Insights into emulsion synthesis of self-assembled suprastructures formed by Janus silica particles with -NH2/-SH surface groups.

Spherical particles with tunable anisotropic structures enabled by multiple surface functionalities have garnered interest for their potential applications in adsorption technologies. The presence of diverse functional groups in the surface layer, exhibiting varying acidity and hydrophilicity, can lead to unique characteristics in terms of surface structure and behaviour. In this study, the particles were synthesised using a two-step approach involving surface functionalisation of previously synthesised SiO2 Stöber particles. This was achieved by employing 3-mercaptopropyltrimethoxysilane (MPTMS) and 3-aminopropyltrimethoxysilane (APTMS) in a toluene-in-water emulsion. The resulting particles were found to be nonporous, with a specific surface area of 8 m2 g-1. Their sizes were determined to be up to 350 nm through photon cross-correlation spectroscopy. Moreover, the particles exhibited a high net content of functional groups (both amino and mercapto) of 2 mmol g-1. The organisation of the particles during synthesis was observed through SEM images, providing insights into their structural characteristics. Additionally, the study of Eu(iii), Au(iii), and Ag(i) ions and fluorescein adsorption demonstrated varying interactions on the surface, highlighting the potential applications and versatility of these functionalised particles.

Diverse Pathway to Obtain Antibacterial and Antifungal Agents Based on Silica Particles Functionalized by Amino and Phenyl Groups with Cu(II) Ion Complexes.

Production of environmentally friendly multitasking materials is among the urgent challenges of chemistry and ecotechnology. The current research paper describes the synthesis of amino-/silica and amino-/phenyl-/silica particles using a one-pot sol-gel technique. CHNS analysis and titration demonstrated a high content of functional groups, while scanning electron microscopy revealed their spherical form and ∼200 nm in size. X-ray photoelectron spectroscopy data testified that hydrophobic groups reduced the number of water molecules and protonated amino groups on the surface, increasing the portion of free amino groups. The complexation with Cu(II) cations was used to analyze the sorption capacity and reactivity of the aminopropyl groups and to enhance the antimicrobial action of the samples. Antibacterial activities of suspensions of aminosilica particles and their derivative forms containing adsorbed copper(II) ions were assayed against Gram-positive (Staphylococcus aureus ATCC 25923) and Gram-negative bacteria (Escherichia coli ATCC 25922 and Pseudomonas aeruginosa ATCC 27853). Meanwhile, antifungal activity was tested against fungi (Candida albicans UCM Y-690). According to zeta potential measurements, its value could be depended on the suspension concentration, and it was demonstrated that the positively charged suspension had higher antibacterial efficiency. SiO2/-C6H5/-NH2 + Cu(II) sample's water suspension (1%) showed complete growth inhibition of the bacterial culture on the solid medium. The antimicrobial activity could be due to occurrence of multiple and nonspecific interactions between the particle surfaces and the surface layers of bacteria or fungi.

Protection of Thiol Groups on the Surface of Magnetic Adsorbents and Their Application for Wastewater Treatment.

The magnetite nanoparticles were functionalized with silica shells bearing mercaptopropyl (monofunctional) and mercaptopropyl-and-alkyl groups (bifunctional) by single-step sol-gel technique. The influence of synthetic conditions leading to increased amounts of active functional groups on the surface and improved capacity in the uptake of Ag(I), Cd(II), Hg(II), and Pb(II) cations was revealed. The physicochemical properties of obtained magnetic nanocomposites were investigated by FTIR, Raman, XRD, TEM, SEM, low-temperature nitrogen ad-/desorption measurements, TGA, and chemical microanalysis highlighting the efficiency of functionalization and mechanisms of the preparation procedures. The removal of the main group of heavy metal cations was studied in dependence from the pH, contact time and equilibrium concentration to analyze the complexes composition for the large scale production of improved adsorbents. It was demonstrated that introduction of the alkyl groups into the surface layer prevents the formation of the disulfide bonds between adjacent thiol groups. The obtained adsorbents were employed to treat real wastewater from Ruskov, Slovakia with concentration of Fe 319 ng/cm3, Cu 23.7 ng/cm3, Zn 36 ng/cm3, Mn 503 ng/cm3, Al 21 ng/cm3, As 34 ng/cm3, Pb 5.8 ng/cm3, Ni 35 ng/cm3, Co 4.2 ng/cm3, Cr 9.4 ng/cm3, Sb 6 ng/cm3, Cd 5 ng/cm3. These materials proved to be highly effective in the removal of 50% of all metal ions, espeсially Zn, Cd, and Pb ions from it and turned recyclable, opening for their sustainable use in water purification.

Sol-Gel Derived Adsorbents with Enzymatic and Complexonate Functions for Complex Water Remediation.

Sol-gel technology is a versatile tool for preparation of complex silica-based materials with targeting functions for use as adsorbents in water purification. Most efficient removal of organic pollutants is achieved by using enzymatic reagents grafted on nano-carriers. However, enzymes are easily deactivated in the presence of heavy metal cations. In this work, we avoided inactivation of immobilized urease by Cu (II) and Cd (II) ions using magnetic nanoparticles provided with additional complexonate (diethylene triamine pentaacetic acid or DTPA) functions. Obtained nanomaterials were characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). According to TGA, the obtained Fe3O4/SiO2-NH2-DTPA nanoadsorbents contained up to 0.401 mmol/g of DTPA groups. In the concentration range Ceq = 0-50 mmol/L, maximum adsorption capacities towards Cu (II) and Cd (II) ions were 1.1 mmol/g and 1.7 mmol/g, respectively. Langmuir adsorption model fits experimental data in concentration range Ceq = 0-10 mmol/L. The adsorption mechanisms have been evaluated for both of cations. Crosslinking of 5 wt % of immobilized urease with glutaraldehyde prevented the loss of the enzyme in repeated use of the adsorbent and improved the stability of the enzymatic function leading to unchanged activity in at least 18 cycles. Crosslinking of 10 wt % urease on the surface of the particles allowed a decrease in urea concentration in 20 mmol/L model solutions to 2 mmol/L in up to 10 consequent decomposition cycles. Due to the presence of DTPA groups, Cu2+ ions in concentration 1 µmol/L did not significantly affect the urease activity. Obtained magnetic Fe3O4/SiO2-NH2-DTPA-Urease nanocomposite sorbents revealed a high potential for urease decomposition, even in presence of heavy metal ions.

Tailoring bifunctional hybrid organic-inorganic nanoadsorbents by the choice of functional layer composition probed by adsorption of Cu2+ ions.

Spherical silica particles with bifunctional (≡Si(CH2)3NH2/≡SiCH3, ≡Si(CH2)3NH2/≡Si(CH2)2(CF2)5CF3) surface layers were produced by a one-step approach using a modified Stöber method in three-component alkoxysilane systems, resulting in greatly increased contents of functional components. The content of functional groups and thermal stability of the surface layers were analyzed by diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, and 13C and 29Si solid-state NMR spectroscopy revealing their composition and organization. The fine chemical structure of the surface in the produced hybrid adsorbent particles and the ligand distribution were further investigated by electron paramagnetic resonance (EPR) and electron spectroscopy of diffuse reflectance (ESDR) spectroscopy using Cu2+ ion coordination as a probe. The composition and structure of the emerging surface complexes were determined and used to provide an insight into the molecular structure of the surfaces. It was demonstrated that the introduction of short hydrophobic (methyl) groups improves the kinetic characteristics of the samples during the sorption of copper(II) ions and promotes fixation of aminopropyl groups on the surface of silica microspheres. The introduction of long hydrophobic (perfluoroctyl) groups changes the nature of the surface, where they are arranged in alternately hydrophobic/hydrophilic patches. This makes the aminopropyl groups huddled and less active in the sorption of metal cations. The size and aggregation/morphology of obtained particles was optimized controlling the synthesis conditions, such as concentrations of reactants, basicity of the medium, and the process temperature.

Magneto-Sensitive Adsorbents Modified by Functional Nitrogen-Containing Groups.

In order to obtain amino-functionalized silica materials with magnetic core, one-step synthesis was carried out. Several materials, differ in number and structure of amino groups, were synthesized on the basis of sol-gel method. The synthesized materials were examined by several analytical techniques. The presence and content of amino groups were measured by using Diffuse Reflectance Infrared Fourier Transform (DRIFT) spectroscopy and acid-base titration, respectively. Specific surface areas were measured by nitrogen/adsorption desorption isotherms. It was proved that sol-gel approach leads to obtain materials with high content of amino groups built into their surfaces (in the range 1.6-2.7 mmol/g). As-obtained materials were tested as potential adsorbents for copper(II) ions. The received maximum adsorption capacities were in the range 0.4-0.7 mmol/g.

Mesoporous silica containing ≡Si(CH2)3NHC(S)NHC2H5 functional groups in the surface layer.

One-step synthesis technique of mesoporous SBA-15 type silica with thiourea ≡Si(CH(2))(3)NHC(S)NHC(2)H(5) groups in the surface layer was developed. According to elemental analysis, the content of surface groups is 1.25 mmol/g, which is consistent with TGA data. FT-IR spectra of the obtained sample contain characteristic absorption bands of thiourea groups (-NH-C(S)-NH-), as well as polysiloxane network (SiOSi). The synthesized sample was studied by XRD, TEM, SEM, and adsorption method. It was demonstrated that the sample features porous microspheres ~0.5 µm with well-ordered internal spatial structure of the hexagonal lattice type due to the usage of template P123 during synthesis. According to XRD and TEM, the diameter of pores is 4.2-5 nm and the wall thickness between them is 2.6 nm. These data are consistent with the structural-adsorption characteristics calculated from nitrogen adsorption-desorption isotherms: S(sp.)=510 m(2)/g, V(s)=0.47 cm(3)/g, and d=4.3 nm. Equilibrium is established within 60 min during sorption of silver(І) and mercury(ІІ) ions from acidified aqueous solutions for this sample, and with the complexes are formed 1.1/1 for Ag(+) and 0.8/1 for Hg(2+) at metal/ligand ratio.