Shao Yu, Ding Minyuan, Xu Yujie, Zhao Fangjia, Dai Hui, Miao Xia-Ran, Yang Shuguang, Li Hui
State Key Laboratory for Modification of Chemical Fibers and Polymer Materials and College of Material Science and Engineering, Center for Advanced Low-Dimension Materials, Donghua University, Shanghai 201620, China.
School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China.
Molecules. 2017 Apr 21;22(4):622. doi: 10.3390/molecules22040622.
Shape has been increasingly recognized as an important factor for self-assembly. In this paper, a series of shape amphiphiles have been built by linking polyhedral oligomeric silsesquioxane (POSS) and a dendron via linkers of different lengths. Three conjugates of octahedral silsesquioxanes (T₈-POSS) and dendron are designed and synthesized and are referred to as isobutyl T₈-POSS gallic acid derivatives (BPOSS-GAD-1, BPOSS-GAD-2, BPOSS-GAD-3). These samples have been fully characterized by ¹H-NMR, C-NMR, Fourier transform infrared (FT-IR) spectroscopy and matrix-assisted laser desorption/ionization time of flight (MALDI-TOF) mass spectrometry to establish their chemical identity and purity. Driven by different interactions between POSS and dendron, ordered superstructure can be found upon self-assembly. The stabilities and structures of these samples are further studied by using differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS), wide-angle X-ray diffraction (WAXD), and molecular simulations. The results show that their melting points range from 74 °C to 143 °C and the molecular packing schemes in the assemblies can form lamellar structure of BPOSS-GAD-3 as determined by the different linkers.
形状已日益被视为自组装的一个重要因素。在本文中，通过不同长度的连接体将多面体低聚倍半硅氧烷（POSS）与树枝状分子相连，构建了一系列形状两亲物。设计并合成了三种八面体倍半硅氧烷（T₈-POSS）与树枝状分子的共轭物，它们被称为异丁基T₈-POSS没食子酸衍生物（BPOSS-GAD-1、BPOSS-GAD-2、BPOSS-GAD-3）。这些样品已通过¹H-NMR、C-NMR、傅里叶变换红外（FT-IR）光谱和基质辅助激光解吸/电离飞行时间（MALDI-TOF）质谱进行了全面表征，以确定其化学特性和纯度。在POSS与树枝状分子之间不同相互作用的驱动下，自组装时可发现有序的超结构。通过差示扫描量热法（DSC）、小角X射线散射（SAXS）、广角X射线衍射（WAXD）和分子模拟进一步研究了这些样品的稳定性和结构。结果表明，它们的熔点范围为74℃至143℃，并且由不同的连接体决定，组装体中的分子堆积方式可形成BPOSS-GAD-3的层状结构。
