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Special Issue "Natural Dyes"

A special issue of Molecules (ISSN 1420-3049).

Deadline for manuscript submissions: closed (30 November 2019).

Special Issue Editors

Prof. Marcella Guiso
Website
Guest Editor
Universita degli Studi di Roma “La Sapienza”, Department of Chemistry, Rome, Italy
Interests: natural dyes; colour chemistry; natural products; cultural heritage
Dr. Ilaria Serafini

Assistant Guest Editor
Universita degli Studi di Roma “La Sapienza”, Department of Chemistry and Technology of drugs, Rome, Italy
Interests: natural dyes; nanomaterial; HPLC-MS; SERS analyses; conservation

Special Issue Information

Dear Colleagues,

There is no doubt that natural dyes are currently one of the most stimulating topics in modern chemistry. Undisputed protagonists of our past from the historical artistic point of view, up to the synthesis of the first synthetic dyes, their application, and the scientific research related to them is far from being exhausted.

In fact, their interest not only concerns the field of cultural heritage conservation, in which advancement in analytical techniques such as surface-enhanced Raman spectroscopy or high-resolution mass spectrometry are revealing new perspectives to unsolved questions, but even more their use in cosmetics, pharmaceuticals, and foods studies. In these fields, the applications of natural dyes are showing a great potentiality, keeping in mind also the concept of green chemistry.

This Special Issue therefore aims to attract contributions concerning the different branches of pure and applied science devoted to the study or application of natural dyes, from cosmetics to cultural heritage, including all aspects of chemistry.

It could represent an opportunity to make a point on the state-of-the-art in the field of natural dyes, and to offer new insights on further possible applications or possibilities which have not yet been fully evaluated.

Prof. Marcella Guiso
Dr. Ilaria Serafini
Guest Editors

Manuscript Submission Information

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Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2000 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Natural dyes
  • cultural heritage
  • cosmetics
  • pharmaceutics
  • foods

Published Papers (7 papers)

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Research

Open AccessArticle
Dyes from the Ashes: Discovering and Characterizing Natural Dyes from Mineralized Textiles
Molecules 2020, 25(6), 1417; https://doi.org/10.3390/molecules25061417 - 20 Mar 2020
Abstract
Vesuvius eruption that destroyed Pompeii in AD 79 represents one of the most important events in history. The cataclysm left behind an abundance of archeological evidence representing a fundamental source of the knowledge we have about ancient Roman material culture and technology. A [...] Read more.
Vesuvius eruption that destroyed Pompeii in AD 79 represents one of the most important events in history. The cataclysm left behind an abundance of archeological evidence representing a fundamental source of the knowledge we have about ancient Roman material culture and technology. A great number of textiles have been preserved, rarely maintaining traces of their original color, since they are mainly in the mineralized and carbonized state. However, one outstanding textile sample displays a brilliant purple color and traces of gold strips. Since the purple was one of the most exclusive dyes in antiquity, its presence in an important commercial site like Pompeii induces us to deepen the knowledge of such artifacts and provide further information on their history. For this reason, the characterization of the purple color was the main scope of this research, and to deepen the knowledge of such artifacts, the SERS (Surface Enhanced Raman Scattering) in solution approach was applied. Then, these data were enriched by HPLC-HRMS analyses, which confirmed SERS-based hypotheses and also allowed to hypothesize the species of the origin mollusk. In this context, a step-by-step integrated approach resulted fundamental to maximize the information content and to provide new data on textile manufacturing and trade in antiquity. Full article
(This article belongs to the Special Issue Natural Dyes)
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Open AccessArticle
Traditional Yellow Dyes Used in the 21st Century in Central Iran: The Knowledge of Master Dyers Revealed by HPLC-DAD and UHPLC-HRMS/MS
Molecules 2020, 25(4), 908; https://doi.org/10.3390/molecules25040908 - 18 Feb 2020
Abstract
This work provides new knowledge on natural yellows used in Iran. Seven biological sources were selected based on interviews with dye masters in Isfahan workshops (Iran). Delphinium semibarbatum, Eremostachys laevigata, Prangos ferulacea, Morus alba, Pistacia vera, Punica granatum [...] Read more.
This work provides new knowledge on natural yellows used in Iran. Seven biological sources were selected based on interviews with dye masters in Isfahan workshops (Iran). Delphinium semibarbatum, Eremostachys laevigata, Prangos ferulacea, Morus alba, Pistacia vera, Punica granatum, and Vitis vinifera are currently used in these workshops. Aiming to study the dye composition of wool samples dyed with the extracts of the selected biological sources, and the changes induced by the dyeing procedures in the original chemical composition of the plant extract, raw materials and dyed wool (by us and in the workshops) were analyzed by HPLC–DAD and UHPLC–HRMS/MS. In solutions extracted from the textiles, the main yellows for E. laevigata are luteolin-O-glycosides. In the other plant sources, the main chromophores are based on 3-O-glycosides of kaempferol, quercetin, and isorhamnetin. In pistachio hulls, myricitin derivatives were detected and we propose their use as markers. Generally, the solutions extracted from the wool displayed a higher amount of more polar compounds, but also a higher amount of aglycones. Importantly, the chromatographic profiles of the samples we prepared compared well with 17th c. yellows in Persian carpets, and therefore can be considered highly characterized references for the study of Persian yellows. Full article
(This article belongs to the Special Issue Natural Dyes)
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Open AccessArticle
Molecular Structures and Spectral Properties of Natural Indigo and Indirubin: Experimental and DFT Studies
Molecules 2019, 24(21), 3831; https://doi.org/10.3390/molecules24213831 - 24 Oct 2019
Cited by 1
Abstract
This paper presents a comparative study on natural indigo and indirubin in terms of molecular structures and spectral properties by using both computational and experimental methods. The spectral properties were analyzed with Fourier transform infrared (FTIR), Raman, UV-Visible, and fluorescence techniques. The density [...] Read more.
This paper presents a comparative study on natural indigo and indirubin in terms of molecular structures and spectral properties by using both computational and experimental methods. The spectral properties were analyzed with Fourier transform infrared (FTIR), Raman, UV-Visible, and fluorescence techniques. The density functional theory (DFT) method with B3LYP using 6-311G(d,p) basis set was utilized to obtain their optimized geometric structures and calculate the molecular electrostatic potential, frontier molecular orbitals, FTIR, and Raman spectra. The single-excitation configuration interaction (CIS), time-dependent density functional theory (TD-DFT), and polarization continuum model (PCM) were used to optimize the excited state structure and calculate the UV-Visible absorption and fluorescence spectra of the two molecules at B3LYP/6-311G(d,p) level. The results showed that all computational spectra agreed well with the experimental results. It was found that the same vibrational mode presents a lower frequency in indigo than that in indirubin. The frontier molecular orbital analysis demonstrated that the UV-Visible absorption and fluorescence bands of indigo and indirubin are mainly derived from π → π* transition. The results also implied that the indigo molecule is more conjugated and planar than indirubin, thereby exhibiting a longer maximum absorption wavelength and stronger fluorescence peak. Full article
(This article belongs to the Special Issue Natural Dyes)
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Open AccessArticle
Compositional and Micro-Morphological Characterisation of Red Colourants in Archaeological Textiles from Pharaonic Egypt
Molecules 2019, 24(20), 3761; https://doi.org/10.3390/molecules24203761 - 18 Oct 2019
Abstract
When the imagination conjures up an image of an Egyptian mummy, it is normally one of a human body wrapped with undyed linen bandages. However, the reality was much more colourful, as shown by the set of red mummy shrouds and textile fragments [...] Read more.
When the imagination conjures up an image of an Egyptian mummy, it is normally one of a human body wrapped with undyed linen bandages. However, the reality was much more colourful, as shown by the set of red mummy shrouds and textile fragments from Pharaonic Egypt considered in this work. The textiles were subjected to scientific investigation with the main aim of shedding light on the sources of red colour and on the possible reasons for the different levels of colour fading. The red colourants were investigated using various non-invasive and micro-invasive approaches. The results pointed towards the presence of three sources of red colour, which, in increasing order of lightfastness, are safflower (Carthamus tinctorius), madder (Rubia spp.), and red ochre. Micro-morphological observations and elemental analyses also enabled some hypotheses to be formulated regarding the application of these colourants to the textiles. The results not only deepen our knowledge of dyeing technologies in ancient Egypt and shed new light on the function of red shrouds and textiles as part of the funerary practices of Pharaonic Egypt, but are also essential in planning the display and future preservation of these mummies and their associated textiles. Full article
(This article belongs to the Special Issue Natural Dyes)
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Open AccessArticle
Deepening Inside the Pictorial Layers of Etruscan Sarcophagus of Hasti Afunei: An Innovative Micro-Sampling Technique for Raman/SERS Analyses
Molecules 2019, 24(18), 3403; https://doi.org/10.3390/molecules24183403 - 19 Sep 2019
Abstract
The Hasti Afunei sarcophagus is a large Etruscan urn, made up of two chalky alabaster monoliths. Dated from the last quarter of the third century BC, it was found in 1826 in the small town of Chiusi (Tuscany- Il Colle place) by a [...] Read more.
The Hasti Afunei sarcophagus is a large Etruscan urn, made up of two chalky alabaster monoliths. Dated from the last quarter of the third century BC, it was found in 1826 in the small town of Chiusi (Tuscany- Il Colle place) by a landowner, Pietro Bonci Casuccini, who made it part of his private collection. The noble owner’s collection was sold in 1865 to the Royal Museum of Palermo (today under the name of Antonino Salinas Regional Archaeological Museum), where it is still displayed. The sarcophagus is characterized by a complex iconography that is meticulously illustrated through an excellent sculptural technique, despite having subjected to anthropic degradation and numerous restorative actions during the last century. During the restoration campaign carried out between 2016 and 2017, a targeted diagnostic campaign was carried out to identify the constituent materials of the artefact, the pigments employed and the executive technique, in order to get an overall picture of conservation status and conservative criticalities. In particular, this last intervention has allowed the use of the innovative micro-sampling technique, patented by the Cultural Heritage research group of Sapienza, in order to identify the employee of lake pigments through SERS analyses. Together with this analysis, Raman and NMR technique have completed the information requested by restorers, for what concerns the wax employed as protective layers, and allowed to rebuild the conservation history of the sarcophagus. In fact, together with the identification of red ocher and yellow ocher, carbon black, Egyptian blue and madder lake, pigments compatible with the historical period of the work, modern pigments (probably green Paris, chrome orange, barium yellow, blue phtalocyanine) have been recognized, attributable with not documented intervention during the eighteenth and twentieth centuries. Full article
(This article belongs to the Special Issue Natural Dyes)
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Open AccessArticle
A Mass Spectrometric Study on Tannin Degradation within Dyed Woolen Yarns
Molecules 2019, 24(12), 2318; https://doi.org/10.3390/molecules24122318 - 22 Jun 2019
Abstract
Natural tannins from various plants have been used throughout human history in textile dyeing, often as mordant dyes. The ageing behavior of these dyes is a challenge in conservation science, requiring a thorough knowledge of the textile–mordant-dye system. In this work, we analyzed [...] Read more.
Natural tannins from various plants have been used throughout human history in textile dyeing, often as mordant dyes. The ageing behavior of these dyes is a challenge in conservation science, requiring a thorough knowledge of the textile–mordant-dye system. In this work, we analyzed reference wool yarns dyed with natural tannins from oak gallnuts, walnut (Juglans regia), and catechu (Acacia catechu), after artificial ageing. To gain insights on the composition of the dyestuffs and on how they aged, an analytical procedure based on extraction with Na2EDTA/DMF (ethylenediaminetetraacetic acid/dimethylformamide) and high-performance liquid chromatography (HPLC) analysis using high-resolution mass spectrometry detection was used. Since conventional reversed-phase (RP) columns usually show poor retention efficiency of highly polar compounds such as tannins, an RP-amide embedded polar group stationary phase was used to achieve optimal retention of the most polar compounds. Tannins from oak gallnuts showed little degradation after ageing, while a significant increase in the content of hydroxybenzoic acids was observed for tannins from walnut and catechu. Finally, the analytical procedure was applied to characterize the tannin dyes in historical tapestries from the 15th to 16th century, and the results were discussed in comparison with the reference yarns. Full article
(This article belongs to the Special Issue Natural Dyes)
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Open AccessArticle
It’s Only a Part of the Story: Analytical Investigation of the Inks and Dyes Used in the Privilegium Maius
Molecules 2019, 24(12), 2197; https://doi.org/10.3390/molecules24122197 - 12 Jun 2019
Abstract
The Privilegium maius is one of the most famous and spectacular forgeries in medieval Europe. It is a set of charters made in the 14th century upon commitment by Duke Rudolf IV, a member of the Habsburg family, to elevate the rank and [...] Read more.
The Privilegium maius is one of the most famous and spectacular forgeries in medieval Europe. It is a set of charters made in the 14th century upon commitment by Duke Rudolf IV, a member of the Habsburg family, to elevate the rank and the prestige of his family. These five charters, now kept at the Österreichisches Staatsarchiv in Vienna, have been subjected to a thorough interdisciplinary study in order to shed light on its controversial story. The charters are composed of pergamenaceous documents bound to wax seals with coloured textile threads. The present contribution concerns the characterisation of the inks used for writing and of the dyes used to colour to the threads: Are they compatible with the presumed age of the charters? Though showing only a part of the whole story of the charters, dyes analysis could contribute in assessing their complex history from manufacturing to nowadays. The dyes were characterised with non-invasive in situ measurements by means of fibre optic (FORS) and with micro-invasive measurements by means of Surface Enhanced Raman Spectroscopy (SERS) and High-Performance Liquid Chromatography with Mass Spectrometry (HPLC-MS) analysis. The results showed that the threads of four of the charters (three dyed with madder, one with orchil) were apparently coloured at different dyeing stages, then re-dyed in the 19–20th century. Full article
(This article belongs to the Special Issue Natural Dyes)
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