bluuebunny/crossref_metadata_2025_split huggingface dataset:
Use of common cardiovascular disease drugs and risk of dementia: A case–control study in Swedish national register data
Authors: Ding Mozhu , Wennberg Alexandra M. , Engström Gunnar , Modig Karin 
Published: November 2024

AbstractINTRODUCTIONCardiovascular drug use may help prevent dementia; however, current evidence is mixed. Using a case–control design, we investigated the association between duration and combination of multiple cardiovascular drug classes and incident dementia.METHODSFrom the Swedish national registers, we included 88,065 incident dementia cases aged ≥ 70 at diagnosis between 2011 and 2016 and 880,650 age‐ and sex‐matched controls. Cardiovascular drug use was ascertained from the Prescribed Drug Register.RESULTSLong‐term users (≥ 5 years) of antihypertensives, diuretics, lipid‐lowering drugs (LLDs), and oral anticoagulants (OACs) had statistically significantly fewer dementia diagnoses (odds ratio [OR] 0.75–0.91) than non‐users. Antiplatelets use was associated with more dementia diagnoses (OR 1.13–1.25). Use of antihypertensives in combination with diuretics, LLDs, and OACs for ≥ 5 years was associated with fewer dementia diagnoses (OR 0.66–0.84).DISCUSSIONPreventing dementia via cardiovascular drug pathways may be possible. It is however important to consider the potential long‐term negative cognitive effect of antiplatelets.Highlights
Use ≥ 5 years of common cardiovascular drugs was associated with lower dementia risk.
Common cardiovascular drug combination use was associated with lower dementia risk.
Anti‐platelet use of any duration was associated with higher dementia risk.
Two‐Phase Perchlorate Activation Enabled by a Dinuclear Fe‐NHC (N‐Heterocyclic Carbene) Complex
Authors: Xu Xinyu , Hua Kai , Zhang Ming‐Tian 
Published: November 2024

AbstractPerchlorate, initially regarded as a weakly coordinating counterion rather than a reactive oxidizing reagent due to its kinetic stability, has garnered attention for its potential in microbial systems. Under anaerobic conditions, microbes utilize perchlorate as a terminal oxidant for methane oxidation, involving two distinct stages: extraction and release of oxidizing ability. This two‐phase activation process necessitates the collaborative action of multiple enzymes, a phenomenon not extensively explored in artificial systems. To address this issue, a dinuclear Fe‐NHC (N‐heterocyclic carbene) complex 1 was designed to enable the two‐phase activation of perchlorate. Initially, complex 1 extracts the oxidative potential of perchlorate, leading to the formation of Fe(III)‐O−Fe(III) complex 2 as the oxidation product. Subsequently, the extracted oxidative potential can be released by photolyzing a mixture of complex 2 and 9,10‐dihydroanthracene. In contrast to the commonly observed selectivity, the homocoupling product 5 was identified as the major product in this C−H activation reaction. Further, a catalytic C−H activation reaction is initiated under anaerobic conditions to selectively form the C−C coupling product, achieving the complete two‐phase activation of perchlorate using a single artificial catalyst. This work provides a new paradigm for constructing biomimetic anaerobic oxidation using kinetically inert high‐valent oxygenated acid anions as oxidants.
Exploiting High Order Magnetic Anisotropy for Advanced Magnetocaloric Refrigerants
Authors: Tacconi Leonardo , Manvell Anna S. , Briganti Matteo , Czernia Dominik , Weihe Høgni , Konieczny Piotr , Bendix Jesper , Perfetti Mauro 
Published: November 2024

AbstractThree new 3 d–4 f complexes of general formula trans‐[MF2(py)4][LnDOTA] (M=Cr3+ or Co3+, Ln=Dy3+ or Y3+, py=pyridine and DOTA=tetraazacyclododecane‐N,N′,N′′,N′′′‐tetraacetate) have been synthetised. The fluoride‐bridged systems were designed to achieve perfect tetragonal symmetry by combining four‐fold symmetric lanthanide and transition metal building blocks. From single crystal measurements, an unprecedented switch of the tetragonal anisotropy of the Dy3+ complexes has been observed. A combination of spectroscopic observations, magnetometry measurements and ab initio calculations allowed us to pinpoint the origin of this phenomenon, which is related to the peculiar energy level structure of the complexes. Moreover, the fourfold anisotropy of the complex has been exploited to design a rotating magnetocaloric experiment showing that tetragonal anisotropy holds great potential to engineer a new class of more efficient magnetic refrigerants.
A Carbazole‐Centered Expanded Helicene Stabilized with Hexabenzocoronene (HBC) Units
Authors: Wang Xin‐Yue , Bai Jinku , Shen Yun‐Jia , Li Zhi‐Ao , Gong Han‐Yuan 
Published: November 2024

AbstractThe synthesis and stabilization of heteroatom‐doped nanocarbon molecules, such as carbazole‐containing (super)helicenes, present significant challenges due to the complexities involved in maintaining structural integrity and electronic functionality. In this study, we successfully synthesized a carbazole‐centered expanded tris‐hexabenzo[7]helicene (1) via a facile FeCl3‐mediated Scholl coupling reaction. 1 exhibits both chemical and chiral stability and demonstrates fluorescence at 628 nm with a quantum yield of 0.40. Additionally, the enantiomers of 1 display pronounced chiroptical properties, including a distinct circular dichroism (CD) signal spanning from 300 to 600 nm. The absorption dissymmetry factor (|gabs|) is determined to be 2.98×10−3, while the circularly polarized luminescence brightness (BCPL) is measured as 32.50 M−1 cm−1.
Enantioselective Three‐Component α‐Allylic Alkylation of α‐Amino Esters by Synergistic Photoinduced Pd/Carbonyl Catalysis
Authors: Han Haohao , Yi Wuqi , Ding Shaojie , Ren Xinyi , Zhao Baoguo 
Published: November 2024

AbstractPhotoinduced excited‐state Pd catalysis has emerged as an intriguing strategy for unlocking new reactivity potential of simple substrates. However, the related transformations are still limited and the enantiocontrol remains challenging. Organocatalysis displays unique capability in substrate activation and stereocontrol. Combination of organocatalysis and photoinduced excited‐state Pd catalysis may provide opportunities to develop new enantioselective reactions from simple substrates. By applying cooperative triple catalysis including excited‐state Pd catalysis, ground‐state Pd catalysis, and carbonyl catalysis, we have successfully realized enantioselective α‐allylic alkylation of α‐amino esters with simple styrene and alkyl halide starting materials. The reaction allows rapid modular assembly of the three reaction partners into a variety of chiral quaternary α‐amino esters in good yields with 90–99 % ee, without protecting group manipulations at the active NH2 group. The cooperation of the chiral pyridoxal catalyst and the chiral phosphine ligand accounts for the excellent chirality induction.
Enhanced Chirality Transfer in Self‐Assembled Nanocomposites Powered by A Trace Amount of Chiral Dimeric Molecules
Authors: Bi Yuting , Zhang Zongze , Wei Jingjing , Yang Zhijie 
Published: November 2024

AbstractChiral‐selective self‐assembly has markedly advanced the development of chiral materials. While the Sergeant and Soldiers principle allows for chirality amplification, it necessitates precise shape‐matching between chiral and achiral molecules, leading to a low chirality transfer efficiency‐where one chiral molecule influences the chirality of a limited number of achiral molecules. Here, we show that this efficiency can be markedly enhanced by introducing chiral dimeric molecules. In this work, a single chiral molecule can control the chirality of up to 200 achiral molecules and even direct the assembly of inorganic nanoparticles into chiral nanocomposites through a sequential chirality transfer process. Moreover, this approach exhibits remarkable robustness, operating effectively without necessitating a precise match between chiral and achiral molecules. Consequently, using the same chiral molecules at an exceptionally low molar fraction (0.5 mol %) allows for the chiral‐selective assembly of achiral molecules over a broad spectrum, regardless of their packing habits, thus facilitating the creation of otherwise inaccessible chiral materials with modulated chiroptical properties. Last but not least, even a trace amount of chiral molecules can enhance the elastic modulus of the self‐assembled nanocomposites by a factor of eight.
A Base‐Free Two‐Coordinate Oxoborane
Authors: Millet Clement R. P. , Willcox Dominic R. , Nichol Gary S. , Anstöter Cate S. , Ingleson Michael J. 
Published: November 2024

AbstractOxoboranes (R‐BO) are transient species that rapidly trimerise to form boroxines. To date, the only method used to stabilise oxoboranes is to add a Lewis base, but this forms a three‐coordinate at boron oxoborane that has a different bonding/reactivity profile. Herein we report a base‐free, two‐coordinate oxoborane that is isolated as a Lewis adduct with AlCl3. This species, Mes*BO‐AlCl3 (Mes*=2,4,6‐tBu‐C6H2), has a ν11ΒΟ stretching frequency of 1843 cm−1, indicating a strong BO bond. Computational analysis indicates this is due to a highly polarised BO bonding interaction combined with modest BO multiple bond character. While the polarisation of the BO bond on AlCl3 coordination enhances the Lewis acidity at boron it also reduces the basicity at oxygen and the latter is key to accessing a base‐free oxoborane. Finally, this oxoborane reacts with PhN3 in a unique way to form an unprecedented boron heterocycle.
Modulating Room‐Temperature Phosphorescence of Phenothiazine Dioxide via External Heavy Atoms
Authors: Li Heyang , Ma Huili , Zhang Peng , An Zhongfu , He Xiaoming 
Published: November 2024

AbstractDeveloping pure organic materials with ultralong lifetimes and balanced quantum efficiency is attractive but challenging. In this study, we propose a novel strategy to investigate external heavy atoms by linking molecular emitters with halogen through a flexible alkyl chain. X‐ray crystal analysis clearly reveal the halogen C−X‐π interactions, which can be tuned by halogen donors, as well as the distance and geometry between them. Impressively, DOPTZ‐C3Cl featuring a chloride atom as donor, exhibits a balanced long phosphorescence lifetime of 1351 ms and a phosphorescence quantum yield of 10.1 %. We also first demonstrate that Cl can induce more positive effect than heavier halogens (Br and I) on prolonging the lifetime. We envisage that the present study will expedite new molecular design to manipulate the room temperature phosphorescence via external heavy atom effect, and highlight a special C−Cl⋅⋅⋅π interaction for the development of ultralong phosphorescent materials.
Proton Relays in Molecular Catalysis for Hydrogen Evolution and Oxidation: Lessons From the Mimicry of Hydrogenases and Electrochemical Kinetic Analyses
Authors: Haake Matthieu , Reuillard Bertrand , Chavarot‐Kerlidou Murielle , Costentin Cyrille , Artero Vincent 
Published: November 2024

AbstractThe active sites of metalloenzymes involved in small molecules activation often contain pendant bases that act as proton relay promoting proton‐coupled electron‐transfer processes. Here we focus on hydrogenases and on the reactions they catalyze, i. e. the hydrogen evolution and oxidation reactions. After a short description of these enzymes, we review some of the various biomimetic and bioinspired molecular systems that contain proton relays. We then provide the formal electrochemical framework required to decipher the key role of such proton relay to enhance catalysis in a single direction and discuss the few systems active for H2 evolution for which quantitative kinetic data are available. We finally highlight key parameters required to reach bidirectional catalysis (both hydrogen evolution and hydrogen oxidation catalyzed) and then transition to reversible catalysis (both reactions catalyzed in a narrow potential range) as well as illustrate these features on few systems from the literature.
Modular Design and Scaffold‐Synthesis of Multi‐Functional Fluorophores for Targeted Cellular Imaging and Pyroptosis
Authors: Zhang Lei , Wang Chunhui , Li Yuanyuan , Wang Haiyang , Sun Kunhui , Lu Siyu , Wang Yahui , Jing Su , Cordes Thorben 
Published: November 2024

AbstractFluorophores are essential tools for optical imaging and biomedical research. Their synthetic modification to incorporate new functions, however, remains a challenging task. Conventional strategies rely on linear synthesis in which a parent framework is gradually extended. We here designed and synthesized a versatile library of multi‐functional fluorophores via a scaffold‐based Ugi four‐component reaction (U‐4CR). The adaptability of the scaffold is achieved through modification of starting materials. This allows to use a small range of starting materials for the creation of fluorogenic probes that can detect reactive‐oxygen species and where the localization into subcellular organelles or membranes can be controlled. We present reaction yields ranging from 60 % to 90 % and discovered that some compounds can even function as imaging and therapeutic agents via Fenton chemistry inducing pyroptosis in living cancer cells. Our study underlines the potential of scaffold‐based synthesis for versatile creation of functional fluorophores and their applications.
Direct Regeneration of Industrial LiFePO4 Black Mass Through A Glycerol‐Enabled Granule Reconstruction Strategy
Authors: Feng Chengzhi , Cao Yang , Song Lixian , Zhao Bo , Yang Qin , Zhang Yaping , Wei Xijun , Zhou Guangmin , Song Yingze 
Published: November 2024

AbstractWith the increasing sales of electric vehicles, lots of spent lithium‐ion batteries (LIBs) assembled with LiFePO4 (LFP) cathodes will retire in the next few years, posing a significant challenge for their effective and environmentally‐friendly recycling. The main reason why spent LFP cathodes fail to re‐utilize lies in the lattice defects caused by lithium loss and structural defects resulting from stress accumulation. In this work, we propose an in situ granule reconstruction strategy to directly regenerate spent LFP black mass (S−BM) using glycerol in industry settings. The hydroxyl groups abundant in glycerol serves as electron donor that help reduce Fe (III) and repair Fe−Li antisite defects (FeLi). Additionally, the chelating properties of glycerol intervene with structurally disintegrated particles, inhibiting Oswald ripening effect and promoting bonding of grain boundaries to generate lamellar microcrystals with homogeneous grain size, recover their morphology and crystal structure after a facile annealing procedure. Furthermore, the regenerated LFP restores Fe−O bonds which further inhibits structural distortion and improve Li+ migration kinetics. As a result, the regenerated industrial LFP black mass (R−BM) exhibits superior lithium storage performance with a discharge capacity of 123.2 mA h g−1 after 500 cycles at 5.0 C (a capacity retention rate of 93.1 %).
Aptamer and DNAzyme Based Colorimetric Biosensors for Pathogen Detection
Authors: Liu Rudi , Li Jiuxing , Salena Bruno J. , Li Yingfu 
Published: November 2024

AbstractThe detection of pathogens is critical for preventing and controlling health hazards across clinical, environmental, and food safety sectors. Functional nucleic acids (FNAs), such as aptamers and DNAzymes, have emerged as versatile molecular tools for pathogen detection due to their high specificity and affinity. This review focuses on the in vitro selection of FNAs for pathogens, with emphasis on the selection of aptamers for specific biomarkers and intact pathogens, including bacteria and viruses. Additionally, the selection of DNAzymes for bacterial detection is discussed. The integration of these FNAs into colorimetric biosensors has enabled the development of simple, cost‐effective diagnostic platforms. Both non‐catalytic and catalytic colorimetric biosensors are explored, including those based on gold nanoparticles, polydiacetylenes, protein enzymes, G‐quadruplexes, and nanozymes. These biosensors offer visible detection through color changes, making them ideal for point‐of‐care diagnostics. The review concludes by highlighting current challenges and future perspectives for advancing FNA‐based colorimetric biosensing technologies for pathogen detection.
Synthesis and Functionalization of Sulfoximine‐Bicyclo[1.1.0]butanes: Functionalizable, Tuneable and Cysteine‐Selective Chiral Warheads
Authors: Zhong Zhenhao , Hocking Brad J. W. , Brown Charles P. , Ma Tsz‐Kan , White Andrew J. P. , Mann David J. , Armstrong Alan , Bull James A. 
Published: November 2024

AbstractElectrophilic covalent warheads with appropriate reactivity and selectivity are crucial to the investigation of protein function and the discovery of therapeutics. Here we report the synthesis of sulfoximine bicyclo[1.1.0] butanes (BCBs) as novel thiol reactive chiral warheads, achieved in one‐pot from methylsulfoximines. Unusually the warhead can then be derivatized, keeping the BCB intact, over 3 vectors: i) sulfoximine N‐modification instills a broad range of strain‐release reactivity; ii) sp2‐cross‐coupling reactions on aryl‐BCB‐sulfoximines allows direct diversification, and iii) functionalization of the BCB motif itself is achieved by metalation and trapping with electrophiles. The BCB sulfoximines are shown to react selectively with cysteine including in a protein model (CDK2) under biocompatible conditions. Preliminary data indicate suitability for chemoproteomic applications, and enantioselective cysteine‐labelling. The reactivity of sulfoximine BCBs with electron withdrawing groups on nitrogen is comparable to acrylamides with low to moderate reactivity.
Synthesis of Iron(IV) Alkynylide Complexes and Their Reactivity to Form 1,3‐Diynes
Authors: Souilah Charafa , Jannuzzi Sergio A. V. , Becker Felix J. , Demirbas Derya , Jenisch Daniel , Ivlev Sergei , Xie Xiulan , Peredkov Sergey , Lichtenberg Crispin , DeBeer Serena , Casitas Alicia 
Published: November 2024

AbstractThe isolation of thermally unstable and highly reactive organoiron(IV) complexes is a challenge for synthetic chemists. In particular, the number of examples where the C‐based ligand is not part of the chelating ligand remains scarce. These compounds are of interest because they could pave the way to designing catalytic cycles of bond forming reactions proceeding via organoiron(IV) intermediates. Herein, we report the synthesis and characterization, including single‐crystal X‐ray diffraction, of a family of alkynylferrates(III) and Fe(IV) alkynylide complexes. The alkynylferrates(III) are formed by transmetalation of the Fe(III) precursor [(N3N’)FeIII] (N3N’3− is tris(N‐tert‐butyldimethylsilyl‐2‐amidoethyl)amine) with lithium alkynylides, and their further one‐electron oxidation enables the synthesis of the corresponding Fe(IV) alkynylides. The electronic structure of this family of organometallic Fe(III) and Fe(IV) complexes has been thoroughly investigated by spectroscopic methods (EPR, NMR, 57Fe Mössbauer, X‐Ray absorption (XAS) and emission (XES) spectroscopies) and theoretical calculations. While alkynylferrates(III) are sluggish to engage into C−C bond forming processes, the Fe(IV) alkynylides react to afford 1,3‐diynes at room temperature. A bimolecular reductive elimination from a bimetallic Fe(IV) intermediate to form the 1,3‐diynes is proposed based on the mechanistic investigations performed.
Rhodolith Beds in a Shifting World: A Palaeontological Perspective
Authors: Aguirre Julio , Braga Juan C. 
Published: November 2024

ABSTRACTThe occurrence of rhodolith beds in the stratigraphic record from the Cretaceous to the Pleistocene was analysed from published papers. Most data refer to low–mid latitude records of rhodolith beds described in the Tethyan–Paratethyan–Mediterranean domain. The first putative rhodolith beds are from Albian (uppermost Lower Cretaceous) deposits. These rhodolith beds are made up mostly of unattached loose branching corallines as well as of nodular structures. From the Coniacian (Upper Cretaceous) to the Langhian (Middle Miocene), abundance of rhodolith beds shows a generally increasing fluctuating trend with two significant expansions in the Priabonian (late Eocene) and during the Aquitanian–Langhian (Early‐Middle Miocene). After the Langhian maximum, rhodolith beds sharply declined to a minimum in the Zanclean (Early Pliocene). During the Pleistocene, they recovered to values similar to those reached in the Langhian. The general increase in rhodolith beds up the Langhian maximum correlates well with global temperature and pCO2 declines and with an ocean pH increase. The tectonic activity leading to important palaeogeographic changes in the Tethyan–Parathetyan–Mediterranean realm might account for the Serravallian–Zanclean downfall of rhodolith‐dominated deposits. The Cretaceous–Pleistocene record of rhodolith beds shows that these ecosystems withstood successfully a highly changing world. The rapid acclimation of particular taxa to environmental changes and the variable reaction of taxa distributed at different water depths can be crucial to understand their success. In this regard, it would be interesting to analyse how different taxa in modern deep rhodolith beds respond to changing oceanic conditions.
Refocusing graduate gross anatomy training: Curating future content experts
Authors: Elliott Gail , Pinhal‐Enfield Grace 
Published: November 2024

AbstractGraduate anatomy courses should be designed based on several needs. These include preparation for how to study in medical school and other healthcare programs, integrating multiple ways of engaging with the material, including repetition for long‐term retention, and training of anatomy educators. Our graduate anatomy course presents an example of a balanced course structure that caters to the varying needs of different learners and encourages interest in anatomy education as a profession. By refocusing graduate gross anatomy training, we aim to support learners pursuing fields that utilize anatomy, including healthcare professions as well as future content experts to address the shortage of qualified anatomy educators.
Injectable Hydrogels for Liver: Potential for Clinical Translation
Authors: Vasudevan Ashwini , Ghosal Doyel , Ram Sahu Sita , Kumar Jha Narsing , Vijayaraghavan Pooja , Kumar Sachin , Kaur Savneet 
Published: November 2024

AbstractInjectable hydrogels are a sub‐type of hydrogels which can be delivered into the host in a minimally invasive manner. They can act as carriers to encapsulate and deliver cells, drugs or active biomolecules across several disease conditions. Polymers, either synthetic or natural, or even a combination of the two, can be used to create injectable hydrogels. Clinically approved injectable hydrogels are being used as dressings for burn wounds, bone and cartilage reconstruction. Injectable hydrogels have recently gained tremendous attention for their delivery into the liver in pre‐clinical models. However, their efficacy in clinical studies remains yet to be established. In this article, we describe principles for the design of these injectable hydrogels, delivery strategies and their potential applications in facilitating liver regeneration and ameliorating injury. We also discuss the several constraints related to translation of these hydrogels into clinical settings for liver diseases and deliberate some potential solutions to combat these challenges.