bluuebunny/crossref_metadata_2025 huggingface dataset:
Open Fluidics: A Cell Culture Flow System Developed Over Wettability Contrast‐Based Chips
Authors: Oliveira Nuno M. , Reis Rui L. , Mano João F.
Published: October 2017

Biological tissues are recurrently exposed to several dynamic mechanical forces that influence cell behavior. On this work, the focus is on the shear stress forces induced by fluid flow. The study of flow‐induced effects on cells leads to important advances in cardiovascular, cancer, stem cell, and bone biology understanding. These studies are performed using cell culture flow (CCF) systems, mainly parallel plate flow chambers (PPFC), and microfluidic systems. Here, it is proposed an original CCF system based on the open fluidics concept. The system is developed using a planar superhydrophobic platform with hydrophilic paths. The paths work as channels to drive cell culture medium flows without using walls for liquid confinement. The liquid streams are controlled just based on the wettability contrast. To validate the concept, the effect of the shear stress stimulus in the osteogenic differentiation of C2C12 myoblast cells is studied. Combining bone morphogenic protein (specifically BMP‐2) stimulation with this mechanical stimulus, a synergistic effect is found on osteoblast differentiation. This effect is confirmed by the enhancement of alkaline phosphatase activity, a well‐known early marker of osteogenic differentiation. The suggested CCF system combines characteristics and advantages of both the PPFC and microfluidic systems.
Geometric Design of Scalable Forward Scatterers for Optimally Efficient Solar Transformers
Authors: Kim Hye‐Na , Vahidinia Sanaz , Holt Amanda L. , Sweeney Alison M. , Yang Shu
Published: October 2017

It will be ideal to deliver equal, optimally efficient “doses” of sunlight to all cells in a photobioreactor system, while simultaneously utilizing the entire solar resource. Backed by the numerical scattering simulation and optimization, here, the design, synthesis, and characterization of the synthetic iridocytes that recapitulated the salient forward‐scattering behavior of the Tridacnid clam system are reported, which presents the first geometric solution to allow narrow, precise forward redistribution of flux, utilizing the solar resource at the maximum quantum efficiency possible in living cells. The synthetic iridocytes are composed of silica nanoparticles in microspheres embedded in gelatin, both are low refractive index materials and inexpensive. They show wavelength selectivity, have little loss (the back‐scattering intensity is reduced to less than ≈0.01% of the forward‐scattered intensity), and narrow forward scattering cone similar to giant clams. Moreover, by comparing experiments and theoretical calculation, it is confirmed that the nonuniformity of the scatter sizes is a “feature not a bug” of the design, allowing for efficient, forward redistribution of solar flux in a micrometer‐scaled paradigm. This method is environmentally benign, inexpensive, and scalable to produce optical components that will find uses in efficiency‐limited solar conversion technologies, heat sinks, and biofuel production.
Flexible, High‐Wettability and Fire‐Resistant Separators Based on Hydroxyapatite Nanowires for Advanced Lithium‐Ion Batteries
Authors: Li Heng , Wu Dabei , Wu Jin , Dong Li‐Ying , Zhu Ying‐Jie , Hu Xianluo
Published: October 2017

Separators play a pivotal role in the electrochemical performance and safety of lithium‐ion batteries (LIBs). The commercial microporous polyolefin‐based separators often suffer from inferior electrolyte wettability, low thermal stability, and severe safety concerns. Herein, a novel kind of highly flexible and porous separator based on hydroxyapatite nanowires (HAP NWs) with excellent thermal stability, fire resistance, and superior electrolyte wettability is reported. A hierarchical cross‐linked network structure forms between HAP NWs and cellulose fibers (CFs) via hybridization, which endows the separator with high flexibility and robust mechanical strength. The high thermal stability of HAP NW networks enables the separator to preserve its structural integrity at temperatures as high as 700 °C, and the fire‐resistant property of HAP NWs ensures high safety of the battery. In particular, benefiting from its unique composition and highly porous structure, the as‐prepared HAP/CF separator exhibits near zero contact angle with the liquid electrolyte and high electrolyte uptake of 253%, indicating superior electrolyte wettability compared with the commercial polyolefin separator. The as‐prepared HAP/CF separator has unique advantages of superior electrolyte wettability, mechanical robustness, high thermal stability, and fire resistance, thus, is promising as a new kind of separator for advanced LIBs with enhanced performance and high safety.
Multiscale Humidity Visualization by Environmentally Sensitive Fluorescent Molecular Rotors
Authors: Cheng Yanhua , Wang Jianguo , Qiu Zijie , Zheng Xiaoyan , Leung Nelson L. C. , Lam Jacky W. Y. , Tang Ben Zhong
Published: October 2017

Building humidity sensors possessing the features of diverse‐configuration compatibility, and capability of measurement of spatial and temporal humidity gradients is of great interest for highly integrated electronics and wearable monitoring systems. Herein, a visual sensing approach based on fluorescent imaging is presented, by assembling aggregation‐induced‐emission (AIE)‐active molecular rotors into a moisture‐captured network; the resulting AIE humidity sensors are compatible with diverse applications, having tunable geometries and desirable architectures. The invisible information of relative humidity (RH) is transformed into different fluorescence colors that enable direct observation by the naked eyes based on the twisted intramolecular charge‐transfer effect of the AIE‐active molecular rotors. The resulting AIE humidity sensors show excellent performance in terms of good sensitivity, precise quantitative measurement, high spatial–temporal resolution, and fast response/recovery time. Their multiscale applications, such as regional environmental RH detection, internal humidity mapping, and sensitive human‐body humidity sensing are demonstrated. The proposed humidity visualization strategy may provide a new insight to develop humidity sensors for various applications.
Synthesis of BSA‐Coated BiOI@Bi2S3 Semiconductor Heterojunction Nanoparticles and Their Applications for Radio/Photodynamic/Photothermal Synergistic Therapy of Tumor
Authors: Guo Zhao , Zhu Shuang , Yong Yuan , Zhang Xiao , Dong Xinghua , Du Jiangfeng , Xie Jiani , Wang Qing , Gu Zhanjun , Zhao Yuliang
Published: October 2017

Developing an effective theranostic nanoplatform remains a great challenge for cancer diagnosis and treatment. Here, BiOI@Bi2S3@BSA (bovine serum albumin) semiconductor heterojunction nanoparticles (SHNPs) for triple‐combination radio/photodynamic/photothermal cancer therapy and multimodal computed tomography/photoacoustic (CT/PA) bioimaging are reported. On the one hand, SHNPs possess strong X‐ray attenuation capability since they contain high‐Z elements, and thus they are anticipated to be a very competent candidate as radio‐sensitizing materials for radiotherapy enhancement. On the other hand, as a semiconductor, the as‐prepared SHNPs offer an extra approach for reactive oxygen species generation based on electron–hole pair under the irradiation of X‐ray through the photodynamic therapy process. This X‐ray excited photodynamic therapy obviously has better penetration depth in bio‐tissue. What's more, the SHNPs also possess well photothermal conversion efficiency for photothermal therapy, because Bi2S3 is a thin band semiconductor with strong near‐infrared absorption that can cause local overheat. In vivo tumor ablation studies show that synergistic radio/photodynamic/photothermal therapy achieves more significant therapeutic effect than any single treatment. In addition, with the strong X‐ray attenuation and high near‐infrared absorption, the as‐obtained SHNPs can also be applied as a multimodal contrast agent in CT/PA imaging.
Monodispersed, Highly Interactive Facet (111)‐Oriented Pd Nanograins by ALD onto Free‐Standing and Flexible Electrospun Polymeric Nanofibrous Webs for Catalytic Application
Authors: Ranjith Kugalur Shanmugam , Celebioglu Asli , Eren Hamit , Biyikli Necmi , Uyar Tamer
Published: October 2017

An atomic layer deposition (ALD) of monodispersed palladium (Pd) nanograins (≈2 nm) onto electrospun polymeric nanofibers (NF) is presented. By ALD, monodispersed Pd nanograins with (111) exposed facets are decorated on the surface of the free‐standing flexible nanofibrous webs (NW). The Pd nanograin‐decorated free‐standing NW exhibit catalytic reduction of 4‐nitrophenol to 4‐aminophenol. Even under low loading capacity (≈20 µg mg−1), Pd nanograins manifest effective catalytic performance which can be referred to direct exposure of Pd single crystalline highly interactive (111) plains with high surface area on the NW. The Pd nanograins and the interactive sites along with the high surface area NW yield effective catalytic reduction of 4‐nitrophenol to 4‐aminophenol with the catalytic reduction rate of 0.0531 min−1. Pd nanograins display thermally tunable effective catalytic reduction properties with activation energy (Ea) of 1.705 J mol−1 on varying the reaction temperature from 12 to 42 °C. Moreover, Pd nanograin‐decorated NW are exhibited the effective reusable behavior with stable structural integrity even after repeated catalytic reactions. The approach of this study opens up synthesis and surface decoration of metal nanostructures onto NF through ALD with controlled size and facet orientation for designing reusable and free‐standing flexible catalytic nanofibrous materials.
Kraft Lignin as Electrode Material for Sustainable Electrochemical Energy Storage
Authors: Chaleawlert‐umpon Saowaluk , Berthold Thomas , Wang Xuewan , Antonietti Markus , Liedel Clemens
Published: October 2017

Electrochemical energy storage using lignin as a renewable electrode material is a cheap and sustainable approach for future organic batteries. Previous reports mainly focus on lignosulfonates (LS) or composites with conductive polymer additives with inherent problems, such as still expensive monomers. Here, composite electrodes are used from more available Kraft lignin and sustainable conductive carbon. Charge storage is evaluated in terms of electrical double layer storage and redox reactions, aiming at a better understanding of desired lignin properties for electrochemical energy storage. Using unmodified, commercial lignin and high surface area conductive carbon, reasonable capacity of ≈80 mAh g−1 is achieved in samples in which a thin layer of lignin covers the interface of high surface area carbon. Non‐faradaic contribution to charge storage is as large as in comparable pure carbon electrodes, and redox reactions in lignin contribute to additional, faradaic charge storage, significantly enhancing capacity in these systems. Resulting electrodes are cheap, reliable, and stable.
Pursuing Polymer Dielectric Interfacial Effect in Organic Transistors for Photosensing Performance Optimization
Authors: Wu Xiaohan , Chu Yingli , Liu Rui , Katz Howard E. , Huang Jia
Published: October 2017

Polymer dielectrics in organic field‐effect transistors (OFETs) are essential to provide the devices with overall flexibility, stretchability, and printability and simultaneously introduce charge interaction on the interface with organic semiconductors (OSCs). The interfacial effect between various polymer dielectrics and OSCs significantly and intricately influences device performance. However, understanding of this effect is limited because the interface is buried and the interfacial charge interaction is difficult to stimulate and characterize. Here, this challenge is overcome by utilizing illumination to stimulate the interfacial effect in various OFETs and to characterize the responses of the effect by measuring photoinduced changes of the OFETs performances. This systemic investigation reveals the mechanism of the intricate interfacial effect in detail, and mathematically explains how the photosensitive OFETs characteristics are determined by parameters including polar group of the polymer dielectric and the OSC side chain. By utilizing this mechanism, performance of organic electronics can be precisely controlled and optimized. OFETs with strong interfacial effect can also show a signal additivity caused by repeated light pulses, which is applicable for photostimulated synapse emulator. Therefore, this work enlightens a detailed understanding on the interface effect and provides novel strategies for optimizing OFET photosensory performances.
Implementation of a Novel Conference Series on Clinical Practice Variations Provides an Opportunity for Constructive Discussion of Faculty Practice Patterns: Do as We Say? … or Do as We Do?
Authors: Dorfsman Michele L. , Hart Danielle E. , Wolfson Allan B.
Published: October 2017

Background

Although evidence‐based medicine (EBM) is routinely used to guide management in the emergency department, there is still considerable variation in clinical practice. Trainees may not fully appreciate the reasons for these clinical practice variations (CPVs) and may find it frustrating when they encounter them. We used areas of CPV among our faculty as the basis for resident educational sessions and assessed the perceived utility of these sessions.

Methods

Topics were identified when residents noticed significant variability among the faculty in their management of particular clinical presentations. Sessions were conducted by facilitator‐led reviews of EBM guidelines, by faculty panel discussions of their management rationale where EBM guidelines are not available, or by pro–con debates. Residents were surveyed after the initial sessions to assess the utility of this series and changes in their understanding of CPV.

Results

There was a 72% response rate. The percentage of residents who were frustrated with CPV decreased from 64% to 35%; the percentage who felt that the presence of CPV enhanced their learning increased from 19% to 48%. Sixty‐five percent felt that the educational series contributed to decreased frustration, 77% felt that the sessions helped them understand why CPV occurs, and 93% felt that they helped their overall learning.

Conclusion

Explicit discussion and exploration of CPV in an educational setting can provide multiple benefits. Trainees may gain a better understanding of why CPV occurs and of the rationale behind practice variations. Faculty may benefit from analyzing CPV to determine whether these truly represent the “art of medicine.”
The role of intragroup agonism in parent‐offspring relationships and natal dispersal in monogamous owl monkeys (Aotus azarae) of Argentina
Authors: Corley Margaret K. , Xia Siyang , Fernandez‐Duque Eduardo
Published: October 2017

Agonistic behaviors are common in many group‐living taxa and may serve a variety of functions, ranging from regulating conflicts over reproduction to defending food resources. However, high rates of agonism are not expected to occur among close relatives or individuals in established mating relationships, which are characteristics of monogamous groups. To contribute to our understanding of agonism within socially monogamous groups, we collected behavioral and demographic data from Azara's owl monkeys (Aotus azarae) in the Gran Chaco of Argentina over 14 years. We examined factors related to age, sex, kinship, and behavioral context to evaluate predictions of the hypotheses that agonism functions to regulate dispersal and that it mediates competition for food and/or mates. Intragroup agonism was relatively rare: the group rate was approximately one event every three and a half hours. Rates of agonism were generally similar for both sexes, but there were marked differences among age categories. Agonism performed by adults was more frequently directed at subadults than at younger offspring. In contrast, agonistic interactions involving infants were very rare. Among interactions between adults and subadults, adults were much more frequently the actors than the recipients, suggesting that agonism from adults may influence natal dispersal of subadults. Agonistic events were most frequent during foraging, but also occurred more frequently than expected during bouts of social behavior. Overall, our results suggest that agonism in owl monkeys serves as a mechanism for regulating dispersal, and also likely plays a role in mediating mating and feeding competition.
Applying systems thinking to inform studies of wildlife trade in primates
Authors: Blair Mary E. , Le Minh D. , Thạch Hoàng M. , Panariello Anna , Vũ Ngọc B. , Birchette Mark G. , Sethi Gautam , Sterling Eleanor J.
Published: October 2017

Wildlife trade presents a major threat to primate populations, which are in demand from local to international scales for a variety of uses from food and traditional medicine to the exotic pet trade. We argue that an interdisciplinary framework to facilitate integration of socioeconomic, anthropological, and biological data across multiple spatial and temporal scales is essential to guide the study of wildlife trade dynamics and its impacts on primate populations. Here, we present a new way to design research on wildlife trade in primates using a systems thinking framework. We discuss how we constructed our framework, which follows a social‐ecological system framework, to design an ongoing study of local, regional, and international slow loris (Nycticebus spp.) trade in Vietnam. We outline the process of iterative variable exploration and selection via this framework to inform study design. Our framework, guided by systems thinking, enables recognition of complexity in study design, from which the results can inform more holistic, site‐appropriate, and effective trade management practices. We place our framework in the context of other approaches to studying wildlife trade and discuss options to address foreseeable challenges to implementing this new framework.
Effect of sensory and motor connectivity on hand function in pediatric hemiplegia
Authors: Gupta Disha , Barachant Alexandre , Gordon Andrew M. , Ferre Claudio , Kuo Hsing‐Ching , Carmel Jason B. , Friel Kathleen M.
Published: October 2017

Objective

We tested the hypothesis that somatosensory system injury would more strongly affect movement than motor system injury in children with unilateral cerebral palsy (USCP). This hypothesis was based on how somatosensory and corticospinal circuits adapt to injury during development; whereas the motor system can maintain connections to the impaired hand from the uninjured hemisphere, this does not occur in the somatosensory system. As a corollary, cortical injury strongly impairs sensory function, so we hypothesized that cortical lesions would impair hand function more than subcortical lesions.

Methods

Twenty‐four children with unilateral cerebral palsy had physiological and anatomical measures of the motor and somatosensory systems and lesion classification. Motor physiology was performed with transcranial magnetic stimulation and somatosensory physiology with vibration‐evoked electroencephalographic potentials. Tractography of the corticospinal tract and the medial lemniscus was performed with diffusion tensor imaging, and lesions were classified by magnetic resonance imaging. Anatomical and physiological results were correlated with measures of hand function using 2 independent statistical methods.

Results

Children with disruptions in the somatosensory connectivity and cortical lesions had the most severe upper extremity impairments, particularly somatosensory function. Motor system connectivity was significantly correlated with bimanual function, but not unimanual function or somatosensory function.

Interpretation

Both sensory and motor connectivity impact hand function in children with USCP. Somatosensory connectivity could be an important target for recovery of hand function in children with USCP. Ann Neurol 2017;82:766–780
Experimental Proof of the Bifunctional Mechanism for the Hydrogen Oxidation in Alkaline Media
Authors: Li Jingkun , Ghoshal Shraboni , Bates Michael K. , Miller Todd E , Davies Veronica , Stavitski Eli , Attenkofer Klaus , Mukerjee Sanjeev , Ma Zi‐Feng , Jia Qingying
Published: October 2017

Realization of the hydrogen economy relies on effective hydrogen production, storage, and utilization. The slow kinetics of hydrogen evolution and oxidation reaction (HER/HOR) in alkaline media limits many practical applications involving hydrogen generation and utilization, and how to overcome this fundamental limitation remains debatable. Here we present a kinetic study of the HOR on representative catalytic systems in alkaline media. Electrochemical measurements show that the HOR rate of Pt‐Ru/C and Ru/C systems is decoupled to their hydrogen binding energy (HBE), challenging the current prevailing HBE mechanism. The alternative bifunctional mechanism is verified by combined electrochemical and in situ spectroscopic data, which provide convincing evidence for the presence of hydroxy groups on surface Ru sites in the HOR potential region and its key role in promoting the rate‐determining Volmer step. The conclusion presents important references for design and selection of HOR catalysts.
Programmierbare transiente Thermogele vermittelt durch eine pH‐ und Redox‐regulierte supramolekulare Polymerisation
Authors: Spitzer Daniel , Rodrigues Leona Lucas , Straßburger David , Mezger Markus , Besenius Pol
Published: October 2017

Wir stellen eine durch mehrfache Stimuli ansprechbare transiente supramolekulare Polymerisation von β‐Faltblatt‐kodierten dendritischen Peptidmonomeren in Wasser vor. Die Glutaminsäure‐ und Methionin‐tragenden Amphiphile gehen eine durch Glucose‐Oxidase katalysierte und Glucose‐getriebene transiente Hydrogelierung ein. Diese basiert auf einem Zusammenspiel eines pH‐ und oxidativen Stimulus, der durch die Produktion reaktiver Sauerstoffspezies (ROS) gefördert wird. Mit Veränderung der Enzym‐ und Glucosekonzentration wird eine Feineinstellung der Assemblierungs‐ sowie Disassemblierungsgeschwindigkeit vorgenommen, wodurch die Steifigkeit und Stabilität des transienten Hydrogels bestimmt wird. Die Verwendung von Triethylenglycolketten führt zu thermoresponsiven Eigenschaften der Materialien. Weiterhin zeigen wir, dass Reparaturenzyme den oxidativen Schaden in den Methionin‐basierten Thioetherseitenketten beheben können. Da reaktive Sauerstoffspezies eine wichtige Rolle in Signaltransduktionskaskaden spielen, bietet unsere Strategie großes Potential zur Anwendung dieser dynamischen Biomaterialien in redoxaktiven Mikroumgebungen.
Reduction of a Cerium(III) Siloxide Complex To Afford a Quadruple‐Decker Arene‐Bridged Cerium(II) Sandwich
Authors: Kelly Rory P. , Maron Laurent , Scopelliti Rosario , Mazzanti Marinella
Published: October 2017

Organometallic multi‐decker sandwich complexes containing f‐elements remain rare, despite their attractive magnetic and electronic properties. The reduction of the CeIII siloxide complex, [KCeL4] (1; L=OSi(OtBu)3), with excess potassium in a THF/toluene mixture afforded a quadruple‐decker arene‐bridged complex, [K(2.2.2‐crypt)]2[{(KL3Ce)(μ‐η6:η6‐C7H8)}2Ce] (3). The structure of 3 features a [Ce(C7H8)2] sandwich capped by [KL3Ce] moieties with a linear arrangement of the Ce ions. Structural parameters, UV/Vis/NIR data, and DFT studies indicate the presence of CeII ions involved in δ bonding between the Ce cations and toluene dianions. Complex 3 is a rare lanthanide multi‐decker complex and the first containing non‐classical divalent lanthanide ions. Moreover, oxidation of 1 by AgOTf (OTf=O3SCF3) yielded the CeIV complex, [CeL4] (2), showing that siloxide ligands can stabilize Ce in three oxidation states.
Oxyfunctionalization of the Remote C−H Bonds of Aliphatic Amines by Decatungstate Photocatalysis
Authors: Schultz Danielle M. , Lévesque François , DiRocco Daniel A. , Reibarkh Mikhail , Ji Yining , Joyce Leo A. , Dropinski James F. , Sheng Huaming , Sherry Benjamin D. , Davies Ian W.
Published: October 2017

Aliphatic amines, oxygenated at remote positions within the molecule, represent an important class of synthetic building blocks to which there are currently no direct means of access. Reported herein is an efficient and scalable solution that relies upon decatungstate photocatalysis under acidic conditions using either H2O2 or O2 as the terminal oxidant. By using these reaction conditions a series of simple and unbiased aliphatic amine starting materials can be oxidized to value‐added ketone products. Lastly, NMR spectroscopy using in situ LED‐irradiated samples was utilized to monitor the kinetics of the reaction, thus enabling direct translation of the reaction into flow.
Synthesis of Anisotropic Hydrogels and Their Applications
Authors: Sano Koki , Ishida Yasuhiro , Aida Takuzo
Published: October 2017

Owing to their water‐rich structures, which are similar to those of biological tissues, hydrogels have long been regarded as promising scaffolds for artificial tissues and organs. However, in terms of the structural anisotropy, most synthetic hydrogels are substantially different from biological systems. Synthetic hydrogels are usually composed of randomly oriented three‐dimensional polymer networks whereas biological systems adopt anisotropic structures with hierarchically integrated building units. Such anisotropic structures often play essential roles in biological systems to exhibit particular functions. In this context, anisotropic hydrogels provide an entry point for exploring biomimetic applications of hydrogels. Reflecting these aspects, an increasing number of studies on anisotropic hydrogels have been reported recently. This Minireview highlights the use and perspectives of these anisotropic hydrogels, particularly focusing on their preparation, structures, and applications.
Living Supramolecular Polymerization of a Perylene Bisimide Dye into Fluorescent J‐Aggregates
Authors: Wagner Wolfgang , Wehner Marius , Stepanenko Vladimir , Ogi Soichiro , Würthner Frank
Published: October 2017

The self‐assembly of a new perylene bisimide (PBI) organogelator with 1,7‐dimethoxy substituents in the bay position affords non‐fluorescent H‐aggregates at high cooling rates and fluorescent J‐aggregates at low cooling rates. Under properly adjusted conditions, the kinetically trapped “off‐pathway” H‐aggregates are transformed into the thermodynamically favored J‐aggregates, a process that can be accelerated by the addition of J‐aggregate seeds. Spectroscopic studies revealed a subtle interplay of π–π interactions and intra‐ and intermolecular hydrogen bonding for monomeric, H‐, and J‐aggregated PBIs. Multiple polymerization cycles initiated from the seed termini demonstrate the living character of this chain‐growth supramolecular polymerization process.
Ligand‐free Mizoroki–heck reaction using reusable modified graphene oxide‐supported Pd(0) nanoparticles
Authors: Veisi Hojat , Mirzaee Najibeh
Published: October 2017

Palladium nanoparticles supported on graphene oxide surfaces modified with metformin was found to be an effective and recyclable nanocatalyst in Mizoroki–Heck coupling reactions under aerobic conditions without requiring any phosphine or ligand coordination. Excellent product yields were achieved with a wide variety of substrates and the catalyst could be recycled seven times without any noticeable loss of its catalytic activity.
HAp‐encapsulated γ‐Fe2O3‐supported dual acidic heterogeneous catalyst for highly efficient one‐pot synthesis of benzoxanthenones and 3‐pyranylindoles
Authors: Kheirkhah Leila , Mamaghani Manouchehr , Yahyazadeh Asieh , Mahmoodi Nosrat Ollah
Published: October 2017

A novel method is reported for the synthesis of benzoxanthenone and 3‐pyranylindole derivatives via one‐pot three‐component reactions using a newly synthesized HAp‐encapsulated γ‐Fe2O3‐supported dual acidic heterogeneous catalyst, as a reusable and highly efficient nanocatalyst. In this protocol the use of the nanocatalyst provided a green, useful and rapid method to generate products in short reaction times (4–20 min) and in excellent yields (87–96%). The paramagnetic nature of the catalyst provided a simple, trouble‐free and facile approach for the separation of the catalyst by applying an external magnet, and it could be used in eight cycles without significant loss in catalytic efficiency.
Cobalt(II)–metformin complexes containing α‐diimine/α‐diamine as auxiliary ligand: DNA binding properties
Authors: Vasantha P. , Sathish Kumar B. , Shekhar B. , Anantha Lakshmi P.V.
Published: October 2017

The cobalt(II) complexes [Co(Cl)2(met)(o‐phen)] (1), [Co(Cl)2(en)(met)] (2) and [Co(Cl)2(met)(opda)] (3) (met = metformin, o‐phen = ortho‐phenanthroline, en = ethylenediamine, opda = ortho‐phenylenediamine) were synthesized and characterized using liquid chromatography–mass spectrometry, elemental analysis, molar conductance measurements, thermal analysis, infrared spectroscopy, magnetic moment measurements, electronic spectroscopy and X‐ray diffraction. The metal centre was found to be in an octahedral geometry. UV–visible absorption, fluorescence and viscosity measurements were conducted to assess the interaction of the complexes with calf thymus DNA. The complexes showed absorption hyperchromism in UV–visible spectra with DNA. The binding constants from UV–visible absorption studies were 1.38 × 105, 2.1 × 105 and 3.1 × 105 M−1 for 1, 2 and 3, respectively, and Stern–Volmer quenching constants from fluorescence studies were 0.146, 0.176 and 0.475, respectively. Viscosity measurements revealed that the binding of the complexes with DNA could be surface binding, mainly due to groove binding. The activities of the complexes in DNA cleavage decrease in the order 3 > 2 > 1. The complexes were docked into DNA topoisomerase II using Discovery Studio 2.1 software.
Sustainable chitosan/starch composite material for stabilization of palladium nanoparticles: Synthesis, characterization and investigation of catalytic behaviour of Pd@chitosan/starch nanocomposite in Suzuki–Miyaura reaction
Authors: Baran Talat , Yılmaz Baran Nuray , Menteş Ayfer
Published: October 2017

We fabricated a green chitosan/starch composite as support material for stabilization of palladium nanoparticles for the first time. The chemical structure of the sustainable palladium nanocomposite was investigated using various techniques. Characterization studies showed that the average dimensions of the palladium nanocomposite ranged between 16 and 21 nm. The synthesized palladium nanocomposite was employed in the synthesis of a series of biphenyl compounds via Suzuki–Miyaura cross‐coupling reactions with an unconventional technique. All coupling reactions were conducted in very short reaction time and excellent biphenyl yields were obtained in the presence of the nanocomposite. The palladium catalyst was tolerant to a wide range of functional groups. We also investigated the recyclability and reusability of the palladium nanocomposite, and found that it could be used for seven successive cycles.
Cu(II) immobilized on guanidinated epibromohydrin‐functionalized γ‐Fe2O3@TiO2 (γ‐Fe2O3@TiO2‐EG‐Cu(II)): A highly efficient magnetically separable heterogeneous nanocatalyst for one‐pot synthesis of highly substituted imidazoles
Authors: Nejatianfar Mahdi , Akhlaghinia Batool , Jahanshahi Roya
Published: October 2017

A simple, efficient and eco‐friendly procedure has been developed using Cu(II) immobilized on guanidinated epibromohydrin‐functionalized γ‐Fe2O3@TiO2 (γ‐Fe2O3@TiO2‐EG‐Cu(II)) for the synthesis of 2,4,5‐trisubstituted and 1,2,4,5‐tetrasubstituted imidazoles, via the condensation reactions of various aldehydes with benzil and ammonium acetate or ammonium acetate and amines, under solvent‐free conditions. High‐resolution transmission electron microscopy analysis of this catalyst clearly affirmed the formation of a γ‐Fe2O3 core and a TiO2 shell, with mean sizes of about 10–20 and 5–10 nm, respectively. These data were in very good agreement with X‐ray crystallographic measurements (13 and 7 nm). Moreover, magnetization measurements revealed that both γ‐Fe2O3@TiO2 and γ‐Fe2O3@TiO2‐EG‐Cu(II) had superparamagnetic behaviour with saturation magnetization of 23.79 and 22.12 emu g−1, respectively. γ‐Fe2O3@TiO2‐EG‐Cu(II) was found to be a green and highly efficient nanocatalyst, which could be easily handled, recovered and reused several times without significant loss of its activity. The scope of the presented methodology is quite broad; a variety of aldehydes as well as amines have been shown to be viable substrates. A mechanism for the cyclocondensation reaction has also been proposed.
New Ni(II), Pd(II) and Pt(II) complexes coordinated to azo pyrazolone ligand with a potent anti‐tumor activity: Synthesis, characterization, DFT and DNA cleavage studies
Authors: Bakr Eman A. , Al‐Hefnawy Gad B. , Awad Mohamed K. , Abd‐Elatty Hossam H. , Youssef Mohamed S.
Published: October 2017

The absolute necessity to fight some class of tumor is perceived as serious health concerns, so the discovery and development of effective anticancer agents are urgently needed. (E)‐4‐((2‐hydroxyphenyl)diazenyl)‐3‐phenyl‐1H‐pyrazol‐5(4H)‐one, HL, and its Ni(II), Pd(II) and Pt(II) complexes were synthesized and the biological activity was evaluated for antitumor, antioxidant and antimicrobial activity as well as DNA cleavage. Their structures were assigned depending on the elemental analysis, conductivity, magnetic moment, spectral measurements (IR, 1HNMR, mass and UV–Vis) and thermal analysis. 3D molecular modeling using DFT method confirmed that the geometrical structures agree well with the suggested experimental ones. The antitumor activity was evaluated against four different cell lines using MTT assay. The ligand HL showed a potent cytotoxic activity compared to 5‐fluorouracil as a reference drug. For metal complexes, the order of activity was: Pd(II) > Ni(II) > Pt(II). A remarkable antioxidant activity for the ligand HL was recorded. It was higher than that of the metal complexes. Results of antimicrobial experiments revealed that all compounds were moderate to highly active against selected bacterial strains but inactive as antifungal except Pd(II) which showed a moderate antifungal activity. Gel electrophoresis showed insignificant nucleases activity for the ligand or its metal complexes even in the presence of H2O2 providing protection of DNA from damage. The antitumor activity of our compounds may be not due to DNA cleavage but may be referred to a mechanism similar to that of 5‐fluorouracil which interfere with DNA replication. The present work suggests the use of this ligand in the design and development of new anticancer drugs.
Cu(II) immobilized on mesoporous organosilica as an efficient and reusable nanocatalyst for one‐pot Biginelli reaction under solvent‐free conditions
Authors: Nasresfahani Zahra , Kassaee Mohammad Zaman
Published: October 2017

Cu(II) immobilized on mesoporous organosilica nanoparticles (Cu2+@MSNs‐(CO2−)2) has been synthesized, as a inorganic–organic nanohybrid catalyst, through a post‐grafting approach. Its characterization is carried out by Fourier transform infrared spectroscopy (FT‐IR), X‐ray diffraction (XRD), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), Energy dispersive X‐ray (EDX), Thermogravimetric/differential thermal analyses (TGA‐DTA), and Nitrogen adsorption–desorption analysis. Cu2+@MSNs‐(CO2−)2 exhibits high catalytic activity in the Biginelli reaction for the synthesis of a diverse range of 3, 4‐dihydropyrimidin‐2(1H)‐ones, under mild conditions. The anchored Cu(II) could not leach out from the surface of the mesoporous catalyst during the reaction and it has been reused several times without appreciable loss in its catalytic activity.
Heck and oxidative boron Heck reactions employing Pd(II) supported amphiphilized polyethyleneimine‐functionalized MCM‐41 (MCM‐41@aPEI‐Pd) as an efficient and recyclable nanocatalyst
Authors: Motevalizadeh Seyed Farshad , Alipour Masoumeh , Ashori Fatemeh , Samzadeh‐Kermani Alireza , Hamadi Hosein , Ganjali Mohammad Reza , Aghahosseini Hamideh , Ramazani Ali , Khoobi Mehdi , Gholibegloo Elham
Published: October 2017

A novel nanocatalyst was developed based on covalent surface functionalization of MCM‐41 with polyethyleneimine (PEI) using [3‐(2,3‐Epoxypropoxy)propyl] trimethoxysilane (EPO) as a cross‐linker. Amine functional groups on the surface of MCM‐41 were then conjugated with iodododecane to render an amphiphilic property to the catalyst. Palladium (II) was finally immobilized onto the MCM‐41@PEI‐dodecane and the resulted MCM‐41@aPEI‐Pd nanocatalyst was characterized by FT‐IR, TEM, ICP‐AES and XPS. Our designed nanocatalyst with a distinguished core‐shell structure and Pd2+ ions as catalytic centers was explored as an efficient and recyclable catalyst for Heck and oxidative boron Heck coupling reactions. In Heck coupling reaction, the catalytic activity of MCM‐41@aPEI‐Pd in the presence of triethylamine as base led to very high yields and selectivity. Meanwhile, the MCM‐41@aPEI‐Pd as the first semi‐heterogeneous palladium catalyst was examined in the C‐4 regioselective arylation of coumarin via the direct C‐H activation and the moderate to excellent yields were obtained toward different functional groups. Leaching test indicated the high stability of palladium on the surface of MCM‐41@aPEI‐Pd as it could be recycled for several runs without significant loss of its catalytic activity.
New anthracene based Schiff base ligands appended Cu(II) complexes: Theoretical study, DNA binding and cleavage activities
Authors: Gubendran Ammavasai , Kumar Gujuluva Gangatharan Vinoth , Kesavan Mookkandi Palsamy , Rajagopal Gurusamy , Athappan Periakaruppan , Rajesh Jegathalaprathaban
Published: October 2017

New anthracene based Schiff base ligands L1 and H(L2), their Cu(II) complexes [Cu(L1)Cl2] (1) and [Cu(L2)Cl] (2), (where L1 = N1,N2‐bis(anthracene‐9‐methylene)benzene‐1,2‐diamine, L2 = (2Z,4E)‐4‐(2‐(anthracen‐9‐ylmethyleneamino)phenylimino)pent‐2‐en‐2‐ol) have been prepared and characterized by elemental analysis, NMR, FAB‐mass, EPR, FT‐IR, UV–Vis and cyclic voltammetry. The electronic structures and geometrical parameters of complexes 1 and 2 were analyzed by the theoretical B3LYP/DFT method. The interaction of these complexes 1 and 2 with CT‐DNA has been explored by using absorption, cyclic voltammetric and CD spectral studies. From the electronic absorption spectral studies, it was found that the DNA binding constants of complexes 1 and 2 are 8.7 × 103 and 7.0 × 104 M−1, respectively. From electrochemical studies, the ratio of DNA binding constants K+/K2+ for 2 has been estimated to be >1. The high binding constant values, K+/K2+ ratios more than unity and positive shift of voltammetric E1/2 value on titration with DNA for complex 2 suggest that they bind more avidly with DNA than complex 1. The inability to affect the conformational changes of DNA in the CD spectrum is the definite evidences of electrostatic binding by the complex 1. It can be assumed that it is the bulky anthracene unit which sterically inhibits these complexes 1 and 2 from intercalation and thereby remains in the groove or electrostatic. The complex 2 hardly cleaves supercoiled pUC18 plasmid DNA in the presence of hydrogen peroxide. The results suggest that complex 2 bind to DNA through minor groove binding.
Is undergraduate debt an impediment to postgraduate enrolment in England?
Authors: Wakeling Paul , Hampden‐Thompson Gillian , Hancock Sally
Published: October 2017

Changes to undergraduate student funding arrangements in England have prompted concerns that increased indebtedness will deter graduates from postgraduate study. While it is clear that student debt has increased substantially in recent years, international evidence is equivocal on whether such debt is a deterrent to further study and there is hardly any prior research on this topic in the UK context. Using a large‐scale survey of 2009 and 2012 graduates from six selective English universities, we investigate the association between undergraduate debt, other graduate characteristics and progression to postgraduate study. We find some association of higher debt levels with lower rates of progression to postgraduate study, although this reduces when controlling for other factors, such as degree‐level attainment and subject discipline. Within a multivariate logistic regression model predicting progression to postgraduate study we find that debt is not a statistically significant predictor, although other characteristics are important. This indicates, we suggest, that underlying financial resources, rather than debt per se, are critical in enabling access to postgraduate study. We consider the implications of recently announced loans for postgraduate study in England given these findings.
Heed the voices of experience for hiring, keeping great coaches
Authors: McCarthy Claudine
Published: October 2017

It happens all too often. You get caught up in the excitement of thinking you've found just the right coach. But you soon discover that you're sadly mistaken. Other times, you think you're settling. But you're pleasantly surprised at the outcome.
Unusual route to the AD's seat brings uncommon results
Authors: McCarthy Claudine
Published: October 2017

After Rutgers University's athletics department endured a series of scandals that tarnished its reputation, it sorely needed a fresh start and new leadership. That's when Patrick E. Hobbs came to the rescue, bringing his own unique blend of academic, legal, and administrative expertise that would prove valuable in leading Rutgers athletics to clean up its image and forge a new path to success.
Optical coherence tomography guided carotid artery stent procedure: technique and potential applications
Authors: Dohad Suhail , Zhu Alexander , Krishnan Sandeep , Wang Frances , Wang Serena , Cox Justin , Henry Timothy D.
Published: October 2017

Objectives

To (1) present a guide on how to perform optical coherence tomography (OCT) in carotid artery stenting (CAS), to (2) highlight several instructive cases illustrating OCT‐guidance as an interventional strategy, and to (3) present the largest case‐series of OCT‐guided CAS performed in North America, demonstrating its feasibility as an imaging modality in this setting.

Background

OCT is an intravascular imaging method that captures images with an axial resolution 10 times higher than intravascular ultrasound. OCT has proven to be a useful modality in coronary angiography and may have similar applications in evaluating carotid atherosclerotic disease.

Methods

We compared our experience in CAS utilizing OCT (40 patients) versus that of CAS without OCT guidance (52 patients).

Results

No strokes or deaths occurred in either group postprocedurally or at 12 months. Fluoroscopy time was reduced in the OCT arm (14 ± 1 vs. 16 ± 1 min). Postprocedural creatinine levels were identical (1 ± 0 mg/dl, P = 0.96). Procedure time (96 ± 8 vs. 80 ± 3 min, P = 0.06) and contrast use (94 ± 4 vs. 83 ± 4 ml, P = 0.05) was slightly elevated in the OCT arm.

Conclusions

We established a standardized protocol to consistently obtain OCT images that helped guide interventional decision‐making during CAS. OCT imaging in the carotids requires a higher contrast load and prolongs procedure time. However, it can be performed without significant increases in fluoroscopy time or negatively affecting renal function. There were no negative safety signals in this pilot study.
Transcoronary pacing to assess myocardial viability prior to percutaneous coronary intervention: Pilot study to assess feasibility
Authors: O'Neill James , Hogarth Andrew J. , Pearson Ian , Law Hannah , Bowes Robert , Kidambi Ananth , Wheatcroft Stephen , Sivananthan U. Mohanaraj , Tayebjee Muzahir H.
Published: October 2017

Background

The assessment of myocardial viability is crucial before percutaneous coronary intervention (PCI) is carried out to ensure that the patient will gain benefit. Trans‐coronary pacing (TCP) has previously been used to pace myocardium but may also provide information on myocardial viability.

Methods

Patients with a single, significant coronary stenosis requiring PCI were recruited. They underwent a cardiac MRI to assess myocardial viability. Prior to PCI, a coronary guidewire was used to measure pacing threshold, impedance, and R‐wave amplitude in different myocardial segments to determine any association between the electrical parameters and myocardial viability.

Results

Eight patients were recruited and six patients underwent intervention. Pacing sensitivity did not demonstrate statistically significant differences between normal and scarred myocardium. Impedance demonstrated a mean of 304.8 ± 74.0 Ω in normal myocardium (NM), 244.1 ± 66.6 Ω in <50% myocardial scar (MS), and 222.3 ± 33.8 Ω in ≥50% MS. Pacing threshold demonstrated a mean of 1.960 ± 1.226 V in NM, 5.009 ± 2.773 V in <50% MS, and 3.950 ± 0.883 V in ≥50% MS. For both impedance and threshold, there was a significant difference among the groups (P = 0.12 and P = 0.002, respectively), and post hoc Tukey's pairwise comparison demonstrated significant differences between NM and scarred myocardium. No significant differences were found between <50% MS and ≥50% MS.

Conclusions

Impedance and pacing threshold, measured during TCP, can be used to differentiate between normal myocardium and scarred myocardium. Further research is needed to determine whether TCP can discriminate between viable and nonviable myocardium.
A Bifunctional Fluorogenic Rhodamine Probe for Proximity‐Induced Bioorthogonal Chemistry
Authors: Werther Philipp , Möhler Jasper S. , Wombacher Richard
Published: October 2017

Bioorthogonal reactions have emerged as a versatile tool in life sciences. The inverse electron demand Diels–Alder reaction (DAinv) stands out due to the availability of reactants with very fast kinetics. However, highly reactive dienophiles suffer the disadvantage of being less stable and prone to side reactions. Herein, we evaluate the extent of acceleration of rather unreactive but highly stable dienophiles by DNA‐templated proximity. To this end, we developed a modular synthetic route for a novel bifunctional fluorogenic tetrazine rhodamine probe that we used to determine the reaction kinetics of various dienophiles in a fluorescence assay. Under proximity‐driven conditions the reaction was found to be several orders of magnitude faster, and we observed almost no background reaction when proximity was not induced. This fundamental study identifies a minimally sized fluorogenic tetrazine dienophile reactant pair that has potential to be generally used for the visualization of biomolecular interactions with temporal and spatial resolution in living systems.
Substitution Reactions at DippBIAN Supported Fluoroantimony Cations Yielding Cyanoantimony and Azidoantimony Cations
Authors: Suter Riccardo , Frazee Christopher , Burford Neil , McDonald Robert , Ferguson Michael J.
Published: October 2017

This work presents new cationic coordination complexes of antimony with the 1,2‐bis[(2,6‐diisopropylphenyl)imino]acenaphthene (DippBIAN) ligand system. The fluoroantimony complexes [SbF(DippBIAN)][OTf]2 and [SbF2(DippBIAN)][OTf] have been successfully isolated and characterized. The fluorine substituent in the Lewis acidic complex [SbF(DippBIAN)][OTf]2 can be selectively replaced without degradation of the Sb‐DippBIAN interaction to give the first dicationic azido and cyano derivatives, [Sb(CN)(DippBIAN)][OTf]2 and [Sb(N3)(DippBIAN)][OTf]2, which have been isolated and structurally characterized.