Crystallization of Keggin Heteropolyanions via a Two-Step Process in Aqueous Solutions

Although the analytical simplicity of the one-step classical theory of nucleation facilitates its use to understand crystallization processes, recent experiments and simulations have shown that many occur via multiple steps. According to the contemporary two-stage theory of nucleation, the onset of crystallization in a solution is preceded by large density fluctuations in the mother liquor that results in the formation of dense liquid-like correlated structures of the constituent solute particles. Here we report the observation of dense liquid-like correlated structures of heteropolyacid salts of α-Keggin anions (heteropolyanions) in aqueous solutions as volume is decreased long before the onset of crystallization by in situ time-dependent small-angle X-ray scattering measurements. Experiments were performed on drying drops of solutions of heteropolyacids to monitor their ordering before and during the onset of their crystallization. A continuous change in the density of the correlated structures is observed up to the onset of crystallization. Moreover, the correlated structures and the onset of crystallization are found to depend upon the charge of the heteropolyanions. The crystals formed within the drying drops of solutions during the crystallization process are found to be metastable polymorphic structures that are different from the stable crystal structures obtained after complete drying of the drops. Our results support a two-step process and Ostwald’s rule of stages for the crystallization of heteropolyanions in their aqueous solutions upon evaporation

Polynuclear Speciation of Trivalent Cations near the Surface of an Electrolyte Solution

Despite long-standing efforts, there is no agreed upon structural model for electrolyte solutions at air–liquid interfaces. We report the simultaneous detection of the near-surface and bulk coordination environments of a trivalent metal cation (europium) in an aqueous solution by use of X-ray absorption spectroscopy. Within the first few nanometers of the liquid surface, the cations exhibit oxygen coordination typical of inner-sphere hydration of an aquated Eu³⁺ cation. Beyond that, outer-sphere ion–ion correlations are observed that are otherwise not present in the bulk electrolyte. The combination of near-surface and bulk sensitivities to probe metal ion speciation in electrolyte solutions is achieved by detecting electron-yield and X-ray fluorescence signals from an inverted pendant drop. The results provide new knowledge about the near-surface chemistry of aqueous solutions of relevance to aerosols and ion transport processes in chemical separations and biological systems

Quantitative Determination of Metal Ion Adsorption on Cellulose Nanocrystals Surfaces

Nanocellulose is a bio-based material that holds significant potential in the field of water purification. Of particular interest is their potential use as a key sorbent material for the removal of metal ions from solution. However, the structure of metal ions adsorbed onto cellulose surfaces is not well understood. The focus of this work is to determine quantitatively the three-dimensional distribution of metal ions of different valencies surrounding negatively charged carboxylate functionalized cellulose nanocrystals (CNCs) using anomalous small-angle X-ray scattering (ASAXS). These distributions can affect the water and ionic permeability in these materials. The data show that increasing the carboxylate density on the surface of the CNCs from 740 to 1100 mmol/kg changed the nature of the structure of the adsorbed ions from a monolayer into a multilayer structure. The monolayer was modeled as a Stern layer around the CNC nanoparticles, whereas the multilayer structure was modeled as a diffuse layer on top of the Stern layer around the nanoparticles. Within the Stern layer, the maximum ion density increases from 1680 to 4350 mmol of Rb+/(kg of CNC) with the increase in the carboxylate density on the surface of the nanoparticles. Additionally, the data show that CNCs can leverage multiple mechanisms, such as electrostatic attraction and the chaotropic effect, to adsorb ions of different valencies. By understanding the spatial organization of the adsorbed metal ions, the design of cellulose-based sorbents can be further optimized to improve the uptake capacity and selectivity in separation applications

Interrogating Encapsulated Protein Structure within Metal–Organic Frameworks at Elevated Temperature

Encapsulating biomacromolecules within metal–organic frameworks (MOFs) can confer thermostability to entrapped guests. It has been hypothesized that the confinement of guest molecules within a rigid MOF scaffold results in heightened stability of the guests, but no direct evidence of this mechanism has been shown. Here, we present a novel analytical method using small-angle X-ray scattering (SAXS) to solve the structure of bovine serum albumin (BSA) while encapsulated within two zeolitic imidazolate frameworks (ZIF-67 and ZIF-8). Our approach comprises subtracting the scaled SAXS spectrum of the ZIF from that of the biocomposite BSA@ZIF to determine the radius of gyration of encapsulated BSA through Guinier, Kratky, and pair distance distribution function analyses. While native BSA exposed to 70 °C became denatured, in situ SAXS analysis showed that encapsulated BSA retained its size and folded state at 70 °C when encapsulated within a ZIF scaffold, suggesting that entrapment within MOF cavities inhibited protein unfolding and thus denaturation. This method of SAXS analysis not only provides insight into biomolecular stabilization in MOFs but may also offer a new approach to study the structure of other conformationally labile molecules in rigid matrices

Relevance of Surface Adsorption and Aqueous Complexation for the Separation of Co(II), Ni(II), and Fe(III)

During the solvent extraction of metal ions from an aqueous to an organic phase, organic-soluble extractants selectively target aqueous-soluble ions for transport into the organic phase. In the case of extractants that are also soluble in the aqueous phase, our recent studies of lanthanide ion–extractant complexes at the surface of aqueous solutions suggested that ion–extractant complexation in the aqueous phase can hinder the solvent extraction process. Here, we investigate a similar phenomenon relevant to the separation of Co­(II), Ni­(II), and Fe­(III). X-ray fluorescence near total reflection and tensiometry are used to characterize ion adsorption behavior at the surface of aqueous solutions containing water-soluble extractants, either bis­(2-ethylhexyl) phosphoric acid (HDEHP) or 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEHEHP), as well as adsorption to a monolayer of water-insoluble extractant dihexadecyl phosphoric acid (DHDP) at the aqueous–vapor interface. Competitive adsorption of Ni­(II) and Fe­(III) utilizing either HDEHP or DHDP illustrates the essential feature of the recent lanthanide studies that the ion, which is preferentially extracted in liquid–liquid extraction, Fe­(III), is found preferentially adsorbed to the water–vapor interface only in the presence of the water-insoluble extractant DHDP. A more subtle competition produces comparable adsorption behavior of Co­(II) and Ni­(II) at the surfaces of both HDEHP- and HEHEHP-aqueous solutions in spite of the known preference for Co­(II) under solvent extraction conditions. Comparison experiments with a monolayer of DHDP reveal that Co­(II) is preferentially adsorbed to the surface. This preference for Co­(II) is also supported by molecular dynamics simulations of the potential of mean force of ions interacting with the soluble extractants in water. These results highlight the possibility that complexation of extractants and ions in the aqueous phase can alter selectivity in the solvent extraction of critical elements

Aggregation of Heteropolyanions in Aqueous Solutions Exhibiting Short-Range Attractions and Long-Range Repulsions

Charged colloids and proteins in aqueous solutions interact via short-range attractions and long-range repulsions (SALR) and exhibit complex structural phases. These include homogeneously dispersed monomers, percolated monomers, clusters, and percolated clusters. We report the structural architectures of simple charged systems in the form of spherical, Keggin-type heteropolyanions (HPAs) by small-angle X-ray scattering (SAXS) and molecular dynamics (MD) simulations. Structure factors obtained from the SAXS measurements show that the HPAs interact via SALR. Concentration and temperature dependences of the structure factors for HPAs with −3<i>e</i> (<i>e</i> is the charge of an electron) charge are consistent with a mixture of nonassociated monomers and associated randomly percolated monomers, whereas those for HPAs with −4<i>e</i> and −5<i>e</i> charges exhibit only nonassociated monomers in aqueous solutions. Our experiments show that the increase in magnitude of the charge of the HPAs increases their repulsive interactions and inhibits their aggregation in aqueous solutions. MD simulations were done to reveal the atomistic scale origins of SALR between HPAs. The short-range attractions result from water or proton-mediated hydrogen bonds between neighboring HPAs, whereas the long-range repulsions are due to the distributions of ions surrounding the HPAs

An Atom-Economic Method for 1,2,3-Triazole Derivatives via Oxidative [3 + 2] Cycloaddition Harnessing the Power of Electrochemical Oxidation and Click Chemistry

An electrochemical method was developed to accomplish the reagentless synthesis of 4,5-disubstituted triazole derivatives employing secondary propargyl alcohol as C-3 synthon and sodium azide as cycloaddition counterpart. The reaction was conducted at room temperature in an undivided cell with a constant current using a pencil graphite (C) anode and stainless-steel cathode in a MeCN solvent system. The proposed reaction mechanism was convincingly established by carrying out a series of control experiments and further supported by electrochemical and density functional theory (DFT) studies

Robust Gold Nanoparticle Sheets by Ligand Cross-Linking at the Air–Water Interface

We report the results of cross-linking of two-dimensional gold nanoparticle (Au-NP) assemblies at the air–water interface <i>in situ</i>. We introduce an aqueous soluble ruthenium benzylidene catalyst into the water subphase to generate a robust, elastic two-dimensional network of nanoparticles containing cyclic olefins in their ligand framework. The most striking feature of the cross-linked Au-NP assemblies is that the extended connectivity of the nanoparticles enables the film to preserve much of its integrity under compression and expansion, features that are absent in its non-cross-linked counterparts. The cross-linking process appears to “stitch” the nanoparticle crystalline domains together, allowing the cross-linked monolayers to behave like a piece of fabric under lateral compression

Silver-Loaded Xerogel Nanostructures for Iodine Capture: A Comparison of Thiolated versus Unthiolated Sorbents

This paper describes the development and provides comparisons of thiolated (−SH) and unthiolated Ag–Al–Si–O xerogels for iodine gas capture. These xerogels were produced from alkoxides and then heat-treated at 350 °C to provide mechanical strength for subsequent processing steps. Then, a portion of the xerogels was thiolated using (3-mercaptopropyl)­trimethoxysilane. Next, thiolated and unthiolated batches were ion-exchanged in AgNO3 solutions where Ag+ replaced Na+ in the gel network on a near 1:1 molar basis. Subsamples of the Ag-exchanged xerogels were subjected to a reduction step in H2/Ar to convert Ag+ to Ag0 where the rest of the Ag-exchanged (Ag+) were not reduced. X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy revealed nanoscale Ag0 in the Ag+ samples despite no active reduction where actively reduced samples had bimodal Ag0 distribution of ∼2–3 nm hexagonal and ∼6–7 nm cubic crystallites. Synchrotron X-ray absorption spectroscopy was used to assess the oxidization states of Ag, S, and I within the different xerogel samples. The specific surface areas of the base xerogels decreased as subsequent treatments were performed on the as-made samples, albeit the decreases were smaller than aerogel equivalents of these samples from a previous study. All iodine-loaded Ag-based samples showed a mixture of β-AgI and γ-AgI. Comparisons of iodine-loading results with other Ag-based iodine sorbents show that the thiolated Ag0-xerogels in this work have one of the highest iodine-loading capacities (qe) reported to date in saturated conditions with the thiolated Ag0-xerogel showing 522 mg iodine per g of the sorbent

Armoring the Interface with Surfactants to Prevent the Adsorption of Monoclonal Antibodies

The pharmaceutical industry uses surface-active agents (excipients) in protein drug formulations to prevent the aggregation, denaturation, and unwanted immunological response of therapeutic drugs in solution as well as at the air/water interface. However, the mechanism of adsorption, desorption, and aggregation of proteins at the interface in the presence of excipients remains poorly understood. The objective of this work is to explore the molecular-scale competitive adsorption process between surfactant-based excipients and two monoclonal antibody (mAb) proteins, mAb-1 and mAb-2. We use pendant bubble tensiometry to measure the ensemble average adsorption dynamics of mAbs with and without the excipient. The surface tension measurements allow us to quantify the rate at which the molecules “race” to the interface in single-component and mixed systems. These results define the phase space, where coadsorption of both mAbs and excipients occurs onto the air/water interface. In parallel, we use X-ray reflectivity (XR) measurements to understand the molecular-scale dynamics of competitive adsorption, revealing the surface-adsorbed amounts of the antibody and excipient. XR has revealed that at a sufficiently high surface concentration of the excipient, mAb adsorption to the surface and subsurface domains was inhibited. In addition, despite the fact that both mAbs adsorb via a similar mechanistic pathway and with similar dynamics, a key finding is that the competition for the interface directly correlates with the surface activity of the two mAbs, resulting in a fivefold difference in the concentration of the excipient needed to displace the antibody