Europium- and Black Phosphorus-Functionalized Porphyrin as an l-Arginine Sensor and l-Arginine-Activated PDT/PTT Agent for Bacterial Treatment.

ABSTRACT

The attenuation of bacterial metabolism provides an adjunct to the treatment of bacterial infections. To develop a bacterial eradication agent, a bioactivatable material (BP@Eu-TCPP) was designed and synthesized by coordination and reduction of europium(III) with thin-layer black phosphorus (BP) and tetrakis (4-carboxyphenyl) porphyrin (TCPP). The existence of the P-Eu bond and Eu2+ 3d5/2 in X-ray photoelectron spectroscopy confirmed the successful synthesis of BP@Eu-TCPP. This material showed high fluorescence sensitivity to l-Arginine (l-Arg) and the main binding ratio of BP@Eu-TCPP to l-Arg was ca. 12 or 13, with the limit of detection of 4.0 µM. The material also showed good photothermal properties and stability, with a photothermal conversion efficiency of 37.3%. Although metal coordination has blocked the generation of 1O2, the addition of l-Arg to BP@Eu-TCPP can restore 1O2 generation upon red light-emitting diode (LED) light irradiation due to the formation of water-soluble Arg-TCPP species. Additionally, BP@Eu-TCPP was enabled to change the bacterial membrane and interfered with the bacterial iron absorption that effectively contributes to bacterial eradication. Such BP@Eu-TCPP is promised to be a novel material for the detection of l-Arg and l-Arg-activated photodynamic therapy.