During the past few decades, thiomers have attracted interest as responsive-polymers in the design of smart hydrogels, due to thiol reactivity to physical stimuli (i.e., pH, oxygen, UV/Vis irradiation). However, thiomer potentialities have been limited by their low thiolation degree and lack of multi-responsiveness to physical cues. In this work, a new class of thiomers with tailored thiolation degree and sensitivity to multiple physical stimuli was developed. To this aim, a polyurethane (33,000 Da) was synthesised from Poloxamer® 407, 1,6-diisocyanatohexane and N-Boc diethanolamine. Secondary amino groups were exposed through Boc-removal (yield 80%, assessed by ¹H NMR) giving up to 4.5 × 10²⁰ ± 1.8 × 10¹⁹ –NH units/g_polymer (Orange II Sodium Salt colorimetric assay) without polymer chemical degradation. Polymer thermo-responsiveness was proved by the increase in micelle hydrodynamic diameter upon system heating up to 45 °C and through estimated critical micellar temperatures. Thioglycolic acid grafting to exposed amines via carbodiimide chemistry was optimised to give up to 1.73 × 10¹⁹ thiols/g_polymer (Ellman's method), while minimising disulphide bond formation. Finally, the best storage conditions against oxidation were investigated by quantifying free thiols at different time points.

在过去的几十年中，由于硫醇对物理刺激（即pH值，氧气，UV / Vis照射）的反应性，在智能水凝胶的设计中，作为响应性聚合物的硫聚物引起了人们的兴趣。然而，由于低硫醇化程度和对物理线索缺乏多反应性，硫醇单体的潜力受到了限制。在这项工作中，开发了一种新的硫代单体，其具有定制的硫醇化度和对多种物理刺激的敏感性。为此，由407、1，6-二异氰酸根合己烷和N-Boc二乙醇胺合成了聚氨酯（33,000 Da）。仲氨基通过Boc去除（产率80％，通过¹ H NMR评估）暴露，最多可得到4.5×10 ²⁰  ±1.8×10 ¹⁹ –NH单位/ g_聚合物（橙色II钠盐比色测定），无需进行聚合物化学降解。通过将系统加热到45°C时胶束流体动力学直径的增加以及估计的临界胶束温度来证明聚合物的热响应性。通过碳二亚胺化学方法将巯基乙酸接枝到裸露的胺上，优化了最多1.73×10 ¹⁹硫醇/ g的_聚合物（Ellman方法），同时最大程度地减少了二硫键的形成。最后，通过定量在不同时间点的游离硫醇，研究了抗氧化的最佳储存条件。