Characterization of Drugs with Good Glass Formers in Loaded-Mesoporous Silica and Its Theoretical Value Relevance with Mesopores Surface and Pore-Filling Capacity

The incorporation of a drug into mesoporous silica (MPS) is a promising strategy to stabilize its amorphous form. However, the drug within MPS has shown incomplete release, despite a supersaturated solution being generated. This indicates the determination of maximum drug loading in MPS below what is experimentally necessary to maximize the drug doses in the system. Therefore, this study aimed to characterize the drugs with good glass former loaded-mesoporous silica, determine the maximum drug loading, and compare its theoretical value relevance to monolayer covering the mesoporous (MCM) surface, as well as pore-filling capacity (PFC). Solvent evaporation and melt methods were used to load each drug into MPS. In addition, the glass transition of ritonavir (RTV) and cyclosporine A (CYP), as well as the melting peak of indomethacin (IDM) and saccharin (SAC) in mesoporous silica, were not discovered in the modulated differential scanning calorimetry (MDSC) curve, demonstrating that each drug was successfully incorporated into the mesopores. The amorphization of RTV-loaded MPS (RTV/MPS), CYP-loaded MPS (CYP/MPS), and IDM-loaded MPS (IDM/MPS) were confirmed as a halo pattern in powder X-ray diffraction measurements and a single glass transition event in the MDSC curve. Additionally, the good glass formers, nanoconfinement effect of MPS and silica surface interaction contributed to the amorphization of RTV, CYP and IDM within MPS. Meanwhile, the crystallization of SAC was observed in SAC-loaded MPS (SAC/MPS) due to its weak silica surface interaction and high recrystallization tendency. The maximum loading amount of RTV/MPS was experimentally close to the theoretical amount of MCM, showing monomolecular adsorption of RTV on the silica surface. On the other hand, the maximum loading amount of CYP/MPS and IDM/MPS was experimentally lower than the theoretical amount of MCM due to the lack of surface interaction. However, neither CYP or IDM occupied the entire silica surface, even though some drugs were adsorbed on the MPS surface. Moreover, the maximum loading amount of SAC/MPS was experimentally close to the theoretical amount of PFC, suggesting the multilayers of SAC within the MPS. Therefore, this study demonstrates that the characterization of drugs within MPS, such as molecular size and interaction of drug-silica surface, affects the loading efficiency of drugs within MPS that influence its relevance with the theoretical value of drugs.

Spectroscopic study on peculiarities of fumed silica hydridesilylation with triethoxysilane under fluidized bed conditions

Fumed silica has found widespread application in industry due to variety of fascinating properties. Owing to its specific manufacturing process, it consists of finely dispersed particles and is featured with large specific surface area covered by profoundly reactive silanol groups which are available for chemical grafting. Spherical shape of fumed silica particles and lacking porosity provides a space-filling structure. These characteristics implement the fume silica’s utilization as high-surface-area carriers for various catalysts, i.e. metallic nanometer-sized particles, organic moieties, etc. Currently a great attention is called to on-surface grafting to improve the silica-based carrier. Most of research is carried out in area of liquid phase chemistry involving an abundance of expensive and often toxic solvents while the space-filling properties of silica are favoring reactions in fluidized bed conditions. In current research fumed silica (A-300) was a subject for hydridesilylation with triethoxysilane under fluidized bed conditions. In all synthesis reported in current research the insignificant amount of solvent (1.00 wt. % of the amount used in typical wet-chemical modifications method) was spent for the silica surface silylation. While the mass ratio of silica/TES was kept constant, other conditions, i.e. solvent/catalyst presence, surface pretreatment, additional treatment with water, and the fluidized bed heating mode have been varied. FTIR spectroscopy revealed the interaction between groups of triethoxysilane and silica surface silanol groups and demonstrated the effect of modification conditions on the density of the hydridesilyl groups coverage. The results of FTIR spectroscopic studies have confirmed the presence of grafted silicon hydride groups on the surface of modified silica, as well as the presence of ethoxy and/or silanol groups – either intact or formed due to hydrolysis of the ethoxy groups. Titrimetric and spectrophotometric analysis was performed to estimate the concentration of grafted SiH groups (in all samples prepared under fluidized bed conditions their concentration ranged within about 0.28–0.55 mmol/g as dependent on the reaction conditions). Other important aspects of fluidization such as the presence of solvent and/or hydrolyzing agent, bed heating mode and the effect of the silica sample thermal pre-treatment are also discussed.

Quantum chemical study on the interaction of arginine with silica surface

The structure and energy characteristics of structures formed during arginine adsorption on silica surface from aqueous solution were studied by the density functional theory (B3LYP) method using a valence-split basis set 6-31++G(d,p) within the continuous solvent model (PCM) and supermolecular approximation. The equilibrium structural and energy parameters of the protonated arginine molecule in the gas phase dependent on the location of the hydrogen atom are considered including those of two possible zwitterions. The structure of the arginine ion Н2А+, which is formed when a proton attaches to a molecule or zwitterion of a given amino acid, has been elucidated. To determine the deprotonation constant of the carboxyl group in an acidic medium, the complexes of the arginine molecule (AH32+) in the state with undissociated and deprotonated carboxyl groups are considered. The simulation of the acid medium was performed by taking into account the interaction with two hydrated HCl ion pairs, which provided the protonation of the a-amino group and the nitrogen atom of amino group within the guanidine group. In the study on the interaction of an arginine molecule with silica surface in an aqueous medium, complexes containing a Si8O12(OH)7O– ion with a deprotonated silanol group, six water molecules, and an arginine molecule with a deprotonated carboxyl group were considered. It has been found that the arginine molecule is most likely to be adsorbed on slica surface with formation of hydrogen bonds between the hydrogen atoms of the a-amino group and the oxygen atom of the deprotonated silanol group. In this case, the formation of a hydrogen bond between the oxygen atom of the carboxyl group and the hydrogen atom of the neighboring silanol group is possible. Slightly less likely is adsorption of arginine molecules due to interaction of the guanidine group with silanol groups of the surface. According to the calculated data, the adsorption of the zwitterionic form of the arginine molecule from the aqueous solution is equally likely to occur due to interaction of silanol groups of silica surface with both the carboxyl group and the guanidine group.

Silica Hydride: A Separation Material Every Analyst Should Know About

This review describes the development, special features and applications of silica hydride-based stationary phases for HPLC. The unique surface of this material is in contrast to ordinary, standard silica, which is the material most frequently used in modern HPLC stationary phases. The standard silica surface contains mainly silanol (Si-OH) groups, while the silica hydride surface is instead composed of silicon-hydrogen groups, which is much more stable, less reactive and delivers different chromatographic and chemical characteristics. Other aspects of this material are described for each of the different bonded moieties available commercially. Some applications for each of these column types are also presented as well as a generic model for method development on silica hydride-based stationary phases.

Laser Fabrication of Nanoholes on Silica through Surface Window Assisted Nano-Drilling (SWAN)

Nano-structures have significant applications in many fields such as chip fabrications, nanorobotics, and solar cells. However, realizing nanoscale structures on hard and brittle materials is still challenging. In this paper, when processing the silica surface with a tightly focused Bessel beam, the smallest nanohole with ~20 nm diameter has been realized by precisely controlling the interior and superficial interaction of the silica material. An effective surface window assisted nano-drilling (SWAN) mechanism is proposed to explain the generation of such a deep subwavelength structure, which is supported by the simulation results of energy depositions.

On the incorporation of nano TiO2 to inhibit concrete deterioration in the marine environment

To develop high deterioration resistance concrete for marine infrastructures, two types of nano TiO2 (NT) including anatase phase NT and silica surface-treated rutile phase NT were incorporated into concrete. The fabricated NT modified concrete was then put into the marine environment for 21 months in this study. The effects and mechanisms of two types of NT on the deterioration of concrete in the marine environment were investigated from three aspects, including seawater physical and biological and chemical actions on concrete with NT. Under the seawater physical action, the exposed degree of coarse sand particles on the surface of control concrete is greater than that of concrete with NT. Owing to the microorganism biodegradation property of NT, the elimination and inhibition rates of concrete with NT on microorganisms can reach up to 76.98% and 96.81%, respectively. In addition, the surface biofilm thickness of concrete can be reduced by 49.13% due to the inclusion of NT. In the aspect of seawater chemical action, NT can increase the pH value inside concrete by 0.81, increase the degree of polymerization of C-S-H gel, and improve the interfacial transition zone between cement paste and aggregate in concrete. Compared to concrete with anatase phase NT, silica surface-treated rutile phase NT is more effective in improving the deterioration resistance of concrete in the marine environment. It can be concluded that incorporating NT can inhibit the deterioration of concrete in the marine environment.