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1.
J Environ Sci (China) ; 148: 350-363, 2025 Feb.
Article in English | MEDLINE | ID: mdl-39095170

ABSTRACT

Pyrrolizidine alkaloids (PAs) and their N-oxides (PANOs) are phytotoxins produced by various plant species and have been emerged as environmental pollutants. The sorption/desorption behaviors of PAs/PANOs in soil are crucial due to the horizontal transfer of these natural products from PA-producing plants to soil and subsequently absorbed by plant roots. This study firstly investigated the sorption/desorption behaviors of PAs/PANOs in tea plantation soils with distinct characteristics. Sorption amounts for seneciphylline (Sp) and seneciphylline-N-oxide (SpNO) in three acidic soils ranged from 2.9 to 5.9 µg/g and 1.7 to 2.8 µg/g, respectively. Desorption percentages for Sp and SpNO were from 22.2% to 30.5% and 36.1% to 43.9%. In the mixed PAs/PANOs systems, stronger sorption of PAs over PANOs was occurred in tested soils. Additionally, the Freundlich models more precisely described the sorption/desorption isotherms. Cation exchange capacity, sand content and total nitrogen were identified as major influencing factors by linear regression models. Overall, the soils exhibiting higher sorption capacities for compounds with greater hydrophobicity. PANOs were more likely to migrate within soils and be absorbed by tea plants. It contributes to the understanding of environmental fate of PAs/PANOs in tea plantations and provides basic data and clues for the development of PAs/PANOs reduction technology.


Subject(s)
Camellia sinensis , Pyrrolizidine Alkaloids , Soil Pollutants , Soil , Pyrrolizidine Alkaloids/chemistry , Pyrrolizidine Alkaloids/analysis , Soil/chemistry , Camellia sinensis/chemistry , Soil Pollutants/analysis , Soil Pollutants/chemistry , Oxides/chemistry , Adsorption
2.
Chemosphere ; 362: 142630, 2024 Aug.
Article in English | MEDLINE | ID: mdl-38897321

ABSTRACT

Microplastics (MPs) and their co-pollutants pose significant threats to soil and marine environments, necessitating understanding of their colonization processes to combat the plastic pandemic and protect ecosystems. MPs can act as invisible carriers, concentrating and transporting pollutants, leading to a more widespread and potentially toxic impact than the presence of either MPs or the pollutants alone. Analyzing the sorption and desorption dynamics of MPs is crucial for understanding pollutants amplification and predicting the fate and transport of pollutants in soil and marine environments. This review provides an in-depth analysis of the sorption and desorption dynamics of MPs, highlighting the importance of considering these dynamics in ecotoxicological risk assessment of MPs pollution. The review identifies limitations of current frameworks that neglect these interactions and proposes incorporating sorption and desorption data into robust frameworks to improve the ability to predict ecological risks posed by MPs and co-pollutants in soil and marine environments. However, failure to address the interplay between sorption and desorption can result in underestimation of the true impact of MPs and co-pollutants, affecting livelihoods and agro-employments, and exacerbate poverty and community disputes (SDGs 1, 2, 3, 8, 9, and 16). It can also affect food production and security (SDG 2), life below water and life on land (DSGs 14 and 15), cultural practices, and natural heritage (SDG 11.4). Hence, it is necessary to develop new approaches to ecotoxicological risk assessment that consider sorption and desorption processes in the interactions between the components in the framework to address the identified limitations.


Subject(s)
Ecotoxicology , Environmental Monitoring , Microplastics , Soil Pollutants , Soil , Water Pollutants, Chemical , Microplastics/analysis , Microplastics/toxicity , Microplastics/chemistry , Risk Assessment , Soil Pollutants/analysis , Soil Pollutants/toxicity , Soil Pollutants/chemistry , Environmental Monitoring/methods , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/chemistry , Water Pollutants, Chemical/toxicity , Soil/chemistry , Ecosystem , Adsorption
3.
Int J Mol Sci ; 25(11)2024 May 23.
Article in English | MEDLINE | ID: mdl-38891887

ABSTRACT

With projections suggesting an increase in the global use of neonicotinoids, contemporary farmers can get caught on the "pesticide treadmill", thus creating ecosystem side effects. The aim of this study was to investigate the sorption/desorption behavior of acetamiprid, imidacloprid, and thiacloprid that controls their availability to other fate-determining processes and thus could be useful in leveling the risk these insecticides or their structural analogues pose to the environment, animals, and human health. Sorption/desorption isotherms in four soils with different organic matter (OC) content were modelled by nonlinear equilibrium models: Freundlich's, Langmuir's, and Temkin's. Sorption/desorption parameters obtained by Freundlich's model were correlated to soil physico-chemical characteristics. Even though the OC content had the dominant role in the sorption of the three insecticides, the role of its nature as well as the chemical structure of neonicotinoids cannot be discarded. Insecticides sorbed in the glassy OC phase will be poorly available unlike those in the rubbery regions. Imidacloprid will fill the sorption sites equally in the rubbery and glassy phases irrespective of its concentration. The sorption of thiacloprid at low concentrations and acetamiprid at high concentrations is controlled by hydrophilic aromatic structures, "trapping" the insecticides in the pores of the glassy phase of OC.


Subject(s)
Insecticides , Neonicotinoids , Nitro Compounds , Thiazines , Neonicotinoids/chemistry , Insecticides/chemistry , Nitro Compounds/chemistry , Thiazines/chemistry , Adsorption , Soil/chemistry , Soil Pollutants/chemistry , Pyridines/chemistry , Imidazoles/chemistry
4.
Ecotoxicol Environ Saf ; 278: 116440, 2024 Jun 15.
Article in English | MEDLINE | ID: mdl-38733806

ABSTRACT

The distribution of polycyclic aromatic hydrocarbons (PAHs) in the ocean is affected by the sorption-desorption process of sediment particles. This process is determined by the concentration of PAHs in seawater, water temperature, and organic matter content of sediment particles. Quantitative relationships between the net sorption rates (=the difference of sorption and desorption rates) and these factors have not been established yet and used in PAH transport models. In this study, phenanthrene was chosen as the representative of PAHs. Three groups of experimental data were collected to address the dependence of the net sorption processes on the initial concentration, water temperature, and organic carbon content representing organic matter content. One-site and two-compartment mass-transfer models were tested to represent the experimental data using various parameters. The results showed that the two-compartment mass-transfer model performed better than the one-site mass-transfer model. The parameters of the two-compartment mass-transfer model include the sorption rate coefficients kafand kas (L g-1 min-1), and the desorption rate coefficients kdf and kds (min-1). The parameters at different temperatures and organic carbon contents were obtained by numerical simulations. Linear relationships were obtained between the parameters and water temperature, as well as organic carbon content. kaf, kas and kdf decreased linearly, while kds increased linearly with temperature. kaf, kas and kdf increased linearly, while kds decreased linearly with organic carbon content. The r2 values between the simulation results based on the relationships and the experimental results reached 0.96-0.99, which supports the application of the model to simulate sorption-desorption processes at different water temperatures and organic carbon contents in a realistic ocean.


Subject(s)
Geologic Sediments , Phenanthrenes , Seawater , Temperature , Water Pollutants, Chemical , Phenanthrenes/chemistry , Geologic Sediments/chemistry , Adsorption , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/chemistry , Seawater/chemistry , Environmental Monitoring/methods , Models, Theoretical , Models, Chemical
5.
Adv Mater ; 36(27): e2314175, 2024 Jul.
Article in English | MEDLINE | ID: mdl-38635920

ABSTRACT

Sorption-based atmospheric water harvesting (SAWH) is a promising technology to alleviate freshwater scarcity. Recently, hygroscopic salt-hydrogel composites (HSHCs) have emerged as attractive candidates with their high water uptake, versatile designability, and scale-up fabrication. However, achieving high-performance SAWH applications for HSHCs has been challenging because of their sluggish kinetics, attributed to their limited mass transport properties. Herein, a universal network engineering of hydrogels using a cryogelation method is presented, significantly improving the SAWH kinetics of HSHCs. As a result of the entangled mesh confinements formed during cryogelation, a stable macroporous topology is attained and maintained within the obtained entangled-mesh hydrogels (EMHs), leading to significantly enhanced mass transport properties compared to conventional dense hydrogels (CDHs). With it, corresponding hygroscopic EMHs (HEMHs) simultaneously exhibit faster moisture sorption and solar-driven water desorption. Consequently, a rapid-cycling HEMHs-based harvester delivers a practical freshwater production of 2.85 Lwater kgsorbents -1 day-1 via continuous eight sorption/desorption cycles, outperforming other state-of-the-art hydrogel-based sorbents. Significantly, the generalizability of this strategy is validated by extending it to other hydrogels used in HSHCs. Overall, this work offers a new approach to efficiently address long-standing challenges of sluggish kinetics in current HSHCs, promoting them toward the next-generation SAWH applications.

6.
Membranes (Basel) ; 14(2)2024 Feb 10.
Article in English | MEDLINE | ID: mdl-38392676

ABSTRACT

Isoamyl alcohol is an important biomass fermentation product that can be used as a gasoline surrogate, jet fuel precursor, and platform molecule for the synthesis of fine chemicals and pharmaceuticals. This study reports on the use of graphene oxide immobilized membra (GOIMs) for the recovery of isoamyl alcohol from an aqueous matrix. The separation was performed using air-sparged membrane distillation (ASMD). In contrast to a conventional PTFE membrane, which exhibited minimal separation, preferential adsorption on graphene oxide within GOIMs resulted in highly selective isoamyl alcohol separation. The separation factor reached 6.7, along with a flux as high as 1.12 kg/m2 h. Notably, the overall mass transfer coefficients indicated improvements with a GOIM. Optimization via response surfaces showed curvature effects for the separation factor due to the interaction effects. An empirical model was generated based on regression equations to predict the flux and separation factor. This study demonstrates the potential of GOIMs and ASMD for the efficient recovery of higher alcohols from aqueous solutions, highlighting the practical applications of these techniques for the production of biofuels and bioproducts.

7.
Nano Lett ; 24(8): 2629-2636, 2024 Feb 28.
Article in English | MEDLINE | ID: mdl-38349527

ABSTRACT

Atmospheric water harvesting (AWH) has been broadly exploited to meet the challenge of water shortage. Despite the significant achievements of AWH, the leakage of hydroscopic salt during the AWH process hinders its practical applications. Herein, inspired by the unique selective permeability of the phospholipid bilayer, a sandwich structural (hydrophobic-hydrophilic-hydrophobic) polyacrylonitrile nanofibrous membrane (San-PAN) was fabricated for AWH. The hydrophilic inner layer loaded with LiCl could capture water from the air. The hydrophobic microchannels in the outer layer could selectively allow the free transmission of gaseous water molecules but confine the hydroscopic salt solution in the hydrophilic layer, achieving continuous and recyclable water sorption/desorption. As demonstrated, the as-prepared AWH devices presented high-efficient adsorption kinetics from 1.66 to 4.08 g g-1 at 30% to 90% relative humidity. Thus, this work strengthens the understanding of the water transmission process along microchannels and provides insight into the practical applications of AWH.

8.
Environ Sci Pollut Res Int ; 31(15): 22962-22975, 2024 Mar.
Article in English | MEDLINE | ID: mdl-38418787

ABSTRACT

As the most common filler in stormwater treatment, zeolite (NZ-Y) has good cation exchange capability and stabilization potential for the removal of heavy metal from aqueous solutions. In this study, sodium dodecyl sulfate (SDS) and NZ-Y were selected to preparing new adsorbent (SDS-NZ) by using a simple hydrothermal method. The sorption-desorption performance and mechanism of Cu(II) onto SDS-NZ were investigated. The results showed that the sorption of Cu(II) on SDS-NZ was in accordance with the pseudo-second-order kinetic model with an equilibrium time of 4 h. The sorption behavior fitted Langmuir isotherm with a saturation sorption capability of 9.03 mg/g, which was three times higher than that of NZ-Y. The modification of SDS increases the average pore size of NZ-Y by 3.96 nm, which results in a richer internal pore structure and more useful sorption sites for Cu(II) sorption. There was a positive correlation between solution pH values and sorption capability of Cu(II) in the range of 3.0-6.0. With the ionic strength increased, the sorption capability of Cu(II) onto SDS-NZ first decreased and then increased, which may be attributed to competitive sorption and compression of the electronic layer. The desorption of Cu(II) on SDS-NZ was favored by the increase in SDS concentration and ionic strength and decrease in solution pH values. The application of SDS-NZ in runoff improved the leaching risk of Cu(II). After several cycles, the ability of reused SDS-NZ to efficiently adsorb most heavy metals was verified with removal rates above 99%.


Subject(s)
Metals, Heavy , Water Purification , Zeolites , Copper/chemistry , Zeolites/chemistry , Surface-Active Agents , Rain , Water Purification/methods , Water Supply , Adsorption , Hydrogen-Ion Concentration , Kinetics , Solutions
9.
Sci Total Environ ; 904: 166384, 2023 Dec 15.
Article in English | MEDLINE | ID: mdl-37597559

ABSTRACT

The effective management of beryllium (Be) in solution is not well established. In this study, zeolite was synthesised from coal fly ash (CFA) and further modified to enhance Be sorption. Results indicated zeolite NaP1 was effectively synthesised, and cross-linked chitosan was grafted in/on the zeolite structure during modification. The Brunauer, Emmett, and Teller (BET) surface area substantially increased from 1.05 m2/g in CFA to 94.0 m2/g in the synthesised zeolite (SZ). Furthermore, the modified zeolite (MZ) showed improved functionality as a reactive site for Be sorption. A comparative sorption study revealed inferior sorption (11.3 %) and higher desorption (56.1 %) of Be using CFA than the sorption using SZ (93.0 % sorption, 2.9 % desorption) and MZ (93.0 % sorption, 1.5 % desorption). Consequently, SZ and MZ exhibited higher sorption efficacy than commercial zeolite (57.4 %) and other commercial sorbents. At an experimental pH of 5.5 [relevant to the pH of Little Forest Legacy Waste Site (LFLS) soil, a representative site for potential Be contamination], MZ showed higher sorption than SZ. The higher sorption in MZ resulted from its elevated ligand complexation [with nitrogen (N), phosphorous (P), and oxygen (O)] and some ion exchange (with Na+, -NH3+, and H+ ions) mechanisms. Moreover, increased sorption (up to 99 %) was observed using colloidal soil solution (CSS) collected from LFLS soil to simulate field conditions after extensive rainfall. Different environmental factors (e.g. pH, temperature, time, CSS, concentrations of sorbate, and sorbent) regulated Be sorption. The sorption mechanism was best described by the Langmuir model, and the pseudo-second-order kinetic model (R2 = 0.999). Moreover, the sorption reaction was spontaneous (ΔG = -Ve), enthalpically, and entropically influenced. Desorption hysteresis (ndesorption/nsorption < 1) suggested irreversible sorption, and the chemisorption mechanism of Be was confirmed by Fourier-transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analysis.

10.
Chemistry ; 29(54): e202301929, 2023 Sep 26.
Article in English | MEDLINE | ID: mdl-37429820

ABSTRACT

Moisture harvesters with favourable attributes such as easy synthetic availability and good processability as alternatives for atmospheric moisture harvesting (AWH) are desirable. This study reports a novel nonporous anionic coordination polymer (CP) of uranyl squarate with methyl viologen (MV2+ ) as charge balancing ions (named U-Squ-CP) which displays intriguing sequential water sorption/desorption behavior as the relative humidity (RH) changes gradually. The evaluation of AWH performance of U-Squ-CP shows that it can absorb water vapor under air atmosphere at a low RH of 20 % typical of the levels found in most dry regions of the world, and have good cycling durability, thus demonstrating the capability as a potential moisture harvester for AWH. To the authors' knowledge, this is the first report on non-porous organic ligand bridged CP materials for AWH. Moreover, a stepwise water-filling mechanism for the water sorption/desorption process is deciphered by comprehensive characterizations combining single-crystal diffraction, which provides a reasonable explanation for the special moisture harvesting behaviour of this non-porous crystalline material.

11.
Chem Biol Technol Agric ; 10(1): 29, 2023.
Article in English | MEDLINE | ID: mdl-37026154

ABSTRACT

Soil organic matter (SOM) has a critical role in regulating soil phosphorus (P) dynamics and producing phytoavailable P. However, soil P dynamics are often explained mainly by the effects of soil pH, clay contents, and elemental compositions, such as calcium, iron, and aluminum. Therefore, a better understanding of the mechanisms of how SOM influences phytoavailable P in soils is required for establishing effective agricultural management for soil health and enhancement of soil fertility, especially P-use efficiency. In this review, the following abiotic and biotic mechanisms are discussed; (1) competitive sorption between SOM with P for positively charged adsorption sites of clays and metal oxides (abiotic reaction), (2) competitive complexations between SOM with P for cations (abiotic reaction), (3) competitive complexations between incorporation of P by binary complexations of SOM and bridging cations with the formation of stable P minerals (abiotic reaction), (4) enhanced activities of enzymes, which affects soil P dynamics (biotic reaction), (5) mineralization/immobilization of P during the decay of SOM (biotic reaction), and (6) solubilization of inorganic P mediated by organic acids released by microbes (biotic reaction).

12.
J Hazard Mater ; 449: 130994, 2023 05 05.
Article in English | MEDLINE | ID: mdl-36821898

ABSTRACT

Microplastics (MPs) usually coexist with heavy metals (HMs) in soil. MPs can influence HMs mobility and bioavailability, but the underlying mechanisms remain largely unexplored. Here, polyethylene and polypropylene MPs were selected to investigate their effects and mechanisms of sorption-desorption, bioaccessibility and bioavailability of cadmium (Cd) in paddy soil. Batch experiments indicated that MPs significantly reduced the Cd sorption in soil (p < 0.05). Accordingly, soil with the MPs had lower boundary diffusion constant of Cd (C1= 0.847∼1.020) and the Freundlich sorption constant (KF = 0.444-0.616) than that without the MPs (C1 = 0.894∼1.035, KF = 0.500-0.655). X-ray diffraction, X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy analyses suggested that the MPs reduced Cd chemisorption, by covering the soil active sites and thus blocking complexation of Cd with active oxygen sites and interrupting the formation of CdCO3 and Cd3P2 precipitates. Such effects of MPs enhanced about 1.2-1.5 times of Cd bioaccessibility and bioavailability in soil. Almost the same effects but different mechanisms of polyethylene and polypropylene MPs on Cd sorption in the soil indicated the complexity and pervasiveness of their effects. The findings provide new insights into impacts of MPs on the fate and risk of HMs in agricultural soil.


Subject(s)
Metals, Heavy , Soil Pollutants , Microplastics/chemistry , Cadmium/chemistry , Plastics/chemistry , Soil , Polyethylene/chemistry , Polypropylenes , Biological Availability , Adsorption , Soil Pollutants/analysis
13.
Int J Biol Macromol ; 232: 123355, 2023 Mar 31.
Article in English | MEDLINE | ID: mdl-36682653

ABSTRACT

Hydrogel membranes are prepared by casting a mixture of gellan gum (associated with PVA) and biochar produced from a local Egyptian plant. The mesoporous material is characterized by a specific surface area close to 134 m2 g-1, a residue of 28 % (at 800 °C), and a pHPZC close to 6.43. After grinding, the material is tested for Methylene Blue sorption at pH 10.5: sorption capacity reaches 1.70 mmol MB g-1 (synergistic effect of the precursors). The sorption isotherms are fitted by both Langmuir and Sips eqs. MB sorption increases with temperature: the sorption is endothermic (∆H°: 12.9 kJ mol-1), with positive entropy (∆S°: 125 J mol-1 K-1). Uptake kinetics are controlled by agitation speed (optimum ≈200 rpm) and resistance to intraparticle diffusion. The profiles are strongly affected by the mode of agitation: the equilibrium time (≈180 min) is reduced to 20-30 min under sonication (especially at frequency: 80 kHz). The mode of agitation controls the best fitting equation: pseudo-first order rate agitation for mechanical agitation contrary to pseudo-second order rate under sonication. The sorption of MB is poorly affected by ionic strength (loss <6 % in 45 g L-1 NaCl solution). Desorption (faster than sorption) is completely achieved using 0.7 M HCl solution. At the sixth recycling, the loss in sorption is close to 5 % (≈ decrease in desorption efficiency). The process is successfully applied for the treatment of MB-spiked industrial solution: the color index decreases by >97 % with a sorbent dose close to 1 g L-1; a higher dose is required for maximum reduction of the COD (60 % at 3 g L-1).


Subject(s)
Methylene Blue , Water Pollutants, Chemical , Thermodynamics , Methylene Blue/chemistry , Kinetics , Hydrogels , Water , Adsorption , Hydrogen-Ion Concentration , Water Pollutants, Chemical/chemistry , Solutions
14.
Vopr Pitan ; 92(6): 135-140, 2023.
Article in Russian | MEDLINE | ID: mdl-38198427

ABSTRACT

The main principle in the enrichment of food with minor bioactive compounds is the prediction and evaluation of possible chemical interactions of the components included in the matrix of the food. These interactions have a impact on the bioavailability of minor bioactive compounds. In our work, we studied the processes of sorption and desorption (release), the main processes affecting the bioavailability of the minor bioactive compound ecdysterone (20 E) in the composition of functional food ingredients obtained from spinach leaves (FFI-1) and quinoa grains (FFI-2) on hydrocolloid matrix - inulin. The objective of the research was to study the completeness of sorption-desorption processes of 20 E in adaptogenic compositions with inulin and functional food ingredients based on spinach and quinoa under the influence of hydrolytic enzymes of the gastrointestinal tract (GIT) in vitro. Material and methods. To obtain experimental compositions, containing FFI-1 and FFI-2 and the polysaccharide (inulin), a mechanical mixing method was used. To study the sorption properties, model solutions of the compositions were prepared. Using an in vitro enzymatic model, the ability of 20 E to be released from the matrix of the compositions was studied. The content of 20 E was determined by HPLC-MS/MS. Results. 6 compositions with different ratios of polysaccharide/FFI were obtained. At the first stage of the study, the maximum sorption of 20E in the model solution was observed for 4 compositions with the ratio of inulin : FFI = 2.50 or 3.75 g : 189.19 mg FFI-1 or 68.40 mg FFI-2. At the second stage of the study, when assessing the desorption of 20 E on the enzymatic GIT model, it was found that 20 E almost completely released only from 2 compositions, in other cases about 25% of 20 E remained in a bound state. Conclusion. The formulation of two compositions with the ratio of inulin (2.50 g) : FFI-1 (189.19 mg)/FFI-2 (68.40 mg) were obtained, which have the most optimal sorption / release parameters of 20 E under the influence of human gastrointestinal enzymes. These compositions can be considered promising for inclusion in the formulation of fortified foods.


Subject(s)
Chenopodium quinoa , Food Ingredients , Humans , Inulin , Ecdysterone , Spinacia oleracea , Tandem Mass Spectrometry , Food, Fortified
15.
Plants (Basel) ; 11(23)2022 Dec 04.
Article in English | MEDLINE | ID: mdl-36501405

ABSTRACT

Nanoformulations have been used to improve the delivery of fertilizers, pesticides, and growth regulators, with a focus on more sustainable agriculture. Nanoherbicide research has focused on efficiency gains through targeted delivery and environmental risk reduction. However, research on the behavior and safety of the application of these formulations in cropping systems is still limited. Organic matter contained in cropping systems can change the dynamics of herbicide−soil interactions in the presence of nanoformulations. The aim of this study was to use classical protocols from regulatory studies to understand the retention and mobility dynamics of a metribuzin nanoformulation, compared to a conventional formulation. We used different soil systems and soil with added fresh organic material. The batch method was used for sorption−desorption studies and soil thin layer chromatography for mobility studies, both by radiometric techniques. Sorption parameters for both formulations showed that retention is a reversible process in all soil systems (H~1.0). In deep soil with added fresh organic material, nanoformulation was more sorbed (14.61 ± 1.41%) than commercial formulation (9.72 ± 1.81%) (p < 0.05). However, even with the presence of straw as a physical barrier, metribuzin in nano and conventional formulations was mobile in the soil, indicating that the straw can act as a barrier to reduce herbicide mobility but is not impeditive to herbicide availability in the soil. Our results suggest that environmental safety depends on organic material maintenance in the soil system. The availability can be essential for weed control, associated with nanoformulation efficiency, in relation to the conventional formulation.

16.
Pharmaceutics ; 14(11)2022 Oct 24.
Article in English | MEDLINE | ID: mdl-36365090

ABSTRACT

A series of new composite materials based on Fe3O4 magnetic nanoparticles coated with SiO2 (or aminated SiO2) were synthesized. It has been shown that the use of N-(phosphonomethyl)iminodiacetic acid (PMIDA) to stabilize nanoparticles before silanization ensures the increased content of a SiO2 phase in the Fe3O4@SiO2 nanocomposites (NCs) in comparison with materials obtained under similar conditions, but without PMIDA. It has been demonstrated for the first time that the presence of PMIDA on the surface of NCs increases the level of Dox loading due to specific binding, while surface modification with 3-aminopropylsilane, on the contrary, significantly reduces the sorption capacity of materials. These regularities were in accordance with the results of quantum chemical calculations. It has been shown that the energies of Dox binding to the functional groups of NCs are in good agreement with the experimental data on the Dox sorption on these NCs. The mechanisms of Dox binding to the surface of NCs were proposed: simultaneous coordination of Dox on the PMIDA molecule and silanol groups at the NC surface leads to a synergistic effect in Dox binding. The synthesized NCs exhibited pH-dependent Dox release, as well as dose-dependent cytotoxicity in in vitro experiments. The cytotoxic effects of the studied materials correspond to their calculated IC50 values. NCs with a SiO2 shell obtained using PMIDA exhibited the highest effect. At the same time, the presence of PMIDA in NCs makes it possible to increase the Dox loading, as well as to reduce its desorption rate, which may be useful in the design of drug delivery vehicles with a prolonged action. We believe that the data obtained can be further used to develop stimuli-responsive materials for targeted cancer chemotherapy.

17.
Molecules ; 27(21)2022 Nov 05.
Article in English | MEDLINE | ID: mdl-36364428

ABSTRACT

The kinetics of adsorption phenomena are investigated in terms of local and non-local kinetic equations of the Langmuir type. The sample is assumed in the shape of a slab, limited by two homogeneous planar-parallel surfaces, in such a manner that the problem can be considered one-dimensional. The local kinetic equations in time are analyzed when both saturation and non-saturation regimes are considered. These effects result from an extra dependence of the adsorption coefficient on the density of adsorbed particles, which implies the consideration of nonlinear balance equations. Non-local kinetic equations, arising from the existence of a time delay characterizing a type of reaction occurring between a bulk particle and the surface, are analyzed and show the existence of adsorption effects accompanied by temporal oscillations.

18.
Materials (Basel) ; 15(7)2022 Apr 01.
Article in English | MEDLINE | ID: mdl-35407925

ABSTRACT

The effect of encapsulation of LaNi4.5Co0.5 powdered hydrogen storage material with ≈0.5 µm thick, magnetron-sputtered amorphous film of TiCrFeCoNi high-entropy alloy (HEA) on functional hydrogenation parameters of the hydride electrode is discussed. The multicycle galvanostatic charge/discharge tests carried out in deaerated, 6 M KOH solution allow for determining specific capacity decrease, exchange current density of the H2O/H2 system, and high rate discharge ability (HRD) of the hydride electrodes. Concentrations of individual constituents of the HEA in the particle coating determined by EDS analysis were practically the same (≈20 at.%) as in the applied TiCrFeCoNi target material. The XRD phase analysis pointed out the amorphous structure of the HEA coating. The presence of HEA coating decreases capacity by 10-15 per cent, but increases exchange current density for H2O/H2 system. The effect of HEA on capacity fade is ambiguous: low for 10-25 cycles (most probably due to effective corrosion inhibition) and distinct at long-term cycling (most probably due to galvanic effects resulting from mechanical degradation of particle surface). The presence of HEA coating considerably improves the HRD of the electrode material: for a discharge rate of 5C, the HRD coefficient becomes 4.6 times greater for HEA modified storage material.

19.
J Hazard Mater ; 429: 128314, 2022 May 05.
Article in English | MEDLINE | ID: mdl-35236021

ABSTRACT

A simple first order approximation was derived to model sorption/desorption kinetics of hazardous compounds in batch experiments based on a coupled film and intraparticle diffusion model. The solution is accurate enough to replace infinite series expansions needed in analytical solution for intraparticle diffusion and it accounts for the mass transfer shift from diffusion in the external aqueous boundary layer to the intraparticle pore space. With increasing distribution coefficient (Kd) and intraparticle particle porosity (ε) or decreasing Sherwood number (Sh) this mass transfer shift from film diffusion to intraparticle pore diffusion is delayed. The simple first order approximation equation allows analyses of mass transfer resistances and calculation of characteristic times which is relevant for the planning of batch experiments. The proposed solution is verified by a semi-analytical solution in Laplace space for fractional mass uptakes in the solid phase at equilibrium ranging from 50% to 91%, representing scenarios typically encountered in batch experiments.

20.
Ecotoxicol Environ Saf ; 234: 113378, 2022 Apr 01.
Article in English | MEDLINE | ID: mdl-35255252

ABSTRACT

Pydiflumetofen, a fungicide of the class of succinate dehydrogenase inhibitors, can disrupt energy metabolism by inhibiting the synthesis of succinate dehydrogenase, thus effectively inhibiting pathogenic fungal growth and related yield losses.We studied the adsorption and desorption behaviors and interaction mechanisms of pydiflumetofen in eight different arable soils by the infrared spectroscopy and batch equilibrium method. Pydiflumetofen adsorption and desorption property of soils conformed with the Freundlich isotherm model and the values for the adsorption capacity KF-ads were in the range of 14.592-102.610. The adsorption constants (KF-ads) exhibited a significantly positive and linear correlation (p < 0.1) with soil organic matter and organic carbon content. Both high and low temperatures weakened the pydiflumetofen sorption capacity of the soil. In addition, the initial pH of the solution, its ionic strength, and the addition of exogenous biochar, humic acid, and different types of surfactants at different concentrations also affected the sorption property of the soil. Pydiflumetofen is weakly mobile and leachable in most soils, and, poses some threat to surface soil and water organisms, but does not contaminate groundwater.

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