achieve high solar‐to‐hydrogen (STH) conversion efficiency. Here, a conjugated polythiophene framework (CPF‐TTB) on Ta3N5 is elaborately electropolymerized, substantiating the hole transport behavior in their heterojunction. Tailored band structures of the CPF‐TTB/Ta3N5 reinforce the separation of photogenerated carriers, elevating a fill factor of the photoanode modified with a cocatalyst. The enhanced hole extraction enables the NiFeOx/CPF‐TTB/Ta3N5/TiN photoanode to generate a remarkable water oxidation photocurrent density of 9.12 mA cm−2 at 1.23 V versus the reversible hydrogen electrode. A tandem device combining the photoanode with a perovskite/Si solar cell implements an unbiased solar water splitting with a STH conversion efficiency of 6.26% under parallel illumination mode. This study provides novel strategies in interface engineering for metal nitride‐based photoelectrodes, suggesting a promise of the organic–inorganic hybrid photoelectrode for high‐efficiency PEC water splitting.
Phase Inversion‐Induced Porous Polymer Coating for High Rate and Stable Zinc Anode
Authors: Bian Haifeng , Wang Changhao , Wang Yongkang , Ren Yilun , Ge Yu , Wu Hao , Wang Biao , Chen Dongyuan , Yang Beibei , Bin Duan , Li Yunsong , Gu Jian , Ma Yujie , Tang Shaochun , Meng Xiangkang , Lu Hongbin
Published: March 2024

Polymer coatings are emerged as promising candidates for zinc anode artificial solid electrolyte interphase (ASEI) owing to their barrier effect and zincophilicity. However, the poor ionic conductivity of conventional polymer coatings limits their application. Herein, inspired by epidermis function, a porous poly(methylmethacrylate) (PMMA) coating is fabricated to stabilize Zn anode via a novel phase inversion method. The modified Zn anode delivers a remarkable lifespan of over 4000 h at 1 mA cm−2, 1 mAh cm−2, and 120 h at 20 mA cm−2, 20 mAh cm−2 in symmetrical cells. Moreover, porous PMMA‐Zn||NVO full cell also exhibits an excellent cycling stability over 500 cycles at 1 A g−1 as well as an ultralong lifespan exceeding 5000 cycles at 5 A g−1. The excellent cycling stability and rate performance are mainly attributed to the avoided side reactions by the coating protection, as well as the enhanced diffusion and reaction kinetics derived from the good zincophilicity and porous structure of porous PMMA. The facile and universal method for fabricating porous polymer ASEI provides a new insight for the application of conventional polymer materials in Zn anode protection.
Genetically Encoded XTEN‐based Hydrogels with Tunable Viscoelasticity and Biodegradability for Injectable Cell Therapies
Authors: Bennett Jennifer I. , Boit Mary O'Kelly , Gregorio Nicole E. , Zhang Fan , Kibler Ryan D. , Hoye Jack W. , Prado Olivia , Rapp Peter B. , Murry Charles E. , Stevens Kelly R. , DeForest Cole A.
Published: March 2024

While direct cell transplantation holds great promise in treating many debilitating diseases, poor cell survival and engraftment following injection have limited effective clinical translation. Though injectable biomaterials offer protection against membrane‐damaging extensional flow and supply a supportive 3D environment in vivo that ultimately improves cell retention and therapeutic costs, most are created from synthetic or naturally harvested polymers that are immunogenic and/or chemically ill‐defined. This work presents a shear‐thinning and self‐healing telechelic recombinant protein‐based hydrogel designed around XTEN – a well‐expressible, non‐immunogenic, and intrinsically disordered polypeptide previously evolved as a genetically encoded alternative to PEGylation to “eXTENd” the in vivo half‐life of fused protein therapeutics. By flanking XTEN with self‐associating coil domains derived from cartilage oligomeric matrix protein, single‐component physically crosslinked hydrogels exhibiting rapid shear thinning and self‐healing through homopentameric coiled‐coil bundling are formed. Individual and combined point mutations that variably stabilize coil association enables a straightforward method to genetically program material viscoelasticity and biodegradability. Finally, these materials protect and sustain viability of encapsulated human fibroblasts, hepatocytes, embryonic kidney (HEK), and embryonic stem‐cell‐derived cardiomyocytes (hESC‐CMs) through culture, injection, and transcutaneous implantation in mice. These injectable XTEN‐based hydrogels show promise for both in vitro cell culture and in vivo cell transplantation applications.
ITPR2 Mediated Calcium Homeostasis in Oligodendrocytes is Essential for Myelination and Involved in Depressive‐Like Behavior in Adolescent Mice
Authors: Zhang Ming , Zhi Na , Feng Jiaxiang , Liu Yingqi , Zhang Meixia , Liu Dingxi , Yuan Jie , Dong Yuhao , Jiang Sufang , Ge Junye , Wu Shengxi , Zhao Xianghui
Published: March 2024

Ca2+ signaling is essential for oligodendrocyte (OL) development and myelin formation. Inositol 1,4,5‐trisphosphate receptor type 2 (ITPR2) is an endoplasmic reticulum calcium channel and shows stage‐dependent high levels in postmitotic oligodendrocyte precursor cells (OPCs). The role and potential mechanism of ITPR2 in OLs remain unclear. In this study, it is revealed that loss of Itpr2 in OLs disturbs Ca2+ homeostasis and inhibits myelination in adolescent mice. Animals with OL‐specific deletion of Itpr2 exhibit anxiety/depressive‐like behaviors and manifest with interrupted OPC proliferation, leading to fewer mature OLs in the brain. Detailed transcriptome profiling and signal pathway analysis suggest that MAPK/ERK‐CDK6/cyclin D1 axis underlies the interfered cell cycle progression in Itpr2 ablated OPCs. Besides, blocking MAPK/ERK pathway significantly improves the delayed OPC differentiation and myelination in Itpr2 mutant. Notably, the resting [Ca2+]i is increased in Itpr2 ablated OPCs, with the elevation of several plasma calcium channels. Antagonists against these plasma calcium channels can normalize the resting [Ca2+]i level and enhance lineage progression in Itpr2‐ablated OPCs. Together, the findings reveal novel insights for calcium homeostasis in manipulating developmental transition from OPCs to pre‐OLs; additionally, the involvement of OLs‐originated ITPR2 in depressive behaviors provides new therapeutic strategies to alleviate myelin‐associated psychiatric disorders.
Leave No Photon Behind: Artificial Intelligence in Multiscale Physics of Photocatalyst and Photoreactor Design
Authors: Loh Joel Yi Yang , Wang Andrew , Mohan Abhinav , Tountas Athanasios A. , Gouda Abdelaziz M. , Tavasoli Alexandra , Ozin Geoffrey A.
Published: March 2024

Although solar fuels photocatalysis offers the promise of converting carbon dioxide directly with sunlight as commercially scalable solutions have remained elusive over the past few decades, despite significant advancements in photocatalysis band‐gap engineering and atomic site activity. The primary challenge lies not in the discovery of new catalyst materials, which are abundant, but in overcoming the bottlenecks related to material‐photoreactor synergy. These factors include achieving photogeneration and charge‐carrier recombination at reactive sites, utilizing high mass transfer efficiency supports, maximizing solar collection, and achieving uniform light distribution within a reactor. Addressing this multi‐dimensional problem necessitates harnessing machine learning techniques to analyze real‐world data from photoreactors and material properties. In this perspective, the challenges are outlined associated with each bottleneck factor, review relevant data analysis studies, and assess the requirements for developing a comprehensive solution that can unlock the full potential of solar fuels photocatalysis technology. Physics‐informed machine learning (or Physics Neural Networks) may be the key to advancing this important area from disparate data towards optimal reactor solutions.
Radar Micro‐Doppler Signature Generation Based on Time‐Domain Digital Coding Metasurface
Authors: Wang Si Ran , Dai Jun Yan , Ke Jun Chen , Chen Zhan Ye , Zhou Qun Yan , Qi Zhen Jie , Lu Ying Juan , Huang Yan , Sun Meng Ke , Cheng Qiang , Cui Tie Jun
Published: March 2024

Micro‐Doppler effect is a vital feature of a target that reflects its oscillatory motions apart from bulk motion and provides an important evidence for target recognition with radars. However, establishing the micro‐Doppler database poses a great challenge, since plenty of experiments are required to get the micro‐Doppler signatures of different targets for the purpose of analyses and interpretations with radars, which are dramatically limited by high cost and time‐consuming. Aiming to overcome these limits, a low‐cost and powerful simulation platform of the micro‐Doppler effects is proposed based on time‐domain digital coding metasurface (TDCM). Owing to the outstanding capabilities of TDCM in generating and manipulating nonlinear harmonics during wave‐matter interactions, it enables to supply rich and high‐precision electromagnetic signals with multiple micro‐Doppler frequencies to describe the micro‐motions of different objects, which are especially favored for the training of artificial intelligence algorithms in automatic target recognition and benefit a host of applications like imaging and biosensing.
Spectral Asymmetry Induces a Re‐Entrant Quantum Hall Effect in a Topological Insulator
Authors: Wang Li‐Xian , Beugeling Wouter , Schmitt Fabian , Lunczer Lukas , Mayer Julian‐Benedikt , Buhmann Hartmut , Hankiewicz Ewelina M. , Molenkamp Laurens W.
Published: March 2024

The band inversion of topological materials in three spatial dimensions is intimately connected to the parity anomaly of 2D massless Dirac fermions, known from quantum field theory. At finite magnetic fields, the parity anomaly reveals itself as a non‐zero spectral asymmetry, i.e., an imbalance between the number of conduction and valence band Landau levels, due to the unpaired zero Landau level. This work reports the realization of this 2D Dirac physics at a single surface of the 3D topological insulator (Hg,Mn)Te. An unconventional re‐entrant sequence of quantized Hall plateaus in the measured Hall resistance can be directly related to the occurrence of spectral asymmetry in a single topological surface state. The effect should be observable in any topological insulator where the transport is dominated by a single Dirac surface state.
Structural Differences at Quadruplex‐Duplex Interfaces Enable Ligand‐Induced Topological Transitions
Authors: Vianney Yoanes Maria , Dierks Dorothea , Weisz Klaus
Published: March 2024

Quadruplex‐duplex (QD) junctions, which represent unique structural motifs of both biological and technological significance, have been shown to constitute high‐affinity binding sites for various ligands. A QD hybrid construct based on a human telomeric sequence, which harbors a duplex stem‐loop in place of a short lateral loop, is structurally characterized by NMR. It folds into two major species with a (3+1) hybrid and a chair‐type (2+2) antiparallel quadruplex domain coexisting in a K+ buffer solution. The antiparallel species is stabilized by an unusual capping structure involving a thymine and protonated adenine base AH+ of the lateral loop facing the hairpin duplex to form a T·AH+·G·C quartet with the interfacial G·C base pair at neutral pH. Addition and binding of Phen‐DC3 to the QD hybrid mixture by its partial intercalation at corresponding QD junctions leads to a topological transition with exclusive formation of the (3+1) hybrid fold. In agreement with the available experimental data, such an unprecedented discrimination of QD junctions by a ligand can be rationalized following an induced fit mechanism.
Enantio‐ and Regioselective Cascade Hydroboration of Methylenecyclopropanes for Facile Access to Chiral 1,3‐ and 1,4‐Bis(boronates)
Authors: Zhou Jian , Meng Ling , Yang Ziyi , Wang Jun (Joelle)
Published: March 2024

Chiral 1, n‐bis(boronate) plays a crucial role in organic synthesis and medicinal chemistry. However, their catalytic and asymmetric synthesis has long posed a challenge in terms of operability and accessibility from readily available substrates. The recent discovery of the C═C bond formation through β‐C elimination of methylenecyclopropanes (MCP) has provided an exciting opportunity to enhance molecular complexity. In this study, the catalyzed asymmetric cascade hydroboration of MCP is developed. By employing different ligands, various homoallylic boronate intermediate are obtained through the hydroboration ring opening process. Subsequently, the cascade hydroboration with HBpin or B2pin2 resulted in the synthesis of enantioenriched chiral 1,3‐ and 1,4‐bis(boronates) in high yields, accompanied by excellent chemo‐ and enantioselectivities. The selective transformation of these two distinct C─B bonds also demonstrated their application potential in organic synthesis.
Regulated Hydrated Eutectic Electrolyte Enhancing Interfacial Chemical Stability for Highly Reversible Aqueous Aluminum‐Ion Battery with a Wide Temperature Range of −20 to 60 °C
Authors: Zhang Xiaoyang , Wang Rui , Liu Zixiang , Ma Quanwei , Li Hongbao , Liu Yangyang , Hao Junnan , Zhang Shilin , Mao Jianfeng , Zhang Chaofeng
Published: March 2024

The development of aqueous aluminum‐ion batteries (AAIBs) is impeded by pronounced side reactions and hydrogen evolution reaction (HER). Here, an eutectic electrolyte named HEE30 (with an optimal molar ratio of 1:8:1:30 for Al(OTf)3, glycerol (Gly), sodium beta‐glycerophosphate pentahydrate (SG), and H2O) to significantly enhance the reversibility of AAIBs across a wide temperature range from −20 to 60 °C is designed. The combination of molecular dynamics simulations and operando synchrotron Fourier‐transform infrared spectroscopy reveals that the unique eutectic network significantly enhances the hydrogen bonding between Gly and H2O, reduces the solvation interaction of Al3+ with active H2O, thereby lowering the freezing point, extending electrochemical windows and suppressing HER. The X‐ray photoelectron spectroscopy (XPS) and X‐ray diffraction (XRD) tests demonstrate that HEE30 is capable of forming a solid electrolyte interface layer consisting of organic and inorganic components, which effectively inhibits corrosion. Additionally, operando synchrotron XRD and ex situ XPS are employed to investigate the changes in lattice peak width and position of the Prussian white cathode, as well as the reversible storage mechanism during cycling This quantitative design offer immediate advantages for the rational development of low‐cost and safe energy storage batteries, specifically tailored for wide‐temperature operation and durable cycling.
Highly efficient capture of CO2 through the synergy of intramolecular amines within piperazine‐derived alcoholamines
Authors: Jia Shaojun , Jiang Yao , Zheng Songtao , Li Yi , Wu Yan , Liu Xiao‐Qin , Cui Peng
Published: March 2024

Amine‐scrubbing‐based chemical absorption remains a prominent CO2 capture process. However, the overall efficiency of conventional amine absorbents is hard to meet the ever‐increasing demands for CO2 capture. Consequently, developing powerful absorbents for efficient and cost‐effective CO2 capture is greatly important but challenging. Here, a new type of amine absorbent with improved solubility and stability was achieved by substituting the secondary amino groups in piperazine (PZ) with aminoethyl and hydroxyalkyl moieties. The developed amine absorbent presents superior CO2 absorption/desorption abilities through the synergy of their intramolecular amines, leading to a low regeneration energy consumption of 2.56 GJ·t−1 CO2. Moreover, the enhancement of CO2 capture and the corresponding mechanism were elucidated using density functional theory calculations and nuclear magnetic resonance analysis. Such newly developed amine absorbent with excellent CO2 capture performance are expected to greatly contribute to ongoing efforts toward carbon neutrality.
Data‐driven plant‐model mismatch quantification in closed‐loop system based on output predictions
Authors: Shi Yimiao , Xu Xiaodong , Dubljevic Stevan
Published: March 2024

The assessment and diagnosis of controller performance for model‐based closed‐loop control systems has received considerable attention in recent years. A recognized factor dilapidating the controller performance is mismatching the true dynamical model of the plant and the mathematic model employed in the controller. In order to reduce the heavy effort to re‐identify the entire model, a large amount of recent works have been focusing on locating the mismatch. To further improve the mathematic model as well as controller performance, in this article, we provide a novel prediction‐based plant‐model mismatch quantification approach, which belongs to the class of moment match methodology. In particular, two cases of output prediction are considered: one‐step ahead prediction and multistep ahead prediction. Compared with existing efforts along the same line of mismatch quantification, when using the one‐step ahead prediction, our method shows an advantage of light computational complexity. On the other hand, when utilizing multistep predictions, it shows better convergence and robustness than the former, especially in the case of structural mismatches, and the long‐term prediction capability of the model is employed. With both predictions and consideration of the existence of unknown noise models in practice, we show that the plant‐model mismatch and unknown parameters of noise models can be quantified as the solution of a minimization issue that penalizes the discrepancy between the sample of plant outputs and the predictions calculated by considering the plant‐model mismatch and noise model parameters. Several examples are provided to demonstrate the effectiveness of the proposed methods, respectively.
Individual and school correlates of body mass index and cardiorespiratory fitness in primary school children from the REACT project: A multivariate multilevel analysis
Authors: Pereira Sara , Katzmarzyk Peter T. , Garbeloto Fernando , Chaput Jean‐Philippe , Hedeker Donald , Barreira Tiago V. , Borges Renata , Garganta Rui , Santos Carla , Farias Cláudio , Stodden David F. , Tani Go , Maia José
Published: March 2024

Objective

This paper examines the relationship between body mass index (BMI) and cardiorespiratory fitness (CRF) using a multivariate multilevel approach and investigates the links between individual and school‐related correlates with children's BMI and CRF.

Methods

This cross‐sectional sample included 1014 children (6–10 years) from 25 Portuguese primary schools. BMI was calculated, and CRF was assessed with the PACER test. Fundamental movement skills (FMS) included five object control tasks. Moderate‐to‐vigorous physical activity (MVPA), sleep, and sedentary time were assessed with the ActiGraph wGT3X‐BT accelerometer. Socioeconomic status (SES) and school variables were also obtained. A multivariate multilevel model was used, and alpha was set at 5%.

Results

BMI and CRF systematically increased with age. Most of the joint variance (94.4%) was explained at the child level, and BMI and CRF were correlated at this level (ρ = −.37). More active children demonstrated higher CRF levels and had lower BMI levels; sedentary and sleep time were not significantly associated with BMI or CRF. FMS were positively associated with CRF but were not significantly associated with BMI. Children at higher SES were more fit and had lower BMI than their peers of lower SES. Finally, school‐level variables were not significantly related to BMI and CRF.

Conclusion

BMI and CRF had a low but statistically significant negative correlation in this sample of children. Most of the variation in BMI and CRF was explained by child‐level characteristics.
Single‐Particle and Single‐Molecule Characterization of Immobilized Enzymes: A Multiscale Path toward Optimizing Heterogeneous Biocatalysts
Authors: Diamanti Eleftheria , López‐Gallego Fernando
Published: March 2024

Heterogeneous biocatalysis is highly relevant in biotechnology as it offers several benefits and practical uses. To leverage the full potential of heterogeneous biocatalysts, the establishment of well‐crafted protocols, and a deeper comprehension of enzyme immobilization on solid substrates are essential. These endeavors seek to optimize immobilized biocatalysts, ensuring maximal enzyme performance within confined spaces. For this aim, multidimensional characterization of heterogeneous biocatalysts is required. In this context, spectroscopic and microscopic methodologies conducted at different space and temporal scales can inform about the intraparticle enzyme kinetics, the enzyme spatial distribution, and the mass transport issues. In this Minireview, we identify enzyme immobilization, enzyme catalysis, and enzyme inactivation as the three main processes for which advanced characterization tools unveil fundamental information. Recent advances in operando characterization of immobilized enzymes at the single‐particle (SP) and single‐molecule (SM) levels inform about their functional properties, unlocking the full potential of heterogeneous biocatalysis toward biotechnological applications.
Atomically Dispersed p‐Block Aluminum‐Based Catalysts for Oxygen Reduction Reaction
Authors: Zhao Lei , Dai Yunkun , Zhang Yunlong , Liu Bo , Guo Pan , Zhang Ziyu , Shen Lixiao , Zhang Nian , Zheng Yongping , Zhang Zhen , Wang Zhenbo , Chen Zhongwei
Published: March 2024

The main group metals are commonly perceived as catalytically inert in the context of oxygen reduction reactions (ORR) due to the delocalized valence orbitals. Regulating the local environment and structure of metal center coordinated by nitrogen ligands (M‐Nx) is a promising approach to accelerate catalytic dynamics. Herein, we, for the first time, report the atomically dispersed Al catalysts coordinated with N and C atoms for 4‐electron ORR. The axial coordinated pyrrolyl N group (No) is constructed in the Al‐N4‐No moiety to regulate the p‐band structure of Al center, effectively steering the local environment and structure of the square planar Al‐N4 sites, which typically exhibit too strong interaction with ORR intermediates. The dynamic covalency competition of axial Al‐No and Al‐O bonding could endow the Al center with moderate hybridization between Al 3p orbital and O 2p orbital, alleviating the binding energy of ORR intermediates. The as‐prepared Al‐N4‐No electrocatalyst exhibits excellent ORR activity, selectivity, and durability, along with the rapid kinetics as demonstrated by in situ Raman spectroscopy. This work offers a fundamental comprehension of the fine regulation on p‐band and guides the rational design of main‐group metal‐based single atom catalysts.
A Highly‐Fluorinated Lithium Borate Main Salt Empowering Stable Lithium Metal Batteries
Authors: Chen Guansheng , Qiao Lixin , Xu Gaojie , Li Longshan , Li Jiedong , Li Lin , Liu Xiaochen , Cui Zili , Zhang Shenghang , Cheng Shaokai , Han Changxing , Wang Shitao , Zhou Xinhong , Cui Guanglei
Published: March 2024

Traditional lithium salts are difficult to meet practical application demand of lithium metal batteries (LMBs) under high voltages and temperatures. LiPF6, as the most commonly used lithium salt, still suffers from notorious moisture sensitivity and inferior thermal stability under those conditions. Here, we synthesize a lithium salt of lithium perfluoropinacolatoborate (LiFPB) comprising highly‐fluorinated and borate functional groups to address the above issues. It is demonstrated that the LiFPB shows superior thermal and electrochemical stability without any HF generation under high temperatures and voltages. In addition, the LiFPB can form a protective outer‐organic and inner‐inorganic rich cathode electrolyte interphase on LiCoO2 (LCO) surface. Simultaneously, the FPB− anions tend to integrate into lithium ion solvation structure to form a favorable fast‐ion conductive LiBxOy based solid electrolyte interphase on lithium (Li) anode. All these fantastic features of LiFPB endow LCO (1.9 mAh cm−2)/Li metal cells excellent cycling under both high voltages and temperatures (e.g., 80 % capacity retention after 260 cycles at 60 °C and 4.45 V), and even at an extremely elevated temperature of 100 °C. This work emphasizes the important role of salt anions in determining the electrochemical performance of LMBs at both high temperature and voltage conditions.
Study on preparation and properties of polyacrylonitrile/jute microcrystalline cellulose ultrafiltration membranes
Authors: Li Xing , Zhang Zhenguo , Li Meng , Zhang Chengqian , Liang Zhengyong
Published: March 2024

Polyacrylonitrile (PAN) is widely used in the preparation of ultrafiltration membranes. However, the hydrophilicity, thermal, and mechanical properties of the PAN ultrafiltration membrane are poor, limiting the applications in water treatment technology. In this study, the hydrophilic jute microcrystalline cellulose (MCC) is utilized as the modifier for the PAN membrane aiming to develop the ultrafiltration membrane with improved performance. The PAN/jute MCC ultrafiltration membranes with varying jute MCC contents are prepared using the phase inversion method and their structure and properties are systematically characterized. The results demonstrate that the hydrophilicity and thermal stability of the PAN membrane are enhanced. Under optimal conditions, compared with pure PAN membrane, the tensile strength and elongation at break of the membrane increase by 22.64% and 9.84%, respectively, and the water flux can reach 88 L/(m2 h), with the bovine serum albumin rejection ratio of 85%. The above results support that jute MCC can improve the performance of the PAN membrane significantly.
New type of tri‐pyridyl inhibitor‐loaded polyaniline nanospheres for durable protection anticorrosion coatings
Authors: Bao Bingtao , Wu Jianhua , Liu Hao , Xue Mingjin , He Jianmin , Ren Hanzhong , Xu Yiting , Zeng Birong , Luo Weiang , Dai Lizong
Published: March 2024

Polyaniline (PANI) is considered as one of the most promising corrosion inhibitors because of its unique redox and environmental stability. Pyridine and its derivatives can chelate metal ions during corrosion, forming an inert protective layer on the metal surface to achieve the anticorrosion effect. Therefore, polyaniline is combined with pyridine together to achieve deep anticorrosion in this work. 4‐((2,2′:6′,2″‐terpyridin)‐4′‐yl)aniline (TPY) and 1,3,5‐benzenetricarbonyl chloride (TMC) were applied to synthesize a novel corrosion inhibitor N1, N3, N5‐tri (4‐((2,2′: 6′, 2′‐tri‐pyridine)‐4′‐yl) phenyl) benzene‐1,3,5‐tri‐formamide (TBT). Then, TBT was in situ loaded onto the PANI surface to obtain the composite TPANI. The TPANI was successfully dispersed in epoxy resin (EP) at various dosages to prepare composite coatings. Electrochemical impedance spectroscopy and salt fog tests were employed to evaluate the performance of the coatings. After experimentation, we discovered that when the TPANI content was 0.25 wt%, the impedance value remained stable at 5.83 × 109 Ω cm2 after immersing the coatings in a 3.5 wt% NaCl solution for 28 days. In contrast, the EP coating exhibited a resistance decrease ranging from 9.56 × 109 to 7.8 × 108 Ω cm2 within the same soaking time, decreasing by an order of magnitude, while the TPANI‐0.25% coating still maintaining a high order of magnitude. These results indicated that the TPANI filler effectively preserved long‐term stability and provided persistent protection against corrosion. The protective mechanism of TPANI composite coatings was further elucidated through detailed analysis. Overall, the incorporation of TPANI into the epoxy resin yielded promising results, demonstrating its potential as an effective corrosion inhibitor for protective coatings.
Clinical value of endoscopic ultrasound sound speed in differential diagnosis of pancreatic solid lesion and prognosis of pancreatic cancer
Authors: Qiu Jianing , Li Kangrong , Long Xiuyan , Yu Xiaoyu , Gong Pan , Long Yu , Wang Xiaoyan , Tian Li
Published: March 2024

Background

Differential diagnosis of pancreatic solid lesion (PSL) and prognosis of pancreatic cancer (PC) is a clinical challenge. We aimed to explore the differential diagnostic value of sound speed (SS) obtained from endoscopic ultrasonography (EUS) in PSL and the prognostic value of SS in PC.

Methods

Patients with PSL in The Third Xiangya Hospital of Central South University from March 2019 to October 2019 were prospectively enrolled, who obtained SS from PSL. Patients were divided into the PC group and the pancreatic benign lesion (PBL) group. SS1 is the SS of lesions and SS2 is the SS of normal tissues adjacent to lesions. Ratio1 is equal to SS1 divided by SS2 of PSL (ratio1 = SS1/SS2).

Results

Eighty patients were enrolled (24 PBL patients, 56 PC patients). SS1 and ratio1 in PC group were higher compared with PBL group (SS1:1568.00 vs. 1550.00, Z = −2.066, p = 0.039; ratio1: 1.0110 vs. 1.0051, Z = −3.391, p = 0.001). The SS1 in PC (Z = −6.503, p < 0.001) was higher compared to SS2. In the nonsurgical group of PC, low ratio1 predicted high overall survival (OS) (7.000 months vs. 4.000 months; p = 0.039). In the surgical group of PC, low SS1 was associated with low median OS (4.000 months vs. 12.000 months; p = 0.033).

Conclusions

SS plays a vital role in distinguishing between PBL and PC. Higher SS1 and ratio1 obtained by EUS are more related to PC than PBL. In PC patients, high SS1 may predict pancreatic lesions. In the nonsurgical group of PC, low ratio1 may predict high OS. However, in the surgical group of PC, low SS1 may predict low OS.
Glycemic traits and colorectal cancer survival in a cohort of South Korean patients: A Mendelian randomization analysis
Authors: Jun So Yon , Cho Sooyoung , Kim Min Jung , Park Ji Won , Ryoo Seung‐Bum , Jeong Seung Yong , Park Kyu Joo , Shin Aesun
Published: March 2024

Background

Clinical diabetic traits have been reported to be associated with increased colorectal cancer (CRC) risk in observational studies. Using the Mendelian randomization (MR) analysis method, we examined the causal association between glycemic traits, such as fasting glucose (FG), fasting insulin (FI), and glycosylated hemoglobin A1c (HbA1c), and survival in a cohort of CRC patients.

Methods

We conducted a two‐sample MR analysis among a cohort of patients with locally advanced CRC at Seoul National University Hospital. Single‐nucleotide polymorphisms robustly associated (p < 5 × 10−8) with the three glycemic traits were obtained from the Meta‐Analyses of Glucose and Insulin‐related traits Consortium, Asian Genetic Epidemiology Network, and Korea Biobank Array. Three‐year and 5‐year overall survival (OS) and progression‐free survival (PFS) were used as outcomes. Survival analysis was conducted using subgroup analysis by cancer stage and subsite in a multivariate Cox proportional hazards model adjusted for age and sex to examine whether glycemic traits affected survival.

Results

A total of 509 patients were included in our final analysis. MR analysis showed that HbA1c levels were associated with poor 3‐year OS (β = 4.20, p = 0.02). Sensitivity analyses did not show evidence of any violations of the MR assumptions. In the cancer subgroup analysis of the Cox proportional hazards model, pooled hazard ratios for FG were significantly associated with poor 3‐year OS and PFS regardless of cancer stage. FI was not significantly associated with any 3‐year survival endpoints. Among Stage III patients, three glycemic traits were significantly associated with both 5‐year OS and PFS. Location‐specific subgroup analysis showed a significant association between three glycemic traits and 5‐year PFS in patients with left‐sided colon cancer. FG was associated with poor 3‐year survival for colon cancer but not rectal cancer.

Conclusions

Our results suggest that FG and HbA1c could be used to predict prognosis in CRC patients. Lifestyle and/or pharmacological interventions targeting glycemic traits could help improve survival for CRC patients.
Identified PAH V230A and PAH V230I mutations in a family with diverse clinical presentations
Authors: Khaghani Faeze , Eshraghi Peyman , Hamzehloei Tayebeh
Published: March 2024

Key Clinical Message

Phenylketonuria (PKU) is a hereditary disorder caused by phenylalanine hydroxylase enzyme (PAH) defects that might cause severe brain damage. The current main treatment, dietary management, can prevent the symptoms if commenced early. However, it has side effects if used for a long time. Additionally, some patients with mild hyperphenylalaninemia (mHPA), who has serum phenylalanine levels <360 μmol/L, do not require treatment. Since the correlation between genotype and metabolic phenotype has been demonstrated earlier, genotype‐based detection of patients who do not need treatment might help with genetic counseling and choosing the most appropriate treatment option. In this study, we report an asymptomatic adult with mHPA who had never taken any medical intervention to control or lower her serum phenylalanine level (Phe). She had 179 μmol/L serum phenylalanine level and carried p.[V230A];[V230I] genotype. Her child was affected with phenylketonuria and had p.[V230A];[V230A] genotype. Both pathogenic variants detected in the asymptomatic adult with mHPA were computationally analyzed to assess their pathogenicity and the p.V230I pathogenic variant was demonstrated to be responsible for the mHPA phenotype in the asymptomatic adult detected in this study. The findings in this study could contribute to genetic counseling and treatment for families and individuals with p.[V2030I];[V230A] genotype.
Composition and Conformation of Hetero‐ versus Homo‐Fluorinated Triazolamers Influence their Activity on Islet Amyloid Polypeptide Aggregation
Authors: Laxio Arenas José , Lesma Jacopo , Ha‐Duong Tap , Ranjan Sahoo Bikash , Ramamoorthy Ayyalusamy , Tonali Nicolo , Soulier Jean‐Louis , Halgand Frédéric , Giraud François , Crousse Benoît , Kaffy Julia , Ongeri Sandrine
Published: March 2024

Novel fluorinated foldamers based on aminomethyl‐1,4‐triazolyl‐difluoroacetic acid (1,4‐Tz−CF2) units were synthesized and their conformational behaviour was studied by NMR and molecular dynamics. Their activity on the aggregation of the human islet amyloid polypeptide (hIAPP) amyloid protein was evaluated by fluorescence spectroscopy and mass spectrometry. The fluorine labelling of these foldamers allowed the analysis of their interaction with the target protein. We demonstrated that the preferred extended conformation of homotriazolamers of 1,4‐Tz−CF2 unit increases the aggregation of hIAPP, while the hairpin‐like conformation of more flexible heterotriazolamers containing two 1,4‐Tz−CF2 units mixed with natural amino acids from the hIAPP sequence reduces it, and more efficiently than the parent natural peptide. The longer heterotriazolamers having three 1,4‐Tz−CF2 units adopting more folded hairpin‐like and ladder‐like structures similar to short multi‐stranded β‐sheets have no effect. This work demonstrates that a good balance between the structuring and flexibility of these foldamers is necessary to allow efficient interaction with the target protein.
Comparative Bioequivalence and Food Effect of Two Formulations of 30‐mg Nifedipine Controlled‐Release Tablets in Healthy Chinese Adults
Authors: Zhang Huizi , Wang Siyang , Wang Hongxia , Zhi Tingting , Ren Jian , Wang Yanhui , Yao Zhiqing , Zhang Pan , Ye Naobei , Zhang Ruiqin
Published: March 2024

Nifedipine is a potent antihypertensive medication classified as a dihydropyridine calcium channel blocker. The objective of this trial was to assess the bioequivalence of a 30‐mg nifedipine controlled‐release tablet and a reference drug in a cohort of healthy Chinese individuals. Two independent open‐label, randomized, single‐dose, crossover studies were conducted, 1 under fasting conditions (N = 44, with 1 participant dropping out midway) and the other under fed conditions (N = 44, with 4 participants dropping out midway). Plasma concentrations of nifedipine were determined using liquid chromatography‐mass spectrometry, and pharmacokinetic (PK) parameters were calculated using noncompartmental analysis with Phoenix WinNonlin 8.0 software. In both fasting and fed studies, reasonable bioequivalence was observed for the PK parameters of both the test product and the reference drug. A good safety profile was demonstrated for both the test product and reference drug, with no serious adverse events reported, and both were similarly well tolerated. An important observation with food coadministration was that systemic exposure to nifedipine (based on area under the curve, AUC0‐∞) was reduced by approximately 12%. The bioequivalence of the test product and reference drug under fasting/fed conditions in healthy subjects in China was demonstrated by the study results.
Photocatalyzed Oxidative Tandem Reaction Mediated by Bipyridinium for Multifunctional Derivatization of Alcohols
Authors: Yao Xin‐Rong , Jia Meng‐Ze , Miao Xiao‐Li , Yu Shi‐Kai , Chen Yun‐Rui , Pan Jia‐Qi , Zhang Jie
Published: March 2024

The multifunctional derivatization of alcohols has been achieved by the bipyridinium‐based conjugated small molecule photocatalysts with redox center and Lewis acid site. Besides exhibiting high activity in the selective generation of aldehydes/ketones, acids from alcohols through solvent modulation, this system renders the first selective synthesis of esters via an attractive cross‐coupling pattern, whose reaction route is significantly different from the traditional condensation of alcohols and acids or esterification from hemiacetals. Following the oxidization of alcohol to aldehyde via bipyridinium‐mediated electron and energy transfer, the Lewis acid site of bipyridinium then activates the aldehyde and methanol to obtain the acetal, which further reacts with methanol to generate ester. This method not only demonstrates a clear advantage of bipyridinium in diverse catalytic activities, but also paves the way for designing efficient multifunctional small molecule photocatalysts. This metal‐ and additive‐free photocatalytic esterification reaction marks a significant advancement towards a more environmentally friendly, cost‐effective and green sustainable approach, attributed to the utilization of renewable substrate alcohol and the abundant, low‐cost air as the oxidant. The mildness of this esterification reaction condition provides a more suitable alternative for large‐scale industrial production of esters.
Enhanced Carbon‐Carbon Coupling at Interfaces with Abrupt Coordination Number Changes
Authors: Wang Xuan , Lu Ruihu , Pan Binbin , Yang Chao , Zhuansun Mengjiao , Li Jun , Xu Yi , Hung Sung‐Fu , Zheng Gengfeng , Li Yanguang , Wang Ziyun , Wang Yuhang
Published: March 2024

Cu‐catalyzed electrochemical CO2 reduction reaction (CO2RR) produces multi‐carbon (C2+) chemicals with considerable selectivities and activities, yet required high overpotentials impede its practical application. Here, we design interfaces with abrupt coordination number (CN) changes that greatly reduce the applied potential for achieving high C2+ Faradaic efficiency (FE). Encouraged by the mechanistic finding that the coupling between *CO and *CO(H) is the most probable C−C bond formation path, we use Cu2O‐ and Cu‐phthalocyanine‐derived Cu (OD−Cu and PD−Cu) to build the interface. Using operando X‐ray absorption spectroscopy (XAS), we find that the Cu CN of OD−Cu is ~11, favoring CO* adsorption, while the PD−Cu has a COH*‐favorable CN of ~4. Operando Raman spectroscopy revealed that the interfaces with abrupt CN changes promote *OCCOH formation. As a result, the designed catalyst achieves a C2+ FE of 85±2 % at 220 mA cm−2 in a zero‐gap CO2 electrolyzer. An improvement of C2+ FE by 3 times is confirmed at the low potential regime where the current density is 60–140 mA cm−2, compared to bare OD−Cu. We report a 45‐h stable CO2RR operation at 220 mA cm−2, producing a C2+ product FE of ~80 %.
Spatial‐Doppler domain precoding for orthogonal time frequency space modulation with rake detector
Authors: Liu Heng , Yang Siyuan , Liu Xin , Liu Gang , Ma Zheng , Fan Pingzhi
Published: March 2024

The orthogonal time frequency space (OTFS) transmission scheme was shown to outperform orthogonal frequency division multiplexing (OFDM) under the doubly dispersive channel. In this paper, the linear precoding is studied for multiple‐input and multiple‐out (MIMO) OTFS systems, in which a spatial‐Doppler domain singular value decomposition (SVD) precoding scheme is proposed. At the transmitter, the Doppler domain symbols from different spatial streams are precoded before projected onto multiple antennas for transmission. At the receiver, multipath components of the transmitted symbols in the delay‐Doppler grid are combined by using maximal ratio combining (MRC) strategy, so as to achieve the multipath diversity gain and increase the reception reliability. The achievable rate and complexity of the proposed scheme are analyzed, revealing that it can increase the achievable rate while reducing the detector complexity as well. The simulation results confirm that the SVD‐based precoding significantly enhances the error performance of the MIMO‐OTFS with MRC‐based detector.
High species diversity of Phintella and Phintella‐like spiders (Araneae: Salticidae) in Vietnam revealed by DNA‐based species delimitation analyses
Authors: Phung Luong Thi Hong , Su Yong‐Chao , Yamasaki Takeshi , Li Yi‐Yen , Eguchi Katsuyuki
Published: March 2024

Salticidae (jumping spiders) usually exhibit pronounced sexual dimorphism in adult morphology, particularly body coloration and size and shape of the first legs. Consequently, the male and female from the same species might be erroneously assigned to different species or even different genera, which could generate synonymies in classification if only morphological data were used. Phintella is a species‐rich genus of Salticidae, which currently exhibits 76 named species. However, the male–female counterpart is unknown for nearly half of the species. In this study, we used a molecular approach to delineate the species boundaries for Phintella and Phintella‐like specimens collected in Vietnam, using morphological information as supporting data. We used three gene fragments (mitochondrial COI, 16S‐ND1, and nuclear 28S) and biogeographical considerations for species delimitation. A total of 22 putative species were recognized: 18 species of the genus Phintella, one species of the genus Lechia (L. squamata), and three species of the genus Phinteloides. Eleven undescribed species were discovered, of which seven have a male–female combination, two species have only males, and two species have only females. The crown age of Phintella was estimated at the Serravallian stage of the Miocene after the increase of species number around 16 MYA. The crown ages of most putative species recognized in this study were estimated in the Pleistocene, and the divergence among sister species likely occurred from the mid‐Miocene to the Pliocene. Our ancestral range reconstruction results showed that the diversification of our ingroup was governed by progressive dispersal events, i.e., Phintella and their related species in Vietnam diversified while expanding their range on the continent. Our results provide fundamental biodiversity data for a high‐diversity genus in Vietnamese Phintella spiders.