Dynamic combinatorial chemistry (DCC) is an ideal tool used to create complex chemical systems, where a variety of components are produced in a combinatorial way by linking building blocks through reversible chemical bonds under thermodynamic control. When changing experimental conditions or adding templates in the library, the equilibrium is shifted, while some specific components that may have non-covalent interactions with the template will be selected and amplified. The dynamic nature of DCC makes it suitable for exploring new functional molecules, such as catalysts, receptors, drug discovery, and materials.

In this thesis, several building blocks were synthesized for preparing functional macrocycles through DCC. In part 1, a molecular mutualistic relationship was found in a library containing three kinds of building blocks. Thermodynamic and kinetic analysis revealed the details of the emergence of mutualism in the library.

In part 2, a building block containing an arginine group was synthesized, which could self-synthesize into macrocycles, and then assemble with doxorubicin and siRNA to form nanoparticles. The macrocyclic delivery system with high drug loading capacity showed pH- and redox-responsiveness for the release. In addition, the macrocyclic delivery system exhibited good biocompatibility, enhanced cellular uptake ability, and synergistic therapeutic effects against cancer cells.

In part 3, an azobenzene-based building block was synthesized, which could self-synthesize into dimeric macrocycles, and then self-assemble with a bolaform surfactant to form supramolecular hydrogel. The hydrogel demonstrated thermal sensitivity and self-healing capability, and could be processed into the humidity-responsive films with considerable mechanical strength. A series kind of actuators that could programmable move triggered by humidity variation were designed. In addition, a new type of autonomous energy transducer was prepared that could transduce mechanical energy into electricity continuously.