bluuebunny/crossref_metadata_2025_split huggingface dataset:
Near‐Infrared Self‐Assembled Hydroxyl Radical Generator Based on Photoinduced Cascade Electron Transfer for Hypoxic Tumor Phototherapy
Authors: Zhao Xueze , He Shan , Wang Junfeng , Ding Junying , Zong Shenglin , Li Guohui , Sun Wen , Du Jianjun , Fan Jiangli , Peng Xiaojun 
Published: August 2023

AbstractThe hydroxyl radical (•OH) is an extremely potent reactive oxygen species that plays a crucial role in photooxidations within the realm of hypoxic tumor therapy. However, the current methods for •OH photogeneration typically rely on inorganic materials that require UV/vis light excitation. Consequently, photogenerators based on organic molecules, especially those utilizing near‐infrared (NIR) light excitation, are rare. In this study, the concept of photoinduced cascade charge transfer (PICET), which utilizes NIR heavy‐atom‐free photosensitizers (ANOR‐Cy5) to generate •OH is introduced. The ANOR‐Cy5 photosensitizer, with its flexible hydrophobic structure, enables the formation of nanoparticles in aqueous solutions through molecular assembly. PICET involves a symmetry‐breaking charge separation‐induced localized charge‐separated state, transitioning to a delocalized charge‐separated state, which governs the efficiency of •OH generation. Thanks to the oxygen‐independent nature of •OH generation and its robust oxidative properties, the ANOR‐Cy5‐based photosensitizer demonstrates highly effective photoinduced anti‐cancer effects, even under severely hypoxic conditions. This discovery emphasizes the potential for achieving •OH photogeneration using a single organic molecule through the engineering of molecular self‐assembly, thereby opening up new possibilities for phototherapy and beyond.
Highly Ordered Graphene Polydopamine Composite Allowing Fast Motion of Cations: Toward a High‐Performance Microsupercapacitor
Authors: Bouzina Adnane , Meng René , Bazin Cyrille , Perrot Hubert , Sel Ozlem , Debiemme‐Chouvy Catherine 
Published: August 2023

AbstractThe simple and eco‐friendly preparation of microsupercapacitor remains a great challenge. Here are presented the preparation and the characterizations of an all‐solid symmetric micro‐supercapacitor based on a new composite formed of highly ordered graphene sheets due to the presence of polydopamine between the layers, which present a d‐spacing of 0.356 nm. This graphene‐polydopamine composite is prepared by electroreduction of graphene oxide (GO) followed by the electrooxidation of dopamine added into the initial solution, i.e., after GO reduction. In Na2SO4 solution, this composite material shows excellent capacitance and stability even at a high scan rate (2 V s−1) and a very low relaxation time (τ0) of 62 ms. This value is in very good agreement with the high transfer kinetic and low transfer resistance values of the ions implied in the charge storage process (Na+·2H2O and Na+) determined by ac‐electrogravimetry. Finally, it is shown that the all‐solid micro‐supercapacitor (interdigitated electrodes obtained using a CO2 laser and Na2SO4/PVA hydrogel) prepared with this new composite delivers a remarkable energy density of 6.36 mWh cm−3 for a power density of 0.22 W cm−3 and exhibits excellent cycling stability (98% of retention after 10 000 cycles at 2 V s−1).
Soft Smart Biopatch for Continuous Authentication‐Enabled Cardiac Biometric Systems
Authors: Lee Sung Hoon , Lee Yoon Jae , Kwon Kangkyu , Lewis Daniel , Romero Lissette , Lee Jimin , Zavanelli Nathan , Yan Emily , Yu Ki Jun , Yeo Woon‐Hong 
Published: August 2023

AbstractBiometric locking systems offer a seamless integration of an individual's physiological characteristics with secure authentication. However, they suffer from limitations such as false positive and negative authentication, environmental interference, and varying disadvantages across multiple authentication methods. To address these limitations, this study develops a soft smart biopatch for a continuous cardiac biometric wearable device that can continuously gather novel biometric data from an individual's heart sound for authentication with minimal error (less than 0.5%). The device is designed to be discreet and user‐friendly, and it employs soft biocompatible materials to ensure comfort and ease of use. The patch system incorporates a miniaturized microphone to monitor sounds over long periods and multiple dimensions, enhancing the reliability of the biometric data. Furthermore, the use of machine‐learning algorithms has enabled the creation of unique identification keys for individuals based on the continuous monitoring properties of the low‐cost device. These advantages make it more effective and efficient than traditional biometric systems, with the potential to enhance the security of mobile devices and door locks.
Coordinative Stabilization of Single Bismuth Sites in a Carbon–Nitrogen Matrix to Generate Atom‐Efficient Catalysts for Electrochemical Nitrate Reduction to Ammonia
Authors: Zhang Wuyong , Zhan Shaoqi , Xiao Jie , Petit Tristan , Schlesiger Christopher , Mellin Maximilian , Hofmann Jan P. , Heil Tobias , Müller Riccarda , Leopold Kerstin , Oschatz Martin 
Published: August 2023

AbstractElectrochemical nitrate reduction to ammonia powered by renewable electricity is not only a promising alternative to the established energy‐intense and non‐ecofriendly Haber–Bosch reaction for ammonia generation but also a future contributor to the ever‐more important denitrification schemes. Nevertheless, this reaction is still impeded by the lack of understanding for the underlying reaction mechanism on the molecular scale which is necessary for the rational design of active, selective, and stable electrocatalysts. Herein, a novel single‐site bismuth catalyst (Bi‐N‐C) for nitrate electroreduction is reported to produce ammonia with maximum Faradaic efficiency of 88.7% and at a high rate of 1.38 mg h−1 mgcat−1 at −0.35 V versus reversible hydrogen electrode (RHE). The active center (described as BiN2C2) is uncovered by detailed structural analysis. Coupled density functional theory calculations are applied to analyze the reaction mechanism and potential rate‐limiting steps for nitrate reduction based on the BiN2C2 model. The findings highlight the importance of model catalysts to utilize the potential of nitrate reduction as a new‐generation nitrogen‐management technology based on the construction of efficient active sites.
Polyethylene Oxide (PEO) Provides Bridges to Silica Nanoparticles to Form a Shear Thickening Electrolyte for High Performance Impact Resistant Lithium‐ion Batteries
Authors: Chen Zhiqi , Chao Yunfeng , Sayyar Sepidar , Tian Tongfei , Wang Kezhong , Xu Yeqing , Wallace Gordon , Ding Jie , Wang Caiyun 
Published: August 2023

AbstractThe development of shear thickening electrolytes is proving to be pivotal in the quest for impact resistant lithium‐ion batteries (LIBs). However, the high viscosity and poor stability associated with the need for high filler content has to date impeded progress. Here, this work reports a new type of polymer‐bridged shear thickening electrolyte that overcomes these shortcomings, by utilizing the interaction between polymer chains and silica nanoparticles. The incorporation of polyethylene oxide (PEO) facilitates hydrocluster formation providing impact resistance with a filler content as low as 2.2 wt%. This low viscosity electrolyte has a high ionic conductivity of ≈5.1 mS cm−1 with excellent long‐term stability, over 30 days. The effectiveness of this electrolyte in LIBs is demonstrated by excellent electrochemical performance and high impact resistance.
A Brain‐To‐Brain Mechanism for Social Transmission of Threat Learning
Authors: Pan Yafeng , Vinding Mikkel C. , Zhang Lei , Lundqvist Daniel , Olsson Andreas 
Published: August 2023

AbstractSurvival and adaptation in environments require swift and efficacious learning about what is dangerous. Across species, much of such threat learning is acquired socially, e.g., through the observation of others’ (“demonstrators’”) defensive behaviors. However, the specific neural mechanisms responsible for the integration of information shared between demonstrators and observers remain largely unknown. This dearth of knowledge is addressed by performing magnetoencephalography (MEG) neuroimaging in demonstrator‐observer dyads. A set of stimuli are first shown to a demonstrator whose defensive responses are filmed and later presented to an observer, while neuronal activity is recorded sequentially from both individuals who never interacted directly. These results show that brain‐to‐brain coupling (BtBC) in the fronto‐limbic circuit (including insula, ventromedial, and dorsolateral prefrontal cortex) within demonstrator‐observer dyads predict subsequent expressions of learning in the observer. Importantly, the predictive power of BtBC magnifies when a threat is imminent to the demonstrator. Furthermore, BtBC depends on how observers perceive their social status relative to the demonstrator, likely driven by shared attention and emotion, as bolstered by dyadic pupillary coupling. Taken together, this study describes a brain‐to‐brain mechanism for social threat learning, involving BtBC, which reflects social relationships and predicts adaptive, learned behaviors.
Catalytic absorption pathway with kinetically favorable dissolution of nitric oxide in aqueous absorbents
Authors: Lian Zheng , Li Guojun , Zhang Shule , Ma Weihua 
Published: August 2023

AbstractNitrogen capture is a crucial strategy for coping with the environmental crisis arising from continually industrial NO emissions, while it suffers from the generally inefficient aquatic absorbent. This work developed a novel absorbent with favorable gas affinity via using sterically hindered imidazole to regulate the gas–liquid interface of typical K2S2O8 solution, initially achieving an efficiently catalytic absorption of poorly soluble NO. The best catalytic absorption efficiencies increased from 17.83% to 91.90% as compared to traditional one. Moreover, an established absorption kinetic model indicated that both capacity and rate of NO dissolution were increased. The imidazole molecules spontaneously migrated to gas–liquid interface of solution and imparted an additional dissolution impetus to NO. This catalytic absorption method overcoming the conventional NO dissolution limitation in water not only improves commercial NO capture, but also provides a new design of aquatic absorbent for heterogeneous reactions requiring transporting poorly soluble gases in aqueous solvents.
Subdural hemorrhage, macrocephaly, rash, and developmental delay in an infant: A pathogenic variant in NLRP3 causes CINCA/NOMID
Authors: Koti Ajay S. , Lanis Aviya , Finlayson Samuel , Canny Susan , Feldman Elana A. , Miller Danny E. , Rosenwasser Natalie , Scott Abbey A. , Wong Stephen C. , Feldman Kenneth W. 
Published: August 2023

AbstractSubdural hemorrhages (SDHs) in children are most often observed in abusive head trauma (AHT), a distinct form of traumatic brain injury, but they may occur in other conditions as well, typically with clear signs and symptoms of an alternative diagnosis. We present a case of an infant whose SDH initially raised the question of AHT, but multidisciplinary evaluation identified multiple abnormalities, including rash, macrocephaly, growth failure, and elevated inflammatory markers, which were all atypical for trauma. These, along with significant cerebral atrophy, ventriculomegaly, and an absence of other injuries, raised concerns for a genetic disorder, prompting genetic consultation. Clinical trio exome sequencing identified a de novo likely pathogenic variant in NLRP3, which is associated with chronic infantile neurological, cutaneous, and articular (CINCA) syndrome, also known as neonatal‐onset multisystem inflammatory disease (NOMID). He was successfully treated with interleukin‐1 blockade, highlighting the importance of prompt treatment in CINCA/NOMID patients. This case also illustrates how atraumatic cases of SDH can be readily distinguished from AHT with multidisciplinary collaboration and careful consideration of the clinical history and exam findings.
Synthesis of Polysubstituted Furans: An Update Since 2019
Authors: Mohapatra Suhasini , Panda Jasmine , Mohapatra Seetaram , Nayak Sabita 
Published: August 2023

AbstractPolysubstituted furans are widespread structural motifs, extensively dispersed in natural products, in numerous bioactive compounds, pharmaceuticals, agrochemicals and organic functional materials. Hence, the development of rapid and competent methodologies for the synthesis of multisubstituted furans has drawn much attention over the years. This review summarizes the synthesis of polysubstituted furans using transition‐metal catalyzed, transition metal‐free, photochemical and electrochemical approaches with plausible mechanistic insights. In each reaction, the highest yields of di‐, tri‐ or tetrasubstituted furans are highlighted and some applications of the methodology towards the synthesis of natural products and biologically active compounds are mentioned. The present review highlights the recent progresses in the synthesis of polysubstituted furans reported from 2019 to 2023.
Symptom‐led staging for semantic and non‐fluent/agrammatic variants of primary progressive aphasia
Authors: Hardy Chris J. D. , Taylor‐Rubin Cathleen , Taylor Beatrice , Harding Emma , Gonzalez Aida Suarez , Jiang Jessica , Thompson Laura , Kingma Rachel , Chokesuwattanaskul Anthipa , Walker Ffion , Barker Suzie , Brotherhood Emilie , Waddington Claire , Wood Olivia , Zimmermann Nikki , Kupeli Nuriye , Yong Keir X. X. , Camic Paul M. , Stott Joshua , Marshall Charles R. , Oxtoby Neil P. , Rohrer Jonathan D. , Volkmer Anna , Crutch Sebastian J. , Warren Jason D. 
Published: August 2023

AbstractINTRODUCTIONHere we set out to create a symptom‐led staging system for the canonical semantic and non‐fluent/agrammatic variants of primary progressive aphasia (PPA), which present unique diagnostic and management challenges not well captured by functional scales developed for Alzheimer's disease and other dementias.METHODSAn international PPA caregiver cohort was surveyed on symptom development under six provisional clinical stages and feedback was analyzed using a mixed‐methods sequential explanatory design.RESULTSBoth PPA syndromes were characterized by initial communication dysfunction and non‐verbal behavioral changes, with increasing syndromic convergence and functional dependency at later stages. Milestone symptoms were distilled to create a prototypical progression and severity scale of functional impairment: the PPA Progression Planning Aid (“PPA‐Squared”).DISCUSSIONThis work introduces a symptom‐led staging scheme and functional scale for semantic and non‐fluent/agrammatic variants of PPA. Our findings have implications for diagnostic and care pathway guidelines, trial design, and personalized prognosis and treatment for PPA.Highlights
We introduce new symptom‐led perspectives on primary progressive aphasia (PPA).
The focus is on non‐fluent/agrammatic (nfvPPA) and semantic (svPPA) variants.
Foregrounding of early and non‐verbal features of PPA and clinical trajectories is featured.
We introduce a symptom‐led staging scheme for PPA.
We propose a prototype for a functional impairment scale, the PPA Progression Planning Aid.
Histopathological Correlates of Lobar Microbleeds in False‐Positive Cerebral Amyloid Angiopathy Cases
Authors: Perosa Valentina , Auger Corinne A. , Zanon Zotin Maria Clara , Oltmer Jan , Frosch Matthew P. , Viswanathan Anand , Greenberg Steven M. , van Veluw Susanne J. 
Published: August 2023

ObjectiveA definite diagnosis of cerebral amyloid angiopathy (CAA), characterized by the accumulation of amyloid β in walls of cerebral small vessels, can only be obtained through pathological examination. A diagnosis of probable CAA during life relies on the presence of hemorrhagic markers, including lobar cerebral microbleeds (CMBs). The aim of this project was to study the histopathological correlates of lobar CMBs in false‐positive CAA cases.MethodsIn 3 patients who met criteria for probable CAA during life, but showed no CAA upon neuropathological examination, lobar CMBs were counted on ex vivo 3T magnetic resonance imaging (MRI) and on ex vivo 7T MRI. Areas with lobar CMBs were next sampled and cut into serial sections, on which the CMBs were then identified.ResultsCollectively, there were 25 lobar CMBs on in vivo MRI and 22 on ex vivo 3T MRI of the analyzed hemispheres. On ex vivo MRI, we targeted 12 CMBs for sampling, and definite histopathological correlates were retrieved for 9 of them, of which 7 were true CMBs. No CAA was found on any of the serial sections. The “culprit vessels” associated with the true CMBs instead showed moderate to severe arteriolosclerosis. Furthermore, CMBs in false‐positive CAA cases tended to be located more often in the juxtacortical or subcortical white matter than in the cortical ribbon.InterpretationThese findings suggest that arteriolosclerosis can generate lobar CMBs and that more detailed investigations into the exact localization of CMBs with respect to the cortical ribbon could potentially aid the diagnosis of CAA during life. ANN NEUROL 2023;94:856–870
A Semisynthetic Bioluminescence Sensor for Ratiometric Imaging of Metal Ions In Vivo Using DNAzymes Conjugated to An Engineered Nano‐Luciferase
Authors: Xiong Mengyi , Wu Yuting , Kong Gezhi , Lewis Whitney , Yang Zhenglin , Zhang Hanxiao , Xu Li , Liu Ying , Liu Qin , Zhao Xuhua , Zhang Xiao‐Bing , Lu Yi 
Published: August 2023

AbstractDNA‐based probes have gained significant attention as versatile tools for biochemical analysis, benefiting from their programmability and biocompatibility. However, most existing DNA‐based probes rely on fluorescence as the signal output, which can be problematic due to issues like autofluorescence and scattering when applied in complex biological materials such as living cells or tissues. Herein, we report the development of bioluminescent nucleic acid (bioLUNA) sensors that offer laser excitation‐independent and ratiometric imaging of the target in vivo. The system is based on computational modelling and mutagenesis investigations of a genetic fusion between circular permutated Nano‐luciferase (NLuc) and HaloTag, enabling the conjugation of the protein with a DNAzyme. In the presence of Zn2+, the DNAzyme sensor releases the fluorophore‐labelled strand, leading to a reduction in bioluminescent resonance energy transfer (BRET) between the luciferase and fluorophore. Consequently, this process induces ratiometric changes in the bioluminescent signal. We demonstrated that this bioLUNA sensor enabled imaging of both exogenous Zn2+ in vivo and endogenous Zn2+ efflux in normal epithelial prostate and prostate tumors. This work expands the DNAzyme sensors to using bioluminescence and thus has enriched the toolbox of nucleic acid sensors for a broad range of biomedical applications.
Photolumineszenz von Mn2+ in dem Borosulfat Zn[B2(SO4)4] : Mn2+ – Eine Möglichkeit zum Nachweis schwach koordinierender Liganden
Authors: Träger Lukas M. , Pasqualini Leonard C. , Huppertz Hubert , Bruns Jörn , Suta Markus 
Published: August 2023

AbstractDer Einfluss des umgebenden Ligandenfelds wird im Fall von Eu2+ erfolgreich genutzt, um die Emission anorganischer photoaktiver Materialien durchzustimmen, die z. B. in phosphor‐konvertierten Weißlicht‐emittierenden Dioden (pc‐wLEDs) Anwendung finden. Allerdings ist auch die Photolumineszenz von Mn2+, die auf intrakonfiguralen 3d5–3d5‐Übergängen basiert, stark von lokalen Ligandenfeldeffekten abhängig. Dieser Aspekt wurde bislang eher vernachlässigt. In der vorliegenden Arbeit wollen wir daher die Idee wieder aufleben lassen, die Emissionsfarbe eines Übergangsmetall‐Ions in anorganischen Wirtsverbindungen durch ungewöhnliche elektronische Effekte in der Metall‐Ligand‐Bindung einzustellen. Das Konzept wird explizit für das schwach koordinierende, schichtartigen Borosulfat‐Anion in den Mn2+‐haltigen festen Lösungen Zn1‐xMnx[B2(SO4)4] (x=0; 0.03; 0.04; 0.05; 0.10) demonstriert. Zn[B2(SO4)4] : Mn2+ zeigt orange Schmalbandlumineszenz bei 590 nm, was eine ungewöhnlich kurze Wellenlänge für oktaedrisch koordiniertes Mn2+ darstellt und auf ein besonders schwaches Ligandenfeld hinweist. Eine Analyse der interelektronischen Racah‐Abstoßungsparameter deutet stark ionische Mn−O‐Bindungen mit Werten nahe der Racah‐Parameter des freien Mn2+‐Ions an. Insgesamt demonstriert diese Strategie, dass elektronische Anpassungen der Metall−Ligand‐Bindung als Instrument genutzt werden können, um Mn2+ zu einem potenten alternativen Emitter anstelle von Eu2+ für anorganische Leuchtstoffe zu machen.
Photoluminescence of Mn2+ in the Borosulfate Zn[B2(SO4)4] : Mn2+—A Tool to Detect Weak Coordination Behavior of Ligands
Authors: Träger Lukas M. , Pasqualini Leonard C. , Huppertz Hubert , Bruns Jörn , Suta Markus 
Published: August 2023

AbstractThe impact of the surrounding ligand field is successfully exploited in the case of Eu2+ to tune the emission characteristics of inorganic photoactive materials with potential application in, e.g., phosphor‐converted white light‐emitting diodes (pc‐wLEDs). However, the photoluminescence of Mn2+ related to intraconfigurational 3d5–3d5 transitions is also strongly dependent on local ligand field effects and has been underestimated in this regard so far. In this work, we want to revive the idea how to electronically tune the emission color of a transition metal ion in inorganic hosts by unusual electronic effects in the metal‐ligand bond. The concept is explicitly demonstrated for the weakly coordinating layer‐like borosulfate ligand in the Mn2+‐containing solid solutions Zn1‐xMnx[B2(SO4)4] (x = 0, 0.03, 0.04, 0.05, 0.10). Zn[B2(SO4)4]:Mn2+ shows orange narrow‐band luminescence at 590 nm, which is an unusually short wavelength for octahedrally coordinated Mn2+ and indicates an uncommonly weak ligand field. On the other hand, the analysis of the interelectronic Racah repulsion parameters reveals ionic Mn−O bonds with values close to the Racah parameters of the free Mn2+ ion. Overall, this strategy demonstrates that electronic control of the metal‐ligand bond can be a tool to make Mn2+ a potent alternative emitter to Eu2+ for inorganic phosphors.