Lactones in the Synthesis of Prostaglandins and Prostaglandin Analogs

In the total stereo-controlled synthesis of natural prostaglandins (PGs) and their structural analogs, a vast class of compounds and drugs, known as the lactones, are encountered in a few key steps to build the final molecule, as: δ-lactones, γ-lactones, and 1,9-, 1,11-, and 1,15-macrolactones. After the synthesis of 1,9-PGF_2α and 1,15-PGF_2α lactones, many 1,15-lactones of E₂, E₃, F₂, F₃, A₂, and A₃ were found in the marine mollusc Tethys fimbria and the quest for understanding their biological role stimulated the research on their synthesis. Then 1,9-, 1,11-, and 1,15-PG lactones of the drugs were synthesized as an alternative to the corresponding esters, and the first part of the paper describes the methods used for their synthesis. The efficient Corey procedure for the synthesis of prostaglandins uses the key δ-lactone and γ-lactone intermediates with three or four stereocenters on the cyclopentane fragment to link the PG side chains. The paper describes the most used procedures for the synthesis of the milestone δ-Corey-lactones and γ-Corey-lactones, their improvements, and some new promising methods, such as interesting, new stereo-controlled and catalyzed enantioselective reactions, and methods based on the chemical/enzymatic resolution of the compounds in different steps of the sequences. The many uses of δ-lactones not only for the synthesis of γ-lactones, but also for obtaining 9β-halogen-PGs and halogen-substituted cyclopentane intermediates, as synthons for new 9β-PG analogs and future applications, are also discussed.     

Vacuum impregnation of chitosan‐based edible coating in minimally processed pumpkin

The goal of this research was to evaluate the use of vacuum impregnation (VI) and soaking techniques (ST) in the application of edible coatings of chitosan and chitosan + lauric acid to minimally processed pumpkins (MPP). The vacuum impregnation method led to greater component incorporation (5.9% and 1.75%, respectively) in the pumpkins when compared to soaking and consequently the formation of more uniform, thicker coatings (25.6 and 22.3 μm, respectively). However, VI caused greater changes in pH, acidity, colour and firmness. Relating to water content and carotenoid content, noncoated pumpkins presented greater losses during the storage period, regardless of impregnation method. The pumpkins with edible coatings, regardless of method, presented lower numbers of psychrotrophic micro‐organisms and coliforms during the storage period. Therefore, soaking was considered the best method for the application of chitosan‐based edible coatings to minimally processed pumpkins, as it led to smaller changes in the properties of the product.     

CO2 sequestration by magnesite mineralisation through interaction of Mg-brine and CO2: integrated laboratory experiments and computerised geochemical modelling

ABSTRACT

Several Carbon Capture and Storage (CCS) techniques have been studied including injections of carbon dioxide (CO₂) into the mature and/or depleted hydrocarbon reservoirs and deep saline aquifers. This work aims to test storing CO₂ into the magnesium-rich evaporite strata and also into the stratigraphic intervals containing Mg-rich brines. The test simulates Mg-carbonation of the synthetic solution obtained from the Mg-evaporite mineral, bischofite – both experimentally in the laboratory condition and also through computerised geochemical simulation. The laboratory experiments, which resulted in the crystallisation of anhydrous magnesite, were analysed. The TOUGHREACT^TM, Geochemist’s Workbench^TM (GWB) and PHREEQC^TM software simulated the experiments as computerised geochemical model and tested the results for natural geological conditions. The geochemical simulations successfully demonstrate the immense CCS potential for the Mg-evaporite (as well as the sedimentary strata charged with Mg-evaporitic brine) at their subsurface geological occurrences at elevated pressure-temperature and high salinity.     

Tribocorrosion and corrosion behavior of stainless steel coated with DLC films in ethanol with different concentrations of water

There has been a recent increase in both the production and consumption of ethanol due to the numerous environmental advantages that it offers, such as the fact that it can be produced from a variety of renewable materials, for instance corn and cellulose, or it can be obtained from sugarcane bagasse and biomass (2nd and 3rd generation ethanol). The result of this is that nowadays ethanol is widely seen as the dominant biofuel – or as a blend component in gasoline or pure fuel - in many countries.However, one disadvantage of the use of ethanol is the high corrosive behavior that occurs when its hygroscopic properties are exposed to a large number of materials. Xiaoyuan Lou and Preet Singh showed that the increase of water concentration in ethanol induces pitting and metal loss. Diamond-Like Carbon (DLC) films may be a solution to this problem due to the fact that they can be deposited inside tubes, offer good protection levels against corrosion, and reduce the friction coefficient and wear.This paper shows the tribocorrosion and corrosion studies of DLC films deposited on stainless steel grade 304 (SS304) substrates in order to gauge its appropriateness usage in the construction of pipelines and fuel storage tanks. The surface morphology was analyzed before and after 14 days of immersion. The tribocorrosion, friction coefficient, and wear rate were studied in ethanol to see the effects of water concentration. The films showed good adherence to the substrates. Corrosion and tribocorrosion results showed that for bare Stainless Steel 304 the increase of the water content increases the corrosion and the friction coefficient. DLC coated samples presented few points of delamination, and the friction coefficient and open circuit potentials were very low compared with the bare sample which was water concentration independent.     

Antioxidant and antimicrobial potential of cajazeira leaves (Spondias mombin) extracts

Cajazeira leaves (Spondias mombin) have their highlighted use as antioxidant and natural antimicrobial, which justifies the objective of this work to evaluate the biological activities of different extracts. In order to evaluate the antioxidant and antimicrobial potentials of the cajazeira leaves, extractions at low pressure and high pressure were performed. The low pressure extractions (PLE) were carried out using Soxhlet (SOX) and tip ultrasound, using different solvents. Supercritical fluid extraction (SFE) was evaluated at temperature of 40?60°C and pressure of 150?300 bar besides extraction with cosolvent. Higher yields were obtained with the use of more polar solvents at LPE. The extracts obtained by SOX with ethanol and others polar solvents presented the best TPC values and antioxidant activity. The extracts at LPE with hexane and ethyl acetate and SFE presented better antimicrobial activity. Through liquid chromatography of high efficiency, it was possible to identify compounds with recognized biological activity, like ellagic acid, gallic acid and catechin.     

Proteome analysis of tissues by mass spectrometry

Tissues and biofluids are important sources of information used for the detection of diseases and decisions on patient therapies. There are several accepted methods for preservation of tissues, among which the most popular are fresh‐frozen and formalin‐fixed paraffin embedded methods. Depending on the preservation method and the amount of sample available, various specific protocols are available for tissue processing for subsequent proteomic analysis. Protocols are tailored to answer various biological questions, and as such vary in lysis and digestion conditions, as well as duration. The existence of diverse tissue‐sample protocols has led to confusion in how to choose the best protocol for a given tissue and made it difficult to compare results across sample types. Here, we summarize procedures used for tissue processing for subsequent bottom‐up proteomic analysis. Furthermore, we compare protocols for their variations in the composition of lysis buffers, digestion procedures, and purification steps. For example, reports have shown that lysis buffer composition plays an important role in the profile of extracted proteins: the most common are tris(hydroxymethyl)aminomethane, radioimmunoprecipitation assay, and ammonium bicarbonate buffers. Although, trypsin is the most commonly used enzyme for proteolysis, in some protocols it is supplemented with Lys‐C and/or chymotrypsin, which will often lead to an increase in proteome coverage. Data show that the selection of the lysis procedure might need to be tissue‐specific to produce distinct protocols for individual tissue types. Finally, selection of the procedures is also influenced by the amount of sample available, which range from biopsies or the size of a few dozen of mm² obtained with laser capture microdissection to much larger amounts that weight several milligrams.     

Touch sensor and photovoltaic characteristics of CuSbS2 thin films

Spin-coated chalcostibite CuSbS₂ thin films (≈500 nm thick) were fabricated and the influence of the drying temperature on the structural, morphological, optical and thermoelectric properties of the films was investigated. Crystalline phase-pure chalcostibite has been obtained for the films dried at 180 °C and 210 °C, while below 180 °C these films are partially amorphous. Surprisingly, at drying temperature of 240 °C, a Cu_xS secondary phase appeared. The increase of the drying temperature leads to the increase of the particle size and the decrease of the optical band gap, which is interesting for optoelectronic applications. The highest power factor value was achieved for the film dried at 210 °C, due to the inexistence of secondary phases, which allowed realizing a stable thermoelectric touch sensor with a V_signal/_noise of 5. In addition, this film was tested as a photovoltaic (PV) device and a power conversion efficiency (PCE) of 0.030% with an open-circuit voltage (V_OC) of 0.36 V, a short-circuit current density (J_SC) of 0.278 mAcm^?2 and a fill factor (FF) of 0.27 were obtained. Therefore, this work evidences a pathway toward developing bi-functional devices with simultaneously thermoelectric touch sensor and photovoltaic functions.     

Juice and by-products from pomegranate to enrich pancake: characterisation and shelf-life evaluation

In this study, a fortified pancake with all parts of pomegranate as juice and by-products, added in the formulation, was designed. The influence of pomegranate addition on nutritional and sensory quality of pancake, as well as on its shelf-life, was assessed. As one would expect, the enrichment significantly improved the pancake polyphenolic content as compared to the control sample. Surprisingly, pomegranate addition did not affect its sensory quality. In fact, the enriched pancake was greatly appreciated from the sensory point of view. Results also suggested that the addition of pomegranate improved the glycemic index (GI). In fact, while a value of GI equal to 100 was obtained for the control sample, a GI of 71 was measured for the fortified sample. In terms of shelf-life, 30 days were obtained for the enriched pancake, whereas the control sample remained acceptable for about 26 days.     

The influence of the processing route on the fragmentation of (Nb,Ti)C stringers and its role on mechanical properties and hydrogen embrittlement of nickel based alloy 718

The nickel-base superalloy 718 is a precipitation hardened alloy widely used in the nuclear fuel assembly of pressurized water reactors (PWR). However, the alloy can experience failure due to hydrogen embrittlement (HE). The processing route can influence the microstructure of the material and, therefore, the HE degree. In particular, the size and distribution of the (Nb,Ti)C particles can be affected by the processing. In this regard, the objective of this work was to analyze the influence of cold and hot deformation processing routes on the development of the microstructure, and the consequences on mechanical properties and hydrogen embrittlement. Tensile samples were hydrogenated through gaseous charging and compared to non-hydrogenated samples. Characterization was performed via scanning and transmission electron microscopies, as well as electron backscattered diffraction. The processing was effective to promote significant variations in average grain size and length fraction of special Σ3ⁿ boundaries, as well as reduction of average (Nb,Ti)C particle size, being these changes more intense for the cold-rolled route. For the mechanical properties, on one side, the cold-rolled route presented the highest increase in ductility for non-hydrogenated samples, while, on the other side, had the highest degree of embrittlement under hydrogen. This dual behavior was attributed to the interaction of hydrogen with the (Nb,Ti)C particles and stringers and its ensuing influence on the fracture processes.