OligoPBAT-bismaleimide and oligoPBAT-dithiol were dissolved in a minimal amount of anhydrous chloroform at 30 °C. Then, oligoPBAT-dithiol was added with thiol and maleimide groups were in an equimolar ratio. An aliquot was collected at this stage for further analyses. 1 molar equivalent, relative to thiol and maleimide groups, of TEA was then added. Aliquots were collected after 1 and 20 minutes of reaction. Then, the mixture was precipitated in diethyl ether, filtered, washed with diethyl ether and dried at 40 °C under vacuum for approximately 15 hours. The aliquots collected during the reaction consisted of 60 µL of the reaction mixture immediately precipitated in diethyl ether to quench the reaction, centrifuged at 6000 rpm for 1 minute and dried at 40 °C under vacuum for 2 hours. Characterizations 1 H, C, C APT and 31 P NMR spectra were recorded on a Bruker Ascend 400 MHz spectrometer (Germany). Samples were dissolved in CDCl3 or DMSO-d6. For 31 P NMR analyses, TMDP, a 0.1 M solution of cholesterol in a CDCl3/pyridine mixture (1:1.6 mass ratio) and Cr(acac)3 were used as phosphitylating agent, internal standard and NMR relaxation agent, respectively, as described in standard protocols . 16 scans were recorded with 1 s delay. In the case of quantitative 1 H NMR spectroscopic analysis, 100 µL of 0.5M PFB solution in DMSO-d6 or TCP in CDCl3 was added as an internal standard. 16 scans were registered with 30 s delay. 1 H- C HSQC and 1 H-15 N HMBC NMR spectra were recorded on a Bruker 500 MHz spectrometer. From literature data, the spectral width for N nucleus was 145 -205 ppm for the molecules containing maleimide groups only, while the spectral width was extended to 145 -420 ppm for the molecules containing maleimide and nitro groups . In a typical procedure for proper dissolution of starch for NMR analyses , 100-150 mg of starch were added into 800 µL of dry DMSO-d6. This suspension was then shaken on a bidirectional mixer at 80 °C during 12 hours. This suspension was finally transferred to a NMR tube (5 mm) for analysis at ambient temperature. Size-exclusion chromatography (SEC) was performed on a Waters Acquity APC (Advanced Polymer Chromatography) system (USA), equipped with three 150-mm APC XT columns (45 Å -1.7 μm column, 200 Å -2.5 μm column, and 450 Å -2.5 μm column) regulated at 40 °C. Tetrahydrofuran was used as the eluent with a flow rate of 0.6 mL min -1 . Prior to the injection, the sample was dissolved in THF at 5 mg mL -1 and filtered through 0.2 μm PTFE syringe filters. The detection was performed with Acquity detectors: a tunable UV detector (operating at 280 nm) and a refractive index (RI) detector. The average molar masses (Mn and Mw) and the dispersity (Ð) were determined from a calibration setup based on polystyrene standards. Differential scanning calorimetry (DSC) was conducted with a TA Instruments Discovery DSC 25 (USA). Samples weighing (1.0-2.5 mg) were encapsulated into conventional aluminum pans. The analysis was carried out in a nitrogen atmosphere, maintaining a flow rate of 50 ml per minute. Initially, the samples underwent rapid heating to reach 250 °C, followed by cooling down to -80 °C to erase the thermal history of the samples. Subsequently, they were reheated to 250 °C at a consistent rate of 10 °C per minute for both the cooling and the reheating phases. Fourier transform infrared (FTIR) spectroscopy analysis was conducted using a Thermo Fisher Nicolet iS10 spectrometer (USA), which was outfitted with a diamond ATR module. This FTIR-ATR setup operated in reflection mode, executing 32 scans at a resolution of 4 cm -1 . Prior each sample measurement, a baseline background scan was established.