Center for Biotechnology and Interdisciplinary Studies (CBIS) and New York State Center for Polymer Synthesis, Rensselaer Polytechnic Institute, Troy, NY, USA.
Org Biomol Chem. 2018 Oct 10;16(39):7178-7190. doi: 10.1039/c8ob01655k.
Structurally complex biosynthesized building blocks whose structures can be systematically varied are of great interest for the synthesis of manipulable self-organizing supramolecular systems. Sophorolipids (SLs) are an important class of glycolipid biosurfactants that consists of a sophorose (glucose disaccharide) polar head group that allows structural diversification by full or selective acetylation at the 6'- and 6''-positions. Porphyrins are a group of naturally-occurring heterocyclic macromolecular organic compounds that have efficient charge transfer properties. Herein we describe the synthesis of SL-porphyrin conjugates where the number of sophorolipid arms, availability of hydrogen bonding sophorose hydroxyl groups and rigidity of the lipid chain were systematically varied. SLs differing in 'sophorose acetylation' and 'lipid unsaturation' were conjugated to zinc-porphyrin dyes by copper(i)-catalyzed azide-alkyne cycloaddition (CuAAC) 'click' chemistry. Mono-, di-, and tetra-conjugation of SL-arms to the zinc-porphyrin core provided variation in SL-arm steric effects. UV-vis spectra in methanol/water reveal features indicative of supramolecular J-type aggregates. The synthesized compounds were designed to provide a library of unique bio-based molecules with built-in variation in non-covalent interactions, hydrogen-bonding, π-π stacking, metal-ligand coordination, dipole-dipole, van der Waals, and hydrophobic interactions for future interrogation of supramolecular self-assembly into functional materials for electro-optical applications.
具有结构复杂性的生物合成构建块，其结构可以系统地变化，对于可操纵的自组织超分子系统的合成非常重要。槐糖脂（SL）是一类重要的糖脂生物表面活性剂，由槐糖（葡萄糖二糖）极性头基组成，通过在 6'位和 6''位的完全或选择性乙酰化允许结构多样化。卟啉是一类天然存在的杂环大分子有机化合物，具有有效的电荷转移特性。本文描述了 SL-卟啉缀合物的合成，其中槐糖脂臂的数量、氢键槐糖羟基的可用性和脂质链的刚性得到了系统的变化。通过铜（I）-催化的叠氮-炔烃环加成（CuAAC）“点击”化学，将具有不同“槐糖乙酰化”和“脂质不饱和”的 SL 与锌卟啉染料偶联。SL 臂与锌卟啉核心的单、二和四偶联提供了 SL 臂空间位阻效应的变化。甲醇/水中的 UV-vis 光谱显示出超分子 J 型聚集的特征。所合成的化合物旨在提供一系列独特的基于生物的分子库，这些分子具有内置的非共价相互作用、氢键、π-π 堆积、金属配体配位、偶极-偶极、范德华和疏水性相互作用的变化，以便将来对超分子自组装成用于电光应用的功能材料进行探究。
