Rate Constants Research Articles

Inter-Antibody Variability in the Clinical Pharmacokinetics of Monoclonal Antibodies Characterized Using Population Physiologically Based Pharmacokinetics Modeling

The objective of this work was to develop a population physiologically based pharmacokinetic (popPBPK) model to characterize the variability in the clinical PK of monoclonal antibodies (mAbs) following intravenous (IV) and subcutaneous (SC) administration. An extensive literature search was conducted and clinical PK data for FDA-approved as well as non-approved mAbs were collected. Training and validation datasets of 44 and 9 mAbs exhibiting linear pharmacokinetics were used for model development. The variability in antibody PK was captured by accounting for different rate constants of pinocytosis (CLup) and intracellular degradation (kdeg) for different mAbs. Typical values for CLup and kdeg and their respective inter-antibody variabilities (ωClup, ωKdeg) were estimated to be 0.32 L/h/L and 26.1 h−1 (73% and 46%). Varied absorption profiles following SC dosing were characterized by incorporating inter-antibody variability in local degradation (kSC) and rate of lymphatic uptake (S_Lu) of mAbs. Estimates for typical kSC and S_Lu values, and ωKsc,ωS_Lu, were found to be 0.0015 h−1 and 0.54 (193%, and 49%). FDA-approved mAbs showed less local degradation (0.0014 h−1 vs. 0.0038 h−1) compared with other clinically tested mAbs, whereas no substantial differences in physiological processes involved in disposition were observed. To evaluate the generalizability of estimated PK parameters and model validation, the final popPBPK model was used to simulate the range of expected PK for mAbs following SC administration of nine different mAbs that were not used for model-building purposes. The predicted PK of all nine mAbs was within the expected range specified a priori. Thus, the popPBPK model presented here may serve as a tool to predict the clinical PK of mAbs with linear disposition before administering them to humans. The model may also support preclinical-to-clinical translation and ‘first-in-human’ dose determination for mAbs.

Mathematical Analysis of Nonlinear Reaction Diffusion Process at Carbon Dioxide Absorption in Concentrated Mixtures of 2-Amino-2-Methyl-1-Proponal and 1,8-Diamino-p-Methane

A mathematical model of carbon dioxide (CO2) absorption in an aqueous solution consisting of two reactants, 2-amino-2-methyl-1-proponal and 1,8-diamino-p-methane is considered. Akbari Ganji Method and Differential Transform Method are implemented to resolve the system of nonlinear equations, yielding an analytical formulation for the concentration of carbon dioxide, 2-amino-2-methyl-1-proponal, 1,8-diamino-p-methane and the molar flux in-terms of reaction rate constants. The obtained analytical findings are used to evaluate the different diffusion parameters and compared with numerical results. By assessing Matlab results with analytical findings, a successful outcome is discovered. Moreover, the influence of parameters on molar flux is examined. Also, graphical representations are presented and discussed here. The new analytical results contribute to optimizing the consistency of this model. The ensuring outcomes have been verified utilizing the existing numerical data with prior findings, and we are then presented with an adequate level of agreement.

The molecular binding sequence transformation of soil organic matter and biochar dissolved black carbon antagonizes the transport of 2,4,6-trichlorophenol

Dissolved organic matter (DOM) and dissolved black carbon (DBC) are significant environmental factors that influence the transport of organic pollutants. However, the mechanisms by which their molecular diversity affects pollutant transport remain unclear. This study elucidates the molecular binding sequence and adsorption sites through which DOM/DBC compounds antagonize the transport of 2,4,6-trichlorophenol (TCP) using column experiments and modelling. DBC exhibits a high TCP adsorption rate (kn = 5.32 × 10−22 mol1–n∙Ln–1∙min−1) and conditional stability constant (logK = 5.19–5.74), indicating a strong binding affinity and antagonistic effect on TCP. This is attributed to the high relative content of lipid/protein compounds in DBC (25.65 % and 30.28 %, respectively). Moreover, the small molecule lipid compounds showed stronger TCP adsorption energy (Ead = −0.0071 eV/−0.0093 eV) in DOM/DBC, combined with two-dimensional correlation spectroscopy model found that DOM/DBC antagonized TCP transport in the environment through binding sequences that transformed from lipid/protein small molecule compounds to lignin/tannin compounds. This study used a multifaceted approach to comprehensively assess the impact of DOM/DBC on TCP transport. It reveals that the molecular diversity of DOM/DBC is a critical factor affecting pollutant transport, providing important insights into the environmental trend and ecological effects of pollutants.

Ultrasonication-assisted synthesis of CuO-decorated montmorillonite K30 nanocomposites for photocatalytic removal of emerging contaminants: A response surface methodology approach

Environmental pollution is increasing worldwide due to population and industrialization. Among the various forms of pollution, water pollution poses a significant challenge in contemporary times. In this study, we synthesized CuO-decorated montmorillonite K30 (MK30) nanosheets via a simple ultrasonication technique. The structural, morphological, compositional, and optical properties of the synthesized nanocomposites were evaluated using advanced instrumentation techniques. The morphology of CuO was cubic and cubic CuO evenly designed on the MK30, which was proved by Field Emission Scanning Electron Microscopy (FESEM). The adsorption photocatalytic activity of the synthesized cubic CuO/MK30 composites was examined through the degradation of MB under visible light irradiation. The apparent reaction rate constant of 20% CuO/MK30 was 12.5 folds higher than that of CuO. These conditions included a catalyst dosage ranging from 5 to 15 mg, a pH level ranging from to 3–11, and a pollutant concentration ranging from 5 to 20 mg/L. The optimal conditions for MB dye removal were determined using response surface methodology (RSM). A scavenger study of the composite was conducted and verified that •O2− and •OH radicals play an important role in the degradation process. This investigation addressed the process of adsorption and potential removal pathways, with a particular emphasis on the role of functional groups. The environmentally friendly CuO/MK30 nanocomposites exhibited potential as photocatalysts for efficiently absorbing and degrading MB dye and TC drug pollutants. They represent promising candidates for the treatment of industrial wastewater, aiming to mitigate the environmental threats posed by organic pollutants.

Ab Initio Chemical Kinetics for Oxidation of CH3OH by N2O4: Elucidation of the Mechanism for Major Product Formation and Its Relevancy to Tropospheric Chemistry.

Next to CH4, CH3OH is the most abundant C1 organics in the troposphere. The redox reaction of CH3OH with N2O4 had been shown experimentally to produce CH3ONO, instead of CH3ONO2. The mechanism for the reaction remains unknown to date. We have investigated the reaction by ab initio MO calculations at the UCCSD(T)/6-311+G(3df,2p)//UB3LYP/6-311+G(3df,2p) level. The result indicates that the reaction takes place primarily by the isomerization of N2O4 to ONONO2 through a very loose transition state within the N2O4-CH3OH collision complex with a 14.3 kcal/mol barrier, followed by the rapid attack of ONONO2 at CH3OH producing CH3ONO and HNO3. The predicted mechanism for the redox reaction compares closely with the hydrolysis of N2O4. The computed rate constant, k1 = 1.43 × 10-8 T1.96 exp (-9092/T) (200-2000 K) cm3molecule-1s-1, for the formation of CH3ONO and HNO3 agrees reasonably with available low-temperature kinetic data and is found to be similar to that of the isoelectronic N2O4 + CH3NH2 reaction. We have also estimated the kinetics for the termolecular reaction, 2 NO2 + CH3OH, and compared it with the direct bimolecular process; the latter was found to be 4.4 × 105 times faster under the troposphere condition. On the basis of the known pollution levels of NO2, N2O4, and CH3OH, both processes were estimated to be of negligible importance to tropospheric chemistry, however.

Ab Initio Chemical Kinetics for Oxidation of CH3OH by N2O4: Elucidation of the Mechanism for Major Product Formation and Its Relevancy to Tropospheric Chemistry.

Next to CH4, CH3OH is the most abundant C1 organics in the troposphere. The redox reaction of CH3OH with N2O4 had been shown experimentally to produce CH3ONO, instead of CH3ONO2. The mechanism for the reaction remains unknown to date. We have investigated the reaction by ab initio MO calculations at the UCCSD(T)/6-311+G(3df,2p)//UB3LYP/6-311+G(3df,2p) level. The result indicates that the reaction takes place primarily by the isomerization of N2O4 to ONONO2 through a very loose transition state within the N2O4-CH3OH collision complex with a 14.3 kcal/mol barrier, followed by the rapid attack of ONONO2 at CH3OH producing CH3ONO and HNO3. The predicted mechanism for the redox reaction compares closely with the hydrolysis of N2O4. The computed rate constant, k1 = 1.43 × 10-8 T1.96 exp (-9092/T) (200-2000 K) cm3molecule-1s-1, for the formation of CH3ONO and HNO3 agrees reasonably with available low-temperature kinetic data and is found to be similar to that of the isoelectronic N2O4 + CH3NH2 reaction. We have also estimated the kinetics for the termolecular reaction, 2 NO2 + CH3OH, and compared it with the direct bimolecular process; the latter was found to be 4.4 × 105 times faster under the troposphere condition. On the basis of the known pollution levels of NO2, N2O4, and CH3OH, both processes were estimated to be of negligible importance to tropospheric chemistry, however.

Experimental and kinetic modeling study on the low-temperature decomposition and autoignition of 2-Azido-N,N-dimethylethanamine: A promising green mono- and bi-propellant

2-Azido-N,N-Dimethylethanamine (DMAZ) is a promising candidate for mono- and bi- propellant. However, the fundamental gas-phase combustion experiments have not been reported, and its chemical kinetic mechanism is not well understood. Therefore, the ignition delay times (IDTs) of DMAZ were measured utilizing a rapid compression machine and a shock tube, covering a wide temperature range of 570 – 960 K, at 10 and 20 bar with varying equivalence ratios. DMAZ was surprisingly found to undergo decomposition at temperatures as low as 600 K, leading to a pressure rise within the chamber. The low-temperature decomposition characteristics of DMAZ were systematically investigated under various fuel concentrations and pressures. A kinetic model of DMAZ was developed, incorporating quantum chemistry calculations for the thermodynamic data of new species and the rate constants of H-atom abstractions. The newly measured IDTs and characteristic decomposition times (CDTs) were further adopted in the model validation. Results show that DMAZ mainly decomposes through N–N2 bond fissions, which are also the major reaction pathways during autoignition. O2 addition to the radicals derived from the decomposition products and subsequent reactions contribute to most of the low-temperature reactivity in DMAZ oxidation. The current kinetic model can reasonably predict the IDTs and CDTs, as well as their dependencies on pressure, equivalence ratio, and fuel concentration.

Arginine-Rich Peptide-Rhodium Nanocluster@Reduced Graphene Oxide Composite as a Highly Selective and Active Uricase-like Nanozyme for the Degradation of Uric Acid and Inhibition of Urate Crystal.

Metal nanozymes have offered attractive opportunities for biocatalysis and biomedicine. However, fabricating nanozymes simultaneously possessing highly catalytic selectivity and activity remains a great challenge due to the lack of three-dimensional (3D) architecture of the catalytic pocket in natural enzymes. Here, we integrate rhodium nanocluster (RhNC), reduced graphene oxide (rGO), and protamine (PRTM, a typical arginine-rich peptide) into a composite facilely based on the single peptide. Remarkably, the PRTM-RhNC@rGO composite displays outstanding selectivity, activity, and stability for the catalytic degradation of uric acid. The reaction rate constant of the uric acid oxidation catalyzed by the PRTM-RhNC@rGO composite is about 1.88 × 10-3 s-1 (4 μg/mL), which is 37.6 times higher than that of reported RhNP (k = 5 × 10-5 s-1, 20 μg/mL). Enzyme kinetic studies reveal that the PRTM-RhNC@rGO composite exhibits a similar affinity for uric acid as natural uricase. Furthermore, the uricase-like activity of PRTM-RhNC@rGO nanozymes remains in the presence of sulfur substances and halide ions, displaying incredibly well antipoisoning abilities. The analysis of the structure-function relationship indicates the PRTM-RhNC@rGO composite features the substrate binding site near the catalytic site in a confined space contributed by 2D rGO and PRTM, resulting in the high-performance of the composite nanozyme. Based on the outstanding uricase-like activity and the interaction of PRTM and uric acid, the PRTM-RhNC@rGO composite can retard the urate crystallization significantly. The present work provides new insights into the design of metal nanozymes with suitable binding sites near catalytic sites by mimicking pocket-like structures in natural enzymes based on simple peptides, conducing to broadening the practical application of high-performance nanozymes in biomedical fields.

Theoretical study on the effect of end groups and core ring numbers in non-fullerene acceptors for organic solar cells

Modifying the skeleton, side chains and end groups of non-fullerene acceptors (NFAs) is important approach to improve the photovoltaic performance of organic solar cells. We selected PBDB-T as the donor and INIC, INIC1, INIC2, ITCC, ITCPTC and ITIC as the acceptors in order to study the difference in NFAs. The geometries, electronic structures, excited state properties, excited-state lifetimes and rate constants of charge transfer (CT), charge recombination (CR) and exciton dissociation (ED) processes of the monomers and PBDB-T:NFA complexes have been investigated by means of density functional theory and time-dependent density functional theory. The research reveals that fluorination of end groups, thienyl substitution and increase in the number of central rings result in the decrease in the energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital. Fluorine substitution and increase in central ring numbers cause redshift of the absorption spectrum for NFAs. NFAs with fluorine substitution have a larger maximum electrostatic potential, which facilitates CT at the donor:NFA heterojunction interfaces. Fluorine substitution and thienyl substitution decrease the NFA's CT distances, indicating that both fluorine and thienyl substitutions affect the CT rate. Fluorine substitution, thienyl modification of end groups and increase in central ring numbers also reduce the exciton binding energy, which is beneficial for decreasing CR and improving ED efficiency.

Microbial fuel cell in long-term operation and providing electricity for intermittent aeration to remove contaminants from sewage

Microbial fuel cells (MFCs) show promise in sewage treatment because they can directly convert organic matter (OM) into electricity. This study aimed to demonstrate MFCs stability over 750 days of operation and efficient removal of OM and nitrogenous compounds from sewage. To enhance contaminant removal, oxygen was provided into the anode chamber via a mini air pump. This pump was powered by the MFCs' output voltage, which was boosted using a DC-DC converter. The experimental system consisted of 12 sets of cylindrical MFCs within a 246L-scale reactor. The boosted voltage reached 4.7 V. This voltage was first collected in capacitors every 5 min and then dispensed intermittently to the air pump for the MFCs reactor in 4 s. This corresponds to receiving average DO concentration reaching 0.34 ± 0.44 mg/L at 10 cm above the air-stone. Consequently, the degradation rate constants (k) for chemical oxygen demand (COD) and biological oxygen demand (BOD) in the presence of oxygen were 0.048 and 0.069, respectively, which surpassed those without oxygen by 0.039 and 0.044, respectively. Aeration also marginally improved the removal of ammonia because of its potential to create a favorable environment for the growth of anammox and ammonia-oxidizing bacteria such as Candidatus brocadia and Nitrospira. The findings of this study offer in-depth insight into the benefits of boosted voltage in MFCs, highlighting its potential to enhance contaminant degradation. This serves as a foundation for future research focused on improving MFCs performance, particularly for the removal of contaminants from wastewater.

Enhanced Interfacial Electron Transfer in Photocatalyst-Natural Enzyme Coupled Artificial Photosynthesis System: Tuning Strategies and Molecular Simulations.

Laccase is capable of catalyzing a vast array of reactions, but its low redox potential limits its potential applications. The use of photocatalytic materials offers a solution to this problem by converting absorbed visible light into electrons to facilitate enzyme catalysis. Herein, MIL-53(Fe) and NH2-MIL-53(Fe) serve as both light absorbers and enzyme immobilization carriers, and laccase is employed for solar-driven chemical conversion. Electron spin resonancespectroscopy results confirm that visible light irradiation causes rapid transfer of photogenerated electrons from MOF excitation to T1 Cu(II) of laccase, significantly increasing the degradation rate constant of tetracycline (TC) from 0.0062 to 0.0127 min-1. Conversely, there is only minimal or no electron transfer between MOF and laccase in the physical mixture state. Theoretical calculations demonstrate that the immobilization of laccase's active site and its covalent binding to themetal-organic frameworksurface augment the coupled system's activity, reducing the active site accessible from 27.8 to 18.1 Å. The constructed photo-enzyme coupled system successfully combines enzyme catalysis' selectivity with photocatalysis's high reactivity, providing a promising solution for solar energy use.

Bivalent affinity binding-inspired PPARγ immobilization with selective conformation and improved ligand-binding activity

Functional protein immobilization forms the basis for bio-detections. A series of one-point, site-specific immobilization methods have been developed, however, it still remains as a challenge how to avoid the proteins to move in all directions as well as conveniently regenerate the bio-devices. Herein, we have developed a bivalent affinity binding-inspired method for PPARγ immobilization using DNA aptamer and nickel-nitrilotriacetic acid (Ni2+-NTA) chelation. The specific DNA aptamer (Apt 2) was selected by an on-column systematic evolution of ligands by exponential enrichment (SELEX) method with affinity of (1.57 ± 0.15) × 105 M−1, determined by isothermal titration calorimetry (ITC). Apt 2 and nickel-nitrilotriacetic acid (Ni2+-NTA) were modified on macroporous silica gels via L-α-allylglycine as a linker. They respectively interacted with PPARγ and 6×His tag via bivalent affinity binding for the receptor immobilization. After comprehensive surface characterization, PPARγ was proved to be successful immobilized. Chromatographic studies revealed that the immobilized PPARγ has conformation selectivity, which discriminated agonist and antagonist of the receptor. Ligand-binding parameters (affinity and rate constant) of four agonists (rosiglitazone, pioglitazone, troglitazone, and magnolol) with PPARγ were determined. Troglitazone showed the lowest dissociation rate constant. The binding affinities (3.28 × 107, 1.91 × 106, 2.25 × 107, and 2.43 × 107 M−1) were highly consistent with the data obtained using purified receptor in solution (2.16 × 107, 4.52 × 106, 1.20 × 107, and 1.56 × 107 M−1), offering reliable bio-detection method for PPARγ and its ligands. Due to the biocompatibility of nuclear receptor with DNA, it is conceivable that the bivalent affinity-based method will be a general method for the immobilization of other nuclear receptors, which may provide selective conformation and improved ligand-binding activity for the receptors.

Predicting decomposition temperatures and carbonization feasibility of heterocycles with their decomposition mechanism

Pyrolysis of heterocyclic compounds such as Meldrum’s acid derivatives was studied with two key mechanisms analysing their energy barrier diagrams by the hybrid density functional theory method M06-2X. The feasibility of these decomposition reactions was calculated specifically for Meldrum’s acid, monomethyl Meldrum’s acid, dimethyl Meldrum’s acid (DMMA), methylene Meldrum’s acid (MeMA) and (dimethylamino)methylene Meldrum’s acid (DMAMeMA), based on previous experimental analysis. Their initial decomposition products (ketene or substituted ketenes with CO2 and acetone) were found endothermic requiring activation energies (∼180–––230 kJ/mol) at the decomposition temperatures of 280, 299, 301, 503 and 414 K respectively. The transition state theory calculations show MeMA and DMAMeMA are thermally more stable than other derivatives with low values for the rate constants and high energy barriers to produce initial decomposition products, suggesting they can produce fine carbon materials during carbonization. DMMA is found the best option for obtaining heteroatoms-doped carbon material formation.

Photolysis of tolfenamic acid in aqueous and organic solvents: a kinetic study.

Tolfenamic acid (TA) is a non-steroidal anti-inflammatory drug that was studied for its photodegradation in aqueous (pH 2.0-12.0) and organic solvents (acetonitrile, methanol, ethanol, 1-propanol, 1-butanol). TA follows first-order kinetics for its photodegradation, and the apparent first-order rate constants (k obs) are in the range of 0.65 (pH 12.0) to 6.94 × 10-2 (pH 3.0) min-1 in aqueous solution and 3.28 (1-butanol) to 7.69 × 10-4 (acetonitrile) min-1 in organic solvents. The rate-pH profile for TA photodegradation is an inverted V (∧) or V-top shape, indicating that the cationic form is more susceptible to acid hydrolysis than the anionic form of TA, which is less susceptible to alkaline hydrolysis. The fluorescence behavior of TA also exhibits a V-top-shaped curve, indicating maximum fluorescence intensity at pH 3.0. TA is highly stable at a pH range of 5.0-7.0, making it suitable for formulation development. In organic solvents, the photodegradation rate of TA increases with the solvent's dielectric constant and solvent acceptor number, indicating solute-solvent interactions. The values of k obs decreased with increased viscosity of the solvents due to diffusion-controlled processes. The correlation between k obs versus ionization potential and solvent density has also been established. A total of 17 photoproducts have been identified through LC-MS, of which nine have been reported for the first time. It has been confirmed through electron spin resonance (ESR) spectrometry that the excited singlet state of TA is converted into an excited triplet state through intersystem crossing, which results in an increased rate of photodegradation in acetonitrile.

Adsorption characteristics and applications of andesite in removing some pollutants from wastewater

Andesite was employed to effectively extract mercury(II) in an aqueous solution. After evaluating its characteristics, andesite was characterized by applying modern techniques such as BET and TGA methods. The study employed SEM and TEM measurements to analyze the variation in the surface shape and crystallinity of the metal due to adsorption. Using the EDX process, the chemical composition, weight, and atomic percentage of each element of andesite were determined. FTIR techniques were also used to confirm the TEM–EDX findings. Zeta potential was estimated. Cycles of regeneration and desorption have been examined. 99.03% was the highest uptake percentage. Adsorbent quantity (0.0025–0.05) g/L, contact time (5–60) min, pH (2–10), temperature (25–60) °C, and dose (0.0027, 0.0044, 0.0125, 0.0155, and 0.0399) mg/L all affect the amount of removal that increases with the increase in contact time, pH, dose, and temperature but drops as the metal ion concentration rises. The ideal values for contact time, pH, metal ion concentration, dose, and temperature were found to be, respectively, 30 min, 0.0155 mg/l, 0.02 g/l, and 40 °C. The calculation of thermodynamic parameters, including ΔH, ΔG, and ΔS, was imperative in establishing that the mechanism of heavy metal adsorption on andesite was endothermic, exhibiting a physical nature that escalated with temperature rise. The Freundlich adsorption equation's linear form is matched by the adsorption of mercury(II) on andesite; constant n was 1.85, 1.06, 1.1, and 1.1, whereas the Langmuir constant qm was found to be 1.85, 2.41, 3.54, and 2.28 mg/g at 25–60 °C. Furthermore, adsorption follows a pseudo-second-order rate constant of (3.08, 3.24, 3.24, and 13) g/mg/min under identical temperature conditions, as opposed to a first-order rate constant of 4, 3, 2.6, and 2. Hg2+, NH4+, Cl−, Br−, NO3−, SO42−, Na+, K+, H2S, and CH3SH were all extracted from wastewater by this application.

Oil-Coated Ammonium Sulfate Improves Maize Nutrient Uptake and Regulates Nitrogen Leaching Rates in Sandy Soil

Ammonium sulfate (AS) has been utilized in agriculture; however, there is a dearth of research on its application in maize cultivation subsequent to the implementation of nitrification inhibitors or coating treatments. This study aimed to analyze the impacts of various combinations of AS fertilizers on soil nutrients, plant nutrient uptake, yield, and fertilizer utilization efficiency in maize cultivation to establish an optimal and stabilized disposal method for AS. A completely randomized design was employed with five treatments (AU, the control using urea; AS, treatment using ammonium sulfate; ASN, treatment using ammonium sulfate with a nitrification inhibitor; ASG, treatment using oil-coated ammonium sulfate; and ASD, treatment using oil–humic acid-coated ammonium sulfate). The results show the following: (1) Compared with AU and AS, ASN, ASG, and ASD decreased the leaching rates of total nitrogen (TN), ammonium nitrogen (NH4+-N), and nitrate nitrogen (NO3−-N), and more residual N had accumulated in the soil. The first-order kinetic equation Nt = N0(1 − e−kt) could better fit the process of N accumulation and release, and the N-release rate constant was in the order of AU > CK > AS > ASG > ASN > ASD. (2) Compared with the AU and AS treatments, the plant dry weight, grain dry weight, spike width, spike length, and yields of maize increased by 8.85–11.08%, 12.98–14.15%, 2.95–3.52%, 5.50–5.65%, and 43.21–51.10%, respectively, under the ASG treatment. A path analysis revealed the main decision coefficient of the effective spike number on the maize yield. Furthermore, the accumulation levels of N, P, and K within above-ground plants significantly increased under the ASG treatment compared with those under the AU and AS treatments. N, P, and K partial factor productivity under the ASG treatment increased by 47.12%, 47.15%, and 73.40% on average, while grain N, P, and K balance increased by 50.45%, 47.10%, 55.61% on average, compared with the AU and AS treatments. Therefore, the ASG treatment exhibited the optimal slow-release effect on nutrients and achieved excellent performance in enhancing the production and efficiency of maize.

BiVO4-Driven photocatalytic degradation of pharmaceutical in Slurry Bubble Column Reactor: Influencing factors and toxicological profiling

As the pursuit for sustainable and effective solutions to address environmental pollution intensifies, a comprehensive approach in photocatalysis has become a subject of increasing interest. In this study, BiVO4 photocatalyst synthesized through a pH-controlled hydrothermal method was used for the degradation of tetracycline (TET), a prevalent pharmaceutical pollutant. Optimal conditions, particularly a pH of 9 and enriched dissolved oxygen (DO), significantly improve TET removal, achieving a 96 % degradation efficiency with a rate constant of k = 0.1069 min−1. The investigation revealed that the degradation predominantly involves the generation of reactive oxygen species (ROS), notably O2•−, which play a crucial role in the degradation of TET. Using the “ecological structure–activity relationships” (ECOSAR) program, the toxicity of the intermediates was assessed, highlighting the environmental implications of the photocatalytic process. In addressing the scalability for industrial applications, a Slurry Bubble Column Reactor (SBCR) was employed, and separation-stability tests of the photocatalyst were conducted. These tests confirmed the photocatalyst’s long-term effectiveness and stability, underscoring its potential for repeated use in large-scale applications. This comprehensive research not only underscores the potential of BiVO4 in removing environmental contaminants but also provides vital insights into ecological safety.

Fulvenallenyl Radical (C7H5·)-Mediated Gas-Phase Synthesis of Bicyclic Aromatic C10H8 Isomers: Can Fulvenallenyl Efficiently React with Closed-Shell Hydrocarbons?

To understand the reactivity of resonantly stabilized radicals, often found in relevant concentrations in gaseous environments, it is important to determine their main reaction pathways. Here, it is investigated whether the fulvenallenyl radical (C7H5·) reacts preferentially with closed-shell molecules or radicals. Electronic structure calculations on the C10H9 potential energy surface accessed by the reactions of C7H5· with methylacetylene (CH3CCH) and allene (H2CCCH2) were combined with RRKM-ME calculations of temperature- and pressure-dependent rate constants using the automated EStokTP software suite and kinetic modeling to assess the reactivity of C7H5· with closed-shell unsaturated hydrocarbons. Experimentally, the reactions were attempted in a chemical microreactor heated to 998 ± 10 K by preparing fulvenallenyl radicals via pyrolysis of trichloromethylbenzene (C7H5Cl3) and seeding the radicals in methylacetylene or allene carrier gas, with product identification by means of photoionization mass spectrometry. The measured photoionization efficiency curve of m/z = 128 was assigned to a linear combination of the reference curves of two C10H8 isomers, azulene (minor) and naphthalene (major), presumably resulting from the C7H5· plus C3H4 reactions. However, the calculations demonstrated that these reactions are too slow, and kinetic modeling of processes in the reactor allowed us to conclude that the observation of naphthalene and azulene is due to the C7H5· plus C3H3· reaction, where propargyl is produced by direct hydrogen atom abstraction by chlorine (Cl) atoms from allene or methylacetylene and Cl stem from the pyrolysis of C7H5Cl3. Modeling results under the copyrolysis conditions of toluene and methylacetylene in high-temperature shock tube experiments confirmed the prevalence of the fulvenallenyl reaction with propargyl over its reactions with C3H4 even when the concentrations of allene and methylacetylene largely exceed that of propargyl. Overall, the reactions of fulvenallenyl with both allene and methylacetylene were found to be noncompetitive in the formation of naphthalene and azulene thus attesting the inefficiency of the fulvenallenyl radical reactions with the prototype closed-shell hydrocarbon species. In the meantime, the new reaction pathways revealed, including H-assisted isomerizations between C10H8 isomers and decomposition reactions of various C10H9 isomers, emerge as relevant and are recommended for inclusion in combustion kinetic models for naphthalene formation.

Esterification of Levulinic Acid with Different Alcohols Using Mesoporous Stannosilicates As the Catalyst.

The mesoporous stannosilicates SnMCM-41-25 and SnMCM-41-80, synthesized, respectively, at 25 and 80 °C and exhibiting a well-ordered hexagonal structure, were applied for the first time as heterogeneous catalysts in the esterification of levulinic acid (LA) with different alcohols. The nonhydrothermal method was effective to obtain materials with a high degree of ordering, high acidity, and promising catalytic activity in this esterification. The SnMCM-41-80 led to conversions of 71.0 and 83.6% in 120 and 180 min, respectively, while the respective values for the material without Sn were 33.2 and 40.1% under the same conditions (MeOH:LA molar ratio of 5:1, 1 wt % catalyst, 3 h, 120 °C). In addition, concerning the use of different alcohols, the reaction rate constants (k ap) were related to the effects of substituents by Taft equation. In general, the polar and steric effects follow the Taft relation, and the length of the chain exerted less influence on the decrease in conversion in comparison to the presence of branches. These results indicate that it is possible to incorporate Sn into the structure of MCM41, thus, making the modified materials more active in the esterification investigated.

Electrocatalytic hydrogen evolution coupled with dye hydrogenation reactions for sustainable wastewater treatment using transition-metal (Fe, Co, Ni, Cu) nanoparticles with ZnO nanowire supports

A water electrolysis coupled with chemical reduction strategy is proposed to realize sustainable wastewater treatment. Correspondingly, a series of transition-metal (e.g., iron, cobalt, nickel and copper) nanoparticles anchored on zinc oxide nanowire array (ZnO NA) with bifunctional catalytic activity for hydrogen evolution reaction together with dye hydrogenation reaction (HER/DHR) are developed, while their catalytic activity are comparatively investigated at the same time. This renewable strategy with environmental and economic benefits exhibits high-efficiency treatment capability towards various dye wastewaters. For example, a typical system based on nickel nanoparticles with ZnO NA supports, which exhibits higher catalytic activity towards the HER/DHR than those of other three counterparts under the same conditions, can transform waste 4-nitrophenol into valuable 4-aminophenol with an apparent rate constant of 36.95 × 10-3 min−1 and a conversion rate of 98.32 %, thereby achieving dye decolorization and resource regeneration simultaneously. Its efficiency is significantly superior to that of chemical method dependent on traditional reducing agents and commercial nickel materials, demonstrating its stronger competitiveness. It is mainly benefited from the interface synergistic effect of nickel nanoparticles and zinc oxide nanowires. This novel system is expected to replace conventional sewage remediation technologies for efficient, inexpensive, and eco-friendly dye degradation, and thus is very important for energy and environmental sustainability.