Search Results (87)

Siloxane bond formation represents a fundamental reaction central to both silicone chemistry and its technological applications. This paper presents a novel ketone-assisted process for the condensation of alkoxy-functional silanes catalyzed by a cationic Ge(II) complex stabilized by pentamethylcyclopentadiene Cp*Ge(II)⁺. This process leads to the formation of siloxane bonds, with dialkoxy ketal as a byproduct. Unlike the analogous reaction involving aldehydes, the ketone-assisted process is reversible, resulting in the formation of a mixture of alkoxy-functionalized silane or siloxane, along with the corresponding disiloxane product. Additionally, the introduced ketone underwent only partial conversion to the corresponding ketal. Furthermore, it was demonstrated that the siloxane bond could be cleaved to form alkoxysilane in the presence of the ketal and a cationic Cp*Ge(II) complex acting as a catalyst. Full article

In the present study, we synthesized fluorocarbon-coated cobalt ferrite (CoFe₂O₄) magnetic nanoparticles using alkoxysilanes such as trimethoxy(3,3,3-trifluoropropyl)silane (TFPTMS), trimethoxy(1H,1H,2H,2H-nonafluorohexyl)silane (NFHTMS), and triethoxy(1H,1H,2H,2H-perfluorodecyl)silane (PFDTES). The synthesized nanoparticles were characterized by various techniques, including X-ray diffractometry (XRD), transmission electron microscopy (TEM/HRTEM/EDXS), Fourier transform infrared spectroscopy (FTIR), specific surface area measurements (BET), and magnetometry (VSM). To understand their surface characteristics, contact angle (CA) measurements were carried out, providing valuable insights into their hydrophobic properties. Among the samples of CoFe₂O₄ coated with fluoroalkoxysilanes, those with PFDTES surface coating had the highest water contact angle of 159.2°, indicating their superhydrophobic character. The potential of the prepared fluoroalkoxysilane-coated CoFe₂O₄ nanoparticles for the removal of waste low-SAPS synthetic engine oil from a model aqueous solution was evaluated based on three key parameters: adsorption efficiency (%), adsorption capacity (mg/g), and desorption efficiency (%). All synthesized CoFe₂O₄ samples coated with fluoroalkoxysilane showed high oil adsorption efficiency, ranging from 87% to 98%. The average oil adsorption capacity for the samples was as follows: F₃-SiO₂@CoFe₂O₄ (3.1 g of oil/g of adsorbent) > F₉-SiO₂@CoFe₂O₄ (2.7 g of oil/g of adsorbent) > F₁₇-SiO₂@CoFe₂O₄ (1.5 g of oil/g of adsorbent) as a result of increasing oleophobicity with increasing fluorocarbon chain length. The desorption results, which showed 77–97% oil recovery, highlighted the possibility of reusing the adsorbents in multiple adsorption/desorption cycles. Full article

Organic electron donors are essential components of Ziegler-Natta (ZN) catalysts to produce isotactic polypropylene. In particular, aromatic or aliphatic diesters are widely used as ‘Internal Donors’ (ID) in MgCl₂/ID/TiCl₄ precatalyst formulations. Diesters are reactive with AlEt₃ (by far the most common ZN precatalyst activator) and are partly removed from the solid phase in the early stages of the polymerization process; this is detrimental for catalyst functioning, and a surrogate donor (‘External Donor’ (ED), usually an alkoxysilane) is added to the system to restore performance. Recent studies, however, demonstrated that even in cases where most of the diester is extracted by AlEt₃, the active sites retain a ‘memory’ of it in several aspects of the catalytic behavior (such as, e.g., the average productivity and the polydispersity index of the polymer produced). Considering that the residual diester is always in molar excess with respect to the active Ti, one may speculate that long-lasting interactions between the latter and diester molecules can occur. In turn, this should imply that the reactivity of AlEt₃ is different with binary MgCl₂/ID or ternary MgCl₂/ID/TiCl₄ mixtures. In this work, the latter hypothesis was explored for a library of diester IDs with large structural diversity. In line with the anticipation, the fractional amount of ID extracted by AlEt₃ was generally lower for ternary mixtures, although to an extent exquisitely dependent on diester structure. Full article

The synthesis and characterization of the tripodal phosphines RSi(CH₂CH₂PPh₂)₃ (R = Me, OMe, OEt) (1–3) is described. The ¹H NMR spectra of all phosphines display virtual coupling patterns. The ligands form the corresponding trinuclear Pd complexes [RSi(CH₂CH₂PPh₂)₃]₂(PdCl₂)₃ (4–6) with three PdCl₂ moieties sandwiched between two tripodal ligands. The complexes 4, 5, and 7 (R = OH) have been analyzed by single crystal X-ray diffraction. The coordination at the Pd center is square planar with the phosphine groups occupying trans positions. The ³¹P{¹H} MAS NMR spectra of polycrystalline 1 are in accordance with the packing motif of the molecules in the unit cell. The tripodal ligand 3 has successfully been immobilized on silica as 3i. It coordinates PdCl₂ on the surface, as demonstrated by ³¹P{¹H} MAS NMR. Hereby, the cis coordination is prevalent when 3i has maximal surface coverage. At low surface coverage, one tripodal linker can accommodate trans coordination at the metal center. A surface-bound trinuclear Pd complex has been generated, as well as a heterobimetallic Pd/Cu complex. All surface species have been characterized by ³¹P{¹H} MAS NMR. Full article

The formation of the siloxane bond is one of the most important reactions used in silicone chemistry and technology. In this paper, a new process for the condensation of alkoxy-functional silanes to form a siloxane bond is presented. The new reaction is catalyzed by a Ge(II)⁺ complex stabilized by pentamethylcyclopentadiene with a weakly coordinated anion, tetrakis(pentafluorophenyl)borane. A mechanistic study of this new condensation process using model alkoxy-functional silanes and propionaldehyde is completed. It is established that the quantitative conversion of alkoxysilanes to the siloxane bond requires stoichiometric amounts of aldehyde. It is also found that paraldehyde can serve as a convenient, higher boiling source of acetaldehyde for the condensation of alkoxysilanes. The results obtained, supported by DFT calculations, allow for us to formulate the mechanism of this reaction. Full article

Silica fillers have been a cornerstone in chemical technology due to their versatility, availability, and ease of integration into various formulations. Recent advancements, including chlorine-free synthesis of alkoxysilanes, have paved the way for alternative materials like polymethylsilsesquioxane (PMSSO). This study explores the structural evolution and properties of a hydrophobic PMSSO xerogel, synthesized through hydrolytic polycondensation of methyltriethoxysilane (MTEOS). PMSSO exhibits exceptional hydrophobicity, high specific surface area, and compatibility with polymer matrices, making it a promising filler for applications in rubber products, lubricants, and cosmetics. We developed a straightforward synthesis method for producing PMSSO xerogel that avoids toxic solvents and organochlorosilanes, ensuring safety and sustainability. The reaction conditions, particularly the amount of alkali and neutralization parameters, were found to significantly influence the properties of the final xerogels, such as specific surface area. Optimization of the synthesis parameters allow for obtaining PMSSO xerogels with a specific surface area about 600 m²/g. These findings underscore PMSSO’s potential as a versatile, eco-friendly alternative to conventional silica fillers, offering tailored properties for diverse industrial applications. Full article

Molecularly imprinted polymers (MIPs) are defined as artificial receptors due to their selectivity and specificity. Their advantageous properties compared to biological alternatives have sparked interest among scientists, as detailed in numerous review papers. Currently, there is significant attention on adhering to the principles of green chemistry and environmental protection. In this context, MIP research groups have focused on developing eco-friendly procedures. The application of “greener” monomers and reagents, along with the utilization of computational methodologies for design and property analysis, are two activities that align with the green chemistry principles for molecularly imprinted technology. This review discusses the application of computational methodologies in the preparation of MIPs based on eco-friendly non-acrylic/vinylic monomers and precursors, such as alkoxysilanes, ionic liquids, deep eutectic solvents, bio-based molecules—specifically saccharides, and biomolecules like proteins. It provides a brief introduction to MIP materials, the green aspects of MIP production, and the application of computational simulations. Following this, brief descriptions of the studied monomers, molecular simulation studies of green monomer-based MIPs, and computational strategies are presented. Finally, conclusions and an outlook on the future directions of computational analysis in the production of green imprinted materials are pointed out. To the best of my knowledge, this work is the first to combine these two aspects of MIP green chemistry principles. Full article

Eugenol-containing oligoorganosilsesquioxanes were synthesized by the method of hydrolytic polycondensation in an active medium under various reaction conditions. The obtained products were characterized by ²⁹Si NMR spectroscopy and MALDI-TOF spectrometry. It was shown that factors such as the reaction temperature, polycondensation duration, and molar ratio between the initial alkoxysilane monomer and acetic acid may affect the molecular weight characteristics and molecular structure of the formed oligomer, like the content of stressed cyclic units (T₃, DTT, TDT) and unstressed silsesquioxane units T_nD_m. In particular, an increase in the ratio of the initial reagents led to an increase in the content of silsesquioxane T_n fragments from 28.2%_mol to 41.7%_mol, while the number of strained cyclic structures decreased by more than two times. An increase in the synthesis time is of no particular practical value since it was found that the composition of the oligomers synthesized for 6 h and 12 h was practically identical, as was that of the oligomers synthesized for 24 h and 48 h. A noticeable transition in the oligomer composition was observed only when the synthesis time was changed from 12 h to 24 h. Finally, it was shown that the choice of synthesis temperature had the strongest effect on the oligomer composition. The oligomer synthesized at 95 °C contained the highest amount of silsesquioxane T_n fragments, >77%_mol, while a T_n fragment content of ~42%_mol was observed during the synthesis at 117 °C. It was shown that silsesquioxanes are devitrified at room temperature (T_g from −6.4 to −10.6 °C), and their thermal stability in an inert atmosphere is 300 °C. The synthesized oligomers, due to the presence of hydroxyl-containing eugenol units, may be promising binders and additives for functional epoxy–silicone paints and coating materials. Full article

Automakers are focusing on lightweight vehicles to address fuel economy and emission challenges and are using high-performance materials such as 2K PU-based joints as alternatives to cast iron, steel, and other metals. This study was conducted with the aim of expanding the application of 2K PU and enhancing its compatibility with steel substrates, which are commonly used in the automotive manufacturing industry, through the use of O-I hybrid nanoparticles containing alkoxysilane groups as additives in the 2K PU formulation. At the same time, the simplified process introduced and examined in this study demonstrates its feasibility for industrial-scale applications; the process offers notable advantages in reducing workload and curing time by eliminating cumbersome surface pretreatment steps before applying the 2K PU layer. Two types of commercial SB PU and EB PU were selected to study the mechanism by which O-I hybrid NPs enhance adhesion when integrated directly into the 2K PU formulation. We optimized various input parameters through practical work and modeling using the response surface method. These parameters included the amounts of AFAP precursor, APTES, and butylene glycol (BG) and the mixing ratio of O-I hybrid NPs in the formulations of two commercial PUs. The results show that O-I hybrid NPs significantly enhance adhesion, increasing performance on stainless surfaces by up to 2.35 times compared to pristine EB and SB PU. Notably, the SB PU’s performance can improve up to 2.5 times according to the RSM predictions, highlighting the substantial impact of O-I hybrid NPs. Full article

Layered Ti₃C₂T_x MXene has been successfully intercalated and exfoliated with the simultaneous generation of a 3D silica network by treating its cationic surfactant intercalation compound (MXene-CTAB) with an alkoxysilane (TMOS), resulting in a MXene–silica nanoarchitecture, which has high porosity and specific surface area, together with the intrinsic properties of MXene (e.g., photothermal response). The ability of these innovative MXene silica materials to induce thermal activation reactions of previously adsorbed compounds is demonstrated here using NIR laser irradiation. For this purpose, the pinacol rearrangement reaction has been selected as a first model example, testing the effectiveness of NIR laser-assisted photothermal irradiation in these processes. This work shows that Ti₃C₂T_x-based nanoarchitectures open new avenues for applications that rely on the combined properties inherent to their integrated nanocomponents, which could be extended to the broader MXene family. Full article

Degradation of ester-based polyurethane (PUR) foams results in extensive fragmentation, stickiness, and brittleness both at surfaces and in the bulk. Current methods to conserve museum objects comprising PUR foams include consolidation with solvent-based polymeric solutions. Besides the limitations of spray and brush application for deep consolidant penetration and the impracticality of immersing large-scale objects in solutions, these methods often require large amounts of toxic solvents that are harmful for both the user and environment. Carbon dioxide can be employed as a green solvent as it can be recovered, recycled, and reused without contributing to the greenhouse effect. Supercritical carbon dioxide (scCO₂)-assisted consolidation premises are that it may carry the consolidant deeper and deposit it consistently throughout the foam, whilst ensuring minimal interaction with the surface and avoiding material losses in severely degraded objects and the use of toxic solvents. The suitability of scCO₂ as a carrier is studied, and the results compared with spray application, a commonly used traditional method. Previous studies have shown that a mixture of alkoxysilanes has great potential for reinforcing the foam’s structure and hydrophobicity when applied by immersion and other impregnation techniques. In this study, scCO₂-assisted consolidation has proven to be an effective and green alternative to consolidation by spray, reducing hazardous solvent emissions. After treatment, no visual changes were detected, the samples became less sticky, and the foam flexibility improved significantly. Analytical techniques confirmed the presence of the consolidant in all tested samples, both on the top surface and in-depth layers, in contrast to foams treated by spray. Full article

The current study reports on the impact of a series of functional alkoxysilanes on the wettability and structure of a well-established silicon/zirconium hybrid anticorrosion sol–gel coating. The selected functional alkoxysilanes comprise tetra ethylorthosilicate (TEOS), 3-glycidyloxypropyltrimethoxysilane (GPTMS), 3-aminopropyltriethoxysilane (APTES) and vinyltriethoxysilane (VTES) and are incorporated at various concentrations (1, 5, 10 and 20%) within the silicon/zirconium sol–gel material. The prepared materials are successfully processed as coatings and cured at different temperatures in the range of 100–150 °C. The characterisation of the structures and surfaces is performed by dynamic light scattering (DLS), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), silicon nuclear magnetic resonance spectroscopy (²⁹Si-NMR), atomic force microscopy (AFM) and static water contact angle (WCA). Structural characterisations (DLS, FTIR,²⁹Si-NMR) show that the functional alkoxysilanes effectively bind at the surface of the reference sol–gel material, resulting in the formation of functional core–shell nanoparticles. WCA results show that the hydrophobic properties of all materials decrease with curing temperature, and AFM analysis demonstrated that this behaviour is associated with a decrease in roughness. The physico-chemical processes taking place are critically assigned and discussed. Full article

The search for improved transducers to fabricate better-performing (bio)sensors is a challenging but rewarding endeavor aiming to better diagnose and treat diseases. In this paper, we report on the decoration of a dense vertical array of ultrathin silicon nanowires (Si NWs), produced by metal-assisted chemical etching, with 20 nm gold nanoparticles (Au NPs) for surface-enhanced Raman scattering (SERS) applications. To optimize the production of a uniform 3D SERS active platform, we tested different Si NW surface functionalizations with various alkoxysilanes before Au decoration. Scanning electron microscopy investigations confirm that Au NPs decorate both bare and (3-glycidiloxypropyl)trimethoxysilane (GPTMS)-modified Si NWs with a high surface coverage uniformity. The SERS response of the decorated NWs was probed using a model dye system (methylene blue; MB) at 633 and 785 nm excitation wavelengths. The GPTMS-modified NWs present the highest enhancements of 2.9 and 2.6 for the 450 cm⁻¹ and 1625 cm⁻¹ peaks under 785 nm excitation and of 10.8 and 5.3 for the 450 cm⁻¹ and 1625 cm⁻¹ peaks under 633 nm excitation. These results demonstrate the perspective role of Si NWs decorated with Au NPs as a low-cost 3D SERS platform. Full article

In this work, a computational spectroscopy approach was used to provide a complete assignment of the inelastic neutron scattering spectra of three title alkoxysilane derivatives—3-aminopropyltrimethoxysilane (APTS), N-methyl-3-aminopropyltrimethoxysilane (MAPTS), and 3-aminopropyltriethoxysilane (APTES). The simulated spectra obtained from density functional theory (DFT) calculations exhibit a remarkable match with the experimental spectra. The description of the experimental band profiles improves as the number of molecules considered in the theoretical model increases, from monomers to trimers. This highlights the significance of incorporating non-covalent interactions, encompassing classical NH···N, N–H···O, as well as C–H···N and C–H···O hydrogen bond contacts, to achieve a comprehensive understanding of the system. A distinct scenario emerges when considering optical vibrational techniques, infrared and Raman spectroscopy. In these instances, the monomer model provides a reasonable description of the experimental spectra, and no substantial alterations are observed in the simulated spectra when employing dimer and trimer models. This observation underscores the distinctive ability of neutron spectroscopy in combination with DFT calculations in assessing the structure and dynamics of molecular materials. Full article

Gold nanoclusters (AuNCs) with fluorescence in the Near Infrared (NIR) by both one- and two-photon electronic excitation were incorporated in mesoporous silica nanoparticles (MSNs) using a novel one-pot synthesis procedure where the condensation polymerization of alkoxysilane monomers in the presence of the AuNCs and a surfactant produced hybrid MSNs of 49 nm diameter. This method was further developed to prepare 30 nm diameter nanocomposite particles with simultaneous NIR fluorescence and superparamagnetic properties, with a core composed of superparamagnetic manganese (II) ferrite nanoparticles (MnFe₂O₄) coated with a thin silica layer, and a shell of mesoporous silica decorated with AuNCs. The nanocomposite particles feature NIR-photoluminescence with 0.6% quantum yield and large Stokes shift (290 nm), and superparamagnetic response at 300 K, with a saturation magnetization of 13.4 emu g⁻¹. The conjugation of NIR photoluminescence and superparamagnetic properties in the biocompatible nanocomposite has high potential for application in multimodal bioimaging. Full article