New molecularly imprinted polymers (MIPs) for the recognition of barbiturates were synthesised by “bulk” polymerisation. These polymers were prepared using pentobarbital as the template in combination with a novel Hamilton receptor functional monomer. The solution binding properties of the monomer were assessed by NMR titration experiments, showing high affinity for barbiturates and lower affinity for related compounds lacking the ability to form as many hydrogen bonds. The properties of the MIP were assessed via equilibrium rebinding experiments and in the chromatographic mode, and compared to the behaviour of a control non-imprinted polymer (NIP). The MIP showed a far higher population of binding sites with higher affinity than the NIP which was reflected in the chromatographic evaluation, where the template and a related barbiturate were not eluted from the MIP within 60 min, while their retention was weak on the NIP, leading to extremely high imprinting factors. Other analytes were weakly retained by MIP and NIP, with those presented an acceptor-donor-acceptor array of hydrogen bonding sites most retained. Preliminary molecular modelling studies support the hypothesis that the presence of the template in the MIP synthesis “chooses” the conformation of the functional monomer that is “locked in” during the polymerisation.

用于识别巴比妥酸盐的新型分子印迹聚合物 (MIP) 是通过“本体”聚合合成的。这些聚合物是使用戊巴比妥作为模板结合新型汉密尔顿受体功能单体制备的。单体的溶液结合特性通过 NMR 滴定实验进行评估，显示对巴比妥酸盐的高亲和力和对缺乏形成尽可能多的氢键能力的相关化合物的低亲和力。MIP 的特性通过平衡再结合实验和色谱模式进行评估，并与对照非印迹聚合物 (NIP) 的行为进行比较。与 NIP 相比，MIP 显示出更多具有更高亲和力的结合位点，这反映在色谱评估中，其中模板和相关的巴比妥酸盐在 60 分钟内未从 MIP 中洗脱，而它们在 NIP 上的保留很弱，导致极高的印迹因子。MIP 和 NIP 对其他分析物的保留较弱，其中那些呈现氢键位点的受体-供体-受体阵列保留得最多。初步的分子建模研究支持这样一种假设，即 MIP 合成中模板的存在“选择”了在聚合过程中“锁定”的功能单体的构象。