Laparoscopic inguinal hernia repair with extraperitoneal double-mesh technique.

Totally extraperitoneal laparoscopic hernia repair is an efficient but technically demanding procedure. As mechanisms of hernia recurrence may be related to these technical difficulties, we have modified a previously described double-mesh technique in an effort to simplify the procedure. Extraperitoneal laparoscopic hernia repairs were performed in 82 male and 17 female patients having inguinal, femoral, and recurrent bilateral hernias. A standard propylene mesh measuring 15 x 15 cm was cut into two pieces of 4 x 15 cm and 11 x 15 cm. The smaller mesh was placed over both inguinal rings without splitting. The larger mesh was then inserted over the first mesh and stapled to low-risk zones, reinforcing the large-vessel area and the nerve transition zone. The mean procedure duration was 60 minutes for unilateral and 100 minutes for bilateral hernia repair. Patients were discharged from the hospital within 48 hours. The mean postoperative follow-up was 22 months, with no recurrences, neuralgia, or bleeding complications. Over a 2-year period, this technique was found to be satisfactory without recurrences or significant complications. In our hands, this technique was easier to perform: it allows for a less than perfect positioning of the meshes and avoids most of the stapling to crucial zones.

Silver-assisted laser desorption ionization for high spatial resolution imaging mass spectrometry of olefins from thin tissue sections.

Silver has been demonstrated to be a powerful cationization agent in mass spectrometry (MS) for various olefinic species such as cholesterol and fatty acids. This work explores the utility of metallic silver sputtering on tissue sections for high resolution imaging mass spectrometry (IMS) of olefins by laser desorption ionization (LDI). For this purpose, sputtered silver coating thickness was optimized on an assorted selection of mouse and rat tissues including brain, kidney, liver, and testis. For mouse brain tissue section, the thickness was adjusted to 23 ± 2 nm of silver to prevent ion suppression effects associated with a higher cholesterol and lipid content. On all other tissues, a thickness of at 16 ± 2 nm provided the best desorption/ionization efficiency. Characterization of the species by MS/MS showed a wide variety of olefinic compounds allowing the IMS of different lipid classes including cholesterol, arachidonic acid, docosahexaenoic acid, and triacylglyceride 52:3. A range of spatial resolutions for IMS were investigated from 150 μm down to the high resolution cellular range at 5 μm. The applicability of direct on-tissue silver sputtering to LDI-IMS of cholesterol and other olefinic compounds presents a novel approach to improve the amount of information that can be obtained from tissue sections. This IMS strategy is thus of interest for providing new biological insights on the role of cholesterol and other olefins in physiological pathways or disease.

Synthetic applications of chiral unsaturated epoxy alcohols prepared by sharpless asymmetric epoxidation

An overview of the synthesis and applications of chiral 2,3-epoxy alcohols containing unsaturated chains is presented. One of the fundamental synthetic routes to these compounds is Sharpless asymmetric epoxidation, which is reliable, highly chemoselective and enables easy prediction of the product enantioselectivity. Thus, unsaturated epoxy alcohols are readily obtained by selective oxidation of the allylic double bond in the presence of other carbon-carbon double or triple bonds. The wide availability of epoxy alcohols with unsaturated chains, the versatility of the epoxy alcohol functionality (e.g. regio- and stereo-selective ring opening; oxidation; and reduction), and the arsenal of established alkene chemistries, make unsaturated epoxy alcohols powerful starting materials for the synthesis of complex targets such as biologically active molecules. The popularization of ring-closing metathesis has further increased their value, making them excellent precursors to cyclic compounds.

Venom alkaloid and cuticular hydrocarbon profiles are associated with social organization, queen fertility status, and queen genotype in the fire ant Solenopsis invicta.

Queens in social insect colonies advertise their presence in the colony to: a) attract workers' attention and care; b) gain acceptance by workers as replacement or supplemental reproductives; c) prevent reproductive development in nestmates. We analyzed the chemical content of whole body surface extracts of adult queens of different developmental and reproductive stages, and of adult workers from monogyne (single colony queen) and polygyne (multiple colony queens) forms of the fire ant Solenopsis invicta. We found that the composition of the most abundant components, venom alkaloids, differed between queens and workers, as well as between reproductive and non-reproductive queens. Additionally, workers of the two forms could be distinguished by alkaloid composition. Finally, sexually mature, non-reproductive queens from polygyne colonies differed in their proportions of cis-piperidine alkaloids, depending on their Gp-9 genotype, although the difference disappeared once they became functional reproductives. Among the unsaturated cuticular hydrocarbons characteristic of queens, there were differences in amounts of alkenes/alkadienes between non-reproductive polygyne queens of different Gp-9 genotypes, between non-reproductive and reproductive queens, and between polygyne and monogyne reproductive queens, with the amounts increasing at a relatively higher rate through reproductive ontogeny in queens bearing the Gp-9 b allele. Given that the genotype-specific piperidine differences reflect differences in rates of reproductive maturation between queens, we speculate that these abundant and unique compounds have been co-opted to serve in fertility signaling, while the cuticular hydrocarbons now play a complementary role in regulation of social organization by signaling queen Gp-9 genotype.

Nitric oxide sustains IL-1β expression in human dendritic cells enhancing their capacity to induce IL-17-producing T-cells.

The role played by lung dendritic cells (DCs) which are influenced by external antigens and by their redox state in controlling inflammation is unclear. We studied the role played by nitric oxide (NO) in DC maturation and function. Human DCs were stimulated with a long-acting NO donor, DPTA NONOate, prior to exposure to lipopolysaccharide (LPS). Dose-and time-dependent experiments were performed with DCs with the aim of measuring the release and gene expression of inflammatory cytokines capable of modifying T-cell differentiation, towardsTh1, Th2 and Th17 cells. NO changed the pattern of cytokine release by LPS-matured DCs, dependent on the concentration of NO, as well as on the timing of its addition to the cells during maturation. Addition of NO before LPS-induced maturation strongly inhibited the release of IL-12, while increasing the expression and release of IL-23, IL-1β and IL-6, which are all involved in Th17 polarization. Indeed, DCs treated with NO efficiently induced the release of IL-17 by T-cells through IL-1β. Our work highlights the important role that NO may play in sustaining inflammation during an infection through the preferential differentiation of the Th17 lineage.

Ativação do peróxido de hidrogênio para a epoxidação de olefinas não-funcionalizadas

A general overview about the more useful activating agents of the hydrogen peroxide in the epoxidation of unfunctionalized alkenes, focusing mechanistic proposals. Moreover, reactivity and stereochemistry, including the stereogenic effect of the hydroxyl group is presented.

Composição química da glândula abdominal da fêmea da mariposa Castnia licus (Drury) (Lepidoptera:Castniidae): possíveis feromônios e precursores

The hexane and methanolic extracts from pheromonal glands of Castnia licus (Drury) virgin females have been studied. Analyses by gas chromatography and mass spectrometry allowed us to determine the major constituents present in the hexane extract as n-alkanes C21 to C30, (Z)-9-hexadecenoic acid (C16), and (Z)-9-octadecenoic acid (C18) and hexadecanoic acid (C16). Aldehyds, alkenes and acetates were also detected in low concentrations in the extracts. Female pheromone glands were analysed for pheromone precursors using the methanolic extract. In addition to the compounds methyl hexadecanoate and methyl (Z)-9-octadecenoate, the glandular tissue contains a homologous series of methyl esters from C12 to C24. The hexane extract of the female abdomenal glands elicited activity from males in a behavioural bioassay.

Coiodação de alquenos com nucleófilos oxigenados: reações intermoleculares

A review on the electrophilic addition of iodine to alkenes in the presence of oxygen containing nucleophiles (cohalogenation reaction) is presented. The intermolecular reactions are discussed with emphasis in methods of reaction and synthetic applications of the resulting vicinal iodo-functionalized products (iodohydrins, beta-iodoethers and beta-iodocarboxylates).

Redução de amidas por boranos

Despite the fact that boranes are frequently used in amide reductions, the reaction mechanisms of the involved are note well known. This work presents the results of a bibliographic search on probable amide reduction mechanisms and an analysis of the existing literature. Steric and electronic effects were considered in light of reactivity since it could be concluded that the formation of intermediates and products depends mainly on the substitution patterns of both the boron and nitrogen atoms. Otherwise, results described in the literature for the reactions of boranes, sodium borohydride, lithium aluminum hydride, alkylboranes or haloboranes with others functional groups such as carboxylic acids, esters, ketones and alkenes were analysed with the aim to obtain something about the N-substituted amide reactions employing boranes.

Aspectos regio- e estereoquímicos da adição de Michael assimétrica via iminas quirais com centros estereogênicos pré-existentes

The asymmetric Michael addition reactions using chiral imines, under neutral conditions (deracemizing alkylation process), constitute one of the main methods for the stereocontrolled elaboration of quaternary carbon centers. This protocol is based on the conjugate addition of secondary chiral enamines to electron-deficient alkenes. The focus of this report deals with the discussion of regio- and stereochemical aspects of the deracemizing alkylation process concerning enamines bearing a resident chiral center.

Estabilidade relativa de alcenos: análise dos critérios encontrados nos livros textos de graduação e uma proposta de explicação operacional para alcenos dissubstituídos

Despite of being used as thermodynamic criterion to rank alkene stability in a number of undergraduate textbooks, the heat of hydrogenation does not describe adequately the relative stability of disubstituted alkenes. In this work, both the heat of formation and the heat of combustion were used as thermodynamic criteria to rank correctly the stability of alkenes according to the degree of alkyl substitution and also in the disubstituted series (geminal > trans > cis). An operational model based on molecular orbital and valence bond representations of hyperconjugation is proposed to show how this effect can explain the order of stability of this class of compounds.

Síntese de novos herbicidas derivados do 1,2alfa,4alfa,5-tetrametil-8-oxabiciclo[3.2.1]oct-6-en-3-ona

In this paper we report the synthesis of biologically active compounds through a [3+4] cycloaddition reaction to produce the main frame structure, followed by several conventional transformations. The 1,2alpha,4alpha,5-tetramethyl-8-oxabicyclo[3.2.1]oct-6-en-3-one (11) obtained from a [3+4] cycloaddition reaction was converted into 1,2alpha,4alpha,5-tetramethyl-6,7-exo-isopropylidenedioxi-8 -oxabicyclo[3.2.1]octan-3-one (13) in 46% yield. This was further converted into the alcohols 1,2alpha,4alpha,5-tetramethyl-6,7-exo-isopropylidenedioxi-8-oxabicyclo[3.2.1]octan-3 alpha-ol (14), 1,2alpha,4alpha,5-tetramethyl-6,7-exo-isopropylidenedioxi-8 -oxabicyclo[3.2.1]octan-3beta-ol (15), 1,2alpha,4alpha,5-tetramethyl-3-butyl-6,7-exo-isopropylidenedioxi-8-oxabicyclo[3.2.1]octan-3 alpha-ol (17), 1,2alpha,4alpha,5-tetramethyl-3-hexyl-6,7-exo-isopropylidenedioxi-8-oxabicyclo[3.2.1]octan-3 alpha-ol (18) and 1,2alpha,4alpha,5-tetramethyl-3-decyl-6,7-exo-isopropylidenedioxi-8-oxabicyclo[3.2.1]octan-3 alpha-ol (19). Dehydration of 17, 18 and 19 with thionyl chloride in pyridine resulted in the alkenes 20, 21 and 22 in ca. 82% - 89% yields from starting alcohols. The herbicidal activity of the compounds synthesized was evaluated at a concentration of 100 µg g-1. The most active compound was 21 causing 42,7% inhibition against Cucumis sativus L.

Síntese de novas fitotoxinas derivadas do 8-oxabiciclo[3.2.1]oct-6-en-3-ona

The [4+3] cycloaddition was utilized in order to prepare 8-oxabicyclo[3.2.1]oct-6-en-3-one (1) derivatives. The correspondent acetonide 6 was converted into several alcohols (11-16). Addition of aryllithium reagents to 6 resulted in 3-(2-fluorophenyl)-6,7-exo-isopropylidenedioxy -8-oxabicyclo[3.2.1]octan-3alpha-ol (11, 72%) and 3-(2,4-dimethoxyphenyl)-6,7-exo-isopropylidenedioxy-8-oxabicyclo[3.2.1]octan -3alpha-ol (16, 20%). The 3-butyl-6,7-exo-isopropylidenedioxy-8-oxabicyclo[3.2.1]octan-3 alpha-ol (15, 56%) was obtained through a Grignard reaction. Reduction of 6 resulted in 6,7-exo-isopropylidenedioxy-8-oxabicyclo[3.2.1]octan-3 beta-ol (7, 62%) and 6,7-exo-isopropylidenedioxy-8-oxabicyclo[3.2.1]octan-3 alpha-ol (8, 20%). The alcohols were treated with thionyl chloride in pyridine, and the corresponding alkenes were obtained with 31-80% yield. The effect of these compounds on the development of radicle and aerial parts of Sorghum bicolor was evaluated.

N-halossacarinas: reagentes úteis (e alternativos) em síntese orgânica

N-halosaccharins proved to be useful and alternative reagents for diverse organic transformations, such as halogenation of aromatic compounds, benzylic and alpha-carbonylic positions, cohalogenation of alkenes, oxidation of secondary alcohols, etc. Their preparation from saccharin, a cheap and readly available starting material, is simple.

Catálise assimétrica na ciclopropanação de olefinas

The main methodologies in the asymmetric cyclopropanation of alkenes with emphasis on asymmetric catalysis are covered. Exemples are the Simmons-Smith reaction, the use of diazoalkanes and reactions carried out by decomposition of alpha-diazoesters in the presence of transition metals.