bluuebunny/crossref_metadata_2025 huggingface dataset:
Aspectos geológicos, históricos e estado de conservação das fortificações da Baixada Santista, litoral paulista
Authors: Mucivuna Vanessa Costa , Del Lama Eliane Aparecida , Garcia Maria da Glória Motta
Published: December 2016

No Brasil, as fortificações militares foram construídas em locais estratégicos com a finalidade de defesa do território. Atualmente, muitas delas encontram-se tombadas como representantes do período colonial e são utilizadas com fins turísticos. Este trabalho tem por objetivo identificar as rochas utilizadas nas construções das fortificações militares construídas entre os séculos XVI e XX na Baixada Santista nos municípios de Bertioga, Guarujá e Praia Grande (SP) e inferir sua provável proveniência. A identificação do tipo de material usado nessas construções permite compreender a história, a cultura, a evolução técnica e a geodiversidade da época. Buscou-se ainda apresentar um histórico dessas fortificações e avaliar seu estado de conservação atual, para poder subsidiar as ações de preservação e manutenção do patrimônio cultural pétreo. As fortificações foram edificadas com granitos e gnaisses que afloram na região. Apesar de algumas serem tombadas pelo Instituto do Patrimônio Histórico e Artístico Nacional (IPHAN) e terem uso voltado à visitação turística, parte delas está deteriorada e necessita-se de indispensáveis reparos para que esse patrimônio, representativo de uma época da defesa do território paulista, seja conservado e preservado.
Anomalias de flúor nas águas subterrâneas do estado de São Paulo
Authors: Ezaki Sibele , Pérez-Aguilar Annabel , Hypolito Raphael , Shinzato Mirian Chieko
Published: December 2016

O presente trabalho apresenta uma compilação de dados da literatura sobre as principais ocorrências de íon fluoreto (F-) nas águas subterrâneas do estado de São Paulo. Os resultados desse estudo revelaram que, pelo menos, 208 poços tubulares apresentam concentrações elevadas de F- (> 1,0 mg dm-3), das quais 122 são consideradas anômalas (> 1,5 mg dm-3) e prejudiciais à saúde, quando ingeridas em excesso. O aquífero mais estudado tem sido o Guarani, devido a sua elevada produtividade e explotação, mas também se destacam os aquíferos Cristalino (Pré-Cambriano), Serra Geral e Tubarão, além do Aquitarde Passa Dois. O enriquecimento pretérito dos aquíferos em F- está relacionado a processos hidrotermais e eventos tectônicos com controles estruturais, como a quebra do supercontinente Gondwana, que teriam propiciado a circulação de soluções residuais do magma, provocando mineralizações, e a remobilização do F- contido nas rochas percoladas. Os processos atuais de liberação de F- para as águas são atribuídos à interação rocha-água sob condições hidroquímicas com pH alcalino, em águas tipicamente Na-HCO3, pobres em Ca2+ e sob influência da força iônica das soluções, do tempo de contato, profundidade, temperatura, capacidade de troca iônica, entre outros fatores. Nos aquíferos fissurais de composição granítica e de rochas vulcânicas, os minerais que podem fornecer flúor para as águas são biotita e anfibólio (onde o F- encontra-se substituindo o OH-, dada à similaridade de seus raios iônicos) e, ocasionalmente, fluorita secundária preenchendo fraturas, além de apatita. Em aquíferos sedimentares, o F- se encontra principalmente na estrutura de argilominerais (illita, muscovita, esmectita, vermiculita, caulinita, entre outros) também substituindo os íons OH-. Portanto, a presença de elevados teores de F- nas águas subterrâneas está intrinsicamente associada às características e aos tipos de minerais de cada aquífero.
Filamin, a synaptic organizer in Drosophila, determines glutamate receptor composition and membrane growth
Authors: Lee GaYoung , Schwarz Thomas L
Published: December 2016

Filamin is a scaffolding protein that functions in many cells as an actin-crosslinker. FLN90, an isoform of the Drosophila ortholog Filamin/cheerio that lacks the actin-binding domain, is here shown to govern the growth of postsynaptic membrane folds and the composition of glutamate receptor clusters at the larval neuromuscular junction. Genetic and biochemical analyses revealed that FLN90 is present surrounding synaptic boutons. FLN90 is required in the muscle for localization of the kinase dPak and, downstream of dPak, for localization of the GTPase Ral and the exocyst complex to this region. Consequently, Filamin is needed for growth of the subsynaptic reticulum. In addition, in the absence of filamin, type-A glutamate receptor subunits are lacking at the postsynapse, while type-B subunits cluster correctly. Receptor composition is dependent on dPak, but independent of the Ral pathway. Thus two major aspects of synapse formation, morphological plasticity and subtype-specific receptor clustering, require postsynaptic Filamin.
Spatial patterning of P granules by RNA-induced phase separation of the intrinsically-disordered protein MEG-3
Authors: Smith Jarrett , Calidas Deepika , Schmidt Helen , Lu Tu , Rasoloson Dominique , Seydoux Geraldine
Published: December 2016

RNA granules are non-membrane bound cellular compartments that contain RNA and RNA binding proteins. The molecular mechanisms that regulate the spatial distribution of RNA granules in cells are poorly understood. During polarization of the C. elegans zygote, germline RNA granules, called P granules, assemble preferentially in the posterior cytoplasm. We present evidence that P granule asymmetry depends on RNA-induced phase separation of the granule scaffold MEG-3. MEG-3 is an intrinsically disordered protein that binds and phase separates with RNA in vitro. In vivo, MEG-3 forms a posterior-rich concentration gradient that is anti-correlated with a gradient in the RNA-binding protein MEX-5. MEX-5 is necessary and sufficient to suppress MEG-3 granule formation in vivo, and suppresses RNA-induced MEG-3 phase separation in vitro. Our findings suggest that MEX-5 interferes with MEG-3’s access to RNA, thus locally suppressing MEG-3 phase separation to drive P granule asymmetry. Regulated access to RNA, combined with RNA-induced phase separation of key scaffolding proteins, may be a general mechanism for controlling the formation of RNA granules in space and time.
Interannual variability in ozone removal by a temperate deciduous forest
Authors: Clifton O. E. , Fiore A. M. , Munger J. W. , Malyshev S. , Horowitz L. W. , Shevliakova E. , Paulot F. , Murray L. T. , Griffin K. L.
Published: December 2016

The ozone (O3) dry depositional sink and its contribution to observed variability in tropospheric O3 are both poorly understood. Distinguishing O3 uptake through plant stomata versus other pathways is relevant for quantifying the O3 influence on carbon and water cycles. We use a decade of O3, carbon, and energy eddy covariance (EC) fluxes at Harvard Forest to investigate interannual variability (IAV) in O3 deposition velocities (
). In each month, monthly mean
for the highest year is twice that for the lowest. Two independent stomatal conductance estimates, based on either water vapor EC or gross primary productivity, vary little from year to year relative to canopy conductance. We conclude that nonstomatal deposition controls the substantial observed IAV in summertime
during the 1990s over this deciduous forest. The absence of obvious relationships between meteorology and
implies a need for additional long‐term, high‐quality measurements and further investigation of nonstomatal mechanisms.
Satellite sea surface temperatures along the West Coast of the United States during the 2014–2016 northeast Pacific marine heat wave
Authors: Gentemann Chelle L. , Fewings Melanie R. , García‐Reyes Marisol
Published: December 2016

From January 2014 to August 2016, sea surface temperatures (SSTs) along the Washington, Oregon, and California coasts were significantly warmer than usual, reaching a maximum SST anomaly of 6.2°C off Southern California. This marine heat wave occurred alongside the Gulf of Alaska marine heat wave and resulted in major disturbances in the California Current ecosystem and massive economic impacts. Here we use satellite and blended reanalysis products to report the magnitude, extent, duration, and evolution of SSTs and wind stress anomalies along the West Coast of the continental United States during this event. Nearshore SST anomalies along the entire coast were persistent during the marine heat wave, and only abated seasonally, during spring upwelling‐favorable wind stress. The coastal marine heat wave weakened in July 2016 and disappeared by September 2016.
Increase in the number of extremely strong fronts over Europe? A study based on ERA‐Interim reanalysis (1979–2014)
Authors: Schemm S. , Sprenger M. , Martius O. , Wernli H. , Zimmer M.
Published: December 2016

Evidence is presented that the frequency of extremely strong fronts, which occur mainly in summer, has increased over Europe in ERA‐Interim reanalyses data (1979–2014). Fronts are defined using a common detection scheme based on gradients of equivalent potential temperature (θe) at 850 hPa. The frequency increase is due to increasing atmospheric humidity, which in turn is reported as statistically significant over Europe in the Fifth Assessment Report of the Intergovernmental Panel on Climate Change (IPCC AR5). There is no trend in the frequency of extremely strong fronts in North America where humidity trends are, according to the IPCC AR5, close to zero. Because frontal precipitation increases with frontal strength, measured by the θe gradient, the increase in the number of extremely strong fronts may help explain regional patterns of longer‐term trends in strong precipitation events.
Tomographic reconstruction of an aerosol plume using passive multiangle observations from the MISR satellite instrument
Authors: Garay Michael J. , Davis Anthony B. , Diner David J.
Published: December 2016

We present initial results using computed tomography to reconstruct the three‐dimensional structure of an aerosol plume from passive observations made by the Multi‐angle Imaging SpectroRadiometer (MISR) instrument on NASA's Terra satellite. MISR views the Earth from nine different angles at four visible and near‐infrared wavelengths. Adopting the 672 nm channel, we treat each view as an independent measure of aerosol optical thickness along the line of sight at 1.1 km resolution. A smoke plume over dark water is selected as it provides a more tractable lower boundary condition for the retrieval. A tomographic algorithm is used to reconstruct the horizontal and vertical aerosol extinction field for one along‐track slice from the path of all camera rays passing through a regular grid. The results compare well with ground‐based lidar observations from a nearby Micropulse Lidar Network site.
Double‐counting challenges the accuracy of high‐latitude methane inventories
Authors: Thornton Brett F. , Wik Martin , Crill Patrick M.
Published: December 2016

Quantification of the present and future contribution to atmospheric methane (CH4) from lakes, wetlands, fluvial systems, and, potentially, coastal waters remains an important unfinished task for balancing the global CH4 budget. Discriminating between these sources is crucial, especially across climate‐sensitive Arctic and subarctic landscapes and waters. Yet basic underlying uncertainties remain, in such areas as total wetland area and definitions of wetlands, which can lead to conflation of wetlands and small ponds in regional studies. We discuss how in situ sampling choices, remote sensing limitations, and isotopic signature overlaps can lead to unintentional double‐counting of CH4 emissions and propose that this double‐counting can explain a pan‐Arctic bottom‐up estimate from published sources, 59.7 Tg yr−1 (range 36.9–89.4 Tg yr−1) greatly exceeding the most recent top‐down inverse modeled estimate of the pan‐Arctic CH4 budget (23 ± 5 Tg yr−1).
Using a Vapor‐Phase Surfactant to Control Gold Metal Plate Growth
Authors: Zhang Weipeng , Dey Gangotri , Mandia David J. , Barry Seán T.
Published: December 2016

Hexamethyldisilazide‐1,3‐diisopropylimidazolidine‐2‐ylidenegold(I) (1) is used to deposit gold microplates with (111) faces. In the absence of any secondary vapor‐phase surfactant, these plates show secondary nucleation and growth of gold metal nanoparticles on the (111) faces. When tetrahydrothiophene (THT) is used as a secondary, vapor‐phase surfactant, plate size increases, and secondary nucleation is controllable by temperature. Deposition of gold microplates at 370 °C using a 45 mTorr overpressure of THT shows the best experimental results, growing 20 µm2 plateaus with no apparent secondary nucleation. Computational modelling demonstrates that THT is a stronger surfactant than the carbene ligand (from the gold precursor) due to steric hindrance from the alkyl groups present in the carbene ligand.
A Multicomponent Strategy for the Regioselective Synthesis of [1,3]‐Thiazinones from an Abundant Feedstock: Scope and Structural Elucidation
Authors: Wadhwa Preeti , Shube Hussen Abdulkadir , Sharma Anuj
Published: December 2016

A novel and regioselective protocol for the synthesis of [1,3]‐thiazinones via multicomponent reactions of readily available isothiocyanates, hydrazine monohydrate, aldehydes and dialkyl acetylenedicarboxylates is described. This approach exhibits operational simplicity, offering a new and expedient strategy for the direct synthesis of synthetically useful [1,3]‐thiazinone compounds in good to excellent yields. The method could provide a low‐cost and environmentally benign alternative to currently employed methods. Moreover, unambiguous determination of the single product regioisomer through detailed 2D NMR spectroscopy, the scope and limitations of this environmentally friendly domino reaction are discussed.
Versatile Trityl Spin Labels for Nanometer Distance Measurements on Biomolecules In Vitro and within Cells
Authors: Jassoy J. Jacques , Berndhäuser Andreas , Duthie Fraser , Kühn Sebastian P. , Hagelueken Gregor , Schiemann Olav
Published: December 2016

Structure determination of biomacromolecules under in‐cell conditions is a relevant yet challenging task. Electron paramagnetic resonance (EPR) distance measurements in combination with site‐directed spin labeling (SDSL) are a valuable tool in this endeavor but the usually used nitroxide spin labels are not well‐suited for in‐cell measurements. In contrast, triarylmethyl (trityl) radicals are highly persistent, exhibit a long relaxation time and a narrow spectral width. Here, the synthesis of a versatile collection of trityl spin labels and their application in in vitro and in‐cell trityl–iron distance measurements on a cytochrome P450 protein are described. The trityl labels show similar labeling efficiencies and better signal‐to‐noise ratios (SNR) as compared to the popular methanethiosulfonate spin label (MTSSL) and enabled a successful in‐cell measurement.
Development of Cell‐Permeable, Non‐Helical Constrained Peptides to Target a Key Protein–Protein Interaction in Ovarian Cancer
Authors: Wiedmann Mareike M. , Tan Yaw Sing , Wu Yuteng , Aibara Shintaro , Xu Wenshu , Sore Hannah F. , Verma Chandra S. , Itzhaki Laura , Stewart Murray , Brenton James D. , Spring David R.
Published: December 2016

There is a lack of current treatment options for ovarian clear cell carcinoma (CCC) and the cancer is often resistant to platinum‐based chemotherapy. Hence there is an urgent need for novel therapeutics. The transcription factor hepatocyte nuclear factor 1β (HNF1β) is ubiquitously overexpressed in CCC and is seen as an attractive therapeutic target. This was validated through shRNA‐mediated knockdown of the target protein, HNF1β, in five high‐ and low‐HNF1β‐expressing CCC lines. To inhibit the protein function, cell‐permeable, non‐helical constrained proteomimetics to target the HNF1β–importin α protein–protein interaction were designed, guided by X‐ray crystallographic data and molecular dynamics simulations. In this way, we developed the first reported series of constrained peptide nuclear import inhibitors. Importantly, this general approach may be extended to other transcription factors.
A Redox‐Induced Spin‐State Cascade in a Mixed‐Valent Fe3(μ3‐O) Triangle
Authors: Govor Evgen V. , Al‐Ameed Karrar , Chakraborty Indranil , Coste Carla S. , Govor Olena , Sanakis Yiannis , McGrady John E. , Raptis Raphael G.
Published: December 2016

One‐electron reduction of a pyrazolate‐bridged triangular Fe3(μ3‐O) core induces a cascade wherein all three metal centers switch from high‐spin Fe3+ to low‐spin Fe2.66+. This hypothesis is supported by spectroscopic data (1H‐NMR, UV‐vis‐NIR, infra‐red, 57Fe‐Mössbauer, EPR), X‐ray crystallographic characterization of the cluster in both oxidation states and also density functional theory. The reduction induces substantial contraction in all bond lengths around the metal centers, along with diagnostic shifts in the spectroscopic parameters. This is, to the best of our knowledge, the first example of a one‐electron redox event causing concerted change in multiple iron centers.
Nickel‐Catalyzed CO2 Rearrangement of Enol Metal Carbonates for the Efficient Synthesis of β‐Ketocarboxylic Acids
Authors: Ninokata Ryo , Yamahira Tatsuya , Onodera Gen , Kimura Masanari
Published: December 2016

4‐Methylene‐1,3‐dioxolan‐2‐ones underwent oxidative addition of a Ni0 catalyst in the presence of Me2Al(OMe), followed by a coupling reaction with alkynes, to form δ,ϵ‐unsaturated β‐ketocarboxylic acids with high regio‐ and stereoselectivity. The reaction proceeds by [1,3] rearrangement of an enol metal carbonate intermediate and the formal reinsertion of CO2.
Small Molecule Microarray Based Discovery of PARP14 Inhibitors
Authors: Peng Bo , Thorsell Ann‐Gerd , Karlberg Tobias , Schüler Herwig , Yao Shao Q.
Published: December 2016

Poly(ADP‐ribose) polymerases (PARPs) are key enzymes in a variety of cellular processes. Most small‐molecule PARP inhibitors developed to date have been against PARP1, and suffer from poor selectivity. PARP14 has recently emerged as a potential therapeutic target, but its inhibitor development has trailed behind. Herein, we describe a small molecule microarray‐based strategy for high‐throughput synthesis, screening of >1000 potential bidentate inhibitors of PARPs, and the successful discovery of a potent PARP14 inhibitor H10 with >20‐fold selectivity over PARP1. Co‐crystallization of the PARP14/H10 complex indicated H10 bound to both the nicotinamide and the adenine subsites. Further structure–activity relationship studies identified important binding elements in the adenine subsite. In tumor cells, H10 was able to chemically knockdown endogenous PARP14 activities.
Improved gas selectivity of polyetherimide membrane by the incorporation of PIM polyimide phase
Authors: García María G. , Marchese José , Ochoa Nelio A.
Published: December 2016

The aim of this work was to prepare blend membranes of a polyetherimide (PEI) and different ratios of a microporous polyimide (PIM‐B) in order to obtain an improved material for gas selectivity. Miscibility of the membranes was studied through fourier transform infrared spectroscopy (FTIR), Fluorescence, ultraviolet‐visible spectroscopy (UV–vis), polarize light microscope images, X‐ray diffraction (XRD), and differential scanning calorimetry analysis. Gas permeability assays were also performed. Results showed blends were partially miscible along the different ratios due to the existence of: (i) absorption shoulders at lower wavenumbers on the carbonyl stretching band; (ii) red‐shifting of Fluorescence and UV–vis absorption bands; (iii) decreasing of d‐spacing as the amount of PIM‐B phase increased; and (iv) composition‐dependent glass transition temperatures (Tgs). The mobility selectivity (Di/j) dominated H2 and O2 gas separations. High solubility coefficients (S) linked to PIM‐B microporosity improved the ideal gas selectivity of the blend membranes. PEI/PIM‐B membrane at the ratio of 80/20 showed impressive H2/CO2 (8.66) and O2/N2 (10.90) gas separation factors. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44682.
Sol–gel preparation of ultralow refractive index silica coatings with hydroxypropyl‐beta‐cyclodextrin as porogen
Authors: Yang Bowen , Luo Jianhui , Xia Bibo , Li Yuanyang , Zhang Shuming , jiang Bo
Published: December 2016

Ultralow refractive index films were prepared based on a base‐catalyzed sol–gel process using methyltriethoxysilane (MTES), tetraethylorthosilicate (TEOS) as co‐precursors, and hydroxypropyl‐beta‐cyclodextrin (HPCD) as porogen. After further modification by hexamethylisilazane (HMDS), the lowest refractive index of these silica coatings obtained from the hybrid sol was 1.05 and the static water contact angles of the coatings increased from 66.4° to 128.7°. The effect of weight ratio of HPCD to SiO2 on the refractive index and on the formation of coating films were systematically studied. The data showed that the films prepared with HPCD as porogen got a pore diameter around 4 nm. Compared with those templates such as poloxamer (F127), HPCD not only perform well in decreasing the refractive index of films, but also eliminate light scattering caused by mesopore of the film, will have potential value in the field of surfactant‐templated methods. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44686.
Optimal inventory and insurance decisions for a supply chain financing system with downside risk control
Authors: Jin Wei , Luo Jianwen
Published: December 2016

This research considers a supply chain financing system consisting of a capital‐constrained retailer, a supplier and a risk‐averse bank. The retailer may be subject to credit limit because of the bank's downside risk control, and hence, credit insurance should be needed to enhance his financing ability. This paper develops a mathematical optimization model by incorporating insurance policy into the well‐known newsvendor financing model. The optimal inventory and insurance decisions under different scenarios, that is, no insurance, insurance with symmetric information and insurance with asymmetric information, are derived. This work also discusses how the retailer's capital level, the bank's risk aversion, and the insurer's loading factor affect the optimal inventory and insurance decisions. The results show that the retailer will use credit insurance if he is sufficiently capital‐constrained or the insurer's risk loading factor is low enough. Moreover, credit insurance can bring Pareto improvement to the supply chain financing system, which verifies the prevalence of credit insurance in practice. Several numerical experiments are presented to examine the sensitivities of key parameters. Copyright © 2016 John Wiley & Sons, Ltd.
Effect of salts and absorption cycles in the capillary coefficient of building materials with different joints
Authors: Guimarães Ana S. , Delgado João M. P. Q. , de Freitas Vasco P.
Published: December 2016

Rising damp can reduce building's aesthetical value, comfort and health mark, when combined with the existence of soluble salts in the building components and in the ground water can even lead to material decomposition and compromise its structural performance.

This research work intended to study the effect of different absorption cycles of two saturated solutions of sodium sulphate and potassium chloride in the capillary absorption curves obtained through the partial immersion of red brick samples without and with different joints. The results revealed significant differences in the capillary coefficients obtained when samples were tested with salt solutions.

Wirkung von Salzen und Absorptionsprozessen auf den Kapillartransportkoeffizienten von Baustoffen mit verschiedenen Fugen. Aufsteigende Feuchte kann den ästhetischen Wert, den Komfort und die Gesundheitswirkung von Gebäuden negativ beeinflussen. Lösliche Salze in den Bauteilen und im Grundwasser können hierbei sogar Zersetzungsprozesse auslösen und die Standsicherheit beeinträchtigen.

Diese Forschungsarbeit untersucht die Wirkung unterschiedlicher Absorptionszyklen von gesättigter Natriumsulfat‐ bzw. Kaliumchlorid‐Lösung auf die kapillaren Absorptionskurven. Für den Versuch wurden Prüfkörper aus Backstein mit und ohne Fugen teilweise eingetaucht. Die Ergebnisse zeigten bei Salzlösungen signifikante Unterschiede der Kapillartransportkoeffizienten.
Modeling low temperature district heating networks for the utilization of local energy potentials
Authors: Heissler Karl Martin , Franke Laura , Nemeth Isabell , Auer Thomas
Published: December 2016

In this paper a modeling approach for the simulation of a low temperature district heating network with seasonal heat storage, collectors and buildings is presented. The approach combines the strengths of the simulation environments Dymola and TRNSYS through the tool “Building Controls Virtual Testbed” to a simulation framework. It is capable of simulating alternating flow conditions within a detailed pipe network along with the heat demand and supply of network‐connected buildings and solar collectors. An ecological model settlement in Munich serves as case study for the framework.

Modellierung von Niedrigtemperaturnetzen zur Nutzung lokaler Energiepotenziale in Quartieren. Dieser Beitrag stellt einen Modellierungsansatz für die Simulation eines Niedrigtemperaturnetzes mit saisonalem Wärmespeicher, Solarkollektoren und Gebäuden vor. Der Ansatz vereint die Stärken der Simulationsumgebungen Dymola und TRNSYS durch das Tool “Building Controls Virtual Testbed” zu einer Co‐Simulationsumgebung. Diese ist in der Lage, wechselnde Strömungsrichtungen innerhalb eines detaillierten Rohrnetzes und Wärmeangebot und ‐bedarf der an das Netz angebundenen Gebäude und Solarkollektoren abzubilden. Eine “Ökologische Mustersiedlung” in München dient als Fallbeispiel.
Messtechnische Bestimmung von Aufwandszahlen unterschiedlicher Flächentemperiersysteme
Authors: Pfafferott Jens , Himmelsbach Sascha , Lang Tobias , Frietsch Mario
Published: December 2016

Mit der Messung des Wärme‐ und Kälteverbrauchs im Labor gelingt es, sowohl thermisch träge als auch agile Flächentemperiersysteme unter praxisnahen, dynamischen Bedingungen messtechnisch zu bewerten. Werden Nutzwärme‐ und Nutzkältebedarf berechnet und ins Verhältnis zu den gemessenen Verbräuchen gesetzt, können die Aufwandzahlen für die Nutzenübergabe ece für verschiedene Flächentemperiersysteme und in Kombinationen mit anderen Übergabesystemen unter verschiedenen Nutzungsbedingungen und für unterschiedliche Betriebsführungsstrategien bestimmt werden. Damit stehen Aufwandszahlen auf Basis kalorischer Messungen zur Verfügung, die je nach Aufgabenstellung entweder produkt‐ oder objektbezogen in der Planung komplexer Energiekonzepte verwendet werden können und die tatsächlichen Aufwandszahlen eh, ce für den Heizfall bzw. ec, ce für den Kühlfall genauer als Literaturwerte bzw. projektbezogen beschreiben.

Measurement of energy expenditure factors of various radiant heating and cooling systems. The measurement of heating/cooling consumption is used to evaluate both thermally inert and agile radiant heating and cooling systems under realistic, dynamic conditions in a laboratory. If the net heating/cooling energy demand is calculated, the ratio between calculated demand and measured consumption defines the energy expenditure factor for the heat transfer ece. Thus, ece can be determined under different conditions of use and for different operation strategies and in combination with other heat transfer systems. This provides energy expenditure factors based on caloric measurement which are available either product or object specific. The actual energy expenditure factors eh, ce for the heating mode or ec, ce for the cooling mode can be used in the planning of complex energy concepts since these specific values are more accurate than literature values.
Copper Zinc Thiolate Complexes as Potential Molecular Precursors for Copper Zinc Tin Sulfide (CZTS)
Authors: Fuhrmann Daniel , Dietrich Stefan , Krautscheid Harald
Published: December 2016

Five copper zinc thiolate complexes [(iPr3PCu)2(ZnEt2)(edt)]2 (1‐Et), [(iPr3PCu)2(Zn(iPr)2)(edt)]2 (1‐iPr), [(iPr3PCu)4(edt)2(ZnMe2)]2 (2), [(iPr3PCu)3(ZnPh2)(ZnPh)(edt)2]2 (3), and [(iPr3PCu)2Zn2(edt)3]6 (4) were prepared by the reaction of [(iPr3PCu)2(edt)]2 with ZnR2 (R=Me, Et, Ph, iPr) with or without addition of ethanedithiol (edt2−=ethane‐1,2‐dithiolate). The molecular structures of these complexes were determined by single crystal X‐ray diffraction. The ethanedithiolate ligands coordinate in μ3–η1:η2:η1 (2, 4), μ4–η1:η1:η2:η1 (1‐R, 3), and μ5–η1:η1:η2:η1:η1 (2) bridging modes, each sulfur atom binds to two or three metal atoms. Evidence for the presence of the weak Zn−S bonds in solution was provided by NMR spectroscopy. Mixtures of 1‐Et, 1‐iPr, or 3 with Sn(edt)2 were examined by thermogravimetry up to 600 °C, whereupon volatile thermolysis products were identified by mass spectrometry. In all thermolysis experiments, the formation of Cu2ZnSnS4 as main product, besides small amounts of binary metal sulfides, was confirmed by X‐ray powder diffraction (PXRD) and EDX (energy dispersive X‐ray spectroscopy) analysis.
A Multi‐Redox Responsive Cyanometalate‐Based Metallogel
Authors: Mitsumoto Kiyotaka , Cameron Jamie M. , Wei Rong‐Jia , Nishikawa Hiroyuki , Shiga Takuya , Nihei Masayuki , Newton Graham N. , Oshio Hiroki
Published: December 2016

A TTF‐based (TTF=tetrathiafulvalene) tridentate ligand (α‐(4′‐methyl‐4,5‐di‐n‐dodecylthylthiotetrathiafulvalene‐5′‐ylthio)‐ α′‐[2,2,2‐tris(1‐pyrazolyl)ethoxy]‐p‐xylene) (L) with long‐chain alkyl moieties was prepared in order to obtain a new multi‐redox active gelator based on a mixed‐metal octanuclear complex [FeIII4NiII4(CN)12(tp)4(L)4](BF4)4 (1). The magnetism, electrochemistry, and gelation behavior of 1 were studied and 1,2‐dichlorobenzene solutions of 1 are shown to display thermoreversible gelation behavior at room temperature. Furthermore, the gel phase of 1 was shown to undergo room‐temperature gel‐to‐sol transformations induced by both the oxidation and reduction of the gelator complex by F4TCNQ or [FeII(Cp*)2], respectively.
Cationic [(Iminophosphine)Nickel(Allyl)]+ Complexes as the First Example of Nickel Catalysts for Direct Hydroamination of Allenes
Authors: Tafazolian Hosein , Schmidt Joseph A. R.
Published: December 2016

The first example of nickel‐catalyzed hydroamination of allenes is reported. The new cationic [(3‐iminophosphine)nickel(allyl)]+ catalysts have been fully characterized and act regioselectively in the catalytic hydroamination of allenes with secondary amines at room temperature.
Intermolecular Aryl C−H Amination through Sequential Iron and Copper Catalysis
Authors: Mostafa Mohamed A. B. , Calder Ewen D. D. , Racys Daugirdas T. , Sutherland Andrew
Published: December 2016

A mild, efficient and regioselective method for para‐amination of activated arenes has been developed through a combination of iron and copper catalysis. A diverse range of products were obtained from an operationally simple one‐pot, two‐step procedure involving bromination of the aryl substrate with the powerful Lewis acid iron(III) triflimide, followed by a copper(I)‐catalysed N‐arylation reaction. This two‐step dehydrogenative process for the regioselective coupling of aromatic C−H bonds with non‐activated amines was applicable to anisole‐, phenol‐, aniline‐ and acetanilide‐type aryl compounds. Importantly, the arene substrates were used as the limiting reagent and required no protecting‐group manipulations during the transformation.
Generation and Application of Homoenolate Equivalents Utilizing [1,2]‐Phospha‐Brook Rearrangement under Brønsted Base Catalysis
Authors: Kondoh Azusa , Aoki Takuma , Terada Masahiro
Published: December 2016

A new method for catalytic generation of a homoenolate equivalent and its application to carbon−carbon bond formation was developed by utilizing the [1,2]‐phospha‐Brook rearrangement under Brønsted base catalysis. The α‐oxygenated allyl anions, which can serve as homoenolate equivalents, were catalytically generated in situ by treating readily available chalcones with diethyl phosphite or the pre‐formed 1,2‐adducts of diethyl phosphite with chalcones in the presence of a catalytic amount of a phosphazene base, P2‐tBu. The resulting allyl anions were subsequently trapped by various electrophiles, including Michael acceptors, imines, and aldehydes, providing the corresponding adducts in good yields with moderate to good diastereoselectivities.
Kampf‐ und Explosivstoffe
Authors: Wöhrle Dieter
Published: December 2016

Nach dem Verhaltenskodex der GDCh stellen sich die Chemiker gegen den Missbrauch der Chemie. Dies betrifft auch die Verwendung chemischer Kampfstoffe und auch terroristische Anschläge mit Explosivstoffen.
Frustrierte Lewis‐Paare erlauben Hydrierung ohne Übergangsmetallkatalyse
Authors: Feil Sylvia
Published: December 2016

Fast jeder Wirkstoff, sei es Medikament, Fungizid, Pestizid oder Dünger, enthält Stickstoffatome. Die leichte Herstellung von Aminen mittels Reduktion von Iminen durch Hydrierung in Abwesenheit von Übergangsmetallen ist daher nicht nur akademisch, sondern auch aus industriellen Aspekten von immensem Interesse.
Herzlichen Glückwunsch zu fünfzig Jahren Chemie in unserer Zeit!
Authors: Hatscher Deike
Published: December 2016

Mit dieser sechsten Ausgabe ist der goldene Jubiläumsjahrgang 2016 vollständig!
Design, Synthesis, and Evaluation of 2,9‐Bis[(substituted‐aminomethyl)phenyl]‐1,10‐phenanthroline Derivatives as G‐Quadruplex Ligands
Authors: Gueddouda Nassima Meriem , Hurtado Miyanou Rosales , Moreau Stéphane , Ronga Luisa , Das Rabindra Nath , Savrimoutou Solène , Rubio Sandra , Marchand Adrien , Mendoza Oscar , Marchivie Mathieu , Elmi Lilian , Chansavang Albain , Desplat Vanessa , Gabelica Valérie , Bourdoncle Anne , Mergny Jean‐Louis , Guillon Jean
Published: December 2016

Genomic sequences able to form guanine quadruplexes (G4) are found in oncogene promoters, in telomeres, and in 5′‐ and 3′‐untranslated regions as well as introns of messenger RNAs. These regions are potential targets for drugs designed to treat cancer. Herein, we present the design and syntheses of ten new phenanthroline derivatives and characterization of their interactions with G4‐forming oligonucleotides. We evaluated ligand‐induced stabilization and specificity and selectivity of ligands for various G4 conformations using FRET‐melting experiments. We investigated the interaction of compound 1 a (2,9‐bis{4‐[(3‐dimethylaminopropyl)aminomethyl]phenyl}‐1,10‐phenanthroline), which combined the greatest stabilizing effect and specificity for G4, with human telomeric sequences using FRET, circular dichroism, and ESI‐MS. In addition, we showed that compound 1 a interferes with the G4 helicase activity of Saccharomyces cerevisiae Pif1. Interestingly, compound 1 a was significantly more cytotoxic toward two human leukemic cell lines than to normal human blood mononuclear cells. These novel phenanthroline derivatives will be a starting point for further development and optimization of potent G4 ligands that have potential as anticancer agents.
Electronic Spectroscopy of Methylcyanodiacetylene (CH3C5N)
Authors: Turowski Michał , Szczepaniak Urszula , Custer Thomas , Gronowski Marcin , Kołos Robert
Published: December 2016

The results of a study devoted to the electronic spectroscopy of gaseous, solid, and cryogenic matrix‐isolated methylcyanodiacetylene (CH3C5N) are reported. UV absorption and optical phosphorescence spectra of the compound are described here for the first time, and the corresponding vibronic assignments are proposed. UV absorption, studied directly or through the excitation of phosphorescence, revealed the
 1E‐‐
 1A1 system, very weak
 1A2–
 1A1 bands, and a strong, broad absorption feature, tentatively identified as
 1E–
 1A1. Spectral measurements were assisted by quantum chemical calculations at the DFT and ab initio (coupled cluster) levels of theory.
High‐Performance Porphyrin‐Based Dye‐Sensitized Solar Cells with Iodine and Cobalt Redox Shuttles
Authors: Xiang Huaide , Fan Wei , Li Jia Hui , Li Tianyue , Robertson Neil , Song Xiongrong , Wu Wenjun , Wang Zhaohui , Zhu Weihong , Tian He
Published: December 2016

Recently, enormous research passion has been devoted to enhance the power conversion efficiency (PCE) of porphyrin sensitizers for dye‐sensitized solar cells (DSSCs), but the major stumbling block is the absorption defect in the visible‐light region. To address this challenge, high‐performance DSSCs are reported based on a new donor–π–acceptor sensitizer FW‐1, 7H‐dibenzo[c,g]carbazole‐substituted and fused zinc porphyrin, co‐sensitized with a benzotriazole‐containing dye (WS‐5) in iodine and cobalt redox systems, and high PCEs of 10.21 and 10.42 %, respectively, were obtained. An unprecedented breakthrough was obtained by making one sensitizer suitable for several electrolyte systems because of its appropriate molecular orbitals and co‐sensitizer.
Platinum Intercalators of DNA as Anticancer Agents
Authors: Pages Benjamin J. , Garbutcheon‐Singh K. Benjamin , Aldrich‐Wright Janice R.
Published: December 2016

The drawbacks of the platinum chemotherapy agents cisplatin, carboplatin and oxaliplatin have inspired the development of compounds with different mechanisms of action. Polyaromatic platinum complexes (PPCs) are a promising anticancer alternative; these bind reversibly with DNA through the insertion of a planar aromatic moiety between nucleobases in a process known as intercalation. PPCs have demonstrated in vitro behaviour remarkably different from that of cisplatin and exhibited cytotoxicity up to one hundred times higher than that of cisplatin in many cell lines. This microreview primarily discusses 1,10‐phenanthroline‐based complexes of the type [Pt(PL)(AL)]2+ (where PL is a polyaromatic ligand and AL is an ancillary ligand), including their cytotoxicity, DNA‐binding behaviour and biological activity in vitro and in vivo. Other PPCs within the field, including dual‐mode DNA binders incorporating tethered acridines and other potently cytotoxic complexes, are also covered.
Fully meta‐Substituted 4,4′‐Biphenyldicarboxylate‐Based Metal–Organic Frameworks: Synthesis, Structures, and Catalytic Activities
Authors: Li Jiawei , Ren Yanwei , Qi Chaorong , Jiang Huanfeng
Published: December 2016

Fully meta‐substituted 2,2′,6,6′‐tetramethoxy‐4,4′‐biphenyldicarboxylic acid (H2L) was synthesized and applied in the construction of three metal–organic frameworks (MOFs), {[Cu3L3(H2O)2(DMF)]n (1), [Zn4OL3]n (2), and [Zn4OL3(H2O)(DEF)]n (3)}. For 1, the approximately vertical twist of two benzene rings in L leads to the formation of a twofold‐interpenetrated 3D structure with 1D open channels (11 × 15 Å). MOFs 2 and 3 have classical twofold‐interpenetrated isoreticular MOF structures, and reversible transformation of the oxozinc carboxylate clusters of 2 and 3 could be realized via a solvent‐exchange‐induced single‐crystal‐to‐single‐crystal pathway, which provides direct structural evidence for a Zn4O core as Lewis acidic site in MOFs. Desolvated framework 1′ exhibits high permanent porosity (Langmuir surface area = 555 m2/g), high thermal stability (up to 300 °C), and highly active catalytic properties for cyanosilylation and olefin epoxidation. MOF 2 exhibits moderate carbon dioxide uptake ability and can efficiently catalyze the cycloaddition of CO2 with epoxides under mild conditions.
Hydroxyquinoline–Calix[4]arene Conjugates as Ligands for Polynuclear Lanthanide Complexes: Preparation, Characterization, and Properties of a Dinuclear EuIII Complex
Authors: Jäschke Astrid , Kischel Marcus , Mansel Alexander , Kersting Berthold
Published: December 2016

The synthesis of calixarene‐based N4O4‐donor ligand H6L, in which two 8‐hydroxyquinoline‐2‐carbaldehyde units are appended via hydrazone‐carbonylmethoxy linkages in a 1,3 arrangement to the lower rim of tert‐butylcalix[4]arene, and its coordination properties towards EuIII are described. The reaction of H6L with Eu(NO3)3·6H2O produced dinuclear complex [Eu2(H3L)2(MeCN)2] (4). The EuIII ions in 4 are well separated from each other (d > 8 Å) and each is coordinated by two tetradentate hydroxyquinoline‐2‐carbaldehyde hydrazone substituents from two triply deprotonated (H3L)3– ligands in a dodecahedral geometry. As a consequence there are no exchange interactions between the EuIII ions, and the magnetic properties are solely associated with thermal population of excited (7F1–7F6) terms. The spin–orbit coupling constant λ is 325.2(4) cm–1. Moreover, H6L was found to extract EuIII and TbIII from aqueous solution at pH 7–8, as established by radiotracing with 160Tb and 152Eu.
Stability of tocopherol homologs in soybean, corn, canola, and olive oils under different moisture contents at 25°C
Authors: Jung Jinyeong , Gim Seo Yeong , Lee Chankyu , Kim Mi‐Ja , Lee JaeHwan
Published: December 2016

The stability of tocopherol homologs and oxidative stability were determined in edible oils including soybean, corn, canola, and olive oils under different relative humidities (RH), ranging from 0 to 93%, at 25°C for 8 months. The degree of oxidation was determined by conjugated dienoic acid (CDA) and p‐anisidine values (p‐AV), and any remaining tocopherols were also analyzed. The stability of tocopherols was significantly influenced by the presence of both moisture and other tocopherol homologs. Soybean and corn oils under low moisture conditions had significant remaining tocopherol levels, whereas canola and olive oils had different stabilities of tocopherols. The presence of δ‐tocopherol, which is found in soybean and corn oils, seems to play an important role in the stability of α‐ and γ‐tocopherols in vegetable oils stored at 25°C. The moisture content of the tested oils was different even when oils were stored at the same RH.

Practical application: Many lipid‐rich foods contain tocopherol homologs to extend the shelf – life of the products. The stability of tocopherol homologs was significantly influenced by the presence of moisture, the types of oils, and the concentration of tocopherol homologs. Using the knowledge obtained in this study, shelf‐life of real foods containing oils can be enhanced by modifying the moisture content and concentration and types of tocol homologs.

(i) Soybean and corn oils under low moisture conditions had significant remaining tocopherol levels, whereas canola and olive oils had different stabilities of tocopherols; (ii) the presence of δ‐tocopherol, which is found in soybean and corn oils, played an important role in the stability of α‐ and γ‐tocopherols in vegetable oils stored at 25°C; and (iii) the moisture content of the tested oils was different even when oils were stored at the same RH.
Electroreduction of Carbon Dioxide to Formic Acid and Methanol over a Palladium/Polyaniline Catalyst in Acidic Solution: A Study of the Palladium Size Effect
Authors: Zheng Weiran , Man Ho Wing , Ye Lin , Tsang Shik Chi Edman
Published: December 2016

We controlled the reaction temperature and feeding rate of the reducing agent to show that Pd nanoparticles (NPs) with different sizes can be synthesized from the reduction of their precursor on polyaniline (PANI) as a solid support. We used UV/Vis spectroscopy, 1H NMR spectroscopy, and IR spectroscopy to identify the electronic and catalytic interactions between Pd NPs and PANI. For the first time, that the unique redox properties of Pd/PANI display a high overpotential for hydrogen evolution, which suppresses this competitive reaction for the electroreduction of CO2 in an acidic solution. As a result, two main liquid products (HCOOH and CH3OH) can be produced selectively with only trace amounts of CO in the gas phase. The current efficiencies for HCOOH and CH3OH increase with the decreasing Pd NP size within the potential range of −0.5 to −0.9 V. The highest current efficiencies for HCOOH (22.8 %) and CH3OH (5.4 %) are thus obtained over Pd(1.31 nm)/PANI at −0.9 V.
Retention of iron and zinc in yam flour and boiled yam processed from white yam (D. rotundata) varieties
Authors: Maziya‐Dixon Busie , Alamu Emmanuel Oladeji , Dufie Wireko‐Manu Faustina , Robert Asiedu
Published: December 2016

This study investigated the impact of processing on retention of iron and zinc in D. rotundata. Fresh tubers were processed into boiled yam and yam flour and analyzed for zinc, iron, and physicochemical properties. Percent true retention (%TR) was assessed using paired samples and a formula that compensated for loss or gain of moisture and soluble solids. The retention of iron ranged from 55.5% to 98.7% in boiled yam and 25.2% to 54.9% in yam flour; retention of zinc ranged from 49.3% to 97.5% in boiled yam and 18. 9% to 43.1% in yam flour. The amount of iron retained in boiled yam correlated with the amount in the fresh samples (r = .79), likewise in yam flour (r = .82). A similar trend was observed for zinc. From our study, we conclude that retention of iron and zinc is dependent on the variety and processing method used. The information from this study can be used by food scientists and nutritionists in choosing the appropriate processing to increase the retention of high levels of micronutrient in yams and by the yam breeders to adjust their germplasm breeding activities.
Genome‐wide survey in African Americans demonstrates potential epistasis of fitness in the human genome
Authors: Wang Heming , Choi Yoonha , Tayo Bamidele , Wang Xuefeng , Morris Nathan , Zhang Xiang , Broeckel Uli , Hanis Craig , Kardia Sharon , Redline Susan , Cooper Richard S , Tang Hua , Zhu Xiaofeng
Published: December 2016

The role played by epistasis between alleles at unlinked loci in shaping population fitness has been debated for many years and the existing evidence has been mainly accumulated from model organisms. In model organisms, fitness epistasis can be systematically inferred by detecting nonindependence of genotypic values between loci in a population and confirmed through examining the number of offspring produced in two‐locus genotype groups. No systematic study has been conducted to detect epistasis of fitness in humans owing to experimental constraints. In this study, we developed a novel method to detect fitness epistasis by testing the correlation between local ancestries on different chromosomes in an admixed population. We inferred local ancestry across the genome in 16,252 unrelated African Americans and systematically examined the pairwise correlations between the genomic regions on different chromosomes. Our analysis revealed a pair of genomic regions on chromosomes 4 and 6 that show significant local ancestry correlation (P‐value = 4.01 × 10−8) that can be potentially attributed to fitness epistasis. However, we also observed substantial local ancestry correlation that cannot be explained by systemic ancestry inference bias. To our knowledge, this study is the first to systematically examine evidence of fitness epistasis across the human genome.