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Water in contact with lipids is an important aspect of most biological systems and has been termed “biological water”. We used time-resolved infrared spectroscopy to investigate the vibrational dynamics of lipid-bound water molecules, to shed more light on the properties of these important molecules. We studied water in contact with a positively charged lipid monolayer using surface-specific two-dimensional sum frequency generation vibrational spectroscopy with subpicosecond time resolution. The dynamics of the O–D stretch vibration was measured for both pure D2O and isotopically diluted D2O under a monolayer of 1,2-dipalmitoyl-3-trimethylammonium-propane. It was found that the lifetime of the stretch vibration depends on the excitation frequency and that efficient energy transfer occurs between the interfacial water molecules. The spectral diffusion and vibrational relaxation of the stretch vibration were successfully explained with a simple model, taking into account the Forster transfer between stretch...

We use intensity and heterodyne-detected vibrational sum-frequency generation (VSFG and HD-VSFG) to study the structure of water at the surface of aqueous tetra-n-alkylammonium bromide (TAABr) solutions. We compare the water structure for four different n-alkyl chains (n = 1, 2, 3, 4). For solutions of tetra-n-alkylammonium bromides with short n-alkyl chains (n = 1, 2), we observe the structure of the surface water to be similar to the structure observed for simple inorganic salt solutions. For these solutions, the presence of Br– at the interface is observed to lead to a small decrease in the average strength of the hydrogen bonds. For solutions of tetra-n-alkylammonium bromides with long n-alkyl chains (n = 3, 4), we observe a strong ordering of the water molecules at the solution surface. The water molecules show a net orientation of their O–H group toward the bulk, which can be explained from the high surface propensity of positively charged tetra-n-alkylammonium ions with long alkyl chains (n = 3, 4)...

We study the ultrafast O-H stretch vibrational relaxation dynamics of protonated water clusters embedded in a matrix of deuterated acetonitrile, using polarization-resolved mid-IR femtosecond spectroscopy. The clusters are produced by mixing triflic (trifluoromethanesulfonic) acid and H2O in molar ratios of 1:1, 1:2, and 1:3, thus varying the degree of hydration of the proton. At all hydration levels the excited O-H stretch vibration of the hydrated proton shows an ultrafast vibrational relaxation with a time constant T1100 fs, leading to an ultrafast local heating of the protonated water cluster. This excess thermal energy, initially highly localized to the region of the excited proton, first re-distributes over the aqueous cluster and then dissipates into the surrounding acetonitrile matrix. For clusters with a triflic acid to H2O ratio of 1:3 these processes occur with time constants of 320 ± 20 fs and 1.4 ± 0.1 ps, respectively. The cooling of the clusters reveals a long-living, underlying transient absorption change with high anisotropy. We argue that this feature stems from the vibrational predissociation of a small fraction of the proton hydration structures, directly following the ultrafast infrared excitation.

Understanding the structure and dynamics of water’s constituent ions, proton and hydroxide, has been a subject of numerous experimental and theoretical studies over the last century. Besides their obvious importance in acid-base chemistry, these ions play an important role in numerous applications ranging from enzyme catalysis to environmental chemistry. Despite a long history of research, many fundamental issues regarding their properties continue to be an active area of research. Here, we provide a review of the experimental and theoretical advances made in the last several decades in understanding the structure, dynamics, and transport of the proton and hydroxide ions in different aqueous environments, ranging from water clusters to the bulk liquid and its interfaces with hydrophobic surfaces. The propensity of these ions to accumulate at hydrophobic surfaces has been a subject of intense debate, and we highlight the open issues and challenges in this area. Biological applications reviewed include proton transport along the hydration layer of various membranes and through channel proteins, problems that are at the core of cellular bioenergetics.

As water is an essential ingredient in protein structure, dynamics, and functioning, knowledge of its behavior near proteins is crucial. We investigate water dynamics around bovine α-lactalbumin by combining molecular dynamics simulations with polarization-resolved femtosecond infrared (fs-IR) spectroscopy. We identify slowly reorienting surface waters and establish their hydrogen-bond lifetime and reorientation dynamics, which we compare to the experimentally measured anisotropy decay. The calculated number of slow surface waters is in reasonable agreement with the results of fs-IR experiments. While surface waters form fewer hydrogen bonds than the bulk, within the hydration layer water is slower when donating more hydrogen bonds. At concave sites the protein-water hydrogen bonds break preferably via translational diffusion rather than via a hydrogen-bond jump mechanism. Water molecules reorient slower near these sites than at convex water-exposed sites. Protein misfolding leads to an increased exposure of hydrophobic groups, inducing relatively faster surface water dynamics. Nevertheless, the larger exposed surface slows down a larger amount of water. While for native proteins hydrating water is slower near hydrophobic than near hydrophilic residues, mainly due to stronger confinement, misfolding causes hydrophobic water to reorient relatively faster because exposure of hydrophobic groups destroys concave protein cavities with a large excluded volume.

Water molecules in hydrated salts often have a well-defined geometrical arrangement and form an excellent model system for studying the effects of the hydrogen-bond environment on vibrational energy relaxation. Hydrated lithium nitrate contains two distinct types of crystal water molecules. One water molecule makes strong and weak hydrogen bonds; the other water molecule makes two bifurcated hydrogen bonds. We use femtosecond two-dimensional infrared spectroscopy to probe the vibrational relaxation dynamics of the OD stretch vibration of dilute HDO molecules in lithium nitrate trihydrate. In the temperature range from 22 to 295 K we observe a decrease in vibrational lifetime from 3.8 ± 0.2 to 2.8 ± 0.1 ps for the strongly hydrogen-bonded species, from 5.41 ± 0.08 to 4.14 ± 0.05 ps for the bifurcated hydrogen-bonded species, and from 10.4 ± 0.2 to 8.8 ± 0.4 ps for weakly hydrogen-bonded species. This temperature dependence is opposite to that of the OD stretch vibration of dilute HDO:H2O ice, for which the...

We present an overview of the studies of ion pairing in aqueous media of the past decade. In these studies, interactions between ions, and between ions and water, are investigated with relatively novel approaches, including dielectric relaxation spectroscopy, far-infrared (terahertz) absorption spectroscopy, femtosecond mid-infrared spectroscopy, and X-ray spectroscopy and scattering, as well as molecular dynamics simulation methods. With these methods, it is found that ion pairing is not a rare phenomenon only occurring for very particular, strongly interacting cations and anions. Instead, for many salt solutions and their interfaces, the measured and calculated structure and dynamics reveal the presence of a distinct concentration of contact ion pairs (CIPs), solvent shared ion pairs (SIPs), and solvent-separated ion pairs (2SIPs). We discuss the importance of specific ion-pairing interactions between cations like Li(+) and Na(+) and anionic carboxylate and phosphate groups for the structure and functioning of large (bio)molecular systems.

Proteins perform specific biological functions that strongly depend on their three-dimensional structure. This three-dimensional structure, i.e. the way the protein folds, is strongly determined by the interaction between the protein and the water solvent. We study the dynamics of water in aqueous solutions of several globular proteins at different degrees of urea-induced unfolding, using polarization-resolved femtosecond infrared spectroscopy. We observe that a fraction of the water molecules is strongly slowed down by their interaction with the protein surface. By monitoring the slow water fraction we can directly probe the amount of water-exposed protein surface. We find that at mild denaturing conditions, the water-exposed surface increases by almost 50%, while the secondary structure is still intact. This finding indicates that protein unfolding starts with the protein structure becoming less tight, thereby allowing water to enter.

Charge separation and recombination are key processes determining the performance of organic optoelectronic devices. Here we combine photoluminescence and photovoltaic characterisation of organic solar cell devices with ultrafast multi-pulse photocurrent spectroscopy to investigate charge generation mechanisms in the organic photovoltaic devices based on a blend of an alternating polyquinoxaline copolymer with fullerene. The combined use of these techniques enables the determination of the contributions of geminate and bimolecular processes to the solar cell performance. We observe that charge separation is not a temperature-activated process in the studied materials. At the same time, the generation of free charges shows a clear external-field and morphology dependence. This indicates that the critical step of charge separation involves the non-equilibrium state that is formed at early times after photoexcitation, when the polaronic localisation is not yet complete. This work reveals new aspects of molecular level charge dynamics in the organic light-conversion systems.

The dynamics of organic cations in metal halide hybrid perovskites (MHPs) have been investigated using numerous experimental and computational techniques because of their suspected effects on the properties of MHPs. In this Perspective, we summarize and reconcile key findings and present new data to synthesize a unified understanding of the dynamics of the cations. We conclude that theory and experiment collectively paint a relatively complete picture of rotational dynamics within MHPs. This picture is then used to discuss the consequences of structural dynamics for electron-phonon interactions and their effect on material properties by providing a brief account of key studies that correlate cation dynamics with the dynamics of the inorganic sublattice and overall device properties.

We find that the reduction in dielectric response (depolarization) of water caused by solvated ions is different for H2O and D2O. This isotope dependence allows us to reliably determine the kinetic contribution to the depolarization, which is found to be significantly smaller than predicted by existing theory. The discrepancy can be explained from a reduced hydrogen-bond cooperativity in the solvation shell: we obtain quantitative agreement between theory and experiment by reducing the Kirkwood correlation factor of the solvating water from 2.7 (the bulk value) to ~ 1.6 for NaCl and ~ 1 (corresponding to completely uncorrelated motion of water molecules) for CsCl.

We report on a molecular dynamics study on the relation between the structure and the orientational (and hydrogen bond) dynamics of hydration water around the ocean pout AFP III anti-freeze protein. We find evidence for an increasing tetrahedral structure from the area opposite to the ice binding site (IBS) towards the protein IBS, with the strongest signal of tetrahedral structure around the THR-18 residue of the IBS. The tetrahedral structural parameter mostly positively correlates with increased reorientation decay times. Interestingly, for several key (polar) residues that are not part of the IBS but are in its vicinity, we observe a decrease of the reorientation time with increasing tetrahedral structure. A similar anti-correlation is observed for the hydrogen-bonded water molecules. These effects are enhanced at a lower temperature. We interpret these results in terms of the structure-making and structure-breaking residues. Moreover, we investigate the tetrahedral structure and dynamics of waters at a partially dehydrated IBS, and for the protein adsorbed at the air-water interface. We find that the mutation changes the preferred protein orientation upon adsorption at an air-water interface. These results are in agreement with the water-air Vibration Sum Frequency Generation spectroscopic experiments showing a strongly reduced tetrahedral signal upon mutation at the IBS.

We have studied the properties of water molecules at the surface of salt solutions containing hydrophobic anions like triflate (CF3SO3–), ethanesulfonate (C2H5SO3–), and butanesulfonate (C4H9SO3–) using vibrational sum-frequency generation (VSFG) spectroscopy. The VSFG spectra reveal a surprisingly strong isotope effect in the intra- and intermolecular mixing of the water molecules contained in the hydration shells of the hydrophobic anions. The O–H stretch vibrations of H2O molecules in the hydration shell are strongly mixed, whereas the O–D stretch vibrations of hydrating D2O molecules are decoupled. This isotope effect is not observed for other ions like perchlorate (ClO4–), and can be explained from the structure of the hydration shells of the hydrophobic ions.

We demonstrate that the enantiomers of chiral macromolecules at an aqueous interface can be distinguished with monolayer sensitivity using heterodyne-detected vibrational sum-frequency generation (VSFG). We perform VSFG spectroscopy with a polarization combination that selectively probes chiral molecular structures. By using frequencies far detuned from electronic resonances, we probe the chiral macromolecular structures with high surface specificity. The phase of the sum-frequency light generated by the chiral molecules is determined using heterodyne detection. With this approach, we can distinguish right-handed and left-handed helical peptides at a water-air interface. We thus show that heterodyne-detected VSFG is sensitive to the absolute configuration of complex, interfacial macromolecules and has the potential to determine the absolute configuration of enantiomers at interfaces.

We study the vibrational relaxation dynamics and the reorientation dynamics of HDO molecules in binary water-dimethyl sulfoxide (DMSO) and water-acetone mixtures with polarization-resolved femtosecond mid-infrared spectroscopy. For low solute concentrations we observe a slowing down of the reorientation of part of the water molecules that hydrate the hydrophobic methyl groups of DMSO and acetone. For water-DMSO mixtures the fraction of slowed-down water molecules rises much steeper with solute concentration than for water-acetone mixtures, showing that acetone molecules show significant aggregation already at low concentrations. At high solute concentrations, the vibrational and reorientation dynamics of both water-DMSO and water-acetone mixtures show a clear distinction between the dynamics of water molecules donating hydrogen bonds to other water molecules and the dynamics of water donating a hydrogen bond to the S═O/C═O group of the solute. For water-DMSO mixtures both types of water molecules show a very slow reorientation. The water molecules forming hydrogen bonds to the S═O group reorient with a time constant that decreases from 46 ± 14 ps at XDMSO = 0.33 to 13 ± 2 ps at XDMSO = 0.95. The water molecules forming hydrogen bonds to the C═O group of acetone show a much faster reorientation with a time constant that decreases from 6.1 ± 0.2 ps at Xacet = 0.3 to 2.96 ± 0.05 ps at Xacet = 0.9. The large difference in reorientation time constant of the solute-bound water for DMSO and acetone can be explained from the fact that the hydrogen bond between water and the S═O group of DMSO is much stronger than the hydrogen bond between water and the C═O group of acetone. We attribute the strongly different behavior of water in DMSO-rich and acetone-rich mixtures to their difference in molecular shape.

We study the ice-binding site (IBS) of a hyperactive antifreeze protein from the beetle Dendroides canadensis (DAFP-1) using vibrational sum-frequency generation spectroscopy. We find that DAFP-1 accumulates at the air-water interface due to the hydrophobic character of its threonine-rich IBS while retaining its highly regular β-helical fold. We observe a narrow band at 3485 cm(-1) that we assign to the O-H stretch vibration of threonine hydroxyl groups of the IBS. The narrow character of the 3485 cm(-1) band suggests that the hydrogen bonds between the threonine residues at the IBS and adjacent water molecules are quite similar in strength, indicating that the IBS of DAFP-1 is extremely well-ordered, with the threonine side chains showing identical rotameric confirmations. The hydrogen-bonded water molecules do not form an ordered ice-like layer, as was recently observed for the moderate antifreeze protein type III. It thus appears that the antifreeze action of DAFP-1 does not require the presence of ordered water but likely results from the direct binding of its highly ordered array of threonine residues to the ice surface.

We study the energy relaxation and structural relaxation dynamics of hydrated protons in Nafion membranes at different hydration levels using femtosecond infrared transient absorption spectroscopy. At low hydration levels we observe that the excitation of the proton vibration of an Eigen-like proton hydration structure leads to a structural relaxation process in which the Eigen-like structure evolves to a Zundel-like proton hydration structure. This reorganization leads to a transfer of the proton charge and closely follows the mechanism of infrared-induced adiabatic proton transfer that has been proposed by S. Hammes-Schiffer, J. T. Hynes, and others. At high hydration levels, the spectral dynamics are dominated by vibrational energy relaxation and subsequent cooling of the proton hydration structures and the surrounding water molecules. Using a kinetic analysis of the transient spectral data, we determine the rates of proton transfer, vibrational energy relaxation, and cooling as a function of hydration level. We find that infrared-induced proton transfer occurs at all hydration levels but becomes less observable at high hydration levels due to the increasingly dominant influence of the vibrational energy relaxation.

The amphiphilic osmolyte trimethylamine-N-oxide (TMAO) is commonly found in natural organisms, where it counteracts biochemical stress associated with urea in aqueous environments. Despite the important role of TMAO as osmoprotectant, the mechanism behind TMAO's action has remained elusive. Here, we study the interaction between urea, TMAO, and water in solution using broadband (100 MHz-1.6 THz) dielectric spectroscopy. We find that the previously reported tight hydrogen bonds between 3 water molecules and the hydrophilic amine oxide group of TMAO, remain intact at all investigated concentrations of urea, showing that no significant hydrogen bonding occurs between the two co-solutes. Despite the absence of direct TMAO-urea interactions, the solute reorientation times of urea and TMAO show an anomalous nonlinear increase with concentration, for ternary mixtures containing equal amounts of TMAO and urea. The nonlinear increase of the reorientation correlates with changes in the viscosity, showing that the combination of TMAO and urea cooperatively enhances the hydrogen-bond structure of the ternary solutions. This nonlinear increase is indicative of water mediated interaction between the two solutes and is not observed if urea is combined with other amphiphilic solutes.

We study the properties of water at the surface of an antifreeze protein with femtosecond surface sum frequency generation spectroscopy. We find clear evidence for the presence of ice-like water layers at the ice-binding site of the protein in aqueous solution at temperatures above the freezing point. Decreasing the temperature to the biological working temperature of the protein (0°C to -2°C) increases the amount of ice-like water, while a single point mutation in the ice-binding site is observed to completely disrupt the ice-like character and to eliminate antifreeze activity. Our observations indicate that not the protein itself but ordered ice-like water layers are responsible for the recognition and binding to ice.

Phase-resolved sum-frequency generation measurements combined with molecular dynamics simulations are employed to study the effect of temperature on the molecular arrangement of water on the basal face of ice. The topmost monolayer, interrogated through its nonhydrogen-bonded, free O-H stretch peak, exhibits a maximum in surface H-bond density around 200 K. This maximum results from two competing effects: above 200 K, thermal fluctuations cause the breaking of H bonds; below 200 K, the formation of bulklike crystalline interfacial structures leads to H-bond breaking. Knowledge of the surface structure of ice is critical for understanding reactions occurring on ice surfaces and ice nucleation.

The surface of ice has been reported to be disordered at temperatures well below the bulk melting point. However, the precise nature of this disorder has been a topic of intense debate. Herein, we study the molecular properties of the surface of ice as a function of temperatures using heterodyne-detected sum-frequency generation spectroscopy. We observe that, down to 245 K, the spectral response of the surface of ice contains a component that is indistinguishable from supercooled liquid water.

We investigate proton-charge mobility in nanoscopic water droplets with tuneable size. We find that the diffusion of confined proton charges causes a dielectric relaxation process with a maximum-loss frequency determined by the diffusion constant. In volumes less than ∼5 nm in diameter, proton-charge diffusion slows down significantly with decreasing size: for diameters 10M for water-pool diameters d

We study the properties of aqueous solution/air interfaces with time-resolved surface sum-frequency generation (SFG) spectroscopy. Using this technique, we monitor the change in SFG signal followin...

We performed time- and polarization-resolved pump-probe and two-dimensional infrared (2D-IR) experiments to study the dynamics of the amide I vibration of a 7 kDa type-III antifreeze protein. In the pump-probe experiments, we used femtosecond mid-infrared pulses to investigate the vibrational relaxation dynamics of the amide mode. The transient spectra show the presence of two spectral components that decay with different lifetimes, indicative of the presence of two distinct amide subbands. The 2D-IR experiments reveal the coupling between the two bands in the form of cross-peaks. On the basis of previous work by Demirdöven et al. ( J. Am. Chem. Soc. 2004 , 126 , 7981 - 7990 ), we assign the observed bands to the two infrared-active modes α(-) and α(+) found in protein β-sheets. The amplitudes of the cross-peak were found to increase with delay time, indicating that the cross-peaks originate from population transfer between the coupled amide oscillators. The time constant of the energy transfer was found to be 6-7 ps.

We study the hydrogen-bond and reorientation dynamics of weakly hydrogen-bonded water molecules by studying their spectral diffusion and anisotropy dynamics with polarization-resolved two-color femtosecond mid-infrared spectroscopy. We selectively excite weakly hydrogen-bonded water molecules by tuning a relatively narrow band excitation pulse far into the high-frequency wing of the O-D stretch vibration of HDO molecules in H2O water. We observe that the spectral diffusion and the anisotropy both show pronounced biexponential dynamics. On the basis of previous work, the fast component of the spectral dynamics with a time constant of ∼100 fs is assigned to rapid hydrogen-bond switching events. We observed that these switching events lead to a pronounced effect on the anisotropy of the excited O-D groups, which shows that the spectral relaxation is accompanied by a large change of the orientation of the O-D groups. The slow component of the spectral relaxation can be assigned to the collective structural reorganization of the hydrogen-bond network of liquid water. With increasing temperature, the spectral relaxation shows a similar acceleration as the average molecular reorientation, showing that these processes are intimately connected.

In this work, we present evidence for ion pair formation of cations with a high surface charge density (Na(+) and Ca(2+)) and phosphate groups of phospholipids. We used femto-second infrared pump-probe and dielectric spectroscopy to probe the dynamics of water molecules in solutions of phosphorylethanolamine and different types of cations. We find that sodium and calcium cooperatively retard the dynamics of water in solutions of phosphorylethanolamine, implying the formation of solvent separated ion pairs. This ion-specific interaction is absent for potassium, cesium and ammonium. We compare our results to dielectric spectroscopy experiments, which probes the rotation of all dipolar molecules and ions in solution. The rotation of the dipolar phosphorylethanolamine ion shows that long-lived ion-pairs are only formed with calcium and not with ammonium, cesium, potassium, and sodium. This finding implies that the association between calcium and the phosphate is strong with lifetimes exceeding 200 ps, while the interaction with sodium is relatively short-lived (∼20-100 ps).

We study the conformation and reorientation dynamics of the inhibitory neurotransmitter γ-aminobutyric acid (GABA) under neutral and acidic conditions using a combination of broadband dielectric relaxation spectroscopy and polarization-resolved femtosecond mid-infrared pump-probe spectroscopy. We find that both zwitterionic and cationic GABA adopt nearly linear conformations in aqueous solution, meaning that the two charged functional groups of the GABA zwitterion are hydrated separately.

Antifreeze glycoproteins (AFGPs) are unique proteins that inhibit the growth of ice by a mechanism that is still unclear. We study the dynamics of water in aqueous solutions of small and large isoforms of AFGPs using polarization-resolved femtosecond infrared spectroscopy. We find that a fraction of the water molecules is strongly slowed down by the interaction with the antifreeze glycoprotein surface. The fraction of slow water molecules scales with the size and concentration of AFGP, and is similar to the fraction of slow water observed for nonantifreeze proteins, both at room temperature and close to biologically relevant working temperatures. We observe that inhibiting AFGP antifreeze activity using borate buffer induces no changes in the dynamics of water hydrating the AFGP. Our findings support a mechanism in which the sugar unit of AFGP forms the active ice-binding site.

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.

We study the effect of antifreeze glycoproteins (AFGPs) on the survival of organoids under hypothermic conditions. We find that the survival of organoids in cold conditions depends on their developmental stage. Mature organoids die within 24 h when being stored at 4 &deg, C, while cystic organoids can survive up to 48 h. We find that in the presence of AFGPs, the organoid survival is prolonged up to 72 h, irrespective of their developmental stage. Fluorescence microscopy experiments reveal that the AFGPs predominately localize at the cell surface and cover the cell membranes. Our findings support a mechanism in which the positive effect of AFGPs on cell survival during hypothermic storage involves the direct interaction of AFGPs with the cell membrane. Our research highlights organoids as an attractive multicellular model system for studying the action of AFGPs that bridges the gap between single-cell and whole-organ studies.

We studied the effects of tetra-n-alkylammonium bromide (N(C(n)H(2n+1))(4)(+)Br(-)) salts on the dynamics of water using polarization-resolved femtosecond infrared spectroscopy. With this technique, we are capable of distinguishing the response of water solvating the hydrophobic cations from that of water solvating the bromide anion. We observe that both types of ions slow down the orientational dynamics of the water molecules in their solvation shells. However, the nature of this slowdown is different for both ions. For the hydrophobic cation, we find an increasing number of retarded water molecules, scaling with the alkyl chain length. Water in the bromide solvation shell experiences a partial decay of its orientation by a fast wobbling motion, after which the remaining anisotropy decays much slower. The dynamics of the wobbling motion are observed to be dependent on the nature of the cation. For Me(4)NBr, the slow reorientation time is not concentration-dependent, and no aggregation is observed. This is in contrast to the tetra-n-alkylammonium salts with longer alkyl chains, for which the slow reorientation time of bromide-bound water molecules increases dramatically with concentration, and clusters of cations and anions appear to be formed.

International audience; The efficiency of solution-processed colloidal quantum dot (QD) based solar cells is limited by poor charge transport in the active layer of the device, which originates from multiple trapping sites provided by QD surface defects. We apply a recently developed ultrafast electro-optical technique, pump-push photocurrent spectroscopy, to elucidate the charge trapping dynamics in PbS colloidal-QD photovoltaic devices at working conditions. We show that IR photoinduced absorption of QD in the 0.2-05 eV region is partly associated with immobile charges, which can be optically detrapped in our experiment. Using this absorption as a probe, we observe that the early trapping dynamics strongly depend on the nature of the ligands used for QD passivation, while it depends only slightly on the nature of the electron-accepting layer. We find that weakly bound states, with a photon-activation energy of 0.2 eV, are populated instantaneously upon photoexcitation. This indicates that the photogenerated states show an intrinsically bound-state character, arguably similar to charge-transfer states formation in organic photovoltaic materials. Sequential population of deeper traps (activation energy 03-05 eV) is observed on the similar to 0.1-10 ns time scales, indicating that most of carrier trapping occurs only after substantial charge relaxation/transport. The reported study disentangles fundamentally different contributions to charge trapping dynamics in the nanocrystal-based optoelectronic devices and can serve as a useful tool for QD solar cell development.

The structure and autoionization of water at the water–phospholipid interface are investigated by ab initio molecular dynamics and ab initio Monte Carlo simulations using local density approximation (LDA) and generalized gradient approximation (GGA) for the exchange–correlation energy functional. Depending on the lipid headgroup, strongly enhanced ionization is observed, leading to the dissociation of several water molecules into H+ and OH– per lipid. The results can shed light on the phenomena of the high proton conductivity along membranes that has been reported experimentally.

Understanding the structure and dynamics of water's constituent ions, proton and hydroxide, has been a subject of numerous experimental and theoretical studies over the last century. Besides their obvious importance in acid-base chemistry, these ions play an important role in numerous applications ranging from enzyme catalysis to environmental chemistry. Despite a long history of research, many fundamental issues regarding their properties continue to be an active area of research. Here, we provide a review of the experimental and theoretical advances made in the last several decades in understanding the structure, dynamics, and transport of the proton and hydroxide ions in different aqueous environments, ranging from water clusters to the bulk liquid and its interfaces with hydrophobic surfaces. The propensity of these ions to accumulate at hydrophobic surfaces has been a subject of intense debate, and we highlight the open issues and challenges in this area. Biological applications reviewed include proton transport along the hydration layer of various membranes and through channel proteins, problems that are at the core of cellular bioenergetics.

Temperature-dependent sum-frequency scattering spectroscopy is used to study the properties of hexadecane and dodecane oil droplets in water. The sum-frequency scattering spectra contain vibrational bands that correspond to the symmetric and antisymmetric CH stretching vibrations of the methylene (CH2) and methyl (CH3) groups of the alkane molecules. The relative amplitudes of the vibrational bands provide information on the surface structure and the shape of the oil droplets. We study the sum-frequency scattering spectra over a temperature range of -48 to 24 degrees C, including the freezing transitions of the water matrix and the oil droplets. Hexadecane oil droplets freeze at a higher temperature than the surrounding water, whereas dodecane oil droplets freeze at a lower temperature than the surrounding water. This allows us to independently study the freezing effect of oil and water on the surface structure of the oil droplets. In both cases, freezing leads to a change in the polarization dependencies that are valid in the case of the spherical-symmetric shapes that the oil droplets assume when both water and oil are liquid. We find that the freezing of water leads to a strong distortion of the liquid dodecane surface but has little effect on the surface of already solidified hexadecane. For completely frozen emulsions a further decrease in temperature is observed to lead to a further distortion of the surface of the solid oil particles, which might be caused by increasing hardness of the ice matrix encapsulating the particles. Published by AIP Publishing.

Using femtosecond two-color infrared pump-probe spectroscopy, we study the vibrational relaxation of the O-H stretch vibrations of liquid H2O after excitation of the overtone transition. The overtone transition has its maximum at 6900 cm(-1) (1.45 μm), which is a relatively high frequency in view of the central frequency of 3400 cm(-1) of the fundamental transition. The excitation of the overtone leads to a transient induced absorption of two-exciton states of the O-H stretch vibrations. When the overtone excitation frequency is tuned from 6600 to 7200 cm(-1), the vibrational relaxation time constant of the two-exciton states increases from 400 ± 50 fs to 540 ± 40 fs. These values define a limited range of relatively long relaxation time constants compared to the range of relaxation time constants of 250-550 fs that we recently observed for the one-exciton O-H stretch vibrational state of liquid H2O ( S. T. van der Post et al., Nature Comm. 2015 , 6 , 8384 ). We explain the high central frequency and the limited range of relatively long relaxation time constants of the overtone transition from the destructive quantum interference of the mechanical and electrical anharmonic contributions to the overtone transition probability. As a result of this destructive interference, the overtone transition of liquid H2O is dominated by molecules of which the O-H groups donate relatively weak hydrogen bonds to other H2O molecules.

Antifreeze proteins (AFPs) are a unique class of proteins that bind to growing ice crystal surfaces and arrest further ice growth. AFPs have gained a large interest for their use in antifreeze formulations for water-based materials, such as foods, waterborne paints, and organ transplants. Instead of commonly used colligative antifreezes such as salts and alcohols, the advantage of using AFPs as an additive is that they do not alter the physicochemical properties of the water-based material. Here, we report the first comprehensive evaluation of thermal hysteresis (TH) and ice recrystallization inhibition (IRI) activity of all major classes of AFPs using cryoscopy, sonocrystallization, and recrystallization assays. The results show that TH activities determined by cryoscopy and sonocrystallization differ markedly, and that TH and IRI activities are not correlated. The absence of a distinct correlation in antifreeze activity points to a mechanistic difference in ice growth inhibition by the different classes of AFPs: blocking fast ice growth requires rapid nonbasal plane adsorption, whereas basal plane adsorption is only relevant at long annealing times and at small undercooling. These findings clearly demonstrate that biomimetic analogs of antifreeze (glyco)proteins should be tailored to the specific requirements of the targeted application.

We study the orientation of water and urea molecules and protein amide vibrations at aqueous α-lactalbumin and α-lactalbumin/urea interfaces using heterodyne-detected vibrational sum frequency generation. We vary the net charge of the protein by changing the pH. We find that the orientation of the water and urea molecules closely follows the net charge of the protein at the surface of the solution. In contrast, the net orientation of the amide groups of the backbone of the protein is independent of pH. We discuss the implications of these results for the mechanism by which urea denatures proteins.

The conformational and hydration behavior of polyacrylic acid (PAA) at the air/water interface is studied using heterodyne-detected vibrational sum frequency generation spectroscopy (HD-VSFG). The amount of adsorption at the water-air interface and the influence of PAA on the water structure at the interface are found to be highly dependent on the degree of ionization (acid dissociation) of the carboxylic acid groups. At a low degree of ionization PAA is surface active and remains in a dense packing arrangement with intrachain hydrogen bonds. The interfacial water molecules show a net orientation with their OH groups pointing to the surface. Ionization of the carboxylic acid groups leads to an increase of the negative charge and to a break-up of the intrachain hydrogen bonds. The increase in negative charge is accompanied by an increase of the VSFG signal of the interfacial water molecules, as a result of their enhanced orientation. At ionization degrees α > 0.203 PAA loses its enhanced surface propensity and is well dissolved in the bulk. Addition of NaCl to the solution is observed to lead to a recurrence of PAA at the interface.

We use surface-specific vibrational sum-frequency generation spectroscopy (VSFG) to study the structure and self-assembling mechanism of the class I hydrophobin SC3 from Schizophyllum commune and the class II hydrophobin HFBI from Trichoderma reesei. We find that both hydrophobins readily accumulate at the water–air interface and form rigid, highly ordered protein films that give rise to prominent VSFG signals. We identify several resonances that are associated with β-sheet structures and assign them to the central β-barrel core present in both proteins. Differences between the hydrophobin classes are observed in their interfacial self-assembly. For HFBI, we observe no changes in conformation upon adsorption to the water surface. For SC3, we observe an increase in β-sheet-specific signals that supports a surface-driven self-assembly mechanism in which the central β-barrel remains intact and stacks into a larger-scale architecture, amyloid-like rodlets.

We performed sum-frequency generation (SFG) spectroscopic measurements on water in contact with supported thin metal and metal-oxide films. We employed an internal reflection configuration and varied the angles of incidence of the visible and infrared beams and measured the SFG signals using different polarization combinations. While SFG is a surface-specific vibrational spectroscopy, the shape of the SFG spectra can be fully accounted for by the bulk response of the materials through the frequency-dependent enhancement of the local incident infrared fields at the interface, i.e., Fresnel effects. We find that the dispersion of the refractive index of the bulk water phase leads to a strong enhancement of the electric field at the interface at specific infrared frequencies. These local, frequency-dependent fields act on the frequency-independent, nonresonant SFG response of the electrons at the surfaces of the metal or metal-oxide films. As a result, the measured SFG spectra closely follow this infrared fr...

We study the molecular rotation of the protic room-temperature ionic liquid ethylammonium nitrate with dielectric relaxation spectroscopy and femtosecond-infrared spectroscopy (fs-IR) of the ammonium N-H vibrations. The results suggest that the rotation of ethylammonium ion takes place via large angular jumps. Such nondiffusive reorientational dynamics is unique to strongly hydrogen-bonded liquids such as water and indicates that the intermolecular interaction is highly directional in this class of ionic liquids.

The potential-dependent water adsorption on gold surfaces in perchloric and sulfuric acid solutions has been studied by surface-enhanced infrared absorption spectroscopy (SEIRAS). It is found that ...

We report the energy relaxation of the OH stretch vibration of HDO molecules contained in an HDO:D(2)O water bridge using femtosecond mid-infrared pump-probe spectroscopy. We found that the vibrational lifetime is shorter (~630 ± 50 fs) than for HDO molecules in bulk HDO:D(2)O (~740 ± 40 fs). In contrast, the thermalization dynamics following the vibrational relaxation are much slower (~1.5 ± 0.4 ps) than in bulk HDO:D(2)O (~250 ± 90 fs). These differences in energy relaxation dynamics strongly indicate that the water bridge and bulk water differ on a molecular scale.

Water is very different from liquids of similar molecular weight, and one of its unique properties is the very efficient transfer of vibrational energy between molecules, which arises as a result of strong dipole-dipole interactions between the O-H oscillators. Although we have a sound understanding of such energy transfer in bulk water, we know less about how, and how quickly, transfer occurs at its interface with a hydrophobic phase, because specifically addressing the outermost monolayer is difficult. Here, we use ultrafast two-dimensional surface-specific vibrational spectroscopy to probe the interfacial energy dynamics of heavy water (D(2)O) at the water/air interface. The measurements reveal the presence of surprisingly rapid energy transfer, both between hydrogen-bonded interfacial water molecules (intermolecular), and between O-D groups sticking out from the water surface and those located on the same molecule and pointing towards the water bulk (intramolecular). Vibrational energy transfer occurs on sub-picosecond timescales, and its rates and pathways can be quantified directly.

We studied the pathways of vibrational energy relaxation of the amide I (~1660 cm-1) and amide II (~1560 cm-1) vibrational modes of N-methylacetamide (NMA) in CCl4 solution using two-color femtosecond vibrational spectroscopy. We measured the transient spectral dynamics upon excitation of each of these amide modes. The results show that there is no energy transfer between the amide I (AI) and amide II (AII) modes. Instead we find that the vibrational energy is transferred on a picosecond time scale to a common combination tone of lower-frequency modes. By use of polarization-resolved femtosecond pump−probe measurements we also study the reorientation dynamics of the NMA molecules and the relative angle between the transition dipole moments of the AI and AII vibrations. The spectral dynamics at later times after the excitation (>40 ps) reveal the presence of a dissociation process of the NMA aggregates, trimers, and higher order structures into dimers and monomers. By measuring the dissociation kinetics at different temperatures, we determined the activation energy of this dissociation Ea = 35 ± 3 kJ mol-1.

We report vibrational lifetime measurements of the OH stretch vibration of interfacial water in contact with lipid monolayers, using time-resolved vibrational sum frequency (VSF) spectroscopy. The dynamics of water in contact with four different lipids are reported and are characterized by vibrational relaxation rates measured at 3200, 3300, 3400, and 3500 cm(-1). We observe that the water molecules with an OH frequency ranging from 3300 to 3500 cm(-1) all show vibrational relaxation with a time constant of T(1) = 180 ± 35 fs, similar to what is found for bulk water. Water molecules with OH groups near 3200 cm(-1) show distinctly faster relaxation dynamics, with T(1)80 fs. We successfully model the data by describing the interfacial water containing two distinct subensembles in which spectral diffusion is, respectively, rapid (3300-3500 cm(-1)) and absent (3200 cm(-1)). We discuss the potential biological implications of the presence of the strongly hydrogen-bonded, rapidly relaxing water molecules at 3200 cm(-1) that are decoupled from the bulk water system.

We study the rate and mechanism of deuteron transfer from the photoacids 1-naphtol-4-sulfonate (1-NPS) and 2-naphtol-3,7-disulphonate (2-NPS) to acetate base in aqueous (D2O) solution. The photoacids are activated by excitation with 100 fs laser pulses at 267 nm. The electronic absorption and stimulated emission spectra of the photoacid and the conjugate photobase and the vibrational absorption spectra of the hydrated deuteron and the acetate base are probed with broad-band delayed 100 fs pulses at visible and mid-infrared wavelengths, respectively. A significant fraction of the deuteron transfer events are observed to occur on a timescale of

The molecular reorientation associated with the dynamics of the hydrogen-bond network in liquid water is investigated using quantum molecular dynamics simulations performed with the ab-initio-based TTM3-F interaction potential. The reorientation dynamics calculated at different temperatures are found to be in excellent agreement with the corresponding experimental results obtained from polarization-resolved, femtosecond mid-infrared, pump−probe spectroscopic measurements. A comparison with analogous results obtained from classical molecular dynamics simulations with the same interaction potential clearly indicates that the explicit inclusion of nuclear quantum effects is critical for reproducing the measured time dependence of the anisotropic signal.