Solvation Layer Research Articles

Probing the structural properties of the water solvation shell around gold nanoparticles: A computational study.

While subjected to radiation, gold nanoparticles (GNPs) have been shown to enhance the production of radicals when added to aqueous solutions. It has been proposed that the arrangement of water solvation layers near the water-gold interface plays a significant role. As such, the structural and electronic properties of the first water solvation layer surrounding GNPs of varying sizes were compared to bulk water using classical molecular dynamics and quantum and semi-empirical methods. Classical molecular dynamics was used to understand the change in macroscopic properties of bulk water in the presence of different sizes of GNP, as well as by including salt ions. The analysis of these macroscopic properties has led to the conclusion that larger GNPs induce the rearrangement of water molecules to form a 2D hydrogen-bond network at the interface. Quantum methods were employed to understand the electronic nature of the interaction between water molecules and GNPs along with the change in the water orientation and the vibrational density of states. The stretching region of vibrational density of states was found to extend into the higher wavenumber region, as the size of the GNP increases. This extension represents the dangling water molecules at the interface, as a result of reorientation of the water molecules in the first solvation shell. This multi-level study suggests that in the presence of GNP of increasing sizes, the first water solvation shell undergoes a rearrangement to maximize the water-water interactions as well as the water-GNP interactions.

Understanding aqueous and non-aqueous proton T1 relaxation in brain

A full picture of longitudinal relaxation in complex heterogeneous environments like white matter brain tissue remains elusive. In tissue, successive approximations, from the solvation layer model to the two pool model, have highlighted how longitudinal magnetization evolution depends on both inter-compartmental exchange and spin–lattice relaxation. In white matter, however, these models fail to capture the behaviour of the two distinct aqueous pools, myelin water and intra/extra-cellular water. A challenge with testing more comprehensive multi-pool models lies in directly observing all pools, both aqueous and non-aqueous. In this work, we advance these efforts by integrating three main experimental and analytical elements: direct observation of the longitudinal relaxation of both the aqueous and the non-aqueous protons in white matter, a wide range of different initial conditions, and application of an analysis pipeline which includes lineshape, CPMG, and fitting of a four pool model. An eigenvector interpretation of the four pool model highlights how longitudinal relaxation in white matter depends on initial conditions. We find that a single set of model parameters is able to describe the entire range of relaxation behaviour observed in all the separable aqueous and non-aqueous pools in experiments involving six different initial conditions. Understanding of the nature and connectedness of the tissue components is crucial in the design and interpretation of many MRI measurements, especially those based on magnetization transfer and longitudinal relaxation. In particular, the dependency of relaxation behaviour on initial conditions is likely the basis for understanding method-dependent discrepancies in in vivo T1.

Insights on the Structural and Dynamic Properties of Corundum–Water Interfaces from First-Principle Molecular Dynamics

The interaction of water with hydroxylated mineral surfaces is central to numerous natural and technological processes; yet, at the atomic level much remains to be understood about the structure and dynamics of interfacial water and H-bonding networks. This work applies first-principle molecular dynamics to examine the relationship between surface structure and interfacial water behavior at four hydroxylated corundum (α-Al2O3) surfaces. The four surfaces studied include the (001), (012), (110), and (113) surfaces; they have distinct surface functional groups (−OH, μ-OH, and μ3-OH) and topography (planar, corrugated, and two-tiered). Interfacial H-bonding was investigated in detail by analyzing atomic density 1-D profiles, angular distribution of surface O–H bonds, and the dipole moment orientation of interface H2O molecules and by calculating vibrational density of states in the high-frequency region. Our results reveal distinct differences in the interaction of interfacial water and H-bonding networks at the four surfaces. Specifically, inter- and intramolecular H-bonding depends on surface site coordination geometry, neighboring functional groups, and surface topography. Moreover, intramolecular H-bonding involving in-plane surface hydroxyl groups may persist, thus limiting intermolecular H-bonding. Equally, first solvation layer water molecules are preferentially orientated at the (001), (012), and (113) surfaces, whereas water molecules at the (110) surface show minimal preferred orientation. The distinct differences in the behavior of interfacial water and H-bonding at the four surfaces may play a substantial role in determining the reactivity of the surfaces toward processes such as ion adsorption–desorption and dissolution–precipitation.

Supramolecular solvent (SUPRASs) extraction method for detecting benzodiazepines and zolpidem in human urine and blood using gas chromatography tandem mass spectrometry.

A high-throughput and sensitive method using supramolecular solvent (SUPRASs) for detecting 9 benzodiazepines and zolpidem in human urine and blood by gas chromatography-tandem mass spectrometry (GC-MS/MS) was newly established and applied to authentic human urine and blood samples in this study. Urine and blood samples were subjected to liquid-liquid extractions with supramolecular solvent mixture which consists of tetrahydrofuran and 1-hexanol. The solvent layer was evaporated to dryness by stream of nitrogen. The residue was reconstituted with methanol, and subjected to analysis by GC-MS/MS in multiple reaction monitoring (MRM) mode; internal standard method was employed for quantifying of each targeted compound. The regression equation has a good linear relationship with correlation coefficients for all tested compounds were not lower than 0.9991. The lower limits of the quantification ranged from 0.20 to 5ng/mL for tested compounds in urine; Meanwhile, the lower limits of the quantification in this method ranged from 1 to 50ng/mL for tested compounds in blood. These results showed that excellent reproducibility and satisfactory extraction recovery rates could be obtained for the established analytical method for 10 drugs in both blood and urine samples. The established method in this study was high-throughput, simple and sufficiently sensitive for determining of benzodiazepinesand zolpidem in human urine and blood. Therefore, this newly established method could be of use for qualitative and quantitative determination of such drugs in urine and blood samples either for clinical poisoning monitoring or for forensic identification.

Varying the Dimensionality of Cu(II)-Based Coordination Polymers Through Solvent Influence

This work reports the synthesis and structure of a large porous zeotype network observed within compound (1) using {Cu2(piv)4} as the linking unit (piv = pivalate). The slow in situ formation of the hmt ligand (hexamethylenetetramine) appears to be key in generating a µ4-bridging mode of the hmt-node. Attempts to improve the low yield of compound (1) using different solvent layer diffusion methods resulted in the µ3-hmt complexes (2) and (3). Both compounds exhibit a 3D network of two intertwined chiral networks. Strong hydrogen bonding present in (3) leads to the formation of intertwined, DNA-like double-helix structures. The use of bulky solvents in the synthesis of compound (4) leads to the structure crystallizing solvent-free. The packing of (4) is dominated by energy minimization, which is achieved when the 1D-“cylinders” pack into the closest possible arrangement. This work highlights the potential for solvent controlled synthesis of extended copper-hmt systems.

High-pressure carbon dioxide–organic solvent mixing layers: Global equilibrium models and the transition to single phase mixing

Transcritical injection is of relevance to many areas of science and engineering. In all applications, one of the most controversial issue is the prediction of the transition point from two-phase to single phase mixing. In this work, we have analysed the applicability of recent transition models, e.g. the Knudsen criterion developed originally for propulsion applications, to analyse the formation and development of mixing layers of carbon dioxide and different organic solvents. Results show that global equilibrium models fail to predict the experimental behaviour reported in the literature and exhibit an inconsistent trend among the different organic solvents/CO2 mixtures. This implies that initial conditions alone are not sufficient to determine the evolution of the mixing layer. As a consequence, research efforts should be directed to the accurate description of the coupled energy and mass diffusive fluxes both at the liquid–gas interface and in the surrounding gaseous mixing layer.

Theoretical characterization of Al(III) binding to KSPVPKSPVEEKG: Insights into the propensity of aluminum to interact with key sequences for neurofilament formation

Classical molecular dynamic simulations and density functional theory are used to unveil the interaction of aluminum with various phosphorylated derivatives of the fragment KSPVPKSPVEEKG (NF13), a major multiphosphorylation domain of human neurofilament medium (NFM). Our calculations reveal the rich coordination chemistry of the resultant structures with a clear tendency of aluminum to form multidentate structures, acting as a bridging agent between different sidechains and altering the local secondary structure around the binding site. Our evaluation of binding energies allows us to determine that phosphorylation has an increase in the affinity of these peptides towards aluminum, although the interaction is not as strong as well-known chelators of aluminum in biological systems. Finally, the presence of hydroxides in the first solvation layer has a clear damping effect on the binding affinities. Our results help in elucidating the potential structures than can be formed between this exogenous neurotoxic metal and key sequences for the formation of neurofilament tangles, which are behind of some of the most important degenerative diseases.

Influence of water on the intrinsic characteristics of cellulose dissolved in an ionic liquid

The local structure of cellulose, dissolved in the frequently used ionic liquid EMIm-OAc, is modelled by a coaxial double layer cylinder. The cylinder’s core consists of a cellulose chain while the sheath is formed by a solvent layer with lower electron density than the bulk solvent. We studied 2% cellulose solutions in EMIm-OAc and their behavior upon addition of increasing amounts of water. At this cellulose concentration, 15 wt% of water induced the precipitation of cellulose. Water molecules did not form an independent phase, but were bound to EMIm-OAc in the cellulose/water/EMIm-OAc solution. The conformational of a cellulose chain changes by adding water into the solution, and the square of the apparent cross-sectional radius of gyration of the cellulose chain becomes zero to negative. This phenomenon is explained by the formation of a solvation shell with lower electron density than the bulk solvent around the cellulose chain.

Structural Heterogeneity in Single Particle Imaging Using X-ray Lasers.

One of the challenges facing single particle imaging with ultrafast X-ray pulses is the structural heterogeneity of the sample to be imaged. For the method to succeed with weakly scattering samples, the diffracted images from a large number of individual proteins need to be averaged. The more the individual proteins differ in structure, the lower the achievable resolution in the final reconstructed image. We use molecular dynamics to simulate two globular proteins in vacuum, fully desolvated as well as with two different solvation layers, at various temperatures. We calculate the diffraction patterns based on the simulations and evaluate the noise in the averaged patterns arising from the structural differences and the surrounding water. Our simulations show that the presence of a minimal water coverage with an average 3 Å thickness will stabilize the protein, reducing the noise associated with structural heterogeneity, whereas additional water will generate more background noise.

Three-dimensional solvation structure of ethanol on carbonate minerals.

Calcite and magnesite are important mineral constituents of the earth’s crust. In aqueous environments, these carbonates typically expose their most stable cleavage plane, the (10.4) surface. It is known that these surfaces interact with a large variety of organic molecules, which can result in surface restructuring. This process is decisive for the formation of biominerals. With the development of 3D atomic force microscopy (AFM) it is now possible to image solid–liquid interfaces with unprecedented molecular resolution. However, the majority of 3D AFM studies have been focused on the arrangement of water at carbonate surfaces. Here, we present an analysis of the assembly of ethanol – an organic molecule with a single hydroxy group – at the calcite and magnesite (10.4) surfaces by using high-resolution 3D AFM and molecular dynamics (MD) simulations. Within a single AFM data set we are able to resolve both the first laterally ordered solvation layer of ethanol on the calcite surface as well as the following solvation layers that show no lateral order. Our experimental results are in excellent agreement with MD simulations. The qualitative difference in the lateral order can be understood by the differing chemical environment: While the first layer adopts specific binding positions on the ionic carbonate surface, the second layer resides on top of the organic ethyl layer. A comparison of calcite and magnesite reveals a qualitatively similar ethanol arrangement on both carbonates, indicating the general nature of this finding.

Insights into the Sensitivity of Arginine Concentration to Preserve the Folded Form of Insulin Monomer under Thermal Stress.

Arginine, although popularly known as aggregation suppressor additive, has been found to quench proteins' structure and function by destabilizing their conformations. Driven by such controversial evidence, in this work we performed a series of atomistic molecular dynamics simulations of insulin monomer, a biologically active hormone protein, in arginine solution of varying concentrations (0.5, 1, and 2 M) at ambient and elevated temperature (400 K) to explore the arginine concentration driven structure-based stability of the protein. Our study reveals that the flexibility of the protein's structure is dependent on the arginine concentration, and among all the used solutions, 2 M arginine, a "neutral crowder" that mimics the cellular environment, can preserve the native folded form of the protein at ambient temperature in an excellent manner. Further, while the protein unfolds at 400 K in pure water, this solution worked satisfactorily to preserve the protein's folded conformation more firmly than the other solutions. The replica-exchange MD of insulin in 2 M arginine solution further supports the fact. In this aspect an important issue in molecular pharmacology is to identify and recognize the physical origin of the stability of a protein, i.e, in this case, how arginine directs the conformational flexibility of the protein and preserves its native folded form. We identified that the exclusion of arginine from the protein surface increases the local structuration of water around the protein, thereby preserving its "biological water" layer, and makes the protein more hydrated at 2 M concentration as compared to the other arginine solutions. Additionally, our microscopic investigation on the interactions of the protein-solvation layer revealed that the structural heterogeneity of the protein surface, arising from the differential physicochemical nature of the amino acid residues, controls the favorable formation of sluggish water-arginine mixed solvation layer at higher arginine concentration that helps the protein to maintain its structural rigidity. Importantly, apart from the protein-solvent hydrogen-bonding interactions, the anion-pi interactions, established between the carboxyl group of arginine and the aromatic amino acid residues of insulin, were recognized to facilitate the protein to maintain its native folded form at the experimental temperatures.

Absorption of CO2 from flue gas under oscillating gas flow conditions in gas-solvent hollow fibre membrane contactors

Membrane gas-solvent contactors are a viable approach for the absorption of carbon dioxide (CO2) into solvents, such as potassium glycinate, compared to traditional solvent absorption. The hollow fibre membrane design does have limitations, as the presence of the membrane adds extra resistance to mass transfer compared to traditional solvent absorption. To reduce the impact of this extra resistance it is necessary to increase mass transfer in the solvent and gas phase boundary layers. This investigation aimed to increase mass transfer in the gas phase boundary layer of a membrane contactor process by applying oscillating gas flow conditions. For an asymmetric polydimethylsiloxane membrane contactor undergoing oscillating gas flow conditions, an average increase of 19% in overall mass transfer coefficient (KG) compared to non-oscillating gas flow was observed, for 15 wt% potassium glycinate solvent. The oscillating frequency of the gas phase had only a minor impact on performance, above 2 Hz, implying that oscillation of the gas phase was important for mixing, not the rate of the oscillation. Alternatively, KG approximately doubled in value as a function of increased oscillating amplitude. This was due to the resulting pressure wave producing localized increases in the partial pressure driving force for mass transfer across the membrane. For the membrane contactors studied, mass transfer correlations, in terms of Sherwood number, were proposed for the oscillating and non-oscillating flow conditions and fitted to the experimental data. This outcome highlighted the importance of inducing mixing within the gas phase to maximise mass transfer in membrane contactors.

Hydrogenated gold clusters from helium nanodroplets: displacement of H2 by H2O

Cationic clusters of gold, containing up to 8 atoms, and decorated with molecular hydrogen and water, were investigated with mass spectrometry. The clusters were grown as neutrals in superfluid helium nanodroplets that were ionized by electron impact. The resulting gas phase cluster cations exhibit magic sizes corresponding to the number of H2 molecules that form the first solvation layer, consistent with previous findings. The presence of water is found to efficiently displace hydrogen, one H2 molecule for each H2O. Our calculations show that the binding energy of water to the charged gold clusters is about twice as large as for hydrogen, though this depends on the charge of the clusters. This suggests that residual water could reduce the efficiency for metal particles to chemically store hydrogen gas, a promising technique for hydrogen fuel storage.Graphical abstract

The archaeal-bacterial lipid divide, could a distinct lateral proton route hold the answer?

The archaea-bacteria lipid divide is one of the big evolutionary enigmas concerning these two domains of life. In short, bacterial membranes are made of fatty-acid esters whereas archaeal ones contain isoprenoid ethers, though at present we do not have a good understanding on why they evolved differently. The lateral proton transfer mode of energy transduction in membranes posits that protons utilize the solvation layer of the membrane interface as the main route between proton pumps and ATPases, avoiding dissipation of energy to the bulk phase. In this article I present the hypothesis on a proton-transport route through the ester groups of bacterial phospholipids as an explanation for the evolutionary divergence seen between bacteria and archaea.ReviewersThis article was reviewed by Uri Gophna (Editorial Board member) and Víctor Sojo.

Structure of the intermediates in the industrial separation of perinone isomers

The industrial synthesis of perinone results in a mixed crystal containing an isomer mixture of trans- and cis-perinone. The isomers are separated by treatment with alcoholic KOH, which leads to a pale yellow precipitate and a yellow solution. The precipitate is subsequently hydrolyzed to produce pure trans-perinone (Pigment Orange 43). The yellow solution is treated with dilute acids to give cis-perinone (Pigment Red 194). The chemical structure and the stoichiometry of the intermediate pale yellow precipitate has never been determined, although this intermediate has been produced on a multi-ton scale for more than 80 years. The intermediate was assumed to be a “potassium hydroxide addition compound”. X-ray single-crystal analyses reveal that this assumption is wrong. The KOH/ethanol treatment actually causes a double ring-opening of the perinone. This results in the tetra-potassium salt of 4,8-bis(benzimidazolato)-naphthalene-1,5-dicarboxylate. Two phases were isolated: The α-phase, K4[C26H12N4O4]·3C2H5OH·6H2O, from the industrial synthesis and the β-phase, 1.5(K4[C26H12N4O4])·5C2H5OH·4H2O, from a recrystallization in KOH/ethanol. The molecular and crystal structures are confirmed by solid-state NMR spectroscopy through combination of 13C CPMAS and MAS experiments, which revealed that the solvent layers in the crystals show a highly dynamic solvent disorder in the solid state. The intermediate of cis-perinone, which is formed in the isomer separation step, has been isolated as well. Also this intermediate has a ring-opened molecular structure, as revealed by single-crystal X-ray diffraction.

Insights on (C, BN, Si, Ge, MoS2) Nanotubes in Reline Deep Eutectic Solvent.

The properties of carbon, boron nitride, silicon, germanium, and molybdenum disulfide nanotubes in reline (cholinium chloride + urea) deep eutectic solvents were studied by using classical molecular dynamics simulations. These nanotubes + reline nanofluids provide a suitable platform for the development of sustainable thermal engineering applications. The reported results lead to the characterization of nanotube solvation and reline layering around the nanotube surfaces as well as the behavior of reline upon confinement inside the considered nanotube cavities. Changes in reline hydrogen bonding in the presence of the nanotubes are also analyzed and related with the development of stable nanotube dispersions, thus showing reline as a suitable vehicle for nanotubes.

Synthesis of Poly(2-aminothiazole)-Coated Polystyrene Particles and Their Excellent Hg(II) Adsorption Properties.

Synthesis of conjugated polymer-coated latex particles is an effective method to improve the poor processability of conjugated polyheterocycles. The key to success is to control the overlayer thickness so it is less than the size of the solvated layer of polymeric stabilizer. This paper presents a protocol to coat polymer latex particles with poly(2-aminothiazole) (PAT), which is a relatively new heterocyclic conjugated polymer. The protocol is based on chemical oxidative polymerizations of 2-aminothiazole using copper chloride as the oxidant at a fixed oxidant/monomer molar ratio of 0.5 in aqueous media in the presence of poly(N-vinyl-2-pyrrolidone)-functionalized polystyrene (PS) latex. The effects of monomer concentration, PS concentration, and polymerization temperature on the morphology of the PAT-coated PS composite particles were investigated by SEM and TEM, and the resulting composite particles characterized by FTIR and XPS. Optimization of the initial monomer concentration allowed colloidally stable PAT-coated PS composite particles to be formed at ambient temperature, and the PAT loading was easily adjusted by varying the initial PS concentration. The Hg(II) adsorption properties of selected PAT-coated PS composite particles were assessed preliminarily. The maximum adsorption capacity at 25 °C reached 440.25 mg/g, which is much higher than many other adsorbents.

Molecular insights into the dispersion stability of graphene oxide in mixed solvents: Theoretical simulations and experimental verification

HypothesisImproving the dispersion stability of graphene oxide (GO) suspensions is of great importance in many potential applications of GO, such as GO-based laminated membranes used for separation, printable electronics, and aqueous liquid crystals. ExperimentsMolecular dynamics (MD) simulations and quantum chemistry (QC) calculations along with complementary experiments were performed to study the dispersion stability of GO in the mixtures of water and polar organic solvents (dimethyl sulfoxide (DMSO), ethanol, and acetone). FindingsGO exhibits better dispersion stability in a solvent mixture than in pure water. The MD simulations uncover the underlying mechanism that mixed solvent layers are formed steadily on the surface of GO sheets and screen the interactions between them. QC calculations reveal that both DMSO and water form hydrogen bonds with the oxidized regions of GO. X-ray diffraction experiments confirm that the GO sheets are intercalated by DMSO and water molecules. Furthermore, the optimal ratio of the organic solvent to water is determined to achieve the best dispersion stability of GO through MD simulations. And such ratio is also verified by ultraviolet absorption spectral experiments. Thus, our findings provide a facile method to prepare GO suspensions with high dispersion stability.

Dependence of cellulose dissolution in quaternary ammonium acetates/DMSO on the molecular structure of the electrolyte: use of solvatochromism, micro-calorimetry, and molecular dynamics simulations

We studied the dissolution of microcrystalline cellulose (MCC) at 60 °C in binary mixtures of dimethyl sulfoxide (DMSO) and the following quaternary ammonium acetates (QAAcOs): benzyl-trimethylammonium, NBzMe3AcO; diallyl-benzyl-methylammonium, NAl2BzMeAcO, tetra(n-butyl)ammonium (NBu4AcO), and tribenzyl-methylammonium, NBz3MeAcO (Al, Bu, Bz, Me, AcO refer to allyl, 1-butyl, benzyl, methyl and acetate group, respectively). We observed the following MCC dissolution order (given as wt%): NBu4AcO > NAl2BzMeAcO > NBz3MeAcO ≫ NBzMe3AcO. To explain this result we used the combined data of: (1) solvatochromism to calculate the following binary solvent (b-solvent) descriptors that are important for MCC dissolution: empirical polarity, Lewis acidity, Lewis basicity, dipolarity, polarizability; (2) isothermal titration micro-calorimetry to calculate the enthalpy of interaction (ΔH) of β-cyclodextrin (cellulose model) with QAAcO/DMSO-acetonitrile; (3) molecular dynamics simulations to calculate solvent-induced separation of cellulose chains; average number of hydrogen bonds between acetate ions and cellulose OH-groups, and average composition of the biopolymer solvation layer. We offer the following pieces of evidence to show the importance of hydrogen bonding for the efficiency of cellulose dissolution: the orders of b-solvent basicity and of |ΔH| are parallel to its cellulose dissolution efficiency; the biopolymer solvation layer of efficient b-solvents (e.g., NBu4AcO-DMSO) contains more ionic liquid ions and less DMSO molecules than that of NBz3MeAcO, leading to pronounced biopolymer chain separation, hence eventual dissolution. Our approach shows the power of the combined use of several techniques to rationalize the requirements for efficient cellulose solvents.

Solvation of quantum dots in 1-alkyl-1-methylpyrrolidinium ionic liquids: toward stably luminescent composites

ABSTRACT CdTe nanoparticles capped with a cationic thiolate ligand were stably dispersed in ionic liquids, 1-alkyl-1-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)amides with an alkyl group of n-propyl, butyl and octyl-chain, and in an ionic plastic crystal, 1-ethyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)amide. Dispersion behavior of CdTe nanoparticles in these ionic media was evaluated, in which the solvation of nanoparticles by the ionic components was particularly interested. The ionic media showed alkyl-chain length-dependent solvation behavior, which was suggested by the thermal analysis of nanocomposites. The longer alkyl-chains led to the greater decrease in the thermal melting enthalpy of ionic media with the introduction of nanoparticles. The ionic liquid with an octyl-chain, which is considered to form a thicker solvation layer, afforded better emission durability of CdTe nanoparticles compared to the ionic liquid with a shorter alkyl chain.