Photoresponsive arylazopyrazole surfactant/PDADMAC mixtures: reversible control of bulk and interfacial properties.

In many applications of polyelectrolyte/surfactant (P/S) mixtures, it is difficult to fine-tune them after mixing the components without changing the sample composition, e.g. pH or the ionic strength. Here we report on a new approach where we use photoswitchable surfactants to enable drastic changes in both the bulk and interfacial properties. Poly(diallyldimethylammonium chloride) (PDADMAC) mixtures with three alkyl-arylazopyrazole butyl sulfonates (CnAAP) with -H, -butyl and -octyl tails are applied and E/Z photoisomerization of the surfactants is used to cause substantially different hydrophobic interactions between the surfactants and PDADMAC. These remotely controlled changes affect significantly the P/S binding and allows for tuning both the bulk and interfacial properties of PDADMAC/CnAAP mixtures through light irradiation. For that, we have fixed the surfactant concentrations at values where they exhibit pronounced surface tension changes upon E/Z photoisomerization with 365 nm UV light (Z) and 520 nm green (E) light and have varied the PDADMAC concentration. The electrophoretic mobility can be largely tuned by photoisomerisation of CnAAP surfactants and P/S aggregates, which can even exhibit a charge reversal from negative to positive values or vice versa. In addition, low colloidal stability at equimolar concentrations of PDADMAC with CnAAP surfactants in the E configuration lead to the formation of large aggregates in the bulk which can be broken up by irradiation with UV light when the surfactant's alkyl chain is short enough (C0AAP). Vibrational sum-frequency generation (SFG) spectroscopy reveals changes at the interface similar to the bulk, where the charging state at air-water interfaces can be modified with light irradiation. Using SFG spectroscopy, we interrogated the O-H stretching modes of interfacial H2O and provide qualitative information on surface charging that is complemented by neutron reflectometry, from which we resolved the surface excesses of PDADMAC and CnAAP at the air-water interface, independently.

Charge Regulation at the Nanoscale as Evidenced from Light-Responsive Nanoemulsions.

Emulsions are indispensable in everyday life, and the demand for emulsions' diversity and control of properties is therefore substantial. As emulsions possess a high internal surface area, an understanding of the oil/water (o/w) interfaces at the molecular level is fundamental but often impaired by experimental limitations to probe emulsion interfaces in situ. Here, we have used light-responsive surfactants (butyl-AAP) that can photoisomerize between E and Z isomers by visible and UV light irradiation to tune the emulsion interfaces. This causes massive changes in the interface tension at the extended o/w interfaces in macroemulsions and a drastic shift in the surfactants' critical micelle concentration, which we show can be used to control both the stability and phase separation. Strikingly different from macroemulsions are nanoemulsions (RH ∼90 nm) as these are not susceptible to E/Z photoisomerization of the surfactants in terms of changes in their droplet size or ζ-potential. However, in situ second-harmonic scattering and pulsed-field gradient nuclear magnetic resonance (NMR) experiments show dramatic and reversible changes in the surface excess of surfactants at the nanoscopic interfaces. The apparent differences in ζ-potentials and surface excess provide evidence for a fixed charge to particle size ratio and the need for counterion condensation to renormalize the particle charge to a critical charge, which is markedly different compared to the behavior of very large particles in macroemulsions. Thus, our findings may have broader implications as the electrostatic stabilization of nanoparticles requires much lower surfactant concentrations, allowing for a more sustainable use of surfactants.

Tailored Monolayers of N-Heterocyclic Carbenes by Kinetic Control.

Despite the substantial success of N-heterocyclic carbenes (NHCs) as stable and versatile surface modification ligands, their use in nanoscale applications beyond chemistry is still hampered by the failure to control the carbene binding mode, which complicates the fabrication of monolayers with the desired physicochemical properties. Here, we applied vibrational sum-frequency generation spectroscopy to conduct a pseudokinetic surface analysis of NHC monolayers on Au thin films under ambient conditions. We observe for two frequently used carbene structures that their binding mode is highly dynamic and changes with the adsorption time. In addition, we demonstrate that this transition can be accelerated or decelerated to adjust the binding mode of NHCs, which allows fabrication of tailored monolayers of NHCs simply by kinetic control.

Photo-Responsive Control of Adsorption and Structure Formation at the Air-Water Interface with Arylazopyrazoles.

Smart interfaces that are responsive to external triggers such as light are of great interest for the development of responsive or adaptive materials and interfaces. Using alkyl-arylazopyrazole butyl sulfonate surfactants (alkyl-AAP) that can undergo E/Z photoisomerization when irradiated with green (E) and UV (Z) lights, we demonstrate through a combination of experiments and computer simulations that there can be surprisingly large changes in surface tension and in the molecular structure and order at air-water interfaces. Surface tensiometry, vibrational sum-frequency generation (SFG) spectroscopy, and neutron reflectometry (NR) are applied to the study of custom-synthesized AAP surfactants with octyl- and H-terminal groups at air-water interfaces as a function of their bulk concentration and E/Z configuration. Upon photoswitching, a drastic influence of the alkyl chain on both the surface activity and the responsiveness of interfacial surfactants is revealed from changes in the surface tension, γ, where the largest changes in γ are observed for octyl-AAP (Δγ ∼ 23 mN/m) in contrast to H-AAP with Δγ < 10 mN/m. Results from vibrational SFG spectroscopy and NR show that the interfacial composition and the molecular order of the surfactants drastically change with E/Z photoisomerization and surface coverage. Indeed, from analysis of the S-O (head group) and C-H vibrational bands (hydrophobic tail), a qualitative analysis of orientational and structural changes of interfacial AAP surfactants is provided. The experiments are complemented by resolution of thermodynamic parameters such as equilibrium constants from ultra-coarse-grained simulations, which also capture details like island formation and interaction parameters of interfacial molecules. Here, the interparticle interaction ("stickiness") and the interaction with the surface are adjusted, closely reflecting experimental conditions.

Influence of interfacial water and cations on the oxidation of CO at the platinum/ionic liquid interface.

CO oxidation is fundamental to the development of new catalyst materials for fuel cells and key for complete oxidation of small alcohols like methanol or ethanol on Pt catalysts. So far, room-temperature ionic liquids (RTIL) have been used to modify the selectivity and activity in electrocatalysis. In order to understand the mechanism of CO oxidation in RTIL in more detail we have investigated this reaction at the Pt(111)/1-butyl-3-methylimidazolium trifluorosulfonylimide [BMIM][NTf2] electrode/electrolyte interface as a function of H2O concentration and electrode potential with in situ sum-frequency generation (SFG) spectroscopy and infrared absorption spectroscopy (IRAS). Using SFG spectroscopy, we address the changes of linearly bonded CO molecules on Pt(111), while we monitor the changes in the bulk electrolyte with IRAS through vibrational bands from H2O, CO2 and CO. The presence of water in [BMIM][NTf2] shifts the onset potential for CO oxidation by more than 200 mV when the water concentration is increased from 0.01 to 1.5 M, which we relate to the incorporation and the availability of water at the electrode/electrolyte interface. The nature of the RTIL cation has also a large effect on the surface excess of H2O since RTILs like [BMMIM][NTf2] and [BMPyrr][NTf2] which are prone to form closed-packed structures, can block the incorporation of water and lead to more sluggish CO oxidation with larger overpotentials and oxidation in a much wider potential range for which we provide evidence by additional SFG measurements. These results clearly show that the choice of the RTIL is important for CO oxidation on Pt(111) electrode surfaces - an observation that is likely highly relevant also to other catalysts and catalytic reactions that require the presence of interfacial water.

Dynamic molecular switches with hysteretic negative differential conductance emulating synaptic behaviour.

To realize molecular-scale electrical operations beyond the von Neumann bottleneck, new types of multifunctional switches are needed that mimic self-learning or neuromorphic computing by dynamically toggling between multiple operations that depend on their past. Here, we report a molecule that switches from high to low conductance states with massive negative memristive behaviour that depends on the drive speed and number of past switching events, with all the measurements fully modelled using atomistic and analytical models. This dynamic molecular switch emulates synaptic behavior and Pavlovian learning, all within a 2.4-nm-thick layer that is three orders of magnitude thinner than a neuronal synapse. The dynamic molecular switch provides all the fundamental logic gates necessary for deep learning because of its time-domain and voltage-dependent plasticity. The synapse-mimicking multifunctional dynamic molecular switch represents an adaptable molecular-scale hardware operable in solid-state devices, and opens a pathway to simplify dynamic complex electrical operations encoded within a single ultracompact component.

Surface Properties of Saponin-Chitosan Mixtures.

The surface properties of saponin and saponin-chitosan mixtures were analysed as a function of their bulk mixing ratio using vibrational sum-frequency generation (SFG), surface tensiometry and dilational rheology measurements. Our experiments show that saponin-chitosan mixtures present some remarkable properties, such as a strong amphiphilicity of the saponin and high dilational viscoelasticity. We believe this points to the presence of chitosan in the adsorption layer, despite its complete lack of surface activity. We explain this phenomenon by electrostatic interactions between the saponin as an anionic surfactant and chitosan as a polycation, leading to surface-active saponin-chitosan complexes and aggregates. Analysing the SFG intensity of the O-H stretching bands from interfacial water molecules, we found that in the case of pH 3.4 for a mixture consisting of 0.1 g/L saponin and 0.001 g/L chitosan, the adsorption layer was electrically neutral. This conclusion from SFG spectra is corroborated by results from surface tensiometry showing a significant reduction in surface tension and effects on the dilational surface elasticity strictly at saponin/chitosan ratios, where SFG spectra indicate zero net charge at the air-water interface.

Adsorption of CTAB on Sapphire-c at High pH: Surface and Zeta Potential Measurements Combined with Sum-Frequency and Second-Harmonic Generation.

The adsorption of cetyltrimethylammonium bromide (CTA+Br-) on sapphire-c surfaces was studied at pH 10 below the surfactants' critical micelle concentration. The evolution of interfacial potentials as a function of CTAB concentration was characterized by surface and zeta potential measurements and complemented by molecular dynamic (MD) simulations as well as by second-harmonic (SHG) and vibrational sum-frequency generation (SFG) spectroscopy. The changes in interfacial potentials suggest that the negative interfacial charge due to deprotonated surface aluminols groups is neutralized and can be even overcompensated by the presence of CTA+ cations at the interface. However, SFG intensities from strongly hydrogen-bonded interfacial water molecules as well as SHG intensities decrease with both increasing CTAB concentration and the magnitude of the surface potential. They do not suggest a charge reversal at the interface, while the change in zeta potential is actually consistent with an apparent charge inversion. This can be qualitatively explained by results from MD simulation, which reveal adsorbed CTA+ cations outside a first strongly bound hydration layer of water molecules, where they can locally distort the structural order and replace some of the interfacial water molecules adjacent to the first layer. This is proposed to be the origin for the significant loss in SFG and SHG intensities with increasing CTAB concentration. Moreover, we propose that CTA+ can act as a counterion and enhance the occurrence of deprotonated surface aluminols that is consistent with the decrease in surface potential.

Dynamic Wetting of Photoresponsive Arylazopyrazole Monolayers is Controlled by the Molecular Kinetics of the Monolayer.

Smart surfaces that can change their wettability on demand are interesting for applications such as self-cleaning surfaces or lab-on-a-chip devices. We have synthesized arylazopyrazole (AAP) phosphonic acids as a new class of photoswitchable molecules for functionalization of aluminum oxide surfaces. AAP monolayers were deposited on α-Al2O3(0001) and showed reversible E/Z photoswitching that can trigger contact angle changes of up to ∼10°. We monitored these changes on the macroscopic level by recording the contact angle while the monolayer was switched in situ. On the molecular level, time-dependent vibrational sum-frequency generation (SFG) spectroscopy provided information on the kinetic changes within the AAP monolayer and the characteristic times for E/Z switching. In addition, vibrational SFG at different relative humidity indicates that the thermal stability of the Z configuration is largely influenced by the presence of water which can stabilize the Z state and hinder E → Z switching of the AAP monolayer when it is wetted with H2O. Having established the switching times on the molecular scale, we additionally measured the dynamic contact angle and show that the time scales of the substrate and droplet dynamics can be extracted individually. For that, we report on a relaxation model that is solved analytically and is verified via a comparison with simulations of a Lennard-Jones system and with experimental data. The slower E to Z switching in the presence of the droplet as compared to the vapor phase is rationalized in terms of specific interactions of water with the exposed AAP moieties.

Responsive Material and Interfacial Properties through Remote Control of Polyelectrolyte-Surfactant Mixtures.

Polyelectrolyte/surfactant (P/S) mixtures find many applications but are static in nature and cannot be reversibly reconfigured through the application of external stimuli. Using a new type of photoswitchable surfactants, we use light to trigger property changes in mixtures of an anionic polyelectrolyte with a cationic photoswitch such as electrophoretic mobilities, particle size, as well as their interfacial structure and their ability to stabilize aqueous foam. For that, we show that prevailing hydrophobic intermolecular interactions can be remotely controlled between poly(sodium styrene sulfonate) (PSS) and arylazopyrazole tetraethylammonium bromide (AAP-TB). Shifting the chemical potential for P/S binding with E/Z photoisomerization of the surfactants can reversibly disintegrate even large aggregates (>4 µm) and is accompanied by a substantial change in the net charging state of PSS/AAP-TB complexes, e.g., from negative to positive excess charges upon light irradiation. In addition to the drastic changes in the bulk solution, also at air-water interfaces, the interfacial stoichiometry and structure change drastically on the molecular level with E/Z photoisomerization, which can also drive the stability of aqueous foam on a macroscopic level.

pH effects on the molecular structure and charging state of ß-Escin biosurfactants at the air-water interface.

Saponins like ß-escin exhibit an unusually high surface activity paired with a remarkable surface rheology which makes them as biosurfactants highly interesting for applications in soft matter colloids and at interfaces. We have applied vibrational sum-frequency generation (SFG) to study ß-escin adsorption layers at the air-water interface as a function of electrolyte pH and compare the results from SFG spectroscopy to complementary experiments that have addressed the surface tension and the surface dilational rheology. SFG spectra of ß-escin modified air-water interfaces demonstrate that the SFG intensity of OH stretching vibrations from interfacial water molecules is a function of pH and dramatically increases when the pH is increased from acidic to basic conditions and reaches a plateau at a solution pH of > 6. These changes are attributable to the interfacial charging state and to the deprotonation of the carboxylic acid group of ß-escin. Thus, the change in OH intensity provides qualitative information on the degree of protonation of this group at the air-water interface. At pH < 4 the air-water interface is dominated by the charge neutral form of ß-escin, while at pH > 6 its carboxylic acid group is fully deprotonated and, consequently, the interface is highly charged. These observations are corroborated by the change in equilibrium surface tension which is qualitatively similar to the change in OH intensity as seen in the SFG spectra. Further, once the surface layer is charge neutral, the surface elasticity drastically increases. This can be attributed to a change in prevailing intermolecular interactions that change from dominating repulsive electrostatic interactions at high pH, to dominating attractive interactions, such as hydrophobic and dispersive interactions, as well as, hydrogen bonding at low pH values. In addition to the clear changes in OH intensity from interfacial H2O, the SFG spectra exhibit drastic changes in the CH bands from interfacial ß-escin which we relate to differences in the net molecular orientation. This orientation change is driven by tighter packing of ß-escin adsorption layers when the ß-escin moiety is in its charge neutral form (pH < 4).

Nanoscale Effects on the Surfactant Adsorption and Interface Charging in Hexadecane/Water Emulsions.

Nanoscale properties at interfaces play a key role in the colloidal stability of emulsions and other soft matter materials where physical properties need to be controlled from the nano to macroscopically visible length scales. Our molecular level understanding of oil-water interfaces arises mostly from results at extended interfaces and the common view that emulsions are stabilized by a large number of surfactant molecules at the droplet's interface which, however, has been recently challenged. In this work, we show that the particle size and the curvature of oil droplets at the nanoscale is of great importance for the interface adsorption of dodecyl sulfate surfactants and possible counterion condensation at the charged hexadecane-water interface. Using second-harmonic scattering, we have studied the surface charge of oil droplets in nanoemulsions where we systematically varied the particle size R between 80 and 270 nm and demonstrate that the surface charge density σ changes drastically with size: For sizes >200 nm, σ is similar to what can be expected at flat extended interfaces, while σ is dramatically reduced by almost an order of magnitude when the particle size of the oil droplet is 80 nm. Using a theoretical approach that considers counterion condensation, we quantify the nanoscale effects on the change in surface charge with particle size and find excellent agreement with our experimental result. Modeling of the experimental results also implies that the charge per particle remains constant and depends on a critical balance of surfactant adsorption and ion condensation.

Memory effects in polymer brushes showing co-nonsolvency effects.

Densely packed polymer chains grafted to a substrate, especially polymer brushes, have been studied intensively. Of special interest are systems that react to changes in external conditions or"remember" previous conditions. With this focus, we explore the properties of PNiPAAm brushes and relate published work to own results. The co-nonsolvency effect leads to a collapse of a PNiPAAm brush for a certain mixing ratio of ethanol in water. This also influences the wetting behavior of PNiPAAm brushes. We show that through prewetting of a brush with different liquids (water and ethanol), the contact angle of subsequent water drops changes significantly. To explain this change, the swelling of the brush was investigated with spectroscopic ellipsometry and the orientation of the molecules at the surface with sum-frequency generation (SFG). Only little change in swelling was found. The SFG measurements reveal in the ethanol prewetted case a well ordered hydrophobic methyl layer at the interface, which is consistent with the contact angle measurement.

Light-induced switching of polymer-surfactant interactions enables controlled polymer thermoresponsive behaviour.

Hydroxypropyl cellulose (HPC) and arylazopyrazole (AAP) mixtures can be remotely controlled by light and temperature. We show that the hydrophobic interactions between HPC polymers with AAP surfactants can be drastically changed by changing the surfactants configuration through E/Z photo-isomerization. E-AAP interacts strongly with HPC which causes a dramatic increase of the critical temperature Tc of the polymers' phase transition and a loss of the coil-to-globule transition, while the hydrophobic interactions of HPC with Z-AAP are drastically reduced. As a result, E/Z photo-isomerization of AAP in mixtures with HPC offers remote control of the polymers phase transition, size and solution viscosity in an unprecedented way, and allows for new directions in colloid science.

A cyclodextrin surfactant for stable emulsions with an accessible cavity for host-guest complexation.

Although cyclodextrins (CDs) have been used as additives to small molecule surfactants, there are only a few examples of this cyclic oligosaccharide being used as a surfactant template. Herein, we present a novel ionic ß-CD derivative that shows significant surface activity and stabilizes oil-in-water emulsions prepared with hexadecane as a model oil. The macrocyclic surfactant strongly reduces the oil-water surface tension with increasing concentration and shows a critical micelle concentration (CMC) around 5 mM. We demonstrate the stability of the oil-in-water emulsions and verify the possibility to address the emulsion droplet surface using molecular recognition of the ß-CD cavity at the oil-water interface.

Potential-Induced Adsorption and Structuring of Water at the Pt(111) Electrode Surface in Contact with an Ionic Liquid.

Water adsorption is important in many fields from surface electrochemistry to electrocatalysis, where molecular-level information is much needed in order to gain a detailed understanding of the role of interfacial water. Here we report on water at Pt(111) surfaces in contact with an [EIMIM][BF4] ionic liquid, which was spectroscopically resolved by using in situ sum-frequency generation (SFG). O-H modes are used to study water adsorption and water structure as a function of electrode potential, while the analysis of C-H modes is used to infer orientational changes of [EMIM] cations at the interface. Different from the bulk where free water molecules are found, SFG spectra provide evidence that an interfacial layer with an extended network of hydrogen-bonded water molecules exists and grows with increasing absolute potential which is used to identify the potential of zero charge at +0.1 V SHE, where a pronounced minimum in O-H intensity is found.

Photo-Switchable Surfactants for Responsive Air-Water Interfaces: Azo versus Arylazopyrazole Amphiphiles.

Arylazopyrazoles (AAPs) as substitutes for azobenzene derivatives have gained considerable attention due to their superior properties offering E/Z photoisomerization with high yield. In order to compare and quantify their performance, azobenzene triethylammonium (Azo-TB) and arylazopyrazole triethylammonium (AAP-TB) bromides were synthesized and characterized in the bulk (water) using NMR and UV/Vis spectroscopy. At the air-water interface, complementary information from vibrational sum-frequency generation (SFG) spectroscopy and neutron reflectometry (NR) has revealed the effects of E/Z isomerization in great detail. In bulk water the photostationary states of >89% for E/Z switching in both directions were very similar for the surfactants, while their interfacial behavior was substantially different. In particular, the surface excess Γ of the surfactants changed drastically between E and Z isomers for AAP-TB (maximum change of Γ: 2.15 µmol/m2); for Azo-TB, the change was only moderate (maximum change of Γ: 1.02 µmol/m2). Analysis of SFG spectra revealed that strong nonresonant contributions that heterodyned the resonant vibrational bands were proportional to Γ, enabling the aromatic C-H band to be interpreted as an indicator for changes in the interfacial molecular order. Close comparison of Γ from NR with the SFG amplitude from the aromatic C-H stretch as a function of concentrations and E/Z conformation revealed substantial molecular order changes for AAP-TB. In contrast, only Γ and not the molecular order varied for Azo-TB. These differences in interfacial properties are attributed to the molecular structure of the AAP center that enables favorable lateral interactions at the air-water interface, causing closed-packed interfacial layers and substantial changes during E/Z photoisomerization.

Unexpected monolayer-to-bilayer transition of arylazopyrazole surfactants facilitates superior photo-control of fluid interfaces and colloids.

Interfaces that can change their chemistry on demand have huge potential for applications and are prerequisites for responsive or adaptive materials. We report on the performance of a newly designed n-butyl-arylazopyrazole butyl sulfonate (butyl-AAP-C4S) surfactant that can change its structure at the air-water interface by E/Z photo-isomerization in an unprecedented way. Large and reversible changes in surface tension (Δγ = 27 mN m-1) and surface excess (ΔΓ > 2.9 µmol m-2) demonstrate superior performance of the butyl-AAP-C4S amphiphile to that of existing ionic surfactants. Neutron reflectometry and vibrational sum-frequency generation spectroscopy reveal that these large changes are caused by an unexpected monolayer-to-bilayer transition. This exceptional behavior is further shown to have dramatic consequences at larger length scales as highlighted by applications like the light-triggered collapse of aqueous foam which is tuned from high (>1 h) to low (<10 min) stabilities and light-actuated particle motion via Marangoni flows.

Spiropyran Sulfonates for Photo- and pH-Responsive Air-Water Interfaces and Aqueous Foam.

Responsive foams and interfaces are interesting building blocks for active materials that respond and adapt to external stimuli. We have used the photochromic reaction of a spiropyran sulfonate surfactant to render interfacial, rising bubbles as well as foaming properties active to light stimuli. In order to address the air-water interface on a molecular level, we have applied sum-frequency generation (SFG) spectroscopy which has provided qualitative information on the surface excess and the interfacial charging state as a function of light irradiation and solution pH. Under blue light irradiation, the surfactant forms a closed ring spiro form (SP), whereas under dark conditions the ring opens and the merocyanine (MC) form is generated. Using SFG spectroscopy, we show that at the interface, different pH conditions of the bulk solution lead to changes in the interfacial charging state. We have exploited the fact that the MC surfactant's O-H group can be deprotonated as a function of pH and used that to tune the molecules net charge at the interface. In fact, SFG spectroscopy shows that with increasing pH the intensity of the O-H stretching band from interfacial water molecules increases, which we associate to an increase in surface net charge. At a pH of 5.3, irradiation with blue light leads to a reversible decrease of O-H intensities, whereas the C-H intensities were unchanged compared to the corresponding intensities under dark conditions. These results are indicative of changes in the surface net charge with light irradiation, which are also expected to influence the foam stability via changes in the electrostatic disjoining pressure. In fact, measurements of the foam stabilities are consistent with this hypothesis and show higher foam stability under dark conditions. At pH 2.7 this behavior is reversed as far as the surface tension and surface charging as well as the foam stability are concerned. This is corroborated by rising bubble experiments, which demonstrated an unprecedented reduction of ∼30% in bubble velocity when the bubbles were irradiated with blue light compared to the velocity of bubbles with the surfactants in the dark state. Clearly, the light-triggered changes can be used to control foams, rising bubbles, and fluid interfaces on a molecular level which renders them active to light stimuli.

Specific Ion Effects of Trivalent Cations on the Structure and Charging State of ß-Lactoglobulin Adsorption Layers.

The properties of proteins at interfaces are important to many processes as well as in soft matter materials such as aqueous foam. Particularly, the protein interfacial behavior is strongly linked to different factors like the solution pH or the presence of electrolytes. Here, the nature of the electrolyte ions can significantly modify the interfacial properties of proteins. Therefore, molecular level studies on interfacial structures and charging states are needed. In this work, we addressed the effects of Y3+ and Nd3+ cations on the adsorption of the whey protein ß-lactoglobulin (BLG) at air-water interfaces as the function of electrolyte concentration. Both cations caused very similar but dramatic changes at the interface and in the bulk solution. Here, measurements of the electrophoretic mobility and with vibrational sum-frequency generation (SFG) spectroscopy were applied and consistently showed a reversal of the BLG net charge at remarkably low ion concentrations of 30 (bulk) and 40 (interface) µM of Y3+ or Nd3+ for a BLG concentration of 15 µM. SFG spectra of carboxylate stretching vibrations from Asp or Glu residues of interfacial BLG showed significant changes in the resonance frequency, which we associate to specific and efficient binding of Y3+ or Nd3+ ions to the proteins carboxylate groups. Characteristic reentrant condensation for BLG moieties with bound trivalent ions was found in a broad concentration range around the point of zero net charge. The highest colloidal stability of BLG was found for ion concentrations <20 µM and >50 µM. Investigations on macroscopic foams from BLG solutions revealed the existence of structure-property relations between the interfacial charging state and the foam stability. In fact, a minimum in foam stability at 20 µM ion concentration was found when the interfacial net charge was negligible. At this concentration, we propose that the persistent BLG molecules and weakly charged BLG aggregates drive foam stability, while outside the bulk reentrant zone the electrostatic disjoining pressure inside foam lamellae dominates foam stability. Our results provide new information on the charge reversal at the liquid-gas interface of protein/ion dispersions. Therefore, we see our findings as an important step in the clarification of reentrant condensation effects at interfaces and their relevance to foam stability.