bluuebunny/crossref_metadata_2025_split huggingface dataset:
Fe2+/Fe3+ Cycling for Coupling Self‐Powered Hydrogen Evolution and Preparation of Electrode Catalysts
Authors: Chen Chang , Fu Zhengqian , Qi Fenggang , Chen Yafeng , Meng Ge , Chang Ziwei , Kong Fantao , Zhu Libo , Tian Han , Huang Haitao , Cui Xiangzhi , Shi Jianlin 
Published: May 2022

AbstractA novel Zn−Fe flow battery featuring an Fe3+ reduction reaction (Fe3+RR)‐coupled zinc oxidation, and an Fe2+ oxidation reaction (Fe2+OR)‐coupled hydrogen evolution reaction (HER) system as well, was established. This battery is capable of driving two Fe2+OR‐coupled HER systems in series based on the above Fe2+/Fe3+ cycling, for efficient self‐powered hydrogen evolution. Meanwhile, this Fe2+/Fe3+ cycling enables the preparation of a multifunctional catalyst, Pt‐3@SXNS (siloxene nanosheet), by the Fe2+OR‐promoted dispersion of Pt nanoparticles on SXNS; alternatively, this support could be obtained by Fe3+RR‐assisted exfoliation using Fe3+ from the anolyte of Fe2+OR‐coupled HER. The Pt‐3@SXNS catalyst exhibits excellent catalytic activities toward Fe3+RR in the Zn−Fe flow battery, HER, and Fe2+OR in the electrolyzer, which is attributed to the strong electronic interaction between Pt and Si. This work offers a new strategy for energy storage and low‐cost hydrogen production from acidic wastewater.
Robust 3D Copper Foam Functionalized with Gold Nanoparticles as Anode for High‐Performance Potassium Metal Batteries
Authors: Li Hongwei , Liu Yao , Wang Jianyi , Yan Wei , Zhang Jiujun 
Published: May 2022

AbstractAs a possible anode for the next generation of electrochemical energy storage batteries, potassium metal has attracted a great deal of attention in recent years. However, potassium metal batteries suffer from poor stability and low coulombic efficiency due to unfavorable dendrite growth and severe volume expansion of potassium metal anodes during charge and discharge processes. Here, a strategy is developed to inhibit dendrite growth, reduce volume expansion and improve the stability of the potassium metal anode by using three‐dimensional (3D) copper foam chemically loaded with a thin layer of uniform gold particles (Au/Cu) as the anode substrate. As the host of potassium deposition for forming K/Au/Cu foam anode, such a 3D copper foam with large specific surface area can reduce the potassium deposition current density. The gold particles on the Cu foam surface with a good affinity to potassium can reduce the potassium deposition overpotential, provide deposition sites and realize uniform and dense deposition. As a result, a stable cycle of more than 500 cycles is achieved by using such a K/Au/Cu foam anode. A full cell with K/Au/Cu foam anode and Prussian blue cathode delivers much better coulombic efficiency, cycle stability and low‐temperature performance when compared to that without gold deposition anode (K/Cu). Both the experimental characterization for material structure/morphology/composition and theoretical DFT calculations are carried out for fundamental understanding of the performance enhancement mechanism. The main advantages of this 3D K/Au/Cu foam are its potassiophilicity and less volume expansion during charge/discharge processes, which can reduce or eliminate the potassium dendrite growth through forming favorable and stable solid electrolyte interface.
Customer Assistance Programs and Water Affordability
Authors: Patterson Lauren A. , McLaughlin Aislinn , Doyle Martin W. 
Published: May 2022

Key TakeawaysWater affordability is a growing concern, with inflation, aging infrastructure, source water protection, climate change, and other factors pushing up the cost of providing water.Customer assistance program (CAP) rate discounts provide needed assistance but may not be sufficient to ensure that water services are affordable.Rather than relying on one approach, such as CAPs, a combination of approaches might be optimal for addressing water affordability issues.
Electrochemical Exfoliation of Two‐Dimensional Phosphorene Sheets and its Energy Application
Authors: Shu Chengyong , Zhou Ph.D. Jiangqi , Jia Ph.D. Zhanhui , Zhang Hong , Liu Zhongxin , Tang Wei , Sun Xiaofei 
Published: May 2022

AbstractRecently, single or few‐layer phosphorene has attracted intense attention due to its exceptional physicochemical properties. To this end, mass production of high‐quality phosphorene nanosheets with specific functionalities represents a pivotal factor for the basic academic studies and practical applications. Among the current synthetic methods, electrochemical exfoliation of black phosphorous is one of the most hopeful ways for mass‐production of phosphorene sheets owing to the uncomplicated apparatus, low cost as well as significant efficiency. Especially, regulating the electrochemical parameters not only induces adjustable phosphorene characteristics but also enables them a promising candidate in energy applications. In this Review, a concise and crucial studies of the recent and most representative developments in this domain was introduced, including the relationship between exfoliation philosophy, internal mechanisms, processing techniques, and multiple applications of phosphorene. At the end, a summary discussion and future perspectives is also provided.
Positive Cooperativity Induced by Interstrand Interactions in Silver(I) Complexes with α,α′‐Diimine Ligands
Authors: Zare Davood , Piguet Claude , Prescimone Alessandro , Housecroft Catherine E. , Constable Edwin C. 
Published: May 2022

AbstractThe allosteric positive cooperativity accompanying the formation of compact [CuI(α,α′‐diimine)2]+ building blocks contributed to the historically efficient synthesis of metal‐containing catenates and knotted assemblies. However, its limited magnitude can easily be overcome by the negative chelate cooperativity that controls the overall formation of related polymetallic multistranded helicates and grids. Despite the more abundant use of analogous dioxygen‐resistant [AgI(α,α′‐diimine)2]+ units in modern entangled metallo‐supramolecular assemblies, a related thermodynamic justification was absent. Solid‐state structural characterizations show the successive formation of [AgI(α,α′‐diimine)(CH3CN)][X] and [AgI(α,α′‐diimine)2][X] upon the stepwise reactions of α,α′‐diimine=2,2′‐bipyridine (bpy) or 1,10‐phenanthroline (phen) derivatives with AgX (X=BF4−, ClO4−, PF6−). In room‐temperature, 5–10 mM acetonitrile solutions, these cationic complexes exist as mixtures in fast exchange on the NMR timescale. Spectrophotometric titrations using the unsubstituted bpy and phen ligands point to the statistical (=non‐cooperative) binding of two successive bidentate ligands around AgI, a mechanism probably driven by the formation of hydrophobic belts, that overcomes the unfavorable decrease in the positive charge borne by the metallic cation. Surprisingly, the addition of methyl groups adjacent to the nitrogen donors (6,6′ positions in dmbpy; 2,9 positions in dmphen) induces positive cooperativity for the formation of [Ag(dmbpy)2]+ and [Ag(dmphen)2]+, a trend assigned to additional stabilizing interligand interactions. Adding rigid and polarizable phenyl side arms in [Ag(Brdmbpy)2]+ further reinforces the positively cooperative process, while limiting the overall decrease in metal–ligand affinity.
A High‐Valent Ru‐PCP Pincer Catalyst for Hydrogenation of Carbonyl and Carboxyl Compounds under Molecular Hydrogen
Authors: Mujahed Shrouq , Hey‐Hawkins Evamarie , Gelman Dmitri 
Published: May 2022

AbstractLow‐valent metals traditionally dominate the domain of catalytic hydrogenation. However, metal‐ligand cooperating (MLC) catalytic systems, operating through heterolytic H−H bond splitting by a Lewis acidic metal and a basic ligand site, do not require an electron‐rich metal. On the contrary, high‐valent metals that induce weaker back donation facilitate heterolytic bond activation. Here we report, for the first time, the efficient hydrogenation of carbonyl and carboxyl compounds under molecular hydrogen catalyzed by a structurally well‐defined RuIV catalyst bearing a bifunctional PCP pincer ligand. The catalyst exhibits reactivity toward molecular hydrogen superior to that of the low‐valent analog and allows hydrogen activation even at room temperature.
Exchanged Metal‐Hydrogen Anagostic Bonds and Resonance of Dithiocarbamate and Thioureide Mesomers**
Authors: Sobczak Szymon , Roszak Kinga , Katrusiak Andrzej 
Published: May 2022

AbstractThe pressure‐induced transformation of plane‐square complex nickel(II) bis(N,N‐diethyldithiocarbamate) between its soft dithiocarbamate (form I) and thioureide (form II) mesomeres is coupled to the interchange of anagostic Ni⋅⋅⋅H−C interactions from methylene to the methyl group, respectively. At 1.23 GPa, the clearly visible giant anomalous compressibility of the crystal reveals a potential‐energy difference of 5.4 kJ mol−1 between the two complex forms. The structural and spectroscopic results, which are supported by quantum‐mechanical calculations, connect this solid‐state phase transition with the mesomeric transition, and this is accompanied by the conformational transformation of anagostic Ni⋅⋅⋅H−C rearrangement and formation of the charge‐assisted S−⋅⋅⋅H−C bond under pressure.
Reductive Elimination at Pb(II) Center of an (Amino)plumbylene‐Substituted Phosphaketene: New Pathway for Phosphinidene Synthesis
Authors: Timofeeva Vladislava , Baeza José Miguel Léon , Nougué Raphael , Syroeshkin Mikhail , Segundo Rojas Guerrero Rene , Saffon‐Merceron Nathalie , Altınbaş Özpınar Gül , Rathjen Saskia , Müller Thomas , Baceiredo Antoine , Kato Tsuyoshi 
Published: May 2022

AbstractA stable (amino)plumbylene‐substituted phosphaketene 3 was synthesized by the successive reactions of PbCl2 with two anionic reagents (lithium amidophosphine and NaPCO). Of particular interest, the thermal evolution of 3, at 80 °C, leads to the transient formation of corresponding amino‐ and phosphanylidene‐phosphaketenes (6 and 7), via a reductive elimination at the PbII center forming new N−P and P−P bonds. Further evolution of 6 gives a new cyclic (amino)phosphanylidene phosphorane 4, which shows a unique reactivity as a phosphinidene. This result provides a new synthetic route to phosphinidenes, extending and facilitating further their access.
Catalytic Asymmetric Synthesis of Axially Chiral 3,3'‐Bisindoles by Direct Coupling of Indole Rings
Authors: Sheng Feng‐Tao , Yang Shuang , Wu Shu‐Fang , Zhang Yu‐Chen , Shi Feng 
Published: May 2022

Comprehensive SummaryA new strategy for the enantioselective synthesis of axially chiral 3,3'‐bisindoles was devised by the direct coupling of two indole rings. This strategy makes use of the C3‐umpolung reactivity of 2‐indolylmethanols, which enables the catalytic asymmetric addition reaction of 2‐indolylmethanols with rationally designed 2‐substituted indoles, thus constructing axially chiral 3,3'‐bisindole scaffolds in overall excellent yields (up to 98%) with high enantioselectivities (up to 96 : 4 er). This approach not only has overcome the challenges in constructing axially chiral five‐five‐membered heterobiaryls, but also represents a new application of the C3‐umpolung reactivity of 2‐indolylmethanols in asymmetric catalysis. More importantly, this class of axially chiral 3,3'‐bisindoles can undergo a variety of post‐functionalizations to give axially chiral 3,3'‐bisindole‐based organocatalysts, which have found their preliminary applications in asymmetric catalysis.
A Core‐Linker‐Polyamine (CLP) Strategy Enables Rapid Discovery of Antileishmanial Aminoalkylquinolinecarboxamides That Target Oxidative Stress Mechanism
Authors: Shah Archana P. , Hura Neha , Kishore Babu Neerupudi , Roy Nibedita , Krishna Rao Vajja , Paul Anindita , Kumar Roy Pradyot , Singh Sushma , Guchhait Sankar K. 
Published: May 2022

AbstractA Core‐Linker‐Polyamine (CLP) strategy has been exploited to develop new antileishmanial agents. It involves the linker‐based assembly of alkyl‐polyamine side chain as a potential pharmacophore motif with a privileged heterocyclic motif, 4‐arylquinoline. A series of aminoalkyl 4‐arylquinoline‐2‐carboxamides and their analogs were synthesized and tested against L. donovani promastigotes. Among all synthesized derivatives, 10 compounds showed significant antipromastigote activities with more efficacy (IC50: 4.75–8 μM) than an antileishmanial oral drug Miltefosine (IC50: 8.9±1.55 μM). Most active aminoalkyl‐quinoline‐carboxamides 9 a and 9 b, displayed negligible cytotoxicity towards human monocytic (THP‐1) macrophages. The compounds show antileishmanial activity by generating mitochondrial superoxide radicals. However, they did not show interference with trypanothione reductase, a redox enzyme of Leishmania. Significant change in the morphology of the L. donovani promastigote by the compounds was observed. The Structure‐activity relationship analysis suggest the pharmacophoric importance of alkylpolyamine and carboxamide motifs. In silico evaluation indicated that the investigated active molecules 9 a and 9 b possess important drug‐likeness, physicochemical and pharmacokinetic‐relevant properties.
Molecular analysis of ascitic fluid cytology reflects genetic changes of malignancies of the ovary equivalent to surgically resected specimens
Authors: Nozaki Takahiro , Sakamoto Ikuko , Kagami Keiko , Amemiya Kenji , Hirotsu Yosuke , Mochizuki Hitoshi , Omata Masao 
Published: May 2022

BACKGROUNDThe objective of this study was to identify the clinical utility of genomic analysis of ascitic fluid cytology (AC) in patients with epithelial ovarian cancer.METHODSTargeted next‐generation sequencing was used to analyze 66 samples from 33 patients who had ovarian (n = 23), fallopian tube (n = 2), and peritoneal (n = 8) carcinoma, and the concordance rate of molecular profiles was compared between surgically resected, formalin‐fixed, paraffin‐embedded (FFPE) tissues and AC samples.RESULTSIn total, 159 mutations were identified (54 oncogenic mutations and 105 nononcogenic mutations) in 66 DNA samples (33 FFPE tissues and 33 AC samples) from 33 patients. Of the 159 mutations, 57 (35.8%) were shared between surgically resected FFPE tissues and AC samples. However, the concordance rate of the molecular profiles between the 2 was significantly higher for oncogenic mutations compared with nononcogenic mutations (85.1% vs 10.5%; P < .01). Indeed, the AC samples covered all oncogenic mutations (n = 46) that were detected in surgically resected specimens and identified additional mutations (n = 8).CONCLUSIONSThe current results indicated that genomic analysis of AC can identify all of the genetic changes associated with epithelial ovarian cancer to understand tumor characteristics without interventional surgery or biopsy and may play an important role in developing personalized precision medicine.
Application of the Milan System for Reporting Salivary Gland Cytopathology: A systematic review and meta‐analysis
Authors: Wang Zhaoyang , Zhao Huan , Guo Huiqin , An Changming 
Published: May 2022

BackgroundThe Milan System for Reporting Salivary Gland Cytopathology (MSRSGC) is a standard, evidence‐based classification system for salivary gland fine‐needle aspiration (SG‐FNA). Since it was published in 2018, many researchers across the world have applied this uniform reporting system to their cohorts.MethodsThe authors comprehensively reviewed cohort studies conducted since publication of the MSRSGC and performed a meta‐analysis. The risk of neoplasm and the risk of malignancy (ROM) were calculated for each diagnostic category, and their diagnostic efficacy was evaluated.ResultsThirty‐five studies were included in the meta‐analysis. The total number of SG‐FNAs was 10,706, and 7168 of those had histopathologic follow‐up. The ROM for each category was: nondiagnostic, 11.4%; nonneoplastic, 10.9%; atypia of undetermined significance, 30.5%; neoplasm–benign, 2.8%; neoplasm–salivary gland neoplasm of uncertain malignant potential, 37.7%; suspicious for malignancy, 83.8%; and malignant, 97.7%. Low‐level heterogeneity was observed in ROM estimation. The sensitivity, specificity, and diagnostic odds ratio for differentiating malignant and benign lesions were 88.0%, 98.5% and 520.3, respectively.ConclusionsThe reporting of SG‐FNA using the MSRSGC demonstrated high diagnostic accuracy. The ROM for each category was generally concordant with the recommendations, except for the suspicious for malignancy category, which was significantly higher than the reference value. The tiered, standardized classification system would benefit the clinical management of salivary gland lesions.
SITH: An R package for visualizing and analyzing a spatial model of intratumor heterogeneity
Authors: Nicol Phillip B. , Barabási Dániel L. , Coombes Kevin R. , Asiaee Amir 
Published: May 2022

AbstractCancer progression, including the development of intratumor heterogeneity, is inherently a spatial process. Mathematical models of tumor evolution may be a useful starting point for understanding the patterns of heterogeneity that can emerge in the presence of spatial growth. A commonly studied spatial growth model assumes that tumor cells occupy sites on a lattice and replicate into neighboring sites. Our R package SITH provides a convenient interface for exploring this model. Our efficient simulation algorithm allows for users to generate 3D tumors with millions of cells in under a minute. For the distribution of mutations throughout the tumor, SITH provides interactive graphics and summary plots. Additionally, SITH can produce synthetic bulk and single‐cell DNA‐seq datasets by sampling from the simulated tumor. A streamlined application programming interface (API) makes SITH a useful tool for investigating the relationship between spatial growth and intratumor heterogeneity. SITH is a part of CRAN and can be installed by running install.packages(“SITH”) from the R console. See https://CRAN.R‐project.org/package=SITH for the user manual and package vignette.
In Silico Optimization of Charge Separating Dyes for Solar Energy Conversion
Authors: Menzel Jan Paul , Boeije Yorrick , Bakker Tijmen M. A. , Belić Jelena , Reek Joost N. H. , de Groot Huub J. M. , Visscher Lucas , Buda Francesco 
Published: May 2022

AbstractDye‐sensitized photoelectrochemical cells are promising devices in solar energy conversion. However, several limitations still have to be addressed, such as the major loss pathway through charge recombination at the dye‐semiconductor interface. Charge separating dyes constructed as push‐pull systems can increase the spatial separation of electron and hole, decreasing the recombination rate. Here, a family of dyes, consisting of polyphenylamine donors, fluorene bridges, and perylene monoimide acceptors, was investigated in silico using a combination of semi‐empirical nuclear dynamics and a quantum propagation of photoexcited electron and hole. To optimize the charge separation, several molecular design strategies were investigated, including modifying the donor molecule, increasing the π‐bridge length, and decoupling the molecular components through steric effects. The combination of a triphenylamine donor, using an extended 2‐fluorene π‐bridge, and decoupling the different components by steric hindrance from side groups resulted in a dye with significantly improved charge separation properties in comparison to the original supramolecular complex.
A Recent Progress for the Synthesis of Thiocarboxylates
Authors: Wang Xi , Dong Zhi‐Bing 
Published: May 2022

AbstractAs a common and integral feature of many natural products, thiocarboxylates play an important role in biologically or pharmaceutically active compounds. Thiocarboxylates often show unique physiological activities in biology and drugs, which inspires many new therapeutic drugs. The related research and developments in thioester‐based medicinal chemistry have been a rapidly developing and increasingly active topic in the last two decades. In this review, we will summarize the main methods for the synthesis of thiocarboxylates, which might provide general ideas to access more effective thioester‐based drugs.
Disentangling the effects of traits with shared clustered genetic predictors using multivariable Mendelian randomization
Authors: Batool Fatima , Patel Ashish , Gill Dipender , Burgess Stephen 
Published: May 2022

AbstractWhen genetic variants in a gene cluster are associated with a disease outcome, the causal pathway from the variants to the outcome can be difficult to disentangle. For example, the chemokine receptor gene cluster contains genetic variants associated with various cytokines. Associations between variants in this cluster and stroke risk may be driven by any of these cytokines. Multivariable Mendelian randomization is an extension of standard univariable Mendelian randomization to estimate the direct effects of related exposures with shared genetic predictors. However, when genetic variants are clustered, due to being located in a single genetic region, a Goldilocks dilemma arises: including too many highly‐correlated variants in the analysis can lead to ill‐conditioning, but pruning variants too aggressively can lead to imprecise estimates or even lack of identification. We propose multivariable methods that use principal component analysis to reduce many correlated genetic variants into a smaller number of orthogonal components that are used as instrumental variables. We show in simulations that these methods result in more precise estimates that are less sensitive to numerical instability due to both strong correlations and small changes in the input data. We apply the methods to demonstrate the most likely causal risk factor for stroke at the chemokine gene cluster is monocyte chemoattractant protein‐1.
Astrocyte‐derived adenosine excites sleep‐promoting neurons in the ventrolateral preoptic nucleus: Astrocyte‐neuron interactions in the regulation of sleep
Authors: Choi In‐Sun , Kim Jae‐Hong , Jeong Ji‐Young , Lee Maan‐Gee , Suk Kyoungho , Jang Il‐Sung 
Published: May 2022

AbstractAlthough ATP and/or adenosine derived from astrocytes are known to regulate sleep, the precise mechanisms underlying the somnogenic effects of ATP and adenosine remain unclear. We selectively expressed channelrhodopsin‐2 (ChR2), a light‐sensitive ion channel, in astrocytes within the ventrolateral preoptic nucleus (VLPO), which is an essential brain nucleus involved in sleep promotion. We then examined the effects of photostimulation of astrocytic ChR2 on neuronal excitability using whole‐cell patch‐clamp recordings in two functionally distinct types of VLPO neurons: sleep‐promoting GABAergic projection neurons and non‐sleep‐promoting local GABAergic neurons. Optogenetic stimulation of VLPO astrocytes demonstrated opposite outcomes in the two types of VLPO neurons. It led to the inhibition of non‐sleep‐promoting neurons and excitation of sleep‐promoting neurons. These responses were attenuated by blocking of either adenosine A1 receptors or tissue‐nonspecific alkaline phosphatase (TNAP). In contrast, exogenous adenosine decreased the excitability of both VLPO neuron populations. Moreover, TNAP was expressed in galanin‐negative VLPO neurons, but not in galanin‐positive sleep‐promoting projection neurons. Taken together, these results suggest that astrocyte‐derived ATP is converted into adenosine by TNAP in non‐sleep‐promoting neurons. In turn, adenosine decreases the excitability of local GABAergic neurons, thereby increasing the excitability of sleep‐promoting GABAergic projection neurons. We propose a novel mechanism involving astrocyte‐neuron interactions in sleep regulation, wherein endogenous adenosine derived from astrocytes excites sleep‐promoting VLPO neurons, and thus decreases neuronal excitability in arousal‐related areas of the brain.