Frontiers in Chemistry最新文献

Polymeric materials have been a great boon to the development and wellbeing of mankind. However, in the main, these materials are flammable and must be flame retarded for most applications. Many substances have been utilized to impart a measure of flame retardancy. The most widely used and most effective have been organic: organohalogen and organophosphorus compounds. Organohalogen compounds have been popular, low-cost, very effective flame retardants for polymeric materials. However, with the recognition that these compounds readily migrate from a polymer matrix into which they have been incorporated, persist in the environment and pose serious risks to human health, the use of organophosphorus compounds has become prominent. In particular, organophosphorus compounds of appropriate structure derived from readily-available, renewable, low-cost, non-toxic biobased precursors are attractive. Avoidance of the issues of environmental persistence and toxicity associated with organohalogen compounds is possible with these materials. Migration from a polymer matrix may be removed as a deficiency through the use of reactive compounds, i.e., compounds that may be incorporated directly into the polymer structure either by copolymerization or grafting, or oligomeric compounds. Oligomeric materials of branched structure display characteristics of broad compatibility, high effectiveness and lack of migration.

The reaction of MnCl₂·4H₂O with HL ((1-methyl-1H-imidazol-2-yl)methanol) and pdH₂ (1, 3 propanediol) in a basic MeCN solution results in the formation of a mixed-valence [Mn₂₀] cationic cluster and two [Mn^IICl₄] counter anions. The metallic skeleton of the cluster describes two geometrically equivalent mixed-valent, linked [Mn^III ₆Mn^II ₄] supertetrahedra in which nearest-neighbor metal ions have a different oxidation state. Magnetic susceptibility, magnetization data and heat capacity measurements support evidence of predominant ferromagnetic correlations, leading to a s = 22 spin ground state for the [Mn^III ₆Mn^II ₄] supertetrahedra, which are pair-linked by a weak antiferromagnetic coupling. The properties are discussed in the context of the magnetocaloric effect and the potential application of this compound in cryogenic refrigeration.

The lack of vaccines shows the need for alternative leishmaniasis treatments. In vitro study previously demonstrated the leishmanicidal activity of A. nitidum extracts. This study describes for the first time, the antileishmanial activity of A. nitidum extracts in infected Balb/c mice and its immunomodulatory effect. The extract (EE) was obtained by maceration of the peel powder with ethanol, which was fractionated by acid-base partition, originating the alkaloid (FA) and neutral (FN) fractions. EE and FA were analyzed using mass spectroscopy. Daily intragastric treatment was performed with EE and FA, at doses of 200 mg/kg and 400 mg/kg, in Balb/c mice with 28 days of infection by Leishmania amazonensis. A thickness gauge was used to assess the progression of the lesion and the MTT method to determine the parasite load in the spleen. The quantification of IL-10 and IFN-γ was performed by ELISA. Analysis of the mass spectrum of EE indicated the presence of the alkaloids corynantheol and yohimbine, while in FA the alkaloid dihydrocorynantheol was identified. To elucidate the mode of interaction of these alkaloids with the TR protein, molecular target of antileishmanial drugs, we used molecular modeling approaches such as docking, molecular dynamics simulations and free energy affinity. Treatment with EE for 28 days at the highest dose tested, significantly reduced the size of the lesion. EE and FA after 28 days of treatment showed dose-dependent antileishmanial activity, which reduced the parasite load in the spleen of infected mice by 42.5% and 22.1%, respectively. Both EE and FA presented immunomodulatory effect, as they decreased IL-10 expression and increased IFN-y levels. The effectiveness of A. nitidum in the treatment of cutaneous leishmaniasis was proven in this study. The results obtained in silico demonstrated that the compounds are capable of interacting with the catalytic residues of the TR. The affinity energy results demonstrated that the complexes formed are favorable for enzymatic inhibition. The alkaloids present in the plant have demonstrated not only antileishmanial activity, but also the ability to modulate the host's immune response. These promising results open perspectives for developing more effective and comprehensive treatments against cutaneous leishmaniasis.

Artemesia tridentata is a foundational plant taxon in western North America and an important medicinal plant threatened by climate change. Low-cost fabrication of sensors is critical for developing large-area sensor networks for understanding and monitoring a range of environmental conditions. However, the availability of materials and manufacturing processes is still in the early stages, limiting the capacity to develop cost-effective sensors at a large scale. In this study, we demonstrate the fabrication of low-cost flexible sensors using laser-induced graphene (LIG); a graphitic material synthesized using a 450-nm wavelength bench top laser patterned onto polyimide substrates. We demonstrate the effect of the intensity and focus of the incident beam on the morphology and electrical properties of the synthesized material. Raman analyses of the synthesized LIG show a defect-rich graphene with a crystallite size in the tens of nanometers. This shows that the high level of disorder within the LIG structure, along with the porous nature of the material provide a good surface for gas adsorption. The initial characterization of the material has shown an analyte response represented by a change in resistance of up to 5% in the presence of volatile organic compounds (VOCs) that are emitted and detected by Artemisia species. Bend testing up to 100 cycles provides evidence that these sensors will remain resilient when deployed across the landscapes to assess VOC signaling in plant communities. The versatile low-cost laser writing technique highlights the promise of low-cost and scalable fabrication of LIG sensors for gas sensor monitoring.

As ionic liquids (ILs) continue to be prepared, there is a growing need to develop theoretical methods for predicting the properties of ILs, such as gas solubility. In this work, different strategies were employed to obtain the solubility of CO₂ and N₂, where a conductor-like screening model for real solvents (COSMO-RS) was used as the basis. First, experimental data on the solubility of CO₂ and N₂ in ILs were collected. Then, the solubility of CO₂ and N₂ in ILs was predicted using COSMO-RS based on the structures of cations, anions, and gases. To further improve the performance of COSMO-RS, two options were used, i.e., the polynomial expression to correct the COSMO-RS results and the combination of COSMO-RS and machine learning algorithms (eXtreme Gradient Boosting, XGBoost) to develop a hybrid model. The results show that the COSMO-RS with correction can significantly improve the prediction of CO₂ solubility, and the corresponding average absolute relative deviation (AARD) is decreased from 43.4% to 11.9%. In contrast, such an option cannot improve that of the N₂ dataset. Instead, the results obtained from coupling machine learning algorithms with the COSMO-RS model agree well with the experimental results, with an AARD of 0.94% for the solubility of CO₂ and an average absolute deviation (AAD) of 0.15% for the solubility of N₂.

Flexible pressure sensors applied in wearable detection often face challenges, such as low sensitivity, large device size, poor flexibility, and long response time. This study aims to design and develop high-performance pressure-sensitive materials for wearable human detection applications. Using a sensitive layer composite and microstructural design, rGO/Fe nanowires (NWs) composites were proposed as the pressure-sensitive material. This approach yields a compact sensor with high flexibility, good mechanical properties, and excellent sensing performance. Firstly, rGO/Fe NWs composites were prepared by the Hummers method and an in situ reduction technique under a magnetic field. Secondly, the structural design, component construction, and sensing mechanism of the sensors were thoroughly investigated. Finally, the performance of the flexible pressure sensor was tested, and its application in the wearable field was explored. The results demonstrate that the sensor exhibits excellent performance with a good response to both large and small pressures within the range of 0-30 kPa, providing an effective method for wearable human health detection.

We report the fabrication of a novel spinel-type Pd₀.₁Cu₀.₉Co₂O₄ nano-flake material designed for Mizoroki-Heck and Suzuki coupling-cum-transesterification reactions. The Pd₀.₁Cu₀.₉Co₂O₄ material was synthesized using a simple co-precipitation method, and its crystalline phase and morphology were characterized through powder XRD, UV-Vis, FESEM, and EDX studies. This material demonstrated excellent catalytic activity in Mizoroki-Heck and Suzuki cross-coupling reactions, performed in the presence of a mild base (K₂CO₃), ethanol as the solvent, and microwave irradiation under ligand-free conditions. Notably, the Heck coupling of acrylic esters proceeded concurrently with transesterification using various alcohols as solvents. The catalyst exhibited remarkable stability under reaction conditions and could be recycled and reused up to ten times while maintaining its catalytic integrity.

We report on an in situ FTIR study of the thermo-oxidative degradation of a flexible epoxy resin. Different and complementary approaches to the analysis of the spectral data were employed, providing a detailed description of the process in terms of kinetics and mechanisms. A preliminary normal coordinate analysis, based on the DFT method, allowed for a reliable interpretation of the observed spectrum, increasing the amount of available structural information. Two-dimensional correlation spectroscopy provided details on the evolution of the reacting network structure. The relative stability of the various functional groups was ranked, and the most likely sites of initiation were identified. Oxygen fixation on the network chains produced amide and ketone groups, with the latter developing at a higher rate. The kinetic profiles of various functional groups were accurately simulated by a first-order, biexponential model, which allowed a quantitative comparison among their relative stabilities. The spectroscopic analysis allowed us to propose likely mechanisms and to identify those that occur preferentially.

Effective removal of organic and inorganic impurities by adsorption technique requires the preparation of new materials characterized by low production costs, significant sorption capacity, and reduced toxicity, derived from natural and renewable sources. To address these challenges, new adsorbents have been developed in the form of polymer microspheres based on ethylene glycol dimethacrylate (EGDMA) and vinyl acetate (VA) (EGDMA/VA) containing starch (St) modified with boric acid (B) and dodecyl-S-thiuronium dodecylthioacetate (DiTDTA) for the removal of dyes: C.I. Basic Blue 3 (BB3) and C.I. Acid Green 16 (AG16) and heavy metal ions (M(II)): Cu(II), Ni(II), and Zn(II) from water and wastewater. The adsorbents were characterized by ATR/FT-IR, DSC, SEM, BET, EDS, and pH_PZC methods. These analyses demonstrated the successful modification of microspheres and the increased thermal resistance resulting from the addition of the modified starch. The point of zero charge for EGDMA/VA was 7.75, and this value decreased with the addition of modified starch (pH_PZC = 6.62 for EGDMA/VA-St/B and pH_PZC = 5.42 for EGDMA/VA-St/DiTDTA). The largest specific surface areas (S_BET) were observed for the EGDMA/VA microspheres (207 m²/g), and S_BET value slightly decreases with the modified starch addition (184 and 169 m²/g) as a consquence of the pores stopping by the big starch molecules. The total pore volumes (V_tot) were found to be in the range from 0.227 to 0.233 cm³/g. These materials can be classified as mesoporous, with an average pore diameter (W) of approximately 55 Å (5.35-6.10 nm). The SEM and EDS analyses indicated that the EGDMA/VA microspheres are globular in shape with well-defined edges and contain 73.06% of carbon and 26.94% of oxygen. The microspheres containing modified starch exhibited a loss of smoothness with more irregular shape. The adsorption efficiency of dyes and heavy metal ions depends on the phases contact time, initial adsorbate concentration and the presence of competing electrolytes and surfactants. The equilibrium data were better fitted by the Freundlich isotherm model than by the Langmuir, Temkin, and Dubinin-Radushkevich models. The highest experimental adsorption capacities were observed for the BB3 dye which were equal to 193 mg/g, 190 mg/g, and 194 mg/g for EGDMA/VA, EGDMA/VA-St/B, EGDMA/VA-St/DiTDTA, respectively. The dyes and heavy metal ions were removed very rapidly and the time required to reach system equilibrium was below 20 min for M(II), 40 min for BB3, and 120 min for AG16. 50% v/v methanol and its mixture with 1 M HCl and NaCl for dyes and 1 M HCl for M(II) desorbed these impurities efficiently.