Reversible control of current across lipid membranes by local heating

Lipid membranes are almost impermeable for charged molecules and ions that can pass the membrane barrier only with the help of specialized transport proteins. Here, we report how temperature manipulation at the nanoscale can be employed to reversibly control the electrical resistance and the amount of current that flows through a bilayer membrane with pA resolution. For this experiment, heating is achieved by irradiating gold nanoparticles that are attached to the bilayer membrane with laser light at their plasmon resonance frequency. We found that controlling the temperature on the nanoscale renders it possible to reproducibly regulate the current across a phospholipid membrane and the membrane of living cells in absence of any ion channels

Reversible control of current across lipid membranes by local heating

Lipid membranes are almost impermeable for charged molecules and ions that can pass the membrane barrier only with the help of specialized transport proteins. Here, we report how temperature manipulation at the nanoscale can be employed to reversibly control the electrical resistance and the amount of current that flows through a bilayer membrane with pA resolution. For this experiment, heating is achieved by irradiating gold nanoparticles that are attached to the bilayer membrane with laser light at their plasmon resonance frequency. We found that controlling the temperature on the nanoscale renders it possible to reproducibly regulate the current across a phospholipid membrane and the membrane of living cells in absence of any ion channels

Membrane composition of jetted lipid vesicles: A Raman spectroscopy study

Microfluidic jetting is a promising method to produce giant unilamellar phospholipid vesicles for mimicking living cells in biomedical studies. We have investigated the chemical composition of membranes of vesicles prepared using this approach by means of Raman scattering spectroscopy. The membranes of all jetted vesicles are found to contain residuals of the organic solvent decane used in the preparation of the initial planar membrane. The decane inclusions are randomly distributed over the vesicle surface area and vary in thickness from a few to several tens of nanometers. Our findings point out that the membrane properties of jetted vesicles may differ considerably from those of vesicles prepared by other methods and from those of living cells.Fil: Kirchner, Silke R.. Ludwig Maximilians Universitat; AlemaniaFil: Ohlinger, Alexander. Ludwig Maximilians Universitat; AlemaniaFil: Pfeiffer, Tom. Ludwig Maximilians Universitat; AlemaniaFil: Urban, Alexander S.. Ludwig Maximilians Universitat; AlemaniaFil: Stefani, Fernando Daniel. Ludwig Maximilians Universitat; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Centro de Investigaciones en Bionanociencias "Elizabeth Jares Erijman"; ArgentinaFil: Deak, Andras. Ludwig Maximilians Universitat; AlemaniaFil: Lutich, Andrey A.. Ludwig Maximilians Universitat; AlemaniaFil: Feldmann, Jochen. Ludwig Maximilians Universitat; Alemani

Scattering Properties of Individual Hedgehog Particles

“Hedgehog” particles (HPs) possess a micrometer-sized dielectric spherical core which is densely coated with nanoscale metal oxide spikes. This unique surface topography, resembling the appearance of a hedgehog, provides the particles with the exclusive physiochemical property to stably disperse in both polar and nonpolar solvents without the necessity of changing the surface chemistry. Optical extinction measurements of HP ensembles in aqueous solution indicate a broad spectral response in the visible range. However, there remains a dearth of fundamental knowledge about the cause of the broad optical resonance, as it can be a consequence of shape polydispersity in the many-particle system or intrinsic to each individual HP. In this paper, we present the first experimental study of the dark-field scattering of individual hydrophilic and hydrophobic HPs. Our measurements disclose that the expansive optical response in the visible spectral range is truly characteristic for the far-field scattering of a single HP. Our results also uncover how intrinsic particle features, such as spike length, as well as environmental changes affect the scattering of individual HPs. In particular, by changing the atmosphere around a hydrophilic HP from air to nitrogen and by completely immersing in water by employing a 3D optical trap, we discovered that the scattering from a hydrophilic HP is strongly modulated by excess water in its interstitial shell

Snapshot Hyperspectral Imaging (SHI) for Revealing Irreversible and Heterogeneous Plasmonic Processes

Plasmon-mediated processes provide unique opportunities for selective photocatalysis, photovoltaics, and electrochemistry. Determining the influence of particle heterogeneity is an unsolved problem because often such processes introduce irreversible changes to the nanocatalysts and/or their surroundings. The challenge lies in monitoring heterogeneous nonequilibrium dynamics via the slow, serial methods that are intrinsic to almost all spectral acquisition methods with suitable spatial and/or spectral resolution. Here, we present a new metrology, snapshot hyperspectral imaging (SHI), that facilitates in situ readout of the tube lens image and first-order diffraction image of the dark-field scattering from many individual plasmonic nanoparticles to extract their respective spectra simultaneously. Evanescent wave excitation with a supercontinuum laser enabled signal-to-noise ratios greater than 100 with a time resolution of only 1 ms. Throughput of ∼100 simultaneous spectra was achieved with a highly ordered nanoparticle array, yielding a spectral resolution of 0.21 nm/pixel. Additionally, an alternative dark-field excitation geometry utilized a combination of a supercontinuum laser and a reflecting objective for polarization-controlled SHI. Using a simplified version of SHI, we temporally resolve on the millisecond time scale the heterogeneous kinetics of an electrochemical surface redox reaction for many individual gold nanoparticles simultaneously

Spectral Response of Plasmonic Gold Nanoparticles to Capacitive Charging: Morphology Effects

We report a study of the shape-dependent spectral response of the gold nanoparticle surface plasmon resonance at various electron densities to provide mechanistic insight into the role of capacitive charging, a topic of some debate. We demonstrate a morphology-dependent spectral response for gold nanoparticles due to capacitive charging using single-particle spectroscopy in an inert electrochemical environment. A decrease in plasmon energy and increase in spectral width for gold nanospheres and nanorods was observed as the electron density was tuned through a potential window of −0.3 to 0.1 V. The combined observations could not be explained by existing theories. A new quantum theory for charging based on the random phase approximation was developed. Additionally, the redox reaction of gold oxide formation was probed using single-particle plasmon voltammetry to reproduce the reduction peak from the bulk cyclic voltammetry. These results deepen our understanding of the relationship between optical and electronic properties in plasmonic nanoparticles and provide insight toward their potential applications in directed electrocatalysis

The complement system drives local inflammatory tissue priming by metabolic reprogramming of articular fibroblasts

Arthritis typically involves recurrence and progressive worsening at specific predilection sites, but the checkpoints between remission and persistence remain unknown. Here, we defined the molecular and cellular mechanisms of this inflammation-mediated tissue priming. Re-exposure to inflammatory stimuli caused aggravated arthritis in rodent models. Tissue priming developed locally and independently of adaptive immunity. Repeatedly stimulated primed synovial fibroblasts (SFs) exhibited enhanced metabolic activity inducing functional changes with intensified migration, invasiveness and osteoclastogenesis. Meanwhile, human SF from patients with established arthritis displayed a similar primed phenotype. Transcriptomic and epigenomic analyses as well as genetic and pharmacological targeting demonstrated that inflammatory tissue priming relies on intracellular complement C3- and C3a receptor-activation and downstream mammalian target of rapamycin- and hypoxia-inducible factor 1α-mediated metabolic SF invigoration that prevents activation-induced senescence, enhances NLRP3 inflammasome activity, and in consequence sensitizes tissue for inflammation. Our study suggests possibilities for therapeutic intervention abrogating tissue priming without immunosuppression