Rigante Elena C L, Calvano Cosima D, Ventura Giovanni, Cataldi Tommaso R I
Department of Chemistry, University of Bari Aldo Moro, via Orabona 4, 70126, Bari, Italy.
Department of Chemistry, University of Bari Aldo Moro, via Orabona 4, 70126, Bari, Italy; Centro Interdipartimentale SMART, University of Bari Aldo Moro, via Orabona 4, 70126, Bari, Italy; Centro Interdipartimentale "Laboratorio di ricerca per la Diagnostica dei Beni Culturali", University of Bari Aldo Moro, via Orabona 4, 70126, Bari, Italy.
Anal Chim Acta. 2025 Jan 15;1335:343251. doi: 10.1016/j.aca.2024.343251. Epub 2024 Sep 17.
Diagnostics on historical art samples are decisive for assessing degradation and understanding the chemical composition of supports and polychromies. These investigations help us in uncovering the artist's style and techniques and provide invaluable information for restoration, preservation and conservation. In paint formulation, the binder, also known as medium, disperses insoluble pigments and creates a homogeneous, adhesive mixture. Various analytical techniques, often used in combination, are usually employed to characterize binders with infrared (IR) and Raman spectroscopies being the most common choices. Recently, mass spectrometry (MS) has gained prominence for its ability to allow detailed structural characterization and identification, thanks to soft ionization sources such as matrix-assisted laser desorption ionization (MALDI) and electrospray ionization (ESI). However, MS typically requires micro-sampling, which is often prohibited for highly valuable artworks. This limitation has driven research toward the development of innovative minimally invasive sampling strategies like enzyme-functionalized gels applied to polychromies for in-situ protein digestion and peptide extraction. These quasi-non-invasive methods offer powerful solutions for extracting and characterizing organic painting binders, unlocking valuable insights into these elusive materials. This review aims to explore both the most common non-invasive analytical techniques used to characterize ancient and contemporary painting binders, and the most recent advancements in minimally invasive sampling strategies, which represent convenient and interesting approaches to enable the use of invasive analytical approaches while preserving the integrity of precious artworks.
对历史艺术样本进行诊断对于评估其降解情况以及了解支撑物和彩色涂层的化学成分至关重要。这些研究有助于我们揭示艺术家的风格和技巧，并为修复、保存和保护提供宝贵信息。在涂料配方中，粘合剂（也称为媒介）分散不溶性颜料并形成均匀的粘性混合物。通常会结合使用各种分析技术来表征粘合剂，其中红外（IR）光谱和拉曼光谱是最常用的选择。近年来，质谱（MS）因其能够借助基质辅助激光解吸电离（MALDI）和电喷雾电离（ESI）等软电离源进行详细的结构表征和鉴定而备受瞩目。然而，质谱通常需要微量采样，这对于极具价值的艺术品来说往往是不允许的。这一限制推动了对创新的微创采样策略的研究，例如将酶功能化凝胶应用于彩色涂层以进行原位蛋白质消化和肽提取。这些准非侵入性方法为提取和表征有机绘画粘合剂提供了有力的解决方案，为深入了解这些难以捉摸的材料提供了宝贵的见解。本综述旨在探讨用于表征古代和当代绘画粘合剂的最常见非侵入性分析技术，以及微创采样策略的最新进展，这些进展代表了既方便又有趣的方法，能够在保护珍贵艺术品完整性的同时使用侵入性分析方法。
