Charged Silica Research Articles

Adenosine Triphosphate Inhibits Cold-Responsive Aggregation.

Adenosine triphosphate (ATP), ubiquitous in all living organisms, is conventionally recognized as a fundamental energy currency essential for a myriad of cellular processes. While its traditional role in energy metabolism requires only micromolar concentrations, the cellular content of ATP has been found to be significantly higher at the millimolar level. Recent studies have attempted to correlate this higher concentration of ATP with its nonenergetic role in maintaining protein homeostasis, leaving the investigation of ATP's nontrivial activities in biology an open question. Here, by coupling computer simulations and experiments, we uncover new insights into ATP's role as a cryoprotectant against cold-salt stress, highlighting the necessity for higher cellular ATP concentrations. We present direct evidence at charged silica interfaces, demonstrating ATP's ability to restore native intersurface interactions disrupted by combined cold-salt stress, thereby inhibiting cold-responsive aggregation in high-salt conditions. ATP desorbs salt cations from negatively charged surfaces through predominant interactions between ATP and the salt cations. Although the mode of ATP's action remains unchanged with temperature, the extent of interaction scales with temperature, requiring less ATP activity at lower temperatures, justifying the reason for reduction in cellular ATP content due to the cold effect, reported in previous experimental studies. The trend observed in inorganic nanostructures is recurrent and robustly transferable to charged protein interfaces. A thorough comparison of ATP's cryoprotective activity with traditionally known biological cryoprotectants (glycine and betaine) reveals ATP's greater efficiency. In retrospect, our findings highlight ATP's additional biological role in cryopreservation, expanding its potential biomedical applications by offering effective protection of cells from cryoinjuries and avoiding the significant challenges associated with the toxicity of organic cryoprotectants.

Butterflies and bifurcations in surface radio-frequency traps: The diversity of routes to chaos.

In the present article, we investigate the charged micro-particle dynamics in the surface radio-frequency trap (SRFT). We have developed a new configuration of the SRFT that consists of three curved electrodes on a glass substrate for massive micro-particles trapping. We provide the results of numerical simulations for the dynamical regimes of charged silica micro-particles in the SRFT. Here, we introduce a term of a "main route" to chaos, i.e., the sequence of dynamical regimes for the given particles with the increase of the strength of an electric field. Using the Lyapunov exponent formalism, typical Reynolds number map, Poincaré sections, bifurcation diagrams, and attractor basin boundaries, we have classified three typical main routes to chaos depending on the particle size. Interestingly, in the system described here, all main scenarios of a transition to chaos are implemented, including the Feigenbaum scenario, the Landau-Ruelle-Takens-Newhouse scenario as well as intermittency.

Insights into gypsum and silica scaling behaviors of dense Janus membranes in membrane distillation: The effect of varied surface properties

Dense Janus membranes (JMs) have emerged as potential candidates to address the tough scaling issue in hypersaline wastewater treatments for membrane distillation (MD). However, behaviors and mechanisms of various scalants on dense JMs have not been systematically investigated. Herein, we designed three dense JMs to simultaneously compare their anti-scaling properties against gypsum and silica in MD and focus on the critical role of varied surface property in scaling control. Results showed that dense JMs with highly positive gypsum-membrane interfacial energy and with strong electrical repulsion against silica species were more effective in resisting gypsum and silica, respectively. Scaled membrane characterization, quartz crystal microbalance monitoring, interfacial energy analysis and AFM force measurement revealed the distinct anti-scaling mechanisms. Highly hydrophilic surfaces without specific interactions with scaling ions provided robust thermodynamic barriers and less kinetically affected local supersaturations, preventing gypsum nucleation and growth. In contrast, positively charged surfaces favorably attracted negatively charged silica species with high reactivity, promoting subsequent polymerization with silicic acid that kinetically dominated silica scaling. Moreover, coexisting oversaturated gypsum and silica influenced the scaling behavior of each other, and surface properties of the preferentially formed scaled layer might also matter in scaling process. This study shall provide useful insights into the anti-scaling mechanisms of dense JMs in MD and highlight the potential of dense surface design as an effective scaling control strategy to pave the way for potential MD applications.

Osmolyte-Induced Modulation of Hofmeister Series.

Natural selection has driven the convergence toward a selected set of osmolytes, endowing them with the necessary efficiency to manage stress arising from salt diversity. This study combines atomistic simulations and experiments to investigate how two osmolytes, glycine and betaine, individually modulate the Hofmeister ion ordering of alkali metal salts (LiCl, KCl, and CsCl) near a charged silica interface. Both osmolytes are found to prevent salt-induced aggregation of the charged entities, yet their mode and degree of relative modulation depend on their intricate interplay with specific salt cations. Betaine's ion-mediated surface interaction maintains Hofmeister ion ordering, whereas glycine alters the relative Hofmeister order of the cation by salt-specific ion desorption from the surface. Experimental validation through surface-enhanced Raman spectroscopy supports these findings, elucidating osmolyte-mediated alterations in interfacial water structures. These observations based on an inorganic interface are reciprocated in amyloid beta 40 dimerization dynamics, highlighting osmolytes' efficacy in mitigating salt-induced aggregation. A molecular analysis suggests that the differential modes of interaction, as found here for glycine and betaine, are prevalent across classes of zwitterionic osmolytes.

Influence of Sodium Ions and Carbon Black on the Formation and Structural Color of Photonic Balls by Silica Particles.

In this study, photonic balls─spherical aggregates of submicrometer-sized silica particles with uniform particle size─were investigated as structural colored materials. The structural color of these photonic balls is influenced by the ordered arrangement of the silica particles. The research focused on how the addition of electrolytes, specifically NaCl, affects the formation of photonic balls to achieve the desired structural color. Without NaCl, the photonic balls formed onion-shaped colloidal crystals. At NaCl concentrations above 0.006 mol/L, the particles aggregated into short-range ordered structures. When the concentration exceeded 0.05 mol/L, the aggregates lost their spherical shape. The study also explored the addition of carbon black (CB), a water-dispersible material due to its surface charge. The findings revealed that NaCl induced the phase separation between the charged silica particles and CB, resulting in Janus-shaped photonic balls─one side exhibiting structural color and the other side appearing black due to the presence of CB. Changing the silica particle size altered the hues of these Janus-shaped photonic balls, though they appeared uniformly colored to the naked eye. While this study did not specifically examine the applications of Janus-shaped photonic balls composed of silica particles and CB, CB is known for its ability to absorb near-infrared radiation and convert it into heat as well as its conductive properties. Silica, on the other hand, has a low thermal conductivity and acts as an electrical insulator. The structurally colored Janus-shaped photonic balls created in this study may serve as pigments in applications requiring anisotropic heat generation and electrical conduction. Additionally, the study's findings suggest the potential for creating various types of Janus-shaped photonic balls from materials with differing densities.

Unraveling the Complexities of Silica Nanoparticle Adsorption onto Polymer Latexes in Pickering Emulsion Polymerization.

Incorporating unmodified silica nanoparticles onto polymer latexes to fabricate aqueous polymer dispersions without relying on electrostatic attraction during the Pickering emulsion polymerization process still faces challenges. For negatively charged silica nanoparticles to successfully adsorb onto polymer latexes, particularly in an anionic initiator emulsion polymerization system, they have remained elusive without the use of auxiliary monomers and cationic initiators. This study investigates various experimental parameters, such as emulsion polymerization temperature, monomer solubility, salt concentration, and cation type, to elucidate the factors influencing the adsorption of unmodified silica nanoparticles in Pickering emulsion polymerization. While poly(methyl methacrylate) (PMMA)/SiO2 hybrid latexes can be obtained under pH conditions of 5-6 and at temperatures of 65 °C or below, the loading rate of silica nanoparticles decreases as the reaction temperature increases, resulting in bare PMMA latexes without silica nanoparticle adsorption at temperatures exceeding 70 °C. Introducing styrene (St) into the monomer mixture with methyl methacrylate in a ratio of up to 10 wt % leads to a gradual decrease in silica nanoparticle loading rate, from 27.3 to 8.2 wt %, attributed to the low solubility of St in water. Furthermore, the presence of sodium ions (Na+) is found to be crucial for silica nanoparticle adsorption onto PMMA latexes, as the sodium ions have a stabilizing effect on both the silica nanoparticles and the silica nanoparticle-armored latexes. These findings highlight the complex nature of Pickering emulsion polymerization in the presence of unmodified silica nanoparticles, demonstrating that the loading rate of silica nanoparticles onto polymer latexes is influenced by various factors. These insights pave the way for developing aqueous polymer dispersions with high silica nanoparticle loading rates onto polymer latexes, which is a desirable trait in the coating industry.

Influence of particle parameters on deposition onto healthy and damaged human hair.

This research investigates how particle parameters, such as zeta potential, size, functional group, material composition, and hydrophobicity affect their affinity and deposition of particles onto hair. Streaming potential was used as the technique for analysis. The streaming potential data obtained was then converted to surface coverage data. Scanning electron microscopy (SEM) was also done to visualize particle localization on the hair surface. This study found stronger particle affinity on healthy than on damaged (oxidatively bleached) hair, due to diminished interaction sites from the removal of the hair shaft's external lipid layer. SEM imaging supported these findings and offered insights into particle localization. Hydrophilic silica particles accumulated along the exposed hydrophilic cuticle edges of healthy hair, due to hydrogen bonding with the exposed endocuticle. This localization is hypothesized to be due to the limited hydrophilic binding sites on the hydrophobic healthy hair cuticle surface. In damaged hair, an abundance of hydrophilic sites across the cuticle surface results in more dispersed binding. Hydrogen bonding and electrostatic attraction were shown to be the predominant forces influencing deposition, with hydrophobic interactions playing a less influential role. The affinity studies also proved that electrostatic attractions work over a longer range and are more effective at lower particle conditions compared with hydrogen bonding which only start to play a bigger role at higher particle concentrations. Steric hindrance of bulky side groups acted as a significant repulsive force. Results also revealed that larger particles deposit poorly on both healthy and damaged hair compared with smaller ones. Compared with neutrally charged silica nanoparticles (SN-2), positively charged PMMA particles (PN+16) have a stronger affinity to healthy hair, with highly charged particles (PN+49) depositing most rapidly. This study provides a fundamental understanding of how particle-surface parameters influence their affinity to hair and how damaging hair affects deposition.

Biofuel cell-based self-powered immunosensor for detection of 17β-estradiol by integrating the target-induced biofuel release and biogate immunoassay.

A novel biofuel cell (BFC)-based self-powered electrochemical immunosensing platform was developed by integrating the target-induced biofuel release and biogate immunoassay for ultrasensitive 17β-estradiol (E2) detection. The carbon nanocages/gold nanoparticle composite was employed in the BFCs device as the electrode material, through which bilirubin oxidase and glucose oxidase were wired to form the biocathode and bioanode, respectively. Positively charged mesoporous silica nanoparticles (PMSN) were encapsulated with glucose molecules as biofuel and subsequently coated by the negatively charged AuNPs-labelled anti-E2 antibody (AuNPs-Ab) serving as a biogate. The biogate could be opened efficiently and the trapped glucose released once the target E2 was recognized and captured by AuNPs-Ab due to the decreased adhesion between the antigen-antibody complex and PMSN. Then, glucose oxidase oxidized the glucose to produce a large number of electrons, resulting in significantly increased open-circuit voltage (EOCV). Promisingly, the proposed BFC-based self-powered immunosensor demonstrated exceptional sensitivity for the detection of E2 in the concentration range from 1.0pgmL-1 to 10.0ngmL -1, with a detection limit of 0.32pgmL-1 (S/N = 3). Furthermore, the prepared BFC-based self-powered homogeneous immunosensor showed significant potential for implementation as a viable prototype for a mobile and an on-site bioassay system in food and environmental safety applications.

QUALITY ASSESSMENT AND STABILITY STUDIES OF METRONIDAZOLE TABLETS FORMULATIONS OBTAINED VIA CRYSTALLO CO-AGGLOMERATION TECHNIQUE

Stability studies are essential for assessing the quality, safety, and efficacy of pharmaceutical products, ensuring they maintain their properties over time. This study aimed to assess the stability of metronidazole tablets stored in a desiccator with charged silica gel following the International council for harmonization of Technical Requirements for Pharmaceuticals for Human Use guidelines. Metronidazole tablets were formulated from metronidazole co-agglomerates using different excipients by direct compression method and stored for 6 and 12 months at 25±2°C/60±5% relative humidity. Quality parameters such as weight variation, diameter, thickness, hardness, friability, content uniformity, and dissolution rate were evaluated at intervals using the United States Pharmacopeia – National Formulary and British Pharmacopeia specifications. The tablets maintained uniformity in weight, diameter, thickness and content over 12 months, meeting pharmacopeial standards. They exhibited high crushing strength, low friability, and consistent disintegration times (<5 min), across formulations and storage durations with no significant changes after storage, indicating stable performance. The sustained high crushing strength, friability ratio (CSFR) and crushing strength, friability, disintegration time (CSFR/Dt) ratios suggested high tablet strength and quality. In-vitro dissolution studies showed release rates of 87.31 – 100.81 %, with a significant decrease at 6 months within pharmacopeial standards but no change at 12 months. Content uniformity was maintained throughout storage. Metronidazole tablets formulated from crystallo co-agglomerates demonstrated good stability and mechanical strength over 12 months of storage. Storage in air-tight containers with desiccants at controlled room temperature (25±2°C) or below their relative humidities is recommended for maintaining tablet quality

An anion exchange membrane sensor detects EGFR and its activity state in plasma CD63 extracellular vesicles from patients with glioblastoma

We present a quantitative sandwich immunoassay for CD63 Extracellular Vesicles (EVs) and a constituent surface cargo, EGFR and its activity state, that provides a sensitive, selective, fluorophore-free and rapid alternative to current EV-based diagnostic methods. Our sensing design utilizes a charge-gating strategy, with a hydrophilic anion exchange membrane functionalized with capture antibodies and a charged silica nanoparticle reporter functionalized with detection antibodies. With sensitivity and robustness enhancement by the ion-depletion action of the membrane, this hydrophilic design with charged reporters minimizes interference from dispersed proteins, thus enabling direct plasma analysis without the need for EV isolation or sensor blocking. With a LOD of 30 EVs/μL and a high relative sensitivity of 0.01% for targeted proteomic subfractions, our assay enables accurate quantification of the EV marker, CD63, with colocalized EGFR by an operator/sample insensitive universal normalized calibration. We analysed untreated clinical samples of Glioblastoma to demonstrate this new platform. Notably, we target both total and “active” EGFR on EVs; with a monoclonal antibody mAb806 that recognizes a normally hidden epitope on overexpressed or mutant variant III EGFR. Analysis of samples yielded an area-under-the-curve (AUC) value of 0.99 and a low p-value of 0.000033, surpassing the performance of existing assays and markers.

Laboratory-scale characterization of slow-release permanganate gel (SRP-G) for the in-situ treatment of chlorinated-solvent groundwater plumes

Significant challenges remain for the remediation of chlorinated-solvent plumes in groundwater, such as trichloroethene (TCE) and tetrachloroethene (PCE). A novel slow-release permanganate gel (SRP-G) technique may show promise for the in-situ treatment (remediation) of chlorinated contaminant plumes in groundwater. A series of laboratory experiments were conducted to characterize the primary physical factors that influence SRP-G gelation processes to optimize SRP-G performance for plume treatment. Specifically, experiments were conducted to quantify gel zeta potential, particle size distribution, and viscosity to determine SRP-G gelation characteristics and processes. These experiments tested various concentrations of two SRP-G amendment solutions (NaMnO4 and KMnO4) prepared with 30-wt.% and 50-wt.% colloidal silica to determine such influences on zeta potential, particle size distribution, and viscosity. The results of this study show that SRP-G solutions with low zeta potential and relatively high pH favor more rapid SRP-G gelation. The concomitant interaction of the predominantly negatively charged colloidal silica particles and the positively charged dissociated cations (Na+ and K+) in the SRP-G solution had the effect of stabilizing charge imbalance via attraction of particles and thereby inducing a greater influence on the gelation process. Gel particle size distribution and changes in viscosity had a significant influence on SRP-G solution gelation. The addition of permanganate (NaMnO4 or KMnO4) increased the average particle size distribution and the viscosity of the SRP-G solution and decreased the overall gelation time. SRP-G amendments (NaMnO4 or KMnO4) prepared with 50-wt.% colloidal silica showed more effective gelation (and reduced gelation time) compared to SRP-G amendments prepared with 30-wt.% colloidal silica. Under the conditions of these experiments, it was determined that both the 7-wt.% NaMnO4 solution and 90 mg/L KMnO4 solution using 50-wt.% colloidal silica would be the optimal injection SRP-G solution concentrations for this in-situ treatment technique.

Short Zwitterionic Sulfobetaine-Modified Silica Nanoparticles: Is Neutrality Possible?

Zwitterionic coatings are an efficient strategy for preventing biomolecule adsorption and enhancing nanoparticle stability in solution. The properties of zwitterions and other antifouling materials, including suppression of nonspecific adsorption and improved colloidal stability of nanoparticles, are believed to derive from their electroneutral and highly hydrophilic nature. Among different zwitterions, short sulfobetaines have been demonstrated to be effective in preventing protein adsorption onto several nanoparticles and providing enhanced colloidal stability. Although zwitterionic sulfobetaine silane (ZS) is electrically neutral, the negatively charged zwitterionic sulfobetaine-functionalized silica nanoparticles (ZS@SiO2NPs) exhibit a similar ζ-potential to nonfunctionalized silica nanoparticles (SiO2NPs). In this work, we present a thorough comprehension of the surface properties of ZS@SiO2NPs, which encompasses the development of meticulous functionalization procedures, detailed characterization approaches, and cutting-edge modeling to address the questions that persist regarding the surface features of ZS@SiO2NPs. The negative charge of ZS@SiO2NPs is due to the stabilization of siloxide from residual surface silanols by the quaternary amine in the sulfobetaine structure. Consequently, we infer that zero-charge ZS@SiO2NPs are unlikely to be obtained since this stabilization increases the dissociation degree of surface silanols, increasing the overall structure negative charge. Additionally, colloidal stability was evaluated in different pH and ionic strength conditions, and it was found that ZS@SiO2NPs are more stable at higher ionic strengths. This suggests that the interaction between ZS and salt ions prevents the aggregation of ZS@SiO2NPs. Together, these results shed light on the nature of the ZS@SiO2NP negative charge and possible sources for the remarkable colloidal stability of zwitterionic nanoparticles in complex media.

Diffusing Wave Spectroscopy Measurements of Colloidal Suspension Dynamics.

Diffusing wave spectroscopy (DWS) is used to measure the dynamics of charged silica particles between the volume fractions 0.065 ≤ ϕ ≤ 0.352 (weight percentages from 12.7 to 55.8 wt %). The short-time diffusivity averaged over the scattering vectors sampled by DWS (ϕ) decreases with an increasing concentration. An effective hard-sphere model that accounts for hydrodynamic interactions and a double-layer repulsion fits the values up to an effective volume fraction , where is the excluded shell radius normalized by the particle radius = b/a = 1.3. While DWS measurements of diffusivity are sensitive to repulsive interactions, we show that they are relatively insensitive to attraction, such as those due to secondary minima in the interaction potential or weak depletion interaction.

PH-responsive composite nanomaterial engineered from silica nanoparticles and luminescent mitochondrion-targeted Pt(II) complex as anticancer agent

The present work introduces a pH-dependent adsorption of water-soluble Pt(II) complex with diimine and alkynylphosphonium ligands ([Pt]2+) onto a surface of silica nanoparticles (SN-OH) as a strategy to develop a carrier function with an acidification-driven release of the complex. The adsorption of the complex onto a negatively charged silica surface shifts the equilibrium between dimeric and monomeric complex forms. The surface loading of [Pt]2+ is efficient at pH 7.0, and the acidification to pH 4.5 triggers the complex release. The interaction of [Pt]2+ with bovine serum albumin (BSA) influences the cell internalization and intracellular pathway of the complex, as well as the formation of the [Pt]2+-loaded SN-OH protein corona. The cytotoxicity data for the series of cancer and normal cell lines reveal the loading of [Pt]2+ into SN-OH as an efficient route for lower cytotoxicity and greater anticancer specificity of the nanoparticles compared to the complex. The flow cytometry and confocal microscopy methods reveal similarities in the cell internalization and intracellular pathway of [Pt]2+ and the [Pt]2+-loaded nanoparticles. The mitochondrial localization of [Pt]2+ and the [Pt]2+-loaded SN-OH does not cause noticeable changes in the membrane potential of mitochondria, and the cytotoxicity of [Pt]2+ in both forms is due to a non-apoptotic mechanism of cell death. Both the cytotoxicity and increased anticancer specificity of nanoparticles are associated with their carrier function, which is more pronounced in cancer cells with overdeveloped lysosomal compartments compared to normal ones.

Monolayer Modification of Spherical Amorphous Silica by Clay Nanosheets.

Clay-silica nanocomposite materials (CSiN) were prepared by an electrostatic interaction between negatively charged clay nanosheets and positively charged spherical silica, which was modified with an alkyl ammonium group by silane coupling. By optimization of the preparation conditions, 84% coverage of the silica surface by the clay nanosheets was achieved. Adsorption experiments using cationic porphyrin dyes on the CSiN revealed that the clay nanosheet covers the spherical silica as a single layer and does not detach from the silica surface under aqueous conditions. In addition, it turned out that the cationic porphyrin dye did not penetrate the space between the silica surface and the clay nanosheet. Porphyrin molecules were adsorbed only at the outer surface of the clay nanosheet without molecular aggregation even under the high-density adsorption conditions. By combining spherical silica and clay nanosheets, it is possible to prepare novel hybrid materials where the surface can act as a unique adsorption field for dyes.

Formation of two-dimensional diamond-like colloidal crystals using layer-by-layer electrostatic self-assembly.

We report here that a two-dimensional (2D) diamond-like structure of micron-sized colloidal particles can be obtained by layer-by-layer self-assembly. Positively and negatively charged silica particles, 1 μm in diameter, were used in the experiments. On a positively charged, flat glass substrate, the first layer of negatively charged particles was prepared to form a non-close-packed 2D crystal. Then the second and third layers were fabricated using electrostatic adsorption. The positions of adsorbed particles were controllable by tuning the zeta-potential of the particles and the salt concentration of the medium. The FDTD calculations show that the 2D diamond structures of particles with higher refractive index (titania) have an absorption band in the wavelength range corresponding to the photonic band gap of the 3D bulk crystal. We expect these findings to be useful for the fabrication of novel photonic materials.

Biomimetic mineralization of positively charged silica nanoparticles templated by thermoresponsive protein micelles: applications to electrostatic assembly of hierarchical and composite superstructures.

High information content building blocks offer a path toward the construction of precision materials by supporting the organization and reconfiguration of organic and inorganic components through engineered functions. Here, we combine thermoresponsiveness with biomimetic mineralization by fusing the Car9 silica-binding dodecapeptide to the C-terminus of the (VPGVG)54 elastin-like polypeptide (ELP). Using small angle X-ray scattering, we show that the short Car9 cationic block is sufficient to promote the conversion of disordered unimers into 30 nm micelles comprising about 150 proteins, 5 °C above the transition temperature of the ELP. While both species catalyze self-limiting silica precipitation, micelles template the mineralization of highly monodisperse (62 nm) nanoparticles, while unimers yield larger polydisperse species. Strikingly, and unlike traditional synthetic silica, these particles exhibit a positive surface charge, likely due to cationic Car9 sidechains projecting from their surface. Capitalizing on the high monodispersity and positive charge of the micelle-templated products, we use smaller silica and gold particles bearing a native negative charge to create a variety of superstructures via electrostatic co-assembly. This simple biomimetic route to positively charged silica eliminates the need for multiple precursors or surface modifications and enables the rapid creation of single-material and composite architectures in which components of different sizes or compositions are well dispersed and integrated.

Conformal Electrodeposition of Mesoporous Silica over High Aspect Ratio (AR>100) Nanomesh Electrodes

The high surface area provided by the nanopores of ordered mesoporous silica thin films enables a wide range of electrochemical applications such as sensors, catalysis, energy storage and ion-selective membranes. Further improvements are possible by coating such thin films on large surface area electrodes with high aspect ratios (> 100) to increase the active surface area. Atomic layer deposition (ALD) is often preferred to deposit conformal thin film oxides on high aspect ratio structures. Such vapor-phase depositions are limited by the available surface reactive sites to deposit thin films of thickness ranging from sub-nanometer to few tens of nanometer. However, there is a tradeoff in terms of deposition time/cycles to achieve quality films especially when high aspect ratios (>100) substrates are introduced. Electrochemistry offers an alternative, versatile method to conformally coat layers on 3D electrode surfaces. The electrochemically assisted self-assembly (EASA) of mesoporous silica, utilizes electrochemical reactions to locally increase the pH near the electrode surface, which in turn catalyzes the silica gelation and surfactant self-assembly, thus causing the controlled growth of mesoporous silica thin films [1]. Recently, our group has shown that good quality mesoporous silica films with thickness between 20-2000 nm could be achieved by controlling the hydrodynamic layer in a rotating disc electrode setup [2]. Moreover, EASA of mesoporous silica offers meso-channels that are aligned perpendicular to the underlaying conductive substrate which is optimal for mass-transport.In this follow-up work, we demonstrate a reliable, electrochemically controlled, conformal deposition of mesoporous silica onto large surface area nanomesh electrodes with an aspect ratio close to 100. Nanomesh electrodes developed in our group at imec, is built up of a regularly spaced (50 nm), inter-connected network of vertical and horizontal nanowires of diameter ~40 nm. These electrodes offer an 80x area enhancement (80 cm2 per geometric cm2) while maintaining a porosity close to 75%. We show that, the extent of silica deposition over these nanomesh electrodes can be electrochemically controlled from conformal coatings (~10 nm thick) uniformly coating the whole nanomesh architecture to complete fill and overfill of the nanomesh electrodes (~4 µm thick). Furthermore, excellent mass-transport properties of various silica coated nanomesh electrodes has been demonstrated using a ruthenium hexaammine redox probe. Finally, the area enhancement offered by the silica coated Ni nanomesh is demonstrated using the characteristic accumulation of a positively charged [Ru(NH3)6]3+ probe within the negatively charged silica nanochannels, which shows 55x increase for the amount of charge from the probe stored in the coated nanomesh, compared to a planar silica layer, consistent with the expected surface area enhancement of the 4 µm thick nanomesh electrodes.

Alkali silica reaction in concrete - Revealing the expansion mechanism by surface force measurements

Alkali-silica reaction (ASR) is a major cause for concrete deterioration worldwide. However, the mechanism leading to cracking has not been identified yet. In this study, the extended Surface Force Apparatus (eSFA) has been used to determine the surface forces of alkali-silica solutions between two atomically smooth mica surfaces. The setup imitates the situation present in reactive concrete aggregates with negatively charged silicate surfaces and negatively charged polynuclear silica in solution. The distance of strong electrostatic repulsion increases with increasing concentration of dissolved silica, leading to the buildup of pressure up to 6 MPa. When the precipitation of ASR products in confined conditions is triggered by the addition of CaCl2 to the alkali-silica solution, the resulting solidification pressure forces the mica platelets apart and reaches 6–13 MPa. The eSFA experiments shows that solidification pressure is the mechanism leading to aggregate cracking and expansion of ASR-affected concrete.

Observing Real-Time Adhesion of Microparticles on Glass Surfaces.

Fouling on glass surfaces reduces the solar panel efficiency and increases water consumption for cleaning. Superhydrophobic coatings on glass enable self-cleaning by allowing water droplets to carry away dirt particles. Observing the interaction between charged particles and surfaces provides insights into effective cleaning. Using a high-speed camera and a long-distance objective, we analyzed the in situ deposition of variously functionalized and charged silica dust microparticles on chemically treated glass. The ambient charges for the control, hydrophobic, and positively charged particles were approximately -0.5, -0.13, and +0.5 nC, respectively. We found that a positively charged particle of 2.3 ± 1.2 μm diameter adhered to hydroxylated glass in ∼0.054 s, compared to 0.40 and 0.45 s for quaternary ammonium- and fluorosilane-functionalized hydrophobic glass. Experiments suggest that quaternary ammonium-functionalized glass surfaces are about 77.8% more resistant to soiling than bare surfaces.