AMOLF Institutional Repository
Not a member yet
1351 research outputs found
Sort by
Direct Observation of the Orientation of Urea Molecules at Charged Interfaces
Get PDFDissolving urea into water induces special solvation properties that play a crucial role in many biological processes. Here we probe the properties of urea molecules at charged aqueous interfaces using heterodyne-detected vibrational sum-frequency generation (HD-VSFG) spectroscopy. We find that at the neat water/air interface urea molecules do not yield a significant sum-frequency generation signal. However, upon the addition of ionic surfactants, we observe two vibrational bands at 1660 and 1590 cm-1 in the HD-VSFG spectrum, assigned to mixed bands of the C O stretch and NH2 bend vibrations of urea. The orientation of the urea molecules depends on the sign of the charge localized at surface and closely follows the orientation of the neighboring water molecules. We demonstrate that urea is an excellent probe of the local electric field at aqueous interfaces
Employing Cathodoluminescence for Nanothermometry and Thermal Transport Measurements in Semiconductor Nanowires
Get PDFThermal properties have an outsized impact on efficiency and sensitivity of devices with nanoscale structures, such as in integrated electronic circuits. A number of thermal conductivity measurements for semiconductor nanostructures exist, but are hindered by the diffraction limit of light, the need for transducer layers, the slow scan rate of probes, ultrathin sample requirements, or extensive fabrication. Here, we overcome these limitations by extracting nanoscale temperature maps from measurements of bandgap cathodoluminescence in GaN nanowires of <300 nm diameter with spatial resolution limited by the electron cascade. We use this thermometry method in three ways to determine the thermal conductivities of the nanowires in the range of 19-68 W/m.K, well below that of bulk GaN. The electron beam acts simultaneously as a temperature probe and as a controlled delta-function-like heat source to measure thermal conductivities using steady-state methods, and we introduce a frequency-domain method using pulsed electron beam excitation. The different thermal conductivity measurements we explore agree within error in uniformly doped wires. We show feasible methods for rapid, in situ, high-resolution thermal property measurements of integrated circuits and semiconductor nanodevices and enable electron-beam-based nanoscale phonon transport studies
Pathways toward 30% Efficient Single-Junction Perovskite Solar Cells and the Role of Mobile Ions
Get PDFPerovskite semiconductors have demonstrated outstanding external luminescence quantum yields, enabling high power conversion efficiencies (PCEs). However, the precise conditions to advance to an efficiency regime above monocrystalline silicon cells are not well understood. Herein, a simulation model that describes efficient p–i–n-type perovskite solar cells well and a range of different experiments is established. Then, important device and material parameters are studied and it is found that an efficiency regime of 30% can be unlocked by optimizing the built-in voltage across the perovskite layer using either highly doped (1019 cm−3) transport layers (TLs), doped interlayers or ultrathin self-assembled monolayers. Importantly, only parameters that have been reported in recent literature are considered, that is, a bulk lifetime of 10 μs, interfacial recombination velocities of 10 cm s−1, a perovskite bandgap ( gap) of 1.5 eV, and an external quantum efficiency (EQE) of 95%. A maximum efficiency of 31% is predicted for a bandgap of 1.4 eV. Finally, it is demonstrated that the relatively high mobile ion density does not represent a significant barrier to reach this efficiency regime. The results of this study suggest continuous PCE improvements until perovskites may become the most efficient single-junction solar cell technology in the near future
Stability-limited Ion-exchange of Calcium with Zinc in Biomimetic Hydroxyapatite
Get PDFThe exchange of Ca2+ ions in hydroxyapatite (HAp) with Zn2+ ions into Zn-HAp is of interest for applications ranging from bone tissue engineering to the use as a precursor in subsequent ion-exchange reactions. Previous studies, using direct synthesis, showed that ∼20 mol% Zn2+ ions can be incorporated into HAp, before byproducts are observed. However, this is realized at the cost of a loss in crystallinity and control over crystal size and shape with increasing amounts of Zn2+ ion incorporation. In this work a simple post-synthetic ion-exchange strategy for the formation of Zn-HAp has been investigated. By merely exposing HAp to high concentrations of zinc nitrate in water, up to 22 mol% of the Ca2+ ions can displaced by Zn2+ ions without any measured loss in crystallinity and preservation of crystallite size and shape. It was found that the incorporation of Zn2+ ions destabilizes the HAp crystals resulting in their gradual dissolution and reprecipitation. Consequently, promoting the exchange of Ca2+ with Zn2+ions using increased reaction times, sonication and increased temperature results in an increased dissolution of HAp and precipitation of hopeite crystals, thereby preventing the formation of more zinc rich Zn-HAp
Continuous learning of emergent behavior in robotic matter
Get PDFOne of the main challenges in robotics is the development of systems that can adapt to their environment and achieve autonomous behavior. Current approaches typically aim to achieve this by increasing the complexity of the centralized controller by, e.g., direct modeling of their behavior, or implementing machine learning. In contrast, we simplify the controller using a decentralized and modular approach, with the aim of finding specific requirements needed for a robust and scalable learning strategy in robots. To achieve this, we conducted experiments and simulations on a specific robotic platform assembled from identical autonomous units that continuously sense their environment and react to it. By letting each unit adapt its behavior independently using a basic Monte Carlo scheme, the assembled system is able to learn and maintain optimal behavior in a dynamic environment as long as its memory is representative of the current environment, even when incurring damage. We show that the physical connection between the units is enough to achieve learning, and no additional communication or centralized information is required. As a result, such a distributed learning approach can be easily scaled to larger assemblies, blurring the boundaries between materials and robots, paving the way for a new class of modular "robotic matter" that can autonomously learn to thrive in dynamic or unfamiliar situations, for example, encountered by soft robots or self-assembled (micro)robots in various environments spanning from the medical realm to space explorations
Accelerated Hot-Carrier Cooling in MAPbI3 Perovskite by Pressure-Induced Lattice Compression
Get PDFHot-carrier cooling (HCC) in metal halide perovskites above the Mott transition is significantly slower than in conventional semiconductors. This effect is commonly attributed to a hot-phonon bottleneck, but the influence of the lattice properties on the HCC behavior is poorly understood. Using pressure-dependent transient absorption spectroscopy, we find that at an excitation density below the Mott transition, pressure does not affect the HCC. On the contrary, above the Mott transition, HCC in methylammonium lead iodide is around 2–3 times faster at 0.3 GPa than at ambient pressure. Our electron–phonon coupling calculations reveal ∼2-fold stronger electron–phonon coupling for the inorganic cage mode at 0.3 GPa. However, our experiments reveal that pressure promotes faster HCC only above the Mott transition. Altogether, these findings suggest a change in the nature of excited carriers above the Mott transition threshold, providing insights into the electronic behavior of devices operating at such high charge-carrier densities
Strong Reduction of the Chain Rigidity of Hyaluronan by Selective Binding of Ca2+ Ions
Get PDFThe biological functions of natural polyelectrolytes are strongly influenced by the presence of ions, which bind to the polymer chains and thereby modify their properties. Although the biological impact of such modifications is well recognized, a detailed molecular picture of the binding process and of the mechanisms that drive the subsequent structural changes in the polymer is lacking. Here, we study the molecular mechanism of the condensation of calcium, a divalent cation, on hyaluronan, a ubiquitous polymer in human tissues. By combining two-dimensional infrared spectroscopy experiments with molecular dynamics simulations, we find that calcium specifically binds to hyaluronan at millimolar concentrations. Because of its large size and charge, the calcium cation can bind simultaneously to the negatively charged carboxylate group and the amide group of adjacent saccharide units. Molecular dynamics simulations and single-chain force spectroscopy measurements provide evidence that the binding of the calcium ions weakens the intramolecular hydrogen-bond network of hyaluronan, increasing the flexibility of the polymer chain. We also observe that the binding of calcium to hyaluronan saturates at a maximum binding fraction of ∼10–15 mol %. This saturation indicates that the binding of Ca2+ strongly reduces the probability of subsequent binding of Ca2+ at neighboring binding sites, possibly as a result of enhanced conformational fluctuations and/or electrostatic repulsion effects. Our findings provide a detailed molecular picture of ion condensation and reveal the severe effect of a few, selective and localized electrostatic interactions on the rigidity of a polyelectrolyte chain
Integrated Molecular Optomechanics with Hybrid Dielectric-Metallic Resonators
Get PDFMolecular optomechanics describes surface-enhanced Raman scattering using the formalism of cavity optomechanics as a parametric coupling of the molecule's vibrational modes to the plasmonic resonance. Most of the predicted applications require intense electric field hotspots but spectrally narrow resonances, out of reach of standard plasmonic resonances. The Fano lineshapes resulting from the hybridization of dielectric-plasmonic resonators with a broad-band plasmon and narrow-band cavity mode allow reaching strong Raman enhancement with high-Q resonances, paving the way for sideband resolved molecular optomechanics. We extend the molecular optomechanics formalism to describe hybrid dielectric-plasmonic resonators with multiple optical resonances and with both free-space and waveguide addressing. We demonstrate how the Raman enhancement depends on the complex response functions of the hybrid system, and we retrieve the expression of Raman enhancement as a product of pump enhancement and the local density of states. The model allows prediction of the Raman emission ratio into different output ports and enables demonstrating a fully integrated high-Q Raman resonator exploiting multiple cavity modes coupled to the same waveguide
Single-molecule studies of membrane protein interactions via continuous DNA-mediated fluorophore exchange
No full textQuantifying protein-protein interactions in cell membranes
is key to understand many cellular processes, including a
cell’s communication with its surroundings via cell surface
receptors. While single-molecule tracking is a valuable tool
to measure receptor-ligand interaction kinetics in cell membranes,
photobleaching limits the observation times of individual
molecules to only a few seconds with commonlyused
fluorescent proteins or dyes. In practice, this makes
it often hard to reliably distinguish real interactions from
random colocalization events. Here, we show that this limitation
can be overcome by a new labelling method based
on DNA-PAINT, with fluorescently-labeled oligonucleotides
transiently binding to a complementary DNA strand attached
to the molecule of interest. Several fluorescentlylabeled
oligonucleotides can be accommodated on the complementary
DNA strand simultaneously, and enable tracking
of individual molecules for unprecedented observation periods.
We present this new method that can be readily combined
with existing protein tagging methods, such as SNAP
or CLIP tags. Furthermore, we show its implementation invitro
and in live cells by studying the dimerization of FKBP
proteins that were reconstituted on a supported lipid bilayer
or expressed at the cell membrane
Forced apart: a microtubule-based mechanism for equidistant positioning of multiple nuclei in single cells
Get PDFCells can position multiple copies of components like carboxysomes, nucleoids, and nuclei at regular intervals. By controlling positions, cells, for example, ensure equal partitioning of organelles over daughter cells and, in the case of nuclei, control cell sizes during cellularization. Mechanisms that generate regular patterns are as yet poorly understood. We used fission yeast cell cycle mutants to investigate the dispersion of multiple nuclei by microtubule-generated forces in single cells. After removing internuclear attractive forces by microtubule-based molecular motors, we observed the establishment of regular patterns of nuclei. Based on live-cell imaging, we hypothesized that microtubule growth within internuclear spaces pushes neighbouring nuclei apart. In the proposed mechanism, which was validated by stochastic simulations, the repulsive force weakens with increasing separation because stochastic shortening events limit the extent over which microtubules generate forces. Our results, therefore, demonstrate how cells can exploit the dynamics of microtubule growth for the equidistant positioning of organelles