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1.南京邮电大学有机电子与信息显示国家重点实验室培育基地 信息材料与纳米技术研究院 江苏先进生物与化学制造协同创新中心 南京 210023
2.南京工业大学江苏省柔性电子重点实验室 先进材料研究院江苏先进生物与化学制造协同创新中心 南京 211816
Published:2017-6,
Received:11 October 2016,
Revised:6 December 2016,
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Xiao-zhen Li, Si-chao Tian, Peng-fei Sun, Qu-li Fan, Wei Huang. Preparation and Properties Investigation on a Kind of Pseudopolyrotaxane Hydrogel with High Intensity. [J]. Acta Polymerica Sinica (6):952-958(2017)
Xiao-zhen Li, Si-chao Tian, Peng-fei Sun, Qu-li Fan, Wei Huang. Preparation and Properties Investigation on a Kind of Pseudopolyrotaxane Hydrogel with High Intensity. [J]. Acta Polymerica Sinica (6):952-958(2017) DOI: 10.11777/j.issn1000-3304.2017.16311.
通过点击化学在聚乙二醇单甲醚(MPEG)端基分别修饰了葡萄糖(Glc)、甘露糖(Man)和半乳糖(Gal),制备了一系列端基为糖的聚乙二醇单甲醚(MPEG-Glc、MPEG-Man和MPEG-Gal),此类端基为糖的MPEG和
α
-环糊精(
α
-CD)混合后能够形成稳定的准聚轮烷(PPR)水凝胶,而端基没有修饰糖的MPEG和
α
-CD只能形成黏度较大的溶液而无法形成稳定存在的凝胶.通过流变仪测试可知水凝胶的弹性模量高达1.0×10
5
Pa,远大于文献中通过黏土等增强的PPR水凝胶的强度,我们认为该MPEG端基的糖之间能够形成新的“糖交联”点从而有效提高了凝胶的强度.通过向水凝胶中加入和MPEG端基的糖具有相互作用的苯硼酸半酯聚合物(PNIPAM-
co
-PBOB)或刀豆蛋白(ConA),发现在凝胶中加入PNIPAM-
co
-PBOB或ConA后可明显降低PPR水凝胶的强度.通过扫描电镜(SEM)和X射线衍射(XRD)对水凝胶的形貌以及微观结构进行表征分析,发现此凝胶的微观结构和文献中报道的PPR水凝胶基本一致,进一步证明了上述结论.
As animportant member of supramolecular hydrogel
pseudopolyrotaxane (PPR) hydrogel has attracted tremendous attention in recent years due to its good biocompatibility. Compared with conventional approaches reported
a new method was developed for PPR hydrogel preparation in this study
which can increase the strength of the hydrogel more efficiently. First
monoaccharide group-functionalized methoxypolyethylene glycols (MPEG)(MPEG-Glc
MPEG-Man and MPEG-Gal) were synthesizedby click chemistry. After that
a series of PPR hydrogels (Glc-PPR
Man-PPR and Gal-PPR) with high stability and strengthwere successfully prepared
via
the "host-guest" interactions between
α
-CD and monoaccharide group-functionalized MPEG(MPEG-Glc
MPEG-Man and MPEG-Gal
respectively). However
similar hydrogel cannot be obtained using
α
-CD and MPEG without monoaccharide modification. The properties of Glc-PPR
Man-PPR and Gal-PPR were characterizedby rheometer test
X-ray diffraction (XRD) and scan electron microscopy (SEM).Surprisingly
rheometer test results indicated that the elasticity modulus of Glc-PPR
Man-PPR and Gal-PPR could be up to 1.0 × 10
5
Pa
which was much higher than that of the clay-enhanced hydrogel in the previous reports. As for this phenomenon
we propose that new sugar cross-linking agents from "carbohydrate-carbohydate interaction" have constructed among monoaccharide terminals of MPEG
so that the strength of Glc-PPR
Man-PPR and Gal-PPR could be improved efficiently. Furthermore
in order to demonstrate the mechanism of the strength enhancement of PPR hydrogel
phenylboronic acid cyclic monoester (PNIPAM-
co
-PBOB) and concanavalin A (Con A) were added into Glc-PPR
Man-PPR and Gal-PPR
respectively to eliminate the sugar cross-linking agents
which led to a significant decrease in the strengthof Glc-PPR
Man-PPR and Gal-PPR. SEM and XRD results showed that the microstructures of Glc-PPR
Man-PPR and Gal-PPR were basically identical withPPR hydrogel reported in the references
which further confirmed that the PPR hydrogel was prepared successfully. Given its many merits of high intensity
non-toxicity and excellent biocompatibility of the obtained PPR hydrogel
it is expected that the PPR as prepared here will play an important role in drug delivery and biomedical engineering.
α-环糊精包结络合PPR水凝胶糖-糖相互作用
α-CyclodextrinsHost-guest inclusion complexationPPR hydrogelCarbohydrate-carbohydate interaction
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