Kinetic Constants Research Articles

Effect of Redox Mediators on Corrosion Behavior and Scanning Electrochemical Microscopy Response.

Scanning electrochemical microscopy (SECM) is widely used to measure local electrochemical reactivity of corroding surfaces. A major criticism of using SECM in feedback mode for corrosion studies is the requirement of an external redox mediator (RM) as it could react with the metal and affect the Nernst potential at the metal-solution interface. Consequently, it becomes challenging to differentiate the interference caused by the RM from the local reactivity of the metal. Herein, a multiscale electrochemical approach is presented to investigate the effect of RM choice on the corroding substrate. Two common RMs, ferrocenemethanol and hexaammineruthenium(III) chloride, were used to perform SECM over copper and aluminum. It was found during macroscale electrochemical measurements that Ru(NH)63+ acted as an oxidant and promoted corrosion. The SECM feedback behavior varied for copper depending on the RM used, suggesting that the corrosion reactions controlled the negative feedback mechanism, not the formation of an insulating passive film. The passivated aluminum surface consistently exhibited negative feedback, regardless of the RM used. SECM approach curves also displayed a distortion in the steady state current, which was caused by the deposition of substrate-generated species on the microelectrode. These deviations in feedback response were accounted for during analysis through incorporation into a finite element model to accurately extract the RM kinetic rate constants. The importance of understanding these processes is highlighted to avoid misinterpretation of passive behavior and advances toward a more quantitative use of SECM for corrosion studies.

Rapid Determination of Kinetic Constants for Slow-Binding Inhibitors and Inactivators of Human Histone Deacetylase 8

The kinetics and mechanism of drug binding to its target are critical to pharmacological efficacy. A high throughput (HTS) screen often results in hundreds of hits, of which usually only simple IC50 values are determined during reconfirmation. However, kinetic parameters such as residence time for reversible inhibitors and the kinact/KI ratio, which is the critical measure for evaluating covalent inactivators, are early predictive measures to assess the chances of success of the hits in the clinic. Using the promising cancer target human histone deacetylase 8 as an example, we present a robust method that calculates concentration-dependent apparent rate constants for the inhibition or inactivation of HDAC8 from dose–response curves recorded after different pre-incubation times. With these data, hit compounds can be classified according to their mechanism of action, and the relevant kinetic parameters can be calculated in a highly parallel fashion. HDAC8 inhibitors with known modes of action were correctly assigned to their mechanism, and the binding mechanisms of some hits from an internal HDAC8 screening campaign were newly determined. The oxonitriles SVE04 and SVE27 were classified as fast reversible HDAC8 inhibitors with moderate time-constant IC50 values of 4.2 and 2.6 µM, respectively. The hit compound TJ-19-24 and SAH03 behave like slow two-step inactivators or reversible inhibitors, with a very low reverse isomerization rate.

Effective degradation of tetracycline under visible light by microwave-assisted reflux synthesis of ZnO/MoS2/rGO ternary nanocomposites

ZnO@MoS2 and conducting rGO based ternary nanocomposites were synthesized by a bottom-up microwave-assisted reflux method and effectively investigated for the photocatalytic degradation of tetracycline hydrochloride (TCH) antibiotic. The XRD, EDAX and XPS results corroborates the formation of nanostructure composite with high phase purity. The ZnO nanorods are well grafted on the curled configuration of layered MoS2 and thin surfaced rGO sheets as visualised from HR-TEM analysis. Upon addition of rGO, there is a significant decrease in the bandgap and improved visible light response in the ternary nanocomposites is elucidated by UV–visible Diffuse Reflectance Spectroscopy (UV-DRS) analysis. The suppression in photo-induced electron/hole pair recombination and allowing easy charge transport of ZnMG-50 were evidenced from photoluminescence (PL) and photo-electrochemical impedance (photo-EIS) spectroscopy. From BET and BJH analysis, the enhancement in surface area and pore volume by loading of rGO (SBET = 264.794 m2/g and 0.548 cm3/g). The optimized ZnMG-50 nano-photocatalyst possess a superior photocatalytic performance with higher removal efficiency of 92.18 % was achieved at pH level 10, catalyst dosage 40 mg and TCH concentration 20 ppm within 180 min under illumination. The degradation process compiles a pseudo-first order reaction with a kinetic rate constant of 0.01365 min−1. The nonstop generation of hydroxyl (˙OH) and superoxide (O2˙-) reactive species were beneficial for free electrons in the active participation, which remains as a core factor in the degradation process. The detailed study on ZnMG-50 nanocomposite substantiated to be an efficient noble metal-free synthetic catalyst for enhanced photocatalytic degradation of antibiotics.

Solvent-free synthesis of defective Zr-based metal–organic framework from waste plastic bottles for highly efficient lomefloxacin removal

Large amount of polyethylene terephthalate (PET) plastics waster and emerging contaminants in water, including fluoroquinolone antibiotics, pose challenges to human survival. In this work, a green synthesis scheme is proposed in which the defective UiO-66 (d-UiO-66) is fabricated via a solvent-free routine by using PET plastics waster as raw materials for lomefloxacin (LOM) removal. In comparison with defect-free UiO-66, the created defect imparts d-UiO-66 with higher porosity and abundant defective Zr sites, which are beneficial to boost LOM adsorption. As expected, d-UiO-66 exhibited excellent LOM adsorption performances, showcasing a saturation adsorption capacity of 588 mg g−1 and a kinetic rate constant of 0.204 g mg−1 h−1, which are 3.5 and 2.0 times higher than those of the pristine UiO-66, respectively. Remarkably, the LOM saturation adsorption capacity of d-UiO-66 surpasses that of all reported adsorbents. Mechanism study reveals that this outstanding adsorption performance of d-UiO-66 is mainly ascribed to the abundant defective sites, high porosity, together with the strong hydrogen bonding interaction and π-π stacking interaction between d-UiO-66 and LOM. Therefore, the d-UiO-66 obtained by the solvent-free method can not only effectively upcycle PET plastic waster, but also efficiently remove LOM, demonstrating a potential routine to simultaneous address the solid PET waster and wastewater.

Rapid Waste Motor Oil Conversion into Diesel-Range Hydrocarbons Using Hydrochar as Catalyst: Kinetic Study and Product Characterization

Herein, raw and alkali-treated hydrochars from biomass waste are prepared as a highly active catalyst for the conversion of waste motor oil into diesel-like fuels. Among all materials, hydrochar obtained at 250 °C and subsequent alkali activation with KOH showed a 600% improvement of the kinetic constant from 0.0088 to 0.0614 m−1. Conversion values at the same conditions were also improved from 66 to 80% regarding thermal and catalytic cracking, respectively. Moreover, the activation energy was also reduced from 293 to 246 kJ mol−1 for thermal and catalytic cracking, respectively. After characterization, the enhanced catalytic activity was correlated to an increased surface area and functionalization due to the alkali activation. Finally, the liquid product characterization demonstrated that catalytic cracking is more effective than thermal cracking for producing hydrocarbons in the diesel range. In particular, hydrochar-based catalysts are suggested to promote the formation of specific hydrocarbons so that the carbon distribution can be tailored by modifying the hydrothermal treatment temperature.

Degradation mechanism and decomposition of sulfamethoxazole aqueous solution with persulfate activated by dielectric barrier discharge

ABSTRACT The present study focused on the degradation of sulfamethoxazole (SMX) aqueous solution and the toxicity of processing aqueous by the dielectric barrier discharge (DBD) activated persulfate (PS). The effects of input voltage, input frequency, duty cycle, and PS dosage ratio on the SMX degradation efficiency were measured. Based on the results of the Response Surface Methodology (RSM), SMX degradation efficiency reached 83.21% which is 10.54% higher than that without PS, and the kinetic constant was 0.067 min−1 in 30 min when the input voltage at 204 V (input power at 110.6 W), the input frequency at 186 Hz, the duty cycle at 63%, and the PS dosage ratio at 5.1:1. The addition of PS can produce more active particles reached 1.756 mg/L (O3), 0.118 mg/L (H2O2), 0.154 mmol/L (·OH) in 30 min. Furthermore, the DBD plasma system effectively activated an optimal amount of PS, leading to improved removal efficiency of COD, and TOC to 30.21% and 47.21%, respectively. Subsequently, eight primary by-products were pinpointed, alongside the observation of three distinct pathways of transformation. Predictions from the ECOSAR software indicated that most of the degradation intermediates were less toxic than SMX. The biological toxicity experiments elucidated that the treatment with the DBD/PS system effectively reduced the mortality of zebrafish larvae caused by SMX from 100% to 20.13% and improved the hatching rate from 55.69% to 80.86%. In particular, it is important to note that the degradation intermediates exhibit teratogenic effects on zebrafish larvae.

Compensación cinética y termodinámica del pardeamiento no enzimático de zumos clarificados de limón

This paper presents a study on kinetic and thermodynamic compensation to evaluate the kinetics of non-enzymatic browning of clarified lemon juices. In a previous work, the kinetic constants of browning were presented using the evolution of the absorbance at 420 nm (A420) and luminosity (L*) for different soluble solids contents (64.6; 50; 35; 20 and 10 ºBrix) and different working temperatures (70, 80, 90 and 95 ºC). The parameters of the Arrhenius equation were obtained by fitting the kinetic constants and temperatures. The variation of lnK0 with Ea follows a linear trend, so there is kinetic compensation, with isokinetic temperature values being 126.6 ºC and 149.7 ºC for A420 and L*, respectively. The transition state equilibrium constants were determined using the Eyring equation for each soluble solids content and each temperature. The equilibrium constants were adjusted to the Van't Hoff equation and the set of pairs of estimated values for the activation enthalpy and the activation entropy also followed a straight line, which causes thermodynamic compensation, with isoequilibrium temperatures of 112.8 ºC and 136.3 ºC for A420 and L*, respectively. It was concluded that the browning mechanism is the same for the ranges of soluble solids content and temperature studied. Since all isokinetic and isoequilibrium temperatures were higher than the working temperature values, it was also concluded that the control was enthalpic for all cases. To avoid the deterioration of these juices, it is advisable to intervene in the working temperature, trying to ensure that the heat treatment is carried out at the lowest possible temperature.

Highly efficient electrocatalysis of oxygen to hydroxyl radical by FeN2O2 single-atom catalyst for refractory organic pollutant removal

The heterogeneous electro-Fenton (Hetero-EF) provides an effective and environmentally friendly method for refractory pollutants removal by strongly oxidative •OH. However, the •OH generation shows an insufficient activity in activating H2O2 to •OH due to the too strong H2O2 binding on the catalytic site. Here, an iron single-atom FeN2O2 catalyst anchored on hollow spherical porous carbon (FeN2O2-HPC) was designed to enhance •OH production by modulating the H2O2 binding. The FeN2O2-HPC Hetero-EF system showed a •OH production rate of 25.0 μmol h−1 and kinetic rate constant of 2.06 h−1 for phenol removal, which exceeded the FeN4 catalyst (the most reported iron single-atom). Density function theory calculations revealed that FeN2O2 could lower the H2O2 adsorption energy and energy barrier of H2O2 activation to •OH compared with FeN4, thus enhancing •OH production. This work gives a new insight into the •OH generation enhancement of Hetero-EF by modulating single-atom coordination environment for refractory pollutants removal.

Efficient electro-Fenton degradation of organic pollutants via the synergistic effect of 1O2 and •OH generated on single Fe[sbnd]N4 sites

The electro-Fenton with in situ generated 1O2 and •OH is a promising method for the degradation of micropollutants. However, its application is hindered by the lack of catalysts that can efficiently generate 1O2 and •OH from electrochemical oxygen reduction. Herein, N-doped stacked carbon nanosheets supported Fe single atoms (Fe-NSC) with FeN4 sites were designed for simultaneous generation of 1O2 and •OH to enhance electro-Fenton degradation. Due to the synergistic effect of 1O2 and •OH, a variety of contaminants (phenol, 2,4-dichlorophenol, sulfamethoxazole, atrazine and bisphenol A) were efficiently degraded with high kinetic constants of 0.037–0.071 min−1 by the electro-Fenton with Fe-NSC as cathode (−0.6 V vs Ag/AgCl, pH 6). Moreover, the superior performance for electro-Fenton degradation was well maintained in a wide pH range from 3 to 10 even with interference of various inorganic salt ions. It was found that FeN4 sites with pyridinic N coordination were responsible for its good performance for electro-Fenton degradation. Its 1O2 yield was higher than •OH yield, and the contribution of 1O2 was more significant than •OH for pollutant degradation.

A novel dual S-scheme heterojunction photocatalyst KBCN/t-BiVO4/m-BiVO4 induced by phase-transformed bismuth vanadate for highly efficient degradation of ciprofloxacin in full-spectrum: Degradation pathway, DFT calculation and mechanism insight

A novel KBr-g-C3N4/t-BiVO4/m-BiVO4 (15KBCN/mtBVO-P, P means PVP) heterojunction photocatalyst is synthesized using a hydrothermal method with the assistance of surfactant polyvinylpyrrolidone (PVP). Field emission scanning electron microscope (FESEM), transmission electron microscope (TEM), and X-ray powder diffraction (XRD) confirm the formation of the heterostructure and changes in the crystal structure. Under sunlight illumination, 15KBCN/mtBVO-P exhibits the strongest photocatalytic degradation performance for ciprofloxacin (CIP), reaching 95.3 % within 240 min, the apparent kinetic constant is approximately 3.4, 2.4, and 3.3 times higher than CN, t-BVO, and m-BVO. The outstanding CIP degradation rate is observed under simulated solar and visible light, with over 93.0 % and 85.8 % in 60 min and 120 min. The enhanced photocatalytic performance is attributed to the in-situ generation of the mixed-phase BiVO4 by precise crystal phase regulation. Furthermore, the charge transport and photocatalytic degradation mechanism of 15KBCN/mtBVO-P is revealed. Degradation pathways and ecotoxicity of CIP and its degradation products were elucidated through LC-MS/MS technology, DFT calculations, and QSAR models. This study presents a pioneering perspective on the fabrication and development of g-C3N4-based dual S-scheme heterojunction photocatalysts for practical application.

Simultaneous degradation of pharmaceutical contaminants and sterilization in real hospital wastewater by a highly efficient electrocatalytic ozonation process: Performance, mechanism and application

Herein, this work investigated an electrocatalytic ozonation (ECO) strategy using stainless steel-graphite plates as cathode–anode for the degradation of the pharmaceutical pollutant dexamethasone (DXMS) and the treatment of real hospital wastewater. The reaction kinetic constant of the ECO degradation of DXMS (0.387 min−1) was 4 times higher than that of single ozone (0.087 min−1). The established efficient ECO system successfully degraded pharmaceutical contaminants and had excellent bactericidal effects against pathogenic microorganisms (Escherichia coli). The results of scavenging experiments, chemical probe experiments, and electron paramagnetic resonance (EPR) analysis indicated that the newly generated 1O2 in the ECO system achieved the synergistic effect of the combined EC-ozonation process. More to the point, the ECO system has a high removal rate of chemical oxygen demand (COD) and total organic carbon (TOC) for real hospital wastewater treatment. After 60 min treatment of the ECO system, the COD removal of hospital wastewater ranged from 70 % to 88.91 %, and the TOC removal ranged from 52.05 % to 71.81 %. The ECO system developed in this work has the capacity for simultaneous degradation of pharmaceutical contaminants and sterilization of pathogenic microorganism for hospital wastewater treatment.

Heterologous expression of nattokinase in E. coli: Biochemical characterization and functional analysis of fibrin binding residues

Heterologous expression of nattokinase, a potent fibrinolytic enzyme, has been successfully carried out in various microorganisms. However, the successful expression of this enzyme as a soluble protein was not achieved in E. coli. This study delves into the expression of nattokinase in E. coli as a soluble protein followed by its biochemical characterization and functional analysis for fibrinolytic activity. E. coli BL21C41 and pET32a vector host strain with pGro7 protein chaperone induced with IPTG at 16 °C 180 rpm for 16 h enabled the production of recombinant nattokinase in soluble fraction. Enzymatic assays demonstrated its protease activity, while characterization revealed optimal catalytic conditions at 37 °C and pH 8.0, with remarkable stability over a broad pH range (6.0–10.0) and up to 50 °C. The kinetic constants were determined as follows: Km = 25.83 ± 3.43 μM, Vmax = 62.91 ± 1.68 μM/s, kcat = 38.45 ± 1.06 s−1, and kcat/Km = 1.49 × 106 M−1 s−1. In addition, the fibrinolytic activity of NK, quantified by the fibrin plate hydrolysis assay was 1038 ± 156 U/ml, with a corresponding specific activity of 1730 ± 260 U/mg and the assessment of clot lysis time on an artificial clot (1 mg) was found to be 51.5 ± 2.5 min unveiling nattokinase's fibrinolytic potential. Through molecular docking, a substantial binding energy of −6.46 kcal/mol was observed between nattokinase and fibrin, indicative of a high binding affinity. Key fibrin binding residues, including Ser300, Leu302, and Asp303, were identified and confirmed. These mutants affected specifically the fibrin binding and not the proteolytic activity of NK. This comprehensive study provides crucial conditions for the expression of protein in soluble form in E. coli and biochemical properties paving the way for future research and potential applications in medicine and biotechnology.

Enhancing the conversion of waste motor oil into diesel-like fuels using mineral-impregnated biochar catalysts

This study shows how the presence of metal-impregnated biochar influences the kinetics of the catalytic conversion of waste motor oil (WMO) into a diesel-like fuel (DLF). First, the initial metal concentration in the wet impregnation process was optimized, showing that high metal concentrations tend to clog the biochar pores, reducing the reaction’s conversion and speed. Zinc and calcium showed higher kinetic constants at the optimized conditions than nickel, while the yield- and selectivity-to-liquid products were unaffected. Then, a reduction method was developed for impregnating metal particles of calcium oxide to enhance the metal dispersion at the biochar surface. This material showed the best performance in the reaction due to the presence of small particles instead of metal agglomerates. An increase of about 280% in the kinetic constant at 420 °C and a much lower activation energy (246 kJ mol−1) compared to the thermal cracking (308 kJ mol−1) was obtained. Finally, the DLF from the best catalytic system was analyzed. Interestingly, the fuel showed similar rheological properties to commercial diesel with a similar hydrocarbon distribution but with the presence of smaller hydrocarbon chains.

Highlighting the “structure–reactivity” relationship and the impact on the kinetics for the autoxidation reaction of hydrocarbons

The interactions between heteroatomic species and the hydrocarbons present in Jet A-1 make the determination of degradation mechanisms difficult to elucidate and predict. This study aims to investigate the reaction mechanisms and kinetics of hydrocarbon molecules constituting jet fuel, excluding molecules with polar species. Five model hydrocarbons were selected (n-dodecane and its isomeric mixture, n-butylcyclohexane, 1,2,4-trimethylbenzene and 1-methylnaphthalene) and individually subjected to oxidation using the PetroOXY apparatus, focusing on the onset of autoxidation (ΔP/Pmax = 2 to 10 %). For the first time, an experimental protocol has been developed for the monitoring of gas and liquid phase reagent consumption and the identification and quantification of oxidation products formed in these phases. The results showed that oxygen consumption was always higher than that of the initial hydrocarbons, suggesting competitive reactions, with alkanes consuming more oxygen than aromatic molecules, as confirmed by induction periods (IP), demonstrating the different reactivity depending on the structure of the oxidized hydrocarbon molecule. A relationship between initial hydrocarbon structure and the type and number of carbon atoms in oxidation products was also demonstrated. A gel, probably a precursor deposit, was obtained after oxidation of the molecules, indicating a potential precipitation of polar species due to the difference in polarity with the hydrocarbon molecules. In addition, the overall kinetic and hydroperoxide dissociation constants of the reaction could be calculated from tests carried out at different temperatures (140, 150 and 160 °C). The Arrhenius parameter values were higher for alkanes than for aromatics, confirming the structure–reactivity relationship of hydrocarbons. A strong correlation between the Arrhenius parameters and the nature of the oxidized molecules was also demonstrated. This experimental study will be useful for the calibration of future kinetic models according to the chemical structure of the oxidized hydrocarbons and for the assessment of thermal stability behavior of 100 % Synthetic Alternative Fuels (SAF).

Enhanced Piezocatalytic Performance of Li-doped BaTiO3 Through a Facile Sonication-Assisted Precipitation Approach.

Piezocatalysis-induced dye degradation has garnered significant attention as an effective method for addressing wastewater treatment challenges. In our study, we employed a room-temperature sonochemical method to synthesize piezoelectric barium titanate nanoparticles (BaTiO3: BTO) with varying levels of Li doping. This approach not only streamlined the sample preparation process but also significantly reduced the overall time required for synthesis, making it a highly efficient and practical method. One of the key findingswas the exceptional performance of theLi-doped BTO nanoparticles. With 20 mg of Li additive, we achieved 90% removal of Rhodamine B (RhB) dye within a relatively short timeframe of 150 minutes, all while subjecting the sample to ultrasonic vibration. This rapid and efficient dye degradation was further evidenced by the calculated kinetic rate constant, which indicated seven times faster degradation rate compared to pure BTO. The enhanced piezoelectric performance observed in the Li-doped BTO nanoparticles can be attributed to the strategic substitution of Li atoms, which facilitated a more efficient transfer of charge charges at the interface. Overall, our study underscores the potential of piezocatalysis coupled with advanced materials like Li-doped BTO nanoparticles as a viable and promising solution for wastewater treatment, offering both efficiency and environmental sustainability.

Biochar-derived organic carbon promoting the dehydrochlorination of 1,1,2,2-tetrachloroethane and its molecular size effects: Synergies of dipole-dipole and conjugate bases

The environmental effects of biochar-derived organic carbon (BDOC) have attracted increasing attention. Nevertheless, it is unknown how BDOC might affect the natural attenuation of widely distributed chloroalkanes (e.g., 1,1,2,2-tetrachloroethane (TeCA)) in aqueous environments. We firstly observed that the kinetic constants (ke) of TeCA dehydrochlorination in the presence of BDOC samples or their different molecular size fractions (<1 kDa, 1∼10 kDa, and >10 kDa) ranged from 9.16×103 to 26.63×103 M−1h−1, which was significantly greater than the ke (3.53×103 M−1h−1) of TeCA dehydrochlorination in the aqueous solution at pH 8.0, indicating that BDOC samples and their different molecular size fractions all could promote TeCA dehydrochlorination. For a given BDOC sample, the kinetic constants (ke) of TeCA dehydrochlorination in the initial pH 9.0 solution was 2∼3 times greater than that in the initial pH 8.0 solution due to more formation of conjugate bases. Interestingly, their DOC concentration normalized kinetic constants (ke/[DOC]) were negatively correlated with SUVA254, and positively correlated with A220/A254 and the abundance of aromatic protein-like/polyphenol-like matters. A novel mechanism was proposed that the C-H dipole of BDOC aliphatic structure first bound with the C-Cl dipole of TeCA to capture the TeCA molecule, then the conjugate bases (-NH-/-NH2 and deprotonated phenol-OH of BDOC) could attack the H atom attached to the β-C atom of bound TeCA, causing a C-Cl bond breaking and the trichloroethylene formation. Furthermore, a fraction of >1 kDa had significantly greater ke/[DOC] values of TeCA dehydrochlorination than the fraction of <1 kDa because >1 kDa fraction had higher aliphiticity (more dipole-dipole sites) as well as more N-containing species and aromatic protein-like/polyphenol-like matters (more conjugate bases). The results are helpful for profoundly understanding the BDOC-mediated natural attenuation and fate change of chloroalkanes in the environment.

Kinetics of ascorbate and dithiothreitol oxidation by soluble copper, iron, and manganese, and 1,4-naphthoquinone: influence of the species concentration and the type of fluid

An alternative metric to account for particulate matter (PM) composition-based toxicity is the ability of PM-species to generate reactive oxygen species (ROS) and deplete antioxidants, the so-called oxidative potential (OP). Acellular OP assays are the most used worldwide, mainly those based on ascorbic acid (AA) and dithiothreitol (DTT) depletion; OP values are calculated from AA/DTT concentration over time kinetic curves. Since a great variability in OP-DTT and OP-AA values can be found in the literature, the understanding of those factors affecting the kinetic rate of AA and DTT oxidation in the presence of PM-bound species will improve the interpretation of OP values. In this work, a kinetic study of the oxidation rate of AA and DTT driven by species usually found in PM (transition metals and naphthoquinone (NQ)) was carried out. In particular, the influence of the concentration of Cu(II), Fe(II), Fe(III), Mn(II), Mn(III), and 1,4-NQ, and the type of fluid used in the assay (phosphate buffer (PB), phosphate buffer saline (PBS) and artificial lysosomal fluid (ALF)) is analysed and discussed. The reaction orders with respect to the AA/DTT and the active compound, and the kinetic rate constants were also determined. The results show great variability in OP values among the studied species depending on the fluid used; the OP values were mostly higher in PB0.05M, followed by PBS1x and ALF. Moreover, different species concentration-responses for OP-DTT/OP-AA were obtained. These differences were explained by the different reaction orders and kinetic rate constants obtained for each active compound in each fluid.

Cellulose nanocrystals mediated spontaneous weaving of ZIF-67 hybrid networks: Enhanced peroxymonosulfate activation and rapid removal of dye

Inter-connected zeolite imidazolate framework-67 (ZIF-67) hybrid networks were successfully synthesized by a cellulose nanocrystals (CNCs) mediated spontaneous weaving strategy, which was denoted as ZIF-67@CNC, and was applied to activate peroxymonosulfate (PMS) for Rhodamine B (RhB) degradation. Characterizations results demonstrated that the ZIF-67 nanocrystals are encapsulated within CNCs and subsequently arranged in a string-like configuration. In comparison to pristine ZIF-67, the ZIF-67@CNC catalyst presented superior performances for RhB dye removal both in terms of degradation efficiency and rate, as the kinetic rate constant increased 5.8-fold. This finding was attributed to the improvement in oxygen-containing groups and meso/microporous structures after the introduction of CNCs, leading to efficient binding to compounds and rapid molecular diffusion. Moreover, the ZIF-67@CNC exhibited remarkable stability throughout the catalysis process in aqueous solutions owing to the robust crosslinking between negatively charged CNCs and positively charged cobalt ions, which significantly mitigated the potential secondary pollution of cobalt to the environment. This research opens up new possibilities for the design of highly efficient and durable ZIF-67-based catalysts to promote future wastewater treatment technology.

Transient spectroscopic insights into nitroindole’s T1 state: Elucidating its intermediates and unique photochemical properties

Indoles are notable for their distinct photophysical and photochemical properties, making them useful indicators in biological systems and promising candidates for a variety of pharmaceutical applications. While some indoles exhibit room temperature phosphorescence, such a phenomenon has not been observed in nitroindoles. Typically, adding of a nitro group into aromatic compounds promotes ultrafast intersystem crossing and increases the formation quantum yield of the lowest excited triplet (T1). Therefore, understanding the reactivity of nitroindoles’ T1 states is imperative. This study investigated the physical properties and chemical reactivities of the T1 state of 6-nitroindole (3HN-6NO2) in both polar aprotic and protic solvents, using transient absorption spectroscopy. Our results demonstrate the basicity and acidity of 3HN-6NO2, emphasizing its potential for protonation and dissociation in mildly acidic and basic conditions, respectively. Furthermore, 3HN-6NO2 has a high oxidizing capacity, participating in electron transfer reactions and proton-coupled electron transfer to produce radicals. Interestingly, in protic solvents like alcohols, 3HN-6NO2 dissociates at the –NH group and forms N-H…O hydrogen-bonded complexes with the nitro group. By identifying transient absorption spectra of intermediates and quantifying kinetic reaction rate constants, we illuminate the unique properties of the T1 state nitroindoles, enriching our understanding of their photophysical and photochemical behaviors. The results of this study have significant implications for their potential application in both biological systems and materials science.

Degradation of diethyl phthalate by photolysis of hydrogen peroxide electrogenerated using a Printex L6 carbon modified with Benzophenone cathode in an improved tangential flow cell

In this work, a gas diffusion electrode (GDE) made of Printex L6 carbon modified with 2.0% w/w of benzophenone-3,3′,4,4′-tetracarboxylic dianhydride (PL6C/BTDA 2%) was employed as cathode in a new 3D printed electrochemical cell with tangential flow. With this configuration, the performance of the technology was evaluated for hydrogen peroxide (H2O2) electrogeneration and remediation of aqueous wastes contaminated with diethyl phthalate (DEP) using different H2O2-based advanced oxidation processes (AOPs). The electrogeneration study was carried out varying the current density applied to the system, and it was found that 50mAcm-2 was the best performing value, resulting in remarkable faradaic efficiencies of nearly 100%. This led to the production of higher amounts of H2O2 (442.5mgL-1) in 90minutes at an acceptable energy consumption (8.5 kWh kg-1) compared to values reported in the literature. Based on these findings, H2O2-based AOPs were employed to investigate the removal of DEP in cathodic compartment, including mediated electrochemical degradation with electrogenerated H2O2 (e-H2O2) and the integration of this technology with ultraviolet-C (UVC) photolysis (e-H2O2/UVC). The integrated e-H2O2/UVC obtained the best performance compared to single photolysis and e-H2O2, leading to the total elimination of DEP (90 μmol L-1) within only 30min of treatment, reaching the highest kinetic rate constant (0.3min-1). Fifteen by-products, generated through oxidation processes studied, were successfully identified by LC-MS/MS, enabling the proposal of the degradation mechanism of DEP.