bluuebunny/crossref_metadata_2025 huggingface dataset:
Plasmon Resonance Hybridization in Self-Assembled Copper Nanoparticle Clusters: Efficient and Precise Localization of Surface Plasmon Resonance (LSPR) Sensing Based on Fano Resonances
Authors: Ahmadivand Arash , Pala Nezih
Published: February 2015

In this work, we have investigated the hybridization of plasmon resonance modes in completely copper (Cu)-based subwavelength nanoparticle clusters from simple symmetric dimers to complex asymmetric self-assembled structures. The quality of apparent bonding and antibonding plasmon resonance modes for all of the clusters has been studied, and we examined the spectral response of each one of the proposed configurations numerically using the finite-difference time domain (FDTD) method. The effect of the geometric sizes of nanoparticles used and substrate refractive index on the cross-sectional profiles of each of the studied structures has been calculated and drawn. We proved that Fano-like resonance can be formed in Cu-based heptamer clusters as in analogous noble metallic particles (e.g., Au and Ag) by determining the coupling strength and interference between sub-radiant and super-radiant resonance modes. Employing certain Cu nanodiscs in designing an octamer structure, we measured the quality of the Fano dip formation along the scattering diagram. Accurate tuning of the geometric sizes for the Cu-based octamer yields an opportunity to observe isotropic, deep, and narrow Fano minima along the scattering profile that are in comparable condition with the response of other plasmonic metallic substances. Immersing investigated final Cu-based octamer in various liquids with different refractive indices, we determined the sensing accuracy of the cluster based on the performance of the Fano dip. Plotting a linear diagram of plasmon energy differences over the refractive index variations as a figure of merit (FoM), which we have quantified as 13.25. With this method, the precision of the completely Cu-based octamer is verified numerically using the FDTD tool. This study paves the way toward the use of Cu as an efficient, low-cost, and complementary metal-oxide semiconductor (CMOS)-compatible plasmonic material with optical properties that are similar to analogous plasmonic substances.
Synthesis of a Red Fluorescent Dye-Conjugated Ag@SiO2 Nanocomposite for Cell Immunofluorescence
Authors: Dong Meicong , Tian Yu , Pappas Dimitri
Published: February 2015

In this work we describe a one-step approach for incorporating a red fluorophore (2SBPO) into core-shell nanoparticles for metal-enhanced fluorescence immunolabels. The 2SBPO-MEF nanoparticles are particularly attractive as cell labels because their ∼ 670 nm emission has minimal overlap with cell autofluorescence and from overlap with many conventional probes. 2SBPO was incorporated through physical entrapment during the Stöber process. Antibody-based cell labels were then synthesized using covalent linkage. The nanoparticle fluorescence was 7.5-fold higher than control nanoparticles lacking a metal core. We demonstrated labeling of CD4 + HuT 78 T lymphocytes using anti-CD4-conjugated nanoparticle labels. Cells labeled with anti-CD4 nanoparticles showed a 35-fold fluorescence signal compared to anti-CD4 coreless controls. This simple synthesis protocol can be applied to a variety of hydrophilic fluorophore types and has broad potential in bioanalytical and biosensing applications.
Hedi Slimane and the reinvention of menswear
Authors: Bowstead Jay McCauley
Published: February 2015

This article analyses the role of designer Hedi Slimane in shaping the development of menswear in the first decade of the twenty-first century. Slimane’s collections for Dior Homme in the early 2000s caught the imagination of the fashion press with their combination of a radically slim silhouette, precise tailoring and androgynous flourishes. Along with the commercial success he brought to Dior, Slimane catalyzed a renewed interest in menswear, the aesthetic he proposed acting as a prototype for men’s fashion throughout the decade. By contrasting Slimane’s slender, ambiguous and self-consciously elegant look with the sporty muscularity of the 1990s catwalk, the article explores the shifting nature of male identity in the new millennium as fashionable men found new ways of consuming their masculinity.
To disseminate is to act: Readers’ theatre in HIV/AIDS community-based research
Authors: Mignone Javier , Harvey Carol D. H. , Elliott Lawrence , Davis Jennifer , Pindera Carla , Migliardi Paula
Published: February 2015

This community-based study sought to understand the caregiving support networks of people living with HIV/AIDS in Winnipeg and Regina, Canada. Qualitative data from 31 participants were gathered from photographs that each individual took of daily life and from in-depth individual interviews. A novel dissemination approach was the creation and performance of a readers’ theatre based on the interview data. This article explains the process of creating and using readers’ theatre with HIV/AIDS service agencies and community members, and it discusses main lessons learned.
Silenced: The impact of mental health themed artwork in a workplace setting
Authors: Tischler Victoria
Published: February 2015

This article discusses the controversy surrounding the display of artwork in a workplace where mental health research and teaching takes place. The exhibition of artwork by a deceased mental health service user provoked strong reactions amongst staff and began a dialogue about the impact of the work on viewers. I review issues of autobiographical artwork, mental health recovery and censorship. Whilst the display of art with potentially distressing themes can be illuminating and an important mode of social inclusion, negotiating the location of exhibitions and providing support for staff who may be affected by the work must be considered.
Dyspraxia, drama and masks: Applying the school curriculum as therapy
Authors: Roy David , Dock Caroline
Published: February 2015

Internationally one in fifteen children have suspected dyspraxia. In the United Kingdom, New Zealand and the United States, speech and occupational therapists and physiotherapists all agree that early intervention can help children with dyspraxia overcome these challenges and be successful participants in education and the wider society. Key to successful learning experiences for children with dyspraxia, drama and mask usage offers the tools to access the curriculum. Because drama is a collaborative, not competitive, methodology, the fear of rejection and failure can be challenged and through development of strengths in academia can support children. This article presents background on dyspraxia, signifiers for identification for children with dyspraxia, challenges facing schools, and practical activities to apply within the curriculum.
Non Expensive 3D Documentation and Modelling of Historical Object and Archaeological Artefacts by Using Close Range Photogrammetry
Authors: Pavelka Karel , Řezníček Jan , Bílá Zdeňka , Prunarová Lucie
Published: February 2015

Nowadays, there are two main approaches to cultural heritage documentation: a precise documentation by several techniques such as professional close range photogrammetry, classical geodetical measurement and 3D scanning, or a simple documentation using non expensive devices and instruments, often based on free  software. In many projects it is not possible to use precise and expensive instruments for time, transportational, financial and authoritative permission reasons. At the Laboratory of Photogrammetry at the CTU Prague, we are focused on both types of documentation and the necessary visualisation of outputs; the long-term and very important aim of our research in this field is to develop small, inexpensive devices and test appropriate technology for the 3D documentation of cultural heritage objects. There is our prototype of an optical correlation system, which uses a motorised calibrated digital camera on a linear base. The second part shows several open source photogrammetric systems compared with Photomodeler PMSC and Agisoft Photoscan software. On a case project, based on our own data from German-Czech expeditions in Peru, the simple photogrammetric documentation of a small archaeological object joined with reverse engineering has been demonstrated.
Integrating DROOLS and R software for intelligent map system
Authors: Růžička Jan
Published: February 2015

The paper describes intelligent map system that allows to check errors in map sheets or to help with a map sheet creation. The system is based on expert system DROOLS, ontology created in Protége and statistical software R. Prototype of the system should evaluate that this kind of integration is possible, so the system is not full of rules. The prototype is filled with twenty rules written in DRL language and with more than thirty items from the ontology. The paper should show how all of these components can be integrated together to allow such kind of a map sheet evaluation. The system is now used for selection of the best method for data classification. The selection is suggested by DROOLS system that uses R software to perform statistical tests of normality and uniformity.
Geostatistical Methods in R
Authors: Volfová Adéla , Šmejkal Martin
Published: February 2015

Geostatistics is a scientific field which provides methods for processing spatial data.  In our project, geostatistics is used as a tool for describing spatial continuity and making predictions of some natural phenomena. An open source statistical project called R is used for all calculations. Listeners will be provided with a brief introduction to R and its geostatistical packages and basic principles of kriging and cokriging methods. Heavy mathematical background is omitted due to its complexity. In the second part of the presentation, several examples are shown of how to make a prediction in the whole area of interest where observations were made in just a few points. Results of these methods are compared.
Panoramic UAV Views for Landscape Heritage Analysis Integrated with Historical Maps Atlases
Authors: Brumana Raffaella , Oreni Daniela , Alba Mario , Barazzetti Luigi , Cuca Branka , Scaioni Marco
Published: February 2015

Analysis of landscape heritage and territorial transformations dedicated to its protection and preservation rely increasingly upon the contribution of integrated disciplines. In 2000 the European Landscape Convention established the necessity ‘to integrate landscape into its regional and town planning policies and in its cultural, environmental, agricultural, social and economic policies’. Such articulated territorial dimension requires an approach able to consider multi-dimensional data and information from different spatial and temporal series, supporting territorial analysis and spatial planning under different points of view. Most of landscape representation instruments are based on 3D models based on top-down image/views, with still weak possibilities to reproduce views similar to the human eye or map surface development along preferential directions (e.g. water front views). A methodological approach of rediscovering the long tradition of historical water front view maps, itinerary maps and human eye maps perspective, could improve content decoding of cultural heritage with environmental dimension and its knowledge transfer to planners and citizens. The research here described experiments multiple view models which can simulate real scenarios at the height of observer or along view front. The paper investigates the possibilities of panoramic views simulation and reconstruction from images acquired by RC/UAV platforms and multisensory systems, testing orthoimage generation for landscape riparian areas and water front wiew representation, verifying the application of automatic algorithms for image orientation and DTM extraction (AtiPE, ATE) on such complex image models, identifying critical aspects for future development. The sample landscape portion along ancient water corridor, with stratified values of anthropogenic environment, shows the potentials of future achievement in supporting sustainable planning through technical water front view map and 3D panoramic views, for Environmental Impact Assessment (EIA) purposes and for the improvement of an acknowledged tourism within geo-atlas based on multi-dimensional and multitemporal Spatial Data Infrastructures (SDI).
Macht und Medien
Authors: Sieber Samuel
Published: February 2015

Neue Medien und digitale Netze prägen maßgeblich die politischen Herausforderungen der Gegenwart. Sogenannte »Medienrevolutionen« versprechen eine Zunahme des weltweit zugänglichen Wissens und der demokratischen Willensbildung - zugleich florieren die Verdatungsregime einer gouvernementalen Netzwerkgesellschaft, die wesentlich eine Überwachungs- und Kontrollgesellschaft ist. Samuel Sieber rekonstruiert minutiös die Bedeutung der Diskurs- und Machtanalyse Michel Foucaults für eine Theorie und Analyse der Dispositive der medienvermittelten Kommunikation, die den politischen Spielraum des Machtgefüges ebenso eingrenzen wie erweitern.
Entangled Inequalities in Transnational Care Chains
Authors: Skornia Anna Katharina
Published: February 2015

Based on a multi-sited ethnographic case study on transnational care chains between Milan (Italy) and Lima, Huancayo, and Cuzco (Peru), the book explores how social inequalities are reproduced through the care practices that follow the introduction of Peruvian migrants into home-based elderly care. Anna Katharina Skornia adopts an innovative approach in combining research on transnational care and migration with a perspective on entangled inequalities. In particular, the study sheds light on the role of state regulations in contributing to these inequalities as well as their ambiguous implications from the perspectives of both caregivers and receivers.
Menschen am Brunnen
Authors: Cless Karlheinz
Published: February 2015

Wasser als erneuerbare Ressource wird in seiner reinen, für den Menschen genießbaren Form knapper. Verstärkt durch den Klimawandel führt das nicht nur zu Vulnerabilität und zunehmender Kommerzialisierung, sondern auch zu Konflikten über Verfügbarkeit und Verwendung. Die menschliche Not wächst. Aus ethnologischer Perspektive beobachtet Karlheinz Cless den Einfluss dieser Phänomene auf die Kultur, lokale Ethnien, Wahrnehmungen und Bedeutungen in semi-ariden Gebieten in Ghana, Indien und China. Mit einem Vorwort von Hans Peter Hahn.
Zeit, Dauer und Veränderung
Authors: Bockrath Franz
Published: February 2015

Bewegungen sind nicht nur an räumliche, sondern auch an zeitliche Verhältnisse gebunden. Die daraus resultierenden Widersprüche gelten bis heute als ungelöst. So ist es zwar möglich, Bewegungen zu messen und zu berechnen - als problematisch erweist sich jedoch die weitergehende Frage, wie ein beweglicher Körper im selben Zeitmoment an unterschiedlichen Orten zugleich sein kann. Da einfache empirische Antworten sowie rein gedankliche Lösungen nicht zu geben sind, fokussiert Franz Bockrath vor allem auf jene sozialphilosophischen und kulturwissenschaftlichen Ansätze, die Zeit und Bewegung in ihrem widersprüchlichen Zusammenhang begreifen.
Microwave Material Properties of Nanoparticle-Doped Nematic Liquid Crystals
Authors: Karabey O. H.
Published: February 2015

This letter presents the material properties of nanoparticle-doped liquid crystal (LC) mixtures at microwave frequencies. A host (undoped) nematic LC material is doped with several concentrations of ferroelectric, gold and silver nanoparticles. The measurements are conducted at 30 GHz by using a cavity perturbation method. Based on these measurements, relative permittivity and dielectric losses are extracted, then the resultant material tunability and figure-of-merit are calculated. Compared to the host LC, some changes in the electrical parameters of the doped samples are observed, reducing the tunability and material figure-of-merit of all samples. Nevertheless, depending on the shape of the nanoparticles, their impact on the material figure-of-merit is more significant than on the tunability, reducing the figure-of-merit drastically once the tunability changed slightly only.
The reaction of dimethyldioxirane with 1,3-cyclohexadiene and 1,3-cyclooctadiene: monoepoxidation kinetics and computational modeling
Authors: McTush-Camp Davita , Vasquez Pedro C. , Baumstark Alfons L.
Published: February 2015

The reaction of dimethyldioxirane (1) with excess 1,3-cyclohexadiene (2a) and 1,3-cyclooctadiene (2b) in dried acetone yielded the corresponding monoepoxides in excellent yield. Second-order rate constants for monoepoxidation were determined using UV methodology. The k2 value for the monoepoxidation of 1,3-cyclohexadiene was found to be 1.14±0.06 m
-1 s-1, whereas that for the monoepoxidation of 1,3-cycloctadiene was 0.31±0.03 m
-1 s-1. Basic density functional calculations at the B3LYP/6-31G level were employed to model the monoepoxidations. As expected, the calculations were consistent with a concerted, electrophilic process with a spiro-transition state. As found for the epoxidation of simple alkenes, the calculated transition-state geometry showed a slight asynchronous tilt of the dioxirane plane relative to that of the remaining alkene portion of the diene and a slight tilt back from the face of the diene. Relative reactivities (relative k2 values) were determined using the difference in the calculated electronic activation energies and were consistent with the experimental relative k2 values without the need to correct for the medium (solvent). Reactivity differences for epoxidation can be quickly predicted by this approach as long as there are reasonable structural similarities between the substrates.
Numerical Prediction of the Thermodynamic Properties of Ternary Al-Ni-Pd Alloys
Authors: Zagula-Yavorska Maryana , Romanowska Jolanta , Kotowski Sławomir , Sieniawski Jan
Published: February 2015

Thermodynamic properties of ternary Al-Ni-Pd system, such as exGAlNPd, µAl(AlNiPd),µNi(AlNiPd) and µPd(AlNiPd) at 1,373 K, were predicted on the basis of thermodynamic properties of binary systems included in the investigated ternary system. The idea of predicting exGAlNiPd values was regarded as calculation of values of the exG function inside a certain area (a Gibbs triangle) unless all boundary conditions, that is values of exG on all legs of the triangle are known (exGAlNi, exGAlPd, exGNiPd). This approach is contrary to finding a function value outside a certain area, if the function value inside this area is known. exG and LAl,Ni,Pd ternary interaction parameters in the Muggianu extension of the Redlich–Kister formalism were calculated numerically using the Excel program and Solver. The accepted values of the third component xx differed from 0.01 to 0.1 mole fraction. Values of LAlNiPd parameters in the Redlich–Kister formula are different for different xx values, but values of thermodynamic functions: exGAlNiPd, µAl(AlNiPd), µNi(AlNiPd) and µPd(AlNiPd) do not differ significantly for different xx values. The choice of xx value does not influence the accuracy of calculations.
Sewage Treatment with a Hybrid Constructed Soil Filter
Authors: Llorens Mercedes , Pérez-Marín Ana B. , Sáez José , Aguilar María I. , Ortuño Juan F. , Meseguer Víctor F. , Ruiz Jose A.
Published: February 2015

The overall aim of this research was to apply a hybrid constructed soil filter for sewage treatment. A hybrid constructed soil filter is an ecological process used for decentralized sewage treatment in villages, small towns or scattered residential areas. Sewage is firstly treated by conventional physicochemical or biological treatment and then allowed to infiltrate through aerated unsaturated zone wherein it gets purified through processes such as filtration, adsorption, chemical reaction and biodegradation. This system has demonstrated a consistent capacity to remove organic matter and nitrogen. Experimental results have shown that under hydraulic load rates of 0.22 m3/m2 · h and organic load rates ranging from 47 to 156 g COD/m2 · h, mean removal efficiencies of 89% for COD, 99% for BOD5, 86% for suspended solids and 52% for total nitrogen can be achieved using an hybrid constructed soil filter. Compared to the conventional activated sludge process, this technology has many advantages, such as simple construction, low operation and maintenance costs, as well as a simple operation.
Measuring Bilateral Market Power in International Markets of Vertically Differentiated Agricultural Commodities
Authors: Yamaura Koichi , Xia Tian
Published: February 2015

Two features of international markets of agricultural commodities are bilateral market power of exporting and importing countries and the coexistence of non-genetically modified (non-GM) and genetically modified (GM) products. The two features were not taken into account in most extant studies on market power in international agricultural commodity markets. This research develops a bilateral oligopoly model with the interaction between non-GM and GM commodity and conducts an empirical estimation for U.S.–Japan soybean trade. The estimation results show that U.S. exporters and Japanese importers are almost equally sharing the dominance of market power. The analysis in this research provides new measures of market power and improves the understanding on world soybean markets.
Erratum to “On the strong metric dimension
of the strong products of graphs”
Authors: Kuziak Dorota , Yero Ismael G. , Rodríguez-Velázquez Juan A.
Published: February 2015

The original version of the article was published in Open Mathematics (formerly Central European Journal
of Mathematics) 13 (2015) 64–74. Unfortunately, the original version of this article contains a mistake: in
Lemma 2.17 appears that for any C1-graph G and any graph H, β (G ⊠ H) ≤ β (G)(β(H)+1), while should
be β (G ⊠ H) ≤ β(H) (β(G)+1). In this erratum we correct the lemma, its proof and some of its consequences.
Modelling aquatic communities: Trophic interactions and the body mass-and-age structure of fish populations give rise to long-period variations in fish population size
Authors: Medvinsky Alexander B. , Nurieva Nailya I. , Rusakov Alexey V. , Bobyrev Alexander E. , Burmensky Vladimir A. , Kriksunov Evgeniy A.
Published: February 2015

We present a mathematical model of an aquatic community, which includes zooplankton and fish reproduction, and age-weight-structured trophic relationships. We show that interactions between separate components of the aquatic community can give rise to long-period oscillations in fish population size. The period of these oscillations is on the order of decades.We show that predatory fish can be an element, which gives rise to the long-period oscillations. With this model we also show that an increase in the zooplankton growth rate may entail a sequence of bifurcations in the fish population dynamics: steady states → regular oscillations → quasicycles → dynamic chaos. Since aquatic, and in particular, lake ecosystems are spatially heterogeneous, they are often considered as consisting of separate habitats, which are distinguished by their hydrophysical and ecological characteristics. We show that interhabitat fish migration can lead to dramatic changes in the fish population dynamics. In particular, the fish migration can destabilize both stationary states and chaotic regimes giving rise to regular and quasiregular oscillations in the fish population size.
Synthese und Reaktivität von γ-Triphenylstannyl-α-aminobuttersäure-derivaten / Synthesis and Reactivity of γ-Triphenylstannyl-α-aminobutyric Acid Derivatives
Authors: Dölling Karin , Krug André , Hartung Helmut , Weichmann Horst
Published: February 2015

Ph3SnCH2CH2CH(NHCOOCH2Ph)COOCH3 (1) is synthesized by hydrostannation of methyl N-(benzyloxycarbonyl)vinylglycinate with Ph3SnH. The reaction of 1 with HCl in CH3OH and with bromine in CHCl13 yields the halostannylsubstituted compounds Ph3-nXnSnCH2CH2CH(NHCOOCH2Ph)COOCH3 (2 - 4) (n = 1, 2; X = Cl, Br). By saponification with one equivalent of NaOH and subsequent acidification with HCl 1 is transformed into the free acid Ph3SnCH2CH2CH(NHCOOCH2Ph)COOH (5) that undergoes cyclization into the 1,2-oxastanninane 6 with intramolecular elimination of benzene. IR, NMR data and the determination of the crystal structure of Ph2BrSnCH2CH2CH(NHCOOCH2Ph)COOCH3(3) reveal for 2 and 3 an intramolecular coordination of the NC(O)O-group at the tin atom to form a seven-membered ring
1-Allylgermatrane. Synthesis, Structure and Reaction with Diazomethane
Authors: Zaitseva Galina S. , Karlov Sergey S. , Alekseyeva Elena S. , Aslanov Leonid A. , Avtomonov Evgeni V. , Lorberth Jörg
Published: February 2015

Reaction of allyltribromogermane (2), readily available from dibromo(1,4-dioxane)germanium(II) (1) and allylbromide, with tris(2-tributylstannoxyethyl)-amine (4) gives 1-allylgermatrane (3) in almost quantitative yield. 3 crystallizes from n-pentane as a colourless crystalline solid which was characterized by 1H and 13C NMR spectroscopy and by an X-ray crystal structure study. The “atrane” skeleton shows a strong conformational disorder; the Ge-N distance of 2.208(3) Å suggests the presence of a coordinative Ge-N bond. Treatment of 1-allylgermatrane (3) with CH2N2 in the presence of catalytic amounts of Pd(OAc)2 affords 1-cyclopropylmethylgermatrane (5) in high yield
Darstellung und spektroskopische Charakterisierung von (η3-Hexahydro-closo-hexaborato)phenylquecksilber(1-) [Hg(η3-B6H6)Ph] sowie Kristallstruktur von [PPh4][Hg(η3-B6H6)Ph] / Preparation and Spectroscopic Characterization of (η3-Hexahydro-closo-hexaborato)phenylmercury(1 -) [Hg(η3-B6H6)Ph]- and Crystal Structure of [PPh4][Hg(η3-B6H6)Ph]
Authors: Schaper T. , Preetz W.
Published: February 2015

By reaction of [B6H7]- with PhHg(CH3COO) in dichloromethane [Hg(η3-B6H6)Ph]- is formed. The crystal structure of [PPh4][Hg(η3-B6H6)Ph] has been determined by single crystal X-ray diffraction analysis; monoclinic space group P 21/c with a = 9.567(5) Å, b = 22.213(5) Å, c = 14.296(5) Å, β = 94.484(5)°. The 11B NMR spectrum exhibits a doublet at -9.9 ppm shifted to lower field as compared with [B6H7]- and the 199Hg NMR spectrum a singlet at -74.5 ppm. In the IR and Raman spectra characteristic B-H vibrations are observed
Ligandenaustauschreaktionen von ReCl4(PPh3)2 mit Salicylaldehyd-2-hydroxy(mercapto)anil. Struktur von Bis[salicylaldehyd-2-hydroxyanilato(2-)]rhenium(IV) / Ligand Exchange Reactions of ReCl4 (PPh3)2 with Salicylaldehyde-2-hydroxy(mercapto)anil. Molecular Structure of Bis[salicylaldehyde-2-hydroxyanilato(2-)]rhenium(IV)
Authors: Sawusch Stefan , Schilde Uwe , Uhlemann Erhard
Published: February 2015

Ligand exchange reactions of tetrachloro-bis(triphenylphosphane)rhenium(IV) with sali-cylaldehyde-2-hydroxy(mercapto)anil were studied. The reaction products were characterized by mass spectroscopy. The crystal structure was determined by X-ray analysis for bis[sali-cylaldehyd-2-hydroxyanilato(2-)]rhenium(IV). Crystal data: a = 1987.1(18); b = 829.0(6), c = 1296.9(7) pm, β = 100.02(7)° ; space group C 2/c; Z = 4
Bis(trifluormethyl)disulfan und -trisulfan: Molekülgeometrie im festen Zustand [1] / Bis(trifluoromethyl)disulfane and Trisulfane: Molecular Geometry in the Solid State [1]
Authors: Meyer Christian , Mootz Dietrich , Bäck Birgit , Minkwitz Rolf
Published: February 2015

The solid-state structures of the low-melting compounds bis(trifluoromethyl)disulfane (CF3SSCF3, triclinic, space group P 1̄, Z = 2) and bis(trifluoromethyl)trisulfane (CF3SSSCF3, monoclinic, space group C2/c, Z = 4) have been determined on single crystals with MoK α radiation at -160°C. The trisulfane has trans conformation. The geometry of both molecules agrees well with results of electron diffraction on the gaseous state. A comparison is made also with the crystal structures of the related molecules CF3TeTeCF3 and CF3OOOCF3
1,3-Dioxolane von N-substituierten 4-Piperidonen als Dehydrierungssubstrat / 1,3-Dioxolanes of N-Substituted 4-Piperidones as Substrates for Dehydrogenations
Authors: Möhrle H. , Jeandrée M.
Published: February 2015

The applicability of ketals was examined for masking the carbonyl group in N-tertiary 4-piperidones during the dehydrogenation using mercury-edta. Various 1,3-dioxolanes showed a different behaviour in dependence on the N-substituent. With simple aliphatic moieties mainly dehydrogenated but hydrolyzed products were received. These enaminones were also available from the dehydrogenations of the corresponding 4-piperidones. Similar applied to para-acyl-aromatic substituted derivatives but with less yields. Aromatic substituents bearing a neighbour group on ortho-position with participation gave rise to different oxidation products partially with preservation of the ketal structure
Kristallstruktur von 1,1,1-Trichloro-cyclo-1λ6-wolframa-3,5-dithia-2,4,6- triazin, [WCl3(N3S2 )]2 / Crystal Structure of 1,1,1-Trichloro-cyclo- 1λ6-tungsta-3,5-dithia-2,4,6-triazine, [WCl3(N3S2)]2
Authors: Kunkel Frank , Harms Klaus , Dehnicke Kurt
Published: February 2015

Single crystals of [WCl3(N3S2)]2 were obtained by the reaction of triphenyl-cycIo-1λ5antimonia-2,4-dithia-3,5-diazine, SbPh3(N2S2), with tungsten hexachloride in dichloromethane. Space group P21/n, Z = 2, lattice dimensions at -80°C: a = 744.8(1), b = 923.5(1), c = 1078.7(1) pm, β = 94.43(1)°, R = 0.036. [WCI3(N3S2)]2 forms centrosymmetric molecules with W2N2-fourmembered rings and planar cyclo-WN3S2 units
Die Kristallstruktur von Tris(trimethylstannyl) acetonitril / Crystal Structure of Tris(trimethylstannyl)- acetonitrile
Authors: Hillwig Ralf , Harms Klaus , Dehnicke Kurt
Published: February 2015

Single crystals of (Me3Sn)3CCN were obtained by the reaction of tris(trimethylstannyl)amine with boiling acetonitrile in the presence of potassium fluoride and trimethylarsane. The compound has been characterized by IR spectroscopy and by a crystal structure determination. Space group P21/n, Z = 4; lattice dimensions at -50 °C: a = 975.4(1), b = 1316.3(2), c = 1485.3(1), β = 98.55(1)°, R = 0.029. (Me3Sn)3CCN forms monomeric molecules with a linear CCN axis (bond angle 178.7(6)°) and bond lengths of CC = 142.1(8) pm and CN = 114.5(8) pm
Methanolothermale Synthese von Rb3AsSe4 · 2Se6 und Cs3AsSe4 · 2Cs2As2Se4 · 6Te4Se2, zwei Selenidoarsenate mit sechsgliedrigen Chalkogenringen/ Methanolothermal Synthesis of Rb3AsSe4 · 2Se6 and Cs3AsSe4 · 2Cs2As2Se4 · 6Te4Se2. Two Selenidoarsenates with Six-Membered Chalcogen Rings
Authors: Wachhold M. , Sheldrick W. S.
Published: February 2015

The methanolothermal reaction of Rb2CO3 with As2Se3 and black selenium leads to the formation of Rb3AsSe4 and the new selenidoarsenate(V) Rb3AsSe4 · 2Se6 (1), which crystallizes in the cubic space group Fd3̄ (No. 203) with a = 16.660(2) Å, V = 4624.1(1) Å , Z = 8. The structural features are isolated tetrahedral AsSe4
3- anions and Se6 rings in a chair conformation. Whereas the similar reaction with Cs2CO3 only affords the known selenides Cs3AsSe4 and Cs4Se16, replacement of As2Se3 by As2Te3 leads to a compound with similar lattice constants to 1 (Fd3̄, a = 17.275(2) A), containing disordered AsSe4
3- and As2Se4
2- anions, the latter of which exhibit a four-membered As2Se2 ring with m-positioned terminal selenium atoms. The six-membered chalcogen ring is likewise disordered with Se and Te site occupation factors of respectively 0.333 and 0.667 with the result that 2 can be formulated as Cs3AsSe4 · 2Cs2As2Se4 · 6Te4Se2. 2 provides the first example of a TexSe6-x ring to be characterized in the solid state.
The Perovskite Carbides A3MC (A = Sc, Y, La - Nd, Sm, Gd - Lu; M = AI, Ga, In, Tl, Sn, Pb)
Authors: Gesing Thorsten M. , Wachtmann Klaus H. , Jeitschko Wolfgang
Published: February 2015

Twentyfive new perovskite carbides have been obtained either by arc-melting cold-pressed pellets of the elemental components with subsequent annealing at 900 °C or by heating stoichiometric quantities of the elements in a high-frequency furnace. Also, thirtyseven compounds of this structure type are confirmed and their lattice constants are reported. The crystal structures of SC3MC (M = Al, Ga, In, Tl) were refined from X-ray powder data, and in all cases only the octahedral voids formed by scandium atoms were found to be fully occupied. The hydrolysis of the carbides Sc3GaC, Y3SnC, Y3PbC and Ho3PbC with diluted hydrochloric acid resulted in about 84 - 97 (wt-)% methane and 3 - 16 % saturated and unsaturated higher hydrocarbons. The cell volumes of the ternary carbides A3MC and the corresponding binary Cu3Au type compounds A3M are compared and several inconsistencies are pointed out.
(CuI)2P14: ein neues Phosphorpolymer in einer Kupferhalogenid-Matrix /(CuI)2P14: a Novel Phosphorus Polymer in a Copper Halide Matrix
Authors: Pfitzner Amo , Freudenthaler Eva
Published: February 2015

(CuI)2P14 is a new adduct of copper iodide to a neutral phosphorus polymer. It is obtained by reaction of Cul and Pred at 400 °C. The compound crystallizes monoclinically, space group P21/c (No. 14), a = 9.919(2), b = 9.718(2), c = 16.478(3) Å, β = 105.71(1)°, V = 1529.0(7) Å3, with Z = 4. The crystal structure was refined to R1 = 0.029 for 2680 reflections and 173 parameters. It contains a new polymeric phosphorus allotrope with the translational unit P14
±0 consisting of experimentally unknown [P12] groups which are linked by [P2] fragments. The phosphorus rods consist of five-and six-membered rings, and are coordinated only by copper atoms.
Gold Coordination by a Tertiary Phosphine with Three Thioether Functions
Authors: Fuchs Stefan , López-de-Luzuriaga José M. , Olmos M. Elena , Sladek Alexander , Schmidbaur Hubert
Published: February 2015

The reaction of tris(phenylthiomethyl)phosphine with equimolecular amounts of [AuPPh3]+[BF4]- affords the complex (tris(phenylthiomethyl)phosphine)(triphenylphosphine)- gold(I) tetrafluoroborate 1 in good yield. The X-ray diffraction analysis of this product shows an unusual conformation with the three ChLSPh arms of the phosphine folded back towards the metal atom shielding the P-Au-P′ unit. The reaction of the same substrate with Bis(tetrahydrothiophene)gold(I) perchlorate in a 1:1 molar ratio leads to the displacement of both weakly coordinated tht ligands, and a dimeric product [AuP(CH2SPh)3]2(ClO4)2 2 is obtained.
Zwölfgliedrige Heteroborancluster durch Copyrolyse von Tetrachlordiboran(4) mit Elementhalogeniden/ Twelve-Vertex Heteroborane Clusters by Copyrolysis of Tetrachlorodiborane(4) and Element Halides
Authors: Einholz Wolfgang , Schäfer Ronald , Keller Willi , Vogler Bernhard
Published: February 2015

The perchlorinated arsaboranes closo-1,2-As2B10Cl10 and As4B8C16 are formed in the co­ pyrolysis of B2C14 and AsCl3 at temperatures of 330-450°C. The icosahedral structure of closo-1,2-As2B10Cl10 is confirmed by 11B-11B-COSY-NMR spectroscopy. As4B8Cl6 is suppo­ sed to be a conjuncto-borane (As2B4Cl3)2 with two boron-boron linked As2B4Cl3 octahedra. The copyrolysis of B2Cl4 andSbCl3 or SbCl5 yields Sb2B10Cl10, and the corresponding reaction of B2Cl4 with S2Cl2 gives the icosahedral thiaborane cluster SB11Cl11 .
Er5Re2C7, Tm5Re2C7, and Lu5Re2C7 with Sc5Re2C7 Type, and Yb2ReC2 with Pr2ReC2 Type Structures
Authors: Pöttgen R. , Wachtmann K. H. , Jeitschko W. , Lang A. , Ebel T.
Published: February 2015

Er5Re2C7, Tm5Re2C7, and Lu5Re2C7 were prepared by arc-melting of the elemental components and subsequent annealing at 800 °C. Er5Re2C7 forms only after the annealing process, whereas the other two carbides were already present in the as cast samples. They crystallize with a Sc5Re2C7 type structure, which was refined from single-crystal X-ray data of Lu5Re2C7: Cmmm, a = 791.44(5), b = 1418.08(8), c = 332.79(2) pm, Z = 2, R = 0.037 for 544 structure factors and 21 variable parameters. The structure contains linear centrosymmetric C3 units with a C-C bond length of 133(2) pm and isolated carbon atoms in octahedral coordination of four lutetium and two rhenium atoms. The rhenium atoms within the two-dimensionally infinite polymeric sheets [Re2C4]n are electronically saturated as is indicated by the diamagnetism and the semiconductivity of this carbide. Yb2ReC2 was prepared by reacting the elements in a sealed tantalum tube with a high-frequency furnace. It crystallizes with a Pr2ReC2 type structure: Pnma, a = 645.91(6), b = 498.64(6), and c = 966.05(6) pm. Magnetic susceptibility measurements indicate the ytterbium atoms to be trivalent in this compound.
Phosphanimin- und Phosphaniminato-Komplexe des Zinks. Kristallstrukturen von [ZnCl2(Me3SiNP(CH2)4CMe3)]2, [ZnI2(Me3SiNPEt3)]2, [ZnI2{Me2Si(NPEt3)2}] und [ZnBr(NPMe3)]4· CH2Cl2/ Phosphaneimine and Phosphoraneiminato Complexes of Zinc. Crystal Structures of [ZnCl2(Me3SiNP(CH2)4CMe3)]2, [ZnI2(Me3SiNPEt3)]2, [Znl2{Me2Si(NPEt3)2}], and [ZnBr(NPMe3)]4· CH2Cl2
Authors: Krieger Matthias , Harms Klaus , Magull Jörg , Dehnicke Kurt
Published: February 2015

The donor-acceptor complexes [ZnCl2(Me3SiNP(CH2)4CMe3)]2 (1)and [ZnI2(Me3SiNPEt3)]2 (2) have been prepared from the zinc dihalides and the corresponding silylated phosphaneimines in CH2Cl2. Thermolysis of 2 leads to the formation of [ZnI2(Me2Si(NPEt3)2)] (3). Znl2 and ZnBr2 react with the silylated phosphaneimines Me3SiNPR3(R = Me, Et) in the presence of NaF at elavated temperatures to give the phosphoraneiminato complexes [ZnI(NPEt3)]4 (4), [ZnBr(NPMe3)]4 (5) and [ZnBr(NPEt3)]4 (6), respectively, which according to the IR spectra and to a crystal structure determination of 5 form heterocubane structures. The corresponding reactions with the more bulky phosphaneimine Me3SiNP(CH2)4CMe3 do not lead to a phosphoraneiminato complex of zinc.

1: Space group P21/n, Z = 2; lattice dimensions at -60 °C: a = 903.3(2), b = 1217.9(3), c = 1591.6(2) pm, β = 93.94(1)°, R = 0.031.

2: Space group P21/n, Z = 2; lattice dimensions at -70°C: a = 947.9(2), b = 1219.2(2), c - 1527.1(2) pm, 0 = 91.17(1)°, β = 0.045.

1 and 2 form centrosymmetric dimeric molecules via Zn2X2 bridges (X = Cl, I); bond lengths Zn-N = 198.7(2) pm (1) and 199.0(6) pm (2).

3: Space group P412121 Z = 8; lattice dimensions at -90°C: a = b = 965.4(1), c = 2796.9(2) pm, R = 0.019.3 forms monomeric molecules with the Me2Si(NPEt3)2 ligand as chelating agent to give a planar ZnN2Si four-membered ring with Zn-N distances of 207.0(2) pm.

5: Space group P42/nmc, Z = 2; lattice dimensions at -70°C: a = b = 1146.9(6), c = 1437.9(7) pm, R = 0.060.
Notizen: Bridging of Trigoldsulfonium Clusters by a Silver(I) Ion
Authors: Sladek Alexander , Schmidbaur Hubert
Published: February 2015

Treatment of tris[(triphenylphosphine)gold(I)]-sulfonium tetrafluoroborate with AgBF4 (molar ratio 2:1) in tetrahydrofuran affords a hepta-nuclear mixed-metal cluster trication {[(Ph3P)6Au6AgS2](thf)}3+ as the tetrafluorobor­ate salt. The crystal structure of the compound has been determined by X-ray diffraction. The sil­ver atom is found in a bridging position between the two Au3S units with short contacts to both sulfur atoms and to three out of six gold atoms. The coordination sphere of the silver atom is complemented by a tetrahydrofuran molecule. In di(tri)chlorom ethane solutions there is rapid site exchange of the silver coordination as shown by virtual equivalence of the phosphine ligands on the NMR time scale at ambient temperature.
Reaktion von Cacodylsäure (CH3)2AsOOH im System HF / MF5 (M = As, Sb) und Kristallstruktur von Difluordimethylarsonium- hexafluoroantimonat (CH3)2AsF2SbF6 / Reaction of Cacodylic Acid (CH3)2AsOOH in the System HF / MF5 (M = As, Sb), and Crystal Structure of Difluorodimethylarsonium Hexafluoroantimonate
Authors: Minkwitz Rolf , Hertel Thomas , Zachwieja Uwe
Published: February 2015

In the reaction of cacodylic acid (CH3)2AsOOH in the superacid system HF / MF5 (M = As, Sb) the difluorodimethylarsonium hexafluorometallates [(CH3)2AsF2]MF6 are formed and have been characterized by i.r. and Raman spectroscopy. The crystal structure of the hexafluoroantimonate has been determined at -100°C (orthorhombic space group Ibca with Z = 4, a = 10.973, b = 11.164, c = 14.200 pm).
Kohlenwasserstoffverbrückte Metallkomplexe, XLIII [1] Addition von η6-Anilin-tricarbonylchrom-Komplexen an den Ethenliganden von [(OC)5Re(η2-C2H4)]+ and [(η5-C5H5)Fe(CO)2(η2-C2H4)]+ / Hydrocarbon Bridged Metal Complexes, XLIII [1] Addition of η6- Aniline Tricarbonyl Chromium Complexes to the Ethene Ligand of [(OC)5Re(η2-C2H4)]+ and [(η5-C5H5)Fe(CO)2(η2-C2H4)]+
Authors: Bentele Hanns-Jörg , Schwenk-Kircher Holger , Nöth Heinrich , Beck Wolfgang
Published: February 2015

Aniline tricarbonyl chromium complexes η6-C6H4(R)NHR1)Cr(CO)3 (R = H, CH3; R1 = H, CH3) are added to [(OC)5Re(η2-C2H4)]+ and [(η5-C5H5)Fe(CO)2(η2-C2H4)]+ to give the heterobimetallic ligand bridged complexes (OC)3Cr(η6-C6H4(R)N(R1)C2H4-η1)Re(CO)5 and (OC)3Cr(η6-C6H4(R)N(R1)C2H4-η1)Fe(CO)2(η5-C5H5). The structure of (OC)3Cr(η6- C6H4(CH3)N(H)C2H4-η1)Re(CO)5 was determined by X-ray diffraction analysis.
Zur Kenntnis eines synthetischen Kentrolits/Melanotekits des Indiums: Pb2In2Si2O9 / On an Synthetic Kentrolite/Melanotekite of Indium: Pb2In2Si2O9
Authors: Werner J.-P. , Müller-Buschbaum Hk.
Published: February 2015

Single crystals of Pb2In2Si2O9 have been prepared by crystallisation from melts of Pb(NO3)2, ln2O3 and SiO2. The compound crystallizes with orthorhombic symmetry, space group C2v
9
- Pna21 with the lattice constants a = 10.529(1), b = 11.372(1) and c = 7.019(3) Å, Z = 4. Despite the fact that the Kentrolite/Melanotekite structure is characterized by dissimilar occupied split positions of lead, Pb2In2Si2O9 shows completely filled and ordered point positions. The location of a dot like lone pair of Pb2+ is estimated by Coulomb term calculations of lattice energy. The results are discussed with respect to published Pb-lone pair distances using the electronic polarizability coefficient of the lone pair cation or simple geometrical considerations.
Polysulfonylamine, XCVI [1]. Homokonjugate aus Di(organosulfonyl)aminen und ihren konjugierten Anionen: Vier Kristallstrukturen mit asymmetrischen [N -H ··· N ]--Wasserstoffbrücken / Polysulfonylamines, XCVI [1]. Homoconjugates Formed from Di(organosulfonyl)amines and their Conjugate Anions: Four Crystal Structures Featuring A symmetric [ N - H ··· N ]- Hydrogen Bonds
Authors: Wijaya Karna , Henschel Dagmar , Moers Oliver , Blaschette Armand , Jones Peter G.
Published: February 2015

The following compounds were prepared by cocrystallization of their components from MeOH or MeCN and structurally characterized by low-temperature X-ray diffraction: Na[N(SO2Me)2]·HN(SO2Me)2·2 (12-crown-4) (2, orthorhombic, space group Pna21). Na[N(SO2Me)·HN(SO2Me)·(15-crown-5) (3, monoclinic. P21/n), Na[N(SO2Ph)2] · HN(SO2Ph)2 · 2 (12-crown-4) (4. monoclinic. P21). (MeNH)2COHN(SO2Ph)2·0.5 MeCN (5, monoclinic. P21/n). The four structures exhibit [(RSO2)2N-H ··· N(SO2R)2]- anions as rare examples of intermolecular [N-H ···N]- homo- conjugates. The N ··· N distances of the asymmetric hydrogen bonds are. in order. 266.9(6). 276.0(3). 291.3(4) and 279.4(2) pm. the corresponding N-H···N angles amounting to 137(10), 176(3), 177(4) and 177(2)°. The asymmetry of the hydrogen bonds is clearly reflected in the geometry of the NS2 groups (amine moieties: N-S 162.3-165.2 pm. S-N-S 124.5-127.1°; amide moieties: N-S 159.7-161.8 pm. S-N-S 119.1-122.6°). The dihedral angles formed by the NS2 planes vary from 51.8° in 4 to 87.6° in 5. The crystal lattices of 2 and 4 consist of discrete ions, sandwich-type [Na(12-crown-4)2]+ complexes acting as the counter-ions. In 3. Na+ is coordinated in an out-of-cavity pattern by the five polyether oxygen atoms and further accepts two Na-O bonds from the amide moiety of the complex anion [Na-O(crown) 241.5(2)-249.9(2), Na-O(anion) 235.0(2) and 263.9(2) pm]. Thе surprising structure of 5 contains homoconjugated 1.3-dimethylurea cations [(MeNH)2C-O-H ··· O=C(NHMe)2]+, which are formed via a very strong asymmetric [O-H ···O]+ hydrogen bond [О···О 247.7(2) pm. O-H ··· O 172(3)°] and are associated with the amide moieties of the anions through a set of N-H···О bonds to form infinite chains: the MeCN molecules occupy lattice cavities.
Experimental and Computational Studies on Aminoguanidine Free Base, Monocation and Dication, Part II: Acid-Base Properties, Gas Phase Protonation Energies and Total Energies of Two Tautomers of the Free Base
Authors: Koskinen Jere T. , Koskinen Mikko , Mutikainen Ilpo , Tilus Pirkko , Mannfors Berit , Elo Hannu
Published: February 2015

The structures and protonation energies of aminoguanidine and aminoguanidinium ion were obtained from quantum chemical calculations by using the density functional method B3-LYP and the standard basis set 6 -31 G(d ). The energy differences between the various forms of the two possible tautomers, the endiamine and the imidamide form, were investigated. The endiamine was found to be more stable than the most stable form of the imidamide by 5 kcal/mol in the gas phase. The proton affinity of am inoguanidine was found to be 241.4 kcal/mol (B3 -LYP/6 -31 G(d )) in the gas phase. The liquidation pKa2 for amininoguanidine and the guanidinium ion was determined to be 11.5 ± 0.1. The reference values for guanidine free base and the guanidinium ion are 235.7 kcal/mol and 13.6, respectively. The difference in the order of basicity in the gas phase and in aqueous solution between aminoguanidine and guanidine is discussed in terms of symmetry, resonance, delocalisation, rehybridisation of nitrogen atoms, and electrostatic repulsion.
Notizen: Synthese und Kristallstruktur von [(Ph2PC2H4PPh2)N]Br / Synthesis and Crystal Structure of [(Ph2PC2H4PPh2)N]Br
Authors: Kunkel Frank , Goesmann Helmut , Dehnicke Kurt
Published: February 2015

The cyclo-phosphazenium bromide [(Ph2PC2H4PPh2)N ]Br has been prepared by the reaction of bromine with Ph2PC2H4PPh2NSiMe3 and subsequent elimination of BrSiMe3 in boiling acetonitrile. According to a crystal structure d e termination the com pound contains bromide ions and cations with a P2C2N heterocycle in a twist conformation with PN bond lengths of 160.6(3) and 161.5(3) pm. Space group Pna21, Z = 4, lattice dimensions at - 70 °C: a = 1702.5(3), b = 1280.8(3), c = 1056.9(2) pm, R = 0.030.
Reaktionen von Cadmium-und Quecksilber(II)halogeniden und -pseudohalogeniden mit Kronenethern: Kristallstrukturen der Komplexe von Benzo-18-krone-6 mit CdX2 und HgX2 (X = CI, Br) und von Dibenzo-18-krone-6 mit Hg(CN)2 / Reactions of Cadmium and Mercury(II) Halides and Pseudohalides with Crown Ethers: Crystal Structures of the Complexes of Benzo-18-crown-6 with CdX2 and HgX2 (X = Cl, Br) and of Dibenzo-18-crown-6 with Hg(CN)2
Authors: Pickardt Joachim , Wiese Sven , Wischlinski Pirka
Published: February 2015

The reactions of benzo-18-crown-6 with MeX2 (Me = Cd, Hg; X = Cl. Br), and of dibenzo-18-crown-6 with Hg(CN)2 afford the compounds [Me(benzo-18-crown-6)X2] (1-4) and [Hg(dibenzo-18-crown-6)(CN)2 (5), resp., the crystal structures of which were determined. They consist of isolated neutral molecules, the crystalline Cd complexes and 5 contain one molecule of water of crystallization per formula unit, which however is not coordinated to the metal atom. The metal atoms are coordinated by the six O atoms of the ligands and the two halide atoms, or the two CN groups for 5, resp., the coordination being more unsymmetrical for the benzo than for the dibenzo ligand.
Crystal Structure of an Ammonium Dithiocyanatocuprate(I) Complex with 18-Crown-6, [NH4(18-Crown-6){Cu(NCS)2}] Obtained from Zero Valent Metal
Authors: Manskaya Julia A. , Kokozay Volodimir N. , Domasevitch Konstantin V.
Published: February 2015

The new macrocyclic dithiocyanatocuprate(I) complex [NH4(18-crown-6){Cu(NCS)2}] has been prepared using a direct method of interaction and characterized by X-ray crystallography (orthorhombic, space group Cmc21, with a = 12.453(2), b = 21.650(4), c = 8.151(2) Å, V = 2197.6(8) Å3, Z = 4 , R1 (F) = 0.054; wR2(F2) = 0.141 for 972 unique reflections with I > 2σ(I) and R1(F) = 0.082; w/?2(F2) = 0.210 for all 1098 unique reflections). The lattice comprises complex cations [NH4(18-crown-6)]+ and infinite polymeric anions [Cu(NCS)2]- of a one-dimensional zig-zag structure. The copper atoms adopt three-fold coordination [CuN2S] (Cu-N 1,89( 1), 1,90( 1) Å; Cu-S 2.278(4) Å).