Interdisciplinary studies on ancient stone: proceedings of the IX Association for the Study of Marbles and Other Stones in Antiquity (ASMOSIA) Conference (Tarragona 2009), 2012, ISBN 978-84-939033-8-1, págs. 344-354, 2012
High quality antique sheets of paper have been characterized by H-1 NMR relaxation, C-13 CP MAS s... more High quality antique sheets of paper have been characterized by H-1 NMR relaxation, C-13 CP MAS spectra, and Electron Paramagnetic Resonance spectroscopy. Paper can be regarded as a bi-component material made by cellulose and water plus a small amount of organic and inorganic additives and impurities. Semi-crystalline fibrous cellulose, rich in water, is present as polymorphs I alpha and I beta. Amorphous cellulose, with a lower water content, presents a higher amount of paramagnetic impurities and is characterized by quite short H-1 spin-lattice relaxation times and by C-13 resonances with noticeable chemical shifts. ''Ad hoc'' tailored sequences are able to produce C-13 CP MAS spectra in which the amorphous content of cellulose in paper is quite well observable. The nature of water as fully bound to the cellulose lattice has also been proved. Low-temperature EPR spectra have shown the presence of measurable amounts of different inorganic paramagnetic impurities, su...
Abstract The low-temperature EPR spectrum of bis(nitroacetonato)bis(pyridine)Cu(II), diluted in a... more Abstract The low-temperature EPR spectrum of bis(nitroacetonato)bis(pyridine)Cu(II), diluted in a single crystal of the isomorphous Zn(H) analog, is reported. The g tensor, the metal hyperfine and quadrupole coupling tensors, and the nitrogen hyperfine tensor have been obtained. Additional hyperfine lines have been detected along some orientations and attributed to the coupling of the unpaired electron with the two out-of-plane hydrogen atoms of the chelate rings. The principal values and orientations of the experimental tensors differ considerably from those of the closely related bis(ω-nitroacetophenonato)- bis(4-methylpyridine)Cu(II). The relevance of lattice effects on the symmetry of the two compounds, and hence on the properties of their magnetic parameters, is discussed. The description of the overall electronic structure appears to be complicated by the fact that “different effective symmetries” are reflected by different spin-Hamiltonian parameters.
ABSTRACTTetrathiafulvalene and bis(ethylenedithio)tetrathiaful-valene radical-cation salts of the... more ABSTRACTTetrathiafulvalene and bis(ethylenedithio)tetrathiaful-valene radical-cation salts of the a-Keggin anion [PMo12O40] have been synthesized and characterized. They both are mixed-valence compounds and contain the paramagnetic anion [PMO12O40] 4-. The former contains irregular TTF ϱ+ chains isolated by the inorganic anions. From the IR spectrum a ϱ=+0.5 is suggested. The latter is two-dimensional, where BEDT-TTF molecules are ionised, ϱ=+0.5, and arranged in irregular chains. They show electrical conductivity typical of organic semiconductors.
Die Komplexe (I)‐(III) werden durch Umsetzung der Metall(Il)‐acetate mit Bipyridyl oder Phenanthr... more Die Komplexe (I)‐(III) werden durch Umsetzung der Metall(Il)‐acetate mit Bipyridyl oder Phenanthrolin und Phenyldinitromethan im entsprechenden stöchiometrischen Verhältnis in Äthanol dargestellt.
Die Nitroketonato‐Komplexe (I) und (II) werden durch Reaktion entsprechender Metallacetate mit de... more Die Nitroketonato‐Komplexe (I) und (II) werden durch Reaktion entsprechender Metallacetate mit den Liganden in absolutem Äthanol, wäßrigem Aceton oder Pyridin‐Lösungen synthetisiert (Ausbeute 47‐97%).
Atti Della Accademia Nazionale Dei Lincei Rendiconti Classe Di Scienze Morali Storiche E Filologiche, 2005
The physical and chemical analysis of the marble of two reliefs representing gladiators, one hous... more The physical and chemical analysis of the marble of two reliefs representing gladiators, one housed in the Glyptotek of Munich and the other in the Museum of Budapest, has demonstrated that all the blocks come from the same area of the Carrara quarries (Torano) and therefore form part of the same work. This, consisting of two rows of blocks, each block measuring two Roman feet, must have continued to the left and especially to the right and have continued upwards for another row, as the relief of Pompeii suggests. It represents a gladiatorial munus with two pairs of opponents with armour composed of scales, with tubicines and lanista. As regards its development and structural composition it can be paralleled with similar reliefs from central Italy; probably belonging to a private funerary monument, it is of excellent quality and most likely the work of urban craftsmen. It can be dated to around 40-20 BC, (end of the Republican period-beginning of the Augustan period), as the quality of the marble, the workmanship, the type of armour and the stylistic analysis demonstrate.
The provenance of the marbles used for the five ancient sculptures on display in the Tribune of t... more The provenance of the marbles used for the five ancient sculptures on display in the Tribune of the Uffizi—the Venere Medici, the Apollo Medici, the Satiro danzante, the Arrotino and the Lottatori—has been determined using a well‐established multi‐method approach that includes isotopic, petrographic and EPR data. The Arrotino was found to be made of Docimium marble from the Phrygian quarries of Iscehisar, whereas Parian lychnites was used for the other four sculptures. Restorations, including the restoration of the Satiro ascribed to Michelangelo or his school, primarily used Pentelicon marble. The Lottatori, however, underwent multiple restorations that used a lychnites analytically different from the original stock, as well as Docimium, Carrara and Göktepe marbles. The right arm of the winner, which was considered to be a later addition, turned out to be made using the original marble—lychnites marble. The marble data provide support for the chronology of the sculptures and give i...
Journal of the Chemical Society, Faraday Transactions 2, 1989
The ENDOR spectra of the metastable expanded layer solid VOPO4·5H2O and its congener VOPO4·2H2O [... more The ENDOR spectra of the metastable expanded layer solid VOPO4·5H2O and its congener VOPO4·2H2O [both containing very small amounts of vanadium (IV)] have been measured at 4 K. The latter gave no ENDOR, whereas the former provided a spectrum in which three different proton signals ascribable to two interlayer water molecules were detected. From a reconstruction of the interlayer, taking into account the layer expansion of 3.1 A due to the intercalated water molecules, it is suggested that VOPO4·5H2O is an example of a ‘pillared’ material.
The marble of seven under-lifesize sculptures of barbarians, now in the archaeological museums of... more The marble of seven under-lifesize sculptures of barbarians, now in the archaeological museums of Naples, Venice and the Vatican, commonly considered to be Roman copies of the Pergamene Lesser Dedication in Athens, comes from the Göktepe marble quarries near Aphrodisias, as is shown by isotopic, electron paramagnetic resonance, trace analyses, and of petrographic data. Since this marble was used mostly by Aphrodisian artists, this finding confirms, on the basis of scientific data, previous hypotheses on the origin of the sculptors who manufactured the statues. Reliable discrimination from similar fine-grained Asiatic marbles, such asDocimium, is possible primarily on the basis of the composition of the Göktepe marbles, which have unusually low concentrations of manganese and high concentrations of strontium. Present knowledge of the history of the quarries and the distribution of their marbles seems to rule out the possibility that the sculptures date from the late Republican period...
Single crystal and powder E.S.R. studies of low-spin N,N'-ethylene bis(thioacetylacetonei... more Single crystal and powder E.S.R. studies of low-spin N,N'-ethylene bis(thioacetylacetoneiminato)Co(II) N,N'-ethylenebis(selenoacetylacetone-iminato)Co(II), and some related compounds, diluted in the corresponding Ni(II) and Zn(II) complexes are reported. The Co(II) complexes and their Ni(II) analogues are all isomorphous. The crystal and molecular structure of N,N'-ethylenebis(thioacetylacetoneiminato)Ni(II) is given. The crystals are orthorhombic, space group P212121, with unit cell dimensions a = 7·297 (2), b
Interdisciplinary studies on ancient stone: proceedings of the IX Association for the Study of Marbles and Other Stones in Antiquity (ASMOSIA) Conference (Tarragona 2009), 2012, ISBN 978-84-939033-8-1, págs. 344-354, 2012
High quality antique sheets of paper have been characterized by H-1 NMR relaxation, C-13 CP MAS s... more High quality antique sheets of paper have been characterized by H-1 NMR relaxation, C-13 CP MAS spectra, and Electron Paramagnetic Resonance spectroscopy. Paper can be regarded as a bi-component material made by cellulose and water plus a small amount of organic and inorganic additives and impurities. Semi-crystalline fibrous cellulose, rich in water, is present as polymorphs I alpha and I beta. Amorphous cellulose, with a lower water content, presents a higher amount of paramagnetic impurities and is characterized by quite short H-1 spin-lattice relaxation times and by C-13 resonances with noticeable chemical shifts. ''Ad hoc'' tailored sequences are able to produce C-13 CP MAS spectra in which the amorphous content of cellulose in paper is quite well observable. The nature of water as fully bound to the cellulose lattice has also been proved. Low-temperature EPR spectra have shown the presence of measurable amounts of different inorganic paramagnetic impurities, su...
Abstract The low-temperature EPR spectrum of bis(nitroacetonato)bis(pyridine)Cu(II), diluted in a... more Abstract The low-temperature EPR spectrum of bis(nitroacetonato)bis(pyridine)Cu(II), diluted in a single crystal of the isomorphous Zn(H) analog, is reported. The g tensor, the metal hyperfine and quadrupole coupling tensors, and the nitrogen hyperfine tensor have been obtained. Additional hyperfine lines have been detected along some orientations and attributed to the coupling of the unpaired electron with the two out-of-plane hydrogen atoms of the chelate rings. The principal values and orientations of the experimental tensors differ considerably from those of the closely related bis(ω-nitroacetophenonato)- bis(4-methylpyridine)Cu(II). The relevance of lattice effects on the symmetry of the two compounds, and hence on the properties of their magnetic parameters, is discussed. The description of the overall electronic structure appears to be complicated by the fact that “different effective symmetries” are reflected by different spin-Hamiltonian parameters.
ABSTRACTTetrathiafulvalene and bis(ethylenedithio)tetrathiaful-valene radical-cation salts of the... more ABSTRACTTetrathiafulvalene and bis(ethylenedithio)tetrathiaful-valene radical-cation salts of the a-Keggin anion [PMo12O40] have been synthesized and characterized. They both are mixed-valence compounds and contain the paramagnetic anion [PMO12O40] 4-. The former contains irregular TTF ϱ+ chains isolated by the inorganic anions. From the IR spectrum a ϱ=+0.5 is suggested. The latter is two-dimensional, where BEDT-TTF molecules are ionised, ϱ=+0.5, and arranged in irregular chains. They show electrical conductivity typical of organic semiconductors.
Die Komplexe (I)‐(III) werden durch Umsetzung der Metall(Il)‐acetate mit Bipyridyl oder Phenanthr... more Die Komplexe (I)‐(III) werden durch Umsetzung der Metall(Il)‐acetate mit Bipyridyl oder Phenanthrolin und Phenyldinitromethan im entsprechenden stöchiometrischen Verhältnis in Äthanol dargestellt.
Die Nitroketonato‐Komplexe (I) und (II) werden durch Reaktion entsprechender Metallacetate mit de... more Die Nitroketonato‐Komplexe (I) und (II) werden durch Reaktion entsprechender Metallacetate mit den Liganden in absolutem Äthanol, wäßrigem Aceton oder Pyridin‐Lösungen synthetisiert (Ausbeute 47‐97%).
Atti Della Accademia Nazionale Dei Lincei Rendiconti Classe Di Scienze Morali Storiche E Filologiche, 2005
The physical and chemical analysis of the marble of two reliefs representing gladiators, one hous... more The physical and chemical analysis of the marble of two reliefs representing gladiators, one housed in the Glyptotek of Munich and the other in the Museum of Budapest, has demonstrated that all the blocks come from the same area of the Carrara quarries (Torano) and therefore form part of the same work. This, consisting of two rows of blocks, each block measuring two Roman feet, must have continued to the left and especially to the right and have continued upwards for another row, as the relief of Pompeii suggests. It represents a gladiatorial munus with two pairs of opponents with armour composed of scales, with tubicines and lanista. As regards its development and structural composition it can be paralleled with similar reliefs from central Italy; probably belonging to a private funerary monument, it is of excellent quality and most likely the work of urban craftsmen. It can be dated to around 40-20 BC, (end of the Republican period-beginning of the Augustan period), as the quality of the marble, the workmanship, the type of armour and the stylistic analysis demonstrate.
The provenance of the marbles used for the five ancient sculptures on display in the Tribune of t... more The provenance of the marbles used for the five ancient sculptures on display in the Tribune of the Uffizi—the Venere Medici, the Apollo Medici, the Satiro danzante, the Arrotino and the Lottatori—has been determined using a well‐established multi‐method approach that includes isotopic, petrographic and EPR data. The Arrotino was found to be made of Docimium marble from the Phrygian quarries of Iscehisar, whereas Parian lychnites was used for the other four sculptures. Restorations, including the restoration of the Satiro ascribed to Michelangelo or his school, primarily used Pentelicon marble. The Lottatori, however, underwent multiple restorations that used a lychnites analytically different from the original stock, as well as Docimium, Carrara and Göktepe marbles. The right arm of the winner, which was considered to be a later addition, turned out to be made using the original marble—lychnites marble. The marble data provide support for the chronology of the sculptures and give i...
Journal of the Chemical Society, Faraday Transactions 2, 1989
The ENDOR spectra of the metastable expanded layer solid VOPO4·5H2O and its congener VOPO4·2H2O [... more The ENDOR spectra of the metastable expanded layer solid VOPO4·5H2O and its congener VOPO4·2H2O [both containing very small amounts of vanadium (IV)] have been measured at 4 K. The latter gave no ENDOR, whereas the former provided a spectrum in which three different proton signals ascribable to two interlayer water molecules were detected. From a reconstruction of the interlayer, taking into account the layer expansion of 3.1 A due to the intercalated water molecules, it is suggested that VOPO4·5H2O is an example of a ‘pillared’ material.
The marble of seven under-lifesize sculptures of barbarians, now in the archaeological museums of... more The marble of seven under-lifesize sculptures of barbarians, now in the archaeological museums of Naples, Venice and the Vatican, commonly considered to be Roman copies of the Pergamene Lesser Dedication in Athens, comes from the Göktepe marble quarries near Aphrodisias, as is shown by isotopic, electron paramagnetic resonance, trace analyses, and of petrographic data. Since this marble was used mostly by Aphrodisian artists, this finding confirms, on the basis of scientific data, previous hypotheses on the origin of the sculptors who manufactured the statues. Reliable discrimination from similar fine-grained Asiatic marbles, such asDocimium, is possible primarily on the basis of the composition of the Göktepe marbles, which have unusually low concentrations of manganese and high concentrations of strontium. Present knowledge of the history of the quarries and the distribution of their marbles seems to rule out the possibility that the sculptures date from the late Republican period...
Single crystal and powder E.S.R. studies of low-spin N,N'-ethylene bis(thioacetylacetonei... more Single crystal and powder E.S.R. studies of low-spin N,N'-ethylene bis(thioacetylacetoneiminato)Co(II) N,N'-ethylenebis(selenoacetylacetone-iminato)Co(II), and some related compounds, diluted in the corresponding Ni(II) and Zn(II) complexes are reported. The Co(II) complexes and their Ni(II) analogues are all isomorphous. The crystal and molecular structure of N,N'-ethylenebis(thioacetylacetoneiminato)Ni(II) is given. The crystals are orthorhombic, space group P212121, with unit cell dimensions a = 7·297 (2), b
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