bluuebunny/crossref_metadata_2025 huggingface dataset:
Low Carbon Economy inChina
Authors: Xue Jinjun , Bai Quan
Published: July 2015

China is the second largest economy, the largest trading country, and the largest carbon emitter and the largest energy consumption country in the world. As the most populous developing country at up‐middle income, economic growth will continually be the primary task of China, by this meaning, China will consumes more energy and emit moreCO2in the next decades. On the other hand, China has been promoting a Green‐Low‐Carbon Development Strategy and making great efforts in energy conservation and emission reduction according to its promised emission reduction target of 40–45% per unitGDP(gross domestic product ) by 2020 and the targets in the 12th five‐year plan. This article presents China's economic growth, introduces its climate change and energy policy, valuates its efforts to energy conservation and emission reduction, analyzes the problems and challenges, and, most importantly, projects China's turning points of energy consumption and carbon emissions by years 2020 and 2050.
Thermal Energy Efficiency in Industrial Processes
Authors: Rajendran Keerthi , Ling‐Chin Janie , Roskilly Anthony P.
Published: July 2015

Thermal energy used for heating and cooling represents a significant proportion of total energy use in industrial processes and is largely supplied by fossil fuels. Mechanical operations primarily powered by electricity also consume a large amount of energy. Both heating and cooling operations as well as mechanical operations release large amounts of heat into the environment; therefore, careful management of thermal energy is a key factor in reducing overall energy consumption and emissions.

Energy‐related pressures, incentives, and opportunities provide a strong business case to invest in improving energy efficiency. These include customer demand for “green” products, national taxes, and financial incentives, and rising fuel costs. Against this backdrop, the prioritization of the sustainability agenda by research funders coupled with the pressure on research organizations to ensure the transfer of novel technologies to industry creates an ideal landscape for substantial advancement in industrial energy efficiency. Successful movement of novel technology to industry should, however, be supported by concepts, methods, and practices derived from industrial context and needs. Accordingly, initial implementations often bring to light new research challenges, both technical and methodological.

To enhance the use of energy‐efficient methods in industry, the definition and measurement of efficiency must be tailored to industrial needs and technologies ready for adoption must be identified and presented in relation to existing technology. In addition, detailed case studies of energy use should be documented to provide insights to both researchers and practitioners, identifying both realistic improvements and barriers to application of energy‐efficient measures.
Emerging Technologies for Waste‐to‐Energy and Fuel Conversion
Authors: Yoshikawa Kunio
Published: July 2015

Up to now, the only solution for utilization of solid wastes including biomass as energy resources is to incinerate them (mass burning) and to use the produced heat directly or to convert the produced heat into electric power employing boilers/steam turbines. This process should be large scale and expensive to install and operate. In this article, new technologies for converting unutilized resources such as solid wastes and biomass into high value added energy resources (solid fuel, gaseous fuel, liquid fuel, and electric power) with small to medium scale are introduced for promoting distributed waste utilization. The content of the technologies are as follows. Solid fuel production technology: the hydrothermal treatment technology can convert unutilized resources with various shapes, heating values, and moisture contents into uniform dry powder‐like solid fuels with the heating value equivalent to coal. Liquid fuel production technology: diesel equivalent fuel oils can be produced from waste plastics by employing the pyrolytic reforming oil production technology and from waste cooking oils by employing the dry‐type alkali catalyst biodiesel fuel production technology. The emulsion fuel that is a mixture of oil and water can reduce the emissions as well as improve the thermal efficiency of boilers. Gasification and power generation technology: the gasification technologies can produce low to medium calorific gases from solid wastes by employing pyrolysis and reforming or steam gasification technologies. Electric power can be generated from this low to medium calorific gases by employing internal combustion engines.
Waste and Biomass to Clean Energy
Authors: Gupta Ashwani K.
Published: July 2015

Waste and biomass include different kinds of organic and inorganic materials including wood, trees, agricultural, municipal, medical, hazardous, electronic, industrial solid wastes, and waste glass, metals, and plastics. Waste is a growing problem to the society worldwide. Increased waste production is directly related to increased gross domestic product (GDP) so that one must seek options for their safe and environmentally benign disposal. The old practice of landfills, although still in use in many countries, is less acceptable as this causes odors and nuisance to the nearby community and can be leachable to ground water. Thermal destruction and incineration is now widely used as it provides energy recovery (both thermal and electricity), mass and volume reduction of the waste, and the remaining residue can be used for construction material or discarded at landfills. Pyrolysis and gasification offers clean reforming of wastes to syngas, which can also be converted into liquid fuels. Much of the work on gasification of wastes is at the laboratory scale so that the favorable results obtained can be used at pilot‐ and demonstration‐scale plants, akin to coal gasification plants. Waste and biomass can also be converted into useful clean refuse‐derived fuel and value added products of activated carbon and torrefied material. It is expected that the fundamental information on pyrolysis and gasification provided here will assist in the design and operation of advanced gasifiers with eliminated tars and char. The reforming of wastes to useful materials and value added products provide clean energy to support energy sustainability.
Pumped Hydro Energy Storage
Authors: Deane Paul , Gallachóir Brian Ó
Published: July 2015

Pumped hydroelectric storage is currently the only commercially proven large‐scale (>100 MW) energy storage technology with over 200 plants installed worldwide with a total installed capacity of over 100 GW. The fundamental principle of pumped hydroelectric storage is to store electric energy in the form of hydraulic potential energy. Pumping typically takes place during off‐peak periods, when both electricity demand and electricity prices are low. Generation takes place during peak periods, when electricity system demand is high. Pumping and generating generally follow a daily cycle but weekly or even seasonal cycling is also possible with larger pumped hydroelectric storage plant. Pumped hydroelectric storage is a flexible form of electricity generation and can contribute many benefits to power systems operation. There has been a renewed commercial and technical interest in pumped hydroelectric storage recently with the advent of increased variable renewable energy generation and the development of liberalized electricity markets.
Methods for Measuring and Evaluating Sustainability: State‐of‐the Art, Challenges, and Future Developments
Authors: Kleeberg Kirstin , Schneider Katja , Nippa Michael
Published: July 2015

By now, the termsustainabilitysuffers from being degenerated into a buzzword resulting in an exceptionally large amount and variety of literature. Likely due to this, the dispersal of descriptions, perspectives, and facets regarding sustainability‐assessing methods reveals deficits in terms of theoretical and methodological rigor, novelty, and practical usefulness. Against this background, this article contains an overview of eight selected methods and tools for sustainability assessment. The qualitative review of current research articles concerning energy technologies highlights objectives and purposes, origins, main procedures, fields of application, and examples as well as a critical acclaim for each method. Next to this, several considerations in general such as the role of principles, criteria, and indicators are being illustrated as well as important challenges for measuring sustainability. Thereby, we develop a six‐stage model that supports the choice of an appropriate method for sustainability assessment. In doing so, we derive two fundamental principles, namely “content‐related” features and “performance‐related” features. At the same time, this article underlines the coexistence of various different, highly complex methods, approaches, and perspectives, as well as practical examples to assess sustainability. We evidence an increasing defragmentation and specialization of research on sustainability assessment. Against this background, our findings are likely to foster further theoretical, conceptual, and analytical developments in this research field. This also promotes a customization and the practical value of sustainability assessment methods.
Materials Issues for Solid Oxide Fuel Cells Design
Authors: Morales Miguel , Segarra Mercè
Published: July 2015

Solid oxide fuel cells (SOFCs) are complex electrochemical devices that convert chemical energy into electrical energy with high efficiency. A single cell contains three basic components, which are a porous anode, a dense electrolyte, and a porous cathode. In order to generate high power for a determined application, the single cells are stacked, thus requiring the use of interconnects and sealants. An important challenge of these devices is the reduction of their operating temperatures for improving materials compatibility between components, reducing energy consumption and time for startup and cooling down, and increasing the durability. Many strategies for lowering operating temperature inSOFCs have been proposed. In comparison to other fuel cell types, anSOFCstack can be designed to operate within a wide temperature range (500–1000°C). Therefore, it is necessary to select the desired operation temperature that is mainly influenced by the specific application, the type of fuel, and the properties of solid electrolyte. It is possible to address theSOFCdesign from different approaches: selecting materials for each cell component, selecting cell geometry, or selecting stack design. In this article, different alternatives of materials selection, cell geometry, and stack design, depending on the operating temperatures and compatibilities among materials, are presented.
Cryogenic Energy Storage
Authors: Ding Yulong , Li Yongliang , Li Dacheng , Radcliffe Jonathan , Huang Yun
Published: July 2015

Cryogenic energy storage (CES) is a large‐scale energy storage technology that uses cryogen (liquid air/nitrogen) as a medium and also a working fluid for energy storage and discharging processes. During off‐peak hours, when electricity is at its cheapest and demand for electricity is at its lowest, liquid air/nitrogen is produced in an air liquefaction and separation plant and stored in cryogenic tanks close to the atmospheric pressure. During peak hours, the cryogenic liquid is heated up using environmental heat and then superheated using other heat sources (if available). The boiling of the cryogenic liquid will form a high pressure gas that drives an expansion device to produce shaft power or electricity. The concept ofCESwas first proposed by University of Newcastle upon Tyne (United Kingdom) in 1977 as an alternative to compressed air energy storage (CAES) technology for peak shaving in an electricity grid. Subsequently, the topic was investigated both numerically and experimentally by both industrial companies such as Mitsubishi Heavy Industries, Hitachi, Expansion Energy, and Highview Power Storage Systems and academic institutions. It is, however, the work from 2005 at the University of Leeds in collaboration with Highview Power Storage Systems that led to the world's first fully operationalMWhpilot grid‐connected plant.
Integration of Energy Storage into Energy Systems
Authors: Hauer Andreas , Teuffel Amadeus
Published: July 2015

The definition of energy storage is followed by an overview of investigated energy storage technologies in the fields of electrical energy storage, thermal energy storage, and storage by chemical conversion. Storage capacity, power, efficiency, storage period, and costs are thereby introduced as important energy storage properties.

The role of energy storage in the energy system is highlighted, and relevant energy storage applications for the integration of renewable electricity and renewable thermal energy are presented. Parameters for technical comparison of energy storage technologies are shown whereby it is explained that storage technologies can only be compared within their actual application.

Lastly, economics of energy storage are discussed, and maximum acceptable storage costs are introduced as a measure for the evaluation of storage technologies' economics depending on storage cycle periods and investment environment.
Hydrogen Production by Electrolysis and Photoelectrochemical System
Authors: Sim Uk , Jin Kyoungsuk , Oh Seungtaeg , Jeong Donghyuk , Moon Junsang , Oh Jihun , Nam Ki Tae
Published: July 2015

Hydrogen energy has been drawing much attention in renewable energy technologies. Hydrogen production by water splitting reaction has especially been widely studied as an environmentally friendly and sustainable energy source. Realization of cost‐effective hydrogen production by water splitting requires electrolysis or photoelectrochemical cells decorated with highly efficient cocatalysts. Here, we briefly summarize the theory of water splitting reaction and discuss various types of catalysts for water splitting reaction (hydrogen evolution reaction and oxygen evolution reaction). Principles of photoelectrochemical hydrogen evolution from light absorbing semiconductors will be described.
Palladium‐Catalyzed Alkene Carboamination Reactions of Electron‐Poor Nitrogen Nucleophiles
Authors: Peterson Luke J. , Wolfe John P.
Published: July 2015

Modified reaction conditions that facilitate Pd‐catalyzed alkene carboamination reactions of electron‐deficient nitrogen nucleophiles are reported. Pent‐4‐enylamine derivatives bearing N‐tosyl or N‐trifluoroacetyl groups are coupled with aryl triflates to afford substituted pyrrolidines in good yield. These reactions proceed via a mechanism involving anti‐aminopalladation of the alkene, which differs from previously reported analogous reactions of N‐aryl‐ and N‐Boc‐pentenylamines. The application of these conditions to a formal synthesis of (±)‐aphanorphine is also described.

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Efficient E‐Selective Transfer Semihydrogenation of Alkynes by Means of Ligand‐Metal Cooperating Ruthenium Catalyst
Authors: Musa Sanaa , Ghosh Amrita , Vaccaro Luigi , Ackermann Lutz , Gelman Dmitri
Published: July 2015

The manuscript describes an efficient protocol for the E‐selective transfer semihydrogenation of internal alkynes employing a previously described bifunctional ruthenium‐based PC(sp3)P complex, 20 mol% of sodium formate and nearly stoichiometric formic acid. Semihydrogenation of the terminal alkynes results in the formation of the corresponding styrenes. The mechanism of the reaction includes stepwise transfer of both the hydride and the proton of the formic acid to the substrate. This fact allowed for the development of a facile protocol for the synthesis of monodeuterated alkenes by simply applying formic acid/sodium formate/D2O mixture as a hydrogen source. High yields, selectivity and functional group compatibility have been generally achieved.

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Enantioselective Hydroalkynylation of Non‐Polar Carbon‐Carbon Double Bonds: Iridium‐Catalyzed Asymmetric Addition Reaction of Terminal Alkyne CH Bonds to Substituted Norbornadienes
Authors: Yang Qingjing , Choy Pui Ying , Fan Baomin , Kwong Fuk Yee
Published: July 2015

This update describes the enantioselective addition of the terminal alkynyl CH bond across a non‐polar CC double bond. Sterically congested substrates are often challenging in this type of reaction as these alkenyl substrates exhibit poor substrate‐metal center coordination, and thus poor stereo‐induction would result. The successful enantioselective hydroalkynylation of this type of system has sporadically been reported. We herein describe our progress for the example of vinyl‐substituted norbornadiene derivatives. With the aid of an iridium complex in combination with the chiral SYNPHOS ligand, the addition products could be obtained smoothly with excellent enantioselectivities (up to 99% ee). In particular, the first examples of an acetylenic CH bond adding across azanorbornadienes are also disclosed.

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Triple Negative Breast Cancer: Nanosolutions for a Big Challenge
Authors: Mendes Tânia Filipa S. , Kluskens Leon D. , Rodrigues Lígia Raquel
Published: July 2015

Triple negative breast cancer (TNBC) is a particular immunopathological subtype of breast cancer that lacks expression of estrogen and progesterone receptors (ER/PR) and amplification of the human epidermal growth factor receptor 2 (HER2) gene. Characterized by aggressive and metastatic phenotypes and high rates of relapse, TNBC is the only breast cancer subgroup still lacking effective therapeutic options, thus presenting the worst prognosis. The development of targeted therapies, as well as early diagnosis methods, is vital to ensure an adequate and timely therapeutic intervention in patients with TNBC. This review intends to discuss potentially emerging approaches for the diagnosis and treatment of TNBC patients, with a special focus on nano‐based solutions that actively target these particular tumors.
Density segregation of dry and wet granular mixtures in gas fluidized beds
Authors: Seah Stella Lin Li , Lim Eldin Wee Chuan
Published: July 2015

The Discrete Element Method combined with Computational Fluid Dynamics was coupled to a capillary liquid bridge force model for computational studies of mixing and segregation behaviors in gas fluidized beds containing dry or wet mixtures of granular materials with different densities. The tendency for density segregation decreased with increasing fluidizing velocity, coefficient of restitution, and amount of liquid present. Due to the presence of strong capillary forces between wet particles, there was a high tendency for particles to form agglomerates during the fluidization process, resulting in lower segregation efficiency in comparison with fluidization of dry particles. Particle‐particle collision forces were on average stronger than both fluid drag forces and capillary forces. The magnitudes of drag forces and particle‐particle collision forces increased with increasing fluidizing velocity and this led to higher mixing or segregation efficiencies observed in dry particles as well as in wet particles at higher fluidizing velocities. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4069–4086, 2015
Paternal age effect: Replication in schizophrenia with intriguing dissociation between bipolar with and without psychosis
Authors: Lehrer Douglas S. , Pato Michele T. , Nahhas Ramzi W. , Miller Brian R. , Malaspina Dolores , Buckley Peter F. , Sobell Janet L. , Walsh‐Messinger Julie ,   Genomic Psychiatry Cohort Consortium, Pato Carlos N.
Published: July 2015

Advanced paternal age (APA) is a risk factor for schizophrenia (Sz) and bipolar disorder (BP). Putative mechanisms include heritable genetic factors, de novo mutations, and epigenetic mechanisms. Few studies have explored phenotypic features associated with APA. The Genomic Psychiatry Cohort established a clinically characterized repository of genomic samples from subjects with a Sz‐BP diagnosis or unaffected controls, 12,975 with parental age information. We estimated relative risk ratios for Sz, schizoaffective depressed and bipolar types (SA‐D, SA‐B), and BP with and without history of psychotic features (PF) relative to the control group, comparing each paternal age group to the reference group 20–24 years. All tests were two‐sided with adjustment for multiple comparisons. Subjects with fathers age 45+ had significantly higher risk for all diagnoses except for BP w/o PF. APA also bore no significant relation to family psychiatric history. In conclusion, we replicated APA as a risk factor for Sz. To our knowledge, this is the first published report of APA in a BP sample stratified by psychosis history, extending this association only in BP w/PF. This suggests that phenotypic expression of the APA effect in Sz‐BP spectrum is psychosis, per se, rather than other aspects of these complex disorders. The lack of a significant relationship between paternal age and familial disease patterns suggests that underlying mechanisms of the paternal age effect may involve a complex interaction of heritable and non‐heritable factors. The authors discuss implications and testable hypotheses, starting with a focus on genetic mechanisms and endophenotypic expressions of dopaminergic function. © 2015 Wiley Periodicals, Inc.
A Structural and Functional Model for the 1‐Aminocyclopropane‐1‐carboxylic Acid Oxidase
Authors: Sallmann Madleen , Oldenburg Fabio , Braun Beatrice , Réglier Marius , Simaan A. Jalila , Limberg Christian
Published: July 2015

The hitherto most realistic low‐molecular‐weight analogue for the 1‐aminocyclopropane‐1‐carboxylic acid oxidase (ACCO) is reported. The ACCOs 2‐His‐1‐carboxylate iron(II) active site was mimicked by a TpFe moiety, to which the natural substrate ACC could be bound. The resulting complex [TpMe,PhFeACC] (1), according to X‐ray diffraction analysis performed for the nickel analogue, represents an excellent structural model, featuring ACC coordinated in a bidentate fashion—as proposed for the enzymatic substrate complex—as well as a vacant coordination site that forms the basis for the first successful replication also of the ACCO function: 1 is the first known ACC complex that reacts with O2 to produce ethylene. As a FeOOH species had been suggested as intermediate in the catalytic cycle, H2O2 was tested as the oxidant, too, and indeed evolution of ethylene proceeded even more rapidly to give 65 % yield.
Iron‐Catalyzed Cross‐Coupling of Alkenyl Acetates
Authors: Gärtner Dominik , Stein André Luiz , Grupe Sabine , Arp Johannes , Jacobi von Wangelin Axel
Published: July 2015

Stable CO linkages are generally unreactive in cross‐coupling reactions which mostly employ more electrophilic halides or activated esters (triflates, tosylates). Acetates are cheap and easily accessible electrophiles but have not been used in cross‐couplings because the strong CO bond and high propensity to engage in unwanted acetylation and deprotonation. Reported herein is a selective iron‐catalyzed cross‐coupling of diverse alkenyl acetates, and it operates under mild reaction conditions (0 °C, 2 h) with a ligand‐free catalyst (1–2 mol %).
The effect of the ring opening polymerization and chain spacing on the coefficient of thermal expansion and modulus of polyimide
Authors: Yoo Taewon , Kim Kwangin , Jang Wonbong , Han Haksoo
Published: July 2015

The features of norbornene (NE) cross‐linked polyimide (PI) were investigated as the ratio of the norbornene monomer was varied. The coefficient of thermal expansion and modulus are important parameters of materials used in the microelectronic industry. Therefore, in this study, 5‐norbornene‐2, 3‐dicarboxylic acid (NE) was introduced as a crosslinking agent to increase the thermal stability at elevated temperatures. 4,4′‐Benzophenonetetracarboxylic dianhydride was utilized as a dianhydride and 4,4′‐diaminodiphenyl ether was introduced as a diamine monomer. By changing the ratio of each monomer, we were able to control the spacing of the chain and ring opening polymerization, which resulted in improved properties. Each sample was thermally cured which led to a ring opening mechanism of the norbornene through the reverse Diels‐Alder reaction. Thermal mechanical analysis was utilized to determine the coefficient of thermal expansion and dynamic mechanical analysis was used to determine the storage modulus (ε′) and loss modulus (ε″) of the PI film. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42607.
More than a neuroanatomical representation in The Creation of Adam by Michelangelo Buonarroti, a representation of the Golden Ratio
Authors: de Campos Deivis , Malysz Tais , Bonatto‐Costa João Antonio , Pereira Jotz Geraldo , Pinto de Oliveira Junior Lino , Oxley da Rocha Andrea
Published: July 2015

Michelangelo Buonarroti (1475–1564) was a master anatomist as well as an artistic genius. He dissected numerous cadavers and developed a profound understanding of human anatomy. Among his best‐known artworks are the frescoes painted on the ceiling of the Sistine Chapel (1508–1512), in Rome. Currently, there is some debate over whether the frescoes merely represent the teachings of the Catholic Church at the time or if there are other meanings hidden in the images. In addition, there is speculation regarding the image of the brain embedded in the fresco known as “The Creation of Adam,” which contains anatomic features of the midsagittal and lateral surfaces of the brain. Within this context, we report our use of Image Pro Plus Software 6.0 to demonstrate mathematical evidence that Michelangelo painted “The Creation of Adam” using the Divine Proportion/Golden Ratio (GR) (1.6). The GR is classically associated with greater structural efficiency and is found in biological structures and works of art by renowned artists. Thus, according to the evidence shown in this article, we can suppose that the beauty and harmony recognized in all Michelangelo's works may not be based solely on his knowledge of human anatomical proportions, but that the artist also probably knew anatomical structures that conform to the GR display greater structural efficiency. It is hoped that this report will at least stimulate further scientific and scholarly contributions to this fascinating topic, as the study of these works of art is essential for the knowledge of the history of Anatomy. Clin. Anat. 28:702–705, 2015. © 2015 Wiley Periodicals, Inc.
Review court ruling on captioning at university football stadiums, basketball arenas and on athletics websites
Authors: Charmatz Marc
Published: July 2015

A Maryland federal court held that it wouldn't be a fundamental alteration for a university to provide captioning at football stadiums and basketball arenas, and on athletics websites, but that factual issues existed as to whether providing captioning would be an undue burden on the university. Innes v. The Board of Regents of the University System of Maryland, Civil Action No. DKC 13‐2800, will now go to trial.
Did a university violate a student's ADA rights?
Authors: Gelpi Aileen
Published: July 2015

Tina Bonneau — a student at the State University of New York at Brockport — notified university officials in 2008 that she had a disability. They provided extended test‐taking time, short breaks during classes, and notes for missed class time.
Functionalized Carbon Nanotubes for Biomass Conversion: The Base‐Free Aerobic Oxidation of 5‐Hydroxymethylfurfural to 2,5‐Furandicarboxylic Acid over Platinum Supported on a Carbon Nanotube Catalyst
Authors: Zhou Chunmei , Deng Weiping , Wan Xiaoyue , Zhang Qinghong , Yang Yanhui , Wang Ye
Published: July 2015

The aerobic oxidation of 5‐hydroxymethylfurfural (HMF) into 2,5‐furandicarboxylic acid (FDCA) is one of the most attractive reactions to establish biomass‐based sustainable chemical processes. Supported Au and Pt catalysts have mainly been reported for this reaction, but excess amounts of base additives are generally required, which makes the process less green. Here, we demonstrate that Pt nanoparticles loaded on functionalized carbon nanotubes (CNTs) can catalyze the aerobic oxidation of HMF to FDCA in water without any base additives. Kinetic studies suggest a tandem reaction mechanism via 2,5‐diformylfuran and 5‐formylfurancarboxylic acid intermediates. It has been clarified that the oxygen‐containing functional groups, in particular carbonyl/quinone and/or phenol groups, on CNT surfaces play crucial roles in FDCA formation. These functional groups could enhance the adsorption of HMF as well as the reaction intermediates from water and might facilitate hydrogen transfer.
The Change in Antioxidant Properties of Dextran‐Coated Redox Active Nanoparticles Due to Synergetic Photoreduction–Oxidation
Authors: Barkam Swetha , Das Soumen , Saraf Shashank , McCormack Rameech , Richardson David , Atencio Leonel , Moosavifazel Vanessa , Seal Sudipta
Published: July 2015

Nanoparticles have proven to be novel material with resourceful applications in the field of nanomedicine. Cerium oxide nanoparticles (CNPs) coated with dextran (Dex–CNPs) have been shown to exhibit anticancer properties which is attributed to the change in oxidation states mediated at the oxygen vacancies on the surface of CNPs. In this study, the extreme sensitivity of Dex–CNPs to visible light is demonstrated using room light with a clear indication of synergetic phenomenon of photoreduction of CNPs in the presence of dextran which undergoes simultaneous oxidation. The phenomenon was further confirmed through a systematic time‐based expedited study using a high intensity visible light source. The physiochemical changes of Dex–CNPs such as dispersion stability, pH, surface chemistry, antioxidant property, cytotoxicity and the surrounding microenvironment of Dex–CNPs were significantly altered on exposure to visible light, thereby affecting the biological response. Given the significance of nanoparticles which are widely researched nanomaterials, in different fields of nanotechnology and biomedicine, this study demonstrates the significant changes in physiochemical properties of Dex–CNPs with light. The photoreduction of Dex–CNPs affects its bifunctional applications in cancer therapy and thereby this study puts forward the necessity to preserve and sustain their properties through proper storage.
Synthesis, Molecular Structure, and Chiroptical Properties of Dibenzylidene Derivatives of Bicyclo[3.3.1]nonane and Brexane
Authors: Stončius Sigitas , Neniškis Algirdas , Loganathan Nagarajan , Wendt Ola F.
Published: July 2015

Synthesis of several enantiomerically pure unsaturated bicyclo[3.3.1]nonane and related brexane (tricyclo[4.3.0.03,7]nonane) derivatives bearing exocyclic benzylidene substituents from readily available (+)‐(1S,5S)‐bicyclo[3.3.1]nonane‐2,6‐dione was accomplished. Molecular geometry and chiroptical properties of compounds with enone and styrene chromophores were studied by X‐ray diffraction analysis, molecular modeling, and circular dichroism (CD) spectroscopy. Difunctional 3,7‐dibenzylidenebicyclo[3.3.1]nonanes, such as 2 and 7, 8, 9, exhibited intense CD couplets, arising from the exciton coupling between the two unsaturated chromophores. The observed negative sign of the exciton couplets is congruent with the negative twist (negative chirality) defined by the two interacting transition dipoles. The sign of the Cotton effect corresponding to the π→π* transitions in the CD spectra of monoenone 4 and tricyclic brexane acetate 11 was correlated with the intrinsic dissymmetry (helicity) of the styrene chromophore. Chirality 27:728–737, 2015. © 2015 Wiley Periodicals, Inc.
Chemieunterricht und Chemiedidaktik an berufsbildenden Schulen
Authors: Laudonia Ivano , Eilks Ingo
Published: July 2015

Beiträge zur beruflichen Bildung sind in den Zeitschriften der deutschsprachigen Chemiedidaktik eher selten. Aber auch an berufsbildenden Schulen findet Chemieunterricht statt. Dieser Beitrag diskutiert die Stellung und den Stand des Chemieunterrichts an berufsbildenden Schulen im deutschsprachigen Raum. Ausgewählte Trends aus der Didaktik der beruflichen Bildung werden diskutiert und mit Entwicklungen in der allgemeinbildenden Chemiedidaktik in Beziehung gesetzt.
Silicone als Bindeglied zwischen anorganischer und organischer Chemie aus fachlicher und fachdidaktischer Sicht
Authors: Feierabend Timo , Haucke Kerstin , Mowka Marie‐Ann
Published: July 2015

Obwohl uns Silicone in allen Bereichen des Alltags begegnen und sie sich durch ihre nützlichen Eigenschaften einen festen Platz im Haushalt, im Auto oder im Baubereich erobert haben, wird ihr Einsatz nicht immer positiv bewertet. So werden z. B. aktuell Debatten um die negativen Auswirkungen von Siliconen in Haarpflegeprodukten geführt. Dem gegenüber steht der Wunsch nach Erhalt von Kulturdenkmälern, die zum Schutz mit Siliconen behandelt werden. Trotz der Präsenz dieser Stoffklasse besteht bei Schülerinnen und Schülern nur ein geringes Fachwissen über Silicone. Der Hauptgrund hierfür liegt sicherlich darin, dass das Element Silicium und die darauf basierenden Silicone als Unterrichtsinhalte in den Lehrplänen der verschiedenen Bundesländer eine eher untergeordnete Rolle spielen und häufig nur als fakultative Inhalte für den Chemieunterricht ausgewiesen werden. Aus diesem Grund wurden im Rahmen zweier Qualifikationsarbeiten experimentelle und konzeptionelle Herangehensweisen für die Schwerpunkte Silicone im Bautenschutz und Silicone in der Haarkosmetik entwickelt. Im Artikel werden ausgewählte Ergebnisse zum Schwerpunkt Silicone im Bautenschutz vorgestellt. Auszüge aus der Qualifikationsarbeit mit dem Schwerpunkt Silicone in der Haarkosmetik werden als Online‐Ergänzung zur Verfügung gestellt. Die Ergebnisse beider Arbeiten können Anregungen für eine kontroverse Diskussion zum Einsatz von Siliconen liefern. Im Artikel wird darüber hinaus aufgezeigt, wie das Thema Silicone auch in der Lehreraus‐ und ‐fortbildung sowie im Rahmen einer Schülerakademie integriert werden kann.
Aptamer for imaging and therapeutic targeting of brain tumor glioblastoma
Authors: Delač Mateja , Motaln Helena , Ulrich Henning , Lah Tamara T.
Published: July 2015

Aptamers are short single‐stranded nucleic acids (RNA or ssDNA), identified by an in vitro selection process, denominated SELEX, from a partially random oligonucleotide library. They bind to a molecular target, a protein or other complex macromolecular structures of interest with high affinity and specificity, comparable to those of antibodies. Recently, aptamer selection protocols were developed for targeting living cells, including tumors. Chemical modifications of the aptamers and modalities of their detection and delivery systems are already available with high selectivity and targeting ability for the desired cancer cell type, making them promising for diagnosis and therapy. Glioblastoma multiformae represents the most malignant and fatal stage of glioma, and is also the most frequent brain tumor. Glioblastoma‐specific aptamers were developed by either targeting the whole cell surface or known glioma biomarkers. These aptamers may gain importance for imaging, tumor cell isolation from biopsies and drug delivery. In biomedical imaging techniques, aptamers coupled with radionuclide or fluorescent labels, bioconjugates and nanoparticles offer an advanced, noninvasive manner for defining the glioblastoma tissue border. Though single modality aptamer imaging probes have some limitations, these are overcome by the use of multimodal probes. Due to selectivity and chemical characteristics, aptamers can be coupled to functionalized nanoparticles and loaded with a drug, appeared promising for in vivo targeting of glioblastoma. Finally, aptamers are effective mediators for gene silencing when coupled to small interfering RNA and a viral vector, thus providing a novel tool with enhanced targeting capability in drug delivery, designed for tailored treatment of glioblastoma patients. © 2015 International Society for Advancement of Cytometry
Prediction of thrombo‐embolic risk in patients with hypertrophic cardiomyopathy (HCMRisk‐CVA)
Authors: Guttmann Oliver P. , Pavlou Menelaos , O'Mahony Constantinos , Monserrat Lorenzo , Anastasakis Aristides , Rapezzi Claudio , Biagini Elena , Gimeno Juan Ramon , Limongelli Giuseppe , Garcia‐Pavia Pablo , McKenna William J. , Omar Rumana Z. , Elliott Perry M. ,   for the Hypertrophic Cardiomyopathy Outcomes Investigators
Published: July 2015

Aims

Atrial fibrillation (AF) and thrombo‐embolism (TE) are associated with reduced survival in hypertrophic cardiomyopathy (HCM), but the absolute risk ofTEin patients with and withoutAFis unclear. The primary aim of this study was to derive and validate a model for estimating the risk ofTEinHCM. Exploratory analyses were performed to determine predictors ofTE, the performance of theCHA2DS2‐VAScscore, and outcome with vitamin K antagonists (VKAs).

Methods and results

A retrospective, longitudinal cohort of seven institutions was used to develop multivariable Cox regression models fitted with pre‐selected predictors. Bootstrapping was used for validation. Of 4821HCMpatients recruited between 1986 and 2008, 172 (3.6%) reached the primary endpoint of cerebrovascular accident (CVA), transient ischaemic attack (TIA), or systemic peripheral embolus within 10 years. A total of 27.5% of patients had aCHA2DS2‐VAScscore of 0, of whom 9.8% developedTEduring follow‐up. Cox regression revealed an association betweenTEand age,AF, the interaction between age andAF,TEprior to first evaluation,NYHAclass, left atrial (LA) diameter, vascular disease, and maximalLVwall thickness. There was a curvilinear relationship betweenLAsize andTErisk. The model predictedTEwith a C‐index of 0.75 [95% confidence interval (CI) 0.70–0.80] and the D‐statistic was 1.30 (95%CI1.05–1.56).VKAtreatment was associated with a 54.8% (95%CI31–97%,P= 0.037) relative risk reduction inHCMpatients withAF.

Conclusions

The study shows that the risk ofTEinHCMpatients can be identified using a small number of simple clinical features.LAsize, in particular, should be monitored closely, and the assessment and treatment of conventional vascular risk factors should be routine practice in older patients. Exploratory analyses show for the first time evidence for a reduction ofTEwithVKAtreatment. TheCHA2DS2‐VAScscore does not appear to correlate well with the clinical outcome in patients withHCMand should not be used to assessTErisk in this population.
A Double‐Cavity‐Containing Porphyrin Host as a Highly Stable Epoxidation Catalyst
Authors: Thomassen Paul J. , Varghese Shaji , Bijsterveld Edward J. A. , Thordarson Pall , Elemans Johannes A. A. W. , Rowan Alan E. , Nolte Roeland J. M.
Published: July 2015

We describe a manganese porphyrin catalyst containing two adjacent cavities, which can be used for the epoxidation of alkenes by sodium hypochlorite. A pyridine ligand bound in one of the cavities regulates the rate and selectivity of the epoxidation reaction that takes place in the adjoining cavity. Pyridine binding studies suggest that site‐to‐site communication exists between the two cavities. The alkene substrates are completely converted into epoxides by the manganese double‐cavity catalyst, but the observed epoxidation rates are low. These low rates are proposed to be a result of the energetically less favourable binding of the substrate into the cavity containing the active site due to an allosteric pinching effect. In the manganese double‐cavity arrangement the catalytically active manganese complex is efficiently protected against decomposition, leading to a catalytic system with enhanced stability. The presented work may open a new route to the construction of highly stable catalysts of which the activity and selectivity may eventually be controlled by allosteric interactions.
Construction of Diverse and Functionalized 2H‐Chromenes by Organocatalytic Multicomponent Reactions
Authors: Cai Hongyun , Xia Likai , Lee Yong Rok , Shim Jae‐Jin , Kim Sung Hong
Published: July 2015

A green and efficient one‐pot process for the construction of diverse and functionalized 2H‐chromenes was developed by using multicomponent reactions of salicylaldehydes, alkynes (i.e., propiolate and acetylenedicarboxylates), and alcohols. This new protocol was achieved by using L‐proline as a mild and green organocatalyst and offers several advantages such as economic availability, low toxicity, ease of handling, high regioselectivity, and environmentally benign nature under mild reaction conditions. As an extension of this method, quinoline derivatives were synthesized by replacing salicylaldehyde with 2‐aminobenzaldehyde, and the 2‐hydroxy‐2H‐chromenes prepared by this approach were also successfully transformed into biologically interesting coumarins through an oxidation reaction.
A rational approach to selecting and ranking some pharmaceuticals of concern for the aquatic environment and their relative importance compared with other chemicals
Authors: Donnachie Rachel L. , Johnson Andrew C. , Sumpter John P.
Published: July 2015

Aquatic organisms can be exposed to thousands of chemicals discharged by the human population. Many of these chemicals are considered disruptive to aquatic wildlife, and the literature on the impacts of these chemicals grows daily. However, because time and resources are not infinite, research must focus on the chemicals that represent the greatest threat. One group of chemicals of increasing concern is pharmaceuticals, for which the primary challenge is to identify which represent the greatest threat. In the present study, a list of 12 pharmaceuticals was compiled based on scoring the prevalence of different compounds from previous prioritization reviews. These included rankings based on prescription data, environmental concentrations, predicted environmental concentration/predicted no-effect concentration (PEC/PNEC) ratios, persistency/bioaccumulation/(eco)toxicity (PBT), and fish plasma model approaches. The most frequently cited were diclofenac, paracetamol, ibuprofen, carbamazepine, naproxen, atenolol, ethinyl estradiol, aspirin, fluoxetine, propranolol, metoprolol, and sulfamethoxazole. For each pharmaceutical, literature on effect concentrations was compiled and compared with river concentrations in the United Kingdom. The pharmaceuticals were ranked by degree of difference between the median effect and median river concentrations. Ethinyl estradiol was ranked as the highest concern, followed by fluoxetine, propranolol, and paracetamol. The relative risk of these pharmaceuticals was compared with those of metals and some persistent organic pollutants. Pharmaceuticals appear to be less of a threat to aquatic organisms than some metals (Cu, Al, Zn) and triclosan, using this ranking approach. Environ Toxicol Chem 2016;35:1021–1027. © 2015 The Authors. Environmental Toxicology and Chemistry Published by Wiley Periodicals, Inc. on behalf of SETAC.
Sorption, uptake, and biotransformation of 17β-estradiol, 17α-ethinylestradiol, zeranol, and trenbolone acetate by hybrid poplar
Authors: Bircher Sam , Card Marcella L. , Zhai Guangshu , Chin Yu-Ping , Schnoor Jerald L.
Published: July 2015

Hormonally active compounds may move with agricultural runoff from fields with applied manure and biosolids into surface waters where they pose a threat to human and environmental health. Riparian zone plants could remove hormonally active compounds from agricultural runoff. Therefore, sorption to roots, uptake, translocation, and transformation of 3 estrogens (17β-estradiol, 17α-ethinylestradiol, and zeranol) and 1 androgen (trenbolone acetate) commonly found in animal manure or biosolids were assessed by hydroponically grown hybrid poplar, Populus deltoides x nigra, DN-34, widely used in riparian buffer strips. Results clearly showed that these hormones were rapidly removed from 2 mg L–1 hydroponic solutions by more than 97% after 10 d of exposure to full poplar plants or live excised poplars (cut-stem, no leaves). Removals by sorption to dead poplar roots that had been autoclaved were significantly less, 71% to 84%. Major transformation products (estrone and estriol for estradiol; zearalanone for zeranol; and 17β-trenbolone from trenbolone acetate) were detected in the root tissues of all 3 poplar treatments. Root concentrations of metabolites peaked after 1 d to 5 d and then decreased in full and live excised poplars by further transformation. Metabolite concentrations were less in dead poplar treatments and only slowly increased without further transformation. Taken together, these findings show that poplars may be effective in controlling the movement of hormonally active compounds from agricultural fields and avoiding runoff to streams. Environ Toxicol Chem 2015;34:2906–2913. © 2015 SETAC
Arabian killifish (Aphanius dispar) embryos: A model organism for the risk assessment of the Arabian Gulf coastal waters
Authors: Saeed Suhur , Al-Naema Nayla , Butler Josh D. , Febbo Eric J.
Published: July 2015

Fish embryos are excellent models for studies aimed at understanding toxic mechanisms and indications of possible acute and chronic effects. For the past 3 yr, an Arabian killifish (Aphanius dispar) fish embryo test has been developed in the authors' laboratory as a routine ecotoxicological test that can be used to support risk assessment of potential contaminants in Arabian Gulf coastal waters. Tests were conducted with 3 reference toxicants (3,4-dichloroaniline [DCA], sodium dodecyl sulfate, and zinc sulfate [Zn]) and chlorine, a disinfectant used widely in industrial cooling systems around the Arabian Gulf region. The 50% effect concentration (EC50) for DCA was 0.47 mg/L and 1.89 mg/L for embryos exposed before 6 hpf and after 168 hpf, respectively. Sublethal effects were mainly observed at concentrations above 2.5 mg/L, the effects included severe pericardial edema and tail shortage. The sodium dodecyl sulfate ionic surfactant caused mortality at both early and late stages of embryo development; it caused coagulation, severe deformity, and hemolysis. Both the EC50 and the 50% lethal concentration (LC50) for sodium dodecyl sulfate were 9.37 mg/L. Salinity influenced the toxicity of Zn to killifish embryos: at 40 psu Zn was found not to be toxic, whereas at 20 psu toxicity had increased significantly (p < 0.05). Values of EC50 and LC50 were 2.5 mg/L and 4 mg/L, respectively. Concentrations above 15 mg/L in embryos were often accompanied by upper abdominal edema and inhibition of growth, especially evident in the tail. Chlorine caused mortality at a lower concentration; for example, at 0.05 mg/L 33% of embryos were found dead at the end of the experiment. The LC50 for chlorine was determined to be 0.08 mg/L. Examination of the existing literature showed similar results to the present study's findings. The results suggest a more comparable sensitivity of killifish embryos to that of other fish embryo test recommended species. The present study's findings support the ability of killifish to be an indicator organism for environmental risk assessments of Arabian Gulf waters. Benefits include sensitivity to a wide range of substances and conditions, animal alternative, ease of fish breeding, and clarity of the embryos. Environ Toxicol Chem 2015;34:2898–2905. © 2015 SETAC