The first step consisted of the synthesis of the RAFT agent 1, following a procedure previously reported in the literature, which was then conjugated to a PEG block (113 units) via esterification to form a macroRAFT agent. Chain extension of this macroRAFT agent with a random copolymer of MAA and TMSPMA enabled the introduction of carboxylic groups and terminal alkyne functionalities (in their protected form) as functional handles. Good control over the polymerisation of PEG-b-P(MAA-co-TMSPMA) 3 was evidenced by low dispersity Đ = 1.07, and a clean shift in the gel permeation chromatography traces (GPC, Figure ). The same polymer (with 113 PEG units, 5 MAA units and 19 TMSPMA units) was used throughout the remainder of the study and chain extended to produce three different libraries of triblock copolymers: (i) a library of PNIPAM-based block copolymers (5a1-5a5) with increasing number of NIPAM units; (ii) a library of PNCPAM-based block copolymers (5b1-5b5) with increasing number of NCPAM units; (iii) a library of P(NIPAM-co-NCPAM)-based block copolymers (5c1-5c3) with different NIPAM/NCPAM (NI/NC) ratios. We hypothesised that the incorporation of cyclopropyl moieties (NCPAM) would lead to an increase in the LCST providing a Tcp (cloud point temperature as measured by DLS) for nanogel self-assembly/disassembly at temperatures just above body temperature. Successful synthesis of the three block copolymer libraries was confirmed by 1 H NMR and GPC yielding degree of polymerisation (DP), number average molecular weight (Mn), and dispersity (Đ) (Table ). Full composition and characterisation details of selected 5a4/5c1-3 block copolymers are reported in Table , whilst data for the remaining block copolymers can be found in Table of the supporting information (SI). For the P(NIPAM-co-NCPAM)-based copolymers (5c1-3), full chain extension was observed for all the copolymers with a minimal amount of macro-RAFT agent left behind and minimal shouldering in the GPC traces (Figure ). Due to the structural similarity and similar degree of reactivity between NIPAM and NCPAM, the formation of a random block stemming from their simultaneous polymerisation rather than two distinct blocks was assumed. In general, the dispersity was Đ < 1.5. The length of the thermo-responsive block was successfully modulated in the separate NIPAM and NCPAM libraries (Table ), whilst the copolymers shown in Table were of similar length, as shown by NMR and GPC. The evolution of Mn and Đ versus DP is shown in Figure . We also determined the block copolymer cloud point temperatures Tcp via temperature sweeps and monitoring by dynamic light scattering (DLS).