A step forward in disclosing the secret of stradivari's varnish by NMR spectroscopy

It is commonly thought that the varnishes used by the great violin-maker Antonio Stradivari may have a role in determining not only the esthetical features but also the acoustic properties of his instruments, and the idea of a "lost secret" is still widespread among musicians and violin-makers. Previous scientific researches on varnish samples of Stradivari's instruments revealed that they were generally made by a mix of linseed oil with and colophony or metal rosinates in different ratios ranging between 75/25 (oil/resin) and 60/40 (oil/rosinate). However, it is still not clear whether the mixture composition can be related to any structural and/or functional feature of the resulting varnish. To investigate this aspect, we prepared varnishes with different linseed oil/colophony (w/w) ratios and applied NMR techniques to achieve information about their chemical-physical characteristics. Here, we show that the two components strongly interact in the solid state and that only the varnish prepared from 75/25 (w/w) linseed oil/colophony mixture displays unique properties in terms of dynamic homogeneity unlike coatings with other compositions. Our results suggest that the so-called "secret" of Stradivari's finish could not be related to unknown ingredient(s) but to a specific oil/resin composition that provides the best performance

Terpyridine derivatives functionalized with (hetero)aromatic groups and the corresponding Ru complexes: synthesis and characterization as SHG chromophores

Push–pull terpyridine derivatives were synthesized and characterized in order to study the variations produced in their optical and electronic properties by linking different (hetero)aromatic electron donor moieties at position 4 of the electron deficient terpyridine moiety. The final donor-acceptor systems were synthesized in fair to good yields by Kröhnke condensation of the precursor aldehydes, with 2-acetylpyridine. Hyper-Rayleigh scattering in dioxane solutions using a fundamental wavelength of 1064 nm was employed to evaluate their second-order nonlinear optical properties. Terpyridine derivative functionalized with the 9-ethyl-9H-carbazolyl group exhibited the largest first hyperpolarizability (beta = 610 × 10-30 esu, using the T convention) thus indicating its potential application as a second harmonic generation (SHG) chromophore. Terpyridine derivatives were also used as ligands for the synthesis of novel [RuII(tpy)(NCS)3]– complexes, prepared in good yields by a two-step procedure involving the preparation of [RuIII(tpy)(Cl3] as precursors. RutheniumII complexes display a broad absorption in the visible range, accounting for their very dark color. Their redox behaviour is mainly characterized by the RuII-RuIII oxidation and by the ligand-centred reduction, whose potentials can be finely tuned by the electronic properties of the aromatic substituents on the terpyridine ligand. Hyper-Rayleigh scattering in methanol solutions using a fundamental wavelength of 1064 nm was also employed to evaluate their second-order nonlinear optical properties.Thanks are due to Fundação para a Ciência e a Tecnologia and FEDERCOMPETE for financial support through Centro de Química (UID/QUI/ 00686/2013 and UID/QUI/0686/2016), and a PhD grant to S. S. M. Fernandes (SFRH/BD/87786/2012). The NMR spectrometer Bruker Avance III 400 is part of the National NMR Network and was purchased with funds from FCT and FEDER. The pulsed laser system was acquired within the framework of the grant (PTDC/CTM/105597/2008) from the Portuguese Foundation for Science and Technology (FCT) with funding from FEDER-COMPETE.info:eu-repo/semantics/publishedVersio

A two-channel Molecular dosimeter for the optical detection of copper(II)

A cyclam-like macrocycle with an integrated push-pull chromophore selectively detects Cu2+ inclusion through both orange-to-yellow colour change and quenching of the green fluorescence

Bimacrocyclic Effect in Anion Recognition by a Copper(II) Bicyclam Complex

The dicopper(II) complex of the bimacrocyclic ligand α,α′-bis(5,7-dimethyl-1,4,8,11-tetraazacyclotetradecan-6-yl)-o-xylene, 2, interacts with selected anions in dimethyl sulfoxide solution according to two different modes: (i) halides (Cl-, Br-, and I-) and N3- coordinate the two metal centers at the same time between the two macrocyclic subunits that face each other and (ii) anionic species that do not fit the bridging coordination mode (e.g., NCO-, SCN-, CH3COO-, NO3-, and H2PO4-) interact with copper(II) ions only at the "external" positions or their interaction is too weak to be detected. Occurrence of the bridging interaction is demonstrated by X-ray crystallographic studies performed on the adduct formed by [Cu2(2)]4+ with azide and by electron paramagnetic resonance investigation, as the anion coordination between the two copper(II) centers induces spin-spin coupling. Isothermal titration calorimetry experiments performed on [Cu2(2)]4+ and, for comparison, on [(5,7-dimethyl-6-benzyl-1,4,8,11-tetraazacyclotetradecane)copper(II)], representing the mononuclear analogue, allowed determination of thermodynamic parameters (log K, ΔH, and TΔS) associated with the considered complex/anion equilibria. Thermodynamic data showed that adducts formed by [Cu2(2)]4+ with halides and azide benefit from an extra stability that can be explained on the basis of the anion advantage of simultaneously binding the two metal centers, i.e., in terms of the bimacrocyclic effect

Surface and interface treatments on wooden artefacts: Potentialities and limits of a non-invasive multi-technique study

Wooden artefacts embrace wide-ranging types of objects, like paintings on panel, sculptures, musical instruments, and furniture. Generally, in the manufacturing process of an artwork, wood is firstly treated with organic and inorganic materials to make it nonporous and morphologically homogeneous, and, at last, the surface treatment consists of varnishes or coatings applied with the aims of conferring aesthetic properties and protecting wood from biological growth and external degradation agents, as well as mechanical damage. In this work, different wooden mock-ups were prepared by varying some parameters: concentration of filler and pigment, respectively, in the ground and paint layers, thickness of the protective varnish coat, and sequence of the layers. The mock-ups were subsequently exposed to time-varying artificial aging processes. The multi-analytical non-invasive approach involved spectroscopic (reflection FT-IR, Raman, and X-ray fluorescence), tomographic (optical coherence tomography) and colorimetric techniques. Data were interpreted using both univariate and multivariate methods. The aim was to evaluate potential and limits of each non-invasive technique into the study of different stratigraphies of wooden artworks. This approach was supported by microscopic observations of cross-sections obtained from selected mock-ups. The methodological approach proposed here would add valuable technical know-how and information about the non-invasive techniques applied to the study of wooden artworks

X-rays investigations for the characterization of two 17th century brass instruments from Nuremberg

A recent finding at the Castello Sforzesco in Milan of two brass natural horns from the end of the 17th century and assigned to the Haas family from Nuremberg brought to light new information about this class of objects. The instruments were heavily damaged, but their historical value was great. In this study, a multidisciplinary approach mainly based on non-invasive analytical techniques and including X-rays investigations (X-ray radiography, X-ray fluorescence and X-ray diffraction) was used. The present study was aimed at: i) pointing out the executive techniques for archaeometric purposes; ii) characterizing the morphological and the chemical features of materials; and iii) identifying and mapping the damages of the structure and the alterations of the surface

Surface and interface treatments on wooden artefacts: Potentialities and limits of a non-invasive multi-technique study

Wooden artefacts embrace wide-ranging types of objects, like paintings on panel, sculptures, musical instruments, and furniture. Generally, in the manufacturing process of an artwork, wood is firstly treated with organic and inorganic materials to make it nonporous and morphologically homogeneous, and, at last, the surface treatment consists of varnishes or coatings applied with the aims of conferring aesthetic properties and protecting wood from biological growth and external degradation agents, as well as mechanical damage. In this work, different wooden mock-ups were prepared by varying some parameters: concentration of filler and pigment, respectively, in the ground and paint layers, thickness of the protective varnish coat, and sequence of the layers. The mock-ups were subsequently exposed to time-varying artificial aging processes. The multi-analytical non-invasive approach involved spectroscopic (reflection FT-IR, Raman, and X-ray fluorescence), tomographic (optical coherence tomography) and colorimetric techniques. Data were interpreted using both univariate and multivariate methods. The aim was to evaluate potential and limits of each non-invasive technique into the study of different stratigraphies of wooden artworks. This approach was supported by microscopic observations of cross-sections obtained from selected mock-ups. The methodological approach proposed here would add valuable technical know-how and information about the non-invasive techniques applied to the study of wooden artworks