Clusters In Aqueous Solutions Research Articles

Modeling of orthosilicate and methanesulfonic acid clusters in aqueous solution

In the work using the quantum-chemical modeling method, the possibility of binding orthosilicate acid with different amounts of methanesulfonate anions was considered. It was demonstrated that methanesulfonic acid forms two hydrogen bonds with a molecule of orthosilicate acid, regardless of the conformation of the cluster itself. According to the results of calculations of energy parameters of systems and frontier molecular orbitals, it was established that the most stable cluster of orthosilicate acid with methanesulfonate anion is [H4SiO4 · 4CH3SO3–]. It was also established that the formation of an eight-membered cycle (S–O···H–O–Si–O–H···O) and (S–O···H –O–Si–O···H–С). Furthermore, it was established that there is no significant dependence of the effective charge on the silicon atom on the number of methanesulfonate anions in the inner sphere. Thus, it is theoretically demonstrated that the methanesulfonate anion is able to stabilize orthosilicate acid and reduce the possibility of its dimerization.

Sub-second pair distribution function using a broad bandwidth monochromator.

Here the use of a broad energy bandwidth monochromator, i.e. a pair of B4C/W multilayer mirrors (MLMs), is demonstrated for X-ray total scattering (TS) measurements and pair distribution function (PDF) analysis. Data are collected both on powder samples and from metal oxo clusters in aqueous solution at various concentrations. A comparison between the MLM PDFs and those obtained using a standard Si(111) double-crystal monochromator shows that the measurements yield MLM PDFs of high quality which are suitable for structure refinement. Moreover, the effects of time resolution and concentration on the quality of the resulting PDFs of the metal oxo clusters are investigated. PDFs of heptamolybdate clusters and tungsten α-Keggin clusters from X-ray TS data were obtained with a time resolution down to 3 ms and still showed a similar level of Fourier ripples to PDFs obtained from 1 s measurements. This type of measurement could thus open up faster time-resolved TS and PDF studies.

Theoretical and mechanistic insights into control factor-assisted CO2 mineralization with olivine

We elucidate the CO2 mineralization mechanism with Mg-rich forsterite via theoretical approach including density functional theory (DFT) calculations and molecular dynamics (MD) simulations. Here, the CO2 mineralization follows two steps: the ion dissolution pathway for dissolving Mg ions from the forsterite surface, and the cluster growth pathway, where ion pairs agglomerate into molecular-sized MgCO3 clusters in aqueous solution. Step-by-step reaction mechanism for the dissolution of Mg ion was investigated via DFT calculations, and the formation procedure of solvated magnesite clusters and their structural changes over time were observed through MD simulations. Afterward, the effects of three control factors of pH, temperature, and hetero-metal ions were studied for both pathways. We found that the adjustment of pH contributed to the structural changes of the mineral surface and clustering ion pairs, which in turn affected the kinetics of reaction pathway. Also, high-temperature condition induced positive effects for accelerating both mineralization pathways. Lastly, calcium and ferrous ions showed opposite effects, promoting and hindering the overall processes, respectively. Importantly, our mechanistic study suggests that the pH of the solution changes alternatively between acid and base conditions during each mineralization pathway and pH condition induced by the preceding mineralization pathway facilitates the subsequent one.

Cover Feature: DOTP versus DOTA as Ligands for Lanthanide Cations: Novel Structurally Characterized CeIV and CeIII Cyclen‐Based Complexes and Clusters in Aqueous Solutions (Chem. Eur. J. 61/2022)

Cover Feature: DOTP versus DOTA as Ligands for Lanthanide Cations: Novel Structurally Characterized Ce^IV and Ce^III Cyclen‐Based Complexes and Clusters in Aqueous Solutions (Chem. Eur. J. 61/2022)

DOTP versus DOTA as Ligands for Lanthanide Cations: Novel Structurally Characterized CeIV and CeIII Cyclen-Based Complexes and Clusters in Aqueous Solutions.

The coordination and redox chemistry of aqueous CeIV/III macrocyclic compounds were studied by using the ligands DOTA and DOTP (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayl)tetraacetic acid and 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetra(methylene phosphonic acid), respectively). The hydrolysis tendency of the tetravalent cation in the presence of DOTA is shown to result in the formation of a highly ordered, fluorite-like [CeIV 6 (O)4 (OH)4 (H2 O)8 (DOTAH)4 ] oxo-hydroxo structure both in solution and in the solid state. The lifetime of the analogous species formed in the presence of DOTP was found to be much shorter. Spectroscopic measurements of the latter suggest its similarity to the former. Its gradual decomposition in solution leads to the accumulation of the in-cage complexes [CeIV DOTP] and [CeIII DOTP(H2 O)], which were crystallographically characterized in this study. The redox energetics and spectroscopic characteristics for the transition between these two in-cage complexes in aqueous solutions were studied as well. Together with the crystallographic structures of the above-mentioned species, the in-cage [CeIV DOTA(H2 O)] complex structure is presented herein for the first time. An elaborative analysis of the X-ray crystallographic structural data obtained for the in-cage complexes studied herein and similar structures published previously suggests that hard-bonding cyclen-derived ligands are, counter-intuitively, better suited for encapsulating, and perhaps kinetically stabilize softer cations than harder ones with DOTP, marked as a possible adequate chelator for the study of the aqueous properties of LnII and AcIII cations.

C60 Fullerene Clusters Stabilize the Biologically Inactive Form of Topotecan.

There is a range of experimental proofs that biologically relevant compounds change their activity in the presence of C60 fullerene clusters in aqueous solution, which most frequently act as a nanoplatform for drug delivery. Inspired by this evidence, we made an effort to investigate the interaction of fullerene clusters with the antibiotic topotecan (TPT). This study proceeded in three steps, namely, UV/vis titration to confirm complexation and in vitro assays on proliferating and nonproliferating cells to elucidate the role of C60 fullerene in the putative change in TPT activity. Surprisingly, although the nonproliferating cell assay is consistent with the titration data and confirms complex formation, it contradicted the results of the proliferating cell assay. The latter showed that the mixture of TPT and fullerene affects the cells in the same way as pure TPT, as if there were no fullerenes in solution at all, whereas the action of TPT was expected to be enhanced. We explained this contradiction by the specific stabilization of the biologically inactive carboxylate form of the antibiotic adsorbed in the alkaline shell of large fullerene clusters, which leads to neutralization of the drug delivery function and almost zero net biological effect of the antibiotic in vitro. The practical outcome of the work is that fullerene clusters can be used for the selective delivery of pH-sensitive drug forms.

Size and structure of hexanuclear plutonium oxo-hydroxo clusters in aqueous solution from synchrotron analysis.

The size and shape of a water-soluble hexanuclear plutonium cluster were probed by combining synchrotron small-angle X-ray scattering (SAXS) and extended X-ray absorption fine structure (EXAFS). A specific setup coupling both techniques and dedicated to radioactive samples on the MARS beamline endstation at Synchrotron SOLEIL is described. The plutonium hexanuclear cores are well stabilized by the 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid ligands and this allows a good evaluation of the setup to probe the very small plutonium core. The results show that, in spite of the constrained conditions required to avoid any risk of sample dispersion, the flux and the sample environment are optimized to obtain a very good signal-to-noise ratio, allowing the detection of small plutonium aggregates in an aqueous phase. The structure of the well defined hexanuclear cluster has been confirmed by EXAFS measurements in solution and correlated with SAXS data processing and modelling. An iterative comparison of classical fit models (Guinier or sphere form factor) with the experimental results allowed a better interpretation of the SAXS signal that will be relevant for future work under environmentally relevant conditions.

Polyacids for producing colloidally stable amorphous calcium carbonate clusters in water

AbstractAs an important precursor of crystalline phases, amorphous calcium carbonate (ACC), especially ultrasmall ACC clusters, have been attracting great interest in fundamental research, materials chemistry, as well as industrial applications. However, it is still challenging to synthesize stable ACC clusters in water that can be isolated and concentrated without severe aggregation. Herein, we report a facile dialysis method for producing colloidally stable ACC clusters that are well dispersed in water with the protection of specific polycarboxylic acids, which could be also easily deprotected by small‐molecule acids like sodium citrate. Inherent proto‐calcite short‐range order is found to be present in all the obtained ACC clusters. The present strategy not only allows for the preparation of monodisperse isolated ACC clusters in aqueous solution but also shows great potential in industrial uses like waste water treatment.

A theoretical study of supramolecular aggregation of polydopamine tetramer subunits in aqueous solution

Conformational search for the most stable geometry connection of 16 sets of polydopamine (PDA) tetramer subunits has been systematically investigated using density functional theory (DFT) calculations. Our results indicated that the more planar subunits are, the more stable they are. This finding is in good agreement with recent experimental observations, which have suggested that PDA are composed of the nearly planar subunits that appear to be stacked together via the π–π interactions to form graphite-like layered aggregates associated with the balance of the intramolecular hydrogen bonds and steric effects from the indole and catechol moieties. Molecular dynamics (MD) simulations of 16 spherical clusters of the tetramer subunits of PDA in the gas and aqueous phase were performed at 298 K and confirmed the stability of supramolecular tetramer aggregates. The complex formation and binding energy of all 16 clusters are very strong although the shapes of the clusters in aqueous solution are not spherical and are very much different from those in the gas phase. The aggregations of all 16 clusters in aqueous solution were also confirmed from the profiles of the Kratky plot and the radius of gyration of all clusters. Our MD results in both gas phase and aqueous solution pointed out that there are high possibilities of aggregations of the 16 kinds of tetramer subunits although the conformations of each tetramer subunit are not flat. In summary, this work brings an insight into the controversial structure of PDA tetramer units and explains some of the important structural features found in the aqueous phase in comparison to the gas phase.

1,7,9,10-Tetrasubstituted PMIs Accessible through Decarboxylative Bromination: Synthesis, Characterization, Photophysical Studies, and Hydrogen Evolution Catalysis.

In this work, we present a new synthetic strategy for fourfold‐substituted perylene monoimides via tetrabrominated perylene monoanhydrides. X‐ray diffraction analysis unveiled the intramolecular stacking orientation between the substituents and semicircular packing behavior. We observed the remarkable influence of the substituent on the longevity and nature of the excited state upon visible light excitation. In the presence of poly(dehydroalanine)‐graft‐poly(ethylene glycol) graft copolymers as solubilizing template, the chromophores are capable of sensitizing [Mo3S13]2− clusters in aqueous solution for stable visible light driven hydrogen evolution over three days.

Icosahedral Cobalt Bis(dicarbollide) Ions with Bridge Linker and Their Electrochemistry in Aqueous Media

Boron cluster compounds (BCC) proved recently promising properties for use in drug design and molecular probes. Their applications in medicine are inherently connected with use of water-based environments. Up to now, the BCC were predominantly characterized in non-aqueous milieus. Therefore, we decided to perform electrochemical research of BCC in water-based electrolytes. We have focused on several boron clusters with structures that follow our previous study on icosahedral cobalt bis(dicarbollide) ions with a central coordination Co(III) atom in phosphate buffers, where we have found the best response for bridge type of exo-skeletal substituent. Therefore, in present study, we decided to focus on the promising structures, in which two 11 vertexes C2B9 dicarbollide ligands are interconnected via short bridge. Such structures may contain side chains usable for bioconjugation experiments.For our electrochemical experiments, we have used phosphate buffers of different pHs (2-10) and polished glassy carbon electrode. As the bridge structure served these exo-skeletal substituents: sulfur, amino group, tolylene, chlorpehenylene, phenylene, xylylene, byphenylene, phosphoric groups.The effect of various exo-skeletally substituted cobaltacarboranes (differing in type and length of the side chain) on the electrochemical response was studied. The results show that all parameters, the peak shape, the potential position and the peak current density height are significantly altered by the endo- and exo- skeletal substituents. Within the range of studied substitution, we were able to detect the signals in a broad potential range from E = -1.38 V to E = 1.73 V. From this follows clear possibilities to tune the position of two potential types in the electrochemical window that alternatively correspond either to the oxidation of the core structure of boron polyhedra or the central Co(III). The results also show that the electrochemical methods represent another tool for fast tracking the aggregation phenomena connected with non-classical amphiphilic behavior of boron clusters in aqueous solutions

Room-temperature formation of CdS magic-size clusters in aqueous solutions assisted by primary amines

Aqueous-phase approaches to semiconductor CdS magic-size clusters (MSCs) and the formation pathway have remained relatively unexplored. Here, we report the demonstration of an aqueous-phase, room-temperature approach to CdS MSCs, together with an exploration of their evolution pathway. The resulting CdS MSCs display a sharp optical absorption peak at about 360 nm and are labeled MSC-360. With CdCl2 and thiourea as the respective Cd and S sources, and 3-mercarpotopropionic acid as the ligand, CdS MSC-360 develops in a mixture of a primary amine and water. We argue that the primary amine facilitates room-temperature decomposition of thiourea when CdCl2 is present, and the formation pathway of MSCs is similar to that in organic-phase approaches. Our findings show there is a viable avenue to room-temperature aqueous-phase formation of CdS MSCs. Providing explanations of the procedure developed including the formation of large aggregates, the present study represents an important advance towards a mechanistic understanding of nanocrystal synthesis.

The Effect of UV Irradiation on the Formation of Silver Molecular Clusters and Their Stabilization in Solutions and Composite and Oxide Coatings

The influence of UV irradiation on the formation of molecular silver clusters in aqueous solutions containing silver, zinc, magnesium nitrates, and polyvinylpyrrolidone has been studied. Solutions and coatings have been investigated using optical and luminescent spectroscopy methods, the morphology of coatings has been analyzed by electron microscopy. It has been shown that irradiation significantly accelerates the processes of reduction of silver ions and of formation of molecular clusters and silver nanoparticles stabilized by polyvinylpyrrolidone.

Monochromatic Photolysis to Generate Silver Quantum Clusters in Polymer Matrices with Efficiently Antibio Property.

Size-control of species via wavelength to selectively synthesize Ag quantum clusters (QCs) was utilized and the synthesis conditions of this system (AgNO3, poly(methacrylic acid) (PMAA) with light) were optimized by changing a variety of parameters. Silver QCs, stabilized by PMAA with different compositions, have been synthesized in aqueous solution by tuning the irradiation monochromatic light wavelengths (300 or 365 nm) and AgNO3/MAA ratio (1 or 2). The novel preparation procedure has demonstrated a new approach to enlarge the population of the Ag QC family and proved the effectiveness of size control to prepare Ag QCs by tuning the light wavelength. Naked Ag QC species Agn (n = 2-9, 11, and 13) in polymer matrices are fully characterized by mass spectrometer, thus providing finger-printing evidence of their presence. Details regarding the photolysis reaction procedure, Ag QC optical properties, and the origins of fluorescence are discussed. Through a combination of results obtained from mass spectroscopy, fluorescence, and time-dependent density functional theory, we can assign the origin of fluorescence from a small silver cluster of Ag2 in organic scaffolds. The kinetics of the photolysis reaction follows first-order kinetics (k = 0.1/h). After thiolphenol (C6H5SH) ligand functionalization of the generated silver clusters in aqueous solution, the low or high resolution mass spectra showed the constant species composites with a molecular formula AgnLn-1 (n = 2-9 and L = C6H5S). More evidence indicated the formation of polymer-wrapped silver clusters. Their antibio property was explored, and we confirmed that they indeed show efficient activity.

The structural elucidation of aqueous H3BO3 solutions by DFT and neutron scattering studies.

The micro-structure of aqueous boric acid (H3BO3) solutions is of broad interest in earth sciences, geochemistry, material science, as well as chemical engineering. In the present study, the structure of aqueous H3BO3 solutions was studied via neutron scattering with 2H and 11B isotope labelling combined with empirical potential structure refinement (EPSR) modelling. In aqueous H3BO3 solutions, B(OH)3 is the dominant borate species. Density function theory (DFT) calculations show that the boron hydroxyl has a lower electrostatic potential (ESP), which makes B(OH)3 a relatively weakly hydrated, compared with the bulk water. In the 0.95 mol L-1 H3BO3 solution at 298 K (saturated), ∼18 water molecules enter the hydration sphere of B(OH)3 with the hydration distance (B-O(W)) of 3.75 Å, while only 4.23 of them hydrate with H3BO3 as the hydrogen bond (H-bond) acceptor or H-bond donor. Both neutron scattering and DFT calculations for 2B(OH)3·6H2O clusters at the ωB97XD/6-311++g(3df,3pd) basis level show that B(OH)3 forms molecular clusters in bidentate contact molecular pairs (BCMP), mono-dentate molecular pairs (MCMP), solvent-shared molecular pairs (SMP), and parallel solvent-shared molecular pairs (PSMP) in aqueous solutions. Their relative contents are both concentration- and temperature-sensitive. BCMP with the B-B distance of ∼4.1 Å is the dominant molecular pair in the aqueous solutions. Relatively less content and van der Waals interactions stabilized PSMP, with a B-B distance of ∼3.6 Å between the two parallel layers, which is a crucial species for the crystallization of H3BO3 from aqueous solution.

The Structure of Polymer Clusters in Aqueous Solutions of Hydroxypropyl Cellulose

The viscosity, turbidity, and heat capacity of dilute aqueous solutions of hydroxypropyl cellulose have been studied in a concentration interval of 0.047–1.5 g/l and a temperature interval of 20–80 ∘C. The data obtained testify that, if the temperature does not exceed 40 ∘C, hydroxypropyl cellulose molecules are prolate spheroidal globules with semiaxis lengths of 7 and 490 ˚ A. At temperatures above 70 ∘C, the hydroxypropyl cellulose solution consists of clusters; every cluster is composed of 11 globules and has a prolate spheroidal form with semiaxes of 41 and 490 ˚ A. In the temperature interval from 40 to 70 ∘C, the solution concerned contains both globules and clusters, with the concentration of the latter increasing, as the temperature grows.

Stabilization of an Unprecedented Hexanuclear Secondary Building Unit in a Thorium-Based Metal-Organic Framework.

The crystal structures of thorium clusters are important for understanding the formation and transformation mechanisms of actinide species in solution, which can in turns benefit nuclear waste processing and management. However, stabilizing thorium clusters in aqueous solution is quite challenging because of their fast olation and oxolation reactions. Here, we report a thorium-based metal-organic framework, NU-905, with the formula [Th6(μ3-O)2(HCOO)4(H2O)6(TCPP)4] [TCPP = tetrakis(4-carboxyphenyl)porphyrin], synthesized by a solvothermal reaction in N, N-dimethylformamide and water at 120 °C. NU-905 contains a hexanuclear secondary building unit (SBU), [Th6(μ3-O)2(HCOO)4(H2O)6], which has never been reported previously. The SBUs are capped and bridged by the tetratopic linker TCPP to form a three-dimensional network with scu topology. The activated NU-905 exhibits permanent porosity and shows high catalytic activity for the selective photooxidation of a mustard gas simulant.

General up-scaled model of ligand binding with C60 fullerene clusters in aqueous solution

In the present work we suggest the general model of C60 fullerene-ligand complexation, adapted for numerical description of UV–Vis titration data and for obtaining equilibrium complexation constants and some other complexation parameters. The principal novelty of the model is the account for two major processes governing the complexation process, and the account for broad dispersion of C60 fullerene clusters by dimension. It removes the existing barrier for the use of absorption spectroscopy for quantitation the C60 fullerene-ligand complexation.

Self-assembly of highly symmetrical, ultrasmall inorganic cages directed by surfactant micelles.

Nanometre-sized objects with highly symmetrical, cage-like polyhedral shapes, often with icosahedral symmetry, have recently been assembled from DNA1-3, RNA 4 or proteins5,6 for applications in biology and medicine. These achievements relied on advances in the development of programmable self-assembling biological materials7-10, and on rapidly developing techniques for generating three-dimensional (3D) reconstructions from cryo-electron microscopy images of single particles, which provide high-resolution structural characterization of biological complexes11-13. Such single-particle 3D reconstruction approaches have not yet been successfully applied to the identification of synthetic inorganic nanomaterials with highly symmetrical cage-like shapes. Here, however, using a combination of cryo-electron microscopy and single-particle 3D reconstruction, we suggest the existence of isolated ultrasmall (less than 10nm) silica cages ('silicages') with dodecahedral structure. We propose that such highly symmetrical, self-assembled cages form through the arrangement of primary silica clusters in aqueous solutions on the surface of oppositely charged surfactant micelles. This discovery paves the way for nanoscale cages made from silica and other inorganic materials to be used as building blocks for a wide range of advanced functional-materials applications.

In-situ discrimination of the water cluster size distribution in aqueous solution by ToF-SIMS

The size distribution and molecular structure of water clusters play a critical role in the chemical, biological and atmospheric process. The common experimental study of water clusters in aqueous solution is challenged due to the influence of local H-bonding environments on vibration spectroscopies or vacuum requirements for most mass spectrometry technologies. Here, the time-of-flight secondary ion mass spectrometry (ToF-SIMS) combining with a microfluidic chip has been applied to achieve the in-situ discrimination of the size distribution for water clusters in liquid water at room temperature. The results demonstrated that the presented method is highly system stable, reproducible and accurate. The comparison of heavy water with pure water was made to further demonstrate the accuracy of this technique. These results showed that (H2O)3H+ and (D2O)4D+ are the most dominant clusters in pure and heavy water, respectively. This one water molecule difference in the dominant cluster size may due to the nuclear quantum effects on water’s hydrogen bonded network. It is the first time to experimentally show the size distribution of water clusters over a wide range ( n =1–30) for pure (H2O) and heavy (D2O) water from molecular level. This technique provides an achievable method for liquid water, which offers a bridge to close the gap between theoretical and experimental study of water cluster in aqueous solution.