Search Results (27)

Over the years, the ammonia concentration in water streams and the environment is increasing at an alarming rate. Many membrane-based processes have been studied to alleviate this concern via adsorption and filtration. On the other hand, ammonia electro-oxidation is an approach of particular interest owing to its energetic and environmental benefits. Thus, a plausible alternative to combine these two paths is by using an electroconductive membrane (ECM) to complete the ammonia oxidation reaction (AOR). This combination of processes has been studied very limitedly, and it can be an area for development. Herein, we developed a multilayered membrane with hydrophilic and electrocatalytic properties capable of completing the AOR. The porosity of carbon black (CB) particles was embedded in the polymeric support (CBES) and the active side was composed of a triple layer consisting of polyamide/CB/Pt nanoparticles (PA:CB:Pt). The CBES increased the membrane porosity, changed the pores morphology, and enhanced water permeability and electroconductivity. The deposition of each layer was monitored and corroborated physically, chemically, and electrochemically. The final membrane CBES:PA:VXC:Pt reached higher water flux than its PSF counterpart (3.9 ± 0.3 LMH), had a hydrophilic surface (water contact angle: 19.8 ± 0.4°), and achieved the AOR at −0.3 V vs. Ag/AgCl. Our results suggest that ECMs with conductive material in both membrane layers enhanced their electrical properties. Moreover, this study is proof-of-concept that the AOR can be succeeded by a polymeric FO-ECMs. Full article

In recent years, the demand of healthier food products and products made with natural ingredients has increased overwhelmingly, led by the awareness of human beings of the influence of food on their health, as well as by the evidence of side effects generated by different ingredients such as some additives. This is the case for several artificial colorants, especially azo colorants, which have been related to the development of allergic reactions, attention deficit and hyperactivity disorder. All the above has focused the attention of researchers on obtaining colorants from natural sources that do not present a risk for consumption and, on the contrary, show biological activity. The most representative compounds that present colorant capacity found in nature are anthocyanins, anthraquinones, betalains, carotenoids and chlorophylls. Therefore, the present review summarizes research published in the last 15 years (2008–2023) in different databases (PubMed, Scopus, Web of Science and ScienceDirect) encompassing various natural sources of these colorant compounds, referring to their obtention, identification, some of the efforts made for improvements in their stability and their incorporation in different food matrices. In this way, this review evidences the promising path of development of natural colorants for the replacement of their artificial counterparts. Full article

The search for a clinically affordable substitute of human blood for transfusion is still an unmet need of modern society. More than 50 years of research on acellular hemoglobin (Hb)-based oxygen carriers (HBOC) have not yet produced a single formulation able to carry oxygen to hemorrhage-challenged tissues without compromising the body’s functions. Of the several bottlenecks encountered, the high reactivity of acellular Hb with circulating nitric oxide (NO) is particularly arduous to overcome because of the NO-scavenging effect, which causes life-threatening side effects as vasoconstriction, inflammation, coagulopathies, and redox imbalance. The purpose of this manuscript is not to add a review of candidate HBOC formulations but to focus on the biochemical and physiological events that underly NO scavenging by acellular Hb. To this purpose, we examine the differential chemistry of the reaction of NO with erythrocyte and acellular Hb, the NO signaling paths in physiological and HBOC-challenged situations, and the protein engineering tools that are predicted to modulate the NO-scavenging effect. A better understanding of two mechanisms linked to the NO reactivity of acellular Hb, the nitrosylated Hb and the nitrite reductase hypotheses, may become essential to focus HBOC research toward clinical targets. Full article

The reaction of mer-(Ru(H)₂(CO)(PPh₃)₃) (1) with one equivalent of thymine acetic acid (THAcH) unexpectedly produces the macrocyclic dimer k¹(O), k²(N,O)-(Ru(CO)(PPh₃)₂THAc)₂ (4) and, concomitantly, the doubly coordinated species k¹(O), k²(O,O)-(Ru(CO)(PPh₃)₂THAc) (5). The reaction promptly forms a complicated mixture of Ru-coordinated mononuclear species. With the aim of shedding some light in this context, two plausible reaction paths were proposed by attributing the isolated or spectroscopically intercepted intermediates on the basis of DFT-calculated energetic considerations. The cleavage of the sterically demanding equatorial phosphine in the mer-species releases enough energy to enable self-aggregation, producing the stable, symmetric 14-membered binuclear macrocycle of 4. The k¹-acetate iminol (C=N-OH) unit of the mer-tautomer k¹(O)-(Ru(CO)(PPh₃)₂(THAc)) (2) likely exhibits a stronger nucleophilic aptitude than the prevalent N(H)-C(O) amido species, thus accomplishing extra stabilization through concomitant k²(N,O)-thymine heteroleptic side-chelation. Furthermore, both the ESI-Ms and IR simulation spectra validated the related dimeric arrangement in solution, in agreement with the X-ray determination of the structure. The latter showed tautomerization to the iminol form. The ¹H NMR spectra in chlorinated solvents of the kinetic mixture showed the simultaneous presence of 4 and the doubly coordinated 5, in rather similar amounts. THAcH added in excess preferentially reacts with 2 or trans-k²(O,O)-(RuH(CO)(PPh₃)₂THAc) (3) rather than attacking the starting Complex 1, promptly forming the species of 5. The proposed reaction paths were inferred by spectroscopically monitoring the intermediate species, for which the results were strongly dependent on the of conditions the reaction (stoichiometry, solvent polarity, time, and the concentration of the mixture). The selected mechanism proved to be more reliable, due to the final dimeric product stereochemistry. Full article

Methanol synthesis from the hydrogenation of carbon dioxide (CO₂) with green H₂ has been proven as a promising method for CO₂ utilization. Among the various catalysts, indium oxide (In₂O₃)-based catalysts received tremendous research interest due to the excellent methanol selectivity with appreciable CO₂ conversion. Herein, the recent experimental and theoretical studies on In₂O₃-based catalysts for thermochemical CO₂ hydrogenation to methanol were systematically reviewed. It can be found that a variety of steps, such as the synthesis method and pretreatment conditions, were taken to promote the formation of oxygen vacancies on the In₂O₃ surface, which can inhibit side reactions to ensure the highly selective conversion of CO₂ into methanol. The catalytic mechanism involving the formate pathway or carboxyl pathway over In₂O₃ was comprehensively explored by kinetic studies, in situ and ex situ characterizations, and density functional theory calculations, mostly demonstrating that the formate pathway was extremely significant for methanol production. Additionally, based on the cognition of the In₂O₃ active site and the reaction path of CO₂ hydrogenation over In₂O₃, strategies were adopted to improve the catalytic performance, including (i) metal doping to enhance the adsorption and dissociation of hydrogen, improve the ability of hydrogen spillover, and form a special metal-In₂O₃ interface, and (ii) hybrid with other metal oxides to improve the dispersion of In₂O₃, enhance CO₂ adsorption capacity, and stabilize the key intermediates. Lastly, some suggestions in future research were proposed to enhance the catalytic activity of In₂O₃-based catalysts for methanol production. The present review is helpful for researchers to have an explicit version of the research status of In₂O₃-based catalysts for CO₂ hydrogenation to methanol and the design direction of next-generation catalysts. Full article

A combined application of step and strut was put forward to achieve reliable ignition and flame stabilization. In this work, the ignition process and temperature distribution have been tested, and a new reduction approach applied to jet fuel oxidation mechanism was developed to present a flow map via tracking C and H reaction paths, then the minor and major reactions were verified according to relative occurrence probabilities. With the half decrease of mechanism size, bias occurred and was controlled within 1.8%. This reduction method had such characteristics as universality, intuition, and quantification, due to its inherent simplification theory. This simulation of ignition process was always consistent with experimental results, which depicted kernel generation, flamelet breakup and flame propagation. Also, the influence of inlet temperature on outlet temperature and component distribution was performed, the biases of experimental and numerical results were within 5%. Chemical characteristics of Kerosene/air premixed combustible had changed and side reactions occurred to jet fuel above 900 K, which led to a converse effect on flame spreading. The side reactions aggravated the increasing coproducts of CO and CH4, which caused the decrease of volumetric heat production. Full article

The catalytic performances of the catalysts and decomposition mechanisms of dimethyl methylphosphonate (DMMP), a commonly used nerve agent simulant, are well understood based on previous studies. However, the effects of the morphology of the catalyst on DMMP decomposition performance and mechanisms remain unexplored. Thus, in this work, experimental studies were conducted on the thermocatalytic decomposition of DMMP on CeO₂ nanomaterials with different morphologies, e.g., irregular nanoparticles, nanorods, and nanocubes. From the performance evaluation, CeO₂ nanorods exhibited higher DMMP thermocatalytic decomposition performance as compared to irregular nanoparticles and nanocubes. The primary reaction pathways were the same on all three morphologies of materials, according to in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) study, whereas side reaction paths showed variable behaviors. According to the catalytic reaction mechanism study, the surface lattice oxygen played a vital role in the thermocatalytic decomposition of DMMP and the accumulation of phosphates, carbonates, and formates were the main factors for deactivation of the catalyst. The behavior of CeO₂ catalyst with different morphologies in the thermocatalytic decomposition of DMMP was revealed in this work, and this will be useful for the future design of high-performing catalysts for the efficient degradation of chemical toxicant. Full article

Orally administered antipsychotic drugs are the first-line treatment for psychotic disorders, such as schizophrenia and bipolar disorder. Nevertheless, adverse drug reactions jeopardize clinical outcomes, resulting in patient non-compliance. The design formulation strategies for enhancing brain drug delivery has been a major challenge, mainly due to the restrictive properties of the blood–brain barrier. However, recent pharmacokinetic and pharmacodynamic in vivo assays confirmed the advantage of the intranasal route when compared to oral and intravenous administration, as it allows direct nose-to-brain drug transport via neuronal pathways, reducing systemic side effects and maximizing therapeutic outcomes. In addition, the incorporation of antipsychotic drugs into nanosystems such as polymeric nanoparticles, polymeric mixed micelles, solid lipid nanoparticles, nanostructured lipid carriers, nanoemulsions, nanoemulgels, nanosuspensions, niosomes and spanlastics, has proven to be quite promising. The developed nanosystems, having a small and homogeneous particle size (ideal for nose-to-brain delivery), high encapsulation efficiency and good stability, resulted in improved brain bioavailability and therapeutic-like effects in animal models. Hence, although it is essential to continue research in this field, the intranasal delivery of nanosystems for the treatment of schizophrenia, bipolar disorder and other related disorders has proven to be quite promising, opening a path for future therapies with higher efficacy. Full article

Secondary problems, such as the occurrence of side reactions and the accumulation of by-products, are a major challenge in the application of wet denitrification technology through urea solution. We revealed the formation mechanism of urea nitrate and clarified the main and side reaction paths and key intermediates of denitrification. Urea nitrate would be separated from urea absorption solution only when the concentration product of [urea], [H⁺] and [NO₃⁻] was greater than 0.87~1.22 mol³/L³. The effects of the urea concentration (5–20%) and reaction temperature (30–70 °C) on the denitrification efficiency could be ignored. Improving the oxidation degree of the flue gas promoted the removal of nitrogen oxides. The alkaline condition was beneficial to the dissolution process, while the acidic condition was beneficial to the reaction process. As a whole, the alkaline condition was the preferred process parameter. The research results could guide the optimization of process conditions in theory, improve the operation efficiency of the denitrification reactor and avoid the occurrence of side reactions. Full article

In order to investigate the effect of optimized reinforcement of cross-section of steel box girders with fatigue cracks on other vulnerable parts (cross-section, U-rib and deck slab, etc.) under wheel load, and to reveal the stress distribution law of critical parts after the optimization of steel plate reinforcement or arc notch. In this work, a suspension bridge with fatigue cracks in the curved notch of the cross-sectional plate is considered as the research object, two types of curved notch optimization reinforcement solutions are considered and finite element analysis is performed. Longitudinal and transverse moving loading tests were conducted with a test vehicle to test the stresses in the critical parts of the curved cutout of the cross-section. Furthermore, the effects of the two optimized strengthening solutions on the stresses in the curved cutout, the sides of the diaphragm, the sides of the U-rib and the deck slab were analyzed, and the effects of the changes in the diaphragm stiffness on other critical vulnerable structures were analyzed. The study shows that when the “arc notch optimization” strengthening scheme is adopted for crack-free or short cracks, although it can effectively improve the stress transfer path of the arc notch of the diaphragm, it also weakens the cross-sectional area of the diaphragm and has little effect on the diaphragm side, U-rib and deck plate. When the long crack is reinforced by “arc notch optimization + steel plate reinforcement”, it is easy to cause a reaction to the diaphragm sides arranged at the junction area of the diaphragm arc notch and U-rib without steel plate coverage, and the stress will be slightly higher than that when the diaphragm is not optimized. The steel plate reinforcement hurts the lateral stress of the U-rib, but the reinforcement effect will not have any effect on the deck plate. Full article

Coal spontaneous combustion (CSC) is a disaster that seriously threatens safe production in coal mines. Revealing the mechanism of CSC can provide a theoretical basis for its prevention and control. Compared with experimental research is limited by the complexity of coal molecular structure, the quantum chemical calculation method can simplify the complex molecular structure and realize the exploration of the mechanism of CSC from the micro level. In this study, toluene and phenylacetaldehyde were used as model compounds, and the quantum chemical calculation method was adopted. The reaction processes of the methyl and aldehyde groups with oxygen were investigated with the aid of the Gaussian 09 software, using the B3LYP functional and the 6-311 + G(d,p) basis set and including the D3 dispersion correction. On this basis, the generation mechanisms of CO and CO₂, two important indicator gases in the process of CSC, were explored. The calculation results show that the Gibbs free energy changes and enthalpy changes in the two reaction systems are both of negative values. Accordingly, it is judged that the reactions belong to spontaneous exothermic reactions. In the reaction processes, the activation energy of CO is less than that of CO₂, indicating that CO is formed more easily in the above-two reaction processes. In addition, the variations in concentrations of important oxidation products (CO and CO₂) and main active functional groups (such as methyl, carboxyl and carbonyl) with temperature were revealed through a low-temperature oxidation experiment. The experimental results verify the accuracy of the above quantum chemical reaction path. Moreover, it is also found that the generation mechanisms of CO and CO₂ in coal samples with different metamorphic degrees are different. To be specific, for low-rank coal (HYH), CO and CO₂ mainly come from the oxidation of alkyl side chains; for high-rank coal (CQ), CO is produced by the oxidation of alkyl side chains, and CO₂ is attributed to the inherent oxygen-containing structure. Full article

We report a series of calculations to elucidate one possible mechanism of SO₂ chemisorption in amino acid-based ionic liquids. Such systems have been successfully exploited as CO₂ absorbents and, since SO₂ is also a by-product of fossil fuels’ combustion, their ability in capturing SO₂ has been assessed by recent experiments. This work is exclusively focused on evaluating the efficiency of the chemical trapping of SO₂ by analyzing its reaction with the amino group of the amino acid. We have found that, overall, SO₂ is less reactive than CO₂, and that the specific amino acid side chain (either acid or basic) does not play a relevant role. We noticed that bimolecular absorption processes are quite unlikely to take place, a notable difference with CO₂. The barriers along the reaction paths are found to be non-negligible, around 7–11 kcal/mol, and the thermodynamic of the reaction appears, from our models, unfavorable. Full article

In this study we investigate the Diels–Alder reaction between methyl acrylate and butadiene, which is catalyzed by BF${}_3$ Lewis acid in explicit water solution, using URVA and Local Mode Analysis as major tools complemented with NBO, electron density and ring puckering analyses. We considered four different starting orientations of methyl acrylate and butadiene, which led to 16 DA reactions in total. In order to isolate the catalytic effects of the BF${}_3$ catalyst and those of the water environment and exploring how these effects are synchronized, we systematically compared the non-catalyzed reaction in gas phase and aqueous solution with the catalyzed reaction in gas phase and aqueous solution. Gas phase studies were performed at the B3LYP/6-311+G(2d,p) level of theory and studies in aqueous solution were performed utilizing a QM/MM approach at the B3LYP/6-311+G(2d,p)/AMBER level of theory. The URVA results revealed reaction path curvature profiles with an overall similar pattern for all 16 reactions showing the same sequence of CC single bond formation for all of them. In contrast to the parent DA reaction with symmetric substrates causing a synchronous bond formation process, here, first the new CC single bond on the CH${}_2$ side of methyl acrylate is formed followed by the CC bond at the ester side. As for the parent DA reaction, both bond formation events occur after the TS, i.e., they do not contribute to the energy barrier. What determines the barrier is the preparation process for CC bond formation, including the approach diene and dienophile, CC bond length changes and, in particular, rehybridization of the carbon atoms involved in the formation of the cyclohexene ring. This process is modified by both the BF${}_3$ catalyst and the water environment, where both work in a hand-in-hand fashion leading to the lowest energy barrier of 9.06 kcal/mol found for the catalyzed reaction R1 in aqueous solution compared to the highest energy barrier of 20.68 kcal/mol found for the non-catalyzed reaction R1 in the gas phase. The major effect of the BF${}_3$ catalyst is the increased mutual polarization and the increased charge transfer between methyl acrylate and butadiene, facilitating the approach of diene and dienophile and the pyramidalization of the CC atoms involved in the ring formation, which leads to a lowering of the activation energy. The catalytic effect of water solution is threefold. The polar environment leads also to increased polarization and charge transfer between the reacting species, similar as in the case of the BF${}_3$ catalyst, although to a smaller extend. More important is the formation of hydrogen bonds with the reaction complex, which are stronger for the TS than for the reactant, thus stabilizing the TS which leads to a further reduction of the activation energy. As shown by the ring puckering analysis, the third effect of water is space confinement of the reacting partners, conserving the boat form of the six-member ring from the entrance to the exit reaction channel. In summary, URVA combined with LMA has led to a clearer picture on how both BF${}_3$ catalyst and aqueous environment in a synchronized effort lower the reaction barrier. These new insights will serve to further fine-tune the DA reaction of methyl acrylate and butadiene and DA reactions in general. Full article

The intra- and intermolecular interactions of selected quinolone carboxylic acid derivatives were studied in monomers, dimers and crystals. The investigated compounds are well-recognized as medicines or as bases for further studies in drug design. We employed density functional theory (DFT) in its classical formulation to develop gas-phase and solvent reaction field (PCM) models describing geometric, energetic and electronic structure parameters for monomers and dimers. The electronic structure was investigated based on the atoms in molecules (AIM) and natural bond orbital (NBO) theories. Special attention was devoted to the intramolecular hydrogen bonds (HB) present in the investigated compounds. The characterization of energy components was performed using symmetry-adapted perturbation theory (SAPT). Finally, the time-evolution methods of Car–Parrinello molecular dynamics (CPMD) and path integral molecular dynamics (PIMD) were employed to describe the hydrogen bond dynamics as well as the spectroscopic signatures. The vibrational features of the O-H stretching were studied using Fourier transformation of the autocorrelation function of atomic velocity. The inclusion of quantum nuclear effects provided an accurate depiction of the bridged proton delocalization. The CPMD and PIMD simulations were carried out in the gas and crystalline phases. It was found that the polar environment enhances the strength of the intramolecular hydrogen bonds. The SAPT analysis revealed that the dispersive forces are decisive factors in the intermolecular interactions. In the electronic ground state, the proton-transfer phenomena are not favourable. The CPMD results showed generally that the bridged proton is localized at the donor side, with possible proton-sharing events in the solid-phase simulation of stronger hydrogen bridges. However, the PIMD enabled the quantitative estimation of the quantum effects inclusion—the proton position was moved towards the bridge midpoint, but no qualitative changes were detected. It was found that the interatomic distance between the donor and acceptor atoms was shortened and that the bridged proton was strongly delocalized. Full article

We characterized the stationary points along the nucleophilic substitution (S_N2), oxidative insertion (OI), halogen abstraction (XA), and proton transfer (PT) product channels of M⁻ + CH₃X (M = Cu, Ag, Au; X = F, Cl, Br, I) reactions using the CCSD(T)/aug-cc-pVTZ level of theory. In general, the reaction energies follow the order of PT > XA > S_N2 > OI. The OI channel that results in oxidative insertion complex [CH₃–M–X]⁻ is most exothermic, and can be formed through a front-side attack of M on the C-X bond via a high transition state OxTS or through a S_N2-mediated halogen rearrangement path via a much lower transition state invTS. The order of OxTS > invTS is inverted when changing M⁻ to Pd, a d¹⁰ metal, because the symmetry of their HOMO orbital is different. The back-side attack S_N2 pathway proceeds via typical Walden-inversion transition state that connects to pre- and post-reaction complexes. For X = Cl/Br/I, the invS_N2-TS’s are, in general, submerged. The shape of this M⁻ + CH₃X S_N2 PES is flatter as compared to that of a main-group base like F⁻ + CH₃X, whose PES has a double-well shape. When X = Br/I, a linear halogen-bonded complex [CH₃−X∙··M]⁻ can be formed as an intermediate upon the front-side attachment of M on the halogen atom X, and it either dissociates to CH₃ + MX⁻ through halogen abstraction or bends the C-X-M angle to continue the back-side S_N2 path. Natural bond orbital analysis shows a polar covalent M−X bond is formed within oxidative insertion complex [CH₃–M–X]⁻, whereas a noncovalent M–X halogen-bond interaction exists for the [CH₃–X∙··M]⁻ complex. This work explores competing channels of the M⁻ + CH₃X reaction in the gas phase and the potential energy surface is useful in understanding the dynamic behavior of the title and analogous reactions. Full article