Cytotoxic clerodane diterpenes from Casearia rupestris.

Four new clerodane diterpenes, casearupestrins A-D (1-4), were isolated from the leaves of Casearia rupestris. Compounds 1 and 4 were acetylated to yield 2,7-di-O-acetylcasearupestrin A (5) and 2,6-di-O-acetylcasearupestrin D (6). All compounds were evaluated for cytotoxicity against a small panel of human cancer cell lines. Casearupestrin A (1) exhibited the most potent activity against MDA/MB-435 (human melanoma) and SF-295 (human glioblastoma) cells, superior to that of the standard drug doxorubicin.

Cytotoxic clerodane diterpenoids from Casearia obliqua.

A crude bioactive EtOH extract of the twigs of Casearia obliqua afforded two new clerodane diterpenes, caseobliquins A (1) and B (2). Additionally, bioactivity-directed fractionation on a bioactive hexane extract of the leaves from this species led to the isolation of the known clerodane diterpenes rel-6beta-hydroxyzuelanin-2beta-benzoate and rel-2alpha-hydroxyzuelanin-6beta-benzoate (3 and 4) as a mixture and 2beta-hydroxyzuelanin-6beta-cinnamate (5). The structures of the new clerodanes 1 and 2 were established on the basis of their 1D and 2D NMR spectroscopic data, and the new compound 1 and the known substance 5 had their absolute configurations determined by circular dichroism spectroscopy. The cytotoxicity of several of the compounds isolated was evaluated against a small panel of human tumor cell lines.

1H NMR determination of adulteration of anabolic steroids in seized drugs.

Counterfeiting and adulteration of pharmaceuticals is a prevalent problem worldwide and represents a major health risk to the population, with anabolic steroids being one of the main classes of drugs consumed and obtained from dubious sources. In this work, we propose the use of the 1H NMR technique to evaluate formulations containing anabolic steroids, with analysis of 40 samples of anabolic drugs that are used in injectable and capsule forms. The samples analyzed presented the following active ingredients: testosterone propionate, testosterone phenylpropionate, testosterone isocaproate, testosterone decanoate, testosterone cypionate, testosterone undecanoate, stanozolol, drostanolone propionate, trenbolone acetate, oxymetholone, and methandrostenolone. The 1H NMR spectroscopic measurements were performed using a 600 MHz Bruker Avance III spectrometer, with deuterated chloroform (CDCl3) containing 0.1% TMS as solvent. Of the 40 samples analyzed, eight did not show the presence of the active principle stated on the label. Three types of adulteration were found in the analyzed samples: absence of the active ingredient, adulteration with other substances, and concentration values below those indicated on the label. Sildenafil citrate was found in four samples. The GC-MS technique was used to confirm the adulteration results found using 1H NMR. Quantitative determination by NMR was performed using internal standard and ERETIC 2 methods, and the results obtained were statistically the same.

Fingerprint and authenticity roasted coffees by 1H-NMR: the Brazilian coffee case.

With globalization, it has become necessary to adopt policies to regulate the coffee market, addressing problems including the authenticity and traceability of products. It is therefore important to establish methodologies that can help to safeguard the interests of producer countries and add value to products. For this purpose, the use of NMR combined with multivariate statistical procedures can be an attractive option. The aim of this study was to develop a fast and effective technique, using 1H NMR coupled with multivariate statistics, to create a fingerprint of roasted coffees, distinguishing them according to the main Brazilian producer regions. Several compounds suitable for differentiating roasted coffees were identified in the fingerprint. Discriminant analysis revealed good distinction among the samples. The compounds catechol, trigonelline, caffeine, and n-methylpyridine were most important for the differentiation. The findings should assist coffee-producing countries in adopting measures to protect their markets and to add value to coffee products.

Evaluation of different electrochemical methods on the oxidation and degradation of Reactive Blue 4 in aqueous solution.

The oxidation of a reactive dye, Reactive Blue 4, RB4, (C.I. 61205), widely used in the textile industries to color natural fibers, was studied by electrochemical techniques. The oxidation on glassy carbon electrode and reticulated vitreous carbon electrode occurs in only one step at 2.0 < pH < 12 involving a two-electron transfer to the amine group leading to the imide derivative. Dye solution was not decolorized effectively in this electrolysis process. Nevertheless, the oxidation of this dye on Ti/SnO2/SbO(x) (3% mol)/RuO2 (1% mol) electrode showed 100% of decolorization and 60% of total organic carbon removal in Na2SO4 0.2 M at pH 2.2 and potential of +2.4V. Experiments on degradation photoelectrocatalytic were also carried out for RB4 degradation in Na2SO4 0.1 M, pH 12, using a Ti/TiO2 photoanode biased at +1.0 V and UV light. After 1h of electrolysis the results indicated total color removal and 37% of mineralization.

Chemical constituents from Casearia spp. (Flacourtiaceae/Salicaceae sensu lato)

ABSTRACT Chemical investigation of the leaves of Casearia gossypiosperma Briq., Salicaceae, led to the isolation of two known flavonoids, (+)-taxifolin and quercetin, the leaves of Casearia decandra Jacq. have afforded hydroquinone, the leaves of Casearia rupestris Eichler and Casearia lasiophylla Eichler have afforded a diterpene, (E)-phytol, and the leaves of C. rupestris and Casearia obliqua Spreng. have afforded sitosterol. The twigs of Casearia lasiophylla Eichler led to the isolation of two compounds (+)-pinoresinol, and N-trans-feruloyltyramine, and the twigs of C. obliqua have afforded N-trans-feruloyltyramine, N-trans-cumaroyltyramine, and cinamic acid. This is the first report of the compounds (+)-taxifolin, quercetin, hydroquinone, (+)-pinoresinol and N-trans-cumaroyltyramine from the Casearia genus.

Carbon nuclear magnetic resonance spectroscopic fingerprinting of commercial gasoline: pattern-recognition analyses for screening quality control purposes.

In this work, the combination of carbon nuclear magnetic resonance ((13)C NMR) fingerprinting with pattern-recognition analyses provides an original and alternative approach to screening commercial gasoline quality. Soft Independent Modelling of Class Analogy (SIMCA) was performed on spectroscopic fingerprints to classify representative commercial gasoline samples, which were selected by Hierarchical Cluster Analyses (HCA) over several months in retails services of gas stations, into previously quality-defined classes. Following optimized (13)C NMR-SIMCA algorithm, sensitivity values were obtained in the training set (99.0%), with leave-one-out cross-validation, and external prediction set (92.0%). Governmental laboratories could employ this method as a rapid screening analysis to discourage adulteration practices.

Screening Brazilian commercial gasoline quality by hydrogen nuclear magnetic resonance spectroscopic fingerprintings and pattern-recognition multivariate chemometric analysis.

The identification of gasoline adulteration by organic solvents is not an easy task, because compounds that constitute the solvents are already in gasoline composition. In this work, the combination of Hydrogen Nuclear Magnetic Resonance ((1)H NMR) spectroscopic fingerprintings with pattern-recognition multivariate Soft Independent Modeling of Class Analogy (SIMCA) chemometric analysis provides an original and alternative approach to screening Brazilian commercial gasoline quality in a Monitoring Program for Quality Control of Automotive Fuels. SIMCA was performed on spectroscopic fingerprints to classify the quality of representative commercial gasoline samples selected by Hierarchical Cluster Analysis (HCA) and collected over a 6-month period from different gas stations in the São Paulo state, Brazil. Following optimized the (1)H NMR-SIMCA algorithm, it was possible to correctly classify 92.0% of commercial gasoline samples, which is considered acceptable. The chemometric method is recommended for routine applications in Quality-Control Monitoring Programs, since its measurements are fast and can be easily automated. Also, police laboratories could employ this method for rapid screening analysis to discourage adulteration practices.

Esteroide e Triterpenos de espécies de Qualea - Bioatividade sobre Mycobacterium tuberculosis / Sterol and Triterpenes from Qualea species: Bioactivity on Mycobacterium tuberculosis

O extrato clorofórmico das cascas de Qualea parviflora (Vochysiaceae) foi fracionado em cromatografia em coluna usando sílica gel para fornecer triterpenos (lupeol, lupenona, betulina, ácido epibetulínico, e friedelina) e um esteroide (β-sitosterol). Os compostos β- sitosterol, lupenona e lupeol foram identificados também em Q. grandiflora e Q. multiflora, enquanto friedelina foi detectada apenas em Q. multiflorautilizando a cromatografia gasosa acoplada à espectrometria de massas. A atividade anti Mycobacterium tuberculosis do extrato clorofórmico e dos compostos isolados foi determinada por MABA e o valor da CIM variou de 250,0 a 31,2 μg/mL. Esta investigação constitui o primeiro relato do estudo químico e antitubercular de compostos apolares das espécies de Qualea.

The chloroform extract of bark of the tropical tree Qualea parviflora (Vochysiaceae) was fractionated by column chromatography on silica gel, yielding triterpenes (lupeol, lupenone, betulin, epibetulinic acid and friedelin) and a steroid (β-sitosterol). β-sitosterol, lupenone and lupeol were also identified in Q. grandiflora and Q. multiflora, while friedelin was detected only in Q. Multiflora, by means of gas chromatography-mass spectrometry. The anti-Mycobacterium tuberculosis activity of the chloroform extract and isolated compounds was assayed by MABA and MIC values ranged from 250.0 to 31.2 μg/mL. This study is the first to investigate the chemistry and antitubercular activity of apolar compounds from Qualeaspecies.