Recent Advances in Sustainable Organocatalysis

The recent advances on green and sustainable organocatalysis are revised in this chapter. An important focus on one of the 12 principles of green chemistry, organocatalysis pursues to reduce energy consumption as well as to optimize the use of different resources, targeting to become a sustainable strategy in organic chemical transformations. In last decades, several experimental methodologies have been performed to make organocatalysis an even greener and sustainable alternative to stoichiometric approaches as well as non-catalytic conditions by the use of benign and friendlier reaction media. In this line, several approaches using water as preferential solvent, alternative solvents such as ionic liquids including chiral ones, deep eutectic solvents, polyethylene glycol (PEG), supercritical fluids and organic carbonates or solvent-free methodologies have been reported. In this chapter, we mainly focus on the recent remarkable advancements in organocatalysis using green and sustainable protocols

Photo-Organocatalysis, Photo-Redox, and Electro- Organocatalysis Processes

The research involving photo-organocatalysis, photoredox, and electro-organocatalysis processes is revised in this chapter. Modern synthetic processes enable the formation of large arrays of organic molecules with precise control over their three-dimensional structure, which is important in a variety of fields ranging from pharmaceutical to materials science. Photochemical reactions may have a substantial impact on these fields by affording direct access to specific structural motifs that are difficult to construct otherwise. The conjugate structural feature shown by most of the photo-organocatalysts seems to enable the production of free radicals or radical ions in an easy fashion. Electro-organocatalysis has also received recent interest from both academia and industry. In this chapter, we mainly review recent remarkable advancements in organocatalysis involving photo-, photoredox, and electrochemical processes with particular emphasis on asymmetric protocols

Novel aqueous biphasic system based on ethyl lactate for sustainable separations: Phase splitting mechanism

Ethyl lactate is a hydrophilic green solvent which is bio-renewable and biodegradable with low toxicity towards humans and animals. For the first time, we report that aqueous solutions of ethyl lactate separate into two aqueous phases upon addition of salts. The performance of trisodium citrate, disodium tartrate and disodium succinate as salting-out media for the separation of natural organic compounds, such as caffeine and catechin, from their aqueous solutions was examined. In this respect, cloud points for the ternary solutions composed of ethyl lactate, water and salt were determined at ambient pressure (0.1 MPa) at 298.2 K. Partition coefficients of caffeine and catechin between two phases were determined by chemical analysis of phases in equilibrium for different initial compositions at 298.2 K. The obtained results clearly demonstrate the ability of the ternary mixture to phase separate, providing good salting-out media for the efficient and sustainable separation from aqueous solution. 1H NMR spectroscopy was employed to elucidate the mechanisms of phase splitting in the ternary (ethyl lactate + water + salt) systems at molecular level. The discovery of aqueous biphasic system (ABS) containing ethyl lactate as hydrophilic solvent opens a new and green platform for extraction of various compounds from aqueous solutions

Avaliação do desempenho produtivo de suínos de raça Alentejana submetidos a acabamento intensivo até elevado peso de abate

A raça autóctone suína Alentejana, com solar na região do Alentejo, tem sido desde sempre explorada em sistemas de produção extensivos ou semi-intensivos, em virtude da sua capacidade para converter os frutos do montado, lande e bolota, em carne e gordura. A montanheira é, no entanto, um recurso limitado, apenas disponível durante uma época do ano e sujeito a variações anuais, pelo que a exploração destes animais em sistema intensivo pode constituir uma alternativa ao sistema tradicional. Avaliou-se o desempenho produtivo, a acumulação de gordura subcutânea e o aumento da espessura do músculo Longissimus dorsi de suínos Alentejanos machos castrados, submetidos a engorda intensiva, até um peso elevado ao abate (160 kg). Analisaram-se dados de 30 animais, ao longo do seu crescimento / engorda intensiva, dos 60 aos 160 kg de PV. Os animais foram pesados semanalmente e a ingestão de alimento, limitada a 4% do PV, controlada individual e diariamente. Avaliou-se por ultra-sonografia aos 60, 90, 120 e 160 kg de PV a espessura do músculo Longissimus dorsi, ao nível do P2 (a 65 mm da linha média ao nível da última costela) e da gordura subcutânea no ponto P2 e sobre a apófise medial da última vertebra lombar. Os GMD dos animais foram de 865 ± 179 g, 1041 ± 207 g e 776 ± 116 g, nos períodos 60-90, 90-120 e 120-160kg, respetivamente. Estes valores de GMD, em acabamento intensivo e, em particular, no período 90-120 kg, são muito superiores aos valores referidos na bibliografia para porcos de raça Alentejana explorados no sistema tradicional. A ingestão alimentar, apesar da sua limitação, foi proporcionalmente mais elevada, que o GMD, o que se traduziu num elevado IC (4,79 ± 0,87, 4,45 ± 1,17 e 6,78 ± 0,92, nos períodos 60-90, 90-120 e 120-160 kg, respetivamente). A espessura de gordura subcutânea ao nível do P2 e da última vertebra lombar apresentaram valores próximos nos vários tempos avaliados. O incremento de acumulação de gordura subcutânea, observado com o aumento de peso do animal, foi particularmente elevado, evidenciando uma elevada capacidade de deposição de tecido adiposo a par do limitado potencial de desenvolvimento muscular, característico da raça suína Alentejana. No sistema de engorda intensivo praticado neste estudo, os animais da raça Alentejana apresentaram um desempenho produtivo pouco interessante, devido a uma reduzida taxa de conversão alimentar, a par do elevado período de tempo necessário para atingir pesos elevados de abate. Os resultados obtidos evidenciaram um forte incremento da gordura subcutânea dorsal, acompanhado de um aumento moderado da espessura do músculo Longissimus dorsi.info:eu-repo/semantics/publishedVersio

Recent advances of metallocenes for medicinal chemistry

This work was supported by LAQV-REQUIMTE; Fundacao para a Ciencia e Tecnologia (FCT, Portugal), through projects and the IF researcher consolidator contract (IF/0041/2013/CP1161/CT005), and Solchemar Company.Background: The recent advances for the synthesis and application of different metallocenes for Medicinal Chemistry is reviewed. Objective: This manuscript presents the different metallocene scaffolds, with special emphasis on ferrocene derivatives, and their potential pharmaceutical application. Over the last years, the synthesis of new metallocene compounds and their biological and medicinal effects against some types of diseases (e.g. anti-tumoral, antibiotics, anti-viral) have been reported. From the medicinal point of view, the attractive properties of metallocene derivatives, such as their high stability, low toxicity and appealing redox behaviors are particularly relevant. Results: This area has attracted many researchers as well as the pharmaceutical industry due to the promising results of some metallocenes, in particular ferrocene compounds, in breast cancer and malaria.authorsversionpublishe

Imidazolium and picolinium-based electrolytes for electrochemical reduction of CO2 at high pressure

ABSTRACT: Ionic liquids (ILs) have been considered among one of the most promising materials under investigation for integration of CO2 capture and electrochemical reduction (ECR). In the design of an IL-based electrolyte that can be employed industrially, the understanding of the influence of IL structure on ECR was considered essential. In this context, electrolytes with trifluoromethanosulfonate (OTf) anion were investigated as aqueous electrolytes for electrochemical reduction of CO2 at high pressure and near room temperature with zinc electrodes. The effect of replacing the 1-ethyl-3-methyl-imidazolium cation [EMIM] by 1-ethyl-3-picolinium [C2(3)pic] and by 1-ethyl-4-picolinium [C2(4)pic] cations was studied. The use of picolinium-based electrolytes in ECR is for the first time reported. A high-pressure single compartment test bed was used for electrolyte screening. Carbon monoxide productivities and selectivities were determined for the several electrolytes with different water contents. The electrolytes were characterized by cyclic voltammetry and electrochemical impedance spectroscopy. Electrolyte conductivities and diffusion coefficients were estimated. The effect of the cations is complex as it affects conductivity, double layer structure, reaction reversibility and even the ionic liquid physical state. Notwithstanding, it is possible to tune these properties to achieve similar CO productions with reduced IL amounts, considering the nature of the cation and the water content, leading to the design of more cost effective electrolytes for efficient ECR process.info:eu-repo/semantics/publishedVersio

Crescimento e qualidade da carcaça de suinos Landrace X Large White submetidos a acabamento intensivo até elevado peso de abate

Ao longo dos últimos anos, em muitos países, e como já é habitual em Itália, o peso vivo de abate de suínos tem registado um progressivo aumento, o que tem sido possível devido ao melhoramento genético de raças industriais, com potencial para produzir mais carne magra. Utilizaram-se 30 suínos, F1 cruzados de Landrace x Large White, castrados, submetidos a acabamento intensivo com alimento composto (Energia Bruta 3833 kcal / kg MS), distribuído ad libitum, até um peso elevado ao abate (90-160 kg de PV). Avaliou-se o desempenho produtivo dos animais, espessura da gordura e profundidade do Longissimus dorsi, in vivo, e peso de carcaça. Os animais foram pesados semanalmente e a ingestão de alimento controlada, individual e diariamente, permitindo calcular os GMD e IC. Efetuaram-se diversas medições, in vivo, da espessura da gordura (P1 - linha média da última vertebra torácica, P2 - a 6 cm da linha média ao nível da última vertebra torácica e P3 - linha média da última vertebra lombar) e da profundidade do Longissimus dorsi, por ultra-sonografia, aos 90, 120 e 160 kg PV. Os animais foram abatidos em matadouro experimental, registando-se o peso de carcaça, a quente e a frio (24 h post mortem), bem como o total das gorduras rejeitadas e miudezas. Os GMD dos animais foram de 828,3 ± 110,3 g e de 673,1 ± 112,2 g, nos períodos 90-120 kg e 120- 160 kg, respetivamente, o que representa um decréscimo de 19% do GMD, entre os períodos considerados. Nos mesmos períodos, os IC foram de 4,27 ± 0,32 e de 4,99 ± 0,49, representando um incremento de 17%. O consumo médio de alimento foi de 3,34 kg / dia. Para as três medições de espessura da gordura efetuadas e da profundidade do Longissimus dorsi, registou-se um crescimento constante ao longo do ensaio, no total de 1,1 cm, e de 1,2 cm, respetivamente. Observou-se apenas uma diferenciação do crescimento do P2, menos acentuado entre os 90 e os 120 kg, mas recuperando, no período 120-160 Kg. Os pesos médios da carcaça, a quente e a frio, foram respectivamente 132,1 Kg e 130 kg, representando 82,4% e 81% do peso vivo ao abate. Obteve-se um peso médio da perna (com chispe) de 19 kg. Os resultados obtidos indiciam uma possível utilização deste cruzamento na produção de suínos em sistema intensivo com objetivo de produção de pernas para presunto e com aproveitamento das restantes peças cárneas.info:eu-repo/semantics/publishedVersio

Highly water soluble room temperature superionic liquids of APIs

Fundacao para a Ciencia e a Tecnologia through project (PEst-C/LA0006/2013). The authors also thank Prof. Madalena Dionisio and Dr Natalia Correia for their support with the DSC analyses.Herein a straightforward approach for the enhancement of the water solubility of common antibiotic and NSAID active pharmaceutical ingredients (APIs) is presented. The APIs are converted into ionic liquids (API-ILs) and molten salts by combination with the organic superbases TMG, DBU and DBN. The prepared superionic liquids were characterized by 1H and 13C NMR as well as FTIR spectroscopy and elemental analysis. Most products are amorphous non-polymorphic room temperature ionic liquids with very high solubility in water, which may enhance the bioavailability of the API-ILs in comparison with the parent drugs.authorsversionpublishe

Lanthanide-based organic salts: Synthesis, characterization, and cytotoxicity studies

This work was supported by Fundação para a Ciência e a Tecnologia through projects (PEst-C/LA0006/2013, PTCD/CTM-NAN/120658/2010, two contracts under Investigador FCT (L. C. Branco and I. M. Marrucho), a doctoral fellowship Andreia Forte (PD/BD/109625/2015), and by the Portuguese Foundation for Science and Technology (FCT) through the strategic project UID/MAR/04292/2020 granted to MARE—Marine and Environmental Sciences Centre and Solchemar company.The formulation of magnetic ionic liquids (MILs) or organic salts based on lanthanides as anions has been explored. In this work, a set of choline-family-based salts, and two other, different cation families, were combined with Gadolinium(III) and Terbium(III) anions. Synthetic methodologies were previously optimized, and all organic salts were obtained as solids with melting temperatures higher than 100 °C. The magnetic moments obtained for the Gd(III) salts were, as expected, smaller than those obtained for the Tb(III)-based compounds. The values for Gd(III) and Tb(III) magnetic salts are in the range of 6.55–7.30 MB and 8.22–9.34 MB, respectively. It is important to note a correlation between the magnetic moments obtained for lanthanides, and the structural features of the cation. The cytotoxicity of lanthanide-based salts was also evaluated using 3T3, 293T, Caco2, and HepG2 cells, and it was revealed that most of the prepared compounds are not toxic.info:eu-repo/semantics/publishedVersio