7.1',8.3'- and 7.3',8.5'-Connected Bicyclo[3.2.1]octanoids and Oxabicyclo[3.2.2]nonane-Type Neolignans from Ocotea aciphylla: Structures and Absolute Configurations.

The phytochemical investigation of the leaves and trunk bark of a specimen of Ocotea aciphylla collected in the southern portion of the Amazon forest led to the isolation of an oxabicyclo[3.2.2]nonane-type neolignan and 15 bicyclo[3.2.1]octanoid neolignans, 14 of which are unreported compounds (2-15), including one with an unusual oxidation pattern of the side chain at C-1' and two rare 7.1',8.3'-connected bicyclo[3.2.1]octanoid derivatives. Their structures and relative configurations were determined by extensive spectrometric analysis based on 1D- and 2D-NMR spectroscopy and HRESIMS data, while their absolute configurations were unambiguously assigned using electronic and vibrational circular dichroism data assisted by density functional theory calculations. Additionally, known sesquiterpenes, phenylpropanoids, and phytosterols were also isolated.

Surface Analysis of a Universal Resin Composite and Effect of Preheating on its Physicochemical Properties.

This study was aimed at analyzing the surface properties of a universal resin composite and evaluating the effect of preheating on its physicochemical properties. Two commercial resin composites were used under two conditions: Filtek Universal Restorative (UR); UR preheated (URH); Filtek Supreme (FS) and FS preheated (FSH). The film thickness (FT) test (n = 10) was done using two glass slabs under compression. Flexural strength (FLS) and modulus (FLM) were evaluated using a three-point flexion test (n = 10). Polymerization shrinkage stress (PSS) was evaluated in a universal testing machine (n = 5). Gap width (GW) between composite and mold was measured in internally polished metallic molds (n = 10). The degree of conversion (DC) was evaluated by Fourier Transform Infrared spectroscopy (n = 3). The morphology of the filler particles was checked by scanning electron microscope (SEM) and EDX analysis. Surface gloss (SG) and surface roughness (SR) were evaluated before and after mechanical brushing (n = 10). The outcomes were submitted to 2-way ANOVA and Tukey's test (α = 0.05). Lower mean values of FT were observed for the preheated groups when compared to the non-preheated groups. URH and FSH showed higher mean values of FLS and FLM when compared with UR and FS. No differences were observed between groups in the PSS test. The GW was higher for the UR and FS groups when compared with URH and FSH. The DC was higher for preheated resin composites when compared to the non-preheated groups. The SR of the UR composite was higher than the FS after mechanical brushing, while the SG was higher for the FS groups. In conclusion, the universal resin composite tested generally presented similar physicochemical properties compared with the nanofilled resin composite and either similar or slightly inferior surface properties. The preheating improved or maintained all properties evaluated.

Surface Analysis of a Universal Resin Composite and Effect of Preheating on its Physicochemical Properties

Abstract This study was aimed at analyzing the surface properties of a universal resin composite and evaluating the effect of preheating on its physicochemical properties. Two commercial resin composites were used under two conditions: Filtek Universal Restorative (UR); UR preheated (URH); Filtek Supreme (FS) and FS preheated (FSH). The film thickness (FT) test (n = 10) was done using two glass slabs under compression. Flexural strength (FLS) and modulus (FLM) were evaluated using a three-point flexion test (n = 10). Polymerization shrinkage stress (PSS) was evaluated in a universal testing machine (n = 5). Gap width (GW) between composite and mold was measured in internally polished metallic molds (n = 10). The degree of conversion (DC) was evaluated by Fourier Transform Infrared spectroscopy (n = 3). The morphology of the filler particles was checked by scanning electron microscope (SEM) and EDX analysis. Surface gloss (SG) and surface roughness (SR) were evaluated before and after mechanical brushing (n = 10). The outcomes were submitted to 2-way ANOVA and Tukey's test (α = 0.05). Lower mean values of FT were observed for the preheated groups when compared to the non-preheated groups. URH and FSH showed higher mean values of FLS and FLM when compared with UR and FS. No differences were observed between groups in the PSS test. The GW was higher for the UR and FS groups when compared with URH and FSH. The DC was higher for preheated resin composites when compared to the non-preheated groups. The SR of the UR composite was higher than the FS after mechanical brushing, while the SG was higher for the FS groups. In conclusion, the universal resin composite tested generally presented similar physicochemical properties compared with the nanofilled resin composite and either similar or slightly inferior surface properties. The preheating improved or maintained all properties evaluated.

Resumo Neste estudo avaliou-se propriedades físico-químicas e de superfície de um compósito universal pré-aquecido e comparado a um compósito convencional. Foram utilizados dois compósitos comerciais: Filtek Universal Restorative (UR); UR pré-aquecido (URH); Filtek Supreme (FS) e FS pré-aquecido (FSH). O teste de espessura de película (EP) (n = 10) foi feito usando duas placas de vidro sob compressão. A resistência à flexão (RF) e o módulo flexural (MF) foram avaliados por meio do teste de flexão de três pontos (n = 10). A tensão de contração de polimerização (TCP) foi avaliada em uma máquina de teste universal (n = 8). A largura da fenda (LF) entre o compósito e o molde foi medida em moldes metálicos polidos internamente (n = 10). O grau de conversão (GC) foi avaliado por espectroscopia de infravermelho com transformada de Fourier (n = 3). A morfologia das partículas de carga foi observada em microscopia eletrônica de varredura (MEV) e sua composição em EDX. Brilho superficial (BS) e rugosidade superficial (RS) foram avaliados antes e após escovação mecânica (n=10). Os resultados foram submetidos à ANOVA 2-fatores e as médias comparadas pelo teste de Tukey (α = 0,05). Menores valores médios de EP foram observados para os grupos pré-aquecidos quando comparados aos grupos não pré-aquecidos. URH e FSH apresentaram maiores valores médios de RF e MF quando comparados com UR e FS. Não foram observadas diferenças entre os grupos no teste TCP. A LF foi maior para os grupos UR e FS quando comparados com URH e FSH. O GC foi maior para os compósitos pré-aquecidos quando comparados aos não pré-aquecidos. A RS do compósito UR foi maior que o FS após a escovação mecânica, enquanto o BS foi maior para os grupos FS. Em conclusão, o compósito universal testado geralmente apresentou propriedades físico-químicas semelhantes em comparação ao compósito nanoparticulado e propriedades de superfície semelhantes ou ligeiramente inferiores. O pré-aquecimento melhorou ou manteve todas as propriedades avaliadas.

Effect of preheating on mechanical properties of a resin-based composite containing elastomeric urethane monomer.

This study investigated the effect of preheating an elastomeric urethane monomer (Exothane-24) experimental resin composite on its physicochemical properties. Two resin matrices were formulated: (a) 50 wt% Bisphenol-glycidyl methacrylate (Bis-GMA) and 50 wt% triethylene glycol dimethacrylate (TEGDMA); and (b) 20 wt% Exothane-24, 40 wt% Bis-GMA and 40 wt% TEGDMA. A photoinitiator system (0.25 wt% camphorquinone and 0.50 wt% ethyl-4-dimethylamino benzoate) and 65 wt% of the inorganic filler (20 wt% 0.05 µm silica and 80 wt% 0.7 µm BaBSiO2 glass) were added to both matrices. These formulations were then assigned to four groups: Exothane-24 (E); Exothane-24 plus preheating (EH); no Exothane-24 (NE); and no Exothane-24 plus preheating (NEH). NEH and EH were preheated at 69 °C. The dependent variables were as follows: film thickness (FT); polymerization shrinkage stress (PSS); gap width (GW); maximum rate of polymerization (Rpmax); and degree of conversion (DC). Data were statistically analyzed by two-way ANOVA and Tukey's test (α = 0.05). Preheating reduced FT for both composites. PSS and GW were significantly lower for EH, when compared with E. The DC for EH and NEH and the Rpmax for EH increased significantly. Preheating improved most of the physicochemical properties (FT, PSS, GW, and DC) of the experimental resin composite containing Exothane-24.

Antibacterial activity of prenylated benzopyrans from Peperomia obtusifolia (Piperaceae).

Peperomia obtusifolia is a herbaceous perennial plant native to the Americas reported as a traditional medicine to treat snake bites and as a skin cleanser. The bioassay-guided fractionation of crude extracts from aerial parts of P. obtusifolia against a panel of clinically important fungi and bacteria, showed that hexane and dichloromethane extracts demonstrated selective bacterial inhibition, allowing the isolation of the known compounds peperobtusin A (1), and 3,4-dihydro-5-hydroxy-2,7-dimethyl-8-(3"-methyl-2"-butenyl)-2-(4'-methyl-1',3'-pentadienyl)-2H-1-benzopyran-6-carboxylic acid (2) from dichloromethane extract. Compound 2 was active against Gram-positive bacteria including community acquired methicillin-resistant Staphylococcus aureus (CA-MRSA) isolates and an Enterococcus faecalis vancomycin-resistant strain, with minimal inhibitory concentration (MIC) values of 4 µg/mL (10.8 µM) and 8 µg/mL (21.6 µM) respectively. The interaction of compound 2 with the bacterial membrane was demonstrated by means of Zeta potential experiments on S. aureus, then confirming the membrane damage by fluorescent microscopy experiments.

Geranylation of benzoic acid derivatives by enzymatic extracts from Piper crassinervium (Piperaceae).

The ability to carry out geranylations on aromatic substrates using enzymatic extracts from the leaves of Piper crassinervium (Piperaceae) was evaluated. A literature analysis pointed out its importance as a source of prenylated bioactive molecules. The screening performed on aromatic acceptors (benzoic acids, phenols and phenylpropanoids) including geranyl diphosphate as prenyl donor, showed the biotransformation of the 3,4-dihydroxybenzoic acid by the crude extract, and the p-hydroxybenzoic acid by both the microsomal fraction and the crude extract, after treating leaves with glucose. The analysis of the products allowed the identification of C- and O-geranylated derivatives, and the protease (subtilisin and pepsin) inhibition performed on the O-geranylated compounds showed weak inhibition. Electrophoretic profiles indicated the presence of bands/spots among 56-58 kDa and pI 6-7, which are compatible with prenyltransferases. These findings show that P. crassinervium could be considered as a source of extracts with geranyltransferase activity to perform biotransformations on aromatic substrates.

Resolution and absolute configuration assignment of a natural racemic chromane from Peperomia obtusifolia (Piperaceae).

The resolution of the natural racemic chromane 3,4-dihydro-5-hydroxy-2,7-dimethyl-8-(3''-methyl-2''-butenyl)-2-(4'-methyl-1',3'-pentadienyl)-2H-1-benzopyran-6-carboxylic acid (1) isolated from the leaves of Peperomia obtusifolia has been accomplished using stereoselective HPLC. The absolute configuration of the resolved enantiomers was determined by the analysis of optical rotations and CD spectra. The finding of a racemic mixture instead of an enantiomerically pure metabolite raises questions about the final steps in the biosynthesis of this class of natural products, suggesting that the intramolecular chromane ring formation step may not be enzymatically controlled at all in P. obtusifolia.

Natural chromenes and chromene derivatives as potential anti-trypanosomal agents.

The aim of the study was to investigate the anti-trypanocidal activities of natural chromene and chromene derivatives. Five chromenes were isolated from Piper gaudichaudianum and P. aduncum, and a further seven derivatives were prepared using standard reduction, methylation and acetylation procedures. These compounds were assayed in vitro against epimastigote forms of Trypanosoma cruzi, the causative agent of Chagas disease. The results showed that the most of the compounds, especially those possessing electron-donating groups as substituents on the aromatic ring, showed potent trypanocidal activity. The most active compound, [(2S)-methyl-2-methyl-8-(3''-methylbut-2''-enyl)-2-(4'-methylpent-3'-enyl)-2H-chromene-6-carboxylate], was almost four times more potent than benznidazole (the positive control) and showed an IC50 of 2.82 microM. The results reveal that chromenes exhibit significant anti-trypanocidal activities and indicate that this class of natural product should be considered further in the development of new and more potent drugs for use in the treatment of Chagas disease.