Spatiotemporal control over the co-conformational switching in pH-responsive flavylium-based multistate pseudorotaxanes

A multistate molecular dyad containing flavylium and viologen units was synthesized and the pH dependent thermodynamics of the network completely characterized by a variety of spectroscopic techniques such as NMR, UV-vis and stopped-flow. The flavylium cation is only stable at acidic pH values. Above pH ≈ 5 the hydration of the flavylium leads to the formation of the hemiketal followed by ring-opening tautomerization to give the cis-chalcone. Finally, this last species isomerizes to give the trans-chalcone. For the present system only the flavylium cation and the trans-chalcone species could be detected as being thermodynamically stable. The hemiketal and the cis-chalcone are kinetic intermediates with negligible concentrations at the equilibrium. All stable species of the network were found to form 1 : 1 and 2 : 1 host : guest complexes with cucurbit[7]uril (CB7) with association constants in the ranges 10(5)-10(8) M(-1) and 10(3)-10(4) M(-1), respectively. The 1 : 1 complexes were particularly interesting to devise pH responsive bistable pseudorotaxanes: at basic pH values (≈12) the flavylium cation interconverts into the deprotonated trans-chalcone in a few minutes and under these conditions the CB7 wheel was found to be located around the viologen unit. A decrease in pH to values around 1 regenerates the flavylium cation in seconds and the macrocycle is translocated to the middle of the axle. On the other hand, if the pH is decreased to 6, the deprotonated trans-chalcone is neutralized to give a metastable species that evolves to the thermodynamically stable flavylium cation in ca. 20 hours. By taking advantage of the pH-dependent kinetics of the trans-chalcone/flavylium interconversion, spatiotemporal control of the molecular organization in pseudorotaxane systems can be achieved.

Light harvesting in solar cells using natural pigments from red fruits adsorbed to mesoporous TiO2

Nature has developed strategies to present us with a wide variety of colours, from the green of leaves to the bright colours seen in flowers. Anthocyanins are between these natural pigments that are responsible for the great diversity of colours seen in flowers and fruits. Anthocyanins have been used to sensitize titanium dioxide (TiO2) in Dye-Sensitized Solar Cells (DSSCs). DSSCs have become one of the most popular research topic in photovoltaic cells due to their low production costs when compared to other alternatives. DSSCs are inspired in what happens in nature during photosynthesis. A primary charge separation is achieved by means of a photoexcited dye capable of performing the electron injection into the conduction band of a wide band-gap semiconductor, usually TiO2. With this work we aimed to synthesize a novel mesoporous TiO2 structure as the semiconductor in order to increase the dye loading. We used natural occurring dyes such as anthocyanins and their synthetic flavylium relatives, as an alternative to the widely used metal complexes of Ru(II) which are expensive and are environmentally unsafe. This offers not only the chance to use safer dyes for DSSCs, but also to take profit of waste biological products, such as wine and olive oil production residues that are heavily loaded with anthocyanin dyes. We also performed a photodegradation study using TiO2 as the catalyst to degrade dye contaminants, such as those from the wine production waste, by photo-irradiation of the system in the visible region of the light spectrum. We were able to succeed in the synthesis of mesoporous TiO2 both powder and thin film, with a high capacity to load a large amount of dye. We proved the concept of photodegradation using TiO2 as catalyst. And finally, we show that wine production waste is a possible dye source to DSSCs application.

Picosecond Dynamics of the Prototropic Reactions of 7-Hydroxyflavylium Photoacids Anchored at an Anionic Micellar Surface

Three water-insoluble, micelle-anchored flavylium salts, 7-hydroxy-3-octyl-flavylium chloride, 4`-hexyl-7-hydroxyflavylium chloride, and 6-hexyl-7-hydroxy-4-methyl-flavylium chloride, have been employed to probe excited-state prototropic reactions in micellar sodium dodecyl sulfate (SDS). In SDS micelles, the fluorescence decays of these three flavylium salts are tetraexponential functions in the pH range from 1.0 to 4.6 at temperatures from 293 to 318 K. The four components of the decays are assigned to Four kinetically coupled excited species in the micelle: specifically, promptly deprotonable (AH(+)*) and nonpromptly deprotonable (AH(h)(+)*) orientations of the acid in the micelle. the base-proton geminate pair (A*center dot center dot center dot H(+)), and the free conjugate base (A*). The initial prompt deprotonation to form the germinate pair occurs at essentially the same rate (k(d) similar to 6-7 x 10(10) s(-1)) for all three photoacids. Recombination of the germinate pair is similar to 3-fold faster than the rate of proton escape from the pair (k(rec) similar to 3 x 10(10) s(-1) and k(diss) similar to 1 x 10(10) s(-1)), corresponding to an intrinsic recombination efficiency of the pair of similar to 75%. Finally, the reprotonation of the short-lived free A* (200-350 ps, depending oil the photoacid) has two components, only one of which depends oil the proton concentration in the intermicellar aqueous phase. Ultrafast transfer of the proton to water and substantial compartmentalization of the photogenerated proton at the micelle surface Oil the picosecond time scale strongly suggest preferential transfer of the proton to preformed hydrogen-bonded water bridges between the photoacid and the anionic headgroups. This localizes the proton in the vicinity of the excited base much more efficiently than ill bulk water, resulting ill the predominance of geminate re reprotonation at the micelle surface.

Picosecond Dynamics of Proton Transfer of a 7-Hydroxyflavylium Salt in Aqueous-Organic Solvent Mixtures

The intermediacy of the geminate base proton pair (A*center dot center dot center dot H(+)) in excited-state proton-transfer (ESPT) reactions (two-step mechanism) has been investigated employing the synthetic flavylium salt 7-hydroxy-4-methyl-flavylium chloride (HMF). In aqueous solution, the ESPT mechanism involves solely the excited acid AH* and base A* forms of HMF as indicated by the fluorescence spectra and double-exponential fluorescence decays (two species, two decay times). However, upon addition of either 1,4-dioxane or 1,2-propylene glycol, the decays become triple-exponential with a term consistent with the presence of the geminate base proton pair A*center dot center dot center dot H(+). The geminate pair becomes detectable because of the increase in the recombination rate constant, k(rec), of (A*center dot center dot center dot H(+)) with increasing the mole fraction of added organic cosolvent. Because the two-step ESPT mechanism splits the intrinsic prototropic reaction rates (deprotonation of AH(+)*, k(d), and recombination, k(rec) of A*center dot center dot center dot H(+)) from the diffusion controlled rates (dissociation, k(diss) and formation, k(diff)[H(+)], of A*center dot center dot center dot H+), the experimental detection of the geminate pair provides a wealth of information on the proton-transfer reaction (k(d) and k(rec)) as well as on proton diffusion/migration (k(diss) and k(diff)).

Hybrid Materials Based on Smectite Clays and Nutraceutical Anthocyanins from the Acai Fruit

Hybrid materials were prepared by combining clay mineral (montmorillonite SWy-2 and saponite SapCa-1) and dyes extracted from the acai (Euterpe oleracea Mart.) fruit, which contains mainly anthocyanins from the 3-glucoside class, to increase the stability of the dye and facilitate its handling and storage. Clay minerals are common ingredients in therapeutic and pharmaceutical products and acai phytochemicals show disease prevention properties. The extract of the acai fruit was mixed with water suspensions of layered silicates in different proportions. The dyeclay hybrids presented incorporated organic material in amounts up to 24 wt.-%. X ray diffractometry and vibrational (FTIR and Raman) and electronic spectroscopic data showed that flavylium cations were successfully intercalated between the inorganic layers. Mass-coupled thermogravimetric analysis (TGA-MS) data showed a significant gain in the thermostability of the organic species in relation to anthocyanins in the extract. MS curves related to CO2 release (m/z = 44) are ascendant above 200 degrees C when the dye cations are confined to the inorganic structure. The radical scavenging activity of the hybrid materials was monitored by electron paramagnetic resonance (EPR) toward the stable radical DPPH (1,1-diphenyl-2-picrylhydrazyl) and compared to the activity of the acai extract. In addition to the fact that interaction with clay minerals improves the stability of the acai dyes against heat, their properties as radical scavengers are preserved after intercalation. The improvement in the properties of the nutraceutical species by intercalation by using biocompatible inorganic structures can be valuable for human therapy.

Photoprotection and the Photophysics of Acylated Anthocyanins

The proposed role of anthocyanins in protecting plants against excess solar radiation is consistent with the occurrence of ultrafast (525 ps) excited-state proton transfer as the major de-excitation pathway of these molecules. However, because natural anthocyanins absorb mainly in the visible region of the spectra, with only a narrow absorption band in the UV-B region, this highly efficient deactivation mechanism would essentially only protect the plant from visible light. On the other hand, ground-state charge-transfer complexes of anthocyanins with naturally occurring electron-donor co-pigments, such as hydroxylated flavones, flavonoids, and hydroxycinnamic or benzoic acids, do exhibit high UV-B absorptivities that complement that of the anthocyanins. In this work, we report a comparative study of the photophysics of the naturally occurring anthocyanin cyanin, intermolecular cyanincoumaric acid complexes, and an acylated anthocyanin, that is, cyanin with a pendant coumaric ester co-pigment. Both inter- and intramolecular anthocyaninco-pigment complexes are shown to have ultrafast energy dissipation pathways comparable to those of model flavylium cationco-pigment complexes. However, from the standpoint of photoprotection, the results indicate that the covalent attachment of co-pigment molecules to the anthocyanin represents a much more efficient strategy by providing the plant with significant UV-B absorption capacity and at the same time coupling this absorption to efficient energy dissipation pathways (ultrafast internal conversion of the complexed form and fast energy transfer from the excited co-pigment to the anthocyanin followed by adiabatic proton transfer) that avoid net photochemical damage.

Photochromism of the complex between 40-(2-hydroxyethoxy)-7-hydroxyflavylium and b-cyclodextrin, studied by 1H NMR, UVeVis, continuous irradiation and circular dichroism

1st International Caparica Conference on Chromogenic and Emissive Materials