Kinetic Analysis Research Articles

Abstract PO2-01-01: Biophysical simulation using DCE-MRI to forecast response to NAT in HER2+ patients, with glucose characterization and orthogonal validation using FDG-PET

Abstract Background: Metabolic reprogramming and tumor angiogenesis are two tightly linked hallmarks of cancer. Regions of high metabolic activity within a tumor can become hypoxic or nutrient starved, eliciting a cascade of pro-angiogenic signals that can lead to increased tumor perfusion and in turn greater metabolic activity. Dynamic contrast enhanced magnetic resonance imaging (DCE-MRI) and 18Fluorodeoxyglucose (FDG) positron emission tomography (PET) are two imaging methods commonly used in the diagnosis of cancer; the former can be also used to identify the perfusion of the tumor microenvironment (TME) and the latter provides a coarse readout of glucose metabolic activity. Here, we are presented with a unique cohort of patients who underwent DCE-MRI, 18FDG-PET and 64Cu-DOTA-Traztuzumab offering potential to perform a pilot analysis. First, we characterize the performance of our perfusion model SimBioSys- Microvasculature (SBS-MV) through a stability analysis, as well as comparison with two PET modalities. Finally, we use this model in 3D simulations of individual HER2+ breast cancer patients to forecast responses to neoadjuvant chemotherapy (NAT). Methods: SBS-MV is a modified Tofts model for pharmacokinetic modeling of DCE-MRI data, utilizing a tissue segmentation model developed in-house to inform parameter fits and ensure that the derived parameters fall within acceptable values on a tissue-by-tissue level, in addition its function for standard fitting of DCE time-course data. We first evaluated the stability of the SBS-MV model by analyzing a separate cohort of 10 patients who underwent ultrafast DCE-MRI. Temporal undersampling was performed on the original high temporal resolution data to mimic low temporal resolution from standard-of-care (SoC) DCE studies. Both datasets were processed with SBS-MV model. Next, we analyzed data from a cohort of 18 patients, each of whom underwent a pre-NAT SoC DCE-MRI study, a mid-treatment FDG PET/CT study, and a mid-treatment 64Cu-DOTA-Trastuzumab/CT study during treatment. Tissue segmentation and SBS-MV fits were performed on the pre-NAT DCE MRI. Tightly cropped boxes encompassing the tumor in the 3D SBS-MV volumes as well as the PET volumes were created. Using these identified regions, all summary statistics were calculated and cross-correlated between imaging modalities. Results: SBS-MV was stable to SoC-mimicking temporally undersampled ultrafast DCE MRI series, demonstrating relatively little variability in the output parameters (a voxel wise median deviation of approximately 0.005 min-1 ). Further, we demonstrate that SBS-MV parameters (Ktrans, ve) are correlated with FDG SUVSA and 64Cu SUVSA. In addition, the glucose concentrations used in the biophysical simulations were correlated with FDG SUVSA, indicating that downstream applications of the SBS-MV models still carry this information about perfusion. Finally, using SBS-MV, our biophysical simulations of HER2-targeted therapy accurately predict patient response. In this small cohort, our biophysical simulation platform performed well, yielding predictive accuracy of 0.83, with sensitivity and specificity of 0.83 and 0.83, respectively. These performance metrics are in line with previously published reports. Conclusion: Our MV model is capable of extracting biologically meaningful perfusion parameters from standard clinical DCE MRI time series, providing the same benefits of a comprehensive kinetic analysis, without impacting current clinical workflow. This approach could be used in both the research and clinical settings, offering actionable information on what drives individual patient therapeutic response for a more personalized care. Citation Format: John Whitman, Vikram Adhikarla, Russell Rockne, Lusine Tumyan, Joanne Mortimer, Wei Huang, Joseph Peterson, Dorys Lopez-Ramos, John Cole. Biophysical simulation using DCE-MRI to forecast response to NAT in HER2+ patients, with glucose characterization and orthogonal validation using FDG-PET [abstract]. In: Proceedings of the 2023 San Antonio Breast Cancer Symposium; 2023 Dec 5-9; San Antonio, TX. Philadelphia (PA): AACR; Cancer Res 2024;84(9 Suppl):Abstract nr PO2-01-01.

Leveraging digital assets: lessons from a 14-year-old isotope tracer course for professional scientists.

The COVID-19 pandemic and subsequent policies (e.g., social distancing, travel restrictions) challenged both organizers for and attendees of programs typically held in-person. Many scientific training programs quickly adapted to virtual formats by incorporating digital assets developed for virtual learning and remote social engagement. At the outset, the value of continuing digital elements with future in-person events was unclear. To examine how virtual resources supported heterogeneous professional training programs, we reviewed survey data for a 14-year-old training program for scientific professionals titled Isotope Tracers in Metabolic Research: Principles and Practice of Kinetic Analysis. We found a positive relationship between survey satisfaction and the post-pandemic, in-person program that included digital assets held in 2022 when compared to pre-pandemic in-person programs. To better understand the post-pandemic program satisfaction, we assessed the 2021 virtual course format and survey data. We found that although there was a desire to return to in-person programs, the digital assets and approaches were valued. In examining the individual programmatic elements in the 2022 in-person course, there was better "value and understandability" of lectures over previous in-person years. These findings highlight how incorporating new digital engagement strategies for professional development benefit even the most established programs in supporting heterogeneous learners.

A review of methane-driven two-step thermochemical cycle hydrogen production

Solar thermochemical cycling is a promising approach to utilizing solar energy to produce H2 and CO, which can be further synthesized into liquid fuels via Fischer-Tropsch reactions, making storage and transportation easier. Despite the potential high theoretical efficiency, factors such as the high temperature and low oxygen partial pressure required for the reduction restrict the large-scale application of this technology. In the near-to-medium term, in order to accelerate the popularization and application of this technology, according to Le Chatelier's principle, the assisted reduction of methane can greatly reduce the demand for high-temperature materials and ultra-low oxygen partial pressure. However, the addition of methane will also bring additional challenges, such as carbon emissions and carbon deposition. Reducing the influence of factors such as material sintering and irreversible loss on system efficiency in the experiment will be essential for the development of this technology. This paper focuses on the methane-driven two-step thermochemical cycle hydrogen production process, summarizes its reaction mechanism, thermodynamic analysis, kinetic analysis, oxygen carrier material doping, and experimental research in detail, and comprehensively analyzes the effect of material properties and irreversible loss on the system. According to thermodynamic and kinetic analysis, rational selection and doping of metal oxygen carrier materials can effectively reduce the reaction temperature, improve gas production rates, and enhance structural stability. Analyzing and trying to reduce various irreversible losses of the system, such as reradiation energy loss, conduction energy loss, etc., and taking appropriate heat recovery measures will help to improve the system efficiency of the actual cycle. This paper would be valuable for the development of this technology and for achieving the goal of carbon neutrality.

Controllable introduction of edged nitrogen sites in CVD-derived carbon materials for enhanced fenton-like reactions

Nitrogen doped carbon materials have great potential in the peroxymonosulfate based advanced oxidation processes due to their high efficiency. However, because of the limitation of prepared method, the doped N species are usually uncontrollable. In this work, a series of metal-free N-doped carbon materials are synthesized by chemical vapor deposition (CVD) with a CaO template and through regulating the deposition temperature we achieve the gradient control of the edged-N species. Taken phenol as the pollutant probe, the catalytic performances of N-doped carbon material are investigated, and 700 °C is determined to be the optimal deposition temperature for carbon material with a reaction rate constant of 0.335 min−1. After the analysis of kinetics and the N species, we demonstrate that the content of pyrrolic N has an exponential relationship with the activity. Radicals quenching experiments, electron paramagnetic resonance and electrochemical test are also employed to verify that O2•–, 1O2, and direct electron transfer are the dominated reactive oxidation species rather than typic hydroxyl and sulfate radicals. Overall，this doped strategy through CVD give a new insight of controlling doped species in carbon materials preparation.

Unveiling kinetics post rate-determining step in Brønsted acid-catalyzed reactions of fructose: A strategy for 5-hydroxymethylfurfural production from concentrated feedstock

The development of high-yielding catalytic systems is pivotal in biomass upgrading. However, the investigation of kinetics in these complex reaction systems is often highly challenging, especially when reactions leading to byproduct formation are obscured by a preceding, slow rate-determining step. In this work, we introduce a unique approach to kinetic analysis that enables the investigation of reactions occurring post rate-determining step. The technique was applied to the conversion of sugars to 5-hydroxymethylfurfural (HMF), an important platform molecule for sustainable chemical production. First, screening experiments were carried out to identify a catalytic solvent system that achieves a balance between solvent stability, HMF yield, and cost-effectiveness. Our kinetic analysis on the identified system reveals that the fructose reactant undergoes a rate-determining dehydration step to form an unstable reactive intermediate. This intermediate further reacts competitively with other reactive species, such as the hexose reactants or the HMF product, ultimately lowering the HMF selectivity. The calculated relative activation energies of these reactions post rate-determining step provide intuitive insights into the effects of temperature, co-existing reactive species, as well as the previously unexplained effect of feed concentration on HMF selectivity. Additionally, we propose a novel reaction strategy that significantly enhances HMF yield when compared to a traditional batch synthesis. Notably, a high HMF yield of 74 % was achieved with an extreme 55 wt% fructose loading on an aqueous basis (20 wt% loading on a total weight basis) in a low-boiling 80 wt% dioxane/water mixture using an HCl catalyst at 393 K.

Kinetics study of photocatalytic oxygen indicator reactions

The indicators are comprised of TiO2, Remazol Brilliant Blue R, glycerol, and polymer. Two different polymer matrices, poly(vinyl acetate) (PVAC) or (carboxy)methyl cellulose (CMC) were used. The indicators were printed on a plastic foil and covered with a UV curable coating. Data for the kinetic study of photocatalytic reduction and oxidation were gathered with reflectance spectrophotometer and the kinetic analysis was based on the change of the indicator's optical density. Both indicators were successfully activated with UVA and both detected oxygen. The rate of oxidation depended on percentual oxygen concentration, increasing with increasing oxygen concentration. The PVAC based indicator was much quicker to detect oxygen than its CMC counterpart, the former having a color change response to oxygen that is easily detected by naked eye in just one minute.

Investigation of the kinetics of imidacloprid adsorption onto bimetallic Cu-BTC MOF

Imidacloprid, which is harmful for humans as well as many other aquatic invertebrate species, is extensively present in water worldwide. Hydrophobic Cu-BTCIPA and a novel composite, Ag@Cu-BTCIPA, was synthesized for adsorption of imidacloprid from water. The synthesis of the composite and the increase in surface area and pore volume were confirmed by FTIR, XRD, SEM, and BET analysis. A comparative study of the adsorption efficiencies of the synthesized composites was performed. The maximum adsorption efficiency achieved was 83.6 % at pH 7 by the Ag@Cu-BTCIPA composite. Kinetic and isotherm analyses suggested multilayer chemisorption involving p-p conjugation and pore-filling mechanisms. Intra-particle diffusion was the rate limiting step. Release studies of imidacloprid from water showed that the percentage release amount was 90.2 % at 70 min. Kinetic analysis of the release process suggested release through chemisorption, with swelling-controlled release from the dosage form, corresponding to the super case II transport mechanism.

Screening of monoamine oxidase B inhibitors in Tibetan strawberry by ligand fishing based on enzyme functionalized cellulose filter paper

Tibetan strawberry (Fragaria nubicola) is a wild medicinal and edible plant in Tibet possessing various health benefits such as neuroprotection and anti-oxidation. However, there has been little study reported on its chemical constituents. To investigate the inhibitors of monoamine oxidase B (MAO-B) in Tibetan strawberry, we immobilized the enzyme onto cellulose filter paper for the first time to develop a new screening method. Two known glycosides (compounds 1 and 2) and one new iridoid glucoside (Compound 3) were fished out by this method, which was found to effectively inhibit MAO-B with IC50 values of 16.95 ± 0.93, 24.69 ± 0.20, and 46.77 ± 0.78 μM, respectively. Molecular docking and kinetic analysis were performed to reveal the inhibition mechanism of these compounds. Furthermore, compound 1 exhibited neuroprotective effects against 6-OHDA-induced injury on PC12 cells. The developed method exhibits the advantages of rapidness and effectiveness in screening of MAO-B inhibitors from complex herbal extracts.

Slow precipitate coarsening kinetics in extremely fine nanograined Ni-Cr alloys

Grain boundaries significantly influence the nucleation and growth of precipitates in supersaturated solid solutions. However, due to the inherent instability of grain boundaries in nanograined metals, the precipitation process usually occurs concurrently with grain growth during thermal annealing, making it difficult to reveal the grain size effect on the precipitate coarsening behavior. In this study, nanograined Ni-48Cr (at.%) supersaturated alloys with grain sizes ranging from about 85 nm to 10 nm were fabricated by plastic deformation, in which the relaxed grain boundaries led to the extremely fine nanograined structure having good thermal stability. During the high-temperature annealing process, nanoscale Cr particles were precipitated from the nanograined matrix, forming a nanograined dual-phase structure. The growth kinetics of the Cr precipitates in the extremely fine nanograined structures are different from the larger grain size samples, showing a trend that the smaller the as-deformed grain size, the slower the precipitate coarsening rate. Detailed microstructural characterization and kinetic analysis indicate that the extremely fine nanograined structure may change the rate-limiting process for precipitate coarsening from lattice diffusion to grain boundary diffusion as grain size is refined to about a few tens nanometers, which leads to a slow coarsening rate. The nanograined dual-phase Ni-Cr alloy of the annealed 10 nm sample shows the highest strength among these samples as well as excellent thermal stability, which provides guidance for the design of high-performance alloys.

Catalytic performance of Pd catalyst supported on CeO2 or ZrO2 modified beta zeolite for methane oxidation

Two kinds of oxide-zeolite composite support, Ce-beta and Zr-beta were prepared by a simple wet impregnation method and adopted for the preparation of palladium-based catalysts for catalytic oxidation of methane. The Pd/6.8Zr-beta catalyst showed superior methane oxidation performance, achieving T50 and T90 of 417 °C and 451 °C, respectively, together with robust hydrothermal stability. Kinetic analysis has shown that incorporating Zr into the catalyst significantly enhanced its efficiency, nearly tripling the turnover frequency (TOF) for methane combustion compared to the Pd/beta catalyst. This enhanced performance was attributed to the dispersion of Zr on the zeolite surface, which not only promoted the formation of active PdO sites but also helped maintain the high Pd2+ content via facilitating the oxygen migration during the reaction, thus improving both the catalyst's activity and stability. In the Pd/8.6Ce-beta catalyst, doped CeO2 tended to aggregate in the zeolite's pores, adversely affecting the catalyst's efficiency. This aggregation promoted the formation of inactive Pd4+ species, a result of the enhanced metal-support interaction. This finding is critical for understanding the implications of dopant selection in the design of high-activity methane oxidation catalysts.

Poly (ionic liquid) cross-linked hydrogel encapsulated with AuPt nanozymes for the smartphone-based colorimetric detection of zearalenone

A poly (ionic liquid) enhanced poly(acrylamide-acrylic acid) (PIL-PAM/AA) hydrogel-based colorimetric sensor was designed to detect zearalenone (ZEN). Different AuxPty nanoparticles were synthesized via the on-pot method. Through the kinetic analysis and the theoretical calculation, Au0.4Pt0.6 possessed the relatively low energy barriers to adsorb and decompose H2O2 so that it exhibited relatively better catalytic activity (Km = 2.02 × 10−3, Vmax = 6.14 × 10−7). AuPt nanoparticles were encapsulated into PIL-PAM/AA hydrogel via the interaction between aptamer and cDNA. In the presence of ZEN, the embedded AuPt nanoparticles were released to complete the catalytic reaction. Coupled with the smartphone application, the established method provided the linear range of 1–250 ng mL−1, with a detection limit of 0.6979 ng mL−1 for ZEN. Meanwhile, it also possessed excellent selectivity and good anti-interference performance. In wheat and corn samples, spiked recoveries were ranging from 75% to 113.30%.

Effect of pretreatment and activation conditions on pore development of coal-based activated carbon

Abundant pore volume and appropriate pore configuration are two crucial characteristics of high-performance carbonaceous adsorbents and catalysts. In this study, influences of pre-treatments (e.g., breaking, sieving and ash removal by acid) and activation conditions (e.g., activation time) on pore parameters (including BET surface area, pore diameter and pore hierarchy degree) of resultant activated carbon were systematically investigated. In addition, the difference between conventional carbonization-activation (i.e., the two-step preparation method) and one-step activation in pore development of activated carbons was revealed. The sample prepared by a 120-minute one-step activation exhibited a BET surface area high to 1038.1 m2/g and a pore hierarchy at 50.7 %. Based on the kinetics analysis using TGA reactor, reaction between the activator (i.e., CO2) and carbon matrix was enhanced in one-step activation, contributing to the generation of mesopores. Remarkably, a new indicator, Effective Activation Rate (EAR) was proposed to accurately describe the activation rate in one-step synthesis after decoupling the release of moisture and volatile compounds. The above conclusions provide guidance for flexibly regulating the pore configurations of activated carbons derived from natural precursors.

Reaction mechanism and kinetics for Pt/C and Au/C catalyzed aqueous phase glycerol oxidation to various carboxylic acids

Fundamental understanding of heterogeneously catalytic aerobic oxidation of polyol is highly desirable for sustainable and efficient chemical synthesis. Herein, based on the purpose of exploring the selectivity of various carboxylic acids on Pt-Au catalysts with different ratios, we conducted a comprehensive investigation into the reaction pathways of glycerol oxidation over pristine Pt/C and Au/C catalysts via experiments, kinetics analysis and DFT calculations. Structural characterizations revealed that Pt/C exhibits a higher metallic state and more d electrons, thus tending to strongly adsorb OH– and promote oxygen activation. Conversely, the weak oxygen activation of Au/C could be attributed to fewer cationic high valence state and d electrons. Furthermore, the Langmuir-Hinshelwood kinetic model and DFT calculations indicate both catalysts exhibit obvious differences in product distribution. Specifically, Pt demonstrated higher selectivity towards lactic acid by facilitating dehydration of C-OH in glyceraldehyde and promoting timely desorption of lactic acid species. In contrast, Au displayed more glycolic acid products caused by strengthening oxidative cleavage of C-C bond in glyceric acid. Expanding to bimetallic catalysts, it was observed that catalysts with higher Au content exhibit enhanced selectivity towards the oxidation of glyceric acid to glycolic acid, while those with a higher Pt ratio demonstrate increased selectivity for the oxidation of glycerol to lactic acid. These findings provide valuable insights for guiding the design and optimization of this catalytic process to achieve targeted product generation.

Investigation for flavanone synthesis in subcritical water with La-ZrO2, Mg-ZrO2, and Ca-ZrO2 as solid base catalysts

In this study, flavanone was synthesized via a two-step process, Claisen–Schmidt condensation between 2’-hydroxyactophenone and benzaldehyde followed by isomerization, in subcritical water with ZrO2 based catalysts. Kinetic analysis was conducted to quantitatively show the catalytic activity of different modified ZrO2. The activity of ZrO2 was improved upon incorporating with active metal species. Compared with La-ZrO2 and Mg-ZrO2, Ca-ZrO2 showed the highest activity attributed to strong basicity, but substantial formation of side product and loss of product were observed. La-ZrO2 showed weaker activity than Mg-ZrO2, though La-ZrO2 had higher basicity. One explanation was the dissociation of water to provide OH− on the catalyst surface was more challenging since containing significantly more active sites with strong water affinity. Moreover, such active sites contributed less to reaction due to dense water surrounding the catalyst surface. The reaction catalyzed by Mg-ZrO2 reached flavanone selectivity of 72.2% in 3hours at 150 °C.

Mechanism of phenols evolution during pyrolysis of Shendong coal macerals swelled with oxygen-containing organic solvents: Experimental and DFT study

Phenols are the important high value-added chemical product of coal tar, and exploring the release behavior of phenols is crucial for clarifying the coal pyrolysis mechanism and regulating the product distribution. The aim of this paper is to investigate the effects of swelling on the pyrolytic properties of de-ashed vitrinite (VD) and de-ashed inertinite (ID). VD and ID prepared by Shendong coal were characterized by 13C NMR, XPS and FTIR to explore physicochemical properties. Acetic acid (AA), ethanol (EA) and acetone (AT) were employed to prepare the swelled VD (VD-AA, VD-EA and VD-AT) and swelled ID (ID-AA, ID-EA and ID-AT). Kinetic analysis was carried out using thermogravimetry, the pyrolysis characteristics and distribution of pyrolysis products were analyzed by fast pyrolysis–gas chromatography/mass spectrometry (Py-GC/MS) and fast pyrolysis fixed bed. Combining with density functional theory (DFT), the possible pyrolysis pathways of phenols generation were proposed. As a result, the macromolecular structures of VD and ID are constructed. TG and kinetic analysis exhibit that swelling promotes the pyrolysis of VD and ID, and the activation energy of the second stage is VD > VD-EA > VD-AT > VD-AA and ID > ID-EA > ID-AT > ID-AA, respectively. Py-GC/MS analysis exhibits that the selectivity of phenol, cresol, xylenol and catechol decreases to 17.53 % (VD-AA) and 12.18 % (ID-AT). By analyzing and comparing the distribution of the full component of Py-GC/MS, seven possible pathways of cresol generation are proposed. DFT calculation exhibits that Path 3 of VD-AT, which produces cresol via sequential decarboxylation, ether bond cleavage, decarbonylation, aliphatic side chain removal and dehydroxylation, demonstrates the lowest reaction energy of −148.38 kJ/mol.

Heterostructure CoSe2/Sb2Se3 Nanocrystals Embedded into Nanocage-in-Nanofiber Carbon Framework for Ultralong-Life Sodium-Ion Batteries

Transition metal selenides are considered as one of the most promising anode materials for sodium-ion batteries (SIBs) on account of their high theoretical specific capacity. However, the poor conductivity, sluggish kinetics and volume expansion during the (de)sodiation process hinder its application. Herein, a novel heterostructure of CoSe2/Sb2Se3 nanocrystals embedded into nanocage-in-nanofiber carbon framework is designed and constructed via electrospinning, carbonization, ion exchange and selenization processes. In this structure, bimetallic selenide heterostructure accelerates electron/ion transfer kinetics and Na+ adsorption capacity, carbon nanocages structure alleviates the volume expansion and maintains structural integrity during the (de)sodiation process, and carbon nanofibers connect the nanocages in series to shorten the electron transmission path and enhance electrical conductivity. As a self-supporting anode for SIBs, as-synthesized CoSe2/Sb2Se3@C@CNF shows a high reversible capacity of 406 mAh g-1 at 0.2Ag-1 after 200 cycles and displays excellent rate capability. More remarkably, the CoSe2/Sb2Se3@C@CNF anode manifests an outstanding cycling stability for over 2000 and 12,000 cycles at 1 and 5Ag-1, with the capacity retention being 97% and 103% respectively. Meanwhile, the excellent sodium storage performance is revealed by kinetic analysis, energy level analysis and density functional theory calculations.

Electrochemical Characterization of Nickel/Gadolinia Doped Ceria Fuel Electrodes under H2/H2O/CO/CO2-Atmospheres

Modelling of the co-electrolysis process requires understanding of the underlying reaction pathways under H2/H2O/CO/CO2-atmospheres. These include the electrochemical steam reduction/hydrogen oxidation, the electrochemical CO2 reduction/CO oxidation and their coupling via the catalytic (reverse) water gas shift reaction ((R)WGS). The assumption of a very fast RWGS and therefore neglectable electrochemical CO2 conversion is commonly used to model the co-electrolysis process. In contrast, previous studies on Ni/GDC fuel electrodes suggest that the electrochemical conversion of CO/CO2 can be present in H2/H2O/CO/CO2-atmospheres. To deconvolute surface-related and non-surface-related processes in the impedance response we present results from a complex variation of operating parameters for process identification by the use of electrochemical impedance spectroscopy and the subsequent impedance analysis by the distribution of relaxation times. A physically meaningful equivalent circuit model, based on a single channel transmission line, is then derived. The model enables quantification of the surface reaction resistance under varied C/H-ratios. From a kinetic analysis it is shown that the electrochemical H2/H2O conversion is dominant for yCO+yCO2≤ 50% and electrochemical CO/CO2-conversion onsets from yCO+yCO2 ≥ 60%.

Novel magnetic N-doped biochar derived from sugarcane bagasse and red mud for effective adsorption of tetracycline hydrochloride

In this work, with sugarcane bagasse (SB) and red mud (RM) as raw materials, magnetic nitrogen (N)-doped biochar (MNSB) was synthesized by a facile one-pot pyrolysis method and then applied as an efficient adsorbent to remove tetracycline hydrochloride (TC-HCl) from wastewater. The results of SEM, EDS, VSM, BET, FT-IR, and XPS demonstrated that the synthesized MNSB adsorbent had a large specific surface area, excellent superparamagnetic properties, and rich mesopore pore structures. The batch adsorption experiments revealed that the TC-HCl could be removed 96.3% with the optimal adsorption conditions: MNSB dosage of 0.25g/L, initial pH of 6.58, TC-HCl initial concentration of 20mg/L, and adsorption temperature of 30oC. The analysis of adsorption kinetics and isotherms showed that the adsorption process was mainly controlled by chemisorption, and the theoretical maximum adsorption capacity of TC-HCl on MNSB was 143.9mg/g. Mechanistic analysis revealed that the excellent adsorption process of MNSB for TC-HCl was mainly contributed by pore filling, π–π interaction, hydrogen bonding, and electrostatic attraction. The recycling and settlement experiments demonstrated that MNSB had good stability and settleability. This study successfully opened new prospects that utilizing RM and SB to prepare a low-cost adsorbent to remove TC-HCl from water.

Isothermal Reduction and Comparative Analysis of Reaction Kinetics of Sponge Iron Produced from Heamatite-Charcoal Reaction Using Non-contact Direct Reduction Method

The challenge of making sponge iron, or direct reduced iron (DRI), is hard to overstate. These are a key feed for metallurgical operations while iron extraction sets these limits, which include scarcity of metallurgical coke, poor environmental impact, and high production cost. Thus, the non-contact direct reduction process of DRIs has the potential to significantly reduce carbon deposition and CO2 emission from the ironmaking process. This work produced sponge iron from commercially acquired hematite ore using an alternative reducing agent (i.e. charcoal) under specified isothermal conditions. Comparative analysis of reaction kinetics models including Ginstein−Brounshtein and Shrinking core models was also performed to ascertain the resistances that control the reaction rate for reduction degree up to 98.1%. The reduction kinetics were found to be described by reaction control time and activation energies based on a shrinking core model as the reduction time lasted for 120minutes at temperatures 843~1273K. At temperatures above 973~1073K, the rate-limiting step was found to be solely an interfacial chemical reaction process, with an apparent activation energy of 196.1kJ/mol. In addition, a slowing trend was observed for iron ore sample sizes 10-20mm as a result of ash layer infiltration around the inner-core structure of the DRI metal matrix. The DRI morphological characteristics were performed using Scanning Electron Microscopy (SEM) and Electron Dispersive Spectrometry (EDS) to ascertain the mineralogical and morphological properties of the DRI samples. The XRF analysis confirms that the raw iron ore sample is hematite. Its iron content is 70.04% metallic iron (TFe) which has 83.59% Fe2O3 The SEM/EDS image also revealed the presence of micropores on the DRI morphology. This indicates that the reduction ratio and swelling extent rise with the temperature and time. This happens for all DRI sizes. However, the EDS result confirms the presence of gangue elements within the DRI metal matrix and mineralogical structure. The DRI contains very high silicon content up to 33.90%. So, a fluxing experiment is needed using limestone (CaCO3) or quicklime (CaO) quicklime to remove gangue (silicate, aluminate) from the DRI matrix. At the set reduction temperatures, the largest metallization degree of 93.05% at 1273K for a reduction time of 120mins was achieved. This showed that the overall reduction process still follows the expected chronological order since the NDR process uses CO gas from preheated charcoal. This makes DRI be produced from raw hematite under non-contact reduction bases. Therefore, the NDR technique offers a viable option for sponge iron production in modern-day iron and steelmaking processes.

High performance adsorptive removal of emerging contaminant paracetamol using a sustainable biobased mesoporous activated carbon prepared from palm leaves waste

In this work, a novel bio-based carbon material was prepared via a facile pyrolysis method using chemically activated dead palm leaves as a sustainable and efficient carbon precursor. The as-prepared activated carbon with KOH activation (AC-KOH) was characterized by XRD, FTIR, SEM, EDS, and BET analysis. The AC-KOH was used for the adsorption of PCT from aqueous solutions and the effect of experimental conditions such as contact time (0.08- 30hours), pH (2.96-12.1), initial drug concentration (1-50mgL-1), adsorbent dosage (0.12-1.2gL-1), and temperature (25-45 °C) was investigated. The system achieved equilibrium in 4hours with nearly 70% removal efficiency and PCT uptake was highly dependent on solution pH. A maximum removal efficiency of 68% was achieved at a pH of around 5.86. Kinetic model analysis indicated that the uptake follows the pseudo-second-order model (R2 = 0.989). The maximum monolayer capacity of the developed AC for PCT was found to be 87.87mgg-1 at time of equilibrium (4hours), solution pH of 5.86, adsorbent dose of 0.2gL-1, concentration of 1-50mgL-1 and temperature of 25 °C. The PCT uptake process was feasible, spontaneous (ΔG0 < 0), and endothermic (ΔH0 > 0) according to the thermodynamics evaluation. The mechanism of PCT adsorption primarily involved pore-filling, π-π interaction, and H-bonding. The adsorbent exhibited reasonable reusability towards PCT adsorption up to two regeneration cycles. The results of this work support that the dead palm leaves are efficient, cheap, and sustainable feedstock for producing activated carbon adsorbent to be used for an efficient removal of PCT from real wastewater samples.