高等学校化学学报
高等學校化學學報
고등학교화학학보
CHEMICAL JOURNAL OF CHINESE UNIVERSITIES
2014年
7期
1570-1578
,共9页
孙小成%杨浩%王建祖%马如江%安英丽%史林启
孫小成%楊浩%王建祖%馬如江%安英麗%史林啟
손소성%양호%왕건조%마여강%안영려%사림계
苯硼酸%二硫键%交联胶束%葡萄糖响应%氧化还原响应%双响应性胶束
苯硼痠%二硫鍵%交聯膠束%葡萄糖響應%氧化還原響應%雙響應性膠束
분붕산%이류건%교련효속%포도당향응%양화환원향응%쌍향응성효속
Boronic acid%Disulfidebond%Cross-linked micelle%Glucose-response%Redox-response%Dual-re-sponsive micelle
分别合成了苯硼酸修饰的嵌段聚合物聚乙二醇-b-聚(天冬氨酸-co-天冬酰氨基苯硼酸)[PEG-b-P(Asp-co-AspPBA)]和含有二硫键及多元二醇的小分子3,3’-二硫代二[1,2(S)-丙二醇](DTBPD)。以 DTBPD 为小分子交联剂,通过二醇单元与苯硼酸之间的共价酯化作用,诱导 PEG-b-P(Asp-co-AspPBA)自组装形成以苯硼酸环酯为核、 PEG 为壳的交联胶束。利用核磁共振氢谱和激光光散射对胶束的结构进行了表征,并分别测定了该胶束在葡萄糖和氧化-还原试剂二硫苏糖醇(DTT)刺激下的响应行为。结果表明, DTBPD 可与聚合物链上的苯硼酸形成苯硼酸环酯,通过交联作用诱导聚合物形成胶束。交联度不同时,胶束对于外界刺激(葡萄糖和 DTT 的响应行为也不同:随着 DTT 和葡萄糖浓度的增加,交联度高的胶束只发生响应性溶胀,交联度低的胶束则先溶胀,之后溶胀程度较大的部分胶束则发生解体,导致胶束的平均粒径减小。
分彆閤成瞭苯硼痠脩飾的嵌段聚閤物聚乙二醇-b-聚(天鼕氨痠-co-天鼕酰氨基苯硼痠)[PEG-b-P(Asp-co-AspPBA)]和含有二硫鍵及多元二醇的小分子3,3’-二硫代二[1,2(S)-丙二醇](DTBPD)。以 DTBPD 為小分子交聯劑,通過二醇單元與苯硼痠之間的共價酯化作用,誘導 PEG-b-P(Asp-co-AspPBA)自組裝形成以苯硼痠環酯為覈、 PEG 為殼的交聯膠束。利用覈磁共振氫譜和激光光散射對膠束的結構進行瞭錶徵,併分彆測定瞭該膠束在葡萄糖和氧化-還原試劑二硫囌糖醇(DTT)刺激下的響應行為。結果錶明, DTBPD 可與聚閤物鏈上的苯硼痠形成苯硼痠環酯,通過交聯作用誘導聚閤物形成膠束。交聯度不同時,膠束對于外界刺激(葡萄糖和 DTT 的響應行為也不同:隨著 DTT 和葡萄糖濃度的增加,交聯度高的膠束隻髮生響應性溶脹,交聯度低的膠束則先溶脹,之後溶脹程度較大的部分膠束則髮生解體,導緻膠束的平均粒徑減小。
분별합성료분붕산수식적감단취합물취을이순-b-취(천동안산-co-천동선안기분붕산)[PEG-b-P(Asp-co-AspPBA)]화함유이류건급다원이순적소분자3,3’-이류대이[1,2(S)-병이순](DTBPD)。이 DTBPD 위소분자교련제,통과이순단원여분붕산지간적공개지화작용,유도 PEG-b-P(Asp-co-AspPBA)자조장형성이분붕산배지위핵、 PEG 위각적교련효속。이용핵자공진경보화격광광산사대효속적결구진행료표정,병분별측정료해효속재포도당화양화-환원시제이류소당순(DTT)자격하적향응행위。결과표명, DTBPD 가여취합물련상적분붕산형성분붕산배지,통과교련작용유도취합물형성효속。교련도불동시,효속대우외계자격(포도당화 DTT 적향응행위야불동:수착 DTT 화포도당농도적증가,교련도고적효속지발생향응성용창,교련도저적효속칙선용창,지후용창정도교대적부분효속칙발생해체,도치효속적평균립경감소。
Phenylboronic acid modified polymer poly(ethylene glycol)-b-poly(aspartic acid-co-aspartamido-phenylboronic acid)[PEG-b-P(Asp-co-AspPBA)] as well as a cross-linker 3,3’-dithiobis[1,2(S)-propane-diol](DTBPD) which contained disulfide bond and dual-diol groups was successfully synthesized. PEG-b-P(Asp-co-AspPBA) could be mildly cross-linked by DTBPD based on the reaction of PBA and the dual-diol groups, leading to the formation of a novel dual-responsive micelle with boronic ester core and PEG shell. The structure, morphology, and the glucose / redox dual-responsive behavior of the micelles were systematically in-vestigated by nuclear magnetic resonance(NMR) spectrum and dynamic laser light scattering(DLS). It was demonstrated that the ratio of diol to PBA(D : B) had influence on the dual-responsive behavior of the mi-celles. At higher ratio of D : B, only responsive swelling of micelles was observed. While for the micelles with lower ratio of D : B, larger degree of swelling happened and the micelles gradually dissociated under higher concentrations of glucose ordithiothreitol(DTT). This kind of dual-responsive micelles may find application in drug delivery in the future.