*4.1. Materials*

Oranges (*Citrus sinensis*) and orange peel bagasse were purchased from a local supermarket in Campinas (Sao Paulo, Brazil). Hesperidin standard was bought from Sigma-Aldrich (St. Louis, MA, USA) at analytical grade (>97%). Calcium(II) chloride, copper(II) acetate, sodium hydroxide, and hydrochloric acid were from Labsynth (Diadema, Sao Paulo, Brazil) at practical grade. Deuterated solvent (DMSO-*d*6) was purchased from Sigma-Aldrich (St. Louis, MA, USA). Methanol and phosphoric acid for the UHPLC assays were analytical grade (Avantor "Performance Materials", Mexico®, Ecatepec de Morelos, Mexico). ABIL® Care 85 (Bis-PEG/PPg-16/16 PEG/PPG16/16 Dimethicone; Caprylic/Capric Triglyceride) were sampled from the EVONIK® group (Essen, Germany). Muru muru (*Astrocaryum murumuru* Seed Butter), Cupuaçu butter (*Theobroma grandiflorum* Seed Butter), and Andiroba oil (*Carapa Guianensis* Seed Oil) were sampled from Amazon oil industry; Glyceryl monostearate, Mineral oil, Carbopol ULTREZ 10, Triethanolamine, and Vit E-acetate (α-Tocopheryl acetate) were bought from Fagron® (Rotterdam, The Netherlands).

#### *4.2. Extraction of HSD from Humid Orange Bagasse*

The fresh chopped orange peel (*Citrus sinensis,* 100 g) was milled in a blender and immersed in 300 mL of aqueous CaCl2 solution (7.5%). The mixture was left to stand for 24 h, then, a NaOH 1 mol L−<sup>1</sup> solution was added dropwise until a pH of 11.50 was reached. It was set to stand for 24 h, the pH was measured, and it dropped to 9.66 overnight. Then, the suspension was filtered, and the pellet was much harder when compared with the starting material, probably because of the interactions between calcium(II) ions and pectin. Concentrated HCl was then added to the solution, and pH was lowered to 4.35. The solution was left to stand at 4 ◦C for 2 days. After 24 h, crystals were formed at the bottom of the glass. However, for the best yields, two days of precipitation is recommended. After 48 h, HSD was filtered onto a MILIPORE® (Burlington, MA, USA) apparatus, using a 0.45 μm pore filter, and dried for 2 h in drying oven (60 ◦C).
