bluuebunny/crossref_metadata_2025_split huggingface dataset:
Programmable Phototaxis of Metal–Phenolic Particle Microswimmers
Authors: Lin Gan , Richardson Joseph J. , Ahmed Heba , Besford Quinn A. , Christofferson Andrew J. , Beyer Sebastian , Lin Zhixing , Rezk Amgad R. , Savioli Marco , Zhou Jiajing , McConville Chris F. , Cortez‐Jugo Christina , Yeo Leslie Y. , Caruso Frank 
Published: February 2021

AbstractLight‐driven directional motion is common in nature but remains a challenge for synthetic microparticles, particularly regarding collective motion on a macroscopic scale. Successfully engineering microparticles with light‐driven collective motion could lead to breakthroughs in drug delivery, contaminant sensing, environmental remediation, and artificial life. Herein, metal–phenolic particle microswimmers capable of autonomously sensing and swimming toward an external light source are reported, with the speed regulated by the wavelength and intensity of illumination. These microswimmers can travel macroscopic distances (centimeters) and can remain illuminated for hours without degradation of motility. Experimental and theoretical analyses demonstrate that motion is generated through chemical transformations of the organic component of the metal–phenolic complex. Furthermore, cargos with specific spectral absorption profiles can be loaded into the particles and endow the particle microswimmers with activated motion corresponding to these spectral characteristics. The programmable nature of the light navigation, tunable size of the particles, and versatility of cargo loading demonstrate the versatility of these metal–phenolic particle microswimmers.
Texture Formation in Polycrystalline Thin Films of All‐Inorganic Lead Halide Perovskite
Authors: Steele Julian A. , Solano Eduardo , Jin Handong , Prakasam Vittal , Braeckevelt Tom , Yuan Haifeng , Lin Zhenni , de Kloe René , Wang Qiong , Rogge Sven M. J. , Van Speybroeck Veronique , Chernyshov Dmitry , Hofkens Johan , Roeffaers Maarten B. J. 
Published: February 2021

AbstractControlling grain orientations within polycrystalline all‐inorganic halide perovskite solar cells can help increase conversion efficiencies toward their thermodynamic limits; however, the forces governing texture formation are ambiguous. Using synchrotron X‐ray diffraction, mesostructure formation within polycrystalline CsPbI2.85Br0.15 powders as they cool from a high‐temperature cubic perovskite (α‐phase) is reported. Tetragonal distortions (β‐phase) trigger preferential crystallographic alignment within polycrystalline ensembles, a feature that is suggested here to be coordinated across multiple neighboring grains via interfacial forces that select for certain lattice distortions over others. External anisotropy is then imposed on polycrystalline thin films of orthorhombic (γ‐phase) CsPbI3‐xBrx perovskite via substrate clamping, revealing two fundamental uniaxial texture formations; i) I‐rich films possess orthorhombic‐like texture (<100> out‐of‐plane; <010> and <001> in‐plane), while ii) Br‐rich films form tetragonal‐like texture (<110> out‐of‐plane; <110> and <001> in‐plane). In contrast to relatively uninfluential factors like the choice of substrate, film thickness, and annealing temperature, Br incorporation modifies the γ‐CsPbI3−xBrx crystal structure by reducing the orthorhombic lattice distortion (making it more tetragonal‐like) and governs the formation of the different, energetically favored textures within polycrystalline thin films.
Diversifying Metal–Ligand Cooperative Catalysis in Semi‐Synthetic [Mn]‐Hydrogenases
Authors: Pan Hui‐Jie , Huang Gangfeng , Wodrich Matthew D. , Tirani Farzaneh Fadaei , Ataka Kenichi , Shima Seigo , Hu Xile 
Published: February 2021

AbstractThe reconstitution of [Mn]‐hydrogenases using a series of MnI complexes is described. These complexes are designed to have an internal base or pro‐base that may participate in metal–ligand cooperative catalysis or have no internal base or pro‐base. Only MnI complexes with an internal base or pro‐base are active for H2 activation; only [Mn]‐hydrogenases incorporating such complexes are active for hydrogenase reactions. These results confirm the essential role of metal–ligand cooperation for H2 activation by the MnI complexes alone and by [Mn]‐hydrogenases. Owing to the nature and position of the internal base or pro‐base, the mode of metal–ligand cooperation in two active [Mn]‐hydrogenases is different from that of the native [Fe]‐hydrogenase. One [Mn]‐hydrogenase has the highest specific activity of semi‐synthetic [Mn]‐ and [Fe]‐hydrogenases. This work demonstrates reconstitution of active artificial hydrogenases using synthetic complexes differing greatly from the native active site.
Unveiling Electrochemical Urea Synthesis by Co‐Activation of CO2 and N2 with Mott–Schottky Heterostructure Catalysts
Authors: Yuan Menglei , Chen Junwu , Bai Yiling , Liu Zhanjun , Zhang Jingxian , Zhao Tongkun , Wang Qin , Li Shuwei , He Hongyan , Zhang Guangjin 
Published: February 2021

AbstractElectrocatalytic C−N bond coupling to convert CO2 and N2 molecules into urea under ambient conditions is a promising alternative to harsh industrial processes. However, the adsorption and activation of inert gas molecules and then the driving of the C–N coupling reaction is energetically challenging. Herein, novel Mott–Schottky Bi‐BiVO4 heterostructures are described that realize a remarkable urea yield rate of 5.91 mmol h−1 g−1 and a Faradaic efficiency of 12.55 % at −0.4 V vs. RHE. Comprehensive analysis confirms the emerging space–charge region in the heterostructure interface not only facilitates the targeted adsorption and activation of CO2 and N2 molecules on the generated local nucleophilic and electrophilic regions, but also effectively suppresses CO poisoning and the formation of endothermic *NNH intermediates. This guarantees the desired exothermic coupling of *N=N* intermediates and generated CO to form the urea precursor, *NCON*.
Cycloparaphenylene–Phenalenyl Radical and Its Dimeric Double Nanohoop**
Authors: Yang Yong , Blacque Olivier , Sato Sota , Juríček Michal 
Published: February 2021

AbstractThe first example of a neutral spin‐delocalized carbon‐nanoring radical was achieved by integration of the open‐shell phenalenyl unit into cycloparaphenylene (CPP). Spin distribution in this hydrocarbon is localized primarily on the phenalenyl segment and partially on the CPP segment as a consequence of steric and electronic effects. The resulting geometry is reminiscent of a diamond ring, with pseudo‐perpendicular arrangement of the radial and the planar π‐surface. The phenylene rings attached directly to the phenalenyl unit give rise to a steric effect that governs a highly selective dimerization pathway, yielding a giant double nanohoop. Its π‐framework made of 158 sp2‐carbon atoms was elucidated by single‐crystal X‐ray diffraction, which revealed a three‐segment CPP‐peropyrene‐CPP structure. This nanocarbon shows a fluorescence profile characteristic of peropyrene, regardless of which segment gets excited. These results in conjunction with DFT suggest that adjusting the size of the CPP segments in this double nanohoop could deliver donor–acceptor systems.
Regulating the Solvation Sheath of Li Ions by Using Hydrogen Bonds for Highly Stable Lithium–Metal Anodes
Authors: Jiang Cheng , Jia Qingqing , Tang Mi , Fan Kun , Chen Yuan , Sun Mingxuan , Xu Shuaifei , Wu Yanchao , Zhang Chenyang , Ma Jing , Wang Chengliang , Hu Wenping 
Published: February 2021

AbstractThe performance of Li anodes is extremely affected by the solvation of Li ions, leading to preferential reduction of the solvation sheath and subsequent formation of fragile solid–electrolyte interphase (SEI), Li dendrites, and low coulombic efficiency (CE). Herein, we propose a novel strategy to regulate the solvation sheath, through the introduction of intermolecular hydrogen bonds with both the anions of Li salt and the solvent by small amount additives. The addition of such hydrogen bonds reduced the LUMO energy level of anions in electrolyte, promoted the formation of a robust SEI, reduced the amount of free solvent molecules, and enhanced stability of electrolytes. Based on this strategy, flat and dense lithium deposition was obtained. Even under lean electrolytes, at a current density of 1 mA cm−2 with a fixed capacity of 3 mAh cm−2, the Li–Cu cells showed an impressive CE value of 99.2 %. The Li‐LiFePO4 full cells showed long‐term cycling stability for more than 1000 cycles at 1 C, with a total capacity loss of only 15 mAh g−1.
Preparation of a Multicarbazole‐Based Nanocapsule Capable of Largely Modulating Guest Spectroscopic Properties in Water
Authors: Kudo Kohi , Ide Tomohito , Kishida Natsuki , Yoshizawa Michito 
Published: February 2021

AbstractA nanocapsule composed of multiple carbazole panels (ca. 12 panels) was quantitatively generated from bent carbazole‐based amphiphiles in water. Unlike previously reported macrocycles and coordination cages bearing several carbazole panels, the resultant nanocapsule displays enhanced emissivity and improved electrochemical stability as compared with the monomeric amphiphile. The spectroscopic properties of substituted coumarin and boron‐dipyrromethene dyes can be modulated upon encapsulation by the nanocapsule in water. In the cavity, a highly blue‐shifted absorption band is observed from largely twisted coumarin dyes and two absorption bands are found from boron‐dipyrromethene dimers stacked in an unusual L‐shaped fashion. Moreover, the encapsulated dimers exhibit unique excimer‐like emission.
Bispecific Aptamer Chimeras Enable Targeted Protein Degradation on Cell Membranes
Authors: Miao Yanyan , Gao Qianqian , Mao Menghan , Zhang Chao , Yang Liqun , Yang Yang , Han Da 
Published: February 2021

AbstractThe ability to regulate membrane protein abundance offers great opportunities for developing therapeutic sites for various diseases. Herein, we describe a platform for the targeted degradation of membrane‐associated proteins using bispecific aptamer chimeras that bind both the cell‐surface lysosome‐shuttling receptor (IGFIIR) and the targeted membrane‐bound proteins of interest. We demonstrate that the aptamer chimeras can efficiently and quickly shuttle the therapeutically relevant membrane proteins of Met and PTK‐7 to lysosomes and degrade them through the lysosomal protein degradation machinery. We anticipate that our method will provide a universal platform for the use of readily synthesized aptamer materials for biochemical research and potential therapeutics.
Digging into blindsnakes' morphology: Description of the skull, lower jaw, and cervical vertebrae of twoAmerotyphlops(Hedges et al., 2014) (Serpentes, Typhlopidae) with comments on the typhlopoidean skull morphological diversity
Authors: Lira Isabelle , Martins Angele 
Published: February 2021

AbstractScolecophidians are small fossorial snakes that exhibit several osteological innovations, most of which driven by their extreme body miniaturization. Considering that data on skull morphology has proven to be relevant in terms of scolecophidian systematics and morphofunctional evolution, herein, we aim to describe in detail the skull, lower jaw, and cervical vertebrae ofAmerotyphlops brongersmianusandA. reticulatus. Our results suggest that the investigated osteology ofAmerotyphlopsresembles several new world typhlopid species, with reduced interspecific variation in the basicranium, lower jaw and cervical vertebrae. Both species exhibit characters states that are typically conserved intragenerically amongst typhlopoids, such as the presence of a single parietal, paired supraoccipitals, and otooccipitals that are in contact medially, and the basioccipital participating in the formation of the foramen magnum. We discuss possible systematically important osteological skull variations among typhlopoids and provide a comprehensive comparison of these taxa based on literature and data gathered herein.
Age‐related parietal GABA alterations in children with autism spectrum disorder
Authors: DeMayo Marilena M. , Harris Ashley D. , Song Yun Ju C. , Pokorski Izabella , Thapa Rinku , Patel Shrujna , Ambarchi Zahava , Thomas Emma E. , Hickie Ian B. , Guastella Adam J. 
Published: February 2021

AbstractGABA is the primary inhibitory neurotransmitter in the brain, and is essential to the balance of cortical excitation and inhibition. Reductions in GABA are proposed to result in an overly excitatory cortex that may cause, or contribute to, symptoms of autism spectrum disorder (ASD). This study employed a cross‐sectional design to explore GABA+ differences in ASD and the impact of age, comparing 4–12 year olds with ASD (N = 24) to typically developing children (N = 35). GABA+ concentration was measured using edited magnetic resonance spectroscopy in the left parietal lobe. This study used a mixed model to investigate group differences between children with ASD and typically developing children. There was a significant difference in GABA+ levels between the groups, a significant effect of age and interaction between age and diagnostic group. The ASD group showed an association between GABA+ and age, with GABA+ levels gradually increasing with age (r = 0.59, p = 0.003). Typically developing children did not show age‐related change in GABA+ concentration (r = 0.09, p = 0.60). By the age of 9, children with ASD showed GABA+ levels that were comparable to their typically developing peers. This study suggests that children with ASD have initially lower levels of GABA+ in the left parietal lobe compared to typically developing children, and that these initially lower levels of GABA+ increase with age in ASD within this region. It is suggested that this developmental shift of GABA+ levels within the left parietal lobe provides a possible explanation for the previously found reductions in childhood that does not persist in adults.Lay SummaryThis study measured levels of GABA in the left parietal lobe using magnetic resonance spectroscopy in children with ASD and typically developing children. GABA levels were initially lower in the ASD group, and increased with age, while GABA did not change with age in the typically developing group. This suggests that alterations in GABA signaling may be associated with ASD in childhood. Autism Res 2021, 14: 859–872. © 2021 International Society for Autism Research, Wiley Periodicals LLC.
Statistische Bewertung der Druckfestigkeit von ultrahochfestem Beton (UHFB)
Authors: Lanwer Jan‐Paul , Javidmehr Sara , Empelmann Martin 
Published: February 2021

AbstractUltrahochleistungsbetone weisen eine Vielzahl von Vorteilen gegenüber normalfesten Betonen auf, z. B. ein extrem dichtes Gefüge, sehr hohe Festigkeiten und exzellente Eigenschaften in Bezug auf die Dauerhaftigkeit. Für eine sichere und zuverlässige Bemessung von Bauteilen aus Ultrahochleistungsbetonen in den Grenzzuständen der Tragfähigkeit und Gebrauchstauglichkeit muss die rechnerisch anzusetzende Druckfestigkeit und deren Streuung bekannt sein. Dazu wurden Ergebnisse aus Druckfestigkeitsprüfungen in einer Datenbank zusammengestellt und statistisch ausgewertet.
Counselling in the third sector: to what extent are older adults accessing these services and how complete are the data third sector services collect measuring client psychological distress?
Authors: O’Donnell Jennifer , Pybis Joanne , Bacon Jeremy 
Published: February 2021

AbstractBackgroundA low number of older adults access Improving Access to Psychological Therapies (IAPT) services in England. Barriers include ageism and stigma. Routine outcome measures (ROMs) assess the effectiveness of counselling, although counsellor and service‐level barriers prevent uptake.AimsAccess rates of older adults to third sector (sometimes called voluntary or community sector) counselling and psychotherapy services were explored. The extent of ROM collection on psychological distress was assessed.MethodologyData collected between 2018 and 2019 were pooled across six third sector counselling services in England, Scotland and Northern Ireland (N = 2,757). Access based on age and gender was assessed, and the chi‐square analysis was used to compare gender distribution within the age groups. Availability of pre‐ and post‐therapy ROMs was assessed, and the chi‐square analysis was used to explore the age and gender differences in completion.FindingsLower access rates in people aged 65 and over (4.4%) were found compared with IAPT (7%). Access rates decreased further as age increased. Access of people aged 50 and over (24.5%) was below the 34.6% of the population in this age category. A third of people accessing counselling in all age groups were men. Only 28.6% completed a pre‐therapy ROM, and 29.5% of those clients subsequently completed a post‐therapy ROM.ImplicationsMental health promotion and adapting communication during counselling may help engage older adults and men in counselling. Training on working with older people and long‐term conditions is also beneficial. Support in using ROMs can improve uptake although organisational barriers may restrict implementation in the third sector.
Analgesia nociception index for early detection of vagal stimulation during carotid body tumor resection: A case report
Authors: Laosuwan Prok , Tangjaturonrasme Napadon 
Published: February 2021

AbstractANI can be used for early detection of parasympathetic signals before the occurrence of bradycardia or to locate unidentified carotid structures in the head and neck region.
Adsorption of Naphthalene on Activated Wood Charcoal Derived from Biomass Gasification
Authors: Gradel Andy , Wünning Joachim Alfred , Plessing Tobias , Jess Andreas 
Published: February 2021

AbstractDuring gasification and/or pyrolysis of wooden biomass, charcoal is formed as a solid intermediate or product. In CO2‐ and H2O‐rich atmospheres at high temperatures, a high specific surface area of several 100 m2 per gram of charcoal may be reached. Common biomass gasifiers aim at a charcoal conversion of 100 %. Up to now, the option of a subsequent usage of the charcoal for adsorption of tar compounds has rarely been considered but is an interesting option to produce a clean syngas in a downstream adsorption unit. Experimental studies show an adsorption capacity of up to 0.4 g of tar per gram of charcoal using naphthalene as a model substance for tar. Respective adsorption isotherms, breakthrough curves in a fixed‐bed adsorber, and a kinetic breakthrough model are presented.
Rational Design and Development of Low‐Price, Scalable, Shelf‐Stable and Broadly Applicable Electrophilic Sulfonium Ylide‐Based Trifluoromethylating Reagents
Authors: Liu Yafei , Ling Yijing , Ge Hangming , Lu Long , Shen Qilong 
Published: February 2021

Main observation and conclusionThe development of two highly reactive electrophilic trifluoromethylating reagents (trifluoromethyl)(4‐nitrophenyl)bis(carbomethoxy)methylide (1g) and (trifluoromethyl)(3‐chlorophenyl)bis(carbomethoxy)methylide (1j) through structure‐activity study was described. Under mild conditions, reagent 1g reacted with β‐ketoesters and silyl enol ethers to give α‐trifluoromethylated‐β‐ketoesters or α‐trifluoromethylated ketones in high yields. In addition, reagent 1g could serve as a trifluoromethyl radical for a variety of trifluoromethylative transformations under visible light irradiation, including radical trifluoromethylation of electron‐rich indoles and pyrroles and sodium aryl sulfinates as well as trifluoromethylative difunctionalization with styrene derivatives. On the other hand, as a complimentary, under reductive coupling conditions, reagent 1j reacted with a variety of (hetero)aryl iodides for the formation of trifluoromethylated (hetero)arenes.
Statistical disease mapping for heterogeneous neuroimaging studies
Authors: Liu Rongjie , Zhu Hongtu ,   for the Alzheimer's Disease Neuroimaging Initiative
Published: February 2021

AbstractMany cancers and neuro‐related diseases display significant phenotypic and genetic heterogeneity across subjects and subpopulations. Characterizing such heterogeneity could transform our understanding of the etiology of these conditions and inspire new approaches to urgently needed prevention, diagnosis, treatment, and prognosis. However, most existing statistical methods face major challenges in delineating such heterogeneity at both the group and individual levels. The aim of this article is to propose a novel statistical disease‐mapping (SDM) framework to address some of these challenges. We develop an efficient estimation method to estimate unknown parameters in SDM and delineate individual and group disease maps. Statistical inference procedures such as hypothesis‐testing problems are also investigated for parameters of interest. Both simulation studies and real data analysis on the ADNI hippocampal surface dataset show that our SDM not only effectively detects diseased regions in each patient but also provides a group disease‐mapping analysis of Alzheimer subgroups.
Cyclopentadienyl‐Based Anticancer Drugs: Improvement of Cytotoxic Activity through Functionalisation of the π Ligand
Authors: Absolonová Monika , Melounková Lucie , Vinklárek Jaromír , Honzíček Jan , Dostál Libor , Mrózek Ondřej 
Published: February 2021

AbstractCytotoxic complexes containing molybdenum are widely studied as a potential substitution for commercially used drugs that often suffer from pronounced side effects and cellular resistance. Compounds of the type [(η5‐Cp′)Mo(CO)2(N,NL)][BF4], where Cp is cyclopentadienyl and N,NL is a bidentate ligand, are well known for their strong anticancer activity. It is a generally accepted paradigm that the nature of the coordinated N,NL ligand has a major impact on the cytotoxicity. In this study, a series of new functionalised Cp complexes of molybdenum was synthesised from derivatised fulvenes as π‐ligand precursors. Indeed, the coordination sphere‘s modulation by various N,N‐chelating ligands afforded species active toward leukemic cell line MOLT‐4 with IC50 values depending on the character of the N,N‐chelator used. However, following study clearly showed that functionalisation of the Cp ring with an amine moiety considerably improved cytotoxicity. These results are of crucial importance for the future design of highly active cytotoxic drugs, as modification of cyclopentadienyl is believed to have a minor effect on biological activity.
Bifunctional versus Defect‐Mediated Effects in Electrocatalytic Methanol Oxidation
Authors: Engstfeld Albert K. , Klein Jens , Brimaud Sylvain 
Published: February 2021

AbstractThe most prominent and intensively studied anode catalyst material for direct methanol oxidation fuel cells consists of a combination of platinum (Pt) and ruthenium (Ru). Classically, their high performance is attributed to a bifunctional reaction mechanism where Ru sites provide oxygen species at lower overpotential than Pt. In turn, they oxidize the adsorbed carbonaceous reaction intermediates at lower overpotential; among these, the Pt site‐blocking carbon monoxide. We demonstrate that well‐defined Pt modified Ru(0001) single crystal electrodes, with varying Pt contents and different local PtRu configurations at the surface, are unexpectedly inactive for the methanol oxidation reaction. This observation stands in contradiction with theoretical predictions and the concept of bifunctional catalysis for this reaction. Instead, we suggest that pure Pt defect sites play a more critical role than bifunctional defect sites on the electrodes investigated in this work.