bluuebunny/crossref_metadata_2025_split huggingface dataset:
Intermolecular Charge‐Transfer Transition Emitter Showing Thermally Activated Delayed Fluorescence for Efficient Non‐Doped OLEDs
Authors: Shi Yi‐Zhong , Wang Kai , Li Xing , Dai Gao‐Le , Liu Wei , Ke Ke , Zhang Ming , Tao Si‐Lu , Zheng Cai‐Jun , Ou Xue‐Mei , Zhang Xiao‐Hong 
Published: June 2018

AbstractA novel molecular model of connecting electron‐donating (D) and electron‐withdrawing (A) moieties via a space‐enough and conjugation‐forbidden linkage (D‐Spacer‐A) is proposed to develop efficient non‐doped thermally activated delayed fluorescence (TADF) emitters. 10‐(4‐(4‐(4,6‐diphenyl‐1,3,5‐triazin‐2‐yl) phenoxy) phenyl)‐9,9‐dimethyl‐9,10‐dihydroacridine (DMAC‐o‐TRZ) was designed and synthesized accordingly. As expected, it exhibits local excited properties in single‐molecule state as D‐Spacer‐A molecular backbone strongly suppress the intramolecular charge‐transfer (CT) transition. And intermolecular CT transition acted as the vital radiation channel for neat DMAC‐o‐TRZ film. As in return, the non‐doped device exhibits a remarkable maximum external quantum efficiency (EQE) of 14.7 %. These results prove the feasibility of D‐Spacer‐A molecules to develop intermolecular CT transition TADF emitters for efficient non‐doped OLEDs.
Ylide‐Functionalized Phosphines: Strong Donor Ligands for Homogeneous Catalysis
Authors: Scherpf Thorsten , Schwarz Christopher , Scharf Lennart T. , Zur Jana‐Alina , Helbig Andreas , Gessner Viktoria H. 
Published: June 2018

AbstractPhosphines are important ligands in homogenous catalysis and have been crucial for many advances, such as in cross‐coupling, hydrofunctionalization, or hydrogenation reactions. Herein we report the synthesis and application of a novel class of phosphines bearing ylide substituents. These phosphines are easily accessible via different synthetic routes from commercially available starting materials. Owing to the extra donation from the ylide group to the phosphorus center the ligands are unusually electron‐rich and can thus function as strong electron donors. The donor capacity surpasses that of commonly used phosphines and carbenes and can easily be tuned by changing the substitution pattern at the ylidic carbon atom. The huge potential of ylide‐functionalized phosphines in catalysis is demonstrated by their use in gold catalysis. Excellent performance at low catalyst loadings under mild reaction conditions is thus seen in different types of transformations.
Hydrophobicity Control in Adaptive Crystalline Assemblies
Authors: Cohen Erez , Soffer Yahel , Weissman Haim , Bendikov Tatyana , Schilt Yaelle , Raviv Uri , Rybtchinski Boris 
Published: June 2018

AbstractAn amphiphile based on polyethylene glycol (PEG) polymer and two molecular moieties (perylene diimide and C7 fluoroalkyl, PDI and C7F) attached to its termini assembles into crystalline films with long‐range order. The films reversibly switch from crystalline to amorphous above the PEG melting temperature. The adaptive behavior stems from the responsiveness of the PEG domain and the robustness of the PDI and C7F assemblies. The hydrophobicity of the film can be controlled by heating, resulting in switching from highly hydrophobic to superhydrophilic. The long‐range order, reversible crystallinity switching, and the temperature‐controlled wettability demonstrate the potential of block copolymer analogues based on simple polymeric/molecular hybrids.
Palladium‐Catalyzed Asymmetric C(sp3)−H Allylation of 2‐Alkylpyridines
Authors: Murakami Ryo , Sano Kentaro , Iwai Tomohiro , Taniguchi Tohru , Monde Kenji , Sawamura Masaya 
Published: June 2018

AbstractThe palladium‐catalyzed asymmetric side‐chain C(α)‐allylation of 2‐alkylpyridines, without using an external base, was developed. The high linear selectivities and enantioselectivities were achieved using new chiral diamidophosphite monodentate ligands. Given that the reaction conditions do not require an external base, this catalyst system enabled chemoselective C(α)‐allylation of 2‐alkylpyridines containing α‐carbonyl C−H bonds, which are more acidic than α‐pyridyl C−H bonds.
Ceria Nanoparticle Systems for Selective Scavenging of Mitochondrial, Intracellular, and Extracellular Reactive Oxygen Species in Parkinson's Disease
Authors: Kwon Hyek Jin , Kim Dokyoon , Seo Kyungho , Kim Young Geon , Han Sang Ihn , Kang Taegyu , Soh Min , Hyeon Taeghwan 
Published: June 2018

AbstractOxidative stress induced by reactive oxygen species (ROS) is one of the critical factors that involves in the pathogenesis and progression of many diseases. However, lack of proper techniques to scavenge ROS depending on their cellular localization limits a thorough understanding of the pathological effects of ROS. Here, we demonstrate the selective scavenging of mitochondrial, intracellular, and extracellular ROS using three different types of ceria nanoparticles (NPs), and its application to treat Parkinson's disease (PD). Our data show that scavenging intracellular or mitochondrial ROS inhibits the microglial activation and lipid peroxidation, while protecting the tyrosine hydroxylase (TH) in the striata of PD model mice. These results indicate the essential roles of intracellular and mitochondrial ROS in the progression of PD. We anticipate that our ceria NP systems will serve as a useful tool for elucidating the functions of various ROS in diseases.
Ruthenium‐Containing Linear Helicates and Mesocates with Tuneable p53‐Selective Cytotoxicity in Colorectal Cancer Cells
Authors: Allison Simon J. , Cooke David , Davidson Francesca S. , Elliott Paul I. P. , Faulkner Robert A. , Griffiths Hollie B. S. , Harper Owen J. , Hussain Omar , Owen‐Lynch P. Jane , Phillips Roger M. , Rice Craig R. , Shepherd Samantha L. , Wheelhouse Richard T. 
Published: June 2018

AbstractThe ligands L1 and L2 both form separable dinuclear double‐stranded helicate and mesocate complexes with RuII. In contrast to clinically approved platinates, the helicate isomer of [Ru2(L1)2]4+ was preferentially cytotoxic to isogenic cells (HCT116 p53−/−), which lack the critical tumour suppressor gene. The mesocate isomer shows the reverse selectivity, with the achiral isomer being preferentially cytotoxic towards HCT116 p53+/+. Other structurally similar RuII‐containing dinuclear complexes showed very little cytotoxic activity. This study demonstrates that alterations in ligand or isomer can have profound effects on cytotoxicity towards cancer cells of different p53 status and suggests that selectivity can be “tuned” to either genotype. In the search for compounds that can target difficult‐to‐treat tumours that lack the p53 tumour suppressor gene, [Ru2(L1)2]4+ is a promising compound for further development.
Cp*CoIII‐Catalyzed Efficient Dehydrogenation of Secondary Alcohols
Authors: Gangwar Manoj Kumar , Dahiya Pardeep , Emayavaramban Balakumar , Sundararaju Basker 
Published: June 2018

AbstractA novel, well‐defined molecular Cp*CoIII complex was isolated and structurally characterized for the first time. The efficiency of this cobalt catalyst was demonstrated in the alcohol dehydrogenation and dehydrative coupling of secondary alcohols under mild conditions into ketones and ethers, respectively.
Nomogram to predict lymph node metastasis in patients with early oesophageal squamous cell carcinoma
Authors: Zheng H , Tang H , Wang H , Fang Y , Shen Y , Feng M , Xu S , Fan H , Ge D , Wang Q , Tan L 
Published: June 2018

AbstractBackgroundLymph node status is crucial in determining the prognosis for early oesophageal squamous cell carcinoma (SCC). This study aimed to develop and validate a nomogram for the prediction of lymph node metastasis in patients with early SCC.MethodsA prediction model was developed in a derivation cohort of patients with clinicopathologically confirmed early SCC. Patients who underwent oesophagectomy for pT1 SCC between January 2010 and December 2013 were identified from an institutional database. Risk factors for lymph node metastasis were assessed using a binary logistic regression modelling technique. A nomogram for the prediction of lymph node metastasis was constructed using the results of multivariable analyses. For internal validation, bootstraps with 1000 resamples were performed. The predictive performance of the nomogram was measured by Harrell's concordance index (C-index). An independent cohort from the same hospital was used to validate the nomogram. This cohort included consecutive patients with early SCC who underwent oesophagectomy from January 2014 to December 2015.ResultsThe derivation cohort included 281 patients. Four variables associated with lymph node metastasis were included in the model: depth of tumour invasion (odds ratio (OR) 4·37, 95 per cent c.i. 1·59 to 12·03; P = 0·004), grade of differentiation (OR 4·47, 1·02 to 19·70; P = 0·048), tumour size (OR 2·52, 1·11 to 5·75; P = 0·028) and lymphovascular invasion (OR 6·58, 2·54 to 17·05; P &lt; 0·001). The C-index was 0·790 (95 per cent c.i. 0·717 to 0·864) in the derivation cohort and 0·789 (0·709 to 0·869) for the validation cohort (198 patients).ConclusionA validated nomogram for patients with early oesophageal SCC can predict the risk of lymph node metastasis.
Predictive value of abdominal CT in evaluating internal herniation after bariatric laparoscopic Roux-en-Y gastric bypass
Authors: Ederveen J C , van Berckel M M G , Nienhuijs S W , Weber R J P , Nederend J 
Published: June 2018

Abstract

Background
Internal herniation, a serious complication after bariatric surgery, is challenging to diagnose. The aim of this study was to determine the accuracy of abdominal CT in diagnosing internal herniation.

Methods
The study included consecutive patients who had undergone laparoscopic gastric bypass surgery between 1 January 2011 and 1 January 2015 at a bariatric centre of excellence. To select patients suspected of having internal herniation, reports of abdominal CT and reoperations up to 1 January 2017 were screened. CT was presumed negative for internal herniation if no follow-up CT or reoperation was performed within 90 days after the initial CT, or no internal herniation was found during reoperation. The accuracy of abdominal CT in diagnosing internal herniation was calculated using two-way contingency tables.

Results
A total of 1475 patients were included (84·7 per cent women, mean age 46·5 years, median initial BMI 41·8 kg/m2). CT and/or reoperation was performed in 192 patients (13·0 per cent) in whom internal herniation was suspected. Internal herniation was proven laparoscopically in 37 of these patients. The incidence of internal herniation was 2·5 per cent. An analysis by complaint included a total of 265 episodes, for which 247 CT scans were undertaken. CT was not used to investigate 18 episodes, but internal herniation was encountered in one-third of these during reoperation. Combining the follow-up and intraoperative findings, the accuracy of CT for internal herniation had a sensitivity of 83·8 (95 per cent c.i. 67·3 to 93·2) per cent, a specificity of 87·1 (81·7 to 91·2) per cent, a positive predictive value of 53·4 (40·0 to 66·5) per cent and a negative predictive value of 96·8 (92·9 to 98·7) per cent.

Conclusion
Abdominal CT is an important tool in diagnosing internal herniation, with a high specificity and a high negative predictive value.
Bioorthogonally Applicable Fluorescence Deactivation Strategy for Receptor Kinetics Study and Theranostic Pretargeting Approaches
Authors: van der Wal Steffen , de Korne Clarize M. , Sand Laurens G. L. , van Willigen Danny M. , Hogendoorn Pancras C. W. , Szuhai Karoly , van Leeuwen Fijs W. B. , Buckle Tessa 
Published: June 2018

AbstractThe availability of a receptor for theranostic pretargeting approaches was assessed by use of a new click‐chemistry‐based deactivatable fluorescence‐quenching concept. The efficacy was evaluated in a cell‐based model system featuring both membranous (available) and internalized (unavailable) receptor fractions of the clinically relevant receptor chemokine receptor 4 (CXCR4). Proof of concept was achieved with a deactivatable tracer consisting of a CXCR4‐specific peptide functionalized with a Cy5 dye bearing a chemoselective azide handle (N3‐Cy5‐AcTZ14011). Treatment with a Cy7 quencher dye (Cy7‐DBCO) resulted in optically silent Cy7‐[click]‐Cy5‐AcTZ14011. In situ, a >90 % FRET‐based reduction of the signal intensity of N3‐Cy5‐AcTZ14011 [KD=(222.4±25.2) nm] was seen within minutes after quencher addition. In cells, discrimination between the membranous and the internalized receptor fraction could be achieved through quantitative assessment of quenching/internalization kinetics. Similar evaluation of an activatable tracer variant based on the same targeting moiety (Cy5‐S‐S‐Cy3‐AcTZ14011) was unsuccessful in vitro. As such, using the described deactivatable approach to screen membrane receptors and their applicability in receptor‐(pre‐)targeted theranostics can become straightforward.
Nanoconfined Nitrogen‐Doped Carbon‐Coated Hierarchical TiCoN Composites with Enhanced ORR Performance
Authors: Tang Haibo , Luo Junming , Yu Jinnan , Zhao Weiyue , Song Huiyu , Liao Shijun 
Published: June 2018

AbstractThe high cost of platinum‐based cathode catalysts for the oxygen reduction reaction (ORR) has long hampered the practical application of fuel cells. In‐depth studies have shown titanium nitride (TiN) is an interesting non‐precious‐metal electrocatalysts for replacing Pt, due to their low cost, excellent catalytic properties, and stability. In this study, we report on a three‐dimensional (3D) nitrogen‐doped carbon‐coated hierarchical Ti0.95Co0.05N composite, created using a one‐step impregnation method followed by nitriding. The catalyst exhibited significantly enhanced ORR activity and excellent electrochemical stability. Our optimal catalyst, 20 %C‐Ti0.95Co0.05N, had an ORR performance almost comparable to 20 % Pt/C in an alkaline medium, and a four‐electron pathway was dominant during the ORR reaction. The significantly enhanced ORR performance of this catalyst is attributable to the following factors: the synergic effect of a carbon coating on the nitride nanoparticles (NPs), including the higher surface area and more exposed active‐sites caused by the well‐defined 3D structure resulting from the carbon coating; better mass transfer and electron transfer due to the carbon coating; the contribution of the doped carbon; and enhancement of the nitride's activity by doping with transition metal.
Helicity Control of Supramolecular Gel Fibers Consisting of an Achiral NiII Complex in a Chiral Nematic Solvent
Authors: Maeda Takatoshi , Kuwajima Yuuki , Akita Takuya , Iwai Yosuke , Komiya Naruyoshi , Uchida Yoshiaki , Naota Takeshi 
Published: June 2018

AbstractThe supramolecular chirality of aggregates consisting of achiral trans‐bis(salicylaldiminato)NiII complex 1 bearing long alkyl chains can be generated and controlled precisely in a chiral nematic liquid‐crystalline (LC) solvent, whereas the complex naturally forms achiral gel fibers in achiral nematic LC solvents and crystals in nonmesogenic solvents. The direction and intensity of the helicity of the gel fibers of 1 in the LC gel state can be adjusted by means of the nature of the helical twisting and the concentration of the chiral dopants. Helicity control was precisely detected in the circular dichroism (CD) spectra of LC gels and by direct SEM observation of the dried gel fibers. XRD analysis revealed that the flexibility of the herringbone‐based lamellar alignment of this complex is the key to the LC‐specific gelation and helicity control of the gel fibers.
Recent Advances in the Development of Indazole‐based Anticancer Agents
Authors: Dong Jinyun , Zhang Qijing , Wang Zengtao , Huang Guang , Li Shaoshun 
Published: June 2018

AbstractCancer is one of the leading causes of human mortality globally; therefore, intensive efforts have been made to seek new active drugs with improved anticancer efficacy. Indazole‐containing derivatives are endowed with a broad range of biological properties, including anti‐inflammatory, antimicrobial, anti‐HIV, antihypertensive, and anticancer activities. In recent years, the development of anticancer drugs has given rise to a wide range of indazole derivatives, some of which exhibit outstanding activity against various tumor types. The aim of this review is to outline recent developments concerning the anticancer activity of indazole derivatives, as well as to summarize the design strategies and structure–activity relationships of these compounds.
Building a scientific workflow framework to enable real‐time machine learning and visualization
Authors: Li Feng , Song Fengguang 
Published: June 2018

SummaryNowadays, we have entered the era of big data. In the area of high performance computing, large‐scale simulations can generate huge amounts of data with potentially critical information. However, these data are usually saved in intermediate files and are not instantly visible until advanced data analytics techniques are applied after reading all simulation data from persistent storages (eg, local disks or a parallel file system). This approach puts users in a situation where they spend long time on waiting for running simulations while not knowing the status of the running job. In this paper, we build a new computational framework to couple scientific simulations with multi‐step machine learning processes and in‐situ data visualizations. We also design a new scalable simulation‐time clustering algorithm to automatically detect fluid flow anomalies. This computational framework is built upon different software components and provides plug‐in data analysis and visualization functions over complex scientific workflows. With this advanced framework, users can monitor and get real‐time notifications of special patterns or anomalies from ongoing extreme‐scale turbulent flow simulations.
Coupling Resonances of Surface Plasmon in Gold Nanorod/Copper Chalcogenide Core−Shell Nanostructures and Their Enhanced Photothermal Effect
Authors: Li Yingying , Pan Guiming , Liu Qiyu , Ma Liang , Xie Ying , Zhou Li , Hao Zhonghua , Wang Ququan 
Published: June 2018

AbstractDual plasmonic Au@Cu2−xS core−shell nanorods (NRs) have been fabricated by using a hydrothermal method and plasmon‐coupled effect between the Au core and Cu2−xS shell in the near‐infrared (NIR) region. The extinction spectrum of Au@Cu2−xS NRs is dominated by the surface plasmon resonance (SPR) of the Cu2−xS shell, the transverse surface plasmon resonance (TSPR), and the longitudinal surface plasmon resonance (LSPR) of the Au NRs. With the Cu2−xS shell increasing (fixed Au NRs), the TSPR peak slightly redshifts and the LSPR and SPR peaks blueshift, owing to competition between the redshift of the refractive index effect and blueshift from the plasmon coupled effect. Although, for Au@Cu2S NRs, only TSPR and LSPR peaks can be seen and a redshift arises with the increasing Cu2S shell thickness, implying that no plasmonic coupling between Au NRs and Cu2S shell occurred. The extinction spectrum of the Au@Cu2−xS NRs with three coupled resonance peaks is simulated by using the FDTD method, taking into account the electron‐transfer effect. The dispersion properties of the coupling of Au@Cu2−xS NRs with the LSPR of the initial Au core are studied experimentally by changing the length of the Au NRs, which are explained theoretically by the coupled harmonic oscillator model. The calculated coupled coefficients between SPR of the Cu2−xS shell and LSPR of the Au NRs is 180 meV, which is much stronger than that of TSPR of Au NRs of 55 meV. Finally, the enhanced photothermal effect of Au@Cu2−xS NRs has been demonstrated.
Chiral Separation via Molecular Sieving: A Computational Screening of Suitable Functionalizations for Nanoporous Graphene
Authors: Fruehwirth Samuel M. , Meyer Ralf , Hauser Andreas W. 
Published: June 2018

AbstractIn a recent study [Angew. Chem. Int. Ed., 2014, 53, 9957–9960] a new concept of chiral separation has been suggested, which is based on functionalized, nanoporous sheets of graphene. In this follow‐up article we discuss the underlying principle in greater detail and make suggestions for suitable pore functionalizations with respect to a selection of chiral prototype molecules. Considering drug molecules as future targets for a chiral separation via membranes, the necessary pore sizes represent a big challenge for standard methods of computational chemistry. Therefore, we test two common force fields (GAFF, CGenFF) as well as a semiempirical tight‐binding approach recently developed by the Grimme group (GFN‐xTB) against the computationally much more expensive density functional theory. We identify the GFN‐xTB method as the most suitable approach for future simulations of functionalized pores for the given purpose, as it is able to produce reaction pathways in very good agreement with density functional theory, even in cases where force fields tend to an extreme overestimation of barrier heights.
Influence of oral bacteria on adhesion of Streptococcus mutans and Streptococcus sanguinis to dental materials
Authors: Nabert‐Georgi Cindy , Rodloff Arne C. , Jentsch Holger , Reissmann Daniel R. , Schaumann Reiner , Stingu Catalina Suzana 
Published: June 2018

AbstractIn this study, the effect of bacterial multispecies communities on the adhesion of Streptococcus mutans and Streptococcus sanguinis to dental restorative material was investigated. The saliva‐coated specimens of zirconia and composite were incubated with the following combinations: single species, S. mutans or S. sanguinis; two species, single species combined with other oral streptococci; multiple species, combination of Actinomyces naeslundii, Fusobacterium nucleatum, and Prevotella ssp.; and the two‐species combinations. The adherent bacteria were counted after plating of serial dilutions. Effects of material and bacteria on adhesion of S. mutans and S. sanguinis were evaluated with multiple linear regression analyses. No significant differences between the materials regarding the adhesion of S. mutans and S. sanguinis were observed. The adhesion of S. mutans was negatively influenced by the presence of other streptococci. Enhancing effects (610.6%) were seen in the presence of Prevotella intermedia. The adhesion of S. sanguinis decreased in the presence of other bacteria, except F. nucleatum (increase of 717.4%). Significant inhibitory effects were detected in the presence of S. mutans and A. naeslundii (reduction of 95.9% and 78.5%, respectively). The results of this study suggest that adhesion of both types of streptococci to restorative materials is influenced by various bacterial interactions.