Dynamics of amphiphilic diblock copolymers at the air-water interface

Two polyisoprene-polyethyleneoxide diblock copolymers with different block length ratios adsorbed to the water surface were investigated by multiple angle of incidence ellipsometry, evanescent wave light scattering, and surface tension experiments. In a semidilute interfacial regime, the transition from a two-dimensional to a "mushroom" regime, in which polymer chains form loops and tails in the subphase, was discussed. A diffusion mechanism parallel to the interface was probed by evanescent wave dynamic light scattering. At intermediate concentrations, the interfacial diffusion coefficient D(∥) scales with the surface concentration Γ, as D(∥) ~ Γ(0.77) in agreement with the scaling observed for polymer solutions in a semidilute regime. At relatively high concentrations a decreasing of D(∥) is discussed in terms of increasing friction due to interactions between polyisoprene chains.     

Toroid morphology by ABC-type amphiphilic rod-coil molecules at the air-water interface

The interfacial and aggregation behavior of the ABC-type amphiphilic molecules with semirigid dumbbell-shaped core and variable length of hydrophobic branched tails (R=(CH2)nCH3 with n=5 (1), 9 (2), 13 (3)) were investigated. At low surface pressure, smooth, uniform monolayers were formed at the air-water interface by molecules 1 and 2, whereas for molecule 3 unique 2D toroid aggregates have been formed. These aggregates were relatively stable within a range of surface pressure and spreading solution concentration. Upon compression, the 2D toroid aggregates collapsed into large, round 3D aggregates. Finally, the choice of spreading solvent has a great influence on aggregation formation into 2D or 3D micelles as a result of the variable balance of the hydrophobic interactions of branched tails and the pi-pi stacking interaction between aromatic segments.     

J-aggregation of a sulfonated amphiphilic porphyrin at the air-water interface as a function of pH

π-A isotherms, ellipsometric measurements, Brewster angle microscopy (BAM) and reflection spectroscopy have been utilized to characterize the films of an amphiphilic porphyrin ((OD)(3)TPPS(3)) at the air-water interface as a function of pH. This porphyrin forms stable mono-molecular layers at such interfaces, and exhibits different J-aggregation as a function of pH. The J-aggregation of (OD)(3)TPPS(3) on neutral pH subphases is notable considering that the nitrogen atoms at the central macrocycle have a pK(a)≈4.9. The type of aggregates at neutral pH is like those detected at pH<4, because the central porphyrin ring is already protonated. However at basic pH the aggregation happens without protonation of the central ring but can be instead controlled by application of the surface pressure. At the air-water interface, (OD)(3)TPPS(3) shows two bands, a red component and a blue component, which have characteristics of non-degenerate linear oscillators being perpendicularly polarized between each other. The spectral behavior observed on subphases at different pHs is qualitatively interpreted by means of exciton coupling theory, assuming that the degenerate transitions attributed to the Soret band are split. Additionally, highly oriented molecular films of these J-aggregates were deposited onto transparent quartz slides.     

Mode of interaction of amphiphilic alpha-helical peptide with phosphatidylcholines at the air-water interface

Surface pressure (pi)-, surface potential (deltaV)-, and dipole moment (mu(perpendicular))-area (A) isotherms and morphological behavior were examined for monolayers of a newly designed 18-mer amphiphilic alpha-helical peptide (Hel 13-5), DPPC, and DPPC/egg-PC (1:1) and their combinations by the Wilhelmy method, ionizing electrode method, fluorescence microscopy (FM), and atomic force microscopy (AFM). The newly designed Hel 13-5 showed rapid adsorption into the air-liquid interface to form interfacial films such as a SP-B function. Regardless of the composition and constituents in their multicomponent system of DPPC/egg-PC, the collapse pressure (pi(c); approximately 42 mN m(-1)) was constant, implying that Hel 13-5 with the fluid composition of egg-PC is squeezed out of Hel 13-5/DPPC/egg-PC monolayers accompanying a two- to three-dimensional phase transformation. FM showed that adding a small amount of Hel 13-5 to DPPC induced a dispersed pattern of ordered domains with a "moth-eaten" appearance, whereas shrinkage of ordered domains in size occurred for the DPPC/egg-PC mixture with Hel 13-5. Furthermore, AFM indicated that (i) the intermediate phase was formed in pure Hel 13-5 systems between monolayer states and excluded nanoparticles, (ii) protrusions necessarily located on DPPC monolayers, and (iii) beyond the collapse pressure of Hel 13-5, Hel 13-5 was squeezed out of the system into the aqueous subphase. Furthermore, hysteresis curves of these systems nicely resemble those of the DPPC/SP-B and DPPC/SP-C mixtures reported before.     

Molecular reorganization of paired assemblies of T-shaped rod-coil amphiphilic molecule at the air-water interface

A T-shaped aromatic amphiphilic molecule based on linear oligo(ethylene oxide) was synthesized. We suggest that its peculiar interfacial behavior at the air-water interface and the structure of the Langmuir-Blodgett monolayer are associated with its peculiar T-shape and competing steric and amphiphilic interactions at different surface pressures. At low surface pressure, uniform and smooth monolayers were formed. Upon compression, the molecular reorganization from spherical to cylindrical transformation occurred, as caused by the submerging of the oligo(ethylene oxide) chains, providing for efficient pi-pi interactions of the central core. At the highest surface pressure, the monolayer collapses into bilayer domains, following a bicontinuous network formation which tends to transform into a perforated film. The unique shape of T-like rigid aromatic cores makes their structural reorganization very peculiar with paired, dimerlike molecular packing dominating in gas and solid states. This paired aggregation is so strong that it is preserved in the course of flipping and formation of vertically oriented backbones.     

Piezoluminescence at the air-water interface through dynamic molecular recognition driven by lateral pressure application

The steroid cyclophanes with a cyclic core consisting of a 1,6,20,25-tetraaza[6.1.6.1]paracyclophane connected to four steroid moieties (cholic acid or cholanic acid) through a flexible l-lysine spacer were spread on water as Langmuir monolayers. The pi-A isotherm of the cholic-type steroid cyclophane includes a transition to the condensed phase with a limiting area of approximately 2 nm(2). This value is close to the cross-sectional area of the steroid cyclophane with a standing-up conformation of the cholic acid moieties, strongly suggesting that the cavity converts from a two-dimensional cavity to a three-dimensional cavity upon compressing the monolayer. Surface-reflective fluorescence spectroscopy of the monolayer using an aqueous fluorescent probe (6-(p-toluidino)naphthalene-2-sulfonate (TNS)) showed an abrupt increase in the TNS fluorescence intensity at a molecular area of 2 nm(2). Efficient binding of the guest probe would occur upon the completion of the three-dimensional cavity. Repeated compression and expansion induces periodic changes in the fluorescence intensity. This indicates a piezoluminescence effect through the catch and release of the TNS guest upon dynamic cavity formation. Analyses of the binding behavior of TNS to the steroid cyclophane resulted in binding constants in the range of approximately (5-9) x 10(4) M(-1) which are similar to that observed in lipid bilayer media (K = 5.1 x 10(4) M(-1)). The fluorescence intensity within the condensed phase was significantly increased with increasing pressure, suggesting that suppression of the molecular motion of the bound TNS may retard the nonemission process. Similar monolayer experiments were carried out with the monolayer of the cholanic-type steroid cyclophane that cannot form an open conformation on water. Both the phase transition in the pi-A isotherm and the change in the fluorescence intensity were negligible, confirming that the dynamic characteristic of the cavity is indispensable for the efficient pressure-induced binding of the guest and the consequent luminescence.     

Enantioselective resolution of chiral aromatic acids by biphasic recognition chiral extraction

This paper reports a new chiral separation technology—biphasic recognition chiral extraction for the separation of aromatic acid enantiomers such as α-cyclohexyl-mandelic acid (CHMA) and naproxen (NAP). The biphasic recognition chiral extraction system was established by adding hydrophobic d(l)-isobutyl tartrate in 1,2-dichloroethane organic phase and hydrophilic β-cyclodextrin (β-CD) derivative in aqueous phase, which preferentially recognize the (R)-enantiomer and (S)-enantiomer, respectively. These studies involve an enantioselective extraction in a biphasic system, where aromatic acid enantiomers form complexes with the β-cyclodextrin derivative in the aqueous phase and d(l)-isobutyl tartrate in the organic phase, respectively. Factors affecting the extraction mechanism are analyzed, namely the influence of the concentrations of the extractants and aromatic acid enantiomers, the types of the extractants, pH, and temperature. The experimental results show that the biphasic recognition chiral extraction is of much stronger chiral separation ability than the monophasic recognition chiral extraction, which utilizes the cooperations of the forces of the tartrate and the β-CD derivative. Hydroxypropyl-β-cyclodextrin (HP-β-CD), hydroxyethyl-β-cyclodextrin (HE-β-CD), and methyl-β-cyclodextrin (ME-β-CD) have stronger recognition abilities for the (S)-aromatic acid enantiomers than those for (R)-aromatic acid enantiomers, among which HP-β-CD has the strongest ability. d-Isobutyl tartrate preferentially recognizes (R)-CHMA and (S)-NAP, while l-isobutyl tartrate preferentially recognizes (S)-CHMA and (R)-NAP. The maximum enantioselectivities of CHMA and NAP are 2.49 and 1.65, under conditions at which the pH values of the aqueous phases are 2.7 and 2.5, at the ratio of 2:1 of [isobutyl tartrate] to [HP-β-CD].     

Hysteresis behavior of amphiphilic model peptide in lung lipid monolayers at the air-water interface by an IRRAS measurement

Pulmonary functions such as rapid adsorption, respreading, and hysteresis behavior of pulmonary surfactants are very important for respiratory movement. The interfacial behavior of pulmonary preparations containing an amphiphilic peptide (Hel 13-5) has recently investigated. An orientation of hydrophobic chains in a dipalmitoylphosphatidylcholine (DPPC) with or without palmitic acid (PA) is associated with a collapse of alveoli during respiration process. Therefore, the present study focused on the acyl chain orientation in model pulmonary surfactants (DPPC/Hel 13-5 and DPPC/PA/Hel 13-5). A successive change in the orientation during cyclic compression and expansion of films at the air-water interface can be probed directly by an infrared reflection-absorption spectrometry (IRRAS) technique. The hysteresis behavior, one of very important pulmonary functions, was previously observed in surface pressure (pi)-molecular area (A) isotherms for the both model pulmonary surfactant systems (Langmuir 22(2006)1182-1192 and Langmuir 22(2006)5792-5803). In addition, it was reported that Hel 13-5 was squeezed-out of the surface on compression like native pulmonary surfactant proteins. The data obtained for the binary and ternary systems were compared with those of the equivalent pure DPPC and DPPC/PA mixtures, respectively. For an asymmetric methylene stretching vibration (nu(a)-CH(2)) RA intensity, the absolute RA values increased with shifting to small surface area, monotonously. For the corresponding wavenumber, on the other hand, the values gradually decreased into approximately 2920cm(-1). However, they were kept constant in the squeeze-out region in spite of a further decrease of surface area. These results suggested that the orientation of hydrophobic chains in DPPC and DPPC/PA mixtures became in the most packed state soon after emergence of the squeeze-out process of Hel 13-5 and then the packed orientation was retained up to the collapse state. This indicated that the squeezed-out Hel 13-5 stabilized monolayers left at the interface. For the DPPC/PA/Hel 13-5 system, in particular, dissociated PA molecules were excluded together with Hel 13-5 and the surface monolayers were refined to DPPC and undissociated PA components during the compression process. And the similar behavior in the second and third cycles supported the good respreading ability of the monolayers containing Hel 13-5.     

Mechanical control of enantioselectivity of amino acid recognition by cholesterol-armed cyclen monolayer at the air-water interface

Monolayers of the cholesterol-armed cyclen Na+ complex at the air-water interface display a remarkable, surface pressure dependent enantioselectivity of amino acid recognition. Upon compression of the monolayer, the binding constants of amino acids increase accompanying an inversion of chiral selectivity from the d- to l-form in the case of valine.     

Enantioselective chromatography: Selection of chiral recognition models

In this brief overview diverse chiral recognition models and chiral host-guest (selector-selectand, SO-SA) relationships which are used in enantioselective chromatography are discussed. In particular it is focussed on aspects of chiral interactions on (a) small molecular brush type chiral stationary phases (CSPs) and on (b) biopolymer and synthetic polymer type CSPs. The importance and the great variability of intermolecular SO-SA bindings via complementary contact sites, also in connection with molecule conformations, is stressed. Some representative and selected examples of chromatographic enantioseparations are presented.     

A comparative study of amphiphilic PAMAM dendrimers at the air-water interface with different hydrophobe attachment groups

Generation 0 through 5 polyamidoamine (PAMAM) dendrimers with three different types of groups connecting to hydrophobic C12 tails and one type of group connecting to C18 tails were synthesized and studied as monolayers at the air-water interface with a Langmuir trough. The molecular areas were significantly influenced by the size and the type of connecting group. Higher-generation (e.g., G4 and G5) amphiphilic PAMAMs with amide connecting groups were more responsive to changes in compression rate and subphase temperature and less stable than the corresponding opened epoxide- or ester-connected counterparts. Intramolecular (and possibly also intermolecular) attractive hydrogen-bond interactions between the amide connectors are proposed as the reason for this behavior.     

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.     

Enantioselective recognition by a highly ordered porphyrin-assembly on a chiral molecular gel

Enantioselective recognition of amino acids was achieved by using a highly ordered chiral assembly of achiral porphyrin on a chiral molecular gel. Exceptionally high enantioselectivity was observed for histidine derivatives by monitoring the CD patterns and fluorescence quenching, K(SV) (l): 26.3 × 10(3) M(-1); K(SV)(D)-enantiomer: 7.03 × 10(3) M(-1).     

Homochiral oligopeptides by chiral amplification within two-dimensional crystalline self-assemblies at the air-water interface; relevance to biomolecular handedness

A possible role that might have been played by ordered clusters at interfaces for the generation of homochiral oligopeptides under prebiotic conditions has been probed by a catalyzed polymerization of amphiphilic activated alpha-amino acids, in racemic and chiral non-racemic forms, which had self-assembled into two-dimensional (2D) ordered crystallites at the air-aqueous solution interface. As model systems we studied N(epsilon)-stearoyl-lysine thioethyl ester (C(18)-TE-Lys), gamma-stearyl-glutamic thioethyl ester (C(18)-TE-Glu), N(alpha)-carboxyanhydride of gamma-stearyl-glutamic acid (C(18)-Glu NCA) and gamma-stearyl-glutamic thioacid (C(18)-thio-Glu). According to in-situ grazing incidence X-ray diffraction measurements on the water surface, (R,S)-C(18)-TE-Lys, (R,S)-C(18)-TE-Glu, and (R,S)-C(18)-Glu-NCA amphiphiles self-assembled into ordered racemic 2D crystallites. Oligopeptides 2-12 units long were obtained at the air-aqueous solution interface after injection of appropriate catalysts into the water subphase. The experimental relative abundance of oligopeptides with homochiral sequence generated from (R,S)-C(18)-TE-Lys and (R,S)-C(18)-TE-Glu, as determined by mass spectrometry on enantioselectively deuterium-labeled samples, was found to be significantly larger than that obtained from (R,S) C(18)-thio-Glu which polymerizes randomly. An efficient chiral amplification was obtained in the polymerization of non-racemic mixtures of C(18)-Glu-NCA since the monomer molecules in the racemic 2D crystallites are oriented such that the reaction occurs between heterochiral molecules related by glide symmetry to yield heterochiral oligopeptides whereas the enantiomer in excess, in the enantiomorphous crystallites, yield oligopeptides of a single handedness.     

Protein assembly at the air-water interface studied by fluorescence microscopy

Protein assembly at the air-water interface (AWI) occurs naturally in many biological processes and provides a method for creating biomaterials. However, the factors that control protein self-assembly at the AWI and the dynamic processes that occur during adsorption are still underexplored. Using fluorescence microscopy, we investigated assembly at the AWI of a model protein, human serum albumin minimally labeled with Texas Red fluorophore. Static and dynamic information was obtained under low subphase concentrations. By varying the solution protein concentration, ionic strength, and redox state, we changed the microstructure of protein assembly at the AWI accordingly. The addition of pluronic surfactant caused phase segregation to occur at the AWI, with fluid surfactant domains and more rigid protein domains revealed by fluorescence recovery after photobleaching experiments. Protein domains were observed to coalesce during this competitive adsorption process.     

Spontaneous polymerization at the air-water interface: a Brewster angle microscopy study

When a dioctadecyldimethylammonium bromide (DODA) monolayer is spread onto a styrene sulfonate (SSt) aqueous solution, this monomer undergoes a spontaneous polymerization process [Fichet, O; Teyssié, D. Macromolecules 2002, 35, 5352]. However, the polymer synthesized in this monolayer cannot be investigated by classical characterization techniques. Brewster angle microscopy has thus been used as a complementary method in order to study this spontaneous polymerization. From these measurements, the threshold concentration above which the spontaneous polymerization occurs has been determined more precisely; the monomer adsorption under the DODA monolayer has been evidenced as being very fast, as supposed previously; moreover, sodium bicarbonate is confirmed as an inhibitor of the polymerization. Also, the replacement of SSt by toluene sulfonate (TSt) confirms the SSt spontaneous polymerization. Finally, the molecular weight and/or the structure of the polymer synthesized in the monolayer seems to be different from those synthesized in solution.     

Enantioselective fluorescent recognition of amino alcohols by a chiral tetrahydroxyl 1,1'-binaphthyl compound

The tetrahydroxyl derivative of BINOL, (S)- or (R)-1, and its analogues are synthesized. (S)- or (R)-1 can be used to conduct the enantioselective recognition of chiral amino alcohols. In comparison with BINOL, the two additional hydroxyl groups of (S)- or (R)-1 have increased the binding of this compound with the amino alcohols and significantly improved the fluorescence quenching efficiency. The fluorescence responses of (S)- or (R)-1 toward amino alcohols are compared with those of its analogues (R)-4 and (R)-6. It shows that the interaction of the central naphthyl hydroxyl groups of (S)- or (R)-1 with the substrates is responsible for the observed fluorescence quenching, and the two additional alkyl hydroxyl groups increase the quenching efficiency.     

Strands, networks, and continents from polystyrene dewetting at the air-water interface: implications for amphiphilic block copolymer self-assembly

We demonstrate that nanoscale aggregates similar to those formed via amphiphilic block copolymer self-assembly at the air-water interface, including strands, networks, and continents, can be generated by the simple spreading of PS homopolymer solutions on water. Two different PS homopolymers of different molecular weight (PS-405k, M(n) = 405?000 g mol(-1) and PS-33k, M(n) = 33?000 g mol(-1)) are spread at the air-water interface at various spreading concentrations ranging from 0.25 to 3.0 mg/mL. Aggregate formation is driven by PS dewetting from water as the spreading solvent evaporates. We propose that a high spreading concentration or a high molecular weight lead to chain entanglements that restrict macromolecular mobility in the solution, enabling the kinetic trapping of nanostructures associated with early and intermediate stages of PS dewetting. Comparison of PS-405k with a mainly hydrophobic PS-b-PEO block copolymer of similar molecular weight (PSEO-392k, M(n) = 392?000 g mol(-1), 2.0 wt % PEO) allows the effect of a relatively short surface active block on aggregate formation to be investigated. We show that whereas the PEO block is not a required component for the formation of strands and other nonglobular aggregates, it does increase the number of these aggregates at a given spreading concentration and decreases the minimum spreading concentration at which these aggregates are observed, along with decreasing the dimensions and polydispersity of specific surface features. The results provide supporting evidence for the role of PS dewetting in the generation of multiple PS-b-PEO aggregate morphologies at the air-water interface, as originally described in earlier paper from our group.