*3.1. Materials*

Chemical standards of phenolic compounds (benzoic acid, carvacrol, catechin, chlorogenic acid, *t*-cinnamic acid, 8-cinnamoyl harpagide (harpagoside), *o*-coumaric acid, *p*-coumaric acid, 2,3-dimethoxybenzoic acid, epicatechin, *t*-ferulic acid, gallic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 3-hydroxy-4-methoxybenzaldehyde, naringin, naringenin, quercetin, rutin, sinapinic acid, syringic acid, vanillic acid (all purity > 98%)), *β*-cyclodextrin (≥97%), *n*-hexane (HPLC-grade), diethyl ether (≥99%), and chloroform (HPLC-grade) were purchased from Sigma-Aldrich (Milan, Italy).

Ethyl acetate (≥99%), acetonitrile (HPLC-grade), methanol (HPLC-grade), ethanol (HPLC-grade), acetic acid (≥99%) as well as D-(+)-glucose were obtained from Carlo Erba Reagents (Milan, Italy). Sodium chloride (≥99%) was obtained from Honeywell (Seelze, Germany). NADES (glycolic acid/betaine mixture) was newly synthesized and supplied by University of Perugia. It was chosen between differently structured novel DES and NADES mixtures for its suitable properties (low freezing point and low viscosity, absence of aromatic compounds in its composition, low cost and natural source of the molecules forming it). Ultra-pure water was obtained using a Millipore Milli-Q Plus water treatment system (18 MΩ cm at 23 ◦C, Millipore Bedford Corp., Bedford, MA, USA).

#### *3.2. Sampling and Sample Preparation*

Samples of *Galium* species were collected from different locations from Romania, as follows: *G. verum* L. from Apuseni mountains region, Sartăs, , Alba County, Transylvania, Romania in June 2017, *G. album* Mill. from Podeni, Cluj Coutry, Romania and from Rimetea, Alba Coutry, Romania, *G. purpureum* L. and *G. pseudoaristatum* Schur from Băile Herculane, Cara¸s-Severin Coutry, in August 2014. All species were authenticated by Dr. Sabin Bădărău and Dr. Andrei Mocan, and voucher specimens were deposited at the herbarium of the Department of Pharmaceutical Botany, "Iuliu Hat ,ieganu" University of Medicine and Pharmacy. Fresh herbal material was dried at room temperature until reaching a constant mass. Afterwards, the plant material was ground into a fine powder using a laboratory mill, mixed to obtain homogenous sample, and kept at 4 ◦C, for further analyses. All assays were carried out three times (three separate samplings) and in triplicate, and the values reported are represented by average and the standard deviation (S.D.).
