Photoinduced Charge Separation Processes in Supramolecular Triad Systems

The nonadiabatic electron transfers in donor-acceptor-acceptor systems are investigated using three potential energy surfaces and two reaction coordinates via the stochastic Liouville equation to describe time evolution of the three excited electronic states: (1) D*-A-A, (2) D$\text{}^{+}$-A$\text{}^{-}$-A and (3) D$\text{}^{+}$-A-A$\text{}^{-}$. The electronic dephasing processes are taken into account phenomenologically in terms of dephasing constants. The couplings between surfaces are effective along the intersections of pairs of surfaces in the two-dimensional coordinate space. Special situations occur in the reaction coordinate space when three surfaces are nearly degenerate. The interplay between the sequential electron transfer processes and the superexchange process is analysed for different: reorganization energies, electronic coupling, free energies for the electron transfer, dephasing rates, and temperature. The time dependent contribution of the superexchange process to the charge separation in the triad system is analysed using the time dependent rate functions. It is shown that in the nonadiabatic limit of electron transfer the influence of the electronic dephasing processes for low barrier reactions can be accounted for by appropriate changes in the reorganization energies. The present model is compared with the experimental results concerning the charge separation in the bacterial photosynthetic reaction centers

Acne Treatment Based on Selective Photothermolysis of Sebaceous Follicles with Topically Delivered Light-Absorbing Gold Microparticles

The pathophysiology of acne vulgaris depends on active sebaceous glands, implying that selective destruction of sebaceous glands could be an effective treatment. We hypothesized that light-absorbing microparticles could be delivered into sebaceous glands, enabling local injury by optical pulses. A suspension of topically applied gold-coated silica microparticles exhibiting plasmon resonance with strong absorption at 800 nm was delivered into human pre-auricular and swine sebaceous glands in vivo, using mechanical vibration. After exposure to 10–50 J cm−2, 30 milliseconds, 800 nm diode laser pulses, microscopy revealed preferential thermal injury to sebaceous follicles and glands, consistent with predictions from a computational model. Inflammation was mild; gold particles were not retained in swine skin 1 month after treatment, and uptake in other organs was negligible. Two independent prospective randomized controlled clinical trials were performed for treatment of moderate-to-severe facial acne, using unblinded and blinded assessments of disease severity. Each trial showed clinically and statistically significant improvement of inflammatory acne following three treatments given 1–2 weeks apart. In Trial 2, inflammatory lesions were significantly reduced at 12 weeks (P=0.015) and 16 weeks (P=0.04) compared with sham treatments. Optical microparticles enable selective photothermolysis of sebaceous glands. This appears to be a well-tolerated, effective treatment for acne vulgaris