More is different: progressive β-thiolation induced-porphyrin aggregation switches singlet oxygen photosensitization.

Incorporating sulfur atoms into photosensitizers (PSs) has been well-established to populate triplet states and increase singlet oxygen (O) production when exposed to light. In this work, we found that progressive thiolation of porphyrin β-periphery does promote intersystem crossing (ISC) between triplets and singlets, as seen in the excited state dynamics in dichloromethane or PS nanoparticles in water. However, in the latter case, more sulfur substitution deactivates O photosensitization, in contrast to the expected trend observed in dichloromethane.

BOINPYs: facile synthesis and photothermal properties triggered by photoinduced nonadiabatic decay.

Photothermal agents (PTAs) represent a core component of photothermal therapy (PTT). However, the current photothermal dyes are almost derived from well-known chromophores such as porphyrins, cyanine, and BODIPYs, and the design of new chromophores as versatile building blocks for PTA is considerably challenging because of the complexity of the modulation of excited-states. Herein, we adopted the concept of photoinduced nonadiabatic decay (PIND) to develop a photothermal boron-containing indoline-3-one-pyridyl chromophore (.

Biomimetically constructing a hypoxia-activated programmable phototheranostics at the molecular level.

The hypoxic microenvironment is considered the preponderant initiator to trigger a cascade of progression and metastasis of tumors, also being the major obstacle for oxygen consumption therapeutics, including photodynamic therapy (PDT). In this work, we report a programmable strategy at the molecular level to modulate the reciprocal interplay between tumor hypoxia, angiogenesis, and PDT outcomes by reinforcing synergistic action between a HO scavenger, O generator and photosensitizer. The modular combination of a catalase biomimetic (tri-manganese cryptand, 1) and a photosensitizer (Ce6) allowed the rational design of a cascade reaction beginning with dismutation of HO to O under hypoxic conditions to enhance photosensitization and finally photooxidation.

Rational design of an "all-in-one" phototheranostic.

We report here porphodilactol derivatives and their corresponding metal complexes. These systems show promise as "all-in-one" phototheranostics and are predicated on a design strategy that involves controlling the relationship between intersystem crossing (ISC) and photothermal conversion efficiency following photoexcitation. The requisite balance was achieved by tuning the aromaticity of these porphyrinoid derivatives and forming complexes with one of two lanthanide cations, namely Gd and Lu.