bluuebunny/crossref_metadata_2025_split huggingface dataset:
Epidemiology of early onset dementia and its clinical presentations in the province of Modena, Italy
Authors: Chiari Annalisa , Vinceti Giulia , Adani Giorgia , Tondelli Manuela , Galli Chiara , Fiondella Luigi , Costa Manuela , Molinari Maria A. , Filippini Tommaso , Zamboni Giovanna , Vinceti Marco 
Published: September 2020

AbstractIntroductionPatients with early onset dementia (EOD), defined as dementia with symptom onset at age <65, frequently present with atypical syndromes. However, the epidemiology of different EOD presentations, including variants of Alzheimer's disease (AD) and frontotemporal dementia (FTD), has never been investigated all together in a population‐based study. Epidemiologic data of all‐cause EOD are also scarce.MethodsWe investigated EOD epidemiology by identifying patients with EOD seen in the extended network of dementia services of the Modena province, Northern Italy (≈700,000 inhabitants) from 2006 to 2019.ResultsIn the population age 30 to 64, incidence was 13.2 per 100,000/year, based on 160 new cases from January 2016 to June 2019, and prevalence 74.3 per 100,000 on June 30, 2019. The most frequent phenotypes were the amnestic variant of AD and behavioral variant of FTD.DiscussionEOD affects a significant number of people. Amnestic AD is the most frequent clinical presentation in this understudied segment of the dementia population.
Circulating Lipoprotein Lipids, Apolipoproteins and Ischemic Stroke
Authors: Yuan Shuai , Tang Bowen , Zheng Jie , Larsson Susanna C. 
Published: September 2020

ObjectiveWe conducted a Mendelian randomization (MR) study to disentangle the comparative effects of lipids and apolipoproteins on ischemic stroke.MethodsSingle‐nucleotide polymorphisms associated with low‐ and high‐density lipoprotein (LDL and HDL) cholesterol, triglycerides, and apolipoprotein A‐I and B (apoA‐I and apoB) at the level of genomewide significance (p < 5 × 10−8) in the UK Biobank were used as instrumental variables. Summary‐level data for ischemic stroke and its subtypes were obtained from the MEGASTROKE consortium with 514,791 individuals (60,341 ischemic stroke cases, and 454,450 non‐cases).ResultsIncreased levels of apoB, LDL cholesterol, and triglycerides were associated with higher risk of any ischemic stroke, large artery stroke, and small vessel stroke in the main and sensitivity univariable MR analyses. In multivariable MR analysis including apoB, LDL cholesterol, and triglycerides in the same model, apoB retained a robust effect (p < 0.05), whereas the estimate for LDL cholesterol was reversed, and that for triglycerides largely attenuated. Decreased levels of apoA‐I and HDL cholesterol were robustly associated with increased risk of any ischemic stroke, large artery stroke, and small vessel stroke in all univariable MR analyses, but the association for apoA‐I was attenuated to the null after mutual adjustment.InterpretationThe present MR study reveals that apoB is the predominant trait that accounts for the etiological basis of apoB, LDL cholesterol, and triglycerides in relation to ischemic stroke, in particular large artery and small vessel stroke. Whether HDL cholesterol exerts a protective effect on ischemic stroke independent of apoA‐I needs further investigation. ANN NEUROL 2020;88:1229–1236
Reflection and Refraction of an Airy Pulse at a Moving Temporal Boundary
Authors: Cai Wangyang , Tian Yingying , Zhang Lifu , He Hairong , Zhao Jiajia , Wang Jin 
Published: September 2020

AbstractReflection and refraction of Airy pulses at a moving step refractive‐index boundary are investigated. A comb‐like reflected spectrum and an Airy‐like transmitted spectrum are formed as an Airy pulse crosses a temporal boundary without initial group velocity mismatch or initial central frequency shift. The reflected and refracted pulses are significantly influenced by the location of temporal boundary and time‐dependent refractive index change. The energy of each lobe of the comb‐like reflected spectra can be controlled by changing the value of decay factor of the Airy pulse. In the case of an Airy pulse with an initial launch frequency shift, the reflected and refracted frequency shifts depend on the dispersion relation of the medium. The results can be used in potential applications involving optical manipulation.
Conjugated Nanohoops Incorporating Donor, Acceptor, Hetero‐ or Polycyclic Aromatics
Authors: Hermann Mathias , Wassy Daniel , Esser Birgit 
Published: September 2020

AbstractIn the last 13 years several synthetic strategies were developed that provide access to [n]cycloparaphenylenes ([n]CPPs) and related conjugated nanohoops. A number of potential applications emerged, including optoelectronic devices, and their use as templates for carbon nanomaterials and in supramolecular chemistry. To tune the structural or optoelectronic properties of carbon nanohoops beyond the size‐dependent effect known for [n]CPPs, a variety of aromatic rings other than benzene were introduced. In this Review, we provide an overview of the syntheses, properties, and applications of conjugated nanohoops beyond [n]CPPs with intrinsic donor/acceptor structure or such that contain acceptor, donor, heteroaromatic or polycyclic aromatic units within the hoop as well as conjugated nanobelts.
Interfacial Structure of Water as a New Descriptor of the Hydrogen Evolution Reaction
Authors: Shen Lin‐fan , Lu Bang‐an , Li Yu‐yang , Liu Jia , Huang‐fu Zhi‐chao , Peng Hao , Ye Jin‐yu , Qu Xi‐ming , Zhang Jun‐ming , Li Guang , Cai Wen‐bin , Jiang Yan‐xia , Sun Shi‐gang 
Published: September 2020

AbstractDriven by the persisting poor understanding of the sluggish kinetics of the hydrogen evolution reaction (HER) on Pt in alkaline media, a direct correlation of the interfacial water structure and activity is still yet to be established. Herein, using Pt and Pt–Ni nanoparticles we first demonstrate a strong dependence of the proton donor structure on the HER activity and pH. The structure of the first layer changes from the proton acceptors to the donors with increasing pH. In the base, the reactivity of the interfacial water varied its structure, and the activation energies of water dissociation increased in the sequence: the dangling O−H bonds < the trihedrally coordinated water < the tetrahedrally coordinated water. Moreover, optimizing the adsorption of H and OH intermediates can re‐orientate the interfacial water molecules with their H atoms pointing towards the electrode surface, thereby enhancing the kinetics of HER. Our results clarified the dynamic role of the water structure at the electrode–electrolyte interface during HER and the design of highly efficient HER catalysts.
Tumor Microenvironment Stimuli‐Responsive Fluorescence Imaging and Synergistic Cancer Therapy by Carbon‐Dot–Cu2+ Nanoassemblies
Authors: Sun Shan , Chen Qiao , Tang Zhongdi , Liu Chuang , Li Zhongjun , Wu Aiguo , Lin Hengwei 
Published: September 2020

AbstractA method is developed to fabricate tumor microenvironment (TME) stimuli‐responsive nanoplatform for fluorescence (FL) imaging and synergistic cancer therapy via assembling photosensitizer (chlorine e6, Ce6) modified carbon dots (CDs‐Ce6) and Cu2+. The as‐obtained nanoassemblies (named Cu/CC nanoparticles, NPs) exhibit quenched FL and photosensitization due to the aggregation of CDs‐Ce6. Their FL imaging and photodynamic therapy (PDT) functions are recovered efficiently once they entering tumor sites by the stimulation of TME. Introducing of Cu2+ not only provides extra chemodynamic therapy (CDT) function through reaction with hydrogen peroxide (H2O2), but also depletes GSH in tumors by a redox reaction, thus amplifying the intracellular oxidative stress and enhancing the efficacy of reactive oxygen species (ROS) based therapy. Cu/CC NPs can act as a FL imaging guided trimodal synergistic cancer treatment agent by photothermal therapy (PTT), PDT, and thermally amplified CDT.
Design and Synthesis of TY‐Phos and Application in Palladium‐Catalyzed Enantioselective Fluoroarylation ofgem‐Difluoroalkenes
Authors: Lin Tao‐Yan , Pan Zhangjin , Tu Youshao , Zhu Shuai , Wu Hai‐Hong , Liu Yu , Li Zhiming , Zhang Junliang 
Published: September 2020

AbstractThe first example of highly enantioselective fluoroarylation of gem‐difluoroalkenes with aryl halides is presented by using a new chiral sulfinamide phosphine (Sadphos) type ligandTY‐Phos. N‐Me‐TY‐Phoscan be easily synthesized on a gram scale from readily available starting materials in three steps. Salient features of this work including readily available starting materials, good yields, high enantioselectivities as well as broad substrate scope make this approach very practical and attractive. Notably, the asymmetric synthesis of an analogue of a biologically active molecule is also reported.
Multiplex‐Nachweis von Analyten auf einem einzelnen Teststreifen mit Antikörper‐gesteuerten und Indikator freisetzenden mesoporösen Nanopartikeln
Authors: Climent Estela , Biyikal Mustafa , Gröninger Delia , Weller Michael G. , Martínez‐Máñez Ramón , Rurack Knut 
Published: September 2020

AbstractVor dem Hintergrund der einzigartigen Modularität, hohen Empfindlichkeit und Selektivität von Antikörper‐gesteuerten Indikatorfreisetzungssystemen (gAID‐Systemen) wurde hier ein Multiplex‐Assay für drei organische Explosivstoffmoleküle (TATP, TNT, PETN) entwickelt, der es erlaubt, die Analyten gleichzeitig in flüssiger Phase mit einem einzelnen Teststreifen und einem Fluoreszenzlesegerät bzw. Smartphone als Detektor in Konzentrationen bis in den unteren ppb‐Bereich in <5 min nachzuweisen. Alle drei Systeme, darunter die hier neu entwickelten Systeme für TNT und PETN, tolerieren zudem nicht nur gepufferte wässrige Modelllösungen, sondern auch komplexere Matrices. Neben einem konventionellen Teststreifen mit einem Kanal erlaubte uns die Anwendung von Wachsdrucktechnologie das Herstellen von mehrkanaligen Streifen mit vergleichbarer analytischer Leistungsfähigkeit, was das enorme Potenzial der modular aufgebauten, hybriden Biosensormaterialien im Hinblick auf eine für den Endanwender maßgeschneiderte Vor‐Ort‐Analytik unterstreicht.
Expedient Synthetic Identification of a P‐Stereogenic Ligand Motif for the Palladium‐Catalyzed Preparation of Isotactic Polar Polypropylenes
Authors: Seidel Falk William , Tomizawa Izumi , Nozaki Kyoko 
Published: September 2020

AbstractThe iso‐specific statistical copolymerization of unprotected polar monomers with propylene remains a grand challenge in the field of polymer chemistry. Current research is hampered because only a single natural‐product‐derived dimenthylphosphine‐motif is known to allow for the preparation of moderately isotactic polypropylene copolymers. To overcome this structural limitation, we developed time‐efficient synthetic methods that facilitate P‐donor ligand development. The strength of these methods was demonstrated with preparation of twenty‐five new P‐stereogenic phosphine/sulfonate‐ and bisphosphine‐monoxide‐type palladium catalysts, which could typically be developed in parallel. A lead candidate was identified for iso‐specific propylene polymerization. The best‐performing catalysts utilizing the P‐stereogenic donor motif achieved triad isotacticities of up to mm=0.75—the highest value within those reported for group 10 metal catalysts—for the homo‐ and copolymerization of propylene with unprotected polar monomers at an industrially relevant temperature of 50 °C.
Supramolecular Catalysis of the oxa‐Pictet–Spengler Reaction with an Endohedrally Functionalized Self‐Assembled Cage Complex
Authors: Ngai Courtney , Sanchez‐Marsetti Colomba M. , Harman W. Hill , Hooley Richard J. 
Published: September 2020

AbstractAn endohedrally functionalized self‐assembled Fe4L6 cage complex can catalyze oxa‐Pictet—Spengler cyclizations of tryptophols and various aldehyde derivatives, showing strong rate accelerations and size‐selectivity. Selective molecular recognition of substrates controls the reactivity, and the cage is capable of binding and activating multiple different species along the multistep reaction pathway. The combination of a functionalized active site, size‐selective reactivity, and multistep activation, all from a single host molecule, illustrates the biomimetic nature of the catalysis.
Turning on Zn 4s Electrons in a N2‐Zn‐B2 Configuration to Stimulate Remarkable ORR Performance
Authors: Wang Jing , Li Hongguan , Liu Shuhu , Hu Yongfeng , Zhang Jing , Xia Meirong , Hou Yanglong , Tse John , Zhang Jiujun , Zhao Yufeng 
Published: September 2020

AbstractA zinc‐based single‐atom catalyst has been recently explored with distinguished stability, of which the fully occupied Zn2+ 3d10 electronic configuration is Fenton‐reaction‐inactive, but the catalytic activity is thus inferior. Herein, we report an approach to manipulate the s‐band by constructing a B,N co‐coordinated Zn‐B/N‐C catalyst. We confirm both experimentally and theoretically that the unique N2‐Zn‐B2 configuration is crucial, in which Zn+(3d104s1) can hold enough delocalized electrons to generate suitable binding strength for key reaction intermediates and promote the charge transfer between catalytic surface and ORR reactants. This exclusive effect is not found in the other transition‐metal counterparts such as M‐B/N‐C (M=Mn, Fe, Co, Ni and Cu). Consequently, the as‐obtained catalyst demonstrates impressive ORR activity, along with remarkable long‐term stability in both alkaline and acid media. This work presents a new concept in the further design of electrocatalyst.
Construction of Cationic Azahelicenes: Regioselective Three‐Component Annulation Using In Situ Activation Strategy
Authors: Wang Zhishuo , Jiang Linfeng , Ji Jinwen , Zhou Fulin , Lan Jingbo , You Jingsong 
Published: September 2020

AbstractDescribed herein is a strategy to construct cationic azahelicenes through the three‐component annulation reaction of isoquinoline, indole, and 1,2‐dichloroethane (DCE), in which DCE serves as an in situ activating agent for C1−H activation of isoquinoline, a vinyl equivalent, and a solvent. This in situ activation annulation reaction features a facile one‐step synthesis and complete regioselectivity. The complete regioselectivity of C1 over C3 for the isoquinoline ring paves a path to the helical structure in a highly ordered sequence. One of the synthesized ionic [5]azahelicenium fluorophores exhibits the potential to serve as a mitochondria‐targeted biomarker with good photostability and low cytotoxicity.
Stimuli‐Responsive Luminescent Properties of Tetraphenylethene‐Based Strontium and Cobalt Metal–Organic Frameworks
Authors: Guo Xiaolei , Zhu Nansong , Wang Shi‐Ping , Li Guanghua , Bai Fu‐Quan , Li Yi , Han Yonghao , Zou Bo , Chen Xiao‐Bo , Shi Zhan , Feng Shouhua 
Published: September 2020

AbstractHerein we report two new TPE‐based 3D MOFs, that is, Sr‐ETTB and Co‐ETTB (TPE=Tetraphenylethylene, H8ETTB=4′,4′′′,4′′′′′,4′′′′′′′‐(ethene‐1,1,2,2‐tetrayl)tetrakis(([1,1′‐biphenyl]‐3,5‐dicarboxylic acid))). Through tailoring outer shell electron configurations of SrII and CoII cations, the fluorescence intensity of the MOFs is tuned from high emission to complete non‐emission. Sr‐ETTB with strong blue fluorescence shows reversible fluorescence variations in response to pressure and temperature, which is directly related to the reversible deformation of the crystal structure. In addition, non‐emissive Co‐ETTB counterpart exhibits a turn‐on fluorescent enhancement under the stimulation of analyte histidine. In the process, TPE‐cored linkers in the MOFs are released through competitive coordination substitution and subsequently reassembled to perform aggregation‐induced luminescence behavior originated from the organic linkers.
In Situ Raman Study of CO Electrooxidation on Pt(hkl) Single‐Crystal Surfaces in Acidic Solution
Authors: Su Min , Dong Jin‐Chao , Le Jia‐Bo , Zhao Yu , Yang Wei‐Min , Yang Zhi‐Lin , Attard Gary , Liu Guo‐Kun , Cheng Jun , Wei Yi‐Min , Tian Zhong‐Qun , Li Jian‐Feng 
Published: September 2020

AbstractThe adsorption and electrooxidation of CO molecules at well‐defined Pt(hkl) single‐crystal electrode surfaces is a key step towards addressing catalyst poisoning mechanisms in fuel cells. Herein, we employed in situ electrochemical shell‐isolated nanoparticle‐enhanced Raman spectroscopy (SHINERS) coupled with theoretical calculation to investigate CO electrooxidation on Pt(hkl) surfaces in acidic solution. We obtained the Raman signal of top‐ and bridge‐site adsorbed CO* molecules on Pt(111) and Pt(100). In contrast, on Pt(110) surfaces only top‐site adsorbed CO* was detected during the entire electrooxidation process. Direct spectroscopic evidence for OH* and COOH* species forming on Pt(100) and Pt(111) surfaces was afforded and confirmed subsequently via isotope substitution experiments and DFT calculations. In summary, the formation and adsorption of OH* and COOH* species plays a vital role in expediting the electrooxidation process, which relates with the pre‐oxidation peak of CO electrooxidation. This work deepens knowledge of the CO electrooxidation process and provides new perspectives for the design of anti‐poisoning and highly effective catalysts.
Direct Imaging of Atomic Permeation Through a Vacancy Defect in the Carbon Lattice
Authors: Cao Kecheng , Skowron Stephen T. , Stoppiello Craig T. , Biskupek Johannes , Khlobystov Andrei N. , Kaiser Ute 
Published: September 2020

AbstractPorous graphene has shown promise as a new generation of selective membrane for sieving atoms, ions and molecules. However, the atomistic mechanisms of permeation through defects in the graphenic lattice are still unclear and remain unobserved in action, at the atomic level. Here, the direct observation of palladium atoms from a nanoparticle passing through a defect in a single‐walled carbon nanotube one‐by‐one has been achieved with atomic resolution in real time, revealing key stages of the atomic permeation. Bonding between the moving atom and dangling bonds around the orifice, immediately before and after passing through the subnano‐pore, plays an important role in the process. Curvature of the graphenic lattice crucially defines the direction of permeation from concave to convex side due to a difference in metal‐carbon bonding at the curved surfaces as confirmed by density functional theory calculations, demonstrating the potential of porous carbon nanotubes for atom sieving.
Kohlenstoff‐Kohlenstoff‐Kupplung auf inerten Oberflächen durch die Abscheidung von en route erzeugten Aryl Radikalen
Authors: Galeotti Gianluca , Fritton Massimo , Lackinger Markus 
Published: September 2020

AbstractZur Realisierung von C‐C‐Kupplungen in der Oberflächensynthese auf inerten Oberflächen haben wir eine Radikal‐Abscheidungs‐Quelle (RAQ) für die direkte Abscheidung von Aryl Radikalen auf beliebige Substrate entwickelt. Das Herzstück ist ein beheiztes reaktives Drift‐Rohr, durch das halogenierte Vorläufer abgeschieden und dabei en route in Radikale umgewandelt werden. Den Machbarkeitsbeweis erbringen wir mit 4,4′′‐Diiod‐p‐terphenyl (DITP)‐Vorläufern auf Iod‐passivierten Metall‐Oberflächen. Aus der Abscheidung mit der RAQ bei Raumtemperatur resultieren sehr regelmäßige Strukturen, die hauptsächlich aus monomeren (Terphenyl) oder dimeren (Sexiphenyl) Biradikalen bestehen. Mildes Heizen aktiviert die fortschreitende C‐C‐Kupplung in ausgedehntere molekulare Drähte. Diese Strukturen unterscheiden sich grundlegend von den nach konventioneller Abscheidung von intaktem DITP beobachteten selbst‐assemblierten Strukturen. Durch die direkte Abscheidung von Radikalen ist die Reaktivität des Substrats nicht mehr notwendig, und damit der Weg zur Synthese auf anwendungsrelevanten inerten Oberflächen geebnet.
Structural Characterization of N‐Linked Glycans in the Receptor Binding Domain of the SARS‐CoV‐2 Spike Protein and their Interactions with Human Lectins
Authors: Lenza Maria Pia , Oyenarte Iker , Diercks Tammo , Quintana Jon Imanol , Gimeno Ana , Coelho Helena , Diniz Ana , Peccati Francesca , Delgado Sandra , Bosch Alexandre , Valle Mikel , Millet Oscar , Abrescia Nicola G. A. , Palazón Asís , Marcelo Filipa , Jiménez‐Osés Gonzalo , Jiménez‐Barbero Jesús , Ardá Ana , Ereño‐Orbea June 
Published: September 2020

AbstractThe glycan structures of the receptor binding domain of the SARS‐CoV2 spike glycoprotein expressed in human HEK293F cells have been studied by using NMR. The different possible interacting epitopes have been deeply analysed and characterized, providing evidence of the presence of glycan structures not found in previous MS‐based analyses. The interaction of the RBD 13C‐labelled glycans with different human lectins, which are expressed in different organs and tissues that may be affected during the infection process, has also been evaluated by NMR. In particular, 15N‐labelled galectins (galectins‐3, ‐7 and ‐8 N‐terminal), Siglecs (Siglec‐8, Siglec‐10), and C‐type lectins (DC‐SIGN, MGL) have been employed. Complementary experiments from the glycoprotein perspective or from the lectin's point of view have permitted to disentangle the specific interacting epitopes in each case. Based on these findings, 3D models of the interacting complexes have been proposed.
Unveiling the Promotion of Surface‐Adsorbed Chalcogenate on the Electrocatalytic Oxygen Evolution Reaction
Authors: Shi Yanmei , Du Wei , Zhou Wei , Wang Changhong , Lu Shanshan , Lu Siyu , Zhang Bin 
Published: September 2020

AbstractTransition metal chalcogenides (TMCs) are efficient oxygen evolution reaction (OER) pre‐electrocatalysts, and will in situ transform into metal (oxy)hydroxides under OER condition. However, the role of chalcogen is not fully elucidated after oxidation and severe leaching. Here we present the vital promotion of surface‐adsorbed chalcogenates on the OER activity. Taking NiSe2 as an example, in situ Raman spectroscopy revealed the oxidation of Se‐Se to selenites (SeO32−) then to selenates (SeO42−). Combining the severe Se leaching and the strong signal of selenates, it is assumed that the selenates are rich on the surface and play significant roles. As expected, adding selenites to the electrolyte of Ni(OH)2 dramatically enhance its OER activity. And sulfates also exhibit the similar effect, suggesting the promotion of surface‐adsorbed chalcogenates on OER is universal. Our findings offer unique insight into the transformation mechanism of materials during electrolysis.
Light‐Induced Efficient Hydroxylation of Benzene to Phenol by Quinolinium and Polyoxovanadate‐Based Supramolecular Catalysts
Authors: Gu Yaqi , Li Qi , Zang Dejin , Huang Yichao , Yu Han , Wei Yongge 
Published: September 2020

AbstractDirect Hydroxylation of benzene to phenol with high yield and selectivity has been the goal of phenol industrial production. Photocatalysis can serve as a competitive method to realize the hydroxylation of benzene to phenol owing to its cost‐effective and environmental friendliness, however it is still a forbidding challenge to obtain good yield, high selectivity and high atom availability meanwhile. Here we show a series of supramolecular catalysts based on alkoxohexavanadate anions and quinolinium ions for the photocatalytic hydroxylation of benzene to phenol under UV irradiation. We demonstrate that polyoxoalkoxovanadates can serve as efficient catalysts which can not only stabilize quinolinium radicals but also reuse H2O2 produced by quinolinium ions under light irradiation to obtain excellent synergistic effect, including competitive good yield (50.1 %), high selectivity (>99 %) and high atom availability.