New insights into lung surfactant monolayers using vibrational sum frequency generation spectroscopy

At the air-water interface, interfacial molecular structure, intermolecular interactions, film relaxation and film respreading of model lung surfactant monolayers were studied using vibrational sum frequency generation (VSFG) spectroscopy combined with a Langmuir film balance. Chain-perdeuterated dipalmitoylphosphatidylcholine (DPPC-d62), palmitoyloleoyl-phosphatidylglycerol (POPG), palmitic acid (PA) and tripalmitin were investigated. In the DPPC-d62-PA binary monolayer, PA showed a condensing effect on the DPPC chains. On the contrary, in the DPPC-d62-POPG binary monolayer, POPG showed a fluidizing effect on the DPPC chains. In the ternary monolayer system of DPPC-d62-POPG-PA, the balance between the fluidizing and the condensing effect was also observed. In addition, the film relaxation behavior of DPPC-d62 and the enhanced film stability of DPPC-d62 caused by the addition of tripalmitin were observed. Real-time VSFG was also employed to study the respreading properties of a complex lung surfactant mixture containing DPPC-d62, POPG, PA and KL4 (a mimic of SP-B) peptide, which revealed DPPC enrichment after film compression.     

Monte Carlo simulations of Lennard-Jones nonionic surfactant adsorption at the liquid/vapor interface

We present Monte Carlo simulations of nonionic surfactant adsorption at the liquid/vapor interface of a monatomic solvent. All molecules in the system, solvent and surfactant, are characterized by the Lennard-Jones (LJ) potential using differing interaction parameters. Surfactant molecules consist of an amphiphilic chain with a solvophilic head and a solvophobic tail. Adjacent atoms along the surfactant chain are connected by finitely extensible harmonic springs. Solvent molecules move via the Metropolis random-walk algorithm, whereas surfactant molecules move according to the continuum configurational bias Monte Carlo (CBMC) method. We generate quantitative thermodynamic adsorption and surface tension isotherms in addition to surfactant radius of gyration, tilt angles, and potentials of mean force. Surface tension simulations compared to those calculated from the simulated adsorbed amounts and the Gibbs adsorption isotherm agree confirming equilibrium in our simulations. We find that the classical Langmuir isotherm is obeyed for our LJ surfactants over the range of head and tail lengths studied. Although simulated surfactant chains in the bulk solution exhibit random orientations, surfactant chains at the interface orient roughly perpendicular and the tails elongate compared to bulk chains even in the submonolayer adsorption regime. At a critical surfactant concentration, designated as the critical aggregation concentration (CAC), we find aggregates in the solution away from the interface. At higher concentrations, simulated surface tensions remain practically constant. Using the simulated potential of mean force in the submonolayer regime and an estimate of the surfactant footprint at the CAC, we predict a priori the Langmuir adsorption constant, KL, and the maximum monolayer adsorption, Gammam. Adsorption is driven not by proclivity of the surfactant for the interface, but by the dislike of the surfactant tails for the solvent, that is by a "solvophobic" effect. Accordingly, we establish that a coarse-grained LJ surfactant system mimics well the expected equilibrium behavior of aqueous nonionic surfactants adsorbing at the air/water interface.     

Monte Carlo simulation of mixed lennard-jones nonionic surfactant adsorption at the liquid/vapor interface

New Monte Carlo simulations are presented for nonionic surfactant adsorption at the liquid/vapor interface of a monatomic solvent specifically investigating the roles of tail attraction and binary mixtures of different tail lengths. Surfactant molecules consist of an amphiphilic chain with a solvophilic head and a solvophobic tail. All molecules in the system, solvent and surfactant, are characterized by the Lennard-Jones (LJ) potential. Adjacent atoms along the surfactant chain are connected by finitely extensible harmonic springs. Solvent molecules move via the Metropolis random-walk algorithm, whereas surfactant molecules move according to the continuum configurational bias Monte Carlo (CBMC) method. We generate thermodynamic adsorption and surface-tension isotherms and compare results quantitatively to single-surfactant adsorption (Langmuir, 2007, 23, 1835). Surfactant tail groups with attractive interaction lead to cooperative adsorption at high surface coverage and higher maximum adsorption at the interface than those without. Moreover, adsorption and surface-tension isotherms with and without tail attraction are identical at low concentrations, deviating only near maximum coverage. Simulated binary mixtures of surfactants with differing lengths give intermediate behavior between that of the corresponding single-surfactant adsorption and surface-tension isotherms both with and without tail attraction. We successfully predict simulated mixture results with the thermodynamically consistent ideal adsorbed solution (IAS) theory for binary mixtures of unequal-sized surfactants using only the simulations from the single surfactants. Ultimately, we establish that a coarse-grained LJ surfactant system is useful for understanding actual surfactant systems when tail attraction is important and for unequal-sized mixtures of amphiphiles.     

Local structure at the air/liquid interface of room-temperature ionic liquids probed by infrared-visible sum frequency generation vibrational spectroscopy: 1-alkyl-3-methylimidazolium tetrafluoroborates

The air/liquid interface of 1-alkyl-3-methylimidazolium tetrafluoroborates with the general formula [C(n)mim]BF(4) (n = 4-11) was studied using infrared-visible sum frequency generation (SFG) vibrational spectroscopy. The probability of the gauche defect per CH2-CH2 bond in the alkyl chain decreases as the number of carbon atoms in the alkyl chain increases. This observation suggests that the interaction between the alkyl chains is enhanced as the alkyl chain length becomes longer. The frequencies of the C-H stretching vibrational modes observed in the SFG spectra are higher than those of the corresponding peak positions observed in the infrared spectra of the bulk liquids. This shift is consistent with a structure in which the alkyl chain protrudes from the bulk liquid into the air. A local structure, which originates from the intermolecular interaction between the ionic liquid molecules, is proposed to explain these observations.     

Thermodynamics of phase transitions in langmuir monolayers observed by vibrational sum frequency spectroscopy

Vibrational sum-frequency spectroscopy (VSFS) was used to study gauche defects in octadecylamine (ODA) monolayers at the air/water interface. The VSFS spectra provide unique insights into phase transitions that occur as a result of changes in the structure of the monolayer's hydrophobic region. These changes can be attributed to the increased presence of gauche conformers in the ODA alkyl chains during the monolayer's transition from the solid to liquid phase. Temperature-dependent spectra from monolayers at several different pressures were used to assign the phase transition temperature based on the observed changes in microscopic structure. Through application of a two-dimensional form of the Clapeyron equation, the first in situ measurements of the entropy and enthalpy changes associated with gauche conformers in a monolayer were made.     

Self-assembly of a nonionic surfactant at the graphite/ionic liquid interface

In this study, we demonstrate by AFM imaging that nonionic surfactants self-assemble into hemicylindrical aggregates at the interface between graphite and the room temperature ionic liquid ethylammonium nitrate. Like aqueous systems, surfactant first adsorbs in a tail-to-tail monolayer arrangement along one of the three symmetry axes of graphite, templating subsequent self-assembly into adsorbed hemicylinders. Longer surfactant tails and higher concentrations are required to produce hemicylindrical aggregates in the ionic liquid than in aqueous solutions.     

Surface vibrational structure at alkane liquid/vapor interfaces

Broadband vibrational sum frequency spectroscopy (VSFS) has been used to examine the surface structure of alkane liquid/vapor interfaces. The alkanes range in length from n-nonane (C(9)H(20)) to n-heptadecane (C(17)H(36)), and all liquids except heptadecane are studied at temperatures well above their bulk (and surface) freezing temperatures. Intensities of vibrational bands in the CH stretching region acquired under different polarization conditions show systematic, chain length dependent changes. Data provide clear evidence of methyl group segregation at the liquid/vapor interface, but two different models of alkane chain structure can predict chain length dependent changes in band intensities. Each model leads to a different interpretation of the extent to which different chain segments contribute to the anisotropic interfacial region. One model postulates that changes in vibrational band intensities arise solely from a reduced surface coverage of methyl groups as alkane chain length increases. The additional methylene groups at the surface must be randomly distributed and make no net contribution to the observed VSF spectra. The second model considers a simple statistical distribution of methyl and methylene groups populating a three dimensional, interfacial lattice. This statistical picture implies that the VSF signal arises from a region extending several functional groups into the bulk liquid, and that the growing fraction of methylene groups in longer chain alkanes bears responsibility for the observed spectral changes. The data and resulting interpretations provide clear benchmarks for emerging theories of molecular structure and organization at liquid surfaces, especially for liquids lacking strong polar ordering.     

The structure of mixed nonionic surfactant monolayers at the air-water interface: the effects of different alkyl chain lengths

The structure of mixed nonionic surfactant monolayers of monodecyl hexaethylene glycol (C10E6) and monotetradecyl hexaethylene glycol (C14E6) adsorbed at the air-water interface has been determined by specular neutron reflectivity. Using partial isotopic labeling (deuterium for hydrogen) of the alkyl and ethylene oxide chains of each surfactant, the distribution and relative positions of the chains at the interface have been obtained. The packing of the two different alkyl chain lengths results in structural changes compared to the pure surfactant monolayers. This results in changes in the relative positions of the alkyl chains and of the ethylene oxide chains at the interface. The role of the alkyl chain length is contrasted with that of the ethylene oxide chain length, determined from results reported previously on the nonionic surfactant mixture of monododecyl triethylene glycol (C12E3) and monododecyl octaethylene glycol (C12E8).     

Molecular level studies of polymer behaviors at the water interface using sum frequency generation vibrational spectroscopy

Industrial plastics, biomedical polymers and numerous other polymeric systems are contacted with water for everyday functions and after disposal. Probing the interfacial molecular interactions between widely used polymers and water yields valuable information that can be extrapolated to macroscopic polymer/water interfacial behaviors so scientists can better understand polymer bio-compatibility, hygroscopic tendencies and improve upon beneficial polymer behavior in water. There is an ongoing concerted effort to elucidate the molecular level behaviors of polymers in water by using sum frequency generation vibrational spectroscopy (SFG). SFG stands out for its utility in probing buried interfaces in situ and in real time without disrupting interfacial chemistry. Included in this review are SFG water interfacial studies performed on poly(methacrylate) and (acrylate)s, poly(dimethyl siloxane)s, poly(ethylene glycol)s, poly(electrolyte)s and other polymer types. The driving forces behind common water/polymer interfacial molecular features will be discussed as well as unique molecular reorientation phenomena and resulting macroscopic behaviors from microscopic polymer rearrangement. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

DPPC Langmuir monolayer at the air-water interface: probing the tail and head groups by vibrational sum frequency generation spectroscopy

Dipalmitoylphosphatidylcholine (DPPC) is the predominant lipid component in lung surfactant. In this study, the Langmuir monolayer of deuterated dipalmitoylphosphatidylcholine (DPPC-d62) in the liquid-expanded (LE) phase and the liquid-condensed (LC) phase has been investigated at the air-water interface with broad bandwidth sum frequency generation (BBSFG) spectroscopy combined with a Langmuir film balance. Four moieties of the DPPC molecule are probed by BBSFG: the terminal methyl (CD3) groups of the tails, the methylene (CD2) groups of the tails, the choline methyls (CH3) in the headgroup, and the phosphate in the headgroup. BBSFG spectra of the four DPPC moieties provide information about chain conformation, chain orientation, headgroup orientation, and headgroup hydration. These results provide a comprehensive picture of the DPPC phase behavior at the air-water interface. In the LE phase, the DPPC hydrocarbon chains are conformationally disordered with a significant number of gauche configurations. In the LC phase, the hydrocarbon chains are in an all-trans conformation and are tilted from the surface normal by 25 degrees. In addition, the orientations of the tail terminal methyl groups are found to remain nearly unchanged with the variation of surface area. Qualitative analysis of the BBSFG spectra of the choline methyl groups suggests that these methyl groups are tilted but lie somewhat parallel to the surface plane in both the LE and LC phases. The dehydration of the phosphate headgroup due to the LE-LC phase transition is observed through the frequency blue shift of the phosphate symmetric stretch in the fingerprint region. In addition, implications for lung surfactant function from this work are discussed.     

Ionization state and structure of l-1,2-dipalmitoylphosphatidylglycerol monolayers at the liquid/air interface

Phosphatidylglycerols are components of biological membranes. The phase behavior of these phospholipids was extensively investigated. However, there is still no definite picture about the dependence of the ionization state and monolayer structure on subphase composition. The major problem of previous investigations is that none of the methods used allow obtaining the ionization degree directly. In the present work we apply techniques developed in the past decades for Langmuir monolayers: infrared reflection absorption spectroscopy (IRRAS) as well as X-ray diffraction and reflectivity techniques, which provide straightforward information about structure and ionization state of a L-1,2-dipalmitoylphosphatidylglycerol (DPPG) monolayer. The Gouy-Chapman model is applied to evaluate the intrinsic pKa. Therewith, the ionization degree can be determined even at low pH values. The experimental titration curves are in good agreement with theoretical curves based on the Gouy-Chapman model. The obtained instrinic pKa amounts to 1. The ionization degree of a DPPG monolayer is independent of the monovalent cation size. In contrast, the structure of a DPPG monolayer is strongly affected by the type of divalent cations.     

Metal cation-induced deformation of DNA self-assembled monolayers on silicon: vibrational sum frequency generation spectroscopy

Nucleic acids possess charged phosphate groups in their backbones, which require counterions to reduce the repulsive Coulombic interactions between the strands. Herein we report how different mono- and divalent metal cations influence the molecular orientations of DNA molecules on silicon surfaces upon immobilization and hybridization. Our sum frequency generation (SFG) spectroscopy studies demonstrated that the degree of conformational variation of DNA self-assembled monolayers on silicon depends on the type of metal cations present. The molecular orientation change of immobilized single-stranded oligonucleotides correlates with DNA-cation affinity (Mg(2+) > Ca(2+) > K(+) approximately Na(+)): metal cations with the strongest affinity disrupt the structure of the underlying linker monolayer the most. Upon hybridization the trend is reversed, which is attributed to the greater ability of divalent cations to mask the negative charges on the DNA backbone. These findings provide useful information for the construction of more sensitive DNA biosensors, particularly the optimization of on-chip hybridization performance.     

Broadband vibrational sum frequency generation spectroscopy of a liquid surface.

An important advance in surface science has been the evolution of sum frequency generation to the application of studying surface structure and chemistry of liquid surfaces at the molecular-level by probing the vibrational signatures of surface molecules. Recently, broad-bandwidth sum frequency generation (BBSFG) spectroscopy has become an important tool for investigating gas-solid interfaces. BBSFG spectroscopy allows, theoretically, a surface sum frequency spectrum to be acquired within one pulse of the laser. In this paper, the viability of BBSFG to study inherently small nonlinear response interfaces and the time-resolving capability of this surface-selective technology are demonstrated. Presented here are the first published accounts of spectra from a liquid surface utilizing the broad-bandwidth sum frequency technology with acquisition times as low as 500 milliseconds.     

A combined vibrational sum frequency generation spectroscopy and atomic force microscopy study of sphingomyelin-cholesterol monolayers

A combination of vibrational sum frequency generation spectroscopy and atomic force microscopy is used to study the changes in morphology and conformational order in monolayers prepared from three natural sphingomyelin (SM) mixtures as a function of surface pressure and cholesterol concentration. The most homogeneous SM gave monolayers with well-ordered acyl chains and few gauche defects with relatively small effects of either increasing surface pressure or cholesterol addition. Heterogeneous SM mixtures with a mixture of acyl chain lengths or with significant fractions of unsaturated acyl chains had much larger contributions from gauche defects at low surface pressure and gave increasingly well-ordered monolayers as the surface pressure increased. They also showed substantial increases in lipid chain order after cholesterol addition. Overall, these results are consistent with the strong hydrogen bonding capacity of SM leading to well-ordered monolayers over a range of surface pressures. The changes in acyl chain order for natural SMs as a function of cholesterol are relevant to formation of sphingolipid-cholesterol enriched domains in cell membranes.     

Ultrafast vibrational dynamics of water at a charged interface revealed by two-dimensional heterodyne-detected vibrational sum frequency generation

Two-dimensional heterodyne-detected vibrational sum frequency generation (2D HD-VSFG) spectroscopy is performed for an aqueous interface for the first time. The 2D HD-VSFG spectra in the OH stretch region are obtained from a positively charged surfactant∕water interface with isotopically diluted water (HOD∕D(2)O) to reveal the femtosecond vibrational dynamics of water at the charged interface. The 2D HD-VSFG spectrum is diagonally elongated immediately after photoexcitation, clearly demonstrating inhomogeneity in the interfacial water. This elongation almost disappears at 300 fs owing to the spectral diffusion. Interestingly, the 2D HD-VSFG spectrum at the 0 fs shows an oppositely asymmetric shape to the corresponding 2D IR spectrum in bulk water: The bandwidth of the bleach signal gets narrower when the pump wavenumber becomes higher. This suggests that the dynamics and mechanism of the hydrogen bond rearrangement at the charged interface are significantly different from those in bulk water.     

Investigations of polyelectrolyte adsorption at the solid/liquid interface by sum frequency spectroscopy: evidence for long-range macromolecular alignment at highly charged quartz/water interfaces

IR-visible sum frequency spectroscopy (SFS) was employed to investigate the molecular level details of the adsorption of the positively charged polyelectrolyte, polydiallyldimethylammonium chloride (PDDA), at the quartz/water interface. Below pH 9.0, signal from the interfacial water structure was visible, but none from the adsorbed polymer could be detected. This indicated that the PDDA was not well enough aligned at the interface under these conditions to elicit a sum frequency response. At more basic pH values (>or=9.6), however, adsorbed PDDA molecules became well-ordered as indicated by the presence of CH stretch peaks from methylene and methyl groups. The intensities of the CH stretch modes were independent of the adsorbed amount of PDDA at pH 12.3 but decreased as the pH of the bulk solution was lowered. The conditions for polymer alignment fell outside the parameters where layer-by-layer growth of oppositely charged polyelectrolytes was possible because the net charge on the surface under high pH conditions remained negative.     

Tunable synergism/antagonism in a mixed nonionic/anionic surfactant layer at the solid/liquid interface

The use of mixed surfactants for modification of solid surfaces is important for many applications, since beneficial synergism often occurs depending on the surfactant type and mixing conditions. Systematical information on the properties of surfactant mixtures at the solid/liquid interface can be helpful for optimizing the interactions between the surfactants and then their corresponding performance. In this work, a nonionic/anionic surfactant combination, n-dodecyl beta-d-maltoside (DM) and sodium dodecyl sulfonate (SDS), was selected for the study of adsorption on an oxide solid, alumina. Interestingly, the mixture of the two surfactants with opposite pH-dependence of adsorption on alumina exhibits some unique synergistic or antagonistic features that were found to be tunable in the region of pH 4-10. In addition, the DM/SDS molar ratio in the adsorbed layer was found to decrease with concentration in the saturated region at all the pH and mixing ratios tested. The decrease is attributed to the monomer concentration changes in solution due to the difference in surface activities of the two surfactants. The tunable features of this mixture at the solid/liquid interface provide a way to optimize the properties by changing the mixing conditions. This can be valuable in many applications, such as enhanced oil recovery, flotation, and solubilization.     

Probing molecular structure at interfaces for comparison with bulk solution behavior: water/2-propanol mixtures monitored by vibrational sum frequency spectroscopy

The orientation of the isopropyl group at the liquid/vapor interface in 2-propanol/water binary mixtures was studied by vibrational sum frequency spectroscopy. The CH(3) stretch modes of the two methyl groups were used to determine the molecule's orientation by employing a novel united atom approach to model the (CH(3))(2)X moiety. For this purpose, the changes in the molecular susceptibility of the isopropyl group stretches were derived in the laboratory frame as a function of the tilt and twist angles. The results indicated that the methyl groups lay down on the surface at low alcohol mole fraction and gradually twisted with increasing mole fraction. At the azeotrope, x(iso) = 0.68, one of the methyl groups aligned approximately parallel to the surface normal, whereas the other was nearly parallel with the liquid/vapor interface. When the mole fraction of 2-propanol was higher than 0.68, the orientation of 2-propanol remained almost constant. The change in the alcohol's orientation with 2-propanol mole fraction closely tracked changes in its bulk activity coefficient. Such results lead to a picture in which the surface structure and bulk properties of the system are closely linked.     

Three distinct water structures at a zwitterionic lipid/water interface revealed by heterodyne-detected vibrational sum frequency generation

Lipid/water interfaces and associated interfacial water are vital for various biochemical reactions, but the molecular-level understanding of their property is very limited. We investigated the water structure at a zwitterionic lipid, phosphatidylcholine, monolayer/water interface using heterodyne-detected vibrational sum frequency generation spectroscopy. Isotopically diluted water was utilized in the experiments to minimize the effect of intra/intermolecular couplings. It was found that the OH stretch band in the Imχ((2)) spectrum of the phosphatidylcholine/water interface exhibits a characteristic double-peaked feature. To interpret this peculiar spectrum of the zwitterionic lipid/water interface, Imχ((2)) spectra of a zwitterionic surfactant/water interface and mixed lipid/water interfaces were measured. The Imχ((2)) spectrum of the zwitterionic surfactant/water interface clearly shows both positive and negative bands in the OH stretch region, revealing that multiple water structures exist at the interface. At the mixed lipid/water interfaces, while gradually varying the fraction of the anionic and cationic lipids, we observed a drastic change in the Imχ((2)) spectra in which spectral features similar to those of the anionic, zwitterionic, and cationic lipid/water interfaces appeared successively. These observations demonstrate that, when the positive and negative charges coexist at the interface, the H-down-oriented water structure and H-up-oriented water structure appear in the vicinity of the respective charged sites. In addition, it was found that a positive Imχ((2)) appears around 3600 cm(-1) for all the monolayer interfaces examined, indicating weakly interacting water species existing in the hydrophobic region of the monolayer at the interface. On the basis of these results, we concluded that the characteristic Imχ((2)) spectrum of the zwitterionic lipid/water interface arises from three different types of water existing at the interface: (1) the water associated with the negatively charged phosphate, which is strongly H-bonded and has a net H-up orientation, (2) the water around the positively charged choline, which forms weaker H-bonds and has a net H-down orientation, and (3) the water weakly interacting with the hydrophobic region of the lipid, which has a net H-up orientation.