Variable Oxidation States Research Articles

Modelling the chemistry of Mn-doped MgO for bulk and (100) surfaces.

We have investigated the energetic properties of Mn-doped MgO bulk and (100) surfaces using a QM/MM embedding computational method, calculating the formation energy for doped systems, as well as for surface defects, and the subsequent effect on chemical reactivity. Low-concentration Mn doping is endothermic for isovalent species in the bulk but exothermic for higher oxidation states under p-type conditions, and compensated by electrons going to the Fermi level rather than cation vacancies. The highest occupied dopant Mn 3d states are positioned in the MgO band gap, about 4.2 eV below the vacuum level. Surface Mn-doping is more favourable than subsurface doping, and marginally exothermic on a (100) surface at high O2 pressures. For both types of isovalent Mn-doped (100) surfaces, the formation energy for catalytically important oxygen defects is less than for pristine MgO, with F0 and F2+-centres favoured in n- and p-type conditions, respectively. In addition, F+-centres are stabilised by favourable exchange coupling between the Mn 3d states and the vacancy-localised electrons, as verified through calculation of the vertical ionisation potential. The adsorption of CO2 on to the pristine and defective (100) surface is used as a probe of chemical reactivity, with isovalent subsurface Mn dopants mildly affecting reactivity, whereas isovalent surface-positioned Mn strongly alters the chemical interactions between the substrate and adsorbate. The differing chemical reactivity, when compared to pristine MgO, justifies further detailed investigations for more varied oxidation states and dopant species.

Ultrapure laser-synthesized Si nanoparticles with variable oxidation states for biomedical applications.

We employ a method of femtosecond laser fragmentation of preliminarily prepared water-dispersed microcolloids to fabricate aqueous solutions of ultrapure bare Si-based nanoparticles (Si-NPs) and assess their potential for biomedical applications. The nanoparticles appear spherical in shape, with low size dispersion and a controllable mean size, from a few nm to several tens of nm, while a negative surface charge (-35 mV ± 0.10 according to z-potential data) provides good electrostatic stabilization of colloidal Si-NP solutions. Structural analysis shows that the Si-NPs are composed of Si nanocrystals with inclusions of silicon oxide species, covered by a SiOx (1 < x < 2) shell, while the total oxide content depends on whether the fragmentation is performed in normal oxygen-saturated water (oxygen-rich conditions) or in water deoxygenated by pumping with noble gases (Ag or He) before and during the experiment (oxygen-free conditions). Our dissolution tests show the excellent water-solubility of all the NPs, while more oxidized NPs demonstrate much faster dissolution kinetics, which is explained by oxidation-induced defects in the core of the Si-NPs. Finally, by examining the interaction of the NPs with human cells after 72 h of incubation at different concentrations, we report the absence of any adverse effects of the NPs up to high concentrations (50 μg mL-1) and a good internalization of NPs via a classical endocytosis mechanism. Possessing far superior purity compared to their chemically synthesized counterparts and enabling a variety of imaging and therapeutic functionalities, the laser-synthesized Si-NPs are promising for safe and efficient applications in nanomedicine.

Metals in surface water of Ukraine: the migration forms, features of distribution between the abiotic components of aquatic ecosystems, and potential bioavailability

We have generalized the results of long-term studies of coexisting forms of a series of metals (Al, Fe, Mn, Zn, Cu, Cr, Pb, Mo, Cd, and V) in surface water bodies of Ukraine, differing in the hydrological regime and the water chemical composition (rivers, reservoirs, lakes, and ponds). The studied metals content has ranged widely, the concentrations of aluminum, iron, and manganese being typically the highest, and the concentration of molybdenum, vanadium, and cadmium being typically the lowest. The ratio between the suspended and the dissolved forms of the metals has been established. Iron and aluminum migrate mostly as part of the suspended matter, whereas the other metals mainly migrate in the dissolved state. The dissolved manganese form predominates in the water bodies under anaerobic conditions. Copper and molybdenum are present almost always in the dissolved state, regardless of the water body type. The data on the relative content of the labile metal fraction (potentially toxic to aquatic organisms) are reported. The relatively low content of this fraction has been found to be majorly owing to the metal ions complexing with natural organic ligands. The humic compounds, the most widespread group of natural organic compounds, play the primary role in the complexation. Even metals with variable oxidation state (Cr, Mo, and V) are found mainly in the form of anionic complexes with the humic substances. Carbohydrates are also involved in the metals binding in the highly bioproductive water bodies, thus increasing the mass fraction of the neutral complexes during the summer and autumn periods. The molecular weight distribution of anionic metal complexes has been discussed; the substantial part of the metals constitutes the compounds with the molecular weight of below 5.0 kDa.

Assessing Covalency in Cerium and Uranium Hexachlorides: A Correlated Wavefunction and Density Functional Theory Study

The electronic structure of a series of uranium and cerium hexachlorides in a variety of oxidation states was evaluated at both the correlated wavefunction and density functional (DFT) levels of theory. Following recent experimental observations of covalency in tetravalent cerium hexachlorides, bonding character was studied using topological and integrated analysis based on the quantum theory of atoms in molecules (QTAIM). This analysis revealed that M–Cl covalency was strongly dependent on oxidation state, with greater covalency found in higher oxidation state complexes. Comparison of M–Cl delocalisation indices revealed a discrepancy between correlated wavefunction and DFT-derived values. Decomposition of these delocalisation indices demonstrated that the origin of this discrepancy lay in ungerade contributions associated with the f-manifold which we suggest is due to self-interaction error inherent to DFT-based methods. By all measures used in this study, extremely similar levels of covalency between complexes of U and Ce in the same oxidation state was found.

Characteristics of morphology, structure and composition of titanium surface under its modification by electrochemical polarization in phosphate‐alkaline solutions

The modification of titanium surface under electrochemical polarization (EP) in the phosphate‐alkaline solutions has been studied using the methods of X‐ray diffraction, electron probe microanalysis, atomic force microscopy, X‐ray photoelectron spectroscopy (XPS), cyclic voltammetry and spectroscopic ellipsometry. It is shown that the morphological parameters of the surface, e.g. roughness and stringiness, as well as its structural‐chemical characteristics, e.g. preferred orientation, size and habit of crystallites, titanium chemical forms, thickness and phase composition of oxide film are generally dependent on the polarization potential. The characteristics of titanium surface modified at low anodic potentials 500, 750 and 1000 mV and 10‐min polarization time have been measured. The processes of Ti surface dissolution and etching along grain boundaries are found to be most intensive at 750 mV. Under 500 mV, these processes are poorly developed yet, while at 1000 mV, the surface passivating film formation limits the previous processes. Despite relatively low polarization potentials (1 V), the surficial oxide films have sufficient thickness (up to ~20 nm) and a specific multilayer structure of variable composition and oxidation state of titanium. The data obtained allow to assert that EP represents an effective tool for morphological and a structural chemical modification of a titanium surface. Copyright © 2015 John Wiley &amp; Sons, Ltd.

Synthesis of LiFePO4 powder by the organic–inorganic steric entrapment method

Abstract

Electrochemically Controlled Multistability of Ultrathin Films of Double-Decker Lanthanides Phthalocyanines

Molecular-scale systems that exhibit intramolecular electron transfer (IET) induced by various external stimuli occupy a special place among the systems whose behaviour is determined by charge transfer processes. Such redox-isomeric materials are indeed promising for applications in the development of nanoscale information storage devices. Complexes in which both metal and ligand are redox-active are target objects for the study of redox isomerism phenomenon (reversible intramolecular metal−ligand electron transfer). From this standpoint, tetrapyrrole complexes of metals with variable oxidation states are one of the most promising compounds. Lanthanides phthalocyaninates proved to be very promising objects for the development of “molecular switches” and memory devices. Herein, we report on the electrochemical properties of Langmuir-Blodgett films of series of lanthanides complexes with bis-tetra-15-crown-5-phthalocyanines1,2. A previously unknown phenomenon of orientation-induced redox isomerism in a Langmuir monolayer is revealed in the case of cerium bis-[tetra-(15-crown-5)-phthalocyaninate] – (Ce[(15C5)4Pc]2)3,4 (Fig.1). The mechanism of genuine redox isomerism was confirmed by the results of in-situUV-Vis spectral measurements performed on monolayers and Langmuir-Blodgett films, AFM, and XPS studies of Langmuir-Blodgett films transferred at different surface pressures. The understanding of this reversible IET mechanism is especially important due to possible applications of such redox-isomeric systems in the development of nanoscale multibit information storage devices. 1. Selector, S. L.; Arslanov, V. V.; Gorbunova, Y. G.; Raitman, O. A.; Sheinina, L. S.; Birin, K. P.; Tsivadze, A. Y. Journal of Porphyrins and Phthalocyanines 2008, 12, 1154. 2. Selector, S. L.; Shokurov, A. V; Arslanov, V. V; Gorbunova, Y. G.; Raitman, O. A.; Isakova, A. A.; Birin, K. P.; Tsivadze, A. Y. Rus. J. of Electrochemistry 2012, 48, 218. 3. Selektor, S. L.; Shokurov, A. V.; Raitman, O. A.; Sheinina, L. S.; Arslanov, V. V.; Birin, K. P.; Gorbunova, Y. G.; Tsivadze, A. Y. Colloid J. 2012, 74, 334. 4. Selektor, S.L.; Shokurov, A.V.; Arslanov, V.V.; Gorbunova, Y.G.; Birin, K.P.; Raitman, O.A.; Morote, F.; Cohen-Bouhacina, T.; Grauby-Heywang, Ch.; Tsivadze, A.Yu. J. Phys. Chem. C ., 2014, 118, 4250. Figure 1

Gold Oxide Nanoparticles with Variable Gold Oxidation State

Gold-oxide-containing nanoparticles have been produced in a range of partial to full oxidation conditions, where the nanoparticle electronic structure and stoichiometry have been characterized. Our results indicate that with the increase of the oxidation degree in these nanoparticles the gold oxidation state possibly changes from lower oxides with mono- or divalent metal to the higher oxide with the trivalent gold. At intermediate oxidation conditions our observations are consistent with a radially segregated structure of such nanoparticles—with the core containing mainly oxide and the surface covered with few monolayers of metallic gold. These results have been possible to obtain combining the vapor aggregation method for the nanoparticle fabrication and synchrotron-based photoelectron spectroscopy for their characterization. The deposition of the oxidized nanoparticles has showed that the species assigned as containing lower oxide could be preserved in the landing and then studied on a substrate for a limited time. The possible lower oxide formation in nanoparticles is discussed in connection to the enhanced catalytic activity of gold nanoparticles.

Gold(III)-pyrrolidinedithiocarbamato Derivatives as Antineoplastic Agents.

Transition metals offer many possibilities in developing potent chemotherapeutic agents. They are endowed with a variety of oxidation states, allowing for the selection of their coordination numbers and geometries via the choice of proper ligands, leading to the tuning of their final biological properties. We report here on the synthesis, physico-chemical characterization, and solution behavior of two gold(III) pyrrolidinedithiocarbamates (PDT), namely [AuIIIBr2(PDT)] and [AuIIICl2(PDT)]. We found that the bromide derivative was more effective than the chloride one in inducing cell death for several cancer cell lines. [AuIIIBr2(PDT)] elicited oxidative stress with effects on the permeability transition pore, a mitochondrial channel whose opening leads to cell death. More efficient antineoplastic strategies are required for the widespread burden that is cancer. In line with this, our results indicate that [AuIIIBr2(PDT)] is a promising antineoplastic agent that targets cellular components with crucial functions for the survival of tumor cells.

Trends in the CO oxidation and PROX performances of the platinum-group metals supported on ceria

PGM–CeO2 (PGM=Pt, Pd, Ir, Rh, Ru) catalysts were prepared by one-step solution combustion synthesis (SCS) and characterized by elemental analysis, N2 volumetry, aberration-corrected HRTEM, X-ray diffraction, and CO-DRIFTS. The samples, consisting of 2–6nm metal nanoparticles supported on mesoporous ceria, were tested in CO oxidation in absence and presence of hydrogen (PROX). To our knowledge, this work presents the first comparison of all the platinum-group metals (except Os) for these reactions in the same conditions. The as-prepared SCS catalysts are active in CO oxidation and a reducing treatment has no significant effect on their performances. While the best catalyst in H2-free CO oxidation is Rh–CeO2, the addition of a high hydrogen excess decreases the Rh catalyst activity but enhances the CO oxidation rate on all other systems, including alumina-supported metals employed as reference catalysts. The resulting PROX turnover frequencies (Pt>Pd>Rh>Ir>Ru) follow the trends predicted by published density-functional-theory calculations considering the COad+Oad elementary reaction as the rate-determining step. Pt–CeO2 is not only the most active but also the most selective catalyst, reaching near 100% CO2 at low temperature (ca. 100°C). The alumina-supported catalysts appeared less active than their ceria-supported counterparts in both reactions. The effect of heating/cooling cycles on the reaction kinetics was also investigated. Whereas the Pt, Pd and Ir ceria-supported catalysts were stable throughout PROX cycles, Rh and Ru ones exhibited apparently chaotic behaviors above ca. 200°C, which are proposed to be induced by favorable CO dissociation and methanation pathways and/or variable metal oxidation states.

Heterometallic complexes with cube-type [MTi3N4] cores containing Group 10 metals in a variety of oxidation states.

Treatment of [{Ti(η5-C5Me5)(μ-NH)}3(μ3-N)] (1) with one equivalent of [Ni(cod)2] (cod = 1,5-cyclooctadiene) in toluene at 60–80 °C and subsequent addition of diphenylacetylene, trans-stilbene or triphenylphosphane afforded the nickel(0) complexes [LNi{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}] (L = PhCCPh (2), PhCH≡CHPh (3), PPh3 (4)). The nickel(II) complex [I2Ni{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}] (5) was prepared by analogous addition of iodine to the solution obtained from the heating of 1 and [Ni(cod)2]. Treatment of 1 with one equivalent of [Pd(dba)2] (dba = dibenzylideneacetone) in toluene at room temperature led to the palladium(0) complex [(dba)Pd{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}] (6). Compound 6 reacted immediately with chloroform-d1 to give the palladium dichloride derivative [Cl2Pd{(μ3-NH)2Ti3(η5-C5Me5)3(μ-NH)(μ3-N)}] (7), which was prepared by treatment of 1 with [PdCl2(cod)] at room temperature. Addition of iodine to a toluene solution of 6 afforded the analogous palladium(II) derivative [I2Pd{(μ3-NH)2Ti3(η5-C5Me5)3(μ-NH)(μ3-N)}] (8). Complex 6 reacted with two equivalents of dimethylacetylenedicarboxylate (dmad) to give the metallacyclopentadiene palladium(II) complex [{(MeOOC)4C4}Pd{(μ3-NH)2Ti3(η5-C5Me5)3(μ-NH)(μ3-N)}] (9) via oxidative coupling. The treatment of 1 with [Pt(nbe)3] (nbe = norbornene) in toluene at room temperature gave the platinum(0) complex [(nbe)Pt{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}] (10). Compound 10 reacted with excess iodine to afford the platinum(IV) ionic derivative [I3Pt{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}]2(I3)(I5) (11) via an intermediate platinum(II) complex [I2Pt{(μ3-NH)2Ti3(η5-C5Me5)3(μ-NH)(μ3-N)}] (12). The X-ray crystal structures of 5, 8, 9 and 11 have been determined.

Effect of size and oxidation state of platinum nanoparticles on the electrocatalytic performance of graphene-nanoparticle composites

Size and oxidation state of Pt nanoparticles significantly influence the electrocatalytic performance of Pt–graphene nanocomposites for methanol oxidation and 2.2 nm Pt with variable oxidation states offers the best catalytic activity and durability.

A comparative study in structure and reactivity of “FeO x -on-Pt” and “NiO x -on-Pt” catalysts

Oxide nanostructures grown on noble metal surfaces are often highly active in many reactions, in which the oxide/metal interfaces play an important role. In the present work, we studied the surface structures of FeO x -on-Pt and NiO x -on-Pt catalysts and their activity to CO oxidation reactions using both model catalysts and supported nanocatalysts. Although the active FeO1−x structure is stabilized on the Pt surface in a reductive reaction atmosphere, it is prone to change to an FeO2−x structure in oxidative reaction gases and becomes deactivated. In contrast, a NiO1−x surface structure supported on Pt is stable in both reductive and oxidative CO oxidation atmospheres. Consequently, CO oxidation over the NiO1−x -on-Pt catalyst is further enhanced in the CO oxidation atmosphere with an excess of O2. The present results demonstrate that the stability of the active oxide surface phases depends on the stabilization effect of the substrate surface and is also related to whether the oxide exhibits a variable oxidation state.

Generalized molybdenum oxide surface chemical state XPS determination via informed amorphous sample model

Accurate elemental oxidation state determination for the outer surface of a complex material is of crucial importance in many science and engineering disciplines, including chemistry, fundamental and applied surface science, catalysis, semiconductors and many others. X-ray photoelectron spectroscopy (XPS) is the primary tool used for this purpose. The spectral data obtained, however, is often very complex and can be subject to incorrect interpretation. Unlike traditional XPS spectra fitting procedures using purely synthetic spectral components, here we develop and present an XPS data processing method based on vector analysis that allows creating XPS spectral components by incorporating key information, obtained experimentally. XPS spectral data, obtained from series of molybdenum oxide samples with varying oxidation states and degree of crystallinity, were processed using this method and the corresponding oxidation states present, as well as their relative distribution was elucidated. It was shown that monitoring the evolution of the chemistry and crystal structure of a molybdenum oxide sample due to an invasive X-ray probe could be used to infer solutions to complex spectral envelopes.

Nanostructured MnOx catalysts for low-temperature NOx SCR

Manganese oxides with different structures and morphologies have been investigated as catalysts for low temperature SCR by preparing a series of samples by both SCS (Solution Combustion Synthesis) and co-precipitation methods. The samples have been characterized by XRD, BET, H2-TPR, NH3-TPD, FESEM and their catalytic activity tested for NOx removal in the range of temperature of interest (120–350°C) both in the presence and in the absence of SO2, and after catalyst regeneration from sulphur deactivation. The different preparation procedures allowed to obtain MnOx systems with variable average oxidation state (measured through H2-TPR) that can be put in correlation with the porosity and the morphology measured by the other techniques, and the resulting catalytic performances in the SCR. The presence of Mn3O4 in the resulting material with low degree of crystallinity seemed to be the key factor to get the best catalyst among those prepared, being this phase not only active, but very selective towards the production of N2. Finally, the presence of a relatively high amount of SO2 among reactants (100ppm) drastically reduces the activity of all samples, but regeneration of catalyst for 2h at 400°C almost completely restores the catalytic performances.

Why Dissolved Organic Matter Enhances Photodegradation of Methylmercury

Methylmercury (MeHg) is known to degrade photochemically, but it remains unclear what roles naturally dissolved organic matter (DOM) and complexing organic ligands play in MeHg photodegradation. Here we investigate the rates and mechanisms of MeHg photodegradation using DOM with varying oxidation states and origins as well as organic ligands with known molecular structures. All DOM and organic ligands increased the rate of MeHg photodegradation under solar irradiation, but the first-order rate constants varied depending on the oxidation state of DOM and the type and concentration of the ligands. Reduced DOM photochemically degraded MeHg 3 times faster than oxidized DOM. Compounds containing both thiol and aromatic moieties within the same molecule (e.g., thiosalicylate and reduced DOM) increased MeHg photodegradation rates far more than those containing only aromatics or thiols (e.g., salicylate or glutathione, or their combinations). The mechanism is attributed in part to strong binding between MeHg and ...

A rhodium(III) complex inhibits LPS-induced nitric oxide production and angiogenic activity in cellulo

Metal-containing complexes have arisen as viable alternatives to organic molecules as therapeutic agents. Metal complexes possess a number of advantages compared to conventional carbon-based compounds, such as distinct geometries, interesting electronic properties, variable oxidation states and the ability to arrange different ligands around the metal centre in a precise fashion. Meanwhile, nitric oxide (NO) plays key roles in the regulation of angiogenesis, vascular permeability and inflammation. We herein report a novel cyclometalated rhodium(III) complex as an inhibitor of lipopolysaccharides (LPS)-induced NO production in RAW264.7 macrophages. Experiments suggested that the inhibition of NO production in cells by complex 1 was mediated through the down-regulation of nuclear factor-κB (NF-κB) activity. Furthermore, complex 1 inhibited angiogenesis in human umbilical vein endothelial cells (HUVECs) as revealed by an endothelial tube formation assay. This study demonstrates that kinetically inert rhodium(III) complexes may be potentially developed as effective anti-angiogenic agents.

Reactive uptake of N&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;O&amp;lt;sub&amp;gt;5&amp;lt;/sub&amp;gt; to internally mixed inorganic and organic particles: the role of organic carbon oxidation state and inferred organic phase separations

Abstract. We measured N2O5 reactive uptake onto mixed organic/inorganic submicron particles using organic compounds with a variety of oxidation states (using mainly atomic O : C ratios as a proxy) and molecular weights. The organic mass fraction, organic molecular composition, and relative humidity (RH) were varied to assess their effects separately on the N2O5 uptake coefficient, γ(N2O5). At a constant RH, mixtures of organic components having an O : C &lt; 0.5 with ammonium bisulfate significantly suppressed the uptake of N2O5(g) compared to pure ammonium bisulfate, even at small organic mass fractions (e.g., ≤ 15%). The effect of the organic component became less pronounced at higher RH. In general, highly oxygenated organic components (O : C &gt; 0.8) had a smaller or even negligible impact on N2O5(g) uptake at all RHs probed; however, a few exceptions were observed. Notably, γ(N2O5) for mixtures of ammonium bisulfate with polyethylene glycol (PEG), PEG-300 (O : C = 0.56), decreased nearly linearly as the PEG mass fraction increased at constant RH until leveling off at the value measured for pure PEG. The response of γ(N2O5) to increasing PEG mass fraction was similar to that measured on ambient atmospheric particles as a function of organic mass fraction. The effects of the organic mass fraction on γ(N2O5), for mixtures having an O : C &lt; ~0.8, were best described using a standard resistor model of reactive uptake assuming the particles had an RH-dependent inorganic core–organic shell morphology. This model suggests that the N2O5 diffusivity and/or solubility in the organic layer is up to a factor of 20 lower compared to aqueous solution particles, and that the diffusivity, solubility, and reactivity of N2O5 within organic coatings and particles depend upon both RH and the molecular composition of the organic medium. We use these dependencies and ambient measurements of organic aerosol from the global aerosol mass spectrometry (AMS) database to show that the typical impact of organic aerosol components is to both uniformly decrease γ(N2O5), by up to an order of magnitude depending on the RH, organic mass fraction, and O : C ratio, and to induce a stronger dependence of γ(N2O5) upon RH compared to purely inorganic aqueous solutions.

Group 10 Metal Complexes Supported by Pincer Ligands with an Olefinic Backbone

The coordination chemistry of 2,2′-bis(di-iso-propylphosphino)-trans-stilbene (tPCH═CHP) with group 10 metal centers in a variety of oxidation states is reported; different coordination modes were observed depending on the oxidation state of the metal. With metal centers in the 0 or +1 oxidation state ((tPCH═CHP)Ni, [(tPCH═CHP)Pd]2, (tPCH═CHP)NiCl, (tPCH═CHP)NiI), η2 coordination of the olefin occurs, whereas, with metals in the +2 oxidation state, C–H activation of the backbone, followed by rapid H–X reductive elimination, was observed, leading to an η1 coordination of the backbone in (tPC═CHP)MCl (M = Ni, Pd, Pt). Employing the methyl-substituted analogue, 2,2′-bis(di-iso-propylphosphino)-trans-diphenyl-1,2-dimethylethene (tPCMe═CMeP), forced an η2 coordination of the olefin in [(tPCMe═CMeP)NiCl]2[NiCl4]. The synthesis of the hydride complex (tPC═CHP)NiH was attempted, but, instead, led to the formation of (tPCH═CHP)Ni, indicating that the vinyl form of the backbone can function as a hydrogen acceptor. All metal complexes were characterized by multinuclei NMR spectroscopy, X-ray crystallography, and elemental analysis.

Adsorption of uranium composites onto saltrock oxides – experimental and theoretical study

The study encompassed experimental mass spectrometric and theoretical quantum chemical studies on adsorption of uranium species in different oxidation states of the metal ion, and oxides of UxOyn+ type, where x = 1 or 3, y = 2 or 8, and n = 0, 1 or 2 onto nanosize-particles of saltrock oxides MO (M = MgII, CaII, NiII, CoII, SrII or BaII), M2Oy (M = AuIII or AgI, y = 3 or 1) silicates 3Al2O3.2SiO2, natural kaolinite (Al2O2·2SiO2·2H2O), illite (K0.78Ca0.02Na0.02(Mg0.34Al1.69FeIII0.02)[Si3.35Al0.65]O10(OH)2·nH2O), CaSiO3, 3MgO·4SiO2,H2O, and M1M2(SiO4)X2 (M1 = M2 = Al or M1 = K, M2 = Al, X = F or Cl), respectively. The UV-MALDI-Orbitrap mass spectrometry was utilized in solid-state and semi-liquid colloidal state, involving the laser ablation at λex = 337.2 nm. The theoretical modeling and experimental design was based on chemical-, physico-chemical, physical and biological processes involving uranium species under environmental conditions. Therefore, the results reported are crucial for quality control and monitoring programs for assessment of radionuclide migration. They impact significantly the methodology for evaluation of human health risk from radioactive contamination. The study has importance for understanding the coordination and red-ox chemistry of uranium compounds as well. Due to the double nature of uranium between rare element and superconductivity like materials as well as variety of oxidation states ∈ (+1)–(+6), the there remain challenging areas for theoretical and experimental research, which are of significant importance for management of nuclear fuel cycles and waste storage.