bluuebunny/crossref_metadata_2025 huggingface dataset:
The Synthesis and Characterization of Low-Cost Mesoporous Silica SiO2 from Local Pumice Rock
Authors: Mourhly Asmaa , Khachani Mariam , Hamidi Adnane El , Kacimi Mohammed , Halim Mohammed , Arsalane Said
Published: December 2015

Pumice is a porous volcanic rock containing a significant proportion of silica and alumina, and which has a low iron content. This natural, silica-rich material attracts wide attention because of its applications in adsorption processes, heterogeneous catalysis and nanotechnology. In this contribution, the white amorphous silica nanoparticles were extracted using an optimized alkaline treatment and an acid-precipitation process using grey pumice powder. The isolated amorphous silica SiO2 was characterized via X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Transmission Electronic Microscopy (TEM-EDS), N2 adsorption/desorption measurements and simultaneous Thermal Gravimetry/Differential Thermal Analysis (TG/DTA). The obtained results indicated that the nanosilica powder was successfully prepared via the acid-base route with a predominantly amorphous mesoporous structure having a high surface area (422m2/g). The TEM images exhibited relatively homogeneous dispersed nanosilica particles with small sizes about 5–15 nm, in accordance with XRD data. Thermal analysis of the silica powder under air atmosphere showed total mass losses of 6.5%, with endothermic effects corresponding to the removal of water molecules and the OH of silanol groups contained in the material. The investigations performed in this work have indicated that there is great scope for pumice exploitation as a raw material in the production of amorphous silica nanopowder on large scale.
Padrões de cobertura e uso da terra e sua influência na temperatura do ar em Rio Claro, SP
Authors: Armani Gustavo , Pereira Carolina Leocádio , Christofoletti Sérgio Ricardo
Published: December 2015

A modificação dos padrões de cobertura e uso da terra de um determinado lugar resulta em alterações na temperatura do ar. A partir desta premissa, este trabalho teve como objetivo analisar os gradientes de temperatura do ar entre cinco locais com diferentes padrões de cobertura e uso da terra, situados na Floresta Estadual Edmundo Navarro de Andrade (FEENA), Rio Claro (SP), e na área urbana do mesmo município. A temperatura do ar foi amostrada a cada 30 min por meio de registradores digitais autônomos, entre setembro de 2010 e agosto de 2011 em cinco padrões de ocupação da terra: 1) floresta de árvores nativas, 2) reflorestamento de eucalipto com sub-bosque de árvores nativas, 3) reflorestamento de eucalipto, 4) áreaurbana mista industrial, comercial e residencial, 5) área urbana residencial e comercial. Com os dados consistidos foram realizadas análises estatísticas de posição, dispersão, regressão/correlação e de séries temporais. Estes resultados foram organizados em tabelas, gráficos e diagramas temporo-espaciais para revelar a estrutura térmica e suas relações com os padrões de cobertura e uso da terra. Os padrões de ocupação com características urbanas apresentam maior diferença térmica em relação à floresta de árvores nativas, com desvios médios de 1,7 ºC no outono e primavera, e de 2,0 ºC no verão e inverno. A baixa variação altimétrica entre os postos da FEENA foi suficiente para mascarar em vários casos a influência das diferenças de vegetação, indicando que o efeito topoclimático se sobrepôs ao microclimático sob determinados tipos de tempo. Na área urbana o efeito topoclimático não foi suficientemente forte para atenuar a influência da mudança da cobertura e uso da terra e da energia dissipada pela dinâmica urbana. Essa influência pôde ser percebida pelas diferenças nas amplitudes térmicas, desvios em relação à temperatura da floresta de árvores nativas e pela modificação do ritmo térmico relacionada à dissipação de calor proveniente das atividades humanas (ciclo de sete dias).
Efeito da adição de lama vermelha nas propriedades eletroquímicas e de adsorção de um latossolo vermelho
Authors: Shinzato Mirian Chieko , Andrade Vanessa da Silva , Martins José Vinícius , Santos Marília Mayumi Augusto dos , Ribeiro Vinícius Tadeu , Carvalho Flávio Machado de Souza
Published: December 2015

Esse estudo teve como objetivo caracterizar o resíduo gerado na produção de alumina a partir do refino de bauxita (lama vermelha) e analisar o seu efeito nas propriedades eletroquímicas e de adsorção de um solo tropical (Latossolo Vermelho). A lama vermelha (LM) é um resíduo extremamente alcalino (pH em torno de 12) e rico em óxido/hidróxidos de ferro. Para estudar o efeito da lama vermelha e do carbonato de cálcio (CaCO3) - comumente utilizado como corretivo de pH - no solo, essas substâncias foram adicionadas em diferentes proporções em amostras de Latossolo Vermelho por 60 dias. Verificou-se que a adição de LM e de CaCO3 no solo elevaram opHeo ponto de carga zero (PCZ) do meio. No entanto, o valor de pH H2O do solo com LM superou ao do respectivo PCZ, possibilitando a ocorrência de dispersão das partículas do solo. Por outro lado, essa adição favoreceu a capacidade de troca catiônica do solo, como pôde ser observado nos testes de remoção de Pb2+ em solução. Verificou-se que a adição mínima de 0,5% de CaCO3 e de 10% de LM no solo aumenta a capacidade de retenção de Pb2+ de 37% para 100%. Essa mesma eficiência foi observada nos testes realizados somente com LM. Mesmo quando submetido a uma lixiviação ácida (solução pH 4,9) os solos incubados com 1% de CaCO3 e 1% de LM liberaram, respectivamente, 7,5% e 11% de Pb2+ adsorvido. Essa pequena taxa de lixiviação de Pb2+ se deve ao aumento do pH do meio, que favorece a adsorção de Pb2+ pelos oxi-hidróxidos de Al e Fe presentes no solo e na lama vermelha. Conclui-se, portanto, que a adição da lama vermelha pode alterar as condições eletroquímicas do solo, tornando as partículas argilosas e coloidais mais dispersas. No entanto, por elevar o pH do sistema e apresentar óxidos e hidróxidos de Fe e Al, esse material pode aumentar a retenção de metais pesados, como o Pb2+, no solo.
Quantifying Local Capillary Trapping Storage Capacity Using Geologic Criteria
Authors: Ren Bo , Bryant Steven L. , Lake Larry W.
Published: December 2015

The capillary pressure heterogeneity or local capillary trapping (LCT) determines the final distribution of CO2 in a saline aquifer during geological carbon sequestration. This locally trapped CO2 would not escape from the storage formation even if caprock integrity is compromised. It is, therefore, essential to predict the extent and storage capacity of LCT during the design of GCS projects.

This work employs a fast method based on the geologic criteria to estimate the structures of local capillary traps. The method assumes a critical capillary entry pressure (CCEP) and a geostatistical realization of the reservoir entry pressure field as inputs. It then finds the capillary barriers inside the domain and identifies the grid blocks beneath clusters of barriers. These grid blocks are the local capillary traps. The criterion for choosing the CCEP is important, and we suggest a criterion in this work.

We verify this algorithm by full-physics simulations in small 2D and 3D domains. We employ a large CO2 injection rate (Ngr~0.1) to fully sweep the storage domain, followed by a long period of buoyant flow to allow for complete charging of those local capillary traps. We test several CCEPs to determine the most physically representative value by comparing the LCT predicted from both methods. We find that a single value of CCEP enables the geologic algorithm to give a very good approximation of LCT distribution as well as LCT volume in uncorrelated and weakly correlated porous media. This means that the concept of CCEP is a reasonable approximation to the physical process by which traps are filled.

LCT can be described in terms of percolation theory. The percolation threshold arises from the competition between connected clusters of barriers and connected clusters of local traps. We show that both the percolated CCEP (corresponding to the percolation of LCT) and optimal CCEP (corresponding to the best match between geologic criteria and full-physics simulation) change with each other in a predictable linear way for the uncorrelated capillary entry pressure field.
Mismatched anti-predator behavioral responses in predator-naïve larval anurans
Authors: Albecker Molly , Vance-Chalcraft Heather D.
Published: December 2015

Organisms are adept at altering behaviors to balance the tradeoff between foraging and predation risk in spatially and temporally shifting predator environments. In order to optimize this tradeoff, prey need to be able to display an appropriate response based on degree of predation risk. To be most beneficial in the earliest life stages in which many prey are vulnerable to predation, innate anti-predator responses should scale to match the risk imposed by predators until learned anti-predator responses can occur. We conducted an experiment that examined whether tadpoles with no previous exposure to predators (i.e., predator-naive) exhibit innate antipredator behavioral responses (e.g., via refuge use and spatial avoidance) that match the actual risk posed by each predator. Using 7 treatments (6 free-roaming, lethal predators plus no-predator control), we determined the predation rates of each predator onLithobates sphenocephalustadpoles. We recorded behavioral observations on an additional 7 nonlethal treatments (6 caged predators plus no-predator control). Tadpoles exhibited innate responses to fish predators, but not non-fish predators, even though two non-fish predators (newt and crayfish) consumed the most tadpoles. Due to a mismatch between innate response and predator consumption, tadpoles may be vulnerable to greater rates of predation at the earliest life stages before learning can occur. Thus, naïve tadpoles in nature may be at a high risk to predation in the presence of a novel predator until learned anti-predator responses provide additional defenses to the surviving tadpoles.
Status of names of Mitrasacme species occurring outside Australia
Authors: Gibbons Kerry Lynne , Conn Barry J , Henwood Murray J
Published: December 2015

Species of Mitrasacme occurring in Australia were revised for the Flora of Australia project in 1996, but the genus has never been revised as a whole. A checklist of the names of Mitrasacme species that occur outside Australia is presented here, together with their taxonomic status, known distribution and notes on their morphological affinities.
Interannual variability of South Equatorial Current bifurcation and western boundary currents along the Madagascar coast
Authors: Yamagami Y. , Tozuka T.
Published: December 2015

The South Equatorial Current (SEC) in the southern Indian Ocean bifurcates at the east coast of Madagascar into the Northeast and Southeast Madagascar Currents (NEMC and SEMC, respectively). In observational and reanalysis data, interannual variations of the NEMC and SEMC transports are strongly correlated with those of the SEC transport, rather than those of the SEC bifurcation latitude (SBL). Their dynamical mechanisms are then examined based on the Time‐Dependent Island Rule for the first time. It is shown that interannual anomalies of the SBL as well as the NEMC and SEMC transports are predominantly a response to the anomalous inflow from the ocean interior that is determined by the meridional interior transport. This, in turn, is a result of westward propagating Rossby waves induced by wind stress curl anomalies mainly in 60°E–90°E. The above mechanism is contrasted with that of the seasonal variation, where the local transport driven by wind stress around the island plays a role. Furthermore, the interannual variations of the SBL and the NEMC and SEMC transports are significantly correlated with the Niño 3.4 index with 5–15 months lag. It is suggested that diabatic heating anomalies associated with the El Niño/Southern Oscillation (ENSO) along with a local process in the southeastern Indian Ocean may generate wind stress curl anomalies over the southern Indian Ocean.
Selected New Articles on the Topic of Space Weather From AGU Journals: Published Between July and September 2015
Authors: Singer Howard J.
Published: December 2015

Key Points

Geomagnetically induced currents at low latitudes

How localized are extreme geoelectric fields that can affect the power grid?

Ionospheric effects on GPS signals at equatorial and high latitudes
The compressed state Kalman filter for nonlinear state estimation: Application to large‐scale reservoir monitoring
Authors: Li Judith Yue , Kokkinaki Amalia , Ghorbanidehno Hojat , Darve Eric F. , Kitanidis Peter K.
Published: December 2015

Reservoir monitoring aims to provide snapshots of reservoir conditions and their uncertainties to assist operation management and risk analysis. These snapshots may contain millions of state variables, e.g., pressures and saturations, which can be estimated by assimilating data in real time using the Kalman filter (KF). However, the KF has a computational cost that scales quadratically with the number of unknowns, m, due to the cost of computing and storing the covariance and Jacobian matrices, along with their products. The compressed state Kalman filter (CSKF) adapts the KF for solving large‐scale monitoring problems. The CSKF uses N preselected orthogonal bases to compute an accurate rank‐N approximation of the covariance that is close to the optimal spectral approximation given by SVD. The CSKF has a computational cost that scales linearly in m and uses an efficient matrix‐free approach that propagates uncertainties using N + 1 forward model evaluations, where
. Here we present a generalized CSKF algorithm for nonlinear state estimation problems such as CO2 monitoring. For simultaneous estimation of multiple types of state variables, the algorithm allows selecting bases that represent the variability of each state type. Through synthetic numerical experiments of CO2 monitoring, we show that the CSKF can reproduce the Kalman gain accurately even for large compression ratios (m/N). For a given computational cost, the CSKF uses a robust and flexible compression scheme that gives more reliable uncertainty estimates than the ensemble Kalman filter, which may display loss of ensemble variability leading to suboptimal uncertainty estimates.
Practical notes on local data‐worth analysis
Authors: Finsterle Stefan
Published: December 2015

These notes discuss the usefulness, limitations, and potential pitfalls of using sensitivity indices as a means to evaluate data worth and to guide the formulation and solution of inverse problems. A sensitivity analysis examines changes in model output variables with respect to changes in model input parameters. It appears straightforward to use this information to select influential parameters that should be subjected to estimation by inverse modeling and to identify the observations that contain information about these parameters and thus may be useful as calibration points. However, the results of such a sensitivity analysis do not account for parameter correlations and redundancies in observations and may not properly separate between calibration and prediction targets if used as criteria that guide inverse modeling; they may thus yield misleading recommendations about parameter identifiability and data worth. These issues (and some remedies) are discussed using an illustrative example, in which we examine the value of data sets potentially used for the calibration of a geothermal reservoir model. These notes highlight the importance of carefully formulating the objectives of a simulation study, which controls the setup of the inverse problem and related data needs.
Large wood transport and jam formation in a series of flume experiments
Authors: Davidson S. L. , MacKenzie L. G. , Eaton B.C.
Published: December 2015

Large wood has historically been removed from streams, resulting in the depletion of in‐stream wood in waterways worldwide. As wood increases morphological and hydraulic complexity, the addition of large wood is commonly employed as a means to rehabilitate in‐stream habitat. At present, however, the scientific understanding of wood mobilization and transport is incomplete. This paper presents results from a series of four flume experiments in which wood was added to a reach to investigate the piece and reach characteristics that determine wood stability and transport, as well as the time scale required for newly recruited wood to self‐organize into stable jams. Our results show that wood transitions from a randomly distributed newly recruited state to a self‐organized, or jam‐stabilized state, over the course of a single bankfull flow event. Statistical analyses of piece mobility during this transitional period indicate that piece irregularities, especially rootwads, dictate the stability of individual wood pieces; rootwad presence or absence accounts for up to 80% of the variance explained by linear regression models for transport distance. Furthermore, small pieces containing rootwads are especially stable. Large ramped pieces provide nuclei for the formation of persistent wood jams, and the frequency of these pieces in the reach impacts the travel distance of mobile wood. This research shows that the simulation of realistic wood dynamics is possible using a simplified physical model, and also has management implications, as it suggests that randomly added wood may organize into persistent, stable jams, and characterizes the time scale for this transition.
Lycopodium Spores: A Naturally Manufactured, Superrobust Biomaterial for Drug Delivery
Authors: Mundargi Raghavendra C. , Potroz Michael G. , Park Soohyun , Park Jae Hyeon , Shirahama Hitomi , Lee Jae Ho , Seo Jeongeun , Cho Nam‐Joon
Published: December 2015

Herein, the exploration of natural plant‐based “spores” for the encapsulation of macromolecules as a drug delivery platform is reported. Benefits of encapsulation with natural “spores” include highly uniform size distribution and materials encapsulation by relatively economical and simple versatile methods. The natural spores possess unique micromeritic properties and an inner cavity for significant macromolecule loading with retention of therapeutic spore constituents. In addition, these natural spores can be used as advanced materials to encapsulate a wide variety of pharmaceutical drugs, chemicals, cosmetics, and food supplements. Here, for the first time a strategy to utilize natural spores as advanced materials is developed to encapsulate macromolecules by three different microencapsulation techniques including passive, compression, and vacuum loading. The natural spore formulations developed by these techniques are extensively characterized with respect to size uniformity, shape, encapsulation efficiency, and localization of macromolecules in the spores. In vitro release profiles of developed spore formulations in simulated gastric and intestinal fluids have also been studied, and alginate coatings to tune the release profile using vacuum‐loaded spores have been explored. These results provide the basis for further exploration into the encapsulation of a wide range of therapeutic molecules in natural plant spores.
Optical Enhancement via Electrode Designs for High‐Performance Polymer Solar Cells
Authors: Chueh Chu‐Chen , Crump Michael , Jen Alex K.‐Y.
Published: December 2015

To capture the essence of the rapid progress in optical engineering exploited in high‐performance polymer solar cells (PSCs), a comprehensive overview focusing on recent developments and achievements in PSC electrode engineering is provided in this review. To date, various kinds of electrode materials and geometries are exploited to enhance light‐trapping in devices through distinct optical strategies. In addition to the widely used nanostructured electrodes that induce plasmonic‐enhanced light absorption, planar ultra‐thin metal films also have attracted significant attention due to their remarkably reflective transparent properties that beget efficient optical microcavities. These microcavities confine incident light with resonant frequencies between two reflective electrodes due to optically coherent interference, boosting the light absorption of thin‐film PSCs while maintaining efficient charge dissociation and extraction. After reviewing the challenges in developing high‐performance microcavity‐enhanced PSCs (MCPSCs), we discuss strategies to improve MCPSC performance further to showcase the potential of harnessing microcavity resonance effects in thin‐film PSCs.
Magnetophoretic Conductors and Diodes in a 3D Magnetic Field
Authors: Abedini‐Nassab Roozbeh , Joh Daniel Y. , Triggiano Melissa A. , Baker Cody , Chilkoti Ashutosh , Murdoch David M. , Yellen Benjamin B.
Published: December 2015

Magnetophoretic conductor tracks are used to transport single magnetized beads and magnetically labeled single cells in a 3D time‐varying magnetic field. The vertical field bias, in addition to the in‐plane rotating field, has the advantage of reducing the attraction between particles, which inhibits the formation of particle clusters. However, the inclusion of a vertical field requires the re‐design of magnetic track geometries, which can transport magnetized objects across the substrate. Following insights from magnetic bubble technology, it is found that successful magnetic conductor geometries defined in soft magnetic materials must be composed of alternating sections of positive (convex) and negative (concave) curvature. In addition to the previously studied magnetic tracks from the magnetic bubble literature, a drop‐shape pattern is found to be even more adept at transporting small magnetic beads and single cells. Symmetric patterns are shown to achieve bi‐directional conduction, whereas asymmetric patterns achieve unidirectional conduction. These designs represent the electrical circuit corollaries of the conductor and diode, respectively. Finally, biological applications are demonstrated in the transport of single cells and in the size‐based separation of magnetic particles.
Plasmon‐Enhanced Photocurrent of Photosynthetic Pigment Proteins on Nanoporous Silver
Authors: Friebe Vincent M. , Delgado Juan D. , Swainsbury David J. K. , Gruber J. Michael , Chanaewa Alina , van Grondelle Rienk , von Hauff Elizabeth , Millo Diego , Jones Michael R. , Frese Raoul N.
Published: December 2015

In a quest to fabricate novel solar energy materials, the high quantum efficiency and long charge separated states of photosynthetic pigment‐proteins are being exploited through their direct incorporation in bioelectronic devices. In this work, a biohybrid photocathode comprised of bacterial reaction center‐light harvesting 1 (RC‐LH1) complexes self‐assembled on a nanostructured silver substrate yields a peak photocurrent of 166 μA cm−2 under 1 sun illumination, and a maximum of 416 μA cm−2 under 4 suns, the highest reported to date on a bare metal electrode. A 2.5‐fold plasmonic enhancement of light absorption per RC‐LH1 complex is observed on the rough silver substrate. This plasmonic interaction is assessed using confocal fluorescence microscopy, revealing an increase of fluorescence yield, and radiative rate of the RC‐LH1 complexes, signatures of plasmon‐enhanced fluorescence. Nanostructuring of the silver substrate also enhanced the stability of the protein under continuous illumination by almost an order of magnitude relative to a nonstructured bulk silver control. Due to its ease of construction, increased protein loading capacity, stability, and more efficient use of light, this hybrid material is an excellent candidate for further development of plasmon‐enhanced biosensors and biophotovoltaic devices.
A Supramolecule‐Triggered Mechanochromic Switch of Cyclodextrin‐Jacketed Rhodamine and Spiropyran Derivatives
Authors: Wan Shulin , Ma Zhiyong , Chen Chen , Li Fangfei , Wang Feng , Jia Xinru , Yang Wantai , Yin Meizhen
Published: December 2015

An innovative approach for covalent‐bond‐activated mechanoresponse by complexing rhodamine or spiropyran with cyclodextrin (CD) is reported. This approach endows diverse fluorophores with perfect mechanochromism by introducing a supramolecular system. Unique characteristics such as noncovalent chemical modification and convenient preparation make this approach promising for practical applications. The strong hydrogen bonds provided by CD play a crucial role in triggering the mechanochromic switch. First, the hydrogen bonds seize both sides of the fluorophore's weak chemical bonds and tightly lock the fluorophore in the cavity of CD. Second, the hydrogen bonds prompt the aggregation of complex inclusions in large ordered arrays and strengthen the molecular interactions. In this way, the weak chemical bonds can focus more external force and stretch more easily upon shearing (quantified). This is the first report of supramolecule‐triggered mechanochromic switches. This study opens an avenue to correlate a mechanochemical reaction with a supramolecular system.
Precise Control of Lamellar Thickness in Highly Oriented Regioregular Poly(3‐Hexylthiophene) Thin Films Prepared by High‐Temperature Rubbing: Correlations with Optical Properties and Charge Transport
Authors: Hamidi‐Sakr Amer , Biniek Laure , Fall Sadiara , Brinkmann Martin
Published: December 2015

Precise control of orientation and crystallinity is achieved in regioregular poly(3‐hexylthiophene) (P3HT) thin films by using high‐temperature rubbing, a fast and effective alignment method. Rubbing P3HT films at temperatures TR ≥ 144 °C generates highly oriented crystalline films with a periodic lamellar morphology with a dichroic ratio reaching 25. The crystallinity and the average crystal size along the chain axis direction, lc, are determined by high‐resolution transmission electron microscopy and differential scanning calorimetry. The inverse of the lamellar period l scales with the supercooling and can accordingly be controlled by the rubbing temperature TR. Uniquely, the observed exciton coupling in P3HT crystals is correlated to the length of the average planarized chain segments lc in the crystals. The high alignment and crystallinity observed for TR > 200 °C cannot translate to high hole mobilities parallel to the rubbing because of the adverse effect of amorphous zones interrupting charge transport between crystalline lamellae. Although tie chains bridge successive P3HT crystals through amorphous zones, their twisted conformation restrains interlamellar charge transport. The evolution of charge transport anisotropy is correlated to the evolution of the dominant contact plane from mainly face‐on (TR ≤ 100 °C) to edge‐on (TR ≥ 170 °C).
Diving–Surfacing Smart Locomotion Driven by a CO2‐Forming Reaction, with Applications to Minigenerators
Authors: Zhang Lina , Song Mengmeng , Xiao Meng , Shi Feng
Published: December 2015

Harvesting energy from environment has attracted increasing attention for its potential applications in fabricating minigenerator. However, most studies in the fabrication of mini‐ or nanogenerators are based on the concept of piezoelectricity or triboelectrification while few of the reports paid attention to the classical theory of Faraday's law. Herein, a pH responsive smart surface is combined with the reaction between CaCO3 and HCl to develop a new minigenerator, which can convert mechanical energy generated from the chemical reaction into electrical energy through cutting magnetic lines with moving conductive lines. The conductive lines are connected with a smart device consisting of a pH‐responsive cube, a hydrophobic cube, and a quartz cell window; the device can perform diving‐surfacing cycled motions with an intelligent initiation through the adjustment of the solution. The device can surface through gathering CO2 bubbles from the reaction between CaCO3 and HCl and dive by releasing the bubbles on the water/air interface. Moreover, the results demonstrate that the inert CO2 was nonhazardous to the smart surfaces, which is meaningful for durable electricity generation.
Extraordinary Performance of Carbon‐Coated Anatase TiO2 as Sodium‐Ion Anode
Authors: Tahir Muhammad Nawaz , Oschmann Bernd , Buchholz Daniel , Dou Xinwei , Lieberwirth Ingo , Panthöfer Martin , Tremel Wolfgang , Zentel Rudolf , Passerini Stefano
Published: December 2015

The synthesis of in situ polymer‐functionalized anatase TiO2 particles using an anchoring block copolymer with hydroxamate as coordinating species is reported, which yields nanoparticles (≈11 nm) in multigram scale. Thermal annealing converts the polymer brushes into a uniform and homogeneous carbon coating as proven by high resolution transmission electron microscopy and Raman spectroscopy. The strong impact of particle size as well as carbon coating on the electrochemical performance of anatase TiO2 is demonstrated. Downsizing the particles leads to higher reversible uptake/release of sodium cations per formula unit TiO2 (e.g., 0.72 eq. Na+ (11 nm) vs only 0.56 eq. Na+ (40 nm)) while the carbon coating improves rate performance. The combination of small particle size and homogeneous carbon coating allows for the excellent electrochemical performance of anatase TiO2 at high (134 mAh g−1 at 10 C (3.35 A g−1)) and low (≈227 mAh g−1 at 0.1 C) current rates, high cycling stability (full capacity retention between 2nd and 300th cycle at 1 C) and improved coulombic efficiency (≈99.8%).
Highly Stable Transparent Conductive Silver Grid/PEDOT:PSS Electrodes for Integrated Bifunctional Flexible Electrochromic Supercapacitors
Authors: Cai Guofa , Darmawan Peter , Cui Mengqi , Wang Jiangxin , Chen Jingwei , Magdassi Shlomo , Lee Pooi See
Published: December 2015

Silver grids are attractive for replacing indium tin oxide as flexible transparent conductors. This work aims to improve the electrochemical stability of silver‐based transparent conductors. A silver grid/PEDOT:PSS hybrid film with high conductivity and excellent stability is successfully fabricated. Its functionality for flexible electrochromic applications is demonstrated by coating one layer of WO3 nanoparticles on the silver grid/PEDOT:PSS hybrid film. This hybrid structure presents a large optical modulation of 81.9% at 633 nm, fast switching, and high coloration efficiency (124.5 cm2 C−1). More importantly, an excellent electrochemical cycling stability (sustaining 79.1% of their initial transmittance modulation after 1000 cycles) and remarkable mechanical flexibility (optical modulation decay of only 7.5% after 1200 compressive bending cycles) is achieved. A novel smart supercapacitor is presented that functions as a regular energy‐storage device and simultaneously monitors the level of stored energy by a rapid and reversible color variation even at high current charge/discharge conditions. The film sustains an optical modulation of 87.7% and a specific capacitance of 67.2% at 10 A g−1 compared to their initial value at a current density of 1 A g−1. The high‐performance silver grid/PEDOT:PSS hybrid transparent films exhibit promising features for various emerging flexible electronics and optoelectronic devices.
Genotype‐phenotype correlation of 16p13.3 terminal duplication and 22q13.33 deletion: Natural history of a patient and review of the literature
Authors: Fontes Marshall I. B. , Santos Ana P. , Molck Miriam C. , Simioni Milena , Nascimento Diogo L. L. , Andrade Ana K. M. , Rosenberg Carla , Krepischi Ana C. V. , Appenzeller Simone , Monlleó Isabella L. , Gil‐da‐Silva‐Lopes Vera Lúcia
Published: December 2015

This article reports a patient with a de novo ∼9.32 Mb duplication at 16p13.3 and a ∼71 Kb deletion at 22q13.33. The patient was followed from 1 month old to 3 years and 8 months of age and presented typical features of the 16p13.3 duplication syndrome. In addition, the patient presents a portal cavernoma, an alteration rarely reported in this condition. Renal agenesis was detected as additional developmental defect. After genomic array and FISH analysis, the karyotype was 46,XX,ins(22;16)(q13;p13.2p13.3). ish ins(22;16)(RP11‐35P16+, RP11‐27M24+). arr16p13.2p13.3(85,880‐9,413,353)×3 dn arr22q13.33 (51,140,789‐51,197,838)×1 dn. The authors provide a comprehensive review of the literature. This approach shed light on the genotype‐phenotype correlation. © 2015 Wiley Periodicals, Inc.
Nutzung eines o‐Chinonmethids in der asymmetrischen Transferhydrierung: enantioselektive Synthese von Brosimin A, Brosimin B und Brosimacutin L
Authors: Keßberg Anton , Metz Peter
Published: December 2015

Erstmals wird eine kurze und hoch enantioselektive Synthese der Flavonoide Brosimin A, Brosimin B und Brosimacutin L beschrieben. Schlüsseltransformation ist eine einstufige Umsetzung eines Flavanons zu einem Flavan durch eine Kaskade aus asymmetrischer Transferhydrierung und Desoxygenierung.
Assembly of MOF Microcapsules with Size‐Selective Permeability on Cell Walls
Authors: Li Wanbin , Zhang Yufan , Xu Zehai , Meng Qin , Fan Zheng , Ye Shuaiju , Zhang Guoliang
Published: December 2015

The assembly of metal–organic frameworks (MOFs) into microcapsules has attracted great interest because of their unique properties. However, it remains a challenge to obtain MOF microcapsules with size selectivity at the molecular scale. In this report, we used cell walls from natural biomaterials as non‐toxic, stable, and inexpensive support materials to assemble MOF/cell wall (CW) microcapsules with size‐selective permeability. By making use of the hollow structure, small pores, and high density of heterogeneous nucleation sites of the cell walls, uniform and continuous MOF layers could be easily obtained by inside/outside interfacial crystallization. The prepared MOF/CW microcapsules have excellent stability and enable the steady, slow, and size‐selective release of small molecules. Moreover, the size selectivity of the microcapsules can be adjusted by changing the type of deposited MOF.
Microtubule‐Binding R3 Fragment from Tau Self‐Assembles into Giant Multistranded Amyloid Ribbons
Authors: Adamcik Jozef , Sánchez‐Ferrer Antoni , Ait‐Bouziad Nadine , Reynolds Nicholas P. , Lashuel Hilal A. , Mezzenga Raffaele
Published: December 2015

Tau protein and its fragments self‐assemble into amyloid fibrils in the presence of polyanions, such as heparin. By combining microscopy, scattering, and spectroscopy techniques, we studied the aggregation of the 26‐mer Tau‐derived peptide alone, Tau306–327, the third repeat fragment (R3) of the microtubule‐binding domain. We show that: i) the sole Tau306–327 can self‐assemble into amyloid fibrils without the need of aggregation‐promoting polyanions; ii) the resulting structures consist of surprisingly large, well‐ordered 2D laminated flat ribbons, with a log‐normal distribution of the lateral width, reaching the unprecedented lateral size of 350 nm and/or 45 individual protofilaments, that is, the largest amyloid laminated structures ever observed for Tau or any other amyloidogenic sequence. Our results provide insight into the molecular determinants of Tau aggregation and open new perspectives in the understanding of the assembly of amyloid fibrils and β‐sheet‐based biomaterials.
Dynamic Inversion of Stereoselective Phosphate Binding to a Bisurea Receptor Controlled by Light and Heat
Authors: Vlatković Matea , Feringa Ben L. , Wezenberg Sander J.
Published: December 2015

A chiral bisurea anion receptor, derived from a first‐generation molecular motor, can undergo photochemical and thermal isomerization operating as a reconfigurable system. The two possible cis configurations in the isomerization cycle are opposite in helicity, as is shown by CD spectroscopy. 1H NMR titrations demonstrate that the P and M helical cis isomers hold opposite enantioselectivity in the binding of binol phosphate, while anion complexation by the intermediate trans isomer is not selective. The difference in the binding affinity of the enantiomers was rationalized by DFT calculations, revealing very distinct binding modes. Thus, the enantiopreferred substrate binding in this receptor can be inverted in a dynamic fashion using light and heat.
Biomimetic Superhydrophobic/Superoleophilic Highly Fluorinated Graphene Oxide and ZIF‐8 Composites for Oil–Water Separation
Authors: Jayaramulu Kolleboyina , Datta Kasibhatta Kumara Ramanatha , Rösler Christoph , Petr Martin , Otyepka Michal , Zboril Radek , Fischer Roland A.
Published: December 2015

Superhydrophobic/superoleophilic composites HFGO@ZIF‐8 have been prepared from highly fluorinated graphene oxide (HFGO) and the nanocrystalline zeolite imidazole framework ZIF‐8. The structure‐directing and coordination‐modulating properties of HFGO allow for the selective nucleation of ZIF‐8 nanoparticles at the graphene surface oxygen functionalities. This results in localized nucleation and size‐controlled ZIF‐8 nanocrystals intercalated in between HFGO layers. The composite microstructure features fluoride groups bonded at the graphene. Self‐assembly of a unique micro‐mesoporous architecture is achieved, where the micropores originate from ZIF‐8 nanocrystals, while the functionalized mesopores arise from randomly organized HFGO layers separated by ZIF‐8 nanopillars. The hybrid material displays an exceptional high water contact angle of 162° and low oil contact angle of 0° and thus reveals very high sorption selectivity, fast kinetics, and good absorbencies for nonpolar/polar organic solvents and oils from water. Accordingly, Sponge@HFGO@ZIF‐8 composites are successfully utilized for oil–water separation.
Multiscale Origami Structures as Interface for Cells
Authors: Angelin Alessandro , Weigel Simone , Garrecht Ruben , Meyer Rebecca , Bauer Jens , Kumar Ravi Kapoor , Hirtz Michael , Niemeyer Christof M.
Published: December 2015

A DNA‐based platform was developed to address fundamental aspects of early stages of cell signaling in living cells. By site‐directed sorting of differently encoded, protein‐decorated DNA origami structures on DNA microarrays, we combine the advantages of the bottom‐up self‐assembly of protein–DNA nanostructures and top‐down micropatterning of solid surfaces to create multiscale origami structures as interface for cells (MOSAIC). In a proof‐of‐principle, we use this technology to analyze the activation of epidermal growth factor (EGF) receptors in living MCF7 cells using DNA origami structures decorated on their surface with distinctive nanoscale arrangements of EGF ligand entities. MOSAIC holds the potential to present to adhered cells well‐defined arrangements of ligands with full control over their number, stoichiometry, and precise nanoscale orientation. It therefore promises novel applications in the life sciences, which cannot be tackled by conventional technologies.
Seaweed‐derived κ‐carrageenan: Modified κ‐carrageenan as a recyclable green catalyst in the multicomponent synthesis of aminophosphonates and polyhydroquinolines
Authors: Rostamnia Sadegh , Doustkhah Esmail , Baghban Ali , Zeynizadeh Behzad
Published: December 2015

A seaweed‐derived biopolymer, κ‐carrageenan (KCAR), with a slight modification was assumed as an organosulfonic‐type Bronsted acid in the catalysis of polyhydroquinoline and α‐aminophosphonate syntheses through one‐pot multicomponent reaction procedures under aqueous conditions. In this investigation, KCAR was found to be an efficient, heterogeneous and homogeneous, recyclable, economical, and green catalyst. Moreover, biocompatibility, ease of separation, high chemoselectivity, and lower reaction time were other aspects of this catalyst. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43190.
A survey of overall life satisfaction and its association with breast diseases in Chinese women
Authors: Bai Aili , Li Haixin , Huang Yubei , Liu Xueou , Gao Ying , Wang Peishan , Dai Hongji , Song Fengju , Hao Xishan , Chen Kexin
Published: December 2015

To investigate the association between overall life satisfaction and healthy lifestyle, knowledge of breast cancer, physical examination, and detection rate of breast cancer and benign breast disease in Chinese women. In a multicentered breast disease screening program in China, we enrolled 33,057 women aged 45–65 years without prior diagnosis of breast cancer. After completing an epidemiological questionnaire, all participants were examined by clinical breast examination, breast ultrasound, and mammography independently. All breast cancer cases and a selected sample of benign breast diseases were confirmed pathologically. Univariate and multivariate odds ratios (ORs) and 95% confidence intervals (CIs) were calculated to estimate the association between life satisfaction and lifestyle, knowledge of breast cancer, physical examination, and detection rate of breast diseases. Overall life satisfaction was positively associated with women's healthy lifestyle. Compared with less satisfied women, satisfied women were less likely to be smokers (OR = 0.54; 95% CI: 0.47–0.62), have more exercise (OR = 1.49; 95% CI: 1.26–1.75), eat less fried (OR = 0.60; 95% CI: 0.50–0.71), smoked (OR = 0.54, 95% CI: 0.47–0.63), pickled (OR = 0.66, 95% CI: 0.55–0.79), and grilled (OR = 0.63, 95% CI: 0.54–0.74) foods. Satisfied women were more likely to have knowledge of breast cancer (OR = 1.48, 95% CI: 1.29–1.70), and have regular physical examinations (OR = 1.11, 95% CI: 1.01–1.12). Compared to less satisfied women, we found significantly lower detection rate of benign breast diseases (OR = 0.90, 95% CI: 0.82–0.99), and lower but nonsignificant detection rate of breast cancer (OR = 0.66, 95% CI: 0.35–1.25) in satisfied women. Women with a higher overall life satisfaction are more likely to have healthy lifestyle, knowledge of breast cancer, and regular physical examination, thus resulting in a lower detection rate of breast diseases in screening.
Perovskite as a Cathode Material: A Review of its Role in Solid‐Oxide Fuel Cell Technology
Authors: Jun Areum , Kim Junyoung , Shin Jeeyoung , Kim Guntae
Published: December 2015

Solid oxide fuel cells (SOFCs) are characterized by low pollution, and are therefore the best alternative both for distributed energy sources and large‐scale integration. Fuel flexibility, including hydrocarbons, is the main advantage of SOFCs. For the successful introduction of SOFC technology to the market, reduced temperature operation at 600–800 °C is an essential factor. One of the important issues for the reduced temperature operation is to get rid of stability issues while maintaining a certain level of performance. Therefore, the development of alternative materials such as perovskite cathodes is essential to create not only practically acceptable performance, but also to ensure the highly reliable and stable operation of the resulting SOFCs. This review provides a critical and comprehensive survey on the perovskite materials for SOFC cathodes and suggests effective and stable alternatives for the realiable operation of SOFCs.
Synthesis and Electrochemistry of Na2.5(Fe1−yMny)1.75(SO4)3 Solid Solutions for Na‐Ion Batteries
Authors: Wei Suhao , Mortemard de Boisse Benoit , Oyama Gyosuke , Nishimura Shin‐ichi , Yamada Atsuo
Published: December 2015

Na2+2xFe2−x(SO4)3 was recently reported as a promising cathode material for Na‐ion batteries with high voltage generation (3.8 V vs. Na/Na+), high energy density, and extreme high‐rate operation, making it competitive to lithium battery cathodes. Following our identification of the narrow off‐stoichiometric region in Na2+2xFe2−x(SO4)3 solid solutions (x around 0.25), we report here the effect of Mn substitution in Na2.5(Fe1−yMny)1.75(SO4)3 (y=0, 0.25, 0.5, 0.75, and 1.0) solid solutions when increasing the voltage of the Fe3+/Fe2+ redox couple, but with a simple capacity decrease, owing to the entire Mn2+ inactivity.
Targeting Innate Immunity with dsRNA‐Conjugated Mesoporous Silica Nanoparticles Promotes Antitumor Effects on Breast Cancer Cells
Authors: Ultimo Amelia , Giménez Cristina , Bartovsky Pavel , Aznar Elena , Sancenón Félix , Marcos M. Dolores , Amorós Pedro , Bernardo Ana R. , Martínez‐Máñez Ramón , Jiménez‐Lara Ana M. , Murguía José R.
Published: December 2015

We describe herein a Toll‐like receptor 3 (TLR3) targeting delivery system based on mesoporous silica nanoparticles capped with the synthetic double stranded RNA polyinosinic–polycytidylic acid (poly(I:C)) for controlled cargo delivery in SK‐BR‐3 breast carcinoma cells. Our results show that poly(I:C)‐conjugated nanoparticles efficiently targeted breast cancer cells due to dsRNA–TLR3 interaction. Such interaction also triggered apoptotic pathways in SK‐BR‐3, significantly decreasing cells viability. Poly(I:C) cytotoxic effect in breast carcinoma cells was enhanced by loading nanoparticles′ mesopores with the anthracyclinic antibiotic doxorubicin, a commonly used chemotherapeutic agent.
Single‐Component Phosphinous Acid Ruthenium(II) Catalysts for Versatile C−H Activation by Metal–Ligand Cooperation
Authors: Zell Daniel , Warratz Svenja , Gelman Dmitri , Garden Simon J. , Ackermann Lutz
Published: December 2015

Well‐defined ruthenium(II) phosphinous acid (PA) complexes enabled chemo‐, site‐, and diastereoselective C−H functionalization of arenes and alkenes with ample scope. The outstanding catalytic activity was reflected by catalyst loadings as low as 0.75 mol %, and the most step‐economical access reported to date to angiotensin II receptor antagonist blockbuster drugs. Mechanistic studies indicated a kinetically relevant C−X cleavage by a single‐electron transfer (SET)‐type elementary process, and provided evidence for a PA‐assisted C−H ruthenation step.
A New Family of Anionic FeIII Spin Crossover Complexes Featuring a Weak‐Field N2O4 Coordination Octahedron
Authors: Takahashi Kazuyuki , Kawamukai Kiko , Okai Mitsunobu , Mochida Tomoyuki , Sakurai Takahiro , Ohta Hitoshi , Yamamoto Takashi , Einaga Yasuaki , Shiota Yoshihito , Yoshizawa Kazunari
Published: December 2015

Unprecedented anionic FeIII spin crossover (SCO) complexes involving a weak‐field O,N,O‐tridentate ligand were discovered. The SCO transition was evidenced by the temperature variations in magnetic susceptibility, Mössbauer spectrum, and coordination structure. The DFT calculations suggested that larger coefficients on the azo group in the HOMO−1 of a ligand might contribute to the enhancement of a ligand‐field splitting energy. The present anionic SCO complex also exhibited the light‐ induced excited‐spin‐state trapping effect.
Fault detection and diagnosis of an industrial copper electrowinning process
Authors: Wang Zhenheng , Wiebe Susan , Shang Helen
Published: December 2015

Electrowinning is a key process in the production of high purity copper from copper sulphide minerals. Fault detection and diagnosis based on the industrial operating data would be desirable to avoid abnormal operation and ensure high product quality. In this paper, a fault detection and diagnosis algorithm using dynamic principal component analysis (DPCA) is applied to the industrial selenium/tellurium removal and copper electrowinning process. From the principal components obtained using DPCA, Hotelling and SPE are calculated to determine whether a fault has occurred. Tests on normal and faulty data sets confirm that the DPCA‐based fault detection method is effective for the industrial system. Contribution plots of variables to are obtained to determine the variables that contribute to the fault and to help locate the root causes of the fault. The DPCA‐based fault detection and diagnosis provide a convenient approach for enhancing the process operation and product quality for the industrial copper electrowinning system.