Green Layer-by-Layer Assembly of Porphyrin/G-Quadruplex-Based Near-Infrared Nanocomposite Photosensitizer with High Biocompatibility and Bioavailability.

A simple and green layer-by-layer assembly strategy is developed for the preparation of a highly bioavailable nanocomposite photosensitizer by assembling near-infrared (NIR) light-sensitive porphyrin/G-quadruplex complexes on the surface of a highly biocompatible nanoparticle that is prepared via Zn2+-assisted coordination self-assembly of an amphiphilic amino acid. After being efficiently delivered to the target site and internalized into tumor cells via enhanced permeability and retention effect and interactions between aptamers and tumor markers, the as-prepared nanoassembly can be directly used as an NIR light-responsive photosensitizer for tumor photodynamic therapy (PDT) since the porphyrin/G-quadruplex complexes are exposed on the nanoassembly surface and kept in an active state. It can also disassemble under the synergistic stimuli of an acidic pH environment and overexpressed glutathione, leasing more efficient porphyrin/G-quadruplex composite photosensitizers while reducing the interference caused by glutathione-dependent 1O2 consumption. Since the nanoassembly can work no matter if it is disassembled or not, the compulsory requirement for in vivo photosensitizer release is eliminated, thus resulting in the great improvement of the bioavailability of the photosensitizer. The PDT applications of the nanoassembly were well demonstrated in both in vitro cell and in vivo animal experiments.

Dinuclear HgII tetracarbene complex-triggered aggregation-induced emission for rapid and selective sensing of Hg2+ and organomercury species.

Rapid, reliable and highly selective detection of mercury species, including Hg2+ ions and organomercury, is of significant importance for environmental protection and human health. Herein, a new fluorescent dye 1,1,2,2-tetrakis[4-(3-methyl-1H-benzimidazol-1-yl)phenyl ethylene tetraiodide (Tmbipe) with aggregation-induced emission (AIE) potential was prepared and characterized. The presence of four positively charged methylated benzimidazole groups endows Tmbipe with excellent water solubility and almost undetectable background fluorescence. However, it can coordinate with two Hg2+ ions or two organomercury molecules (e.g. methylmercury and phenylmercury) to form a planar dinuclear HgII tetracarbene complex, which can then self-aggregate to turn on AIE fluorescence. Such a fluorescence turn-on process can be completed in 3 min. In addition, synergic rigidification of the tetraphenylethylene-bridged Tmbipe molecule by mercury-mediated chelate ring formation and subsequent aggregation results in obviously higher fluorescence enhancement than that given by the single aggregation-induced one. Low background, high fluorescence enhancement and rapid response time make Tmbipe a good fluorescent probe for reliable, sensitive and highly selective quantitation of both inorganic and organic mercury species. This probe was also demonstrated to work well for identification of mercury species accumulation in living cells.

Cationic porphyrins with large side arm substituents as resonance light scattering ratiometric probes for specific recognition of nucleic acid G-quadruplexes.

Specific G-quadruplex-probing is crucial for both biological sciences and biosensing applications. Most reported probes are focused on fluorescent or colorimetric recognition of G-quadruplexes. Herein, for the first time, we reported a new specific G-quadruplex-probing technique-resonance light scattering (RLS)-based ratiometric recognition. To achieve the RLS probing of G-quadruplexes in the important physiological pH range of 7.4-6.0, four water soluble cationic porphyrin derivatives, including an unreported octa-cationic porphyrin, with large side arm substituents were synthesized and developed as RLS probes. These RLS probes were demonstrated to work well for ratiometric recognition of G-quadruplexes with high specificity against single- and double-stranded DNAs, including long double-stranded ones. The working mechanism was speculated to be based on the RLS signal changes caused by porphyrin protonation that was promoted by the end-stacking of porphyrins on G-quadruplexes. This work adds an important member in G-quadruplex probe family, thus providing a useful tool for studies on G-quadruplex-related events concerning G-quadruplex formation, destruction and changes in size, shape and aggregation. As a proof-of-concept example of applications, the RLS probes were demonstrated to work well for label-free and sequence-specific sensing of microRNA. This work also provides a simple and useful way for the preparation of cationic porphyrins with high charges.