bluuebunny/crossref_metadata_2025_split huggingface dataset:
N′‐Alkylaminosulfonyl Analogues of 6‐Fluorobenzylideneindolinones with Desirable Physicochemical Profiles and Potent Growth Inhibitory Activities on Hepatocellular Carcinoma
Authors: Chen Xiao , Yang Tianming , Deivasigamani Amudha , Shanmugam Muthu K. , Hui Kam‐Man , Sethi Gautam , Go Mei‐Lin 
Published: July 2015

AbstractThe benzylideneindolinone 6‐chloro‐3‐(3′‐trifluoromethylbenzylidene)‐1,3‐dihydroindol‐2‐one (4) was reported to exhibit potent and selective growth inhibitory effects on hepatocellular carcinoma (HCC). Corroborative evidence supported multi‐receptor tyrosine kinase (RTK) inhibition as a possible mode of action. However, the poor physicochemical properties of 4 limited its furtherance as a lead compound. In this study, the modification of 4 was investigated with the aim of improving its potency and physicochemical profile. The 6‐fluorobenzylideneindolinone 3‐12 bearing a 3′‐N‐propylaminosulfonyl substituent was found to be a promising substitute. Compound 3‐12 [6‐fluoro‐3‐(3′‐N‐propylaminosulfonylbenzylidene)‐1,3‐dihydroindol‐2‐one] was found to be tenfold more soluble than 4 and to have sub‐micromolar growth inhibitory activities on HCC cells. It is apoptogenic and inhibits the phosphorylation of several RTKs in HuH7, of which the inhibition of FGFR4 and HER3 are prominent. Compound 3‐12 decreased the tumor load in a physiologically relevant orthotopic HCC xenograft murine model. Structure–activity relationships support pivotal roles for the fluoro and N′‐propylaminosulfonyl moieties in enhancing cell‐based activity and moderating the physicochemical profile (solubility, permeability) of 3‐12.
Opioids and breast cancer recurrence: A Danish population‐based cohort study
Authors: Cronin‐Fenton Deirdre P. , Heide‐Jørgensen Uffe , Ahern Thomas P. , Lash Timothy L. , Christiansen Peer M. , Ejlertsen Bent , Sjøgren Per , Kehlet Henrik , Sørensen Henrik T. 
Published: July 2015

BACKGROUNDOpioids may alter immune function, thereby potentially affecting cancer recurrence. The authors investigated the association between postdiagnosis opioid use and breast cancer recurrence.METHODSPatients with incident, early stage breast cancer who were diagnosed during 1996 through 2008 in Denmark were identified from the Danish Breast Cancer Cooperative Group Registry. Opioid prescriptions were ascertained from the Danish National Prescription Registry. Follow‐up began on the date of primary surgery for breast cancer and continued until breast cancer recurrence, death, emigration, 10 years, or July 31, 2013, whichever occurred first. Cox regression models were used to compute hazard ratios and 95% confidence intervals associating breast cancer recurrence with opioid prescription use overall and by opioid type and strength, immunosuppressive effect, chronic use (≥6 months of continuous exposure), and cumulative morphine‐equivalent dose, adjusting for confounders.RESULTSIn total, 34,188 patients were identified who, together, contributed 283,666 person‐years of follow‐up. There was no association between ever‐use of opioids and breast cancer recurrence (crude hazard ratio, 0.98; 95% confidence interval, 0.90‐1.1; adjusted hazard ratio, 1.0; 95% confidence interval, 0.92‐1.1), regardless of opioid type, strength, chronicity of use, or cumulative dose. Breast cancer recurrence rates were lower among users of strongly (but not weakly) immunosuppressive opioids, possibly because of channeling bias among those with a high competing risk, because mortality was higher among users of this drug type.CONCLUSIONSThis large, prospective cohort study provided no clinically relevant evidence of an association between opioid prescriptions and breast cancer recurrence. The current findings are important to cancer survivorship, because opioids are frequently used to manage pain associated with comorbid conditions. Cancer 2015;121:3435–43. © 2015 American Cancer Society.
Correct metric semantics for a language inspired by DNA computing
Authors: Ciobanu Gabriel , Todoran Eneia Nicolae 
Published: July 2015

SummaryWe investigate a language similar to a process algebra introduced by Cardelli for DNA computing. For such a language, we relate two formal semantics. We define a new denotational semantics by using complete metric spaces, in which various semantic functions are defined as fixed points of appropriate higher‐order mappings. We compare this denotational semantics with an operational semantics and establish a formal relationship between them by using an abstraction operator and a fixed point argument. In this way, we prove the correctness of the denotational semantics with respect to the operational one. Copyright © 2015 John Wiley & Sons, Ltd.
Step‐by‐Step Layer‐by‐Layer Assembly Using 1,2,3‐Triazole as a Platform for Controlled Multicharged and Multifunctional Coatings
Authors: Godeau Guilhem , Darmanin Thierry , Guittard Frédéric 
Published: July 2015

AbstractReported for the first time is the use of click chemistry to make layer‐by‐layer multiple post‐functionalization treatments. The use of triazole as a platform for the post‐functionalization allows the introduction of new clickable structures on the surface. The layer‐by‐layer strategy by means of click chemistry allows the introduction of both multiple and/or different consecutive modifications on the surface and multicharged species. Herein it consists of the use of molecules functionalized by a 1‐azido group and propargyl bromide to deposit functionalized triazolium‐type charged oligomers on the substrate. Moreover, different functional groups can be introduced at each step, which amplifies the use of this strategy for many potential applications. Here, to give an example of applications, that strategy is used to introduce alkyl chains and obtain highly hydrophobic materials. Moreover, it is shown that the surface morphology can also change after each treatment.
Kinetic and Theoretical Studies of Beta‐Lactone Reactivity—A Quantitative Scale for Biological Application
Authors: Wiedemann Elija N. , Mandl Franziska A. , Blank Iris D. , Ochsenfeld Christian , Ofial Armin R. , Sieber Stephan A. 
Published: July 2015

AbstractNatural products comprise a rich source for bioactive molecules with medicinal relevance. Many of these contain electrophilic scaffolds that bind conserved enzyme active sites covalently. Prominent examples include beta‐lactams and beta‐lactones, which specifically acylate serine residues in diverse peptidases. Although these scaffolds appear similar, their bioactivities and corresponding protein targets vary. To quantify and dissect these differences in bioactivities, the kinetics of the reactions of beta‐butyrolactone with a set of reference amines in buffered aqueous solution at 37 °C have been analyzed. Different product ratios of C1 versus C3 attack on the beta‐butyrolactone have been observed, depending on the aliphatic or aromatic nature of the standard amine used. Quantum mechanics/molecular mechanics (QM/MM) calculations reveal that a H3O+ molecule has a crucial role in stabilizing C3 attack by aniline, through coordination of the lactone ring oxygen. In agreement with their weak proteome reactivity, monocyclic beta‐lactams did not react with the set of standard nucleophiles studied herein. Bicyclic beta‐lactams, however, exhibited a lower activation barrier, and thus, reacted with standard nucleophiles. This study represents a starting point for semiquantitative reactivity scales for natural products, which, in analogy to chemical reactivity scales, will provide predictions for electrophilic modifications in biological systems.
Thermodynamically Favorable Conversion of Hydrogen Sulfide into Valuable Products through Reaction with Sodium Naphthalenide
Authors: Li Xuemin , Morrish Rachel M. , Yang Yuan , Wolden Colin A. , Yang Yongan 
Published: July 2015

AbstractHydrogen sulfide (H2S) is an extremely hazardous chemical waste that is generated at large scale in many industries; its abatement has long been an energy‐extensive and cost‐ineffective liability due to the thermodynamic limitations of the selected approaches and low value of the final products, sulfur and water. Here we introduce an attractive method for H2S abatement that yields value‐added products via a thermodynamically favorable process. Specifically, sodium naphthalenide (Na‐NAP) is used to capture H2S to produce anhydrous Na2S nanocrystals and 1,4‐dihydronaphthalene, which are important materials for batteries and liquid fuels, respectively. This multipurpose process is driven by the acid/base neutralization reaction between hydrogen cations from H2S and radical anions from naphthalenide. It is spontaneous and irreversible at ambient temperature and pressure, proceeding to completion very rapidly.
Synthesis of BiVO4@C Core–Shell Structure on Reduced Graphene Oxide with Enhanced Visible‐Light Photocatalytic Activity
Authors: Sun Zhihua , Li Chenzhe , Zhu Shenmin , Cho Maenghyo , Chen Zhixin , Cho Kyeongjae , Liao Yongliang , Yin Chao , Zhang Di 
Published: July 2015

AbstractHerein, a facile strategy for the controllable synthesis of BiVO4@C core–shell nanoparticles on reduced graphene oxide (RGO) is reported. The BiVO4 particle size can be controlled in the process by adjusting the volume ratio of glycerol in the sol–gel solution. The glycerol layers adsorbed on BiVO4 (BiVO4@glycerol) made it possible to form hydrogen bonds between BiVO4@glycerol and graphene oxide with the assistance of ultrasound. After thermal treatment, glycerol adsorbed on the BiVO4 particles formed amorphous carbon shells to link the particles and RGO. As a result, the obtained RGO‐BiVO4@C nanocomposite showed a five times higher rate in O2 evolution from water under visible‐light irradiation. Also, it demonstrated a six times higher photocatalytic performance enhancement than that of pure BiVO4 in the degradation of Rhodamine B. The enhanced performance is attributed to the carbon shells that restrict the growth of BiVO4, the reduced graphene oxide that improves the electronic conductivity of the composite, and importantly, the bonds formed between the carbon shells and RGO that reduce the recombination loss of photogenerated charges effectively. The strategy is simple, effective, and can be extended to other ternary oxides with controlled size and high performance.
Reduced Graphene Oxide Bipolar Membranes for Integrated Solar Water Splitting in Optimal pH
Authors: McDonald Michael B. , Bruce Jared P. , McEleney Kevin , Freund Michael S. 
Published: July 2015

AbstractThe integration of light absorbers and catalysts for the water splitting process requires a membrane capable of both ion and electron management and product separation to realize efficient solar fuels systems. Bipolar membranes can maintain a pH gradient for optimal reaction conditions by the dissociation of water. Such membranes that contain graphene in the interfacial layer are fabricated by the chemical reduction of a uniformly deposited graphene oxide layer to convert sp3 catalyst regions to sp2 conductive regions. The resulting electrical and water dissociation properties are optimized by adjusting the exposure conditions, and treatments of less than 5 min render an interface that exceeds the conductivity requirements for integrated solar water splitting and increases the overpotential by <0.3 V. Integration with photoelectrodes is examined by characterizing the electrical interface formed between graphene and Si microwires, and we found that efficient Ohmic junctions are possible.
Efficient channel assignment method for multimedia traffic in wireless mesh networks
Authors: Pounambal M. , Krishna P. Venkata 
Published: July 2015

SummaryIn wireless mesh networks, the availability of spectrum should be utilized efficiently because the exchanging of traffic rate of multimedia applications is increasing day to day. The traffic of multimedia content may degrade the network performance in terms of high packet loss and throughput degradation because of asynchronous behavior between the sender and the receiver. The proposed Efficient Channel Reservation and Assignment (EchRA) results in successful originating and handing off of multimedia call transmissions using the four dimensional Markov chain process. The EChRA algorithm, proposed in this paper, achieves the maximum throughput performance considering the parameters of blocking probability, dropping probability, and synchronized dwell time between the source and destination. The quality of service is guaranteed by sharing the available slots and by using efficient queuing model to service the incoming and handoff calls, and henceforth, the successful completion of handoff calls rate is increased. Copyright © 2015 John Wiley & Sons, Ltd.
Environmental effects on survival rates: robust regression, recovery planning and endangered Atlantic salmon
Authors: Bowlby Heather D. , Gibson A. Jamie F. 
Published: July 2015

AbstractDescribing how population‐level survival rates are influenced by environmental change becomes necessary during recovery planning to identify threats that should be the focus for future remediation efforts. However, the ways in which data are analyzed have the potential to change our ecological understanding and thus subsequent recommendations for remedial actions to address threats. In regression, distributional assumptions underlying short time series of survival estimates cannot be investigated a priori and data likely contain points that do not follow the general trend (outliers) as well as contain additional variation relative to an assumed distribution (overdispersion). Using juvenile survival data from three endangered Atlantic salmon Salmo salar L. populations in response to hydrological variation, four distributions for the response were compared using lognormal and generalized linear models (GLM). The influence of outliers as well as overdispersion was investigated by comparing conclusions from robust regressions with these lognormal models and GLMs. The analyses strongly supported the use of a lognormal distribution for survival estimates (i.e., modeling the instantaneous rate of mortality as the response) and would have led to ambiguity in the identification of significant hydrological predictors as well as low overall confidence in the predicted relationships if only GLMs had been considered. However, using robust regression to evaluate the effect of additional variation and outliers in the data relative to regression assumptions resulted in a better understanding of relationships between hydrological variables and survival that could be used for population‐specific recovery planning. This manuscript highlights how a systematic analysis that explicitly considers what monitoring data represent and where variation is likely to come from is required in order to draw meaningful conclusions when analyzing changes in survival relative to environmental variation to aid in recovery planning.
Response and tolerance to oral vasodilator up‐titration after intravenous vasodilator therapy in advanced decompensated heart failure
Authors: Verbrugge Frederik H. , Dupont Matthias , Finucan Michael , Gabi Alaa , Hawwa Nael , Mullens Wilfried , Taylor David O. , Young James B. , Starling Randall C. , Tang W.H. Wilson 
Published: July 2015

AimsThe aim of this study was to assess the haemodynamic response and tolerance to aggressive oral hydralazine/isosorbide dinitrate (HYD/ISDN) up‐titration after intravenous vasodilator therapy in advanced decompensated heart failure (ADHF).Methods and resultsMedical records of 147 consecutive ADHF patients who underwent placement of a pulmonary artery catheter and received intravenous vasodilator therapy were reviewed. Intravenous sodium nitroprusside and sodium nitroglycerin as first‐line agent for those with preserved blood pressures were utilized in 143 and 32 patients, respectively. Sixty‐one percent of patients were converted to oral HYD/ISDN combination therapy through a standardized conversion protocol. These patients had a significantly higher admission mean pulmonary arterial wedge pressure compared with patients not converted (28 ± 7 vs. 25 ± 8 mmHg, respectively; P‐value 0.024). Beneficial haemodynamic response to decongestive therapy, defined as low cardiac filling pressures and cardiac index ≥2.20 L/min/m2 without emergent hypotension, was achieved in 32% and 29% of patients who did or did not receive oral HYD/ISDN, respectively (P‐value 0.762). HYD/ISDN dosing was progressively and consistently decreased up to the moment of hospital discharge and during outpatient follow‐up, primarily due to incident hypotension.ConclusionThe use of a standardized haemodynamically guided up‐titration protocol for conversion from intravenous to oral vasodilators may warrant subsequent dose reductions upon stabilization.
One‐Pot Synthesis of an Oxalato‐Bridged CuII Coordination Polymer Containing an In Situ Produced Pyrazole Moiety: A Precursor for the Preparation of CuO Nano­structures
Authors: Bahemmat Samira , Neumüller Bernhard , Ghassemzadeh Mitra 
Published: July 2015

AbstractThe synthesis, characterization, and thermal decomposition behaviour of the oxalato‐bridged copper(II) coordination polymer [Cu2(C2O4)(L)2Cl2(MeOH)2]n (1) (L = 3,5‐dimethyl‐1H‐pyrazole) is reported. Complex 1 is prepared in a straightforward fashion by a one‐pot reaction of acetylacetone, thiosemicarbazide, oxalic acid and copper(II) chloride in a molar ratio of 2:2:1:2. Complex 1 was characterized by means of FT‐IR spectroscopy, mass spectrometry and elemental analysis as well as single‐crystal X‐ray diffraction. Furthermore, the electrochemical behavior of 1 was investigated in DMSO by cyclic voltammetry. The thermal stability of complex 1 was studied by thermal gravimetric (TG) and differential thermal analyses (DTA). Solventless thermolysis of complex 1 at 550 °C and 1000 °C under air afforded copper oxide nanoparticles and nanosheets, respectively. The CuO nanostructures were characterized by using a series of techniques including FT‐IR, UV/Vis, XRD, XPS, EDAX, and SEM.
Cytocompatible Fluorescent Quantum Dot/PEG‐Chitosan Bioconjugates for Nanomedicine Applications
Authors: Mansur Alexandra A. P. , de Almeida Camila G. , de Carvalho Sandhra M. , de Faria Lucas V. , de Almeida Mauro V. , Mansur Herman S. 
Published: July 2015

AbstractIn this study, novel nanobioconjugates based on quantum dots and a PEGylated chitosan derivative (PEG‐CHI) have been designed and synthesised by a single‐step aqueous route at room temperature. Chitosan was chemically modified by PEGylation aiming to significantly improve its water solubility and used as the capping ligand in the preparation of CdS quantum dot (QD) colloidal systems. UV/Vis and photoluminescence spectroscopy, transmission electron microscopy, dynamic light scattering, and the zeta potential were used to characterise the biopolymer‐capped semi‐conductor nanocrystals and their relative stability. The results clearly demonstrated that the PEG‐CHI derivative is remarkably effective in nucleating and stabilising ultra‐small colloidal CdS QDs in aqueous suspensions under acidic, neutral and alkaline media with an average size of approximately 2.0–3.0 nm and simultaneously showing luminescent activity in the visible range. In addition, the results of cell viability analysis in vitro using two cell cultures based on MTT bioassays demonstrated no cytotoxicity of the CdS QD/PEG‐chitosan bioconjugates. Thus, based on these findings, it can be envisioned that these bioconjugates have potential use as biocompatible fluorescent biomarkers for nanomedicine applications.
Controlled SBU Approaches to Isoreticular Metal‐Organic Framework Ruthenium‐Analogues of HKUST‐1
Authors: Zhang Wenhua , Kozachuk Olesia , Medishetty Raghavender , Schneemann Andreas , Wagner Ralph , Khaletskaya Kira , Epp Konstantin , Fischer Roland A. 
Published: July 2015

AbstractA controlled secondary building unit approach (CSA) was employed to obtain a series of ruthenium metal‐organic frameworks (MOFs) of the general formula [Ru3(BTC)2Xx]·Gg (BTC = 1,3,5‐benzenetricarboxylate; X = counter‐anion, G = guest molecules) which are structural analogues of [M3(BTC)2] (M = Cu, Zn, Ni, Cr, Mo). The compounds [Ru2(OOCR)4X] and [Ru2(OOCCH3)4]Y were varied as Ru sources for CSA; namely strong coordinating X (Cl–) and weakly coordinating Y ([BF4]– or [BPh4]–) as well as the alkyl groups at the carboxylate ligand [R = CH3 or C(CH3)3] were utilized. Four phase‐pure Ru‐MOFs were obtained: [Ru3(BTC)2Cl0.5(OH)]·(AcOH)1.5 (1), [Ru3(BTC)2Cl1.2(OH)0.3]·(H3BTC)0.15(AcOH)2.4(PivOH)0.45 (2), [Ru3(BTC)2F0.5(OH)]·(AcOH)1.0 (3) and [Ru3(BTC)2(OH)1.5]·(H3BTC)0.5·(AcOH)1.4 (4) {AcOH = CH3COOH, PivOH = (CH3)3CCOOH}. The series of characterization data support the analytical composition and isostructural nature of 1–4, i.e. powder X‐ray diffraction (PXRD), IR‐ and 1H‐NMR spectroscopy, thermal gravimetric analysis (TGA) and N2 sorption were employed. The valence state of the Ru‐sites were studied by X‐ray absorption spectroscopy (XAS). The chosen precursors for CSA and optimized synthesis, work‐up and activation protocols allowed improvement of the overall crystallinity, purity (i.e., residual solvent molecules) and surface area of the Ru‐MOF materials.
Recognition of Prochiral Sulfides in Five‐Coordinate PtII Complexes
Authors: Calvanese Luisa , Cucciolito Maria E. , D'Amora Angela , D'Auria Gabriella , Esposito Antonio , Esposito Roberto , Falcigno Lucia , Ruffo Francesco 
Published: July 2015

AbstractThis article describes a stereochemical study on five‐coordinate complexes of PtII containing a prochiral alkene (E‐R1O2CCH=CHCO2R1) and a prochiral sulfide R2SR3, of general formula [PtMe(R2SR3)(dmphen) (E‐R1O2CCH=CHCO2R1)]BF4. Through mono‐ and two‐dimensional NMR spectroscopy, it was demonstrated that there is mutual recognition between the prochiral ligands in the presence of aryl sulfides R2SAr, whose origin was also explained. The equilibrium constants of sulfide exchange were also evaluated, which are in full agreement with the σ‐donor properties of the ligands.