bluuebunny/crossref_metadata_2025_split huggingface dataset:
Hollow COF Selective Layer Based Flexible Composite Membranes Constructed by an Integrated “Casting‐Precipitation‐Evaporation” Strategy
Authors: Di Mengting , Sun Xiaojun , Hu Lei , Gao Li , Liu Jie , Yan Xiaoming , Wu Xuemei , Jiang Xiaobin , He Gaohong 
Published: February 2022

AbstractCovalent organic frameworks (COFs) have permanent, nanometer‐scale pores endowed with high porosity and thermal and chemical stability, which is widely used as composite membranes and applied in the field of separation. Conventional methods for preparing composite membranes, such as spray coating, spin coating, and pressure‐assisted or vacuum‐assisted filtration, have problems such as the selective layer can easily fall off. Here, an integrated casting–precipitation–evaporation method is proposed to prepare flexible COF composite membranes (DPBI/HTpBD). The DPBI/HTpBD composite membranes constructed with hollow spherical shell COF selective layer (HTpBD) and porous supporting layer are designed and applied in a vanadium flow battery. The excellent coulombic efficiency (CE, 99.5%) and voltage efficiency (VE, 81.1%) of batteries (180 mA cm−2) are achieved by the nanometre‐scale pores of the hollow spherical shell COF selective layer. In addition, the rigid pore structure inside COF bonded by covalent bonds endows the DPBI/HTpBD composite membranes with outstandingly high temperature stability. Compared to that of the Nafion 212 and DPBI pristine membranes (CE reduces by 5.2%, 3.3%), the CE of DPBI/HTpBD‐9 composite membrane‐based cell only reduces by 0.9% as the temperature increases from 25 to 55 °C. This work provides a new preparation method for high ion‐selective and high temperature stable battery membranes.
Supraparticles for Bare‐Eye H2 Indication and Monitoring: Design, Working Principle, and Molecular Mobility
Authors: Reichstein Jakob , Schötz Simon , Macht Moritz , Maisel Sven , Stockinger Nina , Collados Carlos Cuadrado , Schubert Katrin , Blaumeiser Dominik , Wintzheimer Susanne , Görling Andreas , Thommes Matthias , Zahn Dirk , Libuda Jörg , Bauer Tanja , Mandel Karl 
Published: February 2022

AbstractIndicators for H2 are crucial to ensure safety standards in a green hydrogen economy. Herein, the authors report micron‐scaled indicator supraparticles for real‐time monitoring and irreversible recording of H2 gas via a rapid eye‐readable two‐step color change. They are produced via spray‐drying SiO2 nanoparticles, AuPd nanoparticles, and indicator‐dye resazurin. The resulting gas‐accessible mesoporous supraparticle framework absorbs water from humid atmospheres to create a three‐phase‐system. In the presence of H2, the color of the supraparticle switches first irreversibly from purple to pink and further reversibly to a colorless state. In situ infrared spectroscopy measurements indicate that this color change originates from the (ir)reversible H2‐induced reduction of resazurin to resorufin and hydroresorufin. Further infrared spectroscopic measurements and molecular dynamics simulations elucidate that key to achieve this functionality is an established three‐phase‐system within the supraparticles, granting molecular mobility of resazurin. Water acts as transport medium to carry resazurin molecules towards the catalytically active AuPd nanoparticles. The advantages of the supraparticles are their small dimensions, affordable and scalable production, fast response times, straightforward bare‐eye detection, and the possibility of simultaneously monitoring H2 exposure in real‐time and ex post. Therefore, H2 indicator supraparticles are an attractive safety additive for leakage detection and localization in a H2 economy.
Construction of Stable Donor–Acceptor Type Covalent Organic Frameworks as Functional Platform for Effective Perovskite Solar Cell Enhancement
Authors: Li Zhongping , Zhang Zhenwei , Nie Riming , Li Chunzhi , Sun Qikun , Shi Wei , Chu Weicun , Long Yuyang , Li He , Liu Xiaoming 
Published: February 2022

AbstractCovalent organic frameworks (COFs) as a new class of crystalline, porous materials have attracted extensive attention in the fields of photocatalytic and photovoltaic applications. Generally, donor–acceptor (DA) structures play an important role in the charge separation efficiency of solar cells. In this study, two DA‐COFs with high crystallinity, good porosity, and excellent stability are incorporated into the FAPbI3 layer of perovskite solar cells. This addition of DA‐COFs reduces the defect concentration and shallows the defect state. The donor–acceptor system in COFs also possesses strong charge‐transfer pathway, which strongly prevents charge recombination to afford more efficient charge separation efficiency. The highest power‐conversion efficiency of perovskite solar cells constructed with DA‐COFs is 23.19% with excellent humidity stability of the solar cells. Therefore, this work provides a pathway for using DA‐COFs to fabricate perovskite solar cells with higher efficiency and stability.
Single‐Molecule Fluorescence Enhancement by Plasmonic Core–Shell Nanostructures Incorporating Nonlocal Effects
Authors: Kupresak Mario , Zheng Xuezhi , Mittra Raj , Sipus Zvonimir , Vandenbosch Guy A. E. , Moshchalkov Victor V. 
Published: February 2022

AbstractMolecular fluorescence may strongly be affected by plasmonic environments, especially the ones with deep‐nanometer features, associated with the emergence of nonclassical effects. Such effects are largely investigated by a nonlocal hydrodynamic model with additional boundary conditions, describing the collective motion of the free electron gas in metals. The study of a fluorophore in the presence of the nano core–shell topology is performed, by employing the following models: the hard‐wall hydrodynamic model and the generalized nonlocal optical response. The analysis is conducted by investigating the fluorescence rates of the system, while considering the fluorophore located inside and outside the nanoparticle. It is demonstrated that the rates generated by the above models may considerably differ from the ones obtained via the classical approach. The optimal fluorescence enhancements for different size and material parameters are found both inside and outside the studied topology.
FDTD Modeling of Au/Ag Nanoparticles Incorporated Au/Ag Photonic Crystal for Seeking the Maximal Localized Electric Field
Authors: Mu Zhongde , Gu Hongcheng , Chen Qiang , Li Jianqing , He Xia 
Published: February 2022

AbstractPhotonic crystals (PhC) can be elaborately tailored to enhance the electromagnetic properties of materials and are drawing increasing attention in recent years. However, there is no sufficient theoretical framework to optimize photonic crystal designs for electric enhancement. A comprehensive theoretical model is presented to illustrate Au/Ag photonic crystal enhancement on electric fields and obtain a group of optimal photonic crystal parameters after large number of statistics and parameter scans. The second and deeper layers of PhC only contribute to both 5% extinction and absorption in the far‐field, and there is almost no difference in |E|max among different layers with the coefficient variation at ≈1%. Furthermore, increment of both lattice constants and NP diameters can trigger dramatic changes in |E|max, and the maximal |E|max derived from 190 nm AuNP (nanoparticle)‐Au PhC with the lattice constant of 560 nm. This structure is 47.7, 7.39, 4.63, and 2.69 times that of AuNP incorporated silica wafer, silicon wafer, Ag wafer, and Au wafer, respectively. The strong electric field enhancement attributes to not only the plasmonic effect but also the photonic crystal enhancement effect. The simulation procedures open the possibility of precise photonic crystal structure design and pave the way for various electric field enhancement applications.
Giant Room‐Temperature Power Factor inp‐Type Thermoelectric SnSe under High Pressure
Authors: Morozova Natalia V. , Korobeynikov Igor V. , Miyajima Nobuyoshi , Ovsyannikov Sergey V. 
Published: February 2022

AbstractMaterials that can efficiently convert heat into electricity are widely utilized in energy conversion technologies. The existing thermoelectrics demonstrate rather limited performance characteristics at room temperature, and hence, alternative materials and approaches are very much in demand. Here, it is experimentally shown that manipulating an applied stress can greatly improve a thermoelectric power factor of layeredp‐type SnSe single crystals up to ≈180 µW K−2cm−1at room temperature. This giant enhancement is explained by a synergetic effect of three factors, such as: band‐gap narrowing, Lifshitz transition, and strong sample deformation. Under applied pressure above 1 GPa, the SnSe crystals become more ductile, which can be related to changes in the prevailing chemical bonding type inside the layers, from covalent toward metavalent. Thus, the SnSe single crystals transform into a highly unconventional crystalline state in which their layered crystal stacking is largely preserved, while the layers themselves are strongly deformed. This results in a dramatic narrowing in a band gap, fromEg= 0.83 to 0.50 eV (at ambient conditions). Thus, the work demonstrates a novel strategy of improving the performance parameters of chalcogenide thermoelectrics via tuning their chemical bonding type, stimulating a sample deformation and a band‐structure reconstruction.
Efficient Frequency Conversion with Geometric Phase Control in Optical Metasurfaces
Authors: Reineke Matsudo Bernhard , Sain Basudeb , Carletti Luca , Zhang Xue , Gao Wenlong , de Angelis Costantino , Huang Lingling , Zentgraf Thomas 
Published: February 2022

AbstractMetasurfaces have appeared as a versatile platform for miniaturized functional nonlinear optics due to their design freedom in tailoring wavefronts. The key factor that limits its application in functional devices is the low conversion efficiency. Recently, dielectric metasurfaces governed by either high‐quality factor modes (quasi‐bound states in the continuum) or Mie modes, enabling strong light–matter interaction, have become a prolific route to achieve high nonlinear efficiency. Here, an effective way of spatial nonlinear phase control by using the Pancharatnam–Berry phase principle with a high third harmonic conversion efficiency of 10−4 W−2 is demonstrated both numerically and experimentally. It is found that the magnetic Mie resonance appears to be the main contributor to the third harmonic response, while the contribution from the quasi‐bound states in the continuum is negligible. This is confirmed by a phenomenological model based on coupled anharmonic oscillators. Besides, the metasurface provides experimentally a high diffraction efficiency (80%–90%) in both polarization channels. A functional application of this approach is shown by experimentally reconstructing an encoded polarization‐multiplexed vortex beam array with different topological charges at the third harmonic frequency with high fidelity. The approach has the potential viability for future on‐chip nonlinear signal processing and wavefront control.
Arrowhead Composite Microneedle Patches with Anisotropic Surface Adhesion for Preventing Intrauterine Adhesions
Authors: Zhang Xiaoxuan , Chen Guopu , Wang Yuetong , Fan Lu , Zhao Yuanjin 
Published: February 2022

AbstractBiomedical patches are considered as a promising strategy to help tissue repair and regeneration, prevent tissue adhesion, and reduce neighboring friction. Here, novel arrowhead composite microneedle patches (MNPs) are presented with anisotropic surface adhesion and growth factor encapsulation using a heterogeneous template replication approach for endometrium repair and intrauterine adhesions (IUAs) prevention. The arrowhead structures bring about interlocking between the microneedle (MN) tips and tissues, allowing these MNPs to steadily adhere to the tissues. Besides, benefitting from the cytoadhesive needle‐tip material and the antiadhesive base material, these MNPs possess anisotropic surface adhesion and can facilitate cell adhesion on one surface to repair damaged tissues while restrain tissue contact on the other to prevent adverse adhesion. In the meanwhile, the encapsulated growth factor can be delivered through the MNs to the deep tissue, further accelerating tissue repair. Additionally, as the bases are soft and their patterns are highly tunable, the MNPs can change their shapes flexibly to adjust to the irregular morphology of uteri. It is demonstrated that these MNPs show good performances in treating injured endometrium and preventing IUAs of a rat model, indicating their great potential in versatile postoperative adhesion prevention and other clinical applications.
Nonswelling and Hydrolytically Stable Hydrogels Uncover Cellular Mechanosensing in 3D
Authors: Long Hongyan , Vos Bart E. , Betz Timo , Baker Brendon M. , Trappmann Britta 
Published: February 2022

AbstractWhile matrix stiffness regulates cell behavior on 2D substrates, recent studies using synthetic hydrogels have suggested that in 3D environments, cell behavior is primarily impacted by matrix degradability, independent of stiffness. However, these studies did not consider the potential impact of other confounding matrix parameters that typically covary with changes in stiffness, particularly, hydrogel swelling and hydrolytic stability, which may explain the previously observed distinctions in cell response in 2D versus 3D settings. To investigate how cells sense matrix stiffness in 3D environments, a nonswelling, hydrolytically stable, linearly elastic synthetic hydrogel model is developed in which matrix stiffness and degradability can be tuned independently. It is found that matrix degradability regulates cell spreading kinetics, while matrix stiffness dictates the final spread area once cells achieve equilibrium spreading. Importantly, the differentiation of human mesenchymal stromal cells toward adipocytes or osteoblasts is regulated by the spread state of progenitor cells upon initiating differentiation. These studies uncover matrix stiffness as a major regulator of cell function not just in 2D, but also in 3D environments, and identify matrix degradability as a critical microenvironmental feature in 3D that in conjunction with matrix stiffness dictates cell spreading, cytoskeletal state, and stem cell differentiation outcomes.
Single‐Atom Molybdenum Engineered Platinum Nanocatalyst for Boosted Alkaline Hydrogen Oxidation
Authors: Ma Min , Li Guang , Yan Wei , Wu Zhuangzhuang , Zheng Zhiping , Zhang Xibo , Wang Qiuxiang , Du Guifen , Liu Deyu , Xie Zhaoxiong , Kuang Qin , Zheng Lansun 
Published: February 2022

AbstractEngineering the surface electrochemistry at the atomic level can precisely and effectively manipulate the reactivity and durability of catalysts. Herein, a novel single‐atom fine‐tailoring strategy based on a highly hydrophilic Mo‐bifunctional promoter is proposed to greatly boost the hydrogen oxidation reaction (HOR) on Pt catalysts. The single‐atom Mo‐modified nanometer Pt anchored on porous N‐doped carbon (Mo‐Pt/NC) is developed via a pyrolysis–adsorption–reduction process. The designed Mo‐Pt/NC exhibits a remarkable mass‐specific kinetic current reaching 1584 mA mg−1Pt in 0.1 m KOH, which is nearly 11‐fold and fourfold higher than the activities of commercial Pt/C and Pt/NC counterparts respectively, and such extraordinary HOR behavior even exceeds those of documented Pt‐related catalysts. Electrochemical and spectroscopic studies indicate that hydrophilic Mo single‐atom sites can not only regulate the electronic microenvironment of Pt sites for attenuated H* adsorption, but they also serve as energetic H2O*‐adsorption promoters to jointly facilitate the HOR kinetics. Moreover, the anti‐CO poisoning capability of Mo‐Pt/NC is markedly enhanced by this Mo‐modified electronic effect. This work gives a significant guideline for the design of high‐performance HOR catalysts and other advanced catalysts.
Mitigating the Large‐Volume Phase Transition of P2‐Type Cathodes by Synergetic Effect of Multiple Ions for Improved Sodium‐Ion Batteries
Authors: Cheng Zhiwei , Zhao Bin , Guo Yu‐Jie , Yu Lianzheng , Yuan Boheng , Hua Weibo , Yin Ya‐Xia , Xu Sailong , Xiao Bing , Han Xiaogang , Wang Peng‐Fei , Guo Yu‐Guo 
Published: February 2022

AbstractLayered transition metal oxide P2‐Na2/3Ni1/3Mn2/3O2 usually suffers from large‐volume phase transitions and different Na‐vacancy ordering during sodium (de)intercalation, incurring rapid capacity decline and poor rate capability. Herein, an effective strategy based on synergetic effect of selected multiple metal ions is designed for P2‐type cathodes with improved performance. The role of tetravalent titanium provides high redox potential, inactive divalent magnesium stabilizes the structure, and the monovalent lithium smooths the electrochemical curves. The combined analysis of in operando X‐ray diffraction, in operando X‐ray absorption spectroscopy and density functional theory calculations demonstrates the contribution of multi‐metal ions converts the unfavorable and large‐volume P2 to O2 transition into a moderate “Z”‐intergrowth structure by increasing the energy barrier of transition metal slab gliding. As a consequence, the resultant P2‐Na0.7Li0.03Mg0.03Ni0.27Mn0.6Ti0.07O2 electrode delivers a reversible capacity of 134 mAh g−1, a working voltage of 3.57 V, excellent cycling stability (82% of capacity retention after 200 cycles), and superior rate performance (110 mAh g−1 at 4 C). Full cells fabricated with a hard carbon anode achieve an energy density of 296 Wh kg−1. This study presents a route to rationally design cathode materials with this functionalization to improve the cell performance for sodium‐ion batteries.
Cytoplasmic localization of connexin 26 suppresses transition of β‐catenin into the nucleus in intestinal‐ and mix‐type gastric cancer
Authors: Nakazawa Nobuhiro , Sohda Makoto , Yokobori Takehiko , Gombodorj Navchaa , Sano Akihiko , Sakai Makoto , Oyama Tetsunari , Kuwano Hiroyuki , Shirabe Ken , Saeki Hiroshi 
Published: February 2022

AbstractBackgroundConnexin is a basic molecule that forms gap junctions and undergoes localization changes to the cytoplasm in association with carcinogenesis. We aimed to investigate and clarify the significance of cytoplasmic Cx26 expression in gastric cancer.MethodsWe included 87 patients with intestinal‐ and mix‐type gastric cancer and 111 patients with diffuse type gastric cancer who underwent surgery for gastric cancer between 1999 and 2006. Immunohistochemical staining for Cx26, β‐catenin, and Wnt3a was performed and analyses of the relationship to clinicopathological factors were conducted based on the Lauren classification. In an in vitro study, the gastric cancer cell lines MKN7, MKN74, and MKN45 were used to evaluate the proliferative capacity using the water‐soluble tetrazolium salt assay through forced expression of Cx26, and the relationship between Cx26 and β‐catenin was investigated using proximity ligation assay (PLA) and co‐immunoprecipitation. Additionally, functional analysis was performed by Cage analysis.ResultsIn this study, high cytoplasmic Cx26 expression was associated with favorable prognosis in intestinal‐ and mix‐type gastric cancer and could be an independent prognostic factor for overall survival. In terms of the mechanism, in in vitro experiments changes in Cx26 localization to the cytoplasm were shown to suppress the change of localization of β‐catenin to the nucleus by binding to it in the cytoplasm.ConclusionsCytoplasmic Cx26 was found to be a prognostic factor in intestinal‐ and mix‐type gastric cancer. Regarding the mechanism, in vitro studies revealed that cytoplasmic Cx26 inhibits the translocation of β‐catenin to the nucleus.
Evaluation of the degree of rate control via automatic differentiation
Authors: Yang Yilin , Achar Siddarth K. , Kitchin John R. 
Published: February 2022

AbstractThe degree of rate control (DRC) quantitatively identifies the kinetically relevant (sometimes known as rate‐limiting) steps of a complex reaction network. This concept relies on derivatives which are commonly implemented numerically, for example, with finite differences (FDs). Numerical derivatives are tedious to implement, and can be problematic, and unstable or unreliable. In this study, we demonstrate the use of automatic differentiation (AD) in the evaluation of the DRC. AD libraries are increasingly available through modern machine learning frameworks. Compared with the FDs, AD provides solutions with higher accuracy with lower computational cost. We demonstrate applications in steady‐state and transient kinetics. Furthermore, we illustrate a hybrid local‐global sensitivity analysis method, the distributed evaluation of local sensitivity analysis, to assess the importance of kinetic parameters over an uncertain space. This method also benefits from AD to obtain high‐quality results efficiently.
LMOD2‐related dilated cardiomyopathy presenting in late infancy
Authors: Lay Erica , Azamian Mahshid S. , Denfield Susan W. , Dreyer William , Spinner Joseph A. , Kearney Debra , Zhang Lilei , Worley Kim C. , Bi Weimin , Lalani Seema R. 
Published: February 2022

AbstractLeiomodin‐2 (LMOD2) is an important regulator of the thin filament length, known to promote elongation of actin through polymerization at pointed ends. Mice with Lmod2 deficiency die around 3 weeks of age due to severe dilated cardiomyopathy (DCM), resulting from decreased heart contractility due to shorter thin filaments. To date, there have been three infants from two families reported with biallelic variants in LMOD2, presenting with perinatal onset DCM. Here, we describe a third family with a child harboring a previously described homozygous frameshift variant, c.1243_1244delCT (p.L415Vfs*108) with DCM, presenting later in infancy at 9 months of age. Family history was relevant for a sibling who died suddenly at 1 year of age after being diagnosed with cardiomegaly. LMOD2‐related cardiomyopathy is a rare form of inherited cardiomyopathy resulting from thin filament length dysregulation and should be considered in genetic evaluation of newborns and infants with suspected autosomal recessive inheritance or sporadic early onset cardiomyopathy.
Synthesis of Pentasubstituted meta‐Fluoropyridines via [4+2] Cycloaddition and Aromatization between Trifluoromethyl Ketimines and Maleimides
Authors: Zhao Jianbo , Chen Mengzi , Wu Min , Shi Lei , Li Hao 
Published: February 2022

AbstractWe have developed an efficient and convenient strategy for the synthesis of pentasubstituted meta‐fluoropyridines. The annulation‐aromatization cascade reaction between trifluoromethyl ketimines and maleimides was promoted by N‐methyl‐2,2,6,6‐tetramethylpiperidine (PMP) in moderate to high yields. In this approach, two C−F bond cleavages happened in both [4+2] cycloaddition and aromatization separately. The pentasubstituted meta‐fluoropyridines could be reduced to tertiary amines by BH3 in moderate yield.