Water-Induced Separation of Polymers from High Nanoparticle-Content Nanocomposite Films.

Polymer nanocomposites with high loadings of nanoparticles (NPs) exhibit exceptional mechanical and transport properties. Separation of polymers and NPs from such nanocomposites is a critical step in enabling the recycling of these components and reducing the potential environmental hazards that can be caused by the accumulation of nanocomposite wastes in landfills. However, the separation typically requires the use of organic solvents or energy-intensive processes. Using polydimethylsiloxane (PDMS)-infiltrated SiO2 NP films, we demonstrate that the polymers can be separated from the SiO2 NP packings when these nanocomposites are exposed to high humidity and water. The findings indicate that the charge state of the NPs plays a significant role in the propensity of water to undergo capillary condensation within the PDMS-filled interstitial pores. We also show that the size of NPs has a crucial impact on the kinetics and extent of PDMS expulsion, illustrating the importance of capillary forces in inducing PDMS expulsion. We demonstrate that the separated polymer can be collected and reused to produce a new nanocomposite film. The work provides insightful guidelines on how to design and fabricate end-of-life recyclable high-performance nanocomposites.

Long term phase separation dynamics in liquid crystal-enriched microdroplets obtained from binary fluid mixtures.

The dynamics of long term phase separation in binary liquid mixtures remains a subject of fundamental interest. Here, we study a binary liquid mixture, where the minority phase is confined to a liquid crystal (LC)-rich droplet, by investigating the evolution of size, defect and mesogen alignment over time. We track the binary liquid mixture evolving towards equilibrium by visualising the configuration of the liquid crystal droplet through polarisation microscopy. We compare our experimental findings with computational simulations and elucidate differences between bulk phases and confined droplets based on the respective thermodynamics of phase separation. Our work provides insights on how phase transitions on the microscale can deviate from bulk phase diagrams with relevance to other material systems, such as the liquid-liquid phase separation of polymer and protein solutions.

Dual-Mode and Label-Free Detection of Exosomes from Plasma Using an Electrochemical Quartz Crystal Microbalance with Dissipation Monitoring.

The biomolecular contents of extracellular vesicles, such as exosomes, have been shown to be crucial in intercellular communication and disease propagation. As a result, there has been a recent surge in the exploration of novel biosensing platforms that can sensitively and specifically detect exosomal content such as proteins and nucleic acids, with a view toward application in diagnostic assays. Here, we demonstrate dual-mode and label-free detection of plasma exosomes using an electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D). The platform adopts a direct immunosensing approach to effectively capture exosomes via their surface protein expression of CD63. By combining QCM-D with a tandem in situ electrochemical impedance spectroscopy measurement, we are able to demonstrate relationships between mass, viscoelasticity and impedance inducing properties of each functional layer and analyte. In addition to lowering the limit of detection (by a factor of 2-4) to 6.71 × 107 exosome-sized particles (ESP) per mL in 25% v/v serum, the synergy between dissipation and impedance response introduces improved sensing specificity by offering further distinction between soft and rigid analytes, thereby promoting EQCM-D as an important technique for exosome analysis.

Solvent Vapor Annealing for Controlled Pore Expansion of Block Copolymer-Assembled Inorganic Mesoporous Films.

Mesoporous inorganic thin films are promising materials architectures for a variety of high-value applications, ranging from optical coatings and purification membranes to sensing and energy storage devices. Having precise control over the structural parameters of the porous network is crucial for broadening their applicability. To this end, the use of block copolymers (BCP) as sacrificial structure-directing agents via micelle coassembly is a particularly attractive route, since the resultant pore size is directly related to scaling laws for the radius of gyration of the pore-forming macromolecule. However, tailoring the molecular weight of the BCP via bespoke synthesis is an elaborate process that requires precise control over highly sensitive reactions conditions. Alternative methods have emerged, based on supramolecular assembly or the addition of different swelling agents. Nevertheleses, to date, these present a negative impact on the structural order and pore size dispersity of the final inorganic mesoporous films. In this work, we propose a novel and effective method for control over pore size, porosity, and structural order, which relies on a synergistic combination of BCP selective swelling via solvent vapor annealing (SVA) and locking of the structure by condensation of the inorganic sol-gel precursors. The results obtained in this work for TiO2 establish SVA as a new, straightforward, simple, and powerful route for the fabrication of mesoporous thin-film materials with controllable structural characteristics.

Quantifying the Solution Structure of Metal Nanoclusters Using Small-Angle Neutron Scattering.

Metal nanoclusters are a unique class of synthetic material, as their crystal structures can be resolved using X-ray diffraction, and their chemical formula can be precisely determinated from mass spectroscopy. However, a complete structure characterization by these two techniques is often a challenging task. Here, we utilize small-angle neutron scattering (SANS) to directly quantify the key structure parameters of a series of silver and gold nanoclusters in solution. The results not only correlate well to their crystallographic structures, but also allow the quantification of the counterions layer surrounding charged nanoclusters in solution. Furthermore, when combining with X-ray scattering, it is possible to estimate the molecular weight of both the metal core and the ligand shell of nanoclusters. This work offers an alternative characterization tool for nanoclusters without the requirement of crystallization or gas phase ionization.

Long-Life Aqueous Organic Redox Flow Batteries Enabled by Amidoxime-Functionalized Ion-Selective Polymer Membranes.

Redox flow batteries (RFBs) based on aqueous organic electrolytes are a promising technology for safe and cost-effective large-scale electrical energy storage. Membrane separators are a key component in RFBs, allowing fast conduction of charge-carrier ions but minimizing the cross-over of redox-active species. Here, we report the molecular engineering of amidoxime-functionalized Polymers of Intrinsic Microporosity (AO-PIMs) by tuning their polymer chain topology and pore architecture to optimize membrane ion transport functions. AO-PIM membranes are integrated with three emerging aqueous organic flow battery chemistries, and the synergetic integration of ion-selective membranes with molecular engineered organic molecules in neutral-pH electrolytes leads to significantly enhanced cycling stability.

Fluorinated Metal-Organic Coatings with Selective Wettability.

Surface chemistry is a major factor that determines the wettability of materials, and devising broadly applicable coating strategies that afford tunable and selective surface properties required for next-generation materials remains a challenge. Herein, we report fluorinated metal-organic coatings that display water-wetting and oil-repelling characteristics, a wetting phenomenon different from responsive wetting induced by external stimuli. We demonstrate this selective wettability with a library of metal-organic coatings using catechol-based coordination and silanization (both fluorinated and fluorine-free), enabling sensing through interfacial reconfigurations in both gaseous and liquid environments, and establish a correlation between the coating wettability and polarity of the liquids. This selective wetting performance is substrate-independent, spontaneous, durable, and reversible and occurs over a range of polar and nonpolar liquids (60 studied). These results provide insight into advanced liquid-solid interactions and a pathway toward tuning interfacial affinities and realizing robust, selective superwettability according to the surrounding conditions.

Temperature-induced liquid crystal microdroplet formation in a partially miscible liquid mixture.

Liquid-in-liquid droplets are typically generated by the partitioning of immiscible fluids, e.g. by mechanical shearing with macroscopic homogenisers or microfluidic flow focussing. In contrast, partially miscible liquids with a critical solution temperature display a temperature-dependent mixing behaviour. In this work, we demonstrate how, for a blend of methanol (MeOH) and the thermotropic liquid crystal (LC) 4-Cyano-4'-pentylbiphenyl (5CB), cooling from a miscible to an immiscible state allows the controlled formation of microdroplets. A near-room-temperature-induced phase separation leads to nucleation, growth and coalescence of mesogen-rich droplets. The size and number of the droplets is tunable on the microscopic scale by variation of temperature quench depth and cooling rate. Further cooling induces a phase transition to nematic droplets with radial configuration, well-defined sizes and stability over the course of an hour. This temperature-induced approach offers a scalable and reversible alternative to droplet formation with relevance in diagnostics, optoelectronics, materials templating and extraction processes.

Acoustic Immunosensing of Exosomes Using a Quartz Crystal Microbalance with Dissipation Monitoring.

Exosomes are endocytic lipid-membrane bound bodies with the potential to be used as biomarkers in cancer and neurodegenerative disease. The limitations and scarcity of current exosome characterization approaches have led to a growing demand for translational techniques, capable of determining their molecular composition and physical properties in physiological fluids. Here, we investigate label-free immunosensing, using a quartz crystal microbalance with dissipation monitoring (QCM-D), to detect exosomes by exploiting their surface protein profile. Exosomes expressing the transmembrane protein CD63 were isolated by size-exclusion chromatography from cell culture media. QCM-D sensors functionalized with anti-CD63 antibodies formed a direct immunoassay toward CD63-positive exosomes in 75% v/v serum, exhibiting a limit-of-detection of 2.9 × 108 and 1.4 × 108 exosome sized particles (ESPs)/mL for frequency and dissipation response, respectively, i.e., clinically relevant concentrations. Our proof-of-concept findings support the adoption of dual-mode acoustic analysis of exosomes, leveraging both frequency and dissipation monitoring for use in bioanalytical characterization.

Application of the Spatial Distribution Function to Colloidal Ordering.

2D colloidal assembly is a vital process in the fabrication of nanostructured devices and receives widespread attention in fundamental research. Characterizing the ordering is crucial to develop an understanding of the driving forces behind the assembly and to optimize processing conditions. Image analysis offers a direct evaluation pathway, typically via the radial distribution function or the 2D fast Fourier transform. Both methods have inherent limitations; the former provides no angular dependence, while the latter is challenged when confronted with imperfection on the mean size, spacing, and coverage of the building blocks. Here, we introduce the 2D spatial distribution function (SDF) as an alternative pathway to evaluate colloidal ordering. We benchmark the method in case studies of prominent examples and provide a tool kit for implementation, including an ImageJ plugin and the standalone software CORDERLY. Application and interpretation are straightforward and particularly powerful to analyze and compare colloidal assemblies with limited order.

Tuning Pore Dimensions of Mesoporous Inorganic Films by Homopolymer Swelling.

The functionality and applications of mesoporous inorganic films are closely linked to their mesopore dimensions. For material architectures derived from a block copolymer (BCP) micelle coassembly, the pore size is typically manipulated by changing the molecular weight corresponding to the pore-forming block. However, bespoke BCP synthesis is often a costly and time-consuming process. An alternative method for pore size tuning involves the use of swelling agents, such as homopolymers (HPs), which selectively interact with the core-forming block to increase the micelle size in solution. In this work, poly(isobutylene)-block-poly(ethylene oxide) micelles were swollen with poly(isobutylene) HP in solution and coassembled with aluminosilicate sol with the aim of increasing the resulting pore dimensions. An analytical approach implementing spectroscopic ellipsometry (SE) and ellipsometric porosimetry (EP) alongside atomic force microscopy (AFM) and small-angle X-ray scattering (SAXS) in transmission and grazing-incidence (GISAXS) modes enabled us to study the material evolution from solution processing through the manifestation of the mesoporous inorganic film after BCP removal. The in-depth SE/EP analysis evidenced an increase of more than 45% in mesopore diameter with HP swelling and a consistent scaling of the overall void volume and number of pores. Importantly, our analytical toolbox enabled us to study the effect of swelling on the connecting necks between adjacent pores, with observed increases as high as ≈35%, offering novel pathways to sensing, electrochemical, and other mass-transfer-dependent applications.

A Versatile AuNP Synthetic Platform for Decoupled Control of Size and Surface Composition.

While a plethora of protocols exist for the synthesis of sub-10-nm gold nanoparticles (AuNPs), independent control over the size and surface composition remains restricted. This poses a particular challenge for systematic studies of AuNP structure-function relationships and the optimization of crucial design parameters. To this end, we report on a modular two-step approach based on the synthesis of AuNPs in oleylamine (OAm) followed by subsequent functionalization with thiol ligands and mixtures thereof. The synthesis of OAm-capped AuNPs enables fine-tuning of the core size in the range of 2-7 nm by varying the reaction temperature. The subsequent thiol-for-OAm ligand exchange allows a reliable generation of thiol-capped AuNPs with target surface functionality. The compatibility of this approach with a vast library of thiol ligands provides detailed control of the mixed ligand composition and solubility in a wide range of solvents ranging from water to hexane. This decoupled control over the AuNP core and ligand shell provides a powerful toolbox for the methodical screening of optimal design parameters and facile preparation of AuNPs with target properties.

Phase behaviour and applications of a binary liquid mixture of methanol and a thermotropic liquid crystal.

Herein, we report on the phase behaviour of a binary liquid mixture composed of methanol (MeOH) and the thermotropic liquid crystal 4-cyano-4'-pentylbiphenyl (5CB). The corresponding phase diagram combines features of a conventional liquid-liquid mixture with characteristics that are particular to the nematic liquid crystal. We observe four arrangements as a function of composition and temperature, namely monophasic isotropic, monophasic nematic, biphasic isotropic-isotropic and biphasic isotropic-nematic, with an upper critical solution temperature of 24.4 ± 0.5 °C. The interplay of nematogenic and non-nematogenic species offers tunability of phase mixing and phase composition in an accessible temperature window and provides novel routes for the extraction of target compounds, here exemplarily shown for Crystal Violet, Doxorubicin, Eosin Y, Rhodamine 6G and Sudan IV.

Block copolymer self-assembly for nanophotonics.

The ability to control and modulate the interaction of light with matter is crucial to achieve desired optical properties including reflection, transmission, and selective polarization. Photonic materials rely upon precise control over the composition and morphology to establish periodic interactions with light on the wavelength and sub-wavelength length scales. Supramolecular assembly provides a natural solution allowing the encoding of a desired 3D architecture into the chemical building blocks and assembly conditions. The compatibility with solution processing and low-overhead manufacturing is a significant advantage over more complex approaches such as lithography or colloidal assembly. Here we review recent advances on photonic architectures derived from block copolymers and highlight the influence and complexity of processing pathways. Notable examples that have emerged from this unique synthesis platform include Bragg reflectors, antireflective coatings, and chiral metamaterials. We further predict expanded photonic capabilities and limits of these approaches in light of future developments of the field.

Self-cleaning antireflective optical coatings.

Low-cost antireflection coatings (ARCs) on large optical surfaces are an ingredient-technology for high-performance solar cells. While nanoporous thin films that meet the zero-reflectance conditions on transparent substrates can be cheaply manufactured, their suitability for outdoor applications is limited by the lack of robustness and cleanability. Here, we present a simple method for the manufacture of robust self-cleaning ARCs. Our strategy relies on the self-assembly of a block-copolymer in combination with silica-based sol-gel chemistry and preformed TiO2 nanocrystals. The spontaneous dense packing of copolymer micelles followed by a condensation reaction results in an inverse opal-type silica morphology that is loaded with TiO2 photocatalytic hot-spots. The very low volume fraction of the inorganic network allows the optimization of the antireflecting properties of the porous ARC despite the high refractive index of the embedded photocatalytic TiO2 nanocrystals. The resulting ARCs combine high optical and self-cleaning performance and can be deposited onto flexible plastic substrates.

Beyond the Meso/Macroporous Boundary: Extending Capillary Condensation-Based Pore Size Characterization in Thin Films Through Tailored Adsorptives.

The characterization of thin films containing nanopores with diameters exceeding 50 nm poses significant challenges, especially when deploying sorption-based techniques. Conventional volumetric physisorption or mercury intrusion methods have limited applicability in thin films due to constraints in sample preparation and nondestructive testing. In this context, ellipsometric porosimetry represents a viable alternative, leveraging its optical sensitivity to thin films. With existing setups relying on the capillary condensation of volatile compounds such as water, applicability is typically restricted to pore dimensions <50 nm. In this study, we introduce two high-molar-mass hydrocarbon adsorptives, namely ethylbenzene and n-nonane. These adsorptives exhibit substantial potential in improving the accuracy of physisorption measurements beyond mesoporosity (i.e., >50 nm). Specifically, with n-nonane, applicability is extended up to 80 nm pores. Our measurement guidelines propose a nondestructive, expeditious (<60 min), low-pressure (<0.03 bar) approach to investigate nanoporous thin films with potential adaptability to diverse structural architectures.

Recent developments in biosensing methods for extracellular vesicle protein characterization.

Research into extracellular vesicles (EVs) has grown significantly over the last few decades with EVs being widely regarded as a source of biomarkers for human health and disease with massive clinical potential. Secreted by every cell type in the body, EVs report on the internal cellular conditions across all tissue types. Their presence in readily accessible biofluids makes the potential of EV biosensing highly attractive as a noninvasive diagnostic platform via liquid biopsies. However, their small size (50-250 nm), inherent heterogeneity, and the complexity of the native biofluids introduce challenges for effective characterization, thus, limiting their clinical utility. This has led to a surge in the development of various novel EV biosensing techniques, with capabilities beyond those of conventional methods that have been directly transferred from cell biology. In this review, key detection principles used for EV biosensing are summarized, with a focus on some of the most recent and fundamental developments in the field over the last 5 years. This article is categorized under: Diagnostic Tools > Biosensing Diagnostic Tools > In Vitro Nanoparticle-Based Sensing.

Amplified EQCM-D detection of extracellular vesicles using 2D gold nanostructured arrays fabricated by block copolymer self-assembly.

Extracellular vesicles (EVs) are routinely released from nearly all cell types as transport vehicles and for cell communication. Crucially, they contain biomolecular content for the identification of health and disease states that can be detected from readily accessible physiological fluids, including urine, plasma, or saliva. Despite their clinical utility within noninvasive diagnostic platforms such as liquid biopsies, the currently available portfolio of analytical approaches are challenged by EV heterogeneity in size and composition, as well as the complexity of native biofluids. Quartz crystal microbalance with dissipation monitoring (QCM-D) has recently emerged as a powerful alternative for the phenotypic detection of EVs, offering multiple modes of analyte discrimination by frequency and dissipation. While providing rich data for sensor development, further progress is required to reduce detection limits and fully exploit the technique's potential within biosensing. Herein, we investigate the impact of nanostructuring the sensor electrode surface for enhancing its detection capabilities. We employ self-assembly of the block copolymer polystyrene-block-poly(4-vinylpyridine) to create well defined 2D gold islands via selective impregnation of the pyridine domain with gold precursors and subsequent removal of the template. When matched to the EV length scale, we find a 4-fold improvement in sensitivity despite a 4-fold reduction in area for analyte and ligand anchoring in comparison to a flat sensor surface. Creation of tailored and confined sensing regions interspersed by non-binding silica provides optimal spatial orientation for EV capture with reduced steric effects and negative cooperativity of grafted antibodies, offering a promising route for facilitated binding and enhanced performance of sensor platforms.

Glucose Oxidase Loading in Ordered Porous Aluminosilicates: Exploring the Potential of Surface Modification for Electrochemical Glucose Sensing.

Enzymatic electrochemical sensors have become the leading glucose detection technology due to their rapid response, affordability, portability, selectivity, and sensitivity. However, the performance of these sensors is highly dependent on the surface properties of the electrode material used to store glucose oxidase and its ability to retain enzymatic activity under variable environmental conditions. Mesoporous thin films have recently attracted considerable attention as promising candidates for enzyme storage and activity preservation due to their well-defined nanoarchitecture and tunable surface properties. Herein, we systematically compare pathways for the immobilization of glucose oxidase (GOx) and their effectiveness in electrochemical glucose sensing, following modification protocols that lead to the electrostatic attraction (amino functionalization), covalent bonding (aldehyde functionalization), and electrostatic repulsion (oxygen plasma treatment) of the ordered porous aluminosilicate-coated electrodes. By direct comparison using a quartz crystal microbalance, we demonstrate that glucose oxidase can be loaded in a nanoarchitecture with a pore size of ∼50 nm and pore interconnections of ∼35 nm using the native aluminosilicate surface, as well as after amino or aldehyde surface modification, while oxygen plasma exposure of the native surface inhibits glucose oxidase loading. Despite a variety of routes for enzyme loading, quantitative electrochemical glucose sensing between 0 and 20 mM was only possible when the porous surface was functionalized with amino groups, which we relate to the role of surface chemistry in accessing the underlying substrate. Our results highlight the impact of rational surface modification on electrochemical biosensing performance and demonstrate the potential of tailoring porous nanoarchitecture surfaces for biosensing applications.