The swelling of microcrystalline cellulose by the use of polar protic solvents such as ethanol or methanol enables the penetration of benzophenone into submicroscopic pores of the natural polymer, while solvents such as benzene or dichloromethane do not open the polymer chains, thus not producing any entrapped benzophenone. Ground-state diffuse reflectance studies revealed a dramatic blue shift in the 350-nm absorption of benzophenone in the former case, in accordance with a strong interaction of the hydroxyl groups of cellulose with the ketone. Diffuse reflectance laser flash photolysis studies of benzophenone adsorbed on microcrystalline cellulose showed, in cases where benzophenone is entrapped in the polymer chain, the formation of a transient which decays nonexponentially and exhibits a maximum absorption at about 530 nm, assigned to triplet benzophenone. After ca. 25 ps, this transient generates another species with an absorption maximum at 545 nm. We assigned this new species to the diphenylketyl radical. In all cases where the solvent does not swell cellulose, a different behavior was observed typical for benzophenone microcrystals triplet decay. The ketyl radical formation is greatly reduced in this case. Triplet benzophenone decays by complex kinetics and lives about 10 ps when adsorbed onto microcrystalline cellulose, while the ketyl radical, when formed, lives 1 order of magnitude longer than the triplet. Samples which exhibit a high yield of ketyl radical formation also have a smaller phosphorescence emission in accordance with the fact that large amount of triplet molecules were consumed in the process of hydrogen abstraction from the matrix, involving hydrogens linked to carbons bearing a hydroxyl group.

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Complexes formed between (-)-sparteine, 2-methyl- and 2-oxosparteine and 2-cyano-2- methylsparteine with lithium perchlorate (LiClO4) were obtained in the solid state. The complexes, C15H26N2LiClO4, C16H28N2LiClO4, C15H24N2OLiClO4, and C17H27N3Li2Cl2O8 have been isolated and characterised by UV/vis, NMR, and IR, spectroscopy and by their mass spectra. Three of the four complexes present the 1:1 stoichiometry, while the 2-cyano-2-methylsparteine complex has the 1:2 stoichiometry.

There is growing interest in the use of natural agents with antimicrobial (AM) and antioxidant (AOX) properties. Optimization of the AM capacity for mixtures containing carvacrol, grape seed extract (GSE) and chitosan, against gram-negative (Pseudomonas aeruginosa), gram-positive bacteria (Staphylococcus aureus, Listeria innocua and Enterococcus faecalis) and yeast (Saccharomyces cerevisiae) at 106 cfu mL-1 was studied. To observe the synergistic or antagonistic effect and find optimal combinations between the three agents, a simplex centroid mixture design was run for each microorganism, combining carvacrol (0-300 ppm, X1), GSE (0-2000 ppm, X2) and chitosan (0-2% w/v, X3). Results of the response surface analysis showed several synergistic effects for all microorganisms. Combinations of 60 ppm-400 ppm-1.2% w/v (carvacrol-GSE-chitosan; optimal AM combination 1, OAMC-1); 9.6 ppm-684 ppm-1.25% w/v (OAMC-2); 90 ppm-160 ppm-1.24% w/v (OAMC-3) were found to be the optimal mixtures for all microorganisms. Radical scavenging activity (RSA) of the same agents was then compared with a standard AOX (butylated hydroxytoluene; BHT) at different concentrations (25, 50 and 100 ppm; as well as the optimal AM concentrations) by the 1,1-diphenyl-2-picrylhydrazyl (DPPH) method. RSA increased in the following order: chitosan< carvacrol< BHT< GSE and for the OAMC: OAMC-2< OAMC-1< OAMC-3. The best RSA (OAMC-3) was applied as a coating in two different food matrices (strawberries and salmon). For strawberries, P. aeruginosa was more sensitive to the action of OAMC-3 than S. cerevisiae. For salmon, S. aureus was more resistant to the action of OAMC-3 than E. faecalis and L. innocua.

Flavins are a unique class of compounds that combine the features of singlet oxygen generators and redox-dependent fluorophores. From a broad family of flavin derivatives, deazaalloxazines are significantly underdeveloped from the point of view of photophysical properties. Herein, we report photophysics of 5-deazaalloxazine (1a) in water, acetonitrile, and some other solvents. In particular, triplet excited states of 1a in water and in acetonitrile were investigated using ultraviolet–visible (UV–Vis) transient absorption spectroscopy. The measured triplet lifetimes for 1a were all on the microsecond time scale (≈ 60 μs) in deoxygenated solutions. The quantum yield of S1 → T1 intersystem crossing for 1a in water was 0.43 based on T1 energy transfer from 1a to indicaxanthin (5) acting as acceptor and on comparative actinometric measurements using benzophenone (6). 1a was an efficient photosensitizer for singlet oxygen in aerated solutions, with quantum yields of singlet oxygen in methanol of about 0.76, compared to acetonitrile ~ 0.74, dichloromethane ~ 0.64 and 1,2-dichloroethane ~ 0.54. Significantly lower singlet oxygen quantum yields were obtained in water and deuterated water (ФΔ ~ 0.42 and 0.44, respectively). Human red blood cells (RBC) were used as a cell model to study the antioxidant capacity in vitro and cytotoxic activity of 1a. Fluorescence-lifetime imaging microscopy (FLIM) data were analyzed by fluorescence lifetime parameters and distribution for different parts of the emission spectrum. Comparison of multidimensional fluorescent properties of RBC under physiological-like and oxidative-stress conditions in the presence and absence of 1a suggests its dual activity as probe and singlet-oxygen generator and opens up a pathway for using FLIM to analyze complex intracellular behavior of flavin-like compounds. These new data on structure–property relationship contribute to the body of information required for a rational design of flavin-based tools for future biological and biochemical applications. Graphical abstract

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