Tuneable Interactions Research Articles

Influence of the Crystallographic Texture of ITO on the Electrodeposition of Silver Nanoparticles

Metal nanoparticles exhibit physical and chemical properties that differ significantly from macroscopic metal phases. In particular, silver nanoparticles (NPs) had have extensive attention since it has a strong interaction with light due to their high quality localized surface plasmon resonances, which can be tuned all across the visible to the NIR regime. These strong and tuneable interaction of visible light with silver NPs have found many applications, in sensing, surface enhanced Raman spectroscopy, photo(electro)catalysis, and more.Polycrystalline indium tin oxide (ITO) films are highly desired substrates for many of these optoelectronic applications. In many of these applications, it is essential to reliably and precisely control the size and density of silver NPs. Even though it is well known that the electrochemical control over nucleation and growth of silver NPs on foreign substrates highly depends on the surface properties of the substrate, yet, the only parameter that is often specified for these ITO substrates is a bulk property: sheet resistance. As a result, nucleation and growth on ITO is highly irreproducible.In this work, we show that ITO substrates with same technical specifications (i.e. sheet resistance, light transmittance and roughness) and supplier may still have different surface properties such as the crystalline texture. We find that these differences in the surface properties has a strong impact on the nucleation and growth. Even though we used seemingly equal ITO substrates, XRD and EBSD scans clearly differentiate between two types of films based on the ratio between the (222) and (400) related peaks. We controlled the density and size of the silver NPs by making use of the double pulse technique. In this method, where the high overpotential nucleation pulse controls the nucleation density. Previous studies have reported an empirical exponential relationship between island density and nucleation pulse overpotential, where the slope is a measure for the electron kinetics.We find that the preferential presence of lower index surfaces (e.g. (100)) leads to few orders of magnitude lower particle density compared to the preferential presence of higher index surfaces (e.g. (111)). Furthermore, the density on the lower index surface is strongly dependent on the nucleation pulse overpotential, while the higher index surface is barely affected. We find that this difference in the relationship is caused by mass transport limited nucleation. We have verified this through a spatial correlation analysis using the nearest-neighbour distance. For higher index surfaces, the nucleation density is already large compared to the Nernst diffusion length at low nucleation pulse overpotentials, such that the limiting mechanism becomes mass transport instead of electron kinetics. We therefore elucidate that the empirical exponential relationship between island density and nucleation pulse overpotential is not enough to draw conclusions on electrode kinetics, where additional validation of the growth process is essential.Beyond careful control of electrochemical parameters, here we show that neglecting the macroscopic surface characteristics of polycrystalline substrates can lead to major ambiguity in nucleation and growth dynamics of metal nanoparticles. We show here that XRD characterization prior to deposition is a simple additional measure to tailor metal nanoparticle electrochemical growth on ITO.

Quantifying the tuneable interactions between colloid supported lipid bilayers

Colloid supported lipid bilayers (CSLBs) are formed via the rupture and fusion of lipid vesicles to coat spherical colloidal particles. CSLBs are an emerging vector for the controlled self-assembly of colloids due to the ability to include additives into the bilayer, which influence the (a)specific interactions between particles. To evaluate the specificity of CSLB assembly, first a fundamental study on the tunability of the colloidal interaction and resulting colloidal stability of CSLBs without specific interactions is reported here. It was found that both fluid and gel CSLBs showed significant clustering and attraction, while the addition of steric stabilizers induced a profound increase in stability. The interactions were rendered attractive again by the introduction of depletion forces via the addition of free non-adsorbing polymers. The compositions of fluid and gel CSLBs with 5% membrane stabiliser were concluded to be optimal for further studies where both colloidal stability, and contrasting membrane fluidity are required. These experimental findings were confirmed semi-quantitatively by predictions using numerical self-consistent mean-field theory lattice computations.

Review: Nanomaterials for Reactive Oxygen Species Detection and Monitoring in Biological Environments.

Reactive oxygen species (ROS) and dissolved oxygen play key roles across many biological processes, and fluorescent stains and dyes are the primary tools used to quantify these species in vitro. However, spatio-temporal monitoring of ROS and dissolved oxygen in biological systems are challenging due to issues including poor photostability, lack of reversibility, and rapid off-site diffusion. In particular, ROS monitoring is hindered by the short lifetime of ROS molecules and their low abundance. The combination of nanomaterials and fluorescent detection has led to new opportunities for development of imaging probes, sensors, and theranostic products, because the scaffolds lead to improved optical properties, tuneable interactions with cells and media, and ratiometric sensing robust to environmental drift. In this review, we aim to critically assess and highlight recent development in nanosensors and nanomaterials used for the detection of oxygen and ROS in biological systems, and their future potential use as diagnosis tools.

Graphene Oxide Nanosheets Tailored With Aromatic Dipeptide Nanoassemblies for a Tuneable Interaction With Cell Membranes.

Engineered graphene-based derivatives are attractive and promising candidates for nanomedicine applications because of their versatility as 2D nanomaterials. However, the safe application of these materials needs to solve the still unanswered issue of graphene nanotoxicity. In this work, we investigated the self-assembly of dityrosine peptides driven by graphene oxide (GO) and/or copper ions in the comparison with the more hydrophobic diphenylalanine dipeptide. To scrutinize the peptide aggregation process, in the absence or presence of GO and/or Cu2+, we used atomic force microscopy, circular dichroism, UV–visible, fluorescence and electron paramagnetic resonance spectroscopies. The perturbative effect by the hybrid nanomaterials made of peptide-decorated GO nanosheets on model cell membranes of supported lipid bilayers was investigated. In particular, quartz crystal microbalance with dissipation monitoring and fluorescence recovery after photobleaching techniques were used to track the changes in the viscoelastic properties and fluidity of the cell membrane, respectively. Also, cellular experiments with two model tumour cell lines at a short time of incubation, evidenced the high potential of this approach to set up versatile nanoplatforms for nanomedicine and theranostic applications.

Top-Down Polyelectrolytes for Membrane-Based Post-Combustion CO2 Capture.

Polymer-based CO2 selective membranes offer an energy efficient method to separate CO2 from flue gas. ‘Top-down’ polyelectrolytes represent a particularly interesting class of polymer materials based on their vast synthetic flexibility, tuneable interaction with gas molecules, ease of processability into thin films, and commercial availability of precursors. Recent developments in their synthesis and processing are reviewed herein. The four main groups of post-synthetically modified polyelectrolytes discern ionised neutral polymers, cation and anion functionalised polymers, and methacrylate-derived polyelectrolytes. These polyelectrolytes differentiate according to the origin and chemical structure of the precursor polymer. Polyelectrolytes are mostly processed into thin-film composite (TFC) membranes using physical and chemical layer deposition techniques such as solvent-casting, Langmuir-Blodgett, Layer-by-Layer, and chemical grafting. While solvent-casting allows manufacturing commercially competitive TFC membranes, other methods should still mature to become cost-efficient for large-scale application. Many post-synthetically modified polyelectrolytes exhibit outstanding selectivity for CO2 and some overcome the Robeson plot for CO2/N2 separation. However, their CO2 permeance remain low with only grafted and solvent-casted films being able to approach the industrially relevant performance parameters. The development of polyelectrolyte-based membranes for CO2 separation should direct further efforts at promoting the CO2 transport rates while maintaining high selectivities with additional emphasis on environmentally sourced precursor polymers.

Interferometric measurement of micro-g acceleration with levitated atoms

The sensitivity of atom interferometers is usually limited by the observation time of a free falling cloud of atoms in Earth’s gravitational field. Considerable efforts are currently made to increase this observation time, e.g. in fountain experiments, drop towers and in space. In this article, we experimentally study and discuss the use of magnetic levitation for interferometric precision measurements. We employ a Bose–Einstein condensate of cesium atoms with tuneable interaction and a Michelson interferometer scheme for the detection of micro-g acceleration. In addition, we demonstrate observation times of 1s, which are comparable to current drop-tower experiments, we study the curvature of our force field, and we observe the effects of a phase-shifting element in the interferometer paths.

Effective many-body Hamiltonians of qubit-photon bound states

Quantum emitters (QEs) coupled to structured baths can localize multiple photons around them and form qubit-photon bound states. In the Markovian or weak coupling regime, the interaction of QEs through these single-photon bound states is known to lead to effective many-body QE Hamiltonians with tuneable but yet perturbative interactions. In this work we study the emergence of such models in the non-Markovian or strong coupling regime in different excitation subspaces. The effective models for the non-Markovian regime with up to three excitations are characterized using analytical methods, uncovering the existence of doublons or triplon states. Furthermore, we provide numerical results for systems with multiple excitations and demonstrate the emergence of polariton models with optically tuneable interactions, whose many-body ground state exhibits a superfluid-Mott insulator transition.

Dilution effects on combined magnetic and electric dipole interactions: A study of ferromagnetic cobalt nanoparticles with tuneable interactions.

Improved understanding of complex interactions between nanoparticles will facilitate the control over the ensuing self-assembled structures. In this work, we consider the dynamic changes occurring upon dilution in the self-assembly of a system of ferromagnetic cobalt nanoparticles that combine magnetic, electric, and steric interactions. The systems examined here vary in the strength of the magnetic dipole interactions and the amount of point charges per particle. Scattering techniques are employed for the characterization of the self-assembly aggregates, and zeta-potential measurements are employed for the estimation of surface charges. Our experiments show that for particles with relatively small initial number of surface electric dipoles, an increase in particle concentration results in an increase in diffusion coefficients; whereas for particles with relatively high number of surface dipoles, no effect is observed upon concentration changes. We attribute these changes to a shift in the adsorption/desorption equilibrium of the tri-n-octylphosphine oxide (TOPO) molecules on the particle surface. We put forward an explanation, based on the combination of two theoretical models. One predicts that the growing concentration of electric dipoles, stemming from the addition of tri-n-octylphosphine oxide (TOPO) as co-surfactant during particle synthesis, on the surface of the particles results in the overall repulsive interaction. Secondly, using density functional theory, we explain that the observed behaviour of the diffusion coefficient can be treated as a result of the concentration dependent nanoparticle self-assembly: additional repulsion leads to the reduction in self-assembled aggregate size despite the shorter average interparticle distances, and as such provides the growth of the diffusion coefficient.

Multifunctional polymer-capped mesoporous silica nanoparticles for pH-responsive targeted drug delivery.

A highly stable modular platform, based on the sequential covalent attachment of different functionalities to the surface of core-shell mesoporous silica nanoparticles (MSNs) for targeted drug delivery is presented. A reversible pH-responsive cap system based on covalently attached poly(2-vinylpyridine) (PVP) was developed as drug release mechanism. Our platform offers (i) tuneable interactions and release kinetics with the cargo drug in the mesopores based on chemically orthogonal core-shell design, (ii) an extremely robust and reversible closure and release mechanism based on endosomal acidification of the covalently attached PVP polymer block, (iii) high colloidal stability due to a covalently coupled PEG shell, and (iv) the ability to covalently attach a wide variety of dyes, targeting ligands and other functionalities at the outer periphery of the PEG shell. The functionality of the system was demonstrated in several cell studies, showing pH-triggered release in the endosome, light-triggered endosomal escape with an on-board photosensitizer, and efficient folic acid-based cell targeting.

Threading plasmonic nanoparticle strings with light.

Nanomaterials find increasing application in communications, renewable energies, electronics and sensing. Because of its unsurpassed speed and highly tuneable interaction with matter, using light to guide the self-assembly of nanomaterials can open up novel technological frontiers. However, large-scale light-induced assembly remains challenging. Here we demonstrate an efficient route to nano-assembly through plasmon-induced laser threading of gold nanoparticle strings, producing conducting threads 12±2 nm wide. This precision is achieved because the nanoparticles are first chemically assembled into chains with rigidly controlled separations of 0.9 nm primed for re-sculpting. Laser-induced threading occurs on a large scale in water, tracked via a new optical resonance in the near-infrared corresponding to a hybrid chain/rod-like charge transfer plasmon. The nano-thread width depends on the chain mode resonances, the nanoparticle size, the chain length and the peak laser power, enabling nanometre-scale tuning of the optical and conducting properties of such nanomaterials.

Metastability and coherence of repulsive polarons in a strongly interacting Fermi mixture

Ultracold Fermi gases with tunable interactions provide a test bed for exploring the many-body physics of strongly interacting quantum systems. Over the past decade, experiments have investigated many intriguing phenomena, and precise measurements of ground-state properties have provided benchmarks for the development of theoretical descriptions. Metastable states in Fermi gases with strong repulsive interactions represent an exciting area of development. The realization of such systems is challenging, because a strong repulsive interaction in an atomic quantum gas implies the existence of a weakly bound molecular state, which makes the system intrinsically unstable against decay. Here we use radio-frequency spectroscopy to measure the complete excitation spectrum of fermionic (40)K impurities resonantly interacting with a Fermi sea of (6)Li atoms. In particular, we show that a well-defined quasiparticle exists for strongly repulsive interactions. We measure the energy and the lifetime of this 'repulsive polaron', and probe its coherence properties by measuring the quasiparticle residue. The results are well described by a theoretical approach that takes into account the finite effective range of the interaction in our system. We find that when the effective range is of the order of the interparticle spacing, there is a substantial increase in the lifetime of the quasiparticles. The existence of such a long-lived, metastable many-body state offers intriguing prospects for the creation of exotic quantum phases in ultracold, repulsively interacting Fermi gases.

Motif switches: decision-making in cell regulation

Tight regulation of gene products from transcription to protein degradation is required for reliable and robust control of eukaryotic cell physiology. Many of the mechanisms directing cell regulation rely on proteins detecting the state of the cell through context-dependent, tuneable interactions. These interactions underlie the ability of proteins to make decisions by combining regulatory information encoded in a protein's expression level, localisation and modification state. This raises the question, how do proteins integrate available information to correctly make decisions? Over the past decade pioneering work on the nature and function of intrinsically disordered protein regions has revealed many elegant switching mechanisms that underlie cell signalling and regulation, prompting a reevaluation of their role in cooperative decision-making.

Ageing and yield behaviour in model soft colloidal glasses

We use multi-arm star polymers as model soft colloids with tuneable interactions and explore their behaviour in the glassy state. In particular, we perform a systematic rheological study with a well-defined protocol and address aspects of ageing and shear melting of star glasses. Ageing proceeds in two distinct steps: a fast step of O(10(3) s) and a slow step of O(10(4) s). We focus on creep and recovery tests, which reveal a rich, albeit complex response. Although the waiting time, the time between pre-shear (rejuvenation) of the glassy sample and measurement, affects the material's response, it does not play the same role as in other soft glasses. For stresses below the yield value, the creep curve is divided into three regimes with increasing time: viscoplastic, intermediate steady flow (associated with the first ageing step) and long-time evolving elastic solid. This behaviour reflects the interplay between ageing and shear rejuvenation. The yield behaviour, as investigated with the stress-dependent recoverable strain, indicates a highly nonlinear elastic response intermediate between a low-stress Hookean solid and a high-stress viscoelastic liquid, and exemplifies the distinct characteristics of this class of hairy colloids. It appears that a phenomenological classification of different colloidal glasses based on yielding performance may be possible.

Cooperative Tuneable Interactions between a Designed Peptide Biosurfactant and Positional Isomers of SDOBS at the Air−Water Interface

Rationally designed peptide biosurfactant AM1 was mixed with sodium dodecyl benzene sulfonate (SDOBS) to self-assemble a mixed surfactant-biosurfactant layer at the air-water interface. Under optimal conditions in the presence of Zn2+, the interfacial elasticity of the mixed layer was approximately 5-fold higher than for biosurfactant alone. Two head positional isomers, SDOBS-2 and SDOBS-6, were compared for their ability to enhance interfacial film strength. SDOBS-6 forms a stronger layer with AM1 than does SDOBS-2. The highest interfacial elasticity of the AM1/SDOBS-6 layer was 640 mN m(-1) whereas the maximum value for the AM1/SDOBS-2 layer was 440 mN m(-1). Neutron reflection was used to investigate the structure of AM1/SDOBS films at varied bulk SDOBS concentrations. Both deuterated and nondeuterated SDOBS-2 and SDOBS-6 were used to provide contrast variation. It was shown that there is cooperative interaction between AM1 and SDOBS at low SDOBS concentration in the presence of 100 microM Zn2+, promoting AM1 adsorption atthe interface to form a two-layered structure of AM1 resulting in a mechanically strong interfacial film. In the presence of EDTA, only a single AM1 layer was formed at the same SDOBS concentration, and the film did not show lateral force transmission capability. Further increasing the SDOBS concentration to a molar excess of > 10x decreased the peptide population at the interface and resulted in a mechanically weak layer. Compared to SDOBS-6, SDOBS-2 depletes AM1 at a lower bulk concentration. These results demonstrate that the film strength of a self-assembled surfactant-biosurfactant mixed layer can be fine tuned by changing the isomer type and concentration of surfactant and by adding or removing metal ions.

Tuneable electrochemical interactions between polystyrenes with anthracenyl and tetrathiafulvalenyl sidechains.

Polymer 4 and its monomeric counterpart 3 exhibit electrochemically tuneable interactions with anthracene polymer 2 and a structurally similar monomer 1 and seen by the variation of the oxidation waves of TTF groups and the fluorescence of the anthracene.