Adenine nucleobase directed supramolecular architectures based on ferrimagnetic heptanuclear copper(II) entities and benzenecarboxylate anions.

Two planar organic anions, benzoate and benzene-1,4-dicarboxylate (terephthalate), have been selected as potential π-stacking intercalators among ferrimagnetic [Cu7(µ-adeninato)6(µ3-OH)6(µ-H2O)6]2+ heptameric discrete entities. The resulting supramolecular architecture is highly dependent on the negative charge density distribution, mainly located in the carboxylate groups of the organic anions. In this sense, the benzoate anion, with just one carboxylate group, does not allow its intercalation between the adeninato ligands as it would imply a high steric hindrance among the heptameric entities. As a consequence, these benzoate anions are located inside the voids of the crystal structure reducing the accessible volume of compound [Cu7(µ-adeninato)6(µ3-OH)6(µ-H2O)6](benzoate)2·~17H2O (1). On the contrary, the terephthalate anion, containing two carboxylate groups at opposite sites, adopts a π-stacking sandwich arrangement between two adeninato ligands that affords the porous open structure of formula [Cu7(µ-adeninato)6(µ3-OH)6(µ-H2O)6](terephthalate)·nH2O (2a, 2b; n: 12 and 24, respectively). In addition to that, the less directional nature of the π-stacking interactions in comparison to the complementary hydrogen bonding based supramolecular metal-organic frameworks (SMOFs), suits them with a flexible architecture able to reversibly adsorb/desorb water (up to a 25-30% at 20 °C) altogether with the expansion/shrinkage of the crystal structure. The bridging adeninato and hydroxido ligands are effective magnetic exchange mediators to provide a ST = 5/2 ferrimagnetic state for the heptanuclear entity.

Evaluation of biocompatible monomers as substitutes for TEGDMA in resin-based dental composites.

This works reports the synthesis and characterization of diallyl(5-(hydroxymethyl)-1,3-phenylene) dicarbonate (HMFBA) and 5-(hydroxymethyl)-1,3-phenylene bis(2-methylacrylate) (HMFBM) monomers and its evaluation as Bis-GMA eluents in the formulation of composite resins for dental use. The experimental materials formulated with HMFBA and HMFBM monomers presented flexural strength values similar to those of the control group formulated with Bis-GMA/TEGDMA. Regarding volumetric contraction percentage, the values obtained of experimental materials with HMFBA was 1.88% and for HMFBM was 4.15%, both lower than control resin (4.68%). In the case of double bond conversion, the resin formulated with HMFBA monomer exhibited a greater degree of conversion (87%). Besides, the DMA analyses proved that the values for Tg guarantee a good mechanical performance at body temperature. The new resins formulated with HMFBA and HMFBM monomers exhibit a cellular viability close to 100%, which indicates the absence of cytotoxicity towards fibroblastic cells.

Supramolecular Interactions Modulating Electrical Conductivity and Nanoprocessing of Copper-Iodine Double-Chain Coordination Polymers.

Two coordination polymers (CPs), based on Cu(I)-I double zig-zag chains bearing isonicotinic acid or 3-chloroisonicotinic acid as terminal ligands with molecular recognition capabilities, have been synthesized and fully characterized. Both compounds present extended networks with supramolecular interactions directed by the formation of H-bonds between the complementary carboxylic groups, giving supramolecular sheets. The chloro substituent allows establishing additional Cl···Cl supramolecular interactions that reinforce the stability of the supramolecular sheets. These CPs are semiconductor materials; however, the presence of chlorine produces slight changes in the I-Cu-I chains, generating a worse overlap in the Cu-I orbitals, thus determining a decrease in its electrical conductivity value. These experimental results have also been corroborated by theoretical calculations using the study of the morphology of the density of states and 3D orbital isodensities, which determine that conductivity is mostly produced through the Cu-I skeleton and is less efficient in the case of the chloro derivative compound. A fast and efficient bottom-up approach based on the self-assembly of the initial building blocks and the low solutibility of these CPs has proved very useful for the production of nanostructures.

Are Chileans exposed to dietary furan?

Chilean consumer preferences include foods that may contain considerable amounts of furan, a potential human carcinogen. However, there is no information regarding dietary exposure to furan in Chile. Thus, the objective of this work was to determine the Chilean exposure to dietary furan. To accomplish this objective, the furan concentration of 14 types of commercial foods processed at high temperature were analysed based on a modified headspace-GC/MS (HS-GC/MS) method in which the limits of detection for different food matrices ranged from 0.01 to 0.6 ng g(-1). In addition, a risk assessment was made with exposure estimates based on dietary data from national studies on different age groups (9-month-old babies, school children, adults and elderly people). Of the food items surveyed "American"-type coffee (espresso coffee plus hot water) obtained from automatic coffee machine (936 ng g(-1)) and low moisture starchy products like crisps and "soda"-type crackers showed the highest furan concentrations (259 and 91 ng g(-1), respectively). Furthermore, furan was also found in samples of breakfast cereals (approximately 20 ng g(-1)), jarred fruit baby foods (8.5 ng g(-1)) and orange juice (7.0 ng g(-1)). School children (aged 9-13 years) represented the highest intake of furan (about 500 ng kg(-1)(bw) day(-1)), with margins of exposure of 2479 and 2411, respectively, which points to a possible public health risk.

Preparation of O-methyl substituted 2-oxofuro- and 2-oxopyrrolidinoindolines by reductive lactonization of oxindol-3-ylacetic acids.

A practical procedure for the preparation of O-methyl substituted 3a,8-dialkyl-2-oxofuroindolines is described. Reductive lactonization of the corresponding oxindol-3-ylacetic acids provides a route for the formation of this class of compounds. Further transformation of 2-oxofuroindolines into 2-oxopyrrolidinoindolines, and then to pyrrolidinoindolines demonstrates their versatility as key intermediates in natural products synthesis. The results of single-crystal X-ray crystallographic analyses are given for five of the studied compounds.

C-6 regioselective bromination of methyl indolyl-3-acetate.

An efficient route to natural occurring methyl 6-bromoindolyl-3-acetate 1c from methyl indolyl-3-acetate 3 was achieved in 3 steps and 68% overall yield. Thus, in order to regioselectively brominate 3 at the C6-position, introduction of electron withdrawing substituents at N1 and C8 was affected to give intermediate 4 in 82% yield. Bromination of 4 with 8 equiv of bromine in CCl4 and washings with aqueous Na2SO3 gave 5 in 86% yield, which was N- and C-decarbomethoxylated by treatment with NaCN in DMSO, affording 1c in 97% yield. The regioselectivity of bromination was evidenced by NMR spectroscopy and X- ray diffraction analysis.

Mediterranean diet and red wine protect against oxidative damage in young volunteers.

OBJECTIVE: To assess the effect on oxidative damage of the administration of a Mediterranean diet (MD) compared with an Occidental diet (OD), in young adult volunteers, with or without the concomitant intake of red wine. DESIGN: Forty-two omnivorous male students 20-27 years old were given either diet for 3 months. During the first and third month they received the prepared diets alone but during the second month they also had 240 ml/day of red wine. Blood and urine samples were taken at 0, 30, 60, and 90 days for analyses. A linear mixed effect model was used to compare the effect of both diets and wine, controlling values by baseline measurements. RESULTS: MD increased plasma vitamin C, beta-carotene and total antioxidant reactivity (TAR). OD increased plasma vitamin E. Wine supplementation, analyzed combining both diet groups, raised plasma vitamin C, beta-carotene, uric acid, TAR, plasma and urinary polyphenols and decreased plasma vitamin E. Also wine intake increased concentration of red blood cell (RBC) glutathione while significantly decreasing plasma glutathione. In oxidative damage measurements OD group showed higher concentration of 8-hydroxy-2'-deoxyguanosine (8-OHdG) in DNA from peripheral blood leukocytes and plasma nitrotyrosine, when compared with MD group. Wine intake significantly decreased 8-OHdG and plasma nitrotyrosine in both diets, particularly in OD. CONCLUSION: Volunteers on MD showed better antioxidant defenses and less oxidative damage than those on OD. Moderate wine consumption improved antioxidant defenses in both groups and counteracted the oxidative damage observed with OD.

DMD mediated formal synthesis of (+/-)-coerulescine.

A highly efficient method for the formal synthesis of the natural product (+/-)-coerulescine 1 from tetrahydro-beta-carboline 3, mediated by dimethyldioxirane (DMD), is described. Compound 15, the N9-demethylated precursor of 1, was prepared from 3 in 4 steps with an overall yield of 95%. The effect of electron withdrawing groups at the N2,N9 atoms of 3 was explored for the oxidative rearrangement step.

Effects of a dairy product fortified with multiple micronutrients and omega-3 fatty acids on birth weight and gestation duration in pregnant Chilean women.

OBJECTIVE: To test the hypothesis that maternal food fortification with omega-3 fatty acids and multiple micronutrients increases birth weight and gestation duration, as primary outcomes. DESIGN: Non-blinded, randomised controlled study. SETTING: Pregnant women received powdered milk during their health check-ups at 19 antenatal clinics and delivered at two maternity hospitals in Santiago, Chile. SUBJECT: Pregnant women were assigned to receive regular powdered milk (n = 477) or a milk product fortified with multiple micronutrients and omega-3 fatty acids (n = 495). RESULTS: Intention-to-treat analysis showed that mean birth weight was higher in the intervention group than in controls (65.4 g difference, 95% confidence interval (CI) 5-126 g; P = 0.03) and the incidence of very preterm birth (0.80 just for mean birth weight and birth length in the on-treatment analysis; birth length in that analysis had a difference of 0.57 cm (95% CI 0.19-0.96 cm; P = 0.003). CONCLUSIONS: The new intervention resulted in increased mean birth weight. Associations with gestation duration and most secondary outcomes need a larger sample size for confirmation.

Effect of Mediterranean and Occidental diets, and red wine, on plasma fatty acids in humans. An intervention study.

The type of diet consumed by individuals has been associated with the development of some chronic diseases, including cardiovascular disease (CVD), cancer, diabetes, and others. Populations that consume diets rich in fruits and vegetables and drink wine in moderation, as the Mediterranean, have a higher life expectancy and less chronic diseases than other occidental populations. We carried out an intervention study in humans to evaluate the effect of a Mediterranean diet (MD), an Occidental diet (OD) and their supplementation with red wine, on biochemical, physiological and clinical parameters related to atherosclerosis and other chronic diseases. For 3 months, two groups of 21 male volunteers each, received either a MD or an OD; during the second month, red wine was added isocalorically, 240 ml/day. At days 0, 30, 60 and 90, clinical, physiological and biochemical evaluations were made. In this article we report on the results obtained in plasma fatty acids profile that includes saturated fatty acids (SFA), monounsaturated fatty acids (MUFA), polyunsaturated fatty acids (PUFA), omega-6 fatty acids, omega-3 fatty acids and omega-6/omega-3 ratio. Other results have been published previously. Plasma fatty acid percentages in the OD group, compared to the MD group, did not show differences in SFA, but the OD group showed lower levels of MUFA and omega-3 fatty acids, and higher levels of PUFA and omega-6 fatty acids, with a higher omega-6/omega-3 ratio than the MD group. Wine supplementation reduced MUFA and increased PUFA in both dietary groups, suggesting that wine could improve a diet with a good omega-6/omega-3 ratio. Volunteers on MD showed a better fatty acid profile than those on OD, suggesting a lower cardiovascular risk. Moderate consumption of wine improves this profile in the MD group.

Effect of mediterranean and occidental diets, and red wine, on plasma fatty acids in humans: an intervention study

The type of diet consumed by individuals has been associated with the development of some chronic diseases, including cardiovascular disease (CVD), cancer, diabetes, and others. Populations that consume diets rich in fruits and vegetables and drink wine in moderation, as the Mediterranean, have a higher life expectancy and less chronic diseases than other occidental populations. We carried out an intervention study in humans to evaluate the effect of a Mediterranean diet (MD), an Occidental diet (OD) and their supplementation with red wine, on biochemical, physiological and clinical parameters related to atherosclerosis and other chronic diseases. For 3 months, two groups of 21 male volunteers each, received either a MD or an OD; during the second month, red wine was added isocalorically, 240 ml/day. At days 0, 30, 60 and 90, clinical, physiological and biochemical evaluations were made. In this article we report on the results obtained in plasma fatty acids profile that includes saturated fatty acids (SFA), monounsaturated fatty acids (MUFA), polyunsaturated fatty acids (PUFA), ómega-6 fatty acids, ómega-3 fatty acids and ómega-6/ómega-3 ratio. Other results have been published previously. Plasma fatty acid percentages in the OD group, compared to the MD group, did not show differences in SFA, but the OD group showed lower levels of MUFA and ómega-3 fatty acids, and higher levels of PUFA and ómega-6 fatty acids, with a higher ómega-6/ómega-3 ratio than the MD group. Wine supplementation reduced MUFA and increased PUFA in both dietary groups, suggesting that wine could improve a diet with a good ómega-6/ómega-3 ratio. Volunteers on MD showed a better fatty acid profile than those on OD, suggesting a lower cardiovascular risk. Moderate consumption of wine improves this profile in the MD group.