Identical Diffusion Distributions and Co-Cluster Formation Dictate Azeotrope Formation: Microscopic Evidences and Experimental Signatures.

What selects azeotropic pairs and governs the azeotropic conditions (composition and temperature) is an open and intriguing question. A combined simulation and experimental work presented here investigates this by considering ethanol-water mixtures. We find identical distributions of center-of-mass diffusion coefficients for ethanol and water molecules under the azeotropic condition (95.5 wt % ethanol +4.5 wt % water, Tazeo = 351.1K). Moreover, the particle displacements show strong interspecies correlations at Tazeo. Interestingly, simulated reorientation time distributions become identical at Tazeo but at a composition different from that at which the translational diffusion distributions overlapped. Cluster analyses indicate that solutions at Tazeo with xwater ≤ 15 wt % are more microheterogeneous than those with higher water content, although no anomaly in the composition-dependent solution structural properties was detected. Ethanol-water and ethanol-ethanol interaction energies show pronounced nonideal composition dependence, but the size of the relative fluctuations in them remained small (∼0.5kBT). Rare water-water H-bonding, predominant water-ethanol H-bonding, and a sizable population of "free" water molecules characterize the azeotropic solutions. The red edge excitation spectroscopic (REES) measurements with a dissolved anionic fluorescent dye, coumarin343 (C343), support the predicted solution microheterogeneity by showing a nonmonotonic composition dependence of the excitation energy-induced changes in the fluorescence emission spectral frequencies and bandwidths, the largest changes being under the azeotropic condition. Subsequent dynamic anisotropy measurements reveal a nonmonotonic composition dependence of C343 rotation times with a peak under the azeotropic condition. In summary, equalization of the component translational diffusion coefficients and solution microheterogeneity with regular composition dependence of the solution structure appear to characterize the ethanol-water azeotrope.

Interactions and Dynamics in Aqueous Solutions of pH-Responsive Polymers: A Combined Fluorescence and Dielectric Relaxation Study.

Interaction and dynamics of aqueous solutions of pH-responsive smart polymers are investigated via steady-state, time-resolved fluorescence emission spectroscopy with the help of external local reporter coumarin 153 (C153), while MHz to GHz dielectric relaxation spectroscopic (DRS) measurement reports the intrinsic medium relaxation features. A series of pH-responsive random copolymers (DPL-DP60) comprising of a pH-responsive moiety 2-((leucinyl)oxy)ethyl methacrylate (l-Leu-HEMA) and hydrophobic methyl methacrylate (MMA) are synthesized and characterized. A balance between the pH-responsive (l-Leu-HEMA) and the hydrophobic (MMA) content dictates the phase transition pH, which is found to be ∼5-7 for these aqueous copolymer solutions (1 mg/mL). Dynamic light scattering measurements in aqueous solutions of these polymers reflect a small particle size (∼2-8 nm) at solution pH below their individual phase transition pH, while a large particle size (∼140-340 nm) forms beyond their phase transition pH. No signature of a phase transition pH-driven abrupt change in static and dynamic properties of aqueous polymer solutions has been registered from pH-dependent dielectric relaxation as well as solute (C153)-centric fluorescence measurements. A significant impact of varying the l-Leu-HEMA/MMA segment ratio on steady-state fluorescence emission and rotational anisotropy decay of the fluorophore solute (C153) has been observed. MHz to GHz DRS in aqueous solutions of these pH-responsive polymers reflects bulk water-like dielectric features.

Cloud Point Driven Dynamics in Aqueous Solutions of Thermoresponsive Copolymers: Are They Akin to Criticality Driven Solution Dynamics?

Cloud point driven interaction and relaxation dynamics of aqueous solutions of amphiphilic thermoresponsive copolymers were explored through picosecond resolved and steady state fluorescence measurements employing hydrophilic (coumarin 343, C343) and hydrophobic (coumarin 153, C153) solute probes of comparable sizes. These thermoresponsive random copolymers, with tunable cloud point temperatures (Tcp's) between 298 and 323 K, were rationally designed first and then synthesized via reversible addition-fragmentation chain transfer (RAFT) copolymerization of methyl methacrylate (MMA) and poly(ethylene glycol) monomethyl ether methacrylate (PEGMA). Subsequently, copolymers were characterized by NMR spectroscopy and size exclusion chromatography (SEC). A balance between the hydrophilic (PEGMA) and the hydrophobic (MMA) content dictates the critical aggregation concentration (CAC), with CAC ∼ 2-14 mg/L for these copolymers in aqueous media. No abrupt changes in the steady state spectral features of both C153 and C343 in the aqueous solutions of these polymers near but below the cloud point temperatures were observed. Interestingly, spectral properties of C153 in these solutions show the impact of hydrophobic/hydrophilic interaction balance but not by those of C343. More specifically, C153 reported a blue shift (relative to that in neat water) and heterogeneity in its local environment. This suggested different locations for the hydrophilic (C343) and the hydrophobic (C153) probes. In addition, the excited state fluorescence lifetime (⟨τlife⟩) of C153 increased with the increase of hydrophobic (MMA) content in these copolymers. However, C343 reported no such variations, although fluorescence anisotropy decays for both solutes were significantly slowed down in these aqueous solutions compared to neat water. Anisotropy decays indicated bimodal time-dependent friction for these solutes in aqueous solutions of these copolymers but monomodal in neat water. A linear dependence of the average rotational relaxation rates (⟨krot⟩ = ⟨τrot⟩-1) of the type ⟨krot⟩ ∝ (|T - Tcp|/Tcp)γ with negative values for the exponent γ was observed for both solutes. No slowing down of the solute rotation with temperature approaching the Tcp was detected; rather, rotation became faster upon increasing the solution temperature, suggesting domination of the local friction.

Dynamics at the non-ionic micelle/water interface: Impact of linkage substitution.

The impact of atom substitution on the glycoside linkage bridging the head and the tail parts in a nonionic surfactant molecule on aqueous dynamics of the resultant micellar solutions has been explored, employing time-resolved fluorescence and dielectric relaxation (DR) measurements. We have utilized n-octyl-ß-D-glucopyranoside (OG) and n-octyl-ß-D-thioglucopyranoside (OTG) as nonionic surfactants where the oxygen atom in the glucopyranoside unit is substituted by a sulfur atom. The substitution impact is immediately reflected in the dynamic light scattering measurements of aqueous solutions where the estimated size of the OTG micelles is found to be approximately four times larger than the OG micelles. Steady state spectral features obtained by using a fluorescent probe solute, coumarin 153 (C153), in these micellar solutions are quite similar and indicate locations of the solute at the micelle/water interface for both the surfactants. Interestingly, significant differences in the rotational and solvation dynamics of C153 in these two micellar solutions have been registered. The corresponding DR measurements do not indicate any signature of relaxation typical of bound water. The absence of bound water is further supported by the differential scanning calorimetric measurements. However, the typical slow solvation time scale for aqueous micellar solutions has been observed for these surfactants. Fluctuations in the solute-interface interaction energy due to the solute motion has been argued to be the origin for this slow solvation component as DR measurements do not indicate the presence of qualitatively similar relaxation time scale in the medium.