Rate-limiting Step Research Articles

Kinetic and thermodynamic analysis of alizarin Red S biosorption by Alhagi maurorum: a sustainable approach for water treatment

Synthetic dyes, such as Alizarin Red S, contribute significantly to environmental pollution. This study investigates the biosorption potential of Alhagi maurorum biosorbent for the removal of Alizarin Red S (ARS) from aqueous solutions. Fourier transform infrared spectroscopy (FTIR) was used to analyze the biosorbent’s adsorption sites. Various parameters were optimized to maximize dye adsorption. An optimal removal efficiency of 82.26% was attained by employing 0.9 g of biosorbent with a 25 ppm dye concentration at pH 6 and 60 °C over 30 min. The data were modeled using various isothermal and kinetic models to understand the adsorption behavior. Thermodynamic parameters indicated that the adsorption process was spontaneous and endothermic. The pseudo-second-order kinetic model best described the data, indicating chemisorption as the rate-limiting step. The data matched best to the Langmuir model, indicating that the adsorption occurs as a monolayer on uniform surfaces with a finite number of binding sites. The model showed a strong correlation (R² = 0.991) and a maximum adsorption capacity (qmax) of 8.203 mg/g. Principal component analysis (PCA) identified temperature as the dominant factor, with the primary component, PC1 capturing 100% of its effect. The mechanisms involved in ARS biosorption on A. maurorum include electrostatic interactions, hydrogen bonding, hydrophobic interactions, dipole-dipole interactions, and π-π stacking. Alhagi maurorum showed promising potential for biosorbing toxic dyes from contaminated water, suggesting further investigation for practical applications.

First-principles study of selective CO2 activation to methanol on PdZn/TiO2: Unveiling Zn/Pd ratio on catalysis performance

In this study, a series of Pd(8-n)Znn/TiO2(n=0–8) were investigated via density functional theory (DFT) to understand the influence of Zn/Pd ratio on their catalysis performance of conversion CO2 to methanol. It is revealed that Zn prefers to replace the bottom-layered Pd when its molar concentration in composition increases. For all surface models, interface between cluster and support plays a key role in CO2 stabilization and activation. Increasing Zn/Pd ratio could weaken the binding strength of CO2 over catalyst, which further hinders the “RWGS” pathway while promotes the “Formate” pathway. Based on the calculation results, a Brønsted–Evans–Polanyi (BEP) relation between the activation barrier (Ea) of key elementary steps from both mechanisms and the binding strength of key intermediates has been established, from which the optimum Zn/Pd ratio leading to the best catalysis performance has been determined. Moreover, it is found that water inclusion in the system does not change the Ea of rate-determining step much even though it has a promotion effect on OH formation steps. Overall, this work provides some meaningful insight into the influence of cluster composition on the catalysis performance of PdZn-based catalyst and provides valuable information about rational design of the supported bimetallic catalyst.

Optimization of TiO2-based UV-LED Photocatalytic System for Mixed Dyes and Pharmaceutical Contaminants

To optimize the working efficiency of the novel UV-LED system based on TiO2 photocatalyst, the influence mechanism of LED lamp arrangement, light source wavelength and working voltage on photocatalytic efficiency was investigated. Acid red 26 (AR 26), acetaminophen (ACT) and diclofenac (DCF) were used as contaminant targets of the photocatalytic system. LED lamp arrangement had almost no effect on the degradation of AR26. However, the degradation efficiency of ACT and DCF was improved under a higher light uniformity. The ACT concentration and DCF concentration at 360 min decreased by 14% and 15%, respectively, with increasing light distribution from 45% to 66.5%. The main reason for this discrepancy in effect was whether the rate-determining step of the degradation mechanism was affected by the light uniformity. The short wavelength and high working voltage of LEDs were conducive to the photocatalytic degradation of contaminants to a different degree. When the wavelength was reduced from 405nm to 365nm, the conversion of AR26, ACT, and DCF increased by 77%, 227%, and 106%, respectively. The conversion rates of AR26, ACT, and DCF increased by 28%, 54%, and 32%, respectively, with voltage increasing from 3 V to 4 V. The data of this work will provide support for optimizing the working efficiency of UV-LED systems based on TiO2 photocatalysts. Copyright © 2024 by Authors, Published by BCREC Publishing Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

A bacterial transcriptionactivator dedicated to the expression of the enzyme catalyzing the first committed step in fatty acid biosynthesis.

Acetyl-CoA carboxylase (ACCase) catalyzes the first committed and rate-limiting step of de novo fatty acid synthesis (FAS). Although this step is tightly regulated, regulators that specifically control transcription of the ACCase genes remain elusive. In this study, we identified LysR-type transcriptional regulator AccR as a dedicated activator for the transcription of accS, a gene encoding a multiple-domain ACCase in Shewanella oneidensis. We showed that AccR interacts with the accS promoter in vivo in response to changes in acetyl-CoA levels and in vitro. Analysis of the crystal structure of the effector-binding domain (EBD) of AccR identified two potential ligand-binding pockets, one of which is likely to bind acetyl-CoA as a ligand based on results from molecular docking, direct binding assay and mutational analysis of the residues predicted to interact with acetyl-CoA. Despite this, the interaction between AccR and acetyl-CoA alone appears unstable, implying that an additional yet unknown ligand is required for activation of AccR. Furthermore, we showed that AccR is acetylated, but the modification may not be critical for sensing acetyl-CoA. Overall, our data substantiate the existence of a dedicated transcriptional regulator for ACCases, expanding our current understanding of the regulation of FAS.

The conformational landscape of fold-switcher KaiB is tuned to the circadian rhythm timescale

How can a single protein domain encode a conformational landscape with multiple stably folded states, and how do those states interconvert? Here, we use real-time and relaxation-dispersion NMR to characterize the conformational landscape of the circadian rhythm protein KaiB from Rhodobacter sphaeroides. Unique among known natural metamorphic proteins, this KaiB variant spontaneously interconverts between two monomeric states: the "Ground" and "Fold-switched" (FS) states. KaiB in its FS state interacts with multiple binding partners, including the central KaiC protein, to regulate circadian rhythms. We find that KaiB itself takes hours to interconvert between the Ground and FS state, underscoring the ability of a single-sequence to encode the slow process needed for function. We reveal the rate-limiting step between the Ground and FS state is the cis-trans isomerization of three prolines in the fold-switching region by demonstrating interconversion acceleration by the prolyl isomerase Cyclophilin A. The interconversion proceeds through a "partially disordered" (PD) state, where the C-terminal half becomes disordered while the N-terminal half remains stably folded. We found two additional properties of KaiB's landscape. First, the Ground state experiences cold denaturation: At 4 °C, the PD state becomes the majorly populated state. Second, the Ground state exchanges with a fourth state, the "Enigma" state, on the millisecond-timescale. We combine AlphaFold2-based predictions and NMR chemical shift predictions to predict this Enigma state is a beta-strand register shift that relieves buried charged residues, and support this structure experimentally. These results provide mechanistic insight into how evolution can design a single-sequence that achieves specific timing needed for its function.

3D printer fabrication of boron doped Cu-MWCNT/PLA electrodes: Investigation of its efficiency in electrocatalytic hydrogen production

In this study, three-dimensional (3D) electrodes based on MWCNT-Cu/PLA with high electrocatalytic efficiency, large surface area and different amounts of nano‑boron doped MWCNT-Cu/PLA were fabricated using Fused Granular Fabrication (FGF) method with a 3D printer. When FE-SEM images are examined, MWCNT fibers and copper particles are seen more clearly on the surface due to the formation of more dense conductive networks between the conductive carbon fibers trapped in the PLA structure due to the increasing amount of boron. When XRD results are examined, it is observed that the characteristic peaks belonging to the face-centered cubic structure of Cu are dominant and the crystal size increases as MWCNT addition and boron doping increase. When Raman spectra were analyzed to investigate the internal structural changes of MWCNTs, three characteristic bands corresponding to the D band (defect), G band (graphite band) and G' band (D overtone) of MWCNTs were determined and it was observed that the ID/IG ratio decreased with increasing boron doping compared to MWCNT-Cu/PLA electrode. The B1s spectrum of the 3D 0.8B@MWCNT-Cu/PLA electrode confirmed the presence of boron with the peak corresponding to B@C bonds at 191.2 eV. The obtained 3D electrocatalysts were used as cathodes in an electrolysis cell in aqueous solution containing 1 M KOH and their catalytic efficiency in hydrogen evolution reaction (HER) was tested. In order to increase the activity of the 3D electrodes, unlike the literature, they were activated by electrochemical activation process without using organic solvent and HER measurements of the activated electrodes were performed. Before activation, the charge transfer resistance (Rct) value of the Cu/PLA electrode, which was 6219.00 Ω cm−2, decreased to 681.90 Ω cm−2 after 5 % MWCNT doping. It is seen that with boron doping, a greater decrease in Rct value is realized, reaching values of 66.50–74.56 Ω cm−2. The cathodic Tafel slopes show that the Volmer reaction is the rate-determining step for HER and the rate-determining step is the electrochemical adsorption of hydrogen on the metal surface. In addition, energy efficiency tests of the 3D electrodes in HER were also performed and electrochemically active surface areas were determined. Thus, this study has taken an important step toward using 3D electrocatalysts, which are produced with more cost and more flexible designs, unlike previous production techniques, for hydrogen energy production.

Transcriptional response of Methanosarcina acetivorans to repression of the energy-conserving methanophenazine: CoM-CoB heterodisulfide reductase enzyme HdrED

ABSTRACT Methane-producing archaea are key organisms in the anaerobic carbon cycle. These organisms, also called methanogens, grow by converting substrate to methane gas in a process called methanogenesis. Previous research showed that the reduction of the terminal electron acceptor is the rate-limiting step in methanogenesis by Methanosarcina acetivorans . In order to gain insight into how the cells sense and respond to the availability of the terminal electron acceptor, we designed an experiment to deplete cells of the essential terminal oxidase enzyme, HdrED. We found that the depletion of HdrED in vivo results in a higher abundance of transcripts for methyltransferases ( mtaC2, mtaB3, mtaC3 ), coenzyme B biosynthesis, C1 metabolism, and pyrimidine compounds. In most cases, these changes were distinct from transcript abundance changes observed during the transition from exponential growth to stationary phase cultures. These data implicate the methylotrophic methanogenesis regulator MsrC (MA4383) in CoM-S-S-CoB heterodisulfide sensing and indicate cells have a specific mechanism to sense intracellular ratio of CoM-S-S-CoB, coenzyme M, and coenzyme B thiols and further suggest transcripts encoding translation and methanogenesis functions are controlled by feed-forward regulation depending on substrate availability. IMPORTANCE Methanosarcina is an emerging model archaeon and synthetic biology platform for the production of renewable energy and sustainable chemicals to reduce dependence on petroleum. Research into metabolic networks and gene regulation in this organism and other methanogens will inform genome-scale metabolic modeling and microbial function prediction in uncultured or non-model anaerobes and archaea. This study suggests methanogens use unknown mechanisms to efficiently couple methanogenesis to gene regulation via CoM-S-S-CoB and ATP availability.

Application of a Cell-Free Synthetic Biology Platform for the Reconstitution of Teleocidin B and UK-2A Precursor Biosynthetic Pathways.

We report the successful cell-free reconstitution of two natural product biosynthetic pathways of divergent complexity and structural classes. We first constructed the teleocidin biosynthetic pathway using our BY-2 (tobacco) cell-free protein synthesis (CFPS) system. We discovered a direct interaction between TleA and MbtH, and showed that the BY-2 system is capable of producing more than 80 mg/L teleocidin B-3 with cofactor supplementation and ∼20 mg/L with no cofactors supplemented, demonstrating the high metabolic activity of the system. We then extended our methodology and report the first successful cell-free biosynthesis of UK-2 diol (precursor to the commercially valuable secondary metabolite UK-2A) from simple building blocks by refactoring a complex pathway of 10 proteins in the wheat germ CFPS system. We show that plant CFPS systems are suitable for reconstructing pathways and identifying the functions of uncharacterized genes linked to biosynthetic gene clusters and rate-limiting biosynthetic steps.

Sustainable Processing of Ultralow-Cost Petroleum Cokes Into Ultrastable Self-Doped Fe3C@CNT Catalysts for High-Efficiency HER.

Petroleum cokes are largely used as low-cost anodes in aluminum industries and general fuels in cement industries, where large amounts of CO2 are generated. To reduce CO2 release, it is challenging to develop green strategies for processing abundant petroleum cokes into high-value products, because there are abundant hetero-atoms in petroleum cokes. To overcome such issues, a sustainable electrochemical approach is proposed to convert ultralow-cost high sulfur petroleum coke and iron powders into high-efficiency catalysts for hydrogen evolution reaction (HER). During molten-salt electrolysis, raw petroleum cokes are converted into CNTs via heteroatom removal and the catalytic effect of Fe, forming Fe3C nanoparticles on the sulfur and nitrogen co-dopped carbon nanotubes (Fe3C@S, N-CNTs). The electrochemical reaction analysis using the continuum model suggested that the rate-determining step referred to the slow transport of mobile ions inside the porous cathode. Because the self-doped S and N atoms massively alleviated the energy barrier for H* absorption and H2 desorption (i.e., promoting HER kinetics), the as-prepared Fe3C@S, N-CNTs exhibited low overpotentials at 10mAcm-2 in acidic (96mV) and alkaline (106mV) solutions with ultralong-term duration (200h). This study offers a sustainable approach to convert ultralow-cost petroleum cokes into ultrastable catalysts for high-efficiency HER.

Growth Kinetics of Graphene on Cu(111) Foils from Methane, Ethyne, Ethylene, and Ethane

AbstractChemical vapor deposition of carbon precursors on Cu‐based substrates at temperatures exceeding 1000 °C is currently a typical route for the scalable synthesis of large‐area high‐quality single‐layer graphene (SLG) films. Using molecules with higher activities than CH4 may afford lower growth temperatures that might yield fold‐ and wrinkle‐free graphene. The kinetics of growth of graphene using hydrocarbons other than CH4 are of interest to the scientific and industrial communities. We measured the growth rates of graphene islands on Cu(111) foils by using C2H2, C2H4, C2H6 and CH4, respectively (each mixed with H2). From such kinetics data we obtain the activation enthalpy (ΔH≠) of graphene growth as shown in parentheses (C2H2 (0.93±0.09 eV); C2H4 (2.05±0.19 eV); C2H6 (2.50±0.11 eV); CH4 (4.59±0.26 eV)); C2Hy (y=2, 4, 6) show similar growth behavior but CH4 is different. Computational fluid dynamics and density functional theory simulations suggest that C2Hy differs from CH4 due to different values of adsorption energy and the lifetime of relevant carbon precursors on the Cu(111) surface. Combining experimental and simulation results, we find that the rate determining step (RDS) is the dissociation of the first C−H bond of CH4 molecules in the gas phase, while the RDS using C2Hy is the first dehydrogenation of adsorbed C2Hy that happens with assistance of H atoms adsorbed on the Cu(111) surface. By using C2H2 as the carbon precursor, high‐quality single‐crystal adlayer‐free SLG films are achieved on Cu(111) foils at 900 °C.

Growth Kinetics of Graphene on Cu(111) Foils from Methane, Ethyne, Ethylene, and Ethane.

Chemical vapor deposition of carbon precursors on Cu-based substrates at temperatures exceeding 1000 °C is currently a typical route for the scalable synthesis of large-area high-quality single-layer graphene (SLG) films. Using molecules with higher activities than CH4 may afford lower growth temperatures that might yield fold- and wrinkle-free graphene. The kinetics of growth of graphene using hydrocarbons other than CH4 are of interest to the scientific and industrial communities. We measured the growth rates of graphene islands on Cu(111) foils by using C2H2, C2H4, C2H6 and CH4, respectively (each mixed with H2). From such kinetics data we obtain the activation enthalpy (ΔH≠) of graphene growth as shown in parentheses (C2H2 (0.93±0.09 eV); C2H4 (2.05±0.19 eV); C2H6 (2.50±0.11 eV); CH4 (4.59±0.26 eV)); C2Hy (y=2, 4, 6) show similar growth behavior but CH4 is different. Computational fluid dynamics and density functional theory simulations suggest that C2Hy differs from CH4 due to different values of adsorption energy and the lifetime of relevant carbon precursors on the Cu(111) surface. Combining experimental and simulation results, we find that the rate determining step (RDS) is the dissociation of the first C-H bond of CH4 molecules in the gas phase, while the RDS using C2Hy is the first dehydrogenation of adsorbed C2Hy that happens with assistance of H atoms adsorbed on the Cu(111) surface. By using C2H2 as the carbon precursor, high-quality single-crystal adlayer-free SLG films are achieved on Cu(111) foils at 900 °C.

The electrochemical synthesis of urea on triatomic cluster/Cu catalysts: A theoretical study

Urea (NH2CONH2), a crucial nitrogen fertilizer and industrial raw material, is typically synthesized under rigorous reaction conditions. Currently, the electrocatalytic transformation of N2 and CO2 into urea is a promising strategy. However, finding a high-selectivity and high-activity catalyst remains a significant challenge. Herein, the activity of a series of transition metal clusters (VIII and IB groups) on copper-based catalysts for electrochemical coupling of CO2 and N2 has been systematically studied to produce urea via density functional theory (DFT). Most catalysts exhibit good thermodynamic stability and accomplish co-adsorb CO2 and N2. Notably, Fe3 and Ni3/Cu100 catalysts achieve C-N coupling via *CO and *N2, whereas Ru3, Rh3, Os3, and Ir3/Cu100 catalysts accomplish C-N coupling via *CO and *NHNH. Among all catalysts, the Ni3/Cu100 catalyst features excellent catalytic activity with a rate-determining step as low as 0.480 eV, and its C-N coupling only needs to overcome a barrier of 0.844 eV. Additionally, the Ni3/Cu100 catalyst can effectively inhibit the hydrogen evolution reaction (HER), further protonation of *CO and ammonia formation, thereby ensuring high selectivity for urea. Electronic structures analysis further reveals an “acceptance-donation” mechanism for the activation of *CO2 and *N2, with the introduction of the Ni3 cluster showing a decisive role. Therefore, this study may establish the foundation for the electrochemical synthesis of urea.

GD2 in Breast Cancer: A Potential Biomarker and Therapeutic Target.

Expression of disialoganglioside GD2 in normal tissues is primarily limited to the central nervous system, peripheral sensory nerve fibers, dermal melanocytes, lymphocytes, and mesenchymal stem cells. Its widespread overexpression in various cancer types allows it to be classified as a tumor-associated antigen with potential diagnostic and therapeutic implications. This article reviews the synthesis pathways of GD2 and its role in cancer cell adhesion, proliferation, and metastasis with a focus on breast cancer. GD2 appears to be overexpressed on the outer membrane of most breast cancer cells and breast cancer stem cells (BCSCs) and is closely linked to epithelial-mesenchymal transition (EMT). GD3 synthase (GD3S) is considered to be the rate-determining step in GD2 synthesis. Clinical studies indicate that GD2 expression is increased in 35-70% of breast cancer samples, with higher levels in triple-negative breast cancer (TNBC). This overexpression correlates with more aggressive tumor features and worse prognosis. Therapeutic targeting of GD2 with monoclonal antibodies (moABs) like dinutuximab and naxitamab has demonstrated anti-cancer activity in preclinical cancer models and human clinical trials against high-risk neuroblastoma reducing tumor growth and enhancing survival. GD2-specific chimeric antigen receptor (CAR) T-cell therapy and GD3S inhibition present other promising therapeutic strategies to improve clinical outcomes. Furthermore, GD2-targeted vaccines are currently being investigated in cancer therapy. This narrative review article underscores the critical role of GD2 in breast cancer pathogenesis and highlights the promising therapeutic opportunities it offers. It advocates for the initiation of clinical trials to further explore the potential of GD2-targeted treatment in combination with standard breast cancer therapies.

Glucose oxidation on gold in alkaline solution: A DEMS and microkinetic modeling study

The mechanism and kinetics of the electrochemical oxidation of glucose on gold surfaces in 0.1 M NaOH solution are investigated by rotating disk electrode and differential electrochemical mass spectrometry coupled to microkinetic modeling. For this purpose, the glucose mass-transport parameters (solution viscosity and density, glucose diffusion coefficient) were determined in the relevant conditions. Koutecký–Levich analysis of rotating disk electrode current-potential curves revealed that the glucose oxidation reaction (GOR) follows a one-electron mechanism at 0.6 V vs RHE, while H2 production could be evidenced by DEMS in this potential range. This suggests that the glucose oxidation selectively produces gluconate at 0.6 V vs RHE through an electrochemical oxidative dehydrogenation (EOD) mechanism. A microkinetic model of the current-potential curves was developed, taking into account the hydrogen electrode reactions kinetics, the dissociative adsorption/desorption of glucose, and the glucose electrooxidation on gold surfaces. The dissociative adsorption of glucose was found to be the rate-determining step of the reaction. It is also revealed that the release of anodic H2 through the Tafel step is triggered by the consumption of the adsorbed reaction intermediates. The gluconate electrooxidation into further products has to be considered for potential above 0.7 V vs RHE.

Molecular Probing Coupled with Density Functional Theory Calculation to Reveal the Influence of Fe Doping on Fe-NiOOH Electrode for High Current Density of Water Splitting.

Fe-doped NiOOH electrocatalysts have attracted wide interest for the exceptional oxygen evolution reaction (OER) performance, but the precise role of Fe doping on the improved intrinsic activity remains unclear. Herein, the molecular probe technique combined with density functional theory calculation is used to reveal the influence of the Fe atom on the rate-determining step of the OER reaction, where the pre-catalyst of hierarchical self-supporting NiFe layered double hydroxide [LDH] nanosheets equipped on nickel foam (NiFe LDH/NF) is generated via a facile and industrially well-matched one-pot corrosion method. The physical characterization results reveal the reconstruction of NiFe LDH into Fe-doped NiOOH for promoted OER, which has a lower OH* adsorption energy with fast subsequent steps that help in obtaining an improved charge injection efficiency compared to NiOOH. In addition, more exposed electroactive species and facile delivery of mass/electron inside the catalytic procedure actually have a high-quality contribution to the outstanding catalytic activity. Therefore, the NiFe LDH36/NF electrocatalyst provides high catalytic activities of 241 and 320mV at 10mA cm-2 toward the OER and overall water-splitting in 1m KOH. This work provides a promising avenue for the rational design of durable self-supporting electrodes toward large-scale water splitting.

CH4 Carbonylation to Acetic Acid Using H2O as an Oxidant on a Rh-Functionalized UiO-67 Combined with Oriented External Electric Fields: Selectivity and Mechanistic Insights from DFT Calculations.

Acetic acid (CH3COOH), as an industrially important petrochemical product, is predominantly produced via multistep energy-intensive processes. The development of a rhodium single-site heterogeneous catalyst has received considerable attention due to its potential to transform CH4 into CH3COOH in a single step. Herein, the reaction mechanism for the generation of CH3COOH from CH4, CO, and H2O catalyzed by Rh-functionalized metal-organic framework (MOF) UiO-67 and the selectivity of products CH3COOH, formic acid (HCOOH), methanol (CH3OH), and acetaldehyde (CH3CHO) under the oriented external electric fields (OEEFs) were systematically explored by density functional theory (DFT) calculations. The results reveal that the insertion of CO into Rh-CH3 is the rate-determining step with a free energy barrier of 21.0 kcal/mol in CH4 carbonylation to CH3COOH. Upon applying an OEEF of Fx = +0.0050 au along the C-C bond, the rate-determining step shifts toward H2O decomposition with the barrier of 19.6 kcal/mol, significantly improving the selectivity for CH3COOH production, compared to the major competitive HCOOH route. The Brønsted-Evans-Polanyi (BEP) relationships between key transition states, field strength, and NPA charge transfer were established. This study may guide the rational design of atomically dispersed MOF catalysts for the selective coconversion of CH4 and CO to CH3COOH using H2O as the oxidant under the OEEF.

Carbon Nanoparticle Oxidation by NO2and O2: Chemical Kinetics andReaction Pathways.

Carbon nanoparticle interactions with gases are central to many environmental and technical processes, but the underlying reaction kinetics and mechanisms are not well understood. Here, we investigate the oxidation and gasification of carbon nanoparticles by NO2and O2under combustion exhaust conditions. We build on a comprehensive experimental data set and use a kinetic multilayer model (KM-GAP-CARBON) to trace the uptake and release of gas molecules alongside the temporal evolution of particle size and surface composition. The experimental results are captured by a model mechanism that involves different types of carbon atoms (edge/plane-like) and the formation of a reactive oxygen intermediate (activated CO complex) as the rate-limiting step. A transition between distinct chemical regimes driven by NO2at lower temperatures and O2at higher temperatures is reflected by an increase in the observable activation energy from ~60 kJ/mol to ~130 kJ/mol. We derive energy profiles for three alternative reaction pathways that involve uni- or bimolecular decomposition of reactive oxygen intermediates.

Biogenic fabrication of spinel nickel ferrite imprinted on Bifurcaria bifurcata Macro-Alga activated carbon for the adsorption of ciprofloxacin and metronidazole

The rise in globalization and industrialization has led to an increase in population, increasing improperly treated discharge containing dyes, pharmaceuticals, pesticides etc in the water bodies. This has led to the need to remove these contaminants from water sources. The NiFe@BBAL adsorbent was developed and analyzed using various techniques such as FTIR, XRD, SEM, and XPS. The effectiveness of the NiFe@BBAL in adsorbing Ciprofloxacin (CIP) and metronidazole (MET) in water was tested. The adsorption of CIP and MET, both individually and in mixtures, was studied. The kinetic sorption experiments showed that the adsorption followed a pseudo-second-order model, with a higher R2 of 0.9934 for MET compared to 0.9916 for CIP. This suggests that the rate-limiting step is chemisorption. The primary adsorption mechanisms for both CIP and MET were hydrogen bonding, hydrophobic interactions, and electrostatic interactions, while CIP also involved electrostatic and metal complexation interactions. The NiFe@BBAL effluent showed no toxic effects on bacteria, indicating that no harmful material was leached in the effluent. The NiFe@BBAL demonstrated excellent performance and stability in removing 97.64% CIP and 97.62% MET in single contaminant experiments, and 57.33% CIP and 70.69% MET in cocktail mixture experiments. This can be attributed to the smaller structure of MET compared to CIP, allowing it better access to the active site, leading to higher adsorption. Furthermore, the repeated use of the adsorbent proved to be stable in the removal of CIP and MET over five cycles, demonstrating that the material is sustainable and suitable for large-scale experiments.

Adsorption of methyl orange and methylene blue on activated biocarbon derived from birchwood pellets

This study explored the adsorption capacity of a physically activated biocarbon derived from the pyrolysis of birchwood pellets (ABPB) towards two dyes - methyl orange (MO, anionic) and methylene blue (MB, cationic), at pH 2, 7 and 11. Compared to mineral commercial activated carbon (CACmineral), ABPB exhibited lower SSA, pores volume and surface; higher external surface and average pore diameter, similar ash content and aromaticity, and stronger hydrophilicity and polarity. The maximum adsorption capacity on ABPB was equal to 220 mg/g for MO and 91 mg/g for MB after 17 h. Batch tests with variable adsorbent amount (0.5–2.5 g/L) showed for both ABPB and CACmineral better results for lower adsorbent dose. Under all tested conditions, ABPB showed higher or analogous adsorption capacity compared to CACmineral. Based on the pKa of MB (3.80) and MO (3.46) and on the pHPZC of ABPB (5.3), the adsorption was favored at pH 2 for MO and at pH 11 for MB. Kinetics analysis and isotherm modelling revealed that, although many different physicochemical interactions occurred between ABPB and the dyes molecules, chemisorption is the rate-controlling step and prevalent mechanism. In conclusion, this study may provide support to further research aimed at exploring the effect of ABPB's physicochemical properties on the efficiency and mechanisms of dyes adsorption.

Osteopontin is a therapeutic target that drives breast cancer recurrence

Recurrent breast cancers often develop resistance to standard-of-care therapies. Identifying targetable factors contributing to cancer recurrence remains the rate-limiting step in improving long-term outcomes. In this study, we identify tumor cell-derived osteopontin as an autocrine and paracrine driver of tumor recurrence. Osteopontin promotes tumor cell proliferation, recruits macrophages, and synergizes with IL-4 to further polarize them into a pro-tumorigenic state. Macrophage depletion and osteopontin inhibition decrease recurrent tumor growth. Furthermore, targeting osteopontin in primary tumor-bearing female mice prevents metastasis, permits T cell infiltration and activation, and improves anti-PD-1 immunotherapy response. Clinically, osteopontin expression is higher in recurrent metastatic tumors versus female patient-matched primary breast tumors. Osteopontin positively correlates with macrophage infiltration, increases with higher tumor grade, and its elevated pathway activity is associated with poor prognosis and long-term recurrence. Our findings suggest clinical implications and an alternative therapeutic strategy based on osteopontin’s multiaxial role in breast cancer progression and recurrence.