Ultrafast photoinduced electron transfer (PIET) dynamics of a C₇₀-encapsulated bisporphyrin covalent organic polyhedron hybrid (C₇₀@COP-5) is studied in a nonpolar toluene medium with fluorescence and transient absorption spectroscopies. This structurally rigid donor (D)–acceptor (A) molecular hybrid offers a new platform featuring conformationally predetermined cofacial D–A orientation with a fixed edge-to-edge separation, R_EE (2.8 Å), without the aid of covalent bonds. Sub-picosecond PIET (τ_ET ≤ 0.4 ps) and very slow charge recombination (τ_CR ≈ 600 ps) dynamics are observed. The origin of these dynamics is discussed in terms of enhanced D–A coupling (V = 675 cm^–1) and extremely small reorganization energy (λ ≈ 0.18 eV), induced by the intrinsic structural rigidity of the C₇₀@COP-5 complex.

A series of hydrogels with intrinsic antifouling properties was prepared via surface-functionalization of poly(2-hydroxyethyl methacrylate) [p(HEMA)]-based hydrogels with the biomembrane-mimicking zwitterionic polymer, poly(2-methacryloyloxyethyl phosphorylcholine) [p(MPC)]. The p(MPC)-modified hydrogels have enhanced surface wettability, high water content retention (61.0%–68.3%), and good transmittance (>90%). Notably, the presence of zwitterionic MPC moieties at the hydrogel surfaces lowered the adsorption of proteins such as lysozyme and bovine serum albumin (BSA) by 73%–74% and 59%–66%, respectively, and reduced bacterial adsorption by approximately 10%–73% relative to the unmodified control. The anti-biofouling properties of the p(MPC)-functionalized hydrogels are largely attributed to the dense hydration layer formed at the hydrogel surfaces by the zwitterionic moieties. Overall, the results demonstrate that biocompatible and antifouling hydrogels based on p(HEMA)-p(MPC) structures have promising potential for application in biomedical materials.

The synthesis of three water-soluble lactose-modified 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY)-based photosensitizers with tumor-targeting capabilities is reported, including an investigation into their photodynamic therapeutic activity on three distinct cancer cell lines (human hepatoma Huh7, cervical cancer HeLa, and breast cancer MCF-7 cell lines). The halogenated BODIPY dyes exhibited a decreased fluorescence quantum yield compared to their non-halogenated counterpart, and facilitated the efficient generation of singlet oxygen species. The synthesized dyes exhibited low cytotoxicities in the dark and high photodynamic therapeutic capabilities against the treated cancer cell lines following irradiation at 530 nm. Moreover, the incorporation of lactose moieties led to an enhanced cellular uptake of the BODIPY dyes. Collectively, the results presented herein provide promising insights for the development of photodynamic therapeutic agents for cancer treatment.

A series of four lactose-modified BODIPY photosensitizers (PSs) with different substituents (-I, -H, -OCH₃, and -NO₂) in the para-phenyl moiety attached to the meso-position of the BODIPY core were synthesized; the photophysical properties and photodynamic anticancer activities of these sensitizers were investigated, focusing on the electronic properties of the different substituent groups. Compared to parent BODIPY H, iodine substitution (BODIPY I) enhanced the intersystem crossing (ISC) to produce singlet oxygen (¹O₂) due to the heavy atom effect, and maintained a high fluorescence quantum yield (Φ_F) of 0.45. Substitution with the electron-donating methoxy group (BODIPY OMe) results in a significant perturbation of occupied frontier molecular orbitals and consequently achieves higher ¹O₂ generation capability with a high Φ_F of 0.49, while substitution with the electron-withdrawing nitro group (BODIPY NO2) led a perturbation of unoccupied frontier molecular orbitals and induces a forbidden dark S₁ state, which is negative for both fluorescence and ¹O₂ generation efficiencies. The BODIPY PSs formed water-soluble nanoparticles (NPs) functionalized with lactose as liver cancer-targeting ligands. BODIPY I and OMe NPs showed good fluorescence imaging and PDT activity against various tumor cells (HeLa and Huh-7 cells). Collectively, the BODIPY NPs demonstrated high ¹O₂ generation capability and Φ_F may create a new opportunity to develop useful imaging-guided PDT agents for tumor cells.

In this study, a series of rationally designed emissive phenanthrene derivatives were synthesized and their aggregation-induced emission (AIE) properties in tetrahydrofuran (THF)/water mixtures were investigated. Two tetraphenylethene (TPE) segments were conjugated to both ends of the phenanthrene core at the para-positions and meta-positions, resulting in pTPEP and mTPEP derivatives, respectively. While the TPE-conjugated phenanthrene derivatives did not show any emission when dissolved in pure THF, they showed strong sky-blue emissions in water-THF mixtures, which is attributed to the restriction of intramolecular motions of TPE segments by aggregation. Furthermore, silica nanoparticles loaded with these AIE-active compounds were prepared and proved to be promising intracellular imaging agents.

We theoretically investigated the nitrogen substitution effect on the molecular structure and π-electron delocalization in linear nitrogen-substituted polycyclic aromatic hydrocarbons (N-PAHs). Based on the optimized molecular structures and magnetic field-induced parameters of fused bi- and tricyclic linear N-PAHs, we found that the local π-electron delocalization of subcycles (e.g., mono- and bicyclic constituent moieties) in linear N-PAHs is preserved, despite deviation from ideal structures of parent monocycles. The introduction of a fused five-membered ring with a pyrrolic N atom (N-5MR) in linear N-PAHs significantly perturbs the π-electronic condition of the neighboring fused six-membered ring (6MR). Monocyclic pyrrole exhibits substantial bond length alternations, strongly influencing the π-electronic systems of both the fused N-5MR and 6MR in linear N-PAHs, depending on the location of shared covalent bonds. A fused six-membered ring with a graphitic N atom in an indolizine moiety cannot generate monocyclic π-electron delocalization but instead contributes to the formation of polycyclic π-electron delocalization. This is evidenced by bifurcated diatropic ring currents induced by an external magnetic field. In conclusion, the satisfaction of Hückel’s 4n + 2 rule for both mono- and polycycles is crucial for understanding the overall π-electron delocalization. It is crucial to consider the unique characteristics of the three types of substituted N atoms and the spatial arrangement of 5MR and 6MR in N-PAHs.