Entropy and Enthalpy Effects on Metal Complex Formation in Non-Aqueous Solvents: The Case of Silver(I) and Monoamines

Access to the enthalpy and entropy of the formation of metal complexes in solution is essential for understanding the factors determining their thermodynamic stability and speciation. As a case study, in this report we systematically examine the complexation of silver(I) in acetonitrile (AN) with the following monoamines: n-propylamine (n-pr), n-butylamine (n-but), hexylamine (hexyl), diethylamine (di-et), dipropylamine (di-pr), dibutylamine (di-but), triethylamine (tri-et) and tripropylamine (tri-pr). The study shows that the complex stabilities are quite independent of the length of the substitution chain on the N atom and demonstrates that, in general, the overall enthalpy terms associated with the complex formation are strongly exothermic, whereas the entropy values oppose the complex formations. In addition, we examined the similarity of the formation constants of AgL complexes of the primary monoamines in AN, dimethylsulfoxide (DMSO) and water, which were unexpected on the basis of the difference between the donor properties of solvents.     

On the Criticality of Adaptive Boolean Network Robots

Systems poised at a dynamical critical regime, between order and disorder, have been shown capable of exhibiting complex dynamics that balance robustness to external perturbations and rich repertoires of responses to inputs. This property has been exploited in artificial network classifiers, and preliminary results have also been attained in the context of robots controlled by Boolean networks. In this work, we investigate the role of dynamical criticality in robots undergoing online adaptation, i.e., robots that adapt some of their internal parameters to improve a performance metric over time during their activity. We study the behavior of robots controlled by random Boolean networks, which are either adapted in their coupling with robot sensors and actuators or in their structure or both. We observe that robots controlled by critical random Boolean networks have higher average and maximum performance than that of robots controlled by ordered and disordered nets. Notably, in general, adaptation by change of couplings produces robots with slightly higher performance than those adapted by changing their structure. Moreover, we observe that when adapted in their structure, ordered networks tend to move to the critical dynamical regime. These results provide further support to the conjecture that critical regimes favor adaptation and indicate the advantage of calibrating robot control systems at dynamical critical states.     

Development of Novel Polypropylene Syntactic Foams Containing Paraffin Microcapsules for Thermal Energy Storage Applications

polypropylene (PP) syntactic foams (SFs) containing hollow glass microspheres (HGMs) possess low density and elevated mechanical properties, which can be tuned according to the specific application. A possible way to improve their multifunctionality could be the incorporation of organic Phase Change Materials (PCMs), widely used for thermal energy storage (TES) applications. In the present work, a PCM constituted by encapsulated paraffin, having a melting temperature of 57 °C, was embedded in a compatibilized polypropylene SF by melt compounding and hot pressing at different relative amounts. The rheological, morphological, thermal, and mechanical properties of the prepared materials were systematically investigated. Rheological properties in the molten state were strongly affected by the introduction of both PCMs and HGMs. As expected, the introduction of HGMs reduced both the foam density and thermal conductivity, while the enthalpy of fusion (representing the TES capability) was proportional to the PCM concentration. The mechanical properties of these foams were improved by the incorporation of HGMs, while they were reduced by addition of PCMs. Therefore, the combination of PCMs and HGMs in a PP matrix generated multifunctional materials with tunable thermo-mechanical properties, with a wide range of applications in the automotive, oil, textile, electronics, and aerospace fields.     

Resveratrol Analogues as Dual Inhibitors of Monoamine Oxidase B and Carbonic Anhydrase VII: A New Multi-Target Combination for Neurodegenerative Diseases?

Neurodegenerative diseases (NDs) are described as multifactorial and progressive syndromes with compromised cognitive and behavioral functions. The multi-target-directed ligand (MTDL) strategy is a promising paradigm in drug discovery, potentially leading to new opportunities to manage such complex diseases. Here, we studied the dual ability of a set of resveratrol (RSV) analogs to inhibit two important targets involved in neurodegeneration. The stilbenols 1–9 were tested as inhibitors of the human monoamine oxidases (MAOs) and carbonic anhydrases (CAs). The studied compounds displayed moderate to excellent in vitro enzyme inhibitory activity against both enzymes at micromolar/nanomolar concentrations. Among them, the best compound 4 displayed potent and selective inhibition against the MAO-B isoform (IC₅₀ MAO-A 0.43 µM vs. IC₅₀ MAO-B 0.01 µM) with respect to the parent compound resveratrol (IC₅₀ MAO-A 13.5 µM vs. IC₅₀ MAO-B > 100 µM). It also demonstrated a selective inhibition activity against hCA VII (K_I 0.7 µM vs. K_I 4.3 µM for RSV). To evaluate the plausible binding mode of 1–9 within the two enzymes, molecular docking and dynamics studies were performed, revealing specific and significant interactions in the active sites of both targets. The new compounds are of pharmacological interest in view of their considerably reduced toxicity previously observed, their physicochemical and pharmacokinetic profiles, and their dual inhibitory ability. Compound 4 is noteworthy as a promising lead in the development of MAO and CA inhibitors with therapeutic potential in neuroprotection.     

Environmentally Sustainable Achiral and Chiral Chromatographic Analysis of Amino Acids in Food Supplements

Two LC methods were developed for the achiral and chiral reversed-phase (RP) analysis of an amino acid (AA) pool in a food supplement, in compliance with the main paradigms of Green Chromatography. A direct achiral ion-pairing RP-HPLC method was optimized under gradient conditions with a water-ethanol (EtOH) eluent containing heptafluorobutyric acid (0.1%, v/v), to quantify the eight essential AAs (Ile, Leu, Lys, Met, Phe, Thr, Trp, and Val) contained in the food supplement. Thus, the usually employed acetonitrile was profitably substituted with the less toxic and more benign EtOH. The method was validated for Leu and Phe. The chiral LC method performed with a teicoplanin chiral stationary phase was developed with a water-EtOH (60:40, v/v) eluent with 0.1%, v/v acetic acid. The enantioselective analysis was carried out without any prior derivatization step. Both developed methods performed highly for all eight AAs and revealed that: (i) the content of six out of eight AAs was consistent with the manufacturer declaration; (ii) only L-AAs were present. Furthermore, it was demonstrated that a two-dimensional achiral–chiral configuration is possible in practice, making it even more environmentally sustainable. A molecular modelling investigation revealed interesting insights into the enantiorecognition mechanism of Lys.     

Utilization of Agro-Industrial Residues in the Rearing and Nutritional Enrichment of Zophobas atratus Larvae: New Food Raw Materials

Edible insects are a potential alternative food source of high feed conversion efficiency and protein content. Zophobas atratus is an edible insect that adapts to different diets, enabling sustainable rearing by adding value to by-products and agro-industrial residues. This study aimed to evaluate the performance and nutritional characterization of Zophobas atratus larvae fed with different proportions of grape residue. Physicochemical analysis of the diets and larvae (AOAC procedures), fatty acid profile (chromatographic techniques), metals and non-metals (inductively coupled plasma optical emission spectrometry), larval mass gain, feed conversion efficiency, and mortality rate were assessed. The replacement of 25% of the conventional diet with grape residue increased lipid, ash, and fiber contents and reduced protein, carbohydrates, and energy. It promoted greater mass gain, lower mortality rate, and reduced larval growth time by 51%. Among the replacements, 25% resulted in the second-highest content of calcium, sodium, magnesium, and zinc, and the lowest content of potassium and phosphorus in the larvae. The 100% replacement resulted in the highest amounts of C18:2n6 (27.8%), C18:3n3 (2.2%), and PUFA (30.0%). Replacing 25% of the conventional diet with grape residue is equivalent to the conventional diet in many aspects and improves several larvae performance indices and nutritional values.     

A Specific Interaction between Ionic Liquids’ Cations and Reichardt’s Dye

Solvatochromic probes are often used to understand solvation environments at the molecular scale. In the case of ionic liquids constituted by an anion and a cation, which are designed and paired in order to obtain a low melting point and other desirable physicochemical properties, these two indivisible components can interact in a very different way with the probe. This is the case with one of the most common probes: Reichardt’s Dye. In the cases where the positive charge of the cation is delocalized on an aromatic ring such as imidazolium, the antibonding orbitals of the positively charged aromatic system are very similar in nature and energy to the LUMO of Reichardt’s Dye. This leads to an interesting, specific cation-probe interaction that can be used to elucidate the nature of the ionic liquids’ cations. Parallel computational and experimental investigations have been conducted to elucidate the nature of this interaction with respect to the molecular structure of the cation.     

Antioxidants of Amaranth,Quinoa and Buckwheat Wholemeals and Heat-Damage Development in Pseudocereal-Enriched Einkorn Water Biscuits

A viable approach to improve the nutritional quality of cereal-based foods is their enrichment with pseudocereals. The aim of this research was to evaluate the antioxidant properties of amaranth, quinoa and buckwheat, and the heat damage of water biscuits (WB) produced from either wholemeal or refined flour of einkorn and enriched with 50% buckwheat, amaranth or quinoa wholemeal. Buckwheat had the highest tocols content (86.2 mg/kg), and einkorn the most carotenoids (5.6 mg/kg). Conjugated phenolics concentration was highest in buckwheat (230.2 mg/kg) and quinoa (218.6 mg/kg), while bound phenolics content was greatest in einkorn (712.5 mg/kg) and bread wheat (675.7 mg/kg). The all-wholemeal WB had greater heat damage than those containing refined flour (furosine: 251.5 vs. 235.8 mg/100 g protein; glucosylisomaltol: 1.0 vs. 0.6 mg/kg DM; hydroxymethylfurfural: 4.3 vs. 2.8 mg/kg DM; furfural: 8.6 vs. 4.8 mg/kg DM). The 100% bread wheat and einkorn wholemeal WB showed greater heat damage than the WB with pseudocereals (furfural, 9.2 vs. 5.1 mg/kg; glucosylisomaltol 1.1 vs. 0.7 mg/kg). Despite a superior lysine loss, the amino-acid profile of the pseudocereals-enriched WB remained more balanced compared to that of the wheats WB.     

Machine-learning algorithms for asthma,COPD, and lung cancer risk assessment using circulating microbial extracellular vesicle data and their application to assess dietary effects

Although mounting evidence suggests that the microbiome has a tremendous influence on intractable disease, the relationship between circulating microbial extracellular vesicles (EVs) and respiratory disease remains unexplored. Here, we developed predictive diagnostic models for COPD, asthma, and lung cancer by applying machine learning to microbial EV metagenomes isolated from patient serum and coded by their accumulated taxonomic hierarchy. All models demonstrated high predictive strength with mean AUC values ranging from 0.93 to 0.99 with various important features at the genus and phylum levels. Application of the clinical models in mice showed that various foods reduced high-fat diet-associated asthma and lung cancer risk, while COPD was minimally affected. In conclusion, this study offers a novel methodology for respiratory disease prediction and highlights the utility of serum microbial EVs as data-rich features for noninvasive diagnosis.Subject terms: Respiratory tract diseases, Machine learning, Predictive markers     

Magnetic Torus Microreactor as a Novel Device for Sample Treatment via Solid-Phase Microextraction Coupled to Graphite Furnace Atomic Absorption Spectroscopy: A Route for Arsenic Pre-Concentration

This work studied the feasibility of using a novel microreactor based on torus geometry to carry out a sample pretreatment before its analysis by graphite furnace atomic absorption. The miniaturized retention of total arsenic was performed on the surface of a magnetic sorbent material consisting of 6 mg of magnetite (Fe₃O₄) confined in a very small space inside (20.1 µL) a polyacrylate device filling an internal lumen (inside space). Using this geometric design, a simulation theoretical study demonstrated a notable improvement in the analyte adsorption process on the solid extractant surface. Compared to single-layer geometries, the torus microreactor geometry brought on flow turbulence within the liquid along the curvatures inside the device channels, improving the efficiency of analyte–extractant contact and therefore leading to a high preconcentration factor. According to this design, the magnetic solid phase was held internally as a surface bed with the use of an 8 mm-diameter cylindric neodymium magnet, allowing the pass of a fixed volume of an arsenic aqueous standard solution. A preconcentration factor of up to 60 was found to reduce the typical “characteristic mass” (as sensitivity parameter) determined by direct measurement from 53.66 pg to 0.88 pg, showing an essential improvement in the arsenic signal sensitivity by absorption atomic spectrometry. This methodology emulates a miniaturized micro-solid-phase extraction system for flow-through water pretreatment samples in chemical analysis before coupling to techniques that employ reduced sample volumes, such as graphite furnace atomic absorption spectroscopy.