Dynamics of Radical Ion Pairs following Photoinduced Electron Transfer in Solvents with Low and Intermediate Polarities.

Fluorescence quenching of p-xylene, naphthalene, or pyrene by fumaronitrile in apolar solvents and in solvents of intermediate polarities leads to weakly fluorescent radical ion pairs. This emission is assigned to ion pairs in close contact on the basis of their solvent polarity dependence, kinetics, and thermodynamics. The temperature-dependence of the intensity and fluorescence emission maxima of ion pairs in methyl acetate reveals that they have decay channels competitive with their thermal equilibration. The results presented in this work are consistent with the direct formation of contact ion pairs in weakly polar solvents and in solvents of intermediate polarities as the result of bimolecular photoinduced electron transfer reactions between aromatic hydrocarbons and nitriles. The implications of these findings in free-energy relationships of electron transfer reactions are discussed.

Soft machines that are resistant to puncture and that self seal.

A soft machine composed of a composite of elastomer and fibers resists puncture from sharp objects, and continues to operate even if punctured.

Rapid fabrication of pressure-driven open-channel microfluidic devices in omniphobic R(F) paper.

This paper describes the fabrication of pressure-driven, open-channel microfluidic systems with lateral dimensions of 45-300 microns carved in omniphobic paper using a craft-cutting tool. Vapor phase silanization with a fluorinated alkyltrichlorosilane renders paper omniphobic, but preserves its high gas permeability and mechanical properties. When sealed with tape, the carved channels form conduits capable of guiding liquid transport in the low-Reynolds number regime (i.e. laminar flow). These devices are compatible with complex fluids such as droplets of water in oil. The combination of omniphobic paper and a craft cutter enables the development of new types of valves and switches, such as "fold valves" and "porous switches," which provide new methods to control fluid flow.

Robotic tentacles with three-dimensional mobility based on flexible elastomers.

Soft robotic tentacles that move in three dimensions upon pressurization are fabricated by composing flexible elastomers with different tensile strengths using soft lithographic molding. These actuators are able to grip complex shapes and manipulate delicate objects. Embedding functional components into these actuators (for example, a needle for delivering fluid, a video camera, and a suction cup) extends their capabilities.

Analytical solution for time-resolved photoacoustic calorimetry data and applications to two typical photoreactions.

Time-resolved photoacoustic calorimetry (PAC) allows the measurement of lifetimes and energy fractions of molecular nonradiative deactivation processes, as well as structural volume changes associated with such processes. The photoinduced acoustic wave generated by a given photochemical sample, E(t), is the result of the convolution between the heat function H(t), describing the kinetics of the photochemical processes in the sample, and the instrument response given by a calorimetric reference wave, T(t). A relatively simple mathematical description of the T(t) wave parametrized by the rise time, frequencies and damping time of the transducer is presented for transducers of distinct frequencies. This description allows for a non-restrictive analytical solution of the convolution of the T(t) wave with the heat function. Comparison of the analytical solution with the experimental wave E(t) allows the determination of the fractions of excitation energy and lifetimes of the intermediate species. Published photochemical systems with two and three sequential decaying processes were analyzed to validate the efficacy of this method. This new method of analysis, and a software application that simulates E(t), allows a better understanding of the underlying physics through their phenomenological description.

Exothermic rate restrictions in long-range photoinduced charge separations in rigid media.

Glycerol/methanol (9:1) mixtures at 255 K behave as rigid media for photoinduced electron transfers that take place within a few hundred nanoseconds. This media also provides enough polarity and plasticity to accommodate charge separations with reaction free energies ranging from +3 to -34 kcal/mol. The distance dependence of the electron transfer rates from electronically excited aromatic hydrocarbons to nitriles in this medium is accurately described by an exponential decay constant of 1.65 per angstrom. These photoinduced electron transfers display, for the first time in charge separations between independent electron donors and acceptors, a free-energy relationship with a maximum rate followed by a decrease in the rate for more exothermic reactions. According to this free-energy relationship, Franck-Condon factors are maximized at DeltaG(0) approximately -15 kcal/mol. It is suggested that the inverted region observed for these first-order photoinduced charge separations originates from a slower increase of their reorganization energies with DeltaG(0) than that of the analogous second-order photoinduced charge separations, for which inverted regions have never been clearly observed.

Photoacid for extremely long-lived and reversible pH-jumps.

The ability to change the acidity of an aqueous solution within the time of a short laser pulse and use the resulting low pH to drive acid-catalyzed reactions in the irradiated volume opens news perspectives for the spatial and temporal control of a variety of processes. Persistent and reversible acidification of an aqueous solution is achieved with a new molecule, 1-(2-nitroethyl)-2-naphthol, that combines the fast photoacid properties of an aromatic alcohol with the slow proton transfer rates of a nitroalkane. The protons released in a few nanoseconds by pulsed laser excitation of the photoacid last for nearly one second in aqueous solutions. We show that acid-base equilibria with other species is established at the lower pHs of the irradiated volume, that the process is reversible and that it can be maintained under continuous irradiation.

Spectroscopic properties and photodynamic effects of new lipophilic porphyrin derivatives: efficacy, localisation and cell death pathways.

Photodynamic therapy (PDT) and photodynamic diagnostics (PDD) of cancer are based on the use of non-toxic dyes (photosensitisers) in combination with harmless visible light. This paper reports physicochemical properties, cell uptake, localisation as well as photodynamic efficiency of two novel lipophilic porphyrin derivatives, suitable for use as PDT sensitisers. Both compounds are characterised by high quantum yield of singlet oxygen generation which was measured by time-resolved phosphorescence. Photodynamic in vitro studies were conducted on three cancer cell lines. Results of cell survival tests showed negligible dark cytotoxicity but high phototoxicity. The results also indicate that cell death is dependent on energy dose and time following light exposure. Using confocal laser scanning microscopy both compounds were found to localise in the cytoplasm around the nucleus of the tumour cells. The mode of cell death was evaluated based on the morphological changes after differential staining. In summary, good photostability, high quantum yield of singlet oxygen and biological effectiveness indicate that the examined lipophilic porphyrin derivatives offer quite interesting prospects of photodynamic therapy application.

Excited-state proton transfer in gas-expanded liquids: the roles of pressure and composition in supercritical CO2/methanol mixtures.

Excited-state proton transfer from 5,8-dicyano-2-naphthol to methanol takes place in CO2/methanol mixtures, in the pressure and temperature ranges of supercritical CO2. The efficiency of the proton-transfer step decreases with the pressure. This is assigned to the perturbation of the methanol clusters solvating the naphthol.