Photoprotection of Wood Using Polyester-Type UV-Absorbers Derived from the Reaction of 2-hydroxy-4(2,3-epoxypropoxy)-benzophenone with Dicarboxylic Acid Anhydrides

Abstract

Polyester-type UV absorbers were created by reacting the epoxy-functionalized UV absorber 2-hydroxy-4(2,3-epoxypropoxy)-benzophenone (HEPBP) with maleic, phthalic, or succinic anhydride. The ability of the UV absorbers to photostabilize wood was then examined. Fourier transform infra-red (FTIR) spectroscopy confirmed that HEPBP reacted with phthalic anhydride to create a polyester that preserved the UV-absorbing benzophenone group. There was less evidence that the polyester was formed when HEPBP was reacted with maleic or succinic anhydride. HEPBP-phthalic anhydride was the most effective UV absorber at photostabilising wood. This UV absorber showed increased UV absorption around 270 nm, formed a leach-resistant film at wood surfaces and was able to restrict both weight and tensile strength losses of thin wood veneers during accelerated weathering, unlike chromium trioxide and a UV absorber-hindered amine light stabilizer. We conclude that polymeric polyester-type UV absorbers show promise as a way of photostabilizing wood and briefly discuss how more effective systems could be developed in future.     

Phylogenetic distribution of fungal mycosporines within the Pucciniomycotina (Basidiomycota)

The synthesis of the UV Absorbing compounds named mycosporines (MYCs) has been detected in a few basidiomycetous yeast groups. Conspicuous accumulation of mycosporine-glutaminol-glucoside (MGG) in yeasts requires photo-induction and its photoprotective function has been postulated. The distribution of the ability to produce MYCs appeared to be related to the yeast taxonomic affiliation. In view of the potential significance of MYCs in yeast taxonomy, we here studied the distribution of this trait among dimorphic basidiomycetes of the Pucciniomycotina. Of the 94 fungal species (377 strains and 33 genera) tested, almost half were MYC-positive and MGG was the main compound produced. MGG synthesis was observed for representatives of five of seven Pucciniomycotina classes, indicating that this trait is widely distributed in this group. MGG detection proved useful for the differentiation of species of the polyphyletic genera, such as Rhodotorula and Sporobolomyces, that are phylogenetically separated. MGG quantification and UV tolerance studies in Cystobasidiomycetes supported the idea that the habitat of origin of each strains is important in the level of MGG synthesis and that MYCs have a photoprotective function in yeasts. The taxonomic value of this trait in fungal systematics is discussed.     

Fluorescence lifetime imaging of coral fluorescent proteins

Corals, like many other coelenterates, contain fluorescent pigments that show considerable homology with the well known green fluorescent protein of the jellyfish Aequoria. In corals, unlike jellyfish, multiple proteins are present and the range of excitations and emissions suggest the possibility of energy transfer. The occurrence of F?rster resonant energy transfer (FRET) between fluorescent proteins in corals has already been reported and time-resolved spectra have shown the effect on fluorescent lifetime, but without any spatial resolution. Lifetime confocal microscopy offers lower time resolution but excellent spatial resolution. Lifetimes of the isolated A. millepora pigments amilFP490, amilFP504, and amilFP593 (names indicate emission peaks) were 2.8, 2.9, and 2.9 ns, respectively. In the coral sample, imaging the entire emission spectrum from 420 nm, the mean lifetime was reduced to 1.5 ns, implying that FRET was occurring. Looking just at the fluorescence from FRET donors the lifetime was even shorter, at 1.3 ns, supporting this interpretation. In contrast, no reduction in lifetime is seen in the coral Euphyllia ancora, where the pigment distribution also suggests that the pigments are unlikely to be involved in photoprotection. This study set out to determine the extent of FRET between pigments in two corals, Acropora millepora and Euphyllia, ancora which differ in the arrangement of their pigments and hence possibly in pigment function.     

Photoprotective Role of Photosynthetic and Non-Photosynthetic Pigments in Phillyrea latifolia: Is Their “Antioxidant” Function Prominent in Leaves Exposed to Severe Summer Drought?

Carotenoids and phenylpropanoids play a dual role of limiting and countering photooxidative stress. We hypothesize that their “antioxidant” function is prominent in plants exposed to summer drought, when climatic conditions exacerbate the light stress. To test this, we conducted a field study on Phillyrea latifolia, a Mediterranean evergreen shrub, carrying out daily physiological and biochemical analyses in spring and summer. We also investigated the functional role of the major phenylpropanoids in different leaf tissues. Summer leaves underwent the most severe drought stress concomitantly with a reduction in radiation use efficiency upon being exposed to intense photooxidative stress, particularly during the central hours of the day. In parallel, a significant daily variation in both carotenoids and phenylpropanoids was observed. Our data suggest that the morning-to-midday increase in zeaxanthin derived from the hydroxylation of ß-carotene to sustain non-photochemical quenching and limit lipid peroxidation in thylakoid membranes. We observed substantial spring-to-summer and morning-to-midday increases in quercetin and luteolin derivatives, mostly in the leaf mesophyll. These findings highlight their importance as antioxidants, countering the drought-induced photooxidative stress. We concluded that seasonal and daily changes in photosynthetic and non-photosynthetic pigments may allow P. latifolia leaves to avoid irreversible photodamage and to cope successfully with the Mediterranean harsh climate.     

Antenna Protein Clustering In Vitro Unveiled by Fluorescence Correlation Spectroscopy

Antenna protein aggregation is one of the principal mechanisms considered effective in protecting phototrophs against high light damage. Commonly, it is induced, in vitro, by decreasing detergent concentration and pH of a solution of purified antennas; the resulting reduction in fluorescence emission is considered to be representative of non-photochemical quenching in vivo. However, little is known about the actual size and organization of antenna particles formed by this means, and hence the physiological relevance of this experimental approach is questionable. Here, a quasi-single molecule method, fluorescence correlation spectroscopy (FCS), was applied during in vitro quenching of LHCII trimers from higher plants for a parallel estimation of particle size, fluorescence, and antenna cluster homogeneity in a single measurement. FCS revealed that, below detergent critical micelle concentration, low pH promoted the formation of large protein oligomers of sizes up to micrometers, and therefore is apparently incompatible with thylakoid membranes. In contrast, LHCII clusters formed at high pH were smaller and homogenous, and yet still capable of efficient quenching. The results altogether set the physiological validity limits of in vitro quenching experiments. Our data also support the idea that the small, moderately quenching LHCII oligomers found at high pH could be relevant with respect to non-photochemical quenching in vivo.     

Quality by design (QbD), Process Analytical Technology (PAT), and design of experiment applied to the development of multifunctional sunscreens

Multifunctional formulations are of great importance to ensure better skin protection from harm caused by ultraviolet radiation (UV). Despite the advantages of Quality by Design and Process Analytical Technology approaches to the development and optimization of new products, we found in the literature only a few studies concerning their applications in cosmetic product industry. Thus, in this research work, we applied the QbD and PAT approaches to the development of multifunctional sunscreens containing bemotrizinol, ethylhexyl triazone, and ferulic acid. In addition, UV transmittance method was applied to assess qualitative and quantitative critical quality attributes of sunscreens using chemometrics analyses. Linear discriminant analysis allowed classifying unknown formulations, which is useful for investigation of counterfeit and adulteration. Simultaneous quantification of ethylhexyl triazone, bemotrizinol, and ferulic acid presented at the formulations was performed using PLS regression. This design allowed us to verify the compounds in isolation and in combination and to prove that the antioxidant action of ferulic acid as well as the sunscreen actions, since the presence of this component increased 90% of antioxidant activity in vitro.     

Infrared photoprotection properties of cosmetic products: correlation between measurement of the anti-erythemic effect in vivo in man and the infrared reflection power in vitro

Measurements were carried out on 19 commercial cosmetic samples. Initially, their anti-infrared properties were quantified, in vivo , on healthy volunteers, by measuring variations in the Colorimetric Erythema Index ΔCEI, before and after application of a normalized quantity of product. Subsequently, the physico-chemical response of the product was tested in vitro by measuring the infrared reflection coefficient ΔIR at 800 nm.
The correlation established between these two parameters enables products to be ranked in three categories. A good correlation was demonstrated between reflective power (ΔIR) and anti-erythemic properties (—ΔCEI) of the products in the first two groups.
A qualitative examination of the diffraction of X-rays confirms the presence of titanium dioxide, TiO₂ rutile, in most products with high IR protection properties whereas TiO₂ anatase was detected in a sample with no IR reflection properties.     

A novel sunscreen system based on tocopherol acetate incorporated into solid lipid nanoparticles

Synopsis Solid lipid nanoparticles (SLN) have been introduced as a novel carrier system for drugs and cosmetics. It has been found that SLN possess characteristics of physical UV-blockers on their own, thus offering the possibility of developing a more effective sunscreen system with reduced side-effects. Incorporation of the chemical sunscreen tocopherol acetate into SLN prevents chemical degradation and increases the UV-blocking capacity. Aqueous SLN dispersions were produced and incorporated into gels, followed by particle size examination, stability testing upon storage and thermoanalytical examination. Investigation of the UV-blocking capacity using different in vitro techniques revealed that the SLN dispersions produced in this study are at least twice as effective as their reference emulsions (conventional emulsions with identical lipid content). Placebo SLN even show greater UV-blocking efficacy than emulsions containing tocopherol acetate as the molecular sunscreen. Incorporation of tocopherol acetate into SLN leads to an overadditive UV-blocking effect. Furthermore, film formation of SLN on the skin and occlusivity were examined. The obtained data show that incorporation of tocopherol acetate into SLN leads to an improved sunscreen and skin care formulation.