Effect of chronic exposure to fine particulate matter on cardiac tissue of NZBWF1 mice.

Epidemiological and toxicological studies have shown that inhalation of particulate matter (PM) is associated with development of cardiovascular diseases. Long-term exposure to PM may increase the risk of cardiovascular events and reduce life expectancy. Systemic lupus erythematosus (SLE) is a chronic inflammatory disease, autoimmune in nature, that is characterized by the production of autoantibodies that affects several organs, including the heart. Air pollution - which can be caused by several different factors - may be one of the most important points both at the onset and the natural history of SLE. Therefore this study aims to investigate whether exposure to air pollution promotes increased inflammation and cardiac remodelling in animals predisposed to SLE. Female NZBWF1 mice were exposed to an environmental particle concentrator. Aspects related to cardiac remodelling, inflammation and apoptosis were analysed in the myocardium. Body weight gain, cardiac trophism by heart/body weight ratio, relative area of cardiomyocytes and the fibrotic area of cardiac tissue were evaluated during the exposure period. Animals exposed to PM2.5 showed increased area of cardiomyocytes, and area of fibrosis; in addition, we observed an increase in IL-1 and C3 in the cardiac tissue, demonstrating increased inflammation. We suggest that air pollution is capable of promoting cardiac remodelling and increased inflammation in animals predisposed to SLE.

The role of solvents and concentrations in the properties of oxime bearing A2B corroles.

A comprehensive study on the electronic spectral, photophysical and acid-base properties of phenyl- and methyl-oxime corrole derivatives and of triphenylcorrole (model corrole) has been performed, aiming to shed light on the existing species in the ground and excited states. Solvents and corrole concentration are found to govern the properties of the studied compounds and are determinants of their applicability in in vivo studies. In THF, the neutral corrole has two tautomeric forms (T1 and T2). In DMSO, the deprotonated form shows a characteristic long-wavelength Q band slightly shifted to blue when compared with the T1 tautomer and a higher fluorescence quantum yield. In ACN, with the increase of the corrole concentration formation of an aggregate due to homoconjugation (with dimer characteristics) is observed, and pioneeringly reported using UV-Vis and fluorescence studies and confirmed by carrying out titrations with TFA. The effect of the oxime group on the pK values of a corrole is found to influence the formation of a homoconjugate, namely by precluding its formation (at higher concentrations) when compared with the model corrole. TDDFT electronic quantum calculations support the experimental observations, namely the existence of tautomers and deprotonated species, with their respective electronic spectral features, further allowed proposing a structure for the homoconjugate complex in ACN. The characteristics of the oxime-corroles, namely a pK of ∼ 5, absorption and emission at ca. 650 nm and solvent dependent properties, make them good candidates for their use in biological systems either as probes, sensors, or as new sensitizers for photodynamic therapy.

Aggregation-Induced Emission Leading to White Light Emission in Diphenylbenzofulvene Derivatives.

The search for a unique molecular system able to efficiently emit in the total visible range of the electromagnetic spectra, i. e., white light emission (WLE), is a topic of intense research. We here show that aggregates formed by diphenylbenzofulvene (DPBF) derivatives are from two to four orders of magnitude more emissive than their monomers. From a simple strategy, involving structural modification of a DPBF propelled shape core, a close match with the pure white light emission coordinates is obtained with a combination of two derivatives in films, with featured solid-state emission, without involvement of D-A groups or energy transfer processes.

Tuning J-aggregate Formation and Emission Efficiency in Cationic Diazapentacenium Dyes.

Enhancement of the luminescence efficiency of two new diazapentacenium salts (D1 and D2) of more than 55 for D1 and 22 times for D2) in poor solvents, acetonitrile and/or dichloromethane, was observed and rationalized as formation of emissive J-aggregates. Both compounds displaying 4-n-decylphenyl substituents at the 7,14-carbons and phenyl (D1) or 2,6-difluorophenyl (D2) substituents at the quaternary nitrogen atoms in 5,12-positions have been synthetized in a two-step procedure involving a two-fold Buchwald-Hartwig-type CN cross-coupling and an electrophilic Friedel-Crafts-type cyclization. The optical properties of the dicationic diazapentacenium salts in various solvents and in thin films have been investigated by steady-state and time-resolved absorption and photoluminescence spectroscopies. In thin films and in good solvents, isolated molecules coexist with aggregates. Nonetheless, D1 is seven times more emissive than D2, reflecting a higher J-aggregate contribution in the former.

Aggregation-Induced Emission: From Small Molecules to Polymers-Historical Background, Mechanisms and Photophysics.

The enhancement of photoluminescence through formation of molecular aggregates in organic oligomers and conjugated organic polymers is reviewed. A historical contextualization of aggregation-induced emission (AIE) phenomena is presented. This includes the loose bolt or free rotor effect and J-aggregation phenomena, and discusses their characteristic features, including structures and mechanisms. The basis of both effects is examined in key molecules, with a particular emphasis on the AIE effect occurring in conjugated organic polymers with a polythiophene (PT) skeleton with triphenylethylene (TPE) units. Rigidification of the excited state structure is one of the defining conditions required to obtain AIE, and thus, by changing from a flexible ground state to rigid (quinoidal-like) structures, oligo and PTs are among the most promising emerging molecules alongside with the more extensively used TPE derivatives. Molecular structures moving away from the domination of aggregation-caused quenching to AIE are presented. Future perspectives for the rational design of AIEgen structures are discussed.

Highly fluorescent hybrid pigments from anthocyanin- and red wine pyranoanthocyanin-analogs adsorbed on sepiolite clay.

Flavylium cations serve as models for the chemical and photochemical reactivity of anthocyanins, the natural plant pigment responsible for many of the red, blue and purple colors of fruits and flowers. Likewise, pyranoflavylium cations serve as models of the fundamental chromophoric moiety of pyranoanthocyanins, molecules that can form from reactions of grape anthocyanins in red wines during their maturation. In the present work, hybrid pigments are prepared by the adsorption of a series of five synthetic flavylium cations (FL) and five synthetic pyranoflavylium cations (PFL) on sepiolite clay (SEP). The FL are smaller in size than the PFL, but both can in principle fit into the tunnels and/or external grooves (with dimensions of 3.7 × 10.6 Å) of SEP. Measurements of the fluorescence quantum yields of the adsorbed dyes indicate that they are at least as fluorescent as in acidic acetonitrile solution, and in a few cases substantially more fluorescent. The observation of biexponential fluorescence decays is consistent with emission from dye molecules adsorbed at two distinct sites, presumably tunnels and grooves. These hybrid materials also have improved properties in terms of stability of the color in contact with pH 10 aqueous solution and resistance to thermal degradation of the dye. SEP thus appears to be a promising substrate for the development of highly fluorescent flavylium or pyranoflavylium cation-derived hybrid pigments with improved color and thermal stability.

Effect of counterions on the shape, hydration, and degree of order at the interface of cationic micelles: the triflate case.

Specific ion effects in surfactant solutions affect the properties of micelles. Dodecyltrimethylammonium chloride (DTAC), bromide (DTAB), and methanesulfonate (DTAMs) micelles are typically spherical, but some organic anions can induce shape or phase transitions in DTA(+) micelles. Above a defined concentration, sodium triflate (NaTf) induces a phase separation in dodecyltrimethylammonium triflate (DTATf) micelles, a phenomenon rarely observed in cationic micelles. This unexpected behavior of the DTATf/NaTf system suggests that DTATf aggregates have unusual properties. The structural properties of DTATf micelles were analyzed by time-resolved fluorescence quenching, small-angle X-ray scattering, nuclear magnetic resonance, and electron paramagnetic resonance and compared with those of DTAC, DTAB, and DTAMs micelles. Compared to the other micelle types, the DTATf micelles had a higher average number of monomers per aggregate, an uncommon disk-like shape, smaller interfacial hydration, and restricted monomer chain mobility. Molecular dynamic simulations supported these observations. Even small water-soluble salts can profoundly affect micellar properties; our data demonstrate that the -CF3 group in Tf(-) was directly responsible for the observed shape changes by decreasing interfacial hydration and increasing the degree of order of the surfactant chains in the DTATf micelles.