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The coupling of structural transitions to heat capacity changes leads to destabilization of macromolecules at both, elevated and lowered temperatures. DNA origami not only exhibit this property but also provide a nanoscopic observable of cold denaturation processes by directing intramolecular strain to the most sensitive elements within their hierarchical architecture.

Liquid-liquid phase separation (LLPS) is a process through which a homogeneous phase separates into two or multiple phases. This process is observed in systems spanning biology and synthetic polymeric systems. The distinct phases have direct influence on things like material properties, morphology, and material interactions with other interfaces. In my research, I explore how phase separated droplets influence self-assembled polymer morphologies in solution and on solid substrates. I used techniques like cryogenic electron microscopy (cryo-EM), liquid phase electron microscopy (LP-EM), and optical microscopy to study my systems. I developed the first example of nonionic block copolymer coacervates and demonstrated how the coacervates encode morphological information towards the solid phase self-assembly. Using LPEM, I showed block copolymer coacervates are also intermediates during supported bilayer formation. This new mechanism of bilayer assembly should be beneficial for forming pristine supported bilayers. Additionally, I discovered the auto-confining effects within the phase separated droplets were shown to favor complex block copolymer morphologies that are usually accessed by inducing confinement of block copolymers in emulsions. Furthermore, I developed a model block copolymer system in which LLPS occurs during light-induced polymerization mimicking active biological processes. Lastly, I developed a workflow to image phase separated droplets of polymers or proteins using cryo-EM which enabled 2D and 3D nanoscale characterization. The collection of this work informs how phase separated droplets behave and influence block copolymer self-assembly.

In recent years, more and more research was conducted to explore smaller and smaller systems that become similar to an actual micro/nano-robot. The major roadblock regarding their real world implementation is the highly restricted available volume. In this paper, we introduce folding – hence an origami technology using Al2O3 as building material, which is compatible with current Si technology. High quality 50 nm thin Al2O3 film is grown by atomic layer desposition, patterned, thinned and then released from the Si subtrate using SF6 plasma etching. The realized free standing Al2O3 structure would fold itself at predefined regions due to the stress in the as deposited films. We believe such technology could offer a new possibility to tackle the problem of efficiently using the volume. Al2O3 could act as both the structural origami material and the functional gate dielectric material for electronics. This approach enables the feasibility of patterning devices and circuits on every Al2O3 facet of a 3D object, while the inside volume of this object is still available for 3D bulk device components. We demonstrate the optimized etching process as well as an emperical improvement of the folding hinges and of the overall structural stability.

Polyolefins have quickly become one of the world’s most utilized products since their discovery in the 1950s. With 350 million tons produced each year, it is clear that the use of polyolefins is not subsiding in the near future. Instead, it is imperative to develop novel materials that are more efficient than their current counterparts. As the function of a plastic is derived from its properties, creating polyolefins with designable and targetable attributes is a major priority. The Sita group has played a huge role in the development of ‘precision’ polyolefins. The techniques employed allow for the scalable synthesis of a plethora of polyolefins. To do this, input variables such as the monomer, tacticity, molar mass, and molar mass distribution are controlled in an organized manner to affect output properties such as crystallinity, elasticity, and tensile strength. The ability to create diverse plastics is necessary for the functions asked of them, however, the missing element in almost all polyolefin synthesis is chemical functionality. The inert nature of polyolefins leads to limited reactivity, therefore, reducing possible chemical reactions, such as recycling. The goal of this work is to increase the scope of functional polyolefins so that new materials with improved properties can be produced. The first step in adding functionality is choosing the proper functional group. A drawback to many polyolefin functionalities currently under study is that they have a very limited scope. Functional groups are designed and used individually, requiring different compounds for each target functionality. To overcome this obstacle, aryl functional groups were targeted in this report. Phenyl functionalities are known for undergoing a range of chemical transformations leading to a wide variety of possible materials. Described in this report, aryl-functionalized polyolefins were synthesized using three different techniques. Each method has been shown to later undergo post-synth

Colloidal quantum dot (QD) solids have long been considered a promising nanomaterial, combining the wide range of material property-tuning capabilities associated with the nanoscale and the potential for comparable performance in optoelectronic and photovoltaic applications to those of a conventional bulk material. However, most research in this field focuses on amorphous QD solids, the extremely short-range order of which greatly hinders charge transport within the film. To counter this, we have developed a fabrication method for three-dimensional PbSe QD superlattices that utilizes self-assembly on a liquid subphase, as well as photo-triggered formation of the desired epitaxially-fused superlattice (epi-SL). These epi-SLs possess high spatial order, with crystalline grains on the micron length scale, and carrier mobilities several orders of magnitude higher than that of an amorphous QD film. Combining this with atomic layer deposition infilling will passivate any remaining defect states within the epi-SL, eventually triggering mini-band formation and achieving delocalized charge transport similar to that observed in bulk semiconductors.

Intriguing phase morphology was formed through self-assembly of polylactide-polystyrene (PLA-co-PS) graft copolymers blended with polylactide (PLA). PLA-co-PS graft copolymers were synthesized by exploiting a styrene-functionalized 1,3-Dioxolan-4-one (StyDOX) monomer through a two-step procedure and their structure was confirmed. Different amounts of PLA-co-PS and commercial PLA were solution cast to blend films. Etching of amorphous PLA revealed the presence of spherical micrometer sized domains dispersed within the films, arising from the self-assembly behavior of PLA-co-PS caused by the immiscibility of PS-grafts in the PLA matrix. EDS and IR imaging analyses further revealed that these microspheres were characterized by a PS-rich core opposed to the PLA-rich outer shell, which is expected to be miscible and able to form favorable interactions with the PLA matrix. PLA/PS blends were also prepared with different loadings of PLA-co-PS. The ability of PLA-co-PS to compatibilize the two phases was assessed through rheological analyses. Finally, the possibility to chemically recycle the copolymer was evaluated., QC 20230612

Synaptic devices with linear high-speed switching can accelerate learning in artificial neural networks (ANNs) embodied in hardware. Conventional resistive memories however suffer from high write noise and asymmetric conductance tuning, preventing parallel programming of ANN arrays. Electrochemical random-access memories (ECRAMs), where resistive switching occurs by ion insertion into a redox-active channel, aim to address these challenges due to their linear switching and low noise. ECRAMs using 2D materials and metal oxides however suffer from slow ion kinetics, whereas organic ECRAMs enable high-speed operation but face challenges toward on-chip integration due to poor temperature stability of polymers. Here, ECRAMs using 2D titanium carbide (Ti3C2Tx) MXene that combine the high speed of organics and the integration compatibility of inorganic materials in a single high-performance device are demonstrated. These ECRAMs combine the speed, linearity, write noise, switching energy, and endurance metrics essential for parallel acceleration of ANNs, and importantly, they are stable after heat treatment needed for back-end-of-line integration with Si electronics. The high speed and performance of these ECRAMs introduces MXenes, a large family of 2D carbides and nitrides with more than 30 stoichiometric compositions synthesized to date, as promising candidates for devices operating at the nexus of electrochemistry and electronics., QC 20220615

Cellulose nanofibril (CNF) hybrid materials show great promise as sustainable alternatives to oil-based plastics owing to their abundance and renewability. Nonetheless, despite the enormous success achieved in preparing CNF hybrids at the laboratory scale, feasible implementation of these materials remains a major challenge due to the time-consuming and energy-intensive extraction and processing of CNFs. Here, we describe a scalable materials processing platform for rapid preparation (<10 min) of homogeneously distributed functional CNF-gibbsite and CNF-graphite hybrids through a pH-responsive self-assembly mechanism, followed by their application in gas barrier, flame retardancy, and energy storage materials. Incorporation of 5 wt % gibbsite results in strong, transparent, and oxygen barrier CNF-gibbsite hybrid films in 9 min. Increasing the gibbsite content to 20 wt % affords them self-extinguishing properties, while further lowering their dewatering time to 5 min. The strategy described herein also allows for the preparation of freestanding CNF-graphite hybrids (90 wt % graphite) that match the energy storage performance (330 mA h/g at low cycling rates) and processing speed (3 min dewatering) of commercial graphite anodes. Furthermore, these ecofriendly electrodes can be fully recycled, reformed, and reused while maintaining their initial performance. Overall, this versatile concept combines a green outlook with high processing speed and material performance, paving the way toward scalable processing of advanced ecofriendly hybrid materials., QC 20230502

The rapid growth of digital information in the world necessitates a big leap in improving the existing technologies for magnetic recording. For the best modern perpendicular recording, the highest coercivity materials with minimal volume are required. We present a study of a facile technology for establishing mono- and multilayer surfaces from various single-domain flat magnetic nanoparticles that exhibit a strong perpendicular-oriented magnetic moment on solid and flexible substrates. Surfactant-free, hard ferromagnetic, and single-domain anisotropic strontium hexaferrite SrFe12O19nanoparticles with a perpendicular magnetic moment orientation and two different aspect ratios are self-ordered into magnetic thin nanofilms, exploiting the templating effect of cellulose nanofibrils and magnetic fields. Uniform magnetic coatings obtained by the scalable layer-by-layer spray deposition from a monolayer coverage up to thicknesses of a few tens of nanometers show a preferred in-plane orientation of the hard-magnetic nanoparticles. High coercivities of the films of up to 5 kOe and a high perpendicular anisotropy of Mr⊥/Ms> 80% are found. The application of the magnetic field during film deposition ensures additional improvement in perpendicular magnetic anisotropy and the appearance of residual magnetization in the film of up to 0.6Ms. For low-aspect-ratio nanoparticles stacked in periodic planar structures, the signs of the photonic band gap are revealed. The ability to create scalable, thin magnetic structures based on nanosized particles/building blocks opens great opportunities for their application in a wide variety of optoelectronic and magnetic storage devices., QC 20230421

Radiative cooling forms an emerging direction in which objects are passively cooled via thermal radiation to cold space. Cooling materials should provide high thermal emissivity (infrared absorptance) and low solar absorptance, making cellulose an ideal and sustainable candidate. Broadband solar-reflective or transparent coolers are not the only systems of interest, but also more pleasingly looking colored systems. However, solutions based on wavelength-selective absorption generate not only color but also heat and thereby counteract the cooling function. Intended as coatings for solar cells, we demonstrate a transreflective cellulose material with minimal solar absorption that generates color by wavelength-selective reflection, while it transmits other parts of the solar spectrum. Our solution takes advantage of the ability of cellulose nanocrystals to self-assemble into helical periodic structures, providing nonabsorptive films with structurally colored reflection. Application of violet-blue, green, and red cellulose films on silicon substrates reduced the temperature by up to 9 °C under solar illumination, as result of a combination of radiative cooling and reduced solar absorption due to the wavelength-selective reflection by the colored coating. The present work establishes self-assembled cellulose nanocrystal photonic films as a scalable photonic platform for colored radiative cooling., QC 20230404

In this paper, it is shown that the nanoscopic design of combining semiconductors and noble metals has a direct impact on the macroscopic (electrochemical) properties of their assembled, hyperbranched, macroscopic gel networks. Controlled and arbitrary deposition of gold domains on CdSe/CdS nanorods leads to tipped and randomly decorated heteroparticles, respectively. Structural and optical properties of the gel networks depend upon assembling the hybrid particles by means of oxidative or ionic routes. Additionally, the impact of different building block designs on the charge carrier separation processes is investigated from spectroelectrochemical point of view. A more efficient charge carrier separation is revealed in the tipped design manifesting in higher negative photocurrent efficiencies compared to the arbitrary decoration, where the charge recombination processes are more remarkable. This work sheds light on the importance of the nanostructuring on the spectroelectrochemical properties at the macroscale paving the way towards their use in photochemical reactions.

Hydrogen sulfide (H2S) is an important signalling molecule with potential pharmaceutical applications. In pursuit of a suitable delivery system for H2S, herein we apply an amphiphilic trisulfide to concomitantly alter the mesophase behaviour of dispersed lipid particles and enable triggered H2S release. Amperometric release studies indicate the trisulfide acts as a sustained H2S donor, with inclusion into the mesophase attenuating release vs neat dispersed trisulfide. Taken together the results highlight the potential for including trisulfide-based additives in stimuli-responsive drug delivery vehicles.

One of the major challenges in modern robotics is controlling micromanipulation by active and adaptive materials. In the respiratory system, such actuation enables pathogen clearance by means of motile cilia. While various types of artificial cilia have been engineered recently, they often involve complex manufacturing protocols and focus on transporting liquids only. Here, soft magnetic carpets are created via an easy self-assembly route based on the Rosensweig instability. These carpets can transport not only liquids but also solid objects that are larger and heavier than the artificial cilia, using a crowd-surfing effect.This amphibious transportation is locally and reconfigurably tunable by simple micromagnets or advanced programmable magnetic fields with a high degree of spatial resolution. Two surprising cargo reversal effects are identified and modeled due to collective ciliary motion and nontrivial elastohydrodynamics. While the active carpets are generally applicable to integrated control systems for transport, mixing, and sorting, these effects can also be exploited for microfluidic viscosimetry and elastometry.

The HIV-1 viral capsid is a conical-shaped protein shell consisting of approximately 1500 copies of a single capsid (CA) protein, arranged into a lattice of hexamers and precisely 12 pentamers. These pentamers form the vertices that result in the enclosed conical shape. The capsid encapsulates the viral genome and its associated replication machinery (known collectively as the capsid core), and has a functional role in almost every step of the early stage of the virus life cycle, including nuclear translocation, reverse transcription, and nuclear import, before undergoing controlled disassembly inside the nucleus to release the genomic content. The dynamics which control the coordinated behaviour of the capsid subunits are complex and not well understood, yet they remain critical to our understanding of the fundamental principles underlying viral self-assembly.Methods were established to create CA binding sites to specific regions of the DNA scaffolds to provide control over relative spatial positions of multiple subunits at low nanometre resolution. With this system, we were able to probe and measure CA inter-subunit binding kinetics for the first time using surface plasmon resonance. The approach provided sufficient sensitivity to measure extremely weak interactions between CA subunits via the intra-hexamer interface, and showed that binding of the sixth subunit within a hexamer may exhibit weak cooperativity. We also demonstrated that the inter-hexamer interface can be disrupted with a single point mutation.In addition, we structurally characterised the solution structure of the isolated CA hexamer using small-angle X-ray scattering and cryo-electron microscopy, which revealed close structural similarities with existing crystal structures and lattice-derived reconstructions of CA hexamers. We also used DNA scaffolds to assemble stable isolated hexamers without requiring salt-induced lattice assembly for the first time, and used this approach to attempt constructi

Assembly of nanoscale objects into linear architectures resembling molecular polymers is a basic organization resulting from divalent interactions. Such linear architectures occur for particles with two binding patches on opposite sides, known as Janus particles. However, unlike molecular systems where valence bonds can be envisioned as pointlike interactions nanoscale patches are often realized through multiple molecular linkages. The relationship between the characteristics of these linkages, the resulting interpatch connectivity, and assembly morphology is not well-explored. Here, we investigate assembly behavior of model divalent nanomonomers, DNA nanocuboid with tailorable multilinking bonds. Our study reveals that the characteristics of individual molecular linkages and their collective properties have a profound effect on nanomonomer reactivity and resulting morphologies. Beyond linear nanopolymers, a common signature of divalent nanomonomers, we observe an effective valence increase as linkages lengthened, leading to the nanopolymer bundling. The experimental findings are rationalized by molecular dynamics simulations. © 2021 The Authors. Published by American Chemical Society.

The interfacial structuring of three non-halogenated ionic liquids was examined at the air-liquid interface for both dry and humid condition by analysis of X-ray reflectometry data using a slab model approach. The aim was to investigate the effect of humidity on the air-liquid interface. Pure ionic liquids as well as solutions of 5% w/w and 20% w/w in propylene carbonate were examined. Three different cations were used, a phosphonium cation ([P6,6,6,14]+) and two dialkylimidazolium cations ([C6C1Im]+ and [C10C1Im]+). The anion was bis(mandelato)borate ([BMB]-), which is a non-commercial anion that has been shown to exhibit excellent tribological properties. The results reveal that the presence of ambient water has an impact on the interfacial structure and the layering of all pure ionic liquids, as well as most cases of ionic liquid solutions. Exposure to humidity had the largest response in the case of all pure and diluted solutions of [C6C1Im][BMB], for which a more pronounced layering was observed. The [P6,6,6,14][BMB] solutions did not exhibit any significant changes when exposed to ambient water, with the 20% w/w solution proving to be the most stable., Gränsskiktsstrukturen hos tre olika icke-halogenerade jonvätskor undersöktes vid luft-vätskegränsskiktet för både torra och fuktiga förhållanden genom analys av data från en röntgen reflektometer med en “slab model approach”. Målet var att undersöka effekten av luftfuktighet på luft-vätskagränsskiktet. Rena jonvätskor såväl som lösningar av 5 och 20 vikt-% utspädda i propylenkarbonat undersöktes. Tre olika katjoner användes, en fosforkatjon ([P6,6,6,14]+) samt två dialkylimidazoliumkatjoner ([C6C1Im]+ och [C10C1Im]+). Anjonen var bis(madelato)borat ([BMB]-), vilket är en icke-kommersiell anjon som har visat bra tribologiska egenskaper. Resultatet visar att närvaron av omgivande vatten har en påverkan på gränsskiktsstrukturen samt skiktning hos alla rena jonvätskor och de flesta utspädda lösningar. Exponering för fuktighet hade den största inverkan på alla rena och utspädda lösningar av [C6C1Im][BMB], för vilka en mer distinkt skiktning kunde observeras. [P6,6,6,14][BMB] lösningar uppvisade inga signifikanta ändringar vid exponering till fuktig luft, där den lösning med 20 vikt-% visade sig vara mest stabil.

Cooperative self-assembly (co-assembly) of diblock copolymers (DBCs) and inorganic precursors that takes inspiration from the rich phase separation behavior of DBCs can enable the realization of a broad spectrum of functional nanostructures with the desired sizes. In a DBC assisted sol–gel chemistry approach with polystyrene-block-poly(ethylene oxide) and ZnO, hybrid films are formed with slot-die coating. Pure DBC films are printed as control. In situ grazing-incidence small-angle X-ray scattering measurements are performed to investigate the self-assembly and co-assembly process during the film formation. Combining complementary ex situ characterizations, several distinct regimes are differentiated to describe the morphological transformations from the initially solvent-dispersed to the ultimately solidified films. The comparison of the assembly pathway evidences that the key step in the establishment of the pure DBC film is the coalescence of spherical micelles toward cylindrical domains. Due to the presence of the phase-selective precursor, the formation of cylindrical aggregates in the solution is crucial for the structural development of the hybrid film. The pre-existing cylinders in the ink impede the domain growth of the hybrid film during the subsequent drying process. The precursor reduces the degree of order, prevents crystallization of the PEO block, and introduces additional length scales in the hybrid films., QC 20220427

Polyethylene oxide (PEO) is one of the most widely used polymeric ion conductors which has the potential for a wide range of applications in energy storage. The enhancement of ionic conductivity of PEO-based electrolytes is generally achieved by sacrificing the mechanical properties. Using layer-by-layer (LbL) self-assembly with a nanoscale precision, mechanically strong and self-healable PEO/polyacrylic acid composite thin films with a high Li+ conductivity of 2.3 ± 0.8 × 10−4 S cm−1 at 30 °C, and a strength of 3.7 MPa is prepared. These values make the LbL composite among the best recorded multifunctional solid electrolytes. The electrolyte thin film withstands at least 1000 cycles of striping/plating of Li at 0.05 mA cm−2. It is further shown that the LbL thin films can be used as separators for Li-ion batteries to deliver a capacity of 116 mAh g−1 at 0.1 C in an all-LbL-assembled lithium iron phosphate/lithium titanate battery. Finally, it is demonstrated that the thin films can be used as ion-conducting substrates for flexible electrochemical devices, including micro supercapacitors and electrochemical transistors., QC 20220331

COVID-19 is primarily known as a respiratory disease caused by the virus SARS-CoV-2. However, neurological symptoms such as memory loss, sensory confusion, cognitive and psychiatric issues, severe headaches, and even stroke are reported in as many as 30% of cases and can persist even after the infection is over (so-called ‘long COVID’). These neurological symptoms are thought to be caused by brain inflammation, triggered by the virus infecting the central nervous system of COVID-19 patients, however we still don’t fully understand the mechanisms for these symptoms. The neurological effects of COVID-19 share many similarities to neurodegenerative diseases such as Alzheimer’s and Parkinson’s in which the presence of cytotoxic protein-based amyloid aggregates is a common etiological feature. Following the hypothesis that some neurological symptoms of COVID-19 may also follow an amyloid etiology we performed a bioinformatic scan of the SARS-CoV-2 proteome, detecting peptide fragments that were predicted to be highly amyloidogenic. We selected two of these peptides and discovered that they do rapidly self-assemble into amyloid. Furthermore, these amyloid assemblies were shown to be highly toxic to a neuronal cell line. We introduce and support the idea that cytotoxic amyloid aggregates of SARS-CoV-2 proteins are causing some of the neurological symptoms commonly found in COVID-19 and contributing to long COVID, especially those symptoms which are novel to long COVID in contrast to other post-viral syndromes.

Engineered polymeric nanoparticles (NPs) have been comprehensively explored as potential platforms for diagnosis and targeted therapy for several diseases including cancer. Herein, we designed functional poly(acrylic acid)-b-poly(butyl acrylate) (PAA-b-PBA) NPs using reversible addition-fragmentation chain-transfer (RAFT)-mediated emulsion polymerization via polymerization-induced self-assembly (PISA). The hydrophilic PAA-macroRAFT, forming a stabilizing shell (i.e., corona), was chain-extended using the hydrophobic monomer n-butyl acrylate (n-BA), resulting in stable, monodisperse, and reproducible PAA-b-PBA NPs, typically having a diameter of 130 nm. The surface engineering of the PAA-b-PBA NP post-PISA were explored using a two-step approach. The hydrophilic NP-shell corona was modified with allyl groups under mild conditions, using allylamine in water, which resulted in stable allyl-functional NPs (allyl-NPs) suitable for further bioconjugation. The allyl-NPs were subsequently conjugated with a thiol-functional fluorescent dye (BODIPY-SH) to the allyl groups using "thiol-ene"-click chemistry, to mimic the attachment of a thiol-functional target ligand. The successful attachment of BODIPY-SH to the allyl-NPs was corroborated by UV-vis spectroscopy, showing the characteristic absorbance of the BODIPY-fluorophore at 500 nm. Despite modification of NPs with allyl groups and attachment of BODIPY-SH, the NPs retained their colloidal stability and monodispersity as indicated by DLS. This demonstrates that post-PISA functionalization is a robust method for synthesizing functional NPs. Neither the NPs nor allyl-NPs showed significant cytotoxicity toward RAW264.7 or MCF-7 cell lines, which indicates their desirable safety profile. The cellular uptake of the NPs using J774A cells in vitro was found to be time and concentration dependent. The anti-cancer drug doxorubicin was efficiently (90%) encapsulated into the PAA-b-PBA NPs during NP formation. After a small initial bur, QC 20210525

The formation of block copolymer nanoparticles is commonly obtained by switching solvent quality from good solvent for both blocks to a selective solvent for one block. The effect of the selective solvent on particle dimension, shape and inner structure has been analyzed in detail, instead less attention has been focused on the role of the common solvent. Poly(ethylene oxide)-block-poly(lactic acid) (PEO-b-PLA) is widely used for the preparation of nanometric drug delivery systems and the control of the particle morphology has relevant effects on bioactivity. In this work we investigate the effect of using different common solvents (acetone, dioxane, tetrahydrofuran, dimethylformamide) on the self-assembly behavior of narrowly dispersed PEO-b-PLA copolymers, synthesized by metal free ring-opening polymerization, with large variation of molecular weight of the hydrophobic block (from 65 to 1300 lactic units). Dynamic light scattering (DLS) and cryo-electron microscopy (cryo-EM) analyses of PEO-b-PLA nanoparticles reveal that their size and shape are strongly dependent on the hydrogen bonding ability of the common solvent used in the self-assembly process. As consequence of these variations, also the cytoxicity of the nanoparticles is affected.

Control of interactions between nanomaterials and cells remains a biomedical challenge. A strategy is proposed to modulate the intralysosomal distribution of nanoparticles through the design of 3D suprastructures built by hydrophilic nanocrystals (NCs) coated with alkyl chains. The intracellular fate of two water-dispersible architectures of self-assembled hydrophobic magnetic NCs: hollow deformable shells (colloidosomes) or solid fcc particles (supraballs) is compared. These two self-assemblies display increased cellular uptake by tumor cells compared to dispersions of the water-soluble NC building blocks. Moreover, the self-assembly structures increase the NCs density in lysosomes and close to the lysosome membrane. Importantly, the structural organization of NCs in colloidosomes and supraballs are maintained in lysosomes up to 8 days after internalization, whereas initially dispersed hydrophilic NCs are randomly aggregated. Supraballs and colloidosomes are differently sensed by cells due to their different architectures and mechanical properties. Flexible and soft colloidosomes deform and spread along the biological membranes. In contrast, the more rigid supraballs remain spherical. By subjecting the internalized suprastructures to a magnetic field, they both align and form long chains. Overall, it is highlighted that the mechanical and topological properties of the self-assemblies direct their intracellular fate allowing the control intralysosomal density, ordering, and localization of NCs., QC 20201214

Nanocellulose (NC)-based hybrid coatings and films containing CeO2 and SiO2 nanoparticles (NPs) to impart UV screening and hardness properties, respectively, were prepared by solvent casting. The NC film-forming component (75 wt % of the overall solids) was composed entirely of cellulose nanocrystals (CNCs) or of CNCs combined with cellulose nanofibrils (CNFs). Zeta potential measurements indicated that the four NP types (CNC, CNF, CeO2, and SiO2) were stably dispersed in water and negatively charged at pH values between 6 and 9. The combination of NPs within this pH range ensured uniform formulations and homogeneous coatings and films, which blocked UV light, the extent of which depended on film thickness and CeO2 NP content, while maintaining good transparency in the visible spectrum (∼80%). The addition of a low amount of CNFs (1%) reduced the film hardness, but this effect was compensated by the addition of SiO2 NPs. Chiral nematic self-assembly was observed in the mixed NC film; however, this ordering was disrupted by the addition of the oxide NPs. The roughness of the hybrid coatings was reduced by the inclusion of oxide NPs into the NC matrix perhaps because the spherical oxide NPs were able to pack into the spaces between cellulose fibrils. We envision these hybrid coatings and films in barrier applications, photovoltaics, cosmetic formulations, such as sunscreens, and for the care and maintenance of wood and glass surfaces, or other surfaces that require a smooth, hard, and transparent finish and protection from UV damage., QC 20200714.QC 20210318.

Early detection of cancer is likely to be one of the most effective means of reducing the cancer mortality rate. Hence, simple and ultra-quick methods for noninvasive detection of early-stage tumors are highly sought-after. In this study, a nanobiosensing platform with a rapid response time of nearly 30 s is introduced for the detection of matrilysin—the salivary gland cancer biomarker—with a limit of detection as low as 30 nm. This sensing platform is based on matrilysin-digestible peptides that bridge gold nanoparticle (AuNPs) cores (≈30–50 nm) and carbon quantum dot (CDs) satellites (≈9 nm). A stepwise synthesis procedure is used for self-assembly of AuNP-peptide-CDs, ensuring their long-term stability. The AuNP-peptide-CDs produce ideal optical signals, with noticeable fluorescence quenching effects. Upon peptide cleavage by matrilysin, CDs leave the surface of AuNPs, resulting in ultra-fast detectable violet and visible fluorescent signals., QC 20200630

Scalable fabrication of high-rate micro-supercapacitors (MSCs) is highly desired for on-chip integration of energy storage components. By virtue of the special self-assembly behavior of 2D materials during drying thin films of their liquid dispersion, a new inkjet printing technique of passivated graphene micro-flakes is developed to directly print MSCs with 3D networked porous microstructure. The presence of macroscale through-thickness pores provides fast ion transport pathways and improves the rate capability of the devices even with solid-state electrolytes. During multiple-pass printing, the porous microstructure effectively absorbs the successively printed inks, allowing full printing of 3D structured MSCs comprising multiple vertically stacked cycles of current collectors, electrodes, and sold-state electrolytes. The all-solid-state heterogeneous 3D MSCs exhibit excellent vertical scalability and high areal energy density and power density, evidently outperforming the MSCs fabricated through general printing techniques.[Figure not available: see fulltext.]., QC 20200330

Magnetic nanogels represent a cutting edge of magnetic soft matter research due to their numerous potential applications. Here, using Langevin dynamics simulations, we analyse the influence of magnetic nanogel concentration and embedded magnetic particle interactions on the self-assembly of magnetic nanogels at zero field. For this, we calculated radial distribution functions and structure factors for nanogels and magnetic particles within them. We found that, in comparison to suspensions of free magnetic nanoparticles, where the self-assembly is already observed if the interparticle interaction strength exceeds the thermal fluctuations by approximately a factor of three, self-assembly of magnetic nanogels only takes place by increasing such ratio above six. This magnetic nanogel self-assembly is realised by means of favourable close contacts between magnetic nanoparticles from different nanogels. It turns out that for high values of interparticle interactions, corresponding to the formation of internal rings in isolated nanogels, in their suspensions larger magnetic particle clusters with lower elastic penalty can be formed by involving different nanogels. Finally, we show that when the self-assembly of these nanogels takes place, it has a drastic effect on the structural properties even if the volume fraction of magnetic nanoparticles is low. © 2019 Elsevier B.V.

Using Langevin dynamics simulations, we investigate the self-assembly of magnetic nanogels in the presence of applied magnetic fields of moderate strength. We find that even weak fields lead to drastic changes in the structure factors of both, the embedded magnetic nanoparticles and of whole nanogel particles. Nanogels assemble by uniting magnetic particle clusters forming inter-gel bridges. At zero field the average amount of such bridges for a pair of nanogels is close to one, whereas even for weak fields it fastly doubles. Rapid growth of cluster size at low values of the applied field is followed by a broad region of slow increase, caused by the mechanical constraints imposed the polymer matrix. The influence of the latter manifests itself in both, the slow growth of the magnetisation curve at intermediate fields and the slow decay of the total Zeeman energy. © 2020

In this work, we show how and why the interactions between charged cubic colloids range from radially isotropic to strongly directionally anisotropic, depending on tuneable factors. Using molecular dynamics simulations, we illustrate the effects of typical solvents to complement experimental investigations of cube assembly. We find that in low-salinity water solutions, where cube self-assembly is observed, the colloidal shape anisotropy leads to the strongest attraction along the corner-to-corner line, followed by edge-to-edge, with a face-to-face configuration of the cubes only becoming energetically favorable after the colloids have collapsed into the van der Waals attraction minimum. Analysing the potential of mean force between colloids with varied cubicity, we identify the origin of the asymmetric microstructures seen in experiment. This journal is © The Royal Society of Chemistry.

Thermoresponsive poly(glycidyl ether) brushes can be grafted to applied tissue culture substrates and used for the fabrication of primary human cell sheets. The self-assembly of such brushes is achieved via the directed physical adsorption and subsequent UV immobilization of block copolymers equipped with a short, photo-reactive benzophenone-based anchor block. Depending on the chemistry and hydrophobicity of the benzophenone anchor, we demonstrate that such block copolymers exhibit distinct thermoresponsive properties and aggregation behaviors in water. Independent on the block copolymer composition, we developed a versatile grafting-to process which allows the fabrication of poly(glycidyl ether) brushes on various tissue culture substrates from dilute aqueous-ethanolic solution. The viability of this process crucially depends on the chemistry and hydrophobicity of, both, benzophenone-based anchor block and substrate material. Utilizing these insights, we were able to manufacture thermoresponsive poly(glycidyl ether) brushes on moderately hydrophobic polystyrene and polycarbonate as well as on rather hydrophilic polyethylene terephthalate and tissue culture-treated polystyrene substrates. We further show that the temperature-dependent switchability of the brush coatings is not only dependent on the cloud point temperature of the block copolymers, but also markedly governed by the hydrophobicity of the surface-bound benzophenone anchor and the subjacent substrate material. Our findings demonstrate that the design of amphiphilic thermoresponsive block copolymers is crucial for their phase transition characteristics in solution and on surfaces. © 2020 by the authors.

A novel platform of dendritic nanogels is herein presented, capitalizing on the self-assembly of allyl-functional polyesters based on dendritic-linear-dendritic amphiphiles followed by simple cross-linking with complementary monomeric thiols via UV initiated off-stoichiometric thiol-ene chemistry. The facile approach enabled multigram creation of allyl reactive nanogel precursors, in the size range of 190–295 nm, being readily available for further modifications to display a number of core functionalities while maintaining the size distribution and characteristics of the master batch. The nanogels are evaluated as carriers of a spread of chemotherapeutics by customizing the core to accommodate each individual cargo. The resulting nanogels are biocompatible, displaying diffusion controlled release of cargo, maintained therapeutic efficacy, and decreased cargo toxic side effects. Finally, the nanogels are found to successfully deliver pharmaceuticals into a 3D pancreatic spheroids tumor model., QC 20190605

The Type III Secretion System (T3SS) is a protein superstructure, consisting of hundreds of subunits, which self-assemble into a molecular needle and syringe that allows bacteria to inject effector proteins directly into eukaryotic host cells. These effector proteins promote virulence in many pathogenic bacteria. The extracellular needle filament is capped by a pentameric tip complex that is involved in environmental sensing and regulation of a pore-forming complex that is secreted upon host-cell contact.Tip complexes do not self-assemble from in vitro solutions of their subunits alone suggesting that in vivo, other environmental factors are required. During in vivo assembly, each tip complex subunit unfolds within the bacteria and secrets through the needle filament whereupon they refold and localize to the filaments end.We attempt to recapitulate these conditions in vitro. The influence of unfolding and refolding on tip complex assembly was investigated using pH and temperature denaturation combined with small angle X-ray scattering (SAXS). This data confirmed that in vitro refolding can promote oligomer formation in some species but is an inefficient process.To test the effects of needle localisation we developed a novel DNA-templating approach. Nanoscale DNA templates with the same dimensions of the needle filament (~8 nm) were designed, synthesised, and measured with electron microscopy, molecular dynamics simulations, and SAXS. Tip complex subunits were then chemically localized to these DNA templates drastically increasing their relative concentration and interaction frequency.Electron micrographs of these DNA-templated assemblies revealed some particles with compact structures similar to those observed in vivo. Chemical cross-linking and mass-spectroscopy provided distance restraints between residues of subunits in DNA-templated assemblies. These restraints allowed the generation of rigid body models of DNA-templated assemblies that resemble current models o

The family of two-dimensional materials has been expanding rapidly over the last few years. Within it, a special place is occupied by silicene, germanene, and stanene due to their inherent compatibility with the existing semiconductor technology (notably for the case of silicene and germanene). Although obtaining them is not trivial due to the lack of layered bulk counterparts from which they could be mechanically exfoliated, they have been recently synthesized on a number of metallic substrates. The remarkable interaction between metals and these puckered materials, however, strongly modifies their intrinsic electronic properties, and also jeopardizes their integration into functional devices. In this context, first experimental efforts are now being devoted to the synthesis of silicene, germanene, and stanene on nonmetal substrates. Here, we review these pioneering works, present the ongoing debate, analyze, and discuss the major technical challenges and finally suggest possible novel solutions worth exploring.

Conventional grafting-to approaches to DNA-polymer conjugates are often limited by low reaction yields due to the sterically hindered coupling of a presynthesized polymer to DNA. The grafting-from strategy, in contrast, allows one to directly graft polymers from an initiator that is covalently attached to DNA. Herein, we report blue-light-mediated reversible addition-fragmentation chain-transfer (Photo-RAFT) polymerization from two different RAFT agent-terminated DNA sequences using Eosin Y as the photocatalyst in combination with ascorbic acid. Three monomer families (methacrylates, acrylates and acrylamides) were successfully polymerized from DNA employing Photo-RAFT polymerization. We demonstrate that the length of the grown polymer chain can be varied by altering the monomer to DNA-initiator ratio, while the self-assembly features of the DNA strands were maintained. In summary, we describe a convenient, light-mediated approach toward DNA-polymer conjugates via the grafting-from approach.

Aggregates of disordered metallic nano-clusters exhibiting long-range organized fractal properties are amongst the most efficient scattering enhancers, and they are promising as high performance surface-enhanced Raman scattering (SERS) substrates. However, the low reproducibility of the disordered structures hinders the engineering and optimization of well-defined scalable architectures for SERS. Here, a thermophoretically driven Au aerosol deposition process is used for the self-assembly of thin films consisting of plasmonic nano-islands (NIs) with a controllable and highly reproducible degree of disorder. The intrinsic Brownian motion of the aerosol deposition process results in long-range periodicity with self-similar properties and stochastically distributed hot-spots, providing a facile means for the reliable fabrication of crystalline Au substrates with uniform disorder over large-surfaces. These morphological features result in the generation of a high density of hot-spots, benefitting their application as SERS substrates. NI substrates with an optimal uniform disorder demonstrate a SERS enhancement factor (EF) of 107–108 with nanomolar concentrations of Rhodamin-6G. These findings provide new insights into the investigation of light scattering with disordered structures, paving the way toward low-cost scalable self-assembly optoelectronic materials with applications ranging from ultrasensitive spectroscopy to random lasing and photonic devices.