Eco-Friendly Synthesis of an Oxovanadium(IV)-bis(abietate) Complex with Antimicrobial Action

The search for less expensive and viable products is always one of the challenges for research development. Commonly, the synthesis of coordination compounds involves expensive ligands, through expensive and low-yield routes, in addition to generating toxic and unusable residues. In this work, the organic ligand used is derived from the resin of a reforestation tree, Pinus elliottii var. elliottii. The synthesis method used Pinus resin and an aqueous solution of vanadium(III) chloride at a temperature of 80 °C. The procedure does not involve organic solvents and does not generate toxic residues, thus imparting the complex formation reaction a green chemistry character. The synthesis resulted in an unprecedented oxovanadium(IV)-bis(abietate) complex, which was characterized by mass spectrometry (MS), chemical analysis (CHN), vibrational (FTIR) and electronic spectra (VISIBLE), X-ray diffraction (XRD), and thermal analysis (TG/DTA). Colorimetric studies were performed according to the CIELAB color space. The structural formula found, consisted of a complex containing two abietate ligands, [VO(C₂₀H₂₉O₂)₂]. The VO(IV)-bis(abietate) complex was applied against microorganisms and showed promising results in antibacterial and antifungal activity. The best result of inhibitory action was against the strains of Gram-positive bacteria S. aureus and L. monocytogenes, with minimum inhibitory concentration (MIC) values of 62.5 and 125 μmol L⁻¹, respectively. For Gram-negative strains the results were 500 μmol L⁻¹ for E. coli; and 1000 μmol L⁻¹ for Salmonella enterica Typhimurium. Antifungal activity was performed against Candida albicans, where the MIC was 15.62 μmol L⁻¹, and for C. tropicalis it was 62.5 μmol L⁻¹. According to the MFC analysis, the complex presented, in addition to the fungistatic action, a fungicidal action, as there was no growth of fungi on the plates tested. The results found for the tests demonstrate that the VO(IV)-bis(abietate) complex has great potential as an antimicrobial and mainly antifungal agent. In this way, the pigmented ink with antimicrobial activity could be used in environments with a potential risk of contamination, preventing the spread of microorganisms harmful to health.     

Crystallization behavior of isotactic polypropylene based nanocomposites

The effect of clay dispersion on the crystallization behavior of isotactic polypropylene (iPP)-based nanocomposites is reported. The T _m⁰ of the materials was calculated by the method proposed by Marand, the kinetics of crystallization was evaluated by the Avrami analysis and also the Hoffman-Lauritzen theory of crystallization regimes was applied. Montmorillonite was found to depress T _m⁰, to enhance the rate of crystallization and to ease the chain folding of macromolecules. These effects were magnified if clay was exfoliated, rather than intercalated.     

Synthesis of Catechol Derived Rosamine Dyes and Their Reactivity toward Biogenic Amines

Functional organic dyes play a key role in many fields, namely in biotechnology and medical diagnosis. Herein, we report two novel 2,3- and 3,4-dihydroxyphenyl substituted rosamines (3 and 4, respectively) that were successfully synthesized through a microwave-assisted protocol. The best reaction yields were obtained for rosamine 4, which also showed the most interesting photophysical properties, specially toward biogenic amines (BAs). Several amines including n- and t-butylamine, cadaverine, and putrescine cause spectral changes of 4, in UV–Vis and fluorescence spectra, which are indicative of their potential application as an effective tool to detect amines in acetonitrile solutions. In the gas phase, the probe response is more expressive for spermine and putrescine. Additionally, we found that methanolic solutions of rosamine 4 and n-butylamine undergo a pink to yellow color change over time, which has been attributed to the formation of a new compound. The latter was isolated and identified as 5 (9−aminopyronin), whose solutions exhibit a remarkable increase in fluorescence intensity together with a shift toward more energetic wavelengths. Other 9-aminopyronins 6a, 6b, 7a, and 7b were obtained from methanolic solutions of 4 with putrescine and cadaverine, demonstrating the potential of this new xanthene entity to react with primary amines.     

Effects of Lactobacillus rhamnosus on zebrafish oocyte maturation: an FTIR imaging and biochemical analysis

The aim of this study was to verify the effects of probiotic Lactobacillus rhamnosus on zebrafish oocyte maturation using FPA (focal plane array) FTIR imaging together with specific biochemical assays (SDS-PAGE, real-time PCR and enzymatic assay). Oocyte growth is prevalently due to a vitellogenic process which consists of the hepatic synthesis of vitellogenin and its selective uptake during maturation. The administration of L. rhamnosus IMC 501 for 10 days induced chemical changes to oocyte composition, promoting the maturation process. Some interesting biochemical features, linked to protein secondary structure (amide I band) and to phospholipidic and glucidic patterns, were detailed by vibrational analysis. The spectroscopic results were supported by the early increase of the lysosomal enzyme involved in the final oocyte maturation, the cathepsin L. This enzyme increases during follicle maturation, with the highest levels in class IV oocytes. In treated females, class III oocytes showed higher cathepsin L gene expression and enzymatic activity, with levels comparable to class IV oocytes isolated from controls; this can be related to the proteolytic cleavage of the higher molecular mass yolk protein components, as evidenced by SDS-PAGE.     

FTIR microspectroscopy of melanocytic skin lesions: a preliminary study

Fourier transform infrared (FTIR) microspectroscopy has been employed to investigate benign (ordinary dermal and Reed nevi), dysplastic and malignant (invasive melanoma) skin lesions through the analysis of spectral changes of melanocytes as well as in the evaluation of the presence of melanin. Hierarchical cluster analysis and principal component analysis led to a satisfactory separation of malignant from dysplastic and normal melanocytes. Also, on enlarging the clustering with spectra from Reed and dermal nevi, the multivariate analysis segregated well the spectral data into discrete clusters, allowing the obtaining of reliable average spectra for analysis at the molecular level of the main groups or components responsible for the biological and biochemical changes. The most significant spectral characteristics appear to be related to differences in secondary protein structures, in nucleic acid conformation, in intra- and intermolecular bonding. In all cases, supervised and unsupervised spectral analyses resulted in satisfactory agreement with histopathological findings.     

New designs for inhibitors of the NF-κB: DNA binding

We present a series of new inhibitors of the association between nuclear factor kappa B (NF-B) and the corresponding B site in DNA. They were designed using the lead compound 15-deoxy-^12,14 -prostaglandin J₂ (PGJ2), which is a natural product with demonstrated inhibitory efficiency for this system. First, the binding mode of PGJ2 to NF-B was unraveled by GOLD docking calculation. Subsequently, substitutions were made to PGJ2 to optimize its association with NF-B. Care was taken not to strongly increase the reactivity of the new compounds, and to keep the overall shape, size and hydrophilicity of the lead compound, which should render them a similar bioavailability. Molecular mechanics calculations were performed to decide on the suitability of the substitutions, and to evaluate the energies of association with NF-B. Density functional theory calculations were performed also to study the overall reactivity of the substituted drugs towards NF-B. Important general conclusions were obtained, concerning the improvement of these natural inhibitors; namely, a set of rational methodologies were deduced to improve the association between the PGJ2 derivatives and NF-B, and their efficiency demonstrated by generating a set of substituted complexes, some of them with a very much increased affinity for NF-B, opening new doors to enlarge the therapeutic capabilities of this class of drugs.     

Molecular structure-activity relationships for the oxidation of organic compounds using mesoporous silica catalysts derivatised with bis(halogeno)dioxomolybdenum(VI) complexes

Mo K-edge XAFS spectra have been measured for ordered mesoporous silica MCM-41 grafted with the complexes [MoO2X2(thf)2] (X=Cl, Br). For grafting reactions in the absence of triethylamine, materials with 1 wt. % Mo are obtained; the Mo K-edge EXAFS results indicate the co-existence of isolated surface-fixed monomeric species [MoO2[(-O)3SiO]2(thf)(n)] and [MoO2[(-O)3SiO]X(thf)(n)]. When Et3N is used in the grafting reactions, materials with 4 wt. % Mo are obtained. The EXAFS data for the material prepared using [MoO2Cl2(thf)2] and Et3N indicate the presence of dinuclear species with two Mo(VI) centres, each with two Mo=O groups and each linked by one or two oxo bridges (Mo...Mo 3.27 A). The molybdenum centres in the material prepared using the dibromo complex comprise mainly isolated four-coordinate dioxomolybdenum(VI) and trioxomolybdenum(VI) monomeric species, with a small contribution from dimeric species. All materials were further characterised in the solid state by powder X-ray diffraction, N2 adsorption analysis, MAS NMR (13C, 29Si) and FTIR spectroscopy. The derivatised MCMs perform differently as catalysts in the liquid-phase oxidation of various olefins and alcohols with tert-butyl hydroperoxide. The highest alkene epoxidation activity was recorded for the catalysts with low metal loading, whereas the material containing oxo-bridged dimers had the highest activity for oxidation of alcohols. The recyclability of all the catalysts was tested: the catalytic activity of the derivatised materials tended to stabilize with ageing.     

Pharmacological and Therapeutic Potential of Myristicin: A Literature Review

Natural products have been used by humanity for many centuries to treat various illnesses and with the advancement of technology, it became possible to isolate the substances responsible for the beneficial effects of these products, as well as to understand their mechanisms. In this context, myristicin, a substance of natural origin, has shown several promising activities in a large number of in vitro and in vivo studies carried out. This molecule is found in plants such as nutmeg, parsley, carrots, peppers, and several species endemic to the Asian continent. The purpose of this review article is to discuss data published in the last 10 years at Pubmed, Lilacs and Scielo databases, reporting beneficial effects, toxicity and promising data of myristicin for its future use in medicine. From 94 articles found in the literature, 68 were included. Exclusion criteria took into account articles whose tested extracts did not have myristicin as one of the major compounds.     

Determination of ethyl formate in magnesium chloride used as Ziegler-Natta catalyst support by Fourier transform infrared attenuated total reflectance spectrometry

FT-IR Spectroscopy with total attenuated reflectance (ATR) was used for the quantitative determination of ethyl formate coordinated in inorganic matrices such as magnesium chloride. The spectra were recorded directly on solutions obtained by dissolving the inorganic Ziegler-Natta supports in water. The method proposed is sensitive and rapid and appears to be very reliable when compared with other methods, such as solvent extraction followed by gaschromatographic or thermogravimetric analysis.