Ch2cl2

The compositions of other lignocellulosic degradation products in samples were assessed using GCMS (Shimadzu) following the method of Chokwe et al. (9 (link)), with a detection limit for the peak area >2%. The liquid–liquid extraction pretreatment was conducted prior to the GCMS analysis using CH₂Cl₂ (chromatogram pure grade, Thermo Fisher Scientific, Waltham, MA, USA). A 20-mL pre-treated sample was freeze-dried prior to being dissolved in 2 mL of methanol. The sample was then filtered through a 0.22-μm nylon membrane before being analyzed. GCMS was equipped with a DB-5 column (Agilent, Santa Clara, CA, USA) with an internal diameter of 30 m×0.25 mm and film thickness of 0.25 μm. Conditions were set as follows: the initial oven temperature was held at 70°C for 2 min, increased at 20°C min⁻¹ to 230°C, and then elevated to 270°C. Helium was used as the carrier gas at a flow rate of 1 mL min⁻¹. The injector temperature was maintained at 250°C. A 1-μL sample was injected neat with a split ratio of 1:10. Mass spectra were recorded over the 50–650 amu range at 1 scan s⁻¹ with an ionization energy of 70 eV and ion source temperature of 230°C. The compositions of samples were qualitatively identified through comparisons of their mass spectra in a library and published literature.

Two kilograms of the fresh aerial parts of the plant (equal to 50% of the weight of a
wildly-growing plant) were air-dried in the shade at room temperature, grounded, and
exhaustively extracted by cold maceration with aqueous methanol (70%). The extract was
evaporated under reduced pressure at 40°C to yield 80 g residue. The residue was suspended
in distilled water and successfully fractionated with n-hexane, CH2Cl2, EtOAc, and n-BuOH
(Thermo Fisher, USA) saturated with H₂O. Each extract was evaporated under
reduced pressure to yield 3, 7, 12 and 22 g residues, respectively.

PLLA microparticles were produced by oil/water (o/w) emulsion technique and surface modified by combining plasma treatment with collagen I as similarly described in our previous reports22 23 (link). PLLA (5% w/v, Mw~1,600–2,400, 70% crystallinity, Polysciences) was dissolved in methylene chloride (CH₂Cl₂, Fisher Chemical). Under agitation, this solution was added to polyvinyl alcohol (0.5%, PVA, Sigma-Aldrich). After 2 days at RT, the produced microparticles were subsequently collected, washed with distilled water, and lyophilized (Cryodos, Telstar). Microparticles were then placed in a plasma reactor chamber (PlasmaPrep5, Gala Instrumente) fitted with a radio frequency generator. Air was used as the working atmosphere. A glow discharge plasma (0.2mbar, 30V) was created for 15 min. Subsequently, microparticles (500 mg) were immersed in collagen I (1200 μg, rat protein tail, Gibco) diluted in acetic acid (0.02 M) for 4 h at RT.

All fruits were purchased from the local market. All the chemicals, including H₃PO₄, ethanol, CH₂Cl₂, NH₂-PEG, FeCl₃·6H₂O, and 1,6-hexanedioic acid, were purchased from Fisher Scientific and Sigma-Aldrich. The human triple-negative breast cancer (TNBC) cell line MDA-MB-232, the human HER-2(+) breast cancer cell line SK-BR-3, the human ER(+) and PR(+) breast cancer cell line MCF-7 and the HaCaT normal skin cell line were purchased from the American Type Culture Collection (ATCC, Rockville, MD).

2‐(2‐methoxyethoxy)ethyl methacrylate (MEO₂MA, 95%), MAA (98%), ethylene glycol dimethacrylate (98%), GMA (97%), sodium dodecyl sulfate (98.5%), ammonium persulfate (98%), K₂CO₃ (ACS grade), CHCl₃ (≥99.5%), methanol (MeOH, ≥99.9%), methacryloyl chloride (97.0%), Rhodamine B, N‐N′‐methylene bisacrylamide (MBAAm, ≥99.5%), acrylamide (AAm, ≥99.5%), and 2,2′‐azobis(2‐methylpropionamidine) dihydrochloride (V‐50, 97%) were all purchased from Aldrich. 4‐Methylumbelliferone (≥98%), 2‐bromoethanol (95%), N,N‐dimethylformamide (ACS grade), ethanol (100%), triethylamine (99%), CH₂Cl₂ (≥99.8%), and Nile blue A were purchased from Fisher Scientific. Methacryloxyethyl thiocarbamoyl Rhodamine B (Me‐RDB) was purchased from Polysciences. All materials were used as received. Ultrahigh purity water was used that had been doubly filtered and deionized.

The natural polysaccharide, chitosan (C₆H₁₁NO₄)_n, was gained from Sigma-Aldrich (USA). Other reagents, such as phenyl acrylic acid (PA, PhCH = CHCOOH, 99.0%), dimethyl amine (DMA, (CH₃)₂NH, 40.0%), thionyl chloride (SOCl₂, 99.0%), pyridine (C₅H₅N, 99.5%), and triethyl amine (C₆H₁₅N:98.5%), were procured from Darmstadt, Germany, and Loba Chemie, India, respectively. Solvents, including dichloromethane (CH₂Cl₂, 99.0%), methanol (CH₃OH, 99.7%), and acetone (CH₃COCH₃, > 99.5%), were purchased from Fisher Chemicals (United States) and El-Nasr companies (Egypt), respectively. Distilled water was prepared in our research lab. All reagents and solvents for synthesis were of analytical grade and used without extra purification.