Behavior of phenols and phenoxyacids on a bisphenol-a imprinted polymer. Application for selective solid-phase extraction from water and urine samples

A molecularly imprinted polymer (MIP), obtained by precipitation polymerisation with 4-vinylpyridine as the functional monomer, ethylene glycol dimethacrylate as cross-linker, and bisphenol-A (BPA) as template, was prepared. The binding site configuration of the BPA-MIP was examined using Scatchard analysis. Moreover, the behaviour of the BPA-MIP for the extraction of several phenolic compounds (bisphenol-A, bisphenol-F, 4-nitrophenol, 3-methyl-4-nitrophenol) and phenoxyacid herbicides such as 2,4-D, 2,4,5-T and 2,4,5-TP has been studied in organic and aqueous media in the presence of other pesticides in common use. It was possible to carry out the selective preconcentration of the target analytes from the organic medium with recoveries of higher than 70%. In an aqueous medium, hydrophobic interactions were found to exert a remarkably non-specific contribution to the overall binding process. Several parameters affecting the extraction efficiency of the BPA-MIP were evaluated to achieve the selective preconcentration of phenols and phenoxyacids from aqueous samples. The possibility of using the BPA-MIP as a selective sorbent to preconcentrate these compounds from other samples such as urine and river water was also explored.     

Comparison of a pair of synthetic tea-catechin-derived epimers: synthesis, antifolate activity, and tyrosinase-mediated activation in melanoma

Despite bioavailability issues, tea catechins have emerged as promising chemopreventive agents because of their efficacy in various animal models. We synthesized two catechin-derived compounds, 3-O-(3,4,5-trimethoxybenzoyl)-(-)-catechin (TMCG) and 3-O-(3,4,5-trimethoxybenzoyl)-(-)-epicatechin (TMECG), in an attempt to improve the stability and cellular absorption of tea polyphenols. The antiproliferative and pro-apoptotic activities of both compounds were analyzed with various cancer cell systems, and TMCG, which was easily synthesized in excellent yield, was more active than TMECG in both melanoma and non-melanoma cell lines. TMCG was also a better inhibitor of dihydrofolate reductase and was more efficiently oxidized by tyrosinase, potentially explaining the difference in activity between these epimers.     

Photochemistry of group 6 Fischer carbene complexes: beyond the photocarbonylation reaction

The seminal report by Hegedus in 1982, showing that alkoxychromium(0) carbenes reacted with imines under bright Colorado sunlight to yield β-lactams, marked the beginning of a key reaction in organometallic chemistry. Very little was known about the mechanism of this reaction. In fact, Hegedus proposed the reversible generation of a chromium-coordinated ketene, which would react with nucleophiles. This coordinated species would show all the advantages of ketenes without their shortcomings, namely, dimerization, formation of undesired adducts, and so forth. The quest for the detection of these species and the pursuit of the mechanism of the photocarbonylation (a reaction exclusive to Cr(0) and Mo(0) carbene complexes, not W(0) carbene complexes) remained unabated over the next 15 years. In fact, all attempts to experimentally determine the mechanism of this useful reaction have been fruitless. At the same time, the photocarbonylation of Cr(0) carbenes matured into a valuable synthetic reaction, allowing access to several families of organic compounds. Unfortunately, reactions other than photocarbonylation remained elusive. We used a combination of experimental and computational methodologies to study the photocarbonylation of Cr(0) carbene complexes and the subsequent reaction of the photogenerated ketenes with nucleophiles. In parallel, we discovered new photochemical processes and succeeded in making photoreactive the so-called "unreactive" W(0) carbene complexes. In this Account, we discuss the disentangling of the mechanisms of these transformations, thereby shedding some light onto the photochemistry of group 6 metal (Fischer) carbene complexes. The original designation of the electronic transitions of group 6 carbene complexes was reassigned, and the photocarbonylation step was analyzed again, resulting in the sequence S(0)-T(1)-S(0), which is far removed from conventional organic photochemistry. The T(1) species is a chromacyclopropanone; its unpaired electrons are primarily localized in the metal fragment and in the former carbene carbon atom. The T(1)-S(0) intersystem crossing occurs with the participation of the solvent through an unusual loose-bolt radiationless mechanism. The photogenerated S(0) species reacts with imines to form the final β-lactams in a mechanism that resembles the organic Staudinger reaction, but here the metal is present during the entire reaction coordinate. The selectivity of these reactions is defined by the nucleophilic attack on the O-bonded metallaketene instead of the subsequent conrotatory ring closure, a distinct departure from the organic reaction. Appropriate modification of the substituents of the carbene ligand or in the coordination sphere of the complex results in new photoprocesses; these include 1,2-metalladyotropic rearrangements as well as α-fragmentations in which W(0) carbene complexes become photoreactive. Moreover, the inclusion of additional metal centers usually results in new reactions, such as the formation of fulvenes by η(5)→ η(3) photoslippage, or in the complete inhibition of the photoreactivity. The photochemistry of group 6 metal-carbene complexes thus offers unexplored territory for pursuing new reactions and reaction mechanisms.     

Cohesive strength of nanocrystalline ZnO:Ga thin films deposited at room temperature

In this study, transparent conducting nanocrystalline ZnO:Ga (GZO) films were deposited by dc magnetron sputtering at room temperature on polymers (and glass for comparison). Electrical resistivities of 8.8 × 10-4 and 2.2 × 10-3 Ω cm were obtained for films deposited on glass and polymers, respectively. The crack onset strain (COS) and the cohesive strength of the coatings were investigated by means of tensile testing. The COS is similar for different GZO coatings and occurs for nominal strains approx. 1%. The cohesive strength of coatings, which was evaluated from the initial part of the crack density evolution, was found to be between 1.3 and 1.4 GPa. For these calculations, a Young's modulus of 112 GPa was used, evaluated by nanoindentation.     

Beyond transition state theory: accurate description of nuclear quantum effects on the rate and equilibrium constants of chemical reactions using Feynman path integrals

Nuclear tunneling and other nuclear quantum effects have been shown to play a significant role in molecules as large as enzymes even at physiological temperatures. I discuss how these quantum phenomena can be accounted for rigorously using Feynman path integrals in calculations of the equilibrium and kinetic isotope effects as well as of the temperature dependence of the rate constant. Because these calculations are extremely computationally demanding, special attention is devoted to increasing the computational efficiency by orders of magnitude by employing efficient path integral estimators.     

Evaluation of Antioxidant Compounds and Total Sugar Content in a Nectarine [Prunus persica (L.) Batsch] Progeny

Epidemiological studies suggest that consumption of fruit rich in phenolic compounds is associated with health-protective effects due to their antioxidant properties. For these reasons quality evaluation has become an important issue in fruit industry and in breeding programs. Phytochemical traits such as total phenolics, flavonoids, anthocyanins, L-ascorbic acid, sugar content and relative antioxidant capacity (RAC) were analyzed over four years in flesh fruit of an F1 population "Venus" × "Big Top" nectarines. Other traits such as harvesting date, yield, fruit weight, firmness, soluble solids concentration (SSC), pH, titratable acidity (TA) and ripening index (RI) were also determined in the progeny. Results showed high variability among genotypes for all analyzed traits. Total phenolics and flavonoids showed significant positive correlations with RAC implying that both are important antioxidant bioactive compounds in peaches. We found genotypes with enhanced antioxidant capacity and a better performance than progenitors, and in consequence the best marketability.     

gef Gene Expression in MCF-7 Breast Cancer Cells is Associated with a Better Prognosis and Induction of Apoptosis by p53-Mediated Signaling Pathway

Breast cancer research has developed rapidly in the past few decades, leading to longer survival times for patients and opening up the possibility of developing curative treatments for advanced breast cancer. Our increasing knowledge of the biological pathways associated with the progression and development of breast cancer, alongside the failure of conventional treatments, has prompted us to explore gene therapy as an alternative therapeutic strategy. We previously reported that gef gene from E. coli has shown considerable cytotoxic effects in breast cancer cells. However, its action mechanism has not been elucidated. Indirect immunofluorescence technique using flow cytometry and immunocytochemical analysis were used to detect breast cancer markers: estrogen (ER) and progesterone (PR) hormonal receptors, human epidermal growth factor receptor-2 proto-oncogene (c-erbB-2), ki-67 antigen and p53 protein. gef gene induces an increase in ER and PR expressions and a decrease in ki-67 and c-erbB-2 gene expressions, indicating a better prognosis and response to treatment and a longer disease-free interval and survival. It also increased p53 expression, suggesting that gef-induced apoptosis is regulated by a p53-mediated signaling pathway. These findings support the hypothesis that the gef gene offers a new approach to gene therapy in breast cancer.     

Comparative study using different infrared zones of the solventless activation of organic reactions

In this work, the results of a study comparing the use of irradiation from different regions of the infrared spectrum for the promotion of several organic reactions, are presented and discussed. This use of eco-conditions provides a green approach to chemical synthesis. A set of ten different organic reactions were evaluated, including the Knoevenagel, Hantzsch, Biginelli and Meldrum reactions. It is important to highlight the use of a commercial device that produces infrared irradiation in the near infrared region and its distribution by convection providing heating uniformity, significantly reducing reaction times, achieving good yields and proceeding in the absence of solvent. It is also worth noting that a variety of different reactions may be performed at the same time. Finally, the products obtained were identified using TLC, together with corresponding MS-data, complementarily in comparison of NMR (1)H and (13)C data with literature information.