1st generation dendrimers containing polar hydroxyl and both 1st and 2nd generation dendrimers with oxyethyl groups were obtained using a convergent approach and CuAAC reaction. Three types of dendrimer nuclei were utilized: the macrocyclic nucleus of calix[4]arene bearing 2/4 dendron and 2/4 alkyl fragments and the non-macrocyclic analog of calixarene bearing a one dendron/alkyl fragment. Nanoparticle tracking analysis reveals self-organization of the obtained dendrimers in aqueous solution into submicron/nanoparticles with sizes of 80–250 nm. The lowest CAC values in the series are possessed by tetra-alkyl substituted calix[4]arenes (1.6–1.8 μM), while the low molecular weight analog of calixarenes possesses a CAC one to two orders of magnitude larger (44–350 μM). When the obtained dendrimers were used as stabilizers of palladium nanoparticles, the formation of spherical palladium nanodendrites (50–60 nm) consisting of metal Pd and PdO was determined using TEM and SAED. The micellar effect of using stabilized palladium particles with dendrimers at concentrations higher than their CAC in the catalysis of Suzuki reactions and nitro aromatics reduction is shown. In the p-nitrophenol reduction reaction, the catalytic activity of the obtained systems (the maximum k_app in series was 0.47 min⁻¹) exceeds many known Pd-based systems.

中文翻译：

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具有杯[4]芳烃核心和极性羟基/乙氧基端基的基于环氧氯丙烷的 CuAAC 树枝状聚合物：合成、聚集和在催化中的应用


采用收敛方法和 CuAAC 反应获得了含有极性羟基的第一代树枝状聚合物以及含有乙氧基的第一代和第二代树枝状聚合物。使用三种类型的树枝状聚合物核：带有2/4树枝和2/4烷基片段的杯[4]芳烃的大环核和带有1个树枝/烷基片段的杯芳烃的非大环类似物。纳米颗粒跟踪分析揭示了所获得的树枝状聚合物在水溶液中自组织成尺寸为 80-250 nm 的亚微米/纳米颗粒。该系列中最低的 CAC 值是四烷基取代的杯[4]芳烃 (1.6–1.8 μM)，而杯芳烃的低分子量类似物的 CAC 值大一到两个数量级 (44–350 μM) 。当所获得的树枝状聚合物用作钯纳米粒子的稳定剂时，使用 TEM 和 SAED 测定了由金属 Pd 和 PdO 组成的球形钯纳米枝晶（50-60 nm）的形成。显示了在铃木反应和硝基芳烃还原的催化中，使用浓度高于其 CAC 的稳定钯颗粒和树枝状聚合物的胶束效应。在对硝基苯酚还原反应中，所得体系的催化活性（串联最大k _app 为0.47min ⁻¹ ）超过了许多已知的Pd基体系。