Aqueous Solution Chemistry Research Articles

Influence of biodegradable plastics on the generation of disinfection byproducts in the chlorination process

Biodegradable plastics (BPs) have seen a continuous increase in annual production and application due to their environmentally sustainable characteristics. However, research on the formation of disinfection byproducts (DBPs) from biodegradable microplastics (BMPs) during chlorination is limited, and the effects of aqueous solution chemistry on this process have yet to be explored. Therefore, two biodegradable microplastics, polylactic acid (PLA) and polybutylene adipate terephthalate (PBAT), were investigated in this study to examine the changes in their physicochemical properties before and after chlorination, and the formation of DBPs under different environmental conditions. The results showed that PLA was more chlorine-responsive, and generated more DBPs. The pH converted some of the intermediates into more stable DBPs by affecting the concentration of HClO and base-catalyzed reactions, whereas ionic strength slightly reduced DBP concentration by ion adsorption and promoting the aggregation of BMPs. Finally, since PLA has a slightly greater volume of mesopores and micropores compared to PBAT, it may more effectively adsorb DBP precursors beyond natural organic matter (NOM), such as some anthropogenic pollutants, thus potentially decreasing the formation of chlorinated DBPs in surface water. This research explored the potentiality for DBP formation by BMPs under different water quality conditions during the disinfection process, which is useful for assessing the environmental hazards of BMPs.

Response of Ionic Hydration Structure and Selective Transport Behavior to Aqueous Solution Chemistry during Nanofiltration.

The effect of aqueous solution chemistry on the ionic hydration structure and its corresponding nanofiltration (NF) selectivity is a research gap concerning ion-selective transport. In this study, the hydration distribution of two typical monovalent anions (Cl- and NO3-) under different aqueous solution chemical conditions and the corresponding transmembrane selectivity during NF were investigated by using in situ liquid time-of-flight secondary ion mass spectrometry in combination with molecular dynamics simulations. We demonstrate the inextricable link between the ion hydration structure and the pore steric effect and further find that ionic transmembrane transport can be regulated by breaking the balance between the hydrogen bond network (i.e., water-water) and ion hydration (i.e., ion-water) interactions of hydrated ion. For strongly hydrated (H2O)nCl- with more intense ion-water interactions, a higher salt concentration and coexisting ion competition led to a larger hydrated size and, thus, a higher ion rejection by the NF membrane, whereas weakly hydrated (H2O)nNO3- takes the reverse under the same conditions. Stronger OH--anion hydration competition resulted in a smaller hydrated size of (H2O)nCl- and (H2O)nNO3-, showing a lower observed average hydration number at pH 10.5. This study deepens the long-overlooked understanding of NF separation mechanisms, concerning the hydration structure.

Aqueous solution chemistry in silico and the role of data-driven approaches

Aqueous solution chemistry <i>in silico</i> and the role of data-driven approaches

A water-soluble mixed-valent {Mn11} cluster embedded heteropolyoxoniobate with magnetic properties.

A rare all-inorganic high-nuclearity mixed-valent {Mn11} cluster embedded polyoxoniobate, K25H43{(Te4Nb9O33)3(Nb6O19)5(TeVINb5O14)[(TeIVO3)2(MnII7MnIII4O19)]}·97H2O (1), has been synthesized by a one-pot reaction. Compound 1 contains the largest manganese cluster {Mn11} core among polyoxoniobates reported to date. {Mn11} consists of three quasi-cubane {Mn3O4} units and is simultaneously encapsulated by lacunary α-Keggin {Te4Nb9O36} and Lindqvist {Nb6O19} units. Compound 1 exhibits significant magnetic anisotropy and excellent water solubility and stability. The findings suggest a new, all-inorganic polynulear Mn-based structural paradigm for aqueous solution chemistry and magnetic materials.

Probing the self-ionization of liquid water with ab initio deep potential molecular dynamics.

The chemical equilibrium between self-ionized and molecular water dictates the acid-base chemistry in aqueous solutions, yet understanding the microscopic mechanisms of water self-ionization remains experimentally and computationally challenging. Herein, Density Functional Theory (DFT)-based deep neural network (DNN) potentials are combined with enhanced sampling techniques and a global acid-base collective variable to perform extensive atomistic simulations of water self-ionization for model systems of increasing size. The explicit inclusion of long-range electrostatic interactions in the DNN potential is found to be crucial to accurately reproduce the DFT free energy profile of solvated water ion pairs in small (64 and 128 H2O) cells. The reversible work to separate the hydroxide and hydronium to a distance [Formula: see text] is found to converge for simulation cells containing more than 500 H2O, and a distance of [Formula: see text] 8 Å is the threshold beyond which the work to further separate the two ions becomes approximately zero. The slow convergence of the potential of mean force with system size is related to a restructuring of water and an increase of the local order around the water ions. Calculation of the dissociation equilibrium constant illustrates the key role of long-range electrostatics and entropic effects in the water autoionization process.

A twelve-electron conversion iodine cathode enabled by interhalogen chemistry in aqueous solution

The battery chemistry aiming for high energy density calls for the redox couples that embrace multi-electron transfer with high redox potential. Here we report a twelve-electron transfer iodine electrode based on the conversion between iodide and iodate in aqueous electrolyte, which is six times than that of the conventional iodide/iodine redox couple. This is enabled by interhalogen chemistry between iodine (in the electrode) and bromide (in the acidic electrolyte), which provides an electrochemical-chemical loop (the bromide-iodate loop) that accelerates the kinetics and reversibility of the iodide/iodate electrode reaction. In the deliberately designed aqueous electrolyte, the twelve-electron iodine electrode delivers a high specific capacity of 1200 mAh g−1 with good reversibility, corresponding to a high energy density of 1357 Wh kg−1. The proposed iodine electrode is substantially promising for the design of future high energy density aqueous batteries, as validated by the zinc-iodine full battery and the acid-alkaline decoupling battery.

Goethite Mineral Dissolution to Probe the Chemistry of Radiolytic Water in Liquid-Phase Transmission Electron Microscopy.

Liquid-Phase Transmission Electron Microscopy (LP-TEM) enables in situ observations of the dynamic behavior of materials in liquids at high spatial and temporal resolution. During LP-TEM, incident electrons decompose water molecules into highly reactive species. Consequently, the chemistry of the irradiated aqueous solution is strongly altered, impacting the reactions to be observed. However, the short lifetime of these reactive species prevent their direct study. Here, the morphological changes of goethite during its dissolution are used as a marker system to evaluate the influence of radiation on the changes in solution chemistry. At low electron flux density, the morphological changes are equivalent to those observed under bulk acidic conditions, but the rate of dissolution is higher. On the contrary, at higher electron fluxes, the morphological evolution does not correspond to a unique acidic dissolution process. Combined with kinetic simulations of the steady state concentrations of generated reactive species in the aqueous medium, the results provide a unique insight into the redox and acidity interplay during radiation induced chemical changes in LP-TEM. The results not only reveal beam-induced radiation chemistry via a nanoparticle indicator, but also open up new perspectives in the study of the dissolution process in industrial or natural settings.

Anomalous salting-out, self-association and pKa effects in the practically-insoluble bromothymol blue.

The widely-used and practically insoluble diprotic acidic dye, bromothymol blue (BTB), is a neutral molecule in strongly acidic aqueous solutions. The Schill (1964) extensive solubility-pH measurement of bromothymol blue in 0.1 and 1.0 M NaCl solutions, with pH adjusted with HCl from 0.0 to 5.4, featured several unusual findings. The data suggest that the difference in solubility of the neutral-form molecule in 1M NaCl is more than 0.7 log unit lower than the solubility in pure water. This could be considered as uncharacteristically high for a salting-out effect. Also, the study reported two apparent values of pKa1, 1.48 and 1.00, in 0.1 M and 1.0 M NaCl solutions, respectively. The only other measured value found for pKa1 in the literature is -0.66 (Gupta and Cadwallader, 1968). It was reasoned that the there can be only a single pKa1 for BTB. Also, it was hypothesized that salting-out alone might not account for such a large difference in solubility observed at the two levels of salt. A generalized mass action approach incorporating activity corrections for charged species using the Stokes-Robinson hydration equation and for neutral species using the Setschenow equation, was selected to analyze the Schill solubility-pH data to seek a rationalization of these unusual results. BTB reveals complex speciation chemistry in saturated aqueous solutions which had been poorly understood for many years. The appearance of two different values of pKa1 at different levels of NaCl and the anomalously high value of the empirical salting-out constant could be rationalized to normal values by invoking the formation of a very stable neutral dimer (log K2 = 10.0 ± 0.1 M-1). A 'normal' salting-out constant, 0.25 M-1 was then derived. It was also possible to estimate the 'self-interaction' constant. The data analysis in the present study critically depended on the pKa1 = -0.66 reported by Gupta and Cadwallader. A more reasonable salting-out constant and a consistent single value for pKa1 have been determined by considering a self-interacting (aggregation) model involving an uncharged form of the molecule, which is likely a zwitterion, as suggested by literature spectrophotometric studies.

Efficient recovery of bisphenol A from aqueous solution using K2CO3 activated carbon derived from starch-based polyurethane.

Endocrine-disrupting compounds (EDCs) are increasingly polluting water, making it of practical value to develop novel desirable adsorbents for removing these pollutants from wastewater. Here, a simple cross-linking strategy combined with gentle chemical activation was demonstrated to prepare starch polyurethane-activated carbon (STPU-AC) for adsorbing BPA in water. The adsorbents were characterized by various techniques such as FTIR, XPS, Raman, BET, SEM, and zeta potential, and their adsorption properties were investigated comprehensively. Results show that STPU-AC possesses a large surface area (1862.55m2·g-1) and an abundance of functional groups, which exhibited superior adsorption capacity for BPA (543.4mg·g-1) and favorable regenerative abilities. The adsorption of BPA by STPU-AC follows a pseudo-second-order kinetic model and a Freundlich isotherm model. The effect of aqueous solution chemistry (pH and ionic strength) and the presence of other contaminants (phenol, heavy metals, and dyes) on BPA adsorption was also analyzed. Moreover, theoretical studies further demonstrate that hydroxyl oxygen and pyrrole nitrogen are the primary adsorption sites. We found that the efficient recovery of BPA was associated with pore filling, hydrogen-bonding interaction, hydrophobic effects, and π-π stacking. These findings demonstrate the promising practical application of STPU-AC and provide a basis for the rational design of starch-derived porous carbon.

Development of Copper Complexes with Diimines and Dipicolinate as Anticancer Cytotoxic Agents.

Coordination complexes may act as anticancer agents. Among others, the formation of the complex may facilitate the ligand uptake by the cell. Searching for new copper compounds with cytotoxic activity, the complex Cu-dipicolinate was studied as a neutral scaffold to form ternary complexes with diimines. A series of [Cu(dipicolinate)(diimine)] complexes (where diimine: Phenanthroline, phen, 5-NO2-phenanthroline, 4-methyl-phenanthroline, neocuproine, 3,4,7,8-tetramethyl-phenanthroline, tmp, bathophenanthroline, bipyridine, dimethyl-bipyridine, as well as the ligand 2,2-dipyridil-amine, bam) were synthesized and characterized both in the solid state, including a new crystal structure of [Cu2(dipicolinate)2(tmp)2]·7H2O. Their chemistry in aqueous solution was explored by UV/vis spectroscopy, conductivity, cyclic voltammetry, and electron paramagnetic resonance studies. Their DNA binding was analyzed by electronic spectroscopy (determining Kb values), circular dichroism, and viscosity methods. The cytotoxicity of the complexes was assessed on human cancer cell lines MDA-MB-231, MCF-7 (breast, the first triple negative), A549 (lung epithelial) and A2780cis (ovarian, Cisplatin-resistant), and non-tumor cell lines MRC-5 (lung) and MCF-10A (breast). The major species are ternary, in solution and solid state. Complexes are highly cytotoxic as compared to Cisplatin. Complexes containing bam and phen are interesting candidates to study their in vivo activity in triple-negative breast cancer treatment.

The aqueous solution chemistry of germanium under conditions of environmental and biological interest: Inorganic ligands

Available equilibrium constant data for reactions of germanium with inorganic ligands in aqueous solution have been critically evaluated. Even though the relevant literature is sparse and mostly rather old, we have established a working thermodynamic description of germanium in aqueous, multicomponent media for its most important interactions with inorganic ligands. These thermodynamic parameters will be useful in environmental and (eco)toxicology studies. However, within the limitations of the presently available literature, significant uncertainties are inescapable. The implications for thermodynamic modelling in general are far-reaching.

The efficient adsorption of tetracycline from aqueous solutions onto polymers with different N-vinylpyrrolidone contents: equilibrium, kinetic and dynamic adsorption.

Extensive use of antibiotics in the world will cause potential risks to human health and ecosystems. The removal of these antibiotics has attracted much attention. Composite materials are growing attention for diverse pollutants separation and removal based on their specific functionality and surface area. In this study, a series of N-vinylpyrrolidone-divinylbenzene polymers (NVPD) with different N-vinylpyrrolidone (NVP) contents were facilely prepared for the adsorption of tetracycline (TC). The effect of polymer surface properties and aqueous solution chemistry (pH, ionic strength, humic acid) on TC adsorption was further studied. The dynamic adsorption and regeneration experiments were also assessed. The results showed that only 25% of NVP was involved in the reaction. When NVP dosage (%) was 75%, polymer (NVPD-g) owned the largest BET surface area (613.23 m2/g) and obtained the maximum TC adsorption capacities (258.76mg/g). In the kinetic, the adsorption between TC and polymers with NVP was controlled by chemical adsorption and intra-particle diffusion. The TC adsorption process of NVPD-g depended on the contribution of the hydrophobic effect, electrostatic interactions, H-bonding, π-πelectron donor-acceptor(EDA) interactions, and cation-π bonding. Moreover, the removal efficiency of TC by NVPD-g was enhanced in the presence of humic acid (HA) in the dynamic adsorption and 1197 BV (2394mL) of TC simulated wastewater can be treated. These findings suggest that NVPD-g has a potential application inthe purification of TC.

Chemical Variants of the Dicyanamide Anion, and a Landscape for Basic and Superbasic Ionic Liquids

We describe the properties of three new aprotic ionic liquids (ILs) with irreducible cations and anions which are close relatives of the commonly used −N(CN)2 anion, namely −N(CHO)2 (diformylamide) and −N(CO)2(CH2)2 (succinimide), having pK a values which are slightly more basic than the pK a of OH− ions of aqueous solution chemistry. In addition to using the well-known N-butyl-N-methyl pyrrolidinium cation, P14 +, we report the use of the tetrabutylammonium cation, +N[CH3(CH2)3]4, in forming an ionic liquid with the diformylamide anion. The formation and purity of these ILs was assessed by 1H NMR spectroscopy. The broadband dielectric spectra for all three ionic liquids were analyzed and the glass transition temperatures (T g) estimated from the dielectric data matched well with those obtained from differential scanning calorimetry. The results demonstrate that pure aprotic ILs with high-pK a equivalent anions can be obtained by metathesis reactions despite their low pK a difference of 2 to 3. By contrast, protic analogues of these cation-anion pairs would fail to produce ILs, for which larger pK a differences are required. These new aprotic ILs are glass-forming with T g’s near 210 K and show DC-conductivities near 0.1 mS cm−1 at ambient temperatures.

Regulating Water Activity for Rechargeable Zinc-Ion Batteries: Progress and Perspective

Recent emerging rechargeable zinc-ion batteries have inherent benefits of intrinsic battery safety and high elemental abundance and reduce pollution toward an environmentally compatible energy storage system. However, the effort of promoting rechargeable aqueous Zn-ion batteries for large-scale energy storage applications is greatly plagued by the high activity of water molecules. The high activity of water molecules remains a threat to Zn-ion batteries, leading to premature failure of the Zn anode, cathode dissolution, and inferior low-temperature performance. Recently, a wide spectrum of effective strategies has been reported for reducing water’s activity to tackle the above challenges. In view of the shallow understanding of water molecule states and their interwoven associations with Zn-ion battery performance, it becomes urgent to highlight the significance of regulating water activity and summarize recent progress in aqueous Zn-ion batteries. This Perspective aims to provide a fundamental understanding for designing better Zn-ion batteries using aqueous solution chemistry.

Transient Radiation-Induced Berkelium(III) and Californium(III) Redox Chemistry in Aqueous Solution.

Despite the significant impact of radiation-induced redox reactions on the accessibility and lifetimes of actinide oxidation states, fundamental knowledge of aqueous actinide metal ion radiation chemistry is limited, especially for the late actinides. A quantitative understanding of these intrinsic radiation-induced processes is essential for investigating the fundamental properties of these actinides. We present here a picosecond electron pulse reaction kinetics study into the radiation-induced redox chemistry of trivalent berkelium (Bk(III)) and californium (Cf(III)) ions in acidic aqueous solutions at ambient temperature. New and first-of-a-kind, second-order rate coefficients are reported for the transient radical-induced reduction of Bk(III) and Cf(III) by the hydrated electron (eaq-) and hydrogen atom (H•), demonstrating a significant reactivity (up to 1011 M-1 s-1) indicative of a preference of these metals to adopt divalent states. Additionally, we report the first-ever second-order rate coefficients for the transient radical-induced oxidation of these elements by a reaction with hydroxyl (•OH) and nitrate (NO3•) radicals, which also exhibited fast reactivity (ca. 108 M-1 s-1). Transient Cf(II), Cf(IV), and Bk(IV) absorption spectra are also reported. Overall, the presented data highlight the existence of rich, complex, intrinsic late actinide radiation-induced redox chemistry that has the potential to influence the findings of other areas of actinide science.

Low-Temperature High-Pressure Chemistry of Ammonia and Methanol Aqueous Solutions in the Presence of Different Carbon Sources: Application to Icy Bodies

Low-Temperature High-Pressure Chemistry of Ammonia and Methanol Aqueous Solutions in the Presence of Different Carbon Sources: Application to Icy Bodies

Distinct Coordination Chemistry of Fe(III)-Based MRI Probes.

Contrast agents are used in approximately 40% of all magnetic resonance imaging (MRI) procedures to improve the quality of the images based on the distribution and dynamic clearance of the agent. To date, all clinically approved contrast agents are Gd(III) coordination complexes that serve to shorten the longitudinal (T1) and transverse (T2) proton relaxation times of water. Recent interest in replacing Gd with biologically relevant metal ions such as Mn or Fe has led to increased interest in the aqueous coordination chemistry of their complexes. In this Account, we focus on high-spin Fe(III) complexes that have been recently reported as MRI contrast agents or probes in our laboratory.The highly Lewis acidic Fe(III) center has distinct coordination chemistry in aqueous solutions, facilitating alternative strategies in the design of MRI probes. To illustrate this, we describe different classes of Fe(III) MRI probes with a focus on macrocyclic complexes and multinuclear complexes such as self-assembled metal organic polyhedra (MOP). Our initial efforts focused on macrocyclic complexes of Fe(III) in order to tune spin and oxidation states with the goal of stabilizing high-spin Fe(III) in reducing biological environments. Our probes feature six-coordinate Fe(III) complexes of 1,4,7-triazacyclononane with hydroxypropyl, phosphonate, or carboxylate pendant groups to produce Fe(III) complexes that shorten proton T1 times predominantly from second-sphere or outer-sphere interactions at neutral pH. Analogues with pentadentate macrocyclic ligands have an inner-sphere water that does not exchange rapidly on the NMR time scale, yet these complexes are effective relaxation agents. Fe(III) macrocyclic complexes in this class can be modified to modulate their biodistribution and pharmacokinetic clearance in mice. The goal of these studies is for the Fe(III) agents to clear as extracellular fluid agents and produce profiles similar to those of Gd agents. Finally, studies of multimeric Fe(III) complexes are of interest to produce probes that give large proton relaxivity. In this approach the two Fe(III) centers are connected through aryl linkers as demonstrated for several macrocyclic complexes. Even more tightly connected Fe(III) centers are produced in a Fe(III) self-assembled cage with relaxivity of 21 mM-1 s-1 at 4.7 T, 37 °C in the presence of serum albumin to which it is tightly bound. This cage enhances contrast of the vasculature as a blood pool agent and accumulates in tumors. Finally, we present our perspectives on the further development of Fe(III) complexes for various applications in MRI.

Mechanistic modeling of hybrid low salinity polymer flooding: Role of geochemistry

Low salinity polymer (LSP) based enhanced oil recovery (EOR) technique is getting more attention due to its potential of improving both displacement and sweep efficiencies. Modeling LSP flooding is challenging due to the complicated physical processes and the sensitivity of polymers to brine salinity. In this study, a coupled numerical model has been implemented to allow investigating the polymer-brine-rock geochemical interactions associated with LSP flooding along with the flow dynamics. MATLAB Reservoir Simulation Toolbox (MRST) was coupled with the geochemical software IPhreeqc, which is the interface module of Phreeqc (i.e., pH-Redox-Equilibrium in C programming language). The effects of polymer were captured by considering Todd–Longstaff mixing model, inaccessible pore volume, permeability reduction, polymer adsorption as well as salinity and shear rate effects on polymer viscosity. Regarding geochemistry, the presence of polymer in the aqueous phase was considered by adding a new solution specie and related chemical reactions to Phreeqc database files. Thus, allowing for modeling the geochemical interactions related to the presence of polymer. Coupling the two simulators was successfully performed, verified, and validated through several case studies. The coupled MRST–IPhreeqc simulator allows for modeling a wide variety of geochemical reactions including aqueous, mineral precipitation/dissolution, and ion exchange reactions. Capturing these reactions allows for real time tracking of the aqueous phase salinity and its effect on polymer rheological properties. The coupled simulator was verified against Phreeqc for a realistic reactive transport scenario. Furthermore, the coupled simulator was validated through history matching a single-phase LSP coreflood from the literature. This paper provides an insight into the geochemical interactions between partially hydrolyzed polyacrylamide (HPAM) and aqueous solution chemistry (salinity and hardness), and their related effect on polymer viscosity. This work is also considered as a base for future two-phase polymer solution and oil interactions, and their related effect on oil recovery.

Stepwise assembly of heterometallic aluminum oxo clusters

The aqueous solution chemistry of Al(III) is an important subject in the fields of environmental chemistry, geochemistry and coordination chemistry. However, aluminum oxo clusters were generally isolated by the one-step synthesis method. In this paper, we developed a stepwise assembly synthesis strategy and successfully prepared two heterometallic aluminum oxo clusters. [Al4(L)4(Cat)2]·2[Zn(Im)4]·2Im (AlOC-121, H3L ​= ​2,3-dihydroxybenzoic acid, Cat ​= ​catechol Im ​= ​imidazole) and [Al4(L)4(Cat)2]·2[Fe(Im)6]·2Im (AlOC-122). Single crystal structure analysis shows that they are unprecedented structure types, where aluminum oxo cluster precursor, metal complexes and guests co-crystallizing in one structure. These compounds were fully characterized and magnetic properties were also studied.

Stabilizing MXene by Hydration Chemistry in Aqueous Solution

AbstractMXenes attract interest in diverse fields but suffer from fast structural degradation by attacking of dissolved oxygen and water molecules in aqueous solution. This drawback hinders the long‐term storage, applications and understanding of the chemical nature of MXenes. Herein, we report a cost‐effective and environmentally sustainable way for long‐term storage of MXenes in aqueous solution by hydration chemistry of nontoxic inorganic salts. The attacking of MXene by free water and dissolved oxygen molecules is inhibited by decreasing the water activity, which simultaneously lowers the dissolved oxygen concentration, of saline solution. As a result, the storage life of MXene can be prolonged to up to 400 days at ambient conditions without loss of intrinsic surface chemistry and bulk carrier properties. Over 90 % of salt protectant can be recycled by simply evaporating the final waste liquor after fully extracting the MXene to minimize the waste discharge and processing cost. This work offers a commercializable approach with high cost‐effectiveness, processing sustainability and environmental benefit for extending the shelf life of MXenes.