International Journal of Molecular Sciences

Editorial

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3 pages, 178 KiB

Open AccessEditorial

Mesoporous Materials: Materials, Technological, and Environmental Applications

by Izabela Nowak and Agnieszka Feliczak-Guzik

Int. J. Mol. Sci. 2023, 24(11), 9197; https://doi.org/10.3390/ijms24119197 - 24 May 2023

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Abstract

Research on the synthesis and characterization of ordered mesoporous materials with uniquely functionalized external and internal surfaces has intensified in the last decade [...] Full article

(This article belongs to the Special Issue Recent Advances in Mesoporous Materials: Structure, Composition, Properties and Applications)

Research

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14 pages, 2924 KiB

Open AccessArticle

Mechanism of Cs Immobilization within a Sodalite Framework: The Role of Alkaline Cations and the Si/Al Ratio

by Anton Kasprzhitskii, Yakov Ermolov, Vasilii Mischinenko, Andrey Vasilchenko, Elena A. Yatsenko and Victoria A. Smoliy

Int. J. Mol. Sci. 2023, 24(23), 17023; https://doi.org/10.3390/ijms242317023 - 30 Nov 2023

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Abstract

Conditioning of radioactive waste generated from the operation of medical institutions, nuclear cycle facilities, and nuclear facilities is important for the safety of the environment. One of the most hazardous radionuclides is radioactive cesium. There is a need for more effective solutions to [...] Read more.

Conditioning of radioactive waste generated from the operation of medical institutions, nuclear cycle facilities, and nuclear facilities is important for the safety of the environment. One of the most hazardous radionuclides is radioactive cesium. There is a need for more effective solutions to contain radionuclides, especially cesium (Cs+). Geopolymers are promising inorganic materials that can provide a large active surface area with adjustable porosity and binding capacity. The existence of nanosized zeolite-like structures in aluminosilicate gels was shown earlier. These structures are candidates for immobilizing radioactive cesium (Cs⁺). However, the mechanisms of their interactions with the aluminosilicate framework related to radionuclide immobilization have not been well studied. In this work, the influence of alkaline cations (Na⁺ or K⁺) and the aluminosilicate framework structure on the binding capacity and mechanism of interaction of geopolymers with Cs⁺ is explored in the example of a sodalite framework. The local structure of the water molecules and alkaline ions in the equilibrium state and its behavior when the Si/Al ratio was changed were studied by DFT. Full article

(This article belongs to the Special Issue Recent Advances in Mesoporous Materials: Structure, Composition, Properties and Applications)

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20 pages, 3641 KiB

Open AccessArticle

Nanoconfined Water in Pillared Zeolites Probed by ¹H Nuclear Magnetic Resonance

by Marina G. Shelyapina, Denis Y. Nefedov, Anastasiia O. Antonenko, Gleb A. Valkovskiy, Rosario I. Yocupicio-Gaxiola and Vitalii Petranovskii

Int. J. Mol. Sci. 2023, 24(21), 15898; https://doi.org/10.3390/ijms242115898 - 2 Nov 2023

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Abstract

Here, we report the results of our ¹H nuclear magnetic resonance study of the dynamics of water molecules confined in zeolites (mordenite and ZSM-5 structures) with hierarchical porosity (micropores in zeolite lamella and mesopores formed by amorphous SiO₂ in the inter-lamellar [...] Read more.

Here, we report the results of our ¹H nuclear magnetic resonance study of the dynamics of water molecules confined in zeolites (mordenite and ZSM-5 structures) with hierarchical porosity (micropores in zeolite lamella and mesopores formed by amorphous SiO₂ in the inter-lamellar space). ¹H nuclear magnetic resonance (NMR) spectra show that water experiences complex behavior within the temperature range from 173 to 298 K. The temperature dependence of ¹H spin-lattice relaxation evidences the presence of three processes with different activation energies: freezing (about 30 kJ/mol), fast rotation (about 10 kJ/mol), and translational motion of water molecules (23.6 and 26.0 kJ/mol for pillared mordenite and ZSM-5, respectively). For translational motion, the activation energy is markedly lower than for water in mesoporous silica or zeolites with similar mesopore size but with disordered secondary porosity. This indicates that the process of water diffusion in zeolites with hierarchical porosity is governed not only by the presence of mesopores, but also by the mutual arrangement of meso- and micropores. The translational motion of water molecules is determined mainly by zeolite micropores. Full article

(This article belongs to the Special Issue Recent Advances in Mesoporous Materials: Structure, Composition, Properties and Applications)

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22 pages, 2879 KiB

Open AccessArticle

Mucoadhesive Mesoporous Silica Particles as Versatile Carriers for Doxorubicin Delivery in Cancer Therapy

by Mirela-Fernanda Zaltariov, Bianca-Iulia Ciubotaru, Alina Ghilan, Dragos Peptanariu, Maria Ignat, Mihail Iacob, Nicoleta Vornicu and Maria Cazacu

Int. J. Mol. Sci. 2023, 24(19), 14687; https://doi.org/10.3390/ijms241914687 - 28 Sep 2023

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Abstract

Due to their structural, morphological, and behavioral characteristics (e.g., large volume and adjustable pore size, wide functionalization possibilities, excellent biocompatibility, stability, and controlled biodegradation, the ability to protect cargoes against premature release and unwanted degradation), mesoporous silica particles (MSPs) are emerging as a [...] Read more.

Due to their structural, morphological, and behavioral characteristics (e.g., large volume and adjustable pore size, wide functionalization possibilities, excellent biocompatibility, stability, and controlled biodegradation, the ability to protect cargoes against premature release and unwanted degradation), mesoporous silica particles (MSPs) are emerging as a promising diagnostic and delivery platform with a key role in the development of next-generation theranostics, nanovaccines, and formulations. In this study, MSPs with customized characteristics in-lab prepared were fully characterized and used as carriers for doxorubicin (DOX). The drug loading capacity and the release profile were evaluated in media with different pH values, mimicking the body conditions. The release data were fitted to Higuchi, Korsmeyer–Peppas, and Peppas–Sahlin kinetic models to evaluate the release constant and the mechanism. The in vitro behavior of functionalized silica particles showed an enhanced cytotoxicity on human breast cancer (MCF-7) cells. Bio- and mucoadhesion on different substrates (synthetic cellulose membrane and porcine tissue mucosa)) and antimicrobial activity were successfully assessed, proving the ability of the OH- or the organically modified MSPs to act as antimicrobial and mucoadhesive platforms for drug delivery systems with synergistic effects. Full article

(This article belongs to the Special Issue Recent Advances in Mesoporous Materials: Structure, Composition, Properties and Applications)

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11 pages, 5013 KiB

Open AccessArticle

Nanostructured Aluminum Oxyhydroxide—A Prospective Support for Functional Porphyrin-Based Materials

by Stepan M. Korobkov, Kirill P. Birin, Anatole N. Khodan, Oleg Yu. Grafov, Yulia G. Gorbunova and Aslan Yu. Tsivadze

Int. J. Mol. Sci. 2023, 24(15), 12165; https://doi.org/10.3390/ijms241512165 - 29 Jul 2023

Cited by 1 | Viewed by 951

Abstract

A method for the grafting of unsymmetrical A₂BC-type 5,15-bis(4-butoxyphenyl)-10-(4-carboxyphenyl)-20-(phenanthrenoimidazolyl)-porphyrin onto the surface of nanostructured aluminum oxyhydroxide modified with a single SiO₂ layer (NAOM) was successfully developed. A straightforward procedure towards surface modification of NAOM allowed us to prepare a new [...] Read more.

A method for the grafting of unsymmetrical A₂BC-type 5,15-bis(4-butoxyphenyl)-10-(4-carboxyphenyl)-20-(phenanthrenoimidazolyl)-porphyrin onto the surface of nanostructured aluminum oxyhydroxide modified with a single SiO₂ layer (NAOM) was successfully developed. A straightforward procedure towards surface modification of NAOM allowed us to prepare a new porphyrin-containing hybrid material. The obtained 3D heterostructure was extensively characterized using XPS, TEM and diffuse reflectance spectroscopy. Structural and morphological peculiarities of the inorganic support before and after the immobilization procedure were studied and discussed in detail. The stability of the material against leaching and the porphyrin immobilization ratio ca. 14% by weight were also revealed. Full article

(This article belongs to the Special Issue Recent Advances in Mesoporous Materials: Structure, Composition, Properties and Applications)

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20 pages, 2054 KiB

Open AccessArticle

Effect of Non-Modified as Well as Surface-Modified SiO₂ Nanoparticles on Red Blood Cells, Biological and Model Membranes

by Katarzyna Solarska-Ściuk, Katarzyna Męczarska, Vera Jencova, Patryk Jędrzejczak, Łukasz Klapiszewski, Aleksandra Jaworska, Monika Hryć and Dorota Bonarska-Kujawa

Int. J. Mol. Sci. 2023, 24(14), 11760; https://doi.org/10.3390/ijms241411760 - 21 Jul 2023

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Abstract

Nanoparticles are extremely promising components that are used in diagnostics and medical therapies. Among them, silica nanoparticles are ultrafine materials that, due to their unique physicochemical properties, have already been used in biomedicine, for instance, in cancer therapy. The aim of this study [...] Read more.

Nanoparticles are extremely promising components that are used in diagnostics and medical therapies. Among them, silica nanoparticles are ultrafine materials that, due to their unique physicochemical properties, have already been used in biomedicine, for instance, in cancer therapy. The aim of this study was to investigate the cytotoxicity of three types of nanoparticles (

{SiO}_{2}

,

{SiO}_{2} - SH

, and

{SiO}_{2} - COOH

) in relation to red blood cells, as well as the impact of silicon dioxide nanoparticles on biological membranes and liposome models of membranes. The results obtained prove that hemolytic toxicity depends on the concentration of nanoparticles and the incubation period. Silica nanoparticles have a marginal impact on the changes in the osmotic resistance of erythrocytes, except for

{SiO}_{2} - COOH

, which, similarly to

{SiO}_{2}

and

{SiO}_{2} - SH

, changes the shape of erythrocytes from discocytes mainly towards echinocytes. What is more, nanosilica has an impact on the change in fluidity of biological and model membranes. The research gives a new view of the practical possibilities for the use of large-grain nanoparticles in biomedicine. Full article

(This article belongs to the Special Issue Recent Advances in Mesoporous Materials: Structure, Composition, Properties and Applications)

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12 pages, 4373 KiB

Open AccessArticle

Tailoring the Morphology of Monodisperse Mesoporous Silica Particles Using Different Alkoxysilanes as Silica Precursors

by Fabio Fait, Stefanie Wagner, Julia C. Steinbach, Andreas Kandelbauer and Hermann A. Mayer

Int. J. Mol. Sci. 2023, 24(14), 11729; https://doi.org/10.3390/ijms241411729 - 21 Jul 2023

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Abstract

The hard template method for the preparation of monodisperse mesoporous silica microspheres (MPSMs) has been established in recent years. In this process, in situ-generated silica nanoparticles (SNPs) enter the porous organic template and control the size and pore parameters of the final MPSMs. [...] Read more.

The hard template method for the preparation of monodisperse mesoporous silica microspheres (MPSMs) has been established in recent years. In this process, in situ-generated silica nanoparticles (SNPs) enter the porous organic template and control the size and pore parameters of the final MPSMs. Here, the sizes of the deposited SNPs are determined by the hydrolysis and condensation rates of different alkoxysilanes in a base catalyzed sol–gel process. Thus, tetramethyl orthosilicate (TMOS), tetraethyl orthosilicate (TEOS), tetrapropyl orthosilicate (TPOS) and tetrabutyl orthosilicate (TBOS) were sol–gel processed in the presence of amino-functionalized poly (glycidyl methacrylate-co-ethylene glycol dimethacrylate) (p(GMA-co-EDMA)) templates. The size of the final MPSMs covers a broad range of 0.5–7.3 µm and a median pore size distribution from 4.0 to 24.9 nm. Moreover, the specific surface area can be adjusted between 271 and 637 m² g⁻¹. Also, the properties and morphology of the MPSMs differ according to the SNPs. Furthermore, the combination of different alkoxysilanes allows the individual design of the morphology and pore parameters of the silica particles. Selected MPSMs were packed into columns and successfully applied as stationary phases in high-performance liquid chromatography (HPLC) in the separation of various water-soluble vitamins. Full article

(This article belongs to the Special Issue Recent Advances in Mesoporous Materials: Structure, Composition, Properties and Applications)

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16 pages, 3051 KiB

Open AccessArticle

In Vitro Safety Assessment of In-House Synthesized Titanium Dioxide Nanoparticles: Impact of Washing and Temperature Conditions

by Aliyah Almomen, Nasser B. Alsaleh, Ahmed Mohamed El-Toni, Mohamed A. EL-Mahrouky, Adel Ali Alhowyan, Musaed Alkholief, Aws Alshamsan, Nitish Khurana and Hamidreza Ghandehari

Int. J. Mol. Sci. 2023, 24(12), 9966; https://doi.org/10.3390/ijms24129966 - 9 Jun 2023

Cited by 1 | Viewed by 1242

Abstract

Titanium dioxide nanoparticles (TiO₂ NPs) have been widely used in food, cosmetics, and biomedical research. However, human safety following exposure to TiO₂ NPs remains to be fully understood. The aim of this study was to evaluate the in vitro safety and [...] Read more.

Titanium dioxide nanoparticles (TiO₂ NPs) have been widely used in food, cosmetics, and biomedical research. However, human safety following exposure to TiO₂ NPs remains to be fully understood. The aim of this study was to evaluate the in vitro safety and toxicity of TiO₂ NPs synthesized via the Stöber method under different washing and temperature conditions. TiO₂ NPs were characterized by their size, shape, surface charge, surface area, crystalline pattern, and band gap. Biological studies were conducted on phagocytic (RAW 264.7) and non-phagocytic (HEK-239) cells. Results showed that washing amorphous as-prepared TiO₂ NPs (T1) with ethanol while applying heat at 550 °C (T2) resulted in a reduction in the surface area and charge compared to washing with water (T3) or a higher temperature (800 °C) (T4) and influenced the formation of crystalline structures with the anatase phase in T2 and T3 and rutile/anatase mixture in T4. Biological and toxicological responses varied among TiO₂ NPs. T1 was associated with significant cellular internalization and toxicity in both cell types compared to other TiO₂ NPs. Furthermore, the formation of the crystalline structure induced toxicity independent of other physicochemical properties. Compared with anatase, the rutile phase (T4) reduced cellular internalization and toxicity. However, comparable levels of reactive oxygen species were generated following exposure to the different types of TiO_2, indicating that toxicity is partially driven via non-oxidative pathways. TiO₂ NPs were able to trigger an inflammatory response, with varying trends among the two tested cell types. Together, the findings emphasize the importance of standardizing engineered nanomaterial synthesis conditions and evaluating the associated biological and toxicological consequences arising from changes in synthesis conditions. Full article

(This article belongs to the Special Issue Recent Advances in Mesoporous Materials: Structure, Composition, Properties and Applications)

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Review

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23 pages, 8872 KiB

Open AccessReview

State-of-the-Art Review on Amorphous Carbon Nanotubes: Synthesis, Structure, and Application

by Xiaona Ren, Muhammad Irfan Hussain, Yue Chang and Changchun Ge

Int. J. Mol. Sci. 2023, 24(24), 17239; https://doi.org/10.3390/ijms242417239 - 7 Dec 2023

Cited by 2 | Viewed by 1166

Abstract

Carbon nanotubes (CNTs) have rapidly received increasing attention and great interest as potential materials for energy storage and catalyst fields, which is due to their unique physicochemical and electrical properties. With continuous improvements in fabrication routes, CNTs have been modified with various types [...] Read more.

Carbon nanotubes (CNTs) have rapidly received increasing attention and great interest as potential materials for energy storage and catalyst fields, which is due to their unique physicochemical and electrical properties. With continuous improvements in fabrication routes, CNTs have been modified with various types of materials, opening up new perspectives for research and state-of-the-art technologies. Amorphous CNTs (aCNTs) are carbon nanostructures that are distinctively different from their well-ordered counterparts, such as single-walled and multi-walled carbon nanotubes (SWCNTs and MWCNTs, respectively), while the atoms in aCNTs are grouped in a disordered, crystalline/non-crystalline manner. Owing to their unique structure and properties, aCNTs are attractive for energy storage, catalysis, and aerospace applications. In this review, we provide an overview of the synthetic routes of aCNTs, which include chemical vapor deposition, catalytic pyrolysis, and arc discharge. Detailed morphologies of aCNTs and the systematic elucidation of tunable properties are also summarized. Finally, we discuss the future perspectives as well as associated challenges of aCNTs. With this review, we aim to encourage further research for the widespread use of aCNTs in industry. Full article

(This article belongs to the Special Issue Recent Advances in Mesoporous Materials: Structure, Composition, Properties and Applications)

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