Synthesis and characterization of the open-framework barium bisphosphonate [Ba3(O3PCH2NH2CH2PO3)2(H2O)4].3H2O

Following the strategy of using polyfunctional phosphonic acids for the synthesis of open-framework metal phosphonates, the phosphonocarboxylic acid (H2O3PCH2)2NCH2C6H4COOH was used in the hydrothermal synthesis of new Ba phosphonates. Its decomposition led to the first open-framework barium phosphonate [Ba3(O3PCH2NH2CH2PO3)2(H2O)4].3H2O. The synthesis was also successfully performed using iminobis(methylphosphonic acid), (H2O3PCH2)2NH, as a starting material, and the synthesis was optimized to obtain as a pure material. The reaction setup as well as the pH are the dominant parameters, and only a diffusion-controlled reaction led to the desired compound. The crystal structure was solved from single-crystal data: monoclinic; C2/c; a=2328.7(2), b=1359.95(7), and c=718.62(6) pm; beta=98.732(10) degrees ; V=2249.5(3)x10(6) pm3; Z=4; R1=0.036; and wR2=0.072 (all data). The structure of [Ba3(O3PCH2NH2CH2PO3)2(H2O)4].3H2O is built up from BaO8 and BaO10 polyhedra forming BaO chains and layers, respectively. These are connected to a three-dimensional metal-oxygen-metal framework with the iminobis(methylphosphonic acid) formally coating the inner walls of the pores. The one-dimensional pores (3.6x4 A) are filled with H2O molecules that can be thermally removed. Thermogravimetric investigations and temperature-dependent X-ray powder diffraction demonstrate the stability of the crystal structure up to 240 degrees C. The uptake of N,N-dimethylformamide and H2O by dehydrated samples is demonstrated. Furthermore, IR, Raman, and 31P magic-angle-spinning NMR data are also presented.     

An Application of Inverse Reinforcement Learning to Estimate Interference in Drone Swarms

Despite the increasing applications, demands, and capabilities of drones, in practice they have only limited autonomy for accomplishing complex missions, resulting in slow and vulnerable operations and difficulty adapting to dynamic environments. To lessen these weaknesses, we present a computational framework for deducing the original intent of drone swarms by monitoring their movements. We focus on interference, a phenomenon that is not initially anticipated by drones but results in complicated operations due to its significant impact on performance and its challenging nature. We infer interference from predictability by first applying various machine learning methods, including deep learning, and then computing entropy to compare against interference. Our computational framework begins by building a set of computational models called double transition models from the drone movements and revealing reward distributions using inverse reinforcement learning. These reward distributions are then used to compute the entropy and interference across a variety of drone scenarios specified by combining multiple combat strategies and command styles. Our analysis confirmed that drone scenarios experienced more interference, higher performance, and higher entropy as they became more heterogeneous. However, the direction of interference (positive vs. negative) was more dependent on combinations of combat strategies and command styles than homogeneity.     

Co-Production of Dimethyl Carbonate,Dimethoxymethane and Dimethyl Ether from Methanol: Process Design and Exergy Analysis

Dimethyl carbonate is an important green chemical that has been widely used in the chemical industry. In the production of dimethyl carbonate, methanol oxidative carbonylation has been studied, but the conversion ratio of dimethyl carbonate using this method is too low, and the subsequent separation requires a large amount of energy due to methanol and dimethyl carbonate being azeotrope. In this paper, the strategy of “reaction instead of separation” is proposed. Based on this strategy, a novel process is developed to combine the production of DMC with that of dimethoxymethane (DMM) and dimethyl ether (DME). The co-production process was simulated using Aspen Plus software, and the product purity was up to 99.9%. The exergy analysis of the co-production process and the existing process was carried out. The exergy destruction and exergy efficiency were compared with those of the existing production processes. The results show that the exergy destruction of the co-production process is about 276% less than that of the single-production processes, and the exergy efficiencies in the developed co-production process are significantly improved. The utility loads of the co-production process are significantly lower than that of the single-production process. The developed co-production process increases the methanol conversion ratio to 95%, with a reduced energy requirement. It is proved that the developed co-production process can provide an advantageous option over the existing processes with improved energy efficiency and material savings. The strategy of “reaction instead of separation” is feasible. A new strategy is proposed for azeotrope separation.     

GC-MS Chemical Characterization and Antibacterial Effect of the Essential oil of Piper mosenii

Commercialized mouthwashes are generally expensive for the most financially vulnerable populations. Thus, several studies evaluate the antimicrobial potential of herbal products, such as essential oils, to reduce the activity of microorganisms in the mouth. The objective of this research was to carry out the chemical characterization and antibacterial activity of the essential oil of Piper mosenii (EOPm), providing data that enable the development of a low-cost mouthwash formulation aimed at vulnerable communities. The analysis of the antibacterial potential and modulator of bacterial resistance was verified by the microdilution method to determine the minimum inhibitory concentration-MIC. The chemical components were characterized by gas chromatography coupled to mass spectrometry, where 23 chemical constituents were detected, with α-pinene, being the major compound. The EOPm showed a MIC ≥ 1024 µg/mL for all bacterial strains used in the tests. When the EOPm modulating activity was evaluated together with chlorhexidine, mouthwash and antibiotics against bacterial resistance, the oil showed a significant synergistic effect, reducing the MIC of the products tested in combination, in percentages between 20.6% to 96.3%. Therefore, it is recommended to expand the tests with greater variation of EOPm concentration and the products used in this research, in addition to the evaluation of toxicity and in vivo tests, seeking the development of a possible formulation of mouthwash accessible to the vulnerable population.     

Aminoquinolones and Their Benzoquinone Dimer Hybrids as Modulators of Prion Protein Conversion

Prion Diseases or Transmissible Spongiform Encephalopathies are neurodegenerative conditions associated with a long incubation period and progressive clinical evolution, leading to death. Their pathogenesis is characterized by conformational changes of the cellular prion protein—PrP^C—in its infectious isoform—PrP^Sc—which can form polymeric aggregates that precipitate in brain tissues. Currently, there are no effective treatments for these diseases. The 2,5-diamino-1,4-benzoquinone structure is associated with an anti-prion profile and, considering the biodynamic properties associated with 4-quinolones, in this work, 6-amino-4-quinolones derivatives and their respective benzoquinone dimeric hybrids were synthesized and had their bioactive profile evaluated through their ability to prevent prion conversion. Two hybrids, namely, 2,5-dichloro-3,6-bis((3-carboxy-1-pentyl-4-quinolone-6-yl)amino)-1,4-benzoquinone (8e) and 2,5-dichloro-3,6-bis((1-benzyl-3-carboxy-4-quinolone-6-yl)amino)-1,4-benzoquinone (8f), stood out for their prion conversion inhibition ability, affecting the fibrillation process in both the kinetics—with a shortening of the lag phase—and thermodynamics and their ability to inhibit the formation of protein aggregates without significant cytotoxicity at ten micromolar.     

Anticancer Effects of Propolis Extracts Obtained with the Cold Separation Method on PC-3 and DU-145 Prostate Cancer Cell Lines

Plant extracts are increasingly tested for their biological activity and interactions with neoplastic cells. One of such sources of biologically active substances is propolis. This product has been known for thousands of years and is widely used in alternative, folk medicine. Articles describing its effects on the metabolism and cell signaling pathways of neoplastic cells derived from different organs are also published more and more frequently. The purpose of our study was to evaluate the biological activity of propolis extract produced with the cold separation method into hormone-dependent and hormone-independent prostate cancer cell lines. In our study, the propolis extracts showed at least an inhibitory effect on the growth of PC-3 and DU-145 neoplastic cells. Our results suggest that propolis extracts obtained with the cold separation method may be considered as promising compounds for the production of health-promoting supplements.     

Molecular Hybridization Strategy on the Design,Synthesis, and Structural Characterization of Ferrocene-N-acyl Hydrazones as Immunomodulatory Agents

Immunomodulatory agents are widely used for the treatment of immune-mediated diseases, but the range of side effects of the available drugs makes necessary the search for new immunomodulatory drugs. Here, we investigated the immunomodulatory activity of new ferrocenyl-N-acyl hydrazones derivatives (SintMed(141–156). The evaluated N-acyl hydrazones did not show cytotoxicity at the tested concentrations, presenting CC₅₀ values greater than 50 µM. In addition, all ferrocenyl-N-acyl hydrazones modulated nitrite production in immortalized macrophages, showing inhibition values between 14.4% and 74.2%. By presenting a better activity profile, the ferrocenyl-N-acyl hydrazones SintMed149 and SintMed150 also had their cytotoxicity and anti-inflammatory effect evaluated in cultures of peritoneal macrophages. The molecules were not cytotoxic at any of the concentrations tested in peritoneal macrophages and were able to significantly reduce (p < 0.05) the production of nitrite, TNF-α, and IL-1β. Interestingly, both molecules significantly reduced the production of IL-2 and IFN-γ in cultured splenocytes activated with concanavalin A. Moreover, SintMed150 did not show signs of acute toxicity in animals treated with 50 or 100 mg/kg. Finally, we observed that ferrocenyl-N-acyl hydrazone SintMed150 at 100 mg/kg reduced the migration of neutrophils (44.6%) in an acute peritonitis model and increased animal survival by 20% in an LPS-induced endotoxic shock model. These findings suggest that such compounds have therapeutic potential to be used to treat diseases of inflammatory origin.     

Development of a Protein-Rich By-Product by 23 Factorial Design: Characterization of Its Nutritional Value and Sensory Analysis

The aim of this study was the development of a cereal bar based on bee pollen (BP), honey (H), and flour by-products (peel passion fruit flour—PPFF), generating an innovative product. BP is a protein-rich ingredient and can be used in the composition of cereal bars. PPFF is a by-product rich in fibers. The formulations were developed using a 2³ factorial design with four replicates in the center point, studying the sensory analysis as a response variable. The texture and nutritional parameters were performed for the optimal formulation. BP showed ca. 15% of protein. The final formulation (10.35% BP, 6.8% PPFF, and 25% H) presented 22.2% moisture, 1.8% ash, 0.4% total fat, 3.0% fiber, 63.1% carbohydrates, and 74.0 Kcal/25 g. The sensory analysis presented valued around 7 (typical of a traditional bar). Regarding the possibility of purchasing the product, 51% of the panelists said they would probably buy the developed product. The formulated cereal bar had a similar composition as those already marketed. Moreover, it can be considered a source of fiber and is sensory acceptable. This approach opens up new opportunities for developing nutritional and functional foodstuff with improved sensorial aspects.     

Hybrid and multi-field variational principles for geometrically exact three-dimensional beams

This paper addresses the development of several alternative novel hybrid/multi-field variational formulations of the geometrically exact three-dimensional elastostatic beam boundary-value problem. In the framework of the complementary energy-based formulations, a Legendre transformation is used to introduce the complementary energy density in the variational statements as a function of stresses only. The corresponding variational principles are shown to feature stationarity within the framework of the boundary-value problem. Both weak and linearized weak forms of the principles are presented. The main features of the principles are highlighted, giving special emphasis to their relationships from both theoretical and computational standpoints.     

Metal Organic Framework-235 (MOF-235) Modified Carbon Paste Electrode for Catechol Determination in Water

MOF-235 is presented as an orange powder, with crystals of the octahedral formation. It was already used as adsorbent to remove different compounds from water; however, no attempts have been published about the exploration of the MOF-235 application as electrochemical sensor for organic compounds yet. MOF-235 was synthetized and after that, it was characterized by SEM, XRD and FTIR. Graphite electrodes (GEs) were modified with different MOF-235 ratio (5 %, 7 %, 10 %, 12 % and 14 %) and these modified GEs were characterized by cyclic voltammetry (CV) measurements in order to determine the effect of MOF-235 concentration on the current response. Results indicated that, a significant improvement on the current response was attained at MOF-235(10 %)/GE respect to unmodified GE. This behavior is related to the pore structure and multiple active sites on the MOF surface. The performance of the MOF-235(10 %)/GE as electrochemical sensor for detecting catechol was assessed by differential pulse voltammetry (DPV). Catechol detection response of MOF-based sensor provided a detection limit of about 12.79 μmol L⁻¹ with a correlation coefficient (R²) of about 0.9928 ranging from 12 to 514 μmol L⁻¹. Finally, MOF-235(10 %)/GE was used to determine catechol in real water matrixes.