Mechanochemistry in Portugal—A Step towards Sustainable Chemical Synthesis

In Portugal, publications with mechanochemical methods date back to 2009, with the report on mechanochemical strategies for the synthesis of metallopharmaceuticals. Since then, mechanochemical applications have grown in Portugal, spanning several fields, mainly crystal engineering and supramolecular chemistry, catalysis, and organic and inorganic chemistry. The area with the most increased development is the synthesis of multicomponent crystal forms, with several groups synthesizing solvates, salts, and cocrystals in which the main objective was to improve physical properties of the active pharmaceutical ingredients. Recently, non-crystalline materials, such as ionic liquids and amorphous solid dispersions, have also been studied using mechanochemical methods. An area that is in expansion is the use of mechanochemical synthesis of bioinspired metal-organic frameworks with an emphasis in antibiotic coordination frameworks. The use of mechanochemistry for catalysis and organic and inorganic synthesis has also grown due to the synthetic advantages, ease of synthesis, scalability, sustainability, and, in the majority of cases, the superior properties of the synthesized materials. It can be easily concluded that mechanochemistry is expanding in Portugal in diverse research areas.     

New Promising Therapeutic Avenues of Curcumin in Brain Diseases

Curcumin, the dietary polyphenol isolated from Curcuma longa (turmeric), is commonly used as an herb and spice worldwide. Because of its bio-pharmacological effects curcumin is also called “spice of life”, in fact it is recognized that curcumin possesses important proprieties such as anti-oxidant, anti-inflammatory, anti-microbial, antiproliferative, anti-tumoral, and anti-aging. Neurodegenerative diseases such as Alzheimer’s Diseases, Parkinson’s Diseases, and Multiple Sclerosis are a group of diseases characterized by a progressive loss of brain structure and function due to neuronal death; at present there is no effective treatment to cure these diseases. The protective effect of curcumin against some neurodegenerative diseases has been proven by in vivo and in vitro studies. The current review highlights the latest findings on the neuroprotective effects of curcumin, its bioavailability, its mechanism of action and its possible application for the prevention or treatment of neurodegenerative disorders.     

Impact of High-Pressure Homogenization on the Cell Integrity of Tetradesmus obliquus and Seed Germination

Microalgae have almost unlimited applications due to their versatility and robustness to grow in different environmental conditions, their biodiversity and variety of valuable bioactive compounds. Wastewater can be used as a low-cost and readily available medium for microalgae, while the latter removes the pollutants to produce clean water. Nevertheless, since the most valuable metabolites are mainly located inside the microalga cell, their release implies rupturing the cell wall. In this study, Tetradesmus obliquus grown in 5% piggery effluent was disrupted using high-pressure homogenization (HPH). Effects of HPH pressure (100, 300, and 600 bar) and cycles (1, 2 and 3) were tested on the membrane integrity and evaluated using flow cytometry and microscopy. In addition, wheat seed germination trials were carried out using the biomass at different conditions. Increased HPH pressure or number of cycles led to more cell disruption (75% at 600 bar and 3 cycles). However, the highest increase in wheat germination and growth (40–45%) was observed at the lowest pressure (100 bar), where only 46% of the microalga cells were permeabilised, but not disrupted. Non-treated T. obliquus cultures also revealed an enhancing effect on root and shoot length (up to 40%). The filtrate of the initial culture also promoted shoot development compared to water (21%), reinforcing the full use of all the process fractions. Thus, piggery wastewater can be used to produce microalgae biomass, and mild HPH conditions can promote cell permeabilization to release sufficient amounts of bioactive compounds with the ability to enhance plant germination and growth, converting an economic and environmental concern into environmentally sustainable applications.     

The Thermal Characteristics,Sorption Isotherms and State Diagrams of the Freeze-Dried Pumpkin-Inulin Powders

Powders based on plant raw materials have low storage stability due to their sorption and thermal properties and generate problems during processing. Therefore, there is a need to find carrier agents to improve their storage life as well as methods to evaluate their properties during storage. Water adsorption isotherms and thermal characteristics of the pumpkin powder with various inulin additions were investigated in order to develop state diagrams. Differential scanning calorimetry (DSC) was used to obtained glass transition lines, freezing curves and maximal-freeze-concentration conditions. The glass transition lines were developed using the Gordon–Taylor model. Freezing data were modeled employing the Clausius–Clapeyron equation and its development–Chen model. The glass transition temperature of anhydrous material (Tgs) and characteristic glass transition temperature of maximum-freeze-concentration (Tg′) increased with growing inulin additions. Sorption isotherms of the powders were determined at 25 °C by the static-gravimetric method and the experimental data was modeled with four different mathematical models. The Peleg model was the most adequate to describe the sorption data of the pumpkin–inulin powders. Guggenheim-Anderson-de Boer (GAB) monolayer capacity decreased with increasing inulin concentration in the sample.     

Synthesis and characterization of (N→B) phenyl[N-alkyl-N-(2-alkyl)aminodiacetate-O,O′,N]boranes and phenyl[N-alkyl-N-(2-alkyl) aminodiacetate-O,O′,N]boranes

The reaction of boron heterocycles 1 and 2 with n-butyl lithium and alkyl halides led to (N→B) phenyl[N-alky-N-(2-alkyl)aminodiacetate-O,O′,N]boranes 3–6(a–b), 7(b) and 9(b), where alkyl can be in exo and/or endo position, and phenyl[N-alkyl-N-(2-alkyl)aminodiacetate-O,O′,N]boranes 7(c) and 8(c) isomers, which do not display the intramolecular N→B coordination bond. The existence of steric interactions between N-benzyl and the alkyl group at 2 position was indicated by ¹H and ¹³C NMR, while, the δ(¹¹B) values confirm the tetrahedral and trigonal environment of the ¹¹B nucleus in these compounds. Moreover, the compounds were characterized by COSY, HETCOR and homonuclear proton decoupling experiment. The study of the intramolecular N→B coordination by dynamic NMR afforded a ΔG‡ value of 81.09 kJ/mol for compound 6(b).     

Quantification of the effect of nonphotochemical quenching on the determination of in vivo chl a from phytoplankton along the water column of a freshwater reservoir

Nonphotochemical quenching (NPQ) is a well-known collection of different photoprotective mechanisms of plants and algae to avoid photodamage under an excess of light energy. In order to evaluate the overall effect of NPQ processes on the fluorometric determination of in vivo Chl a from a phytoplankton community dominated by diatoms, we compared the results obtained by two different fluorometric field devices with the total concentration of extracted Chl a measured by HPLC ( in vitro Chl a ). A different set of measurements were made to assess the performance of these fluorometers at high, moderate and low irradiance conditions. The Fbbe fluorometer, which is capable of distinguishing different algal groups according to their pigment content, allowed a better determination of in vivo Chl a under high irradiance conditions, with only a 10% mean difference from the in vitro Chl a concentration. In turn, the FMII fluorometer underestimated by as much as 50% the in vitro Chl a concentration under the same light conditions. As data from both fluorometers were in accordance with the in vitro Chl a values at moderate irradiance levels, the differences observed at high irradiances were attributed to the decrease in the yield of Chl a fluorescence caused by photoprotective NPQ processes. Accordingly, we estimated the effect of NPQ processes on the in vivo Chl a determination and the results allow us to provide an equation to correct this effect when in situ fluorometric measurements are carried out under high irradiance regimes. Our results demonstrate that under certain circumstances NPQ seriously compromises the results obtained by in situ fluorometric probes and highlight the need for a cautious interpretation of field data under such environmental conditions.     

Elemental Chemometrics as Tools to Depict Stalked Barnacle (Pollicipes pollicipes) Harvest Locations and Food Safety

The stalked barnacle Pollicipes pollicipes is an abundant species on the very exposed rocky shore habitats of the Spanish and Portuguese coasts, constituting also an important economical resource, as a seafood item with high commercial value. Twenty-four elements were measured by untargeted total reflection X-ray fluorescence spectroscopy (TXRF) in the edible peduncle of stalked barnacles sampled in six sites along the Portuguese western coast, comprising a total of 90 individuals. The elemental profile of 90 individuals originated from several geographical sites (N = 15 per site), were analysed using several chemometric multivariate approaches (variable in importance partial least square discriminant analysis (VIP-PLS-DA), stepwise linear discriminant analysis (S-LDA), linear discriminant analysis (LDA), random forests (RF) and canonical analysis of principal components (CAP)), to evaluate the ability of each approach to trace the geographical origin of the animals collected. As a suspension feeder, this species introduces a high degree of background noise, leading to a comparatively lower classification of the chemometric approaches based on the complete elemental profile of the peduncle (canonical analysis of principal components and linear discriminant analysis). The application of variable selection approaches such as the VIP-PLS-DA and S-LDA significantly increased the classification accuracy (77.8% and 84.4%, respectively) of the samples according to their harvesting area, while reducing the number of elements needed for this classification, and thus the background noise. Moreover, the selected elements are similar to those selected by other random and non-random approaches, reinforcing the reliability of this selection. This untargeted analytical procedure also allowed to depict the degree of risk, in terms of human consumption of these animals, highlighting the geographical areas where these delicacies presented lower values for critical elements compared to the standard thresholds for human consumption.     

A quantitative thermal analysis of cyclists’ thermo-active base layers

It is well known that clothes used in sporting activity are a barrier for heat exchange between the environment and athlete, which should help in thermoregulation improvement. However, it is difficult to evaluate which top is best for each athlete according to the characteristics of the sport. Researchers have tried to measure the athlete’s temperature distribution during exercise at the base layers of tops with different approaches. The aim of this case study was to investigate the use of thermography for thermo-active base layer evaluation. Six new base layers were measured on one cyclist volunteer during a progressive training on a cycloergometer. As a control condition, the skin temperature of the same volunteer was registered without any layer with the same training. A training protocol was selected approximate to cycling race, which started from the warm-up stage, next the progressive effort until the race finished and at the end “cool-down” stage was over. In order to show which layer provided the strongest and weakest barrier for heat exchange in comparison with environment, the temperature parameters were taken into consideration. The most important parameter in the studies was the temperature difference between the body and the layers, which was changing during the test time. The studies showed a correlation between the ergometer power parameter and the body temperature changes, which has a strong and significant value. Moreover, the mass of every layer was checked before and after the training to evaluate the mass of the sweat exuded during the test. From this data, the layer mass difference parameter was calculated and taken into consideration as a parameter, which may correspond with the mean heart rate value from each training. A high and positive correlation coefficient was obtained between the average heart rate and the mass difference for the base layers. Thermal analysis seems to have a new potential application in the objective assessment of sports clothing and may help in choosing the proper clothes, which could support heat transfer during exercising and protect the body from overheating.

     

On the Structure and Chiral Aggregation of Liquid Crystalline Star-Shaped Triazines H-Bonded to Benzoic Acids

The ability of a star-shaped tris(triazolyl)triazine derivative to hierarchically build supramolecular chiral columnar organizations through the formation of H-bonded complexes with benzoic acids was studied from a theoretical and experimental point of view. The combined study has been done at three different levels including the study of the structure of the triazine core, the association with benzoic acids in stoichiometry 1:3, and the assembly of 1:3 complexes in helical aggregates. Although the star-shaped triazine core crystallizes in a non-C₃ conformation, the C₃-symmetric conformation is theoretically predicted to be more stable and gives rise to a favorable C₃ supramolecular 1:3 complex upon the interaction with three benzoic acids in their voids. In addition, calculations at different levels (DFT, PM7, and MM3) for the 1:3 host-guest complex predict the formation of large stable columnar helical aggregates stabilized by the compact packing of the interstitial acids by π–π and CH⋅⋅⋅π interactions. The acids restrict the movement of the the star-shaped triazine cores along the stacking axis causing a template effect in the self-assembly of the complex. Theoretical predictions correlate with experimental results, since the interaction with achiral or chiral 3,4,5-(4-alkoxybenzyloxy)benzoic acids gives rise to supramolecular complexes that organize in bulk hexagonal columnar mesophases stable at room temperature with intracolumnar order. The existence of supramolecular chirality in the mesophase was determined for complexes formed by acids derived from (S)-2-octanol. Chiral aggregation was also evidenced for complexes formed in dodecane.     

A Click Chemistry Approach to Developing Molecularly Targeted DNA Scissors

Nucleic acid click chemistry was used to prepare a family of chemically modified triplex forming oligonucleotides (TFOs) for application as a new gene-targeted technology. Azide-bearing phenanthrene ligands—designed to promote triplex stability and copper binding—were ‘clicked’ to alkyne-modified parallel TFOs. Using this approach, a library of TFO hybrids was prepared and shown to effectively target purine-rich genetic elements in vitro. Several of the hybrids provide significant stabilisation toward melting in parallel triplexes (>20 °C) and DNA damage can be triggered upon copper binding in the presence of added reductant. Therefore, the TFO and ‘clicked’ ligands work synergistically to provide sequence-selectivity to the copper cutting unit which, in turn, confers high stabilisation to the DNA triplex. To extend the boundaries of this hybrid system further, a click chemistry-based di-copper binding ligand was developed to accommodate designer ancillary ligands such as DPQ and DPPZ. When this ligand was inserted into a TFO, a dramatic improvement in targeted oxidative cleavage is afforded.