34 research outputs found
Holographic interferometry (HI), infrared Vision and X-Ray fluorescence (XRF) spectroscopy for the assessment of painted wooden statues : a new integrated approach
Wood has been routinely employed in decorative
arts, as well as in sculptures and paintings (support) during
the Middle Ages, because of its unique aesthetic virtues. It
may safely be assumed that wood, as a material for monumental
sculpture, was much more commonly employed in
the mediaeval period than existing examples would seem
to indicate (Bulletin of the metropolitan Museum of Art,
2013). Wood is easily obtainable; it could be carved and
put in place with less difficulty than stone, it is chemically stable when dry, and its surface offers a compatible substrate
for paint application. However, the use of wood is
not without pitfalls, and requires an understanding of its
anisotropic and hygroscopic nature. It is also dimensionally
unstable and subject to deterioration by fungi and insects.
Moisture-related dimensional changes are certainly
among the most challenging problems in painting conservation.
With the purpose of preventing important damages,
the use of non-or microdestructive testing (NDT) techniques
is undoubtedly of paramount interest for painted wooden
statues of great value. This work has a threefold purpose:
(1) to validate the effectiveness of an integrated approach
using near-infrared (NIR) reflectography, square pulse thermography
(SPT), and holographic interferometry (HI) techniques
for discovering old repairs and/or inclusions of foreign
materials in a wooden structure, (2) to confirm and approximately
date the restoration carried out by x-ray fluorescence
(XRF) spectroscopy and energy-dispersive x-ray
spectroscopy (EDS) (that is assembled with a scanning electron
microscopyâSEM) techniques, and (3) to combine
into a multidisciplinary approach two quantitative NDT results
coming from optical and thermographic methods. The
subject of the present study was a statue named âVirgin with
her Childâ (XIV century), whose origins are mysterious and
not properly documented
NMR study of mixed micelles: zwitterionic â cationic surfactant systems
Surfactant molecules in a solvent self-associate into various kinds of supramolecular assemblies such as micelles, vesicles, and liquid crystals and their mixture, especially those of nonionic and ionic surfactants are used in many practical applications, such as detergents, cosmetics, oil recovery, drug delivery systems, emulsified polymerization, coating technology, and mesostructured nanofilms (1). For these applications, the structural and solution properties of the mixed surfactant systems should be controlled effectively. Therefore, it is useful to understand how the molecular structures of surfactants in mixtures affect the solution properties, such as the size, shape, and surface charge density of the mixed micelles. For these reasons, structural properties of nonionic-ionic surfactant mixed micellar solutions have been investigated theoretically and experimentally (2). In the mixture of two or more different surfactants (nonionic and ionic), the complex aggregation behavior of the mixture of surfactants in solution is a result of a delicate balance of opposing forces, i.e., the steric hindrance among the polar head groups of the surfactant molecules and electrostatic repulsion energy between charges on the polar head of the ionic surfactant molecules (3). Therefore, the structural properties of the nonionic-ionic mixed micellar solutions should be studied as a function of the molar ratio to determine the effect of molecular interaction between the surfactants in a mixed micelle on its formation. Practically, this understanding can help in choosing relevant surfactant structures that will result in the desired properties. NMR spectroscopy is one of the most convenient methods for simultaneous monitoring of changes in aggregate morphologies of interaction between components.
In this study, we investigated the formation in water of mixed micelle using zwitterionic and anionic surfactants employing multinuclear NMR to study the influence of intramicellar interaction and surfactant molecular shape on the properties of mixed micelles.
In our experiments, we kept the surfactant concentration well above their cmc values, so the observed chemical shifts are those of aggregated assemblies formed upon mixing of the surfactants.
Interestingly enough, NMR experiments suggest that under the chosen experimental conditions upon mixing of pure surfactants two different families of mixed aggregates are formed both larger than the original single component micelles. The fact that the different mixed micelles coexist unchanged many days after solution preparation, suggest that the system is under thermodynamic control
Role of Counterions in the Solubilization of Benzene by Cetyltrimethylammonium Aggregates. A Multinuclear NMR Investigation â
A Mild and Versatile Method for Palladium-Catalyzed Cross-Coupling of Aryl Halides in Water and Surfactants
Various aqueous surfactants proved to be excellent media for carrying out palladium-catalyzed SuzukiâMiyaura cross-coupling reactions under mild conditions. The dehalogenation side reaction, which is usually a drawback with the aqueous protocol, was not observed. The concentration of the surfactant in water played a pivotal role for the reaction outcome. Smooth cross-coupling of iodoanisole and a variety of aryl bromides, including electron-rich derivatives, with aryl boronic acids occurred at room temperature in high yields either with [Pd(PPh3)4] or Pd/C as catalyst. The water-surfactant Pd/C system combines high activity under ambient conditions (air), easy separation and recyclability. Palladium acetate was found to be effective in cross-coupling of the less reactive aryl chlorides at 100 °C
Role of Counterions in the Catalytic Activity and Phase Equilibria of Phosphonium Salts in Water â
Supramolecular Assemblies as Promoters of Iodohydrin Formation
Finding alternative reaction media to replace polluting organic solvents is one aim of green chemistry. The ultimate green solvent, water, is the cheapest, non-toxic and most readily available reaction medium: three properties which make it an environmentally and economically attractive solvent. However, a fundamental problem in performing reactions in water is that many organic substrates are hydrophobic and not soluble in water. Several approaches are possible in solubilizing these compounds in aqueous media, one of which is carrying out reactions in aqueous solutions of surfactants at concentrations above their critical micellar concentration (cmc). Reactions of iodine with cyclohexene, 1-octene and styrene in water or in the presence of cationic surfactants do not give useful amounts of iodohydrins, but reactions in anionic surfactants give good yields. Iodohydrins are important functionalizable compounds and are readily prepared in the presence of sodium dodecyl sulfate (SDS) or sodium N-dodecanoyl sarcosinate (SANa). The critical conditions for these reactions were optimized with a rigorous statistical approach, the experimental design method. Use of these newly optimized reaction conditions gave high yields in short times for all of the alkenes examined. The use of anionic surfactants in water to form iodohydrins is a valid alternative to methods previously described
Reverse Micellar Aggregates: Effect on Ketone Reduction. 1. Substrate Role
The reduction of three aromatic ketones, acetophenone (AF), 4-methoxyacetophenone (MAF), and 3-chloroacetophenone (CAF), by NaBH4 was followed by UVâvis spectroscopy in reverse micellar systems of water/AOT/isooctane at 25.0 °C (AOT is sodium 1,4-bis-2-ethylhexylsulfosuccinate). The first-order rate constants, kobs, increase with the concentration of surfactant due to the substrate incorporation at the reverse micelle interface, where the reaction occurs. For all the ketones the reactivity is lower at the micellar interface than in water, probably reflecting the low affinity of the anionic interface for BH4-. Kinetic profiles upon water addition show maxima in kobs at W0 â 5 probably reflecting a strong interaction between water and the ionic headgroup of AOT; at W0 MAF. Application of a kinetic model based on the pseudophase formalism, which considers distribution of the ketones between the continuous medium and the interface, and assumes that reaction take place only at the interface, gives values of the rate constants at the interface of the reverse micellar system. At W0 = 5, we conclude that NaBH4 is wholly at the interface, and at W0 = 10 and 15, where there are free water molecules, the partitioning between the interface and the water pool has to be considered. The results were used to estimate the ketone and borohydride distribution constants between the different pseudophases as well as the second-order reaction rate constant at the micellar interface