Effect of 4-META on microtensile bond strength of cements to ceramics.

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.

Surface Treatment Effect on the Mechanical and Thermal Behavior of the Glass Fabric Reinforced Polysulfone.

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.

Poly(vinyl chloride) Dechlorination Catalyzed by Zirconium.

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).

Durable Superhydrophobic Surfaces with Self-Generated Wenzel Sites for Efficient Fog Collection.

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.

Tribological and Antimicrobial Properties of Two-Component Self-Assembled Monolayers Deposited on Ti-Incorporated Carbon Coatings.

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.

A Heteroatom-Containing Functional Poly(Silylenevinylene): Synthesis, Anion Binding, and Sensing of Anion Extraction Processes.

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.

Catalyst-Free Trifluoromethoxylation of Silyl Enol Ethers and Allyl Silanes with Bis(trifluoromethyl)peroxide.

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.

Cr(II) and Cr(III) NCN pincer complexes: synthesis, structure, and catalytic reactivity.

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.

Water Activation Triggered by Cu-Co Double-Atom Catalyst for Silane Oxidation.

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.

Shear bond strength of composite resins to lithium disilicate ceramics using universal bonding and different methods of surface preparation.

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.

Group I Alkoxides and Amylates as Highly Efficient Silicon-Nitrogen Heterodehydrocoupling Precatalysts for the Synthesis of Aminosilanes.

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.

Recent Progress in the Synthesis of Silaspiranes.

Silaspiranes bearing a spiro-silicon center are promising ring frameworks for the synthesis of novel spirocyclic molecules possessing unique properties. Development of efficient methods towards these ring structures has therefore attracted considerable attentions of synthetic chemists. This minireview highlights the representative advances in the field, and is categorized into four parts according to the ring formation strategies: cyclization, annulation, ring expansion and cycloaddition.

Organosilicon Compounds in Hot-Melt Adhesive Technologies.

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.

The best method of reconditioning ceramic brackets to get an optimum shear bond strength compared with new ceramic brackets - Systematic review and meta-analysis of in vitro studies.

PURPOSE: Bracket debonding is an undesirable problem during fixed orthodontic treatment. As ceramic brackets have no flexibility, there is no change in the slot dimension. So, reconditioning a ceramic bracket can be done without compromising the quality of treatment and could be a cost-effective measure. The objective of this systematic review is to deduce and validate the best method of reconditioning ceramic bracket in order to get optimum clinical shear bond strength. MATERIAL AND METHODS: Studies such as randomized controlled trials (RCTs); In vitro studies comparing different interventions with control group, cross sectional studies were included. Electronic databases such as Cochrane database, PubMed, Web of Science, Embase were searched up to July 2022. Grey literature search and cross-referencing/snowballing methods were also used. Two reviewers independently selected studies and assessed the risk of bias using amalgamation of five tools for in vitro studies. Then meta-analysis was performed using random effects model. RESULTS: Eleven studies were included in which ten studies were considered as good quality studies. According the meta-analysis performed, the best performance in terms of shear bond strength was of new brackets. Among the different reconditioning methods, the meta-analysis showed that the method with the closest bond strength to the new brackets was silicatisation with a mean difference of 6.35MPa (95% CI between 2.39 and 10.31) followed by sandblasting+silane application with a mean difference of 3.36MPa (95% CI between 0.3 and 6.96) compared to other methods. CONCLUSIONS: Due to the lack of in vivo studies, only in vitro studies were evaluated. The data available from the in vitro studies was considered to be of good quality, leading to the conclusion that the best method for reconditioning debonded ceramic brackets is silicatisation followed by sandblasting and silane application.

Iron-Catalyzed Reductive Cross-Coupling of Alkyl Electrophiles with Olefins.

In terms of its abundance and its minimal toxicity, iron has advantages relative to other transition metals. Although alkyl-alkyl bond construction is central to organic synthesis, examples of iron-catalyzed alkyl-alkyl couplings of alkyl electrophiles are relatively sparse. Herein we report an iron catalyst that achieves cross-coupling reactions of alkyl electrophiles wherein olefins, in the presence of a hydrosilane, are used in place of alkylmetal reagents. Carbon-carbon bond formation proceeds at room temperature, and the method employs commercially available components (Fe(OAc)2 , Xantphos, and Mg(OEt)2 ); interestingly, this set of reagents can be applied directly to a distinct hydrofunctionalization of olefins, hydroboration. Mechanistic studies are consistent with the generation of an alkyl radical from the alkyl electrophile, as well as with reversibility for elementary steps that precede carbon-carbon bond formation (olefin binding to iron and ß-migratory insertion).

A Comprehensive Review on Processing, Development and Applications of Organofunctional Silanes and Silane-Based Hyperbranched Polymers.

Since the last decade, hyperbranched polymers (HBPs) have gained wider theoretical interest and practical applications in sensor technology due to their ease of synthesis, highly branched structure but dimensions within nanoscale, a larger number of modified terminal groups and lowering of viscosity in polymer blends even at higher HBP concentrations. Many researchers have reported the synthesis of HBPs using different organic-based core-shell moieties. Interestingly, silanes, as organic-inorganic hybrid modifiers of HBP, are of great interest as they resulted in a tremendous improvement in HBP properties like increasing thermal, mechanical and electrical properties compared to that of organic-only moieties. This review focuses on the research progress in organofunctional silanes, silane-based HBPs and their applications since the last decade. The effect of silane type, its bi-functional nature, its influence on the final HBP structure and the resultant properties are covered in detail. Methods to enhance the HBP properties and challenges that need to be overcome in the near future are also discussed.

Reversible Transition between Discrete and 1D Infinite Architectures: A Temperature-Responsive Cu(I) Complex with a Flexible Disilane-Bridged Bis(pyridine) Ligand.

A thermoresponsive structural change based on a disilane-bridged bis(pyridine) ligand and CuI is reported. Single-crystal X-ray analysis revealed that there are two polymorphs in the Cu(I) complex: octanuclear copper(I) complex at 20 °C and 1D staircase copper(I) polymer complex at -173 °C. The formation of these polymorphs is due to the flexibility of the ligand. Cu-I bond formation is observed upon cooling the sample from -10 °C to -170 °C. The temperature-induced phase transition progression was clarified by DSC, VT-PXRD, and VT-photoluminescence measurements and indicated a reversible temperature-controlled crystal-to-crystal phase transition. Observation on a VT-stage using a high-speed camera showed crystal cracking during single-crystal to single-crystal transitions between these polymorphic forms.

Potential Utilization of Ground Eggshells as a Biofiller for Natural Rubber Biocomposites.

The aim of this work was application of ground eggshells in various amounts by weight as a biofiller for natural rubber (NR) biocomposites. Cetyltrimethylammonium bromide (CTAB), ionic liquids (ILs), i.e., 1-butyl-3-methylimidazolium chloride (BmiCl) and 1-decyl-3-methylimidazolium bromide (DmiBr), and silanes, i.e., (3-aminopropyl)-triethoxysilane (APTES) and bis [3-(triethoxysilyl)propyl] tetrasulfide (TESPTS), were used to increase the activity of ground eggshells in the elastomer matrix and to ameliorate the cure characteristics and properties of NR biocomposites. The influence of ground eggshells, CTAB, ILs, and silanes on the crosslink density, mechanical properties, and thermal stability of NR vulcanizates and their resistance to prolonged thermo-oxidation were explored. The amount of eggshells affected the curing characteristics and crosslink density of the rubber composites and therefore their tensile properties. Vulcanizates filled with eggshells demonstrated higher crosslink density than the unfilled sample by approximately 30%, whereas CTAB and ILs increased the crosslink density by 40-60% compared to the benchmark. Owing to the enhanced crosslink density and uniform dispersion of ground eggshells, vulcanizates containing CTAB and ILs exhibited tensile strength improved by approximately 20% compared to those without these additives. Moreover, the hardness of these vulcanizates was increased by 35-42%. Application of both the biofiller and the tested additives did not significantly affect the thermal stability of cured NR compared to the unfilled benchmark. Most importantly, the eggshell-filled vulcanizates showed improved resistance to thermo-oxidative aging compared to the unfilled NR.

Polyamide 11 Composites Reinforced with Diatomite Biofiller-Mechanical, Rheological and Crystallization Properties.

Amorphic diatomaceous earth is derived from natural sources, and polyamide 11 (PA11) is produced from materials of natural origin. Both of these materials show a low harmfulness to the environment and a reduced carbon footprint. This is why the combination of these two constituents is beneficial not only to improve the physicochemical and mechanical properties of polyamide 11 but also to produce a biocomposite. For the purpose of this paper, the test biocomposite was produced by combining polyamide 11, as well as basic and pre-fractionated diatomaceous earth, which had been subjected to silanization. The produced composites were used to carry out rheological (melt flow rate-MFR), mechanical (tensile strength, bending strength, impact strength), crystallographic (X-ray Diffraction-XRD), thermal and thermo-mechanical (differential scanning calorimetry-DSC, dynamic mechanical thermal analysis-DMTA) analyses, as well as a study of hydrophobic-hydrophilic properties of the material surface (wetting angle) and imaging of the surface of the composites and the fractured specimens. The tests showed that the additive 3-aminopropyltriethoxysilane (APTES) acted as an agent that improved the elasticity of composites and the melt flow rate. In addition, the produced composites showed a hydrophilic surface profile compared to pure polylactide and polyamide 11.

Substituent Effects in Tetrel Bonds Involving Aromatic Silane Derivatives: An ab initio Study.

In this manuscript substituent effects in several silicon tetrel bonding (TtB) complexes were investigated at the RI-MP2/def2-TZVP level of theory. Particularly, we have analysed how the interaction energy is influenced by the electronic nature of the substituent in both donor and acceptor moieties. To achieve that, several tetrafluorophenyl silane derivatives have been substituted at the meta and para positions by several electron donating and electron withdrawing groups (EDG and EWG, respectively), such as -NH2, -OCH3, -CH3, -H, -CF3 and -CN substituents. As electron donor molecules, we have used a series of hydrogen cyanide derivatives using the same EDGs and EWGs. We have obtained the Hammett's plots for different combinations of donors and acceptors and in all cases we have obtained good regression plots (interaction energies vs. Hammet's σ parameter). In addition, we have used the electrostatic potential (ESP) surface analysis as well as the Bader's theory of atoms in molecules (AIM) and noncovalent interaction plot (NCI plot) techniques to further characterize the TtBs studied herein. Finally, a Cambridge Structural Database (CSD) inspection was carried out, retrieving several structures where halogenated aromatic silanes participate in tetrel bonding interactions, being an additional stabilization force of their supramolecular architectures.