bluuebunny/crossref_metadata_2025_split huggingface dataset:
Xantphos Doped POPs‐PPh3 as Heterogeneous Ligand for Cobalt‐Catalyzed Highly Regio‐ and Stereoselective Hydrosilylation of Alkynes
Authors: Li Ren‐Hao , Zhang Guo‐Liang , Dong Jia‐Xing , Li Ding‐Chang , Yang Ying , Pan Ying‐Ming , Tang Hai‐Tao , Chen Li , Zhan Zhuang‐Ping 
Published: September 2018

AbstractA Co(acac)2/POL‐Xantphos@10PPh3‐catalyzed hydrosilylation of unsymmetrical internal alkynes with Ph2SiH2 has been developed for the synthesis of highly selective syn‐α‐vinylsilane products. Furthermore, terminal alkynes were also used and gave the products with excellent regioselectivity and a wide functional group tolerance. Because this porous organic polymer combines the selectivity and activity merits of Xantphos with the stability advantage derived from the high concentration of PPh3, the Co(acac)2/POL‐Xantphos@10PPh3 can be recycled multiple times without loss of activity and selectivity. This heterogeneous catalyst is expected to find promising applications in industrial synthesis.
Spectroscopic and metal binding properties of a de novo metalloprotein binding a tetrazinc cluster
Authors: Chino Marco , Zhang Shao‐Qing , Pirro Fabio , Leone Linda , Maglio Ornella , Lombardi Angela , DeGrado William F. 
Published: September 2018

Abstract
De novo design provides an attractive approach, which allows one to test and refine the principles guiding metalloproteins in defining the geometry and reactivity of their metal ion cofactors. Although impressive progress has been made in designing proteins that bind transition metal ions including iron–sulfur clusters, the design of tetranuclear clusters with oxygen‐rich environments remains in its infancy. In previous work, we described the design of homotetrameric four‐helix bundles that bind tetra‐Zn2+ clusters. The crystal structures of the helical proteins were in good agreement with the overall design, and the metal‐binding and conformational properties of the helical bundles in solution were consistent with the crystal structures. However, the corresponding apo‐proteins were not fully folded in solution. In this work, we design three peptides, based on the crystal structure of the original bundles. One of the peptides forms tetramers in aqueous solution in the absence of metal ions as assessed by CD and NMR. It also binds Zn2+ in the intended stoichiometry. These studies strongly suggest that the desired structure has been achieved in the apo state, providing evidence that the peptide is able to actively impart the designed geometry to the metal cluster.
Determination of Molybdenum Species Evolution during Non‐Oxidative Dehydroaromatization of Methane and its Implications for Catalytic Performance
Authors: Agote‐Arán Miren , Kroner Anna B. , Islam Husn U. , Sławiński Wojciech A. , Wragg David S. , Lezcano‐González Inés , Beale Andrew M. 
Published: September 2018

AbstractMo/H‐ZSM‐5 has been studied using a combination of operando X‐ray absorption spectroscopy and High Resolution Powder Diffraction in order to study the evolution of Mo species and their location within the zeolite pores. The results indicate that after calcination the majority of the species present are isolated Mo‐oxo species, attached to the zeolite framework at the straight channels. During reaction, Mo is first partially carburized to intermediate MoCxOy species. At longer reaction times Mo fully carburizes detaching from the zeolite and aggregates forming initial Mo1.6C3 clusters; this is coincident with maximum benzene production. The Mo1.6C3 clusters are then observed to grow, predominantly on the outer zeolite surface and this appears to be the primary cause of catalyst deactivation. The deactivation is not only due to a decrease in the amount of active Mo surface but also due to a loss in shape‐selectivity which leads to an increased carbon deposition at the outer shell of the zeolite crystals and eventually to pore blockage.
Incorporating Heavy Alkanes in Metal–Organic Frameworks for Optimizing Adsorbed Natural Gas Capacity
Authors: Fang Yu , Banerjee Sayan , Joseph Elizabeth A. , Day Gregory S. , Bosch Mathieu , Li Jialuo , Wang Qi , Drake Hannah , Ozdemir Osman K. , Ornstein Jason M. , Wang Ye , Lu Tong‐Bu , Zhou Hong‐Cai 
Published: September 2018

AbstractMetal–organic frameworks (MOFs) as methane adsorbents are highly promising materials for applications such as methane‐powered vehicles, flare gas capture, and field natural gas separation. Pre‐ and post‐synthetic modification of MOFs have been known to help improve both the overall methane uptake as well as the working capacity. Here, a post‐synthetic modification strategy to non‐covalently modify MOF adsorbents for the enhancement of the natural gas uptake for the MOF material is introduced. In this study, PCN‐250 adsorbents were doped with C10 alkane and C14 fatty acid and their impact on the methane uptake capabilities was investigated. It was found that even trace amounts of heavy hydrocarbons could considerably enhance the raw methane uptake of the MOF while still being regenerable. The doped hydrocarbons are presumably located at the mesoporous defects of PCN‐250, thus optimizing the framework–methane interactions. These findings reveal a general approach that can be used to modify the MOF absorbents, improving their ability to be sustainable and renewable natural gas adsorption platforms.
Cubane‐Type [Mo3S4M] Clusters with First‐Row Groups 4–10 Transition‐Metal Halides Supported by C5Me5 Ligands on Molybdenum
Authors: Ohki Yasuhiro , Uchida Keisuke , Hara Ryota , Kachi Mami , Fujisawa Mayu , Tada Mizuki , Sakai Yoichi , Sameera W. M. C. 
Published: September 2018

AbstractA synthetic protocol was developed for a series of cubane‐type [Mo3S4M] clusters that incorporate halides of first‐row transition metals (M) from Groups 4–10. This protocol is based on the anionic cluster platform [Cp*3Mo3S4]− ([1]−; Cp*=η5‐C5Me5), which crystallizes when K(18‐crown‐6) is used as the counter cation. Treatment of in situ‐generated [1]− with such transition‐metal halides led to the formation of [Mo3S4M] clusters, in which the M/halide ratio gradually changes from 1:2 to 1:1.5 and to 1:1, when moving from early to late transition metals. This trend suggests a tendency for early transition metals to tolerate higher oxidation states and adopt larger ionic radii relative to late transition metals. The properties of the [Mo3S4Fe] cluster 6 a were investigated in detail by using 57Fe Mössbauer spectroscopy and computational methods.
Catalyst‐Free Hydroboration of CO2 With a Nucleophilic Diborane(4)
Authors: Frick Markus , Horn Julian , Wadepohl Hubert , Kaifer Elisabeth , Himmel Hans‐Jörg 
Published: September 2018

AbstractHydroboration generally requires the presence of a catalyst to lower the barrier for hydride transfer. This work reports on the first catalyst‐free CO2 hydroboration with a neutral boron compound, the nucleophilic diborane [HB(hpp)]2, 1 (hpp=1,3,4,6,7,8‐hexahydro‐2H‐pyrimido[1,2‐a]pyrimidinate). Further hydroboration reactions to bis(boryl)acetals are possible. In acetonitrile, but not in dichloromethane solutions, hydroboration of a first CO2 is followed by hydroboration of a second CO2 molecule. Detailed kinetic measurements for both hydroboration steps were carried out and the influence of the solvent and the addition of a Lewis base on the rate constants analyzed. In contrast to catalyst‐free hydroboration of CO2, hydroboration of the less electrophilic acetone requires the presence of an activating Lewis acid.
Proton Exchange Membrane Water Electrolysis Modeling for System Simulation and Degradation Analysis
Authors: Gößling Sönke , Stypka Sebastian , Bahr Matthias , Oberschachtsiek Bernd , Heinzel Angelika 
Published: September 2018

AbstractThis paper presents a numeric model for proton exchange membrane electrolysis, which describes the current‐voltage dependency. Besides physical constants and parameters characterizing material properties, it also contains parameters that cannot be measured ex situ, e.g., charge transfer coefficients and exchange current densities. To determine these parameters, the model includes an automated parameter calibration procedure that is able to find the best parameter combinations. An exemplary integration of the model in MATLAB/Simulink is presented, including a validation with dynamic measurement data.
Gold(I)–Coumarin–Caffeine‐Based Complexes as New Potential Anti‐Inflammatory and Anticancer Trackable Agents
Authors: Trommenschlager Audrey , Chotard Florian , Bertrand Benoît , Amor Souheila , Richard Philippe , Bettaïeb Ali , Paul Catherine , Connat Jean‐Louis , Le Gendre Pierre , Bodio Ewen 
Published: September 2018

AbstractThree new gold(I)–coumarin‐based trackable therapeutic complexes and two non‐trackable analogues have been synthesised and fully characterised. They all display anti‐proliferative properties on several types of cancer cell lines, including those of colon, breast, and prostate. Two complexes displayed significant anti‐inflammatory effects; one displayed pro‐inflammatory behaviour; this highlights the impact of the position of the fluorophore on the caffeine scaffold. Additionally, the three coumarin derivatives could be visualised in vitro by two‐photon microscopy.
Elotuzumab plus lenalidomide and dexamethasone in relapsed/refractory multiple myeloma: Extended 4‐year follow‐up and analysis of relative progression‐free survival from the randomized ELOQUENT‐2 trial
Authors: Dimopoulos Meletios A. , Lonial Sagar , Betts Keith A. , Chen Clara , Zichlin Miriam L. , Brun Alexander , Signorovitch James E. , Makenbaeva Dinara , Mekan Sabeen , Sy Oumar , Weisel Katja , Richardson Paul G. 
Published: September 2018

BackgroundThe randomized phase 3 ELOQUENT‐2 study (NCT01239797) evaluated the efficacy and safety of elotuzumab plus lenalidomide and dexamethasone (ELd) versus lenalidomide and dexamethasone (Ld) in relapsed/refractory multiple myeloma (RRMM), and to date, has the longest follow‐up of any monoclonal antibody in patients with RRMM.MethodsIn this extended 4‐year follow‐up of the ELOQUENT‐2 trial, the coprimary endpoints of progression‐free survival (PFS) and overall response rate as well as the secondary endpoint of overall survival were assessed. In the absence of head‐to‐head trials comparing Ld‐based triplet regimens to guide treatment selection, 4 randomized controlled trials—ELOQUENT‐2, ASPIRE, TOURMALINE‐MM1, and POLLUX—were indirectly compared to provide insight into the relative efficacy of these regimens in RRMM.ResultsData at 4 years were consistent with 2‐ and 3‐year follow‐up data: ELd reduced the risk of disease progression/death by 29% versus Ld (hazard ratio, 0.71) while maintaining safety. The greatest PFS benefit among the assessed subgroups was observed in patients at the median time or further from diagnosis (≥3.5 years) with 1 prior line of therapy, who had a 44% reduction in the risk of progression/death, and in patients in the high‐risk category, who had a 36% reduction in favor of ELd. This regimen also showed a relative PFS benefit that was maintained beyond 50 months.ConclusionsThe sustained PFS benefit and long‐term safety of ELd at 4 years, similar to those observed at 2 and 3 years, support ELd as a valuable therapeutic option for the long‐term treatment of patients with RRMM.
GNAS, GNAQ,andGNA11alterations in patients with diverse cancers
Authors: Parish Austin J. , Nguyen Vi , Goodman Aaron M. , Murugesan Karthikeyan , Frampton Garrett M. , Kurzrock Razelle 
Published: September 2018

BackgroundAdvances in deep sequencing technology have uncovered a widespread, protumorigenic role of guanine nucleotide‐binding (G protein) α (GNA) subunits, particularly GNA subunits Gs (GNAS), Gq (GNAQ), and G11 (GNA11) (GNA*), in a diverse collection of malignancies. The objectives of the current study were: 1) to determineGNA*aberration status in a cohort of 1348 patients with cancer and 2) to examine tumor mutational burden, overall survival rates, and treatment outcomes in patients withGNA*‐positive tumors versus those with tumors that had wild‐typeGNA*.MethodsFor each patient, clinical and genomic data were collected from medical records. Next‐generation sequencing was performed for each patient (range, 182‐236 genes).ResultsAberrations ofGNA*genes were identified in a subset of patients who had 8 of the 12 cancer types examined, and a significant association was observed for appendiceal cancer and ocular melanoma (P< .0001 for both; multivariate analysis). Overall, 4.1% of the cancer population was affected.GNA*abnormalities were associated with higher numbers of co‐alterations in univariate (but not multivariate) analysis and were most commonly accompanied by Aurora kinase A (AURKA), Cbl proto‐oncogene (CBL), and LYN proto‐oncogene (LYN) co‐alterations (allP< .0001; multivariate analysis).GNA*alterations were correlated with a trend toward lower median overall survival (P= .085). The median tumor mutational burden was 4 mutations per megabase in bothGNA*‐altered andGNA*wild‐type tumors. For this limited sample ofGNA*‐positive patients, longer survival was not correlated with any specific treatment regimens.ConclusionsIn the current sample, the genesGNAS,GNAQ, andGNA11were widely altered across cancer types, and these alterations often were accompanied by specific genomic abnormalities inAURKA,CBL, andLYN. Therefore, targetingGNA*alterations may require drugs that address the GNA* signal and important co‐alterations.Cancer 2018;00:000‐000.© 2018 American Cancer Society.
Improved diagnostic precision of urine cytology by implementation of The Paris System and the use of cell blocks
Authors: Chan Emily , Balassanian Ronald , Tabatabai Z. Laura , Lou Hubing , Vohra Poonam 
Published: September 2018

BackgroundThe Paris System for Reporting Urinary Cytology (TPS) published in 2016 provides a standardized approach to evaluating urine cytology. In the authors’ practice, a TPS‐like approach was adopted in 2012 using similarly defined cytologic criteria and correlating cystoscopic findings, and they also began incorporating the use of cell block (CB) material. The objective of the current study was to assess whether this TPS‐like approach with the use of CB, as well as direct implementation of TPS, improved the diagnostic value of urine cytology.MethodsIn total, 188 consecutive urine cytology specimens from 2010 through 2016 that had concurrent or subsequent histologic specimens available were retrospectively analyzed for diagnostic correlation. Urine cytology performance was compared between the periods 2010 to 2012 (pre–TPS‐like), 2013 to 2016 (TPS‐like), and after TPS reclassification, including blind review by a cytopathologist. The contribution of available CB material to final diagnoses also was assessed.ResultsBoth the TPS‐like approach and TPS reclassification resulted in significantly lowering the rate of atypical urothelial cells (AUC) diagnosis from 48%, to 21%, to 9% (from pre‐TPS, to TPS‐like, to after TPS reclassification, respectively; P < 0.01) while increasing the positive predictive value of an AUC diagnosis for high‐grade urothelial carcinoma from 21%, to 43%, to 83%, respectively. The use of CBs contributed to a definitive final diagnosis in 24 of 36 cases (66.7%).ConclusionsIn support of the new TPS recommendations, the application of stringent “TPS‐like” and TPS criteria improves the value of an AUC diagnosis for clinicians and patients by lowering the AUC rate and increasing the positive predictive value of AUC for high‐grade urothelial carcinoma. CBs can be used to help resolve problematic cases for more definitive diagnostic categorization.
Photodynamics and Luminescence of Mono‐ and Tri‐Nuclear Lanthanide Complexes in the Gas Phase and in Solution
Authors: Liedy Florian , Bäppler Florian , Waldt Eugen , Nosenko Yevgeniy , Imanbaew Dimitri , Bhunia Asamanjoy , Yadav Munendra , Diller Rolf , Kappes Manfred M. , Roesky Peter W. , Schooss Detlef , Riehn Christoph 
Published: September 2018

AbstractLanthanide ions (DyIII, EuIII) are stabilized by coordination with two Schiff base ligands in compounds [Dy{H3L}2](NO3)(EtOH)(H2O)8 (1) and [Eu{H3L}2](NO3)(H2O)8 (3) (H4L, 2,2′‐{[(2‐aminoethyl)imino]bis[2,1‐ethanediyl‐nitriloethylidyne]}bis‐2‐hydroxy‐benzoic acid). The latter is reported here for the first time. Both luminescence and ultrafast photodynamics after photoexcitation via a ligand absorption band (∼400 nm) have been studied. In solution, only the [Eu{H3L}2]+ ([3]+) complex displays the typical lanthanide emission lines, whereas in gas phase both, [Dy{H3L}2]+ ([1]+) and [3]+, show their corresponding transitions depending on excitation energy. The ultrafast excited state dynamics, obtained in gas phase and in solution, are assigned to excited state intramolecular proton transfer processes in the ligands. The antenna ligand moiety of these complexes provides pockets for stabilization of two MnII ions so that we additionally investigated the photophysical behavior of the corresponding tri‐nuclear (NHEt3)2[Ln{MnL}2](ClO4)(H2O)2 (Ln=DyIII, EuIII) compounds (2, 4). Interestingly, the related complexes do not show lanthanide emission, neither in solution nor in gas phase. Transient data in solution and gas phase suggests an efficient quenching of the ligand's electronically excited state by strong interaction with the MnII ions. This effect could possibly be developed further into a design principle for luminescence‐based sensing devices for metal cations.
Polar Effects Control the Gas‐Phase Reactivity of para‐Benzyne Analogs
Authors: Sheng Huaming , Ma Xin , Lei Hao‐Ran , Milton Jacob , Tang Weijuan , Jin Chunfen , Gao Jinshan , Wittrig Ashley M. , Archibold Enada F. , Nash John J. , Kenttämaa Hilkka I. 
Published: September 2018

AbstractWe report herein a gas‐phase reactivity study on a para‐benzyne cation and its three cyano‐substituted, isomeric derivatives performed using a dual‐linear quadrupole ion trap mass spectrometer. All four biradicals were found to undergo primary and secondary radical reactions analogous to those observed for the related monoradicals, indicating the presence of two reactive radical sites. The reactivity of all biradicals is substantially lower than that of the related monoradicals, as expected based on the singlet ground states of the biradicals. The cyano‐substituted biradicals show substantially greater reactivity than the analogous unsubstituted biradical. The greater reactivity is rationalized by the substantially greater (calculated) electron affinity of the radical sites of the cyano‐substituted biradicals, which results in stabilization of their transition states through polar effects. This finding is in contrast to the long‐standing thinking that the magnitude of the singlet‐triplet splitting controls the reactivity of para‐benzynes.
Dual‐Channel Photostimulation for Independent Excitation of Two Populations
Authors: Hooks Bryan M. 
Published: September 2018

AbstractManipulation of defined neurons using excitatory opsins, including channelrhodopsin, enables studies of connectivity and the functional role of these circuit components in the brain. These techniques are vital in the neocortex, where diverse neurons are intermingled, and stimulation of specific cell types is difficult without the spatial, temporal, and genetic control available with optogenetic approaches. Channelrhodopsins are effective for mapping excitatory connectivity from one input type to its target. Attempts to use multiple opsins to simultaneously map multiple inputs face the challenge of partially overlapping light spectra for different opsins. This protocol describes one strategy to independently stimulate two comingled inputs in the same brain area to assess convergence and interaction of pathways in neural circuits. This is highly relevant in the neocortex, where pyramidal neurons integrate excitatory inputs from multiple local cell types and long‐range corticocortical and thalamocortical projections. © 2018 by John Wiley & Sons, Inc.
Using the primary process emotional–behavioural system to better meet patient needs in psychotherapy
Authors: Kuei Tien , Tsai Mavis , McLeod Hamish J. , White Ross G. , Kanter Jonathan 
Published: September 2018

AbstractIn order to increase therapeutic impact by enhancing awareness of clients' nonverbal communications, this article operationalizes the therapeutic alliance as a needs‐satisfaction process. The client's competence as a needs seeker and the therapist assisting with the client's expression and satiation of basic social needs are proposed as being key mechanisms of change.Functional model of primary emotions derived from Panksepp's seven primary emotional systems (care seeking, caretaking, lust, fear and anxiety, anger, play, seeking, plus dominance and disgust) is integrated with Functional Analytic Psychotherapy's emphasis on in‐session contingent natural reinforcement of clients' target behaviours. By identifying in‐the‐moment cues of underlying emotional–behavioural functions drawn from a categorization of clients' nonverbal communication can bridge the gap between client private events and therapist observables, in order to maximize therapist attunement and responsiveness to clients, and to increase the effectiveness of clinical interventions.
Generation and Fusion of Human Cortical and Medial Ganglionic Eminence Brain Organoids
Authors: Xiang Yangfei , Yoshiaki Tanaka , Patterson Benjamin , Cakir Bilal , Kim Kun‐Yong , Cho Yee Sook , Park In‐Hyun 
Published: September 2018

AbstractThree‐dimensional brain organoid culture has become an essential tool for investigating human brain development and modeling neurological disorders during the past few years. Given specific regionalization during brain development, it is important to produce distinct brain organoids that represent different brain regions and their interactions. The authors recently established a platform to generate brain organoids resembling the medial ganglionic eminence (MGE), a specific brain region responsible for interneurogenesis, and found that when these organoids were fused with organoids resembling the cortex, the resulting organoids enabled modeling of interneuron migration in the brain. This unit describes four basic protocols that have been successfully applied by the authors, covering the generation of embryonic bodies with neuroectodermal fate, the production of human MGE organoids and cortical organoids, and the fusion of these two organoids. © 2018 by John Wiley & Sons, Inc.
Stimuli‐Responsive Tannin–FeIII Hybrid Microcapsules Demonstrated by the Active Release of an Anti‐Tuberculosis Agent
Authors: Bartzoka Elisavet D. , Lange Heiko , Poce Giovanna , Crestini Claudia 
Published: September 2018

AbstractA simple and facile strategy for the creation of ferric tannin microcapsules around a liquid, non‐sacrificial core is described. The assembly of the capsules occurs rapidly once ferric tannin complexes are subjected to ultrasonic treatment. The driving forces for the rapid capsule assembly reside in the strategy of adding ferric ions into the initial emulsion, which promotes shell formation and stability through well‐known complexation effects. This is the first time that microcapsule assemblies of monomeric tannins like epigallocatechin‐3‐O‐gallate has been demonstrated, which are reportedly unable to form dispersing microcapsules in the absence of a templating metal. The efficacy of the approach is demonstrated by the complete release of a hydrophobic molecule that is active against M. tuberculosis by using Acacia tannin capsules. The release kinetics of the active molecule were of zeroth order over a 12 h time frame.