Organic thin film photofaradaic pixels for on-demand electrochemistry in physiological conditions.

We report ultrathin organic photovoltaic elements optimized to run photofaradaic reactions in biological conditions. We demonstrate concurrent oxygen reduction to hydrogen peroxide and glucose oxidation. The devices are powered by deep-red irradiation in the tissue transparency window. We utilize bilayers of phthalocyanine, acting as the light absorber, and perylene diimide, functioning as both electron-acceptor and the hydrogen peroxide evolution electrocatalyst. These heterojunction bilayers are stable when irradiated in simulated physiological conditions, producing photovoltages sufficient to simultaneously drive cathodic oxygen reduction to H2O2 and anodic oxidation of glucose. We find that optimization of the anode metal is critical for sustained photofaradaic reactivity. Our results demonstrate a robust "wet" thin film photovoltaic with potential for physiological applications where localized electrochemical manipulation is desired, in particular the delivery of reactive oxygen species.

Photocurrent enhancement by a local electric field on DNA-modified electrodes covered with gold nanoparticles.

We here describe a photocurrent generation system exploiting gold nanoparticles (AuNPs) that cover perylenediimide-DNA complexes on electrode surfaces. Enhanced photocurrents were generated by the irradiation of the AuNPs, attributed to the efficient excitation of the perylenediimides by a local electric field on the surface of the AuNPs.

Visible light-harvesting perylenebisimide-fullerene (C60) dyads with bidirectional "ping-pong" energy transfer as triplet photosensitizers for photooxidation of 1,5-dihydroxynaphthalene.

Visible light-harvesting perylenebisimide (PBI)-C(60) dyads were prepared as organic triplet photosensitizers for photooxidation of 1,5-dihydroxynaphthalene and the efficiency of the dyads is 6-fold of the conventional Ir(III) complex triplet photosensitizer.

Microwave-assisted synthesis of N-substituted cyclic imides and their evaluation for anticancer and anti-inflammatory activities.

A number of N-substituted cyclic imides 3a-e, 5a-e, 7a-d, and 9a-e have been synthesized in very high yields, by condensation of various diacids 2, 4, 6, and 8 with different amines under microwave irradiation. These compounds were screened for anticancer and anti-inflammatory activities, and compounds 3c, 3e, 5c, 9c, and 9d exhibited anticancer activity against colon (COLO 205) cancer better than 5-fluorouracil and mitomycin-C, and compound 9b exhibited anti-inflammatory activity better than standard drug phenyl butazone.

Intramolecular electronic excitation energy transfer in donor/acceptor dyads studied by time and frequency resolved single molecule spectroscopy.

Electronic excitation energy transfer has been studied by single molecule spectroscopy in donor/acceptor dyads composed of a perylenediimide donor and a terrylenediimide acceptor linked by oligo(phenylene) bridges of two different lengths. For the shorter bridge (three phenylene units) energy is transferred almost quantitatively from the donor to the acceptor, while for the longer bridge (seven phenylene units) energy transfer is less efficient as indicated by the occurrence of donor and acceptor emission. To determine energy transfer rates and efficiencies at the single molecule level, several methods have been employed. These comprise time-correlated single photon counting techniques at room temperature and optical linewidth measurements at low temperature (1.4 K). For both types of measurement we obtain broad distributions of the rate constants of energy transfer. These distributions are simulated in the framework of Forster theory by properly taking into account static disorder and the flexibility of the dyads, as both effects can substantially contribute to the distributions of energy transfer times. The rate constants of energy transfer obtained from the calculated distributions are smaller on average than those extracted from the experimental distributions, whereby the discrepancy is larger for the shorter bridge. Furthermore, by plotting the experimentally determined transfer rates against the individual spectral overlaps, approximately linear dependencies are found being indicative of a Forster-type contribution to the energy transfer. For a given single molecule such a linear dependence could be followed by spectral diffusion induced fluctuations of the spectral overlap. The discrepancies between measured energy transfer rates and rates calculated by Forster theory are briefly discussed in light of recent results of quantum chemical calculations, which indicate that a bridge-mediated contribution is mainly responsible for the deviations from Forster theory. The availability of the inhomogeneous distributions of donor and acceptor electronic transition frequencies allows for comparing the energy transfer process at liquid helium and room temperature for the same set of molecules via simple simulations. It is found that on average the energy transfer is by a factor of approximately 3 faster at room temperature, which is due to an increase of spectral overlap.

On the inscription of period and half-period surface relief gratings in azobenzene-functionalized polymers.

Laser-light-induced surface relief grating inscription was carried out in the newly synthesized azobenzene-functionalized poly(amide-imide)s having the same main- and side-chain structures but different substituents in the azobenzene groups. The gratings were inscribed employing the two-wave mixing technique with linearly polarized laser beams. Three different polarization configurations were used: s-s, p-p, and s-p. The relatively deep surface relief gratings of period Lambda were formed for the case of s-s and p-p polarizations, whereas the s-p inscription resulted in the half-period grating (Lambda/2) with the weak surface modulation. The origin of the formation of Lambda/2 structure for s-p configuration results from the interference between zeroth- and first-order beams scattered on the polarization refractive index grating and having the same polarization. On the basis of this idea, we presented the simple kinetic model predicting and modeling the half-period grating formation with its temporal evolution. The proposed model is consistent with the experimental findings.

Photoinduced electron transfer between cytochrome c and a novel 1,4,5,8-naphthalenetetracarboxylic diimide with amphiphilic character.

N-dodecyl-N'-(2-phosphonoethyl)-1,4,5,8-naphthalenetetracarboxylic diimide (DNDI) is a novel naphthalenic diimide with amphiphilic character. DNDI was synthesized through the sequential reaction of 1,4,5,8-naphthalenetetracarboxylic dianhydride, first with dodecylamine and then with 2-aminoethylphosphonic acid. Fluorescence measurements showed that DNDI forms excimers in water at sufficiently high concentrations. The fluorescence quantum yield of DNDI in diluted solutions is sensitive to the polarity of the microenvironment, decreasing as going from water to less polar solvents. This property allowed to monitor the incorporation of DNDI into cetyl trimethyl ammonium bromide (CTAB) micelles, with a binding constant of 1.2x10(4) M-1. UV irradiation (365 nm) of solutions containing DNDI and the redox protein cytochrome c (cyt c) resulted in the reduction of the heme iron from the Fe(III) to the Fe(II) state, a reaction that was inhibited by the incorporation of DNDI into CTAB micelles. DNDI formed host-guest complexes with alpha-cyclodextrin (alpha-CD) through the inclusion of the dodecyl group, resulting in an increased aqueous solubility of the compound.

Picosecond-nanosecond laser photolysis studies of a photoacid generator in solutions: Transient absorption spectroscopy and transient grating measurements.

Photochemical reaction profiles of a photoacid generator, N-trifluoromethylsulfonyloxy-1,8-naphthalimide (NI-Sf), in solution phase were investigated by means of picosecond and nanosecond transient absorption spectroscopy as well as transient grating measurements. Picosecond transient absorption spectroscopy directly revealed that the lifetime of the S1 state and the intersystem-crossing yield decreased with increasing solvent polarity. On the other hand, photochemical reaction yield increased with an increase in the solvent polarity. These results indicated that the photochemical reaction started in the S1 state. Transient grating measurement directly detected the diffusion process of the proton and its diffusion coefficient was obtained to be 3.9 x 10(-9) m2 s(-1), which was several times larger than those of the usual solute molecules.

Nonvolatile read-out molecular memory.

A versatile molecule is described that performs as a nondestructible read-out optical-storage molecular memory. This molecular memory is composed of two distinct molecules that are chemically bonded to each other to form a single molecule with unique properties. One component is a photochromic fulgimide, and the other is a strongly fluorescing oxazine dye. This composite molecule was specifically designed and synthesized to display, under specific conditions, both the photochromic functions of the first component and the fluorescence properties of the dye. To store information, the polar, closed form of the photochromic component is illuminated with 530-nm light, which converts it to the open, nonpolar form. The information is accessed by excitation at the 650-nm band of the oxazine dye component, causing the dye to fluoresce. However, the dye emits intense fluorescence under a nonpolar environment, which is attained only when the fulgimide component is in its open, nonpolar structure. The ultrafast kinetics, spectroscopy, and mechanism of the photoreaction of this molecule and its photoinduced intermediates have been measured, and fluorescence quantum yields and cross sections were determined.

Photolability evaluation of the new cytostatic drug mitonafide.

A qualitative and quantitative study on the stability of the new cytostatic drug mitonafide (N-[2-(dimethyl-amino) ethyl]-3-nitronaphthalimide, CAS 54824-17-8) against UVA, UVC and visible radiations was carried out. Initially a test with controlled lighting on samples from mitonafide solution is carried out. This test include the determination of the protector effect of different kinds of glasses (clear and amber glass). The results achieved are verified by means of a test in normal lighting conditions (direct sun light, normal laboratory lighting and darkness). High mitonafide photodecomposition, deeper against UVA radiation, requires conservation of raw material in darkness. Similarly UV sterilizing radiations must be avoided in sterile rooms during manufacture. The use of amber glass ampoules is not enough to protect parenteral solutions from radiations. Direct sunlight must be avoided in the manufacture, control tests and administration in perfusion of pharmaceutical dosage forms, although artificial light can be used during short periods of time.