bluuebunny/crossref_metadata_2025_split huggingface dataset:
Highly Emissive Self‐Trapped Excitons in Fully Inorganic Zero‐Dimensional Tin Halides
Authors: Benin Bogdan M. , Dirin Dmitry N. , Morad Viktoriia , Wörle Michael , Yakunin Sergii , Rainò Gabriele , Nazarenko Olga , Fischer Markus , Infante Ivan , Kovalenko Maksym V. 
Published: July 2018

AbstractThe spatial localization of charge carriers to promote the formation of bound excitons and concomitantly enhance radiative recombination has long been a goal for luminescent semiconductors. Zero‐dimensional materials structurally impose carrier localization and result in the formation of localized Frenkel excitons. Now the fully inorganic, perovskite‐derived zero‐dimensional SnII material Cs4SnBr6 is presented that exhibits room‐temperature broad‐band photoluminescence centered at 540 nm with a quantum yield (QY) of 15±5 %. A series of analogous compositions following the general formula Cs4−xAxSn(Br1−yIy)6 (A=Rb, K; x≤1, y≤1) can be prepared. The emission of these materials ranges from 500 nm to 620 nm with the possibility to compositionally tune the Stokes shift and the self‐trapped exciton emission bands.
Materialien und Strukturen für schluckbare elektromechanische medizinische Funktionseinheiten
Authors: Bettinger Christopher J. 
Published: July 2018

AbstractSchluckbare Biomedizinprodukte diagnostizieren, verhindern und behandeln ein breites Spektrum von Krankheiten und waren über Jahrzehnte der Traum von Ingenieuren und Klinikern. Der steigende Stellenwert der Darmgesundheit für das allgemeine Wohlbefinden sowie die Prävalenz vieler gastrointestinaler Erkrankungen haben die Aufmerksamkeit auf diese aufstrebende Klasse medizinischer Hilfsmittel neu geweckt. Es gibt mehrere prominente Beispiele von kommerziell erfolgreichen, schluckbaren Medizinprodukten. Dennoch bleiben viele technische Herausforderungen zu lösen, bevor schluckbare Medizinprodukte ihr volles klinisches Potenzial ausschöpfen können. Dieser Kurzaufsatz fasst neuste Entdeckungen in diesem interdisziplinären Gebiet zusammen, einschließlich neuartiger Materialien, moderner Verarbeitungstechniken für Materialien und ausgewählter Beispiele integrierter schluckbarer elektromechanischer Systeme. Nach einer kurzen historischen Betrachtung werden diese Themen mit einem speziellen Fokus auf modernen Funktionsmaterialien und Herstellungsstrategien im Kontext der klinischen Translation und potenzieller regulatorischer Überlegungen diskutiert. Zukünftige Perspektiven, Herausforderungen und Chancen des Gebiets werden ebenfalls zusammengefasst.
A Mechanism‐Based Approach to Screening Metagenomic Libraries for Discovery of Unconventional Glycosidases
Authors: Nasseri Seyed Amirhossein , Betschart Leo , Opaleva Daria , Rahfeld Peter , Withers Stephen G. 
Published: July 2018

AbstractFunctional metagenomics has opened new opportunities for enzyme discovery. To exploit the full potential of this new tool, the design of selective screens is essential, especially when searching for rare enzymes. To identify novel glycosidases that employ cleavage strategies other than the conventional Koshland mechanisms, a suitable screen was needed. Focusing on the unsaturated glucuronidases (UGLs), it was found that use of simple aryl glycoside substrates did not allow sufficient discrimination against β‐glucuronidases, which are widespread in bacteria. While conventional glycosidases cannot generally hydrolyze thioglycosides efficiently, UGLs follow a distinct mechanism that allows them to do so. Thus, fluorogenic thioglycoside substrates featuring thiol‐based self‐immolative linkers were synthesized and assessed as selective substrates. The generality of the approach was validated with another family of unconventional glycosidases, the GH4 enzymes. Finally, the utility of these substrates was tested by screening a small metagenomic library.
Synthesis and Reactivity of Multiple Phosphine‐Functionalized Nonagermanide Clusters
Authors: Geitner Felix S. , Klein Wilhelm , Fässler Thomas F. 
Published: July 2018

AbstractHerein we report on the synthesis of the first multiple phosphine‐substituted nonagermanide clusters in a one‐step reaction from K4Ge9. Their reactions towards various transition metal complexes show a large variety of reactive sites. The novel threefold phosphine‐functionalized [Ge9] clusters [Ge9{PRRI}3]− {R: NiPr2; RI: NiPr2 (1 a) or tBu (2 a)} are obtained by reaction of pristine [Ge9]4− clusters with the respective chlorophosphines. Subsequent reactions with NHCDippCuCl yield neutral compounds (NHCDippCu)[Ge9{P(NiPr2)2}3] (3) and (NHCDippCu)[Ge9{P(NiPr2)tBu}3] (4), respectively. The reaction of neutral compound 3 with Cr(CO)5(thf) yields the first uncharged fivefold substituted [Ge9] cluster (NHCDippCu)2[Ge9{P(NiPr2)2}2Cr(CO)5] (5) via a ligand exchange reaction at the [Ge9] cluster core. Compounds 3 and 5 are characterized by single crystal structure determination.
Adsorbed Intermediates in Oxygen Reduction on Platinum Nanoparticles Observed by In Situ IR Spectroscopy
Authors: Nayak Simantini , McPherson Ian J. , Vincent Kylie A. 
Published: July 2018

AbstractThe sluggish kinetics of oxygen reduction to water remains a significant limitation in the viability of proton‐exchange‐membrane fuel cells, yet details of the four‐electron oxygen reduction reaction remain elusive. Herein, we apply in situ infrared spectroscopy to probe the surface chemistry of a commercial carbon‐supported Pt nanoparticle catalyst during oxygen reduction. The IR spectra show potential‐dependent appearance of adsorbed superoxide and hydroperoxide intermediates on Pt. This strongly supports an associative pathway for oxygen reduction. Analysis of the adsorbates alongside the catalytic current suggests that another pathway must also be in operation, consistent with a parallel dissociative pathway.
Metal‐Free Synthesis of Pharmaceutically Important Biaryls by Photosplicing
Authors: Kloss Florian , Neuwirth Toni , Haensch Veit G. , Hertweck Christian 
Published: July 2018

AbstractMany pharmaceuticals feature biaryl motifs that are crucial for their binding to the target. Yet, benchmark methods for selective cross‐couplings rely on highly toxic heavy metal catalysts, which are unfavorable in the synthesis of pharmaceuticals. Metal‐free coupling reactions, on the other hand, may require harsh conditions and lack selectivity. We report a novel, metal‐free cross‐coupling reaction that involves the tethering of two phenyl groups by a temporary, traceless sulfonamide linker that directs a photochemical aryl fusion into a single coupling product. The perfect regio‐ and chemoselectivity of the reaction could be rationalized by a cyclic intermediate, which fragments into the biaryl and volatile side products. Using a flow reactor, we synthesized numerous substituted biaryl building blocks for important therapeutics in high yields, such as antibiotics, antitumor, neuroprotective and cholesterol‐lowering agents as well as antiarthritic non‐steroidal antiinflammatory drugs (NSAIDs). The new method was successfully employed in a total synthesis of cannabinol, an important analgesic and antiemetic therapeutic. We also report a metal‐free synthesis of key building blocks used for the preparation of sartans, antihypertensive agents that rank among the top blockbuster drugs worldwide. This safe and convenient protocol is a valuable alternative for the widely used metal‐dependent aryl cross‐coupling methods.
Determination of vortioxetine and its degradation product in bulk and tablets, by LC‐DAD and MS/MS methods
Authors: de Diego Marta , Correa Diana , Mennickent Sigrid , Godoy Ricardo , Vergara Carola 
Published: July 2018

AbstractVortioxetine hydrobromide (VOR), is a novel antidepressant used for the treatment of major depressive disorder. It has a chemical structure susceptible to degradation, therefore it is important to have suitable analytical methods to determine VOR in presence of its main degradation products (DP), because if the compound degrades, this could result in diminution of the therapeutic activity and safety. A simple HPLC method with photodiode array detection was developed and validated for determination of VOR in bulk and tablets, in the presence of its major DP. The drug was subjected to oxidative, hydrolytic, and photolytic stress conditions, showing significant degradation under oxidation with the formation of one DP, which was identified by ESI‐MS/MS. A C18 column was used, with mobile phase consisting of acetonitrile and water with acetic acid and triethylamine in isocratic elution mode, with detection at 228 nm and 1.0 mL/min flow rate. The assay was linear in the 25–125 μg/mL concentration range. For precision, the RSD was <1.8%, the recovery was 100.0–101.6%, and the method demonstrated adequate selectivity. The method was successfully applied to quantify VOR in tablets. The results showed that the method is useful for routine analysis and for quality control purposes.
The Photosensitising Clinical Agent Verteporfin Is an Inhibitor of SPAK and OSR1 Kinases
Authors: AlAmri Mubarak A. , Kadri Hachemi , Alderwick Luke J. , Jeeves Mark , Mehellou Youcef 
Published: July 2018

AbstractSTE20/SPS1‐related proline/alanine‐rich kinase (SPAK) and oxidative‐stress‐responsive kinase 1 (OSR1) are two serine/threonine protein kinases that play key roles in regulating ion homeostasis. Various SPAK and OSR1 mouse models exhibited reduced blood pressure. Herein, the discovery of verteporfin, a photosensitising agent used in photodynamic therapy, as a potent inhibitor of SPAK and OSR1 kinases is reported. It is shown that verteporfin binds the kinase domains of SPAK and OSR1 and inhibits their catalytic activity in an adenosine triphosphate (ATP)‐independent manner. In cells, verteporfin was able to suppress the phosphorylation of the ion co‐transporter NKCC1; a downstream physiological substrate of SPAK and OSR1 kinases. Kinase panel screening indicated that verteporfin inhibited a further eight protein kinases more potently than that of SPAK and OSR1. Although verteporfin has largely been studied as a modifier of the Hippo signalling pathway, this work indicates that the WNK‐SPAK/OSR1 signalling cascade is also a target of this clinical agent. This finding could explain the fluctuation in blood pressure noted in patients and animals treated with this drug.
Tuning Zeolite Properties for a Highly Efficient Synthesis of Propylene from Methanol
Authors: Palčić Ana , Ordomsky Vitaly V. , Qin Zhengxing , Georgieva Veselina , Valtchev Valentin 
Published: July 2018

AbstractA series of nanosized ZSM‐5 samples was synthesized at 170, 150, 120, and 100 °C. Experimental data show that the decrease of crystallization temperature leads to significant changes in zeolite properties. Crystals synthesized at 100 °C exhibit many framework defects with lower acid‐site density, strength, and a larger external surface area. The selectivity to light olefins and the propylene‐to‐ethylene ratio increases as the crystallization temperature decreases. A propylene‐to‐ethylene ratio of above 6 with the highest selectivity to propylene of 53 % was obtained over ZSM‐5 catalyst prepared at 100 °C. The stability of the nanosized zeolite in methanol to olefins (MTO) was also improved compared to the industrial sample with a similar Si/Al ratio. This catalytic performance is a result of the decrease in the acid‐site density, strength, and the crystals’ size, providing a shorter diffusion path and larger external surface area. The presence of structural defects and a different external surface in the crystals has been shown to play an important role in the MTO catalyst performance.
You won't believe this old test … that does cheap single‐cell mutation detection
Authors: Köbel Martin , Anglesio Michael S. , Brenton James D. 
Published: July 2018

AbstractDetecting mutations in single cells from cancer specimens is now a major area of translational research. In a recent article in this journal, Khalique et al validated an immunohistochemistry assay for ARID1A that reliably identifies loss of function mutations in single cells in tissue sections. This work exemplifies best practice for developing and orthogonally validating immunohistochemical assays to provide clearly interpretable mutational results with spatial context.
In Situ Tracking of Organic Reactions at the Vapor/Liquid Interfaces of Ionic Liquids
Authors: Song Yuting , Huo Feng , Jiang Yi , Zhang Suojiang , Chen Shimou 
Published: July 2018

AbstractThe molecular structures of ionic liquids at interfaces play a crucial role in determining their chemical activities in applications. In situ X‐ray photoelectron spectroscopy (XPS) was used to track the evolution of X‐ray irradiation‐induced chemical reactions in a series of ionic liquids ([Cnmim][AuCl4]; n=4, 6, 8, 10) on the Si (111) single‐crystal surface. Analyses of microstructure and chemical bonding based on the XPS results indicated that reactions occurred at the vapor/liquid interfaces of the ionic liquids. The time‐resolved XPS spectra revealed that with increasing irradiation time, the intensity of the peak corresponding to trivalent Au anion decreased for the four ionic liquids as Au was continually reduced to a lower chemical state and finally converted to gold nanoparticles. The rate and conversion of the reaction were associated with the length of the alkyl chain of the ionic liquids cation. Molecular dynamics simulations further revealed that the alkyl chain of the cation in the ionic liquids was oriented towards the vacuum environment at the vapor/liquid interface. Our results provide a real‐time atomic‐scale experimental evidence of organic reactions at the vapor/liquid interfaces of ionic liquids. The findings are important for understanding the roles of ionic liquids in catalysis, separation, electrochemistry, functional materials, and so on.
Energy‐efficient power control for uplink spectrum‐sharing heterogeneous networks
Authors: Pham Quoc‐Viet , Hwang Won‐Joo 
Published: July 2018

SummaryThis article considers energy‐efficient power control schemes for interference management in uplink spectrum‐sharing heterogeneous networks that maximize the energy efficiency of users, protect the macro base station, and support users with QoS consideration. In the first scenario, we define the objective function as the weighted sum of the energy efficiencies and develop an efficient global optimization algorithm with global linear and local quadratic rate of convergence to solve the considered problem. To ensure fairness among individual user equipments (UEs) in terms of energy efficiency, we consider the max‐min problem, where the objective is defined as the weighted minimum of the energy efficiencies, and a fractional programming theory and the dual decomposition method are jointly used to solve the problem and investigate an iterative algorithm. As by‐products, we further discuss the global energy efficiency problem and consider near‐optimal schemes. Numerical examples are provided to demonstrate significant improvements of the proposed algorithms over existing interference management schemes.
Experimental field tests of Batesian mimicry in the swallowtail butterfly Papilio polytes
Authors: Palmer Daniela H. , Tan Yue Qian , Finkbeiner Susan D. , Briscoe Adriana D. , Monteiro Antónia , Kronforst Marcus R. 
Published: July 2018

AbstractThe swallowtail butterfly Papilio polytes is known for its striking resemblance in wing pattern to the toxic butterfly Pachliopta aristolochiae and is a focal system for the study of mimicry evolution. Papilio polytes females are polymorphic in wing pattern, with mimetic and nonmimetic forms, while males are monomorphic and nonmimetic. Past work invokes selection for mimicry as the driving force behind wing pattern evolution in P. polytes. However, the mimetic relationship between P. polytes and P. aristolochiae is not well understood. In order to test the mimicry hypothesis, we constructed paper replicas of mimetic and nonmimetic P. polytes and P. aristolochiae, placed them in their natural habitat, and measured bird predation on replicas. In initial trials with stationary replicas and plasticine bodies, overall predation was low and we found no differences in predation between replica types. In later trials with replicas mounted on springs and with live mealworms standing in for the butterfly's body, we found less predation on mimetic P. polytes replicas compared to nonmimetic P. polytes replicas, consistent with the predator avoidance benefits of mimicry. While our results are mixed, they generally lend support to the mimicry hypothesis as well as the idea that behavioral differences between the sexes contributed to the evolution of sexually dimorphic mimicry.
Proteome analysis of human CD56neg NK cells reveals a homogeneous phenotype surprisingly similar to CD56dim NK cells
Authors: Voigt Jenny , Malone David F.G. , Dias Joana , Leeansyah Edwin , Björkström Niklas K. , Ljunggren Hans‐Gustaf , Gröbe Lothar , Klawonn Frank , Heyner Maxi , Sandberg Johan K. , Jänsch Lothar 
Published: July 2018

AbstractNK cells lacking CD56 (CD56neg) were first identified in chronic HIV‐1 infection. However, CD56neg NK cells also exist in healthy individuals, albeit in significantly lower numbers. Here, we provide an extensive proteomic characterisation of human CD56neg peripheral blood NK cells of healthy donors and compare them to their CD56dim and CD56bright counterparts. Unbiased large‐scale surface receptor profiling clustered CD56neg cells as part of the main NK cell compartment and indicated an overall CD56dim‐like phenotype. Total proteome analyses of CD56neg NK cells further confirmed their similarity with CD56dim NK cells, and revealed a complete cytolytic inventory with high levels of perforin and granzyme H and M. In the present study, twelve proteins discriminated CD56neg NK cells from CD56dim NK cells with nine up‐regulated and three down‐regulated proteins in the CD56neg NK cell population. Those proteins were functionally related to lytic granule composition and transport, interaction with the extracellular matrix, DNA transcription or repair, and proliferation. Corroborating these results, CD56neg NK cells showed modest cytotoxicity, degranulation, and IFN‐ɣ secretion as compared to CD56dim NK cells. In conclusion, CD56neg NK cells constitute functionally competent cells sharing many features of bona fide CD56dim NK cells in healthy individuals, but with some distinct characteristics.
Simultaneous enantioseparation of methcathinone and two isomeric methylmethcathinones using capillary electrophoresis assisted by 2‐hydroxyethyl‐β‐cyclodextrin
Authors: Nowak Paweł Mateusz , Olesek Katarzyna , Woźniakiewicz Michał , Kościelniak Paweł 
Published: July 2018

AbstractMethcathinone (ephedrone), 4‐methylmethcathinone (mephedrone), and 3‐methylmethcathinone (metaphedrone) are toxicologically‐important cathinone derivatives used commonly as designer drugs. In this work we show the first method allowing to separate simultaneously all these molecules in a chiral medium, ensuring good resolution between all enantiomers. Eight cyclodextrins have been tested as potential chiral selectors, the best results were obtained with 2‐hydroxyethyl‐β‐cyclodextrin, unreported so far for efficient separation of cathinones. After optimization, the method was calibrated and validated with and without the use of internal standard. The addition of standard improved an overall repeatability and precision, the use of electrophoretic mobility ratio was especially favorable (RSD < 1%). It was demonstrated that the method may be easily extended by introducing the additional cathinone‐related drugs to the sample, maintaining satisfactory separation efficiency.
Coordinative similitude law considering fluid‐structure interaction for underwater shaking table tests
Authors: Li Zhong‐Xian , Wu Kun , Shi Yundong , Li Ning , Ding Yang 
Published: July 2018

SummaryGenerally, when a model is made of the same material as the prototype in shaking table tests, the equivalent material density of the scaled model is greater than that of the prototype because mass is added to the model to satisfy similitude criteria. When the water environment is modeled in underwater shaking table tests, however, it is difficult to change the density of water. The differences in the density similitude ratios of specimen materials and water can affect the similitude ratios of the hydrodynamic and wave forces with those of other forces. To solve this problem, a coordinative similitude law is proposed for underwater shaking table tests by adjusting the width of the upstream face of the model or the wave height in the model test to match the similitude ratios of hydrodynamic and wave forces with those of other forces. The designs of the similitude relations were investigated for earthquake excitation, wave excitation, and combined earthquake and wave excitation conditions. Series of numerical simulations and underwater shaking table tests were performed to validate the proposed coordinative similitude law through a comparison of coordinative model and conventional model designed based on the coordinative similitude law and traditional artificial mass simulation, respectively. The results show that the relative error was less than 10% for the coordinative model, whereas it reached 80% for the conventional model. The coordinative similitude law can better reproduce the dynamic responses of the prototype, and thus, this similitude law can be used in underwater shaking table tests.
Kaupapa Māori Evaluation in Aotearoa New Zealand
Authors: Cram Fiona , Pipi Kataraina , Paipa Kirimatao 
Published: July 2018

AbstractKaupapa Māori evaluation is literally about doing evaluation a Māori (Indigenous peoples of Aotearoa New Zealand) way. While the methods we use are often those from western evaluation practice, our methodology and the paradigm within which we operate are Māori. Our use of these methods enables Māori organizations and communities to meet their accountability requirements for the funding they receive to deliver services and programs to their people and to the wider community. At the same time as we are undertaking these evaluations, we are also encouraging those we work with to increase their own evaluation capacity. Part of this is thinking outside of the western evaluation “square” to incorporate traditional decision‐making ways into how they capture outcomes and improve service delivery. The Kaupapa Māori evaluation journey we describe here is about how we currently practice, and our ambitions for the true decolonization of evaluation.
Conceptualizing Evaluation in African Contexts
Authors: Gaotlhobogwe Michael , Major Thenjiwe Emily , Koloi‐Keaikitse Setlhomo , Chilisa Bagele 
Published: July 2018

AbstractThis chapter explores the meaning of decolonization and indigenization and the importance of these terms in conceptualizing research and evaluation in formerly colonized nations. We provide an exploration of ways in which efforts to “Africanize” the theory and practice of evaluation can be translated into widespread practice. In doing so, the rationale for an African‐rooted and African‐driven evaluation is discussed. We describe four evaluation conceptual frameworks: the least indigenized, integrative, predominantly Indigenous, and third space evaluation methodology. At the heart of these conceptual frameworks is the Indigenous knowledge systems that must be restored, protected, revitalized, and afforded justice. Our argument is that philosophical assumptions specific to African cultures and histories should inform evaluation theory and practice. The emerging evaluation practices will then emanate from the cultures and values of the African peoples.