Behavior Of Aqueous Solutions Research Articles

Adsorptive removal of arsenic ions from contaminated water using low-cost schwertmannites and akaganéites

Schwertmannite and akaganéite have potential in treatment of arsenic contaminated waters. In this work, schwertmannite and akaganéite were synthesized by chemical and biological methods. Characterization and analysis results showed about 120 m2/g for schwertmannite spheres with a diameter of 2–5 μm (Sch-Chem) and about 0.5 μm (Sch-Bio) and 240–280 m2/g for akaganéite rod with a length of about 300–500 nm (Aka-Chem) and 150 nm (Aka-Bio). Agglomerated particle average diameters (μm) of synthesized products in solutions were 32.5, 20.6, 0.480 and 26.4, respectively. Schwertmannite and akaganéite were used to investigate arsenic adsorption behaviors in aqueous solutions by batch experiments, under various reaction times, initial arsenic and adsorbent levels, pH values, and anions (Cl−, NO3−, H2PO4−, CO32−, and SO42−). Adsorption data well fitted to pseudo-second-order rate model (R2 = 0.999), and Langmuir (R2 = 0.977–0.998) and Freundlich (R2 = 0.948–0.998) isothermal models at pH 7.0. Maximum adsorption capacities of As(III)/As(V) were 102/98.3, 110/115, 6.40/7.03 and 30.3/34.8 mg/g, respectively. Anions of SO42− and H2PO4− can affect arsenic removal efficiency. Adsorbents with pHZPC of 4.0–5.0 still had a good arsenic removal ability at pH 3.0–9.0, due to a main adsorption mechanism of anionic exchange between hydroxyl group (or sulfate) and arsenic ions. Further, schwertmannite candidates were used in arsenic removal from polluted groundwater. Breakthrough points (bed volume, mL) for Sch-Bio/Sch-Chem were about at 90/120, 70/(100–110) and 80/110 for As(III), As(V), and total As, respectively. It demonstrated that akaganéite and schwertmannite could be potentially applied in treatments of arsenic-polluted waters.

Photoreactive Mercury-Containing Metallosupramolecular Nanoparticles with Tailorable Properties That Promote Enhanced Cellular Uptake for Effective Cancer Chemotherapy.

A new potential route to enhance the efficiency of supramolecular polymers for cancer chemotherapy was successfully demonstrated by employing a photosensitive metallosupramolecular polymer (Hg-BU-PPG) containing an oligomeric poly(propylene glycol) backbone and highly sensitive pH-responsive uracil-mercury-uracil (U-Hg-U) bridges. This route holds great promise as a multifunctional bioactive nano-object for development of more efficient and safer cancer chemotherapy. Owing to the formation of uracil photodimers induced by ultraviolet irradiation, Hg-BU-PPG can form a photo-cross-linked structure and spontaneously forms spherical nanoparticles in aqueous solution. The irradiated nanoparticles possess many unique characteristics, such as unique fluorescence behavior, highly sensitive pH-responsiveness, and intriguing phase transition behavior in aqueous solution as well as high structural stability and antihemolytic activity in biological media. More importantly, a series of cellular studies clearly confirmed that the U-Hg-U photo-cross-links in the irradiated nanoparticles substantially enhance their selective cellular uptake by cancer cells via macropinocytosis and the mercury-loaded nanoparticles subsequently induce higher levels of cytotoxicity in cancer cells (compared to non-irradiated nanoparticles), without harming normal cells. These results are mainly attributed to cancer cell microenvironment-triggered release of mercury ions from disassembled nanoparticles, which rapidly induce massive levels of apoptosis in cancer cells. Overall, the pH-sensitive U-Hg-U photo-cross-links within this newly discovered supramolecular system are an indispensable factor that offers a potential path to remarkably enhance the selective therapeutic effects of functional nanoparticles toward cancer cells.

Interaction of HPC with CTAB and Tween 40 at Water/Air and Water/Soya Oil Interfaces.

The bulk and interfacial shear rheological behavior of aqueous solutions of biocompatible polymer HPC has been investigated in the presence of cationic CTAB and nonionic Tween 40 having the same chain length but different head groups. Steady-state bulk experiments depict two distinct regions in the rheogram (Newtonian followed by pseudoplastic). Dynamic experiments suggest that the stability of HPC hydrogels decreases with the increase in surfactant concentration. Interfacial steady shear tests of 2D monolayers of 1 wt % HPC and 1 wt % HPC with varying concentrations of Tween 40/CTAB show a non-Newtonian dilatant behavior at the solution-air interface. However, two distinct dilatant regions separated by a Newtonian region were observed for the same films at the solution-soya oil interface. The strength of films formed at the two interfaces decreases with the increase of surfactant concentration as observed from oscillatory interfacial tests. HPC interacts more strongly with CTAB than Tween 40 both in bulk as well as at the interfaces studied.

Structure and self-diffusivity of alkali-halide electrolytes in neutral and charged graphene nanochannels.

Understanding the microscopic behaviour of aqueous electrolyte solutions in graphene-based ultrathin nanochannels is important in nanofluidic applications such as water purification, fuel cells, and molecular sensing. Under extreme confinement (<2 nm), the properties of water and ions differ drastically from those in the bulk phase. We studied the structural and diffusion behaviour of prototypical aqueous solutions of electrolytes (LiCl, NaCl, and KCl) confined in both neutral and positively-, and negatively-charged graphene nanochannels. We performed molecular dynamics simulations of the solutions in the nanochannels with either one, two- or three-layer water structures using the effectively polarisable force field for graphene. We analysed the structure and intermolecular bond network of the confined solutions along with their relation to the self-diffusivity of water and ions. The simulations show that Na and K cations can more easily rearrange their solvation shells under the graphene nanoconfinement and adsorb on the graphene surfaces or dissolve in the confinement-induced layered water than the Li cation. The negative surface charge together with the presence of ions orient water molecules with hydrogens towards the graphene surfaces, which in turn weakens the intermolecular bond network. The one-layer nanochannels have the biggest effect on the water structure and intermolecular bonding as well as on the adsorption of ions with only co-ions entering these nanochannels. The self-diffusivity of confined water is strongly reduced with respect to the bulk water and decreases with diminishing nanochannel heights except for the negatively-charged one-layer nanochannel. The self-diffusivity of ions also decreases with the reducing the nanochannel heights except for the self-diffusivity of cations in the negatively-charged one-layer nanochannel, evidencing cooperative diffusion of confined water and ions. Due to the significant break-up of the intermolecular bond network in the negatively-charged one-layer nanochannel, self-diffusion coefficients of water and cations exceed those for the two- and three-layer nanochannels and become comparable to the bulk values.

TFC membrane with in-situ crosslinked ultrathin chitosan layer for efficient water/ethanol separation enabled by multiple supramolecular interactions

Chitosan (CS) membranes have been widely applied in water/ethanol separation via membrane-based pervaporation, but a bottleneck in the practical application always exists due to their severe swelling behavior in aqueous solution and consequently low permeation flux due to the large membrane thickness. Here, thin film composite (TFC) hollow fiber (HF) membrane with an in-situ-crosslinked ultrathin CS selective layer is developed via multiple supramolecular interaction-crosslinking strategy for efficient water/ethanol separation via pervaporation. With Fe3+-phytic acid (PhA) complex pre-deposited on the substrate, the subsequently introduced CS selective layer is in-situ crosslinked via multiple supramolecular interactions, including coordination, electrostatic, and hydrogen bonding interactions. By varying the cycle number of Fe3+/PhA assembly and the species of employed organophosphorus acid, the anti-swelling properties of the resultant TFC CS membrane is enhanced and the separation performance is maximized. The optimal TFC-CS-Fe2PhA2 membrane with two cycles of Fe3+/PhA assembly has a selective layer thickness of 60 ​nm and a corresponding ultrahigh flux of 2.87 ​kg/m2 h, coupled with a permeate water concentration of 99.5 ​wt% and good long-term stability for the dehydration of 85 ​wt% ethanol aqueous solution at 50 ​°C. The supramolecular interaction-crosslinking presented in this work provides an efficient and promising strategy for the construction of TFC CS membrane with excellent anti-swelling property and superior separation performance.

Electrical surface properties of nanoporous alumina membranes: influence of nanochannels' curvature, roughness and composition studied via electrokinetic experiments.

Among classical nanoporous oxide membranes, anodic aluminum oxide (AAO) membranes, made of non-connected, parallel and ordered nanochannels, are very interesting nanoporous model systems widely used for multiple applications. Since most of these applications involve local phenomena at the nanochannel surface, the fine description of the electrical surface behavior in aqueous solution is thus of primordial interest. Here, we use an original experimental approach combining several electrokinetic techniques (tangential and transverse streaming potential as well as electrophoretic mobility experiments) to measure the ζ-potential and determine the surface isoelectric points (IEPs) of several AAOs having different characteristic sizes and compositions. Using such an approach, all the different surfaces available in AAOs can be probed: outer surfaces (top and bottom planes), pore wall surfaces (i.e., inner surfaces) and surfaces created by the grinding of the AAOs. We find clear IEP differences between the outer, pore wall and ground surfaces and discuss these in terms of nanochannel and surface morphology (curvature and roughness) and of modifications of the chemical environment of the surface hydroxyl groups. These results highlight the heterogeneities between the different surfaces of these AAO membranes and emphasize the necessity to combine complementary electrokinetic techniques to properly understand the material, an approach which can be extended to many nanoporous systems.

The Water-Polymer Method of Hydroperforation of Oil and Gas wells

The aim of the study is to develop an efficient, innovative method of perforating oil and gas well casing strings with a high-velocity stream of polymer solution that conserves resources and energy and meets the requirements for environ- mentally friendly hydrocarbon production. New knowledge about the dynamics of polymer solutions in the model conditions of flow through the nozzles of the hydro perforator, which form a high-velocity jet, became the main scientific basis for substantiating the water-polymer method of hydro perforation of oil and gas wells. The study of the reaction of polymer solutions to tension hydrodynamic influence allowed to formulate a structural concept, the "common denominator" of which is the strong deformation effect of tension hydrodynamic field on high molecular weight coils, which, according to nonequilibrium thermodynamics, should cause a kind of high elasticity. Peculiarities of hydrodynamic behavior of aqueous polymer solutions in model conditions of flow through jet-forming nozzles are studied. The possibility of transition to a highly developed state of the tangle of polyethylene oxide macromolecules in the conditions of the inlet section of the nozzle of the hydro perforator has been experimentally proved. The mechanism of perforation of oil and gas wells by a high-velocity jet of an aqueous polymer solution has been elucidated. It is proved that the mechanism of the high cutting ability of the high-velocity jet of aqueous polymer solution is the destructive effect of the dynamic pressure of water-polymer jet "reinforced" by highly developed macromolecular chains in the inlet nozzles of the hydro perforator nozzles under the action of tensile leakage. Experimental and industrial testing of the method of perforation of wells by a high-speed jet of an aqueous solution of polyethylene oxide confirmed the practical and economic feasibility of its use.

Rheology of nano ZnO - Hydroxypropyl Methylcellulose (HPMC) based suspensions and structural properties of resulting films

Effect of polyethylene glycol (PEG) and ZnO nanoparticles concentration on rheological properties of the hydroxypropyl methylcellulose (HPMC) based film forming suspensions (FFS) and, on the structural properties of the resulting films were characterized. Rheological properties of FFS were not significantly affected by PEG concentration and ZnO NPs incorporation. Intrinsic viscosity [η] of aqueous HPMC solution obtained from extrapolation of Huggins and Kraemer plot was 0.115–0.118 (L/g). Coating thickness calculated as a function of coating solution viscosity, concentration and draining time for strawberry coating was 1.26–1.49 μm. Tensile strength (TS) of HPMC film decreased while water vapour permeability (WVP) increased with increasing PEG concentration. Elongation at break (%E) increased up to 25% PEG concentration and decreased afterward. Incorporation of ZnO NPs improved the tensile strength and barrier properties of HPMC film. Relaxation percentage and stress decay rate increased with increasing plasticizer concentration while decreased with incorporation of ZnO NPs. • Rheological behaviour of aqueous HPMC solution (4% w/v) was Newtonian. • Calculated Intrinsic viscosity [η] of aqueous HPMC solution was 0.115–0.118 (L/g). • Relaxation % and stress decay rate showed positive correlation with PEG concentration. • Added ZnO nanoparticles improves the HPMC film properties.

Understanding the Structure and Rheology of Galactomannan Solutions with Coarse-Grained Modeling

Understanding and predicting the behavior of aqueous solutions of galactomannans is of significant interest for a variety of fields and applications, such as hydraulic fracturing in the petroleum industry and thickening in the food industry. Herein, we devise and validate a coarse-grained (CG) model of guar gum─a galactomannan─and study its structure and rheology in aqueous solution. The CG model is computationally efficient, utilizing an implicit solvent and one CG bead per monosaccharide, and exhibits good quantitative agreement with experiments with respect to the radius of gyration of the chain, aggregate structure in solution, and solution viscosity. Using both simulations and experiments, we show that the behavior of guar gum in water can be explained by scaling theory for polymers in good solvents. Namely, the radius of gyration of the chain shows a self-avoiding random walk behavior, and the solution specific viscosity ηsp exhibits the expected power-law scaling with the reduced concentration in different solution regimes (i.e., ηsp ∼ (c[η])1.3 in semidilute and ηsp ∼ (c[η])3.9 in entangled solutions). By extending our CG model to other galactomannans with different mannose-to-galactose ratios (M/G ratios) and different arrangements of unsubstituted mannose units, we show that high M/G ratios and long blocks of unsubstituted mannose units are responsible for aggregate formation in galactomannan solutions, which can reduce solution viscosity moderately.

The choice of μ-vinyliminium ligand substituents is key to optimize the antiproliferative activity of related diiron complexes.

Diiron vinyliminium complexes constitute a large family of organometallics displaying a promising anticancer potential. The complexes [Fe2Cp2(CO)(μ-CO){μ-η1:η3-C(R3)C(R4)CN(R1)(R2)}]CF3SO3 (2a-c, 4a-d) were synthesized, assessed for their behavior in aqueous solutions (D2O solubility, Log Pow, stability in D2O/Me2SO-d6 mixture at 37°C over 48 h) and investigated for their antiproliferative activity against A2780 and A2780cisR ovarian cancer cell lines and the nontumoral one Balb/3T3 clone A31. Cytotoxicity data collected for 50 vinyliminium complexes were correlated with the structural properties (i.e. the different R1-R4 substituents) using the partial least squares methodology. A clear positive correlation emerged between the octanol-water partition coefficient and the relative antiproliferative activity on ovarian cancer cell lines, both of which appear as uncorrelated to the cancer cell selectivity. However, the different effects played by the R1-R4 substituents allow tracing guidelines for the development of novel, more effective compounds. Based on these results, three additional complexes (4p-r) were designed, synthesized and biologically investigated, revealing their ability to hamper thioredoxin reductase enzyme and to induce cancer cell production of reactive oxygen species.

PH-Responsive, Thermo-Resistant Poly(Acrylic Acid)-g-Poly(boc-L-Lysine) Hydrogel with Shear-Induced Injectability.

In this study we report the rheological behavior of aqueous solutions of an amphiphilic graft copolymer constituting a polyacrylic acid (PAA) grafted by poly(boc-L-lysine), P(b-LL). Due to the highly hydrophobic nature of the grafted chains, the copolymer self-assembles spontaneously in aqueous media forming three-dimensional (3D) finite size networks (microgels). The rheological analysis demonstrated that the copolymer behaves as a strong elastic hydrogel, showing characteristics of a "frozen" network. Moreover, it is noteworthy that the formulation shows the above-described characteristics in very small concentrations (0.25-1.20 wt%) compared to other naturally cross-linked hydrogels that have been studied so far. Concentration significantly affects the rheological properties of the hydrogel, showing considerable increase in elastic modulus, following the scaling law G'~C1.93. At the same time, the hydrogels can be described as intelligent stimuli-responsive systems, showing pH and shear responsiveness as well as stability with temperature changes. Thanks to the pH dependance of the degree of ionization of the weak polyelectrolyte PAA backbone, stiffness and swelling of the hydrogels can be tuned effectively by adjusting the pH conditions. Simulating conditions such as those of injection through a 28-gauge syringe needle, the gel demonstrates excellent response to shear, due to its remarkable shear thinning behavior. The combination of pH-sensitivity and shear responsiveness leads to excellent injectability and self-healing properties, given that it flows easily upon applying a low stress and recovers instantly in the site of injection. Therefore, the physically cross-linked PAA-g-P(b-LL) hydrogel exhibits remarkable features, namely biocompatibility, biodegradability of cross-links, pH responsiveness, shear-induced injectability and instantaneous self-healing, making it a potential candidate for various biomedical applications.

Thermodynamic modeling of aqueous lithium salt solutions with association electrolyte nonrandom two-liquid activity coefficient model

The high charge density of lithium ion and the resulting strong association phenomena make thermodynamic modeling of aqueous lithium electrolyte solutions extremely challenging. In this study, the association electrolyte nonrandom two-liquid activity coefficient model of Lin et al. (AIChE J. 2022, 68(2), e17422) is utilized to correlate and predict thermodynamic properties and solubility behavior of aqueous single electrolyte solutions of LiCl, LiBr, LiI, and LiNO3, and their mixed electrolyte solutions. Capturing self-association of water, cross-association of ion and water for hydration, and cross-association of cation and anion for ion-pairing, the association model accurately represents the literature experimental data up to saturation concentrations and at the temperature ranging from 263 K to 523 K. This study further investigated the effect of anions of the lithium salts, and re-confirmed that the order of solution non-ideality as LiI > LiBr > LiCl > LiNO3 because the anions with stronger association strengths are more likely to form ion pairs and thus lower the mean ionic activity coefficients.

Review of Boron Nitride Nanosheet-Based Composites for Construction Applications

Two-dimensional nanoparticles stand out among nanoparticles for their extraordinary mechanical properties, large surface area, and strong interaction with the host matrix, which can boost properties of various construction materials. Boron nitride nanosheets (BNNSs), known as white graphene, show nonsensitive behavior against increasing thickness as well as high chemical and thermal stability that makes them suitable for fabrication of advanced composites in various industries. Despite these proven benefits, the role of BNNS in cementitious composites has not been fully investigated in the literature because of some inconsistent results such as its unfavorable behavior in aqueous solution. This study presents a comprehensive review of BNNS in silicate-based matrices from molecular-level interactions to macroscale properties to give potential avenues for manufacturing boron nitride-based composites for construction applications. The prime focus of this review article is to highlight the role of proper dispersion and stabilization of the dispersed BNNS within both aqueous solutions and cement matrix, which is reflected in the properties of fabricated cementitious composites in their fresh and hardened states. In addition, considering the structural similarity between BNNS and graphene-based nanosheets, the paper also compares BNNS and graphene-based cementitious composites. Finally, the existing gaps of knowledge are highlighted for future studies.

Amphiphilic Molecular Brushes with Regular Polydimethylsiloxane Backbone and Poly-2-isopropyl-2-oxazoline Side Chains. 3. Influence of Grafting Density on Behavior in Organic and Aqueous Solutions

Regular and irregular molecular brushes with polydimethylsiloxane backbone and poly-2-isopropyl-2-oxazoline side chains have been synthesized. Prepared samples differed strongly in the side chain grafting density, namely, in the ratio of the lengths of spacer between the grafting points and the side chains. The hydrodynamic properties and molecular conformation of the synthesized grafted copolymers and their behavior in aqueous solutions on heating were studied by the methods of molecular hydrodynamics and optics. It was found that the regularity and the grafting density do not affect the molecular shape of the studied samples of molecular brushes in the selective solvent. On the contrary, the grafting density is one of the most important factors determining the thermoresponsivity of grafted copolymers. It was shown that in analyzing self-organization and LCST values in aqueous solutions of poly-2-isopropyl-2-oxazolines with complex architecture, many factors should be considered. First is the molar fraction of the hydrophobic fragment and the intramolecular density. It was found that molar mass is not a factor that greatly affects the phase transition temperature of poly-2-isopropyl-2-oxazolines solutions at a passage from one molecular architecture to another.

Effect of Imidazolium Nitrate Ionic Liquids on Conformational Changes of Poly(N-vinylcaprolactam).

Detailed information about molecular interactions and conformational changes of polymeric components in the presence of ionic liquids (ILs) is essential for designing novel polymeric ionic liquid-based biomaterials. In biomaterials science and technology, thermoresponsive polymers (TRPs) are widely viewed as potential candidates for the fabrication of biorelated medical devices. Here, we synthesized thermoresponsive poly(N-vinyl-caprolactam) (PVCL) polymer and investigated the effects of imidazolium-based ILs (1-ethyl-3-methyl imidazolium nitrate and 1-butyl-3-methylimidazolium nitrate) with common anion and different cations on the phase transition behavior of PVCL aqueous solution. The impact of ILs on the phase transition behavior of PVCL was monitored by using UV-visible absorption spectra, steady-state fluorescence spectroscopy, thermal fluorescence spectroscopy, and temperature dependent dynamic light scattering. Results showed significant changes in the absorbance, molecular interactions, agglomeration, and coil to globule transition behaviors of PVCL in the presence of two ILs. PVCL aqueous solution showed significant conformational changes after the addition of ILs.

Differentiating the Structure and Dynamics of Solute-Bound Vs. Bulk Water in Deep-Eutectic Aqueous AlCl3 Solutions

Aqueous solutions of aluminum chloride exhibit a deep eutectic (-52˚C) that is likely due to solute-directed formation of complex network structures in the solvent. It is well known that the solute-bound solvent must have a distinct chemical environment from that of the bulk solvent. Commonly used vibrational spectroscopic measurements of aqueous salt solutions are not selective enough to directly identify distinct water environments in solution. However, variable-temperature 1H-NMR spectroscopy of aqueous solutions, specifically those with high charge density salts, can distinguish water directly bound to the cation from water of the bulk solution. This unique ability to resolve characteristic water peaks by NMR spectroscopy affords the opportunity to explore the hydration structure and dynamics of deep-eutectic aqueous solutions. The aqueous AlCl3 system is an excellent model to study solution structure since we can exploit the high charge density of the ions for which strong ion-dipole interactions are structure-directing to the solvent waters, allowing resolution of distinct water chemical environments. We conducted a thorough investigation of the composition- and temperature-dependent solution structure of the AlCl3 : water system using 1H-NMR spectroscopy, and X-ray and neutron diffraction. The room-temperature proton chemical shift of water proceeds downfield with increasing salt concentration until AlCl3•22H2O, the eutectic composition, after which further increasing concentration results in an upfield chemical shift (see Figure.) Using VT-NMR, we can resolve the first-nearest neighbor water signals from the bulk signal upon cooling. 1H-NMR T1 and T2 relaxation measurement of the distinct water environments reveal stark differences in proton mobility for compositions on the water-rich versus AlCl3-rich sides of the eutectic, implying significant changes in hydration structure. To evaluate the extent to which these changes are structural, a parallel set of composition- and temperature-dependent neutron and X-ray diffraction experiments demonstrate that both cations and anions exhibit significant structure-directing influences on the solution, which we hypothesize underlies deep eutectic behavior in aqueous solutions. Figure 1

Estimation of Nanoparticle's Surface Electrostatic Potential in Solution Using Acid-Base Molecular Probes. III. Experimental Hydrophobicity/Hydrophilicity and Charge Distribution of MS2 Virus Surface.

MS2 bacteriophage is often used as a model for evaluating pathogenic viruses' behavior in aqueous solution. However, the questions of the virus surface's hydrophilic/hydrophobic balance, the charge distribution, and the binding mechanism are open. Using the dynamic light scattering method and laser Doppler electrophoresis, the hydrodynamic diameter and the ζ-potential of the virus particles were measured at their concentration of 5 × 1011 particles per mL and ionic strength 0.03 M. The values were found to be 30 nm and -29 or -34 mV (by Smoluchowski or Ohshima approximations), respectively. The MS2 bacteriophage surface was also investigated using a series of acid-base indicator dyes of various charge type, size, and structure. Their spectral and acid-base properties (pKa) are very sensitive to the microenvironment in aqueous solution, including containing nanoparticles. The electrostatic potential of the surface Ψ was estimated using the common formula: Ψ = 59 × (pKai - pKa) in mV at 25 °C. The Ψ values were -50 and +10 mV, respectively, which indicate the "mosaic" way of the charge distribution on the surface. These data are in good agreement with the obtained ζ-potential values and provide even more information about the virus surface. It was found that the surface of the MS2 virus is hydrophilic in solution in contrast to the commonly accepted hypothesis of the hydrophobicity of virus particles. No hydrophobic interactions between various molecular probes and the capsid were observed.

Evidence of Formation of Monolayer Hydrated Salts in Nanopores.

Despite much effort being devoted to the study of ionic aqueous solutions at the nanoscale, our fundamental understanding of the microscopic kinetic and thermodynamic behaviors in these systems remains largely incomplete. Herein, we reported the first 10 μs molecular dynamics simulation, providing evidence of the spontaneous formation of monolayer hexagonal honeycomb hydrated salts of XCl2·6H2O (X = Ba, Sr, Ca, and Mg) from electrolyte aqueous solutions confined in an angstrom-scale slit under ambient conditions. By using both the classical molecular dynamics simulations and the first-principles Born-Oppenheimer molecular dynamics simulations, we further demonstrated that the hydrated salts were stable not only at ambient temperature but also at elevated temperatures. This phenomenon of formation of hydrated salt in water is contrary to the conventional view. The free energy calculations and dehydration analyses indicated that the spontaneous formation of hydrated salts can be attributed to the interplay between ion hydration and Coulombic attractions in the highly confined water. In addition to providing molecular-level insights into the novel behavior of ionic aqueous solutions at the nanoscale, our findings may have implications for the future exploration of potential existence of water molecules in the saline deposits on hot planets.

Stabilization Effects Induced by Trehalose on Creatine Aqueous Solutions Investigated by Infrared Spectroscopy.

Creatine is a very popular amino acid widely utilized in the sports world due to its functions mainly related to muscle building and increasing performance. The present work investigates the behavior of creatine aqueous solutions and of creatine aqueous in the presence of trehalose as a function of time changes by means of Infrared spectroscopy. Infrared spectra have been gathered and studied over time for both the full spectrum and the intramolecular OH-stretching region for the two mixtures. This latter region was studied more specifically using a cutting-edge technique called Spectral Distance (SD). From this analysis of the spectral features of the investigated samples, it emerges that trehalose has a significant stabilizing effect on creatine aqueous solutions.

Layered silicate edge-linked perylene diimides: Synthesis, self-assembly and energy transfer

The control over intermolecular interactions between chromophores at nanomaterial interfaces is important for sensing and light-harvesting applications. To that aim, inorganic nanoparticles with anisotropic shape and surface chemistry can serve as useful supports for organic modification. Herein, novel asymmetric perylene diimides with aspartic acid and oleyl terminal groups were grafted to the edges of the layered silicate clay Laponite, a water-dispersible discoidal nanoparticle. The photophysical properties and solvent-dependent self-assembly of the nanoclay-grafted perylenes were investigated, revealing that the polarity of the terminating ligand dictates the aggregation behavior in aqueous solution, where increased water content generally led to the formation of perylene H-aggregates. The anionic basal surface of the nanoclay provided a binding site for a cationic fluorophore, leading to energy transfer from the face-bound donor to the edge-bound perylene acceptor. This study encourages further research on the use of functional ligands for the formation of organic–inorganic hybrids, particularly where inorganic template particles with specific surface chemistry can be exploited to study intermolecular interactions. Overall, these findings should advance further design and implementation of novel semiconducting ligands towards inorganic–organic hybrids, with potential applications in sensing and energy harvesting.