Studies On Design,synthesis,self-assembly And Applications Of BODIPY Derivatives

BODIPY is a class of compounds with difluoroboron dipyrromethene(BODIPY)as the central nucleus;it has excellent photochemical and photophysical properties(good chemical and photostability,high molar extinction coefficient and fluorescence quantum production rate,etc.),and contains a number of chemically modified sites.And their absorption and emission wavelengths can be readily tuned to reach near-infrared regions that are critical to biomedicine,such as biofluorescence imaging,photodynamic therapy,etc.In addition,the application of BODIPY has also been extended to the fluorescent probe,supramolecular materials,photocatalysis and other fields.In this thesis,several novel BODIPY derivatives were synthesized based on the BODIPY matrix design,and their applications in supramolecular self-assembly,photodynamic therapy,visible-light catalysis and biomimetic imaging were studied.The following results were obtained:In Chapter 1,we introduce the development history of supramolecular chemistry,the research content of supramolecular chemistry,the basic principle of photochemistry,the principle of fluorescence signal transmission,and then introduces the research course and application field of BODIPY compounds.In Chapter 2,we designe and synthesize adamantane-modified BODIPY derivatives with a "three-arm" structure(denoted TAB).The use of ?-cyclodextrin(?-CD)and adamantane between the supramolecule "host-guest" interaction,the TAB and 7-mannose modified ?-cyclodextrin(denoted ?-CD-Man)co-assembly,formed a stable,uniform size nanoparticle(denoted TAB@?-CD-Man).As the mannose receptor is overexpressed on the surface of MDA-MB-231 breast cancer cells,the nanoparticles TAB@?-CD-Man can target into the breast cancer cells and release the photosensitizer TAB in the cells,LED irradiation can make the cancer cell apoptosis.In Chapter 3,we design and synthesize an amphiphilic BODIPY photosensitizer molecule(denoted BMA)with water solubility and responds to acid.The maximum absorption wavelength is 655 nm,which is the best window for photodynamic therapy area.The compounds have good solubility in water,and by dynamic light scattering and transmission electron microscope studies show that they exist in the form of vesicle aggregates in water,and the size distribution is about 150-180 nm.To the DMSO solution of the compound was added trifluoroacetic acid,and its fluorescence intensity was gradually increased with the addition of acid,indicating that it had a certain responsiveness to the acid.In Chapter 4,we design and synthesis of trimethylammonium cationically functionalized BODIPY photosensitizer(denoted TMA),which can be used in the solubilization of surfactant cetyltrimethylammonium bromide(CTAB)dissolved in water to form a homogeneous solution.The system can efficiently and selectively oxidize benzyl sulfide as sulfoxide compounds under the condition of air and green LED irradiation.Under the same conditions,it can also catalyze the catalysis of N-phenyltetrahydroisoquinoline and indole dehydrogenation coupling between the derivatives of the derivatives.In chapter 5,during the development of novel BODIPY derivatives,amphiphilic bola-type salicylaldehyde derivatives(denoted DSA)were synthesized and found to emit only weak fluorescence in aqueous solution.When adding ?-cyclodextrin(?-CD),DSA and ?-CD formed the [2]quasi-rotaxane complex(denoted DAS@?-CD)by the supramolecular host-guest interaction,leading to,Leading to a significant increase in fluorescence emission.It has been found that the quasi-rotane DAS@?-CD has a selective fluorescence imaging function for the mitochondria of cells.