Silica Condensation Research Articles

Formulation, Characterization and Stability Aspects of Mesoporous Silica Nanoparticles

Mesoporous silica nanoparticles are a type of inorganic nanoparticles having mesopores of 2 to 50 nm in size. The nanosized mesoporous particles of silica facilitate endocytosis in drug targeting without any side effects. Mesoporous silica nanoparticle (MSN) can be used to deliver a variety of therapeutic agents or gene delivery through active or chemical adsorption. MSNs can be used in the field of biomedical for the detection and treatment of various diseases like cancers, infection, inflammation, diabetes, bone-related disorders, cardiac diseases, neurodegenerative diseases, etc. The unique characteristics of MSNs in the form of easily adjustable pore size, surface area, particle size, pore volume, and surface morphology are advantageous not only in the biomedical field but also in the fields of biosensors, imaging, agriculture, thermal energy, and catalysis, etc. MSNs provide high surface area, easy surface functionalization, and controlled drug release. MSNs are formulated after condensation of silica in the presence of molecular templates like surfactants and polymers. This review article focused on giving in-depth knowledge about formulation techniques. Various types of excipients, such as catalysts, silica, solvents and surfactants utilized for the formulation of silica-based nanoparticles, have been summarized. The characterization of MSNs using suitable techniques was also reviewed. The stability of MSNs and factors affecting their stability is a crucial part of formulation development that is discussed here

Should we still be using HCl in the synthesis of SBA-15 and Al-SBA-15?

HCl is not always the best option for synthesizing SBA-15 and Al-SBA-15, and using different acids can bring beneficial structural and surface properties. While SBA-15-HCl and SBA-15-H2SO4 exhibited similar structural and textural characteristics, SBA-15-H2SO4 showed significantly lower contamination of the acid counterion in the final material, making it advantageous in catalytic applications where Cl− poisoning is a concern. On the other hand, SBA-15-HBr demonstrated a narrower pore size distribution. Notably, no residual Br− was detected in the final material for SBA-15-HBr. SBA-15-HNO3 and SBA-15-HBr displayed the highest concentration of 29Si MAS-NMR Q2 species, which can benefit grafting applications. The high degree of silica condensation in SBA-15-HCl and SBA-15-H2SO4 provides superior hydrothermal stability for these samples. From a fundamental perspective, a linear correlation was also identified between the Gibbs Free Energy of Hydration (ΔGhyd) of the anions and the SBA-15 mesopore sizes. Additionally, the study extended to preparing Al-SBA-15, and a facile methodology based on the pH-adjusting method was proposed. The samples displayed a Brønsted/Lewis ratio higher than typically reported, suggesting an efficient incorporation of Al as Brønsted acid sites.

Influence of precursor aging and condensation progression on silica thin films grown by electrochemically induced sol-gel deposition

Electrochemically induced sol-gel enables the fast synthesis of functional oxide coatings. In the case of silica, the condensation reaction can be catalysed by electrogenerated hydroxides. Using this technique, highly organized nanostructured thin films can be deposited onto conductive substrates by combining structure-directing templates with the electrochemically induced silica sol-gel process that occurs locally at the electrode surface. This specific template-directed process, called electrochemically assisted self-assembly (EASA), utilizes a sol-gel precursor solution optimized for a minimal spontaneous condensation (and gelation) rate in the absence of an electrochemical trigger. Despite the slow kinetics of the condensation reaction, the solution remains unstable and some incipient condensation reactions will still occur over time, continuously modifying the Si(IV) precursor solution. In this work, we discuss how precursor's aging affects the deposition rate and the properties of the deposited coatings. Two distinct aging effects are observed: an aging effect which occurs over time and an aging effect which occurs through electrochemical activation during preceding depositions. Both these aging effects result in accelerated film growth rates, up to 200 × faster than the deposition rate from a fresh precursor solution. Additionally, it was observed that time aging yields less resistive, weaker films, while electrochemical aging leads to films which retain similar properties as films grown using fresh precursor solutions. The time aging effect could be inhibited by storing the precursor solution at -35 °C. These observations are explained based on the different condensation pathways during acidic and alkaline condensation, which is known to yield inherently different silica oligomer products. The results and insights described here contribute to upscaling the electrochemical sol-gel process for mesoporous silica films and provides further fundamental insights into the underlying silica condensation reactions.

Systematic study of the implications of calcination and solvent extraction of the surfactant in MCM-41-type mesoporous silica nanoparticles

Mesoporous silica nanoparticles (MSN) have been growing in recent years in a broad range of applications, such as nanomedicine, catalysis, and gas storage. For the preparation of MSN, especially in nanomedicine applications, the extraction of the surfactant template, generally 1-hexadecyltrimethylammonium bromide (CTAB), is required. Several methods to remove the surfactant from MNS have been reported in the literature, such as calcination, solvent extraction, and dialysis. Depending on the method employed, the materials obtained have different properties; however, a systematic study that compares the use of different surfactant extraction methods and their implications in the final characteristics of the MSN has not been reported. Hence, the aim of this work is to study the effect of surfactant removal on MSN by calcination at different temperatures (400 °C, 450 °C, 500 °C and 550 °C) or by extraction with HCl/ethanol or NH4NO3/ethanol. The final materials are fully characterised by different techniques. The study performed shows the removal efficiency when the different methods are used, and their effect on silica condensation degree, mesoporosity, cytotoxicity, and degradation rate. The results allow for obtaining a deeper knowledge of the surfactant removal processes.

Precise tuning of silica pore length and pore diameter on silica-encapsulated gold core–shell nanoparticles and catalytic impact

The ability to individually tune the pore length and pore diameter of silica-encapsulated gold core–shell nanoparticles (CSNPs) via a seeded encapsulation method is demonstrated and their impact on catalysis determined. Reducing the solvent volume during the shell growth phase resulted in CSNPs with shells of increasing thickness from 75 nm to 202 nm, following a linear relationship. The addition of 1, 3, 5-triisopropylbenzene (TIB) during synthesis increased the average pore diameter from 25 Å to 32 Å by swelling the pore template, swelling further to 38 Å when adding both TIB and n-decane. By decoupling the gold core reduction and silica condensation stages, gold core diameters were largely unaffected by silica growth reaction conditions. This was achieved by encapsulating CTAB-stabilized nanoparticles rather than reducing and stabilizing the nanoparticles during silica condensation. When used to catalyze solvent-free benzyl alcohol oxidation, it was found that CSNPs with increasing shell thicknesses demonstrated increased formation of the desirable aldehyde product, holding the undesired ester product yield constant. In contrast, CSNPs with increasing pore diameter exhibit increased formation of both aldehyde and ester products unselectively. These results—uniquely observed through the parametric isolation of pore length and diameter—suggest the reactant concentration at the pore wall due to hydrogen bonding, forming concentric “microphases” within the pores.

Bifunctional Polymer Brush Reactor for In Situ Synthesis of Hollow Silica-Supported Gold Nanocatalysts.

Gold nanoparticles (AuNPs) on carriers have received wide attention as catalysts as a result of their excellent stability and catalytic performance. Herein, we report the design and synthesis of hollow silica-supported gold nanocatalysts (SNPs@AuNPs) composed of highly dispersed AuNPs with approximately 4.30 nm using an in situ colloidal polyelectrolyte template strategy. The monodisperse polystyrene nanospheres accompanied by poly[(2-methacryloyloxyethyl)trimethylammonium chloride] brushes were first synthesized. Subsequently, the facile polymer-brush-engaged strategy for the synthesis of hollow SNPs@AuNPs involves in situ reduction of AuNPs, hydrolytic condensation of silica, and a chemical etching process. In combination with dynamic light scattering, transmission electron microscopy, small-angle X-ray scattering, X-ray powder diffraction, and Fourier transform infrared spectroscopy, the as-obtained polymer brushes were proven as effective versatile nanoreactors for the synthesis of AuNPs and silica nanoparticles without any catalysts. Benefiting from the structural advantages, the resultant hollow SNPs@AuNPs manifested superior catalytic activity and reusability for the reduction of p-nitrophenol by sodium borohydride in aqueous solution. With a delicate design, we believe that this synthetic strategy can be extended to fabricate multifunctional nanomaterials with diverse compositions, which would be of great interest in catalysis, energy, and many other important domains.

Strength of RC Beam Using Geo Polymer Concrete and Adoption Bubble Technology

Abstract: Bubble Deck technology first time in European countries provide consumption of high-density polyethylene hollow spheres to replicate the unproductive material in the mid of the slab, consequently diminishing the deceased burden and escalating the competence of the flooring. This process be used in the concrete floor system. Concrete is superior in firmness and thus is further constructive in the compression section than in the tension section. The diminution in concrete can be done by replacing the tension region concrete. Keeping the equal design in intellect, an effort has been ended to discover out the efficiency of plastic bubbles by replacing concrete in the tension region of Ordinary Portland Cement Concrete (OPCC) and Geo polymer Concrete (GPC) beam. Geo polymer Concrete does not figure calcium- silicate-hydrates (CSHs) for matrix configuration and potency like OPCC however utilizes the poly condensation of silica with alumina precursors to achieve structural potency. In this job, M25 concrete mix is used to practice both OPCC and GPC beams. The trial mix is experienced for compressive potency. Flexure test is completed for 28 days of curing of the beams.

Dual control of external surface and internal pore structure of small ordered mesoporous silica particles directed by mixed polyion complex micelles

A versatile approach has been developed to prepare small mesoporous silica particles with simultaneous control of the internal ordered pore structure and the external particle surface. Mixed polyion complex (PIC) micelles are used as silica structure-directing agents: they result from the complexation of a polybase with two polyacid double-hydrophilic block copolymers (DHBC) having either a poly(ethylene oxide) (PEO) based-block or a polyacrylamide (PAM) block. The ionizable block in both DHBC is poly(acrylic acid), which complexes oligochitosan to form the core of the electrostatic complex. By varying the architecture of the PEO-based block (linear or comb-shaped) and the synthesis parameters, it is possible to modulate the pore structure from 3D cage-like to 2D-hexagonal and lamellar mesostructures. Replacing a fraction of the PEO-based polymers with DHBC having a polyacrylamide block that has no affinity for silica is shown to affect silica-micelle interactions and material growth. While the PEO chains interact with silica to form the hybrid interface, the PAM chains act as capping agents and control the external surface of the particles. Increasing the relative amount of PAM-based DHBC leads to the formation of small discrete mesoporous silica particles that are reduced in size to 200 nm. The particle size reduction and particle surface stabilization by PAM chains can be explained by considering not only the existence of a mixed corona of PAM and PEO in PIC micelles but also the differentiated solubility of these two neutral blocks induced by silica condensation. Thus, the present strategy allows independent decrease of the particle size and tuning of its pore structure.

Sol‐Gel Synthesis of Mesoporous Silica Using a Protein Crystal Template

AbstractMesoporous materials are useful for a wide range of applications, but control over the dimensions of the porous structure in this size regime remains challenging. Protein cages possess regular shape and many of them fall into the mesoporous size‐region, making them potential template materials for inorganic matrices. Here, apoferritin single crystals are used as templates for the production of mesoporous silica. The high free volume and large pore size of the crystals enable silica precursor hydrolysis and condensation inside them and thus templated growth of a silica matrix. Apoferritin can be removed by calcination to yield solid state structures with the crystalline periodicity retained in the mesopores. We foresee that the method is applicable also for other protein cages, enabling production of mesoporous silica with various pore dimensions.

Chain length of bioinspired polyamines affects size and condensation of monodisperse silica particles

Polyamines play a major role in biosilicification reactions in diatoms and sponges. While the effects of polyamines on silicic acid oligomerization and precipitation are well known, the impact of polyamines chain length on silica particle growth is unclear. We studied the effects of polyamine chain length on silica particle growth and condensation in a known, simple, and salt-free biphasic reaction system; with tetraethyl orthosilicate as organic phase and polyamine dissolved in the aqueous phase. The particles at various growth stages were characterized by Cryo- Transmission Electron Microscopy, Scanning Electron Microscopy, Thermogravimetric Analysis, Zeta Potential, and solid-state NMR analysis. Polyamines were found co-localized within silica particles and the particle diameter increased with an increase in polyamine chain length, whereas silica condensation showed the opposite trend. Particle growth is proposed to progress via a coacervate intermediate while the final particles have a core shell structure with an amine-rich core and silica-rich shell. The results presented in this paper would of interest for researchers working in the field of bioinspired materials.

Self-Assembly of Au-Fe3O4 Hybrid Nanoparticles Using a Sol-Gel Pechini Method.

The Pechini method has been used as a synthetic route for obtaining self-assembling magnetic and plasmonic nanoparticles in hybrid silica nanostructures. This manuscript evaluates the influence of shaking conditions, reaction time, and pH on the size and morphology of the nanostructures produced. The characterization of the nanomaterials was carried out by transmission electron microscopy (TEM) to evaluate the coating and size of the nanomaterials, Fourier-transform infrared spectroscopy (FT-IR) transmission spectra to evaluate the presence of the different coatings, and thermogravimetric analysis (TGA) curves to determine the amount of coating. The results obtained show that the best conditions to obtain core–satellite nanostructures with homogeneous silica shells and controlled sizes (<200 nm) include the use of slightly alkaline media, the ultrasound activation of silica condensation, and reaction times of around 2 h. These findings represent an important framework to establish a new general approach for the click chemistry assembling of inorganic nanostructures.

Programmable and Site-Specific Patterning on DNA Origami Templates with Heterogeneous Condensation of Silver and Silica.

DNA origami has been widely used as a modular platform for condensation of functional molecules to assemble optical, electronic, and biological components. However, the heterogeneous condensation with greater diversities in chemical composition templated with DNA origami is still challenging. Herein, a programmable deposition method is developed to precisely condense silver-silica nanohybrids on DNA origami templates. First, the site-specific metallization of Ag is achieved by thiol group-initiated silver reduction at the designed areas of DNA origami. Next, cysteamine is used to selectively modify the condensed Ag surface with positively charged amino groups for creating an electronically different environment for site-specific placement of silica by a modified Stöber method. Using these strategies, customized patterning of both silver and silica on tubular and rectangular DNA origami nanostructures is successfully achieved with nanoscale spatial resolution. These findings will greatly facilitate the development of DNA nanotechnology-based bottom-up nanofabrication.

A TIME DEPENDENT STUDY FOR THE FORMATION OF ULTRASMALL Cs-AlMCM-41 HOLLOW NANOSPHERES

Monitoring of the formation of ultrasmall Cs-AlMCM-41 nanospheres under hydrothermal condition has been performed. It showed that when the CTABr surfactant, silica and alumina were mixed, homogenization of raw materials was first taking place, where CTABr molecules first interacted with the inorganic species via self-assembly into helical rod-like micelles. Hydrolysis, condensation and polymerization of silica and alumina precursors were then initiated. In addition, the Cs+ cation also participated during the formation of MCM-41 structure where it counterbalanced the negative charge of the aluminosilicate surface. After 14 h, the aluminosilicate oligomers were produced and fully enclosed the spherical micelles. Further increasing the hydrothermal treatment to 24 h onwards, polycondensation silanol siloxane would take place leading to the emergence of well-defined and highly ordered MCM-41 structure. This study came up with a clear picture on the formation of Cs-AlMCM-41 hollow nanospheres in cationic-surfactant-templated. This suggested that similar studies for other mesoporous materials such as MCM-48 and MCM-50 under different conditions and approaches could also be explored

The Influence of Silicateins on the Shape and Crystalline Habit of Silica Carbonate Biomorphs of Alkaline Earth Metals (Ca, Ba, Sr)

This contribution presents the effect of two ortholog enzymes from marine sponges called silicateins on the formation of silica carbonate biomorphs of alkaline metals (Ca, Ba, Sr). In vivo, these enzymes participate in the polymerization of silica. Silicateins from Tethya aurantia and Suberitis domuncula were produced recombinantly and presented different degrees of activity, as evidenced by their ability to cleave silyl ether-like bonds in a model compound. Biomorphs are typically inorganic structures that show characteristic shapes resembling those of biological structures such as helices, leaves, flowers, disks or spheres. Irrespective of the concentration or the enzyme used, the presence of silicateins inhibited the formation of classic morphologies of biomorphs, albeit to different extents. Thus, not only the silica condensation activity of the enzyme but also its ability to bind silica compounds is implicated in the inhibition process. The largest effect was observed for the strontium and barium biomorphs, leading to the formation of spheres similar to those observed in diatoms and Radiolaria rather than the classical non-symmetrical forms. Characterization of the samples using Raman spectroscopy showed that silicatein did not affect the crystalline structure of the alkaline earth metal carbonate but did modify the crystalline habit.

Electrogeneration of a Free-Standing Cytochrome c-Silica Matrix at a Soft Electrified Interface.

Interactions of a protein with a solid–liquid or a liquid–liquid interface may destabilize its conformation and hence result in a loss of biological activity. We propose here a method for the immobilization of proteins at an electrified liquid–liquid interface. Cytochrome c (Cyt c) is encapsulated in a silica matrix through an electrochemical process at an electrified liquid–liquid interface. Silica condensation is triggered by the interfacial transfer of cationic surfactant, cetyltrimethylammonium, at the lower end of the interfacial potential window. Cyt c is then adsorbed on the previously electrodeposited silica layer, when the interfacial potential, Δowϕ, is at the positive end of the potential window. By cycling of the potential window back and forth, silica electrodeposition and Cyt c adsorption occur sequentially as demonstrated by in situ UV–vis absorbance spectroscopy. After collection from the liquid–liquid interface, the Cyt c–silica matrix is characterized ex situ by UV–vis diffuse reflectance spectroscopy, confocal Raman microscopy, and fluorescence microscopy, showing that the protein maintained its tertiary structure during the encapsulation process. The absence of denaturation is further confirmed in situ by the absence of electrocatalytic activity toward O2 (observed in the case of Cyt c denaturation). This method of protein encapsulation may be used for other proteins (e.g., Fe–S cluster oxidoreductases, copper-containing reductases, pyrroloquinoline quinone-containing enzymes, or flavoproteins) in the development of biphasic bioelectrosynthesis or bioelectrocatalysis applications.

Vault nanocapsule-mediated biomimetic silicification for efficient and robust immobilization of proteins in silica composites

Silica materials are attractive protein supports for applications in catalysis, sensing, water purification, and protein therapy. However, current approaches for loading proteins in silica are limited by inefficient protein immobilization, unintended leaching, the requirement for large quantities of silica precipitants, and associated protein inactivation. Here, we report a highly efficient and robust strategy that directly synthesizes protein-embedded silica via a vault protein nanocapsule-templated biomimetic silicification route. The vaults serve as nucleation sites for the deposition and condensation of silica precursors to form vault/silica composites. Using vaults encapsulated with proteins as the templating agent enables direct embedding of proteins in silica composites with nearly 100% immobilization efficiency. The vaults also act as protective shelters to preserve high protein activity during silica condensation. With the dual advantages of vault templating and protection, the proteins immobilized via this strategy retained over 90% activity after 30 reuse cycles and exhibited high activity, minimal leaching, and improved stability, which would be valuable in a broad variety of medical, industrial, and environmental applications.

A concise and systematic study of the hydrothermal synthesis of Si-MCM-48: Structural aspects and mechanical stability

The structural collapse of mesoporous molecular sieve Si-MCM-48 by mechanical compression was investigated. Samples were synthesized by modifying temperature and time of a hydrothermal synthesis, according to a 32 experiment design. In this way, flexibility of the synthesis method was evaluated. Structural and textural characteristics were investigated using X-ray diffraction, nitrogen physisorption, and scanning and transmission electronic microscopies. As a consequence of the increase in applied pressure, different behavior was observed in the average wall thickness of samples related to the porous organization of the solid. The collapse of interparticular macropores caused a greater increase in thickness at low compression pressures, while the intraparticular mesopores, supported by the silica walls, supported greater compression. The macropores collapsed by mechanical compression at pressures as low as 60 MPa, while mesoporous ones exhibited reasonable resistance up to 200 MPa. Samples synthesized with high temperatures and long reaction times presented better mechanical resistance due to the favorable kinetics of silica condensation on the walls and, thus, are more interesting for applications in catalysis or adsorption.

Diffusive Formation of Hollow Mesoporous Silica Shells from Core–Shell Composites: Insights from the Hydrogen Sulfide Capture Cycle of CuO@mSiO2 Nanoparticles

Mesoporous silica is often employed as a coating material in core-shell nanoparticles to decrease the possibility of sintering or aggregation of the core particles. In this work, we discovered a surprising morphological transformation during the sulfidation and regeneration (oxidation) of core-shell CuO@mSiO2 materials designed for H2S capture. Although CuS cores were still encapsulated within the silica shells after in situ sulfidation, hollow silica shells formed during the regeneration step as CuO leached out of the shell and aggregated into larger particles. The successful sulfidation of pristine CuO@mSiO2 was facilitated by the restraining effect of silica shells on lattice growth from CuO into CuS, and the mesopores allowed for volume expansion. The phase and morphology changes during the regeneration (oxidation) process leading to the hollow shells were investigated by X-ray diffraction and transmission electron microscopy. It was observed that the cores remained encaged during the disproportionation of CuS to Cu2S, which is the first step in the oxidation of CuS. However, voids were generated when Cu2S was oxidized and reacted with water generated from the condensation of silica. A possible mechanism for this transformation involves the outward diffusion of copper ions through the mesoporous silica, leading to the migration of core particles. This migration was further accelerated by the elevated temperature in the regeneration process and promoted by the formation of the copper sulfate hydroxide through the reaction with water. This work provides key insights into the chemical stability of such core-shell structures under the influence of diffusion-driven structural transformations.

Biogenic synthesis and antimicrobial activity of silica-coated silver nanoparticles for esthetic dental applications

Objectivesthis study aimed to synthesize AgNPs from green tea (GT) extract, forming GT-AgNPs, and to coat their surfaces with silica, resulting in light-colored Ag@SiO2 nanoparticles. Materials and Methodsparticles were characterized and tested for minimal inhibitory concentration (MIC), biofilm formation against Streptococcus mutans and cytotoxicity evaluation on dental pulp fibroblasts. ResultsX-ray diffraction (XRD) confirmed the formation of pure AgNPs, whereas energy dispersive X-ray spectroscopy (EDS) mapped their elemental atoms. Dynamic light scattering (DLS) demonstrated formation of particles at nanoscale, with moderate polydispersity and negative zeta potential, in agreement with nanoparticle tracking analysis (NTA) size measurements. Fourier-transformed infrared (FTIR) spectroscopy confirmed the successful condensation of silica, which significantly increased surface area by 50%, as assayed by surface area analysis (BET). Thermogravimetric analysis showed a 18%-mass of silica on the surface of Ag@SiO2NPs. Transmission electron microscopy (TEM) displayed the spherical shape of nanoparticles and average size of 11 nm for GT-AgNPs and Ag@SiO2NPs. Ag@SiO2NPs demonstrated potent antimicrobial action against S. mutans, with MIC determined as 600 μg/mL, and inhibition of approximately 44% (p < 0.05) of biofilm formation. At the MIC concentrations, both NPs did not exhibit cytotoxicity. ConclusionAg@SiO2NPs might have a useful application in dental materials. Clinical significanceThe possibility of incorporating antimicrobial properties in restorative materials without compromising esthetics makes the AgNPs@SiO2 NPs promising agents against S. mutans biofilm formation, hence the prevention of dental caries. This represents a great step towards the development of more interactive biomaterials in dentistry to overcome clinical problems.

Emulsions Stabilized with Alumina-Functionalized Mesoporous Silica Particles.

Alumina-functionalized ordered mesoporous silica SBA-15 particles have been proposed to stabilize Pickering emulsions. Functionalization of SBA-15 particles have been performed by depositing alumina using a two-step synthesis (first, silica condensation, followed by alumina precipitation). Three different Al to Si ratios have been prepared. The calcined materials have been characterized by TEM, SEM, XRD, N2 physisorption, and zeta potential, in order to determine key physicochemical properties, and the alumina localization. The emulsifying and stabilizing properties of the calcined particles have been evaluated for water/toluene-based Pickering emulsions.