Control of Photoswitching Kinetics with Strong Light-Matter Coupling in a Cavity.

Most photochemistry occurs in the regime of weak light-matter coupling, in which a molecule absorbs a photon and then performs photochemistry from its excited state. In the strong coupling regime, enhanced light-matter interactions between an optical field and multiple molecules lead to collective hybrid light-matter states called polaritons. This strong coupling leads to fundamental changes in the nature of the excited states including multi-molecule delocalized excitations, modified potential energy surfaces, and dramatically altered energy levels relative to non-coupled molecules. The effect of strong light-matter coupling on covalent photochemistry has not been well explored. Photoswitches undergo reversible intramolecular photoreactions that can be readily monitored spectroscopically. In this work, we study the effect of strong light-matter coupling on the kinetics of photoswitching within optical cavities. Reproducing prior experiments, photoswitching of spiropyran/merocyanine photoswitches is decelerated in a cavity. Fulgide photoswitches, however, show the opposite effect, with strong coupling accelerating photoswitching. While modified merocyanine switching can be explained by changes in radiative decay rates or the amount of light in the cavity, modified fulgide switching kinetics suggest direct changes to excited-state reaction kinetics.

Simulating molecular polaritons in the collective regime using few-molecule models.

The study of molecular polaritons beyond simple quantum emitter ensemble models (e.g., Tavis-Cummings) is challenging due to the large dimensionality of these systems and the complex interplay of molecular electronic and nuclear degrees of freedom. This complexity constrains existing models to either coarse-grain the rich physics and chemistry of the molecular degrees of freedom or artificially limit the description to a small number of molecules. In this work, we exploit permutational symmetries to drastically reduce the computational cost of ab initio quantum dynamics simulations for large N. Furthermore, we discover an emergent hierarchy of timescales present in these systems, that justifies the use of an effective single molecule to approximately capture the dynamics of the entire ensemble, an approximation that becomes exact as N → ∞. We also systematically derive finite N corrections to the dynamics and show that addition of k extra effective molecules is enough to account for phenomena whose rates scale as 𝒪(N-k). Based on this result, we discuss how to seamlessly modify existing single-molecule strong coupling models to describe the dynamics of the corresponding ensemble. We call this approach collective dynamics using truncated equations (CUT-E), benchmark it against well-known results of polariton relaxation rates, and apply it to describe a universal cavity-assisted energy funneling mechanism between different molecular species. Beyond being a computationally efficient tool, this formalism provides an intuitive picture for understanding the role of bright and dark states in chemical reactivity, necessary to generate robust strategies for polariton chemistry.

Polariton Assisted Down-Conversion of Photons via Nonadiabatic Molecular Dynamics: A Molecular Dynamical Casimir Effect.

Quantum dynamics of the photoisomerization of a single 3,3'-diethyl-2,2'-thiacynine iodide molecule embedded in an optical microcavity was theoretically studied. The molecular model consisting of two electronic states and the reaction coordinate was coupled to a single cavity mode via the quantum Rabi Hamiltonian, and the corresponding time-dependent Schrödinger equation starting with a purely molecular excitation was solved using the Multiconfigurational Time-Dependent Hartree Method (MCTDH). We show that, for single-molecule strong coupling with the photon mode, nonadiabatic molecular dynamics produces mixing of polariton manifolds with differing number of excitations, without the need of counter-rotating light-matter coupling terms. Therefore, an electronic excitation of the molecule at the cis configuration is followed by the generation of two photons in the trans configuration upon isomerization. Conditions for this phenomenon to be operating in the collective strong light-matter coupling regime are discussed and found to be unfeasible for the present system, based on simulations of two molecules inside the microcavity. Yet, our finding suggests a new mechanism that, without ultrastrong coupling, achieves photon down-conversion by exploiting the emergent molecular dynamics arising in polaritonic architectures.

Schawannoma maligno epitelioide / Malignant epithelioid schawannoma

Presentamos 4 casos de Schawannoma maligno epitelioide, una rara neoplasia de nervios periféricos. Las edades de aparición oscilan entre 12 y 82 años con predominio masculino (3 casos) sobre muy infrecuente. Su pronóstico es muy ominoso, con menor sobrevida (15 a 20% en 5 años) para aquellos casos asociados con enfermedad de Von Recklinghausen, y mejor para aquellos con tumores menores de 5 cm localizados en porciones distales de extremidades (50 a 75%)

Metástasis en el bazo: frecuencia en 10.749 autopsias / Metastasis of the spleen:frecuency in 10.749 autopsys

Se estudiaron 10.749 autopsias durante el período de 1985 a 1988, donde se demostraron 11 casos de metástasis en el bazo. Eliminando las enfermedades linfoproliferativas, la incidencia fue de 0,1%. Las formas macroscópicas de nódulos múltiples los tumores epiteliales y los tipos histológicos, indiferenciados de los mismos, dominaron la frecuencia