bluuebunny/crossref_metadata_2025_split huggingface dataset:
Semiconducting Polymer Dots with Dual‐Enhanced NIR‐IIa Fluorescence for Through‐Skull Mouse‐Brain Imaging
Authors: Zhang Zhe , Fang Xiaofeng , Liu Zhihe , Liu Haichao , Chen Dandan , He Shuqing , Zheng Jie , Yang Bing , Qin Weiping , Zhang Xuanjun , Wu Changfeng 
Published: December 2019

AbstractFluorescence probes in the NIR‐IIa region show drastically improved imaging owing to the reduced photon scattering and autofluorescence in biological tissues. Now, NIR‐IIa polymer dots (Pdots) are developed with a dual fluorescence enhancement mechanism. First, the aggregation induced emission of phenothiazine was used to reduce the nonradiative decay pathways of the polymers in condensed states. Second, fluorescence quenching was minimized by different levels of steric hindrance to further boost the fluorescence. The resulting Pdots displayed a fluorescence QY of ca. 1.7 % in aqueous solution, suggesting an enhancement of ca. 21 times in comparison with the original polymer in tetrahydrofuran (THF) solution. Small‐animal imaging by using the NIR‐IIa Pdots exhibited a remarkable improvement in penetration depth and signal to background ratio, as confirmed by through‐skull and through‐scalp fluorescent imaging of the cerebral vasculature of live mice.
Pingpong‐Energietransfer in kovalent verknüpften Porphyrin‐MoS2‐Architekturen
Authors: Canton‐Vitoria Ruben , Scharl Tobias , Stergiou Anastasios , Cadranel Alejandro , Arenal Raul , Guldi Dirk M. , Tagmatarchis Nikos 
Published: December 2019

AbstractMolybdändisulfid‐Nanoschichten wurden mit Porphyrin kovalent modifiziert und vollständig charakterisiert. Weder die Porphyrin‐Absorption noch die Fluoreszenz wurden durch die kovalente Bindung an MoS2 merklich beeinflusst. Mithilfe transienter Absorptionsspektroskopie konnte jedoch ein komplexer Pingpong‐Energietransfer‐Mechanismus, nämlich vom Porphyrin zum MoS2 und wieder zurück zum Porphyrin, bestätigt werden. Diese Studie zeigt das Potential von Übergangsmetalldichalkogeniden bei Photosensibilisierungsprozessen auf.
Expandierte Carbaporphyrinoide
Authors: Szyszko Bartosz , Latos‐Grażyński Lechosław 
Published: December 2019

AbstractIn diesem Aufsatz sollen die Fortschritte auf dem Gebiet der synthetischen expandierten Carbaporphyrinoide dargelegt werden. Die Entwicklung auf diesem Gebiet wird anhand von expandierten Porphyrin‐verwandten Systemen aufgezeigt, die eine Vielfalt von Bausteinen enthalten, mit deren Hilfe ein oder mehrere Kohlenstoffatome in die Kavität eingeführt werden. Die Ausführungen beginnen mit den Platyrinen – den Makrocyclen, die als Stammmolekül nicht nur der expandierten Carbaporphyrinoide, sondern der Klasse der Carbaporphyrinoide im Allgemeinen gelten. Nach einigen historischen Betrachtungen wird eine Vielzahl von expandierten porphyrinartigen Makrocyclen, die N‐fehlgeordnete oder neo‐fehlgeordnete Pyrrol‐Strukturelemente und verschiedene carbocyclische Untereinheiten enthalten, vorgestellt. Ein besonderer Schwerpunkt wird dabei auf die Anwendungen von expandierten Carbaporphyrinoiden in verschiedenen Bereichen gelegt, z. B. in der Organometallchemie, bei Schaltersystemen oder der Aromatizität. Abschließend wird ein kovalenter Käfig auf der Basis von expandierten Carbaporphyrinoiden vorgestellt.
Self‐Assembly in Water with N‐Substituted Imines
Authors: Jiao Tianyu , Wu Guangcheng , Zhang Yang , Shen Libo , Lei Ye , Wang Cai‐Yun , Fahrenbach Albert C. , Li Hao 
Published: December 2019

AbstractImine synthesis has enjoyed a long history as the dynamic covalent reaction of choice for the construction of purely covalent molecular architectures. In organic solvents, the formation of imine bonds is reversible but leads to thermodynamically stable products. In the presence of water, however, imine bonds are labile, a fact which limits their utility as mediators of self‐assembly in aqueous and biological media. In this Review, we discuss water‐compatible dynamic covalent bonds based on N‐substituted imine derivatives, namely hydrazones and oximes, for the self‐assembly of metal‐free organic architectures with well‐defined structures. The reasons why hydrazones and oximes are more robust in water than their parent imines are explained. Recent progress in the self‐assembly, characterization, and design principles of a variety of complex molecules including macrocycles, cages, catenanes, and knots in aqueous media is highlighted. Emerging applications for these molecules, including guest recognition and separations, are also discussed.
Electrochemical Conversion of CO2 to Syngas with Controllable CO/H2 Ratios over Co and Ni Single‐Atom Catalysts
Authors: He Qun , Liu Daobin , Lee Ji Hoon , Liu Yumeng , Xie Zhenhua , Hwang Sooyeon , Kattel Shyam , Song Li , Chen Jingguang G. 
Published: December 2019

AbstractThe electrochemical CO2 reduction reaction (CO2RR) to yield synthesis gas (syngas, CO and H2) has been considered as a promising method to realize the net reduction in CO2 emission. However, it is challenging to balance the CO2RR activity and the CO/H2 ratio. To address this issue, nitrogen‐doped carbon supported single‐atom catalysts are designed as electrocatalysts to produce syngas from CO2RR. While Co and Ni single‐atom catalysts are selective in producing H2 and CO, respectively, electrocatalysts containing both Co and Ni show a high syngas evolution (total current >74 mA cm−2) with CO/H2 ratios (0.23–2.26) that are suitable for typical downstream thermochemical reactions. Density functional theory calculations provide insights into the key intermediates on Co and Ni single‐atom configurations for the H2 and CO evolution. The results present a useful case on how non‐precious transition metal species can maintain high CO2RR activity with tunable CO/H2 ratios.
Highly Efficient Cyclic Dinucleotide Based Artificial Metalloribozymes for Enantioselective Friedel–Crafts Reactions in Water
Authors: Wang Changhao , Hao Min , Qi Qianqian , Dang Jingshuang , Dong Xingchen , Lv Shuting , Xiong Ling , Gao Huanhuan , Jia Guoqing , Chen Yashao , Hartig Jörg S. , Li Can 
Published: December 2019

AbstractThe diverse secondary structures of nucleic acids are emerging as attractive chiral scaffolds to construct artificial metalloenzymes (ArMs) for enantioselective catalysis. DNA‐based ArMs containing duplex and G‐quadruplex scaffolds have been widely investigated, yet RNA‐based ArMs are scarce. Here we report that a cyclic dinucleotide of c‐di‐AMP and Cu2+ ions assemble into an artificial metalloribozyme (c‐di‐AMP⋅Cu2+) that enables catalysis of enantioselective Friedel–Crafts reactions in aqueous media with high reactivity and excellent enantioselectivity of up to 97 % ee. The assembly of c‐di‐AMP⋅Cu2+ gives rise to a 20‐fold rate acceleration compared to Cu2+ ions. Based on various biophysical techniques and density function theory (DFT) calculations, a fine coordination structure of c‐di‐AMP⋅Cu2+ metalloribozyme is suggested in which two c‐di‐AMP form a dimer scaffold and the Cu2+ ion is located in the center of an adenine‐adenine plane through binding to two N7 nitrogen atoms and one phosphate oxygen atom.
On‐surface Synthesis of a Semiconducting 2D Metal–Organic Framework Cu3(C6O6) Exhibiting Dispersive Electronic Bands
Authors: Zhang Ran , Liu Jing , Gao Yifan , Hua Muqing , Xia Bowen , Knecht Peter , Papageorgiou Anthoula C. , Reichert Joachim , Barth Johannes V. , Xu Hu , Huang Li , Lin Nian 
Published: December 2019

AbstractA 2D metal–organic framework (2D‐MOF) was formed on a Cu(111) substrate using benzenehexol molecules. By means of a combination of scanning tunneling microscopy and spectroscopy, X‐ray photoelectron spectroscopy and density‐functional theory, the structure of the 2D‐MOF is determined to be Cu3(C6O6), which is stabilized by O–Cu–O bonding motifs. We find that upon adsorption on Cu(111), the 2D‐MOF features a semiconductor band structure with a direct band gap of 1.5 eV. The O–Cu–O bonds offer efficient charge delocalization, which gives rise to a highly dispersive conduction band with an effective mass of 0.45 me at the band bottom, implying a high electron mobility in this material.
Controllable Synthesis of Porphyrin‐Based 2D Lanthanide Metal–Organic Frameworks with Thickness‐ and Metal‐Node‐Dependent Photocatalytic Performance
Authors: Jiang Zhong Wei , Zou Yang Chun , Zhao Ting Ting , Zhen Shu Jun , Li Yuan Fang , Huang Cheng Zhi 
Published: December 2019

AbstractSynthesizing 2D metal–organic frameworks (2D MOFs) in high yields and rational tailoring of the properties in a predictable manner for specific applications is extremely challenging. Now, a series of porphyrin‐based 2D lanthanide MOFs (Ln‐TCPP, Ln=Ce, Sm, Eu, Tb, Yb, TCPP=tetrakis(4‐carboxyphenyl) porphyrin) with different thickness were successfully prepared in a household microwave oven. The as‐prepared 2D Ln‐TCPP nanosheets showed thickness‐dependent photocatalytic performances towards photooxidation of 1,5‐dihydroxynaphthalene (1,5‐DHN) to synthesize juglone. Particularly, the Yb‐TCPP displayed outstanding photodynamic activity to generate O2− and 1O2. This work not only provides fundamental insights into structure designing and property tailoring of 2D MOFs nanosheets, but also pave a new way to improve the photocatalytic performance.
Athermal and Soft Multi‐Nanopatterning of Azopolymers: Phototunable Mechanical Properties
Authors: Yang Bowen , Cai Feng , Huang Shuai , Yu Haifeng 
Published: December 2019

AbstractImprinting nanopatterns on flexible substrates has diverse applications in advanced fabrication. However, the traditional thermal nanoimprint lithography (T‐NIL) often causes shrinkage upon cooling. Here, a simple yet versatile method is introduced to fabricate multiple nanopatterns on a flexible substrate coated with an azopolymer by combining athermal nanoimprint lithography (AT‐NIL) and photolithography. The azopolymer has various mechanical properties upon photoirradiation: 1) phototunable glass‐transition temperatures (Tg) and concomitantly photoinduced switch from glassy plastic to viscoplastic polymer; 2) prominent modulation of viscoplasticity under light illumination at different wavelengths. Regionally selective multiple nanopatterns are conveniently fabricated, presenting angle‐dependent structural color images on poly(ethylene terephthalate) (PET) substrates. The flexible, athermal and multiple nanopatterning method has the potential for on‐demand fabrication of complex nanopatterns.
Synthesis and Reactivity of the First Isolated Hydrogen‐Bridged Silanol–Silanolate Anions
Authors: Weitkamp Robin F. , Neumann Beate , Stammler Hans‐Georg , Hoge Berthold 
Published: December 2019

AbstractWe report on the first examples of isolated silanol–silanolate anions, obtained by utilizing weakly coordinating phosphazenium counterions. The silanolate anions were synthesized from the recently published phosphazenium hydroxide hydrate salt with siloxanes. The silanol–silanolate anions are postulated intermediates in the hydroxide‐mediated polymerization of aryl and alkyl siloxanes. The silanolate anions are strong nucleophiles because of the weakly coordinating character of the phosphazenium cation, which is perceptible in their activity in polysiloxane depolymerization.
Ping‐Pong Energy Transfer in Covalently Linked Porphyrin‐MoS2 Architectures
Authors: Canton‐Vitoria Ruben , Scharl Tobias , Stergiou Anastasios , Cadranel Alejandro , Arenal Raul , Guldi Dirk M. , Tagmatarchis Nikos 
Published: December 2019

AbstractMolybdenum disulfide nanosheets covalently modified with porphyrin were prepared and fully characterized. Neither the porphyrin absorption nor its fluorescence was notably affected by covalent linkage to MoS2. The use of transient absorption spectroscopy showed that a complex ping‐pong energy‐transfer mechanism, namely from the porphyrin to MoS2 and back to the porphyrin, operated. This study reveals the potential of transition‐metal dichalcogenides in photosensitization processes.
Fast Lithium Ion Conduction in Lithium Phosphidoaluminates
Authors: Restle Tassilo M. F. , Sedlmeier Christian , Kirchhain Holger , Klein Wilhelm , Raudaschl‐Sieber Gabriele , Deringer Volker L. , van Wüllen Leo , Gasteiger Hubert A. , Fässler Thomas F. 
Published: December 2019

AbstractSolid electrolyte materials are crucial for the development of high‐energy‐density all‐solid‐state batteries (ASSB) using a nonflammable electrolyte. In order to retain a low lithium‐ion transfer resistance, fast lithium ion conducting solid electrolytes are required. We report on the novel superionic conductor Li9AlP4 which is easily synthesised from the elements via ball‐milling and subsequent annealing at moderate temperatures and which is characterized by single‐crystal and powder X‐ray diffraction. This representative of the novel compound class of lithium phosphidoaluminates has, as an undoped material, a remarkable fast ionic conductivity of 3 mS cm−1 and a low activation energy of 29 kJ mol−1 as determined by impedance spectroscopy. Temperature‐dependent 7Li NMR spectroscopy supports the fast lithium motion. In addition, Li9AlP4 combines a very high lithium content with a very low theoretical density of 1.703 g cm−3. The distribution of the Li atoms over the diverse crystallographic positions between the [AlP4]9− tetrahedra is analyzed by means of DFT calculations.
Shape memory CTBN/epoxy resin/cyanate ester ternary resin and their carbon fiber reinforced composites
Authors: Li Zhihua , Hu Jiankang , Ma Li , Liu Hongxin 
Published: December 2019

ABSTRACTCarboxylated‐terminated liquid acrylonitrile rubber (CTBN) and epoxy resin (JEF‐0211) were coreacted with cyanate ester (CE) to form CTBN/EP/CE ternary resin systems. Further, the ternary resin system was applied as prepreg for carbon fiber composites with vacuum bag degassing molding process. CTBN/EP/CE ternary shape memory polymer (SMP) exhibited relatively high tensile strength, Young's modulus, impact strength, and excellent shape memory properties. Compared with CTBN/EP/CE ternary SMP, CTBN/EP/CE carbon fiber composites showed much higher mechanical properties, such as their tensile strength and Young's modulus were high to 570 MPa and 36.7 GPa, respectively. Furthermore, CTBN/EP/CE carbon fiber composites exhibited good shape memory properties, their shape fixity ratio and shape recovery ratio were more than 95% after 30 times repeating shape memory tests. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48756.
A comparison of teaching tacts with and without background stimuli on acquisition and generality
Authors: Mitteer Daniel R. , Luczynski Kevin C. , McKeown Ciobha A. , Cohrs Victoria L. 
Published: December 2019

AbstractWe evaluated whether teaching tacts of images with or without backgrounds would affect acquisition during teaching and generality across untaught targets with four children diagnosed with autism spectrum disorder. Including backgrounds could slow acquisition but bolster generality across other media containing backgrounds, whereas removing backgrounds may improve acquisition but result in poorer generality. Overall, acquisition rates were similar across conditions for three children, although one child displayed consistently slower acquisition during the background condition. We rarely observed generality to untaught targets when programming extinction, but embedding differential reinforcement or teaching additional images with backgrounds led to equally successful outcomes irrespective of initial teaching conditions. Teaching with or without backgrounds may result in marginal differences in acquisition of teaching and untaught targets, especially when arranging supplemental procedures during tests for generality. We discuss the importance of intrasubject replication, considerations when testing for generality, and implications for practice.
Mapping the interlinkages between sustainable development goal 9 and other sustainable development goals: A preliminary exploration
Authors: Mantlana Khanyisa B. , Maoela Malebajoa A. 
Published: December 2019

AbstractThe set of 17 Sustainable Development Goals (SDGs) and 169 targets aims to move the world to a sustainable trajectory of economic development, environmental sustainability, and social inclusion. This paper presents a review of relevant reports as well as scientific publications to assess the interlinkages between SDG 9 dealing with industrial innovation and infrastructure and SDGs relating to social inclusion (SDG 2 and 11), environmental sustainability (SDG 6, 13, and 15), and economic development (SDG 7). The identified interlinkages were mapped and characterized based on compatibility (co‐benefit, trade‐off, neutral) in attaining the targets of the considered SDGs. Our results showed that the co‐benefits were by far the most dominant interactions between the targets of SDG 9 and the targets of the SDGs that were considered. The targets of SDG 2 had the largest number of neutral interlinkages with the targets of SDG 9, while trade‐off interlinkages were found mainly between SDG 9 targets and the targets of SDG 6, 13, and 15. This review will raise awareness of the significance of understanding the nature of interlinkages between the different SDGs to relevant role players and will also inform and stimulate science–policy dialogue on the importance of interlinkages in the implementation, monitoring, and reporting of SDG 9 targets.
The role of psychopathic traits and moral disengagement in cyberbullying among adolescents
Authors: Hoareau Natacha , Bagès Céline , Allaire Mégane , Guerrien Alain 
Published: December 2019

AbstractBackgroundThe prevalence of cyberbullying suggests that about 15% of school‐aged children are involved in some way, although estimates vary widely. Preventing and limiting the behaviour will require more understanding of how mutable variables relate to it. There is some evidence linking higher psychopathy scores to cyberbullying, but the cognitive processes involved in ‘moral disengagement’ may provide better candidates for intervention.AimsTo test the hypothesis that psychopathy scores and moral disengagement ratings would each be associated with cyberbullying, but that sex and age would moderate any associations.MethodWe conducted a cross‐sectional study with 334 11 to 15‐year‐olds (162 girls, 172 boys) from two French schools. Participants completed a self‐report questionnaire which measured cyberbullying, psychopathy traits and moral disengagement.ResultsWe found a significant relationship between moral disengagement scale scores and cyberbullying ratings, but a stronger relationship between psychopathy scores and likelihood of cyberbullying. Neither sex nor age of the students affected these relationships.ConclusionThis study adds to existing knowledge in showing that enduring personal qualities, as captured by a self‐rated psychopathy scale, may increase the risk of cyberbullying among adolescents. The findings suggest that teachers should be helped to monitor students’ emotional and cognitive social skills and consider extra support for those who struggle to recognise or process others’ distress.
Charcot arthropathy: The diagnostic dilemma of a painless, destructive joint
Authors: Galanis Nikiforos , Kyriakou Aikaterini , Delniotis Ioannis , Charanidi Paraskevi , Mavropoulos Paraskevas , Inklebarger James 
Published: December 2019

AbstractThe impressive clinical picture of Charcot joint reflects a high energy trauma injury which in the contrary is a progressive, painless arthropathy. Early and accurate diagnosis is crucial. A favorable outcome is elicited when joint is treated promptly, while late or misdiagnosis may lead to amputation.
Recent Developments in the Modelling of Heterogeneous Catalysts for CO2 Conversion to Chemicals
Authors: Podrojková Natalia , Sans Victor , Oriňak Andrej , Oriňaková Renata 
Published: December 2019

AbstractDensity functional theory (DFT) of the CO2 behavior on the catalyst surface provides valuable insights about the C=O bond activation, information about adsorption and dissociation of CO2, understanding the elementary steps involved in the mechanism of the CO2 hydrogenation reaction. Nowadays, DFT computational studies for the catalytic hydrogenation of CO2 are becoming very popular. Therefore, this article is focused on a comprehensive review of the DFT studies in thermocatalytic hydrogenation of CO2 at the gas‐surface interface and discusses three aspects: 1) processes taking place on the surfaces and facets of transition metal heterogeneous catalysts, 2) adsorption of CO2 on surfaces of different transition metals; 3) current understanding of reaction mechanisms taking place on the catalytic surface for the production of different compounds. A detailed schematic overview of the possible CO2 hydrogenation mechanisms and DFT simulations presented here will enhance the current understanding of the CO2 catalytic hydrogenation.
Implanting Copper−Zinc Nanoparticles into the Matrix of Mesoporous Alumina as a Highly Selective Bifunctional Catalyst for Direct Synthesis of Dimethyl Ether from Syngas
Authors: Sun Yingqi , Zhao Zhongkui 
Published: December 2019

AbstractDimethyl ether (DME) is an industrially important intermediate and clean alternative fuel. Thus, developing an efficient bifunctional catalyst for syngas‐to‐DME is practically important but remains a challenge. In this paper, a copper−zinc implanting into matrix of mesoporous alumina (CuZn@m−Al2O3) catalyst was prepared by introducing the as‐prepared Cu−Zn oxalate nanoparticles into the Al(i‐OPr)3‐containing precursor solution for preparing mesoporous Al2O3 (m‐Al2O3) through evaporation‐inducing assembly method. The preparation of Cu−Zn oxalate in advance for synthesizing CuZn@m−Al2O3 can intensify the Cu−ZnO interaction, confirmed by XRD and H2‐TPR. Thanks to the unique CuZn‐implanting closed structure, CuZn@m−Al2O3 shows 89.0 % of higher selectivity with comparable CO conversion (15.5 %) than the previously reported supported‐type CuZn catalyst on m‐Al2O3 (CuZn/m−Al2O3, 75.2 %) for hydrogenation of syngas to DME. Over the developed CuZn@m−Al2O3 catalyst, 0.16 mmol g−1 cat h−1 of high DME rate can be achieved. CuZn@m−Al2O3 also shows higher methanation resistance (2.7 % CH4) compared to CuZn/m−Al2O3 (6.3 %), ascribed to intensified Cu−Zn interaction owing to the as‐formation of Cu−Zn oxalate in advance. Moreover, Both CuZn@m−Al2O3 and CuZn/m−Al2O3 exhibit high stability. The outstanding catalytic performance of CuZn@m−Al2O3 allows it to be a promising catalyst for DME synthesis from syngas.
Surface Engineering for Advanced Aqueous Supercapacitors: A Review
Authors: Xu Cuixia , Yang Hui , Li Yi , Wang Jianwei , Lu Xihong 
Published: December 2019

AbstractAbstract: Considerable attention has been focused on aqueous supercapacitors (SCs), owing to their large power density and excellent cycling stability, which makes them more suitable for high power applications. However, the lower energy densities (E) of aqueous SCs as compared to batteries have impeded their range of commercial applications. To overcome this challenge, intensive studies have been devoted to the topic, in which surface engineering becomes critical to the high‐performance electrode design due to the efficient manipulation of a material surface to boost energy storage while maintaining the integrity of interior of the material. The purpose of this Minireview article is to highlight recent significant breakthroughs realized through surface engineering approaches such as surface functionalization, heterostructure design, and surface charge modulation. Current challenges, emerging trends, and opportunities for advanced SCs are discussed accordingly.