Solvophobic Effect Research Articles

Self-diffusion coefficients of hexamethylphosphoric triamide and ethylene glycol molecules in ethylene glycol solutions

The self-diffusion coefficients of the molecules of hexamethylphosphoric triamide (HMPT) and ethylene glycol (EG) in ethylene glycol solutions in the concentration range 0-16 mol % HMPT and molecules of pure HMPT in the temperature range 30–60°С are measured by the spin-echo method on protons. Activation energies for the corresponding processes of self-diffusion were calculated. The obtained data are discussed in terms of solvophobic effects in the EG–HMPT system. The self-diffusion coefficient of pure HMPT was 0.344 × 10−5 cm2/s at 33.2°C, and the self-diffusion activation energy was 3.86 kcal/mol.

Modulation of the Emission Mode of a Pt(II) Complex via Intermolecular Interactions.

Compounds with controllable color emissions are potentially useful as photoluminescent materials in imaging and sensing applications. Multimolecular emission can be used realizing variable-color emitters and has been demonstrated in the solid state. However, achieving multimolecular emission in solution is difficult to control. In this study, we used a combination of intermolecular interactions, namely hydrogen bonding and solvophobic effect, to modulate multimolecular emissions. A designed Pt complex demonstrated three emission colors: blue (monomer emission), yellow (emission form hydrogen-bonded dimer), and orange (aggregate emission). All of the emission modes exhibited high luminescence quantum yields, as a result of their uniform assemblies.

Measurement of Solvent OH-π Interactions Using a Molecular Balance.

A molecular torsion balance was designed to study and measure OH-π interactions between protic solvents and aromatic surfaces. These specific solvent-solute interactions were measured via their influence on the folded-unfolded equilibrium of an N-arylimide rotor. Protic solvents displayed systematically weaker solvophobic interactions than aprotic solvents with similar solvent cohesion parameters. This was attributed to the formation of OH-π interactions between the protic solvents and the exposed aromatic surfaces in the unfolded conformer that offset the stronger solvophobic effects for protic solvents.

3-(Phenyl-4-oxy)-5-phenyl-4,5-dihydro-(1H)-pyrazole: A fascinating molecular framework to study the enantioseparation ability of the amylose (3,5-dimethylphenylcarbamate) chiral stationary phase. Part II. Solvophobic effects in enantiorecognition process

The enantiomers of five chiral compounds incorporating the 3-(phenyl-4-oxy)-5-phenyl-4,5-dihydro-(1H)-pyrazole scaffold and differing only in the linear alkyl chain (varying in length from 1 to 5 carbon atoms) linked to the oxygen atom were directly separated on the amylose (3,5-dimethylphenylcarbamate) based Chiralpak AD-3 chiral stationary phase. The effects of the mobile phase composition, the structure of the analytes and temperature on the retention and enantioselectivity were investigated. It was found that the enantiomeric separations were in all cases enthalpy-driven and disfavored by entropic term. U-shape curves obtained by plotting the chromatographic data versus the alcoholic percentage in n-pentane-methanol and n-hexane-ethanol mobile phases highlighted that, at higher alcohol concentrations, solvophobic interactions were operative in the retention mechanism. The unusual trend of such curves was linked to the nature of alkyl chain of the pyrazolines and it was indicative of the solvophobic contribution to the achievement of a high degree of enantioseparation.

Synergistic Behavior and Microstructure Transition in Mixture of Zwitterionic Surfactant, Anionic Surfactant, and Salts in Sorbitol/H2O Solvent: 1. Effect of Surfactant Compositions

AbstractThe phase behavior and rheological properties of a multi‐component system, made of a zwitterionic surfactant cocoamidopropyl betaine (CAPB), an anionic surfactant sodium lauryl sulfate (SLSS), and mixed salts (tetrasodium pyrophosphate, sodium acid pyrophosphate, sacharrin, and sodium fluoride) in sorbitol/H2O mixed solvent at different mass fraction of SLSS (XSLSS) were systematically investigated by steady and dynamic rheology, dynamic light scattering, and diffusion ordered spectroscopy (DOSY). When fixing the salt concentration and the mass ratio of sorbitol in mixed solvent (R), the zero‐shear viscosity increases first and then decreases showing a maximum with increasing XSLSS, resulting from the formation and entanglement of wormlike micelles. Especially when XSLSS is between 0.33 and 0.80, the mixture is dominated by entangled wormlike micelles coexisting with small micelles and separated wormlike micelles, and shows high viscoelasticity. The maximum of the zero‐shear viscosity is ca. 5 orders of magnitude larger than that of sorbitol/H2O mixed solvent or the CAPB/SLSS aqueous solution. The characteristic structural parameters for the micellar solutions at different XSLSS are also estimated from further analysis of the rheological results, and indicate the stronger network structures of the wormlike micelles are formed in our systems compared with the wormlike micelles formed by a traditional zwitterionic/anionic surfactant aqueous solutions. The great improvements of rheological properties are attributed to the strong screening effects of the mixed salts and the strong solvophobic effect of sorbitol on the electrostatic and hydrophobic interaction between the CAPB and SLSS molecules. The present work has improved our understanding about the aggregation behavior of zwitterionic/anionic mixed surfactants with salts in less polar solvent/H2O mixture, which would be of widely practical importance to optimize the formulation of products for personal care and household cleaning.

Investigating Solvent Effects of an Ionic Liquid on Pericyclic Reactions through Kinetic Analyses of Simple Rearrangements.

Simple Cope and Claisen rearrangements were investigated in an ionic liquid and a range of molecular solvents through a series of kinetic studies. Analysis of the solvent effects on the Cope rearrangement of 3-phenyl-1,5-hexadiene indicated that a solvophobic effect was responsible for the observed rate enhancement in the ionic liquid, and that this was due to preferential solvation of the transition state. A similar solvophobic effect contributes to the ionic liquid solvent effect on the Claisen rearrangement of allyl vinyl ether, although the ability of the ionic liquid to stabilise the incipient charges in the transition state also likely contributes to the rate increase observed in the ionic liquid solvent. The activation parameter data suggest that in this case the ionic liquid was interacting with species along the reaction coordinate through general coulombic interactions (more acetonitrile-like) rather than through hydrogen-bonding interactions (less ethanol-like).

Enhanced [4+2] Cycloadditions by Solvophobic Effects and Gravity-Induced Mixing in Core—Shell Droplets

A new way to perform reactions in core—shell double emulsions is reported herein. The phase boundaries of the threephase droplet flow were used to pressurize the reactants in the shell liquid, enhancing the reaction rate of a cycloaddition greatly in comparison to known methods. As key parameters, solvophobic effects and precise control over the droplet sizes were used to exploit a reaction with a negative volume of activation. The internal pressure of the reaction solution was regulated purely by the thickness of the shell liquid without adding additional reagents. Additionally, the reaction performed better when the core droplet was used to stir the shell droplet, considerably improving the mass transfer inside the otherwise diffusion-limited process.

Aggregation of cyclic polypeptoids bearing zwitterionic end-groups with attractive dipole-dipole and solvophobic interactions: a study by small-angle neutron scattering and molecular dynamics simulation.

Aggregation behavior of cyclic polypeptoids bearing zwitterionic end-groups in methanol has been studied using a combination of experimental and simulation techniques. The data from SANS and cryo-TEM indicate that the solution contains small clusters of these cyclic polypeptoids, ranging from a single polypeptoid chain to small oligomers, while the linear counterpart shows no cluster formation. Atomistic molecular dynamics simulations reveal that the driving force for this clustering behavior is due to the interplay between the effective repulsion due to the solvation of the dipoles formed by the charged end-groups in each polypeptoid chain and the attractive forces due to dipole-dipole interactions and the solvophobic effect.

Cationic and anionic surfactants interaction in water and methanol–water mixed solvent media

The micellar properties between dodecyltrimethylammonium bromide (DTAB) and sodium dodecylsulfate (SDS) in water and 0.10, 0.20, and 0.30 volume fractions of methanol in methanol–water mixed solvent media have been studied by conductivity and surface tension measurements at 293.15 K. The concentration of dodecyltrimethylammonium bromide varied from 0.0001 to 0.03 mol·L− 1 in the presence of ~ 0.01 mol·L− 1 sodium dodecylsulfate and the concentration of sodium dodecylsulfate varied from 0.001 to 0.015 mol·L− 1 in the presence of ~ 0.005 mol·L− 1 dodecyltrimethylammonium bromide. Hence, the concentrations of cationic rich (DTAB–SDS) and anionic rich (SDS–DTAB) solutions have been taken in the ratio of 3:1. The critical micelle concentrations (cmc) of DTAB–SDS and SDS–DTAB solutions have been determined by conductivity and surface tension measurements at 293.15 K. The physicochemical properties such as Gibb's free energy of micellization (ΔGmo), free energy of surfactant tail transfer (ΔGtranso), maximum surface excess concentration (Гmax), area occupied by surfactant molecule (Amin), surface pressure at the cmc (πcmc), packing parameters (P) and standard free energy interfacial adsorption (ΔGadso) are calculated in water, 0.10, 0.20 and 0.30 volume fractions of methanol–water at 293.15 K. Addition of methanol significantly affects the physicochemical properties between DTAB and SDS. With increasing concentration of methanol, the cohesive force and the dielectric constant decrease that affects the micellization and other physicochemical properties. The micellization between DTAB and SDS have been assessed in terms of different solvent parameters. The ratio of the solvent surface tension to the limiting surface tension at the cmc has been used as the solvophobic effect.

Effect of surfactant shape on solvophobicity and surface activity in alcohol-water systems.

Here we study the relationship between a surfactant's molecular shape and its tendency to partition to the interface in ethanol-water mixtures. In general, finding surfactants that are effective in alcohol-water mixtures is more challenging than finding ones that are effective in pure water. This is because the solvophobic effect that partitions surfactants from bulk solution to the interface becomes weaker as ethanol concentration increases. We use experiments and molecular dynamics to observe the effects of increasing surfactant tail length or width. The results show that increasing surfactant tail length causes the surfactant to partition to the surface better in low ethanol concentrations, but not at high ethanol concentrations. In comparison, increasing surfactant tail width causes the surfactant to partition to the surface better at higher concentrations of ethanol. We examine the liquid structure to elucidate the mechanisms that weaken the partitioning effect as ethanol concentration increases. Ethanol-water mixtures are nanoscopically heterogeneous with protic and aprotic regions in the bulk solution. We see that the surfactant tail is most likely to be solvated in the aprotic regions where it perturbs fewer hydrogen bonds.

Luminescent Helical Nanofiber Self-Assembled from a Cholesterol-Based Metalloamphiphile and Its Application in DNA Conformation Recognition

Compared to pure organic amphiphiles, metalloamphiphiles display distinctive features, including luminescence, magnetism and catalytic properties. However, the self-organization of metalloamphiphiles is commonly driven by solvophobic effects. Alkyl chains and oligomeric ethylene glycol moieties are thus the most frequently used aggregation units to drive the self-assembly of metalloamphiphiles. We expect novel metallo-supramolecular structures with exciting functions to be created if additional noncovalent interaction modes are incorporated. In this work, a new type of metalloamphiphile, consisting of a Tb(III) complex head and a cholesteryl unit (TbL3+(I)), was designed and synthesized. TbL3+(I) spontaneously self-assembles into helical nanofibers (d = 6 nm) in water. This synthetic multivalent nanoscale binding array displays powerful capability for the recognition of DNA conformations through a turn-on luminescence sensing mechanism. ssDNA-kit1 triggered a 26-fold increase in the luminescence intensity of TbL3+(I). Its corresponding G-quadruplex structure (G-quadruplex-kit1), however, induced a 6.6-fold enhancement under the same conditions. Consequently, TbL3+(I) nanofibers can monitor DNA folding. In contrast, neither ssDNA-kit1 nor G-quadruplex-kit1 markedly promoted the luminescence of molecularly dispersed TbL3+(II), illustrating that the multivalent electrostatic interactions between the phosphate groups on the backbone of DNA and TbL3+(I) self-assembled into nanofibers could greatly improve the efficiency of the energy transfer between the guanine units and the organized TbL3+(I). The TbL3+(I) nanofibers could bind and distinguish not only the kit1-ssDNA/G-quadruplex but also the conformations of other G-rich DNA, such as spb1, htelo, and intermolec-htelo. The self-assembly of luminescent metalloamphiphiles thus provides a general and convenient strategy for the efficient recognition and conversion of molecular information.

Micellization of cationic surfactants in alcohol — water mixed solvent media

The effect of addition of methanol and ethanol on the micellization of cationic surfactants dodecyltrimethylammonium bromide (DTAB) and cetyltrimethylammonium bromide (CTAB) in aqueous medium have been studied by conductance and surface tension measurements at 298.15K. Different physicochemical properties such as Gibb's free energy of micellization (ΔG°m), free energy of surfactant tail transfer (ΔG°trans), maximum surface excess concentration (Гmax), area occupied by surfactant molecule (Amin), surface pressure at the cmc (πcmc), packing parameters (P) and standard free energy interfacial adsorption (ΔG°ads) are calculated in water, 0.10, 0.20, 0.30 and 0.40 volume fractions of methanol–water and in water, 0.10, 0.20, 0.30, 0.40, 0.50 and 0.60 volume fractions of ethanol–water respectively at 298.15K. Addition of alcohol significantly affects the physicochemical properties of both DTAB and CTAB. With increasing concentration of alcohol, cohesive force and dielectric constant decrease that affects the micellization and other physicochemical properties. However, at the higher volume fraction of ethanol–water a slight variation of properties are seen.The micellization of DTAB and CTAB have been assessed in terms of different solvent parameters. The ratio of the solvent surface tension to the limiting surface tension at the cmc has been used as the solvophobic effect. The solvophobic parameter characterized by Gibbs energy of transfer of hydrocarbon from gas into a given solvent can be used to account for the effect of alcohol on the formation and growth of the cationic surfactants aggregate in water.

Thermodynamic description of the solvophobic effect in ionic liquids

The solvophobic effect is a driving force for self-assembly processes that acts in protic molecular organic solvents as well as in both protic and aprotic ionic liquids. It is known to reduce the solubility of apolar compounds and influence the magnitudes of thermodynamic functions of solvation in molecular solvents. In ionic liquids, thermodynamic aspects of the solvophobic effects have not yet been carefully considered. By comparing the relations between the Gibbs free energy and enthalpy of solvation of different compounds, we show that the solvophobic effect in aprotic ionic liquids can be even stronger than in organic solvents forming a network of intermolecular hydrogen bonds, such as formamide and ethylene glycol. The strength of the solvophobic effect expressed in terms of energy contributions is correlated with the average number of ions per unit volume, which is inversely proportional to the molar volume of the liquid. It is shown that the solvophobic effects become stronger when we change the cation or anion of the ionic liquid with another of a smaller size, and can be extremely weak when the cation contains long alkyl chains, but they are a general phenomenon for all ionic liquids.

The effect of solvent and counterion variation on inverse micelle CMCs in hydrocarbon solvents

Critical micelle concentrations (CMCs) for the formation of inverse micelles have been determined for anionic surfactants in nonpolar, hydrocarbon solvents. Sodium dioctylsulfosuccinate (Aerosol OT or AOT) was chosen as the model surfactant, with systematic variations in both the solvent (benzene, cyclohexane, and dodecane) and the surfactant counterion (sodium and tetrapropylammonium). Recent work (Langmuir 29 (2013) 3352–3258) has shown that high-resolution small-angle neutron scattering (SANS) measurements can be used to directly determine the presence or absence of aggregates in solution. No variation in the value of the CMC was found within the resolution of the measurements for changing either solvent or counterion; some effects on the structure of inverse micelles were observed. This lack of a significant difference in the onset of inverse micellization with changes to the molecular species is surprising, and the implications on the solvophobic effect in nonpolar solvents are discussed.

Amphiphilic BODIPY derivatives: the solvophobic effect on their photophysical properties and bioimaging in living cells.

Three novel amphiphilic BODIPY derivatives were prepared and their photophysical properties in THF/water mixtures with varying fractions of water were investigated. BDP-1 could self-assemble into different vesicle architectures in aqueous solution, while BDP-2 and BDP-3 with more hydrophilic abilities formed spherical and worm-like micelles. The BODIPY derivatives could be absorbed by HeLa cells and showed no apparent toxicity during the course of the test. In particular, unlike traditional amines or morpholinyl functionalized lysosome fluorescent probes, BDP-1 nanovesicles without targeted groups exhibit red emission and show effective lysosome biological imaging. Co-staining experiments with lysosome specific trackers further confirmed the disassembly of BDP-1 nanovesicles in lysosomes. This research provides a new avenue of using probes without targeting the structural unit to stain special organelles and shows potential applications in cell imaging fields.

Micellization of long-chain ionic liquids in deep eutectic solvents.

The aggregation behavior of the ionic liquid (IL) 1-alkyl-3-methylimidazolium chloride with different alkyl chain lengths in a deep eutectic solvent (DES, composed of choline chloride and glycerol in a 1 : 2 mole ratio) was studied for the first time. The critical micellar concentration, micellar size and intermolecular interactions in IL/DES solutions were investigated by different techniques including the fluorescence probe technique, small angle X-ray scattering and Fourier transform infrared spectroscopy. The solvophobic effect dominates the micellization of CnmimCl in DES and the intermolecular hydrogen-bond interaction plays a positive role to promote micelle formation. The micellar solutions were utilized for the synthesis of the water-unstable metal-organic framework Cu3(BTC)2 (BTC = 1,3,5-benzenetricarboxylate) at room temperature. X-Ray diffraction, scanning electron microscopy, transmission electron microscopy and nitrogen adsorption-desorption isotherms confirm the formation of crystalline Cu3(BTC)2 nanocrystals with mesoporous structures. The morphologies and porosity properties of Cu3(BTC)2 nanocrystals can be modulated by varying the concentration of CnmimCl.

Activity and conformation of lysozyme in molecular solvents, protic ionic liquids (PILs) and salt-water systems.

Improving protein stabilisation is important for the further development of many applications in the pharmaceutical, specialty chemical, consumer product and agricultural sectors. However, protein stabilization is highly dependent on the solvent environment and, hence, it is very complex to tailor protein-solvent combinations for stable protein maintenance. Understanding solvent features that govern protein stabilization will enable selection or design of suitable media with favourable solution environments to retain protein native conformation. In this work the structural conformation and activity of lysozyme in 29 solvent systems were investigated to determine the role of various solvent features on the stability of the enzyme. The solvent systems consisted of 19 low molecular weight polar solvents and 4 protic ionic liquids (PILs), both at different water content levels, and 6 aqueous salt solutions. Small angle X-ray scattering, Fourier transform infrared spectroscopy and UV-vis spectroscopy were used to investigate the tertiary and secondary structure of lysozyme along with the corresponding activity in various solvation systems. At low non-aqueous solvent concentrations (high water content), the presence of solvents and salts generally maintained lysozyme in its native structure and enhanced its activity. Due to the presence of a net surface charge on lysozyme, electrostatic interactions in PIL-water systems and salt solutions enhanced lysozyme activity more than the specific hydrogen-bond interactions present in non-ionic molecular solvents. At higher solvent concentrations (lower water content), solvents with a propensity to exhibit the solvophobic effect, analogous to the hydrophobic effect in water, retained lysozyme native conformation and activity. This solvophobic effect was observed particularly for solvents which contained hydroxyl moieties. Preferential solvophobic effects along with bulky chemical structures were postulated to result in less competition with water at the specific hydration layer around the protein, thus reducing protein-solvent interactions and retaining lysozyme's native conformation. The structure-property links established in this study are considered to be applicable to other proteins.

Solvent and Substituent Effects on the Aggregation Behavior of Surface-Active Ionic Liquids with Aromatic Counterions and the Dispersion of Carbon Nanotubes in their Hexagonal Liquid Crystalline Phase.

The aggregation behavior of surface-active ionic liquids (SAILs) 1-dodecyl-3-methylimidazolium m- and p-hydroxybenzoate (m-C12mimHB and p-C12mimHB) in water and ethylammonium nitrate (EAN) was investigated. Surface tension measurements indicate that the cmc values of SAILs in EAN are much higher than those in water, resulting from the weaker solvophobic effect of EAN, and the stronger stability of SAILs/EAN complexes proven by DFT calculations. Compared to 1-dodecyl-3-methylimidazolium salicylate (C12mimSal), the effect of substituent position leads to weaker interactions between aromatic counterions and headgroups. The hexagonal liquid crystal (H1) phase formed by C12mimHB in water or EAN at a higher concentration was determined by polarized optical microscopy (POM), small-angle X-ray scattering (SAXS), and rheology techniques. Structural parameters estimated from SAXS curves suggest that the higher SAILs concentration or temperature leads to a smaller lattice parameter (a0) and a denser arrangement of cylinders. For C12mimHB, the formation of the H1 phase in H2O is easier than that in EAN. Furthermore, compared to C12mimSal, C12mimHB exists over a broad region of the hexagonal liquid crystalline (H1) phase, which is due to the different position of the substituents on the aromatic ring of counterions. Therefore, the H1 phase of the lypotropic liquid crystals (LLCs) formed in the C12mimHB/H2O system exhibits excellent performance in uniformly dispersing multiwalled carbon nanotubes (MWCNTs). Increasing the concentration of MWCNTs results in a larger lattice parameter (a0) value, indicating the integration of MWCNTs within the cylinders of the H1 phase. The rheological measurement results demonstrate that MWCNTs/LLCs composites are highly viscoelastic, and the presence of MWCNTs obviously strengthens the apparent viscosity of the H1 phase.

Standard molar Gibbs free energy and enthalpy of solvation of low polar solutes in formamide derivatives at 298 K

Novel experimental values of the limiting activity coefficients and standard molar enthalpies of solution in N-methylformamide at 298.15K are reported and used to calculate the thermodynamic functions of solvation. We compare the plots of the standard molar Gibbs free energy against the standard molar enthalpy of solvation of low polar molecules in N-methylformamide, N,N-dimethylformamide, and formamide. The solvophobic effect is responsible for the deviations of the data points from the straight line corresponding to a correlation between thermodynamic functions of solvation in aprotic solvents. It is shown that the solvophobic effects are strong in formamide solutions, significantly weaker in N-methylformamide, and very weak in N,N-dimethylformamide, which coincides with the average number of intermolecular hydrogen bonds per unit volume of these solvents. Behavior of solutions in binary solvents composed of N-methylformamide or formamide mixed with water and ethylene glycol and a possibility to tune the solvophobic effect by changing the solvent composition are also considered.

Right handed chiral superstructures from achiral molecules: self-assembly with a twist.

The induction and development of chiral supramolecular structures from hierarchical self-assembly of achiral compounds is closely related to the evolution of life and the chiral amplification found in nature. Here we show that the combination of achiral tetraphenylethene (TPE) an AIE-active luminophore bearing four long alkyl chains via amide linkage allows the entire process of induction and control of supramolecular chirality into well-defined uniform right-handed twisted superstructures via solvent composition and polarity, i.e. solvophobic effect. We showed that the degree of twist and the pitch of the ribbons can be controlled to one-handed helical structure via solvophobic effects. The twisted superstructure assembly was visualised by scanning electron microscope (SEM) and transmission electron microscopy (TEM), furthermore, circular dichroism (CD) confirms used to determine controlled right-handed assembly. This controlled assembly of an AIE-active molecule can be of practical value; for example, as templates for helical crystallisation, catalysis and a chiral mechanochromic luminescent superstructure formation.