Highly Hydrated Deformable Polyethylene Glycol-Tethered Lipid Bilayers

The realization of a solid-supported lipid bilayer acting as a workbench for the study of membrane processes is a difficult task. For robustness, the bilayer has to be tethered to the substrate. At the same time, diffusion of the lipids and plastic deformations of the membrane should not be obstructed. Furthermore, a highly hydrated surrounding is mandatory. Here, we show that grafting of a polyethylene glycol–lipid construct (PEG2000–DSPE) to a silicon oxide surface via multiple-step silane chemistry and subsequent deposition of lipids by spin-coating result in a cushioned membrane that has the desired properties. Neutron and X-ray reflectometry measurements are combined to access thickness, density, and hydration of the bilayer and the PEG cushion. We observe a spacer of 55 Å thickness between lipid bilayer and silicon-oxide surface with a rather high hydration of up to 90 ± 3% water. While 11.5 ± 3% of the lipids are grafted to the surface, as determined from the neutron data, the diffusion constant of the lipids, as probed by diffusion of 0.5% Texas Red labeled lipids, remains rather large (<i>D</i> = 2.1 ± 0.1 μm²/s), which is a reduction of only 12% compared to a supported lipid bilayer reference without immobilized lipids. Finally, AFM indentation confirms the plastic behavior of the membrane against deformation. We show that rupture of the bilayer does not occur before the deformation exceeds 40 Å. Altogether, the presented PEG-tethered lipid bilayer mimics the deformability of natural cell membranes much better than standard solid-supported lipid bilayers

Nanostructures in <i>n</i>‑Octanol Equilibrated with Additives and/or Water

Fluid fatty alcohols are believed to be nanostructured but broadly amorphous (i.e., noncrystalline) fluids and solvents, including the most popular fatty tissue mimetic, hydrated <i>n</i>-octanol (i.e., hydro-octanol). To check this premise, we studied dry octanol and hydro-octanol as a model of relatively short fluid <i>n</i>-alkanols with small-angle X-ray scattering (SAXS). We also combined this alkanol with the matching alkane (i.e., octane) and with a common anti-inflammatory pain killer (ketoprofen). This revealed that (hydro-)­octanol and arguably any other short fatty alcohol form a mesophase. Its basic structural motif are regularly packed polar nanoclusters, reflected in the inner peak in the SAXS diffractogram of (hydro-)­octanol and other fluid <i>n</i>-alkanols. The nanoclusters arguably resemble tiny, (inverse) hydrated bilayer fragments, located on a thermally smeared para-crystalline lattice. Additives to hydro-octanol can change the nanoclusters only moderately, if at all. For example, octane and the drug ketoprofen added to hydro-octanol enlarge the nanoclusters only little because of the mixture’s packing frustration. To associate with and to bring more water into hydro-octanol, an additive must hence transform the nanoclusters: it expands them into irregularly distributed aqueous lacunae that form a proto-microemulsion, reflected in the previously unknown Guinier’s SAXS signal. A “weak” (i.e., a weakly polar or nonpolar) additive can moreover create only size-limited lacunae. Coexistence of nanoclusters and lacunae as well as size variability of the latter in hydro-octanol subvert the concept of octanol–water partition coefficient, which relies on the studied compartment homogeneity. In turn, it opens new possibilities for interfacial catalysis. Reinterpreting “octanol–water partition coefficient” data in terms of octanol–water association or binding constant(s) could furthermore diminish the variability of molecular lipophilicity description and pave the ground toward a more precise theoretical quantification and prediction of molecular properties

Lipid Monolayer Formation and Lipid Exchange Monitored by a Graphene Field-Effect Transistor

Anionic and cationic lipids are key molecules involved in many cellular processes; their distribution in biomembranes is highly asymmetric, and their concentration is well-controlled. Graphene solution-gated field-effect transistors (SGFETs) exhibit high sensitivity toward the presence of surface charges. Here, we establish conditions that allow the observation of the formation of charged lipid layers on solution-gated field-effect transistors in real time. We quantify the electrostatic screening of electrolyte ions and derive a model that explains the influence of charged lipids on the ion sensitivity of graphene SGFETs. The electrostatic model is validated using structural information from X-ray reflectometry measurements, which show that the lipid monolayer forms on graphene. We demonstrate that SGFETs can be used to detect cationic lipids by self-exchange of lipids. Furthermore, SGFETs allow measuring the kinetics of layer formation induced by vesicle fusion or spreading from a reservoir. Because of the high transconductance and low noise of the electrical readout, we can observe characteristic conductance spikes that we attribute to bouncing-off events of lipid aggregates from the SGFET surface, suggesting a great potential of graphene SGFETs to measure the on–off kinetics of small aggregates interacting with supported layers

Shape and Interhelical Spacing of DNA Origami Nanostructures Studied by Small-Angle X‑ray Scattering

Scaffolded DNA origami nanostructures enable the self-assembly of arbitrarily shaped objects with unprecedented accuracy. Yet, varying physiological conditions are prone to induce slight structural changes in the nanoscale architecture. Here, we report on high precision measurements of overall shape and interhelical distance of three prototypic DNA origami structures in solution using synchrotron small-angle X-ray scattering. Sheet-, brick-, and cylinder-shaped DNA constructs were assembled and the shape factors determined with angstrom resolution from fits to the scattering profiles. With decreasing MgCl₂ concentration electrostatic swelling of both shape cross section and interhelical DNA spacing of the DNA origami structures is observed. The structures tolerate up to 10% interhelical expansion before they disintegrate. In contrast, with increasing temperature, the cylinder-shaped structures show no thermal expansion in a wide temperature window before they abruptly melt above 50 °C. Details on molecular structure of DNA origami can also be obtained using in-house X-ray scattering equipment and, hence, allow for routine folding and stability testing of DNA-based agents that are designed to operate under varying salt conditions

Position Accuracy of Gold Nanoparticles on DNA Origami Structures Studied with Small-Angle X‑ray Scattering

DNA origami objects allow for accurate positioning of guest molecules in three dimensions. Validation and understanding of design strategies for particle attachment as well as analysis of specific particle arrangements are desirable. Small-angle X-ray scattering (SAXS) is suited to probe distances of nano-objects with subnanometer resolution at physiologically relevant conditions including pH and salt and at varying temperatures. Here, we show that the pair density distribution function (PDDF) obtained from an indirect Fourier transform of SAXS intensities in a model-free way allows to investigate prototypical DNA origami-mediated gold nanoparticle (AuNP) assemblies. We analyze the structure of three AuNP-dimers on a DNA origami block, an AuNP trimer constituted by those dimers, and a helical arrangement of nine AuNPs on a DNA origami cylinder. For the dimers, we compare the model-free PDDF and explicit modeling of the SAXS intensity data by superposition of scattering intensities of the scattering objects. The PDDF of the trimer is verified to be a superposition of its dimeric contributions, that is, here AuNP-DNA origami assemblies were used as test boards underlining the validity of the PDDF analysis beyond pairs of AuNPs. We obtain information about AuNP distances with an uncertainty margin of 1.2 nm. This readout accuracy in turn can be used for high precision placement of AuNP by careful design of the AuNP attachment sites on the DNA-structure and by fine-tuning of the connector types

Molecular Architecture: Construction of Self-Assembled Organophosphonate Duplexes and Their Electrochemical Characterization

Self-assembled monolayers of phosphonates (SAMPs) of 11-hydroxyundecylphosphonic acid, 2,6-diphosphonoanthracene, 9,10-diphenyl-2,6-diphosphonoanthracene, and 10,10′-diphosphono-9,9′-bianthracene and a novel self-assembled organophosphonate duplex ensemble were synthesized on nanometer-thick SiO₂-coated, highly doped silicon electrodes. The duplex ensemble was synthesized by first treating the SAMP prepared from an aromatic diphosphonic acid to form a titanium complex-terminated one; this was followed by addition of a second equivalent of the aromatic diphosphonic acid. SAMP homogeneity, roughness, and thickness were evaluated by AFM; SAMP film thickness and the structural contributions of each unit in the duplex were measured by X-ray reflection (XRR). The duplex was compared with the aliphatic and aromatic monolayer SAMPs to determine the effect of stacking on electrochemical properties; these were measured by impedance spectroscopy using aqueous electrolytes in the frequency range 20 Hz to 100 kHz, and data were analyzed using resistance–capacitance network based equivalent circuits. For the 11-hydroxyundecylphosphonate SAMP, <i>C</i>_SAMP = 2.6 ± 0.2 μF/cm², consistent with its measured layer thickness (ca. 1.1 nm). For the anthracene-based SAMPs, <i>C</i>_SAMP = 6–10 μF/cm², which is attributed primarily to a higher effective dielectric constant for the aromatic moieties (ε = 5–10) compared to the aliphatic one; impedance spectroscopy measured the additional capacitance of the second aromatic monolayer in the duplex (2ndSAMP) to be <i>C</i>_Ti/2ndSAMP = 6.8 ± 0.7 μF/cm², in series with the first

Exciton Dynamics in MoS₂‑Pentacene and WSe₂‑Pentacene Heterojunctions

We measured the exciton dynamics in van der Waals heterojunctions of transition metal dichalcogenides (TMDCs) and organic semiconductors (OSs). TMDCs and OSs are semiconducting materials with rich and highly diverse optical and electronic properties. Their heterostructures, exhibiting van der Waals bonding at their interfaces, can be utilized in the field of optoelectronics and photovoltaics. Two types of heterojunctions, MoS2-pentacene and WSe2-pentacene, were prepared by layer transfer of 20 nm pentacene thin films as well as MoS2 and WSe2 monolayer crystals onto Au surfaces. The samples were studied by means of transient absorption spectroscopy in the reflectance mode. We found that A-exciton decay by hole transfer from MoS2 to pentacene occurs with a characteristic time of 21 ± 3 ps. This is slow compared to previously reported hole transfer times of 6.7 ps in MoS2-pentacene junctions formed by vapor deposition of pentacene molecules onto MoS2 on SiO2. The B-exciton decay in WSe2 shows faster hole transfer rates for WSe2-pentacene heterojunctions, with a characteristic time of 7 ± 1 ps. The A-exciton in WSe2 also decays faster due to the presence of a pentacene overlayer; however, fitting the decay traces did not allow for the unambiguous assignment of the associated decay time. Our work provides important insights into excitonic dynamics in the growing field of TMDC-OS heterojunctions

Quantum Size Effect in Organometal Halide Perovskite Nanoplatelets

Organometal halide perovskites have recently emerged displaying a huge potential for not only photovoltaic, but also light emitting applications. Exploiting the optical properties of specifically tailored perovskite nanocrystals could greatly enhance the efficiency and functionality of applications based on this material. In this study, we investigate the quantum size effect in colloidal organometal halide perovskite nanoplatelets. By tuning the ratio of the organic cations used, we can control the thickness and consequently the photoluminescence emission of the platelets. Quantum mechanical calculations match well with the experimental values. We find that not only do the properties of the perovskite, but also those of the organic ligands play an important role. Stacking of nanoplatelets leads to the formation of minibands, further shifting the bandgap energies. In addition, we find a large exciton binding energy of up to several hundreds of meV for nanoplatelets thinner than three unit cells, partially counteracting the blueshift induced by quantum confinement. Understanding of the quantum size effects in perovskite nanoplatelets and the ability to tune them provide an additional method with which to manipulate the optical properties of organometal halide perovskites