Arrested on heating: controlling the motility of active droplets by temperature

One of the challenges in tailoring the dynamics of active, self-propelling agents lies in arresting and releasing these agents at will. Here, we present an experimental system of active droplets with thermally controllable and reversible states of motion, from unsteady over meandering to persistent to arrested motion. These states depend on the P\'eclet number of the chemical reaction driving the motion, which we can tune by using a temperature sensitive mixture of surfactants as a fuel medium. We quantify the droplet dynamics by analysing flow and chemical fields for the individual states, comparing them to canonical models for autophoretic particles. In the context of these models, we are able to observe in situ the fundamental first transition between the isotropic, immotile base state and self-propelled motility

Nanoparticles Surface Chemistry Influence on Protein Corona Composition and Inflammatory Responses

Nanoparticles are widely used for biomedical applications such as vaccine, drug delivery, diagnostics, and therapeutics. This study aims to reveal the influence of nanoparticle surface functionalization on protein corona formation from blood serum and plasma and the subsequent effects on the innate immune cellular responses. To achieve this goal, the surface chemistry of silica nanoparticles of 20 nm diameter was tailored via plasma polymerization with amine, carboxylic acid, oxazolines, and alkane functionalities. The results of this study show significant surface chemistry-induced differences in protein corona composition, which reflect in the subsequent inflammatory consequences. Nanoparticles rich with carboxylic acid surface functionalities increased the production of pro-inflammatory cytokines in response to higher level of complement proteins and decreased the number of lipoproteins found in their protein coronas. On another hand, amine rich coatings led to increased expressions of anti-inflammatory markers such as arginase. The findings demonstrate the potential to direct physiological responses to nanomaterials via tailoring their surface chemical composition

Prevention of Dominant IgG Adsorption on Nanocarriers in IgG‐Enriched Blood Plasma by Clusterin Precoating

Abstract Nanocarriers for medical applications must work reliably within organisms, independent of the individual differences in the blood proteome. Variation in the blood proteome, such as immunoglobulin levels, is a result of environmental, nutrition, and constitution conditions. This variation, however, should not influence the behavior of nanocarriers in biological media. The composition of the protein corona is investigated to understand the influence varying immunoglobulin levels in the blood plasma have on the interactions with nanocarriers. Specifically, the composition of the nanocarriers' coronas is analyzed after incubation in plasma with normal or elevated immunoglobulin G (IgG) levels, and cellular uptake is monitored in cell lines containing different immunoglobulin receptors. Here, it is reported that upon doubling the IgG concentration in plasma, the IgG fraction in the protein corona increases by a factor of 40 independent of the nanocarrier material. This results in a significant increase in uptake in cells exhibiting IgG binding receptors. Furthermore, precoating nanocarriers with clusterin successfully prevents dominant IgG‐adsorption and additionally reduces cellular internalization, after incubation with IgG‐enriched plasma. Therefore, precoating nanocarriers may be utilized as a powerful method to reduce the influence of individual variations in blood composition on the protein corona

Datasets underlying the paper Frozen by heating

<p>datasets_repo.zip</p> <p>Datasets underlying Frozen by heating: temperature controlled dynamic states in droplet microswimmers, arXiv:2303.13442</p> <p>Source data for all figures in the manuscript. Figures were produced by Python/matplotlib, a corresponding Jupyter notebook is included in the root folder. Raw video data are available from the authors on reasonable request.</p> <p> </p> <p>code.zip</p> <p>Numerical code underlying the simulation data in Fig. 4a.</p&gt

Polyvinylferrocene-Based Amphiphilic Block Copolymers Featuring Functional Junction Points for Cross-Linked Micelles

The synthesis of high-molecular-weight, well-defined poly­(vinylferrocene)-<i>block</i>-poly­(ethylene glycol) (PVFc-<i>b</i>-PEG) diblock copolymers (<i>M</i>_n = 13 000–44 000 g mol^–1; <i>Đ</i> = 1.29–1.34) with precisely one allyl group at the junction point is introduced. Allyl glycidyl ether (AGE) was used to end-functionalize PVFc, resulting in hydroxyl functional macroinitiators for the oxyanionic polymerization of ethylene oxide. The self-assembly behavior of the amphiphilic PVFc-<i>b</i>-PEG copolymers in water has been investigated in a detailed manner, using dynamic light scattering (DLS) and transmission electron microscopy (TEM). The redox activity of the PVFc block was confirmed by UV/vis spectroscopy, while cyclovoltammetry (CV) measurements were carried out to support the stability and full reversibility of the ferrocene/ferrocenium redox couple. Both formation and dissociation of the macromolecular self-assemblies in aqueous solution via oxidation and reduction of the PVFc segments were evidenced by TEM and DLS. The dye Nile Red was used as model compound to investigate the stabilization of a water-insoluble molecule in aqueous solution by the block copolymers via encapsulation inside micellar structures. Oxidation of the PVFc segments lead to instantaneous and quantitative release of the dye. Furthermore, incorporation of the allyl moiety at the block junction point was used to cross-link the shell of the compartments. By this strategy a stable incorporation of the dye was achieved while triggered release via oxidation led to quantitative liberation

Probing nanoparticle-membrane interactions by combining amphiphilic diblock copolymer assembly and plasmonics

International audienceUnderstanding the interactions between nanoparticles (NPs) and boundaries of cells is crucial both for their toxicity and therapeutic applications. Besides specific receptor-mediated endocytosis of surface-functionalized NPs, passive internalization is prompted by relatively unspecific parameters, such as particle size and charge. Based on theoretical treatments, adhesion to and bending of the cell membrane can induce NP wrapping. Experimentally, powerful tools are needed to selectively probe possible membrane-NP motifs at very dilute conditions and avoid dye labeling. In this work, we employ surface resonance-enhanced dynamic light scattering, surface plasmon resonance, electron microscopy, and simulations for sensing interactions between plasmonic AuNPs and polymersomes. We distinguish three different interaction scenarios at nanomolar concentrations by tuning the surface charge of AuNPs and rationalize these events by balancing vesicle bending and electrostatic/van der Waals AuNP and vesicle adhesion. The clarification of the physical conditions under which nanoparticles passively translocate across membranes can aid in the rational design of drugs that cannot exploit specific modes of cellular uptake and also elucidates physical properties that render nanoparticles in the environment particularly toxic

The Transferability from Animal Models to Humans: Challenges Regarding Aggregation and Protein Corona Formation of Nanoparticles

Nanomaterials are interesting candidates for applications in medicine as drug delivery or diagnostic agents. For safe application, they have to be evaluated in in vitro and in vivo models to finally be translated to human clinical trials. However, often those transfer processes fail, and it is not completely understood whether in vitro models leading to these animal models can reliably be compared to the situation in humans. In particular, the interaction of nanomaterials with components from different blood plasma sources is difficult to compare, and the outcomes of those interactions with respect to body distribution and cell uptake are unclear. Therefore, we investigated the interactions of differently functionalized polymeric and inorganic nanoparticles with human, mouse, rabbit, and sheep plasma. The focus was put on the determination of aggregation events of the nanoparticles occurring in concentrated plasma and the correlation with the respectively formed protein coronas. Both the stability in plasma as well as the types of adsorbed proteins were found to strongly depend on the plasma source. Thus, we suggest evaluating the potential use of nanocarriers always in the plasma source of the chosen animal model for in vitro studies as well as in human plasma to pin down differences and eventually enable transfer into clinical trials in humans

The Transferability from Animal Models to Humans: Challenges Regarding Aggregation and Protein Corona Formation of Nanoparticles

Nanomaterials are interesting candidates for applications in medicine as drug delivery or diagnostic agents. For safe application, they have to be evaluated in in vitro and in vivo models to finally be translated to human clinical trials. However, often those transfer processes fail, and it is not completely understood whether in vitro models leading to these animal models can reliably be compared to the situation in humans. In particular, the interaction of nanomaterials with components from different blood plasma sources is difficult to compare, and the outcomes of those interactions with respect to body distribution and cell uptake are unclear. Therefore, we investigated the interactions of differently functionalized polymeric and inorganic nanoparticles with human, mouse, rabbit, and sheep plasma. The focus was put on the determination of aggregation events of the nanoparticles occurring in concentrated plasma and the correlation with the respectively formed protein coronas. Both the stability in plasma as well as the types of adsorbed proteins were found to strongly depend on the plasma source. Thus, we suggest evaluating the potential use of nanocarriers always in the plasma source of the chosen animal model for in vitro studies as well as in human plasma to pin down differences and eventually enable transfer into clinical trials in humans

Redox-Responsive Block Copolymers: Poly(vinylferrocene)‑<i>b</i>‑poly(lactide) Diblock and Miktoarm Star Polymers and Their Behavior in Solution

The synthesis of diblock and miktoarm star polymers containing poly­(vinylferrocene) (PVFc) and poly­(l-lactide) (PLA) blocks is introduced. End functionalization of PVFc was carried out via end capping of living carbanionic PVFc chains with benzyl glycidyl ether (BGE). By hydrogenolysis of the benzyl protecting group a dihydroxyl end-functionalized PVFc was obtained. Both monohydroxyl- and dihydroxyl-functionalized PVFcs have been utilized as macroinitiators for the subsequent polymerization of l-lactide via catalytic ring-opening polymerization. A series of block copolymers and AB₂ miktoarm star polymers was synthesized with varied PLA chain lengths. All polymers were characterized in detail, using ¹H NMR spectroscopy, size exclusion chromatography (SEC), and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-ToF). The molecular weight of the block copolymers and AB₂ miktoarm star polymers are in the range of 8000–15000, containing a PVFc block of weight 7800. In addition, the self-assembly behavior of the polymers in dichloromethane (CH₂Cl₂) was investigated by using dynamic light scattering (DLS) and transmission electron microscopy (TEM). In a selective solvent for PLA the block copolymers and miktoarm star polymers formed vesicle-like structures with different diameters

Denaturation via Surfactants Changes Composition of Protein Corona

The use of nanocarriers as drug delivery vehicles brings them into contact with blood plasma proteins. Polymeric nanocarriers require some sort of surfactant to ensure colloidal stability. Formation of the protein corona is therefore determined not only by the intrinsic properties of the nanocarrier itself but also by the accompanying surfactant. Although it is well-known that surfactants have an impact on protein structure, only few studies were conducted on the specific effect of surfactants on the composition of protein corona of nanocarriers. Therefore, we analyzed the composition of the protein corona on “stealth” nanoparticles with additional surfactant (cetyltrimethyl­ammonium chloride, CTMA-Cl) after plasma incubation. Additional CTMA-Cl led to an enrichment of apolipoprotein-A1 and vitronectin in the corona, while less clusterin could be found. Further, the structural stability of apolipoprotein-A1 and clusterin was monitored for a wide range of CTMA-Cl concentrations. Clusterin turned out to be more sensitive to CTMA-Cl, with denaturation occurring at lower concentrations