Ac 300

All reagents were purchased from commercial sources and used without further purification. Substrates which were not commercially available were synthesized according to known literature procedures (see Supporting Information for details). NMR spectra were performed on a Bruker AC-300 or Bruker Avance-400 (Bruker Corporation, Karlsruhe, Germany) using CDCl₃ as solvent and TMS as internal standard unless otherwise stated. Optical rotations were measured on a Jasco P-1030 Polarimeter with a 5 cm cell (c given in g/100 mL). Enantioselectivities were determined by HPLC analysis (Agilent 1100 Series HPLC) equipped with a G1315B diode array detector and a Quat Pump G1311A (Agilent Technologies, Palo Alto, CA, United States) equipped with the corresponding Daicel chiral column; the retention time of the major enantiomer is highlighted in bold. HRMS were measured using HPLC–HRMS (ESI) equipment (Agilent 1100 Series LC/MSD Trap SL, Agilent Technologies). Analytical TLC was performed on Merck silica gel plates and the spots were visualized with UV light at 254 nm (Merck Millipore, Billerica, MA, USA). Flash chromatography employed Merck silica gel 60 (0.040–0.063 mm) (Merck Millipore, Billerica, MA, USA).

β-Ch and SUP were commercially available. TPA was soxhlet extracted with dichloromethane from Tiafen®. Commercial solvents and reagents were used without additional purification. ¹H NMR and ¹³C NMR spectra were recorded in CDCl₃ as solvent on a Bruker AC-300 at 300 and 75 MHz respectively; NMR chemical shifts are reported in ppm downfield from an internal solvent peak. All reactions were monitored by analytical TLC with silica gel 60 F₂₅₄ revealed with ammonium molybdate reagent. The residues were purified through silica gel 60 (0.063–0.2 mm). Exact mass was obtained by VG Autospec-high-resolution mass and Waters ACQUITY™ XevoQToF spectrometers.

All reagents and solvents were purchased from commercial suppliers and used without further purification. ¹H and ¹³C spectra were measured on a Bruker AC-300 (300 MHz, ¹H) or a Bruker AC-200 (50 MHz, ¹³C) spectrometer. Chemical shifts were measured in DMSO-d₆ or CDCl₃, using tetramethylsilane as an internal standard, and reported as unit (parts per million) values. The following abbreviations are used to indicate multiplicity: s, singlet; d, doublet; t, triplet; m, multiplet; dd, doublet of doublets; brs, broad singlet; brm, broad multiplet. Mass spectra were recorded on a Finnigan MAT INCO 50 mass spectrometer (MS) (electron ionization, 70 eV) with direct injection. Melting points were determined on an Electrothermal 9001 apparatus (10°C per min) and are uncorrected.

UV Spectra were recorded in methanol or chloroform on a Hitachi UV 3200 spectrophotometer. IR Spectra were recorded in CHCl₃ or KBr on a Jasco A-302 IR spectrophotometer. The EI MS spectra were recorded on a double focusing mass spectrometer (Varian MAT 311A). HREI MS measurements were performed on a Jeol HX 110 mass spectrometer. The ¹H-NMR spectra were recorded on Bruker AC-300 and AM-400 MHz instruments, while ¹³C-NMR spectra were recorded at 100 and 125 MHz. Multiplicities of the carbon signals were determined by DEPT 90° and 135° experiments. ¹H-NMR and ¹³C-NMR chemical shifts were reported in δ (ppm) and coupling constants (J) were measured in Hz.

The DM was measured at room temperature using a proton nuclear magnetic resonance (¹H-NMR) with a Bruker AC 300 (300 MHz) and a Bruker AVANCE III 400 MHz. The HA-MA polymer samples were dissolved in D₂O. Spectra were measured by comparing the integral related to protons signal at 5.8 ppm or 6.2 ppm, which was assigned to the methylene protons of the methacrylate group protons (2 s, 2H, -CO-C(CH₃)=CH₂ belonging to MA residues linked to HA), with the integral related to protons in a range between δ = 1.88 ppm and 1.81 ppm (considering only the contribution of NH-CO-CH₃ belonging to HA). Specifically, the DM was measured by comparing the integral related to the methyl group belonging to HA residues (δ = 1.88 ppm) with the integral of the signal of the CH₃ belonging to MA (δ = 1.81 ppm) (Figure S1, Supplementary Information).

Analytical grade reagents were used in this study and purchased from Sigma Aldrich (Milan, Italy). Carlo Erba silica gel 60 (230–400 mesh; Carlo Erba, Milan, Italy) were used for flash chromatography. We purchased plates coated with silica gel 60F 254 nm from Merck (Darmstadt, Germany) to carry out TLC. We recorded the 1H- and 13C-NMR spectra using an AC 300 instrument (Bruker, Billerica, Massachusetts, USA).

Chemical reagents and solvents
were purchased from Aldrich and used without further purification.
Water was purified using a Milli-Q water purification system. Reactions
were monitored by TLC on 0.25 mm Merck silica gel plates (60 F254).
NMR spectra were recorded on a AVIII 500 spectrometer (500 MHz
for 1H frequency) or on a Bruker AC-300 (300 MHz for 1H frequency).
UV–vis absorption spectra were measured on a Varian Cary 50
spectrophotometer with 1 cm path length quartz cuvettes. Fluorescence
spectra were measured on a Varian Cary Eclipse fluorescence spectrophotometer.
Both the spectrophotometers were equipped with thermostated cell holders.
ESI-MS were recorded on an Agilent Technologies 1100 Series system
equipped with a binary pump (G1312A) and MSD SL Trap mass spectrometer
(G2445D SL).
Compounds 1–12 were synthesized
by standard procedures (details in the Supporting Information) and fully characterized.