A new multi analytical approach for the identification of synthetic and natural dyes mixtures. The case of orcein-mauveine mixture in a historical dress of a Sicilian noblewoman of nineteenth century

Abstract

In this paper, the application of a multi-analytical approach for the characterisation of synthetic and natural dyes in a historical textile is presented. The work is focused on a historical dress of a Sicilian noblewoman, dating from about 1865–1870. Firstly, SERS on fibre was performed, in order to individuate the classes of dyes employed. The SERS spectra suggested the presence of two main dyes: mauveine and orcein. In order to confirm these preliminary results, two different extraction protocols were applied. The extracts obtained were analysed by ESI-MS, MALDI-ToF and UHPCL-MS analyses, confirming the SERS results. In particular, the application of the ammonia mild extraction technique allowed to selectively extract the phenoxazonic dyes, separating them already in the extraction step from the synthetic ones. Thanks to this multi-analytical approach, this dress could be considered as one of the first examples of employment of synthetic dyes in association with natural ones.     

Electron-transfer in molecular functional materials

We discuss electron-transfer processes that govern the physics of several materials or systems of interest for advanced applications. The discussion touches upon several topics, ranging from solvatochromism to solvent-induced symmetry breaking, from excitonic to cooperative effects in molecular crystals, from phase transitions to vibrational contributions to the dielectric constant in organic materials, from spectroscopy to molecular transport. In all these diverse systems electron transfer (ET) plays a major role and is discussed with reference to simple models for delocalized charges.     

Production of octadienal in the marine diatom Skeletonema costatum

[reaction: see text] Marine diatoms produce alpha,beta,gamma,delta-unsaturated aldehydes that have detrimental effects on the reproduction of their natural predators. The production of these defensive metabolites is suggested to involve enzymatic oxidation of polyunsaturated fatty acids. In this paper, feeding experiments with labeled precursor provide clear evidence in support of the origin of octadienals 1 and 2 from 6,9,12-hexadecatrienoic acid (5), thus proving the involvement of novel lipoxygenase/lyase activity for the oxidation of C(16) fatty acids.     

Fast folding and comparison of RNA secondary structures

Summary Computer codes for computation and comparison of RNA secondary structures, the Vienna RNA package, are presented, that are based on dynamic programming algorithms and aim at predictions of structures with minimum free energies as well as at computations of the equilibrium partition functions and base pairing probabilities.An efficient heuristic for the inverse folding problem of RNA is introduced. In addition we present compact and efficient programs for the comparison of RNA secondary structures based on tree editing and alignment.All computer codes are written in ANSI C. They include implementations of modified algorithms on parallel computers with distributed memory. Performance analysis carried out on an Intel Hypercube shows that parallel computing becomes gradually more and more efficient the longer the sequences are.

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Schnelle Faltung und Vergleich von Sekundärstrukturen von RNA

Zusammenfassung Die im Vienna RNA package enthaltenen Computer Programme für die Berechnung und den Vergleich von RNA Sekundärstrukturen werden präsentiert. Ihren Kern bilden Algorithmen zur Vorhersage von Strukturen minimaler Energie sowie zur Berechnung von Zustandssumme und Basenpaarungswahrscheinlichkeiten mittels dynamischer Programmierung.Ein effizienter heuristischer Algorithmus für das inverse Faltungsproblem wird vorgestellt. Darüberhinaus präsentieren wir kompakte und effiziente Programme zum Vergleich von RNA Sekundärstrukturen durch Baum-Editierung und Alignierung.Alle Programme sind in ANSI C geschrieben, darunter auch eine Implementation des Faltungs-algorithmus für Parallelrechner mit verteiltem Speicher. Wie Tests auf einem Intel Hypercube zeigen, wird das Parallelrechnen umso effizienter je länger die Sequenzen sind.

     

Characterisation of fresh and aged terpenic resins by micro-FTIR and GC-MS analyses of varnishes in XVI-XVII centuries paintings

Resinous materials, generally added to drying oils, were often employed as final protective films in paintings, both in tempera and oil techniques. Most of the resins used in fine arts come from exudates of plants. Natural resins are mainly composed by terpenoids. Among these resins, dammar, rosin, mastic, elemi gum, Venice turpentine were frequently employed in easel paintings. The aim of this work is the identification of natural resins in samples collected from works of art. In this paper we propose to use micro-FTIR spectrometry as a preliminary and non destructive technique to detect the presence of resinous materials in microsamples collected from paintings, followed by GC-MS analyses to obtain a precise identification of the resin. To reach this aim commercial resins, employed as standard, were analysed previously by micro-FTIR spectrometry and then analysed by GC-MS chromatography, searching characteristic chemical compounds used as "markers" of resins. The results obtained on standards allowed us to successfully analyse samples collected from two works of art: the "Portrait of a Young Gentleman", by Lorenzo Lotto (XVI century), and the "Madonna with the Infant Jesus and Saints": by Carlo Maratta (XVII secolo).     

Vibrational spectroscopy of aqueous solutions at high concentrations: Raman and inelastic neutron scattering

We review work performed by our group on vibrational spectroscopy of water and aqueous solutions of strong II-I electrolytes at high concentrations. Evidence shall be presented for the existence of intermediate range, solute-connected, ordered patches, whose collective vibrational modes yield a continuous vibrational density of states, as in amorphous solids. We shall review Raman and inelastic neutron scattering results, obtained for electrolytes such as ZnCl₂, NiCl₂, CuBr₂, CdCl₂. Other results, such as EXAFS, viscosity and ultrasonic attenuation will also be discussed.     

On the continuity of midpoint hull convex set-valued functions

Summary The concept of hull convexity (midpoint hull convexity) for set-valued functions in vector spaces is examined. This concept, introduced by A. V. Fiacco and J. Kyparisis (Journal of Optimization Theory and Applications,43 (1986), 95–126), is weaker than one of convexity (midpoint convexity).The main result is a sufficient condition for a midpoint hull convex set-valued function to be continuous. This theorem improves a result obtained by K. Nikodem (Bulletin of the Polish Academy of Sciences, Mathematics,34 (1986), 393–399).     

Preparation and characterization of bolaform surfactant vesicles

Vesicular formulations (liposomes and niosomes) play an increasingly important role since they can be used as drug delivery and targeting systems. We described the formation of two niosomal systems based on synthetic bolaform surfactants (4,7,10,13-pentaoxa-16-aza-cyclooctadecane)-hexadecanedioc acid diamide (BD-16) and alpha,omega-(4,7,10,13-pentaoxa-16-aza-cyclooctadecane)-hexadecane (BC-16). Systems containing BD-16 or BC-16 and different amount of cholesterol (CH) were prepared by aqueous dispersion of films, followed by examination of methylene blue (MB) entrapment, particle size and morphology. Indeed, we also studied the hydration in the distilled water and physiological solution, in order to investigate the complexing ability on vesicle formation. The results obtained in this study show a high encapsulation capacity and this ability and the size depends on cholesterol content.     

In situ spectroscopic characterization of rectifying molecular monolayers self-assembled on gold.

We report visible, Raman, and infrared spectra of self-assembled monolayers (SAMs) formed by the donor-(pi-bridge)-acceptor chromophore, Z-beta-[N-(omega-acetylthioalkyl)-4-quinolinium]-alpha-cyano-4-styryldicyanomethanide (CH3CO-S-CnH2n-Q3CNQ where n=8, 10), on gold-coated substrates. The data are compared with the spectra collected for the same compound in solution and in the solid state, and with those obtained for a Langmuir-Blodgett (LB) monolayer of C16H33-Q3CNQ deposited on gold. Spectral analysis confirms that in solution, in the solid state and in the LB film the chromophore has a zwitterionic (D+-pi-A-) ground state. At variance with this well-known result, our data show that in SAMs deposited on gold the chromophore has a more neutral, quinoid ground state. We relate this difference to the different packing of the molecules in the two different films: in SAMs in fact the chromophores stand almost vertical with respect to the substrate, whereas in LB films they make an angle of about 45 degrees. The Q3CNQ molecule is a well-known molecular rectifier, and for SAMs we were able to check the direction of electron flow at forward bias on the same samples that have been characterized spectroscopically, shedding light on the rectification mechanism.     

Study of ruthenium(II) complexes with anticancer drugs as ligands. Design of metal-based phototherapeutic agents

The reaction of trans-[RuCl(2)(PPh(3))(3)] (Ph = C(6)H(5)) with 2-thio-1,3-pyrimidine (HTPYM) and 6-thiopurines (TPs) produced mainly crystalline solids that consist of cis,cis,trans-[Ru(PPh(3))(2)(N,S-TPYM)(2)] (1) and cis,cis,trans-[Ru(PPh(3))(2)(N(7),S-TPs)(2)]X(2) (X = Cl(-), CF(3)SO(3)(-)). In the case of TPs, other coordination isomers have never been isolated and reported. Instead, the mother liquor obtained after filtration of 1 produced red single crystals of trans,cis,cis-[Ru(PPh(3))(2)(N,S-TPYM)(2)].2H(3)O(+).2Cl(-) (2.2H(3)O(+).2Cl(-)). Selected ruthenium(II)-thiobase complexes were studied for their structural, reactivity, spectroscopic, redox, and cytotoxic properties. Single crystals of 1 contain thiopyrimidinato anions chelated to the metal center via N and S. The Ru[bond]N bonds are significantly elongated for 1 [2.122(2) and 2.167(2) A] with respect to 2 [2.063(3) A] because of the trans influence from PPh(3). The coordination pseudo-octahedron for 2 is significantly elongated at the apical sites (PPh(3) ligands). Solutions of cis,cis,trans isomers in air are stable for weeks, whereas those of 2 turn green within 24 h, in agreement with the respective redox potentials. cis,cis,trans- and trans,cis,cis-[Ru(PH(3))(2)(N,S-TPYM)(2)], as optimized through the DFT methods at the Becke3LYP level are in good agreement with experimental geometrical parameters (1 and 2), with cis,cis,trans being more stable than trans,cis,cis by 3.88 kcal. The trend is confirmed by molecular modeling based on semiempirical (ZINDO/1) and molecular mechanics (MM) methods. Cytotoxic activity measurements for cis,cis,trans-[Ru(PPh(3))(N-THZ)(N(7),S -H(2)TP)(2)]Cl(2) (4) (THZ = thiazole, H(2)TP = 6-thiopurine) and cis,cis,trans-[Ru(PPh(3))(2)(N(7),S-HTPR)2]Cl(2) (5) (HTPR = 6-thiopurine riboside) against ovarian cancer cells A2780/S gave IC(50) values of 17 +/- 1 and 29 +/- 9 microM, respectively. Furthermore, the spectral analysis of HTPYM, TPs, and their Ru(II) complexes in solution shows that intense absorptions occur in the UVA/vis region of light, whereas standard nucleobases absorb in the UVB region.