Monodisperse Silica Research Articles

Tailoring the morphological and optical properties of monodisperse silica

Tailoring the morphological and optical properties of monodisperse silica

Protocrystallinity of Monodispersed Ultra-Small Templated Mesoporous Silica Nanoparticles.

Monodisperse and semi-faceted ultra-small templated mesoporous silica nanoparticles (US-MSNs) of 20-25 nm were synthesized using short-time hydrolysis of tetraethoxysilane (TEOS) at room temperature, followed by a dilution for nucleation quenching. According to dynamic light scattering (DLS), a two-step pH adjustment was necessary for growth termination and colloidal stabilization. The pore size was controlled by cetyltrimethylammonium bromide (CTAB), and a tiny amount of neutral surfactant F127 was added to minimize the coalescence between US-MSNs and to favor the transition towards internal ordering. Flocculation eventually occurred, allowing us to harvest a powder by centrifugation (~60% silica yield after one month). Scanning transmission electron microscopy (STEM) and 3D high-resolution transmission electron microscopy (3D HR-TEM) images revealed that the US-MSNs are partially ordered. The 2D FT transform images provide evidence for the coexistence of four-, five-, and sixfold patterns characterizing an "on-the-edge" crystallization step between amorphous raspberry and hexagonal pore array morphologies, typical of a protocrystalline state. Calcination preserved this state and yielded a powder characterized by packing, developing a hierarchical porosity centered at 3.9 ± 0.2 (internal pores) and 68 ± 7 nm (packing voids) of high potential for support for separation and catalysis.

Preparation of Monodisperse Silica Mesoporous Microspheres with Narrow Pore Size Distribution.

The purpose of this study is to prepare monodisperse silica mesoporous microspheres with narrow pore size distribution to promote their application in the field of liquid chromatography. An improved emulsion method was used to prepare silica mesoporous microspheres, and the rotary evaporation temperature, emulsification speed, dosage of porogen DMF, and dosage of the catalyst NH3·H2O were optimized. Subsequently, these microspheres were respectively treated by alkali-heating, calcination, and sieving. The D50 (particle size at the cumulative particle size distribution percentage of 50%) of as-prepared silica mesoporous microspheres is 26.3 μm, and the D90/D10 (the ratio of particle size at a cumulative particle size distribution percentage of 90% to a cumulative particle size distribution percentage of 10%) is 1.94. The resultant silica mesoporous microspheres have distinctive pore structures, with a pore volume of more than 1.0 cm3/g, an average pore size of 11.35 nm, and a median pore size of 13.4 nm. The silica mesoporous microspheres with a large particle size, uniform particle size distribution, large average pore size and pore volume, and narrow mesopore size distribution can basically meet the requirements of preparative liquid chromatographic columns.

Silica Nanoparticles Functionalized with an Ionic Liquid: A Green and Efficient Heterogeneous Catalyst for a Cascade Reaction

AbstractA new strategy for a catalytic C−C bond forming cascade reaction comprising acetal hydrolysis and Knoevenagel condensation is presented here. The heterogeneous nanocatalyst is prepared by immobilizing an ionic liquid on the surface of highly monodisperse silica nanoparticles. This work is the first example of showing that there is no need to use bifunctional acid‐base catalysts for a cascade reaction including the hydrolysis of benzaldehyde dimethyl acetal to benzaldehyde and the subsequent Knoevenagel condensation of the resulting benzaldehyde with malononitrile. It is shown here that these reactions can proceed smoothly with a mono‐functional heterogeneous catalyst that contains a neutral ionic liquid. It has been proposed that such a neutral ionic liquid can “switch on” to an acidic catalyst in conjunction with water. The selected ionic liquid has potentially biodegradability characteristics, which is an important issue to achieve a sustainable catalyst. The simple procedure for preparing both the ionic liquid and the monodisperse silica nanoparticles provides opportunities for a large‐scale synthesis of the catalyst. This work introduces a breakthrough in the design and synthesis of heterogeneous catalysts for acid/base catalyzed cascade organic reactions.

Prediction models for the flux decay profile and initial flux of microfiltration for therapeutic proteins.

Microfiltration (MF) is an essential step during biopharmaceutical manufacturing. However, unexpected flux decay can occur. Although the flux decay profile and initial flux are important factors determining MF filterability, predicting them accurately is challenging, as the root cause of unexpected flux decay remains elusive. In this study, the methodology for developing a prediction model of flux decay profiles was established. First, the filtration profiles of different monodisperse polystyrene latex and silica beads of various sizes were evaluated. These results revealed that the size and surface electrostatic properties of the beads affect the flux decay profile. Taking the size and surface electrostatic properties of protein aggregates into account, we constructed a predictive model using model bead filtration profiles. We showed that this methodology was applicable to two different MF filters to predict the flux decay profile of therapeutic proteins. Because our proposed prediction model is based on normalized flux, the initial flux is required to predict the overall filtration profile. Then, we applied the Hagen-Poiseuille equation using sample viscosity values to estimate the initial flux. The developed prediction models can be used for effective MF scale-up assessment during the early stages of process development.

Synthesis of Monodisperse Silica Nanospheres and Titania Beads from Rotating Cylinder System

Economic raw materials such as low-grade ethanol and Tetraethyl Ortosilicate (TEOS) were adopted as reactants for the synthesis of monodisperse silica nanospheres using a Taylor Vortex flow reactor with a rotating cylinder system. Factors affecting the mean diameter and size distribution of the silica grains were investigated by changing the rotating speed of the inner cylinder and the composition of reactants. In the case of titania beads, grain diameter size was adjusted by changing the amount of precursor (titanium (IV) isopropoxide, TIP), hexadecylamine (HDA) or Potassium Chloride (KCl) and reaction temperature as well as the rotation speed of the cylinder. As a demonstrative application, titania beads could be used for the removal of organic dye as a model contaminant dissolved in an aqueous medium using a photocatalytic decomposition system.

Novel 3D-Printed Microfluidic Magnetic Platform for Rapid DNA Isolation.

This study presents a novel miniaturized device as a 3D-printed microfluidic magnetic platform specifically designed to manipulate magnetic microparticles in a microfluidic chip for rapid deoxyribonucleic acid (DNA) isolation. The novel design enables the movement of the magnetic particles in the same or opposite directions with the flow or suspends them in continuous flow. A computational model was developed to assess the effectiveness of the magnetic manipulation of the particles. Superparamagnetic monodisperse silica particles synthesized in-house are utilized for the isolation of fish sperm DNA and human placenta DNA. It was demonstrated that the proposed platform can perform DNA isolation within 10 min with an isolation efficiency of 50% at optimum operating conditions.

Characterizing stress development and cracking of ceramic particulate coatings during drying

AbstractDuring drying, liquid‐applied particulate coatings develop stress and are consequently prone to stress‐induced defects, such as cracking, curling, and delamination. In this work, the stress development and cracking of coatings, prepared from aqueous silica and zinc oxide particle suspensions, were characterized using cantilever beam deflection with simultaneous imaging of the coating surface. Drying uniformity was improved and lateral or edge‐in drying was discouraged by using thin silicone walls around the perimeter of the cantilever. Coatings prepared from larger monodisperse silica particles (D50 ∼ 0.9 µm) dried uniformly but had a high critical cracking thickness (>150 µm) that prevented simultaneous study of stress development and cracking. Coatings prepared from smaller silica particles (D50 ∼ 0.3 µm) cracked readily at low thicknesses but exhibited edge‐in drying that complicated the stress measurement data. This drying nonuniformity was connected to the potential for these small particles to accumulate at the coating surface during drying. Hence, the selection of particle size and density was critical to drying uniformity when characterizing stress development and cracking. Coatings prepared from suspensions of zinc oxide particles (D50 ∼ 0.4 µm) were well‐suited for these studies, with uniform drying stress peaking at ∼1 MPa. Characteristic features in the stress development data above and below the critical cracking thickness (53 µm) were identified, demonstrating that cantilever beam deflection is a useful tool for studying the effectiveness of crack mitigation methods and the fundamentals of coating fracture during drying.

Facile synthesis of monodispersed mesoporous silica nanoparticles with ultra-large mesopores through a NaBH4-assisted hydrothermal process

This work reports the facile synthesis of monodispersed ultra-large mesopore mesoporous silica nanoparticles (ULP-MSNs) through a new and simple NaBH4-assisted hydrothermal process (NAH process). Such preparation of ULP-MSNs enables the small mesopore size (<3 nm) of as-prepared conventional MSNs to be effectively enlarged to over 20 nm. The synthetic parameters were systematically studied, and it was shown that the initial ethanol added in the synthesis mixture (1st ethanol), NaBH4, HCl(a.q.) and the ethanol added in the mixture (2nd ethanol) during the hydrothermal (HT) process and HT conditions play synergistic roles in enlarging mesopores by NAH process. We also revealed the mesopore-enlargement mechanism. By this method, the resultant ULP-MSNs possess tunable ultra-large mesopore sizes (18–31 nm), monodispersed spherical morphology, and controllable particle sizes (105–268 nm). The method presented here could effectively enlarge and adjust the mesopores of the MSNs. We supposed our approach may provide a platform of nanotechnology for the preparation of porous silica materials with adjustable mesopore sizes, which will be promising for practical applications.

Joint effects of gas bubbles and solid particles on sonochemical inhibition in sonicated aqueous solutions

Wastewater is a multicomponent and multiphase mixture. Gas bubbles and solid particles in the dispersed phase influence sonochemical efficiency during ultrasonic treatment of wastewater, sometimes unfavorably; however, the influencing factors and mechanisms remain unclear. In this paper, the influence of argon gas bubbles (1.2 mm) and monodisperse silica particles (0.1 mm) on sonochemical effects in an aqueous system using a horn-type reactor (20 kHz) is reported. Triiodide formation decreased with an increase in the volume fraction of either or both phases. The two phases started inhibiting sonoreactions as the total volume fraction approached 3.0–4.0 vol% compared to pure water. The effect of the gas-to-solid ratio is also considered. We propose an acoustic attenuation model, which incorporates the scattering effect of solid particles and the thermal effect of gas bubbles. The agreement between the modeling and experimental results demonstrates that the two phases are jointly responsible for sonochemical inhibition by increasing ultrasound attenuation. This enhances the understanding of sonochemistry in gas–solid–liquid systems and helps regulate gases and solids in sonochemical reactors.

Cibacron Blue F3GA ligand dye-based magnetic silica particles for the albumin purification.

Dye-ligand affinity chromatography is among the increasingly popular affinity chromatography based on molecular recognition for the purification of albumin. This study focuses on the binding of Cibacron Blue F3GA ligand dye with magnetic silica particles and purification by separation. Mono-disperse silica particles with bimodal pore size distribution were employed as a high-performance adsorbent for human serum albumin (HSA) protein purification under equilibrium conditions. The synthesized ligand-dye affinity based magnetic silica particles were characterized by electron spin resonance, Fourier-transform infrared spectroscopy, scanning electron microscopy, vibrating sample magnetometer, elemental analysis, and dispersive X-ray analysis. The HSA purification performance of the proposed material in the presence of a magnetic field was relatively investigated using magnetic-based particles with similar morphologies. The maximum adsorption capacity for HSA in an artificial plasma medium was defined as 48.6 mg/g magnetic silica particle. By using the designed magnetic silica particles, 1.0 M NaCl solution was successfully utilized for obtaining quantitative desorption with HSA. However, continued HSA purification performances of magnetic-based particles were significantly lower concerning the ligand-dye magnetic silica particles. The purity of the removed albumin was about 97%. The magnetic silica particles could be utilized many times without decreasing their protein adsorption capacities remarkably.

Wearable nanocomposite hydrogel temperature sensor based on thermally-switchable and mechanical-deformation-insensitive structural colors

Smart and flexible nanocomposite materials with structural colors have great potentials in the field of wearable sensors. However, the mechanochromic property of conventional photonic materials severely interferes with the optical signal outputs that are tunable by non-strain stimuli, which greatly impedes their applications in wearable photonic sensors. Herein, a wearable nanocomposite hydrogel temperature sensor based on thermally-switchable structural colors that are independent of mechanical deformations, is fabricated by the facile in-situ gelation of N-isopropyl acrylamide (NIPAM), nanoclay discs, carbon black, and monodisperse silica or polymeric NPs in their aqueous dispersions. The resulting non-assembled arrangements of the monodisperse NPs account for uniform structural color independent of mechanical deformations and observation angles. Simultaneously, the temperature-induced reconfiguration of the physically cross-linked poly-NIPAM hydrogel matrix, leads to super-large volume changes and in turn wide-range structural color shifts in almost the entire visible spectrum. The smart hydrogel matrix with homogenous polymer chain length by dynamic physical cross-linkings among exfoliated nanoclay discs, makes the photonic hydrogel robust, stretchable, and self-healable. The combination of mechanical-deformation-insensitive and thermally-switchable structural colors in the nanocomposite hydrogel enables skin-based wearable temperature sensing with naked-eye detection. This work opens a new platform for diverse non-invasive wearable photonic sensors beyond the current strain sensing.

Imidazole-octyl mixed-mode stationary phase based on macroporous silica for the purification of ovomucoid and ovotransferrin.

A process-simplified hard template approach was established to synthesize the monodisperse macroporous silica microspheres with homogeneous structures by twice alkali-thermal treatment and calcination routes. Porous vinyl-functionalized polysesquioxane microspheres (V-PMSQ) were synthesized through a hydrolyzation-polycondensation method and used as templates. The template particles with large aperture and high pore volume were obtained by adjusting the pH value and reaction time of the twice alkali-thermal reaction. After calcination, monodisperse silica microspheres with an average pore size of 30nm, homogeneous pore structures, and narrow particle size distribution were fabricated, which can be directly used as chromatographic matrices without classification. After that, a new reversed-phase/strong anion-exchange (RP/SAX) mixed-mode stationary phase Sil-S-VOIM was prepared by bonding the 1-vinyl-3-octyl-imidazole ligands to the above silica microspheres through a "thiol-ene" click reaction. The performance of the Sil-S-VOIM column was evaluated by one acidic protein (transferrin) and two basic proteins (lysozyme, α-chymotrypsin) and compared to a single imidazole-modified Sil-S-VIM column and an octyl-modified Sil-C8 column, respectively. Due to the synergistic effect of electrostatic repulsion and hydrophobic interactions, baseline separations of the above proteins were observed only on the Sil-S-VOIM column, with resolutions of 2.55 and 2.01 between lysozyme and transferrin, and between transferrin and α-chymotrypsin, respectively, indicating good selectivity and separation ability compared with single-mode stationary phases. It was applied to the isolation of egg white samples with peaks identified by SDS-PAGE and MALDI-TOF-MS. The results showed that the selective retention and isolation of ovomucoid and ovotransferrin were successfully achieved, with yields of 78.8% and 67.2%, respectively. The protocol described in this work is simpler, faster, and has higher protein recovery. Overall, this new mixed-mode stationary phase provided a promising potential for the separation and determination of intact proteins.

Sol-Gel-Controlled Size and Morphology of Mesoporous Silica Microspheres Using Hard Templates.

Mesoporous silica microspheres (MPSMs) represent a promising material as a stationary phase for HPLC separations. The use of hard templates provides a preparation strategy for producing such monodisperse silica microspheres. Here, 15 MPSMs were systematically synthesized by varying the sol-gel reaction parameters of water-to-precursor ratio and ammonia concentration in the presence of a porous p(GMA-co-EDMA) polymeric hard template. Changing the sol-gel process factors resulted in a wide range of MPSMs with varying particle sizes from smaller than one to several micrometers. The application of response surface methodology allowed to derive quantitative predictive models based on the process factor effects on particle size, pore size, pore volume, and specific surface area of the MPSMs. A narrow size distribution of the silica particles was maintained over the entire experimental space. Two larger-scale batches of MPSMs were prepared, and the particles were functionalized with trimethoxy(octadecyl) silane for the application as stationary phase in reversed-phases liquid chromatography. The separation of proteins and amino acids was successfully accomplished, and the effect of the pore properties of the silica particles on separation was demonstrated.

Facile and controllable preparation of mesoporous silica nanoparticles with ultra-large mesopores enabled by an ammonium chloride–assisted hydrothermal process

This work reports the facile preparation of monodispersed ultra-large mesopore mesoporous silica nanoparticles (ULP-MSNs) with controllable mesopore sizes and particle sizes. The key design to such preparation lies in the application of ammonium chloride (NH4Cl) assisted-hydrothermal (AAH) process to as-prepared conventional MSNs, whose small mesopore sizes of about 2 nm can be effectively enlarged to over 16 nm. Based on the systematic study of the synthetic parameters, it was recognized that the initial ethanol added in the synthesis mixture (1st ethanol), NH4Cl, and the ethanol added in the mixture (2nd ethanol) during the hydrothermal (HT) process and HT conditions play synergistic roles in enlarging mesopores by AAH process. The mechanism of mesopore enlargement was also studied. By this method, ULP-MSNs with variable mesopore sizes in a range of 14 nm–26 nm, large synthesis domain, and controllable particle sizes ranging from 106 nm to 267 nm can be produced in a facile manner. This work, we believe, represents a new strategy for the preparation of ULP-MSNs and will promote their various applications.

Ultrafine silica aerogels microspheres for adaptive thermal management in large-temperature-fluctuation environment

A large number of areas on earth is suffered from large-temperature fluctuation (LTF) during the days or over the seasons. However, current strategies for adaptive thermal management in the LTF environment are limited. In this study, we developed a simple and cost-effective strategy to synthesize ultrafine and nearly monodispersed silica aerogel microspheres (SAM) with an average diameter of 1.9 μm. The aerogels possess low thermal conductivity of 0.039 W·m−1·K−1 and can preserve heat by reducing heat dissipation in cold environments. Meanwhile, IR emissivities range from 0.13 to 0.98 and a relatively high solar reflectance of 0.65, leading to an impressive sub-ambient cooling of 9.1 °C in a hot daytime. Additionally, a theoretical carbon emission analysis of the aerogels' daytime cooling and night warming suggests a carbon emission reduction of 13.6 tCO2 eq. This study develops a strategy to synthesize ultrafine SAM and provides a strategy for passive cooling and passive warming by SAM with the combination of passive cooling and thermal insulation, which could help to achieve global carbon neutrality and sustainability, and solve the problems of thermal management with large temperature-fluctuation.

Random lasing in composites of CdSe/CdZnS colloidal quantum wells and silica nanoparticles

Colloidal quantum wells (CQWs) are a new type of atomic flat semiconductor nanocrystals, which present excellent opportunities as optical gain materials owing to their ultranarrow emission linewidth, tunable emission wavelength, suppressed Auger effect, and large gain cross-section. Here we synthesized monodispersed silica nanospheres and CdSe(4ML)/CdZnS core/shell CQWs. We observed random lasing by optically pumping the composites of CdSe(4ML)/CdZnS core/shell CQWs and silica nanoparticle scattering layer. The random lasing ranges from 615 nm to 625 nm with a threshold of 0.55 mJ cm−2. Fourier analysis reveals that sufficient Rayleigh scattering is the primary reason for the low threshold in the spatial frequency spectrum of the random laser. Our findings suggest that CQWs can serve as an efficient optical gain medium for random lasing, enabling various applications such as speckle-free laser imaging, random number generation for secure communication, chemical and biological sensing, high brightness and energy-efficient lighting, and label-free bioimaging.

Hollow-polydopamine-nanocarrier-based near-infrared-light/pH-responsive drug delivery system for diffuse alveolar hemorrhage treatment.

Introduction: Diffuse alveolar hemorrhage (DAH) is a serious complication caused by systemic lupus erythematosus (SLE). Tissue damage and changes in immune response are all associated with excessive free radical production. Therefore, removing excess reactive oxygen species are considered a feasible scheme for diffuse alveolar hemorrhage treatment. Cyclophosphamide is often used as the main therapeutic drug in clinics. However, CTX carries a high risk of dose-increasing toxicity, treatment intolerance, and high recurrence rate. The combination of therapeutic drugs and functional nanocarriers may provide an effective solution. PDA is rich in phenolic groups, which can remove the reactive oxygen species generated in inflammatory reactions, and can serve as excellent free radical scavengers. Methods: We developed a hollow polydopamine (HPDA) nanocarrier loaded with CTX by ionization to prepare the novel nanoplatform, CTX@HPDA, for DAH treatment. The monodisperse silica nanoparticles were acquired by reference to the typical Stober method. PDA was coated on the surface of SiO2 by oxidation self-polymerization method to obtain SiO2@PDA NPs. Then, HPDA NPs were obtained by HF etching. Then HPDA was loaded with CTX by ionization to prepare CTX@HPDA. Then we tested the photothermal effect, animal model therapeutics effect, and biosafety of CTX@HPDA. Results: Material tests showed that the CTX@ HPDA nanoplatform had a uniform diameter and could release CTX in acidic environments. The vitro experiments demonstrated that CTX@HPDA has good photothermal conversion ability and photothermal stability. Animal experiments demonstrated that the CTX@HPDA nanoplatform had good biocompatibility. The nanoplatform can dissociate in acidic SLE environment and trigger CTX release through photothermal conversion. Combining HPDA, which scavenges oxygen free radicals, and CTX, which has immunosuppressive effect, can treat pulmonary hemorrhage in SLE. Micro-CT can be used to continuously analyze DAH severity and lung changes in mice after treatment. The pulmonary exudation in the various treatment groups improved to varying degrees. Discussion: In this study, we report a photothermal/PH-triggered nanocarrier (CTX@HPDA) for the precise treatment of SLE-DAH. CTX@HPDA is a simple and efficient nanocarrier system for DAH therapy. This work provides valuable insights into SLE treatment.

Synthesis of Monodisperse Silica Particles by Controlled Regrowth

The development of a simple and reproducible method for the synthesis of monodisperse silica particles is of considerable interest from the point of view of their numerous applications in photonics, biosensing, and biomedicine. When using the well-known Stober method, there is a continuous formation and growth of seeds, which leads to the synthesis of polydisperse colloids. In this work, we used the method of successive growth of silica particles obtained by hydrolytic condensation of tetraethylorthosilicate in an alcoholic-aqueous medium using an alkaline catalyst. It is shown that this technique makes it possible to obtain colloids with a particle size from 50 nm to 3 μm and a standard deviation of less than 5%. An additional advantage of the developed method of stepwise growth is the possibility to include fluorophores and SERS tags into the silica matrix.

SYNTHESIS OF MONODISPERSE SILICA PARTICLES BY CONTROLLED REGROWTH

The development of a simple and reproducible method for the synthesis of monodisperse silica particles is of considerable interest from the point of view of their numerous applications in photonics, biosensing, and biomedicine. When using the well-known Stober method, there is a continuous formation and growth of seeds, which leads to the synthesis of polydisperse colloids. In this work, we used the method of successive growth of silica particles obtained by hydrolytic condensation of tetraethylorthosilicate in an alcoholic-aqueous medium using an alkaline catalyst. It is shown that this technique makes it possible to obtain colloids with a particle size from 50 nm to 3 μm and a standard deviation of less than 5%. An additional advantage of the developed method of stepwise growth is the possibility to include fluorophores and SERS tags into the silica matrix.