In this study, the synthesis, chemical modification and self-assembly in aqueous media of novel temperature-responsive and pH-responsive triblock terpolymers of the type (poly(diethylene glycol methyl ether methacrylate)-b-poly(2-(dimethylamino)ethyl methacrylate)-b-poly(lauryl methacrylate)) (PDEGMA-b-PDMAEMA-b-PLMA) are reported. The triblock terpolymers were synthesized via RAFT polymerization and molecular characterization was achieved by SEC, ¹H-NMR and FTIR spectroscopy. Methyl iodide (CH₃I) was utilized for chemical modification of the PDMAEMA blocks to increase the overall solubility of the triblock terpolymers in aqueous media and to obtain permanent positive charges, converting them to temperature-responsive block polyelectrolytes. PDEGMA-b-PDMAEMA-b-PLMA triblock terpolymers and their quaternized analogs self-assemble in aqueous media forming spherical micellar structures consisting of a hydrophobic PLMA core and stimuli-responsive PDMAEMA and PDEGMA corona, as evidenced by light scattering measurements. The dimensions of the formed micelles were influenced noticeably by variations in the solution temperature and pH. Moreover, we examine the formation of micelleplexes between quaternized PDEGMA-b-QPDMAEMA-b-PLMA thermoresponsive micelles and DNA molecules. The complexation capability of the formed micelleplexes was investigated by ethidium bromide quenching assays utilizing fluorescence spectroscopy techniques and UV-vis spectroscopy. Light scattering techniques are utilized in order to determine the structural characteristics of the formed micelleplexes. The quaternized terpolymer micelles effectively interact with nucleic acid molecules with their surface charge and their size depending on the composition of block terpolymers, the N/P ratio, and the increase of temperature above the LCST value of the temperature responsive PDEGMA block.

中文翻译：

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PDEGMA-b-PDMAEMA-b-PLMA 三嵌段三元共聚物及其阳离子类似物：合成、刺激响应自组装和胶束复合物形成

在这项研究中，新型温度响应性和 pH 响应性三嵌段三元共聚物（聚（二甘醇甲醚甲基丙烯酸酯）-b-聚（2-（二甲氨基）乙基）的合成、化学改性和在水介质中的自组装报道了(PDEGMA- b - PDMAEMA- b -PLMA)。三嵌段三元共聚物通过RAFT 聚合合成，并通过 SEC、 ¹ H-NMR 和 FTIR 光谱进行分子表征。碘甲烷 (CH ₃ I) 用于 PDMAEMA 嵌段的化学改性，以增加三嵌段三元共聚物在水介质中的总体溶解度并获得永久正电荷，将其转化为温度响应型嵌段聚电解质。 PDEGMA- b -PDMAEMA- b -PLMA 三嵌段三元共聚物及其季铵化类似物在水介质中自组装，形成由疏水性 PLMA 核和刺激响应性 PDMAEMA 和 PDEGMA 冠组成的球形胶束结构，如光散射测量所证明。形成的胶束的尺寸明显受到溶液温度和 pH 值变化的影响。此外，我们还研究了季铵化 PDEGMA- b -QPDMAEMA - b -PLMA 热响应胶束和 DNA 分子之间胶束复合物的形成。利用荧光光谱技术和紫外可见光谱通过溴化乙锭猝灭测定研究了所形成的胶束复合物的络合能力。利用光散射技术来确定所形成的胶束复合物的结构特征。季铵化三元共聚物胶束有效地与核酸分子相互作用，其表面电荷和尺寸取决于嵌段三元共聚物的组成、N/P比以及温度高于温度响应性PDEGMA嵌段的LCST值的温度升高。