Search Results (24)

3-Aminopropyltrimethoxysilane (APTS) and tetraethylenepentamine (TEPA)-co-functionalized mesoporous silica gel (MSG) composites were prepared for CO₂ adsorption. The surface functional groups, thermal stability, and pore structures of the composites were tested using FT-IR, TGA, and N₂ adsorption–desorption techniques, respectively. The effects of the amine loading, adsorption temperature, and influent flow rate on CO₂ adsorption were experimentally investigated. The results indicate that the synergistic effects of APTS, TEPA, and Si-OH on MSG enhanced CO₂ adsorption performance. In addition, the amine-co-modified MSG exhibited good cyclic regenerability and rapid adsorption kinetics. Full article

Sitagliptin, an important anti-diabetic drug, can be obtained using transaminase (TA) enzymes, which are known to be promising biocatalysts for the production of highly enantiopure amines under mild reaction conditions. In an industrial context, the use of immobilized enzymes can provide several advantages, such as the improved stability of the biocatalyst and easy product recovery. In this study, a new commercially available transaminase enzyme to produce sitagliptin was immobilized on inorganic and organic supports using two different approaches: adsorption and covalent bond formation. Among the inorganic media, non-functionalized silica gel was chosen for its stability and competitive cost. A range of commercially available resins with different functionalities have also been selected for their characteristics that can meet industrial standards. The immobilized biocatalysts were first tested in the transamination of acetophenone as a model substrate, which obtains, in most cases, higher conversions with respect to soluble enzymes. The best results in the enantioselective synthesis of sitagliptin were achieved with the sample immobilized on the epoxy- and octadecyl-functionalized methacrylic resin, which allowed the complete conversion of the corresponding ketone and high enantioselectivity (>99% ee). Moreover, the recycling of the supported enzyme could be performed in a continuous flow system without loss of activity for five consecutive runs. Full article

The development of targeted drug delivery systems has been a pivotal area in nanomedicine, addressing challenges like low drug loading capacity, uncontrolled release, and systemic toxicity. This study aims to develop and evaluate dual-functionalized mesoporous silica nanoparticles (MSN) for targeted delivery of celecoxib, enhancing drug loading, achieving controlled release, and reducing systemic toxicity through amine grafting and imidazolyl polyethyleneimine (PEI) gatekeepers. MSN were synthesized using the sol–gel method and functionalized with (3-aminopropyl) triethoxysilane (APTES) to create amine-grafted MSN (MSN-NH₂). Celecoxib was loaded into MSN-NH₂, followed by conjugation of imidazole-functionalized PEI (IP) gatekeepers synthesized via carbodiimide coupling. Characterization was conducted using Fourier-transform infrared spectroscopy (FTIR) and proton nuclear magnetic resonance (¹H-NMR). Drug loading capacity, entrapment efficiency, and in vitro drug release at pH 5.5 and 7.4 were evaluated. Cytotoxicity was assessed using the MTT assay on RAW 264.7 macrophages. The synthesized IP was confirmed by FTIR and ¹H-NMR. Amine-grafted MSN demonstrated a celecoxib loading capacity of 12.91 ± 2.02%, 2.1 times higher than non-functionalized MSN. In vitro release studies showed pH-responsive behavior with significantly higher celecoxib release from MSN-NH₂-celecoxib-IP at pH 5.5 compared to pH 7.4, achieving a 33% increase in release rate within 2 h. Cytotoxicity tests indicated significantly higher cell viability for IP-treated cells compared to PEI-treated cells, confirming reduced toxicity. The dual-functionalization of MSN with amine grafting and imidazolyl PEI gatekeepers enhances celecoxib loading and provides controlled pH-responsive drug release while reducing systemic toxicity. These findings highlight the potential of this advanced drug delivery system for targeted anti-inflammatory and anticancer therapies. Full article

Nanocomposite hydrogels offer remarkable potential for applications in bone tissue engineering. They are synthesized through the chemical or physical crosslinking of polymers and nanomaterials, allowing for the enhancement of their behaviour by modifying the properties and compositions of the nanomaterials involved. However, their mechanical properties require further enhancement to meet the demands of bone tissue engineering. Here, we present an approach to improve the mechanical properties of nanocomposite hydrogels by incorporating polymer grafted silica nanoparticles into a double network inspired hydrogel (gSNP Gels). The gSNP Gels were synthesised via a graft polymerization process using a redox initiator. gSNP Gels were formed by grafting 2-acrylamido-2-methylpropanesulfonic acid (AMPS) as the first network gel followed by a sequential second network acrylamide (AAm) onto amine functionalized silica nanoparticles (ASNPs). We utilized glucose oxidase (GOx) to create an oxygen-free atmosphere during polymerization, resulting in higher polymer conversion compared to argon degassing. The gSNP Gels showed excellent compressive strengths of 13.9 ± 5.5 MPa, a strain of 69.6 ± 6.4%, and a water content of 63.4% ± 1.8. The synthesis technique demonstrates a promising approach to enhance the mechanical properties of hydrogels, which can have significant implications for bone tissue engineering and other soft tissue applications. Full article

Porous organic cages (POCs) are a new subclass of porous materials, which are constructed from discrete cage molecules with permanent cavities via weak intermolecular forces. In this study, a novel chiral stationary phase (CSP) has been prepared by chemically binding a [4 + 6]-type chiral POC (C₁₂₀H₉₆N₁₂O₄) with thiol-functionalized silica gel using a thiol-ene click reaction and applied to HPLC separations. The column packed with this CSP presented good separation capability for chiral compounds and positional isomers. Thirteen racemates have been enantioseparated on this column, including alcohols, diols, ketones, amines, epoxides, and organic acids. Upon comparison with a previously reported chiral POC NC1-R-based column, commercial Chiralpak AD-H, and Chiralcel OD-H columns, this column is complementary to these three columns in terms of its enantiomeric separation; and can also separate some racemic compounds that cannot be separated by the three columns. In addition, eight positional isomers (iodoaniline, bromoaniline, chloroaniline, dibromobenzene, dichlorobenzene, toluidine, nitrobromobenzene, and nitroaniline) have also been separated. The influences of the injection weight and column temperature on separation have been explored. After the column has undergone multiple injections, the relative standard deviations (RSDs) for the retention time and selectivity were below 1.0 and 1.5%, respectively, indicating the good reproducibility and stability of the column for separation. This work demonstrates that POCs are promising materials for HPLC separation. Full article

This study is the first report on the synthesis, characterization and application of amine-functionalized mesoporous nanocomposites based on natural rubber (NR) and wormhole-like mesostructured silica (WMS). In comparison with amine-functionalized WMS (WMS-NH₂), a series of NR/WMS-NH₂ composites were synthesized via an in situ sol-gel method in which the organo-amine group was grafted onto the nanocomposite surface via co-condensation with 3-aminopropyltrimethoxysilane (APS) as the amine-functional group precursor. The NR/WMS-NH₂ materials had a high specific surface area (115–492 m² g⁻¹) and total pore volume (0.14–1.34 cm³ g⁻¹) with uniform wormhole-like mesoporous frameworks. The amine concentration of NR/WMS-NH₂ (0.43–1.84 mmol g⁻¹) was increased with an increase in the APS concentration, corresponding to high levels of functionalization with the amine groups of 53–84%. The H₂O adsorption–desorption measurement revealed that NR/WMS-NH₂ possessed higher hydrophobicity than WMS-NH₂. The removal of clofibric acid (CFA), a xenobiotic metabolite of the lipid-lowering drug clofibrate, from the aqueous solution using WMS-NH₂ and NR/WMS-NH₂ materials was investigated using a batch adsorption experiment. The adsorption was a chemical process in which the pseudo-second order kinetic model expressed the sorption kinetic data better than the pseudo first-order and Ritchie-second kinetic order model. In addition, the CFA adsorption sorption equilibrium data of the NR/WMS-NH₂ materials were fitted to the Langmuir isotherm model. The NR/WMS-NH₂ with 5% amine loading had the highest CFA adsorption capacity (6.29 mg g⁻¹). Full article

The Stöber version of a sol-gel method of co-condensation of two alkoxysilanes (structuring tetraethoxysilane (TEOS) and functionalising N-containing silane) in an ammonia medium was used for the one-pot synthesis of spherical silica particles with ≡Si(CH₂)₃NH₂, ≡Si(CH₂)₃NH(CH₂)₂NH₂, and ≡[Si(CH₂)₃NH]₂ functional groups with available groups content of 1.3–2.3 mmol/g. The materials were researched by a range of methods, including SEM, TEM, IR spectroscopy, ¹³C, and ²⁹Si solid-state NMR spectroscopy, acid-base titration, and thermal analysis to identify the peculiarities of the morphology, functional groups content, composition, and thermal resistance of the surface layers in the synthesised samples. The type of N-containing silane was shown to affect the structure and properties of the synthesised spherical particles. The silane with the simplest, 3-aminopropyl, functional group caused the formation of nonporous material composed of large 600–800 nm spherical microparticles. Meanwhile, the complication of functional groups enhanced the emergence of small 15 nm primary particles and the origination of porosity, generated by the slits between particles and particle agglomerates. Thereafter, the sorption properties of the synthesised hybrid materials for nickel(II) and copper(II)ions, and bovine serum albumin (BSA) were also found to be dependent on the structure of the materials and the type of incorporated functional group. The maximal static sorption capacity values towards the targeted adsorbates were shown by the samples with 3-aminopropyl groups (1.27 mmol Ni/g), diamine groups (1.09 mmol Cu/g), and secondary amine groups (204.6 mg BSA/g). The conducted research opens up the prospects of directed one-pot synthesis of amino-functionalised hybrid organosilica materials for different applications. Full article

Mesoporous silica SBA-15 was prepared via sol-gel synthesis and functionalized with different types of organosilanes containing various organic functional groups: (3-aminopropyl)triethoxysilane (SBA-15-NH₂), (3-mercaptopropyl)triethoxysilane (SBA-15-SH), triethoxymethylsilane (SBA-15-CH₃), triethoxyphenylsilane (SBA-15-Ph), and (3-isocynatopropyl)triethoxysilane (SBA-15-NCO). The prepared materials were investigated as drug delivery systems for naproxen. As model drugs, naproxen acid (HNAP) and its sodium salt (NaNAP) were used. Mentioned medicaments belong to the group of non-steroidal anti-inflammatory drugs (NSAIDs). The prepared materials were characterized by different analytical methods such as transmission electron microscopy (TEM), infrared spectroscopy (IR), nitrogen adsorption/desorption analysis (N₂), thermogravimetric analysis (TG), ¹H, ¹³C and ²³Na solid-state nuclear magnetic resonance spectroscopy (¹H, ¹³C and ²³Na ss-NMR). The abovementioned analytical techniques confirmed the successful grafting of functional groups to the SBA-15 surface and the adsorption of drugs after the impregnation process. The BET area values decreased from 927 m² g⁻¹ for SBA-15 to 408 m² g⁻¹ for SBA-15-NCO. After drug encapsulation, a more significant decrease in surface area was observed due to the filling of pores with drug molecules, while the most significant decrease was observed for the SBA-15-NH₂ material (115 m² g⁻¹ for NaNAP and 101 m² g⁻¹ for HNAP). By combining TG and nitrogen adsorption results, the occurrence of functional groups and the affinity of drugs to the carriers’ surface were calculated. The dominant factor was the volume of functional groups and intermolecular interactions. The highest drug affinity values were observed for phenyl and amine-modified materials (SBA-15-Ph = 1.379 μmol m⁻² mmol⁻¹ for NaNAP, 1.761 μmol m⁻² mmol⁻¹ for HNAP and SBA-15-NH₂ = 1.343 μmol m⁻² mmol⁻¹ for NaNAP, 1.302 μmol m⁻² mmol⁻¹ for HNAP) due to the formation of hydrogen bonds and π-π interactions, respectively. Drug release properties and kinetic studies were performed at t = 37 °C (normal human body temperature) in different media with pH = 2 as simulated human gastric fluid and pH = 7.4, which simulated a physiological environment. Determination of drug release quantity was performed with UV-VIS spectroscopy. The surface polarity, pH and naproxen form influenced the total released amount of drug. In general, naproxen sodium salt has a higher solubility than its acid form, thus significantly affecting drug release from surface-modified SBA-15 materials. Different pH conditions involved surface protonation and formation/disruption of intermolecular interactions, influencing both the release rate and the total released amount of naproxen. Different kinetic models, zero-order, first-order, Higuchi and Hixson–Crowell models, were used to fit the drug release data. According to the obtained experimental results, the drug release rates and mechanisms were determined. Full article

Heparin, usually isolated from porcine intestinal mucosa, is an active pharmaceutical ingredient of great material value. Traditionally, diverse types of commercial resins were employed as an adsorbent for heparin retrieval from biological samples. However, more recent years have encouraged the advent of new cost-effective adsorbents to achieve enhanced heparin retrieval. Inexpensive cationic ammonium-functionalized silica gels, monodispersed with larger surface area, porosity, and higher thermal stability, were chosen to evaluate the heparin recovery yield from porcine intestinal mucosa. We demonstrated that higher positively charged and less bulky quaternary modified silica gel (e.g., QDASi) could adsorb ~28% (14.7 mg g⁻¹) heparin from the real samples. In addition, we also determined suitable surface conditions for the heparin molecule adsorption by mechanistic studies and optimized different variables, such as pH, temperature, etc., to improve the heparin adsorption. This is going to be the first reported study on the usage of quaternary amine-functionalized silica gel for HEP uptake. Full article

In a sol–gel co-condensation, a mesoporous silica hybrid integrated with (3-mercaptopropyl)trimethoxysilane (TMPSH) was prepared and then reacted with allylamine via a post-surface functionalization approach. Approximately 15 mol% of TMSPSH was introduced into the mesoporous silica pore walls along with tetraethyl orthosilicate. The mercapto ligands in the prepared mesoporous silica pore walls were then reacted with allylamine (AM) to form the mercapto–amine-modified mesoporous silica adsorbent (MSH@MA). The MSH@MA NPs demonstrate highly selective adsorption of copper (Cu²⁺) ions (~190 mg/g) with a fast equilibrium adsorption time (30 min). The prepared adsorbent shows at least a five times more efficient recyclable stability. The MSH@MA NPs adsorbent is useful for selective adsorption of Cu²⁺ ions. Full article

Biofouling has destructive effects on shipping and leisure vessels, thus producing severe problems for marine and naval sectors due to corrosion with consequent elevated fuel consumption and higher maintenance costs. The development of anti-fouling or fouling release coatings creates deterrent surfaces that prevent the initial settlement of microorganisms. In this regard, new silica-based materials were prepared using two alkoxysilane cross-linkers containing epoxy and amine groups (i.e., 3-Glycidyloxypropyltrimethoxysilane and 3-aminopropyltriethoxysilane, respectively), in combination with two functional fluoro-silane (i.e., 3,3,3-trifluoropropyl-trimethoxysilane and glycidyl-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononylether) featuring well-known hydro repellent and anti-corrosion properties. As a matter of fact, the co-condensation of alkoxysilane featuring epoxide and amine ends, also mixed with two opportune long chain and short chain perfluorosilane precursors, allows getting stable amphiphilic, non-toxic, fouling release coatings. The sol–gel mixtures on coated glass slides were fully characterized by FT-IR spectroscopy, while the morphology was studied by scanning electron microscopy (SEM), and atomic force microscopy (AFM). The fouling release properties were evaluated through tests on treated glass slides in different microbial suspensions in seawater-based mediums and in seawater natural microcosms. The developed fluorinated coatings show suitable antimicrobial activities and low adhesive properties; no biocidal effects were observed for the microorganisms (bacteria). Full article

Atomistic level characterisation of external surface species of mesoporous silica nanoparticles (MSN) poses a significant analytical challenge due to the inherently low content of grafted ligands. This study proposes the use of HR-MAS NMR spectroscopy for a molecular level characterisation of the external surface of carbohydrate-functionalised nanoparticles. MSN differing in size (32 nm, 106 nm, 220 nm) were synthesised using the sol-gel method. The synthesised materials displayed narrow particle size distribution (based on DLS and TEM results) and a hexagonal arrangement of the pores with a diameter of ca. 3 nm as investigated with PXRD and N₂ physisorption. The surface of the obtained nanoparticles was functionalised with galactose and lactose using reductive amination as confirmed by FTIR and NMR techniques. The functionalisation of the particles surface did not alter the pore architecture, structure or morphology of the materials as confirmed with TEM imaging. HR-MAS NMR spectroscopy was used for the first time to investigate the structure of the functionalised MSN suspended in D₂O. Furthermore, lactose was successfully attached to the silica without breaking the glycosidic bond. The results demonstrate that HR-MAS NMR can provide detailed structural information on the organic functionalities attached at the external surface of MSN within short experimental times. Full article

Poly(2,6-dimethyl-1,4-phenylene oxide)/polyamide 11 (PPO/PA11 80/20) blend filled with neat (SiO₂) or modified silica having amine functional groups (A-SiO₂) was melt mixing in a twin-screw extruder. The silica was prepared by the sol–gel process. SEM shows that, with increasing A-SiO₂ content from 1 to 5 wt.%, the morphology of PPO/PA11blend changed from droplet matrix to co-continuous with phase inversion. The phase inversion was also observed for 5 wt.% of neat silica, but the droplet-matrix structure was retained. The overall rheological and mechanical properties improvement of the A-SiO₂-filled composites in comparison with the unfilled blend and neat silica counterpart was drastic, especially in terms of viscosity and stiffness. A-SiO₂ improved PPO and PA11 miscibility and reduced the crystallinity of PA11, without affecting the T_c, owing to the compatibilization effect. On the other hand, neat silica slightly increased the crystallinity of PA11 and decreased the crystallization temperature of PA11 and the glass transition temperature of PPO as a result of its plasticization. Full article

Amine modified nano-silica was prepared via a one-pot route and under very mild conditions in water in oil microemulsion with a non-ionic surfactant to study the effect of changing the amount of N-[3-(Trimethoxysilyl)propyl]ethylenediamine (DA) added to the synthesis mixture on the characteristics of the obtained nanocomposite such as morphology, crystallinity, surface charge, particle size, surface area, and accordingly the effect of all of these factors on the efficiency of the nanocomposite for the removal of heavy metal ions, namely zinc, from aqueous solutions. XRD, SEM, TGA, BET, DLS, FTIR, and pH₀ analysis were performed for samples and the results showed a strong effect for the amount of DA added to the synthesis mixture on the characteristics of the obtained nanocomposites. It was found that increasing the amount of DA added to the synthesis mixture increased the pH₀, hydrodynamic particle size obtained by dynamic light scattering analysis, and the particle size obtained by SEM. Sample prepared without the addition of DA (SNP) and the samples prepared with 1.5 mL of DA (SNP-1.5DA) showed a better adsorption performance compared to the samples prepared with 0.5 and 1.0 mL of DA (SNP-0.5DA and SNP-1.0DA, respectively). The main factor affecting the adsorption efficiency was found to be the available surface area for each nanocomposite, which was directly related to the degree of crystallinity as obtained by XRD analysis. Full article

Hybrid materials, with applications in fuchsine B color removal from wastewaters, were obtained by in situ incorporation of platinum nanoparticles and/or Pt-porphyrin derivatives into silica matrices. The inorganic silica matrices were synthesized by the sol-gel method, conducted in acid-base catalysis in two steps and further characterized by Nitrogen porosimetry, Small Angle Neutron Scattering (SANS), Scanning electron microscopy, Atomic force microscopy and UV-vis spectroscopy. All of the investigated silica hybrid materials were 100% efficient in removing fuchsine B if concentrations were lower than 1 × 10⁻⁵ M. For higher concentrations, the silica matrices containing platinum, either modified with Pt-metalloporphyrin or with platinum nanoparticles (PtNPs), are the most efficient materials for fuchsine B adsorption from wastewaters. It can be concluded that the presence of the platinum facilitates chemical interactions with the dye molecule through its amine functional groups. An excellent performance of 197.28 mg fuchsine B/g adsorbent material, in good agreement with the best values mentioned in literature, was achieved by PtNPs-silica material, capable of removing the dye from solutions of 5 × 10⁻⁴ M, even in still conditions. Full article