Adsorption Features of Various Inorganic Materials for the Drug Removal from Water and Synthetic Urine Medium: A Multi-Technique Time-Resolved In Situ Investigation

Pharmaceutical active compounds, including hundreds of different substances, are counted among the emerging contaminants in waterbodies, whose presence raises a growing concern for the ecosystem. Drugs are metabolized and excreted mainly through urine as an unchanged active ingredient or in the form of metabolites. These emerging contaminants are not effectively removed with the technologies currently in use, making them a relevant environmental problem. This study proposes the treatment of urine and water at the source that can allow an easier removal of dissolved drugs and metabolites. The treatment of synthetic urine, with dissolved ibuprofen as a model compound, by adsorption, using various classes of inorganic materials, such as clays, hierarchical zeolites and ordered mesoporous silica (MCM-41), is presented. A multi-technique approach involving X-ray powder diffraction, solid-state NMR, UV-Vis and Raman spectroscopies was employed to investigate the adsorption process in inorganic adsorbents. Moreover, the uptake, the ensuing competition, the efficiency and selectivity as well as the packing of the model compound in ordered mesoporous silica during the incipient wetness impregnation process were all thoroughly monitored by a novel approach, involving combined complementary time-resolved in situ ¹H and ¹³C MAS NMR spectroscopy as well as X-ray powder diffraction.     

Preparation and Characterization of Paraffin/Mesoporous Silica Shape-Stabilized Phase Change Materials for Building Thermal Insulation

The use of phase change materials (PCMs) is an attractive method for energy storage and utilization in building envelopes. Here, shape-stabilized phase change materials (SS-PCMs) were prepared via direct adsorption using mesoporous silica (MS) with different pore diameters as the support matrix. The leakage properties, microstructure, chemical structure, thermophysical properties, activation energy, thermal stability and thermal storage-release characteristics of paraffin and SS-PCMs were investigated. The results show that the maximum mass proportion of paraffin in SS-PCMs is 70% when the average pore diameter of mesoporous silica is 15 nm, and the phase change temperature and latent heat of the corresponding SS-PCM are 23.6 °C and 135.4 kJ/kg, respectively. No chemical reaction occurs between mesoporous silica and paraffin and the SS-PCMs exhibit high thermal stability. The high activation energy of the paraffin (70%)/MS1 SS-PCM verifies that the shape and thermal properties can be maintained stably during phase change conversions. The time required for SS-PCMs to complete the thermal storage and release process is reduced by up to 34.0% compared with that for pure paraffin, showing a decline in the thermal conductivity of SS-PCMs after the addition of mesoporous silica. Hence, the prepared paraffin/MS SS-PCMs, in particular paraffin (70%)/MS1 SS-PCM, can be used for storing thermal energy and regulating indoor temperature in buildings.     

Magnetic Adsorbents for Wastewater Treatment: Advancements in Their Synthesis Methods

The remediation of water streams, polluted by various substances, is important for realizing a sustainable future. Magnetic adsorbents are promising materials for wastewater treatment. Although numerous techniques have been developed for the preparation of magnetic adsorbents, with effective adsorption performance, reviews that focus on the synthesis methods of magnetic adsorbents for wastewater treatment and their material structures have not been reported. In this review, advancements in the synthesis methods of magnetic adsorbents for the removal of substances from water streams has been comprehensively summarized and discussed. Generally, the synthesis methods are categorized into five groups, as follows: direct use of magnetic particles as adsorbents, attachment of pre-prepared adsorbents and pre-prepared magnetic particles, synthesis of magnetic particles on pre-prepared adsorbents, synthesis of adsorbents on preprepared magnetic particles, and co-synthesis of adsorbents and magnetic particles. The main improvements in the advanced methods involved making the conventional synthesis a less energy intensive, more efficient, and simpler process, while maintaining or increasing the adsorption performance. The key challenges, such as the enhancement of the adsorption performance of materials and the design of sophisticated material structures, are discussed as well.     

A Review on Adsorption of Fluoride from Aqueous Solution

Fluoride is one of the anionic contaminants which is found in excess in surface or groundwater because of geochemical reactions or anthropogenic activities such as the disposal of industrial wastewaters. Among various methods used for defluoridation of water such as coagulation, precipitation, membrane processes, electrolytic treatment, ion-exchange, the adsorption process is widely used. It offers satisfactory results and seems to be a more attractive method for the removal of fluoride in terms of cost, simplicity of design and operation. Various conventional and non-conventional adsorbents have been assessed for the removal of fluoride from water. In this review, a list of various adsorbents (oxides and hydroxides, biosorbents, geomaterials, carbonaceous materials and industrial products and by-products) and its modifications from literature are surveyed and their adsorption capacities under various conditions are compared. The effect of other impurities on fluoride removal has also been discussed. This survey showed that various adsorbents, especially binary and trimetal oxides and hydroxides, have good potential for the fluoride removal from aquatic environments.     

Clay-Polymer Nanocomposites: Preparations and Utilization for Pollutants Removal

Nowadays, people over the world face severe water scarcity despite the presence of several water sources. Adsorption is considered as the most efficient technique for the treatment of water containing biological, organic, and inorganic contaminants. For this purpose, materials from various origins (clay minerals, modified clays, zeolites, activated carbon, polymeric resins, etc.) have been considered as adsorbent for contaminants. Despite their cheapness and valuable properties, the use of clay minerals as adsorbent for wastewater treatment is limited due to many factors (low surface area, regeneration, and recovery limit, etc.). However, clay mineral can be used to enhance the performance of polymeric materials. The combination of clay minerals and polymers produces clay-polymers nanocomposites (CPNs) with advanced properties useful for pollutants removal. CPNs received a lot of attention for their efficient removal rate of various organic and inorganic contaminants via flocculation and adsorption ability. Three main classes of CPNs were developed (exfoliated nanocomposites (NCs), intercalated nanocomposites, and phase-separated microcomposites). The improved materials can be explored as novel and cost-effective adsorbents for the removal of organic and inorganic pollutants from water/wastewater. The literature reported the ability of CPNs to remove various pollutants such as bacteria, metals, phenol, tannic acid, pesticides, dyes, etc. CPNs showed higher adsorption capacity and efficient water treatment compared to the individual components. Moreover, CPNs offered better regeneration than clay materials. The present paper summarizes the different types of clay-polymers nanocomposites and their effective removal of different contaminants from water. Based on various criteria, CPNs future as promising adsorbent for water treatment is discussed.     

Produced Water Treatment with Conventional Adsorbents and MOF as an Alternative: A Review

A large volume of produced water (PW) has been produced as a result of extensive industrialization and rising energy demands. PW comprises organic and inorganic pollutants, such as oil, heavy metals, aliphatic hydrocarbons, and radioactive materials. The increase in PW volume globally may result in irreversible environmental damage due to the pollutants’ complex nature. Several conventional treatment methods, including physical, chemical, and biological methods, are available for produced water treatment that can reduce the environmental damages. Studies have shown that adsorption is a useful technique for PW treatment and may be more effective than conventional techniques. However, the application of adsorption when treating PW is not well recorded. In the current review, the removal efficiencies of adsorbents in PW treatment are critically analyzed. An overview is provided on the merits and demerits of the adsorption techniques, focusing on overall water composition, regulatory discharge limits, and the hazardous effects of the pollutants. Moreover, this review highlights a potential alternative to conventional technologies, namely, porous adsorbent materials known as metal–organic frameworks (MOFs), demonstrating their significance and efficiency in removing contaminants. This study suggests ways to overcome the existing limitations of conventional adsorbents, which include low surface area and issues with reuse and regeneration. Moreover, it is concluded that there is a need to develop highly porous, efficient, eco-friendly, cost-effective, mechanically stable, and sustainable MOF hybrids for produced water treatment.     

“Low Cost” Pore Expanded SBA-15 Functionalized with Amine Groups Applied to CO2 Adsorption

The CO₂ adsorption capacity of different functionalized mesoporous silicas of the SBA-15 type was investigated and the influence of textural properties and the effect of the silicon source on the CO₂ uptake studied. Several adsorbents based on SBA-15 were synthesized using sodium silicate as silicon source, replacing the commonly used tetraethyl orthosilicate (TEOS). Thus, we synthesized three couples of supports, two at room temperature (RT, RT-F), two hydrothermal (HT, HT-F) and two hydrothermal with addition of swelling agent (1,3,5-triisopropylbenzene) (TiPB, TiPB-F). Within each couple, one of the materials was synthesized with ammonium fluoride (NH₄F). The supports were functionalized via grafting 3-aminopropyltriethoxysilane (APTES) and via impregnation with polyethylenimine ethylenediamine branched (PEI). The adsorption behavior of the pure materials was described well by the Langmuir model, whereas for the amine-silicas, a Dualsite Langmuir model was applied, which allowed us to qualify and quantify two different adsorption sites. Among the materials synthesized, only the SBA-15 synthesized at room temperatures (RT) improved its properties as an adsorbent with the addition of fluoride when the silicas were functionalized with APTES. The most promising result was the TiPB-F/50PEI silica which at 75 °C and 1 bar CO₂ captured 2.21 mmol/g.     

A State-of-the-Art Review on Innovative Geopolymer Composites Designed for Water and Wastewater Treatment

There is nothing more fundamental than clean potable water for living beings next to air. On the other hand, wastewater management is cropping up as a challenging task day-by-day due to lots of new additions of novel pollutants as well as the development of infrastructures and regulations that could not maintain its pace with the burgeoning escalation of populace and urbanizations. Therefore, momentous approaches must be sought-after to reclaim fresh water from wastewaters in order to address this great societal challenge. One of the routes is to clean wastewater through treatment processes using diverse adsorbents. However, most of them are unsustainable and quite costly e.g. activated carbon adsorbents, etc. Quite recently, innovative, sustainable, durable, affordable, user and eco-benevolent Geopolymer composites have been brought into play to serve the purpose as a pretty novel subject matter since they can be manufactured by a simple process of Geopolymerization at low temperature, lower energy with mitigated carbon footprints and marvellously, exhibit outstanding properties of physical and chemical stability, ion-exchange, dielectric characteristics, etc., with a porous structure and of course lucrative too because of the incorporation of wastes with them, which is in harmony with the goal to transit from linear to circular economy, i.e., “one’s waste is the treasure for another”. For these reasons, nowadays, this ground-breaking inorganic class of amorphous alumina-silicate materials are drawing the attention of the world researchers for designing them as adsorbents for water and wastewater treatment where the chemical nature and structure of the materials have a great impact on their adsorption competence. The aim of the current most recent state-of-the-art and scientometric review is to comprehend and assess thoroughly the advancements in geo-synthesis, properties and applications of geopolymer composites designed for the elimination of hazardous contaminants viz., heavy metal ions, dyes, etc. The adsorption mechanisms and effects of various environmental conditions on adsorption efficiency are also taken into account for review of the importance of Geopolymers as most recent adsorbents to get rid of the death-defying and toxic pollutants from wastewater with a view to obtaining reclaimed potable and sparkling water for reuse offering to trim down the massive crisis of scarcity of water promoting sustainable water and wastewater treatment for greener environments. The appraisal is made on the performance estimation of Geopolymers for water and wastewater treatment along with the three-dimensional printed components are characterized for mechanical, physical and chemical attributes, permeability and Ammonium (NH₄⁺) ion removal competence of Geopolymer composites as alternative adsorbents for sequestration of an assortment of contaminants during wastewater treatment.     

Nanostructured mesoporous silica matrices in nanomedicine

In the last few years the biomedical research field has shown a growing interest towards nanostructured mesoporous silica materials, whose chemical composition is silica and present nanometric pores. These bioceramics exhibit two important features: they can regenerate osseous tissues – the bond bioactivity of these materials has been confirmed by the formation of biological‐like nanoapatites on their surface when in contact with physiological fluids – and they are able to act as controlled release systems. Drugs in the nanometre scale can be loaded on those matrices and then locally released in a controlled fashion. It is possible to chemically modify the silica walls to favour the adsorption of certain biomolecules such as peptides, proteins or growth factors. It is even possible to design smart biomaterials where the drug is released under an external stimulus. Thus, looking at all those properties, a question arises: Have these bioceramics good expectations to be used in clinical medical practice? Their biocompatibility, bioactivity, capacity to regenerate bone and ability to act as controlled release systems of biologically active species have been confirmed. In fact, their preliminary in vitro and in vivo essays have been positive. Now it is the time to adequate all these properties to the actual clinical problems, and to evaluate their efficiency in comparison with materials already known and currently employed such as bioglasses.     

Activated Graphene Oxide-Calcium Alginate Beads for Adsorption of Methylene Blue and Pharmaceuticals

The remarkable adsorption capacity of graphene-derived materials has prompted their examination in composite materials suitable for deployment in treatment of contaminated waters. In this study, crosslinked calcium alginate–graphene oxide beads were prepared and activated by exposure to pH 4 by using 0.1M HCl. The activated beads were investigated as novel adsorbents for the removal of organic pollutants (methylene blue dye and the pharmaceuticals famotidine and diclofenac) with a range of physicochemical properties. The effects of initial pollutant concentration, temperature, pH, and adsorbent dose were investigated, and kinetic models were examined for fit to the data. The maximum adsorption capacities q_max obtained were 1334, 35.50 and 36.35 mg g⁻¹ for the uptake of methylene blue, famotidine and diclofenac, respectively. The equilibrium adsorption had an alignment with Langmuir isotherms, while the kinetics were most accurately modelled using pseudo- first-order and second order models according to the regression analysis. Thermodynamic parameters such as ΔG°, ΔH° and ΔS° were calculated and the adsorption process was determined to be exothermic and spontaneous.     

Progress of the Application of Mesoporous Silica-Supported Heteropolyacids in Heterogeneous Catalysis and Preparation of Nanostructured Metal Oxides

Mesoporous silica molecular sieves are a kind of unique catalyst support due to their large pore size and high surface area. Several methods have been developed to immobilize heteropolyacids (HPAs) inside the channels of these mesoporous silicas. The mesoporous silica-supported HPA materials have been widely used as recyclable catalysts in heterogeneous systems. They have shown high catalytic activities and shape selectivities in some reactions, compared to the parent HPAs in homogeneous systems. This review summarizes recent progress in the field of mesoporous silica-supported HPAs applied in the heterogeneous catalysis area and preparation of nanostructured metal oxides using HPAs as precursors and mesoporous silicas as hard templates.     

Synergistic Enhanced Thermal Conductivity and Dielectric Constant of Epoxy Composites with Mesoporous Silica Coated Carbon Nanotube and Boron Nitride Nanosheet

Dielectric materials with high thermal conductivity and outstanding dielectric properties are highly desirable for advanced electronics. However, simultaneous integration of those superior properties for a material remains a daunting challenge. Here, a multifunctional epoxy composite is fulfilled by incorporation of boron nitride nanosheets (BNNSs) and mesoporous silica coated multi-walled carbon nanotubes (MWCNTs@mSiO₂). Owing to the effective establishment of continuous thermal conductive network, the obtained BNNSs/MWCNTs@mSiO₂/epoxy composite exhibits a high thermal conductivity of 0.68 W m⁻¹ K⁻¹, which is 187% higher than that of epoxy matrix. In addition, the introducing of mesoporous silica dielectric layer can screen charge movement to shut off leakage current between MWCNTs, which imparts BNNSs/MWCNTs@mSiO₂/epoxy composite with high dielectric constant (8.10) and low dielectric loss (<0.01) simultaneously. It is believed that the BNNSs/MWCNTs@mSiO₂/epoxy composites with admirable features have potential applications in modern electronics.     

Selective Preparation of trans-Carveol over Ceria Supported Mesoporous Materials MCM-41 and SBA-15

Ce-modified mesoporous silica materials MCM-41 and SBA-15, namely 32 wt % Ce–Si–MCM-41, 16 wt % Ce–H–MCM-41 and 20 wt % Ce–Si–SBA-15, were prepared, characterized and studied in the selective preparation of trans-carveol by α-pinene oxide isomerization. The characterizations of these catalysts were performed using scanning electron microscopy, X-ray photoelectron spectroscopy, nitrogen adsorption and FTIR pyridine adsorption. Selective preparation of trans-carveol was carried out in the liquid phase in a batch reactor. The activity and the selectivity of catalyst were observed to be influenced by their acidity, basicity and morphology of the mesoporous materials. The formation of trans-carveol is moreover strongly influenced by the basicity of the used solvent and in order to achieve high yields of this desired alcohol it is necessary to use polar basic solvent.     

Cytokine adsorptive property of various adsorbents in immunoadsorption columns and a newly developed adsorbent: an in vitro study

BACKGROUND/AIMS: Cytokines play important roles in the pathophysiology of systemic inflammatory response syndrome (SIRS) and sepsis. Therefore, some effective measures to remove cytokines from the bloodstream could be effective in the treatment of SIRS and sepsis. The aim of this study was to evaluate the cytokine adsorptive property of various adsorbents for the purpose of the development of new selective cytokine adsorption columns. METHODS: The cytokine adsorptive property of adsorbent in a CF-X column, which consists of cellulose beads cross-linked with hexamethylene-di-isocyanate, was compared with those of various adsorbents in currently available immunoadsorption columns, such as Immusorba TR, Immusorba PH, Selesorb, and Lixelle, in vitro batchwise test using patients' plasma. A newly developed adsorbent, MPCF-X, which was modified by coating the surface of the adsorbent in CF-X with 2-methacryloyloxyethyl phosphorylcholine (MPC), was also tested for its cytokine adsorptive property. RESULTS: The adsorbent in CF-X showed a significantly higher adsorption rate for TNF-alpha, interleukin (IL)-6 and IL-10 compared with other adsorbents (p < 0.05). Adsorbent in Lixelle showed good affinity to TNF-alpha and IL-8. Especially, the adsorbent in CF-X almost completely removed TNF-alpha, whereas it also had considerable affinity to normal IgG. MPCF-X showed decreased affinity to IgG with considerable adsorptive properties to cytokines. CONCLUSION: Selective cytokine adsorption columns could be developed with improvement of currently available adsorbents. Such a new selective cytokine adsorption column could be clinically applied for the treatment of SIRS/sepsis.     

A Review: Fundamental Aspects of Silicate Mesoporous Materials

Silicate mesoporous materials have received widespread interest because of their potential applications as supports for catalysis, separation, selective adsorption, novel functional materials, and use as hosts to confine guest molecules, due to their extremely high surface areas combined with large and uniform pore sizes. Over time a constant demand has developed for larger pores with well-defined pore structures. Silicate materials, with well-defined pore sizes of about 2.0–10.0 nm, surpass the pore-size constraint (<2.0 nm) of microporous zeolites. They also possess extremely high surface areas (>700 m² g⁻¹) and narrow pore size distributions. Instead of using small organic molecules as templating compounds, as in the case of zeolites, long chain surfactant molecules were employed as the structure-directing agent during the synthesis of these highly ordered materials. The structure, composition, and pore size of these materials can be tailored during synthesis by variation of the reactant stoichiometry, the nature of the surfactant molecule, the auxiliary chemicals, the reaction conditions, or by post-synthesis functionalization techniques. This review focuses mainly on a concise overview of silicate mesoporous materials together with their applications. Perusal of the review will enable researchers to obtain succinct information about microporous and mesoporous materials.     

Utilization of Rice Husk Ash in the Preparation of Graphene-Oxide-Based Mesoporous Nanocomposites with Excellent Adsorption Performance

Rice husk is an agricultural biomass waste. Burning rice husks in an oxygenic atmosphere releases thermal energy and produces ash that is rich in silica. Rice husk ash (RHA) can be used as a sustainable source of silica for producing high-value-added products. In this study, mesostructural graphene oxide (GO)/SBA-15, a graphene-based hybrid material, was synthesized from RHA. The materials are inspected by Fourier transform infrared spectrometer, Raman spectrometer, field-emission scanning electron microscopy, transmission electron microscopy, surface area analyzer, and X-ray diffraction analyzer. Studies have revealed that GO/SBA-15 possesses various oxygen functional groups that are helpful for dye adsorption. The material consisted of high pore volume of 0.901 cm³/g, wide pores of diameter 11.67 nm, and high surface area of 499 m²/g. Analysis of the methylene blue (MB) adsorption behavior of GO/SBA-15 composites revealed that their adsorption capacity depended on the gelation pH, GO content, adsorbent dosage, and initial dye (MB) concentration. The highest adsorption capacity of GO/SBA-15 was 632.9 mg/g. Furthermore, the adsorption isotherms and kinetics of GO/SBA-15 were investigated. This study demonstrated the great advantage of treated RHA and the potential of this material for use in organic dye adsorption.     

Correlation of Nitrogen Sorption and Confocal Laser Scanning Microscopy for the Analysis of Amino Group Distributions on Mesoporous Silica

Aminopropylalkoxysilanes are frequently used for the functionalization of mesoporous silica. The analysis of amino group distributions on arrays of silica nanochannels by a combination of nitrogen sorption and confocal laser scanning microscopy provides valuable insight into the mechanisms underlying the interaction of these silanes with mesoporous silica surfaces. Tendencies towards external surface functionalization, non-uniform distribution in the pores, and hydrolysis of the silica framework are shown to depend to a large extent on the mobility of the aminopropylalkoxysilane molecules, which can be adjusted by the number and type of alkoxy groups.     

APTES-Modified SBA-15 as a Non-Toxic Carrier for Phenylbutazone

Improvement of the bioavailability of poorly soluble medicinal substances is currently one of the major challenges for pharmaceutical industry. Enhancing the dissolution rate of those drugs using novel methods allows to increase their bioavailability. In recent years, silica-based mesoporous materials have been proposed as drug delivery systems that augment the dissolution rate. The aim of this study was to analyse the influence of phenylbutazone adsorption on SBA-15 on its dissolution rate. Moreover, we examined the cytotoxicity of the analyzed silica. The material was characterized by SEM, TEM, DSC, ¹H-NMR, XRD, and FT-IR. The phenylbutazone did not adsorb on unmodified SBA-15, while the adsorption on APTES-modified SBA-15 resulted in 50.43 mg/g of loaded phenylbutazone. Phenylbutazone adsorbed on the APTES-modified SBA-15 was then released in the hydrochloric acidic medium (pH 1.2) and phosphate buffer (pH 7.4) and compared to the dissolution rate of the crystalline phenylbutazone. The release profiles of the amorphous form of adsorbed phenylbutazone are constant in different pH, while the dissolution rate of the crystalline phenylbutazone depends on the pH. The cytotoxicity assays were performed using the Caco-2 cell line. Our results indicate that the analyzed material ensured phenylbutazone adsorption in an amorphous state inside the mesopores and increased its dissolution rate in various pH levels. Furthermore, the cytotoxicity assay proved safety of studied material. Our study demonstrated that APTES-modified SBA-15 can serve as a non-toxic drug carrier that improves the bioavailability of phenylbutazone.     

Immusorba TR and Immusorba PH: Basics of Design and Features of Functions

Abstract: Guest Editor's Introduction: Selective adsorption of target substances can be achieved based upon the application of physical and chemical interactions as well. Asahi Medical Co. developed 2 types of selective adsorbent columns, Immusorba PH‐350, and Immusorba TR‐350. These adsorbents consist of crosslinked polyvinyl alcohol gel beds with microporous structures for the base material, which immobilized a specific amino acid with hydrophobic property. Immusorba PH‐350 has phenylalanines as the ligand, which adsorbs the pathogenic substances such as immune complexes and anti‐DNA antibody. Tryptophan is immobilized in the Immusorba TR‐350, which adsorbs antiacetylcholine receptor antibodies. This paper describes the basic designs, adsorption characteristics, and summary of clinical applications of these adsorbents. This paper was printed in Therapeutic Apheresis, vol 2, page 185–192 (1998), and reprinted here with permission. Immusorba was reported by Yamazaki et al. to be the world's first practical immunoadsorbent in 1982. Since then, this immunoadsorbent has accumulated an abundance of clinical achievements. Immusorba has such unique functions that it is used in treating various diseases and holds possibilities for application to more diseases. Immusorba was designed as an artificial receptor for rheumatoid factor (RF) based on structural analysis of heat‐denaturated globulin. Subsequently, new substances that it can adsorb have been found as seen in reports on the adsorption performance of Immusorba to anti‐acetylcholine receptor antibodies (anti‐AChR Abs) and antiganglioside antibodies. Along with this, Immusorba has been used in treating a wide range of diseases. The greatest characteristic of Immusorba is that its adsorption capability is selective rather than specific, making it effective against a great number of diseases.