Żółte barwniki organiczne w XIX-wiecznych farbach Jana Matejki – identyfikacja substancji barwiących, nośników oraz wypełniaczy

Natural organic dyes can be found in many objects of cultural heritage. Identification of coloring substances present in historical paints provides relevant information for a wide range of specialists involved in art science. Determination of the composition of paints allows application of appropriate procedures for restoration and conservation of historical works of art. This information enables treatment in accordance with the ideological and esthetic decisions of the authors. The complexity of the chemical composition of art paints, which, apart from organic dyes can also include inorganic pigments, binders and other additives, hinders isolation and identification of its individual components. Nowadays, there are several analytical techniques and methods for extraction and identification of organic dyes, each of them has its limitations, however. For that reason, the development of the universal methodology for the analysis of colorant composition in art paints remains a challenge for chemists. In present work, an analytical protocol for identification of yellow dyes using reversed phase liquid chromatographymass spectrometry with atmospheric pressure electrospray ionization (LC-ESI/ /MS) is presented. The developed method was successfully applied to identification of the main components of Indian Yellow, weld (Reseda luteola L.), buckthorn berries (Rhamnus) and madder lake (madder plant’s root) extracts, in the historical oil paints from tubes of Richard Ainès company, formerly Mulard, owned before him by recognizable French art materials supplier Eduard. The recognition of paints composition was broadened by identification of non organic compounds – carriers of the dye: aluminum hydroxide, tin chloride, chalk, as well as filler like silica and or lead white. Researched samples of painting materials belonged to 19th century famous Polish painter Jan Matejko (1839–1893) and will be very helpful in understanding paintings of him and of his contemporaries

The Mechanism of a Retro-Diels–Alder Fragmentation of Luteolin: Theoretical Studies Supported by Electrospray Ionization Tandem Mass Spectrometry Results

The mechanisms of retro-Diels–Alder fragmentation of luteolin are studied theoretically using the Density Functional Theory method (B3LYP hybrid functional) together with the 6-311++G(d,p) basis set and supported by electrospray ionization tandem mass spectrometry (ESI-MS) results. The reaction paths leading to the formation of 1,3A− and 1,3B− fragment ions observed as the main spectral features in the ESI-MS spectrum are described and discussed, including the structures of the transition states and intermediate products. The heights of the activation energy barriers which have to be overcome along the reaction paths corresponding to 1,3-retrocyclization cleavage of the ionized luteolin are predicted to span the 69–94 kcal/mol range (depending on the initial isomeric structure) for the concerted retrocyclization mechanism and the 60–89 kcal/mol (first barrier) and 24–52 kcal/mol (second barrier) barriers for the stepwise mechanism (also depending on the initial isomeric structure). It is also demonstrated that the final fragmentation products (1,3A− and 1,3B−) are in fact represented by various isomeric systems which are not experimentally distinguishable. In addition, the absence of the spectral feature corresponding to the [M-B]− fragment ion formed by the rupture of the C-C bond connecting luteolin’s B and C rings (which does not occur during the ESI-MS experiment) is explained by much larger energy barriers predicted for such a process

The Mechanism of a Retro-Diels–Alder Fragmentation of Luteolin: Theoretical Studies Supported by Electrospray Ionization Tandem Mass Spectrometry Results

The mechanisms of retro-Diels–Alder fragmentation of luteolin are studied theoretically using the Density Functional Theory method (B3LYP hybrid functional) together with the 6-311++G(d,p) basis set and supported by electrospray ionization tandem mass spectrometry (ESI-MS) results. The reaction paths leading to the formation of 1,3A− and 1,3B− fragment ions observed as the main spectral features in the ESI-MS spectrum are described and discussed, including the structures of the transition states and intermediate products. The heights of the activation energy barriers which have to be overcome along the reaction paths corresponding to 1,3-retrocyclization cleavage of the ionized luteolin are predicted to span the 69–94 kcal/mol range (depending on the initial isomeric structure) for the concerted retrocyclization mechanism and the 60–89 kcal/mol (first barrier) and 24–52 kcal/mol (second barrier) barriers for the stepwise mechanism (also depending on the initial isomeric structure). It is also demonstrated that the final fragmentation products (1,3A− and 1,3B−) are in fact represented by various isomeric systems which are not experimentally distinguishable. In addition, the absence of the spectral feature corresponding to the [M-B]− fragment ion formed by the rupture of the C-C bond connecting luteolin’s B and C rings (which does not occur during the ESI-MS experiment) is explained by much larger energy barriers predicted for such a process

Isolation and identification of natural dyestuffs present in artistic paints and textiles of historical origin

Natural organic dyes are group of substances that belong to various types of chemical compounds. The most commonly used in paintings and dyeing textiles were naturally occurring dyestuffs from group of anthraquinones, flavones and indigoid dyes. Identification of coloring substances present in historical artistic paints provides relevant information for a wide range of specialists dealing with works of art and in the field of conservation science. This research presents a review of analytical techniques (mainly chromatographic and spectroscopic) used for identification of dyes. It also describes the methods of colorants isolation from historical artistic paints and textiles. Furthermore, the article presents a brief characteristics of fragmentation reactions of selected groups of dyestuffs, which is useful in their identification

Structure and Stability Characterization of Natural Lake Pigments Made from Plant Extracts and Their Potential Application in Polymer Composites for Packaging Materials

Natural dyes were extracted from various plant sources and converted into lake pigments based on aluminum and tin. Three different plants (weld, Persian berries, and Brazilwood) were chosen as representative sources of natural dyes. High-performance liquid chromatography (HPLC) and triple-quadrupole mass spectrometry (QqQ MS) were used to identify dyestuffs in the raw extracts. The natural dyes and lake pigments were further characterized by optical and scanning electron microscopy (SEM), UV-Vis spectrophotometry, and thermogravimetric analysis (TGA). The stabilization of the studied plant extracts onto aluminum and tin salts led to the formation of natural lake pigments characterized by different color shades. The natural lake pigments showed improved thermal and chemical stability, which was confirmed by their higher degradation temperatures and lower solubility in chemical agents compared to natural dyes extracted from plants. This improvement can be attributed to electrostatic attraction due to the process of chelation. Ethylene-norbornene (EN) composites colored with the lake pigments exhibited uniform color and improved resistance to long-term UV exposure aging. After 300 h of UV exposure, the aging factor of the neat EN copolymer reduced to 0.3, indicating an advanced aging process of polymer compared to colored samples. Prolonged UV exposure deteriorated the mechanical properties of EN by approximately 57%, compared to about 43% with the application of BW/Al lake pigment. Natural lake pigments could be used as effective substitutes for commercial colorants in plastics for packaging applications