Hydrochloric acid (hcl)

The hybrid organometallic polymers were synthesised according to published protocols [21 (link),25 (link)] Briefly, the Al-based material was prepared by dissolution of aluminium isopropoxide (AIP, ≥98%, Merck, Kenilworth, NJ, USA) in toluene (ACS, ISO, Reag. Ph Eur, Merck, Kenilworth, NJ, USA). In parallel, 3-(trimethoxysilyl)propyl methacrylate (MAPTMS, 98%, Sigma-Aldrich, St. Louis, MO, USA) was hydrolysed using HCl (0.1 M, Applichem, Darmstadt, Germany). Methacrylic acid (MAA, 99%, Sigma-Aldrich, USA) was then added to the solution of aluminium isopropoxide in toluene at a 1:1 molar ratio and subsequently, hydrolysed MAPTMS was added to the mixture at a 1:1:4 AIP:MAA:MAPTMS molar ratio. Finally, 1% of photoinitiator (4,4′-bis(diethylamino)benzophenone, Sigma-Aldrich, St. Louis, MO, USA) was added to the weight of AIP, MAA and 3-(trihydroxysilyl)propyl methacrylate (the product of MAPTMS hydrolysis) and stirred, while shielding from ambient light to prevent undesired crosslinking.
The Zr-based material was prepared in an analogous manner, with molar ratios of zirconium (IV) propoxide, MAA and MAPTHS being 1:1:4 with 1% of photoinitiator by weight (excluding solvents).

RIT was obtained from AbbVie Deutschland GmbH & Co. KG (Ludwigshafen, Germany). The copolymer PVPVA (Kollidon^®® VA64) with a weight-average molar mass of 65,000 g/mol was purchased from BASF SE (Ludwigshafen, Germany). Hydrochloric acid (10%) was purchased from AppliChem GmbH (Darmstadt, Germany), and potassium acetate (purity ≥ 99%) was purchased from Carl Roth GmbH & Co. KG (Karlsruhe, Germany). Acetone (purity ≥ 99.8%), sodium dihydrogen phosphate (purity ≥ 99%), and disodium hydrogen phosphate dihydrate (purity ≥ 99.5%) were purchased from Merck KGaA (Darmstadt, Germany). Magnesium nitrate hexahydrate (purity ≥ 98%), potassium nitrate (purity ≥ 99%), and potassium sulfate (purity ≥ 99%) were purchased from VWR International GmbH (Darmstadt, Germany). All substances were used without further purification. Water was freshly prepared with a Milli-Q^®® Advantage A10 purification system from Merck KGaA (Darmstadt, Germany).

Chitosan (CAS 9012-76-4) with a molecular weight of ~300 kDa and deacetylation degree of 85% was supplied by Heppe Medical Chitosan GmbH (Halle, Germany). Hydrochloric acid (37% ISO for analysis), sodium hydroxide and 2,2’-diphenyl-1-picrylhydrazyl (DPPH) were purchased from Carlo Erba (Milano, Italy), AppliChem (Darmstatd, Germany), and Merck KGaA (Darmstadt, Germany), respectively. Dibasic sodium phosphate (Na₂HPO₄), acetic acid (99.8%, Romil Pure Chemistry), 99% D₂O for NMR, and FT-IR grade KBr were provided by Merck KGaA. Gallic acid (3,4,5-trihydroxybenzoic acid, 98.0% purity), employed as a bioactive compound, was supplied by Merck KGaA.

Carminic acid of analytical chemical grade was purchased from Fluka (Buchs, Switzerland), kermesic acid was kindly donated by Dr. Ioannis Karapanagiotis (Ormylia Art Diagnosis Center, Greece), and flavokermesic acid was obtained from a mixture of natural product known as lac dye, which was purchased from Kremer-Pigmente (Aichstetten, Germany). Polish cochineal was harvested by Bożena Łagowska and Katarzyna Golan (Department of Entomology, University of Life Sciences, Lublin, Poland) and kindly donated by Jerzy Holc (the head of Conservation Workshop of Historical Textiles at Wawel Royal Castle, Kraków, Poland). American cochineal was purchased from Kremer-Pigmente (Aichstetten, Germany).
Methanol of LC/MS purity was purchased from POCH (Gliwice, Poland), formic acid (>99.5 %) of LC/MS purity, from Fisher Scientific (Fair Lawn, NJ, USA), and hydrochloric acid (35–38 %) of analytical grade, from AppliChem (Darmstadt, Germany). Demineralized water was made using Milli-Q system Model Millipore Elix 3 (Molsheim, France). Examined fibers were taken from seven Polish textiles dated to the 17th–19th century and provided by Ewa Orlińska-Mianowska from the Textile Division of the National Museum in Warsaw.

Standards: carminic acid of analytical chemical grade was purchased from Fluka (Buchs, Switzerland); kermesic acid was kindly donated by Dr. Ioannis Karapanagiotis (“Ormylia” Art Diagnosis Centre, Greece); flavokermesic acid was obtained from a mixture of natural products known as lac dye. Cochineal (Dactylopius coccus Costa) and lac dye were purchased from Kremer-Pigmente (Aichstetten, Germany).
Methanol of LC/MS purity was purchased from POCH (Gliwice, Poland) and analytical grade hydrochloric acid (35–38 %) was obtained from AppliChem (Darmstadt, Germany). Demineralized water was obtained from a Milli-Q Elix 3 system from Millipore (Molsheim, France).
Examined fibers were taken from two pre-Columbian textiles provided by Ewa Soszko from The Textile Conservation Department of Academy of Fine Art in Warsaw:

Red thread from a plaid woollen fabric, in the middle of which is a belt presenting geometrically simplified images of animals. The textile dates from the Inca culture (1200–1532 AD) and belongs to the collection of the State Ethnographic Museum in Warsaw (inventory number 15885).

Purple thread from a woollen tapestry depicting an eight-pointed star. Textile is from the Chuquibamba culture (1200–1450 AD), and is from a private collection (catalog number KPT8G).

Ultrapure water (18.2 MΩ/cm) was generated by a Milli-Q Plus system from Merck Millipore (Darmstadt, Germany). The Ag elemental standard as well as nitric acid (p. A., 65 %) were purchased from Merck (Darmstadt, Germany). The Ti and In elemental standard were purchased from Sigma-Aldrich (TraceCERT^®, Steinheim, Germany). Hydrogen peroxide (H₂O₂) solution (p.A., 30 %), sodium hydroxide (NaOH), Triton X-100 solution, forskolin, 3-isobutyl-1-methylxanthine (IBMX), and paraformaldehyde were purchased from Sigma-Aldrich (Steinheim, Germany). Hydrochloric acid (p.A., 37 %) was bought from Applichem (Darmstadt, Germany). Hydrofluoric acid (p.A., 5 %) was bought from Carl Roth (Karlsruhe, Germany). SuperFrost^®Plus Slides were used as glass slides for cell culture LA-ICP-MS experiments (Thermo Fisher Scientific GmbH, Dreieich, Germany).