bluuebunny/crossref_metadata_2025 huggingface dataset:
EPR Studies of the Binding Properties, Guest Dynamics, and Inner‐Space Dimensions of a Water‐Soluble Resorcinarene Capsule
Authors: Ayhan Mehmet Menaf , Casano Gilles , Karoui Hakim , Rockenbauer Antal , Monnier Valérie , Hardy Micaël , Tordo Paul , Bardelang David , Ouari Olivier
Published: September 2015

Nitroxide free radicals have been used to study the inner space of one of Rebek’s water‐soluble capsules. EPR and 1H NMR spectroscopy, ESI‐MS, and DFT calculations showed a preference for the formation of 1:2 complexes. EPR titrations allowed us to determine binding constants (Ka) in the order of 107 M−2. EPR spectral‐shape analysis provided information on the guest rotational dynamics within the capsule. The interplay between optimum hydrogen bonding upon capsule formation and steric strain for guest accommodation highlights some degree of flexibility for guest inclusion, particularly at the center of the capsule where the hydrogen bond seam can be barely distorted or slightly disturbed.
Molecular Cobalt Clusters as Precursors of Distinct Active Species in Electrochemical, Photochemical, and Photoelectrochemical Water Oxidation Reactions in Phosphate Electrolytes
Authors: Li Xiaobo , Clatworthy Edwin B. , Masters Anthony F. , Maschmeyer Thomas
Published: September 2015

Three cobalt model molecular compounds, Co‐cubane ([Co4(µ3‐O)4(µ‐OAc)4py4]), Co‐trimer ([Co3(μ3‐O)(µ‐OAc)6py3]PF6), and Co‐dimer ([Co2(μ‐OH)2(µ‐OAc)(OAc)2py4]PF6), are investigated as water oxidation reaction (WOR) catalysts, using electrochemical, photochemical, and photoelectrochemical methodologies in phosphate electrolyte. The actual species contributing to the catalytic activity observed in the WOR are derived from the transformation of these cobalt compounds. The catalytic activity observed is highly dependent on the initial compound structure and on the particular WOR methodology used. Co‐cubane shows no activity in the electrochemical WOR and negligible activity in the photochemical WOR, but is active in the photoelectrochemical WOR, in which it behaves as a precursor to catalytically active species. Co‐dimer also shows no activity in the electrochemical WOR, but behaves as a precursor to catalytically active species in both the photochemical and photoelectrochemical WOR experiments. Co‐trimer behaves as a precursor to catalytically active species in all three of the WOR methodologies.
Synthesis, Properties, and π‐Dimer Formation of Oligothiophenes Partially Bearing Orthogonally Fused Fluorene Units
Authors: Ie Yutaka , Okamoto Yuji , Tone Saori , Aso Yoshio
Published: September 2015

A series of oligothiophenes that incorporate cyclopenta[c]thiophene‐based units bearing spiro‐substituted dialkylfluorene was synthesized. Photophysical measurements indicated that there was no interruption in the conjugation along the oligothiophene backbones, irrespective of the number or position of this unit. Electrochemical measurements showed that the thiophene 7‐mers and 11‐mer exhibit reversible multi‐oxidation waves. The formation of cationic species was clearly observed from UV/Vis/NIR measurements. Furthermore, the UV/Vis/NIR spectra at 223 K under one‐electron oxidation conditions revealed that the unsubstituted thiophene or bithiophene units remained in the absence of intermolecular π–π interactions, whereas the formation of π‐dimeric species was observed for the thiophene 7‐mer containing an unsubstituted terthiophene (U3) unit. Theoretical calculations indicated that the combination of the U3 unit and the all‐trans conformation decreased the intermolecular steric repulsion between the fused cyclopentene ring and its facing thiophene, which may contribute to the formation of the dimeric structure.
Human Serum Albumin Conjugated Nanoparticles for pH and Redox‐Responsive Delivery of a Prodrug of Cisplatin
Authors: Shi Hongdong , Cheng Qinqin , Yuan Siming , Ding Xin , Liu Yangzhong
Published: September 2015

Platinum anticancer drugs are particularly in need of controlled drug delivery because of their severe side effects. Platinum(IV) agents are designed as prodrugs to reduce the side effects of platinum(II) drugs; however, premature reduction could limit the effect as a prodrug. In this work, a highly biocompatible, pH and redox dual‐responsive delivery system is prepared by using hybrid nanoparticles of human serum albumin (HSA) and calcium phosphate (CaP) for the PtIV prodrug of cisplatin. This conjugate is very stable under extracellular conditions, so that it protects the platinum(IV) prodrug in HSA. Upon reaching the acidic and hypoxic environment, the platinum drug is released in its active form and is able to bind to the target DNA. The Pt–HSA/CaP hybrid inhibits the proliferation of various cancer cells more efficiently than cisplatin. Different cell cycle arrests suggest different cellular responses of the PtIV prodrug in the CaP nanocarrier. Interestingly, this delivery system demonstrates enhanced cytotoxicity to tumor cells, but not to normal cells.
Chiral Dawson‐Type Hybrid Polyoxometalate Catalyzes Enantioselective Diels–Alder Reactions
Authors: Xuan Wen‐Jing , Botuha Candice , Hasenknopf Bernold , Thorimbert Serge
Published: September 2015

Can achiral organocatalysts linked to chiral polyanionic metal oxide clusters provide good selectivity in enantioselective CC bond formations? The answer to this question is investigated by developing a new active hybrid polyoxometalate‐based catalyst for asymmetric Diels–Alder reaction. Chirality transfer from the chiral anionic polyoxometalate to the covalently linked achiral imidazolidinone allows Diels–Alder cycloaddition products to be obtained with good yields and high enantioselectivities when using cyclopentadiene and acrylaldehydes as partners.
Mechanistic Study of a Photocatalyzed CS Bond Formation Involving Alkyl/Aryl Thiosulfate
Authors: Li Yiming , Xie Weisi , Jiang Xuefeng
Published: September 2015

This study presents thioether construction involving alkyl/aryl thiosulfates and diazonium salt catalyzed by visible‐light‐excited [Ru(bpy)3Cl2] at room temperature in 44–86 % yield. Electron paramagnetic resonance studies found that thiosulfate radical formation was promoted by K2CO3. Conversely, radicals generated from BnSH or BnSSBn (Bn=benzyl) were clearly suppressed, demonstrating the special property of thiosulfate in this system. Transient absorption spectra confirmed the electron‐transfer process between [Ru(bpy)3Cl2] and 4‐MeO‐phenyl diazonium salt, which occurred with a rate constant of 1.69×109 M−1 s−1. The corresponding radical trapping product was confirmed by X‐ray diffraction. The full reaction mechanism was determined together with emission quenching data. Furthermore, this system efficiently avoided the over‐oxidation of sulfide caused by H2O in the photoexcited system containing Ru2+. Both aryl and heteroaryl diazonium salts with various electronic properties were investigated for synthetic compatibility. Both alkyl‐ and aryl‐substituted thiosulfates could be used as substrates. Notably, pharmaceutical derivatives afforded late‐stage sulfuration smoothly under mild conditions.
Structurally Diverse π‐Extended Conjugated Polycarbo‐ and Heterocycles through Pd‐Catalyzed Autotandem Cascades
Authors: Barroso Raquel , Cabal María‐Paz , Badía‐Laiño Rosana , Valdés Carlos
Published: September 2015

The Pd‐catalyzed reaction between 2,2′‐dibromobiphenyls and related systems with tosylhydrazones gives rise to new π‐extended conjugated polycarbo‐ and heterocycles through an autotandem process involving a cross‐coupling reaction followed by an intramolecular Heck cyclization. The reaction shows wide scope regarding both coupling partners. Cyclic and acyclic tosylhydrazones can participate in the process. Additionally, a variety of aromatic and heteroaromatic dibromoderivatives have been employed, leading to an array of diverse scaffolds featuring a fluorene or acridine central nucleus, and containing binaphthyl, thiophene, benzothiophene and indole moieties. The application to appropriate tetrabrominated systems led to greater structural complexity through two consecutive autotandem cascades. The photophysical properties of selected compounds were studied through their absorption and emission spectra. Fluorescence molecules featuring very high quantum yields were identified, showing the potential of this methodology in the development of molecules with interesting optoelectronic properties.
Native Mannose‐Dominant Extraction by Pyridine–Phenol Alternating Oligomers Having an Extremely Efficient Repeating Motif of Hydrogen‐Bonding Acceptors and Donors
Authors: Ohishi Yuki , Abe Hajime , Inouye Masahiko
Published: September 2015

Pyridine–phenol alternating oligomers in which pyridine and phenol moieties are alternatingly linked through acetylene bonds at the 2,6‐positions of the aromatic rings were designed and synthesized. The pyridine nitrogen atom and the neighboring phenolic hydroxyl group were oriented so that they do not form an intramolecular hydrogen bond but cooperatively act as hydrogen‐bonding acceptor and donor in a push–pull fashion for the hydroxyl group of saccharides. The longer oligomer strongly bound to lipophilic glycosides in 1,2‐dichloroethane, and association constants approached 108 M−1. Moreover, the oligomer extracted native saccharides from a solid phase to apolar organic solvents up to the extent of an equal amount of the oligomer and showed mannose‐dominant extraction among naturally abundant hexoses. The oligomer bound to native saccharides even in 20 % DMSO‐containing 1,2‐dichloroethane and exhibited association constants of greater than 10 M−1 for D‐mannose and D‐glucose.
Stereo‐ and Chemodivergent NHC‐Promoted Functionalisation of Arylalkylketenes with Chloral
Authors: Douglas James J. , Churchill Gwydion , Slawin Alexandra M. Z. , Fox David J. , Smith Andrew D.
Published: September 2015

Stereo‐ and chemodivergent enantioselective reaction pathways are observed upon treatment of alkylarylketenes and trichloroacetaldehyde (chloral) with N‐heterocyclic carbenes, giving selectively either β‐lactones (up to 88:12 dr, up to 94 % ee) or α‐chloroesters (up to 94 % ee). Either 2‐arylsubstitution or an α‐branched iPr alkyl substituent within the ketene favours the chlorination pathway, allowing chloral to be used as an electrophilic chlorinating reagent in asymmetric catalysis.
Palladium‐Catalyzed Carbonylative Cyclization of Arenes by CH Bond Activation with DMF as the Carbonyl Source
Authors: Chen Jianbin , Feng Jian‐Bo , Natte Kishore , Wu Xiao‐Feng
Published: September 2015

A novel palladium‐catalyzed CO‐gas‐ and autoclave‐free protocol for the synthesis of 11H‐pyrido[2,1‐b]quinazolin‐11‐ones has been developed. Quinazolinones, which are omnipresent motif in many pharmaceuticals and agrochemicals, were prepared in good yields by CH bond activation and annulation using DMF as the CO surrogate. A 13CO‐labelled DMF control experiment demonstrated that CO gas was released from the carbonyl of DMF with acid as the promotor. The kinetic isotope effect (KIE) value indicated that the CH activation step may not be involved in the rate‐determining step. This methodology is operationally simple and showed a broad substrate scope with good to excellent yields.
Facile, Catalytic Dehydrocoupling of Phosphines Using β‐Diketiminate Iron(II) Complexes
Authors: King Andrew K. , Buchard Antoine , Mahon Mary F. , Webster Ruth L.
Published: September 2015

Catalytic dehydrocoupling of primary and secondary phosphines has been achieved for the first time using an iron pre‐catalyst. The reaction proceeds under mild reaction conditions and is successful with a range of diarylphosphines. A proton acceptor is not needed for the transformation to take place, but addition of 1‐hexene does allow for turnover at 50 °C. The catalytic system developed also facilitates the dehydrocoupling of phenylphosphane and dicyclohexylphosphane. A change in solvent switches off dehydrocoupling to allow hydrophosphination of alkenes.
Large Hexadecametallic {MnIII–LnIII} Wheels: Synthesis, Structural, Magnetic, and Theoretical Characterization
Authors: Vignesh Kuduva R. , Langley Stuart K. , Moubaraki Boujemaa , Murray Keith S. , Rajaraman Gopalan
Published: September 2015

The synthesis, gas sorption studies, magnetic properties, and theoretical studies of new molecular wheels of core type {MnIII8LnIII8} (Ln=Dy, Ho, Er, Y and Yb), using the ligand mdeaH2, in the presence of ortho‐toluic or benzoic acid are reported. From the seven wheels studied the {Mn8Dy8} and {Mn8Y8} analogues exhibit SMM behavior as determined from ac susceptibility experiments in a zero static magnetic field. From DFT calculations a S=16 ground state was determined for the {Mn8Y8} complex due to weak ferromagnetic MnIII–MnIII interactions. Ab initio CASSCF+RASSI‐SO calculations on the {Mn8Dy8} wheel estimated the MnIII–DyIII exchange interaction as −0.1 cm−1. This weak exchange along with unfavorable single‐ion anisotropy of DyIII/MnIII ions, however, led to the observation of SMM behavior with fast magnetic relaxation. The orientation of the g‐anisotropy of the DyIII ions is found to be perpendicular to the plane of the wheel and this suggests the possibility of toroidal magnetic moments in the cluster. The {Mn8Ln8} clusters reported here are the largest heterometallic MnIIILnIII wheels and the largest {3d–4f} wheels to exhibit SMM behavior reported to date.
Cobalt(III)‐Catalyzed Dehydrative [4+2] Annulation of Oxime with Alkyne by CH and NOH Activation
Authors: Sen Malay , Kalsi Deepti , Sundararaju Basker
Published: September 2015

Efficient, scalable cobalt‐catalyzed redox‐neutral [4+2] annulation of readily available oximes and alkyne is reported. The developed synthetic methodology is widely applicable and tolerates various functional groups including heterocycles. A stable Cp*CoIII neutral complex is employed as the catalyst for this redox‐neutral [4+2] annulation reaction, which progresses smoothly by way of a reversible cyclometallation without any external oxidizing agent, and produces only water as the side product.
Enantioselective Degradation Mechanism of Beta‐Cypermethrin in Soil From the Perspective of Functional Genes
Authors: Yang Zhong‐Hua , Ji Guo‐Dong
Published: September 2015

The behavior and mechanisms of the enantioselective degradation of beta‐cypermethrin were studied in soil. The four isomers were degraded at different rates, and the enantiomer fractions of alpha‐cypermethrin and theta‐cypermethrin exceeded 0.5. Moreover, 3‐phenoxybenzoic acid, phenol, and protocatechuic acid were detected; based on the presence of these metabolites, we predicted the degradation pathway and identified the functional genes that are related to this degradation process. We established quantitative relationships between the data on degradation kinetics and functional genes; we found that the quantitative relationships between different enantiomers differed even under the same conditions, and the genes pobA and pytH played key roles in limiting the degradation rate. Data obtained using path analysis revealed that the same gene had different direct and indirect effects on the degradation of different isomers. A mechanism was successfully proposed to explain the selective degradation of chiral compounds based on the perspective of functional genes. Chirality 27:929–935, 2015. © 2015 Wiley Periodicals, Inc.
Contractile actin cables induced by Bacillus anthracis lethal toxin depend on the histone acetylation machinery
Authors: Rolando Monica , Stefani Caroline , Doye Anne , Acosta Maria I. , Visvikis Orane , Yevick Hannah G. , Buchrieser Carmen , Mettouchi Amel , Bassereau Patricia , Lemichez Emmanuel
Published: September 2015

It remains a challenge to decode the molecular basis of the long‐term actin cytoskeleton rearrangements that are governed by the reprogramming of gene expression. Bacillus anthracis lethal toxin (LT) inhibits mitogen‐activated protein kinase (MAPK) signaling, thereby modulating gene expression, with major consequences for actin cytoskeleton organization and the loss of endothelial barrier function. Using a laser ablation approach, we characterized the contractile and tensile mechanical properties of LT‐induced stress fibers. These actin cables resist pulling forces that are transmitted at cell–matrix interfaces and at cell–cell discontinuous adherens junctions. We report that treating the cells with trichostatin A (TSA), a broad range inhibitor of histone deacetylases (HDACs), or with MS‐275, which targets HDAC1, 2 and 3, induces stress fibers. LT decreased the cellular levels of HDAC1, 2 and 3 and reduced the global HDAC activity in the nucleus. Both the LT and TSA treatments induced Rnd3 expression, which is required for the LT‐mediated induction of actin stress fibers. Furthermore, we reveal that treating the LT‐intoxicated cells with garcinol, an inhibitor of histone acetyl‐transferases (HATs), disrupts the stress fibers and limits the monolayer barrier dysfunctions. These data demonstrate the importance of modulating the flux of protein acetylation in order to control actin cytoskeleton organization and the endothelial cell monolayer barrier. © 2015 Wiley Periodicals, Inc.
Specialized survivor clinic attendance is associated with decreased rates of emergency department visits in adult survivors of childhood cancer
Authors: Sutradhar Rinku , Agha Mohammad , Pole Jason D. , Greenberg Mark , Guttmann Astrid , Hodgson David , Nathan Paul C.
Published: September 2015

BACKGROUND

Survivors of childhood cancer are at considerable risk of experiencing treatment‐related adverse health outcomes. To provide survivors with specialized care focused on these risks during adulthood, the government of Ontario funded a provincial network of specialized survivor clinics in 1999. The aim of this study was to determine whether prior attendance at survivor clinics by adult survivors of childhood cancer was associated with rates of emergency department (ED) visits.

METHODS

This was a population‐based, retrospective cohort study using multiple linked administrative health databases. The cohort consisted of all adult survivors of childhood cancer diagnosed between January 1, 1986 and December 31, 2005 in Ontario, Canada. A recurrent event regression model was used to evaluate the association between prior attendance at survivor clinics and the rate of ED visits; adjustments were made for individual, demographic, treatment, and provider characteristics.

RESULTS

The study consisted of 3912 adult survivors of childhood cancer. Individuals who had at least 1 prior visit to a survivor clinic had a 19% decreased rate of ED visits in comparison with individuals who had not visited a survivor clinic (adjusted relative rate, 0.81; 95% confidence interval, 0.78‐0.85). Each additional prior visit to a survivor clinic was associated with a 5% decrease in the rate of ED visits (adjusted relative rate, 0.95; 95% confidence interval, 0.93‐0.96). These results were independent of whether or not survivors received care from a primary care physician.

CONCLUSIONS

Attendance at a specialized survivor clinic was significantly associated with decreased ED visits among adult survivors of childhood cancer. Cancer 2015;121:4389–97. © 2015 American Cancer Society.
Having Tea with Your Demons and Creating in the Tension: A Tribute to Christina Sickles Merchant
Authors: Costantino Cathy A.
Published: September 2015

This article describes the process Christina Sickles‐Merchant and Cathy Costantino used to write Designing Conflict Management Systems. The article explores the interplay of organization development (OD), alternative dispute resolution (ADR), and dispute systems design (DSD), which the authors used to create an approach to interest‐based conflict management systems design (CMSD) that develops systems in concert with the stakeholders.
Waste Tire Derived Carbon–Polymer Composite Paper as Pseudocapacitive Electrode with Long Cycle Life
Authors: Boota M. , Paranthaman M. Parans , Naskar Amit K. , Li Yunchao , Akato Kokouvi , Gogotsi Y.
Published: September 2015

Recycling hazardous wastes to produce value‐added products is becoming essential for the sustainable progress of our society. Herein, highly porous carbon (1625 m2 g−1) is synthesized using waste tires as the precursor and used as a supercapacitor electrode material. The narrow pore‐size distribution and high surface area led to good charge storage capacity, especially when used as a three‐dimensional nanoscaffold to polymerize polyaniline (PANI). The composite paper was highly flexible, conductive, and exhibited a capacitance of 480 F g−1 at 1 mV s−1 with excellent capacitance retention of up to 98 % after 10 000 charge/discharge cycles. The high capacitance and long cycle life were ascribed to the short diffusional paths, uniform PANI coating, and tight confinement of the PANI in the inner pores of the tire‐derived carbon through π–π interactions, which minimized the degradation of the PANI upon cycling. We anticipate that the same strategy can be applied to deposit other pseudocapacitive materials to achieve even higher electrochemical performance and longer cycle life—a key challenge for redox active polymers.
Xenopus Limb bud morphogenesis
Authors: Keenan Samuel R. , Beck Caroline W.
Published: September 2015

Xenopus laevis, the South African clawed frog, is a well‐established model organism for the study of developmental biology and regeneration due to its many advantages for both classical and molecular studies of patterning and morphogenesis. While contemporary studies of limb development tend to focus on models developed from the study of chicken and mouse embryos, there are also many classical studies of limb development in frogs. These include both fate and specification maps, that, due to their age, are perhaps not as widely known or cited as they should be. This has led to some inevitable misinterpretations‐ for example, it is often said that Xenopus limb buds have no apical ectodermal ridge, a morphological signalling centre located at the distal dorsal/ventral epithelial boundary and known to regulate limb bud outgrowth. These studies are valuable both from an evolutionary perspective, because amphibians diverged early from the amniote lineage, and from a developmental perspective, as amphibian limbs are capable of regeneration. Here, we describe Xenopus limb morphogenesis with reference to both classical and molecular studies, to create a clearer picture of what we know, and what is still mysterious, about this process. Developmental Dynamics 245:233–243, 2016. © 2015 Wiley Periodicals, Inc.
Release from belowground enemies and shifts in root traits as interrelated drivers of alien plant invasion success: a hypothesis
Authors: Dawson Wayne
Published: September 2015

Our understanding of the interrelated mechanisms driving plant invasions, such as the interplay between enemy release and resource‐acquisition traits, is biased by an aboveground perspective. To address this bias, I hypothesize that plant release from belowground enemies (especially fungal pathogens) will give invasive plant species a fitness advantage in the alien range, via shifts in root traits (e.g., increased specific root length and branching intensity) that increase resource uptake and competitive ability compared to native species in the alien range, and compared to plants of the invader in its native range. Such root‐trait changes could be ecological or evolutionary in nature. I explain how shifts in root traits could occur as a consequence of enemy release and contribute to invasion success of alien plants, and how they could be interrelated with other potential belowground drivers of invasion success (allelopathy, mutualist enhancement). Finally, I outline the approaches that could be taken to test whether belowground enemy release results in increased competitive ability and nutrient uptake by invasive alien plants, via changes in root traits in the alien range.
Quantitative Analysis of Active Pharmaceutical Ingredients (APIs) Using a Potentiometric Electronic Tongue in a SIA Flow System
Authors: Wesoły M. , Cetó X. , del Valle M. , Ciosek P. , Wróblewski W.
Published: September 2015

An advanced potentiometric electronic tongue and Sequential Injection Analysis (SIA) measurement system was applied for the quantitative analysis of mixtures containing three active pharmaceutical ingredients (APIs): acetaminophen, ascorbic acid and acetylsalicylic acid, in the presence of various amounts of caffeine as interferent. The flow‐through sensor array was composed of miniaturized classical ion‐selective electrodes based on plasticized PVC membranes containing only ion exchangers. Partial Least Squares (PLS) analysis of the steady‐state sensor array responses, measured in API mixtures prepared by the SIA system permitted a correct quantitative analysis of acetylsalicylic acid and ascorbic acid. Further optimization using multiway PLS fed by dynamic responses without additional feature extraction did not improve significantly the resolution of acetaminophen. Lastly, the chemometric treatment, involving the extraction of dynamic components of the transient response employing the Wavelet transform, the removal of less‐significant coefficients by means of Causal Index pruning and training of an Artificial Neural Network (ANN) with the selected coefficients, allowed the simultaneous determination of all the three studied APIs, while counterbalancing any interference due to caffeine.
Voltammetric Lead Determination in Aviation Fuel Samples Using a Screen‐Printed Gold Electrode and Batch‐Injection Analysis
Authors: Almeida Eduardo S. , Richter Eduardo M. , Munoz Rodrigo A. A.
Published: September 2015

This work presents the lead determination in aviation (bio)fuels using disposable screen‐printed gold electrodes (SPGEs) adapted on a batch‐injection cell associated with a micropipette for portable analysis. The method involves injections of 200 µL of sample or standard solutions at controlled dispensing rate (4.8 µL s−1) during deposition step (−550 mV for 90 s), followed by anodic‐stripping voltammetry. Either samples treated by sonication or dry‐ashing can be analyzed with detection limits of 0.0071 and 0.0008 µg g−1 Pb, respectively. A single SPGE can be applied for 60 consecutive measurements (or 120 for samples dry‐ashed). The ultrasound‐assisted treatment is faster, safer, and easily adapted for on‐site analyses, especially considering the portable characteristics of commercially‐available potentiostats and batch‐injection analysis cell using SPGEs.
High‐Performance Hydrazine Sensor Based on Graphene Nano Platelets Supported Metal Nanoparticles
Authors: Liu Yi , Qiu Zhipeng , Wan Qijin , Wang Zhaohao , Wu Kangbing , Yang Nianjun
Published: September 2015

Surface coating of graphene nano platelets with gold‐palladium nanoparticles (AuPd NPs) was conducted via potentiostatic electrodeposition from a mixture of HAuCl4 and H2PdCl4. AuPd NPs were characterized using SEM, TEM, XRD and energy dispersive X‐ray spectroscopy. The AuPd NPs with the diameter of about 30–60 nm were alloyed and well‐dispersed on the graphene surface. Electrochemistry of hydrazine on AuPd NPs was investigated using cyclic voltammetry and chronoamperometry, indicating high electrocatalytic ability of AuPd NPs towards oxidation of hydrazine. Under the optimized conditions, the oxidation current was linear to the hydrazine concentration in the range of 0.02–166.6 µM. The calculated detection limit was 5 nM (S/N=3).
Effects of different henna plant parts on enhanced removal of an azo dye Orange II: Biotic and abiotic contributions
Authors: Tang Junhong , Wu Mengke , Huang Jingang , Chen Jianjun , Han Wei , Xie Zhengmiao
Published: September 2015

The effects of different parts of henna (Lawsonia) plant biomass on the removal of an azo dye Orange II (AO7) were investigated. The batched system of sludge control (R1), and those with the addition of henna flower (R2), stem (R3), and seed (R4) were set up. The results indicated that henna powder all benefit the AO7 removal. At the end of batch test (76 h), the AO7 removal in R1, R2, R3, and R4 were 18.3%, 82.7%, 83.7%, and 65.6%, respectively; and the molar ratios of the reductive byproduct of sulfanic acid to the removed AO7 were 22.1%, 81.7%, 30.4% and 53.9%, respectively. AO7 removal in R2 was mainly attributed to the bio‐reducing pathway, while that in R3 was due to the abiotic adsorption pathway. These two pathways were in comparable role on AO7 removal in R4. In anaerobic conditions, henna plant biomass, especially the flower, played a multiple role in simultaneously providing electron donor and redox mediator (lawsone), thus enhancing the AO7 bio‐reduction. © 2015 American Institute of Chemical Engineers Environ Prog, 35: 404–410, 2016
Synthesis and olfactory evaluation of homologous series of (+)‐ and (−)‐carvone oxime ethers
Authors: Strub Daniel Jan , Kula Józef , Sikora Magdalena , Gibka Julia , Lochyński Stanisław
Published: September 2015

Novel semi‐synthetic fragrant compounds were prepared from both isomers of carvone. Deprotonation of (+) and (−)‐carvone oximes with sodium hydride and subsequent O‐Alkylation with various alkyl halides in DMSO resulted in 18 ethers. Scents of most synthesized compounds are agreeable. A shift of fragrance is observed between substrates. The scent of (−)‐carvone resembles that of spearmint and (+)‐carvone – caraway. The fragrance of carvone oximes is similar, vegetable‐like. Significant differences were observed between homologous series of carvone oxime ethers. Their odours range from vegetable‐like (pickled cucumber, leaves of horseradish and carrot, scallion and onion) and herbaceous to sulphuric, floral (lily) and fruity (blackcurrant and pear). Copyright © 2015 John Wiley & Sons, Ltd.
Coding complexity in the human motor circuit
Authors: Heinrichs‐Graham Elizabeth , Wilson Tony W.
Published: September 2015

Cortical oscillatory dynamics are known to be critical for human movement, although their functional significance remains unclear. In particular, there is a strong beta (15–30 Hz) desynchronization that begins before movement onset and continues during movement, before rebounding after movement termination. Several studies have connected this response to motor planning and/or movement selection operations, but to date such studies have examined only the early aspects of the response (i.e., before movement) and a limited number of parameters. In this study, we used magnetoencephalography (MEG) and a novel motor sequence paradigm to probe how motor plan complexity modulates peri‐movement beta oscillations, and connectivity within activated circuits. We also examined the dynamics by imaging beta activity before and during movement execution and extracting virtual sensors from key regions. We found stronger beta desynchronization during complex relative to simple sequences in the right parietal and left dorsolateral prefrontal cortex (DLPFC) during movement execution. There was also an increase in functional connectivity between the left DLPFC and right parietal shortly after movement onset during complex but not simple sequences, which produced a significant conditional effect (i.e., complex > simple) that was not attributable to differences in response amplitude. This study is the first to demonstrate that complexity modulates the dynamics of the peri‐movement beta ERD, which provides crucial new data on the functional role of this well‐known oscillatory motor response. These data further suggest that execution of complex motor behavior may recruit key regions of the fronto‐parietal network, in addition to traditional sensorimotor regions. Hum Brain Mapp 36:5155–5167, 2015. © 2015 Wiley Periodicals, Inc.
Activation of the p62‐Keap1‐NRF2 pathway protects against ferroptosis in hepatocellular carcinoma cells
Authors: Sun Xiaofang , Ou Zhanhui , Chen Ruochan , Niu Xiaohua , Chen De , Kang Rui , Tang Daolin
Published: September 2015

Ferroptosis is a recently recognized form of regulated cell death caused by an iron‐dependent accumulation of lipid reactive oxygen species. However, the molecular mechanisms regulating ferroptosis remain obscure. Here, we report that nuclear factor erythroid 2‐related factor 2 (NRF2) plays a central role in protecting hepatocellular carcinoma (HCC) cells against ferroptosis. Upon exposure to ferroptosis‐inducing compounds (e.g., erastin, sorafenib, and buthionine sulfoximine), p62 expression prevented NRF2 degradation and enhanced subsequent NRF2 nuclear accumulation through inactivation of Kelch‐like ECH‐associated protein 1. Additionally, nuclear NRF2 interacted with transcriptional coactivator small v‐maf avian musculoaponeurotic fibrosarcoma oncogene homolog proteins such as MafG and then activated transcription of quinone oxidoreductase‐1, heme oxygenase‐1, and ferritin heavy chain‐1. Knockdown of p62, quinone oxidoreductase‐1, heme oxygenase‐1, and ferritin heavy chain‐1 by RNA interference in HCC cells promoted ferroptosis in response to erastin and sorafenib. Furthermore, genetic or pharmacologic inhibition of NRF2 expression/activity in HCC cells increased the anticancer activity of erastin and sorafenib in vitro and in tumor xenograft models. Conclusion: These findings demonstrate novel molecular mechanisms and signaling pathways of ferroptosis; the status of NRF2 is a key factor that determines the therapeutic response to ferroptosis‐targeted therapies in HCC cells. (Hepatology 2016;63:173–184)
Long‐term clinical outcomes after fatty liver screening in patients undergoing coronary angiogram: A prospective cohort study
Authors: Wong Vincent Wai‐Sun , Wong Grace Lai‐Hung , Yeung Judy Ching‐Lam , Fung Chloe Yuk‐Kiu , Chan Jasmine Ka‐Lei , Chang Zoe Hoi‐Yi , Kwan Chelsia Tsz‐Yan , Lam Hiu‐Wan , Limquiaco Jenny , Chim Angel Mei‐Ling , Yu Cheuk‐Man , Chan Henry Lik‐Yuen
Published: September 2015

There is ongoing debate on whether screening for nonalcoholic fatty liver disease (NAFLD) is worthwhile in high‐risk groups. Because of shared risk factors, NAFLD is highly prevalent in patients with coronary artery disease. We aimed to test the hypothesis that NAFLD screening in patients requiring coronary angiogram would identify high‐risk patients and predict long‐term clinical outcomes. This was a prospective cohort study. NAFLD screening was performed by abdominal ultrasonography before coronary angiogram in 612 consecutive patients. At baseline, 356 (58.2%) patients had NAFLD. NAFLD patients, compared with those without, were more likely to have >50% stenosis in one or more coronary arteries (84.6% vs. 64.1%; P < 0.001) and therefore require percutaneous coronary intervention (68.3% vs. 43.4%; P < 0.001). During 3,679 patient‐years of follow‐up, 47 (13.2%) NAFLD patients and 59 (23.0%) patients without NAFLD died (age‐ and sex‐adjusted hazard ratio [aHR]: 0.36; 95% confidence interval [CI]: 0.18‐0.70; P = 0.003). Composite cardiovascular outcomes (cardiovascular deaths, nonfatal myocardial infarction, heart failure, or secondary interventions) were similar between groups (36.5% vs. 37.1%; aHR, 0.90; 95% CI: 0.69‐1.18). Older age and diabetes were the only independent factors associated with cardiovascular events. Only 2 patients, both in the NAFLD group, died of primary liver cancer. No other patients developed liver‐related complications. Conclusion: In patients with clinical indications for coronary angiogram, the presence of NAFLD is associated with coronary artery stenosis and need for coronary intervention, but not increased mortality or cardiovascular complications. Liver cancer and cirrhotic complications are rare. Our data do not support NAFLD screening in this patient group at present, but studies with a longer duration of follow‐up are needed. (Hepatology 2016;63:754–763)
Interferon lambda 4 genotypes and resistance‐associated variants in patients infected with hepatitis C virus genotypes 1 and 3
Authors: Peiffer Kai‐Henrik , Sommer Lisa , Susser Simone , Vermehren Johannes , Herrmann Eva , Döring Matthias , Dietz Julia , Perner Dany , Berkowski Caterina , Zeuzem Stefan , Sarrazin Christoph
Published: September 2015

Single‐nucleotide polymorphisms (SNPs) in the interferon lambda 4 (IFNL4) gene are predictors for treatment success in patients with hepatitis C virus (HCV) infection. For direct‐acting antiviral combinations only weak association with IFNL4 SNPs was observed. Little is known about potential selections of resistance‐associated variants (RAVs) by the IFNL4 genotype. This study analyzed the prevalence of RAVs to currently approved direct‐acting antivirals in a large European population in correlation to SNPs in IFNL4. Samples of 633 patients chronically infected with HCV genotypes 1a (n = 259), 1b (n = 323), and 3 (n = 51) were genotyped for rs12979860 (formerly known as IL28B) and rs368234815. RAVs in NS3, NS5A, and NS5B were detected by population‐based sequencing. In addition, IFNL4 SNPs and NS5A RAVs were analyzed including deep sequencing (n = 109) in an independent replication cohort of HCV genotype 1‐infected patients (n = 201). No significant correlation was found between IFNL4 SNPs and rare and common RAVs within NS3 and NS5B. In contrast, the NS5A RAV Y93H was detected frequently in HCV genotype 1b (14%) and significantly associated with the beneficial IFNL4 SNPs (P < 0.001 and P = 0.002, respectively). Moreover, the presence of Y93H in HCV genotype 1b patients was significantly associated with the second site variant T83M (P < 0.001). Independent factors significantly associated with the presence of Y93H were IFNL4 genotype and high baseline viral load. Conclusion: The NS5A RAV Y93H is significantly associated with the presence of beneficial IFNL4 SNPs and a high baseline viral load in HCV genotype 1‐infected patients, which may explain a lack of correlation or even an inverse correlation of treatment response with IFNL4 genotype in some NS5A inhibitor containing IFN‐free regimens. (Hepatology 2016;63:63–73)
Serial alternative response training as intervention for target response resurgence
Authors: Lambert Joseph M. , Bloom Sarah E. , Samaha Andrew L. , Dayton Elizabeth , Rodewald Andrew M.
Published: September 2015

Failure to reinforce appropriate behavior could result in resurgence of previously extinguished problem behavior and degradation of previously effective treatments such as differential reinforcement of alternative behavior (DRA). We analyzed arbitrary responses (i.e., switch flipping) exhibited by 3 adults with developmental disabilities to compare the effect of a traditional DRA intervention against the effect of a serial DRA intervention on the magnitude of target response resurgence using a 2‐component multiple schedule. The target response served as an analogue to problem behavior, and alternative responses served as analogues to socially appropriate alternative responses. In all cases, the percentage of total responding allocated toward target response resurgence was less in the serial DRA component than in the traditional DRA component. Furthermore, we observed both reversion and recency for 2 of 3 subjects. Our data provide preliminary evidence suggesting that serial DRA may produce more durable and desirable outcomes than traditional DRA.
Psychosocial Functioning and Life Satisfaction in Adults With Autism Spectrum Disorder Without Intellectual Impairment
Authors: Schmidt Lilly , Kirchner Jennifer , Strunz Sandra , Broźus Julia , Ritter Kathrin , Roepke Stefan , Dziobek Isabel
Published: September 2015

Objectives

This study aimed at (a) comparing psychosocial functioning and life satisfaction in adults with autism spectrum disorder (ASD) and nonclinical participants and (b) identifying areas of functioning that are most predictive for life satisfaction in individuals with ASD.

Method

A total of 43 adults with ASD without intellectual impairment (age: mean = 31, standard deviation = 10 years; 63% females) and healthy nonclinical individuals (N = 44) were surveyed.

Results

Individuals with ASD reported significant functional impairments and less life satisfaction compared with nonclinical individuals in many areas of life. Although impairments were prominent in domains involving interaction with other people such asunderstanding and communication,getting along with others, andparticipation in society, daily living skills (e.g.,getting around,self‐care, andhousehold) were not different from nonclinical participants. Participating in society was identified as the only factor predicting life satisfaction in individuals with ASD.

Conclusion

There is a need for interventions facilitating functioning on a broad level and support toward societal inclusion for individuals with ASD.
Co‐creating patient‐oriented discharge instructions with patients, caregivers, and healthcare providers
Authors: Hahn‐Goldberg Shoshana , Okrainec Karen , Huynh Tai , Zahr Najla , Abrams Howard
Published: September 2015

For hospitalized patients, the transition from hospital to home is frequently accompanied by a significant amount of information to absorb. The objective of this work was to engage patients, caregivers, and healthcare providers in codeveloping patient‐oriented discharge instructions, (ie, a brief transition plan with information that patients want). Overseen by a multidisciplinary advisory team, a participatory action approach using mixed methods was employed. Although formal inclusion and exclusion criteria were not used, deliberate efforts were made to engage groups with language barriers and limited health literacy. Symbols were designed and validated with the patient groups to represent each section of information to make the form more understandable for these patients. A prototype was codesigned using an iterative process. The form has been adapted for use in multiple health settings and is currently undergoing a multisite pilot to evaluate its effect on patient and provider experience. Journal of Hospital Medicine 2015;10:804–807. © 2015 Society of Hospital Medicine
Effect of HCAHPS reporting on patient satisfaction with physician communication
Authors: Mann Rupinder K. , Siddiqui Zishan , Kurbanova Nargiza , Qayyum Rehan
Published: September 2015

INTRODUCTION

Prior studies, using limited data from the Hospital Consumer Assessment of Healthcare Providers and Systems (HCAHPS) surveys, reported that public reporting increases satisfaction scores in all domains except physician communication. Our objective was to examine changes in patient satisfaction with physician communication using all available data.

METHODS

We used publicly accessible datasets: HCAHPS (2007–2013), socioeconomic datasets from the US Census Bureau, and hospital service area (HSA) dataset from the Dartmouth Atlas of Health Care. Satisfaction scores were determined by the percentage of responses to “doctors always communicated well.” Hospitals were grouped into quartiles based on 2007 scores. We used multilevel models to account for correlation between within‐hospital observations.

RESULTS

HCAHPS data were reported by 2273 hospitals in 2007. During the 7‐year period, overall satisfaction scores with physician communication increased by 2.8% (P < 0.001). The lowest quartile hospitals had significant increase in satisfaction scores, whereas the highest quartile scores decreased (0.87% per year vs −0.23% per year; P < 0.001). These differences remained significant after adjusting for hospital and local population characteristics. Survey response rate and the number of acute‐care beds and physicians in the HSA were positively associated, whereas HSA population size and being a teaching hospital were negatively associated with patient satisfaction scores (all P < 0.005).

CONCLUSIONS

Although there has been an improvement in patient satisfaction with physicians during the past 7 years, this improvement was not seen in all hospitals. The overall gap between hospitals has narrowed, which can be further improved through sharing best practices. Journal of Hospital Medicine 2016;11:105–110. © 2015 Society of Hospital Medicine
Expression of XBP1s in fibroblasts is critical for TiAl6V4 particle‐induced RANKL expression and osteolysis
Authors: Wang Zhenheng , Liu Naicheng , Zhou Gang , Shi Tongguo , Wang Zhenzhen , Gan Jingjing , Wang Rui , Qian Hongbo , Bao Nirong , Guo Ting , Zhao Jianning
Published: September 2015

Wear particle‐induced osteolysis is a major cause of aseptic loosening, which is one of the most common reasons for total hip arthroplasty (THA) failure. Previous studies have shown that the expression of Receptor activation of nuclear factor (NF)‐kB (RANKL) by fibroblasts in periprosthetic membrane played a crucial role in wear particle‐induced osteolysis. However, the underlying mechanism of RANKL expression remains largely unknown. In the present study, we investigated the effect of TiAl6V4 particle (TiPs)‐induced XBP1s (spliced form of X‐box binding protein 1) on RANKL expression and osteoclastogenesis both in vitro and in vivo. The levels of XBP1s in peri‐implant membrane, animal models, and TiPs‐stimulated fibroblasts were determined by western blots. To assess the effect of XBP1s on RANKL expression, fibroblasts were treated with both a small interfering RNA (siRNA) and an inhibitor of XBP1 prior to exposure to TiPs. The effect of XBP1s on osteoclasts formation was determined by tartrate‐resistant acid phosphatase (TRAP) staining in vitro osteoclastogenesis assay and in animal models. The resorption of bone was assessed by micro‐computed tomography (micro‐CT) with three‐dimensional reconstruction. Our results demonstrated that XBP1s was activated in periprosthetic membrane, mouse calvaria models, and TiPs‐stimulated human synovial fibroblasts. Further, inhibition of XBP1s decreased the expression of RANKL and osteoclasts formation in vitro. In mouse calvaria models, both of the osteoclastogenesis and osteolysis were inhibited XBP1s inhibitor. Our results suggested that XBP1s mediated TiPs‐induced of RANKL expression in fibroblasts, and down regulating XBP1s may represent a potential therapy for wear particle‐induced osteolysis. © 2016 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 35:752–759, 2017.
Optical characterization of OLED displays
Authors: Boher Pierre , Leroux Thierry , Collomb‐Patton Véronique , Bignon Thibault
Published: September 2015

Multispectral viewing angle and imaging characterization have been applied to different organic light‐emitting diode (OLED) displays. Angular dependence of the OLED emission is always complex because of its multilayer structure. Spectral information is also related to the geometry of Fabry–Perot‐like structure of each OLED. High‐resolution viewing angle measurements of different OLED displays are reported and compared. Multispectral viewing angle polarization properties are also reported. Imaging measurements allow to detect wavelength shift on the surface of the displays probably related to thickness non‐uniformities. Local radiance fluctuations from one pixel to the other more related to driving problems due to the dispersion of the electric properties of the driving thin‐film transistors are also detected.