Побожій С.І. Мистецтвознавчі нариси: монографія. - Суми, 2013. - 416 с.: 112 арк. іл.

Рецензія Сергія Дегтярьова на книжку "Побожій С.І. Мистецтвознавчі нариси: монографія. - Суми, 2013. - 416 с.: 112 арк. іл.".Рецензия Сергея Дегтярёва на книгу "Побожій С.І. Мистецтвознавчі нариси: монографія. - Суми, 2013. - 416 с.: 112 арк. іл.".Review of the book "Побожій С.І. Мистецтвознавчі нариси: монографія. - Суми, 2013. - 416 с.: 112 арк. іл." by Sergiy Degtyaryov

Analytical study of waterlogged ivory from the Bajo de la campana site (Murcia, Spain)

[EN] This work reports an analytical study conducted prior to the conservation intervention of a collection of elephant tusks excavated from a wreck site of a 600-500 BC Phoenician trading vessel in Bajo de la campana (Murcia, Spain). The conservation state of ivory, determined by prolongated immersion in a marine environment, was established by a multi-technique methodology: light microscopy, field emission scanning electron microscopy X-ray microanalysis (FESEM-EDX), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), spectrophotometry and gas chromatography-mass spectrometry (GC-MS). The analyses demonstrated that the structure and composition of both tusk parts, namely the inner ivory and outer cementum, were altered due to characteristic diagenetic processes of a marine environment. Ca enrichment was observed in both tusk parts, which gave higher Ca/P molar ratio values than for ideal hydroxyapatite. Mg leaching was observed, together with uptake of exogenous elements (F, Cl, Si, Al, S, Na, Fe, Cu, Sr, Pb, Sn, Ag, V, Ni, Cd and Zn), which were prevalently identified in the external tusk part. Uptake of S and Fe was associated with the neoformation of pyrite framboids. The high carbonate content measured by FTIR, which agreed with the higher Ca/P ratios found in the archaeological tusk, was ascribed to the carbonate substitution of phosphate groups (type-B) in the bioapatite accompanied by some authigenic calcium carbonate that infilled ivory. An increased degree of crystallinity was observed when comparing the values of several crystallinity indices found in the archaeological bioapatite with those of a modern tusk, used as the reference material. Increased crystallinity prevalently took place in the cementurn. In accordance with increased crystallinity, the HPO42- content index indicated that the hydrated layer of bioapatite nanocrystals diminished in the archaeological tusk, and prevalently in the cementum. All these changes correlated with the significant organic matter loss reported for the archaeological tusk. Interestingly, remaining collagenous matter noticeably altered with enrichment in glycine and depletion in acid amino acids. Changes in the secondary structure of proteins were also recognised and associated with collagen gelatinisation. In addition to proteinaceous materials, small amounts of long-chain fatty acids, monoglycerides and cholesteryl oleate were identified by GC-MS. Cholesteryl oleate was associated with blood, which could have precipitated at the time of specimen death. The identification of large amounts of pyrite framboids and the high oleic acid/palmitic acid ratio in the archaeological tusk suggested minimal oxidative degradation processes, probably due to the slightly anoxic conditions of the underwater Bajo de la campana site environment. (C) 2016 Elsevier B.V. All rights reserved.The authors wish to thank CITES Espana and Direccion General de Bienes Culturales y Ensenanzas Artisticas, de la Consejeria de Educacion, Cultura y Universidades de la Comunidad Autonoma de la Region de Murcia, Museo Nacional de Arqueologia Subacuatica. Financial support is gratefully acknowledged from Spanish "I + D + I MINECO" projects CTQ2011-28079-CO3-01 and 02 and CTQ2014-53736-C3-1-P supported by ERDEF funds. The authors also wish to thank Mr. Manuel Planes and Dr. Jose Luis Moya, technical supervisors of the Electron Microscopy Service of the Universitat Politecnica de Valencia.Domenech Carbo, MT.; Buendía Ortuño, MDM.; Pasies Oviedo, T.; Osete Cortina, L. (2016). Analytical study of waterlogged ivory from the Bajo de la campana site (Murcia, Spain). Microchemical Journal. 126:381-405. https://doi.org/10.1016/j.microc.2015.12.022S38140512

Synthetic investigations on the structural diversity of borates and borate-nitrates

Natur der Dinge auf struktureller Ebene zu verstehen ist das Fundament, auf dem Wissen um Eigenschaften und Anwendungsmöglichkeiten von Materialien steht. Je detaillierter dieses Verständnis von Bildungsbedingungen, von physikochemischen Eigenschaften, die sich aus der Harmonie der einzelnen Bausteine ableiten, und von Reaktivitäten einzelner Komponenten und des resultierenden Ensembles, ist, desto stabiler und tragfähiger wird dieses Fundament. Das Forschungsinteresse meiner Arbeit richtete sich darauf, gerade dieses Grundlagenwissen im Bereich der Festkörperchemie zu erweitern. Durch Synthesen unbekannter Verbindungen wurde Wissen über deren Bildung und Reaktivitäten der Umwandlungsprozesse gewonnen. Durch Betrachten der Reaktionsprodukte auf atomarer Ebene wurde ihre Strukturchemie beschrieben. Aufbauend auf den gewonnenen Erkenntnissen, wurden Ausgangspunkte für mögliche Anwendungen aufgezeigt. Gegenstand dieser Forschungsarbeit war eine ganz alltägliche, altbekannte Substanzklasse: die Borate. Besonders an diesen Verbindungen ist ihre einzigartig umfangreiche strukturelle Vielfalt, die es den Boraten erlaubt, feste Materialen facettenreichster Eigenschaften auszubilden. Eine weitere, ebenso bedeutende Rolle in der Natur, kommt der Chemie der Nitrate zu. Im Zusammenspiel schaffen diese beiden Baueinheiten eine besondere Substanzklasse: die Borat-Nitrate. Diese noch ausgedehntere und komplexere Strukturlandschaft zu beschreiben war Bestreben dieser Arbeit. Um zu diesen Borat-Nitraten, neben neuen Boratstrukturen, zu gelangen, wurden Edukte in geschlossenen Gefäßen in Gegenwart von Wasser erhitzt. Durch solche Hydrothermalsynthesen wurden neue Phasen aus beiden Substanzklassen, den Boraten und den Borat-Nitraten, entdeckt. Im Zuge der Optimierung der Bildungsbedingungen und der anschließenden detaillierten Charakterisierung der erhaltenen Kristalle, konnte Einsicht über Zusammenhänge zwischen Struktur und Eigenschaften gewonnen werden. Ein Europiumborat, das eine in Seltenerd-Verbindungen bisher beispiellose Baueinheit, eine freie Borsäure Gruppe, aufweist, konnte synthetisiert werden. Die Kristallstruktur und Lumineszenz-Eigenschaften dieses Eu[B6O8(OH)5] · H3BO3 wurden aufgeklärt und beschrieben. Eine weitere Verbindung, die im Rahmen dieser Arbeit erhalten wurde, ist das Lutetiumborat-Nitrat Lu2B2O5(NO3)2 · 2 H2O, dessen Strukturuntersuchungen ein neuartiges Gerüst mit dem höchsten bisher berichteten Nitratgruppen-Anteil in einer Borat-Struktur zeigten.Understanding nature on a structural level constitutes the fundament on which knowledge of properties and applications of materials stand. The richer this comprehension is in details, concerning formation conditions, reactivity of the single components and the resulting assembly, concerning the physicochemical properties deduced from the harmony of the individual building blocks, the deeper this fundament roots. My research effort in the course of this work was put into adding to such a basic knowledge in the area of solid state chemistry. Through synthetic investigation of unknown compounds, their formation was elaborated, reactivities within these processes were studied, and, looking at the structures at an atomic level, their structural chemistry was described. Building on this understanding, some key points for possible applications were found. Subject to this research interest was a common compound class, used in everyday life since ancient times: borates. Special about this substance is its uniquely vast structural diversity allowing it to form solid materials of multi-faceted properties. Another, equally important entity is found in the chemistry of nitrates. In combination, these fundamental building units form a special substance class, the borate-nitrates, which allows for an even wider, more flexible and complex structural landscape. To access these borate-nitrates, alongside novel borate structures, educts were heated in closed vessels in the presence of water. Through these hydrothermal syntheses, phases pertaining to both substance classes were discovered. Upon optimization of formation conditions and the subsequent detailed characterization of the obtained crystals, insight in structure property relations were elaborated. A europium borate showing a hitherto in rare earth compounds unprecedented building unit, a free boric acid group, was synthesized. The single-crystal structure and also the luminescence properties of this Eu[B6O8(OH)5] · H3BO3 were explored. Another compound found during this thesis work was the first lutetium borate-nitrate Lu2B2O5(NO3)2 · 2 H2O, of which structural investigations showed a novel framework with the highest ever reported nitrate content in a borate structure.by Teresa Sophie OrtnerZusammenfassung in deutscher SpracheKumulative Dissertation aus sieben ArtikelnUniversität Innsbruck, Dissertation, 2016OeBB(VLID)137996

Regioselective Hydromethoxycarbonylation of Terminal Alkynes Catalyzed by Palladium(II)–Tetraphos Complexes

An in situ generated dinuclear palladium hydride complex bearing <i>cis</i>,<i>trans</i>,<i>cis</i>-1,2,3,4-tetrakis­(diphenylphosphanyl)­cyclobutane catalyzed the hydromethoxycarbonylation of terminal alkynes, giving the corresponding branched α,β-unsaturated ester (A) with high regioselectivity

Regioselective Hydromethoxycarbonylation of Terminal Alkynes Catalyzed by Palladium(II)–Tetraphos Complexes

An in situ generated dinuclear palladium hydride complex bearing <i>cis</i>,<i>trans</i>,<i>cis</i>-1,2,3,4-tetrakis­(diphenylphosphanyl)­cyclobutane catalyzed the hydromethoxycarbonylation of terminal alkynes, giving the corresponding branched α,β-unsaturated ester (A) with high regioselectivity

Regioselective Hydromethoxycarbonylation of Terminal Alkynes Catalyzed by Palladium(II)–Tetraphos Complexes

An in situ generated dinuclear palladium hydride complex bearing <i>cis</i>,<i>trans</i>,<i>cis</i>-1,2,3,4-tetrakis­(diphenylphosphanyl)­cyclobutane catalyzed the hydromethoxycarbonylation of terminal alkynes, giving the corresponding branched α,β-unsaturated ester (A) with high regioselectivity

Regioselective Hydromethoxycarbonylation of Terminal Alkynes Catalyzed by Palladium(II)–Tetraphos Complexes

An in situ generated dinuclear palladium hydride complex bearing <i>cis</i>,<i>trans</i>,<i>cis</i>-1,2,3,4-tetrakis­(diphenylphosphanyl)­cyclobutane catalyzed the hydromethoxycarbonylation of terminal alkynes, giving the corresponding branched α,β-unsaturated ester (A) with high regioselectivity

Regioselective Hydromethoxycarbonylation of Terminal Alkynes Catalyzed by Palladium(II)–Tetraphos Complexes

An in situ generated dinuclear palladium hydride complex bearing <i>cis</i>,<i>trans</i>,<i>cis</i>-1,2,3,4-tetrakis­(diphenylphosphanyl)­cyclobutane catalyzed the hydromethoxycarbonylation of terminal alkynes, giving the corresponding branched α,β-unsaturated ester (A) with high regioselectivity