This feature article summarized the recent progress on the construction of metallacycle/metallacage-cored supramolecular polymers by the hierarchical self-assembly, and the potential applications in the areas of light emitting, sensing, bio-imaging, delivery and release, etc., are also presented.

Triple-negative breast cancer (TNBC) is a special subtype of breast cancer, accounting for 10-20% of breast cancers with high intrinsic heterogeneity. Its unique immune microenvironment, including high expression of vascular endothelial growth factors, tumor infiltrating lymphocytes (TILs), tumor-associated macrophages (TAMs), and other molecules that promote the growth and migration of tumor cells, has been shown to play a dual role in the occurrence, growth, and metastasis of TNBC. Understanding the TNBC microenvironment is of great significance for the prognosis and treatment of TNBC. In this article, we describe the composition and function of immune cells in the TNBC microenvironment and summarize the major cytokine growth factors and chemokines in the TNBC microenvironment. Finally, we discuss the progress of TNBC, cytokine-induced killer cell therapy, and immune checkpoint therapy.

Synergistic therapy with nanocarriers is a promising strategy for effective cancer treatment. Here, we synthesized an amphiphilic rhomboidal metallacycle M, in which a glucose-modified pyridine ligand was used to improve water-solubility and an organoplatinum(II) receptor acted as a platinum-based anticancer agent. Moreover, because of the amphiphilic properties, M self-assembled into micelles or nanobelts at different concentrations, and a drug delivery system (DDS) was developed by encapsulating the anticancer drug doxorubicin (DOX) into the micelles. The morphology, cell uptake, cytotoxicity, internalization, and antitumor effect of the DDS were investigated. Under low intracellular pH conditions, the DDS disassembled to release the loaded DOX in situ. The designed DDS exhibited good biocompatibility, synergistic antitumor efficacy, and negligible adverse effects in a U87 tumor-bearing mice model.

Glioma is the most common malignant tumor of the central nervous system (CNS), with high degree of malignancy and poor prognosis. The gut microbiome (GM) is composed of microorganisms with different properties and functions, which play an important role in human physiology and biological activities. It has been proved that GM can affect the development of glioma through natural immunity, but whether GM can affect glioma through adaptive immunity and whether there are some microorganisms in the GM that may affect glioma growth still remain unclear. In our study, we evaluated the relationship between GM and glioma. We proved that (I) glioma growth can induce structural changes of mouse GM, including the decreased abundance of Bacteroidia and increased abundance of Firmicutes. (II) GM dysbiosis can downregulate Foxp3 expression in the brain and promote glioma growth. A balanced environment of GM can upregulate the expression of Foxp3 in the brain and delay the development of glioma. (III) The increased abundance of Bacteroidia is associated with accelerated glioma progression, while its decreased abundance is associated with delayed glioma progression, which may be one of the key microorganisms affecting glioma growth. This study is helpful to reveal the relationship between GM and glioma development and provide new ideas for adjuvant therapy of glioma.

Fluorescent supramolecular assemblies have attracted significant attention for their application as bioimaging agents, biological and chemical sensors, light‐emitting materials, and gene and drug vectors. The introduction of supramolecular coordination complexes constructed by the spontaneous formation of dative metal–ligand bonds through coordination‐driven self‐assembly into fluorescent supramolecular assemblies is of particular interest. This is because the introduction of metal coordination renders the synthesized assemblies excellent stability in addition to providing unique emissions that are different from the fluorescent ligands or metal ions. The discovery of aggregation‐induced emission (AIE), wherein the fluorophores are nonfluorescent in the molecular state, but become highly emissive in the aggregate state, presents new chances for fluorescent supramolecular assemblies since such assemblies are often required to be employed at high concentrations or in the solid state. This progress report provides a summary of the recent design, construction, and application of metallacycle/metallacage‐cored fluorescent supramolecular assemblies based on coordination‐driven self‐assembly, wherein the assemblies exhibit AIE properties. Example applications discussed in detail include light‐emitting materials, chemical and biological sensors, bioimaging agents, and cancer therapy. Moreover, several unsolved issues related to metallacycle/metallacage‐cored fluorescent supramolecular assemblies are discussed in the context of possible future applications of this field.

Conjugated polymers generally contain conjugated backbone structures with benzene, heterocycle, double bond, or triple bond, so that they have properties similar to semiconductors and even conductors. Their energy band gap is very small and can be adjusted via chemical doping, allowing for excellent photoelectric properties. To obtain prominent conjugated materials, numerous well-designed polymer backbones have been reported, such as polyphenylenevinylene, polyphenylene acetylene, polycarbazole, and polyfluorene. 4,4′-Difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY)-based conjugated polymers have also been prepared owing to its conjugated structure and intriguing optical properties, including high absorption coefficients, excellent thermal/photochemical stability, and high quantum yield. Most importantly, the properties of BODIPYs can be easily tuned by chemical modification on the dipyrromethene core, which endows the conjugated polymers with multiple functionalities. In this paper, BODIPY-based conjugated polymers are reviewed, focusing on their structures and applications. The forms of BODIPY-based conjugated polymers include linear, coiled, and porous structures, and their structure–property relationship is explored. Also, typical applications in optoelectronic materials, sensors, gas/energy storage, biotherapy, and bioimaging are presented and discussed in detail. Finally, the review provides an insight into the challenges in the development of BODIPY-based conjugated polymers.

Although boron dipyrromethene (BODIPY)-based metallacycles are expected to be promising candidates for imaging probes and therapeutic agents, their biomedical applications are restricted by their short absorption/emission wavelengths. In this work, we report a rhombic metallacycle M with broad absorption in the near-infrared (NIR) range and emissions at wavelengths >800 nm, which exhibits an efficient photothermal conversion capacity. Metallacycle M was encapsulated via Pluronic F127 to fit the biotic environment, resulting in the generation of F127/M nanoparticles (NPs) with high hydrophilicity and biocompatibility. In vitro studies demonstrated that the F127/M NPs underwent efficient cellular uptake and exhibited satisfactory photothermal therapeutic activity. Furthermore, in vivo experiments revealed that tumor growth was effectively inhibited, and the degree of undesirable biological damage was minimal in treatment with F127/M NPs and laser irradiation. Finally, the F127/M NPs could be visualized through NIR fluorescence imaging in living mice, thereby allowing their distribution to be monitored in order to enhance treatment accuracy during photothermal therapy. We envision that such BODIPY-based metallacycles will provide emerging opportunities for the development of novel therapeutic agents for biomedical applications.

Three rhomboidal metallacycles are formed by metal-ligand interactions. Due to the integration of AIEgens and ACQphores, metallacycles exhibit tunable emission. And the amphiphilic structures promote the formation of micelles used for cell imaging.