Effects of Dye Addition on the Rheological Properties of Aqueous Polymer Solutions.

In many commercial applications, polymer-dye interactions are frequently encountered from food to wastewater treatment, and while shear rheology has been well characterized, the extensional properties are not well known. The extensional viscosity η and relaxation time λ are the extensional rheological parameters that provide valuable insights into how aqueous polymers respond during deformation, and this study investigated the effect of dyes on the extensional rheology of three different aqueous polymer solutions (e.g.

Determining the Surface p of Perfluorooctanoic Acid.

Perfluorooctanoic acid (PFOA) is an environmentally prevalent and persistent organic pollutant with toxic and bioaccumulative properties. Despite the known importance of perfluorinated pollutants in the global environment, molecular-level details of the physicochemical behavior of PFOA on aqueous interfaces remain poorly understood. Here, we utilized two surface-specific techniques, vibrational sum frequency generation spectroscopy (SFG) and surface tensiometry, to investigate the pH-induced structural changes of PFOA and octanoic acid (OA) and determined the apparent p at the air-water surface.

Quantification of anion and cation uptake in ice Ih crystals.

While ice has very low solubility for salts compared to water, small amounts of ions are doped into ice crystals. These small ion dopants can alter the fundamental physical and chemical properties of ice, such as its structure and electrical conductivity. Therefore, these results could have a direct impact on the chemical reactivity of ice and ice surfaces.

Lipid-Specific Direct Translocation of the Cell-Penetrating Peptide NAF-1 across Bilayer Membranes.

The cell-penetrating peptide NAF-1 has recently emerged as a promising candidate for selective penetration and destruction of cancer cells. It displays numerous membrane-selective behaviors including cell-specific uptake and organelle-specific degradation. In this work, we explore membrane penetration and translocation of NAF-1 in model lipid bilayer vesicles as a function of lipid identity in zwitterionic phosphatidylcholine lipids mixed with anionic phosphatidylserine, phosphatidylglycerol, and phosphatidic acid lipids.

Lower degree of dissociation of pyruvic acid at water surfaces than in bulk.

Understanding the acid/base behavior of environmentally relevant organic acids is of key relevance for accurate climate modelling. Here we investigate the effect of pH on the (de)protonation state of pyruvic acid at the air-water interface and in bulk by using the analytical techniques surface-specific vibrational sum frequency generation and attenuated total reflection spectroscopy. To provide a molecular interpretation of the observed behavior, simulations are carried out using a free energy perturbation approach in combination with electronic structure-based molecular dynamics.

Interfacial Vibrational Dynamics of Ice I and Liquid Water.

Insights into energy flow dynamics at ice surfaces are essential for understanding chemical dynamics relevant to atmospheric and geographical sciences. Here, employing ultrafast surface-specific spectroscopy, we report the interfacial vibrational dynamics of ice I. A comparison to liquid water surfaces reveals accelerated vibrational energy relaxation and dissipation at the ice surface for hydrogen-bonded OH groups.

Molecular hydrophobicity at a macroscopically hydrophilic surface.

Interfaces between water and silicates are ubiquitous and relevant for, among others, geochemistry, atmospheric chemistry, and chromatography. The molecular-level details of water organization at silica surfaces are important for a fundamental understanding of this interface. While silica is hydrophilic, weakly hydrogen-bonded OH groups have been identified at the surface of silica, characterized by a high O-H stretch vibrational frequency.

Comparative Adsorption of Acetone on Water and Ice Surfaces.

Small organic molecules on ice and water surfaces are ubiquitous in nature and play a crucial role in many environmentally relevant processes. Herein, we combine surface-specific vibrational spectroscopy and a controllable flow cell apparatus to investigate the molecular adsorption of acetone onto the basal plane of single-crystalline hexagonal ice with a large surface area. By comparing the adsorption of acetone on the ice/air and the water/air interface, we observed two different types of acetone adsorption, as apparent from the different responses of both the free O-H and the hydrogen-bonded network vibrations for ice and liquid water.

Structure from Dynamics: Vibrational Dynamics of Interfacial Water as a Probe of Aqueous Heterogeneity.

The structural heterogeneity of water at various interfaces can be revealed by time-resolved sum-frequency generation spectroscopy. The vibrational dynamics of the O-H stretch vibration of interfacial water can reflect structural variations. Specifically, the vibrational lifetime is typically found to increase with increasing frequency of the O-H stretch vibration, which can report on the hydrogen-bonding heterogeneity of water.

Time-Resolved Sum Frequency Generation Spectroscopy: A Quantitative Comparison Between Intensity and Phase-Resolved Spectroscopy.

Time-resolved and two-dimensional sum frequency generation (TR-SFG and 2D-SFG) spectroscopies are promising tools in the experimental study of molecular dynamics, specifically at interfaces. Most implementations of TR/2D-SFG spectroscopy rely on a pump-probe scheme, where an excitation pulse excites a fraction of interfacial molecules into the first excited state of a specific vibrational mode, and a subsequent SFG probe pair detects the time-dependent changes of the surface vibrational response. In steady state SFG spectroscopy, phase-resolved detection (also known as heterodyne-detection), as opposed to SFG intensity measurements, has been shown to be useful in unraveling the steady-state response of interfacial vibrations.

Probing structural features of self-assembled violanthrone-79 using two dimensional infrared spectroscopy.

Two-dimensional infrared (2D IR) spectroscopy was used to characterize the structure of a self-assembled polycyclic aromatic hydrocarbon (PAH), violanthrone-79. A local mode basis was constructed using spectroscopic and computational results of anthrone and monomer violanthrone-79. The vibrational modes in the spectral region 1550-1700 cm(-1), carbonyl stretching and in-plane ring breathing, are used as vibrational probes.

Active Bragg angle compensation for shaping ultrafast mid-infrared pulses.

Active Bragg angle compensation is demonstrated for shaping ultrafast, mid-infrared pulses. The effects of angular dispersion introduced by the acousto-optic modulator on the temporal characteristics of the pulse are measured by autocorrelating the output from the pulse shaper. The time duration of the output pulses were measured to be thirty times shorter than pulses produced with a constant frequency amplitude waveform.