Estereosseletividade em reações eletródicas

This review discusses the present state of the art of the stereochemistry of electrochemical reactions. The extent of asymmetric induction is progressing, but in general diastereoselectivities and enantioselectivities remain behind those from chemical synthesis. In recent years, new methodological developments have been successful. Effects that play important roles in homogeneous chemistry have been used with success. Lack of expressive enantiomeric excess (ee) could be related to the absence of tightly organized structures during the reaction of interest. The highest ee might be expected for redox reactions where conformational preference in transition state plays the important role or for the ones performed while adsorbed on the electrode, and where the chiral element is also at the surface, either adsorbed or chemically bound to the surface and interacting directly with the substrate. Electroenzymatic synthesis has a promising future.

Alcalóides alquilpiridínicos de esponjas marinhas

The chemistry of alkylpyridine alkaloids originating from marine sponges is comprehensively reviewed, with emphasis on their natural occurrence, methods for their isolation, spectroscopic characterization, biological activities e chemical synthesis. A likely chemotaxonomic role is suggested, as markers for sponges of the Order Haplosclerida (Demospongiae).

Chemistry and light - part 2: light and energy

The conversion of solar energy into more useful forms of energy, such as chemical fuels or electricity, is one of the central problems facing modern science. Progress in photochemistry and chemical synthesis has led to a point where light energy conversion by means of artificial molecular devices can be rationally attempted. In this article, a general approach towards this challenging goal is presented.

Os DNA sintéticos anti-sentido

One old dream of the chemist in the field of the drug research is to create molecules capable of reaching their target with the precision of a missile. To accomplish it these molecules must have the propriety of distinguishing qualitative differences between healthy and diseased cells. A therapy based on this principle, able of eradicating specifically defective cells, or cells affected by a pathogen has an enormous advantage with the regard to the classical approach in which the cytotoxic drugs merely exploit quantitative biochemical and kinetic differences between abnormal and normal cells. We present in this article a review on the chemical synthesis of analogues of desoxyribonucleotides and on results obtained on the specific and irreversible inhibition of undesired genetic expression using the antisense principle.

Oxochloroalkoxide of the Cerium (IV) and Titanium (IV) as oxides precursor

The Cerium (IV) and Titanium (IV) oxides mixture (CeO2-3TiO2) was prepared by thermal treatment of the oxochloroisopropoxide of Cerium (IV) and Titanium (IV). The chemical route utilizing the Cerium (III) chloride alcoholic complex and Titanium (IV) isopropoxide is presented. The compound Ce5Ti15Cl16O30 (iOPr)4(OH-Et)15 was characterized by elemental analysis, FTIR and TG/DTG. The X-ray diffraction patterns of the oxides resulting from the thermal decomposition of the precursor at 1000 °C for 36 h indicated the formation of cubic cerianite (a = 5.417Å) and tetragonal rutile (a = 4.592Å) and (c = 2.962 Å), with apparent crystallite sizes around 38 and 55nm, respectively.

Nanocompósitos de matriz polimérica: estratégias de síntese de materiais híbridos

Associating the well known advantages of hybrid materials to the wide potential of nanomaterials, the new and featuring class of polymer nanocomposites turned into one of the most intensively researched areas. This review highlights recent developments in the field of the synthesis of polymer based nanocomposites. Important issues related to the surface modification of fillers, in order to promote the compatibility between the inorganic/organic components, are also reported. The enhancement of the physical properties and the potential applications of polymer nanocomposites are considered in typical examples, given for each synthetic method described.

Os nanomateriais e a descoberta de novos mundos na bancada do químico

In recent years there has been great progress in the field of nanotechnology largely driven by research into nanomaterials. Chemistry appears in this context for its relevant role in the synthesis and surface modification of nanomaterials. This review article discusses fundamental concepts related to the synthesis and properties of inorganic nanoparticles with diverse properties. Aspects related to unique size dependent optical and magnetic properties are discussed and the chemistry involved in the preparation of nanomaterials reviewed. Fundamental aspects of the chemical modification of nanoparticles envisaging potential applications for these materials are also addressed.

Hemocidinas derivadas da hemoglobina: estruturas, propriedades e perspectivas

The increasing incidence of microbial infections, high toxicity, and high level of resistance associated with conventional antibiotics has created a need for new drugs. Antimicrobial peptides (AMPs) constitute a promising alternative and/or an important source of knowledge given their ability to inhibit the growth and/or to kill bacteria, fungi, parasites and/or viruses through mechanisms of action different from those of non-peptide drugs. This review focused on this important class of organic compounds that includes hemocidins resulting from hemoglobin proteolysis in vivo and in vitro or from chemical synthesis, subject of research in foreign and Brazilian laboratories.

1,3-propanodiol: produção, aplicações e potencial biotecnológico

1,3-propanediol is a high-value specialty chemical which has many industrial applications. Its main use is the production of the polymer polypropylene terephthalate, a thermoplastic used in the textile and automobile industries. The interest in 1,3-propanediol production from glycerol bio-conversion has increased after the employment of biodiesel by various countries, being produced by chemical synthesis from petroleum intermediates or biotechnologically by microbial fermentation. Glycerol is an abundant low-cost byproduct from biodiesel refineries, and it is the only substrate that can be naturally or enzymatically converted to 1,3-propanediol by microbial fermentation. In this review, information on 1,3-propanediol's importance, production and purification are presented, along with results from recent research on glycerol microbial conversion to 1,3-propanediol. The bio-production of this intermediate compound from glycerol is very attractive both economically and environmentally, since it allows the replacement of fossil fuels by renewable resources.

pH effect on the synthesis of magnetite nanoparticles by the chemical reduction-precipitation method

This work aimed at putting in evidence the influence of the pH on the chemical nature and properties of the synthesized magnetic nanocomposites. Saturation magnetization measurements evidenced a marked difference of the magnetic behavior of samples, depending on the final pH of the solution after reaction. Magnetite and maghemite in different proportions were the main magnetic iron oxides actually identified. Synthesis with final pH between 9.7-10.6 produced nearly pure magnetite with little or no other associated iron oxide. Under other synthetic conditions, goethite also appears in proportions that depended upon the pH of the synthesis medium.

Chemical and pharmacological investigation of Solanum species of Brazil: a search for solasodine and other potentially useful therapeutic agents

A systematic search for solasodine, an important staring material for the partial synthesis of steroidal hormones as well as other potentially bioactive constituents of various Solanum species of Brazil has been undertaken. Thus, the fruits of S. paludosum, S. asperum, S. sessiliforum and Solanum sp. were found to contain significant amounts of solasodine. The root bark of S. paludosum which showe durare like activity yelded tomatidenol and another yet unidentified alkaloid responsible for the biological activity. The fruits of S. asperum yelded a new spirosolane alkaloid, solaparnaine. The stem bark of S. pseudo-quina showed convulsive and exitatory activity from which (25S)-isosolafloridine was identified as the active principle. In addition, the latter alkaloid was also found to show antimicrobial activity.

Effect of the chitin synthesis inhibitor triflumuron on the development, viability and reproduction of Aedes aegypti

The control of Aedes aegypti is impaired due to the development of resistance to chemical insecticides. Insect Growth Regulators (IGR) exhibit distinct mechanisms of action and are considered potential vector control alternatives. Studies regarding the effects of sublethal IGR doses on the viability of resulting adults will contribute to eval-uating their impact in the field. We analyzed several aspects of Ae. aegypti adults surviving exposure to a partially lethal dose of triflumuron, a chitin synthesis inhibitor. A highly significant difference in the proportion of males and females was noted in the triflumuron-exposed group (65.0% males) compared to the controls (50.2% males). Triflumuron affected adult longevity, particularly for females; after 16 days, only 29.2% of males and 13.8% of females were alive, in contrast with 94% survival of the control mosquitoes. The locomotor activity was reduced and the blood-feeding ability of the treated females was also affected (90.4% and 48.4% of the control and triflumuron-exposed females, respectively, successfully ingested blood). Triflumuron-surviving females ingested roughly 30% less blood and laid 25% fewer eggs than the control females. The treated males and females exhibited a diminished ability to copulate, resulting in less viable eggs.

The efficacy of a chitin synthesis inhibitor against field populations of organophosphate-resistant Aedes aegypti in Brazil

The mosquito Aedes aegypti is the main focus of dengue control campaigns. Because of widespread resistance against conventional chemical insecticides, chitin synthesis inhibitors (CSIs) are considered control alternatives. We evaluated the resistance status of four Brazilian Ae. aegypti populations to both the organophosphate temephos and the pyrethroid deltamethrin, which are used in Brazil to control larvae and adults, respectively. All vector populations exhibited high levels of temephos resistance and varying rates of alterations in their susceptibility to pyrethroids. The effect of the CSI novaluron on these populations was also investigated. Novaluron was effective against all populations under laboratory conditions. Field-simulated assays with partial water replacement were conducted to evaluate novaluron persistence. Bioassays were continued until an adult emergence inhibition of at least 70% was attained. We found a residual effect of eight weeks under indoor conditions and novaluron persisted for five-six weeks in assays conducted in an external area. Our data show that novaluron is effective against the Ae. aegypti populations tested, regardless of their resistance to conventional chemical insecticides.

Chemical and biological properties of phosphorus-fertilized soil under legume and grass cover (Cerrado region, Brazil)

The use of cover crops has been suggested as an effective method to maintain and/or increase the organic matter content, while maintaining and/or enhancing the soil physical, chemical and biological properties. The fertility of Cerrado soils is low and, consequently, phosphorus levels as well. Phosphorus is required at every metabolic stage of the plant, as it plays a role in the processes of protein and energy synthesis and influences the photosynthetic process. This study evaluated the influence of cover crops and phosphorus rates on soil chemical and biological properties after two consecutive years of common bean. The study analyzed an Oxisol in Selvíria (Mato Grosso do Sul, Brazil), in a randomized block, split plot design, in a total of 24 treatments with three replications. The plot treatments consisted of cover crops (millet, pigeon pea, crotalaria, velvet bean, millet + pigeon pea, millet + crotalaria, and millet + velvet bean) and one plot was left fallow. The subplots were represented by phosphorus rates applied as monoammonium phosphate (0, 60 and 90 kg ha-1 P2O5). In August 2011, the soil chemical properties were evaluated (pH, organic matter, phosphorus, potential acidity, cation exchange capacity, and base saturation) as well as biological variables (carbon of released CO2, microbial carbon, metabolic quotient and microbial quotient). After two years of cover crops in rotation with common bean, the cover crop biomass had not altered the soil chemical properties and barely influenced the microbial activity. The biomass production of millet and crotalaria (monoculture or intercropped) was highest. The biological variables were sensitive and responded to increasing phosphorus rates with increases in microbial carbon and reduction of the metabolic quotient.

Calcium phosphate biomaterials from marine algae. Hydrothermal synthesis and characterisation

Calcium phosphate compounds such as Hydroxyapatite (HAp) were prepared by hydrothermal synthesis with phycogenic CaCO3 as starting material. Material obtained was characterised by usual methods (XRD, FTIR, TG, N2-adsorption, SEM and EDX) in order to study its physical-chemical characteristics. The prepared HAp showed that it may be suitable for use as a biomaterial.