Antifreeze proteins (AFPs) are a unique class of proteins that bind to ice crystal surfaces and arrest their growth. The working mechanism of AFPs is not well understood because, as of yet, it was not possible to perform molecular-scale studies of AFPs adsorbed to the surface of ice. Here, we study the structural properties of an AFP from the insect Rhagium mordax (RmAFP) adsorbed to ice with surface specific heterodyne-detected vibrational sum-frequency generation spectroscopy and molecular dynamic simulations. We find that RmAFP, unlike other proteins, retains its hydrating water molecules upon adsorption to the ice surface. This hydration water has an orientation and hydrogen-bond structure different from the ice surface, thereby inhibiting the insertion of water layers in between the protein and the ice surface.
Spectroscopic studies of aqueous surfaces can provide a fundamental understanding of interfacial processes. These studies have largely focused on the OH stretch vibrations of water, which is unfortunate as the bending mode is an attractive feature to probe as it is relatively free of inter-and intramolecular couplings. However, the origin of the response of the bending mode is highly debated and has been assigned to either surface-specific or to bulk effects. Here, we study the bending mode of pure water and charged aqueous surfaces using heterodyne-detected vibrational sum frequency generation spectroscopy (HD-VSFG) to quantify the two effects. Our results show a low -(1626 cm −1 ) and a high -(1656 cm −1 ) frequency component which can be unambiguously assigned to an interfacial dipole and a bulk quadrupolar response, respectively. We thus demonstrate that probing the bending mode provides structural and quantitative information on both the surface and the bulk.
Dissolving urea into
water induces special solvation properties
that play a crucial role in many biological processes. Here we probe
the properties of urea molecules at charged aqueous interfaces using
heterodyne-detected vibrational sum-frequency generation (HD-VSFG)
spectroscopy. We find that at the neat water/air interface urea molecules
do not yield a significant sum-frequency generation signal. However,
upon the addition of ionic surfactants, we observe two vibrational
bands at 1660 and 1590 cm–1 in the HD-VSFG spectrum,
assigned to mixed bands of the CO stretch and NH2 bend vibrations of urea. The orientation of the urea molecules depends
on the sign of the charge localized at surface and closely follows
the orientation of the neighboring water molecules. We demonstrate
that urea is an excellent probe of the local electric field at aqueous
interfaces.
We use surface-specific heterodyne-detected vibrational sum-frequency generation spectroscopy (HD-VSFG) and surface tension measurements to investigate the molecular structure of the surface of aqueous solutions of poly(vinyl alcohol) (PVA) polymers with average molecular weights of 10000 and 125000 g/mol. We find that the interfacial water molecules have a preferred orientation with their hydrogen-bonded O−H groups pointing away from the bulk, for both PVA 10000 and PVA 125000 . This observation is explained from the ongoing hydrolysis of the acetyl impurities on the PVA polymer chains. This hydrolysis yields negatively charged acetate ions that have a relatively high surface propensity. For both PVA 10000 and PVA 125000 the strong positive signal vanishes when the pH is decreased, due to the neutralization of the acetate ions. For solutions with a high concentration of PVA 10000 the interfacial water signal becomes very small, indicating that the surface gets completely covered with a disordered PVA polymer film. In contrast, for high concentrations of PVA 125000 , the strong positive water signal persists at high pH, which shows that the water surface does not get completely covered. The HD-VSFG data combined with surface tension data indicate that concentrated PVA 125000 solutions form a structured surface layer with pores containing a high density of interfacial water.
We study the properties of formate (HCOO−) and acetate (CH3COO−) ions at the surface of water using heterodyne-detected vibrational sum-frequency generation (HD-VSFG) spectroscopy. For both ions we observe a response...
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