bluuebunny/crossref_metadata_2025_split huggingface dataset:
Optimize Lithium Deposition at Low Temperature by Weakly Solvating Power Solvent
Authors: Ma Tao , Ni Youxuan , Wang Qiaoran , Zhang Weijia , Jin Song , Zheng Shibing , Yang Xian , Hou Yunpeng , Tao Zhanliang , Chen Jun 
Published: August 2022

AbstractFor lithium (Li) metal batteries, the decrease in operating temperature brings severe safety issues by more disordered Li deposition. Here, we demonstrate that the solvating power of solvent is closely related to the reversibility of the Li deposition/stripping process under low‐temperature conditions. The electrolyte with weakly solvating power solvent shows lower desolvation energy, allowing for a uniform Li deposition morphology, as well as a high deposition/stripping efficiency (97.87 % at −40 °C). Based on a weakly solvating electrolyte, we further built a full cell by coupling the Li metal anode with a sulfurized polyacrylonitrile electrode at a low anode‐to‐cathode capacity ratio for steady cycling at −40 °C. Our results clarified the relationship between solvating power of solvent and Li deposition behavior at low temperatures.
Colloidal Jamming by Interfacial Self‐Assembled Polymers: A Robust Route for Ultrahigh Efficient Encapsulation
Authors: Huo Qingqing , Gao Yue , Wu Wenbo , Hu Shuai , Zhang Zifan , Li Zhi , Tian Yuling , Quan Peng , Li Wen , Liu Dongfei 
Published: August 2022

AbstractThe control of cargo phase‐transfer is of interest for many applications in science and technology. Herein, we report a simple, versatile and robust method to block the phase‐transfer of cargo colloids by interfacial self‐assembled amphiphilic polymer molecules. After simply increasing the concentration of amphiphilic polymers, the orientation of interfacial polymer molecules changed from flat to upright, forming a thick three‐dimensional polymer layer at the oil‐water interface. Even under fierce external force, this thick interfacial layer robustly prevented the phase‐transfer of cargo colloids, resulting in an ultrahigh encapsulation efficiency (up to 97.1 %) for proteins and peptides. One single injection of high insulin‐loaded microcomposites (58.3 wt%) kept the blood glucose level within the normoglycemic state for 10 days in type 1 diabetic rats. The mass of administrated amphiphilic polymers was 1889 times smaller than that of microcomposites prepared with non‐amphiphilic ones.
A Double‐Helix Metal‐Chain Metal‐Organic Framework as a High‐Output Triboelectric Nanogenerator Material for Self‐Powered Anticorrosion
Authors: Shao Zhichao , Chen Junshuai , Gao Kexin , Xie Qiong , Xue Xiaojing , Zhou Shuangyan , Huang Chao , Mi Liwei , Hou Hongwei 
Published: August 2022

AbstractThe development of novel metal organic framework (MOF) friction power generation materials with high stability is important. This paper reports the first example of a double‐helix metal chain organic framework with a network structure (ZUT‐8). ZUT‐8 shows high chemical stability, functional adjustability, and excellent output performance of friction power generation, which is superior to traditional coordination polymer materials. The cathodic protection system with ZUT‐8 can prevent metal corrosion significantly. The output performance can be improved effectively by enhancing the conjugate effect of the linker. The theoretical calculation results showed that an increase in the degree of conjugation could significantly reduce the band gap, thereby affecting the friction power output signal. This study opens the door to constructing MOF materials with a double‐helix metal chain and will promote their potential applications in self‐powered electrochemical cathodic protection.
Energy Transfer Chemiluminescent Spiroadamantane 1,2‐Dioxetane Probes for Bioanalyte Detection and Imaging
Authors: Kagalwala Husain N. , Lippert Alexander R. 
Published: August 2022

AbstractChemiluminescence imaging of bioanalytes using spiroadamantane 1,2‐dioxetanes has gained significant attention due to improved signal‐to‐noise ratios and imaging depth compared to excitation‐based probes, as well as their modifiable scaffolds that offer analyte‐specific responses and tunable emissive properties. Among several strategies employed to amplify signals under aqueous conditions and to shift the emission into the bio‐relevant red region, energy transfer to an adjacent fluorophore is a popular and effective method. This Minireview highlights spiroadamantane 1,2‐dioxetane‐based probes that operate via an energy transfer mechanism to detect bioanalytes both in vitro and in vivo. Probes that display both non‐covalent and covalent interactions with fluorophores, as well as their applications in imaging specific analytes will be discussed.
Comprehensive identification of VX‐adducted plasma proteins using high‐resolution mass spectrometry
Authors: Mohammad Hazara Begum , Park Ji Hwan , Lee Jun Hyung , Vu Minh Hung , Lee Jin‐Young , Jeong Woo‐Hyeon , Kim Min‐Sik 
Published: August 2022

AbstractVX is one of the chemical warfare agents that attack victims' nervous systems and ultimately lead to their death. Upon VX exposure, circulating proteins in the bloodstream can be modified with VX that may produce diagnostic VX adducts. Thus, these adducts would be key evidence for the forensic investigation against chemical warfare or terrorism. In this study, we discovered a list of potential blood protein biomarkers for VX exposure. To do so, we employed high‐resolution mass spectrometry‐based proteomics and identified 18 VX‐adducted proteins with 32 adduct sites from VX‐treated human plasma samples. Furthermore, we examined these targets using a data‐independent acquisition method and obtained eight practically detectable biomarkers. Our results may serve as a valuable resource for verifying nerve agent exposure under chemical attack.
FRET‐Based Cathepsin Probes for Simultaneous Detection of Cathepsin B and D Activities
Authors: Zhang Zhengxiao , Nakata Eiji , Shibano Yuya , Morii Takashi 
Published: August 2022

AbstractFluorescent cathepsin probes were prepared by modification of peptidic substrates for cathepsin B (CTSB) and cathepsin D (CTSD) with FRET pairs. Fluorophores with distinguishable emission characteristics were applied to CTSB and CTSD probes with their appropriate quenchers to simultaneously monitor the activity of CTSB and/or CTSD. Conjugation of both the CTSB and CTSD probes with short single‐stranded DNA drastically increased their reactivity to cathepsins over the parent probes possibly by improving their solubility. The activity of CTSB and CTSD were simultaneously detected by using these orthogonal FRET‐based cathepsin probes.
Incorporation of an Asymmetric Mo−Fe−S Cluster as an Artificial Cofactor into Nitrogenase
Authors: Tanifuji Kazuki , Jasniewski Andrew J. , Lee Chi Chung , Solomon Joseph B. , Nagasawa Takayuki , Ohki Yasuhiro , Tatsumi Kazuyuki , Hedman Britt , Hodgson Keith O. , Hu Yilin , Ribbe Markus W. 
Published: August 2022

AbstractNitrogenase employs a sophisticated electron transfer system and a Mo−Fe−S−C cofactor, designated the M‐cluster [(cit)MoFe7S9C]), to reduce atmospheric N2 to bioaccessible NH3. Previously, we have shown that the cofactor‐free form of nitrogenase can be repurposed as a protein scaffold for the incorporation of a synthetic Fe−S cluster [Fe6S9(SEt)2]4−. Here, we demonstrate the utility of an asymmetric Mo−Fe−S cluster [Cp*MoFe5S9(SH)]3− as an alternative artificial cofactor upon incorporation into the cofactor‐free nitrogenase scaffold. The resultant semi‐artificial enzyme catalytically reduces C2H2 to C2H4, and CN− into short‐chain hydrocarbons, yet it is clearly distinct in activity from its [Fe6S9(SEt)2]4−‐reconstituted counterpart, pointing to the possibility to employ molecular design and cluster synthesis strategies to further develop semi‐artificial or artificial systems with desired catalytic activities.
An oleanolic acid derivative, K73‐03, inhibits pancreatic cancer cells proliferation in vitro and in vivo via blocking EGFR/Akt pathway
Authors: Zhou Zheng , Dong Yaokun , Li Na , Niu Mengyue , Wang Shisheng , Zhou Yuanzhang , Sun Zhaolin , Chu Peng , Tang Zeyao 
Published: August 2022

AbstractOleanolic acid (OA) and its derivatives show potent anticancer function. Pancreatic cancer (PC) is the fourth core motive of cancer‐related deaths worldwide. Epidermal growth factor receptor (EGFR) has been implicated in PC and has been validated as a therapeutic target. Our study demonstrated that K73‐03, an OA derivative, was identified as a potent inhibitor of EGFR by using reverse pharmacophore screening and molecular dynamics simulation assays. Moreover, Western blot analysis showed that K73‐03 markedly suppressed the levels of phosphorylated‐EGFR (p‐EGFR) and phosphorylated‐Akt (p‐Akt). The inhibitory effect of K73‐03 on PC cells was assessed in vitro and in vivo. Mechanistically, K73‐03 effectively inhibited the cell proliferation of PC cells, and induced apoptosis and autophagy of ASPC‐1 cells in a dose‐dependent manner. Additionally, pretreatment with chloroquine, an autophagy inhibitor, significantly inhibited K73‐03‐induced autophagy and enhanced K73‐03‐induced apoptotic cell death. K73‐03 also strongly repressed ASPC‐1 cells xenograft growth in vivo. Thus, all these findings provided new clues about OA analog K73‐03 as an effective anticancer agent targeted EGFR against ASPC‐1 cells, it is worth further evaluation in the future.
Estrogen receptor variant ER‐α36 facilitates estrogen signaling via EGFR in glioblastoma
Authors: Qu Chao , Wang Cui , Li Hongyan , Li Ying , Han Chao , Tao Xiaofeng , Guan Xin , Zhang Yejun , Chen Meng , Liu Jing , Zou Wei 
Published: August 2022

AbstractGlioblastoma (GBM) is a deadly and common primary brain tumor. Poor prognosis is linked to high proliferation and cell heterogeneity. Sex differences may play a role in patient outcome. Previous studies showed that ER‐α36, a variant of the estrogen receptor (ER), mediated non‐genomic estrogen signaling and is highly expressed in many ER‐negative malignant tumors. ER‐α36 also associates with epidermal growth factor receptor (EGFR). The primary purpose of this study is to investigate the cross talk between ER‐α36 and EGFR in estrogen‐mediated GBM cell proliferation. Here, we showed that ER‐α36 was highly expressed and confirmed that ER‐α36 co‐labels with EGFR in human GBM samples using immunohistochemical techniques. We also investigated the mechanisms of estrogen‐induced proliferation in ER‐α‐negative cell lines. We found that GBM cells showed varying responsive to mitogenic estrogen signaling which correlated with ER‐α36 expression, and knockdown of ER‐α36 diminished the response. Exposure to estrogen also caused upregulation of cyclin protein expression in vitro. We also found that low concentration of estrogen promoted SRC‐Y‐416 and inhibited SRC‐Y‐527 phosphorylation, corresponding with activated SRC signaling. Inhibiting SRC or EGFR abolished estrogen‐induced mitogenic signaling, including cyclin expression and MAPK phosphorylation. Cumulatively, our results demonstrate that ER‐α36 promotes non‐genomic estrogen signaling via the EGFR/SRC/MAPK pathway in GBM. This may be important for the treatment of ER‐α‐negative GBMs that retain high level of ER‐α36, since estrogen may be a viable therapeutic target for these patients.
Heterobimetallic Gold/Ruthenium Complexes Synthesized via Post‐functionalization and Applied in Dual Photoredox Gold Catalysis
Authors: Bayer Lea , Birenheide Bernhard S. , Krämer Felix , Lebedkin Sergei , Breher Frank 
Published: August 2022

AbstractThe synthesis of heterobimetallic AuI/RuII complexes of the general formula syn‐ and anti‐[{AuCl}(L1∩L2){Ru(bpy)2}][PF6]2 is reported. The ditopic bridging ligand L1∩L2 refers to a P,N hybrid ligand composed of phosphine and bipyridine substructures, which was obtained via a post‐functionalization strategy based on Diels‐Alder reaction between a phosphole and a maleimide moiety. It was found that the stereochemistry at the phosphorus atom of the resulting 7‐phosphanorbornene backbone can be controlled by executing the metal coordination and the cycloaddition reaction in a different order. All precursors, as well as the mono‐ and multimetallic complexes, were isolated and fully characterized by various spectroscopic methods such as NMR, IR, and UV‐vis spectroscopy as well as cyclic voltammetry. Photophysical measurements show efficient phosphorescence for the investigated monometallic complex anti‐[(L1∩L2){Ru(bpy)2}][PF6]2 and the bimetallic analogue syn‐[{AuCl}(L1∩L2){Ru(bpy)2}][PF6]2, thus indicating a small influence of the {AuCl} fragment on the photoluminescence properties. The heterobimetallic AuI/RuII complexes syn‐ and anti‐[{AuCl}(L1∩L2){Ru(bpy)2}][PF6]2 are both active catalysts in the P‐arylation of aryldiazonium salts promoted by visible light with H‐phosphonate affording arylphosphonates in yields of up to 91 %. Both dinuclear complexes outperform their monometallic counterparts.
Modulation of the Sorption Characteristics for an H‐bonded porous Architecture by Varying the Chemical Functionalization of the Channel Walls
Authors: Roques Nans , Tovar‐Molle Anthony , Duhayon Carine , Brandès Stéphane , Spieß Alex , Janiak Christoph , Sutter Jean‐Pascal 
Published: August 2022

AbstractFive isostructural microporous supramolecular architectures prepared by H‐bonded assembly between the hexa‐anionic complex [Zr2(Ox)7]6− (Ox=oxalate, (C2O4)2−) and tripodal cations (H3‐TripCH2‐R)3+ with R=H, CH3, OH and OBn (Bn=CH2Ph) are reported. The possibility to obtain the same structure using a mixture of tripodal cations with different R group (R=OH and R=CH3) has also been successfully explored, providing a unique example of three‐component H‐bonded porous framework. The resulting SPA‐1(R) materials feature 1D pores decorated by R groups, with apparent pore diameters ranging from 3.0 to 8.5 Å. Influence of R groups on the sorption properties of these materials is evidenced through CO2 and H2O vapor sorption/desorption experiments, as well as with I2 capture/release experiments in liquid media. This study is one of the first to demonstrate the possibility of tuning the porosity and exerting precise control over the chemical functionalization of the pores in a given H‐bonded structure, without modifying the topology of the reference structure, and thus finely adjusting the sorption characteristics of the material.
Nachhaltige Unterrichtsvorschläge zur (Mikro)‐Plastikproblematik
Authors: Kreienhop Nils , Beeken Marco 
Published: August 2022

ZusammenfassungPlastikmüll und Mikroplastik lassen sich mittlerweile selbst an den entlegensten Orten der Erde nachweisen. Auch wenn die konkreten Gefahren und Folgen für Menschen und Tiere noch unbekannt sind, gilt als gesichert, dass der Mensch auch mit der Freisetzung neuartig modifizierter Substanzen einen großen Einfluss auf das ökologische Gleichgewicht der Erde hat. In diesem Artikel wird das Themenfeld (Mikro)‐Plastik im Kontext der Bildung für nachhaltige Entwicklung diskutiert, um darauf aufbauend Impulse für eine erfolgreiche Thematisierung im schulischen Unterricht zu geben. Anhand ausgewählter Experimente für den Chemieunterricht werden wichtige Aspekte wie das Verhalten von Kunststoffen in der Umwelt und die Entwicklung aktueller Lösungsansätze zur Reinigung unserer Umwelt von Plastikpartikeln erörtert. Ziel ist es, junge Menschen für wissenschaftliche Forschung zu begeistern und zu befähigen, sich aktiv an gesellschaftlichen Diskursen für eine nachhaltige Entwicklung zu beteiligen.
Detection and localization of image tampering in digital images with fused features
Authors: Ahmad Mohassin , Khursheed Farida 
Published: August 2022

SummaryIn digital forensics, image tamper detection and localization have attracted increased attention in recent days, where the standard methods have limited description ability and high computational costs. As a result, this research introduces a novel picture tamper detection and localization model. Feature extraction, tamper detection, as well as tamper localization are the three major phases of the proposed model. From the input digital images, a group of features like “Scale‐based Adaptive Speeded Up Robust Features (SA‐SURF), Discrete Wavelet Transform (DWT) based Patched Local Vector Pattern (LVP) features, HoG feature with harmonic mean based PCA and MBFDF” are extracted. Then, with this extracted feature strain the “optimized Convolutional Neural Network (CNN)” will be trained in the tamper detection phase. Since it is the key decision‐maker about the presence/absence of tamper, its weighting parameters are fine‐tuned via a novel improved Sea‐lion Customized Firefly algorithm (ISCFF) model. This ensures the enhancement of detection accuracy. Once an image is recognized to have tampers, then it is essential to identify the tamper localization. In the tamper localization phase, the copy‐move tampers are localized using the SIFT features, splicing tampers are localized using the DBN and the noise inconsistency is localized with a newly introduced threshold‐based tamper localization technique. The simulation outcomes illustrate that the adopted model attains better tamper detection as well as localization performance over the existing methods.
Prediction of the Phase Composition Profile of Three‐Compound Mixtures in Liquid‐Liquid Equilibrium: A Chemoinformatics Approach
Authors: Carrera Gonçalo V. S. M. , Cruz Mariana L. , Klimenko Kyrylo , Esperança José M. S. S. , Aires‐de‐Sousa João 
Published: August 2022

AbstractMachine‐learning models were developed to predict the composition profile of a three‐compound mixture in liquid‐liquid equilibrium (LLE), given the global composition at certain temperature and pressure. A chemoinformatics approach was explored, based on the MOLMAP technology to encode molecules and mixtures. The chemical systems involved an ionic liquid (IL) and two organic molecules. Two complementary models have been optimized for the IL‐rich and IL‐poor phases. The two global optimized models are highly accurate, and were validated with independent test sets, where combinations of molecule1+molecule2+IL are different from those in the training set. These results highlight the MOLMAP encoding scheme, based on atomic properties to train models that learn relationships between features of complex multi‐component chemical systems and their profile of phase compositions.
In SilicoInteractions of the Components from theSchinus terebinthifoliusExtract with Human Tyrosinase
Authors: Bezerra Julia N. , Spadeto João Paulo M. , Daré Joyce K. , Almeida Wanda Pereira , Freitas Matheus P. , Cormanich Rodrigo A. 
Published: August 2022

AbstractThe anti‐tyrosinase activity of the leaf extract ofSchinus terebinthifolius, also known as Brazilian peppertree, was evaluated using multiplein silicoapproaches, such as molecular homology, molecular docking, MM‐GBSA, molecular dynamics, MM‐PBSA, QSAR, and skin permeability predictions. With these computational tools, the compounds that downregulate tyrosinase enzyme activity could be evaluated, and more potent molecules could be identified. The results indicated that various compounds, especially luteolin, are accountable for the anti‐tyrosinase activity ofS. terebinthifolius. For cosmetic application, further studies with luteolin are especially recommended, for having presented a good performance both in theoretical inhibition (30.92 kJ mol−1) and skin permeability (LogKp=−6.62 cm−1).
Tailoring Electronic Structure of Copper Twin Boundaries Toward Highly Efficient Nitrogen Reduction Reaction
Authors: Dai Tianyi , Wang Zhili , Wen Zi , Lang Xingyou , Jiang Qing 
Published: August 2022

AbstractElectrocatalytic nitrogen reduction reaction (NRR) is a promising technique to resolve the carbon emission in energy‐intensive ammonia production in industry, which, however, is hampered by the lack of efficient catalysts. Herein, by density functional theory (DFT) calculations, it was demonstrated that the twin boundary (TB) of copper could effectively relieve the N2 activation barrier in NRR. The d orbitals overlapping mode on twin boundary edge (TBE) was quite different from that on its basal plane, where the dxz, dyz orbitals induced unbalanced electron occupation states in π*–px, py orbitals of the adsorbed N2, which could effectively activate the N≡N bond. Particularly, doping transition metals (TMs) onto Cu‐TBE could further improve its NRR catalytic behavior, and the Re−Cu(111)‐TBE showed the lowest limiting potential (UL) of −0.27 V among 25 considered TMs. Moreover, the Re−Cu(111)‐TBE could effectively suppress the competing hydrogen evolution reaction even under working potentials. This work has provided a deep understanding of TB in catalysis from an electronic structure point of view, paving a way for further studies of TB into advanced utilization.
Nitrogen Disturbance Awakening the Intrinsic Activity of Nickel Phosphide for Boosted Hydrogen Evolution Reaction
Authors: Yang Caixia , Wang Zhiqiang , Li Zhendong , Pan Yichen , Jiang Linwei , Li Caicai , Wang Chao , Sun Qingfeng 
Published: August 2022

AbstractInvited for this month′s cover is the group of Qingfeng Sun at the Zhejiang A&F University. The image shows that the N‐doped Ni2P exhibits excellent electrocatalytic activity for hydrogen evolution reaction (HER). The Research Article itself is available at 10.1002/cssc.202200072.
CRMP2 and CRMP4 are required for the formation of commissural tracts in the developing zebrafish forebrain
Authors: Guo Youjia , Oliveros Carolina Fiallos , Ohshima Toshio 
Published: August 2022

AbstractAxonal connections between the two sides of the brain are essential for processing sensorimotor functions, especially in animals with bilateral symmetry. The anterior commissure and postoptic commissure are two crucial axonal projections that develop early in the zebrafish central nervous system. In this study, we characterized the function of collapsin response mediator protein 2 (CRMP2) and CRMP4 in patterning the development of the anterior and postoptic commissures by analyzing morpholino‐knockdown zebrafish morphants and CRISPR/Cas9‐edited gene‐knockout mutants. We observed a loss of commissural structures or a significant reduction in axon bundles connecting the two hemispheres, but the defects could be largely recovered by co‐injecting CRMP2 or CRMP4 mRNA. Loss of both CRMP2 and CRMP4 function resulted in a synergistic increase in the number of commissural defects. To elucidate the mechanism by which CRMP2 and CRMP4 provide guidance cues for the development of the anterior and postoptic commissures, we included neuropilin 1a (Nrp1a) morphants and double morphants (CRMP2/Nrp1a and CRMP4/Nrp1a) for analysis. Our experimental results indicated that CRMP2 and CRMP4 might mediate their activities through the common semaphorin 3/Nrp1a signaling pathway.