Desorption Process Research Articles

Numerical simulation model of water quality evolution in urban rivers considering adsorption–desorption process of nitrogen and phosphorus in sediments

In order to more realistically simulate the river channel water quality considering the characteristics of sediment release, it is necessary to couple the simulation model of sediment release to the hydrology-hydrodynamics-water quality model to quantify the complexities involved in the nitrogen and phosphorus cycle in river channel sediments. However, in the existing studies, most of the water–sediment models constructed in the analysis of single pollutants such as NH3-N or BOD, but fail to consider the interaction between multiple pollutants, and the model software related to water quality simulation fails to establish complex river sediment pollution simulations, there are still challenges in the application of the existing water quality module of the MIKE simulation software to the nitrogen and phosphorus cycle of sediments. In this study, based on the new sediment nitrogen and phosphorus release mechanism, we rewrite the water quality module ECOLab of the MIKE 21 model. The laboratory test results and the measured data are applied to the calibration of the model parameters. The new water quality module considering the adsorption–desorption process of sediments was embedded into the MIKE 21 model. The new module couples the MIKE model and the SWWM model to establish a 2D water quality model of river channel hydrology-hydrodynamics-water quality-sediment release coupling. This model targeted applies in urban river channels with sediment releasion as the main pollution. The results show that the new model has significantly improved the simulation accuracy of BOD and NH3-N, and has an optimized effect on the simulation of TP. The R, NSE, and RMSE values of the model for NH3-N simulation are 0.904, 0.845, and 0.612. This model is more suitable for numerical simulation of urban river water quality where sediment release is the main cause of endogenous pollution.

Phosphorus desorption regulates phosphorus fraction dynamics in soil aggregates of revegetated ecosystems

To elucidate the mechanisms and effects of phosphorus (P) desorption on P fractions in soil aggregates of revegetated ecosystems is fundamental for regulating the P supply and biogeochemical cycle. We selected four aggregate sizes (1–5, 0.5–1, 0.25–0.5, and <0.25 mm) from a desert revegetation chronosequence (11, 31, 40, 57, and 65 years) as our study targets and used the Freundlich model to reveal the dynamics of P desorption and changes in P fractions. The results showed that the calibrated model Q=A−KFdtnd for different size aggregates in seven deserts (two natural and five revegetated) described the P desorption characteristics well. In soil aggregates of revegetated deserts, smaller aggregates with higher specific surface area did not desorb more P, nor did older aggregates after revegetation. The natural P desorption process in aggregates resulted in significant changes in Ca2–P, Ca8–P, Al–P and Fe–P fractions (p < 0.05), and revegetation years also affected P fraction dynamics significantly (p < 0.05). This study highlights that the calibrated kinetic model in the revegetated soil aggregates elucidated the P desorption characteristics, and that the P desorption process drove P fraction changes.

Post-Removal of Phosphorus from Biologically Treated Wastewater and Recovering It as Fertilizer: Pilot-Scale Attempt—Project PhoReSe

The major issue of raw materials’ depletion, and more specifically, of phosphorous (an important fertilizer) has currently become an emergent aspect due to expected depletion problems needing immediate handling. This was the reason for the implementation of the PhoReSe project that aimed to remove and recover phosphorus from the secondary (biologically treated) effluent of a municipal wastewater (biological) treatment plant (WWTP “AINEIA”, located near Thessaloniki, N. Greece), treating the wastewaters of the nearby touristic area. Regarding the phosphorous supplementary removal and recovery treatment options, two methods were examined, initially at the laboratory scale (batch experiments), i.e., (1) the adsorption of phosphorous, and (2) the chemical precipitation of phosphorus. Both methods were further applied at the pilot scale by initially performing the adsorption of phosphorous onto the AquAsZero commercial sorbent, which is a mixed manganese iron oxy-hydroxide, followed by the chemical precipitation of phosphorous implemented after the desorption process of the previously saturated adsorbent. The final precipitate of this procedure was examined as an alternative/supplementary fertilizer, this way returning phosphorus into the natural cycle. These experiments, as applied successfully in at the pilot scale, set the basis for larger-scale relevant applications for similar WWTP facilities.

Computational investigation of NLi4-cluster decorated phosphorene for reversible hydrogen storage

The use of lithium-decorated phosphorene for hydrogen storage is significantly limited due to metal aggregation on substrates. Despite considerable research and effort in the literature to address this issue, no one has succeeded in enhancing the capacity of phosphorene through metal atom decoration. Based on density functional theory (DFT) and AIMD simulations, superalkali NLi4-decorated black phosphorene monolayer is developed as a new hydrogen storage solid-state material. Our results show that the NLi4-cluster exhibits a significant binding energy of −3.18 eV when attached to one side of the phosphorene on a stable site, indicating a strong affinity between the NLi4-cluster and phosphorene surfaces. Moreover, 2(NLi4)@phosphorene can store up to 30H2 molecules with a suitable average hydrogen adsorption-energy and a maximum hydrogen storage capacity of 6.8 wt%. Using the van't Hoff equation and increasing the pressure, we find that the desorption temperature is higher than the critical point for hydrogen. AIMD simulations at different temperatures demonstrate the thermal stability of the hydrogenated 2(NLi4)@phosphorene and the H2 desorption process. The findings of the present study suggest the potential utilization of the 2(NLi4)@phosphorene adsorptive material for hydrogen storage applications.

Gas Sorption Characterization of Porous Materials Employing a Statistical Theory for Bethe Lattices.

In the present work, a recently developed statistical theory for adsorption and desorption processes in mesoporous solids, modeled by random Bethe lattices, has been applied to obtain pore size distributions and interpore connectivity from sorption isotherms in real random porous materials, employing a robust and validated methodology. Using the experimental adsorption-desorption N2 isotherms at 77.4 K on Vycor glass, a porous material with random pore structure, we demonstrate the solution of the inverse problem resulting in extracted pore size distribution and interpore connectivity, notably different from the predictions of earlier theories. The results presented are corroborated by the analysis of 3D digital images of reconstructed Vycor porous glass, showing excellent agreement between the predictions of geometric analysis and the new statistical theory.

Coupled bulk and interfacial transport of surfactants governs the settling of a drop towards a wall

Surfactant-like impurities are omnipresent in multiphase emulsions and may substantially affect the motion of small droplets by altering their interfacial properties. Usually these surfactants are soluble in the bulk and undergo adsorption–desorption onto the interface which modifies their surface concentration and hence their overall influence on droplet motion. Yet, the impact of the bulk solubility and transport of surfactants on droplet dynamics, especially in the presence of bounding walls, remains poorly understood. As such, in this article, we assess the impact of bulk soluble surfactants on the settling of a spherical drop towards a plane wall. We consider coupled bulk and interfacial transport of surfactants, mediated by adsorption–desorption processes and construct a semi-analytical framework for arbitrary values of ‘bulk interaction parameter’, which dictates the strength of adsorption–desorption kinetics compared with bulk diffusion. Our results indicate that while mass exchange between the bulk and the interface can remobilize the drop, a finite bulk diffusion rate restricts this process and therefore slows down the drop. This also results in bulk concentration depletion near the south pole and accumulation near the north pole, the extent of which becomes strongly asymmetric with an enhanced intensity of depletion, as the drop approaches the wall. Presence of the wall and bulk solubility are found to aid each other towards remobilizing the drop by aptly modifying the interfacial concentration. Our results may provide fundamental insights into the kinetics of surfactant-laden drops, with potential applications in food and pharmaceutical industries, separation processes, etc.

Study on size effect and model optimization of methane desorption-diffusion in high rank coal

ABSTRACT Methane diffusion models are numerous, but their application, pros, and cons need to be summarized urgently, the link between particle size and methane desorption-diffusion is uncertain. Therefore, this paper carries out the methane desorption-diffusion experiments under multi-scale pressure and particle size conditions to study the effect of coal sample particle size on methane desorption-diffusion. Based on MATLAB, different diffusion models were fitted and comparatively analyzed, and the models were improved in view of their deficiencies. The results showed that the cumulative methane desorption amount and rate are inversely related to the particle size of coal. Comparative analysis of the models revealed that diffusion model under the third type of boundary conditions has a low fitting accuracy for full process of methane desorption, whereas it has a high fitting accuracy of 0.9831 for the first 1000 s of desorption data. Unipore diffusion model, bidisperse diffusion model and new model of dynamic diffusion coefficient have high fitting accuracy for the desorption data of high homogeneous coal, reaching above 0.97, but unipore diffusion model has only 0.5434 fitting accuracy for non-homogeneous coal samples. The fitting accuracy of improved classical unipore diffusion model for both homogeneous and non-homogeneous coals reaches 0.99, which is more extensive than that of unipore diffusion model, only take the first term can satisfy the accuracy requirement, so it is more convenient in the practical engineering application, and has certain reference significance for engineering calculations of gas content and prediction of gas protrusion.

Multifactor orthogonal analysis on the desorption performances of P/N/S-doped activated carbon for acetone

As a widely used industrial material, the recovery of volatile organic compounds (VOCs) has great economic value and environmental significance. Improving the desorption performance of modified activated carbon in treating volatile organic compounds emissions is the key to the utilization of adsorbent and the recovery of adsorbate. In this study, five kinds of activated carbons and acetone were selected for orthogonal experiments to analyze the effect of multi-factors on the performances of major concern in engineering. The desorption process was divided into three zones, concentration fast rise zone, concentration fast decay zone and concentration slow decay zone, and quantitively evaluated for each zone. The results show that the enrichment ratio of SC800 is the highest in these sample, can reach 5.16, which is mainly affected by the chemical functional group with the highest adsorption energy, and is negatively correlated with the specific surface area. Combined the kinetic analysis and the quantitative evaluation of the total effects of chemical functional groups, the desorption rates are mainly related to the adsorbent surface saturation in the concentration fast decay zone and the total chemical effect in the concentration slow decay zone. In addition, the PC500 has the highest desorption efficiency of 69%, which can be measured by the desorption activation energy.

Understanding Substrate Effects on 2D MoS2 Growth: A Kinetic Monte Carlo Approach

AbstractControlling the morphology of 2D transition metal dichalcogenides (TMDs) plays a key role in their applications. Although chemical vapor deposition can achieve wafer‐scale growth of 2D TMDs, a comprehensive theoretical framework for effective growth optimization is lacking. Atomistic modeling methods offer a promising approach to delve into the intricate dynamics underlying the growth. In this study, kinetic Monte Carlo (kMC) simulations are employed to identify crucial parameters that govern the morphology of MoS2 flakes grown on diverse substrates. The simulations reveal that large adsorption rates significantly enhance growth speed, which however necessitates rapid edge migration to achieve compact triangles. Substrate etching can tune the adsorption–desorption process of adatoms and enable preferential growth within a specific substrate region, controlling the flake morphology. This study unravels the complex dynamics governing 2D TMD morphology, offering a theoretical framework for decision‐making in the design and optimization of TMD synthesis processes.

Synthesis, characterization, hysteretic two-step CO2 adsorption, and fluorescence properties of two isoreticular mixed-ligand pillared-layer frameworks

Two isostructural and isomorphrous metal–organic frameworks (MOFs), namely [Zn2(Brtpt)2 (bpBTD)]n (1) and {[Zn2 (ntpt)2 (bpBTD)]∙solvent}n (2), where bpBTD = bis(pyridin-4-yl)benzothiadiazole, H2Brtpt = 2-bromoterephthalic acid, H2ntpt = 2-nitroterephthalic acid, with thermal stability of 355 °C for 1 and 265 °C for 2 were hydro (solvo)thermally synthesized in DMF/H2O media at 100 °C. Single-crystal X-ray diffraction analysis revealed that 1 and 2 both possess 2-fold interpenetrating pillared-layer frameworks showing pcu net topology with the point symbol of 41,263. The sufficient extra-framework void spaces are approximately 30.1 % for 1 and 32.0 % for 2 with open channels along the b axis, where the window sizes are ca. 5.51 × 3.15 Å2 in edge for the former and ca. 5.47 × 3.44 Å2 and 3.12 × 3.44 Å2 in edge for the latter. Gas adsorption isotherms revealed that thermally activated 1 and 2 both hardly adsorb N2 with very low N2 uptakes at 77 K. Comparably, the CO2 adsorption isotherms of thermally activated 1 and 2 both revealed gate-opening (two-step) sorption behaviors with an apparent hysteretic adsorption–desorption process, where the maximum uptakes are 135.4 and 171.5 cm3 g−1 STP for 1 and 2, respectively, at 195 K and P/P0 = 1. Photoluminescence studies showed that 1 and 2 both emitted bpBTD-dominated ligand-centered emissions, being as cyan and pearl aqua color fluorescence centered at λem = 467 and 495 nm, respectively, in solid-state and as cyan color fluorescence centered at λem = 455 and 458 nm, respectively, in H2O suspensions.

Evaluating the Fe-doping effect on intermediate adsorption modulation for Co-based vanadates toward separation of hydrogen from water electrolysis

The optimization of intermediate adsorption is pivotal for enhancing the efficacy of catalysts in oxygen evolution reaction (OER). However, many Co-based catalysts exhibit excessive binding energy toward intermediates, thereby restricting the desorption process. To address this issue, we utilized the Co-based vanadates (CoV) as a model and observed that the incorporation of Fe can effectively mitigate the substantial accumulation of intermediates around the catalysts, achieving a balance between the adsorption and desorption. It can be attributed to the Fe-doping, which modulated the electronic structure of CoV, subsequently increasing the catalytic sites and intrinsic activity. As a result, the CoV-Fe exhibited a low overpotential of 260 mV at 20 mA cm−2, which decreased by 82 mV compared to pristine CoV. Besides, the electrolyzer based on CoV-Fe maintained a low cell of 1.46 V for water splitting and held a considerable attenuation of 4.49 % after 200 h of long-term operation.

Synergistic Catalysis of SO42-/TiO2-CNT for the CO2 Desorption Process with Low Energy Consumption.

To address the issue of high energy consumption associated with monoethanolamine (MEA) regeneration in the CO2 capture process, solid acid catalysts have been widely investigated due to their performance in accelerating carbamate decomposition. The recently discovered carbon nanotube (CNT) catalyst presents efficient catalytic activity for bicarbonate decomposition. In this paper, bifunctional catalysts SO42-/TiO2-CNT (STC) were prepared, which could simultaneously catalyze carbamate and bicarbonate decomposition, and outstanding catalytic performance has been exhibited. STC significantly increased the CO2 desorption amount by 82.3% and decreased the relative heat duty by 46% compared to the MEA-CO2 solution without catalysts. The excellent stability of STC was confirmed by 15 cyclic absorption-desorption experiments, showing good practical feasibility for decreasing energy consumption in an industrial CO2 capture process. Furthermore, associated with the results of experimental characterization and theoretical calculations, the synergistic catalysis of STC catalysts via proton and charge transfer was proposed. This work demonstrated the potential of STC catalysts in improving the efficiency of amine regeneration processes and reducing energy consumption, contributing to the design of more effective and economical catalysts for carbon capture.

Fabrication of MXene/chitosan/polyurea nanocomposite decorated on a graphenized substrate for electro-enhanced solid-phase microextraction of diclofenac followed by its determination using differential pulse voltammetry.

A novel solid-phase microextraction fiber based on MXene-chitosan-polyurea (MXene/CS/EPPU) nanocomposite decorated on a graphenized pencil lead fiber (MXene/CS/EPPU/GPLF) was prepared and utilized for electro-enhanced solid-phase microextraction (EE-SPME) of diclofenac (DCF) in biological samples. After extraction and desorption of DCF, it was determined by differential pulse voltammetry (DPV). For this purpose, the working electrode was prepared by deposition of the mentioned MXene/CS/EPPU nanocomposite onto the graphenized pencil lead. The synthesized SPME fiber was characterized using scanning electron microscopy and X-ray diffraction techniques. The effect of various parameters influencing the extraction and the desorption process were investigated, including applied voltage in the extraction and desorption steps, extraction and desorption times, and pH. The developed method exhibited a rather wide linearity in the range 2-1200 ng mL-1 (R2 = 0.985) for the determination of DCF in plasma samples. The limit of detection and the limit of quantification for plasma samples were estimated to be 0.58 and 1.9 ng mL-1 based on the 3Sb/m and 10Sb/m definitions, respectively. The method's accuracy and applicability have been evaluated by the analysis of plasma samples, leading to the relative recoveries in the range 87.0% and 98.0% with the relative standard deviations lower than 3.1%.

Bioinspired H-Bonding Connected Gradient Nanostructure Actuators Based on Cellulose Nanofibrils and Graphene.

The construction of flexible actuators with ultra-fast actuation and robust mechanical properties is crucial for soft robotics and smart devices, but still remains a challenge. Inspired by the unique mechanism of pinecones dispersing seeds in nature, a hygroscopic actuator with interlayer network-bonding connected gradient structure is fabricated. Unlike most conventional bilayer actuator designs, the strategy leverages biobased polyphenols to construct strong interfacial H-bonding networks between 1D cellulose nanofibers and 2D graphene oxide, endowing the materials with high tensile strength (172MPa) and excellent toughness (6.64MJm-3). Furthermore, the significant difference in hydrophilicity between GO and rGO, along with the dense interlayer H-bonding, enables ultra-fast water exchange during water absorption and desorption processes. The resulted actuator exhibits ultra-fast driving speed (154°s-1), excellent pressure-resistant and cyclic stability. Taking advantages of these benefits, the actuator can be fabricated into smart devices (such as smart grippers, humidity control switches) with significant potential for practical applications. The presented approach to constructing interlayer H-bonding in gradient structures is instructive for achieving high performance and functionalization of biomass nanomaterials and the complex of 1D/2D nanomaterials.

Effect of Bystander Hydrogen Atoms on Hydrogen Desorption on Single-Atom Alloy Surfaces: Insights from Simulated Temperature-Programmed Desorption Spectra.

Single-atom alloy (SAA) catalysts exhibit unique and excellent catalytic properties in heterogeneous hydrogenation/dehydrogenation reactions. A thorough understanding of the microscopic surface processes is essential to improve the catalytic performance. Here, from a new perspective of the temperature-programmed desorption (TPD) spectra of hydrogen (H) on two common SAA surfaces, Pt@Cu(111) and Pd@Cu(111), we reveal and confirm the key influence of H atoms attached to Pt/Pd dopants, i.e., the H atom bystander, on the desorption process of surface H atoms. It is found that only after considering the effect of the H atom bystander can the simulated TPD spectra well reproduce the experimentally observed higher desorption temperature on Pt@Cu(111) than on Pd@Cu(111) and the leftward shift of the TPD peak with increasing H atom coverage; otherwise, the features are inconsistent with experiments. Our work provides direct evidence for the effect of bystander H atoms from a simulation perspective.

Understanding the dynamics of enhanced light non-aqueous phase liquids (LNAPL) remediation at a polluted site: Insights from hydrogeophysical findings and chemical evidence

This study intricately unfolds a pioneering methodology for remediating contaminants in a persistent light non-aqueous phase liquids (LNAPL)-contaminated site. The remediation strategy seamlessly integrates enhanced desorption and in-situ chemical oxidation (ISCO), orchestrating the injection of PetroCleanze® (a desorbent) and RegenOx® (an oxidizer) through meticulously designed wells. These injections, based on detailed geological and hydrogeological assessments, aim at mobilizing residual contaminants for subsequent extraction. Real-time subsurface dynamics are investigated through geophysical monitoring, employing electrical resistivity tomography (ERT) to trace reagent migration pathways via their effect on bulk electrical conductivity. The integration of groundwater sampling data aims at providing additional insights into the transformations of contaminants in the spatiotemporal context. Vivid two-dimensional time-lapse ERT sections showcase the evolution of resistivity anomalies, providing high-resolution evidence of the heterogeneity, dispersion pathways of desorbent and oxidant, and residual LNAPL mobilization. Hydrochemical analyses complement this, revealing effective mobilization processes with increasing aqueous concentrations of total petroleum hydrocarbons (TPH) over time. Speciation analysis unveils the intricate interplay of desorption and oxidation, portraying the dynamic fractionation of hydrocarbon components. The hydrogeophysical and data-driven framework not only delivers qualitative and quantitative insights into reagent and contaminant distribution but also enhances understanding of spatial and temporal physio-chemical changes during the remediation process. Time-lapse ERT visually narrates the reagent's journey through time, while chemical analyses depict the unfolding processes of desorption and oxidation across space and time. The coupling of hydrogeophysical and chemical findings pictures the transformations of pollutants following the sequence of product injection and the push and pull activities, capturing the removal of mobilized contaminants through hydraulic barrier wells. This enhanced understanding proves instrumental towards optimizing and tailoring remediation efforts, especially in heterogeneous environmental settings. This study establishes a new standard for a sophisticated and innovative contaminant remediation approach, advancing environmental practices through the harmonized analysis of geophysical and chemical data.

Application of chemically modified waste tucumã (Astrocaryum aculeatum) seeds in the biosorption of methylene blue: kinetic and thermodynamic parameters.

Dye effluents cause diverse environmental problems. Methylene blue (MB) dye stands out since it is widely used in the textile industry. To reduce the pollution caused by the MB, we developed biosorbents from tucumã seeds, where the in natura seeds were treated with NaOH (BT) and H3PO4 (AT) solutions and characterized by Boehm titration, point of zero charges, FTIR, TGA, BET, and SEM. It was observed that the acid groups predominate on the surface of the three biosorbents. The process was optimized for all biosorbents at pH = 8, 7.5g/L, 240min, C0 = 250mg/L, and 45 ℃. BT was more efficient in removing MB (96.20%; QMax = 35.71mg/g), while IT and AT removed around 60% in similar conditions. The adsorption process best fits Langmuir and Redlich-Peterson isotherms, indicating a hybrid adsorption process (monolayer and multilayer) and pseudo-second-order kinetics. Thermodynamic data confirmed an endothermic and spontaneous adsorption process, mainly for BT. MB was also recovered through a desorption process with ethanol, allowing the BT recycling and reapplication of the dye. Thus, an efficient and sustainable biosorbent was developed, contributing to reducing environmental impacts.

Experimental investigation of a mixed desiccant solution of potassium formate and ionic liquid

Liquid desiccant technology is a promising energy-efficient alternative to conventional temperature and humidity control systems. In the quest to identify the optimal fluid for liquid desiccant systems, alternative desiccant solutions have been explored in terms of their feasibility and compatibility in dehumidification systems. This study proposes and characterises a new type of less expensive mixture of potassium formate (HCO2K) and 1-ethyl-3-methylimidazolium acetate ([EMIM][OAc]). This novel desiccant solution was investigated in terms of corrosiveness to metals, moisture absorption and desorption ability, cost-effectiveness compared to conventional desiccant solutions. The corrosiveness of desiccant solutions to copper-nickel, copper and steel was tested at room temperature and at 60 °C. Experiments were conducted in a climatic chamber with temperatures of 25–31 °C and relative humidities of 80–90% for the absorption process and temperatures of 50–70 °C and relative humidities of 20–30% for the desorption process to assess the moisture absorption and desorption capacities and mass fraction variations of the desiccant solutions. The mixed desiccant of HCO2K/[EMIM][OAc] in the ratio 60/10% wt. showed a moisture absorption capacity of 0.146 gH2O/gsol (compared to 0.18 gH2O/gsol for aqueous lithium chloride at 33.3% wt.) for a temperature and relative humidity of the climatic chamber of 25 °C and 90%, respectively. Its low corrosiveness, good moisture absorption and desorption capacity and higher cost-effectiveness make it a promising alternative to conventional desiccants, such as aqueous solutions of lithium chloride.

Amino acids to reduce the escape of organic amines in the CO2 capture process

Carbon neutrality and carbon peaking are important strategic policies for our country. Carbon dioxide capture technology is the bottom of the realization of this strategy, in which amine escape is an important issue for the development of this technology. Herein, the proposal to utilize amino acids for reducing volatilization of organic amines was introduced for the first time. Diethylaminoethanol (DEEA), widely applied and highly volatile, was selected as the primary target for volatility reduction, while hydroxyethyl ethylenediamine (AEEA) and piperazine (PZ) were chosen as the main absorbents for absorption and desorption processes. The effects of DEEA addition on the main absorbent, different types of amino acid additives on volatility, and amino acids on absorption and desorption performance were investigated, respectively. Glutamine (Tyr) demonstrated significant potential in reducing the volatilization of organic amines; when 2% Tyr was added during gas–liquid equilibrium experiments, it resulted in a 74.5% decrease in DEEA volatilization within the absorbent system. Simulated gas–liquid entrainment escape showed that CO2 loading reduced volatilization by 42.31%, with a further reduction of 53.93% achieved when loaded with 0.5 molCO2/mol amine; this loading also had a promotional effect on absorption and desorption processes. Moreover, Tyr exhibited excellent stability without generating any degradation products, thereby prolonging absorber lifespan and minimizing economic cost losses.

Optimization of Cyanocobalamin (Vitamin B12) Sorption onto Mesoporous Superparamagnetic Iron Oxide Nanoparticles.

The techniques used to detect and quantify cyanocobalamin (vitamin B12) vary considerably in terms of detection sensitivity, from the most sensitive, based on radioisotopes and mass spectrometry (MS) with limits of detection (LOD) in fg mL-1, to fluorescence (FL) and surface plasmon resonance (SPR) biosensors with LOD values in the range of a few µg mL-1. For accurate quantification of an analyte present at trace levels in complex biological matrices, a selective separation and enrichment step is required to overcome matrix interferences and ensure sufficient detection sensitivity. In this study, iron oxide magnetic nanoparticles (IONPs) were used for the extraction and initial preconcentration of cyanocobalamin (vitamin B12). In the dependence of the magnetization on the H-field (hysteresis loop), no coercivity and remanence values were found at 300 K, indicating the superparamagnetic properties of the tested IONPs. Perfluorinated acids were used as amphiphilic agents to allow the sorption of cyanocobalamin onto the IONPs. FT-IR/ATR spectroscopy was used to confirm the sorption of cyanocobalamin on the IONPs. The influence of the addition of a homologous series of perfluorinated acids such as trifluoroacetic acid (TFAA), heptafluorobutyric acid (HFBA), and trichloroacetic acid (TCAA) to the extraction mixture was tested considering their type, mass, and time required for effective sorption. The adsorption kinetics and isotherm, described by the Freundlich and Langmuir equations, were analyzed. The maximum adsorption capacity (qm) exceeded 6 mg g-1 and was 8.9 mg g-1 and 7.7 mg g-1 for HFBA and TCAA, respectively, as the most efficient additives. After the desorption process using aqueous KH2PO4 solution, the sample was finally analyzed spectrophotometrically and chromatographically. The IONP-based method was successfully applied for the isolation of cyanocobalamin from human urine samples. The results showed that the developed approach is simple, cheap, accurate, and efficient for the determination of traces of cyanocobalamin in biological matrices.