Rate Constants Research Articles

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 (MA) derivatives has been studied with focus on two key mechanisms analysing their energy barrier diagrams using the hybrid density functional theory method M06-2X. The feasibility of these decomposition reactions was calculated specifically for MA, monomethyl Meldrum’s acid (MMA), dimethyl Meldrum’s acid (DMMA), methylene Meldrum’s acid (MeMA) and (dimethylamino)methylene Meldrum’s acid (DMAMeMA), based on previous experimental analysis. The barrier to initial decomposition products (ketene or substituted ketenes with CO2 and acetone) were found to be endothermic requiring activation energies (∼180 – 230 kJ/mol) at decomposition temperatures of 280, 299, 301, 503 and 414 K respectively. 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.

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.

Bryophyllum Pinnatum leaf extract mediated MoS2/ZnO nanocomposite for robust photocatalysis applications

One of the primary problems of the twenty-first century is the removal or degradation of organic dyes and antibiotics from water systems since they both contribute significantly to water pollution. To address this issue, molybdenum disulfide and zinc oxide nanocomposite (MoS2/ZnO) were produced by simple, eco-friendly and low cost process using Bryophyllum pinnatum (leaf) phytoextract (BPP) as a reducing as well as capping agent. The prepared BPP-mediated MoS2/ZnO nanocomposite (BP-MoS2/ZnO NC) samples were characterized through various techniques including powder XRD, Rietveld refinement, UV–Vis spectroscopy, FESEM, DLS and FT-IR spectroscopy. The BP-MoS2/ZnO samples were further tested for their use in the sunlight-powered photocatalytic breakdown of methylene blue (MB) and their efficiency to break MB molecules was contrasted with the BPP-mediated ZnO (BP-ZnO), Chemical ZnO (Ch-ZnO) and pure MoS2. The photocatalytic investigation reveals a remarkable enhancement in the photocatalytic activity of pristine ZnO when sensitized with MoS2. These results underscore the synergistic effect achieved by combining ZnO and MoS2. Notably, we found that the optimal catalytic performance is achieved at a Mo atomic percentage of 2 % relative to Zn, emphasizing the importance of precise control for maximizing efficacy. Under sun exposure, 0.5 g/L of BP-MoS2/ZnO resulted in 89.35 % photodegradation of a 20 mg/L MB solution with a rate constant of 0.07537 min-1, which was around 10.42 %, 28.51 %, and 51.86 % greater than BP-ZnO, Ch-ZnO, and pure MoS2, respectively. Further, the efficacy of the BP-MoS2/ZnO NC as solar-driven photocatalysts for removal of pharmaceutical drugs (Amoxicillin & Metronidazole) and textile dyes (Methyl orange) pollutants in sunlight was also investigated. These results show that Bryophyllum extract-mediated MoS2/ZnO is a promising material for solar-based photocatalytic applications.

Absorption in a pseudo-first-order regime with two irreversible reactions: Influence of the second reaction on the transfer rate

Gas-absorbing liquids such as CO2 often undergo two reactions: a main reaction and a secondary reaction. The solute flux transferred is a result of both reactions. Kinetics is one of the most important properties in the design of an absorber. To access the rate constant of the main reaction, the assumption of a pseudo-first-order (PFO) regime is often made, but the criteria for the system to be in a pseudo-first-order regime change between researchers. Furthermore, the impact of the secondary reaction is either neglected or overestimated. Recently, some researchers carried out simulations of multiple parallel gas–liquid reactions in the instantaneous regime and developed generalized criteria for this regime. In this study, to estimate the impact of the secondary reaction in a PFO regime, hundreds of simulations were carried out with two irreversible reactions within the framework of the film theory. This work proves that for Ha1 > 10, Ha2 > 10, Ha1/E∞,1 < 0.5, Ha2/E∞,2 < 0.5, normalized concentration profiles depend only on three factors: Ha1/ E∞,1, Ha2/ E∞,2, and Ha1/Ha2. Curves and generalized equations are provided enabling the estimation of the concentrations of reactants at the interface, the enhancement factor, and the influence of each reaction on the gas transfer flux (average absolute relative deviation ≤ 0.50 %). New criteria for determining whether the system can be considered in a pseudo-first-order regime are defined, giving accurate predictions with a success rate of 96.2 %.

Influence of inorganic solid particles on the stability of water-in-crude oil emulsions: Evaluating the role of surface charge

This study examines the effect of inorganic solid particles on the stability of water-in-oil (W/O) emulsions formed during the transportation, refining, and storage of crude oil. The surface properties of inorganic particles, such as kaolinite and calcite, can influence the interface between crude oil and water, affecting the stability of the emulsion. The study evaluates the quantitative effect of these particles on emulsion stability and investigates how surface properties affect the emulsions. Emulsions were prepared using crude oil and synthetic brine, with calcite and kaolinite added as inorganic solid particles. Adding inorganic solids increased the volume of released water and altered the emulsion stability, with high concentrations decreasing the formation of stable emulsions. The dissolution of inorganic solids increased the pH of the solution and promoted demulsification due to the high surface potential of crude oil. The solid particles enhanced the formation of oil-in-water-in-oil (O/W/O) emulsions, generating unstable emulsions. The study also found that increasing temperature and adding inorganic solids decreased the emulsion height over time, which was predicted by the emulsion layer growth model. The coagulation rate constant was a tuning parameter, with a higher value implying higher internal repulsion and stronger coagulation between water droplets, facilitating emulsion instability. It has been observed that elevating the storage temperature and introducing kaolinite accelerates the coagulation rate constant, whereas the addition of calcite decreases this value, ultimately contributing to the stabilisation of the emulsions.

Efficient removal of moxifloxacin through PMS activation by CuFeS2/MXene.

Due to the frequent detection and potential toxicity of moxifloxacin (MOX), its removal technology had attracted attention in recent years. In this research, CuFeS2/MXene was prepared and used to activate peroxymonosulfate (PMS) to remove MOX. The degradation efficiencies, kinetics, influences, and reaction mechanism of MOX by CuFeS2/MXene/PMS were investigated. The synergistic effect of CuFeS2 and MXene significantly enhanced PMS activation, producing SO4•-, HO•, and 1O2 as the main active species. By adding 0.12g/L CuFeS2/MXene and 0.12mM PMS, MOX removal efficiency reached 99.1% within 40min, with a rate constant of 0.1073min-1. The composite ratios of CuFeS2/MXene impacted PMS activation more significantly than catalyst dosages and PMS concentrations. Acidic conditions were favorable for the degradation of MOX, while HCO3-, HPO42-, Mn2+, and HA had the inhibitory effects. Twelve major products were detected by HPLC-MS, and DFT was used to illustrate possible degradation pathways of MOX, including the removal of nitrogen-containing heterocycle and transformations of quinolone moieties. Toxicity analysis showed that the developmental toxicity, mutagenicity, and acute toxicity of degradation products tended to decrease. CuFeS2/MXene could exhibit excellent reusability, maintaining an average MOX degradation efficiency of 90.8% in the 7-cycle experiments.

Influence of chemical structures on reduction rates and defluorination of fluoroarenes during catalytic reduction using a rhodium-based catalyst

Continuous growth in fluoroarene production has led to environmental pollution and health concerns owing to their persistence, which is attributed to the stable C–F bond in their structures. Herein, we investigated fluoroarene decomposition via hydrodefluorination using a rhodium-based catalyst, focusing on the effects of the chemical structure and functional group on the defluorination yield. Most compounds, except (pentafluoroethyl)benzene, exhibited full or partial reduction with pseudo-first-order rate constants in the range of 0.002–0.396 min−1 and defluorination yields of 0%–100%. Fluoroarenes with hydroxyl, methyl, and carboxylate groups were selected to elucidate how hydrocarbon and oxygen-containing functional groups influence the reaction rate and defluorination. Inhibition of the reaction rate and defluorination yield based on functional groups increased in the order of hydroxyl < methyl < carboxylate, which was identical to the order of the electron-withdrawing effect. Fluoroarenes with polyfluoro groups were also assessed; polyfluoro groups demonstrated a different influence on catalyst activity than non-fluorine functional groups because of fluorine atoms in the substituents undergoing defluorination. The reaction kinetics of (difluoromethyl)fluorobenzenes and their intermediates suggested that hydrogenation and defluorination occurred during degradation. Finally, the effects of the type and position of functional groups on the reaction rate and defluorination yield were investigated via multivariable linear regression analysis. Notably, the electron-withdrawing nature of functional groups appeared to have a greater impact on the defluorination yield of fluoroarenes than the calculated C–F bond dissociation energy.

Taming Two‐Dimensional Polymerization by a Machine‐Learning Discovered Crystallization Model

Rapidly synthesizing high‐quality two‐dimensional covalent organic frameworks (2D COFs) is crucial to their practical applications. Here, we use a machine‐learning approach that overcomes the challenges associated with bottom‐up model derivation for the non‐classical 2D COF crystallization processes. The resulting model, referred to as NEgen1, establishes correlations among the induction time, nucleation rate, growth rate, bond‐forming rate constants, and common solution synthesis conditions for 2D COFs that grow by a nucleation‐elongation mechanism. The results elucidate the detailed competition between the nucleation and growth dynamics in solution, which has been inappropriately described previously by classical, empirical models with assumptions invalid for 2D COF polymerization. By understanding the dynamic processes at play, the NEgen1 model reveals a simple strategy of gradually increasing monomer addition speed for growing large 2D COF crystals. This insight enables us to rapidly synthesize large COF‐5 colloids, which could only be achieved previously by prolonged reaction times or by introducing chemical modulators. These results highlight the potential for systematically improving the crystal quality of 2D COFs, which has wide‐reaching relevance for many of the applications for which 2D COFs are speculated to be valuable.

The First Steps of the Visual Cycle in Human Rod and Cone Photoreceptors.

Light detection destroys the visual pigment. Its regeneration, necessary for the recovery of light sensitivity, is accomplished through the visual cycle. Release of all-trans retinal by the light-activated visual pigment and its reduction to all-trans retinol comprise the first steps of the visual cycle. In this study, we determined the kinetics of all-trans retinol formation in human rod and cone photoreceptors. Single living rod and cone photoreceptors were isolated from the retinas of human cadaver eyes (ages 21 to 90 years). Formation of all-trans retinol was measured by imaging its outer segment fluorescence (excitation, 360nm; emission, >420nm). The extent of conversion of released all-trans retinal to all-trans retinol was determined by measuring the fluorescence excited by 340 and 380nm. Measurements were repeated with photoreceptors isolated from Macaca fascicularis retinas. Experiments were carried out at 37°C. We found that ∼80% to 90% of all-trans retinal released by the light-activated pigment is converted to all-trans retinol, with a rate constant of 0.24 to 0.55 min-1 in human rods and ∼1.8 min-1 in human cones. In M. fascicularis rods and cones, the rate constants were 0.38 ± 0.08 min-1 and 4.0 ± 1.1 min-1, respectively. These kinetics are several times faster than those measured in other vertebrates. Interphotoreceptor retinoid-binding protein facilitated the removal of all-trans retinol from human rods. The first steps of the visual cycle in human photoreceptors are several times faster than in other vertebrates and in line with the rapid recovery of light sensitivity exhibited by the human visual system.

Mechanisms Associated with Superoxide Radical Scavenging Reactions Involving Phenolic Compounds Deduced Based on the Correlation between Oxidation Peak Potentials and Second-Order Rate Constants Determined Using Flow-Injection Spin-Trapping EPR Methods.

Flow-injection spin-trapping electron paramagnetic resonance (FI-EPR) methods that involve the use of 5,5-dimethyl-pyrroline-N-oxide (DMPO) as a spin-trapping reagent have been developed for the kinetic study of the O2•- radical scavenging reactions occurring in the presence of various plant-derived and synthetic phenolic antioxidants (Aox), such as flavonoid, pyrogallol, catechol, hydroquinone, resorcinol, and phenol derivatives in aqueous media (pH 7.4 at 25 °C). The systematically estimated second-order rate constants (ks) of these phenolic compounds span a wide range (from 4.5 × 10 to 1.0 × 106 M-1 s-1). The semilogarithm plots presenting the relationship between ks values and oxidation peak potential (Ep) values of phenolic Aox are divided into three groups (A1, A2, and B). The ks-Ep plots of phenolic Aox bearing two or three OH moieties, such as pyrogallol, catechol, and hydroquinone derivatives, belonged to Groups A1 and A2. These molecules are potent O2•- radical scavengers with ks values above 3.8 × 104 (M-1 s-1). The ks-Ep plots of all phenol and resorcinol derivatives, and a few catechol and hydroquinone derivatives containing carboxyl groups adjacent to the OH groups, were categorized into the group poor scavengers (ks < 1.6 × 103 M-1 s-1). The ks values of each group correlated negatively with Ep values, supporting the hypothesis that the O2•- radical scavenging reaction proceeds via one-electron and two-proton processes. The processes were accompanied by the production of hydrogen peroxide at pH 7.4. Furthermore, the correlation between the plots of ks and the OH proton dissociation constant (pKa•) of the intermediate aroxyl radicals (ks-pKa• plots) revealed that the second proton transfer process could potentially be the rate-determining step of the O2•- radical scavenging reaction of phenolic compounds. The ks-Ep plots provide practical information to predict the O2•- radical scavenging activity of plant-derived phenolic compounds based on those molecular structures.

Catalytic Dechlorination of Three Organochlorides by Recyclable Nano-Palladium-Engineered Natural Sponge with Formic Acid

Catalytic dechlorination of organic chlorides by palladium (Pd) with HCOOH represents one of the most effective and promising techniques for environmental remediation. In this study, we adopted alkaline-modified porous natural sponge as support of a Pd nanocatalyst (Pd@M-Sponge) and HCOOH as a hydrogen source for the hydrodechlorination of florfenicol (FF), o-chlorophenol (o-CP), and p-chlorophenol (p-CP). Favorable conversion efficiency of FF, o-CP, and p-CP was achieved at 25 °C and atmospheric pressure attributed to the small diameter and high catalytic reactivity of the prepared Pd NPs, in addition to the slight internal mass transfer limitation of the prepared Pd@M-Sponge. High reaction rate constants were obtained even in the conditions of a low molar ratio of HCOOH to p-CP (10:1) and a high concentration of p-CP (500 mg/L). The prepared catalyst also demonstrated superior recyclability without any obvious decrease in catalytic reactivity in 20 successive p-CP dechlorination cycles. This work provides an ideal recyclable and cost-effective catalyst based on renewable and biocompatible natural material for the catalytic hydrodechlorination of chlorinated organic pollutants with formic acid and a new view for the exploration and designing of highly reactive and stable catalysts for hydrodechlorination.

Taming Two-Dimensional Polymerization by a Machine-Learning Discovered Crystallization Model.

Rapidly synthesizing high-quality two-dimensional covalent organic frameworks (2D COFs) is crucial to their practical applications. Here, we use a machine-learning approach that overcomes the challenges associated with bottom-up model derivation for the non-classical 2D COF crystallization processes. The resulting model, referred to as NEgen1, establishes correlations among the induction time, nucleation rate, growth rate, bond-forming rate constants, and common solution synthesis conditions for 2D COFs that grow by a nucleation-elongation mechanism. The results elucidate the detailed competition between the nucleation and growth dynamics in solution, which has been inappropriately described previously by classical, empirical models with assumptions invalid for 2D COF polymerization. By understanding the dynamic processes at play, the NEgen1 model reveals a simple strategy of gradually increasing monomer addition speed for growing large 2D COF crystals. This insight enables us to rapidly synthesize large COF-5 colloids, which could only be achieved previously by prolonged reaction times or by introducing chemical modulators. These results highlight the potential for systematically improving the crystal quality of 2D COFs, which has wide-reaching relevance for many of the applications for which 2D COFs are speculated to be valuable.

Novel FeOOH-decorated La-doped Bi4O5I2 microspheres for boosting photocatalysis-Fenton synergy degradation of emerging contaminants

Photocatalytic-Fenton synergistic degradation of pollutants in wastewater is considered a promising technology for environmental treatment. Herein, FeOOH quantum dots decorated La-doped Bi4O5I2 hybrids were prepared using an in-situ deposition strategy and applied for the removal of 2,4-dinitrophenylhydrazine. The FeOOH-1/La10-Bi4O5I2 sample exhibits the highest catalytic activity in degradation experiments, eliminating 93.8 % of 2,4-dinitrophenylhydrazine within 30 min at a reaction rate constant of 0.117 min−1. In addition, the impacts of several operational parameters on the catalytic activity were comprehensively examined, including H2O2 concentration, catalyst dosage, reaction solution pH and co-existing ions. In degradation process of 2,4-dinitrophenylhydrazine, the major reactive oxygen species are ·OH and ·O2–, with ·OH generated by Fenton reaction. Optical property characterization, cyclic voltammetry tests, and photoelectrochemical measurements confirmed that the FeOOH-1/La10-Bi4O5I2 composite has excellent light absorption capacity, abundant active centers, and excellent carrier separation efficiency. Finally, the degradation mechanism of FeOOH-1/La10-Bi4O5I2 composites for 2,4-dinitrophenylhydrazine is rationally discussed based on experimental and theoretical calculations. This study presents a fresh design idea for developing bismuth oxyhalide-based composites with high activity.

Visible light responsive SiO2/g-C3N4/BiOBr/Bi heterojunction photocatalyst for degradation of rhodamine B

For the purpose of alleviating the negative influence of rhodamine B (RhB) abuse on the environment, it is imperative to design a green and efficient photocatalyst for tackling organic dye-contaminated wastewater. Herein, a novel SiO2/g-C3N4/BiOBr/Bi (denoted as Si/CN/BiOB/Bi) photocatalyst with enhanced photodegradation activity has been successfully created. The influence of variable parameters including Bi doping amount, initial concentration of RhB, photocatalyst dosage, and reaction temperature on the photocatalytic performance of Si/CN/BiOB/Bi under visible light illumination are analyzed in detail. Results indicated that the degradation rate constant of RhB over Si/CN/BiOB/Bi-0.5 is 25.1, 18.1, and 2.2 times higher than that of CN, Si/CN, and Si/CN/BiOB, respectively. The Si/CN/BiOB/Bi-0.5 photocatalyst displayed high photocatalytic performance after 5 recycled runs. The improved photocatalytic performance can be attributed to the novel morphology as well as the excellent synergetic effects of Si/CN, BiOBr, and Bi, which enables the catalysts to accelerate the separation of photogenerated carriers. In brief, a new Si/CN/BiOB/Bi photocatalyst has a great application perspective for the purification of RhB wastewater.