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101.
Austin Nevin Daniela Comelli Iacopo Osticioli Lucia Toniolo Gianluca Valentini Rinaldo Cubeddu 《Analytical and bioanalytical chemistry》2009,395(7):2139-2149
The assessment of the influence of natural and artificial ageing on the spectrofluorescence of triterpenoid varnishes dammar
and mastic is the focus of this work. Both Fourier transform infrared (FTIR) microscopy using attenuated total reflectance
and Raman spectroscopy have been employed for complementary molecular analysis of samples. Synchronous fluorescence spectroscopy,
excitation emission spectroscopy, and statistical analysis of data have been used to monitor changes in the optical properties
of varnish samples. Assessment of naturally and artificially aged samples using excitation emission spectroscopy suggests
that extensive exposure to visible light does not lead to easily appreciable differences in the fluorescence of mastic and
dammar; cluster analysis has been used to assess changes, which occur with artificial ageing under visible light, indicating
that differences in the fluorescence spectra of aged triterpenoids may be insufficient for their discrimination. The results
highlight significant differences between the initial fluorescence of films of dammar and mastic and the fluorescence, which
develops with ageing and oxidation, and specific markers, which change with ageing in FTIR and Raman spectra, have been identified. 相似文献
102.
103.
The Baeyer-Villiger reactions of acetone and 3-pentanone, including their fluorinated and chlorinated derivatives, with performic acid have been studied by ab initio and DFT calculations. Results are compared with experimental findings for the Baeyer-Villiger oxidation of aliphatic fluoro and chloroketones. According to theoretical results, the first transition state is rate-determining for all substrates even in the presence of acid catalyst. Although the introduction of acid into the reaction pathway leads to a dramatic decrease in the activation energy for the first transition state (TS), once entropy is included in the calculations, the enthalpic gain is lost. Of all substrates examined, pentanone reacts with performic acid via the lowest energy transition state. The second transition state is also lowest for pentanone, illustrating the accelerating effect of the additional alkyl group. Interestingly, there is only a small energetic difference in the transition states leading to migration of the fluorinated substituent versus the alkyl substituent in fluoropentanone and fluoroacetone. These differences match remarkably well with the experimentally obtained ratios of oxidation at the fluorinated and nonfluorinated carbons in a series of aliphatic ketones (calculated, 0.3 kcal/mol, observed, 0.5 kcal/mol), which are reported herein. The migration of the chlorinated substituent is significantly more difficult than that of the alkyl, with a difference in the second transition state of approximately 2.6 kcal/mol. 相似文献
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106.
Prof. Francesca Caterina Izzo Matilde Kratter Dr. Austin Nevin Prof. Elisabetta Zendri 《ChemistryOpen》2021,10(9):904-921
Up to 70 % of the oil paintings conserved in collections present metal soaps, which result from the chemical reaction between metal ions present in the painted layers and free fatty acids from the lipidic binders. In recent decades, conservators and conservation scientists have been systematically identifying various and frequent conservation problems that can be linked to the formation of metal soaps. It is also increasingly recognized that metal soap formation may not compromise the integrity of paint so there is a need for careful assessment of the implications of metal soaps for conservation. This review aims to critically assess scientific literature related to commonly adopted analytical techniques for the analysis of metal soaps in oil paintings. A comparison of different analytical methods is provided, highlighting advantages associated with each, as well as limitations identified through the analysis of reference materials and applications to the analysis of samples from historical paintings. 相似文献
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This review provides analysts with critical insights of current approaches for quantification by laser ablation-inductively coupled plasma-mass spectrometry in the field of elemental imaging. This encompasses both calibration strategies that have been used with success in imaging biological samples, as well as those with potential to improve analytical accuracy and precision if applied to imaging. Methods reviewed include the use of CRMs, laboratory prepared matrix matched standards, internal standardisation, online standard addition and a variety of novel approaches that makes elemental imaging accessible to a wider base of analysts. The importance of quantification and factors affecting its use in imaging will also be considered. 相似文献
110.
Solvent-free films of poly (ethylene oxide)–silver triflate (PEO–AgCF3SO3)/MgO-based nanocomposite polymer electrolytes (PEO)50AgCF3SO3–x wt.% MgO (x = 1, 3, 5, 7, and 10) obtained using solution casting technique were found to exhibit an appreciably good complexation of
MgO nanofiller within the polymer electrolyte system and non-Debye type of relaxation as revealed by Fourier transform infrared
and complex impedance analyses. Optimized filler (5 wt.% MgO) when incorporated into the polymer electrolyte resulted in a
maximum electrical conductivity of 2 × 10−6 S cm−1 in conjunction with a silver ionic transference number (t
Ag+) of 0.23 at room temperature (298 K). Detailed structural, thermal, and surface morphological investigation indicated a slight
reduction in the degree of crystallinity owing to the addition of MgO nanofiller. 相似文献