bluuebunny/crossref_metadata_2025 huggingface dataset:
Numerical study on CO2 leakage detection using electrical streaming potential data
Authors: Büsing Henrik , Vogt Christian , Ebigbo Anozie , Klitzsch Norbert
Published: December 2016

We study the feasibility of detecting carbon dioxide (CO2) movement in the overburden of a storage reservoir due to CO2 leakage through an abandoned well by self‐potential (SP) measurements at the surface. This is achieved with three‐dimensional numerical (SP) modeling of two‐phase fluid flow and electrokinetic coupling between flow and streaming potential. We find that, in typical leakage scenarios, for leaky and/or injection wells with conductive metal casing, self‐potential signals originating from injection can be identified at the surface. As the injection signal is also observed at the leaky well with metal casing, SP monitoring can be applied for detecting abandoned wells. However, leakage signals are much smaller than the injection signal and thus masked by the latter. We present three alternatives to overcome this problem: (i) simulate the streaming potential of the nonleaky scenario and subtract the result from the measured streaming potential data; (ii) exploit the symmetry of the injection signal by analyzing the potential difference of dipoles with the dipole center at the injection well; or (iii) measure SP during periods where the injection is interrupted. In our judgement, the most promising approach for detecting a real‐world CO2 leakage is by combining methods (i) and (ii), because this would give the highest signal from the leakage and omit signals originating from the injection well. Consequently, we recommend SP as monitoring method for subsurface CO2 storage, especially because a leakage can be detected shortly after the injection started even before CO2 arrives at the leaky well.
Extended and direct evaluation of RT‐QuIC assays for Creutzfeldt‐Jakob disease diagnosis
Authors: Groveman Bradley R. , Orrú Christina D. , Hughson Andrew G. , Bongianni Matilde , Fiorini Michele , Imperiale Daniele , Ladogana Anna , Pocchiari Maurizio , Zanusso Gianluigi , Caughey Byron
Published: December 2016

Real‐Time Quaking‐Induced Conversion (RT‐QuIC) testing of human cerebrospinal fluid (CSF) is highly sensitive and specific in discriminating sporadic CJD patients from those without prion disease. Here, using CSF samples from 113 CJD and 64 non‐prion disease patients, we provide the first direct and concurrent comparison of our improved RT‐QuIC assay to our previous assay, which is similar to those commonly used internationally for CJD diagnosis. This extended comparison demonstrated a ~21% increase in diagnostic sensitivity, a 2‐day reduction in average detection time, and 100% specificity.
Hydrogels That Actuate Selectively in Response to Organophosphates
Authors: Gkikas Manos , Avery Reginald K. , Mills Carolyn E. , Nagarajan Ramanathan , Wilusz Eugene , Olsen Bradley D.
Published: December 2016

Nerve agents and pesticides represent a category of extremely toxic organophosphate compounds (OPs) that irreversibly inhibit the enzyme acetylcholinesterase, disturbing transmission in the synaptic clefts of muscles and nerves. Protection from these compounds necessitates the development of breathable barriers that can selectively block the passage of OPs. Hydrogels prepared from acrylamide, N,N′‐methylenebis(acrylamide), N,N′‐bis(acryloyl)cystamine, and hydrophilic pendant oximes are herein prepared, showing the ability to decontaminate and respond to the presence of OPs through a change in swelling. The oxime‐based hydrogels show selective response only to malaoxon when tested against chemicals that are found in sweat as well as other reactive chemicals that are found in the environment. Pore sealing is demonstrated in perforated equilibrated gels within 3–4 h after the addition of malaoxon, showing actuation of the gel in response to organophosphates. This strategy demonstrates the ability to couple oxime‐based decontamination and disulfide chemistry to produce hydrogels that can decontaminate organophosphate compounds, sense the decontamination product, and transduce this sensing response into actuation of the gel, which can be used to close pores in gel sheets or between fibers in a protective fabric coating.
Fluorescent Block Copolymer‐MoS2 Nanocomposites for Real‐Time Photothermal Heating and Imaging
Authors: Park Chan Ho , Yun Hongseok , Yang Hyunseung , Lee Junhyuk , Kim Bumjoon J.
Published: December 2016

Novel self‐monitoring photothermal (PT) agents are developed using optothermally responsive block copolymer‐MoS2 composites (BCP‐MoS2), which enable simultaneous PT heating and imaging of temperature profiles. In particular, upon near‐infrared light exposure, PT energy from MoS2 successfully increases local temperature and induces thermally activated conformational transitions of the BCP on MoS2. This leads to fluorescent signal changes caused by distance‐dependent Förster resonance energy transfer between the BCP and MoS2. Importantly, it is demonstrated that the use of BCP‐MoS2 for PT heating and optical mapping is fully reversible with excellent stability. The detailed mechanism of the responsive behavior of BCP‐MoS2 is elucidated by measurements of time‐resolved fluorescence and dynamic light scattering. In addition, the BCP‐MoS2 system is integrated into organogel matrices to demonstrate its potential as aportable, self‐monitoring PT system suitable for biological and environmental applications.
Activating Basal Planes and S‐Terminated Edges of MoS2 toward More Efficient Hydrogen Evolution
Authors: Huang Xiaolei , Leng Mei , Xiao Wen , Li Meng , Ding Jun , Tan Teck Leong , Lee Wee Siang Vincent , Xue Junmin
Published: December 2016

Molybdenum disulfide (MoS2) has been considered as a promising alternative to platinum (Pt)‐based catalyst for hydrogen evolution reaction (HER) due to its low cost and high catalytic activity. However, stable 2H phase of MoS2 (2H‐MoS2) exhibits low catalytic activity in HER due to the inert basal plane and S‐edge. Thus, to exploit the basal plane and S‐edge for additional electrocatalytic activity, a facile strategy is developed to prepare P‐doped 2H‐MoS2 film on conductive substrate via low‐temperature heat treatment. Due to the inherent difficulty of P‐doping into MoS2 crystal structure, oxygen (O)‐doping is utilized to aid the P‐doping process, as supported by the first‐principles calculations. Interestingly, P‐doping could dramatically reduce Mo valence charge, which results in the functionalization of the inert MoS2 basal plane and S‐edge. In agreement with simulation results, P‐doped 2H‐MoS2 electrode exhibits enhanced catalytic performance in H2 generation with low onset potential (130 mV) and small Tafel slope of 49 mV dec−1. The enhanced catalytic performance arises from the synergistic effect of the activated basal plane, S‐edge, and Mo‐edge sites, leading to favorable hydrogen adsorption energies. Most importantly, improved cyclic stability is achieved, which reveals chemically inert properties of P‐doped 2H‐MoS2 in acidic electrolyte.
Synthetic vs Natural: Diatoms Bioderived Porous Materials for the Next Generation of Healthcare Nanodevices
Authors: Rea Ilaria , Terracciano Monica , De Stefano Luca
Published: December 2016

Nanostructured porous materials promise a next generation of innovative devices for healthcare and biomedical applications. The fabrication of such materials generally requires complex synthesis procedures, not always available in laboratories or sustainable in industries, and has adverse environmental impact. Nanosized porous materials can also be obtained from natural resources, which are an attractive alternative approach to man‐made fabrication. Biogenic nanoporous silica from diatoms, and diatomaceous earths, constitutes largely available, low‐cost reservoir of mesoporous nanodevices that can be engineered for theranostic applications, ranging from subcellular imaging to drug delivery. In this progress report, main experiences on nature‐derived nanoparticles with healthcare and biomedical functionalities are reviewed and critically analyzed in search of a new collection of biocompatible porous nanomaterials.
Materials with Giant Mechanocaloric Effects: Cooling by Strength
Authors: Mañosa Lluís , Planes Antoni
Published: December 2016

The search for materials with large caloric effects has become a major challenge in material science due to their potential in developing near room‐temperature solid‐state cooling devices, which are both efficient and clean, and that can successfully replace present refrigeration technologies. There are three main families of caloric materials: magnetocaloric, electrocaloric, and mechanocaloric. While magnetocaloric and electrocaloric materials have been studied intensively in the last few decades, mechanocaloric materials are only very recently receiving a great deal of attention. The mechanocaloric effect refers to the reversible thermal response of a solid when subjected to an external mechanical field, and encompasses both the elastocaloric effect, corresponding to a uniaxial force, and the barocaloric effect, which corresponds to the response to hydrostatic pressure. Here, the state of the art in giant mechanocaloric effects is reviewed and a critical analysis of the thermodynamic quantities that characterize the major families of barocaloric and elastocaloric materials is provided. Finally perspectives for further development in this area are given.
3D In Situ ToF‐SIMS Imaging of Perovskite Films under Controlled Humidity Environmental Conditions
Authors: Lin Wei‐Chun , Chang Hsun‐Yun , Abbasi Kevin , Shyue Jing‐Jong , Burda Clemens
Published: December 2016

Since CH3NH3PbI3 perovskites are discovered as a viable active material for next‐generation photovoltaic devices, their instability in humid environments is a constant challenge. Therefore, understanding the exact spatially resolved degradation process is a crucial need before being able to improve the stability and durability of these exceptional materials. In this work, it is demonstrated that the CH3NH3PbI3 perovskite will eventually degrade irreversibly at high humidity through a slow leaching and vaporization process of CH3NH2. Deuterium oxide (D2O) is used as a humidity source instead of H2O to distinguish the exogenous water diffusing into the perovskite from moisture embedded during sample fabrication. The degradation process of CH3NH3PbI3 perovskite is examined in situ by using time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) and an argon ion cluster beam for layer‐by‐layer in situ sputtering and then compared to their corresponding solar cell performances. 3D images are constructed from the layer‐by‐layer spatially resolved elemental distribution analysis and the D2O moisture penetration through the sample. It is observed that the H/D exchange on the organic methylammonium ion is the first indication for moisture uptake in a given volume element. The intermediate products of interaction with moisture are also analyzed by ToF‐SIMS and X‐ray photoelectron spectroscopy. The initial products of this deuterium exchange reaction are CH3NH2D, CH3NHD2, and CH3ND3. In the following, the D2O molecule stepwise replaces the methylammonium, which leads to evaporation of the organic molecules and eventually to erosion of the perovskite along with drastic changes in morphology, crystallography, and photovoltaic performance.
Water‐Based Assembly of Polymer–Metal Organic Framework (MOF) Functional Coatings
Authors: De Souvik , Nandasiri Manjula I. , Schaef Herbert T. , McGrail Benard Peter , Nune Satish K. , Lutkenhaus Jodie L.
Published: December 2016

Metal organic frameworks (MOFs) have gained attention for their porosity, size selectivity, and structural diversity. There is a need for MOF‐based coatings, particularly in applications such as separations, electronics, and energy; yet forming thin, functional, conformal coatings is prohibitive because MOFs exist as a powder. Layer‐by‐layer assembly, a versatile thin film coating approach, offers a unique solution to this problem, but this approach requires MOFs that are water‐dispersible and bear a surface charge. Here, these issues are addressed by examining water‐based dispersions of MIL‐101(Cr) that facilitate the formation of robust polymer–MOF hybrid coatings. Specifically, the substrate to be coated is alternately exposed to an aqueous solution of poly(styrene sulfonate) and nano MIL‐101(Cr) dispersion, yielding linear film growth and coatings with a MOF content as high as 77 wt%. This approach is surface‐agnostic, in which the coating is successfully applied to silicon, glass, flexible plastic, and even cotton fabric, conformally coating individual fibers. By contrast, prior attempts at forming MOF‐coatings are severely limited to a handful of surfaces, require harsh chemical treatment, and are not conformal. The approach presented here unambiguously confirms that MOFs can be conformally coated onto complex and unusual surfaces, opening the door for a wide variety of applications.
Boron Nitride Quantum Dots with Solvent‐Regulated Blue/Green Photoluminescence and Electrochemiluminescent Behavior for Versatile Applications
Authors: Liu Mengli , Xu Yuanhong , Wang Yao , Chen Xu , Ji Xuqiang , Niu Fushuang , Song Zhongqian , Liu Jingquan
Published: December 2016

Exploration of novel optical features, generation mechanisms, and versatile applicability of boron nitride quantum dots (BNQDs) is still in nascent stage. Herein, BNQDs are prepared using liquid exfoliation–solvothermal treatment of bulk BN in three different solvents. The photoluminescence of BNQDs is blue in ethanol (or N,N‐dimethylformamide (DMF)) and green in N‐methyl‐2‐pyrrolidone (NMP) under the same UV‐irradiation, respectively. The quantum yields (QYs) and average lateral sizes of the BNQDs are 12.6% and 4.1 ± 0.2 nm, 16.4%, and 2.8 ± 0.3 nm, as well as 21.3% and 2.0 ± 0.2 nm in solvents of ethanol, DMF, NMP, respectively. The distinct sizes, QYs, and optical properties of the BNQDs are found to depend on the polarity of these solvents. Different BNQDs can be chosen on‐demand for versatile applications. For example, the green BNQDs are much more competitive than the blue ones when serving as a fluorescent sensing platform for label‐free specific detection of ferric ions, while the blue ones in ethanol are much handier for cell imaging and fiber staining. More importantly, electrochemiluminescence (ECL) property of the BNQDs is observed and studied for the first time using cysteine as a co‐reactant. The possible ECL response mechanism of the BNQDs system is also proposed.
Polarization‐Induced Chirality in Metamaterials via Optomechanical Interaction
Authors: Liu Mingkai , Powell David A. , Guo Rui , Shadrivov Ilya V. , Kivshar Yuri S.
Published: December 2016

A novel type of metamaterial is introduced, where the structural symmetry can be controlled by optical forces. Since symmetry sets fundamental bounds on the optical response, symmetry breaking changes the properties of metamaterials qualitatively over the entire resonant frequency band. This is achieved by a polarized pump beam, exerting optical forces which are not constrained by the structural symmetry. This new concept is illustrated for a metasurface composed of zig‐zag chains of dipole meta‐atoms, in which a highly asymmetric optical force exists for an appropriate incident polarization. The effect is employed to transform a planar achiral metasurface into a stereoscopic chiral structure. Importantly, the handedness of the induced chirality can be actively switched by changing the incident polarization. The proposed concept can be employed to achieve dynamic spatial control of metamaterials and metasurfaces at infrared and optical frequencies with subwavelength resolution.
Significant Enhancement of Blue OLED Performances through Molecular Engineering of Pyrimidine‐Based Emitter
Authors: Nakao Kohei , Sasabe Hisahiro , Komatsu Ryutaro , Hayasaka Yuya , Ohsawa Tatsuya , Kido Junji
Published: December 2016

Although pyrimidine‐based emitters are one of the most promising classes of compounds, a structure–property relationship for an effective molecular design strategy has not yet been elucidated. In this study, the authors develop three types of blue pyrimidine emitters for high‐performance thermally activated delayed fluorescence (TADF) organic light‐emitting devices (OLEDs). 2,4,6‐triphenylpyrimidine is used as an acceptor, and tri‐ or penta‐substituted acridine as a donor unit for the blue TADF emitters. The authors investigate the effects of the nitrogen position on the photophysical properties and OLED performances, and develop a blue device with a high external quantum efficiency close to 25%. The device performances are among the best so far for blue TADF OLEDs.
One‐Dimensional Earth‐Abundant Nanomaterials for Water‐Splitting Electrocatalysts
Authors: Li Jun , Zheng Gengfeng
Published: December 2016

Hydrogen fuel acquisition based on electrochemical or photoelectrochemical water splitting represents one of the most promising means for the fast increase of global energy need, capable of offering a clean and sustainable energy resource with zero carbon footprints in the environment. The key to the success of this goal is the realization of robust earth‐abundant materials and cost‐effective reaction processes that can catalyze both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), with high efficiency and stability. In the past decade, one‐dimensional (1D) nanomaterials and nanostructures have been substantially investigated for their potential in serving as these electrocatalysts for reducing overpotentials and increasing catalytic activity, due to their high electrochemically active surface area, fast charge transport, efficient mass transport of reactant species, and effective release of gas produced. In this review, we summarize the recent progress in developing new 1D nanomaterials as catalysts for HER, OER, as well as bifunctional electrocatalysts for both half reactions. Different categories of earth‐abundant materials including metal‐based and metal‐free catalysts are introduced, with their representative results presented. The challenges and perspectives in this field are also discussed.
Electron‐Transfer Reactions Triggered by Uncharged or Cationic Photosensitizer: Methodology for Generation of o‐Quinodimethane and Analysis of Back Electron‐Transfer Process
Authors: Matsui Yasunori , Ikeda Teruyo , Takahashi Yasutake , Kamata Masaki , Akagi Megumi , Ohya Yukako , Fujino Ryota , Namai Hayato , Ohta Eisuke , Ogaki Takuya , Miyashi Tsutomu , Tero‐Kubota Shozo , Mizuno Kazuhiko , Ikeda Hiroshi
Published: December 2016

Photoinduced electron transfer (PET) followed by back electron transfer (BET) reactions of 1,2‐bis(α‐styryl)benzenes 1, generates o‐quinodimethane derivative 2 via the corresponding radical cation 2⋅+. This process serves as a facile method to form o‐quinodimethane intermediates. The intermediacy of 2⋅+ and 2 were confirmed by using various spectroscopic methods and trapping reactions with 3O2 and dienophiles. Kinetic analysis using nanosecond time‐resolved absorption showed that 2⋅+ was transformed to 2 via a BET process, in which the decay of 2⋅+ and rise of 2 have almost the same rate constants of kDECAY=5.6×105 s−1 and kRISE=5.9×105 s−1, respectively. The net BET rate constant evaluated by using Marcus theory is much faster than these experimental values, owing to the reduction based on diffusion.
Out‐of‐time‐order correlations in many‐body localized and thermal phases
Authors: Chen Xiao , Zhou Tianci , Huse David A. , Fradkin Eduardo
Published: December 2016

We use the out‐of‐time‐order (OTO) correlators to study the slow dynamics in the many‐body localized (MBL) phase. We investigate OTO correlators in the effective (“l‐bit”) model of the MBL phase, and show that their amplitudes after disorder averaging approach their long‐time limits as power‐laws of time. This power‐law dynamics is due to dephasing caused by interactions between the localized operators that fall off exponentially with distance. The long‐time limits of the OTO correlators are determined by the overlaps of the local operators with the conserved l‐bits. We demonstrate numerically our results in the effective model and three other more “realistic” spin chain models. Furthermore, we extend our calculations to the thermal phase and find that for a time‐independent Hamiltonian, the OTO correlators also appear to vanish as a power law at long time, perhaps due to coupling to conserved densities. In contrast, we find that in the thermal phase of a Floquet spin model with no conserved densities the OTO correlator decays exponentially at long times.

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Elucidation of the Dexter‐Type Energy Transfer in DNA by Thymine–Thymine Dimer Formation Using Photosensitizers as Artificial Nucleosides
Authors: Antusch Linda , Gaß Nadine , Wagenknecht Hans‐Achim
Published: December 2016

C‐nucleosides of 4‐methylbenzophenone, 4‐methoxybenzophenone, and 2′‐methoxyacetophenone were synthetically incorporated as internal photosensitizers into DNA double strands. This structurally new approach makes it possible to study the distance dependence of thymidine dimer formation because the site of photoinduced triplet energy transfer injection is clearly defined. The counterstrands to these modified strands lacked the phosphodiester bond between the two adjacent thymidines that are supposed to react with each other. Their dimerization could be evidenced by gel electrophoresis because the covalent connection by cyclobutane formation between the two thymidines changes the mobility. A shallow exponential distance dependence for the formation of thymidine dimers over up to 10 A‐T base pairs was observed that agrees with a Dexter‐type triplet–triplet energy transfer mechanism. Concomitantly, a significant amount of photoinduced DNA crosslinking was observed.
Titanium complexes bearing amine bis(phenolate) ligands: Synthesis, structure and catalysis in ring‐opening polymerization of lactide
Authors: Wang Baolong , Zhang Jianing , Zhao Huanqin , Huang He , Zheng Junpei , Wang Liying , Sun Junmin , Zhang Yongfeng , Cao Zhenzhu
Published: December 2016

Monomeric bis(isopropoxy) titanium complexes LTi(OiPr)2 (L = ─OC6H2–4‐R1–6‐R2–2‐CH2N[(CH2)2N(R3)2]CH2–4‐R4–6‐R5‐C6H2O─, R1 = R2 = tBu, R3 = Et, R4 = R5 = Cl, (L1)Ti(OiPr)2; R1 = R2 = Me, R3 = Et, R4 = R5 = Me, (L2)Ti(OiPr)2; R1 = R2 = tBu, R3 = Et, R4 = OMe, R5 = tBu, (L3)Ti(OiPr)2; R1 = R4 = OMe, R3 = Et, R2 = R5 = tBu, (L4)Ti(OiPr)2; R1 = R2 = tBu, R3 = Me, R4 = OMe, R5 = tBu, (L5)Ti(OiPr)2) supported by amine bis(phenolate) ligands were synthesized and characterized using NMR spectroscopy and elemental analysis. The solid‐state structure of (L3)Ti(OiPr)2 was determined using single‐crystal X‐ray diffraction. (L1–5)Ti(OiPr)2 were all found to initiate the ring‐opening polymerization of l‐lactide and rac‐lactide in a controlled manner at 110–160°C. As shown by kinetic studies, (L1)Ti(OiPr)2 polymerized l‐lactide faster than did (L2–5)Ti(OiPr)2. In addition, good number‐average molecular weight and narrow polydispersity index (1.00–1.71) of polymers were also obtained. The microstructure of the polymers and a possible mechanism of coordination–insertion of polymerization were evidenced by MALDI‐TOF and 1H NMR spectra of the polylactides.
Use of the Monte Carlo Method for OECD Principles‐Guided QSAR Modeling of SIRT1 Inhibitors
Authors: Kumar Ashwani , Chauhan Shilpi
Published: December 2016

SIRT1 inhibitors offer therapeutic potential for the treatment of a number of diseases including cancer and human immunodeficiency virus infection. A diverse series of 45 compounds with reported SIRT1 inhibitory activity has been employed for the development of quantitative structure–activity relationship (QSAR) models using the Monte Carlo optimization method. This method makes use of simplified molecular input line entry system notation of the molecular structure. The QSAR models were built up according to OECD principles. Three subsets of three splits were examined and validated by respective external sets. All the three described models have good statistical quality. The best model has the following statistical characteristics: R2 = 0.8350, Q2test = 0.7491 for the test set and R2 = 0.9655, Q2ext = 0.9261 for the validation set. In the mechanistic interpretation, structural attributes responsible for the endpoint increase and decrease are defined. Further, the design of some prospective SIRT1 inhibitors is also presented on the basis of these structural attributes.
Inhibitory effect of ezetimibe can be prevented by an administration interval of 4 h between α‐tocopherol and ezetimibe
Authors: Nashimoto Shunsuke , Sato Yuki , Takekuma Yoh , Sugawara Mitsuru
Published: December 2016

Tocopherol is used not only as an ethical drug but also as a supplement. In 2008, it was reported that α‐tocopherol is partly transported via an intestinal cholesterol transporter, Niemann‐Pick C1‐Like 1 (NPC1L1). Ezetimibe, a selective inhibitor of NPC1L1, is administered for a long time to inhibit cholesterol absorption and there is a possibility that the absorption of α‐tocopherol is also inhibited by ezetimibe. This study investigated the influence of ezetimibe on the absorption of α‐tocopherol with single administration and long‐term administration. An approach to avoid its undesirable consequence was also examined. α‐Tocopherol (10 mg/kg) and ezetimibe (0.1 mg/kg) were administered to rats, and the plasma concentration profiles of α‐tocopherol and tissue concentrations were investigated. The plasma concentration of α‐tocopherol was decreased by the combination use of ezetimibe in the case of concurrent single administration. On the other hand, inhibition of the absorption of α‐tocopherol was prevented by an administration interval of 4 h. In a group of rats administered for 2 months with a 4 h interval, not only the plasma concentration but also the liver concentration was increased compared with those in a group with concurrent combination intake of α‐tocopherol and ezetimibe. The absorption of α‐tocopherol was inhibited by ezetimibe. The inhibitory effect of ezetimibe can be prevented by an administration interval of 4 h, although ezetimibe is a medicine of enterohepatic circulation. Attention should be paid to the use of ezetimibe and components of NPC1L1 substrates such as α‐tocopherol. Copyright © 2016 John Wiley & Sons, Ltd.
Chromatin priming elements establish immunological memory in T cells without activating transcription
Authors: Bevington Sarah L. , Cauchy Pierre , Cockerill Peter N.
Published: December 2016

We have identified a simple epigenetic mechanism underlying the establishment and maintenance of immunological memory in T cells. By studying the transcriptional regulation of inducible genes we found that a single cycle of activation of inducible factors is sufficient to initiate stable binding of pre‐existing transcription factors to thousands of newly activated distal regulatory elements within inducible genes. These events lead to the creation of islands of active chromatin encompassing nearby enhancers, thereby supporting the accelerated activation of inducible genes, without changing steady state levels of transcription in memory T cells. These studies also highlighted the need for more sophisticated definitions of gene regulatory elements. The chromatin priming elements defined here are distinct from classical enhancers because they function by maintaining chromatin accessibility rather than directly activating transcription. We propose that these priming elements are members of a wider class of genomic elements that support correct developmentally regulated gene expression.
Synthesis and crystal structure of a highly selective colorimetric and fluorometric sensor for hydrogen sulfide
Authors: Ren Kui , Shang Xuefang , Chen Yanmei , Zhang Xueli , Fu Jiajia , Zhao Peipei , Zhang Jinlian
Published: December 2016

A novel Cu(II) complex chemosensor for hydrogen sulfide with azo as the colorimetric group has been synthesized. The complex and ligand crystals were obtained and the molecular structures were characterized by X‐ray diffraction and Electrospray ionization High resolution mass spectrometer (ESI‐HRMS). The photophysical and recognition properties were examined. The complex can recognize S2−, with an obvious color change from yellow to red based on a copper ion complex displacement mechanism. By contrast, no obvious changes were observed in the presence of other anions (AcO−, H2PO4−, F−, Cl−, Br− and I−). We present a simple, easily prepared, yet efficient, inorganic reaction‐based sensor for the detection of S2−. The complex should have many chemical and analytical applications in the sensing of hydrogen sulfide.
Sensitivity Control of Label‐free DNA Hybridization Detection Based on Poly(thionine)‐Modified Glassy Carbon and Gold Electrodes
Authors: Rahman Md. Mahbubur , Kim Young Jun , Lee Jae‐Joon
Published: December 2016

Poly(thionine) (PTH)‐modified glassy carbon (PTH‐S/GCE and PTH‐D/GCE) and gold (PTH‐S/Au) electrodes were prepared for the label‐free detection of DNA hybridizations and their performances in terms of sensitivity and selectivity were compared. Single‐strand probe DNA (pDNA) was immobilized on the PTH films via covalent bonding between the amine (−NH2) group of PTH and the phosphate (PO43−) group at the 5' end of the pDNA. The PTH oxidation current was decreased because of the increase in the stiffness of PTH films. The current was further decreased after the duplex was formed by the hybridization of the target complementary DNA (cDNA). The pDNA/PTH‐S/GCE, pDNA/PTH‐D/GCE, and pDNA/PTH‐S/Au sensors showed excellent sensitivities of ca. 2.1, 55, and 1.9 μA/cm2/nM, respectively, and the detection limits (S/N = 3) were ca. 40.6, 1.5, and 45 pM, respectively, for the hybridization of target cDNA.
Pinecone of Pinus koraiensis Inducing Apoptosis in Human Lung Cancer Cells by Activating Caspase‐3 and its Chemical Constituents
Authors: Lee Tae Kyoung , Roh Hyun‐Soo , Yu Jae Sik , Baek Jiwon , Lee Seul , Ra Moonjin , Kim Sun Young , Baek Kwan‐Hyuck , Kim Ki Hyun
Published: December 2016

Pinecones from Pinus koraiensisSiebold & Zucc. (Pinaceae), which have historically been treated as an undesired waste by‐product in the processing of seeds, have recently been shown to contain ingredients with potent biological activities, such as polyphenols exhibiting antitumor activity. With this study, we seek to broaden our understanding of antitumor compounds contained in these pinecones beyond just polyphenols. We found that the water extract of P. koraiensis pinecones exhibits significant cytotoxic activity, with IC50 values ranging from 0.62 to 1.73 mg/ml in four human lung cancer cell lines, A549, H1264, H1299, and Calu‐6, irrespective of their p53 status. We also demonstrate that pinecone water extract induces apoptosis associated with caspase‐3 activation in the same cancer cell lines. Chemical investigation of the pinecone water extract revealed eight main components (1 – 8), and their structures were identified as dehydroabietic acid (1), 15‐hydroxy‐7‐oxodehydroabietic acid (2), 7β,15‐dihydroxydehydroabietic acid (3), β‐d‐glucopyranosyl labda‐8(17,13)‐diene‐(15,16)‐lactone‐19‐oate (4), 7α,15‐dihydroxydehydroabietic acid (5), (+)‐(1S,2S,4R)‐limonene‐1,2‐diol (6), sobrerol (7), and 4‐hydroxybenzoic acid (8). These findings suggest a novel biological application of P. koraiensis pinecones in combatting human lung cancer, and further identify the major compounds that could contribute to this anticancer activity.
Graphene/V2O5Cryogel Composite As a High‐Energy Cathode Material For Lithium‐Ion Batteries
Authors: Maroni Fabio , Birrozzi Agnese , Carbonari Gilberto , Croce Fausto , Tossici Roberto , Passerini Stefano , Nobili Francesco
Published: December 2016

This work reports the synthesis and characterization of an amorphous V2O5cryogel/graphene nanosheet composite as a high‐performance cathode material. The optimization of electrode processing is conducted by using the environmentally friendly poly acrylic acid as the binder and ethanol as the solvent. The nanocomposite material shows outstanding capacity values, exceeding 300 mAhg−1reversible capacity upon galvanostatic cycling tests at 280 mAg−1(C/2 charge/discharge rate), and more than 100 mAhg−1at 5600 mAg−1(10C). A subsequent electrochemical impedance spectroscopy study gives useful insights into the cathode/electrolyte interface.
Antianginal medications and long‐term outcomes after elective catheterization in patients with coronary artery disease
Authors: Shen Lan , Vavalle John P. , Broderick Samuel , Shaw Linda K. , Douglas Pamela S.
Published: December 2016

Background

Antianginal medications are a class I recommendation by the American College of Cardiology/American Heart Association guidelines for stable ischemic heart disease. We sought to better understand guidance in drug selection and real‐life outcomes of antianginal medication use.

Hypothesis

In patients with stable ischemic heart disease, antianginal medications lower mortality.

Methods

We evaluated 5608 patients with obstructive coronary artery disease (CAD) on elective cardiac catheterization with follow‐up through self‐administered questionnaires. Patients were classified as being prescribed a particular medication if they received that medication at index catheterization, or within 3 months postcatheterization. The association between antianginal medication use and outcomes was evaluated using Cox proportional hazards models.

Results

Compared with the 11% not prescribed any antianginal medication, patients prescribed antianginal medication were more likely to be older and female; have a history of hypertension, diabetes mellitus, peripheral vascular disease, or 3‐vessel CAD; have lower adjusted mortality (hazard ratio [HR]: 0.75, 95% confidence interval [CI]: 0.63‐0.89); and experience mortality or myocardial infarction (HR: 0.83, 95% CI: 0.71‐0.98). Compared with patients not taking β‐blockers (17%), those taking β‐blockers had a lower risk of mortality (HR: 0.76, 95% CI: 0.66‐0.88). Patients prescribed calcium channel blockers or long‐acting nitrates had a higher risk of mortality compared with nonusers (HR: 1.16, 95% CI: 1.04‐1.29; HR: 1.20, 95% CI: 1.08‐1.34; respectively).

Conclusions

Antianginal medications are not universally prescribed among obstructive CAD patients; nonuse was associated with higher mortality. For CAD patients with or without prior myocardial infarction, β‐blockers were associated with improved long‐term survival.
Patterns and predictors of lipid‐lowering therapy in patients with atherosclerotic cardiovascular disease and/or diabetes mellitus in 2014: Insights from a large US managed‐care population
Authors: Steen Dylan L. , Khan Irfan , Becker Laura , Foody JoAnne M. , Gorcyca Katherine , Sanchez Robert J. , Giugliano Robert P.
Published: December 2016

Background

Lowering low‐density lipoprotein cholesterol with statins reduces risk of cardiovascular events. We examined patterns and predictors of filled prescriptions for lipid‐lowering therapy (LLT) in subgroups of patients with atherosclerotic cardiovascular disease (ASCVD) and/or diabetes mellitus (DM).

Hypothesis

Statin treatment remains underutilized across subgroups of high CV risk patients.

Methods

Patients in the Optum Research Database with these criteria were included: age ≥20 years, 2 years continuous enrollment, and ASCVD and/or DM. Patients were hierarchically classified by the presence of recent acute coronary syndrome, other coronary heart disease, ischemic stroke, peripheral arterial disease (PAD), or only DM. Predictors of filled LLT regimens were examined using multinomial logistic regression.

Results

A total of 1 055 932 individuals met all inclusion criteria. Evidence by point‐in‐time analysis of filled (not only written) statin prescriptions was 45% for the overall cohort. By subgroups, this was 62%, 52%, 43%, 36%, and 40% for recent acute coronary syndrome, other coronary heart disease, ischemic stroke, PAD, and only DM, respectively. Predictors of higher rates of any statin regimen included age 50 to 69 years, male sex, absence of comorbidities, and filled prescriptions of other standard‐of‐care therapies.

Conclusions

In 2014, only 49% of patients with ASCVD and 40% with only DM had evidence for a filled statin prescription. Those with indications of ischemic stroke, PAD, and DM were less likely to receive statins than those with coronary conditions. Other characteristics such as advanced age, female sex, and noncardiac conditions predicted less statin utilization, thereby representing good targets for quality improvement.
Towards a molecular architecture of the centrosome in Toxoplasma gondii
Authors: Morlon‐Guyot Juliette , Francia Maria E. , Dubremetz Jean‐François , Daher Wassim
Published: December 2016

Toxoplasma gondii is the causative agent of toxoplasmosis. The pathogenicity of this unicellular parasite is tightly linked to its ability to efficiently proliferate within its host. Tachyzoites, the fast dividing form of the parasite, divide by endodyogeny. This process involves a single round of DNA replication, closed nuclear mitosis, and assembly of two daughter cells within a mother. The successful completion of endodyogeny relies on the temporal and spatial coordination of a plethora of simultaneous events. It has been shown that the Toxoplasma centrosome serves as signaling hub which nucleates spindle microtubules during mitosis and organizes the scaffolding of daughter cells components during cytokinesis. In addition, the centrosome is essential for inheriting both the apicoplast (a chloroplast‐like organelle) and the Golgi apparatus. A growing body of evidence supports the notion that the T. gondii centrosome diverges in protein composition, structure and organization from its counterparts in higher eukaryotes making it an attractive source of potentially druggable targets. Here, we summarize the current knowledge on T. gondii centrosomal proteins and extend the putative centrosomal protein repertoire by in silico identification of mammalian centrosomal protein orthologs. We propose a working model for the organization and architecture of the centrosome in Toxoplasma parasites. Experimental validation of our proposed model will uncover how each predicted protein translates into the biology of centrosome, cytokinesis, karyokinesis, and organelle inheritance in Toxoplasma parasites.
Pioglitazone together with imatinib in chronic myeloid leukemia: A proof of concept study
Authors: Rousselot Philippe , Prost Stéphane , Guilhot Joelle , Roy Lydia , Etienne Gabriel , Legros Laurence , Charbonnier Aude , Coiteux Valérie , Cony‐Makhoul Pascale , Huguet Francoise , Cayssials Emilie , Cayuela Jean‐Michel , Relouzat Francis , Delord Marc , Bruzzoni‐Giovanelli Heriberto , Morisset Laure , Mahon François‐Xavier , Guilhot François , Leboulch Philippe ,   on behalf of the French CML Group
Published: December 2016

BACKGROUND

We recently reported that peroxisome proliferator‐activated receptor γ agonists target chronic myeloid leukemia (CML) quiescent stem cells in vitro by decreasing transcription of STAT5. Here in the ACTIM phase 2 clinical trial, we asked whether pioglitazone add‐on therapy to imatinib would impact CML residual disease, as assessed by BCR‐ABL1 transcript quantification.

METHODS

CML patients were eligible if treated with imatinib for at least 2 years at a stable daily dose, having yielded major molecular response (MMR) but not having achieved molecular response 4.5 (MR4.5) defined by BCR‐ABL1/ABL1IS RNA levels ≤ 0.0032%. After inclusion, patients started pioglitazone at a dosage of 30 to 45 mg/day in addition to imatinib. The primary objective was to evaluate the cumulative incidence of patients having progressed from MMR to MR4.5 over 12 months.

RESULTS

Twenty‐four patients were included (age range, 24‐79 years). No pharmacological interaction was observed between the drugs. The main adverse events were weight gain in 12 patients and a mean decrease of 0.4 g/dL in hemoglobin concentration. The cumulative incidence of MR4.5 was 56% (95% confidence interval, 37%‐76%) by 12 months, despite a wide range of therapy duration (1.9‐15.5 months), and 88% of 17 evaluable patients who were still on imatinib reached MR4.5 by 48 months. The cumulative incidence of MMR to MR4.5 spontaneous conversions over 12 months was estimated to be 23% with imatinib alone in a parallel cohort of patients.

CONCLUSION

Pioglitazone in combination with imatinib was well tolerated and yielded a favorable 56% rate. These results provide a proof of concept needing confirmation within a randomized clinical trial (EudraCT 2009‐011675‐79). Cancer 2017;123:1791–1799. © 2016 The Authors. Cancer published by Wiley Periodicals, Inc. on behalf of American Cancer Society. This is an open access article under the terms of the Creative Commons Attribution NonCommercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.
Factors predicting skeletal‐related events in patients with bone metastatic castration‐resistant prostate cancer
Authors: Klaassen Zachary , Howard Lauren E. , de Hoedt Amanda , Amling Christopher L. , Aronson William J. , Cooperberg Matthew R. , Kane Christopher J. , Terris Martha K. , Freedland Stephen J.
Published: December 2016

BACKGROUND

Skeletal‐related events (SREs) are common complications of bone metastatic castration‐resistant prostate cancer (mCRPC). To the authors' knowledge, there are limited data regarding which factors predict SREs. The authors identified risk factors for SREs in men with bone mCRPC using characteristics commonly available in the medical record.

METHODS

Data from 454 patients with nonmetastatic CRPC were identified from 2 Veteran Affairs Medical Centers from 2000 through 2013. Among these men, 233 (51%) developed bone metastases during follow‐up and represented the study cohort. First occurrence of an SRE was abstracted from the medical records. A stepwise multivariable Cox model was used to select the strongest predictors of time to SRE.

RESULTS

The median age of the patients at the time of diagnosis of bone mCRPC was 75 years (interquartile range, 68‐81 years), and there were 153 nonblack patients (66%). During follow‐up (median, 7.8 months [interquartile range, 2.9‐18.3 months]), 88 patients (38%) had an SRE. On univariable analysis, more recent year of metastasis (hazard ratio [HR], 0.91), prostate‐specific antigen doubling time of ≥9 months versus <9 months (HR, 0.50), and bone pain (HR, 3.34) were all found to be associated with SRE risk. On multivariable analysis, year of metastasis (HR, 0.93), biopsy Gleason score of 7 versus ≤6 (HR, 1.74), radiotherapy as the primary localized treatment versus none (HR, 2.33), and bone pain (HR, 3.64) were associated with SRE risk. The area under the curve for a multivariable model based upon these risk factors was 0.744.

CONCLUSIONS

The authors identified several significant predictors of SREs among men with mCRPC. In particular, men with bone pain are at high risk of an SRE. If confirmed, future trials should focus on prolonging life and reducing SRE risk in patients with mCRPC with bone pain. Cancer 2017;123:1528–1535. © 2017 American Cancer Society.
Crystal Engineering of a Two‐Dimensional Lead‐Free Perovskite with Functional Organic Cations by Second‐Sphere Coordination
Authors: Cortecchia Daniele , Soci Cesare , Cametti Massimo , Petrozza Annamaria , Martí‐Rujas Javier
Published: December 2016

Invited for this month's cover are collaborators from the Istituto Italiano di Tecnologia, Nanyang Technological University, and Politecnico di Milano. The cover picture shows the 2 D layered nature of lead‐free perovskite having a functional organic cation. Read the full text of the article at 10.1002/cplu.201600477.
Effects of dams and geomorphic context on riparian forests of the Elwha River, Washington
Authors: Shafroth Patrick B. , Perry Laura G. , Rose Chanoane A. , Braatne Jeffrey H.
Published: December 2016

Understanding how dams affect the shifting habitat mosaic of river bottomlands is key for protecting the many ecological functions and related goods and services that riparian forests provide and for informing approaches to riparian ecosystem restoration. We examined the downstream effects of two large dams on patterns of forest composition, structure, and dynamics within different geomorphic contexts and compared them to upstream reference conditions along the Elwha River, Washington, USA. Patterns of riparian vegetation in river segments downstream of the dams were driven largely by channel and bottomland geomorphic responses to a dramatically reduced sediment supply. The river segment upstream of both dams was the most geomorphically dynamic, whereas the segment between the dams was the least dynamic due to substantial channel armoring, and the segment downstream of both dams was intermediate due to some local sediment supply. These geomorphic differences were linked to altered characteristics of the shifting habitat mosaic, including older forest age structure and fewer young Populus balsamifera subsp. trichocarpa stands in the relatively static segment between the dams compared to more extensive early‐successional forests (dominated by Alnus rubra and Salix spp.) and pioneer seedling recruitment upstream of the dams. Species composition of later‐successional forest communities varied among river segments as well, with greater Pseudotsuga menziesii and Tsuga heterophylla abundance upstream of both dams, Acer spp. abundance between the dams, and P. balsamifera subsp. trichocarpa and Thuja plicata abundance below both dams. Riparian forest responses to the recent removal of the two dams on the Elwha River will depend largely on channel and geomorphic adjustments to the release, transport, and deposition of the large volume of sediment formerly stored in the reservoirs, together with changes in large wood dynamics.
Evidence of Ligand Elasticity Occurring in Temperature‐, Light‐, and Pressure‐Induced Spin Crossover in 1D Coordination Polymers [Fe(3ditz)3]X2 (X = ClO4–, BF4–)
Authors: Weselski Marek , Książek Maria , Kusz Joachim , Białońska Agata , Paliwoda Damian , Hanfland Michael , Rudolf Mikołaj F. , Ciunik Zbigniew , Bronisz Robert
Published: December 2016

The complexes [M(3ditz)3]X2 [X = ClO4–, M = FeII (1), ZnII (2); X = BF4–, M = FeII (3), ZnII (4); 3ditz = 1,3‐di(tetrazol‐1‐yl)propane] were prepared. Disordering of the propylene chain in 3ditz is not affected by thermally induced spin crossover in 1 (T1/2↓ = 149 K, T1/2↑ = 150 K) and 3 (T1/2↓ = 158, T1/2↑ = 161 K). Low‐spin to high‐spin (LS→HS) switching triggered by laser‐light irradiation (520 nm) also does not influence the disordering of the ligand, leading to restoration of the initial HS phase. Pressurization of crystals results in a reduction of the Fe–N distances by about 0.19 Å, which indicates practically complete spin crossover (SCO). Also, in this case, the disordering of the ligand remains unchanged, although thermally and pressure‐induced SCO is accompanied by different changes of 3ditz molecules. Upon thermally induced SCO, perturbation resulting from the reduction of the Fe–N distances is accompanied by a slight elongation of the bridging ligand. In contrast, in the range 0.25–0.55 GPa, the pressure‐induced SCO is associated with shrinkage of the 3ditz molecule. Further elevation of pressure results in the inversion of structural changes and – similar to temperature‐induced spin crossover – a slight elongation of the ligand molecule takes place.