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This study is aimed at the analysis of the pyrolysis kinetics of Nanche stone BSC (Byrsonima crassifolia) as an agro-industrial waste using non-isothermal thermogravimetric experiments by determination of triplet kinetics; apparent activation energy, pre-exponential factor, and reaction model, as well as thermodynamic parameters to gather the required fundamental information for the design, construction, and operation of a pilot-scale reactor for the pyrolysis this lignocellulosic residue. Results indicate a biomass of low moisture and ash content and a high volatile matter content (≥70%), making BCS a potential candidate for obtaining various bioenergy products. Average apparent activation energies obtained from different methods (KAS, FWO and SK) were consistent in value (~123.8 kJ/mol). The pre-exponential factor from the Kissinger method ranged from 105 to 1014 min-1 for the highest pyrolytic activity stage, indicating a high-temperature reactive system. The thermodynamic parameters revealed a small difference between EA and ∆H (5.2 kJ/mol), which favors the pyrolysis reaction and indicates the feasibility of the energetic process. According to the analysis of the reaction models (master plot method), the pyrolytic degradation was dominated by a decreasing reaction order as a function of the degree of conversion. Moreover, BCS has a relatively high calorific value (14.9 MJ/kg) and a relatively low average apparent activation energy (122.7 kJ/mol) from the Starink method, which makes this biomass very suitable to be exploited for value-added energy production.

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Clay materials and nanoclays have gained recent popularity in the vaccinology field, with biocompatibility, simple functionalization, low toxicity, and low-cost as their main attributes. As elements of nanovaccines, halloysite nanotubes (natural), layered double hydroxides and hectorite (synthetic) are the nanoclays that have advanced into the vaccinology field. Until now, only physisorption has been used to modify the surface of nanoclays with antigens, adjuvants, and/or ligands to create nanovaccines. Protocols to covalently attach these molecules have not been developed with nanoclays, only procedures to develop adsorbents based on nanoclays that could be extended to develop nanovaccine conjugates. In this review, we describe the approaches evaluated on different nanovaccine candidates reported in articles, the immunological results obtained with them and the most advanced approaches in the preclinical field, while describing the nanomaterial itself. In addition, complex systems that use nanoclays were included and described. The safety of nanoclays as carriers is an important key fact to determine their true potential as nanovaccine candidates in humans. Here, we present the evaluations reported in this field. Finally, we point out the perspectives in the development of vaccine prototypes using nanoclays as antigen carriers.

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Pollution by dyes and heavy metals is one of the main concerns at the environmental level due to their toxicity and inefficient elimination by traditional water treatment. Orange peel (OP) without any treatment was applied to effectively eliminate methylene blue (MB) and cadmium ions (Cd2+) in mono- and multicomponent systems. Although the single adsorption processes for MB and Cd2+ have been investigated, the effects and mechanisms of interactions among multicomponent systems are still unclear. Batch experiments showed that in monocomponent systems, the maximum adsorption capacities were 0.7824 mmol g-1 for MB and 0.2884 mmol g-1 for Cd2+, while in multicomponent systems (Cd2+ and MB), both contaminants competed for the adsorption sites on OP. Particularly, a synergic effect was observed since the adsorption capacity of Cd2+ increased compared to the monocomponent system. Results of desorption and adsorbent reuse confirmed that the adsorbent presents good regeneration performance. The low cost of this material and its capacity for the individual or simultaneous removal of Cd2+ and MB in aqueous solutions makes it a potential adsorbent for polluted water treatment processes.

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In the current work, a deep study to understand the adsorption phenomena occurring in single and multicomponent systems was conducted by using spectroscopic characterization, and computational tools. The experimental results showed that the adsorption capacity of chili seed is higher for Pb2+ (48 mg/g) than Cu2+ (4.1 mg/g) ions in single systems. However, the adsorption study in multicomponent systems provides important conclusions of the concentration effect of the metal ions, showing a significant antagonistic and competitive effect of both ions under equivalent concentrations of them (qPb2+ is 56% reduced) or high concentration of Pb2+ (qCu2+ is 50% reduced). Computational results correlated well with the experimental ones and evidenced all interactions proposed from spectroscopy results, accounting for the occurrence of complexation and electrostatic mechanisms between metal ions and the surface oxygenated functional groups (hydroxyl, carboxyl, and carboxylate) onto chili seed. Chemistry quantum descriptors supported the reactivity behavior of the chemical species implicated. All results evidenced that Pb2+ and Cu2+ adsorption on chili seed surface is governed by the occurrence of combined ionic exchange, π-interaction, complexation, and electrostatic attraction.

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In this work, it was analyzed the behavior of three commercial activated carbons with different textural and chemical properties to adsorb individually metronidazole and lead ions from aqueous solution. Afterwards, the activated carbons were modified with citric acid to remove both compounds simultaneously. Both sets of activated carbons were characterized chemically and texturally. XPS analysis was performed to corroborate the adsorption mechanism of lead on the surface of the carbons. Finally, the intraparticle diffusion of both adsorbates was elucidated by the application of diffusional model in three dimensions. The results evidenced that adsorption mechanism for MNZ and Pb(II) is independent, the adsorption for MNZ is governed by π-π dispersive interactions, whereas Pb(II) adsorption is mainly controlled by electrostatic interactions. The binary adsorption equilibrium shows that the adsorption of MNZ is independent from the concentration of Pb(II), whereas the adsorption of Pb(II) is affected by the presence of MNZ at low concentrations (0.1 mmol L-1), but it remains almost constant at concentrations of MNZ between 0.1 and 1.5 mmol L-1. Finally, the mass transport of MNZ was faster than Pb(II) from the solution to the external surface of activated carbon and the mass flux of MNZ inside the particle was superior to the mass flux of Pb(II). Lastly, there might be an obstruction phenomenon with MNZ impeding Pb(II) to reach the active sites placed into the carbon's microporosity structure. Graphical abstract.

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The competitive sorption of the antibiotics sulfamethoxazole (SMX) and trimethoprim (TMP) and SMX-Cd(II) on a hybrid clay nanosorbent (NanoSorb) was investigated in detail in this work. NanoSorb was synthesized by sorbing a surfactant on bentonite. Besides, the sorption of SMX on the NanoSorb was confirmed by FTIR analysis, and SMX was mainly sorbed on NanoSorb by a partition mechanism due to hydrophobic interactions. Otherwise, the single adsorption of Cd(II) and TMP onto NanoSorb were due to electrostatic interaction and hydrophobic partition, respectively. The capacity of NanoSorb for sorbing single SMX was very similar to that for single Cd(II), but more than 10 times higher than that for single TMP. The competitive sorption of SMX-TMP was antagonistic because the sorption of one antibiotic on NanoSorb was decreased by the presence of the other antibiotic. The uptake of SMX was reduced up to 43.4% by the presence of TMP, whereas the presence of SMX decreased the uptake of TMP up to 29.6%. The non-modified Langmuir multicomponent isotherm (NLMI) interpreted quite well the experimental competitive sorption data of SMX-TMP. On the other hand, the competitive sorption of SMX-Cd(II) on NanoSorb revealed that the sorption of SMX was non-interactive because it was not influenced by the presence of Cd(II). Whereas, the sorption of Cd(II) was synergistic or cooperative since the uptake of Cd(II) sorbed increased considerably with the uptake of SMX sorbed on NanoSorb. The two-site Langmuir model fitted the experimental competitive sorption data of Cd(II) on NanoSorb saturated with SMX. The application of this isotherm was based on the fact that Cd(II) sorbed on two types of sites: a) cationic sites of the NanoSorb and b) Pi-cation interactions between the aromatic ring of the SMX sorbed on NanoSorb and Cd2+.

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Bimetallic Ag@Au nanoparticles (NPs) have received significant research interest because of their unique optical properties and molecular sensing ability through surface-enhanced Raman scattering (SERS). However, the synthesis of Ag@Au core-shell plasmonic nanostructures with precisely controlled size and shape remained a great challenge. Here, we report a simple approach for the synthesis of bimetallic Ag@Au nanodisks of about 13.5 nm thickness and different diameters through a seed-mediated growth process. The synthesis involves the conformal deposition of Au atoms at the corner sites of Ag nanoplate (AgNPL) seeds coupled with site-selective oxidative etching of AgNPL edges to generate Ag@Au nanodisks. The resultant Ag@Au nanodisks manifest significantly improved chemical stability and tunable localized surface plasmon resonance from the visible to the near-infrared spectral range. Moreover, in comparison to AgNPLs, the Ag@Au nanodisks showed greatly enhanced SERS performance with an enhancement factor up to 0.47 × 105, which is nearly 3-fold higher than that of the original AgNPLs (0.18 × 105). Furthermore, the Ag@Au nanodisks show a high sensitivity for detecting probe molecules such as crystal violet of concentration as low as 10-9 M and excellent reproducibility, with the SERS intensity fluctuation less than 12.5%. The synthesis route adapted for the controlled fabrication of Ag@Au nanodisks can be a potential platform for maneuvering other bimetallic plasmonic nanostructures useful for plasmonics and sensing applications.

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Tebuconazole (TBZ) nanoemulsions (NEs) were formulated using a low energy method. TBZ composition directly affected the drop size and surface tension of the NE. Water fraction and the organic-to-surfactant-ratio (RO/S) were evaluated in the range of 1-90 and 1-10 wt %, respectively. The study was carried out with an organic phase (OP) consisting of an acetone/glycerol mixture containing TBZ at a concentration of 5.4 wt % and Tween 80 (TW80) as a nonionic and Agnique BL1754 (AG54) as a mixture of nonionic and anionic surfactants. The process involved a large dilution of a bicontinuous microemulsion (ME) into an aqueous phase (AP). Pseudo-ternary phase diagrams of the OP//TW80//AP and OP//AG54//AP systems at T = 25 °C were determined to map ME regions; these were in the range of 0.49-0.90, 0.01-0.23, and 0.07-0.49 of OP, AP, and surfactant, respectively. Optical microscope images helped confirm ME formation and system viscosity was measured in the range of 25-147 cP. NEs with drop sizes about 9 nm and 250 nm were achieved with TW80 and AG54, respectively. An innovative low-energy method was used to develop nanopesticide TBZ formulations based on nanoemulsion (NE) technology. The surface tension of the studied systems can be lowered 50% more than that of pure water. This study's proposed low-energy NE formulations may prove useful in sustainable agriculture.