bluuebunny/crossref_metadata_2025_split huggingface dataset:
DNA‐Barcoded Plasmonic Nanostructures for Activity‐Based Protease Sensing
Authors: Pandit Subrata , Duchow Mark , Chao Wilson , Capasso Anna , Samanta Devleena 
Published: November 2023

AbstractWe report the development of a new class of protease activity sensors called DNA‐barcoded plasmonic nanostructures. These probes are comprised of gold nanoparticles functionalized with peptide‐DNA conjugates (GPDs), where the peptide is a substrate of the protease of interest. The DNA acts as a barcode identifying the peptide and facilitates signal amplification. Protease‐mediated peptide cleavage frees the DNA from the nanoparticle surface, which is subsequently measured via a CRISPR/Cas12a‐based assay as a proxy for protease activity. As proof‐of‐concept, we show activity‐based, multiplexed detection of the SARS‐CoV‐2‐associated protease, 3CL, and the apoptosis marker, caspase 3, with high sensitivity and selectivity. GPDs yield >25‐fold turn‐on signals, 100‐fold improved response compared to commercial probes, and detection limits as low as 58 pM at room temperature. Moreover, nanomolar concentrations of proteases can be detected visually by leveraging the aggregation‐dependent color change of the gold nanoparticles. We showcase the clinical potential of GPDs by detecting a colorectal cancer‐associated protease, cathepsin B, in three different patient‐derived cell lines. Taken together, GPDs detect physiologically relevant concentrations of active proteases in challenging biological samples, require minimal sample processing, and offer unmatched multiplexing capabilities (mediated by DNA), making them powerful chemical tools for biosensing and disease diagnostics.
Iron‐Catalyzed Asymmetric α‐Alkylation of 2‐Acylimidazoles via Dehydrogenative Radical Cross‐Coupling with Alkanes
Authors: Xu Nian , Pu Maoping , Yu Han , Yang Gaofei , Liu Xiaohua , Feng Xiaoming 
Published: November 2023

AbstractThe direct α‐alkylation of acyclic carbonyls with nonactivated hydrocarbons through C(sp3)−H functionalization is both extremely promising and notably challenging, especially when attempting to achieve enantioselectivity using iron‐based catalysts. We have identified a robust chiral iron complex for the oxidative cross‐coupling of 2‐acylimidazoles with benzylic and allylic hydrocarbons, as well as nonactivated alkanes. The readily available and tunable N,N′‐dioxide catalysts of iron in connection with oxidants exhibit precise asymmetric induction (up to 99 % ee) with good compatibility in moderate to good yields (up to 88 % yield). This protocol provides an elegant and straightforward access to optically active acyclic carbonyl derivatives starting from simple alkanes without prefunctionalization. Density functional theory (DFT) calculations and control experiments were made to gain insight into the nature of C−C bond formation and the origin of enantioselectivity. We propose a radical‐radical cross‐coupling process enabled by the immediate interconversion between chiral ferric species and ferrous species.
α‐Functionalisation of Cyclic Sulfides Enabled by Lithiation Trapping
Authors: Seling Nico , Atobe Masakazu , Kasten Kevin , Firth James D. , Karadakov Peter B. , Goldberg Frederick W. , O'Brien Peter 
Published: November 2023

AbstractA general and straightforward procedure for the lithiation trapping of cyclic sulfides such as tetrahydrothiophene, tetrahydrothiopyran and a thiomorpholine is described. Trapping with a wide range of electrophiles is demonstrated, leading to more than 50 diverse α‐substituted saturated sulfur heterocycles. The methodology provides access to a range of α‐substituted cyclic sulfides that are not easily synthesised by the currently available methods.
Covalent Organic Frameworks: Opportunities for Rational Materials Design in Cancer Therapy
Authors: Zhou Le‐Le , Guan Qun , Dong Yu‐Bin 
Published: November 2023

AbstractNanomedicines are extensively used in cancer therapy. Covalent organic frameworks (COFs) are crystalline organic porous materials with several benefits for cancer therapy, including porosity, design flexibility, functionalizability, and biocompatibility. This review examines the use of COFs in cancer therapy from the perspective of reticular chemistry and function‐oriented materials design. First, the modification sites and functionalization methods of COFs are discussed, followed by their potential as multifunctional nanoplatforms for tumor targeting, imaging, and therapy by integrating functional components. Finally, some challenges in the clinical translation of COFs are presented with the hope of promoting the development of COF‐based anticancer nanomedicines and bringing COFs closer to clinical trials.
Prediction of Early Atherosclerotic Plaques Using a Sequence‐Activated Fluorescence Probe for the Simultaneous Detection of γ‐Glutamyl Transpeptidase and Hypobromous Acid
Authors: Wang Hui , Zhang Xiaoting , Li Ping , Huang Fang , Xiu Tiancong , Wang HongTong , Zhang Wei , Zhang Wen , Tang Bo 
Published: November 2023

AbstractAtherosclerosis is a lipoprotein‐driven disease, and there is no effective therapy to reverse atherosclerosis or existing plaques. Therefore, it is urgently necessary to create a noninvasive and reliable approach for early atherosclerosis detection to prevent initial plaque formation. Atherosclerosis is intimately associated with inflammation, which is accompanied by an excess of reactive oxygen species (ROS), leading to cells requiring more glutathione (GSH) to resist severe oxidative stress. Therefore, the GSH‐hydrolyzed protein γ‐glutamyl transpeptidase (GGT) and the ROS‐hypobromous acid (HBrO) are potential biomarkers for predicting atherogenesis. Hence, to avoid false‐positive diagnoses caused by a single biomarker, we constructed an ingenious sequence‐activated double‐locked TP fluorescent probe, C‐HBrO‐GGT, in which two sequential triggers of GGT and HBrO are meticulously designed to ensure that the probe fluoresces in response to HBrO only after GGT hydrolyzes the probe. By utilization of C‐HBrO‐GGT, the voltage‐gated chloride channel (CLC‐1)‐HBrO‐catalase (CAT)‐GGT signaling pathway was confirmed in cellular level. Notably, the forthcoming atherosclerotic plaques were successfully predicted before the plaques could be observed via the naked eye or classical immunofluorescent staining. Collectively, this research proposed a powerful tool to indicate the precise position of mature plaques and provide early warning of atherosclerotic plaques.
Reaktivität von [Cp*Fe(η5‐As5)] gegenüber Carbenen, Silylenen und Germylenen
Authors: Reichl Stephan , Riesinger Christoph , Yadav Ravi , Timoshkin Alexey Y. , Roesky Peter W. , Scheer Manfred 
Published: November 2023

AbstractDas Reaktionsverhalten von [Cp*Fe(η5‐As5)] (I) (Cp*=C5Me5) gegenüber Carbenen und ihren schwereren Analoga wurde untersucht. Die Reaktion von I mit NHCs (NHCs=N‐heterocyclische Carbene) gibt die ersten Substitutionsprodukte von Polyarsen‐Ligandkomplexen mittels NHCs [Cp*Fe(η4‐As5NHC)] (1 a: NHC=IMe=1,3,4,5‐Tetramethylimidazolin‐2‐yliden, 1 b: NHC=IMes=1,3‐Bis(2,4,6‐trimethylphenyl)‐imidazolin‐2‐yliden). Im Gegensatz dazu führt die Reaktion von I mit EtCAAC (EtCAAC=2,6‐Diisopropylphenyl)‐4,4‐diethyl‐2,2‐dimethyl‐pyrrolidin‐5‐yliden) zu einer Fragmentierung und Bildung einer neuartigen As6‐sägebockartigen Verbindung [As2(AsEtCAAC)4] (2). Die Reaktion von (LE)2 (L=PhC(NtBu)2; E=Si, Ge) mit I resultiert in einer Umlagerung und einer Insertion von LE‐Fragmenten, was zur Bildung einzigartiger silizium‐ (4: [Cp*Fe(η4‐As4SiL)], 5 a: [Cp*Fe(η4‐As6SiL)) und germanium‐haltiger (5 b: [Cp*Fe(η4‐As6GeL)) cyclischer Polyarsen‐Ligandkomplexe führt.
Effect of Feature Shape and Dimension of a Confinement Geometry on Selectivity of Electrocatalytic CO2 Reduction
Authors: Kim Yesol , Yun Geun‐Tae , Kim Minki , Jamal Aqil , Gereige Issam , Ager Joel W. , Jung Woo‐Bin , Jung Hee‐Tae 
Published: November 2023

AbstractThe local confinement effect, which can generate a high concentration of hydroxide ions and reaction intermediates near the catalyst surface, is an important strategy for converting CO2 into multi‐carbon products in electrocatalytic CO2 reduction. Therefore, understanding how the shape and dimension of the confinement geometry affect the product selectivity is crucial. In this study, we report for the first time the effect of the shape (degree of confinement) and dimension of the confined space on the product selectivity without changing the intrinsic property of Cu. We demonstrate that geometry influences the outcomes of products, such as CH4, C2H4, and EtOH, in different ways: the selectivity of CH4 and EtOH is affected by shape, while the selectivity of C2H4 is influenced by dimension of geometry predominantly. These phenomena are demonstrated, both experimentally and through simulation, to be induced by the local confinement effect within the confined structure. Our geometry model could serve as basis for designing the confined structures tailored for the production of specific products.
High Gas Permeability in Aged Superglassy Membranes with Nanosized UiO‐66−NH2/cPIM‐1 Network Fillers
Authors: Qiu Boya , Yu Ming , Luque‐Alled Jose Miguel , Ding Shengzhe , Foster Andrew B. , Budd Peter M. , Fan Xiaolei , Gorgojo Patricia 
Published: November 2023

AbstractSuperglassy membranes synthesised by polymers of intrinsic microporosity (PIMs) suffer from physical aging and show poor gas permeance over time, especially thin membranes, due to the fast rearrangement of nonequilibrium polymer chains. Herein, we constructed a novel PIM‐1 thin film nanocomposite membrane (TFN) using nanosized UiO‐66−NH2 (≈10 nm)/carboxylated PIM‐1 (cPIM‐1) as the composite filler. Unlike conventional fillers, which interact with the polymer only via the surface, the UiO‐66−NH2/cPIM‐1 forms a stable three‐dimensional (3D) network intertwining with the polymer chains, being very effective to impede chain relaxation, and thus physical aging. Nanosizing of UiO‐66−NH2 was achieved by regulating the nucleation kinetics using carbon quantum dots (CQD) during the synthesis. This led to increased surface area, and hence more functional groups to bond with cPIM‐1 (via hydrogen bonding between −NH2 and −COOH groups), which also improved interfacial compatibility between the 3D network and polymer chains avoiding defect formation. As a result, the novel TFN showed significantly improved performance in gas separation along with reduced aging (i.e. ≈6 % loss in CO2 permeability over 63 days); the aged membranes had a CO2 permeance of 2504 GPU and ideal selectivity values of 37.2 and 23.8 for CO2/N2 and CO2/CH4, respectively.
The missing father: why can't infant mental health services keep dads in mind?
Authors: Lim Izaak , McMillan Hannah , Robertson Paul , Fletcher Richard 
Published: November 2023

AbstractDespite the weight of scientific evidence demonstrating the importance of fathers in the social and emotional development and well‐being of infants, infant mental health services struggle to engage fathers. Commonly, fathers are assumed to be unavailable, uninterested, unnecessary, or even unsafe in relation to infant mental health work. These outdated perspectives perpetuate the myth that this work pertains exclusively to the infant–mother dyad. This paper aims to explore some of the reasons for and barriers to involving fathers in infant mental health services. We present an imagined conversation between three mental health professionals working in a child and adolescent mental health service. Presented as a script, the various arguments, counterarguments, and reflections made by the three characters aim to bring the subject matter to life and capture something akin to an actual discussion between colleagues working in a child mental health service. A junior clinician notices that an infant case presented at the multidisciplinary team meeting did not mention the child's father. A senior clinician explains that the team's work usually focuses on the infant–mother relationship, as this is considered of primary importance clinically. A psychiatrist, who has only recently joined the team, explores some of the aspects of team culture that might exclude fathers from participating in the service. Several plausible objections to involving fathers are explored as the discussion unfolds between the three professionals. Infant mental health services should consider how their culture and processes influence whether fathers and/or other adult caregivers engage in these services. For clinicians, thinking about the infant's immediate interpersonal context from their unique development perspective can reveal opportunities and resources within the family that may lead to effective systemic treatment approaches.
Thinking three, revisited: infants, coparents, gender roles, and cultural contexts
Authors: McHale James P. , Jenkins Kacey L. 
Published: November 2023

AbstractTracing its beginnings to the mid‐1990s, coparenting theory and research, guided greatly by Minuchin's structural family theory, have deepened socialisation perspectives in the field of developmental psychology. Coparenting theory has perhaps had its largest impact in the field of infant‐family mental health, where empirical investigations of coparenting and family‐level dynamics have dovetailed with studies of family alliances and triangles and inspired creative interventions to support families of infants and toddlers. In this article, the authors retrace some of the early accounts of coparenting and triangular interactions during infancy, highlighting symmetries with analogue conceptualisations discovered in the field of family therapy. Emphasising key concepts and lessons divined from the infant‐family mental health literature holding value for the practice of family therapy, the article also recognises the dominant Euro‐Western bias that has shaped much of the extant literature to date. A closing section addresses two important areas calling for more concerted attention by infant‐family mental health experts and family therapists alike – under‐appreciated and misunderstood elements of men's psychology connected to their core self‐definition, and cultural distinctions in normal family processes. In both cases, if misread or misunderstood by the helping professional, the recipients of therapeutic services may experience failures of empathy.
Preparation of rigidity toughness balance and stable poly(glycolic acid) based on chain extension reaction
Authors: Chen Shiyuan , Meng Xin , Xin Zhong , Gong Weiguang , Li Chenyang , Wen Wei 
Published: November 2023

AbstractAs a completely degradable material, poly(glycolic acid) (PGA) has excellent rigidity, barrier properties, degradability and biocompatibility. However, the inherent brittleness and easily hydrolysable characteristics limit its widespread application. Herein, we introduced chain extension ADR to modify PGA to ameliorate these defects. The results showed that ADR could react with PGA to form “comb‐like” and “cross‐linked” chain extension structures resulting in the improvement of complex viscosity and formation of gel. Because of the chain entanglement of chain extension structures, the toughness of modified PGA was improved (which was verified by the impact strength value of 4.3 kJ/m2 that was about 126% of virgin PGA) without sacrificing its rigidity. Furthermore, the hydrolysis results indicated that the representative PGA/1.0ADR had better hydrolysis stability, it had more complete morphology and slower degradation rate than virgin PGA in the 17‐day hydrolysis experiment. Apart from better toughness and hydrolysis stability, there was also improvements in crystallization performance, the sample PGA/1.0ADR endowed with higher crystallization peak temperature (2.3°C higher than virgin PGA) and lower crystallization activation energy. In short, this work prepared a kind of modified PGA with rigidity toughness balance and better hydrolysis stability, which could expand the application range of PGA‐based materials.
Experimental study on the availability of polyurethane foam used as compressible layers in subsea tunnels
Authors: Zhang Zheyuan , Tian Hongming , Chen Weizhong , Qiu Xin 
Published: November 2023

AbstractThe yielding support comprising a compressive layer is considered as a solution to the time‐dependent damage of the lining in squeezing tunnels. The feasibility of the use of polyurethane foam (PUF) as the compressible layers in subsea tunnels was investigated in this study. Confined compression tests were conducted to investigate the compression performance degradation of PUF immersed in artificial seawater for 400 days. The yield strength and elastic modulus of PUF decreased within 180 days but then increased to over 80% of their initial values within the subsequent following 220 days, the degradation rate and strengthening rate of these parameters are of the same order of magnitude. The degradation rate of the yield strength and elastic modulus can be significantly inhibited by ions in artificial seawater, thus causing samples immersed in low‐salt‐concentration solutions to exhibit worse compression performance than those of samples immersed in a high‐salt‐concentration solution. The stress at the end of the yielding plateau and yielding plateau strain range were slightly affected by hydrolysis aging. The shape of the yielding plateau stage of the aged samples changed from a horizontal line to an inclined line owing to the variation in the yield strength. Even after immersion for 400 days, all the aged samples still exhibited compression failure and neither crumbled into pieces nor fractured into parts. The strengthening effect, unchanged failure mode, and almost constant yielding plateau strain range guarantee the safe utilization of PUF in marine environments.
Creation of NV Centers in Diamond under 155 MeV Electron Irradiation
Authors: Losero Elena , Goblot Valentin , Zhu Yuchun , Babashah Hossein , Boureau Victor , Burkart Florian , Galland Christophe 
Published: November 2023

AbstractSingle‐crystal diamond substrates presenting a high concentration of negatively charged nitrogen‐vacancy centers (NV−) are on high demand for the development of optically pumped solid‐state sensors such as magnetometers, thermometers, or electrometers. While nitrogen impurities can be easily incorporated during crystal growth, the creation of vacancies requires further treatment. Electron irradiation and annealing is often chosen in this context, offering advantages with respect to irradiation by heavier particles that negatively affect the crystal lattice structure and consequently the NV− optical and spin properties. A thorough investigation of electron irradiation possibilities is needed to optimize the process and improve the sensitivity of NV‐based sensors. In this work, the effect of electron irradiation is examined in a previously unexplored regime: extremely high energy electrons, at 155 MeV. A simulation model is developed to estimate the concentration of created vacancies and an increase of NV− concentration by more than three orders of magnitude following irradiation of a nitrogen‐rich HPHT diamond over a very large sample volume is experimentally demonstrated, which translates into an important gain in sensitivity. Moreover, the impact of electron irradiation in this peculiar regime on other figures of merits relevant for NV sensing is discussed, including charge state conversion efficiency and spin relaxation time. Finally, the effect of extremely high energy irradiation is compared with the more conventional low energy irradiation process, employing 200 keV electrons from a transmission electron microscope, for different substrates and irradiation fluences, evidencing 60‐fold higher yield of vacancy creation per electron at 155 MeV.
The decrease in uncited articles and its effect on the concentration of citations
Authors: Kozlowski Diego , Andersen Jens Peter , Larivière Vincent 
Published: November 2023

AbstractEmpirical evidence demonstrates that citations received by scholarly publications follow a pattern of preferential attachment, resulting in a power‐law distribution. Such asymmetry has sparked significant debate regarding the use of citations for research evaluation. However, a consensus has yet to be established concerning the historical trends in citation concentration. Are citations becoming more concentrated in a small number of articles? Or have recent geopolitical and technical changes in science led to more decentralized distributions? This ongoing debate stems from a lack of technical clarity in measuring inequality. Given the variations in citation practices across disciplines and over time, it is crucial to account for multiple factors that can influence the findings. This article explores how reference‐based and citation‐based approaches, uncited articles, citation inflation, the expansion of bibliometric databases, disciplinary differences, and self‐citations affect the evolution of citation concentration. Our results indicate a decreasing trend in citation concentration, primarily driven by a decline in uncited articles, which, in turn, can be attributed to the growing significance of Asia and Europe. On the whole, our findings clarify current debates on citation concentration and show that, contrary to a widely‐held belief, citations are increasingly scattered.
Molecular Reconstruction with Stereochemical Relay: An Investigation into the Rearrangement of Spiro[4.5]decadienone to Benzoxepane
Authors: Sittihan Satapanawat , Harada Shingo , Isono Tomohiro , Nemoto Tetsuhiro , Ruchirawat Somsak 
Published: November 2023

AbstractHerein, we report the unusual skeletal rearrangement of spiro[4.5]decadienone to benzoxepane. In particular, Lewis acid‐promoted epoxide‐opening ipso‐cyclization of aryl epoxides afforded spiro[4.5]decadienone intermediates. Subsequent thermal activation assembled a benzoxepane core via rearomative molecular reorganization. The sequence was high‐yielding and highly diastereoselective but sensitive to the aromatic substitution pattern and the epoxide side chain. Mechanistic studies suggested that the rearrangement proceeded via an uncommon intramolecular enolate attack onto the electrophilic O of p‐quinone oxonium zwitterion. DFT calculations helped rationalize the product distribution and the origin of diastereoselectivity. Initial investigation into the application of this chemical transformation is also presented.
The miR‐17‐92 cluster in cardiac health and disease
Authors: Cao Yuhan , Zheng Mingjie , Sewani Maham A. , Wang Jun 
Published: November 2023

AbstractMicroRNAs (miRs) are small noncoding RNAs that play important roles in both physiological and pathological processes through post‐transcriptional regulation. The miR‐17‐92 cluster includes six individual members: miR‐17, miR‐18a, miR‐19a, miR‐19b‐1, miR‐20a, and miR‐92a‐1. The miR‐17‐92 cluster has been extensively studied and reported to broadly function in cancer biology, immunology, neurology, pulmonology, and cardiology. This review focuses on its roles in heart development and cardiac diseases. We briefly introduce the nature of the miR‐17‐92 cluster and its crucial roles in both normal development and the pathogenesis of various diseases. We summarize the recent progress in understanding the versatile roles of miR‐17‐92 during cardiac development, regeneration, and aging. Additionally, we highlight the indispensable roles of the miR‐17‐92 cluster in pathogenesis and therapeutic potential in cardiac birth defects and adult cardiac diseases.