The integration of nanoencapsulation techniques with foliar application presents a promising approach to enhance selenium (Se) biofortification in agriculture. This study examined the foliar uptake of liposome-encapsulated Se in wheat leaves (Triticum aestivum) using synchrotron-based micro-X-ray fluorescence (μ-XRF) and confocal microscopy. μ-XRF mapping showed Se accumulation at leaf edges after 24 h, suggesting initial uptake via stomata, while free Se was absorbed and transported more rapidly, highlighting the slow-release effect provided by liposomal encapsulation, longer than the analyzed time. No immediate translocation of Se to the stem was observed, suggesting that more time is required for this internal movement. Micro-X-ray absorption near-edge structure (μ-XANES) speciation analysis demonstrated that Se was metabolized into organic forms within the plant. Finally, confocal fluorescence microscopy confirmed liposome absorption through the plant surface within 24 h, corroborating the μ-XRF findings. These results are crucial for optimizing liposome formulation to maximize Se transfer to edible parts.

Understanding how trace-metal doping directs the electrochemical reconstruction of MOF precatalysts into the true active phase remains a key challenge in designing efficient oxygen evolution reaction (OER) electrocatalysts. Here, a bimetallic Mn-Co zeolitic imidazolate framework-67 material, denoted as Mn-ZIF-67, was prepared through a facile room-temperature self-assembly route that incorporated trace Mn into the ZIF-67 lattice. Compared with undoped ZIF-67, Mn-ZIF-67 exhibits enhanced alkaline OER performance, with the overpotential at 10 mA cm-2 (η10) value decreasing from 276 to 235 mV, a reduced Tafel slope of 36.49 mV dec-1, and sustained stability during long-term durability testing. A combination of structural characterization and density functional theory (DFT) calculations demonstrates that Mn-ZIF-67 undergoes electrochemical surface reconstruction into Mn-modified Co (oxy)hydroxides, which serve as the real catalytically active phase. Mn-mediated electronic modulation optimizes intermediate adsorption energetics and lowers reaction free energies, thereby accelerating reaction kinetics. Notably, the catalyst sustains stable oxygen evolution during 100 h of continuous alkaline seawater electrolysis at 50 mA cm-2, and the assembled electrolyzer can additionally be driven by a commercial solar panel, demonstrating practical applicability. Overall, this work highlights transition-metal doping as a viable route for tailoring the reconstruction of MOF-derived precursors, paving the way for durable and scalable OER electrocatalysts.

Controlling the spatial distribution of defects in metal-organic frameworks (MOFs) remains a fundamental challenge in defect engineering. Here, we report a cage-directed assembly strategy that enables the programmed introduction of topologically correlated defects and induces aperiodicity in HKUST-1-type frameworks. Pre-synthesised Rh(II) metal-organic cages or polyhedra (MOPs) act as persistent cavities that template the formation of HKUST-1-based networks containing linker-induced Cu-vacancy domains confined within discrete cuboctahedral cavities. The use of dicarboxylate linkers, in which one carboxylate group is missing compared to the original 1,3,5-benzenetricarboxylate linker, gives rise to nine distinct local defect configurations that are independently distributed throughout the lattice. This results in an aperiodic framework with preserved long-range crystallinity. The resulting materials exhibit hierarchical micro-mesoporosity, reversible loss and recovery of crystallinity, and a pronounced solvent-induced breathing response. This work demonstrates that combining pre-formed cages with linkers with reduced connectivity can be a new strategy to localise defects and access aperiodic MOFs with emergent structural adaptability.

Selenium (Se) is an essential micronutrient, yet its deficiency remains a global concern. This study investigates the biofortification of alfalfa (Medicago sativa cv. ProINTA Super Monarca GR9) via foliar Se application to enhance Se accumulation and transformation into bioavailable organic forms. A controlled environment experiment in a plant growth chamber and a one-season open-field trial (January 2023, Argentina) were conducted. Treatments included sodium selenate (Se(VI)), sodium selenite (Se(IV)), and a 1:1 mixture, applied at 45 and 90 g Se ha−1, with and without the biostimulant BIOFORGE®. Treated plants exhibited increased Se content, correlating with the applied doses. X-ray absorption spectroscopy (XAS) confirmed that most inorganic Se was transformed into organic Se forms, with Se(IV) treatments yielding the highest concentrations of organic Se species such as selenocysteine (SeCys) and selenomethionine (SeMet). Open-field trials showed a complete conversion of Se, though total Se accumulation was lower than in controlled conditions. Se treatments did not affect forage quality or biomass production. The biostimulant slightly reduced Se uptake but did not compromise biofortification. These results highlight Se(IV) as the optimal treatment for alfalfa biofortification, presenting a sustainable strategy to enhance dietary Se intake through functional foods.

The impact of selenium (Se) enrichment on bioactive compounds and sugars and Se speciation was assessed on different microgreens (green pea, red radish, and alfalfa). Sodium selenite and sodium selenate at a total concentration of 20 mu M (1:1) lead to a noticeable Se biofortification (40-90 mg Se kg(-1) DW). In green pea and alfalfa, Se did not negatively impact phenolics and antioxidant capacity, while in red radish, a significant decrease was found. Regarding photosynthetic parameters, Se notably increased the level of chlorophylls and carotenoids in green pea, decreased chlorophyll levels in alfalfa, and had no effect on red radish. Se treatment significantly increased sugar levels in green pea and alfalfa but not in red radish. Red radish had the highest Se amino acid content (59%), followed by alfalfa (34%) and green pea (28%). These findings suggest that Se-biofortified microgreens have the potential as functional foods to improve Se intake in humans.

In the present work, liposomes have been used as nanocarriers in the biofortification of wheat plants with selenium (Se) through foliar application. Liposomal formulations were prepared using 1,2-dipalmitoyl-sn-glycero3-phosphocholine (DPPC) and Phospholipon (R) 90H (P90H) (average size <100 nm), loaded with different concentrations of inorganic Se (selenite and selenate) and applied twice to the plants in the stage of vegetative growth. Liposomes enhanced Se uptake by wheat plants compared to direct application. The highest Se enrichment was achieved using the phospholipid DPPC and a concentration of 1000 mu mol & sdot;L-1 of Se without affecting the biomass, chlorophylls, carotenoids, and the concentration of mineral nutrients of the plants. The chemical speciation of Se in the plants was further investigated by X-ray absorption spectroscopy (XAS). The results from XAS spectra revealed that most of the inorganic Se was transformed to organic Se and that the use of liposomes influenced the proportion of C-Se-C over C-Se-Se-C species.

Mercury (Hg) pollution in agricultural soils and its potential pathway to the human food chain can pose a serious health concern. Understanding the pathway of Hg in plants and how the speciation may change upon interaction with other elements used for biofortification can be critical to assess the real implications for the final plant-based product. In that respect, selenium (Se) biofortification of crops grown in Se-poor soil regions is becoming a common practice to overcome Se deficient diets. Therefore, it is important to assess the interplay between these two elements since Se may form complexes with Hg reducing its bioavailability and toxicity. In this work, the speciation of Hg in wheat plants grown hydroponically under the presence of Hg (HgCl2) and biofortified with Se (selenite, selenate, or a 1:1 mixture of both) has been investigated by X-ray absorption spectroscopy at the Hg L3-edge. The main Hg species found in wheat grains was the highly toxic methylmercury. It was found that the Se-biofortification of wheat did not prevent, in general, the Hg translocation to grains. Only the 1:1 mixture treatment seemed to have an effect in reducing the levels of Hg and the presence of methylmercury in grains.

A commercial open-celled cellulose sponge, along with its modification through loading iron oxide nanoparticles, were used as adsorbents for As(V) removal in both a dynamic fixed-bed laboratory column and a scaled-up pilot plant. The results indicated that the type of adsorbent material used and the initial concentration, rather than the flow rate, were the parameters that more significantly influenced the breakthrough curves. The As(V) removal rates in both column systems consistently exceeded 95% under all tested conditions. The breakthrough curve data could be adequately agreed with both Thomas and Yoon-Nelson kinetic models. This suggested the potential applicability of both models in the prediction of As(V) behaviors in the real industrial fixed-bed column adsorption process. The operation of the pilot plant system with sponge under a realistic concentration of As(V) solution (1 mg·L-1) has been capable of concentrating arsenic in the desorbed effluent more than two orders of magnitude upon regeneration of the material with 0.5 M NaOH. These findings hold significant implications for industrial applications, demonstrating the successful implementation of three-dimensional sponge-loaded superparamagnetic iron oxide nanoparticles (SPION) adsorbents within pilot-scale fixed-bed column systems.

This study presents functionalized open-celled cellulose Metalzorb & REG; sponge (Sponge) with 3-mercaptopropionic acid (MPA) and L-Cysteine (Cys), and the resulting MPA@Sponge and Cys@Sponge showed significantly improved removal efficiency towards trace cisplatin and carboplatin against Sponge. MPA@Sponge achieved maximum removal of 88.9 & PLUSMN; 0.5% for cisplatin and 85.2 & PLUSMN; 0.4% for carboplatin, while Cys@Sponge achieved maximum removal of 75 & PLUSMN; 2% and 59 & PLUSMN; 1%. In contrast, Sponge only achieved removal of 29 & PLUSMN; 4% and 4 & PLUSMN; 1%, respectively. It suggests that thiol groups serve as favourable binding sites for Pt complexation. Carboplatin exhibits lower adsorption compared to cisplatin due to its limited hydration. However, the presence of Cl- in stock and high temperature facilitate the hydration and the formation of active derivatives of carboplatin, thereby enhancing its adsorption. The rapid adsorption processes of cisplatin and carboplatin are well described by the pseudo-second-order kinetic model involving diffusion and chemisorption. The results from adsorption isotherms revealed a monolayer adsorption that aligns with the principles proposed by the Langmuir model. High temperature significantly enhances the adsorption, and the positive enthalpies indicate that the binding of Pt with thiol groups is endothermic process. X-ray absorption spectroscopy measurements at the Pt L3-edge revealed a similar coordination environment of the adsorbed Pt on both functionalized adsorbents, which can be attributed to the formation of four Pt-S bonds during the adsorption. To assess the validity of the adsorption results under realistic medium conditions, an adsorption study was carried out by using diluted urine spiked with trace platinum cytostatic drugs to simulate hospital wastewater. 90.2 & PLUSMN; 0.3% of cisplatin and 77.0 & PLUSMN; 0.2% of carboplatin was effectively removed by MPA@Sponge from diluted urine.

Developing efficient materials for the removal of boron from aqueous solutions is becoming an important task to overcome boron pollution. Herein, we present hierarchical alumina microspheres (HAM) as an outstanding adsorbent, synthesized via a microwave-assisted co-precipitation method. The microstructure, morphology, and textural characterization of the HAM particles carried out by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) revealed hollow gamma-Al2O3 particles with a porous dandelion-like shape and an average size of 1.5 mu m. The analysis of the adsorption data indicated that the adsorption was homogeneous in a single layer and that chemical adsorption was the controlling step in the process. The adsorption capacity obtained at an initial concentration of 800 mg center dot L-1 was 51.60 mg center dot g- 1, and the theoretically calculated maximum adsorption capacity using the Langmuir model was 138.50 mg center dot g- 1, which outperforms previously reported adsorbents. The determination of thermodynamic parameters indicated that the adsorption is an exothermic and non-spontaneous process. The XPS spectra of HAM after adsorption indicated the formation of Al-O-B bonds. Of particular interest for industrial applications, the HAM adsorbent showed excellent selectivity for boron in the presence of competing cations or anions and at different ionic strengths. In addition, HAM maintained a high adsorption capacity after five consecutive adsorption/desorption cycles. These findings highlight the potential of HAM as a highly microporous material for boron removal in real industrial applications.

Increasing levels of boron in water exceeding acceptable thresholds have triggered concerns regarding environmental pollution and adverse health effects. In response, significant efforts are being made to develop new adsorbents for the removal of boron from contaminated water. Among the various materials proposed, inorganic adsorbents have emerged as promising materials due to their chemical, thermal, and mechanical stability. This review aims to comprehensively examine recent advances made in the development of inorganic adsorbents for the efficient removal of boron from water. Firstly, the adsorption performance of the most used adsorbents, such as magnesium, iron, aluminum, and individual and mixed oxides, are summarized. Subsequently, diverse functionalization methods aimed at enhancing boron adsorption capacity and selectivity are carefully analyzed. Lastly, challenges and future perspectives in this field are highlighted to guide the development of innovative high-performance adsorbents and adsorption systems, ultimately leading to a reduction in boron pollution.

Wheat can be biofortified with different inorganic selenium (Se) forms, selenite or selenate. The choice of Se source influences the physiological response of the plant and the Se metabolites produced. We looked at selenium uptake, distribution and metabolization in wheat exposed to selenite, selenate and a 1:1 molar mixture of both to determine the impact of each treatment on the Se speciation in roots, shoots, and grains. To achieve a comprehensive quantification of the Se species, the complementarity of high-performance liquid chromatography coupled with inductively coupled plasma mass spectrometry and X-ray absorption spectroscopy was exploited. This approach allowed the identification of the six main selenium species: selenomethionine, selenocysteine, selenocystine, selenite, selenate, and elemental selenium. The three treatments resulted in similar total selenium concentration in grains, 90-150 mg Se kg(-1), but produced different effects in the plant. Selenite enhanced root accumulation (66% of selenium) and induced the maximum toxicity, whereas selenate favored shoot translocation (46%). With the 1:1 mixture, selenium was distributed along the plant generating lower toxicity. Although all conditions resulted in > 92% of organic selenium in the grain, selenate produced mainly C-Se-C forms, such as selenomethionine, while selenite (alone or in the mixture) enhanced the production of C-Se-Se-C forms, such as selenocystine, modifying the selenoamino acid composition. These results provide a better understanding of the metabolization of selenium species which is key to minimize plant toxicity and any concomitant effect that may arise due to Se-biofortification.

Kale (Brassica oleracea L. var. sabellica L.), kohlrabi (Brassica oleracea L. var. gongylodes L.) and wheat (Triticum aestivum L. cv. Bancal) microgreens were cultivated in presence of selenium 20 mu mol L-1 as sodium selenite and sodium selenate mixture. The influence of this biofortification process was evaluated in terms of biomass production, total Se, macro-and micronutrients concentration, polyphenols, antioxidant activity, chlorophylls and carotenoids levels and total soluble proteins content. The results obtained have shown a significant concentration of total Se in the biofortified microgreens of kale (133 mu g Se center dot g(-1) DW) and kohlrabi (127 mu g Se center dot g(-1) DW) higher than that obtained for wheat (28 mu g Se center dot g(-1) DW). The Se uptake in all the species did not produce oxidative damage to the plants reflected in the bioactive compounds, antioxidant capacity or pigments concentration. These Se-enriched microgreens may contribute to the recommended intake of this nutrient in human diet as to overcome Se-deficiency.

Hypothesis: The easy aggregation of superparamagnetic iron oxide nanoparticles (SPION) greatly reduces their adsorption performance for removing arsenic (As) from polluted water. We propose to exploit the porosity and good diffusion properties of a cube-shaped cellulose sponge for loading SPION to reduce the aggregation and to develop a composite adsorbent in the cm-scale that could be used for industrial applications. Experiments: SPION were in-situ synthesized by co-precipitation using a commercial cube-shaped sponge (MetalZorb (R)) as support. The morphology, iron-oxide phase, adsorption performance and thermodynamic parameters of the composite adsorbent were determined to better understand the adsorption process. X-ray absorption spectroscopy (XAS) was used to investigate the chemical state of the adsorbed As (III). Findings: The adsorption of the supported SPION outperforms the unsupported SPION (ca. 14 times higher adsorption capacity). The modelling of the adsorption isotherms and the kinetic curves indicated that chemisorption is controlling the adsorption process. The thermodynamic analysis shows that the adsorption retains the spontaneous and endothermic character of the unsupported SPION. The XAS results revealed an adsorption-oxidation mechanism in which the adsorbed As(III) was partially oxidized to less toxic As(V) by the hydroxyl free radical (.OH) generated from Fe(III) species and by the hydroxyl groups. (c) 2022 The Authors. Published by Elsevier Inc.

In this study, a commercial cube-shaped open-celled cellulose sponge adsorbent was mod-ified by in-situ co-precipitation of superparamagnetic iron oxide nanoparticles (SPION) and used to remove As(V) from aqueous solutions. Fe K-edge X-ray absorption spectroscopy (XAS) and TEM identified maghemite as the main iron phase of the SPION nanoparticles with an average size 13 nm. Batch adsorption experiments at 800 mg/L showed a 63% increase of adsorption capacity when loading 2.6 wt.% mass fraction of SPION in the cube-sponge. Experimental determination of the adsorption thermodynamic parameters indicated that the As(V) adsorption on the composite material is a spontaneous and exothermic process. As K-edge XAS results confirmed that the adsorption enhancement on the composite can be attributed to the nanoparticles loaded. In addition, adsorbed As(V) did not get reduced to more toxic As(III) and formed a binuclear comer-sharing complex with SPION. The advan-tageous cube-shape of the sponge-loaded SPION composite together with its high affinity and good adsorption capacity for As(V), good regeneration capability and the enhanced-diffusion attributed to its open-celled structure make this adsorbent a good candidate for industrial applications.

Objectives: To compare the side effects of typical whitening treatments (by means of oxidation) compared to the new treatment developed by the authors through reduction. The aim is to provide information about the chemical interactions of the encapsulated reductant agent (metabisulfite, MBS) with the enamel structure compared with carbamide peroxide (CP) and to study their penetration in the hydroxyapatite (HAP) and the changes produced in the mineral and its hardness. Methods: Chemical imaging is performed by synchrotron-based micro Fourier transformed infrared spectroscopy (SR-mu FTIR). Continuous Stiffness Measurements (CSM) were used to determine the depth reached by the treatments in order to delimitate the area of study. Results: The SR-mu FTIR studies showed that MBS treatments softened the first 10 mu m of enamel, as happens in the initial stages of tooth decay. Principal component analysis (PCA) showed that the main differences between treatments were found in the intensity of the nu 3 PO43-peak related to tooth demineralization. CP and MBS promoted different changes in the HAP mineral, observed as opposite shifts of the peak: CP shortened the P-O bond while MBS seemed to elongate it. Moreover, MBS promoted the loss of carbonates while CP did not, which is probably related to the solution's pH. When comparing MBS and MBS Liposomes, it was observed how liposomes favoured the diffusion of MBS to inner layers, since the effects of MBS were observed in deeper enamel. Thus, the encapsulated MBS whitening effect is highly improved in terms of time when compared to MBS alone or CP. Significance: The obtained results indicated that using oxidizing (CP) or reducing (MBS) treatments, promote different HAP mineral changes, and that liposomes favour the diffusion of MBS into the enamel. It is the first time that synchrotron light is used to map the bovine incisor's enamel chemically, and to determine the effect of a whitening treatment in terms of chemical HAP modifications, and the extent in deep of these effects.(c) 2022 The Author(s). Published by Elsevier Inc. on behalf of The Academy of Dental Materials.CC_BY_NC_ND_4.0

Nephrolithiasis is a multifactor disease that produces nephrolites in the kidneys. Calcium oxalate hydrate (dihydrated, COD, or monohydrated, COM) stones are the most common ones with more than sixty percent incidence worldwide. They are related to different pathologies, COD with hypercalciuria and COM with hyperoxaluria. COD is an unstable species and transforms into COM (herein named TRA to distinguish the origin of the monohydrated species). TRA and COM are chemically and crystallographically identical leading to misdiagnosis and recurrence increase. In the current study, the composition and crystalline structures of several calcium oxalate stones, classified by morpho-constitutional analysis, were examined by IR and synchrotron through-the-substrate micro-X-ray diffraction (tts-μXRD). Both IR and linear diffractogram studies were able to distinguish between the monohydrated and dihydrated phases but not between COM and TRA, as expected. The analysis of 2D diffraction patterns revealed that TRA showed a lower degree of crystallinity and less texture with respect to COM which can be used as a signature to distinguish between the two. This study confirms that despite the subtle differences between COM and TRA, the origin of the monohydrate oxalates can be unraveled using tts-μXRD. This valuable information should be taken into account in order to improve patients' diagnosis and reduce recurrence by considering and treating the origin of the formed stones.

The local structural changes associated with the ZIF-8 frameworkflexibility upon nitrogen gas adsorption have beenstudied byin situX-ray absorption spectroscopy (XAS) and high-energy-resolutionfluorescence-detected X-ray absorption near-edgestructure (HERFD-XANES) spectroscopy. Different thermodynamic conditions (isobar and isotherm) have been used to explorethe so-called"gate opening"transition in which the hexagonal pore windows of the sodalite cage open, increasing the accessiblevolume for gas adsorption. To elucidate the source of the spectral changes in the XANES region of the absorption spectra observedalong the gas adsorption and through the transition from the closed to the open pore configuration,ab initiocalculations have beenperformed. Our results demonstrate that the transition from the closed to the open pore configurations involves not only therotation of the MeIM ligand but also a further bend of the Me group away from the plane defined by the IM ring. Additionally, thecontribution of the N2molecules adsorbed in the center of the 4-ring window has been included in the scattering model to fullyreproduce the main features of the X-ray absorption spectra in the open pore configuration

Pine biomass (Pine), pine gasification biochar (PG) and pine biomass loaded with TiO2 (Pine/TiO2) were used as sorbent materials to remove Cr(III) or Cr(VI) ions from aqueous solutions. Our results showed that Pine/TiO2 had an improved adsorption capacity respect to Pine being the adsorption capacity for Cr(VI), 12.8 mg/g, much larger than for Cr(III), 1.23 mg/g. On the other hand, PG showed much higher adsorption for Cr(III), 12.4 mg/g, than Pine/TiO2, and negligible adsorption for Cr(VI). To understand this species-dependent adsorption behavior, the adsorption mechanisms, sorbents morphology and functional sites were characterized using a multi-technique approach. The chemical state and local coordination structure of the adsorbed Cr species was studied by X-ray absorption spectroscopy (XAS). Our results show that the adsorption of Cr(III) occurred mainly through cation exchange with mineral elements in PG biochar, whereas the Cr(III) adsorption by functional groups (carboxyl and hydroxyl groups) dominate in the biomass sorbent. The enhancement of Cr(VI) adsorption in Pine/TiO2 can be explained by the presence of TiOH2+groups present in the surface of the TiO2 microparticles. X-ray absorption spectroscopy (XAS) results reveal that Cr(VI) reduces to Cr(III) after being adsorbed by the sorbent materials.