bluuebunny/crossref_metadata_2025 huggingface dataset:
Hydrothermal Synthesis of 3D Porous Structure Bi2WO6/Reduced Graphene Oxide Hydrogels for Enhancing Supercapacitor Performance
Authors: Zheng Huajun , Yang Guang , Chen Sanming , Jia Yi
Published: December 2016

Three‐dimensional (3D) porous Bi2WO6/reduced graphene oxide hydrogels (BWO/rGO HGs) have been prepared via a facile one‐pot hydrothermal process for supercapacitor applications. Compared with the pristine Bi2WO6 electrode, the 3D porous BWO/rGO HGs exhibit much higher capacitive performances with a specific capacitance of 268.7 F g−1 at a current density of 0.75 A g−1 and good cycling stability with 81% capacitance retention after 1000 cycles at 3 A g−1. The remarkable electrochemical properties could be attributed to unique architecture of 3D porous rGO HGs supported Bi2WO6, which provided an excellent electrical conductivity substrate and more channels for ions diﬀusion. The results indicate that a new synthesis route of 3D porous structure hydrogel loaded binary metal oxide have potential applications in energy storage device.
Self‐Doped Oligoaniline Electrochromic Devices: Fabrication and Effect of the Oligoaniline Molecular Architecture
Authors: Gong Chen , Yang Jiping , Cao Linyu , Gao Yuchong
Published: December 2016

A series of self‐doped oligoaniline derivatives, that is, carboxyl‐capped tetraaniline (HOOC‐(Ani)4‐COOH), carboxyl‐capped pentaaniline (HOOC‐(Ani)5‐COOH), carboxyl‐capped hexaaniline (HOOC‐(Ani)6‐COOH), and carboxyl‐capped star‐shaped tetraaniline (Tri‐(Ani)4‐COOH) in leucoemeraldine base state, were synthesized and characterized. The number of the aniline units was varied and a star‐shaped structure was designed to detect the influence of the molecular architecture on the electrochromic properties. The introduction of carboxylic groups into oligoaniline derivatives produced intermolecular hydrogen bonds, which contributed to their self‐doping capability. As a result, these oligoaniline derivatives presented reversible electrochromic properties at pH≥7, which could not be seen in pristine oligoanilines or polyanilines. Then, these oligoaniline derivatives were fabricated into electrochromic devices without an external acid dopant in the assembling process. Comprehensive electrochemical tests were conducted to investigate their electrochromic properties. The resulting devices showed good performances in spectroscopic, electrochemical, and in situ tests. Increasing the chain length contributed to an improved optical contrast, coloration efficiency, response time, and cycling stability. Meanwhile, introducing a star‐shaped structure also led to a better electrochromic performance. Moreover, electrochemical impedance spectroscopy and AFM tests were used to explore the mechanism to understand how the star‐shaped molecule facilitated the redox process.
Microarray Analysis of Antibodies Induced with Synthetic Antitumor Vaccines: Specificity against Diverse Mucin Core Structures
Authors: Pett Christian , Cai Hui , Liu Jia , Palitzsch Björn , Schorlemer Manuel , Hartmann Sebastian , Stergiou Natascha , Lu Mengji , Kunz Horst , Schmitt Edgar , Westerlind Ulrika
Published: December 2016

Glycoprotein research is pivotal for vaccine development and biomarker discovery. Many successful methodologies for reliably increasing the antigenicity toward tumor‐associated glycopeptide structures have been reported. Deeper insights into the quality and specificity of the raised polyclonal, humoral reactions are often not addressed, despite the fact that an immunological memory, which produces antibodies with cross‐reactivity to epitopes exposed on healthy cells, may cause autoimmune diseases. In the current work, three MUC1 antitumor vaccine candidates conjugated with different immune stimulants are evaluated immunologically. For assessment of the influence of the immune stimulant on antibody recognition, a comprehensive library of mucin 1 glycopeptides (>100 entries) is synthesized and employed in antibody microarray profiling; these range from small tumor‐associated glycans (TN, STN, and T‐antigen structures) to heavily extended O‐glycan core structures (type‐1 and type‐2 elongated core 1–3 tri‐, tetra‐, and hexasaccharides) glycosylated in variable density at the five different sites of the MUC1 tandem repeat. This is one of the most extensive glycopeptide libraries ever made through total synthesis. On tumor cells, the core 2 β‐1,6‐N‐acetylglucosaminyltransferase‐1 (C2GlcNAcT‐1) is down‐regulated, resulting in lower amounts of the branched core 2 structures, which favor formation of linear core 1 or core 3 structures, and in particular, truncated tumor‐associated antigen structures. The core 2 structures are commonly found on healthy cells and the elucidation of antibody cross‐reactivity to such epitopes may predict the tumor‐selectivity and safety of synthetic vaccines. With the extended mucin core structures in hand, antibody cross‐reactivity toward the branched core 2 glycopeptide epitopes is explored. It is observed that the induced antibodies recognize MUC1 peptides with very high glycosylation site specificity. The nature of the antibody response is characteristically different for antibodies directed to glycosylation sites in either the immune‐dominant PDTR or the GSTA domain. All antibody sera show high reactivity to the tumor‐associated saccharide structures on MUC1. Extensive glycosylation with branched core 2 structures, typically found on healthy cells, abolishes antibody recognition of the antisera and suggests that all vaccine conjugates preferentially induce a tumor‐specific humoral immune response.
New Charge‐Transfer Complexes with 1,2,5‐Thiadiazoles as Both Electron Acceptors and Donors Featuring an Unprecedented Addition Reaction
Authors: Chulanova Elena A. , Pritchina Elena A. , Malaspina Lorraine A. , Grabowsky Simon , Mostaghimi Farzin , Beckmann Jens , Bagryanskaya Irina Yu. , Shakhova Margarita V. , Konstantinova Lidia S. , Rakitin Oleg A. , Gritsan Nina P. , Zibarev Andrey V.
Published: December 2016

The design and synthesis of novel charge‐transfer (CT) complexes are of interest for fundamental chemistry and applications to materials science. In addition to the recently described first CT complex with both electron acceptor (A) and donor (D) groups belonging to the 1,2,5‐thiadiazole series (1; A: 4‐nitro‐2,1,3‐benzothiadiazole; D: 4‐amino‐2,1,3‐benzothiadiazole), herein novel CT complexes2and3with 1,2,5‐thiadiazoles as both A (4,6‐dinitro‐2,1,3‐benzothiadiazole and [1,2,5]thiadiazolo[3,4‐c][1,2,5]thiadiazole) and D (4‐amino‐2,1,3‐benzothiadiazole) were synthesized. The series is completed by complex4with [1,2,5]thiadiazolo[3,4‐c][1,2,5]thiadiazole as A and phenoxatellurine as D. Structures of complexes2–4were characterized by single‐crystal X‐ray diffraction (XRD), as well as solution and solid‐state UV/Vis spectroscopy. Thermodynamics of their formation were obtained by density functional theory (DFT) calculations, their bonding situations were analyzed by quantum theory of atoms in molecules (QTAIM) calculations and dimer model energies of interactions quantified in the framework of the Hirshfeld surface (HS) analysis. With DFT calculations, the largest value of CT between D and A was found for complex2, with 0.027 e in the XRD structure and 0.150 e in the optimized structure in MeCN. In the UV/Vis spectra, theλmaxof the CT bands of2–4varied in the rangeλ=517–705 nm. Model energy calculations for1–4revealed the importance of both dispersion interactions and hydrogen bonding between D and A as contributors to CT in the crystalline state. In an attempt to enlarge the CT value with bis[1,2,5‐thiadiazolo][3,4‐b;3′,4′‐e]pyrazine as A and 4‐amino‐2,1,3‐benzoselenadiazole as D, an unprecedented 1:1 addition reaction was observed upon formation of a C−N bond between atom C7 of D and pyrazine atom N4 of A, accompanied by hydrogen atom transfer from C7 to another pyrazine atom N8 (compound5). According to DFT calculations, the reaction is a multistep process featuring diradical intermediates and hydrogen atom intramolecular migration over four positions. Molecular and crystal structures of5(solvate with toluene) were elucidated by XRD and the crystal structure revealed a rather unusual porous framework.
Photoinduced Thiol‐ene Chemistry Applied to the Synthesis of Self‐Assembling Elastin‐Inspired Glycopeptides
Authors: Piccirillo Germano , Pepe Antonietta , Bedini Emiliano , Bochicchio Brigida
Published: December 2016

Synthetic (glyco)peptides inspired by proteins able to self‐assemble are appealing biomaterials in the field of tissue engineering and regenerative medicine. Herein, for the first time, taking advantage of thiol‐ene chemistry coupled to solid‐phase peptide synthesis, a self‐assembling peptide inspired by elastin protein was bioconjugated to three carbohydrates in order to obtain the corresponding glycopeptides. They were studied at the molecular and supramolecular level. The results show that the carbohydrate influences the molecular conformation of the glycopeptide and its self‐aggregation properties as well. As future perspective, the results could enable us to tune the final self‐aggregation properties of the glycopeptide by changing the sugar moiety.
Self‐Propelled Soft Protein Microtubes with a Pt Nanoparticle Interior Surface
Authors: Kobayakawa Satoshi , Nakai Yoko , Akiyama Motofusa , Komatsu Teruyuki
Published: December 2016

Human serum albumin (HSA) microtubes with an interior surface composed of Pt nanoparticles (PtNPs) are self‐propelled in aqueous H2O2 medium. They can capture cyanine dye and Escherichia coli (E. coli) efficiently. Microtubes were prepared by wet templating synthesis by using a track‐etched polycarbonate (PC) membrane with alternate filtrations of aqueous HSA, poly‐l‐arginine (PLA), and citrate‐PtNPs. Subsequent dissolution of the PC template yielded uniform hollow cylinders made of (PLA/HSA)8PLA/PtNP stacking layers (1.16±0.02 μm outer diameter, ca. 23 μm length). In aqueous H2O2 media, the soft protein microtubes are self‐propelled by jetting O2 bubbles from the open‐end terminus. The effects of H2O2 and surfactant concentrations on the velocity were investigated. The swimming microtube captured cyanine dye in the HSA component of the wall. Addition of an intermediate γ‐Fe3O4 layer allowed manipulation of the direction of movement of the tubule by using a magnetic field. Because the exterior surface is positively charged, the bubble‐propelled microtubes adsorbed E. coli with high efficiency. The removal ratio of E. coli by a single treatment reached 99 %.
Reductive Elimination of Hydrogen from Bis(trimethylsilyl)methyltin Trihydride and Mesityltin Trihydride
Authors: Maudrich Jakob‐Jonathan , Sindlinger Christian Patrick , Aicher Frederik Sebastian William , Eichele Klaus , Schubert Hartmut , Wesemann Lars
Published: December 2016

Alkyltin trihydride [(Me3Si)2CHSnH3] was synthesized and the reductive elimination of hydrogen from this species was investigated. A methyl‐substituted N‐heterocyclic carbene reacts with the organotrihydride in dependence on stoichiometry and solvent to give a series of products of the reductive elimination and dehydrogenative tin–tin bond formation. Besides characterization of the carbene adduct of the alkyltin(II) hydride, a Sn4 chain was also isolated, encompassing two stannyl–stannylene sites, which are stabilized each as NHC‐adducts. Complete dehydrogenation resulted to give either a carbene‐stabilized distannyne or a metalloid Sn9‐cluster salt. Reductive elimination of hydrogen was also achieved with an excess of diethylmethylamine to give the alkyltin(II) hydride as a Lewis base free tetramer [(RSnH)4]. The method of cluster formation at low temperatures by hydrogen elimination was also transferred to the mesityl‐substituted tin trihydride MesSnH3. In this case [(MesSn)10], showing a [5]prismane structure, was isolated in good yield and characterized. NMR spectroscopic features of the propellane‐type cluster [Trip6Sn6] are reported.
Efficient Synthetic Routes to (±)‐Hippolachnin A, (±)‐Gracilioethers E and F and the Alleged Structure of (±)‐Gracilioether I
Authors: Xu Ze‐Jun , Wu Yikang
Published: December 2016

Two monocyclic members in the gracilioether family were synthesized in only three steps. The monocyclic products were further elaborated into advanced precursors to hippolachnin A and gracilioether E, respectively. Gracilioether F and the alleged structure for gracilioether I were also synthesized using a late‐stage C(sp3)–H thermo‐oxidation.
ChemInform Abstract: Synthesis of Ultra‐Incompressible sp3‐Hybridized Carbon Nitride with 1:1 Stoichiometry.
Authors: Stavrou Elissaios , Lobanov Sergey , Dong Huafeng , Oganov Artem R. , Prakapenka Vitali B. , Konopkova Zuzana , Goncharov Alexander F.
Published: December 2016

Superhard CN is produced from pre‐compressed single crystal natural graphite powder positioned on top of a thin Ir or Pt spacer loaded in a diamond anvil cell with an initial 200 MPa N2 pressure.
ChemInform Abstract: Iron‐Catalyzed Cross‐Coupling of 1‐Alkynylcyclopropyl Tosylates and Related Substrates.
Authors: Tindall Daniel J. , Krause Helga , Fuerstner Alois
Published: December 2016

The first examples of iron catalyzed cross‐coupling reactions of tertiary alkynyl or alkenyl substituted cyclopropyl tosylates with alkyl Grignard reagents are reported.
ChemInform Abstract: Divergent Synthesis of 3,3‐Disubstituted Oxindoles Initiated by Palladium‐Catalyzed Intramolecular Arylation of Unsaturated Amides.
Authors: Wei Fang , Wei Lei , Zhou Ling , Tung Chen‐Ho , Ma Yudao , Xu Zhenghu
Published: December 2016

Diverse boron‐substituted oxindoles are successfully synthesized by a Pd‐catalyzed intramolecular arylation and borylation cascade of unsaturated amides.
ChemInform Abstract: Phase Transition and Hydrogen Storage Properties of Mg17Ba2 Compound.
Authors: Wu Daifeng , Ouyang Liuzhang , Wu Cong , Gu Qinfen , Wang Hui , Liu Jiangwen , Zhu Min
Published: December 2016

Mg17Ba2 hydrogen storage alloy is prepared by induction melting of the elements (Mg excess of 5 wt.% for loss compensation; ≈1073 K, 15 min).
ChemInform Abstract: The Modern Face of Synthetic Heterocyclic Chemistry
Authors: Cabrele Chiara , Reiser Oliver
Published: December 2016

Review: [76 refs.
ChemInform Abstract: Synthesis of Non‐Racemic α‐Hydroxyphosphonates via Asymmetric Phospho‐Aldol Reaction
Authors: Spilling Christopher D. , Malla Raj K.
Published: December 2016

Review: 130 refs.
ChemInform Abstract: Azomethine Ylides from Nitrones: Using Catalytic nBuLi for the Totally Stereoselective Synthesis of trans‐2‐Alkyl‐3‐oxazolines.
Authors: Juste‐Navarro Veronica , Delso Ignacio , Tejero Tomas , Merino Pedro
Published: December 2016

The reaction proves successful starting from C‐alkyl nitrones and aryl, hetaryl, alkenyl as well as alkyl aldehydes.
ChemInform Abstract: Synthesis of Highly Substituted Imidazo[1,5‐a]quinoxalines Through a Multicomponent Reaction Followed by Deprotection—Cyclization.
Authors: Sashidhara Koneni V. , Prasad Dodda. Ranga , Upadhyay Akanksha , Reddy Palnati Gopala , Modukuri Ram K. , Kant Ruchir
Published: December 2016

The title synthesis starts from aryl aldehydes, ortho‐N‐Boc‐phenylenediamines, and azidochalcones and uses erbium triflate as catalyst.
ChemInform Abstract: A Novel Method for the Synthesis of Pyrimido[1,2‐a]benzimidazoles.
Authors: Vandyshev Dmitriy Yu. , Shikhaliev Khidmet S. , Kokonova Anna V. , Potapov Andrei Yu. , Kolpakova Maria G. , Sabynin Artem L. , Zubkov Fedor I.
Published: December 2016

via AcOH‐catalyzed condensation of 1,2‐diaminobenzimidazole (I) with N‐arylitaconimides (II)
ChemInform Abstract: Three New Isoindolin‐1‐ones from the Leaves of Yunnan Local Sun Cured Tobacco and Their Bioactivities.
Authors: Liu Zhi‐Hua , Ding Zhong‐Tao , Wang Jia‐Qiang , Zhang Feng‐Mei , Xia Jian‐Jun , Yang Pei‐Song , Shen Qin‐Peng , Liu Chun‐Bo , He Pei
Published: December 2016

Three new isoindolin‐1‐ones (Ia—c) together with a known one are isolated from the leaves of Yunnan local sun cured tobacco, and their molecular structures are elucidated.
ChemInform Abstract: Cooperative Self‐Assembly of Porphyrins with Polymers Possessing Bioactive Functions
Authors: Zhao Lizhi , Qu Rui , Li Ang , Ma Rujiang , Shi Linqi
Published: December 2016

Review: 127 refs.
New heterogeneous process for continuous biodiesel production in microreactors
Authors: Aghel Babak , Mohadesi Majid , Sahraei Sasan , Shariatifar Mehrdad
Published: December 2016

This contribution investigates the transesterification of soybean oil with methanol in the presence of demineralized (DM) water plant sedimentation as a heterogeneous catalyst in a microreactor, which has not been studied in previous works. The catalyst systems were characterized by the X‐ray diffraction (XRD) method. The effects of catalyst concentration, methanol/oil volume ratio, and residence time on the transesterification efficiency were investigated and the purity of methyl ester was optimized using response surface methodology (RSM). The optimal conditions for the transesterification process were as follows: catalyst concentration of 0.0837 g/g, methanol to oil volume ratio of 1:1.89, and residence time of 10 min during which methyl ester purity was measured at ∼93.14 %. However, the purity value obtained by experimental model is equal to 87.06 %. Through the analysis of model and experimental data, mean relative error was obtained as 7.17 %. Experimental results indicated that time for the production of methyl ester with high purity (93.14 %) can be shortened significantly in an optimized microreactor compared to conventional stirred reactors (residence time of only 10 min).
The Role of Surfactants in the Stability of NiO Nanofluids: An Experimental and DFT Study
Authors: Sánchez‐Coronilla Antonio , Navas Javier , Aguilar Teresa , Martín Elisa I. , Gallardo Juan Jesús , Gómez‐Villarejo Mr. Roberto , Carrillo‐Berdugo Mr. Iván , Alcántara Rodrigo , Fernández‐Lorenzo Concha , Martín‐Calleja Joaquín
Published: December 2016

This study shows an analysis of the stability of nanofluids based on a eutectic mixture of diphenyl oxide and biphenyl, which is used as a heat transfer fluid (HTF) in concentrating solar energy, and NiO nanoparticles. Two surfactants are used to analyse the stability of the nanofluids: benzalkonium chloride (BAC) and 1‐octadecanethiol (ODT). From an experimental perspective, the stability is analysed by means of UV/Vis spectroscopy, particle size measurements through the dynamic light‐scattering technique, andζ‐potential measurements. The results show that the stability of the nanofluids improves with the use of BAC. DFT calculations are performed to understand the role played by the surfactants. The interaction of the surfactants with both the fluid and the NiO (100) surface is studied. Quantum theory of atoms in molecules (QTAIM) analysis shows that hydrogen bridge interactions favour the stability of the fluid–surfactant mixture. The more stabilising NiO–surfactant interaction involves the Ni−H interaction of the −SH and −CH3groups of ODT and BAC. Also, nanofluids with BAC are favoured over those with ODT, which is in agreement with experimental results. The structural and electronic effects of incorporating the surfactant onto the NiO (100) surface are shown by using electron localisation function analysis, the non‐covalent interaction index and projected density of states.
Color Fine‐Tuning of Optical Materials Through Rational Design
Authors: Holzer Brigitte , Bintinger Johannes , Lumpi Daniel , Choi Christopher , Kim Youngwan , Stöger Berthold , Hametner Christian , Marchetti‐Deschmann Martina , Plasser Felix , Horkel Ernst , Kymissis Ioannis , Fröhlich Johannes
Published: December 2016

We report on the feasibility for color fine‐tuning of optical materials using rational design principles based on chemical reasoning. For this purpose, a modular framework for the construction of symmetrical cap‐linker‐cap compounds, using triarylamine caps and oligothiophene linkers, is applied. The chosen structural scaffolds are heavily used in recent industrial applications and provide five possibilities for altering their electronic and steric properties: electron donor/acceptor groups, planarization/deplanarization, and modulation of the π‐conjugation length. Permutation of the used building blocks leads to a set of 54 different molecules, out of which 32 are synthesized and characterized in solution as well as in example fabricated OLED devices. This setup allows for color fine‐tuning in the range of 412 nm to 540 nm with typical steps of 4 nm. In addition, to further benefit from the large experimental data set the spectroscopic results are used to benchmark quantum chemical computations, which show excellent agreement thus highlighting the potential of these calculations to guide future syntheses.
Doping‐Induced Absorption Bands in P3HT: Polarons and Bipolarons
Authors: Enengl Christina , Enengl Sandra , Pluczyk Sandra , Havlicek Marek , Lapkowski Mieczyslaw , Neugebauer Helmut , Ehrenfreund Eitan
Published: December 2016

The front cover artwork is provided by Dr. Christina Enengl, Dr. Sandra Enengl and Dr. Helmut Neugebauer (Johannes Kepler University, Austria), Dr. Marek Havlicek (Czech Metrology Institute, Czech Republic; Johannes Kepler University, Austria), Sandra Pluczyk and Prof. Mieczyslaw Lapkowski (Silesian University of Technology, Poland) as well as Prof. Eitan Ehrenfreund (Technion‐Israel Institute of Technology, Israel). The image illustrates the formation of bipolarons in P3HT at higher doping levels observed by in situ spectroscopic techniques. Read the full text of the article at 10.1002/cphc.201600961.
Mechanistic Insights into the Carbon Dioxide/Cyclohexene Oxide Copolymerization Reaction: Is One Metal Center Enough?
Authors: González‐Fabra Joan , Castro‐Gómez Fernando , Kleij Arjan W. , Bo Carles
Published: December 2016

A detailed study on the mechanism for the alternating copolymerization of cyclohexene oxide (CHO) and CO2 mediated by an [Al{amino‐tri(phenolate)}]/NBu4I binary catalyst system was performed by using DFT‐based methods. Four potential mechanisms (one monometallic and three bimetallic) were considered for the first propagation cycle of the CHO/CO2 copolymerization. The obtained Gibbs free energies provided a rationale for the relative high activity of a non‐covalent dimeric structure formed in situ and thus for the feasibility of a bimetallic mechanism to obtain polycarbonates quantitatively. Gibbs free energies also indicated that the alternating copolymerization was favored over the cyclic carbonate formation.
Cyanuric Acid‐Based Organocatalyst for Utilization of Carbon Dioxide at Atmospheric Pressure
Authors: Yu Bing , Kim Daeun , Kim Seoksun , Hong Soon Hyeok
Published: December 2016

A organocatalytic system based on economical and readily available cyanuric acid has been developed for the synthesis of 2‐oxazolidinones and quinazoline‐2,4(1H,3H)‐diones from propargylamines and 2‐aminobenzonitriles under atmospheric pressure carbon dioxide. Notably, a low concentration of carbon dioxide in air was directly converted into 2‐oxazolidinone in excellent yields without an external base. Through mechanistic investigation by in situ FTIR spectroscopy, cyanuric acid was demonstrated to be an efficient catalyst for carbon dioxide fixation.
Side‐channel analysis of the modular inversion step in the RSA key generation algorithm
Authors: Cabrera Aldaya Alejandro , Cuiman Márquez Raudel , Cabrera Sarmiento Alejandro J. , Sánchez‐Solano Santiago
Published: December 2016

This paper studies the security of the RSA key generation algorithm with regard to side‐channel analysis and presents a novel approach that targets the simple power analysis (SPA) vulnerabilities that may exist in an implementation of the binary extended Euclidean algorithm (BEEA). The SPA vulnerabilities described, together with the properties of the values processed by the BEEA in the context of RSA key generation, represent a serious threat for an implementation of this algorithm. It is shown that an adversary can disclose the private key employing only one power trace with a success rate of 100 % – an improvement on the 25% success rate achieved by the best side‐channel analysis carried out on this algorithm. Two very different BEEA implementations are analyzed, showing how the algorithm's SPA leakages could be exploited. Also, two countermeasures are discussed that could be used to reduce those SPA leakages and prevent the recovery of the RSA private key. Copyright © 2016 John Wiley & Sons, Ltd.
Burglary resistance of thermal insulating clay unit masonry / Einbruchwiderstand von wärmedämmendem Ziegelmauerwerk
Authors: Meyer Udo
Published: December 2016

The number of burglaries in Germany has increased during the last 10 years. The weak points in external walls are windows and doors. One important aspect is the fixing of these elements in the external masonry walls. The German Clay Masonry Industry has carried out a number of tests verifying the resistance class RC2 of windows fixed in external thermal insulating clay masonry walls.
Fixing of windows with fall protection / Befestigung von absturzsichernden Fensterelementen
Authors: Küenzlen Jürgen , Scheller Eckehard , Hamm Hermann
Published: December 2016

Glass areas in modern building are becoming ever larger and in refurbishment, window openings are sometimes enlarged. Window elements with fall protection are often used, which undertake the additional function of fall protection, for example of a handrail. Furthermore, opening casements over the entire window height are often installed and “French balconies" of metal are replaced, for example, by appropriate glass panel fillings screwed directly to the window frames. This means that the fixing of the window frame is as important as that of glazing with fall protection. The article describes the current status of this subject and explains fixing into the structure.
Practical application of a non‐linear earthquake analysis according to DIN EN 1998‐1 / Praktische Anwendung einer nichtlinearen Erdbebenanalyse nach DIN EN 1998‐1
Authors: Gellert Christoph , Rosin Julia
Published: December 2016

Seismic safety verification can be performed by maintaining constructive rules or by calculation. Verification by calculation can be performed with a linear simplified or linear multi‐modal response spectrum analysis. Alternatively, a non‐linear quasi‐static verification is also possible according to DIN EN 1998‐1, which was not available in DIN 4149. In this article, the non‐linear quasi‐static earthquake verification according to DIN EN 1998‐1 is presented in practice, using the example of a building in Mittenwald/Germany. The verification has been checked and accepted by an independent building supervision report.
Co‐Crystallization of Half‐Sandwich (RM,RC)/(SM,RC) Diastereomers in Single Crystals
Authors: Brunner Henri , Tsuno Takashi , Bodensteiner Michael , Gärtner Stefanie , Miyahara Chiemi , Ito Seera , Kurosawa Takaki , Koyama Kazuhiro
Published: December 2016

Invited for the cover of this issue is the group of Takashi Tsuno from Nihon University, Narashino, Japan, in collaboration with the group of Henri Brunner from Universität Regensburg, Germany. The cover image shows two pairs of half‐sandwich (RM,RC)/(SM,RC) diastereomers that co‐crystallize, although each diastereomer should crystallize in its own lattice.
Electronic Effects of Aromatic Rings on the Catalytic Activity of Dioxidomolybdenum(VI)–Hydrazone Complexes
Authors: Bikas Rahman , Lippolis Vito , Noshiranzadeh Nader , Farzaneh‐Bonab Hossein , Blake Alexander J. , Siczek Milosz , Hosseini‐Monfared Hassan , Lis Tadeusz
Published: December 2016

Nine dioxidomolybdenum(VI) complexes were synthesized through the reactions of MoO3 with tridentate hydrazone Schiff base ligands obtained from the reactions of aromatic acid hydrazides (3‐hydroxy‐2‐naphthoic acid hydrazide, 4‐pyridinecarboxylic acid hydrazide and 2‐furoic acid hydrazide) and ortho‐hydroxy aldehyde derivatives (5‐iodo‐2‐hydroxybenzaldehyde, 2‐hydroxy‐1‐naphthaldehyde and 2‐hydroxy‐3‐methoxybenzaldehyde). All of the ligands and complexes were characterized by elemental analysis and spectroscopic methods. The structures of seven complexes were further elucidated by single‐crystal X‐ray diffraction analysis, which indicated distorted octahedral geometries at the metal centres. Spectroscopic and X‐ray analyses indicated that the ligands are coordinated to the molybdenum(VI) ions as dianionic ligands owing to the deprotonation of the phenolic OH and amidic NH groups upon complexation. These complexes were used as catalysts for the oxidation of cyclooctene and thioanisole in the presence of hydrogen peroxide as an environmentally friendly oxidant. To achieve the highest catalytic activity, the effects of important parameters such as the solvent, temperature and molar ratio of the oxidant to the substrate were optimized. The results indicate that electron‐withdrawing substituents on the ligands increase the catalytic activities of dioxidomolybdenum(VI) hydrazone complexes.
Diastereoselective Intramolecular Cyanoamidation with Alkenes
Authors: Dreis Ashley M. , Otte Sadie C. , Eastwood Matthew S. , Alonzi Elizabeth R. , Brethorst Jason T. , Douglas Christopher J.
Published: December 2016

Reported herein is a diastereoselective intramolecular alkene cyanoamidation, wherein high d.r. values are imparted by chiral directing groups. Lactams with an α‐all‐carbon quaternary stereocenter are readily synthesized, which may enable access to structures frequently found in biologically active molecules and natural products.
Expanding the Hammett Correlations for the Vinylheptafulvene Ring‐Closure Reaction
Authors: Kilde Martin Drøhse , Hansen Mia Harring , Broman Søren Lindbæk , Mikkelsen Kurt V. , Nielsen Mogens Brøndsted
Published: December 2016

A selection of 2,3‐diarylated photochromic dihydroazulenes (DHAs) was prepared by following two different protocols. The first protocol relies on the synthesis of a 3‐bromo‐substituted dihydroazulene, which is subjected to a Suzuki cross‐coupling reaction in the final step. In the second protocol, the two aryl substituents are introduced early in the synthesis. The DHAs are photoactive and undergo light‐induced ring‐opening reactions to form vinylheptafulvene (VHF) isomers. These VHFs are quickly converted back to DHAs at room temperature in thermal ring‐closure reactions. The kinetics of these reactions was studied at –20 °C for two series for which the substituent at the C‐2 position (DHA numbering) was kept constant, and a linear free‐energy relationship (Hammett correlation) was revealed in both cases. The relationships show that an electron‐donating substituent at C‐3 (the exocyclic VHF carbon atom) enhances the ring‐closure reaction, in contrast to its influence when placed at C‐2. In a computational study (density functional theory), three different methods were benchmarked against the experimental results. Overall, this work shows for the first time how the VHF to DHA switch is influenced by donor–acceptor substitution at the exocyclic heptafulvene carbon atom.
Novel approach for the prediction of cell densities and viability in standardized translucent cell culture biochips with near infrared spectroscopy
Authors: Gröger Marko , Lange Matthias , Rennert Knut , Kaschowitz Tobias , Plettenberg Holger , Hoffmann Martin , Mosig Alexander S.
Published: December 2016

Near infrared spectroscopy is a rapid and nondestructive method for compositional analysis of biological material. The technology is widely used within bioreactors and possesses potential as a standardized method for quality control in miniaturized microfluidic cell culture systems. Here, we established a method for quantification of cell density and viability of adherent HepaRG cells cultured in a translucent, miniaturized cell culture biochip. The newly developed statistical models for interpretation of near infrared spectroscopy from biochips are the basis for a novel method of fast, continuous, and contact‐free analysis of cell viability and real‐time monitoring of cell growth. The technique thus paves the way for a robust and reliable high‐throughput analysis of biochip‐embedded cell cultures.
Can we weather proof our insurance?
Authors: Lyubchich Vyacheslav , Gel Y. R.
Published: December 2016

The last few years were particularly volatile for the insurance industry in North America and Europe, bringing a record number of claims due to severe weather. According to a 2013 World Bank study, annual average losses from natural disasters have increased from $50 billion in the 1980s to about $200 billion nowadays. Adaptation to such changes requires early recognition of vulnerable areas and the extent of the future risk due to weather factors. Despite the well‐documented impact of climate change on the insurance sector, there exists a relatively limited number of studies addressing the effect of the so‐called “normal” extreme weather (i.e., higher frequency and lower individual but high cumulative impact events) on the insurance dynamics. To reduce financial repercussions of such weather events, we develop a nonlinear attribution analysis of integer‐valued insurance claims and atmospheric variables. Using data‐driven nonparametric procedures, we identify triggering thresholds, or tipping points, leading to an increase in the number of claims. We develop a new data‐adaptive method to compare tails of observed and projected weather variables and employ its outcomes to assess future dynamics of insurance claims. We illustrate our approach by application to modeling and forecasting of flood‐related home insurance claims in Norway.
A ruin theoretic design approach for wireless cellular network sharing with facilities
Authors: Egan Malcolm , Peters Gareth W. , Nevat Ido , Shirvanimoghaddam Mahyar , Collings Iain B.
Published: December 2016

With the rise of cheap small cells in wireless cellular networks, there are new opportunities for third party providers to service local regions via sharing arrangements with traditional operators. In fact, such arrangements may be particularly desirable for large facilities—such as stadiums, universities, and mines—as they already need to cover property costs, and often have fiber backhaul and efficient power infrastructure. In this paper, we propose a network‐sharing arrangement between large facilities and traditional operators. Our network‐sharing arrangement consists of two aspects: leasing of data access and spectrum from traditional operators; and service agreements with users. As a consequence of the incorporation of the user service agreements into the sharing arrangement, financial as well as physical resource constraints need to be accounted for. This introduces a new dimension into wireless network resource allocation, which requires a new evaluation framework. To this end, we develop a framework based on ruin theory, where the key metric is the probability that the facility is insolvent within a fixed time period. We then investigate the effect of initial capital and physical layer parameters on the ruin probability, which provides insight into the robustness of the network‐sharing arrangement to varying conditions.
A Gold‐ and Brønsted Acid Catalytic Interplay Towards the Synthesis of Highly Substituted Tetrahydrocarbazoles
Authors: Garayalde David , Rusconi Giulia , Nevado Cristina
Published: December 2016

The reaction of indoles and stabilized cyclopropyl alkynes under gold‐ and/or gold & Brønsted acid‐catalysis provided access to highly substituted tetrahydrocarbazoles. A mechanistic study revealed the complex mechanism underlying these processes and the opportunistic cooperation of Lewis and Brønsted acid‐catalysts towards the formation of complex molecular scaffolds.
Differences in Trabecular Microstructure Between Black and White Women Assessed by Individual Trabecular Segmentation Analysis of HR-pQCT Images
Authors: Putman Melissa S , Yu Elaine W , Lin David , Darakananda Karin , Finkelstein Joel S , Bouxsein Mary L
Published: December 2016

Black women have lower fracture risk compared with white women, which may be partly explained by improved volumetric bone mineral density (vBMD) and bone microarchitecture primarily within the cortical bone compartment. To determine if there are differences in trabecular microstructure, connectivity, and alignment according to race/ethnicity, we performed individual trabecular segmentation (ITS) analyses on high-resolution peripheral quantitative computed tomography (HR-pQCT) scans of the distal radius and tibia in 273 peri- and postmenopausal black (n = 100) and white (n = 173) women participating in the Study of Women's Health Across the Nation in Boston. Unadjusted analyses showed that black women had greater trabecular plate volume fraction, plate thickness, plate number density, and plate surface area along with greater axial alignment of trabeculae, whereas white women had greater trabecular rod tissue fraction (p < 0.05 for all). Adjustment for clinical covariates augmented these race/ethnicity-related differences in plates and rods, such that white women had greater trabecular rod number density and rod-rod connectivity, whereas black women continued to have superior plate structural characteristics and axial alignment (p < 0.05 for all). These differences remained significant after adjustment for hip BMD and trabecular vBMD. In conclusion, black women had more plate-like trabecular morphology and higher axial alignment of trabeculae, whereas white women had more rod-like trabeculae. These differences may contribute to the improved bone strength and lower fracture risk observed in black women. © 2016 American Society for Bone and Mineral Research.
Identification of Thermal Decomposition Products and Reactions for Liquid Ammonium Nitrate on the Basis of Ab Initio Calculation
Authors: Izato Yu‐Ichiro , Koshi Mitsuo , Miyake Atsumi
Published: December 2016

This work analyzed the thermal decomposition of ammonium nitrate (AN) in the liquid phase, using computations based on quantum mechanics to confirm the identity of the products observed in past experimental studies. During these ab initio calculations, the CBS‐QB3//ωB97XD/6–311++G(d,p) method was employed. It was found that one of the most reasonable reaction pathways is HNO3 + NH4+ → NH3NO2+ + H2O followed by NH3NO2+ + NO3– → NH2NO2 + HNO3. In the case in which HNO3 accumulates in the molten AN, alternate reactions producing NH2NO2 are HNO3 + HNO3 → N2O5 + H2O and subsequently N2O5 + NH4+ → NH2NO2 + H2O. In both scenarios, HNO3 plays the role of a catalyst and the overall reaction can be written as NH4+ + NO3– (AN) → NH2NO2 + H2O. Although the unimolecular decomposition of NH2NO2 is thermodynamically unfavorable, water and bases both promote the decomposition of this molecule to N2O and H2O. Thus AN thermal decomposition in the liquid phase can be summarized as NH4+ + NO3– (AN) → N2O + 2H2O.
Shining a light on the effects of omega‐3 polyunsaturated fatty acids on the brain: The relationship between cerebral blood flow parameters and cognition
Authors: Patan Michael J. , Jackson Philippa A.
Published: December 2016

Higher dietary intake of omega‐3 polyunsaturated fatty acids (n‐3 PUFAs) is associated with better cognitive function in older adults and reduced incidence of dementia. One potential mechanism underpinning this relationship is via modulation of cerebrovascular parameters and therefore increasingly, neuroimaging techniques such as near‐infrared spectroscopy (NIRS) and fMRI have been applied to investigate the effect of n‐3 PUFAs on cerebral blood flow in humans. These studies have revealed that n‐3 PUFA supplementation has subtle effects on cerebral blood flow which may indeed underpin the positive relationship between their intake and cognition across the lifespan; at present these changes are more apparent in children and younger adults.
Concentrated second‐harmonic generation from a single Al‐covered ZnS nanobelt
Authors: Hu Hongbo , Wang Kai , Long Hua , Han Xiaobo , Chen Jiawei , Wang Bing , Lu Peixiang
Published: December 2016

Here we report on the hybrid nanostructures where a single ZnS nanobelt was half‐covered with an aluminum (Al) film, which is an ideal platform for studying the second‐harmonic generation (SHG) enhancement effects of the Al coating. It was fabricated by the lift‐off process and allowed for the accurate comparison of the SHG intensity between the Al‐covered and the same bare ZnS nanobelt under consistent test conditions. The results indicate that the Al coating in the hybrid nanostructures not only confines the pumping laser in the ZnS effectively, but also concentrates the emitted SHG signal greatly, increasing the signal collection efficiency. By the combination of these two effects, ∼60 times enhancement of the SHG intensity is achieved at the optimized geometry size (width and thickness) of the ZnS nanobelts. The Al‐based hybrid nanostructures open up new possibilities for low‐cost, highly efficient and directional coherent nanolight sources at short wavelengths.

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Enzyme Tunnels and Gates As Relevant Targets in Drug Design
Authors: Marques Sergio M. , Daniel Lukas , Buryska Tomas , Prokop Zbynek , Brezovsky Jan , Damborsky Jiri
Published: December 2016

Many enzymes contain tunnels and gates that are essential to their function. Gates reversibly switch between open and closed conformations and thereby control the traffic of small molecules—substrates, products, ions, and solvent molecules—into and out of the enzyme's structure via molecular tunnels. Many transient tunnels and gates undoubtedly remain to be identified, and their functional roles and utility as potential drug targets have received comparatively little attention. Here, we describe a set of general concepts relating to the structural properties, function, and classification of these interesting structural features. In addition, we highlight the potential of enzyme tunnels and gates as targets for the binding of small molecules. The different types of binding that are possible and the potential pharmacological benefits of such targeting are discussed. Twelve examples of ligands bound to the tunnels and/or gates of clinically relevant enzymes are used to illustrate the different binding modes and to explain some new strategies for drug design. Such strategies could potentially help to overcome some of the problems facing medicinal chemists and lead to the discovery of more effective drugs.
Outcome and prognostic factors in high‐risk childhood adrenocortical carcinomas: A report from the European Cooperative Study Group on Pediatric Rare Tumors (EXPeRT)
Authors: Cecchetto Giovanni , Ganarin Alba , Bien Ewa , Vorwerk Peter , Bisogno Gianni , Godzinski Jan , Dall'Igna Patrizia , Reguerre Yves , Schneider Dominik , Brugières Laurence , Leblond Pierre , Ferrari Andrea , Brecht Ines , De Paoli Angela , Orbach Daniel
Published: December 2016

Objectives

The aim of this retrospective international analysis was to evaluate the role of risk factors in pediatric patients with adrenocortical carcinoma (ACC) observed in European countries (2000–2013) in an attempt to identify factors associated with poor prognosis.

Procedures

Data were retrieved from databases of Germany, France, Poland, and Italy, which form the European Cooperative Study Group on Pediatric Rare Tumors (EXPeRT). Patients were less than 18 years old, with at least one of the following tumor‐related risk factors: metastases, volume more than 200 cm3, Cushing syndrome, vascular or regional lymph node invasion, initial biopsy, or incomplete excision. Role of patients’ age was also evaluated.

Results

Eighty‐two patients were evaluated: 62 with localized disease and 20 with metastases. The 3‐year progression‐free survival (PFS) and overall survival (OS) were 39% and 55% for the whole population, respectively, and 51% and 73% for localized diseases, respectively. Concerning the whole population, PFS and OS were influenced by distant metastases, tumor volume, lymph node involvement, age, and presence of two or more risk factors. Factors significant only at OS were vascular involvement and incomplete surgery. At multivariable analysis, the main factors at PFS were volume more than 200 cm3 (hazard ratio [HR]: 2.6, 95% confidence interval [CI]: 1.18–5.70) and presence of distant metastases (HR: 8.26, 95% CI: 3.49–19.51). The OS was significantly influenced by the presence of metastases (P < 0.0001). Concerning patients with localized tumors, the only significant prognostic factor was volume more than 200 cm3 with a HR of 4.38 (95% CI: 1.60–12.00) for PFS and of 3.68 (95% CI: 1.02–13.30) for OS.

Conclusions

Distant metastases and large tumor volume were the main unfavorable prognostic factors. Presence of two or more factors related to ACC was associated with an aggressive behavior of disease.
Data Intelligence for Local Government? Assessing the Benefits and Barriers to Use of Big Data in the Public Sector
Authors: Malomo Fola , Sena Vania
Published: December 2016

The concept of Big Data has become very popular over the last decade, with large technology companies successfully building their business models around its exploitation. The public sector in the United Kingdom has tried to follow suit and local governments in particular have tried to introduce new models of service delivery based on the routine extraction of information from their own Big Data. These attempts have been hailed as the beginning of a new era for the public sector where service delivery and commissioning are shaped by data intelligence on local needs and by evidence on the outcomes. In this article we assess this claim and the extent to which it captures the way local governments in the United Kingdom use intelligence from Big Data in light of the structural barriers they face when trying to exploit their data. We also present a case study on the development and deployment of an integrated data model for children services in a large county council in the South‐East of England.
Diodes based on semi‐insulating CdTe crystals with Mo/MoOx contacts for X‐ and γ‐ray detectors
Authors: Maslyanchuk O. , Kulchynsky V. , Solovan M. , Gnatyuk V. , Potiriadis C. , Kaissas I. , Brus V.
Published: December 2016

This paper reports on the possible applications of molybdenum oxide (Mo/MoOx) contacts in combination with semi‐insulating CdTe crystals. The electrical contacts to p‐type Cl‐doped CdTe crystals were formed by the deposition of molybdenum oxide and pure molybdenum thin films by the DC reactive magnetron sputtering. Electrical properties of the prepared Mo‐MoOx/р‐CdTe/MoOx‐Mo surface‐barrier structures were investigated at different temperatures. It is shown that the rapid growth of the reverse current with increasing bias voltage higher than 10 V is caused by the space‐charge limited currents. Spectrometric properties of the Mo‐MoOx/р‐CdTe/MoOx‐Mo structures have been also analyzed. It is revealed that the developed heterojunction has shown promising characteristics for its practical application in X‐ and γ‐ray radiation detector fabrication.