Exploiting Mass Spectrometry to Unlock the Mechanism of Nanoparticle-Induced Inflammasome Activation.

Nanoparticles (NPs) elicit sterile inflammation, but the underlying signaling pathways are poorly understood. Here, we report that human monocytes are particularly vulnerable to amorphous silica NPs, as evidenced by single-cell-based analysis of peripheral blood mononuclear cells using cytometry by time-of-flight (CyToF), while silane modification of the NPs mitigated their toxicity. Using human THP-1 cells as a model, we observed cellular internalization of silica NPs by nanoscale secondary ion mass spectrometry (nanoSIMS) and this was confirmed by transmission electron microscopy. Lipid droplet accumulation was also noted in the exposed cells. Furthermore, time-of-flight secondary ion mass spectrometry (ToF-SIMS) revealed specific changes in plasma membrane lipids, including phosphatidylcholine (PC) in silica NP-exposed cells, and subsequent studies suggested that lysophosphatidylcholine (LPC) acts as a cell autonomous signal for inflammasome activation in the absence of priming with a microbial ligand. Moreover, we found that silica NPs elicited NLRP3 inflammasome activation in monocytes, whereas cell death transpired through a non-apoptotic, lipid peroxidation-dependent mechanism. Together, these data further our understanding of the mechanism of sterile inflammation.

Liquid foams as sensors for the detection of biomarkers.

Bioassays are widely used in healthcare to detect and quantify biomarkers, such as molecules or enzymes, which are crucial in monitoring diseases and health conditions. In developed countries, healthcare professionals use specialized reagents and equipment's to perform these bioassays. However, in less-industrialized countries, the creation of low cost, fast, and technically simple bioassays is required. Herein, we propose a simple approach for detecting biochemical markers using host-guest complexes containing a surfactant. When the biochemical marker is present, the host-guest complex is disrupted, releasing the surfactant and producing foam. The read-out mechanism relies on the change of foam volume as function of biomarker concentration. This change is quantifiable by the naked eye and can be measured with a simple ruler. We claim that the use of foams as sensing tool is an attractive, inexpensive, fast, and easy to handle on-site detection method.

Wet spinning of strong cellulosic fibres with incorporation of phase change material capsules stabilized by cellulose nanocrystals.

Incorporating a phase change material (PCM) into fibres allows the fabrication of smart textiles with thermo-regulating properties. Previously, such fibres have been made from thermoplastic polymers, usually petroleum-based and non-biodegradable, or from regenerated cellulose, such as viscose. Herein, strong fibres are developed from aqueous dispersions of nano-cellulose and dispersed microspheres with phase changing characteristics using a wet spinning technique employing a pH shift approach. Good distribution of the microspheres and proper compatibility with the cellulosic matrix was demonstrated by formulating the wax as a Pickering emulsion using cellulose nanocrystals (CNC) as stabilizing particles. The wax was subsequently incorporated into a dispersion of cellulose nanofibrils, the latter being responsible for the mechanical strength of the spun fibres. It was possible to produce fibres highly loaded with the microspheres (40 wt%) with a tenacity of 13 cN tex-1 (135 MPa). The fibres possessed good thermo-regulating features by absorbing and releasing heat without undergoing structural changes, while maintaining the PCM domain sizes intact. Finally, good washing fastness and PCM leak resistance were demonstrated, making the fibres suitable for thermo-regulative applications. Continuous fabrication of bio-based fibres with entrapped PCMs may find applications as reinforcements in composites or hybrid filaments.

Contact-free measurement of surface tension on single droplet using machine learning and acoustic levitation.

HYPOTHESIS: Acoustic levitation provides the possibility to deform levitated droplets in a controllable, and quantifiable manner, thus offering a means to measure the surface tension of a liquid droplet based on its deviation from sphericity. However, for new generation of multi-source and highly stable acoustic levitators, no model relates the acoustic pressure field to the deformation and surface tension. Utilizing a machine learning algorithm is expected to identify correlations between the experimental data without any set preconditions. EXPERIMENTS: A series of aqueous surfactant solutions with a large range of surface tensions were prepared, and evaporated under levitation, while the acoustic pressure was varied. A dataset of over 50,000 images was used for the training and evaluation of the machine learning algorithm. Prior to that, the machine learning approach was validated on in silico data that also included artificial noise. FINDINGS: We achieved high accuracy in predicting the surface tension of single standing droplets (±0.88 mN/m), and we surpassed certain physical conditions related to the size, and shape of the suspended samples that simpler theoretical models are subject to.

Radial discharge high shear homogenization and ultrasonication assisted pH-shift processing of herring co-products with antioxidant-rich materials for maximum protein yield and functionality.

Cross-processing herring co-products with antioxidant-rich helpers including lingonberry-press-cake, shrimp-shells and seaweed was reported to mitigate lipid oxidation but reduce protein yield. Here, four strategies were used to counteract such yield-reduction; optimizing solubilization/precipitation pH, increasing raw-material-to-water-ratio, replacing single-stage-toothed- by radial-discharge- high-shear-mechanical-homogenization (RD-HSMH) and ultrasonication (US). The effects of RD-HSMH and US on lipid oxidation, protein structural and functional properties were studied. Combining four strategies improved total protein yield by 5-12 %, depending on helper type. More than the confirmed antioxidant effects, cross-processing also improved protein water solubility and emulsification activity but reduced gelation properties. RD-HSMH generally improved protein emulsifying and gelation properties but reduced protein water solubility. US reduced protein water solubility and gelation properties. Altogether, it was recommended for all helpers to increase solubilization pH to 12 and raw-material-to-water-ratio to 1:6 followed by RD-HSMH at 8000 rpm for 90 s, aiming for maximum protein yield and emulsifying and gelation properties.

pH-Controlled assembly of polyelectrolyte layers on silica nanoparticles in concentrated suspension.

HYPOTHESIS: Preparation of suspensions of nanoparticles (>1 wt%) coated with a polyelectrolyte multilayers is a challenging task because of the risk of flocculation when a polyelectrolyte is added to a suspension of oppositely charged nanoparticles. This situation can be avoided if the charge density of the polymers and particles is controlled during mixing so as to separate mixing and adsorption events. EXPERIMENTS: The cationic polyethylenimine (PEI) and the anionic carboxymethylcellulose (CMC) were used as weak polyelectrolytes. Polyelectrolyte multilayers build-up was conducted by reducing the charge of one of the components during the addition of the next component. Charge density was controlled by tuning pH. Analysis of the suspension of coated nanoparticles was done by means of dynamic light scattering, electrophoresis and small angle x-ray scattering measurements, while quartz crystal microbalance was used to study the build-up process on flat silica surfaces. FINDINGS: Charge density, controlled through pH, can be used as a tool to avoid flocculation during layer-by-layer deposition of polyelectrolytes on 20 nm silica particles at high concentration (∼40 wt%). When added to silica at pH 3, PEI did not induce flocculation. Adsorption was triggered by raising the pH to 11, pH at which CMC could be added. The pH was then lowered to 3. The process was repeated, and up to five polyelectrolyte layers were deposited on concentrated silica nanoparticles while inducing minimal aggregation.

Formation of oleogels based on emulsions stabilized with cellulose nanocrystals and sodium caseinate.

HYPOTHESIS: In the preparation of oleogels based on Pickering-emulsions, the choice of the preparation route is critical to withstand drying under ambient conditions, as it conditions the composition of the interfacial layer at the oil-water interface. EXPERIMENTS: Hexadecane and olive oil oleogels were prepared using an emulsion-template approach from oil-in-water emulsions formulated with cellulose nanocrystals (CNC) and sodium caseinate (CAS) added in different orders (CNC/CAS together; first CAS then CNC; first CNC then CAS). The oleogels were formed from preconcentrated emulsions by drying at ambient temperature. The structure of the gels was characterised by confocal laser scanning microscopy, and the gels were assessed in terms of viscoelastic properties and redispersibility. FINDINGS: The properties of oleogels were controlled by 1) the composition of the surface layer at oil-water interface; 2) the amount and type of non-adsorbed stabilizer; and 3) the composition and viscosity of oils (hexadecane vs. olive oil). For the oleogels prepared from starting emulsions stabilized with CNC with subsequent addition of CAS, and free CAS present in aqueous phase, the elastic component was prevalent. Overall, the dominating species at the oil-water interface controlled the emulsion behaviour and stability, as well as viscoelastic behaviour of the resulting oleogels and their redispersibility.

Development of Microfluidic, Serum-Free Bronchial Epithelial Cells-on-a-Chip to Facilitate a More Realistic In vitro Testing of Nanoplastics.

Most cell culture models are static, but the cellular microenvironment in the body is dynamic. Here, we established a microfluidic-based in vitro model of human bronchial epithelial cells in which cells are stationary, but nutrient supply is dynamic, and we used this system to evaluate cellular uptake of nanoparticles. The cells were maintained in fetal calf serum-free and bovine pituitary extract-free cell culture medium. BEAS-2B, an immortalized, non-tumorigenic human cell line, was used as a model and the cells were grown in a chip within a microfluidic device and were briefly infused with amorphous silica (SiO2) nanoparticles or polystyrene (PS) nanoparticles of similar primary sizes but with different densities. For comparison, tests were also performed using static, multi-well cultures. Cellular uptake of the fluorescently labeled particles was investigated by flow cytometry and confocal microscopy. Exposure under dynamic culture conditions resulted in higher cellular uptake of the PS nanoparticles when compared to static conditions, while uptake of SiO2 nanoparticles was similar in both settings. The present study has shown that it is feasible to grow human lung cells under completely animal-free conditions using a microfluidic-based device, and we have also found that cellular uptake of PS nanoparticles aka nanoplastics is highly dependent on culture conditions. Hence, traditional cell cultures may not accurately reflect the uptake of low-density particles, potentially leading to an underestimation of their cellular impact.

On the effect of particle surface chemistry in film stratification and morphology regulation.

Combinations of colloids and binders are often used to formulate functional coatings. In these mixtures, competition between particle migration, polymer chain diffusion, evaporation and sedimentation affects their respective spatial location and therefore can govern the surface features. In addition to this, the surface chemistry of the nanoparticles (NPs) and the resulting interparticle interactions can play a significant role in dictating the morphology and the properties of resultant films. Hence it would be possible to tune the surface and bulk topology of the films by controlling these parameters. A combination of various acrylic binders with two types of silica sols, bare (BSiO2) and modified silica (MSiO2), differing in their ability to gel, were formulated and dried under controlled conditions. Factors influencing the mobility and migration of binder and silica particles were evaluated with respect to particle concentration and drying rate. MSiO2 films showed prominent pores with gradual increase in Si% across the cross-section of the films, whereas, BSiO2 films had no pores and showed a uniform Si content across the cross-section of the films. This difference is explained by the variation in gelation between BSiO2 compared to MSiO2, that hindered the NPs migration and affects the infiltration and stratification process. This study paves a path forward to achieve desired surface and bulk porosity from colloidal silica coatings by effective control of chemistry of particles along with process parameters.

Nanomaterials for Combined Stabilisation and Deacidification of Cellulosic Materials-The Case of Iron-Tannate Dyed Cotton.

The conservation of textiles is a challenge due to the often fast degradation that results from the acidity combined with a complex structure that requires remediation actions to be conducted at several length scales. Nanomaterials have lately been used for various purposes in the conservation of cultural heritage. The advantage with these materials is their high efficiency combined with a great control. Here, we provide an overview of the latest developments in terms of nanomaterials-based alternatives, namely inorganic nanoparticles and nanocellulose, to conventional methods for the strengthening and deacidification of cellulose-based materials. Then, using the case of iron-tannate dyed cotton, we show that conservation can only be addressed if the mechanical strengthening is preceded by a deacidification step. We used CaCO3 nanoparticles to neutralize the acidity, while the stabilisation was addressed by a combination of nanocellulose, and silica nanoparticles, to truly tackle the complexity of the hierarchical nature of cotton textiles. Silica nanoparticles enabled strengthening at the fibre scale by covering the fibre surface, while the nanocellulose acted at bigger length scales. The evaluation of the applied treatments, before and after an accelerated ageing, was assessed by tensile testing, the fibre structure by SEM and the apparent colour changes by colourimetric measurements.

Conductive textiles prepared by spray coating of water-based graphene dispersions.

In the development of embedding devices on textiles like sensors and detectors the controlled formation of a conductive coating remains a critical point. Although there are several approaches for imparting conductivity to any textile, the challenges remain in balancing the practical aspects of the coating procedure that affect the conductivity with the associated mechanical properties of the textile along with a feasible economic viability of the process. In this research we developed an approach to deposit uniform conductive graphene surface coatings on polyester (PET) fabric using graphene oxide (GO) particles. Instead of using pre-reduced graphene oxide (rGO), an approach of coating an aqueous dispersion of hydrophilic GO particles was adopted. Stable aqueous dispersions of GO were formulated, and the dispersion properties were characterized using DLS and zeta potential before coating them onto the PET textiles. This approach not only helped in developing an aqueous coating technique but also helped in avoiding the need of any organic solvents which might have been required for coating hydrophobic rGO moieties onto the textile substrates. The uniformity of the coating was analyzed using scanning electron microscopy (SEM). Later, the GO coated textiles were reduced via thermal and chemical approaches and their effects on the conductive and mechanical properties of the fabric were assessed and compared. The reduction efficacy was analyzed and compared using XPS. The conductivity and water adsorption properties were correlated to the uniformity and retainment of rGO on the surface of the conductive textiles.

Recovery of a protein-rich biomass from shrimp (Pandalus borealis) boiling water: A colloidal study.

Flocculation and sedimentation of a protein-rich biomass from shrimp boiling water (SBW) using food grade polysaccharides (carrageenan, alginate and carboxymethyl cellulose (CMC)) as flocculants was investigated at different pH-values. The effect of flocculant concentration on particle size and viscosity of SBW was also evaluated. Flocculation with carrageenan (0.45 g/L) at pH = 4 exhibited the most efficient protein sedimentation; protein concentration of the upper phase was here reduced by 77%, allowing 86% protein to be sedimented from SBW. Flocculation by alginate and CMC at pH = 4 showed 67% and 60% protein reduction of the upper phase at concentrations of 0.5 and 0.2 g/L, respectively. Contrary to alginate and CMC, carrageenan concentration affected the size distribution of flocs. Finally, carrageenan at 0.45 g/L and pH = 4 was successfully tested in a scaled up trial (5L) providing 78.5% protein recovery and a biomass with 75% protein on dry weight basis.

How Promoting and Breaking Intersurfactant H-Bonds Impact Foam Stability.

On the basis of previous results revealing that intersurfactant H-bonds improve foam stability, we now focus on how foams stabilized by two different N-acyl amino acid surfactants are affected by different salts (NaF, NaCl, NaSCN), which can promote or break intersurfactant H-bonds. The chosen surfactants, namely, sodium N-lauroyl sarcosinate (C12SarcNa) and sodium N-lauroyl glycinate (C12GlyNa), differ only by one methyl group at the nitrogen of the amide bond that blocks intersurfactant H-bonds in the case of C12SarcNa. The salts were chosen because they are kosmotropic (NaF), chaotropic (NaSCN), and in between (NaCl) and thus influence the formation of an H-bond network in different ways. Surface tension measurements showed that the addition of salts decreased the cmcs of both surfactants and increased the packing density, as expected. Moreover, in presence of the salts, the head groups of the H-bond forming surfactant C12GlyNa were more tightly packed at the surface than the C12SarcNa head groups. The effect of the salts on foam stability was studied by analysis of the foam height, the foam liquid fraction, and by image analysis of the foam structure. As expected, the salts had no significant effect on foams stabilized by C12SarcNa, which is unable to form intersurfactant H-bonds. In contrast, the stability of C12GlyNa-containing foams followed the trend NaF > NaCl > NaSCN, which is in agreement with NaF promoting and NaSCN breaking intersurfactant H-bonds. Surface rheology measurements allowed us to correlate foam stability with surface elasticity. This study provides new insights into the importance of H-bond promoters and breakers, which should be used in the future design of tailor-made surfactants.

Interfacial and Aggregation Behavior of Dicarboxylic Amino Acid-Based Surfactants in Combination with a Cationic Surfactant.

The interfacial and micellization behavior of three dicarboxylic amino acid-based anionic surfactants, abbreviated as AAS (N-dodecyl derivative of -aminomalonate, -aspartate, and -glutamate) in combination with hexadecyltrimethylammonium bromide (HTAB) were investigated by surface tension, conductance, UV-vis absorption/emission spectroscopy, dynamic light scattering (DLS), and viscosity studies. Critical micelle concentration (CMC) values of the surfactant mixtures are significantly lower than the predicted values, indicating associative interaction between the components. Surface excess, limiting molecular area, surface pressure at the CMC, and Gibbs free energy indicate spontaneity of the micellization processes compared to the pure components. CMC values were also determined from the sigmoidal variation in the plot of micellar polarity and pyrene UV-vis absorption/emission intensities with surfactant concentration. The aggregation number, determined by static fluorescence quenching method, increases with decreasing mole fraction of the AAS (αAAS), where the micelles are mainly dominated by the HTAB molecules. The size of the micelle increases with decreasing αAAS, leading to the formation of larger and complex aggregates, as also supported by the viscosity studies. Micelles comprising 20-40 mol % AAS are highly viscous, in consonance with their sizes. Some of the mixed surfactant systems show unusual viscosity (shear thickening and increased viscosity with increasing temperature). Such mixed surfactant systems are considered to have potential in gel-based drug delivery and nanoparticle synthesis.

Role of protein-cellulose nanocrystal interactions in the stabilization of emulsion.

HYPOTHESIS: The interactions between two bio-based emulsifiers, namely cellulose nanocrystals (CNC) and the surface active sodium caseinate (CAS), can influence the formation and stability of oil-in-water emulsion (O/W). EXPERIMENTS: After studying the interactions between CNC and CAS, in bulk, and at air-water and liquid-liquid interfaces, emulsions have been prepared through different routes of addition, at pH 7 and 3, at which CNC and CAS had repulsive and attractive interactions, respectively. The routes of addition were (1) CAS and CNC simultaneously, (2) CAS first followed by CNC in a subsequent emulsification step and (3) CNC first, followed by CAS. The emulsions were characterized by laser diffraction and optical microscopy. FINDINGS: At pH 7, in the case of repulsive interactions, the surface activity of CAS was balanced by the irreversible adsorption of CNC, irrespectively of the route of emulsification. At pH 3, in the case of attractive interactions, using route (1), the aggregates CAS-CNC provided better emulsification than CNC and CAS alone. For emulsions prepared by route (2) and (3), gelling was observed which could be controlled through the order of addition. Emulsions prepared at pH 7 then adjusted to pH 3 exhibited an increase in viscosity, while the droplet size was not affected.

Functionalized magnetic particles for water treatment.

In this study, we have taken the concept of water treatment by functionalized magnetic particles one step forward by integrating the technology into a complete proof of concept, which included the preparation of surface modified beads, their use as highly selective absorbents for heavy metals ions (Zinc, Nickel), and their performance in terms of magnetic separation. The separation characteristics were studied both through experiments and by simulations. The data gathered from these experimental works enabled the elaboration of various scenarios for Life Cycle Analysis (LCA). The LCA showed that the environmental impact of the system is highly dependent on the recovery rate of the magnetic particles. The absolute impact on climate change varied significantly among the scenarios studied and the recovery rates. The results support the hypothesis that chelation specificity, magnetic separation and bead recovery should be optimized to specific targets and applications.

Directed self-assembly of silica nanoparticles in ionic liquid-spun cellulose fibers.

The application range of man-made cellulosic fibers is limited by the absence of cost- and manufacturing-efficient strategies for anisotropic hierarchical functionalization. Overcoming these bottlenecks is therefore pivotal in the pursuit of a future bio-based economy. Here, we demonstrate that colloidal silica nanoparticles (NPs), which are cheap, biocompatible and easy to chemically modify, enable the control of the cross-sectional morphology and surface topography of ionic liquid-spun cellulose fibers. These properties are tailored by the silica NPs' surface chemistry and their entry point during the wet-spinning process (dope solution DSiO2 or coagulation bath CSiO2). For CSiO2-modified fibers, the coagulation mitigator dimethylsulphoxide allows for controlling the surface topography and the amalgamation of the silica NPs into the fiber matrix. For dope-modified fibers, we hypothesize that cellulose chains act as seeds for directed silica NP self-assembly. This results for DSiO2 in discrete micron-sized rods, homogeneously distributed throughout the fiber and for glycidoxy-surface modified DSiO2@GLYEO in nano-sized surface aggregates and a cross-sectional core-shell fiber morphology. Furthermore, the dope-modified fibers display outstanding strength and toughness, which are both characteristic features of biological biocomposites.

Reversible flocculation of nanoparticles by a carbamate surfactant.

Fatty alkyldiamine readily reacts with CO2 in aqueous solution at pH 12 to reversibly form surface active carbamate species. The carbamate can be reverted to the amine by exposure to N2 and heat. In this work, a carbamate-based surfactant (Y12-carbamate) has been used to disperse and stabilize hydrophobic nanoparticles. This state could be regarded as the "on" state of a series of cycle. The nanoparticles were then flocculated when the carbamate groups were cleaved by exposure to N2 and heating, corresponding to the "off" state. In a subsequent cycle, the nanoparticles were re-dispersed by exposure to CO2, while the pH remained at 12. This cycle of re-dispersion and flocculation could be repeated two times without impairing the particle size. However, further cycles increased the particle size, indicating that all particles could not be completely re-dispersed. In addition, we also investigated the effect of pH on the colloidal stability with sodium Y12-carbamate, by measuring particle size and electrophoretic mobility. The results showed that pH strongly influenced the stability of the nanoparticles. Sodium Y12-carbamate stabilized the particles with a negative electrophoretic mobility at pH well above pKa whereas at pH close to pKa of Y12-amine (pKa = 9.0), the particles quickly flocculated, as a result of an ion-pair formation between Y12-ammonium and Y12-carbamate.

Evaluation of the Adhesion and Performance of Natural Consolidants for Cotton Canvas Conservation.

Recent developments in paper and canvas conservation have seen the introduction of nanocellulose (NC) as a compatible treatment for the consolidation of historical cellulosic artifacts and manuscripts. However, as part of the assessment of these new materials for canvas consolidation, the adhesion of the consolidation treatment (which takes place between the applied material and the substrate) has not yet been evaluated, and as a result, it is poorly understood by both the scientific and conservation communities. After evaluating the potential of NC treatments for the consolidation of cotton painting canvas, we investigate a route to promote the interaction between the existing canvas and the nanocellulose treatment, which is in our case made of cellulose nanofibrils (CNF). This was carried out by introducing a cationic polymer, polyamidoamine-epichlorohydrin (PAAE), as an intermediate layer between the canvas and the CNF. The morphological, chemical, and mechanical evaluation of the canvas samples at different relative humidity (RH) levels demonstrated how the adhesion of the added PAAE layer is a dominant factor in the consolidation process. Improvement in the coating of canvas single fibers by the CNF, higher adhesion energy between the canvas fibers and the CNF treatment, and finally overall stronger canvas reinforcement were observed following the introduction of PAAE. However, an increase in mechanical response to moisture sorption and desorption was also observed for the PAAE-treated canvases. Overall, this study shows the complexity of such systems and, as such, the relevance of using a multiscale approach for their assessment.

A reverse degradation vs. temperature relationship for a carbonate-containing gemini surfactant.

The rate of hydrolysis of cleavable surfactant is known to have a strong temperature dependence. A nonionic gemini surfactant with a readily hydrolysable carbonate bond as spacer unit has been synthesized and evaluated. A carbonate linkage is special as spacer unit in a gemini surfactant because the hydrolysis results in two identical molecules, in this case a hydroxy-substituted nonionic surfactant, along with carbon dioxide. The critical micelle concentration for the gemini surfactant was an order of magnitude lower than that of the degradation product. The degradation of the new surfactant and specifically the effect of temperature on the rate of hydrolysis was investigated in detail. It was found that alkaline hydrolysis was rapid at 15 °C but very slow at 30 °C, i.e. there was a reverse relationship between rate of hydrolysis and temperature. The same behavior was found for monomeric nonionic carbonate-containing surfactants that were synthesized and used as references. This unusual behavior, which can be of practical use, is explained by the reverse solubility vs. temperature profile for amphiphiles carrying a polyoxyethylene chain.