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CO2 is an abundant C1 resource but a green-house gas and chemically inert. Thus, its utilization has been a promising but challenging project. Herein, we report the unprecedented polymerization of CO2 and C6H4(SiMe2H)2 using B(C6F5)3 alone under mild conditions to give poly(silphenylene siloxane) accompanied by releasing CH4. The copolymerization can be extended to comonomers of phenylene silanes bearing functional groups. Moreover, it combines with Piers-Rubinsztajn reaction to establish a tandem polymerization system to achieve super thermal resistant poly(siloxane-co-silphenylene siloxane)s. Density functional theory reveals that B(C6F5)3 is activated by silanes to form free HB(C6F5)2, which is the true active species for CO2 reducing to borylformate, the rate controlling step of the polymerization procedure. The subsequent multiple reductions of borylformate to CH4 and the step-growth to poly(silphenylene siloxane)s can be fulfilled by both B(C6F5)3 and HB(C6F5)2, and the former shows a slightly higher activity. This work opens a new avenue of utilizing CO2 to fabricate polysiloxanes that is unable to access using current manners.

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This article describes the synthesis of a hydrophobic protective coating for concrete based on a silane derivative of fatty acids. The coating was obtained through a thiol-ene click addition reaction using methyl oleate and 3-mercaptopropyltrimethoxysilane in the presence of the photoinitiator 2,2-dimethoxy-2-phenylacetophenone (DMPA). This reaction proved to be more efficient compared with other tested (photo)initiators, considering the double bond conversion of oleate. The coating was applied to concrete using two methods: immersion and brushing. Both methods exhibited similar consumption of methyl oleate-based silane (UVMeS) at approximately 20 g/m2. The hydrophobic properties of the coatings were evaluated based on the contact angle, which for the modified surfaces was above 93°, indicating their hydrophobic nature. The penetration depth of the silane solution into the concrete was also studied; it was 5-7 mm for the immersion method and 3-5 mm for the brushing method. The addition of tetraethoxysilane (TEOS) to the silane solution slightly improved the barrier properties of the coating.

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A concise hydrosilylation of alkynes for synthesizing ß-(E)-vinylsilanes catalyzed by dirhodium(II)/XantPhos has been developed. In this reaction, ß-(E)-vinylsilanes were generated from the isomerization of ß-(Z)-vinylsilanes catalyzed by dirhodium(II) hydride species rather than the direct insertion of triple bond into M-H or M-Si bond (traditional Chalk-Harrod mechanism or modified Chalk-Harrod mechanism). The hydrosilylation displayed a broad substrate scope for alkynes and tertiary silanes, tolerating diverse functional groups including halides, nitrile, amines, esters, and heterocycles.

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The dehydrocoupling reaction between alcohols and hydrosilanes is considered to be one of the most atom-economical ways to produce Si-O coupling compounds because its byproduct is only hydrogen (H2), which make it extremely environmentally friendly. In past decades, various kinds of homogeneous catalysts for the dehydrocoupling of alcohols and hydrosilanes, such as transition metal complexes, alkaline earth metals, alkali metals, and noble metal complexes, have been reported for their good activity and selectivity. Nevertheless, the practical applications of these catalysts still remain unsatisfactory, which is mainly restricted by environmental impact and non-reusability. A facile and recyclable heterogeneous catalyst, ultra-small Ag nanoparticles supported on porous carbon (Ag/C) for the etherification of silanes, has been developed. It has high catalytic activity for the Si-O coupling reaction, and the apparent activation energy of the reaction is about 30 kJ/mol. The ultra-small Ag nanoparticles dispersed in the catalyst through the carrier C have an enrichment effect on all reactants, which makes the reactants reach the adsorption saturation state on the surface of Ag nanoparticles, thus accelerating the coupling reaction process and verifying that the kinetics of the reaction of the catalyst indicate a zero-grade reaction.

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The adducts 2M,R of general formula trans-[(L)M{R2P(CH2)2PR2}2{N2B(C6F5)3}] (L=ø or N2, M=Mo or W, R=Et or Ph), formed from Lewis acid-base pairing of B(C6F5)3 to a dinitrogen ligand of zero-valent group 6 bis(phosphine) complexes trans-[M{R2P(CH2)2PR2}2(N2)2] are shown to react with dihydrogen to afford hepta-coordinated bis(hydride) complexes [M(H)2{R2P(CH2)2PR2}{N2B(C6F5)3}] 3M,R which feature the rare ability to activate both dinitrogen and dihydrogen at a single metal center, except in the case where M=Mo and R=Ph for which fast precipitation of insoluble [Mo(H)4(dppe)2] (dppe=1,2-bis(diphenylphosphino)ethane) occurs. The frustrated Lewis pair (FLP)-related reactivity of the B-N linkage in compounds 3W,R was explored and led to distal N functionalization without involvement of the hydride ligands. It is shown in one example that the resulting bis(hydride) diazenido compounds may also be obtained through a sequence involving first FLP-type N-functionalization followed by oxidative addition of H2. Those oily compounds were found to have limited stability in solution or in their isolated states. Finally, treatment of 3W,Et with the Lewis base N,N-dimethylaminopyridine (DMAP) affords the simple but unknown bis(hydride)-dinitrogen species [W(H)2(depe)2(N2)] 11Et (depe=1,2-bis(diethylphosphino)ethane) which direct, selective formation from trans-[W(N2)2(depe)2] is not possible.

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In the present study, tests were carried out on composite samples on a polylactide matrix containing 25% by weight of mineral filler in the form of diatomaceous earth, base, and silanized with GPTMOS (3-glycidoxypropyltrimethoxysilane), OTES (n-octyltriethoxysilane), and MTMOS (methyltrimethoxysilane) silanes. The addition of two types of waxes, synthetic polyamide wax and natural beeswax, were used as a factor to increase the rheological properties of the composites. The obtained samples were characterized in terms of the effect of filler silanization on the degradation rate of the composites. The tests were conducted under different conditioning conditions, i.e., after exposure to strong UV radiation for 250 and 500 h, and under natural sunlight for 21 days. The conditioning carried out under natural conditions showed that the modified samples exhibit up to twice the degradation rate of pure polylactide. The addition of synthetic wax to the composites increases the tendency to agglomerate diatomaceous earth, while natural wax has a positive effect on filler dispersion. For composites modified with GPTMOS and OTES silanes, it was noted that the addition of natural wax inhibited the degree of surface degradation, compared to the addition of synthetic wax, while the addition of MTMOS silane caused the opposite effect and samples with natural wax degraded more strongly. It was shown that, despite the high degree of surface degradation, the process does not occur significantly deep into the composite and stops at a certain depth.

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The current longevity of dental resins intraorally is limited by susceptibility to acidic attacks from bacterial metabolic byproducts and vulnerability to enzymatic or hydrolytic degradation. Here, we demonstrate synthesizing an ionic liquid-based antibiofilm silane effective against Streptococcus mutans, a major caries pathogen. Furthermore, we incorporate this silane into dental resins, creating antibiofilm- and degradation-resistant materials applicable across resin types. FTIR, UV-vis, and NMR spectroscopy confirmed the synthesis of the expected ionic liquid-based silane. The characterization of SiO2 after the silanization indicated the presence of the silane and how it interacted with the oxide. All groups achieved a degree of conversion similar to that found for commercial resin composites immediately and after two months of storage in water. The minimum of 2.5 wt % of silane led to lower softening in solvent than the control group (GCTRL) (p < 0.05). While the flexural strength indicated a lower value from 1 wt % of silane compared to GCTRL (p < 0.05), the ultimate tensile strength did not indicate differences among groups (p > 0.05). There was no difference within groups between the immediate and long-term tests of flexural strength (p > 0.05) or ultimate tensile strength (p > 0.05). The addition of at least 5 wt % of silane reduced the viability of S. mutans compared to GCTRL (p < 0.05). The fluorescence microscopy analysis suggested that the higher the silane concentration, the higher the amount of bacteria with membrane defects. There was no difference among groups in the cytotoxicity test (p > 0.05). Therefore, the developed dental resins displayed biocompatibility, proper degree of conversion, improved resistance against softening in solvent, and stability after 6 months of storage in water. This material could be further developed to produce polymeric antimicrobial layers for different surfaces, supporting various potential avenues in developing novel biomaterials with enhanced therapeutic characteristics using ionic liquid-based materials.

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RESUMEN

Hydrosilanes are highly attractive compounds, which can be processed as liquids with printing technology to amorphous silicon films on nearly any solid substrate. The silicon layers can be processed for electronic devices like transistors or thin-film solar cells. The endothermic character of hydrosilanes with their positive enthalpies of formation results in favorable properties for processing. The larger the molecules, the lower their decomposition temperature and the higher their photoactivity. Cyclic hydrosilanes such as cyclopentasilane and cyclohexasilane can be easily deposited. The branched neopentasilane is more difficult to deposit but yields better-quality films after processing. The key challenge is the complex synthesis of the precursors and the hydrosilanes. The available preparative methods are presented in this review and their advantages and disadvantages are evaluated. The following synthesis methods are presented and discussed in this article: Wurtz coupling and other reductive coupling processes, dehydrogenative coupling of silanes, plasma synthesis of chlorinated polysilanes, amine- or chloride-induced disproportionations, and transformation of monosilane to higher silanes. Plasma synthesis is already carried out today as a continuous industrial process. The most effective synthesis methods in the laboratory are currently amine- and chloride-induced disproportionations. There is a great need to further optimize the syntheses of hydrosilanes and to develop new simple synthesis variants.

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Background: This study assessed the effect of different concentrations of 4-methacryloyloxyethy trimellitate anhydride (4-META) added to silane on microtensile bond strength (µTBS) of light-cure and dual-cure resin cement to hybrid and zirconia-reinforced lithium silicate ceramics. Materials and Methods: This in vitro, experimental study was conducted on 32 Celtra Duo and 32 VITA Enamic ceramics bonded to Allcem Veneer light-cure and Allcem dual-cure resin cements using silane impregnated with 4-META in 0%, 2.5%, 5%, and 10 wt% concentrations in 16 groups (n = 4). The µTBS of specimens was measured by a universal testing machine and analyzed by the Kruskal-Wallis and Mann-Whitney tests, and the mode of failure was determined under a stereomicroscope and analyzed by the Chi-square test (alpha = 0.05). Results: The lowest mean µTBS was recorded in the Enamic ceramic group with 4-META (0%) bonded to dual-cure cement (14.26 MPa), and the highest mean µTBS was recorded in Enamic ceramic with 4-META (10%) bonded to light-cure cement (18.59 MPa) (P < 0.001). The µTBS of Celtra Duo was significantly higher than that of Enamic in bonding to light-cure cement using 4-META (2.5%) (P = 0.003). All failures (100%) were adhesive in most groups. The frequency of adhesive failure was the lowest (90%) in Celtra Duo bonded to dual-cure cement with 4-META (5%). Conclusion: According to the results of this pilot study, the addition of 4-META (10%) to silane caused a significant improvement in µTBS to light-cure cement. The addition of 4-META in all concentrations significantly improved the µTBS to Enamic ceramic in the use of dual-cure cement; however, it had no significant effect on µTBS of Celtra Duo. Nonetheless, the results should be interpreted with caution due to the relatively small sample size.

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The chemical structure of the surface of glass fibers, including silanized fibers, was studied. Highly efficient heat-resistant composites were obtained by impregnating silanized glass fiber with a polysulfone solution, and the effect of modification of the surface of glass fibers on the physical, mechanical and thermophysical properties of the composite materials was studied. As a result of the study, it was found that the fiber-to-polymer ratio of 70/30 wt.% showed the best mechanical properties for composites reinforced with pre-heat-treated and silanized glass fibers. It has been established that the chemical treatment of the glass fibers with silanes makes it possible to increase the mechanical properties by 1.5 times compared to composites reinforced with initial fibers. It was found that the use of silane coupling agents made it possible to increase the thermal stability of the composites. Mechanisms that improve the interfacial interaction between the glass fibers and the polymer matrix have been identified. It has been shown that an increase in adhesion occurs both due to the uniform distribution of the polymer on the surface of the glass fibers and due to the improved wettability of the fibers by the polymer. An interpenetrating network was formed in the interfacial region, providing a chemical bond between the functional groups on the surface of the glass fiber and the polymer matrix, which was formed as a result of treating the glass fiber surface with silanes, It has been shown that when treated with aminopropyltriethoxysilane, significant functional unprotonated amino groups NH+/NH2+ are formed on the surface of the fibers; such free amino groups, oriented in the direction from the fiber surface, form strong bonds with the matrix polymer. Based on experimental data, the chemical structure of the polymer/glass fiber interface was identified.

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Harvesting freshwater from fog is one of the possible solutions to the global water scarcity crisis. Surfaces with both hydrophobic and hydrophilic regions are extensively employed for this purpose. Nevertheless, the longevity of these surfaces is still constrained by their delicate surface structures. The hydrophilic zones may become damaged or contaminated after repeated use, thereby compromising their effectiveness in fog collection. The preparation of generally applicable durable superhydrophobic coatings with self-generated Wenzel sites is reported here for long-term efficient and stable fog collection. The coatings are prepared by depositing the poly(tannic acid) coating as the primer layer on various substrates, self-assembly of trichlorovinylsilane into staggered silicone nanofilaments, and then thiol-ene click reaction with 1H,1H,2H,2H-perfluorodecanethiol. The coatings demonstrate remarkable static superhydrophobicity, robust impalement resistance, and stable self-generated Wenzel sites for water droplets. Therefore, the fog collection rate (FCR) of the coatings reaches 2.13 g cm-2 h-1 during 192 h continuous fog collection, which is triple that of bare substrate and outperforms most previous studies. Moreover, the systematic experiments and models have revealed that the key factors for achieving high FCR on superhydrophobic coatings are forming condensed droplets ≈1 mm in critical radius and a Wenzel site proportion of 0.3-0.4.

RESUMEN

Poly(vinyl chloride) undergoes dechlorination in the presence of triethylsilane (Et3SiH) and a catalytic amount of [Cp2Zr(NPh2)][CH3B(C6F5)3] (1 b) at 40-80 °C, with up to 91 % efficiency. Stoichiometric reactivity studies conducted on cyclohexyl chloride as a model suggest that 1 b dechlorinates PVC by initial chloride abstraction, followed by hydride transfer to the cationic PVC chain from Et3SiH. Consumer items such as pipe fitting, vinyl disc or electric cable insulation undergo either dechlorination or hydrosilylation of the carbonyl-containing copolymer (polyvinyl acetate) or plasticizer (phthalate).

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In this work, Ti-incorporated carbon coatings were used as substrates for modification with one- and two-component self-assembled monolayers of organosilane compounds using a polydimethylsiloxane (PDMS) stamp. This enabled the selective functionalization of surfaces with micrometric dimensions. The topography of the modified surfaces was defined using an atomic force microscope (AFM). The effectiveness of the modification was confirmed by measurements of the water contact angle and surface free energy using the Oss and Good method. Using a T-23 microtribometer with counterparts in the shape of balls that were made of steel, silicon nitride (Si3N4), and zirconium dioxide (ZrO2), the tribological properties of the obtained coatings were tested. These investigations showed that modification by using a PDMS stamp makes it possible to produce two-component ultrathin silane layers on Ti-containing carbon substrates. Two-component organosilane layers had higher hydrophobicity, a lower friction coefficient, and a smaller width of wear tracks than the one-component analogs. It was also found that the work of adhesion of the created surfaces had a significant influence on the value of the friction coefficient and the percentage value of the growth inhibition of bacteria.

RESUMEN

Catalytic hydrosilylation is one of the important synthetic approaches to prepare functional organosilicon polymers. Herein, a functional silicon copolymer is constructed by polyhydrosilylation reaction between a novel 3,7-bis(dimethyl silane)-10-(2-ethylhexyl)-10H-phenothiazine monomer and a neutral tetrapyrrolic macrocycle, namely, 5,5,10,15,15,20-hexamethyl-10α, 20α-bis(4-[ethynylphenyl]) calix[4]pyrrole. The as-constructed copolymer (Mn  = 9609, PDI = 2.2) is investigated as an extractant for organic anions as their tetrabutylammonium salts under interfacial aqueous-organic (water-chloroform) conditions. In this context, a distinctive naked-eye colorimetric as well as fluorescence detection method is developed based on anion-directed hydrogen-bonding interactions. This kind of color/fluorescence monitoring serves as a handy tool for rapid screening of anion extraction processes. The copolymer exhibits high selectivity toward extraction of chloride anion. This study augments the field of polycarbosilanes, poly(silylenevinylene)s in particular, allowing access to a new application window that can be further advanced with good grace in near future.

Asunto(s)

RESUMEN

Radical trifluoromethoxylation is an attractive approach to prepare compounds featuring the important OCF3 group, however most existing methods have focused on aromatic substrates. Here, we report novel methodologies with alkenyl substrates employing bis(trifluoromethyl)peroxide (BTMP) as a practical and comparatively atom economical trifluoromethoxylating reagent. With silyl enol ether substrates, switching reaction solvent allows for the synthesis of either α-(trifluoromethoxy)ketone products or unprecedented alkenyl-OCF3 species. Furthermore, allyl silanes have been employed as substrates for the first time, affording allyl(trifluoromethyl)ether products in good yields. In each case, the methods operate at room temperature without large excesses of the alkene substrate while, in contrast to previous radical trifluoromethoxylation reactions, no catalyst, light or other activators are required.

RESUMEN

The synthesis, characterization, and reactivity of several new Cr(II) and Cr(III) complexes featuring an NCN pincer ligand with an arene backbone connected to amine donors NEt2 and NiPr2 via CH2-linkers is described. Reacting the in situ lithiated ligand precursor N(C-Br)NCH2-Et with [CrCl3(THF)3] resulted in the formation of the Cr(III) complex trans-[Cr(κ3NCN-NCNCH2-Et)(Cl)2(THF)]. Upon reaction of lithiated N(C-Br)NCH2-iPr with a suspension of anhydrous CrCl2, the Cr(II) complex [Cr(κ2NC-NCNCH2-iPr)2] is formed featuring two NCN ligands bound in κ2NC-fashion. In contrast, when lithiated N(C-Br)NCH2-iPr is reacted with a homogeneous solution of anhydrous CrX2 (X = Cl, Br), complexes [Cr(κ3NCN-NCNCH2-iPr)X] are obtained. Treatment of [Cr(κ3NCN-NCNCH2-iPr)Cl] with 1 equiv of PhCH2MgCl and LiCH2SiMe3 afforded the alkyl complexes [Cr(κ3NCN-NCNCH2-iPr)(CH2Ph)] and [Cr(κ3NCN-NCNCH2-iPr)(CH2SiMe3)]. All Cr(II) complexes exhibit effective magnetic moments in the range of 4.7-4.9 µB which is indicative for d4 high spin systems. If a solution of lithiated N(C-Br)NCH2-iPr is treated with CrCl2, followed by addition of an excess of Na[HB(Et)3], the dimeric complex [Cr(κ2NC-NCNCH2-iPr)(µ2-H)]2 is obtained bearing two bridging hydride ligands. [Cr(κ3NCN-NCNCH2-iPr)(CH2SiMe3)] turned out to be catalytically active for the hydrosilylation of ketones at room temperature with a catalyst loading of 1 mol%. X-ray structures of all complexes are presented. Supplementary Information: The online version contains supplementary material available at 10.1007/s00706-023-03128-6.

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High-performance catalysts sufficient to significantly reduce the energy barrier of water activation are crucial in facilitating reactions that are restricted by water dissociation. Herein we present a Cu-Co double-atom catalyst (CuCo-DAC), which possesses a uniform and well-defined CuCoN6 (OH) structure, and works together to promote water activation in silane oxidation. The catalyst achieves superior catalytic performance far exceeding that of single-atom catalysts (SACs). Various functional silanes are converted into silanols with up to 98 % yield and 99 % selectivity. Kinetic studies show that the activation energy of silane oxidation by CuCo-DAC is significantly lower than that of Cu single-atom catalyst (Cu-SAC) and Co single-atom catalyst (Co-SAC). Theoretical calculations demonstrate two different reaction pathways where water splitting is the rate-determining step and it is accelerated by CuCo-DAC, whereas H2 formation is key for its single-atom counterpart.

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Background: Porcelain fracture or chipping is one of the limitations of all ceramic restorations. This study investigated the shear bond strength (SBS) of composite resins to lithium disilicate ceramics using universal bondings and different methods of surface preparation. Materials and Methods: In this experimental study, 72 specimens of e.max computer-aided design and computer-aided manufacturing (CAD/CAM) ceramic blocks were divided into six groups of 12 according to surface treatment: Group I-Hydrofluoric (HF) acid etching + All-Bond Universal bonding (ABU), Group II-Bur roughening (BR) + HF + ABU, Group III-BR + HF + Bis-Silane (Si) + ABU, Group IV-Sandblasting (SB) + ABU, Group V-SB + HF + ABU, Group VI-SB + HF + Si + ABU. After bonding of composite resin to the prepared ceramic surface and storage of samples in distilled water for 24 h, SBS test was done using the universal testing machine at a crosshead speed of 0.5 mm/min. Data were analyzed using the analysis of variance and Tukey's post hoc test (α = 0.05). Results: The mean values of SBS in six studied groups were 6.65 ± 2.78 MPa, 8.56 ± 2.69 MPa, 8.49 ± 2.14 MPa, 3.13 ± 1.66 MPa, 7.94 ± 2.4 MPa, and 10.04 ± 2.47 MPa, respectively. The mean values of SBS were significantly different (P < 0.001). The highest value of SBS was observed in Group VI and the lowest in Group IV. Conclusion: Ceramic sandblasting followed by HF etching, Bis Si, and ABU resulted in a higher SBS of composite resins to lithium disilicate ceramics.

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Hot-melt adhesives (HMAs) are thermoplastic materials that can bond various substrates by solidifying rapidly upon cooling from the molten state, and their modification with organosilicon compounds can result in crosslinking behavior, characteristic of gels. Organosilicon compounds are hybrid molecules that have both inorganic and organic components and can enhance the properties and performance of HMAs. The gel aspect of HMA with and without organosilicon modifiers can be considered in organosilicon-modified systems, the modifiers are often either sol-gel condensation products or their mechanism of action on the adherent surface can be considered of sol-gel type. The purpose of this manuscript is to present the current state of the art on the formulation, characterization, and application of HMAs and optimize their performance with organosilicon compounds for application in various industries such as automotive, construction, and photovoltaics. This review covers articles published within the period of 2018-2022. The article is divided into sections, in which information about hot-melt adhesives is described at the beginning. The following part of the presented review focuses on the composition of hot-melt adhesives, which takes into account the use of organosilicon compounds. The last part of this review outlines the future trends in hot-melt adhesives.

RESUMEN

Group I alkoxides are highly active precatalysts in the heterodehydrocoupling of silanes and amines to afford aminosilane products. The broadly soluble and commercially available KOt Amyl was utilized as the benchmark precatalyst for this transformation. Challenging substrates such as anilines were found to readily couple primary, secondary, and tertiary silanes in high conversions (>90 %) after only 2 h at 40 °C. Traditionally challenging silanes such as Ph3 SiH were also easily coupled to simple primary and secondary amines under mild conditions, with reactivity that rivals many rare earth and transition-metal catalysts for this transformation. Preliminary evidence suggests the formation of hypercoordinated intermediates, but radicals were detected under catalytic conditions, indicating a mechanism that is rare for Si-N bond formation.