A convenient one-pot method for the controlled synthesis of polystyrene-block -polycaprolactone (PS-b -PCL) copolymers by simultaneous reversible addition-fragmentation chain transfer (RAFT) and ring-opening polymerization (ROP) processes is reported. The strategy involves the use of 2-(benzylsulfanylthiocarbonylsulfanyl)ethanol (1) for the dual roles of chain transfer agent (CTA) in the RAFT polymerization of styrene and co-initiator in the ROP of ε -caprolactone. One-pot poly merizations using the electrochemically stable ROP catalyst diphenyl phosphate (DPP) yield well-defi ned PS-b -PCL in a relatively short reaction time (≈4 h; M n = 9600−43 600 g mol −1 ; M w / M n = 1.21−1.57). Because the hydroxyl group is strategically located on the Z substituent of the CTA, segments of these diblock copolymers are connected through a trithiocarbonate group, thus offering an easy way for subsequent growth of a third segment between PS and PCL. In contrast, an oxidatively unstable Sn(Oct) 2 ROP catalyst reacts with (1) leading to multimodal distributions of polymer chains with variable composition.

Branched copolymers are a special class of polymeric materials in which are reflected the combined effects of polymer segments and architectural constraints of the branched architecture. This study employed two methodologies to obtain copolymers with different branching density. In the first case, poly(hydroxyethyl methacrylate‐graft‐poly(ε‐caprolactone)‐block‐poly(ε‐caprolactone), P(HEMA‐g‐PCL)‐b‐PCL, copolymers were synthesized by a “grafting through” method in a three‐step reaction pathway involving ring opening polymerization (ROP) and radical addition fragmentation transfer (RAFT) polymerization. In the second case, a combination of simultaneous “grafting through” and “grafting from” methods in a one‐pot RAFT and ROP reaction afforded P(HEMA‐co‐HEMA‐g‐PCL)‐b‐PCL comb‐like copolymers with comparatively less dense branching. Samples with molar masses between 5500 and 46 000 g mol−1 and polydispersity indexes (Mw/Mn) lower than 1.3 were successfully obtained through both approaches. According to thermal analyses, the presence of branches reduces PCL melting temperature by as much as 20 °C, without affecting thermal stability. This fact was particularly evident for the most densely branched copolymers with higher molar masses. Nonisothermal crystallization process was successfully described using Ozawa's method, which showed a clear dependence of crystallization rate and cooling on grafting density.

Summary In this work we report the synthesis of poly(hydroxyethyl‐methacrylate‐graft‐polycaprolactone)‐block‐poly(caprolactone) copolymers, P(HEMA‐g‐PCL)‐b‐PCL, by combining ring‐opening polymerization (ROP) and reversible addition‐fragmentation chain‐transfer polymerization (RAFT). The successful synthesis of the targeted “comb‐like” block copolymers obtained was confirmed by 1H‐Nuclear Magnetic Resonance, Fourier Transform Infrared Spectroscopy and Size Exclusion Chromatography. Thermal behavior of the copolymers was studied by Differential Scanning Calorimetry, and their thermal stability was investigated by modulated thermogravimetric analysis. In this sense, the “comb‐like” block copolymers exhibited controlled molar masses between 6,000 g/mol and 45,000 g/mol, and polydispersity indexes lower than 1.3. Besides, thermal analysis evidenced a noticeable reduction in the melting temperature compared with linear PCL homopolymer, as well as, in the activation energy for the degradation process.

The intracellular delivery of nucleic acids requires a vector system as they cannot diffuse across lipid membranes. Although polymeric transfecting agents have been extensively investigated, none of the proposed gene delivery vehicles fulfill all of the requirements needed for an effective therapy, namely, the ability to bind and compact DNA into polyplexes, stability in the serum environment, endosome-disrupting capacity, efficient intracellular DNA release, and low toxicity. The challenges are mainly attributed to conflicting properties such as stability vs efficient DNA release and toxicity vs efficient endosome-disrupting capacity. Accordingly, investigations aimed at safe and efficient therapies are still essential to achieving gene therapy clinical success. Taking into account the mentioned issues, herein we have evaluated the DNA condensation ability of poly(ethylene oxide)113-b-poly[2-(diisopropylamino)ethyl methacrylate]50 (PEO113-b-PDPA50), poly(ethylene oxide)113-b-poly[2-(diethylamino)ethyl methacrylate]50 (PEO113-b-PDEA50), poly[oligo(ethylene glycol)methyl ether methacrylate]70-b-poly[oligo(ethylene glycol)methyl ether methacrylate10-co-2-(diethylamino)ethyl methacrylate47-co-2-(diisopropylamino)ethyl methacrylate47] (POEGMA70-b-P(OEGMA10-co-DEA47-co-DPA47), and poly[oligo(ethylene glycol)methyl ether methacrylate]70-b-poly{oligo(ethylene glycol)methyl ether methacrylate10-co-2-methylacrylic acid 2-[(2-(dimethylamino)ethyl)methylamino]ethyl ester44} (POEGMA70-b-P(OEGMA10-co-DAMA44). Block copolymers PEO113-b-PDEA50 and POEGMA70-b-P(OEGMA10-co-DEA47-co-DPA47) were evidenced to properly condense DNA into particles with a desirable size for cellular uptake via endocytic pathways (R(H) ≈ 65-85 nm). The structure of the polyplexes was characterized in detail by scattering techniques and atomic force microscopy. The isothermal titration calorimetric data revealed that the polymer/DNA binding is endothermic; therefore, the process in entropically driven. The combination of results supports that POEGMA70-b-P(OEGMA10-co-DEA47-co-DPA47) condenses DNA more efficiently and with higher thermodynamic outputs than does PEO113-b-PDEA50. Finally, circular dichroism spectroscopy indicated that the conformation of DNA remained the same after complexation and that the polyplexes are very stable in the serum environment.

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Ring-opening homo- and co-polymerization reactions of ϵ-caprolactone were performed by employing anionic polymerization (high vacuum techniques) and lithium silanolates (LS) as initiators. LS were obtained by reaction between hexamethyl(cyclotrisiloxane) and sec-Bu–Li+, or from living poly(dimethylsiloxanyl)lithium chains. The results indicated that LS are efficient initiators for the ring-opening polymerization of ϵ-caprolactone, providing the respective homogeneous polymers in good yields.

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