A phase-change thermochromic system was designed through the reversible transformation of the 4-substituted flavylium dye 4-(2-carboxyphenyl)-7-diethylamino-4'-dimethyl-amino-1-benzopyrylium into its leuco form, in the presence of a developer (ethyldiisopropylamine) and a suitable solvent (e.g., acetonitrile, n-pentadecanonitrile). The leuco form of the flavylium-based dye is a spirolactone species whose ring opens at low temperature (below the solvent melting point) to form the blue flavylium cation. Decarboxylation of the lactone to give 4-phenyl-7-diethylamino-4'-dimethylamino-1-benzopyrylium was observed upon irradiation of the system with UV light, erasing the thermochromic effect.

The formation of Eu(III) nanoparticles in borosilicate sol-gels and the glass formation heat treatment effect on those particles were studied using luminescence techniques. The presence of the particles was observed using transmission electron microscopy (TEM) images followed by analysis with energy dispersive X-ray spectroscopy (EDS). These experiments showed the presence of particles with a large quantity of europium and chlorine and only small amounts of oxygen with sizes ranging from 30 to 100 nm. Heat treatment at 400, 600, and 800 degrees C lead to glass samples in which those particles were no longer observed. Steady-state and time-resolved luminescence techniques allowed a detailed study of Eu(III) photophysics in sot-gel and glass samples. In sol-gel matrices, the (5)D(0) -> (7)F(0) transition is very weak, hinting at Eu(III) species experiencing a rather symmetric crystal field. The (5)D(0) -> (7)F(2) transition intensity is not very strong, which according to a Judd-Ofelt analysis indicates low interaction with the anions present in the sol-gel matrices. This picture reverses after heat treatment, indicating a replacement of chloride anions with oxygen as preferential ligands of Eu(III). Time-resolved luminescence shows in a more detailed way these aspects. Sol-gel samples display nonexponential kinetics, which are attributed to Eu(III) species present in the nanoparticles surface (bound to oxygen) and Eu(III) in the core of the nanoparticles (bound to chloride). Glass samples display single-exponential luminescence decays, in which the decay constant approaches the values calculated for the radiative rate constant with Judd-Ofelt analysis. It is concluded that, in sol-gel, mechanisms like electron-phonon coupling suppress the Eu(III) luminescence, which disappear as soon as the nanoparticles are disrupted after heat treatment.

Substitution of the phenyl group in 2-hydroxychalcones by a 4-pyridine unit dramatically changes the network of chemical reactions of this compound: trans-chalcone-type (Ct), cis-chalcone-type (Cc), and a hemiketal (hydroxy-4-pyridinechromene) (B) and their protonated forms are formed, but the presence of a flavylium-type cation could not be detected even at very acidic pH Values. Moreover, whereas in 2-phenyl-2-benzopyrylium compounds B and Cc are generally elusive species whose kinetic processes in aqueous solutions occur oil the sub-second time-scale, in the present compound these species equilibrate on a timescale four orders of magnitude lower. Complete characterization of the equilibrium and kinetics of the reaction network could thus be achieved by (1)H NMR spectroscopy and UV/Vis spectrophotometry. ne network of chemical reactions exhibits cis-trans photoisomerization, as well as photochromism between the hemiketal and the chalcone-type species. The irradiation of Ct in MeOH/ H(2)O (1:1) at 365 nm produces B almost quantitatively through two Consecutive photochemical reactions: Ct -> Cc photoisomerization followed by Cc -> B photo ring Closure with a global quantum yield of 0.02. On the other hand, irradiation of B at 254 nm leads to it photostationary state composed by 80% Ct and 20%, B. with a quantum yield of 0.21.

There are numerous reports of coumarin ester derivatives, in particular phosphate esters, as photocleavable cages in biological systems. Despite the comprehensive analysis of the photocleavage mechanism, studies of 4-methylcoumarin caged phosphates and/or nucleotides were always performed at constant pH. In this work. we present the study of the pH effect on the photochemistry of (7-diethylaminocoumarin-4-yl)methyl phosphate (DEACM-P). Fluorescence and photocleavage quantum yields, as well as the fluorescence decay times were measured as a function of the pH. It was found that the pH produces significant changes in the overall photochemical quantum yield of DEACM-P, and the observed changes are complementary to those obtained from the fluorescence quantum yield. Deprotonation of DEACM-HPO(4)(-) to yield DEACM -PO(4)(2-), produces a decrease in the photochemical quantum yield (from 0.0045 to 0.0003) and an increase in the fluorescence quantum yield (from 0.072 to 0.092). Moreover, from the analysis of the decay times, we have also found that hydroxyl ion is not only relevant, but it is mechanistically involved in the photoreaction of DEACM-HPO(4)(-).

We show photorheology in aqueous solutions of weakly entangled wormlike micelles prepared with cetyltrimethylammonium bromide (CTAB), salicylic acid (HSal), and dilute amounts of the photochromic multistate compound trans-2,4,4'-trihydroxychalcone (Ct). Different chemical species of Ct are associated with different colorations and propensities to reside within or outside CTAB micelles. A light-induced transfer between the intra- and intermicellar space is used to alter the mean length of wormlike micelles and hence the rheological properties of the fluid, studied in steady-state shear Bow and in dynamic rheological measurements. Light-induced changes of fluid rheology are reversible by a the relaxation process. at relaxation rates which depend on pH and which are consistent with photochromic reversion rates measured by UV-vis absorption spectroscopy. Parameterizing viscoelostic rheological states by their effective relaxation time tau(c) and corresponding response modulus G(c), we find the light and dark states of the system to fall onto a characteristic state curve defined by comparable experiments conducted without photosensitive components. These reference experiments were prepared with the same concentration of CTAB, but different concentrations of HSal or sodium salicylote (NaSal), and tested at different temperatures.

A systematic study of the electrochromic (EC) behavior of electropolymerized poly[M(salen)] films (M = Ni, Cu, and Pd) was performed by spectroelectrochemistry. Color contrast between oxidized and reduced states, stability under square wave potential cycling, coloration efficiency, and switching rate were evaluated. Five polymers were selected to assemble solid-state EC cells in a symmetrical configuration (electrode/poly[M(salen)] film/opaque electrolyte/poly[M(salen)] film/electrode). The best EC performance was found for poly[Pd(3-Mesalen)], poly[1], with 38% of initial diffuse reflectance variation and loss of 50% after 6769 cycles. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3457474] All rights reserved.

Flexible, transparent and self-supporting electrolyte films based on poly(trimethylene carbonate)/poly(ethylene oxide) (p(TMC/PEO) interpenetrating networks doped with LiClO(4) were prepared by the solvent casting technique. These novel solid polymer electrolyte (SPE) systems were characterized by measurements of conductivity, cyclic voltammetry, differential scanning calorimetry and thermogravimetry. The incorporation of solid electrolytes as components of electrochromic devices can offer certain operational advantages in real-world applications. In this study, all-solid-state electrochromic cells were characterized, using Prussian blue (PB) and poly-(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT) as complementary electrochromic compounds on poly(ethyleneterphthalate) (PET) coated with indium tin oxide (ITO) as flexible electrodes. Assembled devices with PET/ITO/PB/SPE/PEDOT/ITO/PET "sandwich-like" structure were assembled and successfully cycled between light and dark blue, corresponding to the additive optical transitions for PB and PEDOT electrochromic layers. The cells required long cycle times (>600 s) to reach full color switch and have modest stability towards prolonged cycling tests. The use of short duration cycling permitted the observation of changes in the coloration-bleaching performance in cells with different electrolyte compositions. (C) 2009 Elsevier Ltd. All rights reserved.

We report a spectroscopic study of the network of reactions of a flavylium dye encapsulated in the one-dimensional channels of zeolite L. The positively charged 7,4'-dihydroxyflavylium (AH(+)) is easily incorporated and remains stable in zeolite L channels. Once encapsulated, the flavylium exhibits a red shift in the excitation spectrum comparative to aqueous solutions. Moreover, contrary to the observed behavior in water, no excited state proton transfer takes place in the loaded crystals, corroborating the encapsulation of AH(+). The trans-chalcone (Ct) form from the same flavylium network could also be encapsulated inside the zeolite L, using toluene with 20% triethylamine as solvent and K(+) as counter ion of the negative framework of the zeolite. The encapsulation of Ct is confirmed by changes on the excitation spectrum and by a blue shift in the emission. The encapsulated Ct was shown to generate AH(+) when the Ct-loaded crystals were suspended in water, which proves that isomerization, tautomerization and dehydration reactions take place inside the zeolite L.

We recently reported on the use of caged nucleotides to attain full control of enzymatic polymerization of RNA solely by light. In the absence of light no RNA formation was possible due to the efficient caging by the coumarin moiety: after irradiation, caged ATP was released with quantitative precision and RNA polymerization was resumed. As photolabile protecting group [7-(diethylamino)coumarin-4-yl]methyl] (DEACM) was used due to its high absorbance in the visible region of the spectrum, fast deprotection kinetics and absence of radical intermediates. However, the 7-diethylamino-4-hydroxymethylcoumarin photo-product (DEACM-OH) was shown to inhibit the transcription reaction for concentrations higher than 30 mu M [5]. This inhibition has been associated with poor water solubility, which is commonly dealt with via cumbersome chemical modifications of the protecting moiety. To overcome inhibition, we evaluated the use of molecular scavengers to sequester DEACM-OH formed after irradiation. Determination of association constants of coumarin with beta-cyclodextrins allowed the assessment of its capability to remove free coumarin molecules from solution. The influence of beta-cyclodextrin in transcription reaction was also assessed. Results show that beta-cyclodextrin can be successfully used as scavenger as it increases the DEACM-OH threshold concentration for inhibition, amplifying the efficiency of light controlled in vitro transcription. (C) 2010 Elsevier B.V. All rights reserved.