Spectroscopic probes of the quasi-liquid layer on ice

Raman spectra of the water OH-stretch region were acquired at air-ice and air-water interfaces at a glancing angle, which allowed observation of surface characteristics. The shapes of the OH-stretch bands indicate that the environment at the air-ice interface is different from that at the air-water interface and from that seen in bulk water. Water spectra measured at the surface of dodecane under low relative humidity indicate that this method is sensitive to fewer than 50 monolayers of water. Changes in the local environment of the surfacial water molecules may be induced by the presence of different solute species, giving rise to changes in the shape of the band. Dissolved sodium chloride disrupts hydrogen bonding in liquid water and has the same effect at the air-ice interface. However, when either HCl or HNO(3) is adsorbed from the gas phase onto an ice surface, the opposite effect is seen: Their presence appears to increase the extent of hydrogen bonding at the ice surface. At the same time, shifts in the laser-induced fluorescence spectra of acridine, a fluorescent pH-probe present at the air-ice interface, indicate that dissociation of acids occurs there. These observations suggest that the formation of hydronium ions at the air-ice interface enhances the hydrogen bonding of surfacial water molecules.     

Heterogeneous surface crystallization observed in undercooled water

We report laboratory observations of higher freezing temperatures when an ice-forming nucleus is near the surface of an undercooled water drop than when the nucleus is immersed in the drop. The nucleation rate at the water surface is a factor of 10(10) greater than in bulk water, thereby complementing and providing evidence for homogeneous surface crystallization, which has been hypothesized recently. Interpretation of the data via classical nucleation theory shows that the free energy of formation of a critical ice germ is decreased by a factor of approximately 2 when the substrate is near the air-water interface. Furthermore, the analysis suggests that the jump frequency of molecules from the liquid to the solid may be greatly enhanced at the interface.     

Resonance frequencies of meniscus waves as a physical mechanism for a DNA biosensor

This paper presents a liquid surface biosensor whose potential applications are analogue to the well-known quartz crystal microbalance. The technique involved is based on the resonance of meniscus capillary waves here excited at a functionalized air-water interface. The strategy proposed in this paper can be seen as a promising way to avoid as much as possible any transfer of Blodgett type. Meniscus capillary waves supplied by the electrodynamical vibration of a brimful cylinder filled with water are used as a way to characterize the surface aging of an air-water interface covered by a lipidic monolayer. An optical technique based on one-dimensional interferometry is developed to measure continuously the resonant behavior of the surface elevation at the center of the cell around the natural frequencies of the meniscus waves. The frequency dependence of the wave amplitude is investigated during the transient regime associated to the immobilization of DNA strands at the lipidic matrix. Resonant frequencies are found to be very sensitive to the chemical loading supported by the air-water interface. The technique is seen as a mean to discriminate between single- and double-stranded DNA.     

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. Adsorption on ice occurs preferentially through interactions with the free OH group, while the interaction of acetone with the surface of liquid water appears less specific.     

Adsorption of polycyclic aromatic hydrocarbons at the air-water interface: molecular dynamics simulations and experimental atmospheric observations

Adsorption of benzene, naphthalene, anthracene, and phenanthrene at the aqueous surface is investigated by means of molecular dynamics simulations. Potentials of mean force, i.e., free energy profiles obtained when moving the studied molecules across an aqueous slab were evaluated. In all cases, deep surface free energy minima, corresponding to orders of magnitude of surface enhancement of the aromatic molecule, were located. This enhancement, which increases with the size of the solute, points to the importance of the aqueous surface for the chemistry of polycyclic aromatic hydrocarbons (PAHs). Supporting evidence in the atmospheric environment related to the heterogeneous chemistry of PAHs on water droplets and planar surfaces is summarized. There is good agreement between the hydration free energies computed from MD calculations and the experimentally determined values. Data pertaining to the importance of the air-water interface in the adsorption and transport of PAHs on micron sized water droplets are described. The relevant data on adsorption and reaction (ozonation and photochemical) at the air-water interface of planar surfaces and droplets are also summarized.     

Development and Evaluation of Sampling and Analytical Techniques for Investigating Air-Water Exchange of Chemicals

Abstract

Gas exchange across the air-water interface is one of the three major transport pathways for atmospheric inputs of organic pollutants in the Great Lakes. It is essential to advance our knowledge of the air-water exchange processes to improve our understanding of the environmental pathways and fate of a variety of persistent and toxic chemicals. Two complementary prototype devices were developed and tested for direct characterization of air-water exchange processes. One was a sparger device which was used to determine the (truly) dissolved concentration of a given chemical in water, and hence its potential for diffusive transfer at the air-water interface. The other was a flux chamber with which the chemical mass transfer rate from the water surface to the atmosphere (or vice versa) was determined. Ambient air and air from the sparger and flux chamber were collected/concentrated on multi-bed adsorbent tubes, followed by thermal desorption GC-MS analysis. Collected water samples were filtered and then concentrated on adsorbent tubes which were subject to similar thermal desorption GC-MS analytical procedures. The combination of these techniques provides a useful means for the estimation of the mass transfer rates of chemicals across the air-water interface.     

Enhanced photolysis in aerosols: evidence for important surface effects

While there is increasing evidence for unique chemical reactions at interfaces, there are fewer data on photochemistry at liquid-vapor junctions. This paper reports a comparison of the photolysis of molybdenum hexacarbonyl, Mo(CO)(6), in 1-decene either as liquid droplets or in bulk-liquid solutions. Mo(CO)(6) photolysis is faster by at least three orders of magnitude in the aerosols than in bulk-liquids. Two possible sources of this enhancement are considered: (1) increased light intensity due to either Morphology-Dependent Resonances (MDRs) in the spherical aerosol particles and/or to increased pathlengths for light inside the droplet due to refraction, which are termed physical effects in this paper; and (2) interface effects such as an incomplete solvent-cage at the gas-liquid boundary and/or enhanced interfacial concentrations of Mo(CO)(6), which are termed chemical effects. Quantitative calculations of the first possibility were carried out in which the light intensity distribution in the droplets averaged over 215-360 nm was obtained for 1-decene droplets. Calculations show that the average increase in light intensity over the entire droplet is 106%, with an average increase of 51% at the interface. These increases are much smaller than the observed increase in the apparent photolysis rate of droplets compared to the bulk. Thus, chemical effects, i.e., a decreased solvent-cage effect at the interface and/or enhancement in the surface concentration of Mo(CO)(6), are most likely responsible for the dramatic increase in the photolysis rate. Similar calculations were also carried out for broadband (290-600 nm) solar irradiation of water droplets, relevant to atmospheric conditions. These calculations show that, in agreement with previous calculations by Mayer and Madronich [B. Mayer and S. Madronich, Atmos. Chem. Phys., 2004, 4, 2241] MDRs produce only a moderate average intensity enhancement relative to the corresponding bulk-liquid slabs when averaged over a range of wavelengths characteristic of solar radiation at the Earth's surface. However, as in the case of Mo(CO)(6) in 1-decene, chemical effects may play a role in enhanced photochemistry at the aerosol-air interface for airborne particles.     

Hydroxyl radical at the air-water interface

Interaction of the hydroxyl radical with the liquid water surface was studied using classical molecular dynamics computer simulations. From a series of scattering trajectories, the thermal and mass accommodation coefficients of OH on liquid water at 300 K were determined to be 0.95 and 0.83, respectively. The calculated free energy profile for transfer of OH across the air-water interface at 300 K exhibits a minimum in the interfacial region, with the free energy of adsorbtion (DeltaGa) being about 1 kcal/mol more negative than the hydration free energy (DeltaGs). The propensity of the hydroxyl radical for the air-water interface manifests itself in partitioning of OH radicals between the bulk water and the surface. The enhancement of the surface concentration of OH relative to its concentration in the aqueous phase suggests that important OH chemistry may be occurring in the interfacial layer of water droplets, aqueous aerosol particles, and thin water films adsorbed on solid surfaces. This has profound consequences for modeling heterogeneous atmospheric chemical processes.     

Photolysis of Retinol in Liposomes and Its Protection with Tocopherol and Oxybenzone

Abstract— In this work the stabilities of retinol in methanolic solutions and liposomal suspensions exposed to UV light were compared using absorbance spectroscopy and the ability of a-tocopherol and the sunscreen additive, oxybenzone, to reduce the rate of retinol decomposition assessed. Retinol in methanol decolorized almost completely within a few minutes of exposure to a 6 W 350 nm wavelength lamp. From the concentration dependence of the reaction rates it appears that retinol activated by light can decompose either directly or after collision with a second retinol molecule. Several reaction products are formed, α-Tocopherol solutions were unaffected by 350 nm light but they did darken when irradiated with 250 nm wavelength light. Addition of a-tocopherol or removal of oxygen from the retinol in methanol solutions reduced only slightly the rates of retinol photolysis. When dispersed in water within liposomes made of equimolar egg phosphatidylcholine (PC) and cholesterol, up to six-fold increases in the decomposition rate of the retinol were observed. The reaction rate could be reduced but only slightly by increasing the ratio of PC to retinol. A mechanism that explains the concentration dependence of the retinol photolysis is that the reduction in reaction rate on diluting the retinol concentration within a given liposome was due to the prevention of the reaction between one light-activated retinol molecule with another within the same liposome. Incorporation of oxybenzone into the liposomes reduced the reaction rates. The results suggested that most of the protection in this case arises through the oxybenzone closest to the light source absorbing the light, thereby preventing it reaching retinol much further into the sample. Incorporation of a-tocopherol into the liposomes could also reduce substantially the photolysis rate of co-entrapped retinol. The mechanism of protection in this case appears to be via the tocopherol quenching activated retinol molecules. The close proximity of the tocopherol to the retinol within a single liposome has shown to be important in this case. Only slight protection of retinol in one liposome by tocopherol in another was observed under the conditions studied. This means that the protection by tocopherol will still be observed if the liposome dispersions are diluted considerably or if only thin samples are exposed to light.     

Application of 1H NMR spectroscopy method for determination of characteristics of thin layers of water adsorbed on the surface of dispersed and porous adsorbents

The paper presents 1H NMR spectroscopy as a perspective method of the studies of the characteristics of water boundary layers in the hydrated powders and aqueous dispergated suspensions of the adsorbents. The method involves measurements of temperature dependence proton signals intensity in the adsorbed water at temperatures lower than 273 K. Free energy of water molecules at the adsorbent/water interface is diminished due to the adsorption interactions causing the water dosed to the adsorbent surface freezes at T < 273 K. Thickness of a non-freezing layer of water can be determined from the intensity of the water signal of 1H NMR during the freezing-thawing process. Due to a disturbing action of the adsorbent surface, water occurs in the quasi-liquid state. As a result, it is observed in the 1H NMR spectra as a relatively narrow signal. The signal of ice is not registered due to great differences in the transverse relaxation times of the adsorbed water and ice. The method of measuring the free surface energy of the adsorbents from the temperature dependence of the signal intensity of non-freezing water is based on the fact that the temperature of water freezing decreases by the quantity which depends on the surface energy and the distance of the adsorbed molecules from the solid surface. The water at the interface freezes when the free energies of the adsorbed water and ice are equal. To illustrate the applicability of the method under consideration the series of adsorption systems in which the absorbents used differed in the surface chemistry and porous structure. In particular, the behaviour of water on the surface of the following adsorbents is discussed: non-porous and porous silica (aerosils, silica gels); chemically and physically modified non-porous and porous silica (silanization, carbonization, biopolymer deposition); and pyrogeneous Al2O3 and aluminasilicas. The effect of preliminary treatment of the adsorbent (thermal, high pressure, wetting with polar and non-polar solvents) on the characteristics of the structurized water layers was discussed. The influence of the adsorbent porous structure on the free energy of the adsorbed water was also studied. The discussion of the obtained results was made.     

玫瑰红作用下γ-六氯环己烷在冰相中的光敏化降解

考察了在玫瑰红(RB)存在下γ-六氯环己烷(γ-HCH)在冰中的光降解.结果表明,光敏剂RB通过其激发态[RB]~*及其产生的~1O_2~*加速了γ-HCH的光降解,RB浓度是影响光降解率最显著的因素;γ-HCH在较低初始浓度下的光敏化降解更快;无机盐离子的种类和浓度可以改变冰表面上类液层(LLL)的比例从而影响γ-HCH的光解.通过分析γ-HCH光降解产物提出了RB存在时冰中γ-HCH的光降解作用机理.     

Study of the aggregation of human insulin Langmuir monolayer

The human insulin (HI) Langmuir monolayer at the air-water interface was systematically investigated in the presence and absence of Zn(II) ions in the subphase. HI samples were dissolved in acidic (pH 2) and basic (pH 9) aqueous solutions and then spread at the air-water interface. Spectroscopic data of aqueous solutions of HI show a difference in HI conformation at different pH values. Moreover, the dynamics of the insulin protein showed a dependence on the concentration of Zn(II) ions. In the absence of Zn(II) ions in the subphase, the acidic and basic solutions showed similar behavior at the air-water interface. In the presence of Zn(II) ions in the subphase, the surface pressure-area and surface potential-area isotherms suggest that HI may aggregate at the air-water interface. It was observed that increasing the concentration of Zn(II) ions in the acidic (pH 2) aqueous solution of HI led to an increase of the area at a specific surface pressure. It was also seen that the conformation of HI in the basic (pH 9) medium had a reverse effect (decrease in the surface area) with the increase of the concentration of Zn(II) ions in solution. From the compression-decompression cycles we can conclude that the aggregated HI film at air-water interface is not stable and tends to restore a monolayer of monomers. These results were confirmed from UV-vis and fluorescence spectroscopy analysis. Infrared reflection-absorption and circular dichroism spectroscopy techniques were used to determine the secondary structure and orientation changes of HI by zinc ions. Generally, the aggregation process leads to a conformation change from α-helix to β-strand and β-turn, and at the air-water interface, the aggregation process was likewise seen to induce specific orientations for HI in the acidic and basic media. A proposed surface orientation model is presented here as an explanation to the experimental data, shedding light for further research on the behavior of insulin as a Langmuir monolayer.     

Comparative study of electron transfer reactions at the ionic liquid/water and organic/water interfaces

The rates of electron transfer (ET) reactions at the water/ionic liquid (IL) interface have been measured for the first time using scanning electrochemical microscopy. The standard bimolecular rate constant of the interfacial ET between ferrocene dissolved in 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide and aqueous ferricyanide (0.4 M-1 cm s-1) was found to be approximately 30 times higher than the corresponding rate constant measured at the water/1,2-dichloroethane interface. The driving force dependence of the ET rate was investigated over a wide range of the interfacial potential drop values (>200 mV). The observed Butler-Volmer-type dependence is discussed in terms of the interfacial model. The ET was also probed at the interface between aqueous solution and the mixture of the IL and 1,2-dichloroethane. The mole fractions in this mixture were varied systematically to investigate the transition from the water/organic to the water/IL interface. The observed decrease in the rate constant with increasing mole fraction of 1,2-dichloroethane is in contrast with the previously reported direct correlation between the electrochemical rate constant and the diffusion coefficient of redox species in solution.     

Formation of ice-like water structure on the surface of an antifreeze protein

Antifreeze proteins (AFPs) are found in different species from polar, alpine, and subarctic regions where they serve to inhibit ice crystal growth by adsorption to ice surfaces. Computational methods have the power to investigate the antifreeze mechanism in atomic detail. Molecular dynamics simulations of water under different conditions have been carried out to test our water model for simulations of biological macromolecules in extreme conditions: very low temperatures (200 K) and at the ice/liquid water interface. We show that the flexible F3C water model reproduces properties of water in the solid phase (ice I(h)), the supercooled liquid phase, and at the ice/liquid water interface. Additionally, the hydration of the type III AFP from ocean pout was studied as a function of temperature. Hydration waters on the ice-binding surface of the AFP were less distorted and more tetrahedral than elsewhere on the surface. More ice-like hydrating water structures formed on the ice-binding surface of the protein such that it created an ice-like structure in water within its first hydration layer but not beyond, suggesting that this portion of the protein has high affinity for ice surfaces.     

Behavior of β-amyloid 1-16 at the air-water interface at varying pH by nonlinear spectroscopy and molecular dynamics simulations

The adsorption and aggregation of β-amyloid (1-16) fragment at the air-water interface was investigated by the combination of second harmonic generation (SHG) spectroscopy, Brewster angle microscopy (BAM), and molecular dynamics simulations (MD). The Gibbs free energy of surface adsorption was measured to be -10.3 kcal/mol for bulk pHs of 7.4 and 3, but no adsorption was observed for pH 10-11. The 1-16 fragment is believed not to be involved in fibril formation of the β-amyloid protein, but it exhibits interesting behavior at the air-water interface, as manifested in two time scales for the observed SHG response. The shorter time scale (minutes) reflects the surface adsorption, and the longer time scale (hours) reflects rearrangement and aggregation of the peptide at the air-water interface. Both of these processes are also evidenced by BAM measurements. MD simulations confirm the pH dependence of surface behavior of the β-amyloid, with largest surface affinity found at pH = 7. It also follows from the simulations that phenylalanine is the most surface exposed residue, followed by tyrosine and histidine in their neutral form.     

Electrodipping force acting on solid particles at a fluid interface

We report experimental results which show that the interfacial deformation around glass particles (radius, 200-300 microm) at an oil-water (or air-water) interface is dominated by an electric force, rather than by gravity. It turns out that this force, called for brevity "electrodipping," is independent of the electrolyte concentration in the water phase. The force is greater for oil-water than for air-water interfaces. Under our experimental conditions, it is due to charges at the particle-oil (instead of particle-water) boundary. The derived theoretical expressions, and the experiment, indicate that this electric force pushes the particles into water. To compute exactly the electric stresses, we solved numerically the electrostatic boundary problem, which reduces to a set of differential equations. Convenient analytical expressions are also derived. Both the experimental and the calculated meniscus profile, which are in excellent agreement, exhibit a logarithmic dependence at long distances. This gives rise to a long-range electric-field-induced capillary attraction between the particles, detected by other authors. Deviation from the logarithmic dependence is observed at short distances from the particle surface due to the electric pressure difference across the meniscus. The latter effect gives rise to an additional short-range contribution to the capillary interaction between two floating particles. The above conclusions are valid for either planar or spherical fluid interfaces, including emulsion drops. The electrodipping force, and the related long-range capillary attraction, can engender two-dimensional aggregation and self-assembly of colloidal particles. These effects could have implications for colloid science and the development of new materials.     

Interactions of anthracyclines with zwitterionic phospholipid monolayers at the air-water interface

The present note describes the use of surface pressure measurements (Langmuir monolayer technique) for the analysis of interactions of two different anthracyclines (adriamycin and daunorubicin) with a non-ionic, zwitterionic phospholipid monolayer, at the air-water interface. Because the surface membrane of the cell is the first barrier encountered by the anthracyclines in the treatment of cancer, drug-membrane interactions studied in model (monolayers or bilayers) and natural systems play an important role in the understanding of the bioactivity properties of these molecules. We report here the rate constants of the adsorption process of adriamycin and daunorubicin in the presence of a zwitterionic phospholipid monolayer at the air-water interface. Because interactions with the lipid monolayer strongly depend on the molecular packing of the lipid, we investigated this process at a relatively low surface pressure (7 mN/m), the interactions being favoured by the gaseous and liquid expanded structure of the lipid monolayer. The apparent molecular area of these molecules during the insertion into the lipid film and their interactions with the phospholipid polar head groups was evaluated and the estimated percentage of anthracyclines at the interface after adsorption into the lipid monolayer is briefly discussed. The rate constants for the adsorption and desorption process at the water-monolayer interface have been calculated on the basis of a single-exponential model. The observed difference of these parameters for daunorubicin and adriamycin suggests a different interaction of these anthracyclines during the adsorption to and/or penetration across the phospholipid monolayer.     

Novel two-dimensional "ring and chain" morphologies in Langmuir-Blodgett monolayers of PS-b-PEO block copolymers: effect of spreading solution concentration on self-assembly at the air-water interface

A polystyrene-b-poly(ethylene oxide) (PS-b-PEO) (MW = 141k, 11.4 wt% PEO) diblock copolymer in the hydrophobic regime was spread from chloroform solutions of various concentrations at the air-water interface, and the resultant monolayers were transferred to glass substrates and imaged using atomic force microscopy. Monolayers prepared under identical conditions were also characterized at the air-water interface via Langmuir compression isotherms. The effects of spreading solution concentration on surface features, compressibility, and limiting mean molecular area were determined, revealing several interesting trends that have not been reported for other systems of PS-b-PEO. Spreading solutions > or = 0.50 mg/mL resulted almost exclusively in dot and spaghetti morphologies, with no observed continent features, which have been commonly found in more hydrophobic systems. For lower spreading solutions, < or = 0.25 mg/mL, we observed a large predominance of two novel surface morphologies, nanoscale rings and chains. The surface pressure (pi)-area (A) isotherms also exhibited a unique dependence on the spreading solution concentration, with limiting mean molecular areas and isothermal compressibilities of PS-b-PEO monolayers increasing below a critical concentration of spreading solution, suggesting a greater contribution from the PEO blocks. These results suggest that PS chain entanglement prior to solvent evaporation plays an important kinetic role in the extent of PEO adsorption at the air-water interface and in the morphologies of the resulting self-assembled surface aggregates.     

Rat osseous plate alkaline phosphatase as Langmuir monolayer--an infrared study at the air-water interface

A glycosylphosphatidylinositol (GPI)-anchored enzyme (rat osseous plate alkaline phosphatase-OAP) was studied as monolayer (pure and mixed with lipids) at the air-water interface. Surface pressure and surface potential-area isotherms showed that the enzyme forms a stable monolayer and exhibits a liquid-expanded state even at surface pressure as high as 30 mN m(-1). Isotherms for mixed dimyristoylphosphatidic acid (DMPA)-OAP monolayer showed the absence of a liquid-expanded/liquid-condensed phase transition as observed for pure DMPA monolayer. In both cases, pure or mixed monolayer, the enzyme preserves its native conformation under compression at the air-water interface as observed from in situ p-polarized light Fourier transform-infrared reflection-absorption spectroscopic (FT-IRRAS) measurements. Changes in orientation and conformation of the enzyme due to the presence or absence of DMPA, as well as due to the surface compression, are discussed.     

Detection of Single Molecule on Water Surface by Confocal Fluorescence Microscopy

In the past decade,several research groups have succeeded in observing single molecule in liquid, and more recently at silica surface in the near-field mode as well as at polymer-air interface in far-field mode. Due to the significance of air-water interface in surface chemistry, we prospect that research works on single molecule detection (SMD) of the air-water surface could open a new era in surface photochemistry and photophysics.