bluuebunny/crossref_metadata_2025_split huggingface dataset:
Logic Gating by Macrocycle Displacement Using a Double‐Stranded DNA [3]Rotaxane Shuttle
Authors: Lohmann Finn , Weigandt Johannes , Valero Julián , Famulok Michael 
Published: July 2014

AbstractMolecular interlocked systems with mechanically trapped components can serve as versatile building blocks for dynamic nanostructures. Here we report the synthesis of unprecedented double‐stranded (ds) DNA [2]‐ and [3]rotaxanes with two distinct stations for the hybridization of the macrocycles on the axle. In the [3]rotaxane, the release and migration of the “shuttle ring” mobilizes a second macrocycle in a highly controlled fashion. Different oligodeoxynucleotides (ODNs) employed as inputs induce structural changes in the system that can be detected as diverse logically gated output signals. We also designed nonsymmetrical [2]rotaxanes which allow unambiguous localization of the position of the macrocycle by use of atomic force microscopy (AFM). Either light irradiation or the use of fuel ODNs can drive the threaded macrocycle to the desired station in these shuttle systems. The DNA nanostructures introduced here constitute promising prototypes for logically gated cargo delivery and release shuttles.
3D Printed High‐Throughput Hydrothermal Reactionware for Discovery, Optimization, and Scale‐Up
Authors: Kitson Philip J. , Marshall Ross J. , Long Deliang , Forgan Ross S. , Cronin Leroy 
Published: July 2014

Abstract3D printing techniques allow the laboratory‐scale design and production of reactionware tailored to specific experimental requirements. To increase the range and versatility of reactionware devices, sealed, monolithic reactors suitable for use in hydrothermal synthesis have been digitally designed and realized. The fabrication process allows the introduction of reaction mixtures directly into the reactors during the production, and also enables the manufacture of devices of varying scales and geometries unavailable in traditional equipment. The utility of these devices is shown by the use of 3D printed, high‐throughput array reactors to discover two new coordination polymers, optimize the synthesis of one of these, and scale‐up its synthesis using larger reactors produced on the same 3D printer. Reactors were also used to produce phase‐pure samples of coordination polymers MIL‐96 and HKUST‐1, in yields comparable to synthesis in traditional apparatus.
Biomimetic design of chelating interfaces
Authors: Tian Fang , Roman Maxine J. , Decker Eric A. , Goddard Julie M. 
Published: July 2014

ABSTRACTSiderophores are naturally occurring small molecules with metal binding constants greater than many synthetic chelators. Herein, we report a two‐step process to graft a siderophore‐mimetic metal chelating polymer from a polypropylene (PP) surface. Poly(methyl acrylate) was first grafted from the PP surface by photoinitiated graft polymerization, followed by the conversion into poly(hydroxamic acid) (PHA) to obtain PP‐g‐PHA films. ATR/FTIR, contact angle, SEM, and AFM were performed to characterize surface properties of films. Iron binding kinetics and the influence of pH (3.0–5.0) on the chelating ability of films were determined. PP‐g‐PHA exhibited significant iron chelating activity (∼80 nmol/cm2) with an equilibration time of 24 h. The materials retained 50% chelating ability at pH 3.0 compared with pH 5.0, almost double the retention of previously reported polycarboxylate chelating interfaces. By using siderophore‐mimetic surface chemistry, such effective metal chelating interfaces can extend the applications of metal chelating polymers in environmental remediation, water purification, and active packaging areas. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41231.
Carbon nanomaterial‐based copolymer of styrene–divinylbenzene resins: Efficient interaction through graphene/CNTs polymer network
Authors: Li Yanan , Yu Fengping , He Wenjun , Yang Weimin 
Published: July 2014

ABSTRACTCarbon nanotubes (CNTs) and graphene were separately incorporated into the cross‐linked network of styrene–divinylbenzene composites via in situ suspension polymerization. The prepared copolymers were first chloromethylated and then aminated with trimethylamine to obtain ion exchange resins (IERs). The CNTs‐based and graphene‐based composites exhibited good dispersion throughout the polymer matrix with strong interaction within the network. Remarkable enhancement in antiswelling properties and thermal stabilities confirmed that graphene showed better compatibility and stronger interfacial adhesion than CNTs. The structural and thermal properties of the CNTs‐based and graphene‐based IERs were also significantly improved even at low loadings of 0.4 wt % compared with those when no CNTs and graphene were added. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41234.
Poly(amino ether)/organoclay nanocomposites: Preparation and characterization
Authors: Granado Ainhoa , Eguiazábal Jose Ignacio 
Published: July 2014

ABSTRACTDispersed polymer nanocomposites based on a poly(amino ether) resin and organically modified laminar clays were obtained. The chemical nature of the organic modifier of the clay and the processing temperature were first chosen using Young's modulus of the nanocomposites as a measure of the dispersion level. The Cloisite® 20A organoclay and a processing temperature of 170°C were the fixed parameters. Additionally, the clay content of the nanocomposites was changed and their nanostructure and properties were measured. A significant increase in the modulus of elasticity (35% with 4.3% montmorillonite addition) was observed, together with an unusual increase in ductility. The ductility behavior is attributed to a high degree of confinement of polymer chains inside the silicate layers, and the modulus values are discussed taking into account not only the dispersion level, but also the length of the clay particles. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41239.
Flame retardation of dibromoneopentyl glycol on intumescent flame‐retardant/low‐density polyethylene composites
Authors: Ma Zhi‐Ling , Wang Xian‐Ling , Wei Hui‐Mian , Song Hong‐Zan 
Published: July 2014

ABSTRACTOn the basis of ammonium polyphosphate (APP) microencapsulated with pentaerythritol/dibromoneopentyl glycol (DBNPG) mixed phosphate melamine salt as an intumescent flame retardant (IFR), the influence of DBNPG on the flame retardancy of IFR/low‐density polyethylene was investigated. The results prove that DBNPG could influence the combustion heat and the thermal barrier properties of the char layer in combustion. The intumescent degree (ID), compactness, and closure were the determinants of the thermal barrier properties of the char layer. A greater ID below 500°C and then a more compact and closed char layer above 500°C contributed to the better thermal barrier properties. An appropriate DBNPG reduced the combustion heat and promoted the formation of a compact and closed char layer by increasing of the melting viscosity of the composites. However, excessive DBNPG destroyed the closure of the char layer and increased the combustion heat because of a decrease in the melting viscosity of the composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2015,132, 41244.
The Politics of Tax Reform in Australia
Authors: Hewson John 
Published: July 2014

AbstractIncreasingly short‐term, opportunistic, adversarial politics has consistently constrained and compromised significant and genuine tax reform in Australia. This article reviews the various attempts at tax reform since Asprey in the mid‐1970s, assesses the existing tax system and attempts to set out the major essential ingredients of genuine tax reform in this country. Tax reform is seen as particularly urgent.
Methotrexate Inhibits NF‐κB Activity Via Long Intergenic (Noncoding) RNA–p21 Induction
Authors: Spurlock Charles F. , Tossberg John T. , Matlock Brittany K. , Olsen Nancy J. , Aune Thomas M. 
Published: July 2014

ObjectiveTo determine interrelationships between the expression of long intergenic (noncoding) RNA–p21 (lincRNA‐p21), NF‐κB activity, and responses to methotrexate (MTX) in rheumatoid arthritis (RA) by analyzing patient blood samples and cell culture models.MethodsExpression levels of long noncoding RNA and messenger RNA (mRNA) were determined by quantitative reverse transcription–polymerase chain reaction. Western blotting and flow cytometry were used to quantify levels of intracellular proteins. Intracellular NF‐κB activity was determined using an NF‐κB luciferase reporter plasmid.ResultsPatients with RA expressed reduced basal levels of lincRNA‐p21 and increased basal levels of phosphorylated p65 (RelA), a marker of NF‐κB activation. Patients with RA who were not treated with MTX expressed lower levels of lincRNA‐p21 and higher levels of phosphorylated p65 compared with RA patients treated with low‐dose MTX. In cell culture using primary cells and transformed cell lines, MTX induced lincRNA‐p21 through a DNA‐dependent protein kinase catalytic subunit (DNA PKcs)–dependent mechanism. Deficiencies in the levels of PRKDC mRNA in patients with RA were also corrected by MTX in vivo. Furthermore, MTX reduced NF‐κB activity in tumor necrosis factor α–treated cells through a DNA PKcs–dependent mechanism via induction of lincRNA‐p21. Finally, we observed that depressed levels of TP53 and lincRNA‐p21 increased NF‐κB activity in cell lines. Decreased levels of lincRNA‐p21 did not alter NFKB1 or RELA transcripts; rather, lincRNA‐p21 physically bound to RELA mRNA.ConclusionOur findings support a model whereby depressed levels of lincRNA‐p21 in RA contribute to increased NF‐κB activity. MTX decreases basal levels of NF‐κB activity by increasing lincRNA‐p21 levels through a DNA PKcs–dependent mechanism.
Supramolecular Phosphatases Formed by the Self‐Assembly of the Bis(Zn2+–Cyclen) Complex, Copper(II), and Barbital Derivatives in Water
Authors: Zulkefeli Mohd , Hisamatsu Yosuke , Suzuki Asami , Miyazawa Yuya , Shiro Motoo , Aoki Shin 
Published: July 2014

AbstractIn our previous paper, we reported that a dimeric Zn2+ complex with a 2,2′‐bipyridyl linker (Zn2L1), cyanuric acid (CA), and a Cu2+ ion automatically assemble in aqueous solution to form 4:4:4 complex 3, which selectively catalyzes the hydrolysis of mono(4‐nitrophenyl)phosphate (MNP) at neutral pH. Herein, we report that the use of barbital (Bar) instead of CA for the self‐assembly with Zn2L1 and Cu2+ induces 2:2:2 complexation of these components, and not the 4:4:4 complex, to form supramolecular complex 6 a, the structure and equilibrium characteristics of which were studied by analytical and physical measurements. The finding show that 6 a also accelerates the hydrolysis of MNP, similarly to 3. Moreover, inspired by the crystal structure of 6 a, we prepared barbital units that contain functional groups on their side chains in an attempt to produce supramolecular phosphatases that possess functional groups near the Cu2(μ‐OH)2 catalytic core so as to mimic the catalytic center of alkaline phosphatase (AP).
Analysis of biomarkers for risk of acute kidney injury after primary angioplasty for acute ST‐segment elevation myocardial infarction: Results of the HORIZONS‐AMI trial
Authors: Guerchicoff Alejandra , Stone Gregg W. , Mehran Roxana , Xu Ke , Nichols Dru , Claessen Bimmer E. , Guagliumi Giulio , Witzenbichler Bernhard , Henriques José P.S. , Dangas George D. 
Published: July 2014

ObjectivesContrast‐induced acute kidney injury (CI‐AKI) may occur after percutaneous coronary intervention (PCI).MethodsWe evaluated patients with ST‐elevation myocardial infarction (STEMI) undergoing emergency PCI with serial biomarkers.ResultsOf the 390 patients enrolled in the HORIZONS‐AMI biomarker substudy, 56 (14.3%) developed AKI. In the AKI group, the levels of B‐type natriuretic peptide were consistently higher than in the no‐AKI group at baseline (P = 0.0327), hospital discharge (P = 0.0002), 30‐day follow‐up (P = 0.0193), and 1‐year follow‐up (P = 0.031). At hospital discharge, the AKI group had elevated biomarkers compared to the no‐AKI group: D‐dimer (P = 0.0066), C‐reactive protein (P = 0.0468), endothelial cell‐selective adhesion molecule (P = 0.0169), adiponectin (P = 0.0346), and von Willebrand factor (P = 0.0168); there was also a trend toward higher cystatin C (P = 0.0585) in the AKI group. Similar correlations between biomarker panel increase and the development of CI‐AKI were consistent at baseline, 30‐day, and 1‐year follow‐up. Chemokine (C‐C motif) ligand 23 showed an opposite pattern with an increase at all time points in the no‐AKI compared to the AKI group.ConclusionsThe risk of CI‐AKI after primary PCI for STEMI may be associated with hemostatic imbalances, activation of procoagulants, decreased endogenous anticoagulants, enhanced inflammation, platelet activation, or decreased fibrinolytic activity. © 2014 Wiley Periodicals, Inc.
Synthesis and Activity of Plasmonic Photocatalysts
Authors: Lou Zaizhu , Wang Zeyan , Huang Baibiao , Dai Ying 
Published: July 2014

AbstractPlasmonic photocatalysts, which have intensive light absorption and high charge‐separation efficiencies, are regarded as promising candidates to solve energy and environmental issues in the future. In this Review, we summarize recent developments in the synthesis, activity, and mechanism of plasmonic photocatalysts, with the aim of stimulating improvements in photocatalytic activities and promoting the development of photocatalysis. The materials systems, energy‐transfer mechanisms, and factors that influence the photocatalytic activities of plasmonic photocatalysts are discussed. Some perspectives for the future development of the design of highly efficient plasmonic photocatalysts are proposed.
Effect of Temperature on Fluidization Regimes
Authors: Hagh‐Shenas‐Lari Mohammad‐Javad , Mostoufi Navid 
Published: July 2014

AbstractThe probability of fluidization regimes at high temperature was determined experimentally by frequency domain analysis of pressure fluctuations. Fluidization regime probabilities were calculated for various gas velocities and temperatures. By increasing the temperature, larger bubbles became more stable which resulted in postponing transition from bubbling to turbulent fluidization. Results showed that the transition velocity from bubbling to turbulent increases by raising the temperature. A probability model was proposed and compared with experimental data indicating good accordance.
Gold(III) Chloride Catalyzed Synthesis of Chiral Substituted 3‐Formyl Furans from Carbohydrates: Application in the Synthesis of 1,5‐Dicarbonyl Derivatives and Furo[3,2‐c]pyridine
Authors: Mal Kanchan , Sharma Abhinandan , Das Indrajit 
Published: July 2014

AbstractThis report describes a gold(III)‐catalyzed efficient general route to densely substituted chiral 3‐formyl furans under extremely mild conditions from suitably protected 5‐(1‐alkynyl)‐2,3‐dihydropyran‐4‐one using H2O as a nucleophile. The reaction proceeds through the initial formation of an activated alkyne–gold(III) complex intermediate, followed by either a domino nucleophilic attack/anti‐endo‐dig cyclization, or the formation of a cyclic oxonium ion with subsequent attack by H2O. To confirm the proposed mechanistic pathway, we employed MeOH as a nucleophile instead of H2O to result in a substituted furo[3,2‐c]pyran derivative, as anticipated. The similar furo[3,2‐c]pyran skeleton with a hybrid carbohydrate–furan derivative has also been achieved through pyridinium dichromate (PDC) oxidation of a substituted chiral 3‐formyl furan. The corresponding protected 5‐(1‐alkynyl)‐2,3‐dihydropyran‐4‐one can be synthesized from the monosaccharides (both hexoses and pentose) following oxidation, iodination, and Sonogashira coupling sequences. Furthermore, to demonstrate the potentiality of chiral 3‐formyl furan derivatives, a TiBr4‐catalyzed reaction of these derivatives has been shown to offer efficient access to 1,5‐dicarbonyl compounds, which on treatment with NH4OAc in slightly acidic conditions afforded substituted furo[3,2‐c]pyridine.
Palladium‐Catalyzed Chemoselective Allylic Substitution, Suzuki–Miyaura Cross‐Coupling, and Allene Formation of Bifunctional 2‐B(pin)‐Substituted Allylic Acetate Derivatives
Authors: Kim Byeong‐Seon , Hussain Mahmud M. , Hussain Nusrah , Walsh Patrick J. 
Published: July 2014

AbstractA formidable challenge at the forefront of organic synthesis is the control of chemoselectivity to enable the selective formation of diverse structural motifs from a readily available substrate class. Presented herein is a detailed study of chemoselectivity with palladium‐based phosphane catalysts and readily available 2‐B(pin)‐substituted allylic acetates, benzoates, and carbonates. Depending on the choice of reagents, catalysts, and reaction conditions, 2‐B(pin)‐substituted allylic acetates and derivatives can be steered into one of three reaction manifolds: allylic substitution, Suzuki–Miyaura cross‐coupling, or elimination to form allenes, all with excellent chemoselectivity. Studies on the chemoselectivity of Pd catalysts in their reactivity with boron‐bearing allylic acetate derivatives led to the development of diverse and practical reactions with potential utility in synthetic organic chemistry.
Base‐Promoted C→N Acyl Rearrangement: An Unconventional Approach to α‐Amino Acid Derivatives
Authors: Ugarriza Iratxe , Uria Uxue , Carrillo Luisa , Vicario Jose L. , Reyes Efraim 
Published: July 2014

AbstractWe have discovered that N‐alkyl aminomalonates undergo a fast and selective intramolecular C→N acyl rearrangement reaction in the presence of a strong base, leading to N‐protected glycinates in excellent yield. Moreover, the fact that the reaction proceeds through a nucleophilic enolate intermediate has been used for implementing a tandem rearrangement/alkylation sequence that has been applied to the preparation of synthetically relevant nonproteinogenic tertiary and quaternary N‐alkyl α‐amino acids in a very simple and reliable way.
A Magnetically Drivable Nanovehicle for Curcumin with Antioxidant Capacity and MRI Relaxation Properties
Authors: Magro Massimiliano , Campos René , Baratella Davide , Lima Giuseppina , Holà Katerina , Divoky Clemens , Stollberger Rudolf , Malina Ondrej , Aparicio Claudia , Zoppellaro Giorgio , Zbořil Radek , Vianello Fabio 
Published: July 2014

AbstractCurcumin possesses wide‐ranging anti‐inflammatory and anti‐cancer properties and its biological activity can be linked to its potent antioxidant capacity. Superparamagnetic maghemite (γ‐Fe2O3), called surface‐active maghemite nanoparticles (SAMNs) were surface‐modified with curcumin molecules, due to the presence of under‐coordinated FeIII atoms on the nanoparticle surface. The so‐obtained curcumin‐modified SAMNs (SAMN@curcumin) had a mean size of 13±4 nm. SAMN@curcumin was characterized by transmission and scanning electron microscopy, UV/Vis, FTIR, and Mössbauer spectroscopy, X‐ray powder diffraction, bulk susceptibility (SQUID), and relaxometry measurements (MRI imaging). The high negative contrast proclivity of SAMN@curcumin to act as potential contrast agent in MRI screenings was also tested. Moreover, the redox properties of bound curcumin were probed by electrochemistry. SAMN@curcumin was studied in the presence of different electroactive molecules, namely hydroquinone, NADH and ferrocyanide, to assess its redox behavior. Finally, SAMN@curcumin was electrochemically probed in the presence of hydrogen peroxide, demonstrating the stability and reactivity of bound curcumin.
Synthesis and Characterization of a Family of POCOP Pincer Complexes with Nickel: Reactivity Towards CO2 and Phenylacetylene
Authors: Jonasson Klara J. , Wendt Ola F. 
Published: July 2014

AbstractA cyclohexyl‐based POCOP pincer ligand (POCOP=cis‐1,3‐bis(di‐tert‐butylphosphinito)cyclohexyl) cyclometalates with nickel to generate a series of new POCOP‐supported NiII complexes, including the halide, hydride, methyl, and phenyl species. trans‐[NiCl{cis‐1,3‐bis(di‐tert‐butylphosphinito)cyclohexane}], [(POCOP)NiCl] (1 a) and the analogous bromide complex (1 b) were synthesized and fully characterized by NMR spectroscopy and X‐ray crystallography. Cyclic voltammetry measurements of 1 a and 1 b alongside their bis(phosphine) analogues [(PCP)NiCl] (2 a) and [(PCP)NiCl] (2 a) (PCP=cis‐1,3‐bis(di‐tert‐butylphosphino)cyclohexyl) indicate a reduced electron density at the metal center upon introducing electron‐withdrawing oxygen atoms in the pincer arms. The methyl [(POCOP)NiMe] (3) and phenyl [(POCOP)NiPh] (4) complexes were formed from 1 a by reaction with the corresponding organolithium reagents. 1 a also reacts with LiAlH4 to give the hydride complex [(POCOP)NiH] (5). The methyl complex 3 reacts with phenyl acetylene to give the acetylide complex [(POCOP)NiCCPh] (6). The reactivity of compounds 3–5 towards CO2 was studied. The hydride complex 5 and the methyl complex 3 both underwent CO2 insertion to form the formate species [(POCOP)NiOCOH] (7) and acetate species [(POCOP)NiOCOCH3] (8), respectively, although with a higher barrier of insertion in the latter case. Compound 4 was unreactive towards CO2 even at elevated temperatures. Complexes 3–8 were all characterized by NMR spectroscopy and X‐ray crystallography.
Spindle‐Like Polypyrrole Hollow Nanocapsules as Multifunctional Platforms for Highly Effective Chemo–Photothermal Combination Therapy of Cancer Cells in Vivo
Authors: Wang Yang , Xiao Yun , Tang Ruikang 
Published: July 2014

AbstractThe monodispersed spindle‐like polypyrrole hollow nanocapsules (PPy HNCs) as the multifunctional platforms for combining chemotherapy with photothermal therapy for cancer cells are reported. Whereas the hollow cavity of nanocapsules can be used to load the anticancer drug (i.e., doxorubicin) for chemotherapy, the PPy shells can convert NIR light into heat for photothermal therapy. The release of the drug from the spindle‐like PPy HNCs is pH‐sensitive and near‐infrared (NIR) light‐enhanced. More importantly, the spindle‐like PPy HNCs can penetrate cells more rapidly and efficiently in comparison with the spherical PPy HNCs. Both in vitro and in vivo experiments demonstrated that the combination of DOX‐loaded spindle‐like PPy HNCs and NIR light provide a highly effective and feasible chemo‐photothermal therapy cancer method with a synergistic effect. Owing to their high photothermal conversion efficiency, large hollow cavity, and good biocompatibility, the spindle‐like PPy HNCs could be used as a promising new cancer drug‐nanocarrier and photothermal agent for localized tumorous chemo‐photothermal therapy.
Naphthocrown‐Strapped Calix[4]pyrroles: Formation of Self‐Assembled Structures by Ion‐Pair Recognition
Authors: Kim Sung Kuk , Lee Hong Gyu , Vargas‐Zúñiga Gabriela I. , Lynch Vincent M. , Kim Cheal , Sessler Jonathan L. 
Published: July 2014

AbstractA new approach to the construction of self‐assembled structures is reported that is based on ion‐pair recognition. Towards this end, the calix[4]pyrrole naphthocrown‐4 hybrid structures 2 and 3 were prepared. These multitopic receptors contain recognition sites for both anions and cations. On the basis of solution‐phase 1H NMR spectroscopic analysis and solid‐state single‐crystal X‐ray diffraction structural studies, it was established that receptors 2 and 3 are able to bind specific ion pairs with high selectivity via different binding modes. In the case of CsF and CsCl, the ion‐pair complexes formed from receptors 2 and 3 were found to self‐assemble to produce either linear supramolecular polymeric crystalline solids or nanotube‐like cyclic hexamers depending on the specific choice of ion pairs and crystallization solvents. Proton NMR studies provided evidence for solution‐phase self‐association in organic media.