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Composite materials designed by nature, such as nacre, can display unique mechanical properties and have therefore been often mimicked by scientists. In this work, we prepared composite materials mimicking the nacre structure in two steps. First, we synthesized a silica gel skeleton with a layered structure using a bottom-up approach by modifying a sol-gel synthesis. Magnetic colloids were added to the sol solution, and a rotating magnetic field was applied during the sol-gel transition. When exposed to a rotating magnetic field, magnetic colloids organize in layers parallel to the plane of rotation of the field and template the growing silica phase, resulting in a layered anisotropic silica network mimicking the nacre's inorganic phase. Heat treatment has been applied to further harden the silica monoliths. The final nacre-inspired composite is created by filling the porous structure with a monomer, leading to a soft elastomer upon polymerization. Compression tests of the platelet-structured composite show that the mechanical properties of the nacre-like composite material far exceed those of nonstructured composite materials with an identical chemical composition. Increased toughness and a nearly 10-fold increase in Young's modulus were achieved. The natural brittleness and low elastic deformation of silica monoliths could be overcome by mimicking the natural architecture of nacre. Pattern recognition obtained with a classification of machine learning algorithms was applied to achieve a better understanding of the physical and chemical parameters that have the highest impact on the mechanical properties of the monoliths. Multivariate statistical analysis was performed to show that the structural control and the heat treatment have a very strong influence on the mechanical properties of the monoliths.

Soft photonic materials formed from nanoscale colloidal crystals are versatile platforms for sensing and signaling in biomedical, chemical, and mechanical application scenarios. A particularly leve...

Using a one-step synthetic route for block copolymers avoids the repeated addition of monomers to the polymerization mixture, which can easily lead to contamination and, therefore, to the unwanted termination of chain growth. For this purpose, monomers (M1-M5) with different steric hindrances and different propagation rates are explored. Copolymerization of M1 (propagating rapidly) with M2 (propagating slowly), M1 with M3 (propagating extremely slowly) and M4 (propagating rapidly) with M5 (propagating slowly) yielded diblock-like copolymers using Grubbs' first (G1) or third generation catalyst (G3). The monomer consumption was followed by 1 H NMR spectroscopy, which revealed vastly different reactivity ratios for M1 and M2. In the case of M1 and M3, we observed the highest difference in reactivity ratios (r1 =324 and r2 =0.003) ever reported for a copolymerization method. A triblock-like copolymer was also synthesized using G3 by first allowing the consumption of the mixture of M1 and M2 and then adding M1 again. In addition, in order to measure the fast reaction rates of the G3 catalyst with M1, we report a novel retardation technique based on an unusual reversible G3 Fischer-carbene to G3 benzylidene/alkylidene transformation.

Here we report the adaptation of formaldehyde crosslinked phenolic resin-based aerogel and xerogel synthesis to ethanol-based solvent systems. Three specific formulations, namely one resorcinol–formaldehyde (RF) and two resorcinol– melamine–formaldehyde (RMF) systems were studied. As-prepared resins were characterized in terms of envelope and skeletal density. Furthermore, resin samples were pyrolyzed and activated in a CO2 gas atmosphere using a single-step protocol. The corresponding carbon materials featured high surface areas, moderate water uptake capacity and thermal conductivities in the 0.1 W.m−1K−1 range, in line with comparable activated carbons. The amount of formaldehyde in the synthesis of the RMF derived carbons proved to be a critical parameter in terms of both structural features and amount of N dopant in the carbonaceous matrix. Furthermore, a high formaldehyde concentration also has a drastic effect on the pore structure of the corresponding RMF carbons, leading primarily to mesopore formation without almost any macropore formation. Perhaps more importantly, the effect of the ammonia curing catalyst concentration on the material microstructure showed the opposite effect as observed in classical, water-based phenolic resin preparations. The ethanol-based synthesis clearly affects the pore structure of the resulting materials but also opens up the possibility to create inorganic/organic hybrid materials by simple combination with classical alkoxide-based silica sol–gel chemistry.

Biopolymer aerogels are an emerging class of materials with potential applications in drug delivery, thermal insulation, separation, and filtration. Chitosan is of particular interest as a sustainable, biocompatible, and abundant raw material. Here, we present urea-modified chitosan aerogels with a high surface area and excellent thermal and mechanical properties. The irreversible gelation of an acidic chitosan solution is triggered by the thermal decomposition of urea at 80 °C through an increase in pH and, more importantly, the formation of abundant ureido terminal groups. The hydrogels are dried using either supercritical CO2 drying (SCD) or ambient pressure drying (APD) methods to elucidate the influence of the drying process on the final aerogel properties. The hydrogels are exchanged into ethanol prior to SCD, and into ethanol and then heptane prior to APD. The surface chemistry and microstructure are monitored by solid-state NMR and Fourier transform infrared spectroscopy, scanning electron microscopy, and nitrogen sorption. Surprisingly, large monolithic aerogel plates (70 × 70 mm2) can be produced by APD, albeit at a somewhat higher density (0.17-0.42 g/cm3). The as prepared aerogels have thermal conductivities of ∼24 and ∼31 mW/(m·K) and surface areas of 160-170 and 85-230 m2/g, for SCD and APD, respectively. For a primarily biopolymer-based material, these aerogels are exceptionally stable at elevated temperature (TGA) and char and self-extinguish after direct flame exposure. The urea-modified chitosan aerogels display superior mechanical properties compared to traditional silica aerogels, with no brittle rupture up to at least 80% strain, and depending on the chitosan concentration, relatively high E-moduli (1.0-11.6 MPa), and stress at 80% strain values (σ80 of 3.5-17.9 MPa). Remarkably, the aerogel monoliths can be shaped and machined with standard tools, for example, drilling and sawing. This first demonstration to produce monolithic and machinable, mesoporous aerogels from bio-sourced, renewable, and nontoxic precursors, combined with the potential for reduced production cost by means of simple APD, opens up new opportunities for biopolymer aerogel applications and marks an important step toward commercialization of biopolymer aerogels.

The preparation of particles with non-spherical shapes is a challenging endeavor, often requiring a significant ingenuity, complex experimental procedures and difficulties to obtain reproducible results. In this work we prove that monodisperse non-spherical polymer particles possessing asymmetric Janus structure can be easily produced by using an activated swelling method in combination with a control of the rate of free radical polymerization through the addition of the inhibitors 4-methoxyphenol (MEHQ) and O2. Monodisperse non cross-linked polystyrene particles, used as seeds, are activated by the addition of an initiator, which promotes their swelling ability, and then swollen with a monomers mixture (methyl methacrylate, glycidyl methacrylate and ethylene glycol dimethacrylate), before being polymerized in presence of both MEHQ and O2. Our results show that only when both MEHQ and O2 are present during the course of the polymerization, the particles shape can be controlled, from spherical to asymmetrical. A variety of particles shapes can be obtained, ranging from dimpled spheres, flattened spheres and Janus particles by varying the swelling ratio, always with excellent monodispersity and reproducibility. Finally, to provide even more complex functionalities to these non-spherical polymer particles, iron oxide nanocrystals were grown within the polymer matrix resulting in superparamagnetic particles.

Magnetic hyperthermia has the potential to play an important role in cancer therapy and its efficacy relies on the nanomaterials selected. Superparamagnetic iron oxide nanoparticles (SPIONs) are excellent candidates due to the ability of producing enough heat to kill tumor cells by thermal ablation. However, their heating properties depend strongly on crystalline structure and size, which may not be controlled and tuned during the synthetic process; therefore, a postprocessing is needed. We show how thermal annealing can be simultaneously coupled with ligand exchange to stabilize the SPIONs in polar solvents and to modify their crystal structure, which improves hyperthermia behavior. Using high-resolution transmission electron microscopy, X-ray diffraction, Mössbauer spectroscopy, vibrating sample magnetometry, and lock-in thermography, we systematically investigate the impact of size and ligand exchange procedure on crystallinity, their magnetism, and heating ability. We describe a valid and simple approach to optimize SPIONs for hyperthermia by carefully controlling the size, colloidal stability, and crystallinity.

Silica aerogels display an ultra-low thermal conductivity (λ) and are used as thermal superinsulators. Here, we study the influence of aging and drying processes on the microstructure and thermal conductivity of fiber-reinforced silica aerogel composites. Glass wool-silica gel composites were aged for variable times, hydrophobized, and dried either at ambient pressure or from supercritical CO2 (scCO2). The X-ray micro-tomographic data display three distinct phases: silica aerogel, glass fibers, and macroscopic pores and cracks. The silica aerogel appears as a continuous medium in the tomograms because the spatial resolution (6–11 μm) is insufficient to resolve the aerogel mesopores (∼0.02–0.10 μm). For the composites prepared by ambient pressure drying, insufficient aging led to prominent drying shrinkage and cracking, and a high macro-porosity, as quantified by 3D image analysis. Insufficient aging also led to an increase in λ from 15.7 to 21.5 mW m−1 K−1. On the contrary, composites that were nearly free of cracks and displayed a constant λ of 16.3 ± 0.8 mW m−1 K−1 could be prepared by scCO2, independent of aging time. The thermal conductivity was reproduced from the macro-porosity to within 0.7 mW m−1 K−1 using simple thermal transport models consisting of thermal elements connected in series or parallel. Our results illustrate the usefulness of X-ray micro-tomography to quantify the 3D microstructure and its effects on the bulk composite properties and the data highlight the importance of aging for the production of low λ aerogel-fiber composites by ambient pressure drying.

Silica aerogel is the ultimate thermal insulator thanks to its record-breaking low thermal conductivity (λ), open porosity and hydrophobicity. Silica aerogel's thermal conductivity is lowest at intermediate densities (ρ ≈ 0.11 g/cm ) and, because of the strong, power-law dependence of the E modulus on density, this rather low density so far led to low E moduli. Even with polymer reinforcement, increasing stiffness is only possible at higher density, thus higher conductivity. This paper explores the synthesis of silica aerogel granules using ambient pressure drying to provide enhanced mechanical stiffness whilst maintaining thermal conductivities well below 20 mW m K . The aging and drying conditions affect the interplay between mechanical and thermal properties, and are varied to optimize the physical properties. The dense (ρ≤0.29 g/cm ), but superinsulating (λ≈15 mW m K ) silica aerogels presented in this paper challenge the community's understanding of heat transport in aerogels, and do not rely on polymer reinforcement. The underlying microscopic structural parameters affecting the mechanical and thermal transport properties are investigated by modelling and simulation of the aerogel back-bone. Short aging times reduce the cross-section of, and heat transport through, inter-particle necks, leading to an overall decrease in thermal conductivity through the solid skeleton (λ ). In addition, short-aged gels undergo a partial pore collapse during ambient pressure drying of the pore fluid due to less aged, hence weaker network structures. The resulting denser structure contains additional point contacts that increase stiffness, by up to an order of magnitude. However, heat transport through these newly formed point-contacts is limited and the gas phase conduction (λ ) is further suppressed due to the even smaller pore sizes. Strong and superinsulating particles are ideal fillers for aerogel composites, concrete and renders. The optimized APD aerogels, available as granules, are finally compiled in a composite thermal insulation board with an effective thermal conductivity down to 20 mW m K with improved strength: a 2-fold increase for E, compared to a board produced from classical silica aerogel granulate. The possibility to improve mechanical properties of pure silica aerogels can help aerogels to break into new high-strength, superinsulating structural applications needed to reduce carbon emissions of the built environment., Acta Materialia, 213, ISSN:1359-6454

Magnetite nanocrystal clusters are being investigated for their potential applications in catalysis, magnetic separation, and drug delivery. Controlling their size and size distribution is of paramount importance and often requires tedious trial-and-error experimentation to determine the optimal conditions necessary to synthesize clusters with the desired properties. In this work, magnetite nanocrystal clusters were prepared via a one-pot solvothermal reaction, starting from an available protocol. In order to optimize the experimental factors controlling their synthesis, response surface methodology (RSM) was used. The size of nanocrystal clusters can be varied by changing the amount of stabilizer (tribasic sodium citrate) and the solvent ratio (diethylene glycol/ethylene glycol). Tuning the experimental conditions during the optimization process is often limited to changing one factor at a time, while the experimental design allows for variation of the factors’ levels simultaneously. The efficiency of the design to achieve maximum refinement for the independent variables (stabilizer amount, diethylene glycol/ethylene glycol (DEG/EG) ratio) towards the best conditions for spherical magnetite nanocrystal clusters with desirable size (measured by scanning electron microscopy and dynamic light scattering) and narrow size distribution as responses were proven and tested. The optimization procedure based on the RSM was then used in reverse mode to determine the factors from the knowledge of the response to predict the optimal synthesis conditions required to obtain a good size and size distribution. The RSM model was validated using a plethora of statistical methods. The design can facilitate the optimization procedure by overcoming the trial-and-error process with a systematic model-guided approach.

The use of plasmonic nanoparticles for biological applications has been gaining momentum in the last two decades. The ability of these particles to generate heat when exposed to light with a given ...

Magnetosomes are near-perfect intracellular magnetite nanocrystals found in magnetotactic bacteria. Their synthetic imitation, known as superparamagnetic iron oxide nanoparticles (SPIONs), have found applications in a variety of (nano)medicinal fields such as magnetic resonance imaging contrast agents, multimodal imaging and drug carriers. In order to perform these functions in medicine, shape and size control of the SPIONs is vital. We sampled SPIONs at ten-minutes intervals during the high-temperature thermal decomposition reaction. Their shape (sphericity and anisotropy) and geometric description (volume and surface area) were retrieved using three-dimensional imaging techniques, which allowed to reconstruct each particle in three dimensions, followed by stereological quantification methods. The results, supported by small angle X-ray scattering characterization, reveal that SPIONs initially have a spherical shape, then grow increasingly asymmetric and irregular. A high heterogeneity in volume at the initial stages makes place for lower particle volume dispersity at later stages. The SPIONs settled into a preferred orientation on the support used for transmission electron microscopy imaging, which hides the extent of their anisotropic nature in the axial dimension, there by biasing the interpretation of standard 2D micrographs. This information could be feedback into the design of the chemical processes and the characterization strategies to improve the current applications of SPIONs in nanomedicine.

The efficacy of magnetic hyperthermia treatment depends on the optimal available magnetic nanoparticles (MNPs) that are excited in a given alternating magnetic field and viscosity of the region of interest. In this regard, assessing the relevant relaxation parameters is of upmost importance and could improve the speed of development of efficient applications. Here, we demonstrate how to deduce all relevant magnetic parameters from fast, independent, and simple experimental measurements such as dynamic light scattering, vibrating sample magnetometer, and lock-in thermography. We study the thermal behaviour of two MNPs with different forms, i.e. spherical and cubical, synthesized in-house by thermal decomposition and coated with 4 different surface agents. By determination of specific absorption rate (SAR) values, hydrodynamic diameters and M−H curves it is possible to compute the magnetic particle volume, dominant relaxation time and magnetocrystalline anisotropy constant. The calculated SAR values derived from these parameters, show good agreement with the experimental determined SAR data, demonstrating the applicability of the reported procedure. Additionally, our results indicate that surface coatings can have minor impacts on the thermal dissipation of Néel relaxation dominated MNPs.

Silica aerogels have only half the thermal conductivity of conventional insulation, but their application potential is limited by the poor mechanical properties. The fragility arises from the thin necks between the silica nanoparticle building blocks. Here, we produce strong silica aerogels through co-gelation of the polyethoxydisiloxane precursor with a variety of silane terminated prepolymers that reinforce the inter-particle necks, followed by hydrophobization and supercritical CO2 drying. All prepolymers enabled the synthesis of aerogels with excellent thermal and mechanical properties, but the shortest prepolymer (∼2–3 nm long) yielded the best results. The hybrid aerogels can sustain uniaxial compression without brittle rupture to at least 80% strain for all prepolymer concentrations (5–50 wt%), leading to a final strength of up to 21 MPa, an E modulus up to 3.4 MPa, and an up to 400 times lower dust release rate. In contrast to classical reinforcement strategies, the mechanical improvement does not come with a penalty in thermal conductivity, which remains between 14 and 17 mW m−1 K−1. The hybrid aerogels are a unique class of superinsulating materials with superior thermal and mechanical properties and a scalable production process.

Magnetic nanoparticles and their ability to convert electromagnetic energy into heat are of explicit interest for various applications. However, precise quantification of their heating efficiency is not always upfront, and several parameters render comparative studies challenging. This paper describes the theory behind lock-in thermography, a new technique for quantifying the heating properties of magnetic nanoparticles. This technique allows the investigation of some of the potential sources of variability: key factors such as magnetic field inhomogeneity and its effects on the heating power are explored in detail. The presented results, obtained from various nanoparticle batches of different origins, highlight the importance of pursuing a standardized and systematic approach when quantifying the heating efficiency of magnetic nanoparticles.

Block copolymer (BCP) nanocomposite systems are of broad interest; however, reports on the role of nanoparticles on microphase separation behavior are rare. The goal of present study is to investigate the preparation of composite nanostructured materials containing Multi-Walled Carbon Nanotubes (MWCNTs) or graphene nanoplates. BCP nanocomposites based on the linear triblock copolymer, Polystyrene-b-poly(ethylene-butylene)-b-polystyrene (SEBS), with different morphological structure were prepared by melt mixing. The results of temperature sweep experiments showed an enhancing effect of both MWCNT and graphene nanosheets on increasing the microphase separation temperature as well as accelerating its kinetic, resulting from the confinement of BCP segments, with graphene nanosheets providing a more severely confined geometry for polystyrene segments in contrast to MWCNTs. Additionally, DMTA results indicated a promotion of the BCP microphase separation by incorporation of nanoparticles. Transient flow measurements followed by time sweep test suggested the existence of a special 3D network microstructure caused by nanoparticles/domain interactions.

Silica aerogels’ unique physical and chemical properties make them fascinating materials for a wide variety of applications. In addition to hydrophobization by silylation, aging is very important in the synthesis of silica aerogel by ambient pressure drying. Here we systematically study the effect of aging on the physico-chemical properties of silica aerogel with emphasis on ambient dried materials. Silica gels were aged for different times and at different temperatures in their gelation liquid (without solvent exchange), hydrophobized in hexamethyldisiloxane and subsequently dried either at ambient pressure or from supercritical CO2. Dynamic oscillatory rheological measurements demonstrate that aging reinforces the alcogels, particularly at high strain. The specific surface area decreases with increasing aging time and temperature as a consequence of Ostwald ripening processes during aging. With increasing aging time and temperature, the linear shrinkage and bulk density decrease and the pore size and pore volume increase for the ambient dried gels, but remain nearly constant for supercritically dried gels. Small-Angle X-ray scattering does not detect significant structural changes at length scales smaller than about hundred nanometers, but hints at systematic variations at larger length scales. The findings of this study highlight the importance of aging to increase the ability of the gel particle network to withstand irreversible pore collapse during ambient pressure drying.

Abstract: Magnetic nanoparticles have been the subject of enormous investigations for their potential use as cancer treatment via hyperthermia. This is due to their ability to generate heat when exposed to an external magnetic field oscillating at sufficiently high frequency. There are many different parameters that need to be considered when designing the optimal nanoparticle formulation for hyperthermia. The effect of the formation of clusters of nanoparticles, which is either an unwanted side effect of poor colloidal stability of the particles, or a desired for- mulation strategy, has poorly understood consequences on the amount of heat generated by the nanoparticles. The objective of this work is to address this problem from the theoretical side by performing detailed simulations to investigate the effect of incorporation of magnetic nanoparticles in clusters on the amount of heat generated as a function of the particle size, cluster size and particles magnetic properties.

This article belongs to the Special Issue Polymer Nanocomposites: Preparation, Characterisation and Applications., In this work, the effective mechanical reinforcement of polymeric nanocomposites containing spherical particle fillers is predicted based on a generalized analytical three-phase-series-parallel model, considering the concepts of percolation and the interfacial glassy region. While the concept of percolation is solely taken as a contribution of the filler-network, we herein show that the glassy interphase between filler and matrix, which is often in the nanometers range, is also to be considered while interpreting enhanced mechanical properties of particulate filled polymeric nanocomposites. To demonstrate the relevance of the proposed generalized equation, we have fitted several experimental results which show a good agreement with theoretical predictions. Thus, the approach presented here can be valuable to elucidate new possible conceptual routes for the creation of new materials with fundamental technological applications and can open a new research avenue for future studies., This research was funded by the Catalan government within the Beatriu de Pinos program, grant number NB615798.

The aspect ratio of nanoparticles governs their percolation threshold in polymer composites, and thus exerts a significant influence on the materials properties. We explored how the combination of two rod-like particle types with different aspect ratio, but otherwise similar characteristics, affects the properties of nanocomposites. Using experimental data of composites made with two different cellulose nanocrystal (CNC) types, we show that a substantial fraction of the high-aspect-ratio CNCs can be substituted with the low-aspect-ratio nanoparticles without significantly affecting the properties. Exploring the boundary limits of aspect ratios, where random contact criterions and mean field approximations are valid, we formulated a generalized theoretical model that permits predicting the modulus of nanocomposites with two rod-like nanoparticle types having different length distributions. The model shows that the modulus of such nanocomposites is strongly weighted by the particles with higher aspect ratio.

Magnetic hyperthermia describes a novel strategy to generate temperatures up to 45-47°C in tumor tissue through the use of magnetic nanoparticles. Measuring the heating power of magnetic nanoparticles is essential to improve therapy systems currently used by maximizing therapeutic efficiency while minimizing administrated dose. This review reports an overview about available measurement set-ups described in literature, addressing advantages and disadvantages, and includes several more recent approaches developed to fulfill the requirements of accurate and reproducible heating power determination.

In this work, amyloid fibrils are used as a template for the preparation of long silica fibers, with a variety of aspect ratios and surface roughness. Starting with β‐ lactoglobulin fibrils with typical diameters of about 20 nm and a length of several micrometers, two different strategies are followed to grow silica: either in water at acidic pH values, or in ethanol–water mixtures under Stöber conditions and an excellent control of both the thickness and the roughness of the silica layer has been achieved. Silica nanofibers with a thickness ranging from a few nanometers to hundreds of nanometers are prepared. As an application, the rough silica nanotubes are used to create superhydrophobic surfaces by mimicking the structure of the lotus leaf. The papillary structure of the lotus leaf is replicated by depositing 10 μm colloidal particles in either a single colloidal crystal, or in a binary colloidal crystal made with smaller sub‐micrometer particles. Then, silica nanofibers are deposited on the binary colloidal crystal surfaces through a layer‐by‐layer deposition procedure to replicate the nanoscale roughness provided by wax nanotubes. Upon hydrophobization of the silica nanotubes, the final surfaces are highly superhydrophobic, with a water contact angle of 165.5°.

A combination of two models previously developed by Faran, and Atkinson and Kytömaa (Faran-AK model) was used to calculate the ultrasonic attenuation and the backscattering signal of a suspension of particles. The model of Atkinson and Kytömaa yielded the viscoelastic contributions while the model of Faran yielded the scattering contribution. A comparison with the more fundamental model by Epstein, Carhart, Allegra, and Hawley validated the combination, where the combination used here proved to be computationally less intensive and more stable. The Faran-AK model outputs were also compared with ultrasound measurements of glass beads with two different particle size distributions and varying concentrations. The comparison showed a very reasonable agreement of model and experiment.

Low-power light upconversion is a highly desirable feature for a broad range of applications and new materials enabling this process are sought in both bulk and particulate form. Here, the preparation of upconverting nanoparticles is reported from a methacrylic terpolymer bearing diphenylanthracene and meso-phenoxytris(heptyl)porphyrin pendant groups by a microemulsion technique. The use of a terpolymer in which the upconvering dye molecules are covalently attached mitigates some of the drawbacks of triplet-triplet annihilation upconverting nanoparticles made by other techniques, in particular dye leakage from the nanoparticles, and limited control of the sensitizer and emitter concentration within each nanoparticle. Size and morphology of the new upconverting nanoparticles are investigated by dynamic light scattering and transmission electron microscopy and elucidated their upconverting properties by luminescence spectroscopy.

In the present work, the aggregation behavior of polymeric particles possessing different glass transition temperatures (i.e., different "softnesses") has been studied to shed light on the interplay between aggregation and coalescence. In particular, the time evolution of the clusters hydrodynamic and gyration radii as well as of their structure factor has been monitored. With the help of an ad hoc developed deterministic model, based on population balance equations, it was possible to establish a link between the experimentally obtained light scattering data and the predicted particle size distribution. The simplicity of the model, involving one single adjustable parameter based on the coalescence characteristic time, allowed us to obtain a good accordance between simulations and experimental results with little computational effort.

The preparation of anisotropic nanoparticles has drawn much attention in the literature, with most of the efforts being dedicated to convex particles. In this work, instead, we present a reliable method to synthesis silica nanobowls with one well-defined opening, covering a broad range of sizes. The nanobowls have been obtained from asymmetrically functionalized silica-polymer Janus nanodumbbells, used as templates, by removing of the polymer. Polystyrene seeds having different sizes as well as surface chemistry have been used as starting material in a two-step seeded emulsion polymerization, which leads to polymer nanodumbbells. These dumbbells are also asymmetrically functionalized due to the presence of silane groups on only one of their two hemispheres. This allows us to selectively coat the silane-bearing hemisphere of the dumbbells with a silica layer by means of a Stoeber process. The silica nanobowls are eventually obtained after either calcination or dissolution of the polymeric template. Depending on the route followed to remove the polymer, nanobowls made of pure silica (from calcination) or hybrid Janus nanobowls with a silica outer shell and a covalently bound hydrophobic polymer layer inside the cavity (from dissolution) could be prepared. The difference between the two types of nanobowls has been proved by electrostatically binding oppositely charged silica nanoparticles, which adhere selectively only on the outer silica part of the nanobowls prepared by polymer dissolution, while they attach both inside and outside of nanobowls prepared by calcination. We also show that selective functionalization of the outer surface of the Janus nanobowls from dissolution is possible. This work is one of the first examples of concave objects bearing different functionalities in the inner and outer parts of their surface.

Surface chemistry is believed to be the key parameter affecting the aggregation and breakage of colloidal suspensions when subjected to shear. To date, only a few works dealt with the understanding of the role of the physical and chemical properties of the particles’ surface upon aggregation under shear. Previous studies suggested that surface modifications strongly affect polymer particles’ adhesion, but it was very challenging to demonstrate this effect and monitor these alterations upon prolonged exposure to shear forces. More importantly, the mechanisms leading to these changes remain elusive. In this work, shear-induced aggregation experiments of polymer colloidal particles have been devised with the specific objective of highlighting material transfer and clarifying the role of the softness of the particle’s surface. To achieve this goal, polymer particles with a core–shell structure comprising fluorescent groups have been prepared so that the surface’s softness could be tuned by the addition of monomer acting as a plasticizer and the percentage of fluorescent particles could be recorded over time via confocal microscopy to detect eventual material transfer among different particles. For the first time, material exchange occurring on the soft surface of core–shell polymer microparticles upon aggregation under shear was observed and proved. More aptly, starting from a 50% labeled/nonlabeled mixture, an increase in the percentage of particles showing a fluorescent signature was recorded over time, reaching a fraction of 70% after 5 h.

Stimuli-responsive colors are a unique characteristic of certain animals, evolved as either a method to hide from enemies and prey or to communicate their presence to rivals or mates. From a material science perspective, the solutions developed by Mother Nature to achieve these effects are a source of inspiration to scientists for decades. Here, an updated overview of the literature on bioinspired stimuli-responsive color-changing systems is provided. Starting from natural systems, which are the source of inspiration, a classification of the different solutions proposed is given, based on the stimuli used to trigger the color-changing effect.

The mechanical reinforcement of nanocomposites containing nanorods-like fillers such as cellulose nanocrystals (CNCs) is often interpreted by adapting the classical parallel–series model, assuming a simple hyperbolic dependence between the percolation threshold and aspect ratio. However, such assumptions are valid only for nanorods with high aspect ratio and often are misinterpreting the reinforcement obtained at low volume fraction of filler loading. To elucidate this intriguing scenario, we proposed a new approach and validated it by compiling and reinterpreting some of available literature that represent the experimental reinforcement with CNCs. Our approach showed better accuracy, specifically for the cases of CNC nanorods with lower aspect ratio. We conclude that this route permits a more realistic evaluation of the mechanical reinforcement, where a physical parameter accounting the polymer filler association is introduced. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45254.

The magnetic separation of pathogenic compounds from body fluids is an appealing therapeutic concept. Recently, removal of a diverse array of pathogens has been demonstrated using extracorporeal dialysis-type devices. The contact time between the fluid and the magnetic beads in such devices is limited to a few minutes. This poses challenges, particularly if large compounds such as bacteria or cells need to be removed. Here, we report on the feasibility to remove cells from body fluids in a continuous dialysis type of setting. We assessed tumor cell removal efficiencies from physiological fluids with or without white blood cells using a range of different magnetic bead sizes (50–4000 nm), concentrations, and contact times. We show that tumor cells can be quantitatively removed from body fluids within acceptable times (1– 2 min) and bead concentrations (0.2 mg per mL). We further present a mathematical model to describe the minimal bead number concentration needed to remove a certain number of cells, in the presence of competing nonspecific uptake. The present study paves the way for investigational studies to assess the therapeutic potential of cell removal by magnetic blood purification in a dialysis-like setting.

A major hurdle in the development of biomedical nanoparticles (NP) is understanding how they interact with complex biological systems and navigate biological barriers to arrive at pathological targets. It is becoming increasingly evident that merely controlling particle physicochemical properties may not be sufficient to mediate particle biodistribution in dynamic environments. Thus, researchers are increasingly turning toward more complex but likewise more physiological in vitro systems to study particle–-cell/particle–system interactions. An emerging paradigm is to utilize naturally migratory cells to act as so-called “Trojan horses” or cellular shuttles. We report here the use of monocytes/macrophages to transport NP across a confluent endothelial cell layer using a microfluidic in vitro model. With a custom-built flow chamber, we showed that physiological shear stress, when compared to low flow or static conditions, increased NP uptake by macrophages. We further provided a mathematical explanation for the effect of flow on NP uptake, namely that the physical exposure times of NP to cells is dictated by shear stress (i.e., flow rate) and results in increased particle uptake under flow. This study was extended to a multicellular, hydrodynamic in vitro model. Because monocytes are cells that naturally translocate across biological barriers, we utilized a monocyte/macrophage cell line as cellular NP transporters across an endothelial layer. In this exploratory study, we showed that monocyte/macrophage cells adhere to an endothelial layer and dynamically interact with the endothelial cells. The monocytes/macrophages took up NP and diapedesed across the endothelial layer with NP accumulating within the cellular uropod. These data illustrate that monocytes/macrophages may therefore act as active shuttles to deliver particles across endothelial barriers.

We report on theoretical and experimental considerations on bacteria capturing and enrichment via magnetic separation enabling integrated diagnosis and treatment of blood stream infections. We show optimization of carrier-pathogen interactions based on a mathematical model followed by an experimental proof-of-concept study along with investigations on the process safety.

Abstract: While coupling mechanical and chemical processes is widespread in living organisms, the idea to harness the mechanically induced dissociation of weak covalent and non-covalent bonds to create artificial materials that respond to mechanical stimulation has only recently gained attention. Here we summarize our activities that mainly revolve around the exploitation of non-covalent interactions in (supramolecular) polymeric materials with the goal to translate mechanical stresses into useful, pre-defined events. Focusing on mechano- chromic polymers that alter their optical absorption or fluorescence properties, several new operating principles, mechanosensitive entities, and materials systems were developed. Such materials are expected to be useful for technical applications that range from the detection of very small forces in biological systems to the monitoring of degradation processes and damage in coatings and structural objects.

Microreactors have attracted wide attention in the nano- and biotechnology fields because they offer many advantages over standard liquid phase reactions. We report the development of a magnetic microreactor for reliable, fast and efficient surface functionalization of superparamagnetic iron oxide nanoparticles (SPIONs). A comprehensive study of the development process in terms of setup, loading capacity and efficiency is described. We performed experimental and computational studies in order to evaluate the trapping efficiencies, maximum loading capacity and magnetic alignment of the nanoparticles. The results showed that capacity and trapping efficiencies are directly related to the flow rate, elution time and reactor type. Based on our results and the developed magnetic microreactor, we describe a model multistep surface derivatization procedure of SPIONs.

Combining liposomes with magnetic nanoparticles is an intriguing approach to create multifunctional vesicles for medical applications, which range from controlled drug delivery vehicles to diagnostic imaging enhancers. Over the past decade, significant effort has been invested in developing such hybrids – widely known as magnetoliposomes – and has led to numerous new concepts. This review provides an overview on of the current state of the art in this field. The concept of magnetic fluid hyperthermia and stimuli-responsive nanoparticles for drug delivery is briefly recapitulated. The materials needed for these hybrids are addressed as well. The three typically followed approaches to associate magnetic nanoparticles to the liposomes are described and discussed more in detail. The final chapters are dedicated to the analytical methods used to characterize these hybrids and to theoretical considerations relevant for bilayer-embedded nanoparticles.

Biodegradable polymers are very attractive materials because of the possibility to degrade them back naturally to their monomeric forms, with clear advantages for many applications. Degradable polyesters are the most widely used group of synthetic biodegradable polymers for medical applications, with many of its members already Food and Drug Administration approved and used as suture materials, implants, and drug delivery vehicles. This class of polymers has the ability to control molecular weight, and this ability is a key feature in tuning their mechanical properties and their degradation behaviors. In this chapter, we review the properties of most common types of poly(α-esters), starting from their monomers. We focus on the development of suitable mathematical models to describe both their polymerization kinetics, carried out by ring-opening polymerization, and their degradation kinetics, and we show how these models can be beneficial to understand and control the preparation and fate of these materials.

We propose a new methodology based on lock-in thermography to study and quantify the heating power of magnetic nanoparticles. Superparamagnetic iron oxide nanoparticles exposed to a modulated alternating magnetic field were used as model materials to demonstrate the potency of the system. Both quantitative and qualitative information on their respective heating power was extracted at high thermal resolutions under increasingly complex conditions, including nanoparticles in the liquid, solid and aggregated states. Compared to conventional techniques, this approach offers a fast, sensitive and non-intrusive alternative to investigate multiple and dilute specimens simultaneously, which is essential for optimizing and accelerating screening procedures and comparative studies.

Sol-gel accompanied by phase separation is an established method for the preparation of porous silica monoliths with well-defined macroporosity, which find numerous applications. In this work, we demonstrate how the addition of (superpara)magnetic nanocolloids as templates to a system undergoing a sol-gel transition with phase separation leads to the creation of monoliths with a strongly anisotropic structure. It is known that magnetic nanocolloids respond to the application of an external magnetic field by self-assembling into columnar structures. The application of a magnetic field during the chemically driven spinodal decomposition induced by the sol-gel transition allows one to break the symmetry of the system and promote the growth of elongated needle-like silica domains incorporating the magnetic nanocolloids, aligned in the direction of the field. It is found that this microstructure imparts a strong mechanical anisotropy to the materials, with a ratio between the Young's modulus values measured in a direction parallel and perpendicular to the one of the field as high as 150, and an overall smaller average macropores size as compared to isotropic monoliths. The microstructure and properties of the porous monoliths can be controlled by changing both the system composition and the strength of the applied magnetic field. Our monoliths represent the first example of materials prepared by magnetically controlling a phase transition occurring via spinodal decomposition.

Summary Research on Janus nanoparticles has been thriving over the past few years, focusing both on novel preparation strategies and on investigations of their unique properties. In this paper we review the main contributions to this field reported in the literature, dividing Janus nanoparticles into three main categories, depending on the route followed for their preparation. The first group of Janus nanoparticles is those obtained via self-assembly, of, e.g. , block copolymers, and mixtures of ligands that in some cases show competitive adsorption on the surfaces of the nanoparticles. The second group comprises Janus nanoparticles obtained through a masking step, in which particles are trapped at the interface between two phases, so that a modification to the particle surface is made only on one side. Preparation of the third group of Janus nanoparticles relies on the phase separation of two different substances, usually either two polymers, or a polymer and an inorganic material. The peculiar properties of Janus nanoparticles, derived from their asymmetric structure, allow for their controlled self-assembly and surface activity. As a result of the simultaneous presence of two different regions in Janus nanoparticles, which can be designed to have different hydrophobicity and thereby mimic the behavior of surfactants, they can form stable clusters with defined size, and substantially reduce the interfacial tension between two different phases. Additionally, Janus nanoparticles can bring together different materials in a segregated manner at the nanoscale, thus combining widely different properties in single entity, as in the case of heterodimers.

In this work we present experimental and simulation analysis of the breakage and restructuring of colloidal aggregates in dilute conditions under shear. In order to cover a broad range of hydrodynamic and interparticle forces, aggregates composed of primary particles with two sizes, d(p) = 90 and 810 nm, were generated. Moreover, to understand the dependence of breakage and restructuring on the cluster structure, aggregates grown under stagnant and turbulent conditions, having substantially different initial internal structures with fractal dimension d(f) equal to 1.7 and 2.7, respectively, were used. The aggregates were broken by exposing them to a well-defined elongational flow produced in a nozzle positioned between two syringes. To investigate the evolution of aggregate size and morphology, respectively, the mean radius of gyration,R(g), and d(f) were monitored during the breakup process using light scattering and confocal laser scanning microscopy. It was found that the evolution of aggregates' fractal dimension during breakage is solely controlled by their initial structure and is independent of the primary particles size. Similarly, the scaling of the steady-stateR(g)vs the applied hydrodynamic stress is independent of primary particle size, however, depends on the history of aggregate structure. To quantitatively explain these observations, the breakage process was modeled using stokesian dynamics simulations incorporating DLVO and contact interactions among particles. The required flow-field for these simulations was obtained from computational fluid dynamics. The complex flow pattern was simplified by considering a characteristic stream line passing through the zone with the highest hydrodynamic stress inside the nozzle, this being the most critical flow condition experienced by the clusters. As the flow-field along this streamline was found to be neither pure simple shear nor pure extensional flow, the real flow was approximated as an elongational flow followed by a simple shear flow, with a stepwise transition between them. Using this approach, very good agreement between the measured and simulated aggregate size values and structure evolution was obtained. The results of this study show that the process of cluster breakup is very complex and strongly depends on the initial aggregate structure and flow-field conditions.

We report a new strategy for the production via supercritical fluid extraction of emulsion of biocompatible magnetic nanocomposite particles made of magnetite nanocrystals dispersed in a poly(lactic-co-glycolic) acid (PLGA) matrix. Ricinoleic acid-stabilized magnetic nanocrystals have been prepared via coprecipitation of two iron salts in alkaline environment, and subsequently dispersed in a solution of PLGA in dichloromethane. The obtained oil phase has then been dispersed in an aqueous solution of polyvinyl alcohol (PVA) in order to obtain a kinetically stable oil-in-water miniemulsion. The solvent was finally extracted via supercritical fluid extraction of emulsions. The continuous extraction of dichloromethane by means of supercritical CO2 leads directly to a stable suspension of magnetite–PLGA composite nanoparticles in water. The influence of those parameters affecting the final particle size distribution and morphology, primarily emulsifier amount and magnetite content, has been investigated, so as to optimize the process. Analysis of the products, performed through light scattering and electron microscopy, indicates that narrower size distributions are obtained with larger amounts of emulsifier and lower amounts of magnetite. The morphology of the particles tends to be of Janus type, with the magnetite accumulated on one hemisphere of the particle. The proposed approach is suitable for the preparation of large quantities of high-quality magnetite–PLGA composite nanoparticles for biomedical applications.

Structures of colloidal gels prepared in the reaction-limited aggregation regime from fluorinated colloidal particles with two different sizes and different salt concentrations have been characterized by combining small-angle and wide-angle light scattering and small-angle neutron scattering techniques. In all cases, the scattering structure factors indicate the coexistence of two types of fractal structures at different scale lengths: a mass fractal scaling at the scale length of the clusters that constitute the gel and a surface fractal scaling for larger scale lengths. It has been found that, at the same particle volume fraction, the mass fractal dimension of the clusters in the gel increases as the primary particle size decreases. On the other hand, we show that both the mass and the surface fractal gel structures are independent of the salt concentration.

The characterization of complex colloidal dispersions is a relevant and challenging problem in colloidal science. In this work, we show how asymmetric flow-field flow fractionation (AF4) coupled to static light scattering can be used for this purpose. As an example of complex colloidal dispersions, we have chosen two systems undergoing aggregation. The first one is a conventional polystyrene latex undergoing reaction-limited aggregation, which leads to the formation of fractal clusters with well-known structure. The second one is a dispersion of elastomeric colloidal particles made of a polymer with a low glass transition temperature, which undergoes coalescence upon aggregation. Samples are withdrawn during aggregation at fixed times, fractionated with AF4 using a two-angle static light scattering unit as a detector. We have shown that from the analysis of the ratio between the intensities of the scattered light at the two angles the cluster size distribution can be recovered, without any need for calibration based on standard elution times, provided that the geometry and scattering properties of particles and clusters are known. The nonfractionated samples have been characterized also by conventional static and dynamic light scattering to determine their average radius of gyration and hydrodynamic radius. The size distribution of coalescing particles has been investigated also through image analysis of cryo-scanning electron microscopy (SEM) pictures. The average radius of gyration and the average hydrodynamic radius of the nonfractionated samples have been calculated and successfully compared to the values obtained from the size distributions measured by AF4. In addition, the data obtained are also in good agreement with calculations made with population balance equations.

Janus nanoparticles have been synthesized consisting of approximately 5 nm magnetite nanoparticles coated on one side with a pH-dependent and temperature-independent polymer (poly(acrylic acid), PAA), and functionalized on the other side by a second (tail) polymer that is either a pH-independent polymer (polystyrene sodium sulfonate, PSSNa) or a temperature-dependent polymer (poly(N-isopropyl acrylamide), PNIPAM). These Janus nanoparticles are dispersed stably as individual particles at high pH values and low temperatures, but can self-assemble at low pH values (PSSNa) or at high temperatures (>31 degrees C) (PNIPAM) to form stable dispersions of clusters of approximately 80-100 nm in hydrodynamic diameter. The Janus nanoparticle compositions were verified using FTIR and XPS, and their structures observed directly by TEM. Their clustering behavior is analyzed by dynamic light scattering and zeta potential measurements.

In this work, the influence of carbon nanotubes (CNTs) on the self-assembly of nanocomposite materials made of cylinder-forming polystyrene-block-poly(ethylene- butylene)-block-polystyrene (SEBS) is studied. CNTs are modified with polystyrene (PS) brushes by surface-initiated atom transfer radical polymerization to facilitate both their dispersion and the orientation of neighboring PS domains of the block copolymer (BCP) along modified CNT-PS. Dynamic rheology is utilized to probe the viscoelastic and thermal response of the nanoscopic structure of BCP nanocomposites. The results indicate that nonmodified CNTs increase the BCP microphase separation temperature because of BCP segmental confinement in the existing 3D network formed between CNTs, while the opposite holds for the samples filled with modified CNT-PS. This is explained by severely retarded segmental motion of the matrix chains due to their preferential interactions with the PS chains of the CNT-PS. Moreover, transient viscoelastic analysis reveals that modified CNT-PS have a more pronounced effect on flow-induced BCP structural orientation with much lower structural recovery rate. It is demonstrated that dynamic-mechanical thermal analysis can provide valuable insights in understanding the role of CNT incorporation on the microstructure of BCP nanocomposite samples. Accordingly, the presence of CNT has a significant promoting effect on microstructural development, comparable to that of annealing.

A major contemporary concern in developing effective liposome–nanoparticle hybrids is the present inclusion size limitation of nanoparticles between vesicle bilayers, which is considered to be around 6.5 nm in diameter. In this article, we present experimental observations backed by theoretical considerations which show that greater structures can be incorporated within vesicle membranes by promoting the clustering of nanoparticles before liposome formation. Cryo-transmission electron microscopy and cryo-electron tomography confirm these observations at unprecedented detail and underpin that the liposome membranes can accommodate flexible structures of up to 60 nm in size. These results imply that this material is more versatile in terms of inclusion capabilities and consequently widens the opportunities in developing multivalent vesicles for nanobiotechnology applications.

Nanoclusters (NCs) composed of nanoparticles (NPs) with different functionalities and having final size in the sub-micrometer range are of great interest for biomedical imaging, drug delivery, sensors, etc. Because some of the functionalities cannot be incorporated into a single NP, e.g., high drug loading combined with strong magnetic properties, here, we present a proof of the concept using an alternative way to combine these properties using different NPs. In particular, starting from polymer and magnetite nanoparticles (MNPs), we produce NCs made out of a statistical distribution of the two components through a process based on aggregation and breakup. The effect of all involved operating parameters, i.e., primary NP size and composition, surfactant type and concentration, and applied hydrodynamic stress on the NC size and internal structure, was systematically investigated using dynamic light scattering (DLS), static light scattering (SLS), and transmission electron microscopy (TEM) analyses. It was found that, by properly tuning the balance between attractive and steric repulsive forces on one side and hydrodynamic stress on the other, NCs as small as 100 nm can be produced. In all cases, the produced NCs have a very compact internal structure characterized by fractal dimension around 2.6. The proposed production strategy to synthesize hetero-NCs composed of mixtures of various primary particles is suitable for the production of multifunctional devices of nanometer size (i.e., approximately 100 nm) for material and biomedical applications.