bluuebunny/crossref_metadata_2025_split huggingface dataset:
Progress through Temporal Analysis of Products and Steady‐state Isotopic Transient Kinetic Analysis to Elucidate Oxidation, CO2 Hydrogenation and Lower Olefins Production Reactions
Authors: Otroshchenko Tatiana , Kondratenko Vita A. , Zanina Anna , Zhang Qiyang , Kondratenko Evgenii V. 
Published: March 2024

AbstractA prerequisite for the development or optimization of heterogeneous catalysts is a comprehensive understanding of the reaction mechanism and kinetics at the level as elementary as possible. In comparison with steady‐state catalytic tests typically used for this purpose, non‐steady‐state (transient) studies provide deeper insights due to higher time resolution. For several decades, temporal analysis of products (TAP) and steady‐state isotopic transient kinetic analysis (SSITKA) have been successfully applied to the analysis of various heterogeneous reactions. In this review, we highlight the contributions made by TAP and SSITKA studies between 2017 and 2023 to the understanding of reaction mechanisms and to the derivation of microkinetics. The versatility of these methods is illustrated by the examples of oxidative coupling of methane, CO/CO2 hydrogenation to hydrocarbons or methanol, metathesis of ethylene with 2‐butenes to propene, acrolein oxidation to acrylic acid, methanol conversion to olefins and non‐oxidative propane dehydrogenation to propene. We also provide our personal views on possible developments in this area.
Interface Engineering of Electrocatalysts for Efficient and Selective Oxygen Evolution in Alkaline/Seawater
Authors: Kim Daekyu , Zu Wenhan , Lam Kwok Ching , Lee Lawrence Yoon Suk 
Published: March 2024

AbstractElectrochemical water splitting is regarded as an effective technology for producing green hydrogen, which is crucial for addressing energy and environmental challenges. In particular, direct seawater splitting offers significant economic and environmental advantages. However, its efficiency is hindered by the high overpotential required for the oxygen evolution reaction (OER) and the competition from chloride oxidation. This review highlights the potential of interface engineering to overcome these limitations and develop efficient OER electrocatalysts. We comprehensively explore recent advancements in interface engineering for OER in both alkaline and seawater environments. We begin by introducing the mechanisms of freshwater and seawater electrolysis, emphasizing key considerations for OER catalyst design. Subsequently, we review the recent progress made in various interface engineering strategies, analyzing their impact on OER performance in both electrolytes. Finally, we outline promising future directions for developing efficient seawater oxidation catalysts through interface engineering.
Operando Monitoring of Homolytic Cleavage of H2 into Surface Hydrides on Defective Cerium Dioxide Nanoparticles
Authors: André Rémi F. , Gallet Jean‐Jacques , Bournel Fabrice , Carenco Sophie 
Published: March 2024

AbstractThe use of ceria as catalyst in hydrogenation reactions is a recent trend, as they were uncovered to be active on a number of substrates, including alkynes, alkenes, and enones. While some studies focused on the use of well‐defined shapes, others emphasized the interest of defective structures. Overall, the meeting point of these studies is the need to characterize the surface reactivity vs. H2, by considering a number of interesting textures (films, nanopowders with various grain size or porosity), using monitoring techniques that preserve the original features of the materials. A key question is in particular to assess the possibility to form surface hydride through homolytic H2 splitting at cerium sites rather than at the oxygen one, a route recently highlighted as plausible. To address this question on small crystallites of CeO2, we designed a low‐temperature synthetic route for nanorods with an average grain size of 10 nm. Then, we employed near‐ambient‐pressure X‐ray photoelectron spectroscopy as an operando tool to monitor the cerium surface oxidation state during the initial annealing of the nanopowders, followed by exposure to a moderate pressure of H2 (0.52 mbar). We demonstrate that H2 homolytic splitting at cerium sites is the main activation process on this surface at 100 °C, leading to the oxidation of ca. 30 % of the surface cerium atoms from Ce3+ to Ce4+. The surface hydride species were however not stable at 250 °C, H2 was released, and cerium reduced back to Ce3+. A similar mechanism was observed on a defective ceria material obtained by calcination of CeO(OH)2, with comparable intensities. Overall, we report here CeO2 nanorods, exposing predominantly {100} and {110} facets, as showing an interesting surface reactivity for potential application in hydrogenation reactions, and we expose a straight operando methodology to delineate suitable temperatures to be used.
Accelerating Cellular Uptake with Unnatural Amino Acid for Inhibiting Immunosuppressive Cancer Cells
Authors: Yi Meihui , Ashton‐Rickardt Gabriel , Tan Weiyi , Liu Zhiyu , He Hongjian , Hsieh Jer‐Tsong , Xu Bing 
Published: March 2024

AbstractTargeting immunosuppressive metastatic cancer cells is a key challenge in therapy. We recently have shown that a rigid‐rod aromatic, pBP−NBD, that responds to enzymes and kill immunosuppressive metastatic osteosarcoma (mOS) and castration resistant prostate cancer (CRPC) cells in mimetic bone microenvironment. However, pBP−NBD demonstrated moderate efficacy against CRPC cells. To enhance activity, we incorporated the unnatural amino acid L‐ or D‐4,4′‐biphenylalanine (L‐ or D−BiP) into pBP−NBD, drastically increasing cellular uptake and CRPC inhibition. Specifically, we inserted BiP into pBP−NBD to target mOS (Saos2 and SJSA1) and CRPC (VCaP and PC3) cells with overexpressed phosphatases. Our results show that the D‐peptide backbone with an aspartate methyl diester at the C‐terminal offers the highest activity against these immunosuppressive mOS and CRPC cells. Importantly, imaging shows that the peptide assemblies almost instantly enter the cells and accumulate primarily within the endoplasmic reticulum of Saos2, SJSA1, and PC3 cells and at the lysosomes of VCaP cells. By using BiP to boost cellular uptake and self‐assembly within cancer cells, this work illustrates an unnatural hydrophobic amino acid as a versatile and effective residue to boost endocytosis of synthetic peptides for intracellular self‐assembly.
Ferromagnetically Coupled Chromium(III) Dimer Shows Luminescence and Sensitizes Photon Upconversion
Authors: Trippmacher Simon , Demeshko Serhiy , Prescimone Alessandro , Meyer Franc , Wenger Oliver S. , Wang Cui 
Published: March 2024

AbstractThere has been much progress on mononuclear chromium(III) complexes featuring luminescence and photoredox activity, but dinuclear chromium(III) complexes have remained underexplored in these contexts until now. We identified a tridentate chelate ligand able to accommodate both meridional and facial coordination of chromium(III), to either access a mono‐ or a dinuclear chromium(III) complex depending on reaction conditions. This chelate ligand causes tetragonally distorted primary coordination spheres around chromium(III) in both complexes, entailing comparatively short excited‐state lifetimes in the range of 400 to 800 ns in solution at room temperature and making photoluminescence essentially oxygen insensitive. The two chromium(III) ions in the dimer experience ferromagnetic exchange interactions that result in a high spin (S=3) ground state with a coupling constant of +9.3 cm−1. Photoinduced energy transfer from the luminescent ferromagnetically coupled dimer to an anthracene derivative results in sensitized triplet‐triplet annihilation upconversion. Based on these proof‐of‐principle studies, dinuclear chromium(III) complexes seem attractive for the development of fundamentally new types of photophysics and photochemistry enabled by magnetic exchange interactions.
Flexible and Stretchable Electrodes for In Vivo Electrophysiological and Electrochemical Monitoring†
Authors: Sheng Kai‐Kai , Lu Yi‐Fei , Fan Wen‐Ting , Liu Yan‐Ling 
Published: March 2024

Comprehensive SummaryIn vivo monitoring of bioelectrical and biochemical signals with implanted electrodes has received great interest over the past decades. However, this faces huge challenges because of the severe mechanical mismatch between conventional rigid electrodes and soft biological tissues. In recent years, the emergence of flexible and stretchable electrodes offers seamless and conformable biological‐electronic interfaces and has demonstrated significant advantages for in vivo electrochemical and electrophysiological monitoring. This review first summarizes the strategies for electrode fabrication from the point of substrate and conductive materials. Next, recent progress in electrode functionalization for improved performance is presented. Then, the advances of flexible and stretchable electrodes in exploring bioelectrical and biochemical signals are introduced. Finally, we present some challenges and perspectives ranging from electrode fabrication to application.Key ScientistsIn 2001, a seminal work by Kipke et al. first showed flexible polyimide‐based intracortical electrode arrays.[1] This electrode was further expanded to 252‐channel using microelectromechanical systems technology by Stieglitz et al. in 2009 and achieved large‐scale cortical recordings.[2] Later, Lieber et al. created mesh electronics that allow for seamless and minimally invasive three‐dimensional interpenetration with nerve tissues, opening up unique applications for flexible electronics.[3] Subsequently, Rogers et al. described bioresorbable electronics for transient electrical activity recordings in 2016.[4] And Frank et al. proposed polymer electrode arrays capable of resolving single neurons in 2019.[5] It wasn't until 2020 that a significant breakthrough in biochemical signals monitoring by Peng et al. demonstrated functionalized carbon nanotube fibre bundles for multiple disease biomarkers monitoring.[6] Later on, Mooney et al. established the first fully viscoelastic electrode arrays for neural recordings from the brain and heart in 2021.[7] Recently, Bao et al. presented tissue‐mimicking, stretchable neurotransmitter interfaces for monitoring the brain and gut.[8]
C9‐Functionalized Doxycycline Analogs as Drug Candidates to Prevent Pathological α‐Synuclein Aggregation and Neuroinflammation in Parkinson's Disease Degeneration
Authors: Rose Clémence , Tomas‐Grau Rodrigo Hernán , Zabala Brenda , Michel Patrick Pierre , Brunel Jean‐Michel , Chehín Rosana , Raisman‐Vozari Rita , Ferrié Laurent , Figadère Bruno 
Published: March 2024

AbstractDoxycycline, a semi‐synthetic tetracycline, is a widely used antibiotic for treating mild‐to‐moderate infections, including skin problems. However, its anti‐inflammatory and antioxidant properties, combined with its ability to interfere with α‐synuclein aggregation, make it an attractive candidate for repositioning in Parkinson's disease. Nevertheless, the antibiotic activity of doxycycline restricts its potential use for long‐term treatment of Parkinsonian patients. In the search for non‐antibiotic tetracyclines that could operate against Parkinson's disease pathomechanisms, eighteen novel doxycycline derivatives were designed. Specifically, the dimethyl‐amino group at C4 was reduced, resulting in limited antimicrobial activity, and several coupling reactions were performed at position C9 of the aromatic D ring, this position being one of the most reactive for introducing substituents. Using the Thioflavin‐T assay, we found seven compounds were more effective than doxycycline in inhibiting α‐synuclein aggregation. Furthermore, two of these derivatives exhibited better anti‐inflammatory effects than doxycycline in a culture system of microglial cells used to model Parkinson's disease neuroinflammatory processes. Overall, through structure‐activity relationship studies, we identified two newly designed tetracyclines as promising drug candidates for Parkinson's disease treatment.
Last Advances on Hydrogel Nanoparticles Composites in Medicine: An Overview with Focus on Gold Nanoparticles
Authors: Molinelli Alessandro , Schirato Andrea , Moretti Luca , Della Valle Giuseppe , Maiuri Margherita , Rossi Filippo 
Published: March 2024

AbstractHydrogel nanocomposites have lately taken part in the biomaterials scenario for several applications in the biomedical field, e. g., drug delivery, biosensing and cancer therapy. The inclusion of a broad variety of nanomaterials inside the hydrogel matrix leads to the successful development of hybrid platforms with superior and advantageous features. In this way, finely designed nano‐systems can be obtained, which are able to overcome the intrinsic limitations of conventional hydrogels, such as weak mechanical properties, burst drug delivery, extremely high hydrophilicity and lack of multifunctionality. This review aims to outline the last advances in the manufacturing of nanocomposite systems and their novel applications to the biomedical field, providing an overview of the most used nanoparticles with a special focus on gold nanoparticles.
Probing the Dynamic Landscape: From Static to Time‐Resolved X‐Ray Absorption Spectroscopy to Investigate Copper Redox Chemistry in Neurodegenerative Disorders
Authors: De Santis Emiliano , Alleva Stefania , Minicozzi Velia , Morante Silvia , Stellato Francesco 
Published: March 2024

AbstractCopper (Cu), with its ability to exist in various oxidation states, notably Cu(I) and Cu(II), plays a crucial role in diverse biological redox reactions. This includes its involvement in pathways associated with oxidative stress in neurodegenerative disorders such as Alzheimer's disease, Parkinson's disease, and Transmissible Spongiform Encephalopathies. This paper offers an overview of X‐ray Absorption Spectroscopy (XAS) studies designed to elucidate the interactions between Cu ions and proteins or peptides associated with these neurodegenerative diseases. The emphasis lies on XAS specificity, revealing the local coordination environment, and on its sensitivity to Cu oxidation states. Furthermore, the paper focuses on XAS applications targeting the characterization of intermediate reaction states and explores the opportunities arising from recent advancements in time‐resolved XAS at ultrabright synchrotron and Free Electron Laser radiation sources.
Perylene Diimide‐Based Dimeric Electron Acceptors with Molecular Conformations for Perovskite Solar Cells
Authors: Saltan Gözde Murat , Yeşil Tamer , Ötken Aysun Albayrak , Zafer Ceylan , Dinçalp Haluk 
Published: March 2024

AbstractThis paper reports five novel PDI dimer type electron transport materials (ETMs) employing o‐indoloquinoxaline (o‐Iq), m‐indoloquinoxaline (m‐Iq), and cibalackrot (Ci) groups as the core building blocks and presents the twisted structures of PDI dimers coded as PDI‐NHR‐o‐Iq, PDI‐o‐Iq, PDI‐NHR‐m‐Iq, PDI‐m‐Iq and PDI‐NHR‐Ci dyes (see Scheme 1 and 2). We have systematically compared their photophysical, electrochemical, and optoelectronic properties with respect to the reference dye (2PDI‐NHR), which is directly connected of two PDI planes. Their calculated HOMO‐LUMO energy levels are sufficient for charge transfer to the perovskite material so that structure‐photovoltaic performance relationship of synthesized ETM dyes can be evaluated. When the binding position of indoloquinoxaline group between PDI rings are changed from o‐ to m‐ positions, most of the photophysical and electrochemical properties of PDI dimer are dramatically changed, finally improving the photovoltaic performances.
Development and validation of a practical clinical risk prediction model for post‐endoscopic retrograde cholangiopancreatography pancreatitis
Authors: Meng Zhao Wu , Ruan Yibing , Fisher Stacey , Bishay Kirles , Chau Millie , Howarth Megan , Cartwright Shane , Chen Yen‐I , Dixon Elijah , Heitman Steven J. , Brenner Darren R. , Forbes Nauzer 
Published: March 2024

AbstractBackgroundPancreatitis following endoscopic retrograde cholangiopancreatography (ERCP) can lead to significant morbidity and mortality. We aimed to develop an accurate post‐ERCP pancreatitis risk prediction model using easily obtainable variables.MethodsUsing prospective multi‐center ERCP data, we performed logistic regression using stepwise selection on several patient‐, procedure‐, and endoscopist‐related factors that were determined a priori. The final model was based on a combination of the Bayesian information criterion and Akaike's information criterion performance, balancing the inclusion of clinically relevant variables and model parsimony. All available data were used for model development, with subsequent internal validation performed on bootstrapped data using 10‐fold cross‐validation.ResultsData from 3021 ERCPs were used to inform models. There were 151 cases of post‐ERCP pancreatitis (5.0% incidence). Variables included in the final model included female sex, pancreatic duct cannulation, native papilla status, pre‐cut sphincterotomy, increasing cannulation time, presence of biliary stricture, patient age, and placement of a pancreatic duct stent. The final model was discriminating, with a receiver operating characteristic curve statistic of 0.79, and well‐calibrated, with a predicted risk‐to‐observed risk ratio of 1.003.ConclusionsWe successfully developed and internally validated a promising post‐ERCP pancreatitis clinical prediction model using easily obtainable variables that are known at baseline or observed during the ERCP procedure. The model achieved an area under the curve of 0.79. External validation is planned as additional data becomes available.
An easily implemented single‐visit survey method for intermittently available and imperfectly detectable wildlife applied to the Florida east coast diamondback terrapin (Malaclemys terrapin tequesta)
Authors: Stolen Eric D. , Breininger David R. , Breininger Daniel J. , Breininger Robert D. 
Published: March 2024

AbstractSingle‐visit surveys of plots are often used for estimating the abundance of species of conservation concern. Less‐than‐perfect availability and detection of individuals can bias estimates if not properly accounted for. We developed field methods and a Bayesian model that accounts for availability and detection bias during single‐visit visual plot surveys. We used simulated data to test the accuracy of the method under a realistic range of generating parameters and applied the method to Florida's east coast diamondback terrapin in the Indian River Lagoon system, where they were formerly common but have declined in recent decades. Simulations demonstrated that the method produces unbiased abundance estimates under a wide range of conditions that can be expected to occur in such surveys. Using terrapins as an example we show how to include covariates and random effects to improve estimates and learn about species‐habitat relationships. Our method requires only counting individuals during short replicate surveys rather than keeping track of individual identity and is simple to implement in a variety of point count settings when individuals may be temporarily unavailable for observation. We provide examples in R and JAGS for implementing the model and to simulate and evaluate data to validate the application of the method under other study conditions.
On the distribution and habitat use of the sub‐Antarctic fly Hyadesimyia clausa Bigot (Diptera, Tachinidae) according to citizen science
Authors: Barahona‐Segovia Rodrigo M. , Mulieri Pablo R. , González Christian R. , Osorio Zúñiga Felipe , Pañinao‐Monsálvez Laura 
Published: March 2024

AbstractHyadesimyia clausa Bigot is a morphologically striking tachinid that inhabits the Sub‐Antarctic Ecoregion of the Magallanes Region in Chile and Tierra del Fuego province in Argentina. Much of the distributional information about this species is restricted to the Cape Horn islands, which have extreme environmental conditions, but the species' natural history, range limits, and habitat use have never been described or confirmed. Our goals were to describe the distributional limits of this sub‐Antarctic fly with the help of citizen science and use this information type to describe this tachinid's habitat use and potential biological interactions with nonvascular and vascular flora. We found that citizen science significantly increased our understanding of the extent of occurrence, expanding the known distributional range by 195 km to the north and 153 km to the west. On the contrary, the values for the area of occupancy were not significant, but the occupancy overlap between different records was very low. We confirmed that H. clausa's habitat uses peatlands and although we have not provided evidence of pollination or movement of spores, we hypothesized, that the walking activity of H. clausa could help move sperm from mosses and pollen from the flowers of vascular plants, so they could act as potential pollinators. Citizen science can reduce and eliminate some scientific knowledge shortfalls and propose new ecological questions that could increase our knowledge of extreme ecosystems.
Exchange Couplings and Magneto‐Structural Correlations of Trinuclear MII‐UIV‐MII (MII=Co, Ni, Cu) Complexes
Authors: Belkhiri Lotfi , Maurice Rémi , Le Guennic Boris , Boucekkine Abdou , Ephritikhine Michel 
Published: March 2024

AbstractThe magnetic properties of the trinuclear Schiff base complexes M2UL7 (MII=Co, Ni, Cu; L7=N,N’‐bis(3‐hydroxysalicylidene)‐2,2‐dimethyl‐1,3‐propanediamine), exhibiting the [M(μ‐O)2]2U core structure (3d‐5 f‐3d subsystem), have been investigated theoretically using scalar relativistic ZORA/DFT computations combined with the broken symmetry (BS) approach. The calculated coupling constants JMU between the adjacent M1−U and M2−U agree with the observed ferromagnetic (Ferro) character observed in the case of the Cu2UL7 complex, the antiferromagnetic (AF) character of the Ni2UL7 one is consistent with the experimentally observed AF behaviour for Co2UL7. The structural parameters, in particular the M−U distances and the M−Ob−U angles, as well as the electronic factors driving the superexchange couplings are discussed. The bond orders and the magnetic molecular orbital analyses reveal that the U(5 f) covalent contribution to the bonding within the M−O−U coordination is more important in the Co2UL7 and Ni2UL7 complexes than in the Cu2UL7 congener, thus favouring AF coupling between the transition metal and the uranium magnetic centers, in the first complexes. The analyses are supported by the study of the mixed ZnMUL7 and M2ThL7 systems, where the CoII (3d7) and NiII (3d8) paramagnetic ions are replaced by the diamagnetic ZnII(3d10) one, whereas in the second complex, the UIV(5f2) paramagnetic center is replaced by the diamagnetic ThIV(5f0) one. The Natural Populations Analyses confirm the crucial role of spin delocalization that is at work in favour of the AF vs. Ferro magnetic character of the M−U−M (M=Ni, Co) and Cu−U−Cu coordination, respectively.