Nearby Solvent Research Articles

Understanding the Droplet Diffusion in Ionic Liquid Microemulsions.

Ionic liquids (ILs) as polar components in nonaqueous microemulsions are complex formulations that have interesting transport and structural properties, and offer broader applicability of ILs in areas such as drug delivery and cleaning technology. The phase behavior, electrical conductivity, and nanostructures of these formulations have been investigated for quite some time, but the characteristics of the diffusion of nanodroplets were rarely explored─ and hence little understood. This work investigates the droplet diffusion processes in a series of IL-microemulsions containing 1-butyl-3-methylimidazolium tetrafluoroborate ([C4mim]BF4) by means of viscosity and depolarized dynamic light scattering (DDLS) measurements. The intensity correlation functions are strikingly similar to polymeric solutions in nonaqueous media and aqueous microemulsions containing block copolymers─having bimodal relaxations that are separated by three to four decades of correlation delay times. The "faster" diffusion process is likely a collective process characterizing the correlated motions of droplets in droplet clusters. The collective diffusion coefficient Dcol values are quite comparable to aqueous microemulsions. The "slower" diffusion is likely due to the "caging" effect caused by nearby clusters and/or bulk solvent─this mode may be linked to the microemulsion bulk viscosity. Interestingly, the Dcol variations on increasing [C4mim]BF4 concentration are strongly correlated to the microemulsion viscosity changes as well as locations of these compositions on the microemulsion phase diagram.

The influence of a solvent environment on direct non-covalent interactions between two molecules: A symmetry-adapted perturbation theory study of polarization tuning of π–π interactions by water

High-level quantum chemical computations have provided significant insight into the fundamental physical nature of non-covalent interactions. These studies have focused primarily on gas-phase computations of small van der Waals dimers; however, these interactions frequently take place in complex chemical environments, such as proteins, solutions, or solids. To better understand how the chemical environment affects non-covalent interactions, we have undertaken a quantum chemical study of π–π interactions in an aqueous solution, as exemplified by T-shaped benzene dimers surrounded by 28 or 50 explicit water molecules. We report interaction energies (IEs) using second-order Møller–Plesset perturbation theory, and we apply the intramolecular and functional-group partitioning extensions of symmetry-adapted perturbation theory (ISAPT and F-SAPT, respectively) to analyze how the solvent molecules tune the π–π interactions of the solute. For complexes containing neutral monomers, even 50 explicit waters (constituting a first and partial second solvation shell) change total SAPT IEs between the two solute molecules by only tenths of a kcal mol−1, while significant changes of up to 3 kcal mol−1 of the electrostatic component are seen for the cationic pyridinium–benzene dimer. This difference between charged and neutral solutes is attributed to large non-additive three-body interactions within solvated ion-containing complexes. Overall, except for charged solutes, our quantum computations indicate that nearby solvent molecules cause very little “tuning” of the direct solute–solute interactions. This indicates that differences in binding energies between the gas phase and solution phase are primarily indirect effects of the competition between solute–solute and solute–solvent interactions.

Translational, rotational and vibrational relaxation dynamics of a solute molecule in a non-interacting solvent.

Spectroscopically observing the translational and rotational motion of solute molecules in liquid solutions is typically impeded by their interactions with the solvent, which conceal spectral detail through linewidth broadening. Here we show that unique insights into solute dynamics can be made with perfluorinated solvents, which interact weakly with solutes and provide a simplified liquid environment that helps to bridge the gap in our understanding of gas- and liquid-phase dynamics. Specifically, we show that in such solvents, the translational and rotational cooling of an energetic CN radical can be observed directly using ultrafast transient absorption spectroscopy. We observe that translational-energy dissipation within these liquids can be modelled through a series of classic collisions, whereas classically simulated rotational-energy dissipation is shown to be distinctly faster than experimentally measured. We also observe the onset of rotational hindering from nearby solvent molecules, which arises as the average rotational energy of the solute falls below the effective barrier to rotation induced by the solvent.

Fluorescence Quenching of Benzaldehyde in Water by Hydrogen Atom Abstraction.

We computed the mechanism of fluorescence quenching of benzaldehyde in water through relaxed potential energy surface scans. Time-dependent density functional theory calculations along the protonation coordinate from water to benzaldehyde reveal that photoexcitation to the bright ππ* (S3 ) state is immediately followed by ultrafast decay to the nπ* (S1 ) state. Evolving along this state, benzaldehyde (BA) abstracts a hydrogen atom, resulting in a BAH(.) and OH(.) radical pair. Benzaldehyde does not act as photobase in water, but abstracts a hydrogen atom from a nearby solvent molecule. The system finally decays back to the ground state by non-radiative decay and an electron transfers back to the OH(.) radical. Proton transfer from BAH(+) to OH(-) restores the initial situation, BA in water.

Ligand-Mediated Interactions between Nanoscale Surfaces Depend Sensitively and Nonlinearly on Temperature, Facet Dimensions, and Ligand Coverage.

Nanoparticles are often covered in ligand monolayers, which can undergo a temperature-dependent order-disorder transition that switches the particle-particle interaction from repulsive to attractive in solution. In this work, we examine how changes in the ligand surface coverage and facet dimensions affect the ordering of ligands, the arrangement of nearby solvent molecules, and the interaction between ligand monolayers on different particles. In particular, we consider the case of strongly bound octadecyl ligands on the (100) facet of CdS in the presence of an explicit n-hexane solvent. Depending on the facet dimensions and surface coverage, we observe three distinct ordered states that differ in how the ligands are packed together, and which affect the thickness of the ligand shell and the structure of the ligand-solvent interface. The temperature dependence of the order-disorder transition also broadens and shifts to lower temperature in a nonlinear manner as the nanoscale is approached from above. We find that ligands on nanoscale facets can behave very similarly to those on macroscopic surfaces in solution, and that some facet dimensions affect the ligand alignment more strongly than others. As the ligands order, the interaction between opposing monolayers becomes attractive, even well below full surface coverage. The strength of attraction per unit surface area is strongly affected by ligand coverage, but only weakly by facet width. Conversely, we find that bringing two monolayers together just above the order-disorder transition temperature can induce ordering and attraction.

Structure and spectroscopic properties of N,S-coordinating 2-methyl-sulfanyl-N-[(1H-pyrrol-2-yl)methyl-idene]aniline methanol monosolvate.

The reaction of pyrrole-2-carboxaldehyde and 2-(methyl-sulfan-yl)aniline in refluxing methanol gave an olive-green residue in which yellow crystals of the title compound, C12H12N2S·CH3OH, were grown from slow evaporation of methanol at 263 K. In the crystal, hydrogen-bonding inter-actions link the aniline mol-ecule and a nearby methanol solvent mol-ecule. These units are linked by a pair of weak C-H⋯Omethanol interactions, forming inversion dimers consisting of two main molecules and two solvent molecules.

X-ray spectroscopic study of solvent effects on the ferrous and ferric hexacyanide anions.

We present an Fe Kα resonant inelastic X-ray scattering (RIXS) and X-ray emission (XES) study of ferrous and ferric hexacyanide dissolved in water and ethylene glycol. We observe that transitions below the absorption edge show that the solvent has a distinct effect on the valence electronic structure. In addition, both the RIXS and XES spectra show a stabilization of the 2p levels when dissolved in water. Using molecular dynamics simulations, we propose that this effect arises from the hydrogen-bonding interactions between the complex and nearby solvent molecules. This withdraws electron density from the ligands, stabilizing the complex but also causing a slight increase in π-backbonding.

An Overview of Electrostatic Free Energy Computations for Solutions and Proteins.

Free energy simulations for electrostatic and charging processes in complex molecular systems encounter specific difficulties owing to the long-range, 1/r Coulomb interaction. To calculate the solvation free energy of a simple ion, it is essential to take into account the polarization of nearby solvent but also the electrostatic potential drop across the liquid-gas boundary, however distant. The latter does not exist in a simulation model based on periodic boundary conditions because there is no physical boundary to the system. An important consequence is that the reference value of the electrostatic potential is not an ion in a vacuum. Also, in an infinite system, the electrostatic potential felt by a perturbing charge is conditionally convergent and dependent on the choice of computational conventions. Furthermore, with Ewald lattice summation and tinfoil conducting boundary conditions, the charges experience a spurious shift in the potential that depends on the details of the simulation system such as the volume fraction occupied by the solvent. All these issues can be handled with established computational protocols, as reviewed here and illustrated for several small ions and three solvated proteins.

Orientational Ordering of Passivating Ligands on CdS Nanorods in Solution Generates Strong Rod–Rod Interactions

We present the first nearly atomistic molecular dynamics study of nanorod-nanorod association in explicit solvent, showing that inter-rod forces can be dominated by microscopic factors absent in common continuum descriptions. Specifically, we find that alkane ligands on faceted CdS nanorods in n-hexane undergo a temperature-dependent order-disorder transition akin to that of self-assembled monolayers on macroscopic substrates. This collective ligand alignment organizes nearby solvent molecules, strongly influencing the statistics of rod-rod separation. The strong temperature dependence of this mechanism could be exploited in the laboratory to manipulate and optimize the assembly of ordered structures.

Elucidating the higher stability of vanadium(V) cations in mixed acid based redox flow battery electrolytes

The vanadium(V) cation structures in mixed acid based electrolyte solution were analyzed by density functional theory (DFT) based computational modeling and 51V and 35Cl nuclear magnetic resonance (NMR) spectroscopy. The vanadium(V) cation exists as di-nuclear [V2O3Cl2·6H2O]2+ compound at higher vanadium concentrations (≥1.75 M). In particular, at high temperatures (>295 K) this di-nuclear compound undergoes ligand exchange process with nearby solvent chlorine molecule and forms chlorine bonded [V2O3Cl·6H2O]2+ compound. This chlorine bonded [V2O3Cl2·6H2O]2+ compound might be resistant to the de-protonation reaction which is the initial step in the precipitation reaction in vanadium based electrolyte solutions. The combined theoretical and experimental approach reveals that formation of chlorine bonded [V2O3Cl2·6H2O]2+ compound might be central to the observed higher thermal stability of mixed acid based vanadium(V) electrolyte solutions.

Studying the Effect of Site-Specific Hydrophobicity and Polarization on Hydrogen Bond Energy of Protein Using a Polarizable Method.

Quantification of backbone hydrogen bond energies in protein folding has remained elusive despite extensive theoretical and experimental investigations over the past 70 years. This is due to difficulties in experimental mutagenesis study as well as the lack of quantitatively reliable methods in theoretical calculation. Recent advance in experiment has enabled accurate measurement of site-specific backbone hydrogen bond energy in protein. In the present work, we developed an accurate and practical polarizable method to study site-specific hydrogen bond energies in the PIN WW domain. Excellent quantitative agreement between our calculated hydrogen bonding energy and recent experimental measurement is obtained. The direct comparison between theory and experiment helps uncover the microscopic mechanism of experimentally observed context dependent hydrogen bond contribution to protein stability in beta-sheet. In particular, our study reveals two effects that act in a cooperative manner to impact the strength of a hydrogen bond. One is the dynamic stability of the hydrogen bond determined by nearby solvent molecules, and the other is the polarization state of the hydrogen bond influenced by local electrostatic environment. The polar character of the hydrogen bond results in strong coupling between hydrophobic and polarization interactions in a cooperative manner. This nonadditive character in hydrogen bonding should help us better understand the microscopic mechanism in protein folding. Our study also investigated the possible structural effect of backbone amide to ester mutation which should be helpful to experimentalists using this technique in mutagenesis study.

Fluorescent molecular rotors under pressure: synergistic effects of an inert polymer

Sterically unhindered boron dipyrromethene dyes bearing aryl hydrocarbons at the meso position can function as fluorescent probes for monitoring changes in rheology of the surrounding environment. The key aspect of such behaviour relates to the ease of rotation of the aryl ring, which is set in part by frictional forces with nearby solvent molecules. For the target dye under consideration here, gyration of the meso-phenylene ring shows a pronounced temperature dependence but only a modest sensitivity towards applied pressure. Changing the specific viscosity of the solvent by adding a linear polymer has but a small effect on the fluorescence yield of the dye under ambient conditions and thereby indicates that there is little contact between dye and polymer. Under pressure in the presence of polymer, the fluorescence yield increases dramatically and allows design of an effective fluorescence-based pressure sensor. The simplest explanation of this phenomenon has the polymer wrapping around the dye under pressure and curtailing the rotary action. In addition, it has to be considered that the inert polymer renders the chloroform solvent more susceptible to a pressure-induced increase in density by minimising electrostatic repulsion between chlorine lone pairs. In this respect, the polymer acts as a lubricant for compression of chloroform under pressure.

Hydrogen Evolution from Formic Acid in an Ionic Liquid Solvent: A Mechanistic Study by ab Initio Molecular Dynamics

The reversible decomposition of formic acid (HCOOH ⇌ CO(2) + H(2)) has been attracting attention for its potential utility in hydrogen storage and production. It is therefore of interest to explore the influence of solvents on the decomposition reaction. To this end, Born-Oppenheimer (BO) molecular dynamics (MD) calculations have been performed to explore the mechanism involved in hydrogen (H(2)) evolution from formic acid decomposition in an ionic liquid solvent. Specifically, for a solvent consisting of 1,3-dimethylimidazolium cations and formate anions, evolution of hydrogen (H(2)) and carbon dioxide (CO(2)) was observed within a few picoseconds when BO-MD trajectories were carried out at an elevated temperature of 3000 K. The observed dehydrogenation involved a reaction between a formic acid solute and a nearby solvent formate anion. The observed mechanism contrasts with the unimolecular mechanism proposed in the gas phase. Specifically, in the ionic liquid, the reaction is initiated from a C-H bond dissociation of a formate anion to produce a short-lived hydride anion, which subsequently captures the acidic proton of a nearby formic acid molecule. The present BO-MD computations suggest that the high reducing ability of formic acid in the ionic liquid is due in part to its acid-dissociated form: the formate anion, which is encouraged to dissociate into a hydride anion and CO(2) by the strong electrostatic field of the ionic liquid solvent.

Ultrafast Vibrational Stark-Effect Spectroscopy: Exploring Charge-Transfer Reactions by Directly Monitoring the Solvation Shell Response

We present the first implementation of transient vibrational Stark-effect spectroscopy as an ultrafast probe of solvation dynamics. The method is applied to the phototriggered intramolecular charge-transfer reaction of Betaine-30, where the vibrational Stark shifts of the nearby solvent molecules--arising from the change in the electrostatic environment--are measured using a three-pulse photon echo probe. This new experiment provides a direct subpicosecond measure of the chromophore's excited-state dynamics and back electron transfer as viewed from the solvent's perspective. We develop a simple ab initio model that offers semiquantitative prediction of the experimental Stark shifts.

Vibrational Spectroscopy and Dynamics of the Hydrazoic and Isothiocyanic Acids in Water and Methanol

Small anions in polar solvents are benchmark systems for fast vibrational energy relaxation (VER) due to the Coulombic effects that promote solute-solvent interactions. In order to investigate the effects of solute charge and solvent isotope effects on vibrational spectra and dynamics, infrared pump-probe studies have been used to determine VER (T(1)) times for the pseudohalide acids, XNCS and XN(3) (X = H, D), in protic solvents, H(2)O, D(2)O, CH(3)OH, and CD(3)OD. These results are compared with the well-studied azide and thiocyanate anions. Solvent isotope effects of the vibrational frequency shifts of azide and for VER rates of both azide and thiocyanate are similar to those for the hydro- and deutero-protonated species in water. VER times are longer for HN(3)/H(2)O, HN(3)/CH(3)OH, and DN(3)/CD(3)OD (T(1) = 2.3, 5.6, and 3.7 ps, respectively) than for the corresponding anions in solution (0.8, 3.0, and 2.1 ps), which is consistent with the idea that ions relax more quickly than neutrals. But the times measured for DN(3)/D(2)O, HNCS/H(2)O, and DNCS/D(2)O (T(1) = 1.2, 1.5, and 4.4 ps, respectively) are shorter than for the corresponding ions (2.3, 2.7, and 22.0 ps). Fast VER for DN(3) in D(2)O is attributed to strong coupling to nearby solvent bands and/or to Fermi resonances that promote intramolecular vibrational relaxation. For the HNCS and DNCS, the faster rates can be understood by recognizing that the charge displacements are similar to those for the anion.

A molecular dynamics study of chirality transfer from chiral surfaces to nearby solvent

The presence of a chiral surface can alter the characteristics of nearby solvent molecules such that, on average, these molecules become chiral. The extent of this induced chirality and its dependence on the surface and solvent characteristics are explored in this article. Three surfaces employed in chiral chromatography are examined: The Whelk-O1 interface, a phenylglycine-derived chiral stationary phase (CSP), and a leucine-derived CSP. All three interfaces are "brush type" in that the chiral molecules are attached to the underlying substrate via an achiral tether. The solvents consist of ethanol, a binary n-hexane/ethanol solvent, 2-propanol, and a binary n-hexane/2-propanol solvent. Molecular dynamics simulations of the solvated chiral interfaces form the basis of the analysis. The chirality induced in the solvent is assessed based on a chirality index originally proposed by Osipov et al. [Mol. Phys. 84, 1193 (1995)]. Solvent chirality will depend on the solvent position relative to the surface. For this reason, a position-dependent chirality index is analyzed in detail.

Solvent suppression without crosspeak attenuation in iZQC experiments

The observation of solvent–solute iZQC peaks is often hampered by strong nearby solvent peaks. Previous researchers have overcome this problem by adding conventional solvent suppression modules during the dipolar evolution time. Here we show that these solvent suppression modules refocus the dipolar field and lead to a substantial signal intensity reduction, which is particularly damaging for the detection of low concentration species. We analyze, in detail, the effect of such modules on the signal formation, and demonstrate a method for solvent suppression that does not interfere with dipolar field evolution, leading to cleaner spectra.

Structure and Dynamics of the Solvated Electron in Alcohols from Resonance Raman Spectroscopy

Resonance Raman (RR) spectroscopy is used to probe the structure and excited-state dynamics of the solvated electron in the primary liquid alcohols methanol (MeOH), ethanol (EtOH), n-propanol (n-PrOH), and n-butanol (n-BuOH). The strong resonance enhancements (>or=10(4) relative to pure solvent) of the libration, CO stretch, COH bend, CH3 bend, CH2 bend, and OH stretch reveal significant Franck-Condon coupling of the intermolecular and intramolecular vibrational modes of the solvent to the electronic excitation of the solvated electron. All enhanced bands are fully accounted for by a model of the solvated electron that is comprised of several nearby solvent molecules that are only perturbed by the presence of the electron; no new molecular species are required to explain our data. The 340 cm(-1) downshift observed for the OH stretch frequency of e-(MeOH), relative to pure solvent, strongly suggests that the methanol molecules in the first solvent shell have the hydroxyl group directed linearly toward the excess electron density. The smaller downshifts observed for e-(EtOH), e-(n-PrOH), and e-(n-BuOH) are explained in terms of a OH group that is bent 28-40 degrees from linear. The Raman cross sections and absorption spectra are modeled, lending quantitative support for the inhomogeneous origin of the broad absorption spectra, the necessity of OH local motion in all enhanced Raman modes of the alcohols, and the dominant librational response of the solvent upon photoexcitation of the electron.

Solvation-Shell Effect on the Cyanine-Dye Fluorescence in Binary Liquid Mixtures

The steady-state fluorescence anisotropy and the relative quantum yield of fluorescence of cyanine dyes, 3,3′-diethyl-thiacarbocyanine iodide (DTCI) and chloride (DTCC), were measured in toluene/dimethyl sulfoxide (DMSO) liquid mixtures. It has been found that in toluene-rich mixtures the fluorescence quantum yield of DTCC is larger by about one order of magnitude than that of DTCI, the fluorescence quantum yields being the same for both cyanines in neat DMSO. Estimations based on the Perrin formula show that on decreasing DMSO volume fraction (less than 20 vol.%) the size of the preferential solvation shell around the DTCI increases up to 23 DMSO molecules at 3 vol.% DMSO as the solvation shell of DTCC does not vary. The influence of nearby solvent environment on the cyanine dye photophysics can be explained in terms of the Onsager model by taking into account the effect of the dynamic properties of DMSO solvation shell on the dye fluorescent rate constant.

Syntheses, structures and vibrational spectroscopy of some 1:2 and 1:3 adducts of silver(I) oxyanion salts with pyridine and piperidine bases containing non-coordinating 2(,6)-substituents

Synthetic, single crystal X-ray structural characterizations and vibrational spectroscopic studies are recorded for a number of adducts of 1:2 stoichiometry of silver(I) oxyanion salts for oxyanions of differing basicity (perchlorate, nitrate, carboxylate (as trifluoroacetate (≡‘tfa’))), with a variety of pyridine (≡‘py’) or piperidine (≡‘pip’) bases hindered in the 2- (and, sometimes, 6-) position(s) by methyl or non-coordinating functionalities of other types, the ligands employed being 2-methylpyridine (‘2mp’), 2,6-dimethylpyridine (‘lut’), 2,4,6-trimethylpyridine (‘coll’), quinoline (‘quin’), 2,2,6,6-tetramethylpiperidine (‘tmp’), 2-amino-,6-methylpyridine (‘nmp’), 2-methoxypyridine (‘mop’) and 2-cyanomethylpyridine (‘pcn’); studies are also recorded of adducts with the parent, ‘py’, base and with 4-cyanopyridine (‘cnp’). In the majority of the complexes, the NAgN motif predominates, as might be expected, variously distorted from linearity in response to changes in (competing) basicities of the nitrogen base and any nearby anion or solvent molecule; an unusual variation is found in the highly hindered tmp/tfa adduct which is a monohydrate with interacting water displacing the rather basic anion, the converse being the case in the corresponding nitrate, also a monohydrate. With the less-hindered base mpy, both nitrate and trifluoroacetate are binuclear, with O and OCO bridges corresponding to centrosymmetric four- and eight-membered rings, respectively; the quin/nitrate adduct is more complex, also binuclear but with bis(chelating) nitrate. AgNO 3:py (1:3) is found to be binuclear, while with Agtfa/py, a 3:2 adduct [Ag(py) 2][Ag 2(tfa) 3] (∞|∞) is found with a novel, polymeric, strongly interacting anion. A further pair of 1:3 adducts, AgNO 3:2np (2np = 2-aminopyridine) and Agtfa:nmp, both mononuclear [AgL 3] +X − are described, differing in the modes of interaction of silver with the three N-bases. In all simple NAgN systems with aromatic ligands, the pair of ligand ‘planes’ is disposed quasi-parallel. The far-IR spectra of [AgL 2]Y (L = lut, coll; Y = ClO 4, NO 3, tfa) and of [Ag(py) n ](ClO 4) ( n = 2,4) have been recorded and the ν(AgN) bands assigned in the range 80–240 cm −1. For the L = lut, coll complexes, there is a clear trend of decreasing ν(AgN) following increasing r(AgN) as the interaction with the counterion increases along the series Y = ClO 4, NO 3, tfa.