ABSTRACT
The synthesis and photophysical properties of six new abietic acid based amine end-capped p-phenylenevinylene trimers (AECPV3) in their lowest excited singlet states are presented. The AECPV3 compounds show a large red-shift of both the absorption (25-30 nm) and emission (37-42 nm) maxima with respect to those of the corresponding trimers. Picosecond time-resolved fluorescence data reveal the presence of a fast conformational relaxation process (40-62 ps) of the initially excited compounds, leading to more planar conformers. The conformational relaxation time is proportional to the volume of both the side chain and the amine groups.
Subject(s)
Abietanes/chemistry , Amines/chemistry , Polyvinyls/chemistry , Fluorescence , Molecular Conformation , Photochemistry , Polyvinyls/chemical synthesis , Solutions/chemistry , Solvents/chemistry , Spectrometry, Fluorescence/methods , Temperature , Time FactorsABSTRACT
The antifungal activity of 10 dehydroabietic acid derivatives with different configuration in A and B rings (cis/trans A/B junction) and different substituents and/or functionalities was evaluated in bioassays in vitro and in situ (pine wood blocks). The test compounds dissolved in acetone were assayed at several concentrations w/w (test compound/culture medium) against the fungi. The Relative Inhibition (RI) was determined by measuring the radial growth of colonies of the fungi treated with the test compounds by comparison with those of control cultures; the results are expressed as EC(50). The results of bioassays in vitro have shown that hydroxyl and aldehyde functions are required for antifungal activity in this group of compounds and deisopropylation can increase the activity. Our assay of antifungal activity in situ (in pine wood blocks) provides a means to investigate the preservative activities of these antifungal compounds under actual conditions of use. The dehydroabietic acid derivative cis-deisopropyldehydroabietanol (10) inhibited the growth of several of the fungi tested, in vitro and in situ. The results obtained in situ with the test compound (10) at 6% and 8% were not significantly different from the reference products and a good level of protection of the wood against the organisms tested was achieved. The results in wood bioassays present new possibilities in the search for natural new compounds in the wood protection, as an alternative to conventional fungicides.
Subject(s)
Abietanes/pharmacology , Antifungal Agents/pharmacology , Fungi/drug effects , Wood/microbiology , Abietanes/chemistry , Antifungal Agents/chemistry , Fungi/isolation & purification , Structure-Activity RelationshipABSTRACT
The wide potential of resin acids as bioactive agents gave rise to a growing effort in the search for new applications of the natural forms and their derivatives. In some of these compounds, the antimicrobial activity is associated to the presence in the molecules of functional groups such as the hydroxyl, aldehyde, and ketone or to their cis or trans configurations. The resin acid family covers a spectrum of antimicrobial activities against several microorganisms, from bacteria to fungi, in which the mode of action was studied by electron microscopy. The morphological alterations are consistent with an unspecific mode of action causing inhibition of the fungal growth or damaging the fungal cells in parallel with a mechanism of resistance based on the retention of the compound by the lipid accumulation. The sterol composition of phytopathogenic fungi Botrytis cinerea and Lophodermium seditiosum treated with methyl cis-7-oxo-deisopropyldehydroabietate revealed the presence of ergosterol (M+ 396) and dihydroergosterol (M+ 398) in both cultures showing that this compound did not interfere with the ergosterol metabolic pathway of both fungi.
Subject(s)
Anti-Bacterial Agents/pharmacology , Antifungal Agents/pharmacology , Bacteria/drug effects , Diterpenes/pharmacology , Fungi/drug effects , Resins, Plant/pharmacology , Anti-Bacterial Agents/chemistry , Antifungal Agents/chemistry , Antifungal Agents/pharmacokinetics , Diterpenes/chemistry , Diterpenes/pharmacokinetics , Fungi/chemistry , Fungi/cytology , Resins, Plant/chemistry , Resins, Plant/pharmacokinetics , Structure-Activity RelationshipABSTRACT
The fluorescence properties of new [60] and [70] fullerene-coumarin diads are studied. These diads were synthesized by covalently linking a coumarin dye to a fullerene (C60 or C70) by a cyclopropanation reaction. The absorption and fluorescence spectra, quantum yields and lifetimes of the diads are reported. The fluorescence quenching of the coumarin moiety by the fullerene was observed in all diads, indicating the occurrence of resonance energy transfer between the coumarin and fullerene moieties.
Subject(s)
Coumarins/chemistry , Fluorescence Resonance Energy Transfer , Fullerenes/chemistry , FluorescenceABSTRACT
The demand for novel effective antioxidant-based drugs has led to the synthesis and evaluation of the antioxidant potential in several molecules derived from natural compounds. In this work the in vitro antioxidant activity of an abietic acid-derived catechol (methyl 11,12-dihydroxyabietate-8,11,13-trien-18-oate, MDTO) was evaluated. This substance, possessing important biological properties, is similar to carnosic acid, a natural antioxidant from rosemary or sage leaves. Aiming to understand the antioxidant activity of MDTO, the energetics of its O-H bond, using time-resolved photoacoustic calorimetry (TR-PAC), was investigated. On energetic grounds it is predicted that MDTO is a good free radical scavenger, although its activity is lower than that of quercetin, a very effective antioxidant, which was used for comparison. In agreement with these predictions, the DPPH(*) and ABTS(*+) radical scavenging activities are lower than those of quercetin. In addition, MDTO also reacts with HOCl, a powerful proinflammatory oxidant produced by activated neutrophils, and protects liposomes against iron-ascorbate-induced oxidation. The discussion of these results foresees potential applications of MDTO as an antioxidant.
Subject(s)
Abietanes/chemistry , Antioxidants/pharmacology , Catechols/chemistry , Catechols/pharmacology , Phenanthrenes/chemistry , Benzothiazoles , Biphenyl Compounds , Calorimetry/methods , Free Radical Scavengers/chemistry , Lipid Peroxidation/drug effects , Liposomes/chemistry , Picrates , Sulfonic Acids , ThermodynamicsABSTRACT
Several heterocycles, such as benzimidazoles, quinoxalines and indoles incorporated into a hydrophenanthrene and naphthalene skeleton, were synthesised from two useful ortho-bromonitro precursors derived from dehydroabietic acid: methyl 12-bromo-13-nitro-deisopropyldehydroabietate and methyl 12-bromo-13,14-dinitro-deisopropyldehydroabietate. The new heterocycles were evaluated for their activity in vitro against several RNA and DNA viruses.
Subject(s)
Abietanes/chemical synthesis , Antiviral Agents/pharmacology , Benzimidazoles/chemical synthesis , Indoles/chemical synthesis , Quinoxalines/chemical synthesis , Abietanes/pharmacology , Animals , Benzimidazoles/pharmacology , Cell Line , Chlorocebus aethiops , Cytomegalovirus/drug effects , Drug Evaluation, Preclinical/methods , Fibroblasts/drug effects , Fibroblasts/virology , HeLa Cells , Herpesvirus 1, Human/drug effects , Herpesvirus 2, Human/drug effects , Herpesvirus 3, Human/drug effects , Humans , Indoles/pharmacology , Quinoxalines/pharmacology , Sindbis Virus/drug effects , Vero CellsABSTRACT
A chiral vanadyl salen complex having two peripheral trimethoxysilyl groups has been used to obtain a chiral periodic mesoporous organosilica having MCM-41 periodicity and the two Si-CH2 groups anchored on the framework; this solid induces 30% enantioselectivity in the cyanosilylation of benzaldehyde.
ABSTRACT
The synthesis and the evaluation of the antimicrobial activity against a filamentous fungus, yeasts and bacteria of 15 hydrophenanthrene compounds derived from dehydroabietic acid, bearing different functional groups and different stereochemistry of the A/B ring junction are disclosed. The results obtained showed how their activity is dependent of the functionality at C-18, which can be increased by deisopropylation or introduction of other groups into the molecule. While the filamentous fungus tested is sensitive to almost all of the compounds under study, the aldehyde function showed to be of major importance to the inhibition of yeast. Alcohols and aldehyde C-18 derivatives also inhibit the growth of a Gram-positive bacteria, whereas Gram-negative are not sensitive.
