Graphene Oxide and Lipid Membranes: Interactions and Nanocomposite Structures

We have investigated the interaction between graphene oxide and lipid membranes, using both supported lipid membranes and supported liposomes. Also, the reverse situation, where a surface coated with graphene oxide was exposed to liposomes in solution, was studied. We discovered graphene oxide-induced rupture of preadsorbed liposomes and the formation of a nanocomposite, bio-nonbio multilayer structure, consisting of alternating graphene oxide monolayers and lipid membranes. The assembly process was monitored in real time by two complementary surface analytical techniques (the quartz crystal microbalance with dissipation monitoring technique (QCM-D) and dual polarization interferometry (DPI)), and the formed structures were imaged with atomic force microscopy (AFM). From a basic science point of view, the results point toward the importance of electrostatic interactions between graphene oxide and lipid headgroups. Implications from a more practical point of view concern structure–activity relationship for biological health/safety aspects of graphene oxide and the potential of the nanocomposite, multilayer structure as scaffolds for advanced biomolecular functions and sensing applications

Integration of Quartz Crystal Microbalance with Vibrational Sum Frequency Spectroscopy–Quantification of the Initial Oxidation of Alkanethiol-Covered Copper

We report the first integration of the interface sensitive technique vibrational sum frequency spectroscopy (VSFS) and the mass sensitive technique quartz crystal microbalance (QCM). VSFS–QCM has been applied in-situ to follow the formation of a thin Cu₂O-like oxide on octadecanethiol-covered copper in dry air at ambient pressure conditions. We observed significant changes and an evolution of the VSF spectra caused by alterations in the electronic properties of the metal surface, and simultaneous shifts in the QCM resonance frequency due to a mass change during the formation of the oxide. QCM and VSFS exhibit a resolution corresponding to the formation of around 2% and 5% of an ideal monolayer of Cu₂O, respectively. The successful integration of QCM increases the versatility of VSFS in numerous applications, where simultaneous in situ mass and spectroscopic information is desirable

Time-Resolved Indirect Nanoplasmonic Sensing Spectroscopy of Dye Molecule Interactions with Dense and Mesoporous TiO₂ Films

Indirect nanoplasmonic sensing (INPS) is an experimental platform exploiting localized surface plasmon resonance (LSPR) detection of processes in nanomaterials, molecular assemblies, and films at the nanoscale. Here we have for the first time applied INPS to study dye molecule adsorption/impregnation of two types of TiO₂ materials: thick (10 μm) mesoporous films of the kind used as photoanode in dye-sensitized solar cells (DSCs), with particle/pore size in the range of 20 nm, and thin (12–70 nm), dense, and flat films. For the thick-film experiments plasmonic Au nanoparticles were placed at the hidden, internal interface between the sensor surface and the mesoporous TiO₂. This approach provides a unique opportunity to selectively follow dye adsorption locally in the hidden interface region inside the material and inspires a generic and new type of nanoplasmonic hidden interface spectroscopy. The specific DSC measurement revealed a time constant of thousands of seconds before the dye impregnation front (the diffusion front) reaches the hidden interface. In contrast, dye adsorption on the dense, thin TiO₂ films exhibited much faster, Langmuir-like monolayer formation kinetics with saturation on a time scale of order 100 s. This new type of INPS measurement provides a powerful tool to measure and optimize dye impregnation kinetics of DSCs and, from a more general point of view, offers a generic experimental platform to measure adsorption/desorption and diffusion phenomena in solid and mesoporous systems and at internal hidden interfaces

Nanofabricated Catalyst Particles for the Investigation of Catalytic Carbon Oxidation by Oxygen Spillover

The catalytic oxidation of carbon by molecular oxygen was studied using C/Pt, Pt/C, Pt/Al₂O₃/C, Pt/CeO₂/C, Al₂O₃/C, and CeO₂/C model samples prepared by hole-mask colloidal lithography. By this technique, the degree of contact between platinum and carbon was controlled with high precision. The oxidation of carbon was monitored using atomic force microscopy and scanning electron microscopy. The results show that Pt in direct contact with carbon catalyzes the oxidation of carbon by spillover of dissociated oxygen from Pt to carbon. By physically separating Pt and carbon with a 10 nm thin spacer layer of Al₂O₃, the oxygen spillover was entirely blocked. However, through a corresponding spacer layer of CeO₂, carbon oxidation was still observed, either by oxygen spillover from Pt to carbon or directly dissociated on the ceria, although at a slower rate compared to the case with no spacer layer between Pt and carbon

Influence of Divalent Cations on Deformation and Rupture of Adsorbed Lipid Vesicles

The fate of adsorbed lipid vesicles on solid supports depends on numerous experimental parameters and typically results in the formation of a supported lipid bilayer (SLB) or an adsorbed vesicle layer. One of the poorly understood questions relates to how divalent cations appear to promote SLB formation in some cases. The complexity arises from the multiple ways in which divalent cations affect vesicle–substrate and vesicle–vesicle interactions as well as vesicle properties. These interactions are reflected, e.g., in the degree of deformation of adsorbed vesicles (if they do not rupture). It is, however, experimentally challenging to measure the extent of vesicle deformation in real-time. Herein, we investigated the effect of divalent cations (Mg²⁺, Ca²⁺, Sr²⁺) on the adsorption of zwitterionic 1,2-dioleoyl-<i>sn</i>-glycero-3-phosphocholine (DOPC) lipid vesicles onto silicon oxide- and titanium oxide-coated substrates. The vesicle adsorption process was tracked using the quartz crystal microbalance-dissipation (QCM-D) and localized surface plasmon resonance (LSPR) measurement techniques. On silicon oxide, vesicle adsorption led to SLB formation in all cases, while vesicles adsorbed but did not rupture on titanium oxide. It was identified that divalent cations promote increased deformation of adsorbed vesicles on both substrates and enhanced rupture on silicon oxide in the order Ca²⁺ > Mg²⁺ > Sr²⁺. The influence of divalent cations on different factors in these systems is discussed, clarifying experimental observations on both substrates. Taken together, the findings in this work offer insight into how divalent cations modulate the interfacial science of supported membrane systems

Combined in Situ Quartz Crystal Microbalance with Dissipation Monitoring, Indirect Nanoplasmonic Sensing, and Vibrational Sum Frequency Spectroscopic Monitoring of Alkanethiol-Protected Copper Corrosion

In this study, we have applied three techniques to simultaneously and in situ study the initial stage of corrosion of copper protected by a self-assembled monolayer of octadecanethiol (ODT). We combined quartz crystal microbalance with dissipation monitoring (QCM-D), indirect nanoplasmonic sensing (INPS), and vibrational sum frequency spectroscopy (VSFS) and obtained complementary information about mass uptake and optical and spectroscopic changes taking place during the initial corrosion phase. All three techniques are very sensitive to the formation of a corrosion film (thickness in the range 0–0.41 nm) under mildly corrosive conditions (dry air, <0.5% relative humidity). The three techniques yield information about the viscoelasticity of the corrosion film (QCM-D), the homogeneity of the corrosion reaction on the surface (INPS), and the stability of the ODT protection layer (VSFS). Furthermore, by also studying the corrosion process in humid air (ca. 70% relative humidity), we illustrate how the combination of these techniques can be used to differentiate between simultaneously occurring processes, such as water adsorption and corrosion product formation