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A high-efficiency biosorbent based on the low-priced jute fiber was developed, characterized, and applied to remove the emerging organic contaminant diclofenac from aqueous solutions. Jute fiber was treated by NaOH (named AJF) followed by grafting different amounts of trimethyl[3-(trimethoxysilyl) propyl] ammonium chloride (named AJF-TTSAC). The composition, morphology, porosity, and adsorption features of the neat and modified jute fiber were evaluated and compared. The surface of neat JF was smooth, nonporous, and free of cracks. NaOH treatment increased the fibrillation, created cracks and grooves, and increased the oxygen content, total pore volume, and surface area. In comparison to AJF, grafting TTSAC filled in the crevices, grooves, and spaces between fibrillates, and decreased the total pore volume and surface area. The adsorption of diclofenac by the neat and modified JF occurred at highly acidic pHo and peaked at pHo 3. Among the neat and modified JF, AJF-TTSAC5 was the most efficient followed by AJF. The efficiency of AJF and AJF-TTSAC5 was highest using 1.00 g/L, at 35 °C and was not affected by the presence of NaCl. The Elovich, pseudo-first-order, and pseudo-second-order models described the adsorption kinetic satisfactorily with the marginal advantage of Elovich for AJF and pseudo-second-order for AJF-TTSAC5. The isotherm study exposed the multilayer and physisorption nature of the adsorption of diclofenac onto AJF and AJF-TTSAC5. The Langmuir monolayer saturation capacity of AJF-TTSAC5 was 37.43 mg/g which revealed its great potential relative to other adsorbents in the literature. The AJF and AJF-TTSAC5 were easily regenerated using distilled water and kept good performance for 5 repetitive cycles. [ABSTRACT FROM AUTHOR]

This article analyzes the effect of the type of surface modification (using silane coupling agents and dicarboxylic acids) on titanium dioxide particles used as fillers in polylactic acid composites, which were exposed to a photodegradative process. The thermomechanical properties of the composites were analyzed; it was found that the silane coupling agent with Imidazole allowed the composites to have Young’s modulus values 60% lower than the composite without filler. On the other hand, the crystallization rate was 30% higher for composites with azelaic Acid attached to TiO2 particles than for composites without filler at a cooling rate of 5°C min−1. Once degraded composites containing azelaic acid were the least brittle, with a minor increment in Young’s Modulus compared to pure polylactic acid composites. When a mixture of modified titanium dioxide particles (with imidazole and either azelaic acid or pimelic acid) was used, there was a synergistic effect regarding photostability. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

• Materials conservation utilizes alkoxysilanes with VOC's. • Sonocatalysis creates eco-friendlier, water-based inorganic sonogels. • Water reduces gelling time and affects gel rate deposition in miscible mixtures. • Sonogels are capable to enhance stone hardness and depth resistance of stone. • Potential for inorganic-organic sonogels with dual-roles (protection and consolidation). Products designed to form continuous inorganic networks from alkoxysilanes frequently include organic solvents because of the necessity to turning the precursors miscible with water and because dilution is required for certain applications. Thus, there is a demand for efficient mixtures employing eco-design strategies. This study explores the feasibility of sonocatalysis to prepare homogeneous mixtures with water to initiate sol-gel reactions and as the dilution agent. The approach allowed to design and prepare viable mixtures with unique tetraethoxysilane(TEOS):H2O ratios (1:4 to 1:32). By managing the ultrasonic irradiation parameters, it was possible to formulate mixtures with high degree of hydrolysis, appropriate condensation ratios, and capable to create sonogel materials containing other desired features for stone conservation. The water content manages the gelling times and gel deposition rates through a dilution effect, which might be useful to minimize undesirable side effects of conservation treatments, such as excessive pore occlusion. For instance, a TEOS:H2O ratio of 1:32 results in a very low gel deposition rate. Furthermore, the applicability and efficacy of successful mixtures was preliminary assessed, and it was demonstrated that the resulting inorganic networks, primarily composed of Si O Si bonds, can enhance the hardness and surface resistance of soft stones. This potential strengthening effect improves gradually with increasing TEOS:H2O ratios. The mixtures deserve further studies aimed at enhancing understanding of their consolidation characteristics. The advances achieved also opens the door for producing innovative dual-role hybrid inorganic-organic sonogels that can be used for materials protection and surface consolidation. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

A yellow-emitting cationic iridium(III) complex [(dfppy)2Ir(TBD)]PF6 (TBD: N4,N4′-bis(3-(triethoxysilyl)propyl)-[2,2′-bipyridine]-4,4′-dicarboxamide; dfppy: 2-(2,4-difluorophenyl)pyridine) containing hydrolysable alkoxysilanes was synthesized. Then, a series of silica-based hybrid nanospheres with diameters of around 400 nm was prepared via the hydrolysis of this complex together with tetraethyl orthosilicate (TEOS, a silica source). When the amount of the complex used was 5.0 wt%, hybrid nanospheres showed the best photoluminescence (PL) properties, relative to the PL quantum yield of pure solid [(dfppy)2Ir(TBD)]PF6 (12.7%), that of hybrid nanospheres increased to 26.2%. Moreover, the thermal decomposition temperature (Td) of pure solid [(dfppy)2Ir(TBD)]PF6 was 331 °C, the Td of the complex in hybrid nanospheres increased to 447 °C. However, the yellow light emission was almost unchanged and was still located at 500–750 nm with a maximum wavelength (λem,max) of 577 nm. Under the excitation of blue-emitting chips (λem,max ≈ 455 nm), cold/neutral/warm white light-emitting diodes (WLEDs) with good luminous quality can all be fabricated using these hybrid nanospheres as phosphors in epoxy resin at different blending concentrations. Compared with two or three iridium(III) complexes being contained in silica-based particles as phosphors as described in literatures, in this study, silica-based hybrid nanospheres covalently containing only one yellow-emitting cationic iridium(III) complex as phosphors provide a more effective and simpler method for preparation high-performance WLEDs. [ABSTRACT FROM AUTHOR]

A low palladium‐loading heterogeneous catalyst has been developed for the hydrolysis of hydrosilanes to silanols and alkoxysilanes under mild and neutral reaction conditions with broad substrate scope. After five recycling runs, this low palladium‐loading catalyst keeps good activity for this transformation. [ABSTRACT FROM AUTHOR]

Currently, the use of composites, based on natural fibers and polymeric matrix, in diverse industrial sectors is gaining interest. The interaction between fibers and polymeric matrix is essential to have a composite with the desired thermal and mechanical properties. Nevertheless, most of the natural fibers do not have a good interaction with polymers and they need to be modified to enhance such interaction. Therefore, in this work, the chemical modification of coconut fibers, using different silanes agents like glycydoxipropyl trimetoxi slane (GLYMO), vinyl trimetoxi silane (VTMS), and tetraetoxi silane (TEOS) was carried out to promote the interfacial interaction with the polymeric matrix of poly (lactic acid) (PLA). The FTIR spectra confirmed the silanization of the fibers by detecting the bands related to Si–O–Si, at 1133 y 1106 cm−1, and Si–O–Cellulose bonds, at 1165 y 955 cm−1, as the product of the silanols reactions. The thermal stability was determined by thermal thermogravimetric analysis, which shows that the chemical modification of fibers increased their thermal stability regarding the fibers non-modified. On the other hand, the DSC showed that interfacial interactions between the fiber and PLA chains increased when the fiber was previously silanized because the silanes promoted the crystallinity of PLA from 48.95 to 60.08% with GLYMO, to 63.94 with VTMS and to 63.35 with TEOS. Regarding the crystallization study, the composites with VTMS presented higher activation energy at the beginning, but as the relative crystallinity increased, the polymer chains' arrangement was facilitated, considerably increasing the elastic modulus of PLA by 325%. The increase in crystallinity due to the incorporation of the silanized fibers shifted the maximum Tan δ value toward lower temperatures, increasing the application window of the polymer. [ABSTRACT FROM AUTHOR]

The aza-Michael reaction of 3-aminopropyltriethoxysilane (1) and -silatrane (2) with acrylates affords functionalized silyl-(3–8) and silatranyl-(9–14) mono- and diadducts with up to a 99% yield. Their structure has been proved with IR and NMR spectroscopies, mass spectrometry and XRD analysis. The hydrolytic homo-condensation of triethoxysilanes 3–5 gives siloxanes 3a–5a, which form complexes with Ag, Cu, and Ni salts. They are also able to adsorb these metals from solutions. The hetero-condensation reaction of silanes 4–8 with OH groups of zeolite (Z), silica gel (S) and glass (G) delivers the modified materials (Z4, S7, G4, G5, G7, G8, etc.), which can adsorb ions of noble metal (Au, Rh, Pd: G4 + Au, G5 + Pd, G7 + Rh). Thus, the synthesized Si-organic polymers and materials turned out to be promising sorbents (enterosorbents) of noble, heavy, toxic metal ions and can be applied in industry, environment, and medicine. [ABSTRACT FROM AUTHOR]

Organic‐silica hybrid monoliths attracted attention as an alternative to extensively researched organic polymer‐based and silica‐based counterparts. The development and applications of these materials as extraction and separation media in capillary liquid chromatography and capillary electrochromatography were previously reviewed in several manuscripts. In this review, we will concentrate on work published since mid‐2016 focusing on advances in their development using sol‐gel chemistry of tetra‐ and trialkoxysilanes and subsequent surface modification with organic monomers, and "one‐pot" strategy incorporating sol‐gel chemistry of alkoxysilanes and free‐radical polymerization, ring‐opening polymerization, or thiol‐based click polymerization with organic monomers. Approaches adapted to the preparation of hybrid monoliths made with polyhedral oligomeric silsesquioxanes will be covered as well. [ABSTRACT FROM AUTHOR]

Organic-inorganic hybrids (OIHs) are a type of material that can be obtained using the sol-gel process and has the advantages of organic and inorganic moieties in a single material. Polyetheramines have been widely used in the preparation of this type of material, particularly in combination with epoxy-based alkoxysilanes. Nevertheless, epoxyciclohexylethyltrimethoxysilane (ECHETMS) is a promising alkoxysilane with an epoxy terminal group that is quite unexplored. In this work, four novel OIH materials were synthesized using the sol-gel method. The OIHs were based on Jeffamines® of different molecular weights (D-230, D-400, ED-600, and ED-900), together with ECHETMS. The materials were characterized using multinuclear solid state NMR, FTIR, BET, UV/Vis spectroscopy, EIS, and TGA. The influence of the Jeffamine molecular weight and the suitability of these materials to act as a supporting matrix for heteroaromatic probes were assessed and discussed. The materials show interesting properties in order to be applied in a wide range of sensing applications. [ABSTRACT FROM AUTHOR]

Tris(pentafluorophenyl)borane (TPFPB) is a unique Lewis acid that catalyzes the condensation between hydrosilanes (Si-H) and alkoxysilanes (Si-OR), leading to the formation of siloxane bonds (Si-OSi) with the release of hydrocarbon (R-H) as a byproduct—the so-called Piers–Rubinsztajn reaction. The analogous reactions of hydrosilanes with silanols (Si-OH), alcohols (R-OH), ethers (R-OR′) or water in the presence of TPFPB leads to the formation of a siloxane bond, alkoxysilane (Si-OR or Si-OR′) or silanol (Si-OH), respectively. The above processes, often referred to as Piers–Rubinsztajn reactions, provide new synthetic tools for the controlled synthesis of siloxane materials under mild conditions with high yields. The common feature of these reactions is the TPFPB-mediated hydride transfer from silicon to carbon or hydrogen. This review presents a summary of 20 years of research efforts related to this field, with a focus on new synthetic methodologies leading to numerous previously difficult to synthesize well-defined siloxane oligomers, polymers and copolymers of a complex structure and potential applications of these new materials. In addition, the mechanistic aspects of the recently discovered reactions involving hydride transfer from silicon to silicon are discussed in more detail. [ABSTRACT FROM AUTHOR]

In this work, the effect of the side group of a series of silane coupling agents, as well as the subsequent anchoring of an imidazole derivative, for TiO2 particles, within the PLA polymeric matrix, with emphasis on their mechanical properties and their crystallization kinetics, and their rate of degradation Differences were the following: the chlorine group was the best in terms of low variability in Young's modulus (values around 4 GPa), good resistance to degradation, and lower values for both activation energy (below 100 kJ) and crystallization enthalpy. The amine, glycidoxy, and Imidazole groups were similar concerning the thermal and viscoelastic behavior. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

The article describes the modifying effect of methylcyclohexyldimethoxysilane (CH3)(cyclo‐C6H11)Si(OCH3)2 in propylene polymerization reactions with a pseudo‐homogeneous catalyst system: Ti(Oi‐C3H7)4‐Al(C2H5)2Cl/Mg(C4H9)2. This catalyst system is a convenient model for the analysis of modifier effects (effects of 'external donors') in supported Ziegler–Natta polymerization catalysts of the fourth generation. A combination of chromatographic, spectroscopic and calorimetric data for crystalline and amorphous fractions of polypropylene prepared in the presence of the silane shows that it has a dual modification effect: (i) the silane is a potent poison of stereo‐aspecific active centers in the catalyst (the centers producing amorphous polypropylene fraction) and (ii) silane molecules coordinate at isospecific centers in the catalyst and changes their nature: the centers produce isotactic polypropylene of higher molecular weight and a higher isotacticity level. © 2023 Society of Industrial Chemistry. [ABSTRACT FROM AUTHOR]

The dynamic covalent chemistry (DCvC) of the Si−O bond holds unique opportunities, but has rarely been employed to assemble discrete molecular architectures. This may be due to the harsh conditions required to initiate exchange reactions at silicon in aprotic solvents. Herein, we provide a comprehensive experimental and computational account on the reaction of trialkoxysilanes with alcohols and identify mild conditions for rapid exchange in aprotic solvents. Substituent, solvent and salt effects are uncovered, understood and exploited for the construction of sila‐orthoester cryptates. A sharp, divergent pH‐response of the obtained cages renders this substance class attractive for future applications well beyond host‐guest chemistry, for instance, in drug delivery. [ABSTRACT FROM AUTHOR]

A one-component organosilicon composition based on a Lestosil SM-NT block copolymer solution containing an optimal ratio of linear polydimethylsiloxane and ladder phenylsilsesquioxane units in an organic solvent was developed. A heterosiloxane solution containing boron and zirconium atoms in alkoxysilane in the siloxane chain and special additives that increase the operational properties of coatings was used as a curing system. The composition is to be used to obtain heat-resistant electrically insulating and moisture-resistant coatings with improved physical and chemical properties for use as protective materials in microelectronics and electronic devices. [ABSTRACT FROM AUTHOR]

The eligibility of applying the Owens–Wendt approach to determining the free surface energy of liquid-repellent aluminum surfaces, with micro- and nanotextures formed by a femtosecond laser, was considered. This approach has been shown to be applicable using two essential parameters that can be derived from the graphs. The first is related to the fraction of the contact area between the liquid and the solid surface in the Cassie state. The second is related to the degree of intrinsic polarity of the surface material or the applied organic modifier. The presented interpretation was used to compare the liquid repellency of the obtained textures. A microtexture with a period of 60 μm and a groove width of 45 μm has been shown to be the most liquid repellent. Among the modifiers, 1H,1H,2H,2H-perfluoroctyltriethoxysilane was the most effective, and stearic acid was only slightly inferior, but promising in terms of cost and environmental friendliness. It was shown that spontaneous hydrophobization provided a contact angle with water up to 159°, but the stability of such textures was inferior to the considered modifiers. [ABSTRACT FROM AUTHOR]

This paper discusses the historical beginnings and the current state of knowledge of the synthesis of organosilicon compounds and chlorine derivatives of silicon. The key importance of these compounds for modern industry, including the semiconductor industry (photovoltaic cells, microprocessors, memory chips and many other electronic elements) is highlighted. Significant environmental threats related to the production of these compounds and the research challenges aimed at their elimination are discussed. The complexity of the catalytic mechanism of direct reaction of silicon with CH3Cl and alcohols is presented in an accessible way. In the last part of the work, the directions of the development of direct synthesis technology in line with the principles of green chemistry are indicated.

Polypyrrole adhesion to indium–tin oxide electrodes was improved by adding pre-hydrolyzed alkoxysilanes to the electrodeposition media. The pyrrole oxidation and film growth rates were studied by potentiostatic polymerization in acidic media. The morphology and thickness of the films were studied by contact profilometry and surface-scanning electron microscopy. The bulk and surface semiquantitative chemical composition was studied by Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy. Finally, the adhesion was studied by scotch-tape adhesion test, where both alkoxysilanes showed a significant improvement in adhesion. We proposed a hypothesis for the improvement in adhesion, that involves the formation of siloxane material as well as in situ surface modification of the transparent metal oxide electrode. [ABSTRACT FROM AUTHOR]

Many strategies have been adopted to prepare silica materials with highly controlled structures, typically using sol–gel chemistry. Frequently, the alkoxysilanes used in sol–gel chemistry are based on monoalcohols, e.g., Si(OEt)4. The structural control over silica synthesis achieved by these precursors is highly sensitive to pH and solvency. Alkoxysilanes derived from the sugar alcohol glycerol (diglycerylsilane) react more slowly and with much less sensitivity to pH. We report that, in the presence of cooled aqueous starch solutions, glyceroxysilanes undergo transesterification with the sugars on starch, leading to (hollow) microtubules resembling worms of about 400 nm in diameter. The tubes arise from the pre-assembly of starch bundles, which occurs only well below room temperature. It is straightforward to treat the first-formed starch/silica composite with the enzyme amylase to, in a programmed fashion, increasingly expose porosity, including the worm morphology, while washing away untethered silica and digested starch to leave an open, highly porous materials. Sintering at 600 °C completely removes the starch silane moieties. [ABSTRACT FROM AUTHOR]

A number of polycarbosilanes (PCS) with various types of terminal groups were synthesized by the Grignard reaction with (chloroalkyl)alkoxysilanes. Their structure and properties were studied by NMR, IR spectroscopy, GPC, and TGA method. The dependence of the coke residue formation on the structure of the polymer and the nature of its terminal groups has been estimated. It was demonstrated that PCS based on (chloroalkyl)trialkoxysilanes with terminal ethynyl groups are perspective precursors for SiC ceramics fabrication. [ABSTRACT FROM AUTHOR]

This paper discusses the historical beginnings and the current state of knowledge of the synthesis of organosilicon compounds and chlorine derivatives of silicon. The key importance of these compounds for modern industry, including the semiconductor industry (photovoltaic cells, microprocessors, memory chips and many other electronic elements) is highlighted. Significant environmental threats related to the production of these compounds and the research challenges aimed at their elimination are discussed. The complexity of the catalytic mechanism of direct reaction of silicon with CH3Cl and alcohols is presented in an accessible way. In the last part of the work, the directions of the development of direct synthesis technology in line with the principles of green chemistry are indicated. [ABSTRACT FROM AUTHOR]

Superhydrophobic surfaces fabricated by grafting 1H,1H,2H,2H-heptadecafluorodecyl trimethoxysilane (FD-TMS) and polydimethylsiloxane triethoxysilane (PDMS-TES) onto a nano-micro hierarchical aluminum (Al) surface are considered to possess substantial anti-icing functionality, with delayed freezing and low ice-adhesion strength (IAS). Verifying the impacts of PDMS and the synergism of PDMS and FD on the anti-icing performance is the goal of this study. Roughness, one of the prerequisites for superhydrophobicity, was obtained by etching Al substrates in aqueous HCl, followed by immersion in boiling water. FD-TMS and PDMS-TES were then coated on the rough Al substrates layer by layer; a congener coated with a single layer was also prepared for comparison. The FD-PDMS1.92 (1.92 wt.%) coating, in which FD-TMS and PDMS-TES were used as primary and secondary coating materials, respectively, exhibited superior icephobicity, with the lowest IAS of 28 kPa under extremely condensing weather conditions (−20 °C and 70% relative humidity, RH) and the longest freezing delay time of 230 min (at −18 °C). These features are attributed to the incorporation of a dense coating layer with a low-surface-tension FD and the high mobility of PDMS, which lowered the contact area and interaction between the ice and substrate. The substrate coated with FD-PDMS1.92 exhibited improved durability with an IAS of 63 kPa after 40 icing/melting cycles, which is far less than that achieved with the FD single-layer coating. [ABSTRACT FROM AUTHOR]

Polyester fibers are widely employed in a multitude of sectors and applications from the technical textiles to everyday life thanks to their durability, strength, and flexibility. Despite these advantages, polyester lacks in dyeability, adhesion of coating, hydrophilicity, and it is characterized by a low wettability respect to natural fibers. On this regard, beyond the harmful hydrophobic textile finishings of polyester fabrics containing fluorine-compounds, and in order to avoid pre-treatments, such as laser irradiation to improve their surface properties, research is moving towards the development of fluorine-free and safer coatings. In this work, the (3-glycidyloxypropyl)trimethoxysilane (GPTMS) and various long alkyl-chain alkoxysilanes were employed for the fabrication in the presence of a catalyst of a water-based superhydrophobic finishing for polyester fabrics with a simple sol-gel, non-fluorinated, sustainable approach and the dip-pad-dry-cure method. The finished polyester fabrics surface properties were investigated by static and dynamic water repellency tests. Additionally, the resistance to common water-based liquids, abrasion resistance, moisture adsorption, and air permeability measurements were performed. Scanning electron microscopy was employed to examine the micro- and nano-morphology of the functionalized polyester fabrics surfaces. The obtained superhydrophobic finishings displayed high water-based stain resistance as well as good hydrophobicity after different cycles of abrasion. [ABSTRACT FROM AUTHOR]

This work aims to reveal the recent research trends in the consolidation of stone-built heritage and discuss the advantages and drawbacks of the options and strategies followed by researchers over the last 10 years. Peer-reviewed articles were used to build a database and analyze the details of the stone samples (chemical nature, type of voids, and condition), treatment protocols (application methods and consolidation products), and testing methods to assess the strengthening results of the treatments. In addition, the reported increments in the mechanical properties were also examined to reveal the strengthening capabilities of recent consolidation treatments. The statistical treatment of the results allowed pinpointing the stone varieties that need more frequent consolidation actions (limestone, biocalcarenite, and sandstone) and the aspects that make them more difficult and riskier. Other tendencies were discussed, for example, the predominant use of sound samples over decayed samples (61% vs. 39%) or the predominant use of alkoxysilanes (~46%) over other families of consolidants (e.g., nanolime, ~21%). The current consolidation treatments were found to improve stone strength; however, the most problematic issue in state-of-the-art is the difficulty of identifying high-risk situations of over-consolidation or poor distribution in depth because of either the lack of testing or limitations of the various assessment techniques. [ABSTRACT FROM AUTHOR]

The catalyst-free hydrolytic polycondensation of methyltrimethoxysilane under microwave radiation has been studied. The effect of molar ratios of the reagents (MTMS/H2O = 1/0.5–1/9), radiation power (20–300 W), temperature (30–50 °C) and duration of exposure (2.5–90 min) on the course of the process is considered. It has been shown that the use of microwave radiation promotes the activation of the process, and almost complete conversion of the monomer can be achieved in 5 min at 30 °C, 20 W and an MTMS/H2O ratio of 1/3. The optimal radiation power for the maximum conversion of the monomer and MeO-groups is in the range from 20 to 100 W. An increase in the water amount, the duration and temperature of the process contribute to an increase in the monomer conversion, a decrease in the content of residual MeO-groups and the yield of non-volatile oligomethylsilsesquioxanes. The limits of this approach using to the synthesis of multifunctional branched polyorganosilsesquioxanes are determined. Depending on the process conditions, homogeneous water–alcohol solutions of oligomethylsilsesquioxane with a concentration of 20 to 50 wt.% can be obtained. The OH-group content and the molecular weight of the obtained oligomers vary from 10 to 30 wt.% and from 1000 to 600 Da, respectively. [ABSTRACT FROM AUTHOR]

In this work, we present the electrochemical behavior and microstructural analysis of silicon oxycarbide (SiOC) ceramics influenced by an addition of polystyrene (PS). Polymer‐derived ceramics were obtained by pyrolysis (1000°C, Ar atmosphere) of different polysiloxanes prepared by sol–gel synthesis. This method is very effective to obtain desired composition of final ceramic. Two alkoxysilanes phenylthriethoxysilane and diphenyldimethoxysilane were used as precursors. Before pyrolysis polysiloxanes were mixed with PS using toluene as a solvent. Blending with PS affects the microstructure and free carbon content in the final ceramic material. Free carbon phase has been confirmed to be a major lithium storage host. Nevertheless, we demonstrate here that capacity does not increase linearly with increasing carbon content. We show that the amount of SiO4 units in the SiOC microstructure increases the initial capacity but decreases the cycling stability and rate capability of the material. Furthermore, the microstructure of the free carbon influences the electrochemical performance of the ceramic: More ordered graphitic clusters favor better rate capability performance. [ABSTRACT FROM AUTHOR]

The optimal restoration agent for the brittle walls of Idout's tomb built 4400 years ago in Saqqara, Egypt, which is located underground in a desert area, was investigated. From x‐ray diffraction analysis of the sand collected near the tomb, the main ingredient is silica. Alkoxysilane and its oligomer are used because its alkoxy groups can react readily with silica. The compressive test of solidified model sand its main component is silica was done. The increase of both molecular weight of oligomer and the content of oligomer with higher molecular weight effectively developed the compressive force. When an earthquake occurs, it is desirable that the reinforced wall will be crushed in ductility. The addition of di‐alkoxy type alkoxysilane to oligomers changed the failure mode from brittle to ductile, because the network becomes looser. When a moderate quantity of di‐alkoxy type is added to oligomers, the solidified model sand deforms with greater displacement, while maintaining a high compressive force. From scanning electron microscopic observation of fractured solidified specimen, alkoxysilane was making the sand particles connect as a binder. Many cracks were clearly observed in the binder layer. Whereas, the formed crack was far smaller for di‐alkoxy added system. [ABSTRACT FROM AUTHOR]

Based on a recently developed selective etching process for silicon samples with buried implants, this work presents a method for utilizing the generated material contrast between silicon and silicon oxide to selectively deposit polymers on the patterned surface. Besides depositing polystyrene selectively on the etched parts via drop‐casting and dewetting, polymer chains are selectively grafted to the oxidic surface parts. To this end, the oxide surfaces are selectively modified via functional alkoxysilanes, whereas etched silicon surfaces are unreactive. Using either a two‐step or a straight‐forward one‐step process employing commercially available chemicals, atom transfer radical polymerization (ATRP) initiator functions are attached selectively to the non‐etched surface areas, and subsequently used to polymerize either methyl methacrylate (MMA) or N‐isopropyl acrylamide (NIPAM) in a controlled surface‐initiated activator regenerated by electron transfer (ARGET)‐ATRP process. This procedure allows for the further self‐aligned functionalization of the micropatterned samples, enabling the production of highly functional, patterned surfaces, potentially suitable for applications in areas such as cell adsorption, microfluidics, or functional microsystems, e.g., MEMS. [ABSTRACT FROM AUTHOR]

Although liquid-repellent surfaces are in demand in many applications, their use is limited by the Cassie state's sustainability to environmental factors, such as the repellency of liquids with a surface tension lower than that of water. This phenomenon remains not fully understood, despite a well-developed theory. In the current work, wetting of femtosecond laser-textured aluminum surfaces for probe liquids with a surface tension of 72.8–21.2 mN/m was considered. The resulting patterns were an array of pillars at the micro level and fractal-like structures at the nano level. These structured surfaces were treated with alkoxysilanes and oleic acid. All textured samples exhibited a Cassie state with water, and contact angles greater than 150° were achieved with silane-treated surfaces. A decrease in the surface tension of the probe liquid led to а transition to the Wetzel state at 44–46 mN/m for alkoxysilanes and at 52 mN/m for oleic acid. A typical shape of the textured surface wetting curve is proposed. It was shown that the determined values of the surface tension of the Cassie-Wenzel transition were 10–15 mN/m lower than those predicted by the Cassie equations. [ABSTRACT FROM AUTHOR]

[Display omitted] • 94 mol% yield of alkoxysilanes was obtained from mixed rice straw and husk ash. • 400–625 °C calcined ash was favorable for alkoxysilanes preparation. • The intrinsic complexity of biomass allowed the effective synthesis of TEOS. • Alkaline strength, concentration of K, and the co-existence of P pave the reaction. • A possible reaction mechanism for alkoxysilanes formation was proposed. Synthesis of alkoxysilanes from renewable silica resources could promote their sustainability but remain grand challenges. Herein, we present a simple, effective strategy to synthesize tetraethyl orthosilicate (TEOS) directly from bio-derived silica through supercritical ethanol processing, where no catalyst nor additives are required. Crucially, calcination temperature is demonstrated to play a critical role in altering the structure of silica in rice husk ash (RHA), which directly influences its conversion activity to alkoxysilanes. Specifically, under optimized conditions at 280 °C and 1 h, RHA obtained at 400–625 °C calcination allows for an amorphous silica structure and as high as 85 mol% yield to alkoxysilanes. Moreover, the ash obtained from mixed rice straw and rice husk yields over 94 mol% alkoxysilanes, demonstrating the self-catalytic potential of the natural complexity of the ash. The effects of typical minerals contained in ash on the reaction are probed. It is revealed that potassium oxide is the main catalytic species in ash, which provide a suitable alkaline strength. The concentration of potassium ion exhibits a pronounced positive effect on catalyzing the synthesis of alkoxysilanes, and the co-existed phosphorus species exhibits promotional effect to TEOS selectivity. Furthermore, 29Si MAS NMR and Laplacian bond order analysis reveal that the cleavage of Si-O-Si bond predominates in the supercritical ethanol environment, providing a viable path for the production of TEOS. [ABSTRACT FROM AUTHOR]

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). [ABSTRACT FROM AUTHOR]

In this contribution, three redistributed arylgermanium-bearing mono-, bis- and tris-triethoxysilyl arms were designed through metal-free radical-initiated hydrogermylation. Their cooperative assembly using amphiphilic Pluronic P123 afforded novel functionalized SBA-15-type materials with embedded arylgermanium in the silica walls. The formation of an ordered mesostructure depended to some extent on the bulkiness of the precursors and the experimental conditions. A nicely distributed germanium pattern was observed through elemental mapping along the siloxane framework, thereby providing a new rational design for stabilizing single atoms in a confined network. When introduced in an aqueous colloidal solution of polyglucosaminated chitosan, evaporative-induced co-assembly of the mixture enables the entrapment of arylgermanium-containing siloxane within the polysaccharide network with the simultaneous formation of transparent bioplastics. The occurrence of phase-separation resulted in texturally engineered polysaccharide–siloxane hybrid nanostructures. [ABSTRACT FROM AUTHOR]

Polypyrrole adhesion to indium–tin oxide electrodes was improved by adding pre-hydrolyzed alkoxysilanes to the electrodeposition media. The pyrrole oxidation and film growth rates were studied by potentiostatic polymerization in acidic media. The morphology and thickness of the films were studied by contact profilometry and surface-scanning electron microscopy. The bulk and surface semiquantitative chemical composition was studied by Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy. Finally, the adhesion was studied by scotch-tape adhesion test, where both alkoxysilanes showed a significant improvement in adhesion. We proposed a hypothesis for the improvement in adhesion, that involves the formation of siloxane material as well as in situ surface modification of the transparent metal oxide electrode.

[Display omitted] • Local Electronic Additional Energy (LEAE) is used to analyze the ability of sites on MgCl 2 (1 1 0 surface) to attract external electron donors. • The Interaction Region Indicator (IRI) method was used to graphically display the interactions between atoms in the adsorption model. • The analysis of the regioselectivity and stereoselectivity of four alkoxysilanes aims to identify external electron donors with superior performance. • The research found that external electron donors with higher adsorption energy can more effectively enhance the activity of the active center. Ziegler-Natta catalysts are widely used in the production of polyolefin with the advantages of low cost and high efficiency. The external electron donors are usually used during the polymerization to obtain the polyolefins with higher isotacticity. Four alkoxysilanes external electron donors were investigated by Density Functional Theory (DFT) calculations. Local Electron Attachment Energy (LEAE) calculations showed that alkoxysilanes tend to adsorb at the Mg1 site and the Mg4 site of the MgCl 2 (1 1 0) surface (The first and fourth Mg atoms from right to left on the MgCl 2 (1 1 0) surface, respectively), and that differences in substituents have a large effect on the stability of alkoxysilanes adsorption. In addition, it was found that the adsorption of alkoxysilanes at the Mg1 site affects the active center in two ways, decreasing the electron cloud density of the active center Ti and increasing the steric hindrance of the active center Ti. Comparing the four alkoxysilanes, it is found that DIPMS can maximize the regional selectivity of catalysts, while DCPDMS can maximize the stereoselectivity of catalysts. [ABSTRACT FROM AUTHOR]

We found that the transfer of diphenylsilylene (Ph2Si:) from Ph2(Et2N)Si−B(pin) (1 a) takes place in toluene or p‐xylene at 110–135 °C under transition‐metal‐free conditions. The reaction of alkoxysilanes with 1 a affords alkoxydisilanes through the insertion of diphenylsilylene into the Si−O bond. Dihydrosiloles and a 1,4‐disilacyclohexa‐2,5‐diene are synthesized by the reaction of 1 a with 1,3‐dienes and an alkyne, respectively, through cycloaddition of the carbon‐carbon unsaturated bonds with diphenylsilylene. Me2(Et2N)Si−B(pin) (10) is applicable to the transition‐metal‐free transfer of dimethylsilylene (Me2Si:). [ABSTRACT FROM AUTHOR]

As an alternative to standard silicon biofunctionalization protocol based on alkoxysilanes that bind to SiO2 on oxidized silicon substrates, several protocols to form bifunctional interlayers that directly bind to the silicon surface via a strong SiC bond have been developed during the last decades. These interlayers are more stable, and the lack of an insulating layer between the substrate and the interlayer reduces electric noise in biosensor devices. SiC monolayers are not yet regularly applied as the protocols are more complex and generally require an inert gas atmosphere. However, a variety of applications and new methods to form bifunctional SiC interlayers are recently developed. Here, the role these innovative protocols and interlayers play in biofunctionalization of silicon surfaces is reviewed and their applications in electrochemical, microelectromechanical, and optical biosensing are reported. From the analysis of the current situation, it can be concluded that the advantageous properties offered with this approach in many cases more than outweigh the additional processes to form SiC bonded interlayers and the approach is predicted to expand the applications of future silicon‐based biosensors. [ABSTRACT FROM AUTHOR]

Polyester fibers are widely employed in a multitude of sectors and applications from the technical textiles to everyday life thanks to their durability, strength, and flexibility. Despite these advantages, polyester lacks in dyeability, adhesion of coating, hydrophilicity, and it is characterized by a low wettability respect to natural fibers. On this regard, beyond the harmful hydrophobic textile finishings of polyester fabrics containing fluorine-compounds, and in order to avoid pre-treatments, such as laser irradiation to improve their surface properties, research is moving towards the development of fluorine-free and safer coatings. In this work, the (3-glycidyloxypropyl)trimethoxysilane (GPTMS) and various long alkyl-chain alkoxysilanes were employed for the fabrication in the presence of a catalyst of a water-based superhydrophobic finishing for polyester fabrics with a simple sol-gel, non-fluorinated, sustainable approach and the dip-pad-dry-cure method. The finished polyester fabrics surface properties were investigated by static and dynamic water repellency tests. Additionally, the resistance to common water-based liquids, abrasion resistance, moisture adsorption, and air permeability measurements were performed. Scanning electron microscopy was employed to examine the micro- and nano-morphology of the functionalized polyester fabrics surfaces. The obtained superhydrophobic finishings displayed high water-based stain resistance as well as good hydrophobicity after different cycles of abrasion.

The catalyst-free hydrolytic polycondensation of methyltrimethoxysilane under microwave radiation has been studied. The effect of molar ratios of the reagents (MTMS/H2O = 1/0.5–1/9), radiation power (20–300 W), temperature (30–50 °C) and duration of exposure (2.5–90 min) on the course of the process is considered. It has been shown that the use of microwave radiation promotes the activation of the process, and almost complete conversion of the monomer can be achieved in 5 min at 30 °C, 20 W and an MTMS/H2O ratio of 1/3. The optimal radiation power for the maximum conversion of the monomer and MeO-groups is in the range from 20 to 100 W. An increase in the water amount, the duration and temperature of the process contribute to an increase in the monomer conversion, a decrease in the content of residual MeO-groups and the yield of non-volatile oligomethylsilsesquioxanes. The limits of this approach using to the synthesis of multifunctional branched polyorganosilsesquioxanes are determined. Depending on the process conditions, homogeneous water–alcohol solutions of oligomethylsilsesquioxane with a concentration of 20 to 50 wt.% can be obtained. The OH-group content and the molecular weight of the obtained oligomers vary from 10 to 30 wt.% and from 1000 to 600 Da, respectively.

Organosilanols typically show a high condensation tendency and only exist as stable isolable molecules under very specific steric and electronic conditions at the silicon atom. In the present work, various novel representatives of this class of compounds were synthesized by hydrolysis of alkoxy‐ or chlorosilanes. Phenyl, 1‐naphthyl, and 9‐phenanthrenyl substituents at the silicon atom were applied to systematically study the influence of the aromatic substituents on the structure and reactivity of the compounds. Chemical shifts in 29Si NMR spectroscopy in solution, correlated well with the expected electronic situation induced by the substitution pattern on the Si atom. 1H NMR studies allowed the detection of strong intermolecular hydrogen bonds. Single‐crystal X‐ray structures of the alkoxides and the chlorosilanes are dominated by π‐π interactions of the aromatic systems, which are substituted by strong hydrogen bonding interactions representing various structural motifs in the respective silanol structures. [ABSTRACT FROM AUTHOR]

A Rh-catalyzed enantioselective intermolecular dehydrogenative Si–O coupling of dihydrosilanes with alcohols and silanols is demonstrated. Rh(I) catalyst equipped with a Josiphos ligand enables the highly enantioselective alcoholysis process of dihydrosilanes, giving access to a variety of functionalized triorgano-substituted silicon-stereogenic alkoxysilanes and siloxanes in decent yields and ee , which significantly expand the chemical space of the silicon-centered chiral molecules. Utility of this methodology is illustrated by the construction of circularly polarized luminescence (CPL) active chiral alkoxysilane small organic molecules. 1 Introduction 2 Conditions Optimization 3 Substrate Scope 4 Application 5 Conclusions 6 Experimental Procedure [ABSTRACT FROM AUTHOR]

In the presented research, two trialkoxysilanes were used to investigate their reactivity with microcrystalline cellulose (MCC) applied as a model material. As a continuation of the previous study, the research aimed at evaluation of the durability and potential reversibility of the silane treatment. Two different solvents and a mixture thereof were used for cellulose modification. The influence of amino group/pH, an excess of silanes and re-soaking with water on binding with cellulose was examined. The results obtained confirm that both selected silanes can effectively modify MCC. However, the treatment with 3-(2-aminoethylamino)propyltrimethoxysilane occurred more effective than with Methyltrimethoxysilane due to the presence of amino groups. Among the three tested solvents, the most effective was pure water. In contrast, the use of ethanol and a mixture of ethanol and water gave significantly worse results. Summarising, the presented research clearly shows how important the type of the functional group in alkoxysilanes is for its chemical reactivity with natural polymers, which is crucial for their application in waterlogged wood conservation. [ABSTRACT FROM AUTHOR]

We describe here a method to synthesize ultrasmall nanocapsules with a diameter of 6 nm, exhibiting a well‐defined core–shell morphology. Remarkably, the nanocapules are synthesized in a miniemulsion process without the need of large amounts of surfactant as commonly used in the microemulsion process. Ultrasmall nanocapsules with an oil core and a silica shell are formed by the concurrent processes of a sol–gel reaction and Ostwald ripening. Using solvents with different water solubilities and alkoxysilanes with different reactivities, we demonstrate that sizes of obtained nanocapsules depend on the ripening rate and alkoxysilane conversion rate. The method can be also used for encapsulating natural oils such as peppermint oil and limonene. This work shows that the Ostwald ripening phenomenon can be employed beneficially for the preparation of very small colloids. [ABSTRACT FROM AUTHOR]

An integrated biorefinery will transition towards a comprehensive refining and zero-waste utilization process of all the biomass components, including the largely wasted or ignored inorganics. Here, we report an effective process of combined valorization of both organic components and inorganics. Small molecules from carbohydrates (32.5 wt%) and lignin (22.5 wt%) were obtained under catalyst-free conditions, in addition to a large amount of alkoxysilanes (>80 mol%) from silicon in rice straw. The connection of silicon with other components in rice straw was probed with XPS etching, SEM mapping, and CP/MAS 29Si NMR, etc. Pretreatment of rice straw with physical, chemical, and biological methods helps us reveal the plant's active silicon. It was indicated that both organosilicon connected with organic components in rice straw and the inorganic silica deposited in silica cell exists in rice straw can be converted to alkoxysilanes. Furthermore, exogenous silica could be converted to alkoxysilanes directly when mixed with biomass, indicating a new conversion process. We also demonstrate efficient methods for separating and purifying tetraethyl orthosilicate (TEOS) and recycling the solvent. An ex-ante life-cycle assessment of the processes has been established. The ex-ante LCA supports the economic viability and predicts minimized waste and clean production of TEOS in the new process. [Display omitted] • A comprehensive refining and zero-waste utilization of rice straw are studied. • Valuable products from carbohydrate, lignin and silicon are obtained without catalyst. • Rice straw acts as a transfer station of inorganic silica to prepare alkoxysilanes. • The ex-ante LCA supports the economic viability and clean production of process. [ABSTRACT FROM AUTHOR]

Interlayer silylation of layered sodium octosilicate (Na-Oct) with various organoalkoxysilanes was conducted using hexadecyltrimethylammonium ion-exchanged layered octosilicate (C16TMA-Oct) as an intermediate in the presence or absence of tetrabutylammonium fluoride (TBAF). The degree of silylation was increased by adding TBAF. It is suggested that F- ions perform a nucleophilic attack on the alkoxysilanes, which promotes the silylation reaction. C16TMA-Oct was silylated with octyltriethoxysilane (C8TES) or 3-mercaptopropyltriethoxysilane (MPTES) to compare the reactivity of the two organoalkoxysilanes in the presence or absence of TBAF. A higher degree of silylation of C16TMA-Oct was observed with MPTES, suggesting the higher accessibility of this silylating agent into the interlayer polar region of C16TMA-Oct. Overall TBAF appears as a relevant catalyst for the covalent interlayer surface modification of layered silicates with organic functional groups. [ABSTRACT FROM AUTHOR]