Pyrimidine-Derived Prolinamides as Recoverable Bifunctional Organocatalysts for Enantioselective Inter- and Intramolecular Aldol Reactions under Solvent-Free Conditions

Chiral L-prolinamides 2 containing the (R,R)- and (S,S)-trans-cyclohexane-1,2-diamine scaffold and a 2-pyrimidinyl unit are synthesized and used as general organocatalysts for intermolecular and intramolecular aldol reactions with 1,6-hexanedioic acid as a co-catalyst under solvent-free conditions. The intermolecular reaction between ketone–aldehyde and aldehyde–aldehyde must be performed under wet conditions with catalyst (S,S)-2b at 10 °C, which affords anti-aldols with high regio-, diastereo-, and enantioselectivities. For the Hajos–Parrish–Eder–Sauer–Wiechert reaction, both diastereomers of catalyst 2 give similar results at room temperature in the absence of water to give the corresponding Wieland–Miescher ketone and derivatives. Both types of reactions were scaled up to 1 g, and the organocatalysts were recovered by extractive workup and reused without any appreciable loss in activity. DFT calculations support the stereochemical results of the intermolecular process and the bifunctional role played by the organocatalyst by providing a computational comparison of the H-bonding networks occurring with catalysts 2a and 2b.

Generalized Fractional Calculus, Special Functions and Integral Transforms: What is the Relation?

Виржиния С. Кирякова - В този обзор илюстрираме накратко наши приноси към обобщенията на дробното смятане (анализ) като теория на операторите за интегриране и диференциране от произволен (дробен) ред, на класическите специални функции и на интегралните трансформации от лапласов тип. Показано е, че тези три области на анализа са тясно свързани и взаимно индуцират своето възникване и по-нататъшно развитие. За конкретните твърдения, доказателства и примери, вж. Литературата.

Fractional variational problems depending on indefinite integrals and with delay

The aim of this paper is to exhibit a necessary and sufficient condition of optimality for functionals depending on fractional integrals and derivatives, on indefinite integrals and on presence of time delay. We exemplify with one example, where we nd analytically the minimizer.

Raman Spectroscopy and DFT calculations for the Electronic Structure Characterization of Conjugated Polymers

In the last three decades, there has been a broad academic and industrial interest in conjugated polymers as semiconducting materials for organic electronics. Their applications in polymer light-emitting diodes (PLEDs), polymer solar cells (PSCs), and organic field-effect transistors (OFETs) offer opportunities for the resolution of energy issues as well as the development of display and information technologies1. Conjugated polymers provide several advantages including low cost, light weight, good flexibility, as well as solubility which make them readily processed and easily printed, removing the conventional photolithography for patterning2. A large library of polymer semiconductors have been synthesized and investigated with different building blocks, such as acenes or thiophene and derivatives, which have been employed to design new materials according to individual demands for specific applications. To design ideal conjugated polymers for specific applications, some general principles should be taken into account, including (i) side chains (ii) molecular weights, (iii) band gap and HOMO and LUMO energy levels, and (iv) suited morphology.3-6 The aim of this study is to elucidate the impact that substitution exerts on the molecular and electronic structure of π-conjugated polymers with outstanding performances in organic electronic devices. Different configurations of the π-conjugated backbones are analyzed: (i) donor-acceptor configuration, (ii) 1D lineal or 2D branched conjugated backbones, and (iii) encapsulated polymers (see Figure 1). Our combined vibrational spectroscopy and DFT study shows that small changes in the substitution pattern and in the molecular configuration have a strong impact on the electronic characteristics of these polymers. We hope this study can advance useful structure-property relationships of conjugated polymers and guide the design of new materials for organic electronic applications.

Gold Catalyzed Functionalization Of Alkynes And Allenamides

The gold(I)-catalyzed chemoselective dearomatization of β-naphthols is reported through a straightforward approach via [3,3]-sigmatropic rearrangement /allene-cyclyzation cascade processes. Easily accessed naphthyl-propargyl ethers and derivatives in this work are employed as starting materials. Delightfully, an array of deoramatized dyhydrofuryl -naphthalen-2(1H)-ones featured densely functional groups are obtained in high yields (up to 98%) in 10 min reaction time under extremely mild reaction conditions like reagent grade solvent and exposure to air. The potential of accessing to high enantioselectivety on the dearomatized dyhydrofuryl- naphthalen-2(1H)-ones is also approved by the good ee (65%) relying on (R)-xylyl- BINAP(AuCl)2. In addition, complete theoretical elucidation of the reaction pathway is also proposed which addresses a rationale for essential motivation such as regio- and chemoselectivity. Moreover, an efficient gold catalyzed intermolecular dearomatization of substituted β-naphthols with allenamides is presented here. PPh3AuTFA (5 mol %) approves the efficient dearomatively allylation protocol under mild conditions and exhibits high tolerance on substrates scope (24 examples) in good to excellent yield accompanied with high regioselectivity and stereoselectivity. Moreover, the synergistic catalytic system also highlight the synergistic function between the [PPh3Au]+ (π-acid) and TFA− (Lewis base). At last, a new chiral BINOL phosphoric acid silver salt is successfully synthesized and used as the chiral counter anion, which strongly promotes the enantioselectivity (up to 92%). At last but not least, crucially, SmI2 induced enantioselective formal synthesis of strychnine, a complex alkaloid and a classical target used to benchmark new synthetic methods is developed. Enantioselective dearomatising radical cyclisation on to the indole unit and further ET will then give organosamarium that is quenched diastereoselectively by the ester to deliver Strychnine in 7 steps.

Molecular Variations In Aromatic Cosolutes: Critical Role In The Rheology Of Cationic Wormlike Micelles.

Wormlike micelles formed by the addition to cetyltrimethylammonium bromide (CTAB) of a range of aromatic cosolutes with small molecular variations in their structure were systematically studied. Phenol and derivatives of benzoate and cinnamate were used, and the resulting mixtures were studied by oscillatory, steady-shear rheology, and the microstructure was probed by small-angle neutron scattering. The lengthening of the micelles and their entanglement result in remarkable viscoelastic properties, making rheology a useful tool to assess the effect of structural variations of the cosolutes on wormlike micelle formation. For a fixed concentration of CTAB and cosolute (200 mmol L(-1)), the relaxation time decreases in the following order: phenol > cinnamate> o-hydroxycinnamate > salicylate > o-methoxycinnamate > benzoate > o-methoxybenzoate. The variations in viscoelastic response are rationalized by using Mulliken population analysis to map out the electronic density of the cosolutes and quantify the barrier to rotation of specific groups on the aromatics. We find that the ability of the group attached to the aromatic ring to rotate is crucial in determining the packing of the cosolute at the micellar interface and thus critically impacts the micellar growth and, in turn, the rheological response. These results enable us for the first time to propose design rules for the self-assembly of the surfactants and cosolutes resulting in the formation of wormlike micelles with the cationic surfactant CTAB.

Analysis of small signal stability margins using genetic optimization

Power system small signal stability analysis aims to explore different small signal stability conditions and controls, namely: (1) exploring the power system security domains and boundaries in the space of power system parameters of interest, including load flow feasibility, saddle node and Hopf bifurcation ones; (2) finding the maximum and minimum damping conditions; and (3) determining control actions to provide and increase small signal stability. These problems are presented in this paper as different modifications of a general optimization to a minimum/maximum, depending on the initial guesses of variables and numerical methods used. In the considered problems, all the extreme points are of interest. Additionally, there are difficulties with finding the derivatives of the objective functions with respect to parameters. Numerical computations of derivatives in traditional optimization procedures are time consuming. In this paper, we propose a new black-box genetic optimization technique for comprehensive small signal stability analysis, which can effectively cope with highly nonlinear objective functions with multiple minima and maxima, and derivatives that can not be expressed analytically. The optimization result can then be used to provide such important information such as system optimal control decision making, assessment of the maximum network's transmission capacity, etc. (C) 1998 Elsevier Science S.A. All rights reserved.

Sustentabilidade na construção metálica

O desenvolvimento sustentável é um dos grandes desafios dos nossos tempos com inúmeras consequências em várias áreas da nossa sociedade. É uma questão abrangente e essencial para a sobrevivência do modo de vida tal como o conhecemos actualmente. A construção sustentável tem um papel muito importante no desenvolvimento, não só ao nível económico mas também social e cultural. Embora não contemple a energia incorporada, a avaliação do ciclo de vida (ACV), no sector da construção, é um dos métodos mais comuns para avaliar o nível de sustentabilidade. Este trabalho visa os metais como uma das mais promissoras e actuais respostas do sector da construção às crescentes preocupações em relação ao desenvolvimento sustentável. O ferro e derivados são normalmente a base das construções metálicas, residindo no seu potencial de reutilização e reciclagem um dos seus principais factores de sustentabilidade. As estruturas metálicas apresentam características especificas que se coadunam com os requisitos da construção sustentável e que tornam este tipo de construção extremamente versátil e interessante. Neste trabalho, é efectuada uma abordagem sobre a construção metálica ao longo de três partes. A primeira parte é constituída por uma introdução histórica ao ferro e seus derivados enunciando exemplos de construções até aos nossos dias, e pela classificação dos vários tipos de metais e ligas metálicas. Na segunda parte, é abordado o conceito de sustentável e o seu enquadramento no sector da construção, e é feita uma introdução à metodologia de avaliação de ciclo de vida. Na terceira parte, é abordado um exemplo prático de uma estrutura metálica em que são elaboradas e comparadas três soluções. Na origem da diversidade dos elementos comparativos estão o tipo de aço, a origem da energia utilizada no seu fabrico e o tipo de solução técnica adoptada. O objectivo deste trabalho é compreender as repercussões do conceito de sustentabilidade no sector da construção, e desenvolver um método simplificado de avaliação dos impactos ambientais e económicos de soluções metálicas.

Avaliação da exposição a aditivos alimentares em crianças dos 0 aos 3 anos: estudo exploratório

RESUMO - O aumento dos produtos processados na alimentação diária, em especial das crianças, tem repercussões no consumo aumentado de aditivos, cujas consequências são ainda ambíguas. Associado ao aumento do consumo deste tipo de alimentos encontra-se a prevalência de excesso de peso e obesidade infantil. O presente estudo exploratório pretendeu avaliar a exposição a aditivos alimentares em crianças dos 0 aos 3 anos, com base nos Limites Máximos de Utilização e nas Doses Diárias Admissíveis, e estudar a sua associação com variáveis como a idade, sexo, percentil de Índice de Massa Corporal e nível de escolaridade dos Pais. Pretendeu-se também identificar as categorias de alimentos consumidas que mais contribuíram para a exposição aos aditivos alimentares em estudo. Com base numa amostra de dados reportados em diários alimentares, foram selecionados 12 aditivos. Observaram-se ingestões estimadas superiores às DDA, para o dióxido de enxofre (E220), o ácido fumárico (E297) e o nitrito de sódio (E250). As categorias de alimentos “Açúcar, confeitaria e sobremesas açucaradas”, “Leite e produtos lácteos”, “Cereais e derivados” e “Pratos compostos”, foram as que mais contribuíram para a exposição dos aditivos selecionados. O presente trabalho permitiu inferir o perfil de exposição a aditivos alimentares em crianças, lançar resultados preliminares para justificar a necessidade de estudos mais pormenorizados, e a criação do sistema de monitorização nacional da ingestão de aditivos. Estudos sobre consumos de aditivos alimentares podem servir de base para elaboração de estratégias de saúde pública, com a finalidade de reduzir o consumo destas substâncias e promover hábitos alimentares mais saudáveis.

Antileishmanial activity of lapachol analogues

The antileishmanial activity of lapachol, isolapachol, and dihydrolapachol, along with soluble derivatives (potassium salt) and acetate was obtained. All the compounds were assayed against metacyclic promastigotes of two different species of Leishmania associated to tegumentar leishmaniasis: L. amazonensis and L. braziliensis. All compounds presented significant activity, being isolapachol acetate the most active against promastigotes, with IC50/24h = 1.6 ± 0.0 µg/ml and 3.4 ± 0.5 µg/ml for, respectively, L. amazonensis and L. braziliensis. This compound was also assayed in vivo against L. amazonensis and showed to be active. Its toxicity in vitro was also established, and at concentration similar to the IC50, no toxicity was evidenced. In all experiments, pentamidine isethionate was used as a reference drug. The present results reinforce the potential use of substituted hydroxyquinones and derivatives as promising antileishmanial drugs and suggest a continuing study within this class of compounds.

Métodos de preparação e atividade biológica do ácido quinolínico e derivados

In 1981 2,3-pyridine dicarboxylic acid (quinolinic acid) was discovery to be a selective agonist for the N-methyl -D-aspartic acid (NMDA) receptor. As a consequence it possesses neurotoxic activity resulting from overstimulation of the receptor. Quinolinic acid is implicated as an etiological factor in a range of neurodegenerative disease including AIDS related dementia, Huntington´s disease and Lyme disease. In the design of novel therapies to treat these diseases, some molecules have been identified as an important target. In this paper we described different methods to prepare quinolinic acid and derivatives.

Microesferas de quitosana reticuladas com tripolifosfato utilizadas para remoção da acidez, ferro(III) e manganês(II) de águas contaminadas pela mineração de carvão

Considerable attention has been paid to chitosan and derivatives as efficient adsorbents of pollutants such as metal ions and dyes in aqueous medium. Nevertheless, no report can be found on the remedial actions of chitosan microspheres crosslinked with tripolyphosphate to control acidity, iron (III) and manganese (II) contents in wastewaters from coal mining. In this work, chitosan microspheres crosslinked with tripolyphosphate were used for the neutralization of acidity and removal of Fe (III) and Mn (II) from coal mining wastewaters. The study involved static and dinamic methods. The neutralization capacity of the surface of the static system was 395 mmol of H3O+ per kilogram of microspheres, higher than that of the dynamic one (223 mmol kg-1). The removal of Fe(III) in wastewater was of 100% and that of Mn(II) was 90%.

Estrutura, reatividade e propriedades biológicas de hidantoínas

Hydantoin (imidazolidine-2,4-dione) is a 2,4-diketotetrahydroimidazole discovered by Baeyer in 1861. Thiohydantoins and derivatives were prepared, having chemical properties similar to the corresponding carbonyl compounds. Some biological activities (antimicrobial, anticonvulsant, schistosomicidal) are attributed to the chemical reactivity and consequent affinity of hydantoinic rings towards biomacromolecules. Therefore, knowledge about the chemistry of hydantoins has increased enormously. In this review, we present important aspects such as reactivity of hydantoins, acidity of hydantoins, spectroscopy and cristallographic properties, and biological activities of hydantoin and its derivatives.

Carboidratos como fonte de compostos para a indústria de química fina

Coal, oil, natural gas, and shale gas are biomass that is formed millions of years ago. These are non-renewable and depleting, even considering the recent discovery of new sources of oil in the presalt and new technologies for the exploitation of shale deposits. Currently, these raw materials are used as a source of energy production and are also important for the production of fine chemicals. Since these materials are finite and their (oil) price is increasing, it is clear that there will be a progressive increase in the chemical industry to use renewable raw materials as a source of energy, an inevitable necessity for humanity. The major challenge for the society in the twenty first century is to unite governments, universities, research centers, and corporations to jointly act in all areas of science with one goal of finding a solution to global problems, such as conversion of biomass into compounds for the fine chemical industry.Non-renewable raw materials are used in the preparation of fuels, chemical intermediates, and derivatives for the fine chemical industry. However, their stock in nature has a finite duration, and their price is high and will likely increase with their depletion. In this scenario, the alternative is to use renewable biomass as a replacement for petrochemicals in the production of fine chemicals. As the production of biomass-based carbohydrates is the most abundant in nature, it is judicious to develop technologies for the generation of chain products (fuels, chemical intermediates, and derivatives for the fine chemicals industry) using this raw material. This paper presents some aspects and opportunities in the area of carbohydrate chemistry toward the generation of compounds for the fine chemical industry.

Separação e determinação quantitativa dos alcanos lineares e dos cíclicos/ramificados em petróleos brasileiros por aduto de ureia e cromatografia gasosa: um estudo de caso revisitado

A complete analysis of oils and their fractions allows correlations to be defined between their composition and derivatives or related geological materials. This work focused on optimization and implementation of a method for separation and quantification of n-alkanes in Brazilian oil samples by urea adduction and GC-FID techniques. Ten samples with different ºAPI were analyzed in triplicate to quantify individual n-alkanes and cyclic/branched alkane fraction. For individual quantification of n-alkanes, internal standardization with deuterated n-tetracosane was used. The use of urea adduction for the separation and quantification of n-alkanes was highly effective, with recovery values of above 80%.