Photopharmacology can be implemented in a way of regulating drug activities by light-controlling the molecular configuations. Three photochromic ligands (PCLs) that bind on one or two sites of GABARs and nAChRs were reported here. These multiphoton PCLs, including FIP-AB-FIP, IMI-AB-FIP, and IMI-AB-IMI, are constructed with an azobenzene (AB) bridge that covalently connects two fipronil (FIP) and imidacloprid (IMI) molecules. Interestingly, the three PCLs as well as FIP and IMI showed great insecticidal activities against Aedes albopictus larvae and Aphis craccivora. IMI-AB-FIP in both trans/cis isomers can be reversibly interconverted depending on light, accompanied by insecticidal activity decrease or increase by 1.5-2.3 folds. In addition, IMI-AB-FIP displayed synergistic effects against A. craccivora (LC50, IMI-AB-FIP = 14.84-22.10 μM, LC50, IMI-AB-IMI = 210.52-266.63 μM, LC50, and FIP-AB-FIP = 36.25-51.04 μM), mainly resulting from a conceivable reason for simultaneous targeting on both GABARs and nAChRs. Furthermore, modulations of wiggler-swimming behaviors and cockroach neuron function were conducted and the results indirectly demonstrated the ligand-receptor interactions. In other words, real-time regulations of receptors and insect behaviors can be spatiotemporally achieved by our two-photon PCLs using light.

Utilization of multiphotons to achieve high reduction potentials is a highly demanding but still challenging task for reductive cleavage of inert bonds. Herein, we report a new charge transfer approach that simultaneously excites the electron-rich dye and the radical anionic of the electron-deficient one for photocatalytic activation of aryl chlorides with high reduction potentials (Ered ≈ -1.9 to -2.9 V). Interactions between the tetraphenylbenzene-1,4,-diamine dyes in the large pores of metal-organic frameworks and the adsorbed 9,10-dicyanoanthracene partly endows charge transfer in the ground state. The first photoexcitation led to the formation charge separation pairs containing both radical cation and anion for second photon excitation. The possibility of modifying each absorption band of the two dyes independently innovated the resultant aryl radicals applied in various useful transformations, expanding multiphoton manifolds on both the dye scopes and reaction versions. A comparison of the catalytic performance between different structural patterns of metal-organic frameworks with the same ligand demonstrated that the incorporating of the organic dyes within the pores of the frameworks was essential to form charge-transfer species and accelerate the interesting chemical conversion.

Multiphoton absorption chromophores have emerged as an attractive class of fluorescent agents for bioimaging in recent years. Here, we first report a cyclometalated Iridium(III)-organotin(IV) dimetal complex, which exhibits efficient multiphoton (from two- to three-photon) fluorescence. The three-photon absorption of IrSn1 is located in the NIR-II (second near-infrared window (900-1700 nm)) region. IrSn1 obtained aggregation-induced emission (AIE), emitting bright orange fluorescence (595 nm). IrSn1 can specifically target tyrosine, which shows an obvious multiphoton fluorescence enhancement under NIR-II region. Importantly, IrSn1 is alsoprovided a visible antibacterial activity toward Staphylococcus aureus in vitro and in vivo. Two-photon fluorescence bioimages and stimulated emission depletion (STED) microscopy indicated that IrSn1 could specifically recognize the nuclear thus leading DNA breaking in Staphylococcus aureus and cancer cells.

Multiphoton electron extraction spectroscopy (MEES) is an analytical method for direct analysis of solids under ambient conditions in which the samples are irradiated by short UV laser pulses and the photocharges emitted are recorded as a function of the laser wavelength. The method is very sensitive, and many peaks are observed at wavelengths that are in resonance with the surface molecules. The analytical capabilities of MEES have recently been demonstrated, and here we perform a systematic comparison with some traditional spectroscopies that are commonly applied to material analysis. These include absorption, reflection, excitation and emission fluorescence, Raman, Fourier transform IR, and Fourier transform near-IR spectroscopies. The comparison is conducted for powders and for thin films of compounds that are active in all spectroscopies tested. Besides the obvious spectral parameters (signal-to-noise ratio, peak density, and resulting limits of detection), we introduce two additional variables-the spectral quality and the spectral quality density-that represent our intuitive perception of the analytical value of a spectrum. It is shown that by most parameters MEES is a superior analytical tool to the other methods tested for both sample morphologies.