Catalytic enantioselective arylations: boron to zinc exchange as a powerful tool for the generation of transferable aryl groups

The transmetalation between boron and zinc is of great importance for application in organic synthesis, since it allows the formation of new carbon-carbon bonds between organometallic units and electrophiles. The direct arylation of aldehydes or more scarcely ketones, in a catalytic, enantioselective manner using chiral catalysts has been described recently. The enantiomerically enriched diarylmethanols obtained in these reactions are valuable precursors for important bioactive molecules. This review provides a synopsis of this ever-growing field and highlights some of the challenges that still remain.

Diastereoselective Addition of Arylzinc Reagents to Sugar Aldehydes

The diastereoselective arylation of sugar-derived aldehydes is described. The arylating reagents are generated in situ by a boron-to-zinc exchange reaction of arylboronic acids with Et2Zn to generate arylethylzinc reagents. The exquisite reactivity of the arylzinc reagents allowed for an efficient and mild arylation, delivering the corresponding products in diastereolsomeric ratios of up to >20:1. The utility of the methodology is highlighted with an efficient formal synthesis of (+)-7-epl-goniofufurone, a member of the styryllactone family of natural products.

Effect of boron and zinc fertilization on white oats grown in soil with average content of these nutrients

The objective of this study was to evaluate the effect of fertilization with zinc or boron on the growth and dry matter production, nutritional value and accumulation of nutrients in white oats. The study comprised two experiments conducted in glasshouses, the first consisting of the application of four doses of zinc (0, 0.2, 0.4 and 0.6 mg/dm³) in the form of zinc sulphate (20% Zn), and the second consisting of the application of four doses of boron (0, 0.2, 0.4 and 0.6 mg/dm³) in the form of Borax (11% B). The experimental design in each case was a randomized block design, with five replicates. Fertilization with zinc and boron increased the growth of white oats, but had no significant effect on the nutritional value of the forage. Higher levels of absorption and accumulation of nutrients in plant tissues were observed following the application of boron and zinc at rates of up to 0.60 mg/dm³ of soil.

Leaf spray fertilization of boron and zinc on productivity and fruit quality of Japanese pear tree

The cultivation of fruit plants from temperate climate in tropical or subtropical regions can be a good income alternative for the producer. However, due to the little existent information about cultivation of those fruit plants, the producers use imported techniques of other producing areas, or even an association of practices used for other fruit plants, pointing out the leaf spray fertilization of micronutrients without appropriate scientific base. In this context, the objective of this study was to verify the effect of the leaf spray fertilization of B and Zn on productivity and fruit quality of Japanese pear tree. The experiment was conducted from 2004 to 2005, in Ilha Solteira, in northwestern São Paulo State-Brazil. The climate is, according to the Köpppen Classification, tropical wet and dry (Aw). The 'Okusankichi' cultivar, grafted on Pyrus communis L. rootstock was used as well as doses of 110 g.ha-1 of B and 250 g.ha-1 of Zn in each application. The treatments were: T1. water, T2. boric acid, T3. zinc sulfate, T4. T2 + T3, T5. boric acid + urea + citric acid + EDTA, T6. zinc sulfate + urea + citric acid + EDTA, T7. T5 + T6, T8. boric acid + urea + citric acid + EDTA + sodium molibdate + sulfur + calcium chloride, T9. zinc sulfate + urea + citric acid + EDTA + Fe sulfate + Mn sulfate + Mg sulfate and, T10. T8+T9. A randomized blocks design was used and the averages were compared by Tukey test. In the first crop the mixture of boric acid with quelating agents were efficient to supply B to the plants and zinc sulfate plus quelating agents were efficient to increase Zn leaf content. However, the productivity and the fruit quality were not influenced by the leaf spray of B and Zn. In the second crop the leaf content of B and Zn and the productivity were not influenced by the leaf spray; the boric acid and the zinc sulfate with or without quelating agents increased the contents of total soluble solids and, the boric acid with or without quelating agents increased the contents of total titratable acidity.

Contribution of the second Landau level to the exchange energy of the three-dimensional electron gas in a high magnetic field

We derive a closed analytical expression for the exchange energy of the three-dimensional interacting electron gas in strong magnetic fields, which goes beyond the quantum limit (L=0) by explicitly including the effect of the second, L=1, Landau level and arbitrary spin polarization. The inclusion of the L=1 level brings the fields to which the formula applies closer to the laboratory range, as compared to previous expressions, valid only for L=0 and complete spin polarization. We identify and explain two distinct regimes separated by a critical density n(c). Below n(c), the per particle exchange energy is lowered by the contribution of L=1, whereas above n(c) it is increased. As special cases of our general equation we recover various known more limited results for higher fields, and we identify and correct a few inconsistencies in some of these earlier expressions.

Altered plasma response to zinc and iron tolerance test after Roux-en-Y gastric bypass

Background: The duodenum and proximal jejunum are excluded after Roux-en-Y gastric bypass but these intestinal sites are where iron and zinc are most absorbed. Therefore, they are among the nutrients whose digestive and absorptive process can be impaired after surgery. The aim of the present study was to investigate the iron and zinc plasma response to a tolerance test before and after bariatric surgery. The study was performed at Sao Paulo University School of Medicine of Ribeirao Preto, Brazil. Methods: In a longitudinal paired study, 9 morbidly obese women (body mass index >= 40 kg/m(2)) underwent an iron and zinc tolerance test before and 3 months after surgery. The iron and zinc levels were determined at 0, 1, 2, 3, and 4 hours after a physiologic unique oral dose. The mineral concentrations in die plasma and 24-hour urine sample were assayed using an atomic absorption spectrophotometer. The anthropometric measurements and 3-day food record were also evaluated. A linear mixed model was used to compare the plasma concentration versus interval after the oral dose, before and after surgery. Results: The pre- and postoperative test results revealed a significantly lower plasma zinc response (P <.01) and a delayed response to iron intake after surgery. The total plasma iron concentration area, during the 4 hours, was not different after surgery (P >.05). The 24-hour urinary iron and zinc excretion did not differ between the pre- and postoperative phases. Conclusion: The present data showed a compromised response to the zinc tolerance test after gastric bypass surgery, suggesting an impaired absorption of zinc. More attention must be devoted to zinc nutritional status after surgery. (Surg Obes Relat Dis 2011;7:309-314.) (C) 2011 American Society for Metabolic and Bariatric Surgery. All rights reserved.

Histological alterations in liver and testis of Astyanax aff. bimaculatus caused by acute exposition to zinc

This study investigated the effect of acute exposition to zinc (Zn) on histology of the liver and testes of yellow tail lambari (Astyanax aff. bimaculatus). The exposure consisted of six concentrations of Zn (0, 3, 5, 10, 15, and 20 mg/L) for 96 hours of exposure. Fragments of liver and testis were routinely processed and embedded in plastic resin based on glycol methacrylate. Fragments of bones, muscles, liver and testis were dehydrated and digested to quantify the absorption levels of Zn in the tissue. Acute exposure to concentrations above 10mg/L has produced structural changes in the liver and gonads. The changes found in the liver were vascular congestion; decrease of cellular volume; displacement of the hepatocyte nucleus; necrosis; disarrangement of cordon structure; leukocyte infiltrate and vacuolization. The changes found in the gonads were ruptured cyst, delayed development of germ cells, pyknotic nucleus, cell cluster, displacement of cyst wall and vacuolization. The histological changes observed were compatible with the increasing concentration of zinc in environment, compromising liver and reproductive functions, because there was an increase in relative frequency of hepatocytes and reduced sperm production

The sheeping technique or how to avoid exchange maneuvers.

INTRODUCTION: The arteries of bifurcation aneurysms are sometimes so angulated or tortuous that an exchange maneuver is necessary to catheterize them with a balloon or stent delivery catheter. Because of the risk of distal wire perforation associated with exchange maneuvers, we sought to find an alternative technique. METHODS: Our experience shows that a microcatheter tends to preferentially follow a previously placed microcatheter, even if the initial catheterization might be challenging. Accessing an artery with two microcatheters simultaneously may thus be an alternative to an exchange maneuver. Because of this tendency for catheters to behave like sheep following one another, we named this method the sheeping technique (ST). The ST consists of (a) first placing a 1.7 French microcatheter into the division branch requiring balloon or stent protection to straighten the course of the arteries in order to facilitate and (b) positioning in the same artery of a larger and stiffer balloon or stent microcatheter. Once the second balloon or stent microcatheter is in place, the first microcatheter can be pulled back and used to coil the aneurysm. RESULTS: Between January 2009 and December 2012, The ST was successfully used in 208/246 procedures (85 %). Conversion to an exchange maneuver was necessary in 38/246 (15 %). There were no arterial perforations or ischemic events related to the handling of both microcatheters. CONCLUSION: The sheeping technique may improve safety by replacing the need for an exchange maneuver during difficult balloon- or stent-assisted coiling.

A simple halide-to-anion exchange method for heteroaromatic salts and ionic liquids

A broad and simple method permitted halide ions in quaternary heteroaromatic and ammonium salts to be exchanged for a variety of anions using an anion exchange resin (A− form) in non-aqueous media. The anion loading of the AER (OH− form) was examined using two different anion sources, acids or ammonium salts, and changing the polarity of the solvents. The AER (A− form) method in organic solvents was then applied to several quaternary heteroaromatic salts and ILs, and the anion exchange proceeded in excellent to quantitative yields, concomitantly removing halide impurities. Relying on the hydrophobicity of the targeted ion pair for the counteranion swap, organic solvents with variable polarity were used, such as CH3OH, CH3CN and the dipolar nonhydroxylic solvent mixture CH3CN:CH2Cl2 (3:7) and the anion exchange was equally successful with both lipophilic cations and anions.

A simple halide-to-anion exchange method for heteroaromatic salts and ionic liquids

A broad and simple method permitted halide ions in quaternary heteroaromatic and ammonium salts to be exchanged for a variety of anions using an anion exchange resin (A− form) in non-aqueous media. The anion loading of the AER (OH− form) was examined using two different anion sources, acids or ammonium salts, and changing the polarity of the solvents. The AER (A− form) method in organic solvents was then applied to several quaternary heteroaromatic salts and ILs, and the anion exchange proceeded in excellent to quantitative yields, concomitantly removing halide impurities. Relying on the hydrophobicity of the targeted ion pair for the counteranion swap, organic solvents with variable polarity were used, such as CH3OH, CH3CN and the dipolar nonhydroxylic solvent mixture CH3CN:CH2Cl2 (3:7) and the anion exchange was equally successful with both lipophilic cations and anions.

Response to zinc deficiency of two rice lines with contrasting tolerance is determined by root growth maintenance and organic acid exudation rates, and not by zinc-transporter activity

Zinc (Zn)-deficient soils constrain rice (Oryza sativa) production and cause Zn malnutrition. The identification of Zn-deficiency-tolerant rice lines indicates that breeding might overcome these constraints. Here, we seek to identify processes underlying Zn-deficiency tolerance in rice at the physiological and transcriptional levels. A Zn-deficiency-tolerant line RIL46 acquires Zn more efficiently and produces more biomass than its nontolerant maternal line (IR74) at low Zn(ext) under field conditions. We tested if this was the result of increased expression of Zn(2+) transporters; increased root exudation of deoxymugineic acid (DMA) or low-molecular-weight organic acids (LMWOAs); and/or increased root production. Experiments were performed in field and controlled environment conditions. There was little genotypic variation in transcript abundance of Zn-responsive root Zn(2+)-transporters between the RIL46 and IR74. However, root exudation of DMA and LMWOA was greater in RIL46, coinciding with increased root expression of putative ligand-efflux genes. Adventitious root production was maintained in RIL46 at low Zn(ext), correlating with altered expression of root-specific auxin-responsive genes. Zinc-deficiency tolerance in RIL46 is most likely the result of maintenance of root growth, increased efflux of Zn ligands, and increased uptake of Zn-ligand complexes at low Zn(ext); these traits are potential breeding targets.

The trasition from fixed to floating exchange rate regimes: the case of Brazil

This dissertation evaluates macroeconomic management in Brazil from 1994 to the present, with particular focus on exchange rate policy. It points out that while Brazil's Real Plan succeeded in halting the hyperinflation that had reached more than 2000 percent in 1993, it also caused significant real appreciation of the exchange rate situation that was only made worse by the extremely high interest rates and ensuing bout of severe financial crises in the intemational arena. By the end of 1998, the accumulation of internai and externai imbalances led the authorities to drop foreign exchange controls and allow the currency to float. In spite of some initial scepticism, the flexible rate regime cum inflation target proved to work well. Inflation was kept under control; the current account position improved significantly, real interest rates fell and GDP growth resumed. Thus, while great challenges still lie ahead, the recent successes bestow some optimism on the well functioning of this exchange rate regime. The Brazilian case suggests that successful transition from one foreign exchange system to another, particularly during financial crisis, does not depend only on one variable be it fiscal or monetary. In reality, it depends on whole set of co-ordinated policies aimed at resuming price stability with as little exchange rate and output volatility as possible.

Altered plasma response to zinc and iron tolerance test after Roux-en-Y gastric bypass

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)