Colorants, Volume 3, Issue 2 (June 2024) – 7 articles

Transition metal complexes have historically played a pivotal role in creating vibrant pigments utilized across artistic mediums such as ceramics, paintings, and glass mosaics. Despite their extensive historical use, our understanding of the mechanisms governing transition metal complex behavior has predominantly emerged in recent times, leaving numerous aspects of this process ripe for exploration. These complexes exhibit striking color variations under diverse conditions when employed in pigment formulations. This review utilizes a bottom-up scientific approach, spanning from microscopic to macroscopic scales, to unravel the molecular origins of the colors generated by transition metal complexes in pigments and ceramic glazes. Advanced spectroscopy techniques and computational chemistry play pivotal roles in this endeavor, highlighting the significance of understanding and utilizing analytical data effectively, with careful consideration of each technique’s specific application. Furthermore, this review investigates the influence of processing conditions on color variations, providing valuable insights for artists and manufacturers aiming to enhance the precision and quality of their creations while mitigating environmental impact. Full article

Magnesium oxide is typically white and can be colorized with transition metal insertion by doping. We present the preparation of a green-colored hydroxide by the exchange of Mg²⁺ on the crystalline lattice with Ni²⁺ in MgO, using three nickel salts. MgO_st was prepared by the colloidal starch suspension method, using cassava starch. The oxides and hydroxides, before and after, were characterized by X-ray diffraction (XRD), and show that a phase change occurs: a transition from periclase (MgO) to brucite (Mg(OH)₂) due to the incorporation of nickel ions from different salts (acetate, chloride, and nitrate), resulting in the solid solution [Ni_xMg_1−x(OH)₂]. The FTIR spectrum corroborates the crystallographic structure identified through XRD patterns, confirming the formation of a crystal structure resembling brucite. The new samples present a green color, indicative of the incorporation of the Ni²⁺ ions. The antimicrobial activity of products resulting from the doping of magnesium oxide with nickel and the precursor MgO_st was assessed through the minimum inhibitory concentration (MIC) test. The evaluation included three bacterial strains: Staphylococcus aureus (ATCC 25923), Escherichia coli (ATCC 25922), Salmonella gallinarum (ATCC 9184), and a yeast strain, Candida albicans (ATCC 10231). The obtained results were promising; the tested samples exhibited antimicrobial activity, with a MIC ranging from 0.312 to 0.625 μg.μL⁻¹. The nickel compound, derived from the precursor chloride salt, demonstrated superior MIC activity. Notably, all tested samples displayed bactericidal activity against the S. aureus strain and exhibited a broad spectrum of inhibition, encompassing both Gram-positive and Gram-negative strains. Only the nickel compounds derived from precursors with acetate and nitrate anions demonstrated antimicrobial activity against C. albicans, exhibiting a fungistatic behavior. Based on the conducted studies, [Ni_xMg_1−x(OH)₂] has emerged as a promising antimicrobial agent, suitable for applications requiring the delay or inhibition of bacterial growth. Full article

Structural hydroxide groups in layered magnesium–aluminum double hydroxides were partially replaced by fluoride ions. Fluorinated and fluorine-free materials were used as hosts for two dyes, carminic acid and hydroxyl naphthol blue, resulting in a hybrid pigment color palette. The pigments were produced by two ways, either incorporating chromophore during the synthesis of the layered double hydroxide or in a post-synthesis step through the memory effect of the LDHs. Additionally, the pigments were protected with a magnesium hydroxide phase to prevent the color from fading over time. The pigments were stable for periods as long as 10 years. The color properties of the pigments were significantly influenced by the host of dye since the presence of fluorine directly influences the acid–base properties of the layered double hydroxides. The pigments conferred their color to white cream in the preparation of colored creams. The colored creams acquired the color of the layered pigment. Full article

The ceramic pastes of ca. 31 samples recovered from the Almaraz archaeological site, located in the south bench of Tagus River, were studied in detail using XRF, micro-Raman and GSDR spectroscopies, as well as the XRD technique. The ceramic sherds could be grouped into six categories, red slip tableware, decorated tableware, yellow slip tableware, grey tableware, common tableware, and handmade pottery. Our studies of the mineralogic composition of the sherds’ body indicate all ceramics were produced locally, using siliceous clays in most cases and calcareous clays in a few ones. Micro-Raman and ground state diffuse reflectance absorption spectroscopy provided useful information regarding the materials used to produce the coloured ceramics: hematite and brookite for the red slip and decorated ceramics, jacobsite or carbon black for the black decoration or grey ceramics. For the yellow slip tableware, a simple engobe rich in yellow clay was used. XRF spectroscopic studies provided the elemental composition of all samples, and biplots of the potassium (K) versus calcium (Ca) contents, normalized to the silicon content of each ceramic paste, clearly show Pliocene and Miocene local clays sources were used to produce most ceramics. Only one sherd can be considered a Lisbon production. Full article

Herein, we present the preparation of solid-state photoactive starches with a large Stokes shift, along with the resulting materials. In this investigation, 2-(2′-hydroxyphenyl)benzazole derivatives responsive to intramolecular proton transfer in the excited state (ESIPT) were covalently bonded to the polymeric structure of starch through a reaction involving an isothiocyanate group and the hydroxyl groups of starch. These compounds exhibit absorption at approximately 350 nm, which is related to fully spin- and symmetry-allowed π → π* electronic transitions, and solid-state fluorescence at approximately 500 nm, which features a significant separation between the absorption and emission maxima (~9000 cm⁻¹). Due to the minimal use of fluorophores in functionalized starch preparation, this modification does not affect the original properties of the starch. Finally, photoactive starch-based films with significantly high transparency were successfully produced. Full article

Smart solvatochromic isocyano-aminoarenes (ICAArs) have been gaining attention owing to their unique photophysical, antifungal and anticancer properties. Using a simple dehydration reaction with in situ-generated dichlorocarbene, we prepared 2-amino-7-isocyanofluorene (2,7-ICAF). We studied the effect of the longer polarization axis provided by the fluorene core on the spectral properties and we also compared it to those of the starting diamine. 2,7-ICAF shows a clear solvatochromic behavior close to the blue part (370–420 nm) of the visible spectrum. Quantum chemical calculations show internal charge transfer (ICT) between the donor amino and the electron-withdrawing isocyano groups. 2,7-ICAF has high molar absorptivity (ε = 15–18·10³ M⁻¹cm⁻¹) and excellent quantum yield (Φ_f = 70–95%) in most solvents; however, its fluorescence is completely quenched in water. The high brightness (ε·Φ_f) and close to zero quantum yield in water may be favorable in biolabeling applications, where background fluorescence should be kept minimal. Overall, 2,7-ICAF shows enhanced photophysical properties compared to its previously investigated relative 4-amino-4′-isocyano-1,1′-biphenyl (4,4′-ICAB). Full article