Adsorption of stereoregular poly(vinyl alcohols) at air-water interface

Summary The time dependency of the surface tension of the aqueous solutions of syndiotactic, isotactic and atactic poly(vinyl alcohols) (PVAs) for various concentrations were studied.The rate of the decrease in the surface tension was highest for syndiotactic PVA and lowest for atactic PVA at the same concentration. The results were analysed as crystallization and diffusion processes. The rate is controlled by an intermolecular hydrogen bond formation of syndiotactic sequences at the surface for syndiotactic PVA and the easy arrangement of segments at the surface for isotactic and syndiotactic PVAs to influence the rate of diffusion of PVA molecules.A filament could be made by picking up the multilayer formed at the surface of the syndiotactic PVA solution. The filament had the high orientation of PVA molecules and the similar properties as that from commercial PVA.

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Zusammenfassung Die Zeitabhängigkeit der Oberflächenspannung der wäßrigen Lösungen von syndiotaktischem, isotaktischem und ataktischem Poly(vinylalkohol) (PVA) wurde für verschiedene Konzentrationen untersucht.Die Geschwindigkeit der zeitlichen Zunahme der Oberflächenspannung für das syndiotaktische PVA war die höchste und diejenige für ataktischen PVA die niedrigste. Die Ergebnisse wurden als Folge der Kristallisation und der Diffusionsprozesse gedeutet. Die Geschwindigkeit wird auf Grund einer zwischenmolekularen Wasserstoffbriickensbildung der syndiotaktischen Sequenzen bei syndiotaktischem PVA an die Oberfläche und mit der leichteren Einordnung der Segmente der isotaktischen und ataktischen PVA-Moleküle erklärt. Dies-beeinflußt die Diffusionsgeschwindigkeit der PVA-Moleküle entsprechend.Man kann einen Faden dadurch spinnen, daß man die an die Oberfläche erzeugte Multischicht herauszupft. Das Filament hat die hohe Orientierung der PVA-Moleküle und ähnliche Eigenschaften wie die im Handel befindlichen PVAFasern.

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With 6 figures and 5 tables     

Mixed films of poly(n-hexyl isocyanate) and poly(vinyl acetate) at the air-water interface

We study interfacial properties of rigid-rod-like poly(n-hexyl isocyanate) (PHIC), flexible poly(vinyl acetate) (PVAc), and mixed films of PHIC and PVAc spread at the air-water interface as a function of the molar fraction of PHIC by surface pressure measurements and fluorescence microscopy. From the plots of the experimental mean area of the mixed polymer films at a constant surface pressure as a function of the molar fraction of PHIC in the mixed films, the binary mixtures of PHIC/PVAc were concluded to be compatible at the air-water interface. This means that the hydrophobic hexyl group of PHIC takes a horizontal orientation to the air-water interface rather than a perpendicular one, leading to PHIC and PVAc having the same interfacial orientation. Compatibility of the binary mixtures of PHIC/PVAc at the air-water interface is also confirmed by their fluorescence microscopic images, since PHIC proves to be inhomogeneous and PVAc is homogeneous with the aid of a fluorescence probe, respectively.     

Two-dimensional self-assembly of linear poly(ethylene oxide)-b-poly(epsilon-caprolactone) copolymers at the air-water interface

The interfacial properties of amphiphilic linear diblock copolymers based on poly(ethylene oxide) and poly(epsilon-caprolactone) (PEO-b-PCL) were studied at the air-water (A/W) interface by surface pressure measurements (isotherms and hysteresis experiments). The resulting Langmuir monolayers were transferred onto mica substrates and the Langmuir-Blodgett (LB) film morphologies were investigated by atomic force microscopy (AFM). All block copolymers had the same PEO segment (Mn = 2670 g/mol) and different PCL chain lengths (Mn = 1270; 2110; 3110 and 4010 g/mol). Isothermal characterization of the block copolymer samples indicated the presence of three distinct phase transitions around 6.5, 10.5, and 13.5 mN/m. The phase transitions at 6.5 and 13.5 mN/m correspond to the dissolution of the PEO segments in the water subphase and crystallization of the PCL blocks above the interface similarly as for the corresponding homopolymers, respectively. The phase transition at 10.5 mN/m was not observed for the homopolymers alone or for their blends and arises from a brush formation of the PEO segments anchored underneath the adsorbed hydrophobic PCL segments. AFM analysis confirmed the presence of PCL crystals in the LB films with unusual hairlike/needlelike architectures significantly different from those obtained for PCL homopolymers.     

Swelling of poly(N-isopropylacrylamide) gels in water-aprotic solvent mixtures

The swelling volume of poly(N-isopropylacrylamide) (PIPAAm) gel in aprotic solvents (acetonitrile (AcN)-, tetrahydrofuran (THF)-, 1,4-dioxane (DO)- and dimethylsulfoxide (DMSO))-water mixtures was measured at 25°C. The gel swollen in water shrank first and then reswelled with addition of the aprotic solvents. At an intermediate mole fraction (XDMSO) range of DMSO-water mixtures, the gel demonstrated a reentrant swelling phenomenon the hydrated gel shrank first on addition of a small amount of solvent, showed a typical wide reentrant transition, and gradually reswelled in the range near pure solvent. On the other hand, the gels in AcN-, THF-, and DO-water mixtures demonstrated a reentrant-convex swelling phenomenon: the gels reswelled after a reentrant phase transition in low Xorg (XAcN, XTHF and XDO), showed a maximum swelling in the intermediate Xorg region, and shrank again gradually in the high Xorg region. Such a swelling behavior of the gel was interpreted by correlating with solution properties of the aqueous aprotic solvent mixtures.The strength of hydrogen bonding around amide groups of the homopolymer was examined in pure solvents (water, THF, and DMSO) and in all proportion of aqueous THF to observe the relation with swelling behavior of gel by spectrum analysis of the amide I and II bands of Fourier Transform Infrared Spectroscopy (FT-IR). The swelling properties of gels in solvents and the aqueous mixtures were well correlated with the peak shifts of amide groups of the homopolymer.     

Dynamic properties of poly(styrene)-poly(ethylene oxide) diblock copolymer films at the air-water interface

The complex dynamic elasticity of monolayers of the diblock copolymer poly(styrene)-poly(ethylene oxide) at the air-water interface in the pancake, quasi-brush, and brush regimes has been studied by means of three experimental techniques--the surface transverse and longitudinal waves and the oscillating barrier method. In the pancake regime the surface viscoelastic properties in the frequency range under investigation (0.01-520 Hz) prove to be indistinguishable from the surface properties of the homopolymer PEO. Transition to the quasi-brush regime is accompanied by rather abrupt changes in both components of the surface viscoelasticity. The surface viscosity in the brush regime exceeds significantly the results calculated from the theory of D. M. A. Buzza et al. (J. Chem. Phys.109, 5008 (1998)), which takes into account the dissipation arising from the flow of solvent through the brush phase. Possible reasons of this discrepancy are discussed.     

Interactions of poly(tert-butyl acrylate)-poly(styrene) diblock copolymers with lipids at the air-water interface

Diblock copolymers with hydrophilic poly(tert-butyl acrylate) (PtBA) and hydrophobic poly(styrene) (PS) blocks were synthesized with a view to use them as a surfactant in tear film for increasing the ocular comfort in dry eye syndrome. Interactions of six PtBA-PS copolymers with four important lipids found in the tear film, namely cholesterol, cholesteryl palmitate, dipalmitoyl phosphatidylcholine, and phosphatidylinositol, were studied at the air-water interface using a Langmuir trough. Thermodynamics of mixing of the copolymers and the lipids in the mixed monolayers was determined by calculating excess free energy of mixing. The diblock copolymers showed repulsive interactions with cholesteol and cholesteryl palmitate, near neutral interactions with dipalmitoyl phosphatidylcholine, and attractive interactions with phosphatidylinositol. The lipids interacted with the PS component of the copolymer. The results indicate that a copolymer with a small hydrophilic group and a big hydrophobic group can be a likely candidate for forming stable interactions with the lipids present in the tear film and hence increase the ocular comfort.     

Adsorption behavior of hydrophobin and hydrophobin/surfactant mixtures at the air-water interface

The adsorption of the surface-active protein hydrophobin, HFBII, and the competitive adsorption of HFBII with the cationic, anionic, and nonionic surfactants hexadecyltrimethylammonium bromide, CTAB, sodium dodecyl sulfate, SDS, and hexaethylene monododecyl ether, C(12)E(6), has been studied using neutron reflectivity, NR. HFBII adsorbs strongly at the air-water interface to form a dense monolayer ～30 ? thick, with a mean area per molecule of ～400 ?(2) and a volume fraction of ～0.7, for concentrations greater than 0.01 g/L, and the adsorption is independent of the solution pH. In competition with the conventional surfactants CTAB, SDS, and C(12)E(6) at pH 7, the HFBII adsorption totally dominates the surface for surfactant concentrations less than the critical micellar concentration, cmc. Above the cmc of the conventional surfactants, HFBII is displaced by the surfactant (CTAB, SDS, or C(12)E(6)). For C(12)E(6) this displacement is only partial, and some HFBII remains at the surface for concentrations greater than the C(12)E(6) cmc. At low pH (pH 3) the patterns of adsorption for HFBII/SDS and HFBII/C(12)E(6) are different. At concentrations just below the surfactant cmc there is now mixed HFBII/surfactant adsorption for both SDS and C(12)E(6). For the HFBII/SDS mixture the structure of the adsorbed layer is more complex in the region immediately below the SDS cmc, resulting from the HFBII/SDS complex formation at the interface.     

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.     

Interfacial behavior of poly(isoprene-b-methyl methacrylate) diblock copolymers and their blends with polystyrene at the air-water interface

The interfacial behavior of poly(isoprene-b-methyl methacrylate) diblock copolymers (PI-b-PMMA), with similar PMMA blocks but differing in the percentage of PI segments, SP19 (5% PI) and SP38 (52% PI), was studied at the air-water interface. The surface pressure-area (pi-A) isotherms, compression-expansion cycles, and relaxation curves were compared with those of the PMMA homopolymer. The short hydrophobic PI block of SP19 does not contribute to the mean molecular area at low surface pressures and yet has a negative contribution (condensing effect) when the surface pressure increases. On the contrary, the long PI block of SP38 contributes considerably to the surface area from low to high surface pressures. The A-t relaxation curves compare well with those of PMMA at low surface pressures (pi = 2 mN.m-1), but not at intermediate and high pressures (pi = 10, 30 mN.m-1), where a clear dependence on the length of the PI block was observed. The quantitative analysis of the relaxation curves at high pressures shows both a fast and slow component, attributed mostly to the local and middle-to-long-range reorganization of PMMA chains, respectively. PI-b-PMMA diblocks and PMMA were further blended with PS. The PS and PMMA are immiscible at the air-water interface. The addition of PS does not change the pi-A isotherm of PMMA, but the copolymers blended with PS form films that are more condensed at low pressures. The Langmuir-Blodgett (LB) films transferred onto mica substrates were analyzed by atomic force microscopy (AFM). The LB films of single diblocks are uniform, while those of PI-b-PMMA and PMMA blended with PS show aggregates with variable patterns.     

Comparative studies of nontoxic and toxic amyloids interacting with membrane models at the air-water interface

Many in vitro studies have pointed out the interaction between amyloids and membranes, and their potential involvement in amyloid toxicity. In a previous study, we generated a yeast toxic mutant (M8) of the harmless model amyloid protein HET-s((218-289)). In this study, we compared the self-assembling process of the nontoxic wild-type (WT) and toxic (M8) protein at the air-water interface and in interaction with various phospholipid monolayers (DOPE, DOPC, DOPI, DOPS and DOPG). We first demonstrate using ellipsometry measurements and polarization-modulated infrared reflection absorption spectroscopy (PMIRRAS) that the air-water interface promotes and modifies the assembly of WT since an amyloid-like film was instantaneously formed at the interface with an antiparallel β-sheet structuration instead of the parallel β-sheet commonly observed for amyloid fibers generated in solution. The toxic mutant (M8) behaves in a similar manner at the air-water interface or in bulk, with a fast self-assembling and an antiparallel β-sheet organization. The transmission electron microscopy (TEM) images established the fibrillous morphology of the protein films formed at the air-water interface. Second, we demonstrate for the first time that the main driving force between this particular fungus amyloid and membrane interaction is based on electrostatic interactions with negatively charged phospholipids (DOPG, DOPI, DOPS). Interestingly, the toxic mutant (M8) clearly induces perturbations of the negatively charged phospholipid monolayers, leading to a massive surface aggregation, whereas the nontoxic (WT) exhibits a slight effect on the membrane models. This study allows concluding that the toxicity of the M8 mutant could be due to its high propensity to interact with membranes.     

Two-dimensional center-of-mass diffusion of lipid-tethered poly(2-methyl-2-oxazoline) at the air-water interface studied at the single molecule level

The two-dimensional (2D) center-of-mass diffusion, D, of end-tethered poly(2-methyl-2-oxazoline) (PMOx) lipopolymer chains was studied in a Langmuir monolayer at the air-water interface using wide-field single molecule fluorescence microscopy. In this case, tethering and stabilization of hydrophilic PMOx chains at the air-water interface is accomplished via end-tethering to lipid molecules forming a hydrophobic anchor. To explore the influence of molecular weight, M n, and surface concentration, c s, on lateral mobility, two different PMOx chain lengths of n = 30 and 50 ( n, number of monomer units) were analyzed over a wide range of c s. Using multiparticle tracking analysis of TRITC-labeled PMOx lipopolymers, we found two regimes of lipopolymer lateral mobility. At low c s, D is independent of surface concentration but increases with decreasing n. Here diffusion properties are well described by the Rouse model. In contrast, at more elevated c s, the data do not follow Rouse scaling but are in good agreement with a free area-area model of diffusion. The current study provides for the first time experimental insight into the 2D center-of-mass diffusion of end-tethered polymers at the air-water interface. The obtained results will be of importance for the understanding of diffusion processes in polymer-tethered phospholipid bilayers mimicking biomembranes at low and high tethering concentrations.     

Adsorption of nonionic mixtures at the air-water interface: effects of temperature and electrolyte

Specular neutron reflection has been used to investigate the effects of temperature and added electrolyte on the adsorption of nonionic surfactants and nonionic surfactant mixtures at the air-water interface. For the alkyl poly-oxyethylene oxide nonionic surfactants, C(n)EO(m), the adsorption at the air-water interface is independent of temperature for surfactants with shorter ethylene oxide groups, whereas there is an increasing tendency for increased adsorption with temperature for surfactants with longer ethylene oxide groups. The addition of "salting in" (sodium thiocyanate, NaSCN) and "salting out" (sodium chloride, NaCl, sodium sulphate, Na2SO4) electrolyte results in reduced and enhanced adsorption, respectively, for C12EO8, whereas both types of electrolyte result in enhanced adsorption for C12EO12. The addition of electrolyte does not substantially alter the temperature dependence of the adsorption of the pure monolayers. For the nonionic mixtures of C12EO3/C12EO8 increasing temperature results in a surface richer in the least surface-active component, C12EO8. For the same nonionic mixture, the addition of "salting in" and "salting out" electrolyte results in an reduced and increased adsorption, respectively. The addition of "salting in" electrolyte results in a surface more rich in C12EO3, whereas for the addition of both "salting in" and "salting out" electrolyte the surface composition is essentially unaltered.     

Organization and properties of a conjugated poly(heteroarylene methines) at the air-water interface and in the Langmuir-Blodgett films

A poly(heteroarylene methine) derivative, poly[(2,5-thiophenediyl) (p-n-methyl, n-octylaminobenzylidene) (2,5-thiophenequinodimethaneiyl)] (PTABQ), has been synthesized and spread at the air-water interface. The influences of three kinds of solutions on PTABQ monolayer behavior at the air-water interface have been investigated via the measurements of the pi-A isotherm and film stability. The results show that all three kinds of PTABQ solutions are apt to form the stable and transferable monolayer film organized with the plane of its pi-system nearly perpendicular to the air-water interface. Moreover, the monolayer-forming ability of PTABQ can be improved by introducing a water-soluble amphiphilie as an extractable spread-aiding component, which is further proved by the AFM images and FTIR spectra of the transferred films. UV-visible absorption spectra indicate that the well-ordered layer-by-layer structure is successfully controlled in the LB films. The optical bandgap of PTABQ is reduced for the ordered arrangement of its molecules in LB films. The intrinsic electrical conductivity of PTABQ LB films is 8.1 x 10(-8) S/cm and the conductivity of iodine-doped films is 5.7 x 10(-7) S/cm.     

Surface dilatational moduli of poly(vinyl acetate) (PVAc) and PVAc-poly(n-hexyl isocyanate) (PHIC) blend films at the air-water interface

Surface dilatational moduli of poly(vinyl acetate) (PVAc) film and blend films of PVAc and poly(n-hexyl isocyanate) (PHIC) were measured at the air-water interface. PVAc formed a film that was looser and also more stable against strain than the PHIC film. The apparent surface dilatational modulus and surface pressure of the blend films were superimposed on the lower concentration of PVAc, irrespective of the composition of PVAc. However, the additivity rule was not applicable to the apparent surface dilatational modulus and surface pressure. The scaling exponents of the apparent surface dilatational modulus against the added surface concentration decreased with an increase in the proportion of PVAc, suggesting that blend films gradually change from glass material to expanded films.     

Interaction of polymer and surfactant at the air-water interface: poly(2-(dimethylamino)ethyl methacrylate) and sodium dodecyl sulfate

The interactions between the weak polyelectrolyte, poly(2-(dimethylamino) ethyl methacrylate) or PDMAEMA, and the anionic surfactant sodium dodecyl sulfate (SDS) at the air-water interface have been investigated at pH = 3 and 9 using a combination of neutron reflectivity and surface tension measurements. By using deuterated PDMAEMA in combination with h-SDS and d-SDS, we have been able to directly determine the distribution of both the polymer and the surfactant at the air-water interface. At pH = 3, the polyelectrolyte is positively charged while at pH = 9 it is essentially uncharged. The enhancement in the adsorption of SDS at low coverage suggests that surface active polymer surfactant complexes are forming and adsorbing at the interface. This leads to close to monolayer adsorption of SDS, suggesting that it is surfactant monomers that are complexing with polymers that are in extended conformations parallel to the surface. As the concentration of SDS in the mixtures changes so does the surfactant content of the complexes, which affects the surface activity and hence the coverage of the complexes. Multilayer structures are formed at SDS concentrations of 0.1 and 1 mM, for pH = 3 and 9, respectively.     

Surface chemistry studies of (CdSe)ZnS quantum dots at the air-water interface

Trioctylphosphine oxide- (TOPO-) capped (CdSe)ZnS quantum dots (QDs) were prepared through a stepwise synthesis. The surface chemistry behavior of the QDs at the air-water interface was carefully examined by various physical measurements. The surface pressure-area isotherm of the Langmuir film of the QDs gave an average diameter of 4.4 nm, which matched very well with the value determined by transmission electron microscopy (TEM) measurements if the thickness of the TOPO cap was counted. The stability of the Langmuir film of the QDs was tested by two different methods, compression/decompression cycling and kinetic measurements, both of which indicated that TOPO-capped (CdSe)ZnS QDs can form stable Langmuir films at the air-water interface. Epifluorescence microscopy revealed the two-dimensional aggregation of the QDs in Langmuir films during the early stage of the compression process. However, at high surface pressures, the Langmuir film of QDs was more homogeneous and was capable of being deposited on a hydrophobic quartz slide by the Langmuir-Blodgett (LB) film technique. Photoluminescence (PL) spectroscopy was utilized to characterize the LB films. The PL intensity of the LB film of QDs at the first emission maximum was found to increase linearly with increasing number of layers deposited onto the hydrophobic quartz slide, which implied a homogeneous deposition of the Langmuir film of QDs at surface pressures greater than 20 mN.m(-1).     

Interfacial characteristics of food emulsifiers (proteins and lipids) at the air-water interface

Factors affecting the interfacial characteristics (structure, stability, interfacial rheology, molecular diffusion, and rate of film formation) of food emulsifiers (polar lipids and proteins) at the air-aqueous phase interface are reviewed. The effect of interfacial and aqueous phase (water, and aqueous solutions of ethanol, glycerol, sugars, electrolytes, and pH) compositions have been analyzed as variables. Many measurement methods—such as tensiometry (Wilhelmy plate and pendant drop methods), and Langmuir- and Wilhelmy-type film balances—have been used in the experiments. The effect of the interfacial, aqueous phase composition, and operational conditions (surface density, surface pressure, and temperature) of food emulsifiers (lipids and proteins) at the air-aqueous phase interface are discussed.     

Thermoresponsive poly(N-isopropylacrylamide) nanogels/poly(acrylamide) nanostructured hydrogels

Here we report the preparation and characterization of nanostructured thermo-responsive poly(acrylamide) (PAM)-based hydrogels. The addition of slightly crosslinked poly(N-isopropylacrylamide) (PNIPA) nanogels to AM reactive aqueous solution produces nanostructured hydrogels that exhibit a volume phase transition temperature (T_VPT). Their swelling kinetics, T_VPT's and mechanical properties at the equilibrium-swollen state (H_eq) are investigated as a function of the concentration of PNIPA nanogels in the nanostructured hydrogels. Nanostructured hydrogels with PNIPA nanogels/AM mass ratios of 20/80 and above exhibit higher H_eq and longer time to reach the equilibrium swelling than those of the conventional PAM hydrogels. However, the PNIPA nanogels possess thermo-responsive character missing in conventional PAM hydrogels. The T_VPT of nanostructured hydrogels depends on PNIPA nanogel content but their elastic and Young moduli are larger than those of conventional hydrogels at similar swelling ratios. Swelling kinetics, T_VPT, and mechanical properties are explained in terms of the controlled in-homogeneities introduced by the PNIPA nanogels during the polymerization.     

Phosvitin-calcium aggregation and organization at the air-water interface

Phosvitin, an egg yolk protein constituted by 50% of phosphorylated serines, presents good emulsifying properties whereas its interfacial properties are not yet clearly elucidated and remain object of discussion. Phosvitin has a high charge density and naturally forms aggregates through phosphocalcic bridges in egg yolk. This high charge density, doubled by this capacity to aggregate, limits the adsorption of the protein at the air-water interface. In this work, we investigated the aggregation impact by calcium ions on the organization of the phosvitin interfacial film using the atomic force microscopy. Phosvitin interfacial films without calcium ions are compared to phosvitin interfacial films formed in the presence of calcium ions in the subphase. We demonstrated that phosvitin is able to anchor at air-water interfaces in spite of its numerous negative charges. In the compression isotherm a transition was observed just before 28 mN/m signifying a possible modification of the interfacial film structure or organization. Calcium ions induce a reorganization towards a greater compaction of the phosvitin interfacial film even at low surface pressure. In conclusion we suggest that, in diluted regime, phosvitin molecules could adsorb by their two hydrophobic extremities exhibiting loops in the aqueous phase, whereas in concentred regime (high interfacial concentration) it would be adsorbed at the interface by only one extremity (brush model).