bluuebunny/crossref_metadata_2025_split huggingface dataset:
Incarceration of Higher‐Order Fullerenes within Cyclotriveratrylene‐Based Hemicarcerands Allows Selective Isolation of C76, C78, and C84 from a Commercial Fullerene Mixture
Authors: Liu Kuang‐Shun , Li Ming‐Jhe , Lai Chien‐Chen , Chiu Sheng‐Hsien 
Published: October 2016

AbstractSize‐complementary cyclotriveratrylene (CTV)‐based hosts can incarcerate C76, C78, and C84, thus allowing the selective isolation of these higher‐order fullerenes from a commercially available mixture of fullerenes. The hemicarceplexes, formed after the encapsulation of the size‐complementary fullerenes within the hosts, are isolated by column chromatography and released at elevated temperature, thereby leading to the isolation of C76/C78 and C84 in good purities (up to 95 and 88 %, respectively).
Azulene‐Based Macrocyclic Receptors for Recognition and Sensing of Phosphate Anions
Authors: Lichosyt Dawid , Dydio Paweł , Jurczak Janusz 
Published: October 2016

AbstractHerein we report the synthesis and detailed studies of the anion‐binding properties of two 20‐membered macrocyclic tetramide receptors: one symmetrical, containing two identical azulene‐based bisamide units, the other a hybrid, containing a dipicolinic bisamide unit and an azulene‐based bisamide unit. Analysis of the crystal structures of the macrocyclic receptors revealed their preference for adopting similar well‐preorganized bent‐sheet conformations, both as free receptors and in their complexes with anions. Studies of the optical properties of both receptors revealed abilities to selectively sense phosphate anions (H2PO4−, HP2O73−), allowing for naked‐eye detection of the presence of these guests in DMSO. Binding studies in solution confirmed that the receptors bind strongly to a series of anions even in highly demanding media, such as mixtures of DMSO with water or with methanol. Comparison of the anion affinity of linear analogues with that of the macrocyclic receptors evidenced the importance of macrocyclic topology. Quantitative analysis revealed that the macrocyclic receptors are selective for H2PO4− over other anions. The affinity to H2PO4− seen for the symmetrical receptor, containing two azulene‐based subunits, is much higher than for the hybrid macrocycle containing both the azulene‐based and pyridine‐derived subunits. This highlights that the azulene‐based building block serves efficiently as both a binding site and a structure‐preorganizing motif.
Enhanced π‐Back‐Donation as a Way to Higher Coordination Numbers in d10 [M(NHC)n] Complexes: A DFT Study
Authors: Nitsch Jörn , Wolters Lando P. , Fonseca Guerra Célia , Bickelhaupt F. Matthias , Steffen Andreas 
Published: October 2016

AbstractWe aim to understand the electronic factors determining the stability and coordination number of d10 transition‐metal complexes bearing N‐heterocyclic carbene (NHC) ligands, with a particular emphasis on higher coordinated species. In this DFT study on the formation and bonding of Group 9–12 d10 [M(NHC)n] (n=1–4) complexes, we found that all metals form very stable [M(NHC)2] complexes, but further coordination depends on the specific interplay of 1) the interaction energy (ΔEint) between the [M(NHC)n−1] (n=2–4) fragment and the incoming NHC ligand, and 2) the strain energy (ΔEstrain) associated with bending of the linear NHC‐M‐NHC arrangement. The key observation is that ΔEstrain, which is an antagonist for higher coordination numbers, can significantly be lowered by M→NHC π*‐back‐donation. This leads to favorable thermodynamics for n=3–4 for highly electrophilic metals in our study, and thus presents a general design motif to achieve coordination numbers beyond two. The scope of our findings extends beyond the NHC model systems and has wider implications for the synthesis of d10 [MLn] complexes and their catalytic activity.
N‐Methylanilines as Simple and Efficient Promoters for Radical‐Type Cross‐Coupling Reactions of Aryl Iodides
Authors: Yang Huan , Zhang Li , Jiao Lei 
Published: October 2016

AbstractActivation of the carbon–halogen bonds in aryl halides is a key step in transition‐metal‐free cross‐coupling reactions. In this paper, a new and efficient radical initiation system for the activation of iodoarenes to produce aryl radicals was discovered, which employs the combination of N‐methylanilines and tBuOK. This radical initiation system is robust and versatile, enabling various types of aryl‐radical‐related reactions.
Postsynthetic Incorporation of a Singlet Oxygen Photosensitizer in a Metal–Organic Framework for Fast and Selective Oxidative Detoxification of Sulfur Mustard
Authors: Howarth Ashlee J. , Buru Cassandra T. , Liu Yangyang , Ploskonka Ann M. , Hartlieb Karel J. , McEntee Monica , Mahle John J. , Buchanan James H. , Durke Erin M. , Al‐Juaid Salih S. , Stoddart J. Fraser , DeCoste Jared B. , Hupp Joseph T. , Farha Omar K. 
Published: October 2016

AbstractA fullerene‐based photosensitizer is incorporated postsynthetically into a Zr6‐based MOF, NU‐1000, for enhanced singlet oxygen production. The structural organic linkers in the MOF platform also act as photosensitizers which contribute to the overall generation of singlet oxygen from the material under UV irradiation. The singlet oxygen generated by the MOF/fullerene material is shown to oxidize sulfur mustard selectively to the less toxic bis(2‐chloroethyl)sulfoxide with a half‐life of only 11 min.
Catalytic Activity of Thiolate‐Bridged Diruthenium Complexes Bearing Pendent Ether Moieties in the Oxidation of Molecular Dihydrogen
Authors: Yuki Masahiro , Sakata Ken , Kikuchi Shoma , Kawai Hiroyuki , Takahashi Tsuyoshi , Ando Masaki , Nakajima Kazunari , Nishibayashi Yoshiaki 
Published: October 2016

AbstractThiolate‐bridged diruthenium complexes bearing pendent ethers have been found to work as effective catalysts toward the oxidation of molecular dihydrogen into protons and electrons in water. The pendent ether moiety in the complex plays an important role to facilitate the proton transfer between the metal center and the external proton acceptor.
Can we eliminate neoadjuvant chemoradiotherapy in favor of neoadjuvant multiagent chemotherapy for select stage II/III rectal adenocarcinomas: Analysis of the National Cancer Data base
Authors: Cassidy Richard J. , Liu Yuan , Patel Kirtesh , Zhong Jim , Steuer Conor E. , Kooby David A. , Russell Maria C. , Gillespie Theresa W. , Landry Jerome C. 
Published: October 2016

BACKGROUNDStage II and III rectal cancers have been effectively treated with neoadjuvant chemoradiotherapy (NCRT) followed by definitive resection. Advancements in surgical technique and systemic therapy have prompted investigation of neoadjuvant multiagent chemotherapy (NMAC) regimens with the elimination of radiation (RT). The objective of the current study was to investigate factors that predict for the use of NCRT versus NMAC and compare outcomes using the National Cancer Data Base (NCDB) for select stage II and III rectal cancers.METHODSIn the NCDB, 21,707 patients from 2004 through 2012 with clinical T2N1 (cT2N1), cT3N0, or cT3N1 rectal cancers were identified who had received NCRT or NMAC followed by low anterior resection. Kaplan‐Meier analyses, log‐rank tests, and Cox‐proportional hazards regression analyses were conducted along with propensity score matching analysis to reduce treatment selection bias.RESULTSThe 5‐year actuarial overall survival (OS) rate was 75% for patients who received NCRT versus 67.2% for those who received NMAC (P < .01). On MVA, those who received NCRT had improved OS (hazard ratio, 0.77. P < .01), and this effect was confirmed on propensity score matching analysis (hazard ratio, 0.72; P = .01). In the same model, the following variables improved OS: age < 65 years, having private insurance, treatment at an academic center, living in an affluent zip code, a low comorbidity score, receipt of adjuvant chemotherapy, and a shorter interval before surgery (all P < .05). African Americans, men, patients with high‐grade tumors, those with cT3N1 tumors, and those who underwent incomplete (R1) resection had worse OS (all P < .05).CONCLUSIONSIn this series, the elimination of neoadjuvant RT for select patients with stage II and III rectal adenocarcinoma was associated with worse OS and should not be recommended outside of a clinical trial. Cancer 2017;123:783–93. © 2016 American Cancer Society.
Computational resource management for data‐driven applications with deadline constraints
Authors: Tolosana‐Calasanz Rafael , Diaz‐Montes Javier , Rana Omer F. , Parashar Manish , Xydas Erotokritos , Marmaras Charalampos , Papadopoulos Panagiotis , Cipcigan Liana 
Published: October 2016

SummaryRecent advances in the type and variety of sensing technologies have led to an extraordinary growth in the volume of data being produced and led to a number of streaming applications that make use of this data. Sensors typically monitor environmental or physical phenomenon at predefined time intervals or triggered by user‐defined events. Understanding how such streaming content (the raw data or events) can be processed within a time threshold remains an important research challenge. We investigate how a cloud‐based computational infrastructure can autonomically respond to such streaming content, offering quality of service guarantees. In particular, we contextualize our approach using an electric vehicles (EVs) charging scenario, where such vehicles need to connect to the electrical grid to charge their batteries. There has been an emerging interest in EV aggregators (primarily intermediate brokers able to estimate aggregate charging demand for a collection of EVs) to coordinate the charging process. We consider predicting EV charging demand as a potential workload with execution time constraints. We assume that an EV aggregator manages a number of geographic areas and a pool of computational resources of a cloud computing cluster to support scheduling of EV charging. The objective is to ensure that there is enough computational capacity to satisfy the requirements for managing EV battery charging requests within specific time constraints.
IVM‐based parallel branch‐and‐bound using hierarchical work stealing on multi‐GPU systems
Authors: Gmys J. , Mezmaz M. , Melab N. , Tuyttens D. 
Published: October 2016

SummaryTree‐based exploratory methods, like Branch‐and‐Bound (B&B) algorithms, are highly irregular applications which makes their design and implementation on graphics processing unit (GPU) challenging. In this paper, we present a multi‐GPU B&B algorithm for solving large permutation‐based combinatorial optimization problems. To tackle the problem of the irregular workload, we propose a hierarchical work stealing (WS) strategy that balances the workload inside the GPU and between different GPUs and CPU cores. Our B&B is based on an Integer‐Vector‐Matrix data structure instead of a pool of permutations, and work units exchanged are intervals of factoradics instead of sets of nodes. Two variants of the algorithm, using the same hierarchical WS strategy, are proposed: one for combinatorial optimization problems where the evaluation of nodes is costly and one for fine‐grained problems. The latter variant uses a new hypercube‐based WS strategy and a trigger mechanism to balance the work load inside the GPU. The proposed approach has been extensively experimented using the flowshop scheduling, the n‐queens and the asymmetric travelling salesman problems as test‐cases. The reported results show that the proposed hierarchical WS mechanism is capable of handling fine and coarse‐grained types of workloads efficiently, reaching near‐linear speed‐up on up to four GPUs for a set of ten flowshop instances and large instances of fine‐grained problems. Copyright © 2016 John Wiley & Sons, Ltd.
Extending the Domain‐Averaged Exchange‐Correlation Energies Within the Context of the MC‐QTAIM: Tracing Subtle Variations Induced by Isotope Substitution
Authors: Goli Mohammad , Shahbazian Shant 
Published: October 2016

AbstractRecently, it has been demonstrated that the domain‐averaged exchange‐correlation energies,Vxc, are capable of tracing the covalent character of atom–atom interactions unequivocally and thus pave the way for detailed bonding analysis within the context of the quantum theory of atoms in molecules (QTAIM) [M. García‐Revilla, E. Francisco, P. L. Popelier, A. Martín Pendás,ChemPhysChem2013,14, 1211–1218]. Herein, the concept ofVxcis extended within the context of the newly developed multicomponent QTAIM (MC‐QTAIM). The extended version,, is capable of analyzing nonadiabatic wavefunctions and thus is sensitive to the mass of nuclei and can trace “locally” the subtle electronic variations induced by isotope substitution. To demonstrate this capability in practice, ab initio nonadiabatic wavefunctions for three isotopically substituted hydrogen cyanide molecules, in which the hydrogen nucleus was assumed to be a proton, deuterium, or tritium, were derived. The resulting wavefunctions were then used to computeand it emerged that for the hydrogen–carbon bond, thewas distinct for each isotopic composition and varied in line with chemical expectations. Indeed, the introduction ofpaves the way for the investigation of vast numbers of structural and kinetic isotope effects within the context of the MC‐QTAIM.
Mass, phylogeny, and temperature are sufficient to explain differences in metabolic scaling across mammalian orders?
Authors: Griebeler Eva Maria , Werner Jan 
Published: October 2016

AbstractWhether basal metabolic rate‐body mass scaling relationships have a single exponent is highly discussed, and also the correct statistical model to establish relationships. Here, we aimed (1) to identify statistically best scaling models for 17 mammalian orders, Marsupialia, Eutheria and all mammals, and (2) thereby to prove whether correcting for differences in species’ body temperature and their shared evolutionary history improves models and their biological interpretability. We used the large dataset from Sieg et al. (The American Naturalist 174, 2009, 720) providing species’ body mass (BM), basal metabolic rate (BMR) and body temperature (T). We applied different statistical approaches to identify the best scaling model for each taxon: ordinary least squares regression analysis (OLS) and phylogenetically informed analysis (PGLS), both without and with controlling for T. Under each approach, we tested linear equations (log‐log‐transformed data) estimating scaling exponents and normalization constants, and such with a variable normalization constant and a fixed exponent of either ⅔ or ¾, and also a curvature. Only under temperature correction, an additional variable coefficient modeled the influence of T on BMR. Except for Pholidata and Carnivora, in all taxa studied linear models were clearly supported over a curvature by AICc. They indicated no single exponent at the level of orders or at higher taxonomic levels. The majority of all best models corrected for phylogeny, whereas only half of them included T. When correcting for T, the mathematically expected correlation between the exponent (b) and the normalization constant (a) in the standard scaling model y = a x b was removed, but the normalization constant and temperature coefficient still correlated strongly. In six taxa, T and BM correlated positively or negatively. All this hampers a disentangling of the effect of BM, T and other factors on BMR, and an interpretation of linear BMR‐BM scaling relationships in the mammalian taxa studied.
A genetically distinct hybrid zone occurs for two globally invasive mosquito fish species with striking phenotypic resemblance
Authors: Wilk Rebecca J. , Horth Lisa 
Published: October 2016

AbstractHybrid zones allow for the investigation of incipient speciation and related evolutionary processes of selection, gene flow, and migration. Interspecific dynamics, like competition, can impact the size, shape, and directional movement of species in hybrid zones. Hybrid zones contribute to a paradox for the biological species concept because interbreeding between species occurs while parental forms remain distinct. A long‐standing zone of intergradation or introgression exists for eastern and western mosquito fish (Gambusia holbrooki and G. affinis) around Mobile Bay, AL. The region has been studied episodically, over decades, making it perfect for addressing temporal dynamics and for providing a deeper understanding of the genetics of these periodically reclassified fishes (as species or subspecies). We used six microsatellite markers to assess the current population structure and gene flow patterns across 19 populations of mosquito fish and then compared our results with historical data. Genetic evidence demonstrates that the current hybrid zone is located in a similar geographic region as the historical one, even after three decades. Hybrid fish, however, demonstrate relatively low heterozygosity and are genetically distinct from western and eastern mosquito fish populations. Fin ray counts, sometimes used to distinguish the two species from one another, demonstrate more eastern (G. holbrooki) phenotype fish within the molecular genetic hybrid zone today. Mosquito fish are globally invasive, often found on the leading edge of flooded waters that they colonize, so the impact of hurricanes in the wake of climate change was also evaluated. An increase in the frequency and intensity of hurricanes in the hybrid region has occurred, and this point warrants further attention since hurricanes are known to move these aggressive, invasive species into novel territory. This work contributes to our classical understanding of hybrid zone temporal dynamics, refines our understanding of mosquito fish genetics in their native range, evaluates important genotype–phenotype relationships, and identifies a potential new impact of climate change.
Different Electrocatalytic Response Related to the Morphological Structure of TiO2 Nanomaterial: Hydroquinone as an Analytical Probe
Authors: Mazloum‐Ardakani Mohammad , Yavari Mozhgan , Khoshroo Alireza 
Published: October 2016

AbstractTwo shapes of TiO2 nanomaterial will largely affect the catalytic activity. TiO2 nanoparticles (NPs) and TiO2 nanofibers (NFs) were used to investigate the effect of shape on catalytic activities and get the optimum shape of catalysis. Electrochemical behaviors of two modified electrodes by TiO2 nanomaterial were evaluated by cyclic voltammetry and electrochemical impedance spectroscopy. Various electrochemical parameters such as electrode surface area and electron‐transfer rate constant were also studied and calculated in the aqueous solution. Results showed that the response of NF is better than NP for electrooxidation of hydroquinone (HQ). The different electrochemical response of TiO2 is related to the various morphological structures, so controlling the shape and structure of nanomaterial is very important factor which is because of the powerful correlation between these parameters and their optical, catalytic and electrical properties.
General Preparation of Heme Protein Functional Fe3O4@Au‐Nps Magnetic Nanocomposite for Sensitive Detection of Hydrogen Peroxide
Authors: Xu Xuan , Song Lishu , Zheng Qiqin , Cao Xiaodong , Yao Cheng 
Published: October 2016

AbstractStable magnetic nanocomposite of gold nanoparticles (Au‐NPs) decorating Fe3O4 core was successfully synthesized by the linker of Boc‐L‐cysteine. Transmission electron microscope (TEM), energy dispersive X‐ray spectroscopy (EDX) and cyclic voltammograms (CV) were performed to characterize the as‐prepared Fe3O4@Au‐Nps. The results indicated that Au‐Nps dispersed homogeneously around Fe3O4 with the ratio of Au to Fe3O4 nanoparticles as 5–10/1 and the apparent electrochemical area as 0.121 cm2. After self‐assembly of hemoglobin (Hb) on Fe3O4@Au‐Nps by electrostatic interaction, a hydrogen peroxide biosensor was developed. The Fe3O4@Au‐Nps/Hb modified GCE exhibited fast direct electron transfer between heme center and electrode surface with the heterogeneous electron transfer rate constant (Ks) of 3.35 s−1. Importantly, it showed excellent electrocatalytic activity towards hydrogen peroxide reduction with low detection limit of 0.133 μM (S/D=3) and high sensitivity of 0.163 μA μM−1, respectively. At the concentration evaluated, the interfering species of glucose, dopamine, uric acid and ascorbic acid did not affect the determination of hydrogen peroxide. These results demonstrated that the introduction of Au‐Nps on Fe3O4 not only stabilized the immobilized enzyme but also provided large surface area, fast electron transfer and excellent biocompatibility. This facile nanoassembly protocol can be extended to immobilize various enzymes, proteins and biomolecules to develop robust biosensors.
Alternative approaches to vertebrate ecotoxicity tests in the 21st century: A review of developments over the last 2 decades and current status
Authors: Lillicrap Adam , Belanger Scott , Burden Natalie , Pasquier David Du , Embry Michelle R. , Halder Marlies , Lampi Mark A. , Lee Lucy , Norberg-King Teresa , Rattner Barnett A. , Schirmer Kristin , Thomas Paul 
Published: October 2016

Abstract

The need for alternative approaches to the use of vertebrate animals for hazard assessment of chemicals and pollutants has become of increasing importance. It is now the first consideration when initiating a vertebrate ecotoxicity test, to ensure that unnecessary use of vertebrate organisms is minimized wherever possible. For some regulatory purposes, the use of vertebrate organisms for environmental risk assessments has been banned; in other situations, the number of organisms tested has been dramatically reduced or the severity of the procedure refined. However, there is still a long way to go to achieve a complete replacement of vertebrate organisms to generate environmental hazard data. The development of animal alternatives is based not just on ethical considerations but also on reducing the cost of performing vertebrate ecotoxicity tests and in some cases on providing better information aimed at improving environmental risk assessments. The present Focus article provides an overview of the considerable advances that have been made toward alternative approaches for ecotoxicity assessments over the last few decades. Environ Toxicol Chem 2016;35:2637–2646. © 2016 SETAC
An in silico approach to cytotoxicity of pharmaceuticals and personal care products on the rainbow trout liver cell line RTL-W1
Authors: Önlü Serlİ , Saçan Melek Türker 
Published: October 2016

Abstract

The authors constructed novel, robust, and validated linear Quantitative Structure-Toxicity Relationship (QSTR) models in line with Organisation of Co-operation and Development (OECD) criteria using 2 cytotoxicity data sets which were obtained from the Alamar Blue and 5-carboxyfluorescein diacetate acetoxymethyl ester (CFDA-AM) assays. The data sets comprise the cytotoxic effect of structurally diverse and widely used pharmaceuticals, synthetic musks, and industrial chemicals on the rainbow trout (Oncorhynchus mykiss) liver cell line RTL-W1. Common descriptors defined the relationship between structure and cytotoxicity for both the Alamar Blue and the CFDA-AM assays which measure the metabolic activity and membrane integrity, respectively. Only the statistical parameters of the best Alamar Blue-based model were given (nTR = 13; R2 = 0.839; the root-mean-square error of the training set [RMSETR] = 0.261; nTEST = 5; R2 TEST = 0.903; RMSETEST = 0.181; CCCTEST = 0.939). The proposed QSTR model was able to predict the cytotoxicity of 101 diverse chemicals on the RTL-W1 cell line with 91% structural coverage. The authors found that in vitro-derived cytotoxicity data are promising predictors of in vivo fish toxicity and may provide an initial, rapid screening tool for acute fish toxicity assessment and reduce the need for extensive in vivo toxicity testing. Environ Toxicol Chem 2017;36:1162–1169. © 2016 SETAC