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Smart Air-Water Interfaces with Arylazopyrazole Surfactants and Their Role in Photoresponsive Aqueous Foam.

ABSTRACT: A new light-switchable azo-surfactant arylazopyrazole tetraethylene glycol carboxylic acid (AAP-E4) was used as a molecular building block to functionalize macroscopic foams. AAP-E4 was studied in the bulk solution with UV/vis spectroscopy and at the interface with sum-frequency generation (SFG) as well as tensiometry. Additional foaming experiments were performed with a dynamic foam analyzer to study the role of AAP-E4 surfactants at the ubiquitous air-water interface as well as within macroscopic foam. In the bulk, it is possible to switch the AAP-E4 surfactant reversibly from trans to cis configurations and vice versa using 380 nm UV and 520 nm green light, respectively. At the interface, we demonstrate the excellent switching ability of AAP-E4 surfactants and a substantial modification of the surface tension. In addition, we show that the response of the interface is strongly influenced by lateral electrostatic interactions, which can be tuned by the charging state of AAP-E4. Consequently, the electrostatic disjoining pressure and thus the foam stability are highly dependent on the bulk pH and the charging state of the interface. For that reason, we have studied both the surface net charge (SFG) and the surface excess (tensiometry) as important parameters that determine foam stability in this system and show that neutral pH conditions lead to the optimal compromise between switching ability, surface excess, and surface charging. Measurements on the foam stability demonstrated that foams under irradiation with green light are more stable than foams irradiated with UV light.

SUBMITTER: Schnurbus M

PROVIDER: S-EPMC5981290 | biostudies-literature | 2018 May

REPOSITORIES: biostudies-literature

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Smart Air-Water Interfaces with Arylazopyrazole Surfactants and Their Role in Photoresponsive Aqueous Foam.

Schnurbus Marco M Stricker Lucas L Ravoo Bart Jan BJ Braunschweig Björn B

Langmuir : the ACS journal of surfaces and colloids 20180515 21

A new light-switchable azo-surfactant arylazopyrazole tetraethylene glycol carboxylic acid (AAP-E4) was used as a molecular building block to functionalize macroscopic foams. AAP-E4 was studied in the bulk solution with UV/vis spectroscopy and at the interface with sum-frequency generation (SFG) as well as tensiometry. Additional foaming experiments were performed with a dynamic foam analyzer to study the role of AAP-E4 surfactants at the ubiquitous air-water int ...[more]

PMID: 29718669

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Project description:Air/water interfaces were modified by oppositely charged poly(sodium 4-styrenesulfonate) (NaPSS) and hexadecyltrimethylammonium bromide (CTAB) polyelectrolyte/surfactant mixtures and were studied on a molecular level with vibrational sum-frequency generation (SFG), tensiometry, surface dilatational rheology and ellipsometry. In order to deduce structure property relations, our results on the interfacial molecular structure and lateral interactions of PSS-/CTA+ complexes were compared to the stability and structure of macroscopic foam as well as to bulk properties. For that, the CTAB concentration was fixed to 0.1 mM, while the NaPSS concentration was varied. At NaPSS monomer concentrations <0.1 mM, PSS-/CTA+ complexes start to replace free CTA+ surfactants at the interface and thus reduce the interfacial electric field in the process. This causes the O-H bands from interfacial H2O molecules in our SFG spectra to decrease substantially, which reach a local minimum in intensity close to equimolar concentrations. Once electrostatic repulsion is fully screened at the interface, hydrophobic PSS-/CTA+ complexes dominate and tend to aggregate at the interface and in the bulk solution. As a consequence, adsorbate layers with the highest film thickness, surface pressure, and dilatational elasticity are formed. These surface layers provide much higher stabilities and foamabilities of polyhedral macroscopic foams. Mixtures around this concentration show precipitation after a few days, while their surfaces to air are in a local equilibrium state. Concentrations >0.1 mM result in a significant decrease in surface pressure and a complete loss in foamability. However, SFG and surface dilatational rheology provide strong evidence for the existence of PSS-/CTA+ complexes at the interface. At polyelectrolyte concentrations >10 mM, air-water interfaces are dominated by an excess of free PSS- polyelectrolytes and small amounts of PSS-/CTA+ complexes which, however, provide higher foam stabilities compared to CTAB free foams. The foam structure undergoes a transition from wet to polyhedral foams during the collapse.

Dataset Information

Smart Air-Water Interfaces with Arylazopyrazole Surfactants and Their Role in Photoresponsive Aqueous Foam.

Publications

Smart Air-Water Interfaces with Arylazopyrazole Surfactants and Their Role in Photoresponsive Aqueous Foam.

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