Mycosporines: are they nature's sunscreens?
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Biosynthetic incorporation of labeled sodium acetate into oxosorbicillinol in Trichoderma sp. USF-2690 suggests that oxosorbicillinol is derived from six acetate units, and subsequent bioconversion of the labeled oxosorbicillinol to bisvertinolone in the fermentation of the strain suggests that bisvertinolone is biosynthesized from oxosorbicillinol and sorbicillinol in a Michael-type reaction.
A potent antioxidant, bisorbicillinol, which is a member of the bisorbicillinoid family isolated from the culture broth of Trichoderma sp. USF-2690, produces a stable radical-terminated symmetric dimer by donating two hydrogen atoms to the 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical.
The first synthesis of two new antiprotozoal and natural products was performed using concomitant deprotecting dithiane-phenolic oxidative reactions to form in one-step the 1,7-dioxadispiro[5.1.5.2]pentadecane core.
The intramolecular Diels-Alder adduct 12 was converted via dimesylate 20 into dienone 7, which represents the unusual, and apparently quite stable, core of the antitumor agent ottelione B (1).
The Diels-Alder reaction of spirolactones with cyclopentadiene afforded the adduct with high pi-facial selectivity; a hydrophilic analogue of scyphostatin was synthesized from the Diels-Alder adduct.
A straightforward, low-cost fluoroimmunoassay (FIA) for the determination of the new triketone herbicide mesotrione has been developed and optimized. The protein-mesotrione conjugate, immobilized on white opaque microtitration wells competes with the mesotrione in the sample or standard for the limited binding sites of a liquid phase anti-mesotrione antibody. The assay is based on the measurement of fluorescence intensity directly onto the solid support, using a fluorescein labeled second antibody and a fluorescence plate reader. To stabilize and enhance the fluorescence signal a glycerine-based treatment of the microtitration wells was included in the protocol. The detection limit of the assay is 40 ng 1(-1) (4 pg per well), the working range extends up to 9 microg l(-1), whereas the within and between run CVs are 0.7-4.2% and 2.1-5.5%, respectively. To evaluate the assay specificity, the cross-reactivities of two mesotrione metabolites: 4-methylsulfonyl-2-nitrobenzoic acid and 2-amino-4-methylsulfonyl-benzoic acid and several other compounds similar in structure to mesotrione such as: fomesafen, prosulfocarb, fluazinam, sulcotrione, 1,2-cyclohexanedione, 1,3-cyclohexanedione, 2-acetyl-1,3-cyclohexanedione were assessed. Most of the substances tested presented very low ( < 0.05%) cross-reactivity values with the exception of sulcotrione that cross-reacted 23% in the mesotrione assay. The assay was used for the determination of mesotrione in bottled natural waters fortified with the analyte and in a commercial herbicide formulation, namely CALLISTO.
The immobilized resting-cell of Geotrichum candidum was used as a catalyst for the reduction of a ketone in a semi-continuous flow process using supercritical carbon dioxide for the first time; it was also applied for the asymmetric reduction of a ketone and resulted in excellent enantioselectivity (ee > 99%) and a higher space-time yield than that of the corresponding batch process.
We describe a concise and convergent synthesis of (rac)-5-methoxy-6-azatricyclco[7.3.1.0(2,7)]trideca-2(7),3,5,11-tetraen-13-ol, which has the basic ring system of huperzine A, a potent inhibitor of acetylcholinesterase. We also describe the synthesis of the novel system 5-methoxy-6-azatricyclo[7.2.2.0(2,7)]trideca-2(7),3,5-trien-10-one and a series of related systems.
The sonochemical asymmetric hydrogenation of isophorone (3,3,5-trimethyl-2-cyclohexenone) by proline-modified Pd/Al2O3 catalysts is described; presonication of a commercial Pd/Al2O3-proline catalytic system resulted in highly enhanced enantioselectivities (up to 85% ee).
In vitro studies on the structurally related mycosporine-like amino acids (MAAs) porphyra-334 and shinorine in aqueous solutions were carried out aiming at their full photochemical and photophysical characterization and expanding the evidence on the assigned UV-photoprotective role of the molecules in vivo. The experiments on shinorine confirmed a high photostability and a poor fluorescence quantum yield, in concordance with previous results on porphyra-334. The estimation of triplet production quantum yields for both MAAs was achieved by laser-flash photolysis measurements. In particular, photosensitization experiments on porphyra-334 support the participation of the triplet state in the photodecomposition mechanism yielding a more precise value of [capital Phi](T). As well, photoacoustic calorimetry experiments allowed the first direct quantification of the nonradiative relaxation pathways of the excited MAAs in solution, corroborating that the vast majority (ca. 97%) of the absorbed energy is promptly delivered to the surroundings as heat, consistently with the low photodecomposition and emission yields observed.
Under the conditions of a rapid injection experiment, the conjugate addition reactions of butyl Gilman reagents with 2-cyclohexenone undergo oscillations of a complex nature.
alpha-Allylcyclohexane-1,3-diones undergo one-pot iodine-methanol promoted iodocyclization and oxidative aromatization to afford variously substituted 2-iodomethyltetrahydrobenzofuran-4-ones (minor) and 2-iodomethyl-4-methoxydihydrobenzofuran derivatives (major). On the other hand, the alpha-allyl-1,3-cyclohexanediones react with pyridinium hydrobromide perbromide in dichloromethane to afford mixtures of 2-bromomethyltetrahydrobenzofuran-4-ones (major) and 3-bromomethyltetrahydrobenzopyran-5-ones (minor). The prepared products and their derivatives were characterized using a combination of NMR, FT-IR and mass spectroscopic techniques.
The mycosporine-like amino acid (MAA), porphyra-334 (lambda(max) = 334 nm; epsilon = 42,300 M(-1) cm(-1)), was isolated from the aquatic cyanobacterium Aphanizomenon flos-aquae (AFA) and its structure was verified by spectroscopic methods. The UVA absorption properties of the crude methanolic extract were determined against two commercial sun care products in terms of mean critical wavelength, mean UVA/UVB ratios and UVA protection category (Boots the Chemists, Ltd.). The crude methanolic extract from AFA exhibited maximum UVA protection comparable to that determined for Boots SPF 4.
Optically active 2,5-disubstituted-cyclohexen-2-one derivatives have been prepared in a one-pot process consisting of five reaction steps: an organocatalytic asymmetric conjugated addition of beta-ketoesters to alpha,beta-unsaturated aldehydes that proceeds in aqueous solutions or under solvent-free conditions has been implemented in a multi-step process.
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Explore the source record for details and available documents.