Divalent Ions Research Articles

Co-emulsified Alginate-Eudragit Nanoparticles: Potential Carriers for Localized and Time-defined Release of Tenofovir in the Female Genital Tract

This research aimed to explore the possibilities of Eudragit S100 (ES100) and sodium alginate as carriers for tenofovir disoproxil fumarate (TDF) in the female genital tract. Alginate and alginate-ES100 nanoparticles were prepared using the ionic gelation and emulsion/gelation complexation method, respectively. The nanocarriers were tested using morphological, physicochemical, in vitro drug release, and cytotoxicity analyses. In SEM and TEM images, the presence of spherical and uniformly distributed nanoparticles was revealed. The FTIR spectrum showed that alginate and calcium chloride interacted due to ionic bonds linking divalent calcium ions and the -COO- of alginate groups. Alginate and ES100 interacted via the ester C=O amide stretching. The results obtained from XRD and DSC, on the other hand, revealed a favorable interaction between sodium alginate and ES100 polymers, as evidenced by the crystallization peaks observed. Under experimental design analysis and optimization, overall size distribution profiles ranged from 134.9 to 228.0 nm, while zeta potential results showed stable nanoparticles (−17.8 to −38.4 MV). The optimal formulation exhibited a maximum cumulative in vitro release of 72% (pH 4.2) up to 96 h. The cytotoxicity tests revealed the safety of TDF-loaded nanoparticles on vaginal epithelial cells at concentrations of 0.025 mg/mL, 0.5 mg/mL, and 1 mg/mL for 72 h. These results indicated that alginate-ES100 nanoparticles have the potential to preserve and sustain the release of the TDF drug in the FGT. The future goal is to develop a low-dose non-toxic microbicide that can be administered long term in the vagina to cater to both pregnant and non-pregnant HIV patients.

New Approach for Enhancing Sensitivity in Liquid‐Gated Nanowire FET Biosensors Under Optical Excitation

AbstractThe results obtained for liquid‐gated (LG) nanowire (NW) field‐effect transistor (FET) sensors analyzed in divalent ion (MgCl2) solutions, which play a crucial role in the human body, are reported. Liquid‐gated NW FET sensors fabricated in‐house are investigated using I–V characteristics and noise spectroscopy in a wide range of voltages and different intensities of optical infrared irradiation. A new effect is revealed under the influence of external optical excitation. The effect allows for the control of characteristic times of single‐trap phenomena: capture time to a single trap, emission time from the trap, and its ratio represented by the dimensionless ratio parameter (R‐factor). These parameters enabled an improvement in sensor sensitivity. The findings open prospects for controlling charge states in LG NW FET structures to optimize new parameters for achieving ultrahigh sensitivity in biosensors.

Enhancing Dendritic Cell Activation Through Manganese-Coated Nanovaccine Targeting the cGAS-STING Pathway.

Nanovaccines have emerged as a promising vaccination strategy, exhibiting their capacity to deliver antigens and adjuvants to elicit specific immune responses. Despite this potential, optimizing the design and delivery of nanovaccines remains a challenge. In this study, we engineered a dendritic mesoporous silica-based nanocarrier enveloped in a metal-phenolic network (MPN) layer containing divalent manganese ions and tannic acid (MSN@MT). This nanocarrier was tailored for antigen loading to serve as a nanovaccine, aiming to activate the cyclic GMP-AMP synthase-stimulator of interferon genes (cGAS-STING) pathway in dendritic cells (DCs). Our experimental approach encompassed both cellular assays and mouse immunizations, allowing a comprehensive evaluation of the nanovaccine's impact on DC activation and its influence on the generation of antigen-specific T-cell responses. MSN@MT demonstrated a remarkable enhancement in humoral and cellular immune responses in mice compared to control groups. This highlights the potential of MSN@MT to effectively trigger the cGAS-STING pathway in DCs, resulting in robust immune responses. Our study introduces MSN@MT, a unique nanocarrier incorporating divalent manganese ions and tannic acid, showcasing its exceptional ability to amplify immune responses by activating the cGAS-STING pathway in DCs. This innovation signifies a stride in refining nanovaccine design for potent immune activation.

Investigation of the impact of A-site cation disorder on the structure, magnetic properties, and magnetic entropy change of trisubstituted divalent ions in La0.7(Ba,Ca,Sr)0.3MnO3 manganite.

This study investigates the effect of A-site disorder, characterized by the average ionic radius (〈rA〉) and the cation mismatch (σ2), on the structural, magnetic, critical behavior, and magnetic entropy changes in La0.7(Ba,Ca,Sr)0.3MnO3 manganites with trisubstituted Ba, Ca, and Sr. The sol-gel method was used to prepare polycrystalline samples. All series of compounds crystallize in rhombohedral symmetry with the R3̄c space group. A linear relationship between lattice parameters, unit cell volume, and 〈rA〉 was observed. This reveals an unusual behavior in the correlation between 〈rA〉 and σ2 concerning magnetic properties, which is attributed to the complex simultaneous trisubstitution of divalent ions. Energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) were utilized to validate the chemical composition of compounds. All the samples crystallized in rhombohedral symmetry, and the lattice parameters increased continuously with increasing 〈rA〉. A-site disorder causes distortions in the Mn-O bond length and Mn-O-Mn bond angle in the MnO6 octahedral structure, which influences the double-exchange interaction and electronic bandwidth (W). The Curie temperature (TC) increases linearly with increasing W. The critical behavior around TC for all the samples was investigated by determining the values of the critical exponents (β, γ, and δ) using the modified Arrott plot (MAP) method. The estimated critical exponents show that the unconventional model establishes a short-range ferromagnetic order. The maximum magnetic entropy change (-ΔSM) was obtained with the lowest 〈rA〉 and σ2 value. The analysis of the critical behavior and universal curve indicates a second-order phase transition (SOPT) nature for all samples.

Selective ion transport in large-area graphene oxide membrane filters driven by the ionic radius and electrostatic interactions.

Filters made of graphene oxide (GO) are promising for purification of water and selective sieving of specific ions; while some results indicate the ionic radius as the discriminating factor in the sieving efficiency, the exact mechanism of sieving is still under debate. Furthermore, most of the reported GO filters are planar coatings with a simple geometry and an area much smaller than commercial water filters. Here, we show selective transport of different ions across GO coatings deposited on standard hollow fiber filters with an area >10 times larger than typical filters reported. Thanks to the fabrication procedure, we obtained a uniform coating on such complex geometry with no cracks or holes. Monovalent ions like Na+ and K+ can be transported through these filters by applying a low electric voltage, while divalent ions are blocked. By combining transport and adsorption measurements with molecular dynamics simulations and spectroscopic characterization, we unravel the ion sieving mechanism and demonstrate that it is mainly due to the interactions of the ions with the carboxylate groups present on the GO surface at neutral pH.

Granular aqueous suspensions with controlled interparticular friction and adhesion.

We present a simple route to obtain large quantities of suspensions of non-Brownian particles with stimuli-responsive surface properties to study the relation between their flow and interparticle interactions. We perform an alkaline hydrolysis reaction on poly(methyl methacrylate) (PMMA) particles to obtain poly(sodium methacrylate) (PMAA-Na) particles. We characterize the quasi-static macroscopic frictional response of their aqueous suspensions using a rotating drum. The suspensions are frictionless when the particles are dispersed in pure water. We relate this state to the presence of electrosteric repulsion between the charged surfaces of the ionized PMAA-Na particles in water. Then we add monovalent and multivalent ions (Na+, Ca2+, La3+) and we observe that the suspensions become frictional whatever the valency. For divalent and trivalent ions, the quasi-static avalanche angle θc at large ionic strength is greater than that of frictional PMMA particles in water, suggesting the presence of adhesion. Finally, a decrease in the pH of the suspending solution leads to a transition between a frictionless plateau and a frictional one. We perform atomic force microscopy (AFM) to relate our macroscopic observations to the surface features of the particles. In particular, we show that the increase in friction in the presence of multivalent ions or under acidic conditions is driven by a nanoscopic phase separation and the bundling of polyelectrolyte chains at the surface of the particle. Our results highlight the importance of surface interactions in the rheology of granular suspensions. Our particles provide a simple, yet flexible platform to study frictional suspension flows.

RNA-binding peptide and endosomal escape-assisting peptide (L2) improved siRNA delivery by the hexahistidine-metal assembly.

Small interfering RNAs (siRNAs), comprising 21-23 nucleotides, function by complementary binding to specific mRNA sequences, thereby suppressing target protein expression. Despite their vast potential in disease therapy, siRNAs face challenges due to their susceptibility to degradation and high electronegativity, rendering them unstable in the bloodstream and impeding their passage across endothelial barriers. Moreover, successful intracellular delivery necessitates overcoming endosomal entrapment, posing a significant hurdle for carrier material development. In this study, leveraging the strong affinity of histidine oligomers (His6) for metal ions, we engineered nanoparticles (HmA) by gentle assembly with divalent zinc ions under pH = 8 conditions. We designed the RNA-binding functional peptide L2-NTD to enhance siRNA stability and delivery efficiency when complexed with HmA. The resulting siRNA+L2-NTD@HmA nanoparticles were formed via in situ encapsulation, ensuring efficient siRNA delivery into cells with minimal cytotoxicity and degradation. This approach presents a novel strategy for the design and artificial fabrication of carriers for effective RNA delivery.

Amine-directed synthesis, valence state control, and optical properties of two new organic-inorganic tin chlorides.

Two organic-inorganic tin chlorides, namely (C9H26N3Cl)SnCl4 (1) and (C9H26N3Cl)SnCl6 (2), were prepared via valence state control using N,N,N',N'',N''-pentamethyldiethylenetriamine as a structure-directing agent. The two compounds have zero-dimensional structures crystallized in non-centrosymmetric orthorhombic space group Cmc21 and P212121, respectively. In compound 1, the divalent tin ion forms a seesaw coordination configuration with four chloride ions, whereas in compound 2, the tetravalent tin ion forms an octahedral coordination configuration with six chloride ions. The two compounds show a moderate second-harmonic generation response under 1064 nm laser irradiation. Notably, compound 2 displays a bright orange luminescence with a photoluminescence quantum yield of 19.67%. Theoretical calculations were performed to gain insights into the optical properties of the two compounds.

PH-responsive on-demand release of eugenol from metal-organic frameworks for synergistic bacterial killing.

Bacterial infections are a big challenge in clinical treatment, making it urgent to develop innovative antibacterial systems and therapies to combat bacterial infections. In this study, we developed a novel MOF-based synergistic antibacterial system (Eu@B-UiO-66/Zn) by loading a natural antibacterial substance (eugenol) with hierarchically porous MOF B-UiO-66 as a carrier and further complexing it with divalent zinc ions. Results indicate that the system achieved a controlled release of eugenol under pH responsive stimulation, with the complexation ability of eugenol and Zn2+ ions as a switch. Due to the destruction of a coordination bond between eugenol and Zn2+ ions by an acidic medium, the release of eugenol loaded in Eu@B-UiO-66/Zn reached 80% at pH 5.8, which was significantly higher than that under pH 8.0 (51%). Moreover, the inhibitory effect of Eu@B-UiO-66/Zn against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) after 24 h was 96.4% and 99.7%, respectively, owing to the synergistic antibacterial effect of eugenol and Zn2+ ions, which was significantly stronger than free eugenol and Eu@B-UiO-66. We hope that this strategy for constructing responsive MOF-based antibacterial carriers could have potential possibilities for the application of MOF materials in antibacterial fields.

Hydrophilicity and surface charge modulation of Ti3C2T x MXene based membranes for water desalination.

Lamellar membranes obtained by stacking 2D layers possess ample transport pathways due to their intricate network of interlayer gaps. This makes them suitable for molecular separation applications. However, controlling the surface chemistry of the nanochannels within the membrane to tune the desired transport properties of water and ions is challenging. Ti3C2T x has been considered for water desalination because of its hydrophilic surface and negative surface charge. Most of the studies of Ti3C2T x membranes have presented promising salt rejection values in forward osmosis mode, which is less practical for water purification. Here, we investigate two types of reverse osmosis MXene-based lamellar membranes consisting of Ti3C2T x nanosheets hybridized with (i) WS2 nanosheets and (ii) polyvinyl phosphonic acid (PVPA). When hydrophilic and flexible Ti3C2T x nanosheets are interleaved with softer and more hydrophobic WS2 nanosheets in 2 : 1 mass ratio, nano capillaries with Janus chemistry are created with comparable rejection to bare Ti3C2T x membrane and threefold higher permeance values. Further, we find that decorating Ti3C2T x nanosheets with anionic polymers improves salt rejection. Our Ti3C2T x /PVPA composite membranes reject ∼97% of divalent ions and ∼80% of monovalent ions with ∼0.2 Lm-2 h-1 bar-1 of water permeance when tested with brackish water, and exhibit significantly improved chlorine resistance and cost benefits over the commercial Toray membranes.

Development in desalination and wastewater treatment: state of the art challenges, role of solar energy, and recommendations

Abstract Water purification is crucial to ensure the availability of safe and clean water for protecting human health and helping in a sustainable environment. This review explicitly provides an overview of the major developments related to seawater desalination and wastewater treatments as a unit. Anticipating these traditional independent facilities will operate together in the future mainly for economic benefits. The advances in seawater desalination are primarily focused on the production of membranes using different types of nanoparticles (CeO2, UiO-66, CS-NPs) and carboxylated multi-walled CNTs into a polyamide that provides high salt rejection (as high as 90%) with excellent selectivity and permeability. Further, the use of nanoporous reduced graphene oxide (rGO) membranes provided 27.7–62.6% desalination rates and up to 96.8% salt rejection, along with protection against membrane fouling. Metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) showed excellent rejection of divalent ions during desalination. It is anticipated that the use of solar energy for membrane and thermal desalination may be promising since it reduces the reliance on fossil energy and significantly minimizes greenhouse gas emissions (up to 94%). Solar energy can integrate with the reverse osmosis (RO) process bearing the cost of energy-intensive compressors, making the RO economically attractive.

Differential electrophoretic mobility of synthetic DNA motifs and duplex DNA in various counter ions.

In this work, we analyzed the electrophoretic behavior of a double crossover (DX) DNA motif in various counter ions. The influence of the type and concentration of counter ions on electrophoretic behavior is different for the DX motif compared to a duplex of the same molecular weight. Higher concentrations of divalent ions Mg2+ and Ca2+ in the gel and running buffer reduce the electrophoretic migration of the DX motif. This effect is less pronounced in the monovalent ion Na+ while K+ ion did not have any significant effect on the electrophoretic behavior.

Salinity and pH effects on water-oil-calcite interfaces by using molecular dynamics.

Smart water injection is a technology that allows changing the wettability of the oil rock by injecting water at different salinities, in a cheap and environmentally friendly way compared to other traditional methods. In this study, the individual effect of some typical salts on the wettability of the (104) surface of calcite toward non-polar and polar crude oil models was explored by molecular dynamics as a function of the salinity and pH. The results obtained show that the electrical double layer plays a principal role in the detachment of crude oil models. The divalent ion salts, i.e., CaCl2, CaSO4, MgCl2, and MgSO4, do not form the electrical double layer on calcite, but salts of NaCl and Na2SO4 form it. Moreover, the surface affinity of calcite to the non-polar crude oil is not affected by the salinity. However, the affinity of the calcite surface toward polar crude is affected by salinity and pH conditions. This research provides new insights into the action mechanisms that could help optimize its uses in enhanced oil recovery.

Investigation of the solid oxidizer effect on the metal geotechnology efficiency

Purpose. The research is aimed at increasing the useful component content in a pregnant solution during in-situ leaching (ISL) using a solid oxidizer and increasing the ferric iron concentration in the leaching solution based on laboratory research. Methods. Laboratory research is performed on a specially developed model electrolyzer for obtaining comparative data on divalent iron oxidation to trivalent iron and the change in the useful component content in a pregnant solution. Firstly, tests are conducted with a basic leaching solution, then on the oxidation of the leaching solution with a solid oxidizer in the form of a lead dioxide plate. Tests are conducted by changing sulphuric acid concentration within 5-50 g/l, amount of divalent iron ions in the solution from 0.5 up to 4.0 g, lead dioxide plate surface area from 19 to 76 cm2. The leaching time is up to 10 hours. Findings. The results of laboratory research on determining the oxidation degree of divalent iron ions and change in the oxidation-reduction potential (ORP) depending on the sulphuric acid concentration and on the initial concentration of divalent iron ions in the initial solution are presented. With a change in the sulphuric acid concentration from 5 to 50 g/l, the oxidation value of divalent iron ions increases from 26.5 to 96.5%, and with an increase in the initial solution concentration of divalent iron, the oxidation degree of divalent iron naturally decreases from 95.2 to 58.8%. In the initial leaching solution, the divalent solution concentration is 312 mg/l, and that of the trivalent solution is 288 mg/l. After oxidation with a solid oxidizer, the divalent and trivalent iron concentrations are 56 and 392 mg/l, respectively. In the course of further laboratory research using core materials from a uranium deposit, it has been revealed that when leaching with a basic solution, the uranium content in the pregnant solution is 19.36 mg/l, and when leaching with a solution after oxidation with a solid oxidizer, it is 27.9 mg/l, which is by 8.54 mg/l more. Originality. New dependences have been determined of the oxidation degree of divalent iron ions to trivalent one on the sulphuric acid concentration and on the initial concentration of divalent iron ions, as well as the useful component content in the pregnant solution on the leaching time when using a solid oxidizer. Practical implications. Using of a solid oxidizer, it is possible to increase the trivalent iron concentration in the leaching solution and the useful component content in the pregnant solution compared with the basic technology, thereby reducing the time of mining uranium reserves. Proposed technology is environmentally friendly, with low capital costs.

Preparation of whey protein isolate-iron-curcumin ternary composite nanoparticles and investigation of formation mechanism

Whey protein isolate (WPI) exhibits mineral binding and acts as a potentially versatile carrier of the nutritional properties of curcumin. This study aimed to investigate the synthesis of WPI-Fe-Curcumin by combining iron and curcumin with WPI, to determine whether the antioxidant capacity of curcumin can protect the high-quality iron source Fe2+ when it binds to divalent iron ions, to describe the mechanism of WPI-Fe-Curcumin complex formation and to investigate the solubility stability of the complex. The results showed that (i) The iron content was 3.561 mg/g protein, and the encapsulation efficiency for curcumin was 99.98% efficiency. (ii) After dehydration, the high solubility of the WPI-Fe-Curcumin dry powder was 85.41% at 0 day and 82.84% at day 30. (iii) The addition of curcumin resulted in a 6.04% increase in Fe2+ content, indicating that curcumin provided an antioxidant reducing environment for the iron ions. (iv) The introduction of iron reduced the particle size and promoted the formation of β-sheet structures of whey protein. These results suggest that WPI-Fe-Curcumin can facilitate the development of effective nutrient delivery systems for applications in food, iron supplement, and pharmaceutical industries.

Antioxidant Activity of Auricularia auricula Polysaccharides with Different Molecular Weights and Cytotoxicity Difference of Polysaccharides Regulated CaOx to HK-2 Cells.

This study aimed to investigate the growth of calcium oxalate (CaOx) crystals regulated by Auricularia auricular polysaccharides (AAPs) with different viscosity-average molecular weights (Mv), the toxicity of AAP-regulated CaOx crystals toward HK-2 cells, and the prevention and treatment capabilities of AAPs for CaOx stones. The scavenging capability and reducing capacity of four kinds of AAPs (Mv of 31.52, 11.82, 5.86, and 3.34 kDa) on hydroxyl, ABTS, and DPPH free radicals and their capability to chelate divalent iron ions were detected. AAP-regulated CaOx crystals were evaluated by using zeta potential, thermogravimetric analysis, X-ray diffraction, and scanning electron microscopy. The cytotoxicity of AAP-regulated crystals was evaluated through examination of cell viability, cell death, malondialdehyde (MDA) content, and cell surface hyaluronic acid (HA) expression. The in vitro antioxidant activities of the four AAPs were observed in the following order: AAP0 < AAP1 < AAP2 < AAP3. Thus, AAP3, which had the smallest Mv, had the strongest antioxidant activity. AAPs can inhibit the growth of CaOx monohydrate (COM), induce the formation of CaOx dihydrate (COD), and reduce the degree of crystal aggregation, with AAP3 exhibiting the strongest capability. Cell experiments showed the lowest cytotoxicity in AAP3-regulated CaOx crystals, along with the lowest MDA content, HA expression, and cell mortality. In addition, COD presented less cytotoxicity than COM. Meanwhile, the cytotoxicity of blunt crystals was less than that of sharp crystals. AAPs, particularly AAP3, showed an excellent antioxidative capability in vitro, and AAP3-regulated CaOx crystals presented minimal cytotoxicity.

Low temperature regulated reverse interfacial polymerization for fabricating thin film composite membranes based on nanofibrous substrates

In this study, a novel thin film nanofibrous composite (TFNC) nanofiltration (NF) membranes comprised of polyacrylonitrile (PAN) nanofibrous supporting layer and polyamide (PA) compact separating layer was constructed by low-temperature-controlled reverse interfacial polymerization (LTIP-R) at − 5 °C. The strategy for lowering the temperature of organic phase solution played a crucial role in forming a dense and thin PA layer on the PAN nanofibrous substrate with submicron pores. The results revealed that the reduced evaporation rate of organic phase at low temperature was contributed to maintaining a complete and uniform interface for the following reverse IP process, effectively overcoming shortcomings of surface incompleteness and easy infiltration of PA barrier layer. Owing to the reduced thickness and the enhanced wholeness of the PA separating layer via LTIP-R, the optimized TFNC membranes exhibited NF performance with great rejection of divalent salt ions (98.2%) and an improved permeation (13.3 L‧m−2‧h−1‧bar−1). This work would provide an efficient and facile method to fabricate high performance NF membranes for practical applications.

DNA Probes for Cas12a-Based Assay with Fluorescence Anisotropy Enhanced Due to Anchors and Salts.

CRISPR/Cas12a is a potent biosensing tool known for its high specificity in DNA analysis. Cas12a recognizes the target DNA and acquires nuclease activity toward single-stranded DNA (ssDNA) probes. We present a straightforward and versatile approach to transforming common Cas12a-cleavable DNA probes into enhancing tools for fluorescence anisotropy (FA) measurements. Our study involved investigating 13 ssDNA probes with linear and hairpin structures, each featuring fluorescein at one end and a rotation-slowing tool (anchor) at the other. All anchors induced FA changes compared to fluorescein, ranging from 24 to 110 mr. Significant FA increases (up to 180 mr) were obtained by adding divalent metal salts (Mg2+, Ca2+, Ba2+), which influenced the rigidity and compactness of the DNA probes. The specific Cas12a-based recognition of double-stranded DNA (dsDNA) fragments of the bacterial phytopathogen Erwinia amylovora allowed us to determine the optimal set (probe structure, anchor, concentration of divalent ion) for FA-based detection. The best sensitivity was obtained using a hairpin structure with dC10 in the loop and streptavidin located near the fluorescein at the stem in the presence of 100 mM Mg2+. The detection limit of the dsDNA target was equal to 0.8 pM, which was eight times more sensitive compared to the common fluorescence-based method. The enhancing set ensured detection of single cells of E. amylovora per reaction in an analysis based on CRISPR/Cas12a with recombinase polymerase amplification. Our approach is universal and easy to implement. Combining FA with Cas12a offers enhanced sensitivity and signal reliability and could be applied to different DNA and RNA analytes.

Structural ordering studies of Nd3+ ion in eulytite-type M3Y(PO4)3 (M=Sr2+ or Ba2+) phosphates. First translucent ceramics from micro-crystalline cubic powders

Cubic phosphates of M3Y(PO4)3 (M = Sr2+ or Ba2+) from the eulytite family were studied as potential candidates for new optical polycrystalline ceramics showing transparency. Two series of Nd3+-doped Ba3Y(PO4)3 and Sr3Y(PO4)3 micro-powders were synthesized via solid-state reaction method. The correlation between their structure and spectroscopic properties and the effect of divalent Sr2+/Ba2+ cation creating a network was analyzed in detail. The crystal structure of Ba3Y(PO4)3 and Sr3Y(PO4)3 was solved ab initio based on their single crystals. Y3+ and Sr2+/Ba2+ ions do not share the same symmetry site and some slight distortion over crystallographic positions occupied by divalent and trivalent ions in the cationic sublattice was visible. Nd3+ reside at the Y3+ site but partial substitution of Ba2+ or Sr2+ cannot be excluded. The cationic and anionic disorder is reflected in spectroscopic properties. Nd3+ ion used as a structural probe shows multisite character and inhomogeneous distribution in both types of material, as determined using absorption spectroscopy at 4.2 K and laser-excited site-selective luminescence spectroscopy at 77 K. This is also clearly seen in excited state dynamics of 4F3/2 doublet analysis. A greater order for barium host lattice was observed. Also, the first un-doped translucent ceramics were obtained from micro-crystalline powders.

Ligand exchange provides new insight into the role of humic substances in the marine iron cycle

Organic complexation of iron plays a crucial role in preventing its precipitation, facilitating its transport, and modulating its reactivity and bioavailability in natural waters. Although humic substances (HS) complexes serve as the primary source of terrestrial iron reaching ocean waters, the transition from Fe-HS species to other forms of organic complexation with ocean autochthonous ligands has not yet been properly described. Taking advantage of the electrolability of Fe-HS complexes, we monitored the ligand exchange of iron-saturated Suwannee River fulvic and humic acids (SRFA and SRHA) after the addition of desferrioxamine B (DFOB) and other ligands for comparison. We observed that Fe-HS concentrations gradually decreased until reaching an apparent steady state, typical of a reversible reaction within 1 to 15 h. The dissociation kinetics and species partitioning of Fe-SRHS complexes at the equilibrium showed some features contrary to the current paradigm of HS iron complexation. The affinity of SRFA to bind iron is close to that of DFOB and for SRHA is even higher. The heterogeneity of the HS iron binding groups was confirmed, although experiments in NaCl solutions revealed that in seawater it is substantially caused by the interaction of major divalent ions. The different dissociation kinetics of Fe-SRHS complexes obtained with different competing ligands and the absence of Fe-DFOB dissociation in the presence of iron-free SRFA indicate an intimate associative mechanism of ligand exchange, with the presence of a ternary complex (SRHS-Fe-DFOB) that does not form if the departing complex is Fe-DFOB. We hypothesize that at the concentrations of HS and siderophores found in the open ocean, iron ligand exchange is limited and organic iron speciation will be close to being regulated on a “first come, first served” basis. Experiments conducted under saturation of all iron complexes support the formation of a permanent concentration of a ternary complex. Our findings show the real complexity of cation-ligand interactions in seawater, with implications for the interpretation of recent chromatographic and electrochemical measurements and for the understanding of iron partitioning in the presence of ubiquitous HS.