Synthese von 15-Hydroxy[9]metacyclophan

Synthesis of 15-Hydroxy[9]metacyclophane 3-(1-Nitro-2-oxocyclododecyl)propanal ( 1 ) was converted to 15-hydroxy[9]metacyclophane ( 3 ) on two different routes. In the first case the internal aldol reaction product of 1 was treated with K₂CO₃/THF to give 3 in 29 % yield with regard to cyclododecanone. Alternatively, the aldehyde 1 reacted with a primary amine to form e.g. 4 which gave 3 in the presence of CH₃I/K₂CO₃ in 48 % yield.     

Synthese makrocyclischer Lactone durch Ringerweiterung. Vorläufige Mitteilung

Synthesis of Macrocyclic Lactones by Ring Enlargement Reaction Treatment of 3-(1-nitro-2-oxocyclohexyl)propanal ( 1 ) prepared by Michael addition of 2-nitrocyclohexanon and acrylaldehyde with methyltri (2-propoxy)tita-nium yielded a mixture of 2 and 3 which was converted into 6-nitro-9-decanolide ( 4 ).     

"Oscillating" metallocene catalysts: what stops the oscillation?

The 150 MHz (13)C NMR microstructural analysis of polypropylene samples produced with two representative "oscillating" metallocene catalysts of largely different steric hindrance, namely [(2-(3,5-di-tert-butyl-4-methoxyphenyl)indenyl)(2)ZrP](+) and [(2-phenylindenyl)(2)ZrP](+) (P = polymeryl), and the implications on the origin of the stereocontrol are presented and discussed in detail. The original mechanistic proposal of an "oscillation" between a rac-like (isotactic-selective) and a meso-like (nonstereoselective) conformation cannot explain the observed polymer configuration. The isotactic-stereoblock nature of the polymers obtained with the former catalyst proves unambiguously that the active cation "oscillates" between the two enantiomorphous rac-like conformations at an average frequency that, even at high propene concentration, is only slightly lower than that of monomer insertion. The less-hindered [(2-phenylindenyl)(2)ZrP](+) gives instead a largely stereoirregular polypropylene, which is the logical consequence of a faster ligand rotation; however, depending on the use conditions (in particular, on the nature of the cocatalyst and the polarity of the solvent), the polymerization products may also contain appreciable amounts of a fairly isotactic fraction. The peculiar microstructure of this fraction, with isotactic blocks of the same relative configuration spanned by very short atactic ones, rules out the possibility that the latter are due to an active species in meso-like conformation and points rather to a conformationally "locked" rac-like species with restricted ring mobility. The hypothesis of a stereorigidity induced by the proximity to a counteranion, which would play the role of the interannular bridge in the rac-bis(indenyl) ansa-metallocenes, was tested by computer modeling on a [rac-(2-phenylindenyl)(2)ZrMe(C(3)H(6))][B(C(6)F(5))(4)] ion couple and found viable.     

Degradation of stone materials in the archaeological context of the Greek–Roman Theatre in Taormina (Sicily, Italy)

In the present work results on the degradation phenomena of stone materials in the Ancient Theatre of Taormina, one of the most important Greek–Roman monuments of Sicily, are reported. Artificial stone materials in different conservation conditions were investigated. Samples of salt efflorescences from brick walls and degraded setting mortars were taken from the open gallery in “summa cavea”. The chemical, physical and structural characterization was performed by means of X-Ray Photoelectron Spectroscopy (XPS), X-Ray Diffraction (XRD) and X-Ray Fluorescence (XRF), both in situ and ex situ.     

Integrated analytical methodologies for the study of corrosion processes in archaeological bronzes

The investigations on structure and micro-chemical composition of archaeological metal alloys are needed in archaeometry. The aim of this study is devoted both to acquire information about their provenance and production technology, and to improve our understanding about the corrosion processes. In this paper we present the study of the corrosion phenomena of bronze samples, laboratory-made according to binary, ternary and quaternary alloys typical of Roman archaeometallurgical production through an integrated methodology based on the use of non or micro invasive physical techniques. Among the analysed samples, two were artificially aged through burial in the archaeological site of Tharros, along the west coast of Sardinia (Italy). The corrosion products, typical of the bronzes in archaeological sites near the sea, have been characterized by non invasive and micro-destructive measurements. In particular, the corrosion patinas were examined through optical microscopy, scanning electron microscopy and microanalysis, X-ray fluorescence and laser ablation spectroscopy. The use of integrated technologies allowed us to determine both the elemental composition and surface morphology of the patina, highlighting the correlation between patina nature and chemical composition of the burial context. Moreover, data obtained by the laser-induced breakdown spectroscopy along the depth profile on the samples, have yielded information about the stratigraphic layers of corrosion products and their growth. Finally, the depth profiles allowed us to verify both the chemical elements constituting the patina, the metal ions constituting the alloy and the occurrence of migration phenomena from bulk to the surface.     

Primitive symmetric designs with up to 2500 points

By this article we conclude the construction of all primitive ( v, k,λ ) symmetric designs with v < 2500 , up to a few unsolved cases. Complementary to the designs with prime power number of points published previously, here we give 55 primitive symmetric designs with v ≠ p ^m , p prime and m positive integer, together with the analysis of their full automorphism groups. The research involves programming and wide‐range computations. We make use of the software package GAP and the library of primitive groups which it contains. © 2011 Wiley Periodicals, Inc. J Combin Designs 19:463‐474, 2011     

Preliminary 1H NMR study on archaeological waterlogged wood

Magnetic Resonance Relaxation (MRR) and Magnetic Resonance Imaging (MRI) are powerful tools to obtain detailed information on the pore space structure that one is unlikely to obtain in other ways. These techniques are particularly suitable for Cultural Heritage materials, because they use water 1H nuclei as a probe. Interaction with water is one of the main causes of deterioration of materials. Porous structure in wood, for example, favours the penetration of water, which can carry polluting substances and promote mould growth. A particular case is waterlogged wood from underwater discoveries and moist sites; in fact, these finds are very fragile because of chemical, physical and biological decay from the long contact with the water. When wood artefacts are brought to the surface and directly dried in air, there is the collapse of the cellular structures, and wood loses its original form and dimensions and cannot be used for study and museum exhibits. In this work we have undertaken the study of some wood finds coming from Ercolano's harbour by MRR and MRI under different conditions, and we have obtained a characterization of pore space in wood and images of the spatial distribution of the confined water in the wood.     

Characterization of foxing stains in early twentieth century photographic and paper materials

Abstract

The subject of this present work is a group of nine historical pictures shot in Palermo by the Sicilian photographer E. Interguglielmi in 1912. They are nine matte-collodion prints mounted on the original cardboard supports and all of them show foxing stains affecting the paper surface. In order to characterise the chemical composition of the supports and investigate foxing spots, non-destructive and micro-destructive analysis were carried out. X-rays fluorescence (XRF) analysis was used to characterise the elemental composition of all the mounting boards, allowing a comparison between the foxing spots and non-affected areas. Laser-Induced Breakdown Spectroscopy was used to investigate the presence of lower atomic number elements, not detectable by XRF, while SEM imaging allowed the investigation of surface appearance and nature of original paper samples from the cardboards.