Role of Solvent Water in the Temperature-Induced Self-Assembly of a Triblock Copolymer

Water-soluble triblock copolymers have received much attention in industrial applications and scientific fields. We here show that femtosecond mid-IR pump–probe spectroscopy is useful to study the role of water in the temperature-induced self-assembly of triblock copolymers. Our experimental results suggest two distinct subpopulations of water molecules: those that interact with other water molecules and those involved in the hydration of a triblock copolymer surface. We find that the vibrational dynamics of bulk-like water is not affected by either micellation or gelation of triblock copolymers. The increased population of water interacting with ether oxygen atoms of the copolymer during the unimer to micelle phase transition is important evidence for the entropic role of water in temperature-induced micelle formation at a low copolymer concentration. In contrast, at the critical gelation temperature and beyond, the population of surface-associated water molecules interacting with ether oxygen atoms decreases, which indicates important enthalpic control by water. The present study on the roles of water in the two different phase transitions of triblock copolymers sheds new light on the underlying mechanisms of temperature-induced self-aggregation behaviors of amphiphiles that are ubiquitous in nature

Effect of Osmolytes on the Conformational Behavior of a Macromolecule in a Cytoplasm-like Crowded Environment: A Femtosecond Mid-IR Pump–Probe Spectroscopy Study

Osmolytes found endogenously in almost all living beings play an important role in regulating cell volume under harsh environment. Here, to address the longstanding questions about the underlying mechanism of osmolyte effects, we use femtosecond mid-IR pump–probe spectroscopy with two different IR probes that are the OD stretching mode of HDO and the azido stretching mode of azido-derivatized poly­(ethylene glycol) dimethyl ether (PEGDME). Our experimental results show that protecting osmolytes bind strongly with water molecules and dehydrate polymer surface, which results in promoting intramolecular interactions of the polymer. By contrast, urea behaves like water molecules without significantly disrupting water H-bonding network and favors extended and random-coil segments of the polymer chain by directly participating in solvation of the polymer. Our findings highlight the importance of direct interaction between urea and macromolecule, while protecting osmolytes indirectly affect the macromolecule through enhancing the water–osmolyte interaction in a crowded environment, which is the case that is often encountered in real biological systems

Evaluation of pH at Charged Lipid/Water Interfaces by Heterodyne-Detected Electronic Sum Frequency Generation

Although the interface pH at a biological membrane is important for biological processes at the membrane, there has been no systematic study to evaluate it. We apply novel interface-selective nonlinear spectroscopy to the evaluation of the pH at model biological membranes (lipid/water interfaces). It is clearly shown that the pH at the charged lipid/water interfaces is substantially deviated from the bulk pH. The pH at the lipid/water interface is higher than that in the bulk when the head group of the lipid is positively charged, whereas the pH at the lipid/water interface is lower when the lipid has a negatively charged head group

Studying Water Hydrogen-Bonding Network near the Lipid Multibilayer with Multiple IR Probes

A critical difference between living and nonliving is the existence of cell membranes, and hydration of membrane surface is a prerequisite for structural stability and various functions such as absorption/desorption of drugs, proteins, and ions. Therefore, a molecular level understanding of water structure and dynamics near the membrane is important to perceive the role of water in such a biologically relevant environment. In our recent paper [J. Phys. Chem. Lett. 2016, 7, 741] on the IR pump–probe study of the OD stretch mode of HDO near lipid multibilayers, we have observed two different vibrational lifetime components of OD stretch mode in the phospholipid multibilayer systems. The faster component (0.6 ps) is associated with OD groups interacting with the phosphate moiety of the lipid, while the slower component (1.9 ps) is due to choline-associated water molecules that are close to bulklike water. Here, we additionally use hydrazoic acid (HN₃) as another IR probe of which frequency is highly sensitive to its local H-bonding water density. Interestingly, we found that the vibrational lifetime of the asymmetric azido stretch mode of HN₃ in the lipid multibilayer system is similar to that in neat water, whereas its orientational relaxation is a bit slower than that in bulk water. This indicates that due to the tight packing of lipid molecules, particularly the head parts, in the gel phase, HN₃ molecules mostly stay near the choline group of lipid and interact with water molecules in the vicinity of choline groups. This suggests that membrane surface-adsorbed molecules such as hydrophilic drug molecules may interact with choline-associated water molecules, when the membrane is in the gel phase, instead of phosphate-associated water molecules

Water Dynamics in Cytoplasm-Like Crowded Environment Correlates with the Conformational Transition of the Macromolecular Crowder

Polyethylene glycol (PEG) is a unique polymer material with enormous applicability in many industrial and scientific fields. Here, its use as macromolecular crowder to mimic the cellular environment <i>in vitro</i> is the focus of the present study. We show that femtosecond mid-IR pump–probe spectroscopy using three different IR probes, HDO, HN₃, and azido-derivatized crowder, provides complete and stereoscopic information on water structure and dynamics in the cytoplasm-like macromolecular crowding environment. Our experimental results suggest two distinct subpopulations of water molecules: those that interact with other water molecules and those that are part of a hydration shell of crowder on its surface. Interestingly, water dynamics even in highly crowded environment remains bulk-like in spite of significant perturbation to the tetrahedral H-bonding network of water molecules. That is possible because of the formation of water aggregates (pools) even in water-deficient PEGDME-water solutions. In such a crowded environment, the conformationally accessible phase space of the macromolecular crowder is reduced, similar to biopolymers in highly crowded cytoplasm. Nonetheless, the hydration water on the surface of crowders slows down considerably with increased crowding. Most importantly, we do not observe any coalescing of surface hydration water (of the crowder) with bulk-like water to generate collective hydration dynamics at any crowder concentration, contrary to recent reports. We anticipate that the present triple-IR-probe approach is of exceptional use in studying how conformational states of crowders correlate with structural and dynamical changes of water, which is critical in understanding their key roles in biological and industrial applications

Water Hydrogen-Bonding Network Structure and Dynamics at Phospholipid Multibilayer Surface: Femtosecond Mid-IR Pump–Probe Spectroscopy

The water hydrogen-bonding network at a lipid bilayer surface is crucial to understanding membrane structures and its functional activities. With a phospholipid multibilayer mimicking a biological membrane, we study the temperature dependence of water hydrogen-bonding structure, distribution, and dynamics at a lipid multibilayer surface using femtosecond mid-IR pump–probe spectroscopy. We observe two distinguished vibrational lifetime components. The fast component (0.6 ps) is associated with water interacting with a phosphate part, whereas the slow component (1.9 ps) is with bulk-like choline-associated water. With increasing temperature, the vibrational lifetime of phosphate-associated water remains constant though its relative fraction dramatically increases. The OD stretch vibrational lifetime of choline-bound water slows down in a sigmoidal fashion with respect to temperature, indicating a noticeable change of the water environment upon the phase transition. The water structure and dynamics are thus shown to be in quantitative correlation with the structural change of liquid multibilayer upon the gel-to-liquid crystal phase transition

The Bend+Libration Combination Band Is an Intrinsic, Collective, and Strongly Solute-Dependent Reporter on the Hydrogen Bonding Network of Liquid Water

Water is an extensively self-associated liquid due to its extensive hydrogen bond (H-bond) forming ability. The resulting H-bonded network fluid exhibits nearly continuous absorption of light from the terahertz to the near-IR region. The relatively weak bend+libration water combination band (centered at 2130 cm^–1) has been largely overlooked as a reporter of liquid water’s structure and dynamics despite its location in a convenient region of the IR for spectroscopic study. The intermolecular nature of the combination band leads to a unique absorption signal that reports collectively on the rigidity of the H-bonding network in the presence of many different solutes. This study reports comprehensively how the combination band acts as an intrinsic and collective probe in various chemically and biologically relevant solutions, including salts of varying character, denaturants, osmolytes, crowders, and surfactants that form reverse micelles and micelles. While we remark on changes in the line width and intensity of this combination band, we mainly focus on the frequency and how the frequency reports on the collective H-bonding network of liquid water. We also comment on the “association band” moniker often applied to this band and how to evaluate discrete features in this spectral region that sometimes appear in the IR spectra of specific kinds of aqueous samples of organic solutes, especially those with very high solute concentrations, with the conclusion that most of these discrete spectral features come exclusively from the solutes and do not report on the water. Contrasts are drawn throughout this work between the collective and delocalized reporting ability of the combination band and the response of more site-specific vibrations like the much-investigated OD stretch of HDO in H₂O: the combination band is a unique reporter of H-bonding structure and dynamics and fundamentally different than any local mode probe. Since this band appears as the spectroscopic “background” for many local-mode reporter groups, we note the possibility of observing both local and collective solvent dynamics at the same time in this spectral region

Short-Range Cooperative Slow-down of Water Solvation Dynamics Around SO₄^2––Mg²⁺ Ion Pairs

The presence of ions affects the structure and dynamics of water on a multitude of length and time scales. In this context, pairs of Mg2+ and SO42– ions in water constitute a prototypical system for which conflicting pictures of hydration geometries and dynamics have been reported. Key issues are the molecular pair and solvation shell geometries, the spatial range of electric interactions, and their impact on solvation dynamics. Here, we introduce asymmetric SO42– stretching vibrations as new and most specific local probes of solvation dynamics that allow to access ion hydration dynamics at the dilute concentration (0.2 M) of a native electrolyte environment. Highly sensitive heterodyne 2D-IR spectroscopy in the fingerprint region of the SO42– ions around 1100 cm–1 reveals a specific slow-down of solvation dynamics for hydrated MgSO4 and for Na2SO4 in the presence of Mg2+ ions, which manifests as a retardation of spectral diffusion compared to aqueous Na2SO4 solutions in the absence of Mg2+ ions. Extensive molecular dynamics and density functional theory QM/MM simulations provide a microscopic view of the observed ultrafast dephasing and hydration dynamics. They suggest a molecular picture where the slow-down of hydration dynamics arises from the structural peculiarities of solvent-shared SO42––Mg2+ ion pairs

Bend Vibration of Surface Water Investigated by Heterodyne-Detected Sum Frequency Generation and Theoretical Study: Dominant Role of Quadrupole

Heterodyne-detected vibrational sum frequency generation spectroscopy was applied to the water surface for measuring the imaginary part of second-order nonlinear susceptibility (Im χ⁽²⁾) spectrum in the bend frequency region for the first time. The observed Im χ⁽²⁾ spectrum shows an overall positive band around 1650 cm^–1, contradicting former theoretical predictions. We further found that the Im χ⁽²⁾ spectrum of NaI aqueous solution exhibits an even larger positive band, which is apparently contrary to the flip-flop orientation of surface water. These unexpected observations are elucidated by calculating quadrupole contributions beyond the conventional dipole approximation. It is indicated that the Im χ⁽²⁾ spectrum in the bend region has a large quadrupole contribution from the bulk water