Simple preparation of broadband UV filters based on TiO2 coated with aqueous extracts of native trees from the Chaco region of Argentina.

The native forest of northwestern Argentina, as part of the Chaco region, is a rich and unexploited source of phytochemical compounds for medicinal/cosmetic applications. In the present study, fruit, leaf, branch, and bark organs of the native trees Sarcomphalus mistol (Mistol, M) and Schinopsis lorentzii (Quebracho Colorado santiagueño, QC) were harvested, and aqueous plant extracts (PE) were prepared. The spectroscopic (UV-Vis absorbance, diffuse reflectance, ATR-FTIR) and antioxidant (TEAC, Folin-Ciocalteu) properties of PE were characterized and used as TiO2 coating material to obtain a series of TiO2@PE nanocomposites. These materials showed almost null photocatalytic activity compared to aqueous suspensions of bare TiO2, displaying yellowish to brownish coloration and high long-term stability in both freshwater and seawater model solutions. The loss of photocatalytic activity in TiO2@PE was associated with the combination of the internal filter effect and the antioxidant/radical capacity exerted by the phytochemicals of the PE coating, with higher broadband photoprotection for the nanocomposites prepared with QC extracts. Thus, this study shows the potential capacity of the forest resources of the Chaco region of Argentina for the development of new cosmetic and/or sun protection formulations.

Heteroleptic Ruthenium(II) Complexes with 2,2'-Bipyridines Having Carbonitriles as Anchoring Groups for ZnO Surfaces: Syntheses, Physicochemical Properties, and Applications in Organic Solar Cells.

Heteroleptic ruthenium (II) complexes were used for sensitizing ZnO surfaces in organic solar cells (OSCs) as mediators with photoactive layers. The complexes [Ru(4,4'-X2-bpy)(Mebpy-CN)2]2+ (with X = -CH3, -OCH3 and -N(CH3)2; bpy = 2,2'-bipyridine; Mebpy-CN = 4-methyl-2,2'-bipyridine-4'-carbonitrile) were synthesized and studied by analytical and spectroscopical techniques. Spectroscopic, photophysical, and electrochemical properties were tuned by changing the electron-donating ability of the -X substituents at the 4,4'-positions of the bpy ring and rationalized by quantum mechanical calculations. These complexes were attached through nitrile groups to ZnO as interfacial layer in an OSC device with a PBDB-T:ITIC photoactive layer. This modified inorganic electron transport layer generates enhancement in photoconversion of the solar cells, reaching up to a 23% increase with respect to the unsensitized OSCs. The introduction of these dyes suppresses some degradative reactions of the nonfullerene acceptor due to the photocatalytic activity of zinc oxide, which was maintained stable for about 11 months. Improving OSC efficiencies and stabilities can thus be achieved by a judicious combination of new inorganic and organic materials.

Photocatalytic Efficiency Tuning by the Surface Roughness of TiO2 Coatings on Glass Prepared by the Doctor Blade Method.

A set of opaque films were prepared with Degussa P25® or Hombikat UV100® TiO2 powders by the doctor blade method on glass slides with different compositions of polyethylene glycol of 20 kDa (PEG20), and they were characterized by spectroscopy, microscopy and photochemical kinetics measurements. After annealing treatment at 450 °C, about 5-7% C atom was incorporated into the films, as a consequence of the degradation of the organic complexing agents, inducing a small reduction of the energy band gap of TiO2 (i.e. 3.02 ≤ Eg (eV) ≤ 3.08). All films were about 15 ± 2 µm thick but their micro-morphological characteristics depended on the content of PEG20, showing different patterns of cracks and aggregates that produce intense light scattering and retransmission phenomena with the result of a three-dimensional excitation of the TiO2 particles in the thick film. Back-face excitation with UVA light (365 ± 42 nm) of the opaque films in contact with an aqueous solution produced both surface-bound and free hydroxyl radicals (HO• ), as detected using a coumarin solution as a radical dosimeter. The photogeneration efficiency of HO• decreased with the surface roughness of the films, which varied between 135 and 439 nm depending on the film's composition.

Synthesis, UV-visible spectroelectrochemistry and theoretical characterization of new polypyridyl Ru(II) complexes containing 2,4,6-tris(2-pyridyl)-1,3,5-triazine as precursors for water oxidation catalysts.

In this work, we report the syntheses and physicochemical characterization of new chloro and aqua complexes of Ru(ii) with 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz) and 2,2'-bipyridines substituted with donor and acceptor groups in the 4,4'-positions. The aqua complexes behave as precursors for water oxidation catalysts at pH = 1 using Ce(iv) as a sacrificial oxidant. Besides, the oxidized forms Ru(iv) and Ru(v) have been characterized at different pH values by electrochemistry, UV-Visible spectroscopy and spectroelectrochemistry. The reaction mechanisms were studied by combining mixing and stopped-flow experiments with spectrophotometric monitoring in the UV-visible region and all the rate constants were determined together with the corresponding TON and TOF values at pH = 1. Calculations based on Density Functional Theory (DFT and TD-DFT) were performed to support the experimental data.

Kinetics and growth mechanism of the photoinduced synthesis of silver nanoparticles stabilized with lysozyme.

A fast and single-step procedure is reported for the preparation of stable solutions of spherical-shaped silver nanoparticles (AgNPs) coated with lysozyme (LZ). The preparation of the AgNP@LZ nanocomposites was based on the reduction of Ag+ with ketyl radicals photo-generated by the UVA-photolysis of the benzoin I-2959. Both reaction precursors bind to LZ, modifying its superficial charge and conformational structure. The photo-induced kinetics of formation of the AgNPs as a function of the LZ concentration was monitored in-situ by UV-vis absorption spectroscopy. The multivariate curve resolution-alternating least square (MCR-ALS) method was used for the deconvolution of the kinetic curves for each transient species formed before the growth of the final AgNPs colloids. The Kolmogorov-Johnson-Mehl-Avrami (KJMA) model to describe the formation of the AgNPs was used, and the respective first-order rate constants for the growth of the AgNPs as a function of the lysozyme concentration were calculated and the role of the protein capping in the growth kinetics was evaluated. Despite the protein being partially oxidized by the photo-generated radicals, it was strongly adsorbed onto the silver surface forming a tight coating shell around the AgNPs of approximately 30-60 protein molecules. As a result of the partial denaturation and crowded packing, its intrinsic lytic activity was strongly reduced.

Integration of Temperature and Blue-Light Sensing in Acinetobacter baumannii Through the BlsA Sensor.

BlsA is a BLUF photoreceptor present in Acinetobacter baumannii, responsible for modulation of motility, biofilm formation and virulence by light. In this work, we have combined physiological and biophysical evidences to begin to understand the basis of the differential photoregulation observed as a function of temperature. Indeed, we show that blsA expression is reduced at 37°C, which correlates with negligible photoreceptor levels in the cells, likely accounting for absence of photoregulation at this temperature. Another point of control occurs on the functionality of the BlsA photocycle itself at different temperatures, which occurs with an average quantum yield of photoactivation of the signaling state of 0.20 ± 0.03 at 15°C < T < 25°C, but is practically inoperative at T > 30°C, as a result of conformational changes produced in the nanocavity of FAD. This effect would be important when the photoreceptor is already present in the cell to avoid almost instantaneously further signaling process when it is no longer necessary, for example under circumstances of temperature changes possibly faced by the bacteria. This complex interplay between light and temperature would provide the bacteria clues of environmental location and dictate/modulate light photosensing in A. baumannii.

Physicochemical characterization of water-soluble chitosan derivatives with singlet oxygen quenching and antibacterial capabilities.

New water-soluble chitosan derivatives (WSCh) were obtained by Maillard reaction (MR) between glucosamine (GA) with both low and medium molecular weight chitosans (Ch). The WSCh showed larger solubility than the respective Ch, while their deacetylation degree (DD) decreased by approximately 12%. Infrared spectroscopy experiments of WSCh confirmed the formation of imine bonds after MR with intensified pyranose structure, and sugar molecules as polymer branches. However, a 6-times reduction of the molecular weight of WSCh was measured, indicating the breakdown of the polysaccharide chain during the MR. The polysaccharides quenched singlet molecular oxygen (1O2), with rate quenching constants correlating with the DD value of the samples, suggesting the important role of amino groups (-NH2) in the deactivation of 1O2. Additionally, all polysaccharides presented antimicrobial activity against pathogenic bacteria, e.g. Staphylococcus aureus, Escherichia coli, Salmonella sp., Enterococcus faecalis and Listeria ivanovii, as tested by their minimum inhibitory concentration (MIC). This way we obtained new water-soluble polysaccharides, with similar functional properties to those presented by native Ch, enhancing its potential application as carrier material for bioactive compounds.

Interaction of singlet oxygen with bovine serum albumin and the role of the protein nano-compartmentalization.

Singlet molecular oxygen ((1)O2) contributes to protein damage triggering biophysical and biochemical changes that can be related with aging and oxidative stress. Serum albumins, such as bovine serum albumin (BSA), are abundant proteins in blood plasma with different biological functions. This paper presents a kinetic and spectroscopic study of the (1)O2-mediated oxidation of BSA using the tris(2,2'-bipyridine)ruthenium(II) cation [Ru(bpy)3](2+) as sensitizer. BSA quenches efficiently (1)O2 with a total (chemical+physical interaction) rate constant kt(BSA)=7.3(±0.4)×10(8)M(-1)s(-1), where the chemical pathway represented 37% of the interaction. This efficient quenching by BSA indicates the participation of several reactive residues. MALDI-TOF MS analysis of intact BSA confirmed that after oxidation by (1)O2, the mass protein increased the equivalent of 13 oxygen atoms. Time-resolved emission spectra analysis of BSA established that Trp residues were oxidized to N'-formylkynurenine, being the solvent-accessible W134 preferentially oxidized by (1)O2 as compared with the buried W213. MS confirmed oxidation of at least two Tyr residues to form dihydroxyphenylalanine, with a global reactivity towards (1)O2 six-times lower than for Trp residues. Despite the lack of MS evidences, kinetic and chemical analysis also suggested that residues other than Trp and Tyr, e.g. Met, must react with (1)O2. Modeling of the 3D-structure of BSA indicated that the oxidation pattern involves a random distribution of (1)O2 into BSA; allowing also the interaction of (1)O2 with buried residues by its diffusion from the bulk solvent through interconnected internal hydrophilic and hydrophobic grooves.

Effect of dye localization and self-interactions on the photosensitized generation of singlet oxygen by rose bengal bound to bovine serum albumin.

The spectroscopic and photophysical properties of rose bengal (RB) encased in bovine serum albumin (BSA) have been examined to evaluate the photosensitized generation of singlet molecular oxygen ((1)O2). The results show that RB photophysical and photosensitizing properties are highly modulated by the average number of dye molecules per protein (n). At n ≪ 1, the dye molecule is tightly located into the hydrophobic nanocavity site I of the BSA molecule with a binding constant Kb = 0.15 ± 0.01 µM(-1). The interaction with surrounding amino acids induces heterogeneous decay of both singlet and triplet excited states of RB and partially reduce its triplet quantum yield as compared with that in buffer solution. However, despite of the diffusive barrier imposed by the protein nanocavity to (3)O2, the quenching of (3)RB(∗):BSA generates (1)O2 with quantum yield ΦΔ = 0.35 ± 0.05. In turns, the intraprotein generated (1)O2 is able to diffuse through the bulk solution, where is dynamically quenched by BSA itself with an overall quenching rate constant of 7.3 × 10(8) M(-1) s(-1). However, at n>1, nonspecific binding of up to ≈ 6RB molecules per BSA is produced, allowing efficient static quenching of excited states of RB preventing photosensitization of (1)O2. These results provide useful information for development of dye-protein adducts suitable for using as potential intracellular photosensitizers.

FAD binding properties of a cytosolic version of Escherichia coli NADH dehydrogenase-2.

Respiratory NADH dehydrogenase-2 (NDH-2) of Escherichia coli is a peripheral membrane-bound flavoprotein. By eliminating its C-terminal region, a water soluble truncated version was obtained in our laboratory. Overall conformation of the mutant version resembles the wild-type protein. Considering these data and the fact that the mutant was obtained as an apo-protein, the truncated version is an ideal model to study the interaction between the enzyme and its cofactor. Here, the FAD binding properties of this version were characterized using far-UV circular dichroism (CD), differential scanning calorimetry (DSC), limited proteolysis, and steady-state and dynamic fluorescence spectroscopy. CD spectra, thermal unfolding and DSC profiles did not reveal any major difference in secondary structure between apo- and holo-protein. In addition, digestion site accessibility and tertiary conformation were similar for both proteins, as seen by comparable chymotryptic cleavage patterns. FAD binding to the apo-protein produced a parallel increment of both FAD fluorescence quantum yield and steady-state emission anisotropy. On the other hand, addition of FAD quenched the intrinsic fluorescence emission of the truncated protein, indicating that the flavin cofactor should be closely located to the protein Trp residues. Analysis of the steady-state and dynamic fluorescence data confirms the formation of the holo-protein with a 1:1 binding stoichiometry and an association constant KA=7.0(±0.8)×10(4)M(-1). Taken together, the FAD-protein interaction is energetically favorable and the addition of FAD is not necessary to induce the enzyme folded state. For the first time, a detailed characterization of the flavin:protein interaction was performed among alternative NADH dehydrogenases.

Singlet oxygen quenching by anthocyanin's flavylium cations.

The quenching of singlet molecular oxygen ((1)O(2)) by the flavylium cation form of six widespread anthocyanin derivatives: cyanidin 3-glucoside (CG), cyanidin 3-rutinoside (CR), cyanidin 3-galactoside (CGL), malvidin (M), malvidin 3-glucoside (MG) and malvidin 3,5-diglucoside (MDG) was studied in 1% HCl methanol solution by time-resolved phosphorescence detection (TRPD) of (1)O(2) and photostationary actinometry using perinaphthenone and methylene blue as sensitizers, respectively. The average value of the total (k(0)) and chemical (k(c)) quenching rate constants were approximately 4 x 10(8) M(-1) s(-1) and 3 x 10(6) M(-1) s(-1), respectively, indicating the good performance of the studied anthocyanins as catalytic quenchers of (1)O(2). The quenching efficiency was larger for malvidin than for cyanidin derivatives, probably by the extra electron-donating methoxy group in ring B of the malvidin derivatives; and it was also dependent on the number and type of glycosylated substitution. As observed for other phenolic-like derivatives, the quenching of (1)O(2) by anthocyanins was mediated by a charge-transfer mechanism, which was modulated by the total number of -OR substituents that increases the electron-donating ability of these compounds.