bluuebunny/crossref_metadata_2025_split huggingface dataset:
MicroRNA expression in extracellular vesicles as a novel blood‐based biomarker for Alzheimer's disease
Authors: Kumar Ashish , Su Yixin , Sharma Mitu , Singh Sangeeta , Kim Susy , Peavey Jeremy J. , Suerken Cynthia K. , Lockhart Samuel N. , Whitlow Christopher T. , Craft Suzanne , Hughes Timothy M. , Deep Gagan 
Published: April 2023

AbstractINTRODUCTIONBrain cell–derived small extracellular vesicles (sEVs) in blood offer unique cellular and molecular information related to the onset and progression of Alzheimer's disease (AD). We simultaneously enriched six specific sEV subtypes from the plasma and analyzed a selected panel of microRNAs (miRNAs) in older adults with/without cognitive impairment.METHODSTotal sEVs were isolated from the plasma of participants with normal cognition (CN; n = 11), mild cognitive impairment (MCI; n = 11), MCI conversion to AD dementia (MCI‐AD; n = 6), and AD dementia (n = 11). Various brain cell–derived sEVs (from neurons, astrocytes, microglia, oligodendrocytes, pericytes, and endothelial cells) were enriched and analyzed for specific miRNAs.RESULTSmiRNAs in sEV subtypes differentially expressed in MCI, MCI‐AD, and AD dementia compared to the CN group clearly distinguished dementia status, with an area under the curve (AUC) > 0.90 and correlated with the temporal cortical region thickness on magnetic resonance imaging (MRI).DISCUSSIONmiRNA analyses in specific sEVs could serve as a novel blood‐based molecular biomarker for AD.Highlights
Multiple brain cell–derived small extracellular vesicles (sEVs) could be isolated simultaneously from blood.
MicroRNA (miRNA) expression in sEVs could detect Alzheimer's disease (AD) with high specificity and sensitivity.
miRNA expression in sEVs correlated with cortical region thickness on magnetic resonance imaging (MRI).
Altered expression of miRNAs in sEVCD31 and sEVPDGFRβ suggested vascular dysfunction.
miRNA expression in sEVs could predict the activation state of specific brain cell types.
Altered limbic functional connectivity in individuals with subjective cognitive decline: Converging and diverging findings across Chinese and German cohorts
Authors: Jiang Xueyan , Hu Xiaochen , Daamen Marcel , Wang Xiaoqi , Fan Chunqiu , Meiberth Dix , Spottke Annika , Roeske Sandra , Fliessbach Klaus , Spruth Eike Jakob , Altenstein Slawek , Lohse Andrea , Hansen Niels , Glanz Wenzel , Incesoy Enise I. , Dobisch Laura , Janowitz Daniel , Rauchmann Boris‐Stephan , Ramirez Alfredo , Kilimann Ingo , Munk Matthias H. , Wang Xiao , Schneider Luisa‐Sophie , Gabelin Tatjana , Roy Nina , Wolfsgruber Steffen , Kleineidam Luca , Hetzer Stefan , Dechent Peter , Ewers Michael , Scheffler Klaus , Amthauer Holger , Buchert Ralph , Essler Markus , Drzezga Alexander , Rominger Axel , Krause Bernd J. , Reimold Matthias , Priller Josef , Schneider Anja , Wiltfang Jens , Buerger Katharina , Perneczky Robert , Teipel Stefan , Laske Christoph , Peters Oliver , Düzel Emrah , Wagner Michael , Jiang Jiehui , Jessen Frank , Boecker Henning , Han Ying 
Published: April 2023

AbstractINTRODUCTIONIt remains unclear whether functional brain networks are consistently altered in individuals with subjective cognitive decline (SCD) of diverse ethnic and cultural backgrounds and whether the network alterations are associated with an amyloid burden.METHODSCross‐sectional resting‐state functional magnetic resonance imaging connectivity (FC) and amyloid‐positron emission tomography (PET) data from the Chinese Sino Longitudinal Study on Cognitive Decline and German DZNE Longitudinal Cognitive Impairment and Dementia cohorts were analyzed.RESULTSLimbic FC, particularly hippocampal connectivity with right insula, was consistently higher in SCD than in controls, and correlated with SCD‐plus features. Smaller SCD subcohorts with PET showed inconsistent amyloid positivity rates and FC–amyloid associations across cohorts.DISCUSSIONOur results suggest an early adaptation of the limbic network in SCD, which may reflect increased awareness of cognitive decline, irrespective of amyloid pathology. Different amyloid positivity rates may indicate a heterogeneous underlying etiology in Eastern and Western SCD cohorts when applying current research criteria. Future studies should identify culture‐specific features to enrich preclinical Alzheimer's disease in non‐Western populations.Highlights
Common limbic hyperconnectivity across Chinese and German subjective cognitive decline (SCD) cohorts was observed.
Limbic hyperconnectivity may reflect awareness of cognition, irrespective of amyloid load.
Further cross‐cultural harmonization of SCD regarding Alzheimer's disease pathology is required.
Evolutionary Algorithm Directed Synthesis of Mixed Anion Compounds LaF2X (X=Br, I) and LaFI2
Authors: Kato Daichi , Song Peng , Ubukata Hiroki , Taguro Haruki , Tassel Cédric , Miyazaki Kohei , Abe Takeshi , Nakano Kousuke , Hongo Kenta , Maezono Ryo , Kageyama Hiroshi 
Published: April 2023

AbstractMixed‐anion compounds have attracted growing attentions, but their synthesis is challenging, making a rational search desirable. Here, we explored LaF3‐LaX3 (X=Cl, Br, I) system using ab initio structure searches based on evolutionary algorithms, and predicted LaF2X and LaFX2 (X=Br, I), which are respectively isostructural with LaHBr2 and YH2I, consisting of layered La‐F blocks with single and double ordered honeycomb lattices, separated by van der Waals gaps. We successfully synthesized these compounds: LaF2Br and LaFI2 crystallize in the predicted structure, while LaF2I is similar to the predicted one but with different layer stacking. LaF2I exhibits fluoride ion conductivity comparable to that of non‐doped LaF3, and has the potential to show better ionic conductivity upon appropriate doping, given the theoretically lower diffusion energy barrier and the presence of soft iodine anions. This study shows the structure prediction using evolutionary algorithms will accelerate the discovery of mixed‐anion compounds in future, in particular those with an ordered anion arrangement.
NIR‐Absorbing B,N‐Heteroarene as Photosensitizer for High‐Performance NIR‐to‐Blue Triplet‐Triplet Annihilation Upconversion
Authors: Li Ji‐Kun , Zhang Ming‐Yu , Zeng Le , Huang Ling , Wang Xiao‐Ye 
Published: April 2023

AbstractTriplet‐triplet annihilation upconversion (TTA‐UC) with near‐infrared (NIR) photosensitizers is highly desirable for a variety of emerging applications. However, the development of NIR‐to‐blue TTA‐UC with a large anti‐Stokes shift is extremely challenging because of the energy loss during the intersystem crossing (ISC). Here, we develop the first NIR‐absorbing B,N‐heteroarene‐based sensitizer (BNS) with multi‐resonance thermally activated delayed fluorescence (MR‐TADF) characters to achieve efficient NIR‐to‐blue TTA‐UC. The small energy gap between the singlet and triplet excited states (0.14 eV) of BNS suppresses the ISC energy loss, and its long‐delayed fluorescence lifetime (115 μs) contributes to efficient triplet energy transfer. As a result, the largest anti‐Stokes shift (1.03 eV) among all heavy‐atom‐free NIR‐activatable TTA‐UC systems is obtained with a high TTA‐UC quantum yield of 2.9 % (upper limit 50 %).
Preserving Macroporosity in Type III Porous Liquids
Authors: Dai Dejun , Luo Lianshun , Zhu Qinlin , Wang Dongxu , Li Tao 
Published: April 2023

AbstractPreserving large permanent pore structures in a fluid may endow conventional liquids with emergent physical properties. However, such materials are challenging to make because of the tendency of the pores to be filled and occupied by the solvent molecules. Here, we report the design and synthesis of the first Type III porous liquid (PL) containing uniform yet stable 480 nm cavities. This was achieved by first constructing a single crystalline hollow metal–organic framework (MOF), UiO‐66‐NH2, through chemical etching. The thin yet defect‐free MOF shell effectively excludes the bulky poly(dimethylsiloxane) solvent molecules from entering the cavity through its 4 Å aperture, resulting in the preservation of both micro‐ and macroporosity in the PL. These enormous void spaces allow the PL to reversibly host and release up to 27 wt % water for up to 10 cycles. The switching between the “dry” state and the “wet” state led to a large changes of the thermal conductivity of the PL from 0.140 to 0.256 W m−1 K−1, affording a guest‐responsive liquid thermal switch with a switching ratio of 1.8.
Modulation of Colloidal Assembly Behavior Enables Printable Low‐Dimensional Perovskite Photovoltaics
Authors: Xing Zhi , Meng Xiangchuan , Li Dengxue , Zhang Yanyan , Fan Baojin , Huang Zengqi , Wang Fuyi , Hu Xiaotian , Hu Ting , Chen Yiwang 
Published: April 2023

AbstractThe multiple quantum wells (QWs) distribution in low‐dimensional perovskite films hinders charge transport due to the fundamental difficulty of controlling crystal growth from precursor solutions, yielding poorly homogeneous low‐dimensional perovskite solar cells (PSCs), especially in upscaling fabrication. Here, efficient low‐dimensional PSCs are realized by modulating the colloidal assembly behavior in the precursor solution to induce intermediate structures. In combination with in situ liquid time‐of‐flight secondary ion mass spectrometry, the assembly behavior of organic cations involved lead iodide‐dominated colloidal soft framework is visualized by investigating the precursor species differences under hydrogen bonding interactions. Subsequently, solid‐state reactions emerge and the formamidine (FA)‐based perovskite films exhibit significantly suppressed multiple QWs distribution. Encouragingly, the FA device (n=9, by meniscus‐assisted coating) achieves a power conversion efficiency (PCE) of 20.28 % for a size of 0.04 cm2 and a PCE of 15.35 % for a mini‐module of 16.94 cm2 with superior stability.
Fluorescence Enhancement of a Metal‐Organic Framework for Ultra‐Efficient Detection of Trace Benzene Vapor
Authors: Li Wen‐Bin , Wu Ying , Zhong Xiao‐Feng , Chen Xiong‐Hai , Liang Gang , Ye Jia‐Wen , Mo Zong‐Wen , Chen Xiao‐Ming 
Published: April 2023

AbstractIndoor detection of volatile organic compounds (VOCs) concentration is necessary due to the serious toxicity hazards even at trace level. However, physisorbents usually exhibit weak interactions especially in the presence of trace concentrations of VOCs, thus exhibiting poor responsive signal. Herein, we report a new flexible metal–organic framework (MOF) that exhibits interesting pore‐opening behavior after immersing in H2O. The pore‐opening phase shows significant (≈116 folds) and extremely fast (<1 minute) fluorescence enhancement after being exposed to saturated benzene vapor. The limit of detection concentration for benzene vapor can be calculated as 0.133 mg L−1. Thus this material represents the first MOF to achieve visual detection of trace benzene vapor by the naked eyes. Theoretical calculations and single‐crystal structure reveal that the special “bilateral π–π stacking” interactions between the host and guest, which facilitate electron transfer and greatly enhance the intensity of fluorescence.
Levocetirizin‐Dihydrochlorid: Die Aufklärung einer lang verborgenen Struktur mittels Elektronenbeugung
Authors: Karothu Durga Prasad , Alhaddad Zainab , Göb Christian R. , Schürmann Christian J. , Bücker Robert , Naumov Panče 
Published: April 2023

AbstractLevocetirizin ist ein oral verabreichtes Antihistaminikum der zweiten Generation, dass seit über 25 Jahren zur Behandlung von Allergiesymptomen und langanhaltender Nesselsucht eingesetzt wird. Trotz der weiten Verbreitung dieser Verbindung war ihre Kristallstruktur bisher unbekannt. Hier berichten wir über die Anwendung der 3D‐Elektronenbeugung (3D ED)/Mikrokristallbeugung (MicroED) zur Bestimmung der Kristallstruktur von Levocetirizindihydrochlorid direkt aus kristallinen Pulvern, handelsüblicher Tabletten, die diese Verbindung enthalten. Weiterhin zeigen wir auch den Nutzen der dynamischen Verfeinerung zur eindeutigen Zuordnung der absoluten Konfiguration. Die Ergebnisse unterstreichen das immense Potenzial der 3D‐ED/MicroED für die Strukturaufklärung von Komponenten mikrokristalliner Gemische, wodurch sich die Züchtung großer Einkristalle und der Einsatz ergänzender Analysetechniken erübrigt. Dies wird nicht nur dazu beitragen, dass die Methode für die Identifizierung, sondern auch für die primäre strukturelle Charakterisierung neuer Verbindungen in Zukunft an Bedeutung gewinnt.
Realizing Abundant Chirality Inversion of Supramolecular Nanohelices by Multiply Manipulating the Binding Sites in Molecular Blocks
Authors: Gao Laiben , Dou Xiaoqiu , Xing Chao , Gao Fengli , Jiang Zichao , Yang Kaikai , Zhao Changli , Feng Chuanliang 
Published: April 2023

AbstractThe induction of diverse chirality regulation in nature by multiple binding sites of biomolecules is ubiquitous and plays an essential role in determining the biofunction of biosystems. However, mimicking this biological phenomenon and understanding at a molecular level its mechanism with the multiple binding sites by establishing an artificial system still remains a challenge. Herein, abundant chirality inversion is achieved by precisely and multiply manipulating the co‐assembled binding sites of phenylalanine derivatives (D/LPPF) with different naphthalene derivatives (NA, NC, NP, NF). The amide and hydroxy group of naphthalene derivatives prefer to bind with the carboxy group of LPPF, while carboxylic groups and fluoride atoms tend to bind with the amide moiety of LPPF. All these diverse interaction modes can precisely trigger helicity inversion of LPPF nanofibers. In addition, synergistically manipulating the carboxy and amide binding sites from a single LPPF molecule to simultaneously interact with different naphthalene derivatives leads to chirality regulation. Typically, varying the solvent may switch the interaction modes and the switched new interaction modes can be employed to further regulate the chirality of the LPPF nanofibers. This study may provide a novel approach to explore chirality diversity in artificial systems by regulating the intermolecular binding sites.
Sculpting In‐plane Fractal Porous Patterns in Two‐Dimensional MOF Nanocrystals for Photoelectrocatalytic CO2 Reduction
Authors: Dutta Soumen , Gurumoorthi Akshay , Lee Shinbi , Jang Sun Woo , Kumari Nitee , Hong Yu‐Rim , Choi Wonyong , Son Chang Yun , Lee In Su 
Published: April 2023

AbstractHerein, by choosing few‐nm‐thin two‐dimensional (2D) nanocrystals of MOF‐5 containing in‐planner square lattices as a modular platform, a crystal lattice‐guided wet‐chemical etching has been rationally accomplished. As a result, two attractive pore patterns carrying Euclidean curvatures; precisely, plus(+)‐shaped and fractal‐patterned pores via ⟨100⟩ and ⟨110⟩ directional etching, respectively, are regulated in contrast to habitually formed spherical‐shaped random etches on MOF surface. In agreement with the theoretical calculations, a diffusion‐limited etching process has been optimized to devise high‐yield of size‐tunable fractal‐pores on the MOF surface that tenders for a compatibly high payload of catalytic ReI‐complexes using the existing large edge area once modified into a free amine‐group‐exposed inner pore surface. Finally, on benefiting from the long‐range fractal opening in 2D MOF support structure, while loaded on an electrode surface, a facilitated cross‐interface charge‐transportation and well‐exposure of immobilized ReI‐catalysts are anticipated, thus realizing enhanced activity and stability of the supported catalyst in photoelectrochemical CO2‐to‐CO reduction.
Bifunctional Interphase with Target‐Distributed Desolvation Sites and Directionally Depositional Ion Flux for Sustainable Zinc Anode
Authors: Zhang Ruochen , Feng Yang , Ni Youxuan , Zhong Beidou , Peng Maoyu , Sun Tianjiang , Chen Shan , Wang Huan , Tao Zhanliang , Zhang Kai 
Published: April 2023

AbstractAqueous zinc batteries (AZBs) feature high safety and low cost, but intricate anodic side reactions and dendrite growth severely restrict their commercialization. Herein, ethylenediaminetetraacetic acid (EDTA) grafted metal organic framework (MOF‐E) is proposed as a dually‐functional anodic interphase for sustainable Zn anode. Specifically, the target‐distributed EDTA serves as an ion‐trapped tentacle to accelerate the desolvation and ionic transport by powerful chemical coordination, while the MOFs offer suitable ionic channels to induce oriented deposition. As a result, MOF‐E interphase fundamentally suppresses side reactions and guides horizontally arranged Zn deposition with (002) preferred orientations. The Zn|MOF‐E@Cu cell exhibits a markedly improved Coulombic efficiency of 99.7 % over 2500 cycles, and the MOF‐E@Zn|KVOH (KV12O30‐y ⋅ nH2O) cell yields a steady circulation of 5000 cycles@90.47 % at 8 A g−1.
Thioethers as Dichotomous Electrophiles for Site‐Selective Silylation via C−S Bond Cleavage
Authors: Chen Shuai , Guo Xueying , Hou Haoran , Geng Shasha , Liu Zhengli , He Yun , Xue Xiao‐Song , Feng Zhang 
Published: April 2023

AbstractThe development of aryl alkyl sulfides as dichotomous electrophiles for site‐selective silylation via C−S bond cleavage has been achieved. Iron‐catalyzed selective cleavage of C(aryl)−S bonds can occur in the presence of β‐diketimine ligands, and the cleavage of C(alkyl)−S bonds can be achieved by t‐BuONa without the use of transition metals, resulting in the corresponding silylated products in moderate to excellent yields. Mechanistic studies suggest that Fe−Si species may undergo metathesis reactions during the cleavage of C(aryl)−S bonds, while silyl radicals are involved during the cleavage of C(alkyl)−S bonds.
Vibrational Circular Dichroism Spectroscopy of Chiral Molecular Crystals: Insights from Theory
Authors: Jähnigen Sascha 
Published: April 2023

AbstractChirality is a curious phenomenon that appears in various forms. While the concept of molecular (RS‐)chirality is ubiquitous in chemistry, there are also more intricate forms of structural chirality. One of them is the enantiomorphism of crystals, especially molecular crystals, that describes the lack of mirror symmetry in the unit cell. Its relation to molecular chirality is not obvious, but still an open question, which can be addressed with chiroptical tools. Vibrational circular dichroism (VCD) denotes chiral infrared (IR) spectroscopy that is susceptible to both, the molecular as well as the intermolecular space by means of vibrational transitions. When carried out in the solid state, VCD delivers a very rich set of non‐local contributions that are determined by crystal packing and collective motion. Since its discovery in the 1970s, VCD has become the method of choice for the determination of absolute configurations, but its applicability reaches beyond towards the study of different crystal forms and polymorphism. This brief review summarises the theoretical concepts of crystal chirality and how computations of solid‐state VCD can shed light into the intimate connection of chiral structure and vibrational optical activity.
The Elusive Structure of Levocetirizine Dihydrochloride Determined by Electron Diffraction
Authors: Karothu Durga Prasad , Alhaddad Zainab , Göb Christian R. , Schürmann Christian J. , Bücker Robert , Naumov Panče 
Published: April 2023

AbstractLevocetirizine is an orally administrated, second‐generation antihistaminic active pharmaceutical ingredient that has been used to treat symptoms of allergy and long‐term hives for over 25 years. Despite the wide use of this compound, its crystal structure has remained unknown. Here we report the application of 3D electron diffraction (3D ED)/Micro‐crystal electron diffraction (MicroED) to determine the crystal structure of Levocetirizine dihydrochloride directly from crystalline powders that were extracted from commercially available tablets containing the compound. We also showcase the utility of dynamical refinement to unambiguously assign absolute configuration. The results highlight the immense potential of 3D ED/MicroED for structure elucidation of components of microcrystalline mixtures that obviates the need to grow large‐size single crystals and the use of complementary analytical techniques, which could be important for identification as well as for primary structural characterization.
Synthesis and properties of water‐dispersible polyurethanes based on various diisocyanates and PEG as the hard segment
Authors: Oprea Stefan , Potolinca Violeta Otilia 
Published: April 2023

AbstractWater‐dispersible polyurethanes are a greener alternative to polyurethane solutions in organic solvents. Various polyurethane materials were prepared by a two‐step polymerization procedure of polypropylene glycol with Mn of 2000, polyethylene glycol with Mn of 1500, and diisocyanates with different chemical structures, aliphatic, cycloaliphatic and aromatic. It was investigated how the diisocyanate structure affected the molecular morphology, contact angle measurements, and physical characteristics of water‐dispersible polyurethanes. FTIR and NMR measurements showed a close relationship between the intermolecular connections and the hard segment structure, mainly of the diisocyanate used. Also, the polarized light method showed that the presence of the PEG in the hard domain improved aggregation through physical interactions due to its structural flexibility and mobility. These water‐dispersible polyurethanes can assure the use of these polyurethane materials in a broad range of applications with increased environmental protection.
Synthesis and performance evaluation of water‐absorbing resin coated with polymethyl methacrylate as a lost circulation material
Authors: Bai Xiaodong , Deng Licheng , Yan Yancheng , Hu Hua , Luo Yumei , Cai Xuetong 
Published: April 2023

AbstractLost circulation will cause huge economic losses every year. In order to effectively reduce the harm of lost circulation to drilling, it is particularly important to use reasonable and efficient lost circulation materials (LCM). As a kind of water‐absorbing, expandable and deformable LCM, water‐absorbing resin can adapt to holes and cracks of different sizes. In this study, a kind of encapsulated water‐absorbing resin LCM (PMMA/PNAD) was proposed. The water‐absorbing resin is synthesized by acrylamide (AM), 2‐acrylamide‐2‐methyl‐propane sulfonic acid (APMS) and diallyl dimethyl ammonium chloride (DMDAAC) as reaction monomers through aqueous solution polymerization. The shell material is polymethylmethacrylate (PMMA), which is coated on the surface of the water‐absorbing resin by oil phase separation method. The results of the experimental evaluation indicate that the water‐absorbing resin possesses robust water‐absorbing and swelling properties, which significantly affect the rheological properties of the drilling fluid. However, the coated shell can effectively mitigate the impact of the absorbent resin on the drilling fluid. Under the formation environment of 100°C or 2 Mpa, the shell can soften or break to release the absorbent resin. The lost circulation control performance test results show that PMMA/PNAD has good pressure bearing capacity, and can still maintain good lost circulation control at 6.9 Mpa.
Characterization of the STA1600 CCD for the high‐resolution spectrograph PEPSI
Authors: Ilyin Ilya 
Published: April 2023

AbstractCharacterization of the STA1600 CCD for the high‐resolution spectrograph Potsdam Echelle Polarimetric and Spectroscopic Instrument (PEPSI) is presented. We tested the fixed‐pattern noise reduction efficiency with sufficient number of master flat fields and show that the noise reduction follows the expected value. The lateral charge diffusion is measured with photon transfer technique versus CCD binning factor and by measuring the change of spectral lines width versus their amplitude. The charge diffusion effect versus wavelength follows the behavior of the back‐illuminated CCD while also showing a strong positional dependence on the CCD.