HPLC-based method using sample pre-column clean-up for the determination of methanethiol and ethanethiol in parenteral amino acid solutions

A method has been developed for the chromatographic determination of methanethiol (MT) and ethanethiol (ET) as contaminants in amino acid parenteral nutrition (PN) solutions. The clean-up of the samples before chromatographic analysis was investigated by solid-phase extraction (SPE) on pre-columns filled with polyethylene powder (PE), aluminium oxide (AlOx), silica (SiOx), or polyurethane foam (PUF) as adsorbents. The thiols were more efficiently separated from the matrices by SPE on PUF pre-columns. Simultaneous derivatization and elution with DTNB (5,5′-dithiobis(2-nitrobenzoic acid)) enabled further discrimination between MT and ET by reversed-phase HPLC with spectrophotometric detection. The retention times for the derivatized MT and ET species were 12.5 and 23.0 min, respectively. Recoveries from spiked PN samples were calculated to be approximately 90%, and the MT and ET content of commercial PN solutions was determined using the methodology described. Detection limits of 15 and 10 μg L^–1 were calculated for MT and ET, respectively.     

Synthesis and mechanism of formation of novel 2,5-dihydro-2,5-diimino-3,4-di[(N,N-dimethylamino)methylideneamino]pyrroles and 5-amino-3,4-di[(N,N-dimethylamino)methylideneamino]-2H-2-iminopyrroles

Formation of 5-amino-3,4-di[(N,N-dimethylarnino)methylidenearnino]-2H-2-iminopyrroles 3 from the reaction of (Z)-N¹-(2-amino-1,2-dicyanovinyl)-N²-substituted-formamidines 1 with dimethylformamide diethyl acetal has been shown to occur by initial formation of (Z)-N¹-{l,2-dicyano-2-[N,N-dimethylamino)methylideneamino]vinyl}formamidines 8 (isolated), followed by base catalysed cyclisation and imi dazole ring opening by dimethyl amine. The kinetic product of the ring opening reaction is the 2,5-diimino2,5-dihydropyrrole derivatives 11, which have been isolated and characterized spectroscopically and by a single crystal X-ray analysis on the R = Ph derivative. In solution at room temperature the N-aryl derivatives undergo a rapid Dimroth rearrangement to give the thermodynamic ally more stable isomer 3 , but compound 11 (R = Me) is much more stable in solution.     

Brazilian bioethanol program

Brazil is the largest producer of bioethanol, and sugarcane is the main raw material. Bioethanol, is produced by both batch and continuous processes, and in some cases, flocculating yeast is use. This article analyzes the Bracilian Ethanol Program. for the 1996–1997 havest, Brazil produced 14.16 billion L of ethanol and 13.8 million metrict of sugar, from 286 million metrict of sugarcane. These products were produced by 328 industries inactivity, with 101 autonomousethanol plants producing only ethanol, and 227 sugar mills producing sugar and ethanol. The sugar-ethanol market reaches about 7.5 billion US$/yr, accounting for direct and indirect revenues.     

Identification of vertebrate type steroid hormones in the shrimp Penaeus japonicus by tandem mass spectrometry and sequential product ion scanning

The identification of testosterone, pregnelonone, and 17α-hydroxyprogesterone by tandem mass spectrometry and of progesterone by sequential product ion scanning in the shrimp gonads of Penaeus japonicus is described. The identification of these substances in biological samples is usually done by gas chromatography-mass spectrometry and involves several liquid chromotographic purification steps followed by derivatization. The utilization of tandem mass spectrometry in this analysis has simplified considerably the sample pretreatment and provided a very simple method of screening these substances in complex mixtures.     

Monitoring Stimulated Darkening from UV-C Light on Different Bean Genotypes by NMR Spectroscopy

The use of UV-C cool white light on bean (Phaseolus vulgaris L.) seeds significantly increases the biochemical seed coat post-harvest darkening process, whilst preserving seed germination. The aim of this work consists in monitoring the effect caused by the incidence of UV-C light on different bean genotypes using NMR spectroscopy. The genotype samples named IAC Alvorada; TAA Dama; BRS Estilo and BRS Pérola from the Agronomic Institute (IAC; Campinas; SP; Brazil) were evaluated. The following two methodologies were used: a prolonged darkening, in which the grain is placed in a room at a controlled temperature (298 K) and humidity for 90 days, simulating the supermarket shelf; an accelerated darkening, where the grains are exposed to UV-C light (254 nm) for 96 h. The experiments were performed using the following innovative time-domain (TD) NMR approaches: the RK-ROSE pulse sequence; one- and two-dimensional high resolution (HR) NMR experiments (¹H; ¹H-¹H COSY and ¹H-¹³C HSQC); chemometrics tools, such as PLS-DA and heat plots. The results suggest that the observed darkening occurs on the tegument after prolonged (90 days) and accelerated (96 h) conditions. In addition, the results indicate that phenylalanine is the relevant metabolite within this context, being able to participate in the chemical reactions accounted for by the darkening processes. Additionally, it is possible to confirm that a UV-C lamp accelerates oxidative enzymatic reactions and that the NMR methods used were a trustworthy approach to monitor and understand the darkening in bean seeds at metabolite level.     

Piper tectoniifolium Kunth: A New Natural Source of the Bioactive Neolignan (−)-Grandisin

The Piper species are a recognized botanical source of a broad structural diversity of lignans and its derivatives. For the first time, Piper tectoniifolium Kunth is presented as a promising natural source of the bioactive (−)-grandisin. Phytochemical analyses of extracts from its leaves, branches and inflorescences showed the presence of the target compound in large amounts, with leaf extracts found to contain up to 52.78% in its composition. A new HPLC-DAD-UV method was developed and validated to be selective for the identification of (−)-grandisin being sensitive, linear, precise, exact, robust and with a recovery above 90%. The absolute configuration of the molecule was determined by X-ray diffraction. Despite the identification of several enantiomers in plant extracts, the major isolated substance was characterized to be the (−)-grandisin enantiomer. In vascular reactivity tests, it was shown that the grandisin purified from botanical extracts presented an endothelium-dependent vasorelaxant effect with an IC₅₀ of 9.8 ± 1.22 μM and around 80% relaxation at 30 μM. These results suggest that P. tectoniifolium has the potential to serve as a renewable source of grandisin on a large scale and the potential to serve as template for development of new drugs for vascular diseases with emphasis on disorders related to endothelial disfunction.     

Thermal and oxidative stability of Sacha Inchi oil and capsules formed with biopolymers analyzed by DSC and <Superscript>1</Superscript>H NMR

The oxidative stability of edible oils is an important feature to know due the undesirable changes that can occur in the storage. In this way, the oxidative induction time (OIT) value is an indicative to prevent this effect. The objectives of this study were to evaluate the omega-3 content and kinetic parameters of Sacha Inchi oil (SIO) and capsules that are formed with biopolymers, in addition, there were analyzed with differential scanning calorimetry (DSC) and proton nuclear magnetic resonance (¹H NMR). The SIO and capsules, formed using an emulsion, were analyzed with DSC in an oxygen atmosphere to determine the OIT value in isothermal conditions at 100, 120 and 150 °C. The kinetic parameters (activation energy, pre-exponential factor and z value) of SIO were obtained, and the stability time was predicted at different temperatures. The ¹H NMR spectra enabled us to assess the identification and percentage relative before and after the isothermal DSC oxidation of omega-3 concentration and formation of their oxidized compounds. (E-E)-2,4-Alkadienals were the primary oxidized compound and is strongly correlated with the decrease in omega-3 content. Isothermal DSC is a useful to determine the OIT (min) and kinetic parameters to predict the stability oxidation in different edible oils and thus prevent the inadequate consumption of edible oils oxidized.     

Development of a Library of Thiophene-Based Drug-Like Lego Molecules: Evaluation of Their Anion Binding,Transport Properties,and Cytotoxicity

The anion-binding and transport properties of an extensive library of thiophene-based molecules are reported. Seventeen bis-urea positional isomers, with different binding conformations and lipophilicities, have been synthesized by appending α- or β-thiophene or α-, β-, or γ-benzo[b]thiophene moieties to an ortho-phenylenediamine central core, yielding six subsets of positional isomers. Through ¹H NMR, X-ray crystallography, molecular modelling, and anion efflux studies, it is demonstrated that the most active transporters adopt a pre-organized binding conformation capable of promoting the recognition of chloride, using urea and C−H binding groups in a cooperative fashion. Additional large unilamellar vesicle-based assays, carried out under electroneutral and electrogenic conditions, together with N-methyl-d -glucamine chloride assays, have indicated that anion efflux occurs mainly through an H⁺/Cl⁻ symport mechanism. On the other hand, the most efficient anion transporter displays cytotoxicity against tumor cell lines, while having no effects on a cystic fibrosis cell line.     

Antiangiogenic and Antioxidant In Vitro Properties of Hydroethanolic Extract from açaí (Euterpe oleracea) Dietary Powder Supplement

The Euterpe oleracea fruit (açaí) is a promising source of polyphenols with health-promoting properties. To our knowledge, few studies have focused on the influence of açaí phytochemicals on angiogenesis, with a significant impact on cancer. This study aimed at investigating the phytochemical profile of a purple açaí hydroethanolic extract (AHE) obtained from a commercial dietary powder supplement by high-performance liquid chromatography coupled to diode array detection and electrospray ionization mass spectrometry, and evaluate its in vitro effects on distinct angiogenic steps during vessel growth and on oxidative markers in human microvascular endothelial cells (HMEC-1). The phenolic profile of AHE revealed the presence of significant levels of anthocyanins, mainly cyanidin-3-O-rutinoside, and other flavonoids with promising health effects. The in vitro studies demonstrated that AHE exerts antiangiogenic activity with no cytotoxic effect. The AHE was able to decrease HMEC-1 migration and invasion potential, as well as to inhibit the formation of capillary-like structures. Additionally, AHE increased antioxidant defenses by upregulating superoxide dismutase and catalase enzymatic activities, accompanied by a reduction in the production of reactive oxygen species. These data bring new insights into the potential application of angiogenic inhibitors present in AHE on the development of novel therapeutic approaches for angiogenesis-dependent diseases.