Soft Synthetic Cells with Mobile Membrane Ligands for Ex Vivo Expansion of Therapy-Relevant T Cell Phenotypes.

The expansion of T cells ex vivo is crucial for effective immunotherapy but currently limited by a lack of expansion approaches that closely mimic in vivo T cell activation. Taking inspiration from bottom-up synthetic biology, a new synthetic cell technology is introduced based on dispersed liquid-liquid phase-separated droplet-supported lipid bilayers (dsLBs) with tunable biochemical and biophysical characteristics, as artificial antigen presenting cells (aAPCs) for ex vivo T cell expansion. These findings obtained with the dsLB technology reveal three key insights: first, introducing laterally mobile stimulatory ligands on soft aAPCs promotes expansion of IL-4/IL-10 secreting regulatory CD8+ T cells, with a PD-1 negative phenotype, less prone to immune suppression. Second, it is demonstrated that lateral ligand mobility can mask differential T cell activation observed on substrates of varying stiffness. Third, dsLBs are applied to reveal a mechanosensitive component in bispecific Her2/CD3 T cell engager-mediated T cell activation. Based on these three insights, lateral ligand mobility, alongside receptor- and mechanosignaling, is proposed to be considered as a third crucial dimension for the design of ex vivo T cell expansion technologies.

A printed luminescent flier inspired by plant seeds for eco-friendly physical sensing.

Continuous and distributed monitoring of environmental parameters may pave the way for developing sustainable strategies to tackle climate challenges. State-of-the-art technologies, made with electronic systems, are often costly, heavy, and generate e-waste. Here, we propose a new generation of self-deployable, biocompatible, and luminescent artificial flying seeds for wireless, optical, and eco-friendly monitoring of environmental parameters (i.e., temperature). Inspired by natural Acer campestre plant seeds, we developed three-dimensional functional printed luminescent seed-like fliers, selecting polylactic acid as a biocompatible matrix and temperature as a physical parameter to be monitored. The artificial seeds mimic the aerodynamic and wind dispersal performance of the natural ones. The sensing properties are given by the integration of fluorescent lanthanide-doped particles, whose photoluminescence properties depend on temperature. The luminescent artificial flying seeds can be optically read from a distance using eye-safe near-infrared wavelengths, thus acting as a deployable sensor for distributed monitoring of topsoil environmental temperatures.

Ultrathin Homogenous AuNP Monolayers as Tunable Functional Substrates for Surface-Assisted Laser Desorption/Ionization of Small Biomolecules.

A series of ultrathin, homogenous gold nanoparticle (AuNP) substrates for surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS) were prepared using a simple air/water interface approach. These SALDI substrates enabled soft ionization and provided significant improvements in terms of signal intensities and reduced background levels in comparison to other AuNP morphologies for different analytes such as fatty acids, peptides, amino acids, saccharides, and drugs. Through different microscopic and spectroscopic methods, we determined that the packing homogeneity of the [AuNP]n substrates played a vital role in the efficiency of the SALDI process. We demonstrated that the signal intensities of the investigated analytes were readily optimized by manipulating the thickness of the [AuNP]n substrates. The desorption/ionization efficiency increased as a function of the number of layers and then reached a saturation point. The optimized [AuNP]n substrates not only exhibited high SALDI-MS desorption/ionization efficiencies but also showed excellent reproducibilities of the analyte signals.

When Like Destabilizes Like: Inverted Solvent Effects in Apolar Nanoparticle Dispersions.

We report on the colloidal stability of nanoparticles with alkanethiol shells in apolar solvents. Small-angle X-ray scattering and molecular dynamics simulations were used to characterize the interaction between nanoparticles in linear alkane solvents ranging from hexane to hexadecane, including 4 nm gold cores with hexadecanethiol shells and 6 nm cadmium selenide cores with octadecanethiol shells. We find that the agglomeration is enthalpically driven and that, contrary to what one would expect from classical colloid theory, the temperature at which the particles agglomerate increases with increasing solvent chain length. We demonstrate that the inverted trend correlates with the temperatures at which the ligands order in the different solvents and show that the inversion is due to a combination of enthalpic and entropic effects that enhance the stability of the ordered ligand state as the solvent length increases. We also explain why cyclohexane is a better solvent than hexadecane despite the two having very similar solvation parameters.

Colloidal Solubility and Agglomeration of Apolar Nanoparticles in Different Solvents.

We studied the concentration-dependent agglomeration of apolar nanoparticles in different solvents. Octanethiol-stabilized gold nanoparticles (AuNPs) in evaporating liquid droplets were observed in situ using small-angle X-ray scattering. Concurrent analysis of liquid volume and particle agglomeration provided time-dependent absolute concentrations of free and agglomerated particles. All dispersions underwent an initial stage where the particle concentration increased but no agglomerates formed. Subsequently, agglomeration started at concentrations that varied by several orders of magnitude for different solvents. While agglomerates grew, the concentration of the dispersed particles remained at a constant "colloidal solubility" in most solvents. We consistently found that the colloidal stability of AuNPs decreased as cyclohexane > heptane > nonane > decane > toluene and suggest that details of the molecular interactions between solvent and ligand shell set this order.

Colloidal Stability of Apolar Nanoparticles: Role of Ligand Length.

Inorganic nanoparticle cores are often coated with organic ligands to render them dispersible in apolar solvents. However, the effect of the ligand shell on the colloidal stability of the overall hybrid particle is not fully understood. In particular, it is not known how the length of an apolar alkyl ligand chain affects the stability of a nanoparticle dispersion against agglomeration. Here, small-angle X-ray scattering and molecular dynamics simulations have been used to study the interactions between gold nanoparticles and between cadmium selenide nanoparticles passivated by alkanethiol ligands with 12-18 carbons in the solvent decane. We find that increasing the ligand length increases colloidal stability in the core-dominated regime but decreases it in the ligand-dominated regime. This unexpected inversion is connected to the transition from ligand-dominated to core-dominated agglomeration when the core diameter increases at constant ligand length. Our results provide a microscopic picture of the forces that determine the colloidal stability of apolar nanoparticles and explain why classical colloid theory fails.

A Translucent Nanocomposite with Liquid Inclusions of a Responsive Nanoparticle Dispersion.

Active nanocomposites are created with liquid inclusions that contain plasmonic gold nanoparticles inside a polymeric matrix. The alkylthiol-coated gold particles are designed to reversible agglomerate at certain temperatures, which changes the plasmonic coupling and thus optical properties. It is found that particles confined to the liquid inclusions inside the active composite retain this capability and cause macroscopic, temperature-dependent color change of the solid. The transition is fully reversible for at least 100 times and tunable in temperature via particle size and ligand. This method is suitable to "package" responsive dispersion in solid composites to exploit their dynamic properties in materials.

Colloidal Stability of Apolar Nanoparticles: The Role of Particle Size and Ligand Shell Structure.

Being able to predict and tune the colloidal stability of nanoparticles is essential for a wide range of applications, yet our ability to do so is currently poor due to a lack of understanding of how they interact with one another. Here, we show that the agglomeration of apolar particles is dominated by either the core or the ligand shell depending on the particle size and materials. We do this by using small-angle X-ray scattering and molecular dynamics simulations to characterize the interaction between hexadecanethiol passivated gold nanoparticles in decane solvent. For smaller particles, the agglomeration temperature and interparticle spacing are determined by ordering of the ligand shell into bundles of aligned ligands that attract one another and interlock. In contrast, the agglomeration of larger particles is driven by van der Waals attraction between the gold cores, which eventually becomes strong enough to compress the ligand shell. Our results provide a microscopic description of the forces that determine the colloidal stability of apolar nanoparticles and explain why classical colloid theory fails.

Supraparticles: Functionality from Uniform Structural Motifs.

Under the right process conditions, nanoparticles can cluster together to form defined, dispersed structures, which can be termed supraparticles. Controlling the size, shape, and morphology of such entities is a central step in various fields of science and technology, ranging from colloid chemistry and soft matter physics to powder technology and pharmaceutical and food sciences. These diverse scientific communities have been investigating formation processes and structure/property relations of such supraparticles under completely different boundary conditions. On the fundamental side, the field is driven by the desire to gain maximum control of the assembly structures using very defined and tailored colloidal building blocks, whereas more applied disciplines focus on optimizing the functional properties from rather ill-defined starting materials. With this review article, we aim to provide a connecting perspective by outlining fundamental principles that govern the formation and functionality of supraparticles. We discuss the formation of supraparticles as a result of colloidal properties interplaying with external process parameters. We then outline how the structure of the supraparticles gives rise to diverse functional properties. They can be a result of the structure itself (emergent properties), of the colocalization of different, functional building blocks, or of coupling between individual particles in close proximity. Taken together, we aim to establish structure-property and process-structure relationships that provide unifying guidelines for the rational design of functional supraparticles with optimized properties. Finally, we aspire to connect the different disciplines by providing a categorized overview of the existing, diverging nomenclature of seemingly similar supraparticle structures.

Ligand-Dependent Nanoparticle Assembly and Its Impact on the Printing of Transparent Electrodes.

Metal grids with submicron line diameters are optically transparent, mechanically flexible, and suitable materials for transparent and flexible electronics. Printing such narrow lines with dilute metal nanoparticle inks is challenging because it requires percolation throughout the particle packing. Here, we print fully connected submicron lines of 3.2 nm diameter gold nanoparticles and vary the organic ligand shell to study the relation between colloidal interactions, ligand binding to the metal core, and conductivity of the printed lines. We find that particles with repulsive potentials aid the formation of continuous lines, but the required long ligand molecules impede conductivity and need to be removed after printing. Weakly bound alkylamines provided sufficient interparticle repulsion and were easy to remove with a soft plasma treatment after printing, so that grids with a transparencies above 90% and a conductivity of 150 Ω sq-1 could be printed.

Structure diagram of binary Lennard-Jones clusters.

We analyze the structure diagram for binary clusters of Lennard-Jones particles by means of a global optimization approach for a large range of cluster sizes, compositions, and interaction energies and present a publicly accessible database of 180 000 minimal energy structures (http://softmattertheory.lu/clusters.html). We identify a variety of structures such as core-shell clusters, Janus clusters, and clusters in which the minority species is located at the vertices of icosahedra. Such clusters can be synthesized from nanoparticles in agglomeration experiments and used as building blocks in colloidal molecules or crystals. We discuss the factors that determine the formation of clusters with specific structures.

Pressure-controlled formation of crystalline, Janus, and core-shell supraparticles.

Binary mixtures of nanoparticles self-assemble in the confinement of evaporating oil droplets and form regular supraparticles. We demonstrate that moderate pressure differences on the order of 100 kPa change the particles' self-assembly behavior. Crystalline superlattices, Janus particles, and core-shell particle arrangements form in the same dispersions when changing the working pressure or the surfactant that sets the Laplace pressure inside the droplets. Molecular dynamics simulations confirm that pressure-dependent interparticle potentials affect the self-assembly route of the confined particles. Optical spectrometry, small-angle X-ray scattering and electron microscopy are used to compare experiments and simulations and confirm that the onset of self-assembly depends on particle size and pressure. The overall formation mechanism reminds of the demixing of binary alloys with different phase diagrams.