bluuebunny/crossref_metadata_2025_split huggingface dataset:
Significance of Engineering the Octahedral Units to Promote the Oxygen Evolution Reaction of Spinel Oxides
Authors: Zhou Ye , Sun Shengnan , Wei Chao , Sun Yuanmiao , Xi Pinxian , Feng Zhenxing , Xu Zhichuan J. 
Published: July 2019

AbstractThe clean energy carrier, hydrogen, if efficiently produced by water electrolysis using renewable energy input, would revolutionize the energy landscape. It is the sluggish oxygen evolution reaction (OER) at the anode of water electrolyzer that limits the overall efficiency. The large spinel oxide family is widely studied due to their low cost and promising OER activity. As the distribution of transition metal (TM) cations in octahedral and tetrahedral site is an important variable controlling the electronic structure of spinel oxides, the TM geometric effect on OER is discussed. The dominant role of octahedral sites is found experimentally and explained by computational studies. The redox‐active TM locating at octahedral site guarantees an effective interaction with the oxygen at OER conditions. In addition, the adjacent octahedral centers in spinel act cooperatively in promoting the fast OER kinetics. In remarkable contrast, the isolated tetrahedral TM centers in spinel prohibit the OER mediated by dual‐metal sites. Furthermore, various spinel oxides preferentially expose octahedral‐occupied cations on the surface, making the octahedral cations easily accessible to the reactants. The future perspectives and challenges in advancing fundamental understanding and developing robust spinel catalysts are discussed.
Effect of Evaporation Rate on Meniscus Splitting with Formation of Vertical Polysaccharide Membranes
Authors: Okeyoshi Kosuke , Yamashita Miki , Sakaguchi Tadashi , Budpud Kulisara , Joshi Gargi , Kaneko Tatsuo 
Published: July 2019

AbstractEvaporative self‐assembly of polymeric colloids is among the most attractive strategies for the preparation of soft materials with submicrometer‐scale ordered structures. In this study, meniscus splitting from an aqueous solution of liquid crystalline (LC) polysaccharide xanthan gum is verified under conditions of controlled evaporative rate in a limited space. Under fast evaporation rate with a steep gradient of humidity above the air–LC interface, the meniscus splitting is induced to bridge the gap and a vertical membrane with uniaxial orientation is obtained. The process is thermodynamically and polariscopically validated focusing on the ordered polymeric adsorption and the bridging of the millimeter‐scale gap. This clarification will serve not only as a method for immobilization of fluidically ordered structures but also in the control of the evaporative interface for the ordering of polymer solutions into advanced membranes with uniaxial orientation.
Highly Luminescent Gold Nanocluster Frameworks
Authors: Chandra Sourov , Nonappa  , Beaune Grégory , Som Anirban , Zhou Shaochen , Lahtinen Jouko , Jiang Hua , Timonen Jaakko V. I. , Ikkala Olli , Ras Robin H. A. 
Published: July 2019

AbstractMetal nanoclusters (NCs) are being intensely pursued as prospective luminophores because of their tunable electronic and optical properties. Among the various fluorescent NCs, gold nanoclusters (GNCs) are attractive due to their biocompatibility and excellent photostability, even if so far, they have had limited application potential due to poor quantum yield (QY). In this context, a facile route is demonstrated to tune up the photophysical and photochemical activities of water‐borne luminescent GNCs through the formation of self‐assembled nanocluster superstructures. The approach involves the controlled introduction of Sn2+ ions, directing GNCs from individual particles into 3D spherical gold nanocluster colloidal frameworks (GNCFs). In these, the reduction in the nonemissive relaxation pathways leads to significant enhancement of luminescence signals (QY from ≈3.5% to ≈25%), likely owing to restricted movements of ligands. This approach paves ways for GNCFs as a potent agent for biomedical imaging and therapies, while their high photocatalytic activity is an added advantage.
Copper‐Promoted Tandem Three‐Component Access to Quinazolin‐4(H)‐imines and Benzimidazo[1,2‐c]quinazolines
Authors: Rodrigues Romain , Tran Lam Quang , Darses Benjamin , Dauban Philippe , Neuville Luc 
Published: July 2019

AbstractA copper‐catalyzed three‐component assembly of cyanamides, 2‐cyanoarylboronic acids and amines has been developed, providing functionalized quinazolin‐4(H)‐imines. Subsequent access to benzimidazo[1,2‐c]quinazolines is achieved building again on copper‐catalysis. One pot hydrolysis of quinazolin‐4(H)‐imines to quinazolin‐4(3H)‐ones is also described. Guanidine formation, cyclization and intramolecular C−H bond amination are key features of the process fully mediated by copper.magnified image
Triboelectric‐TFT Flip‐Flop for Bistable Latching of Dielectric Elastomer Actuators
Authors: Marette Alexis , Haque Rubaiyet Iftekharul , Ji Xiaobin , Hinchet Ronan , Shea Herbert R. , Briand Danick 
Published: July 2019

AbstractA high‐voltage flip‐flop combining two self‐powered soft sensors with a flexible high‐voltage thin film transistor (HVTFT) is reported, and is used to electrically latch dielectric elastomer actuators (DEAs) in zero and high‐strain states. Two touch‐actuated triboelectric generators (TENGs) provide the gate input for the HVTFT that drives a DEA. One TENG is of positive polarity, while the other is of negative polarity, thus generating voltages either higher (100 V) or lower (−6 V) than the HVTFT threshold voltage. Used in a high‐voltage inverter configuration, there are two stable output voltage states, here 650 V (the “reset” state) and 50 V (the “set” state). The DEA is thus latched in one of two states, at 17.5% and 0% strain. The 650 V output is stable in time, while the 50 V state drifts up to 350 V after 10 s. Due to the highly nonlinear strain–voltage curve of the DEA, the drift of the output voltage in the “set” state leads only to a 2% increase of the DEA actuation strain in 10 s. By enabling bistable control of DEAs with TENGs, the TENG‐HVTFT latch paves the way toward soft robots with flexible embedded control circuitry.
Boosting Organic–Metal Oxide Heterojunction via Conjugated Small Molecules for Efficient and Stable Nonfullerene Polymer Solar Cells
Authors: Liu Haoran , Liu Zhi‐Xi , Wang Shuxu , Huang Jiang , Ju Huanxin , Chen Qi , Yu Junsheng , Chen Hongzheng , Li Chang‐Zhi 
Published: July 2019

AbstractCharge events across organic–metal oxide heterointerfaces routinely occur in organic electronics, yet strongly influence their overall performance and stability. They become even more complicated and challenging for the heterojunction conditions in polymer solar cells (PSCs), especially when nonfullerene acceptors with varied energetics are employed. In this work, an effective interfacial strategy that utilizes novel small molecule self‐assembled monolayers (SAMs) is developed to improve the electronic and electric, as well as chemical properties of organic–zinc oxide (ZnO) interfaces for nonfullerene PSCs. It is revealed that the tailored SAMs with well‐controlled energy levels and molecular dipoles can effectively optimize the energetic barrier and work function (WF) of heterointerface for optimal electron extraction. In addition, the introduction of SAMs atop of ZnO facilitates not only acceptor segregation near the n‐contact interface, but also passivation of the photocatalytic activities for ZnO, to improve overall performance and photo stability of the derived nonfullerene PSCs. Overall, the methodology and structure–property relationship revealed herein would be beneficial for a wide range of hybrid electronics.
In Situ Revealing the Electroactivity of PO and PC Bonds in Hard Carbon for High‐Capacity and Long‐Life Li/K‐Ion Batteries
Authors: Qian Yong , Jiang Song , Li Yang , Yi Zheng , Zhou Jie , Li Tieqiang , Han Ying , Wang Yusong , Tian Jie , Lin Ning , Qian Yitai 
Published: July 2019

AbstractThe low capacity and unsatisfactory rate capability of hard carbon still restricts its practical application for Li/K‐ion batteries. Herein, a low‐cost and large‐scale method is developed to fabricate phosphorus‐doped hard carbon (PHC‐700) by crosslinking phosphoric acid and epoxy resin and followed by annealing at 700 °C. H3PO4 acts not only as a crosslinker to solidify epoxy resin for promoting the degree of graphitization and lowering the specific surface area, but also as phosphorus source for forming PC and PO bonds, thus providing more active sites for Li/K storage. As a result, the PHC‐700 electrode delivers a highly reversible capacity of 1294.8 mA h g−1 at 0.1 A g−1 and a capacity of 214 mA h g−1 after 10 000 cycles at 10 A g−1. As for potassium‐ion batteries, PHC‐700 exhibits a reversible capacity of 381.9 mA h g−1 at 0.1 A g−1 and a capacity of 260 mA h g−1 after 1000 cycles at 0.2 A g−1. In situ Raman and in situ NMR measurements reveal that the P‐containing bonds can enhance the adsorption to alkali metal ions, and the PC bond can participate in electrochemical redox reaction by forming Lix
PCy
. Additionally, P‐doped hard carbon shows better structural/interfacial stability for improved long‐term cycling stability.
Versatile N‐Doped MXene Ink for Printed Electrochemical Energy Storage Application
Authors: Yu Lianghao , Fan Zhaodi , Shao Yuanlong , Tian Zhengnan , Sun Jingyu , Liu Zhongfan 
Published: July 2019

AbstractPrinting is regarded as a revolutionary and feasible technique to guide the fabrication of versatile functional systems with designed architectures. 2D MXenes are nowadays attractive in printed energy storage devices. However, owing to the van der Waals interaction between the MXene layers, the restacking issues within the printed electrodes can significantly impede the ion/electrolyte transport and hence handicap the electrochemical performances. Herein, a melamine formaldehyde templating method is demonstrated to develop crumpled nitrogen‐doped MXene (MXene‐N) nanosheets. The nitrogen doping boosts the electrochemical performances of MXene via enhanced conductivity and redox activity. Accordingly, two types of MXene‐N inks are prepared throughout the optimization of the ink viscosity to fit the 2D screen printing and 3D extrusion printing, respectively. As a result, the screen printed MXene‐N microsupercapacitor delivers an areal capacitance of 70.1 mF cm−2 and outstanding mechanical robustness. Furthermore, the 3D‐printed MXene‐N based supercapacitor manifests an areal capacitance of 8.2 F cm−2 for a three‐layered electrode and readily stores a high areal energy density of 0.42 mWh cm−2. The approach to harnessing such versatile MXene‐N inks offers distinctive insights into the printed energy storage systems with high areal energy density and large scalability.
Research platform for children with arthrogryposis multiplex congenita: Findings from the pilot registry
Authors: Dahan‐Oliel Noémi , van Bosse Harold J. P. , Bedard Tanya , Darsaklis Vasiliki B. , Hall Judith G. , Hamdy Reggie C. 
Published: July 2019

AbstractA pediatric registry for arthrogryposis multiplex congenita (AMC) proposes to advance research by providing the platform to inform the distribution, etiology, and natural history of AMC. The registry was piloted on 40 families of children (mean = 8.25 years, 48% males) presenting with AMC across two hospitals in North America. Data on the child's demographic and newborn variables, mothers' and fathers' demographic variables, lifestyle habits, and medical history were collected using a telephone interview with the primary caregiver and review of medical charts. Mean gestational age was 38 weeks, 97% of children presented with lower extremity deformities, and 74% of neonatal interventions targeted the lower extremity. Newborns spent an average of 14 days in the hospital (range 2–56 days) mostly for diagnostic workup and feeding difficulties. Half (49%) of the sample had internal organ involvement. Genetic testing was done on 48% of the children, including chromosome studies, single gene, whole‐exome/genome sequencing, and/or microarray studies. Genetic findings were inconclusive in most. Two‐thirds of mothers (67%) reported inconsistently feeling fetal movements. This pilot study contributed to the refinement of participant selection, identification of data source, expansion of data sets, and areas for future exploration prior to the implementation of a multisite AMC pediatric registry.
Synthesis of Pyrrolone‐ and Isoindolinone‐Fused Benzimidazole‐4,7‐diones by Stepwise Palladium‐Catalyzed Carbonylative Cyclization and Oxidation
Authors: Kim Dong Young , Dao Pham Duy Quang , Yoon Nam Sik , Cho Chan Sik 
Published: July 2019

Abstract2‐(2‐Bromovinyl)‐ and 2‐(2‐bromoaryl)‐4,7‐dimethoxybenzimidazoles react with carbon monoxide (10 atm) in toluene in the presence of a catalytic amount of PdCl2 and PPh3 along with NaOAc to produce the corresponding pyrrolone‐ and isoindolinone‐fused 4,7‐dimethoxybenzimidazoles, respectively, in good yields. Oxidation of such binuclear N‐fused hybrid scaffolds with ceric ammonium nitrate in acetonitrile‐H2O gives unprecedented pyrrolone‐ and isoindolinone‐fused benzimidazole‐4,7‐diones in high yields.
Oxytocin and pair compatibility in adult male rhesus macaques (Macaca mulatta)
Authors: Berg Melissa R. , Heagerty Allison , Coleman Kristine 
Published: July 2019

AbstractPair housing is considered one of the best ways of promoting psychological wellbeing for caged macaques. However, incompatible partnerships can result in stress or aggression. Though previous studies have analyzed the role of variables such as age, weight, gender, and temperament on pair compatibility, few have examined the relationship between physiological parameters and pair compatibility. Oxytocin is known to promote prosocial nonsexual behavior in various primate species and may serve as an indicator of pair compatibility. In this study, we examined the association between peripheral oxytocin levels and prosocial behaviors in isosexual pairs of male rhesus macaques. We hypothesized that animals that demonstrated high levels of prosocial behaviors would have higher oxytocin levels than those showing low levels of the behavior. In addition, to elucidate the relationship between oxytocin and compatibility, we compared peripheral oxytocin between the highly affiliative animals and single‐housed males identified as having multiple unsuccessful pair attempts with multiple partners. We collected plasma oxytocin on 40 pairs of monkeys that had lived together for at least 1 month and 20 single‐housed animals. Further, we simultaneously collected behavioral data on the pairs, recording prosocial interactions (e.g., groom, play). Oxytocin varied among individuals, but was highly correlated between members of a pair (r = 0.58,p < .001). Additionally, prosocial behavior was positively correlated with plasma oxytocin (r = 0.38,p < .02). However, contrary to our expectations, oxytocin did not differ between single and highly affiliative pair‐housed animals (F(1,38) = 0.71,p = .40). Our results suggest that oxytocin may be associated with the quality of isosexual pairs of male macaques. More work is needed to determine the nature of this relationship.
Reaktive Oberflächenplanarisierung von Pt(II)‐Komplexen
Authors: Ren Jindong , Cnudde Marvin , Brünink Dana , Buss Stefan , Daniliuc Constantin G. , Liu Lacheng , Fuchs Harald , Strassert Cristian A. , Gao Hong‐Ying , Doltsinis Nikos L. 
Published: July 2019

AbstractEine Reihe von Pt(II)‐Komplexen mit tetradentaten Luminophoren wurde entworfen, synthetisiert und mit dem Ziel auf Edelmetalloberflächen aufgebracht, hochplanare selbstassemblierte Monolagen herzustellen. Tieftemperatur‐Rastertunnelmikroskopie (STM) sowie Dichtefunktionaltheorie (DFT)‐Rechnungen zeigen eine erhebliche initiale Nichtplanarität für alle Komplexe. Anschließend wurde eine metallkatalysierte Spaltung der nichtplanaren Brückeneinheit via C−N Bindungsbruch beobachtet, die einen größtenteils planaren Kernkomplex zurücklässt. Die Aktivierungsbarriere für diesen Bindungsbruch hängt stark von der chemischen Struktur sowohl der Brückengruppe als auch der Koordinationsebene ab und steigt von Cu(111) über Ag(111) zu Au(111).
Manipulating the Stacking of Triplet Chromophores in the Crystal Form for Ultralong Organic Phosphorescence
Authors: Gan Nan , Wang Xuan , Ma Huili , Lv Anqi , Wang He , Wang Qian , Gu Mingxing , Cai Suzhi , Zhang Yanyun , Fu Lishun , Zhang Meng , Dong Chaomin , Yao Wei , Shi Huifang , An Zhongfu , Huang Wei 
Published: July 2019

AbstractProvided here is evidence showing that the stacking between triplet chromophores plays a critical role in ultralong organic phosphorescence (UOP) generation within a crystal. By varying the structure of a functional unit, and different on‐off UOP behavior was observed for each structure. Remarkably, 24CPhCz, having the strongest intermolecular interaction between carbazole units exhibited the most impressive UOP with a long lifetime of 1.06 s and a phosphorescence quantum yield of 2.5 %. 34CPhCz showed dual‐emission UOP and thermally activated delayed fluorescence (TADF) with a moderately decreased phosphorescence lifetime of 770 ms, while 35CPhCz only displayed TADF owing to the absence of strong electronic coupling between triplet chromophores. This study provides an explanation for UOP generation in crystal and new guidelines for obtaining UOP materials.
Direct Observation of Aliphatic Peroxy Radical Autoxidation and Water Effects: An Experimental and Theoretical Study
Authors: Nozière Barbara , Vereecken Luc 
Published: July 2019

AbstractThe autoxidation of organic peroxy radicals (RO2) into hydroperoxy‐alkyl radicals (QOOH), then hydroperoxy‐peroxy radicals (HOOQO2) is now considered to be important in the Earth's atmosphere. To avoid mechanistic uncertainties these reactions are best studied by monitoring the radicals. But for the volatile and aliphatic RO2 radicals playing key roles in the atmosphere this has long been an instrumental challenge. This work reports the first study of the autoxidation of aliphatic RO2 radicals and is based on monitoring RO2 and HOOQO2 radicals. The rate coefficients, kiso (s−1), were determined both experimentally and theoretically using MC‐TST kinetic theory based on CCSD(T)//M06‐2X quantum chemical methodologies. The results were in excellent agreement and confirmed that the first H‐migration is strongly rate‐limiting in the oxidation of non‐oxygenated volatile organic compounds (VOCs). At higher relative humidity (2–30 %) water complexes were evidenced for HOOQO2 radicals, which could be an important fate for HOO‐substituted RO2 radicals in the atmosphere.
Boosting Hydrogen Oxidation Activity of Ni in Alkaline Media through Oxygen‐Vacancy‐Rich CeO2/Ni Heterostructures
Authors: Yang Fulin , Bao Xi , Li Peng , Wang Xuewei , Cheng Gongzhen , Chen Shengli , Luo Wei 
Published: July 2019

AbstractThe search for highly efficient platinum group metal (PGM)‐free electrocatalysts for the hydrogen oxidation reaction (HOR) in alkaline electrolytes remains a great challenge in the development of alkaline exchange membrane fuel cells (AEMFCs). Here we report the synthesis of an oxygen‐vacancy‐rich CeO2/Ni heterostructure and its remarkable HOR performance in alkaline media. Experimental results and density functional theory (DFT) calculations indicate the electron transfer between CeO2 and Ni could lead to thermoneutral adsorption free energies of H* (ΔGH*). This, together with the promoted OH* adsorption strength derived from the abundance of oxygen vacancies in the CeO2 species, contributes to the excellent HOR performance with the exchange current density and mass activity of 0.038 mA cmNi−2 and 12.28 mA mgNi−1, respectively. This presents a new benchmark for PGM‐free alkaline HOR and opens a new avenue toward the rational design of high‐performance PGM‐free electrocatalysts for alkaline HOR.
Hexahalodiborate Dianions: A New Family of Binary Boron Halides
Authors: Bélanger‐Chabot Guillaume , Braunschweig Holger 
Published: July 2019

AbstractThe electron‐precise binary boron subhalide species [B2X6]2− X=F, Br, I) were synthesized and their structures confirmed by X‐ray crystallography. The existence of the previously claimed [B2Cl6]2−, which had been questioned, was also confirmed by X‐ray crystallography. The dianions are isoelectronic to hexahaloethanes, are subhalide analogues of the well‐known tetrahaloborate anions (BX4−), and are rare examples of molecular electron‐precise binary boron species beyond B2X4, BX3, and [BX4]−.
Conditionally Gaussian random sequences for an integrated variance estimator with correlation between noise and returns
Authors: Peluso Stefano , Mira Antonietta , Muliere Pietro 
Published: July 2019

AbstractCorrelation between microstructure noise and latent financial logarithmic returns is an empirically relevant phenomenon with sound theoretical justification. With few notable exceptions, all integrated variance estimators proposed in the financial literature are not designed to explicitly handle such a dependence, or handle it only in special settings. We provide an integrated variance estimator that is robust to correlated noise and returns. For this purpose, a generalization of the forward filtering backward sampling algorithm is proposed, to provide a sampling technique for a latent conditionally Gaussian random sequence. We apply our methodology to intraday Microsoft prices and compare it in a simulation study with established alternatives, showing an advantage in terms of root‐mean‐square error and dispersion.
Comparison of physics‐based and data‐driven modelling techniques for dynamic optimisation of fed‐batch bioprocesses
Authors: Del Rio‐Chanona Ehecatl Antonio , Ahmed Nur Rashid , Wagner Jonathan , Lu Yinghua , Zhang Dongda , Jing Keju 
Published: July 2019

AbstractThe development of digital bioprocessing technologies is critical to operate modern industrial bioprocesses. This study conducted the first investigation on the efficiency of using physics‐based and data‐driven models for the dynamic optimisation of long‐term bioprocess. More specifically, this study exploits a predictive kinetic model and a cutting‐edge data‐driven model to compute open‐loop optimisation strategies for the production of microalgal lutein during a fed‐batch operation. Light intensity and nitrate inflow rate are used as control variables given their key impact on biomass growth and lutein synthesis. By employing different optimisation algorithms, several optimal control sequences were computed. Due to the distinct model construction principles and sophisticated process mechanisms, the physics‐based and the data‐driven models yielded contradictory optimisation strategies. The experimental verification confirms that the data‐driven model predicted a closer result to the experiments than the physics‐based model. Both models succeeded in improving lutein intracellular content by over 40% compared to the highest previous record; however, the data‐driven model outperformed the kinetic model when optimising total lutein production and achieved an increase of 40–50%. This indicates the possible advantages of using data‐driven modelling for optimisation and prediction of complex dynamic bioprocesses, and its potential in industrial bio‐manufacturing systems.