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Adamantane-type organotin sulfide clusters were recently shown to react with coinage metal phosphine complexes under replacement of an organic substituent by a metal-phosphine unit. An extension of such studies involving the silicon-based congener [(PhSi)4S6] (A) revealed that the cluster core will be partly disassembled and a {PhSi} moiety is replaced by a coinage metal phosphine complex to form [(Et3PAg)3(PhSi)3S6] (B) and [Na2(thf)2.33][(Me3PCu)(PhSi)3S6] (C). Herein, we present an extension of this work upon variation of the reactants and reaction conditions. Besides the isolation of crystalline precursor complexes [CuCl(PMe2Ph)3] (1) and [AgCl(PMe2Ph)2]2 (2), the study addresses reactions of A with AgCl and a phosphine ligand in CH2Cl2, upon which A is completely disassembled to form [(Ph3P)3Ag(µ-S)SiCl2Ph] (3). In another case a CH2 group, most likely stemming from CH2Cl2, was attached to the ligand, thus generating [{PhCl(S)SiSCH2P(Ph2)CH2CH2}2] (4). Upon using CuCl and 1,4-bis(diphenylphosphino)butane (dppb) we isolated the phosphine-bridged analog of B, [{(dppbCu2)CuP(Ph2)(CH2CH2)(PhSi)3S6}2] (5). In order to receive the yet elusive silver homolog of C, we used PMe2Ph as a bulkier ligand. This way we generated a 2D coordination polymer of the desired composition, [Na2(thf)1.5][(Me2PhPAg)(PhSi)3S6] (6). UV-visible spectra of 6 indicated a bandgap of 3.89 eV, thus blue-shifted in regards to B and C.

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The assessment of residue, absorption, conduction, and degradation of agricultural organosilicon surfactants in the environment is hindered by the lack of information on active ingredients and corresponding quantitative standards for organosilicon spray adjuvants. The spray adjuvant 'Jiexiaoli,' a primary organosilicon spray agent in China, was identified as hydroxy (polyethylene) propyl-heptamethyl trisiloxane (TSS-H) with 3-15 ethoxy (EO) groups. Purification of TSS-H was achieved through semi-preparative separation using high-performance liquid chromatography (HPLC), resulting in TSS-H purity exceeding 96%. An accurate residual detection method for nine oligomers (4-12 EO) of TSS-H in rice roots, stems, leaves, and culture solution samples was developed using HPLC tandem high-resolution mass spectrometry (HPLC-HRMS). Recoveries for nine oligomers of TSS-H in the four matrices ranged from 80.22% to 104.01%. Foliar application experiments demonstrated that TSS-H did not transfer from the upper to the lower parts of the rice plant. The half-lives of each oligomer (4-12 EO) in leaves were less than 3.21 days. Root application experiments revealed a root concentration factor (RCF) ranging from 0.20 to 0.56, a biological enrichment factor (BCF) ranging from 0.36 to 0.68, a transpiration factor (TSCF) ranging from 0.069 to 0.086, and a transport factor (TF) ranging from 0.08 to 0.43. These results indicated that TSS-H could be absorbed by rice roots and conducted to the above-ground parts of rice plants. This study fills the data gap in the environmental risk and food safety assessment of agricultural silicone spray adjuvants. © 2024 Society of Chemical Industry.

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Preparation of hydrophobic coatings is still a challenge for researchers in various fields of science. One of the easiest ways consists of the use of special modifiers. However, usually such modifiers are poorly compatible with organic polymeric matrixes, which leads to segregation of modifiers and deterioration of coating properties. In this work, we have synthesized a number of organosilicon copolymers and studied their compatibility with epoxy matrix and hydrophobic efficiency. It was shown that the increase of phenyl-containing units leads to increase of compatibility but decreases hydrophobic efficiency. Addition of small amounts of such modifiers into commercial epoxy paint material can lead to an increase of contact angle of the final coating from 63 to 87° without deterioration of other physico-mechanical properties. These results open new perspectives in preparation of organosilicon hydrophobic modifiers with directed properties for fields of application such as paints and coating materials.

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We present a novel approach for iodide sensing based on the heavy-atom effect to quench the green fluorescent emission of organosilicon nanoparticles (OSiNPs). The fluorescence of OSiNPs was significantly quenched (up to 97.4% quenching efficiency) in the presence of iodide ions (I-) through oxidation by hydrogen peroxide. Therefore, OSiNPs can serve as a fluorescent probe to detect I- with high selectivity and sensitivity. The highly selective response is attributed to the hydrophilic surface enabling good dispersion in aqueous solutions and the lipophilic core allowing the generated liposoluble I2 to approach and quench the fluorescence of OSiNPs. The linear working range for I- was from 0 to 50 µM, with a detection limit of 0.1 µM. We successfully applied this nanosensor to determine iodine content in edible salt. Furthermore, the fluorescent OSiNPs can be utilized for the determination of total antioxidant capacity (TAC). Antioxidants reduce I2 to I-, and the extent of quenching by the remaining I2 on the OSiNPs indicates the TAC level. The responses to ascorbic acid, pyrogallic acid, and glutathione were investigated, and the detection limit for ascorbic acid was as low as 0.03 µM. It was applied to the determination of TAC in ascorbic acid tablets and fruit juices, indicating the potential application of the OSiNP-based I2 sensing technique in the field of food analysis.

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4-(trimethylsilyl)morpholine O(CH2CH2)2NSi(CH3)3 (TMSM) was investigated as a single-source precursor for SiCNO films synthesis. Optical emission spectroscopy of plasma generated from TMSM/He, TMSM/H2, and TMSM/NH3 gas mixtures revealed the presence of N2, CH, H, CN, and CO species. The last two are suggested to be responsible for the lowering of carbon concentration in the films in comparison with the precursor. The refractive index ranged from 1.5 to 2.0, and bandgap varied from 2.0 to 4.6 eV, which pointed that some of the films can be used as antireflective coatings in silicon photovoltaic cell technologies and dielectric layers in electronic devices.

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Bio-based coating materials have received increased attention because of their low-cost, environmentally friendly, and sustainable properties. In this paper, a novel coating material was developed to coat ureas using bio-based coating material derived from liquefied eggplant branches to form controlled-release ureas (CRUs). Also, the optimum proportion of liquefier was studied. Furthermore, dimethyl siloxane was used to modify liquified eggplant branches to make them hydrophobic, resulting in hydrophobic controlled-release ureas (SCRUs). This hydrophobic-enabled coating is environmentally friendly and highly efficient. The products were characterized by specific scanning electron microscopy, energy-dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, and differential scanning calorimetry, and the water contact angles of CRUs and SCRUs were determined. The nutrient-release characteristics of the SCRUs in water were determined at 25 °C and compared with those of CRUs. The results showed that the modification with dimethyl siloxane reduced the N release rate and increased the longevity of the fertilizer coated with hydrophobic bio-based coating material. In addition, organosilicon atoms on the SCRU surface also block the micro-holes on the coating and thus reduce the entry of water onto the coating. The results suggest that the new coating technology can create a hydrophobic surface on bio-based coating material and thus improve their controlled-release characteristics.

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The structural and electro-thermophysical characteristics of organosilicon elastomers modified with multilayer carbon nanotubes (MWCNTs) synthesized on Co-Mo/Al2O3-MgO and metallic (Cu or Ni) microparticles have been studied. The structures were analyzed with scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, and energy-dispersive X-ray spectroscopy (EDX). The main focus of this study was the influence of metallic dispersed fillers on the resistance of a modified elastomer with Cu and Ni to the degradation of electrophysical parameters under the action of applied electrical voltage. The distribution of the temperature field on the surface of a modified polymer composite with metallic micro-dimensional structures has been recorded. The collected data demonstrate the possibility of controlling the degradation caused by electrical voltage. It has been found that repeated on/off turns of the elastomer with an MWCNTs on 50 and 100 cycles leads to a deterioration in the properties of the conductive elastomer from the available power of 1.1 kW/m2 (-40 °C) and, as a consequence, a decrease in the power to 0.3 kW/m2 (-40 °C) after 100 on/off cycles. At the same time, the Ni additive allows increasing the power by 1.4 kW/m2 (-40 °C) and reducing the intensity of the degradation of the conductive structures (after 100 on/off cycles up to 1.2 kW/m2 (-40 °C). When Ni is replaced by Cu, the power of the modified composite in the heating mode increases to 1.6 kW/m2 (-40 °C) and, at the same time, the degradation of the conductive structures in the composite decreases in the mode of cyclic offensives (50 and 100 cycles) (1.5 kW/m2 (-40 °C)). It was found that the best result in terms of heat removal is typical for an elastomer sample with an MWCNTs and Cu (temperature reaches 93.9 °C), which indicates an intensification of the heat removal from the most overheated places of the composite structure. At the same time, the maximum temperature for the Ni additives reaches 86.7 °C. A sample without the addition of a micro-sized metal is characterized by the local unevenness of the temperature field distribution, which causes undesirable internal overheating and destruction of the current-conducting structures based on the MWCNTs. The maximum temperature at the same time reaches a value of 49.8 °C. The conducted studies of the distribution of the micro-sizes of Ni and Cu show that Cu, due to its larger particles, improves internal heat exchange and intensifies heat release to the surface of the heater sample, which improves the temperature regime of the MWCNTs and, accordingly, increases resistance to electrophysical degradation.

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Perovskite nanocrystals (PNCs) bear a huge potential for widespread applications, such as color conversion, X-ray scintillators, and active laser media. However, the poor intrinsic stability and high susceptibility to environmental stimuli including moisture and oxygen have become bottlenecks of PNC materials for commercialization. Appropriate barrier material design can efficiently improve the stability of the PNCs. Particularly, the strategy for packaging PNCs in organosilicon matrixes can integrate the advantages of inorganic-oxide-based and polymer-based encapsulation routes. However, the inert long-carbon-chain ligands (e.g., oleic acid, oleylamine) used in the current ligand systems for silicon-based encapsulation are detrimental to the cross-linking of the organosilicon matrix, resulting in performance deficiencies in the nanocrystal films, such as low transparency and large surface roughness. Herein, we propose a dual-organosilicon ligand system consisting of (3-aminopropyl)triethoxysilane (APTES) and (3-aminopropyl)triethoxysilane with pentanedioic anhydride (APTES-PA), to replace the inert long-carbon-chain ligands for improving the performance of organosilicon-coated PNC films. As a result, strongly fluorescent PNC films prepared by a facile solution-casting method demonstrate high transparency and reduced surface roughness while maintaining high stability in various harsh environments. The optimized PNC films were eventually applied in an X-ray imaging system as scintillators, showing a high spatial resolution above 20 lp/mm. By designing this promising dual organosilicon ligand system for PNC films, our work highlights the crucial influence of the molecular structure of the capping ligands on the optical performance of the PNC film.

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Significant progress has been made in recent years in the use of atmospheric pressure plasma techniques for surface modification. This research focused on the beneficial effects of these processes on natural by-products, specifically those involving natural fiber-based materials. The study explored the deposition of hydrophobic organosilicon-like thin films onto flax fibres through plasma-enhanced chemical vapour deposition (PECVD), using tetramethylcyclotetrasiloxane (TMCTS) as the precursor. After the successful deposition of hydrophobic organosilicon-like thin films onto the flax fibres, polylactic acid (PLA) composite materials were fabricated. This fabrication process sets the stage for an in-depth analysis of the modified materials. Subsequently, these flax fabrics were subjected to meticulous characterization through scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and contact angle measurements. The results demonstrated successful TMCTS deposition on the surface which led to a complete hydrophobization of the flax fibers. Mechanical tests of the PLA/flax fibre composites revealed a significant improvement in load transfer and interfacial compatibility following the surface modification of the flax fibres. This improvement was attributed to the enhanced adhesion between the modified fibres and the PLA matrix. The findings highlight the potential of TMCTS-based PECVD as a practical surface modification technique, effectively enhancing the mechanical properties of PLA/flax fibre composites. These developments open exciting possibilities for sustainable and high-performance composite materials in various industries.

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HYPOTHESIS: The nano-delivery platform, -SS-HMONs@MB@MnO2 nanoparticles (SMM NPs) loaded with methylene blue (MB) as photosensitizer have excellent photodynamic therapy (PDT) effect. The disulfide bond and MnO2 give the shell redox-responsive properties. SMM NPs consume glutathione (GSH) in tumor cells, reducing the scavenging of reactive oxygen species (ROS) by GSH and enhancing the PDT effect of MB. EXPERIMENTS: The GSH dual-responsive nano-delivery platform, was designed and constructed by using disulfide-doped hollow mesoporous organosilicon nanoparticles (-SS-HMONs) as intermediate responsive layer, loaded with MB as photosensitizer and coated with MnO2 as shells. The MB photosensitizer release and GSH response were characterized. The PDT effect of nanoparticles was evaluated. FINDINGS: The SMM NPs were uniform in size and well dispersed. The nanoparticles could react with GSH, leading to the decomposition of MnO2 shells and the breakage of disulfide bonds in -SS-HMONs, resulted in the release of MB photosensitizer. The cell experiment showed that SMM NPs had good ROS generating ability and PDT effect after being sucked by tumor cells, which could effectively kill tumor cells. However, in vivo experiments demonstrated that SMM NPs showed slight inhibition on tumor growth. The actual effect in animals was different from the effect in cells.

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Carbon dots (CDs) are a newly discovered type of fluorescent material that has gained significant attention due to their exceptional optical properties, biocompatibility, and other remarkable characteristics. However, single CDs have some drawbacks such as self-quenching, low quantum yield (QY), and poor stability. To address these issues, researchers have turned to organosilicon, which is known for its green, economical, and abundant properties. Organosilicon is widely used in various fields including optics, electronics, and biology. By utilizing organosilicon as a synthetic precursor, the biocompatibility, QY, and resistance to self-quenching of CDs can be improved. Meanwhile, the combination of organosilicon with CDs enables the functionalization of CDs, which significantly expands their original application scenarios. This paper comprehensively analyzes organosilicon in two main categories: precursors for CD synthesis and matrix materials for compounding with CDs. The role of organosilicon in these categories is thoroughly reviewed. In addition, the paper presents various applications of organosilicon compounded CDs, including detection and sensing, anti-counterfeiting, optoelectronic applications, and biological applications. Finally, the paper briefly discusses current development challenges and future directions in the field.

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A palladium-catalyzed skeletal rearrangement of 2-(2-allylarylsilyl)aryl triflates has been developed to give highly fused tetrahydrophenanthrosilole derivatives via unprecedented 1,5-C-Pd/C-Si bond exchange. The reaction pathways can be switched toward 4-membered ring-forming C(sp2 )-H alkylation by tuning the reaction conditions to give completely different products, fused dihydrodibenzosilepin derivatives, from the same starting materials. The inspection of the reaction conditions revealed the importance of carboxylates in promoting the C-Pd/C-Si bond exchange.

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This study presents a novel ″3-in-1″ hybrid biocatalyst design that combines the individual efficiency of microorganisms while avoiding negative interactions between them. Yeast cells of Ogataea polymorpha VKM Y-2559, Blastobotrys adeninivorans VKM Y-2677, and Debaryomyces hansenii VKM Y-2482 were immobilized in an organosilicon material by using the sol-gel method, resulting in a hybrid biocatalyst. The catalytic activity of the immobilized microorganism mixture was evaluated by employing it as the bioreceptor element of a biosensor. Optical and scanning electron microscopies were used to examine the morphology of the biohybrid material. Elemental distribution analysis confirmed the encapsulation of yeast cells in a matrix composed of methyltriethoxysilane (MTES) and tetraethoxysilane (TEOS) (85 and 15 vol %, respectively). The resulting heterogeneous biocatalyst exhibited excellent performance in determining the biochemical oxygen demand (BOD) index in real surface water samples, with a sensitivity coefficient of 50 ± 3 × 10-3·min-1, a concentration range of 0.3-31 mg/L, long-term stability for 25 days, and a relative standard deviation of 3.8%. These findings demonstrate the potential of the developed hybrid biocatalyst for effective pollution monitoring and wastewater treatment applications.

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Agronomic biofortification of crops is a promising approach that can improve the nutritional value of staple foods by alleviating dietary micronutrient deficiencies. Iodine deficiency is prevalent in many countries, including Australia, but it is not clear what foliar application strategies will be effective for iodine fortification of grain. This study hypothesised that combining adjuvants with iodine in foliar sprays would improve iodine penetration in wheat, leading to more efficient biofortification of grains. The glasshouse experiment included a total of nine treatments, including three reference controls: 1) Water; 2) potassium iodate (KIO3) and 3) potassium chloride (KCl); and a series of six different non-ionic surfactant or oil-based adjuvants: 4) KIO3 + BS1000; 5) KIO3 + Pulse® Penetrant; 6) KIO3 + Uptake®; 7) KIO3 + Hot-Up®; 8) KIO3 + Hasten® and 9) KIO3 + Synerterol® Horti Oil. Wheat was treated at heading, and again during the early milk growth stage. Adding the organosilicon-based adjuvant (Pulse®) to the spray formulation resulted in a significant increase in grain loading of iodine to 1269 µg/kg compared to the non-adjuvant KIO3 control at 231µg/kg, and the water and KCl controls (both 51µg/kg). The second most effective adjuvant was Synerterol® Horti Oil, which increased grain iodine significantly to 450µg/kg. The Uptake®, BS1000, Hasten®, and Hot-Up® adjuvants did not affect grain iodine concentrations relative to the KIO3 control. Importantly, iodine application and the subsequent increase in grain iodine had no significant effects on biomass production and grain yield relative to the controls. These results indicate that adjuvants can play an important role in agronomic biofortification practices, and organosilicon-based products have a great potential to enhance foliar penetration resulting in a higher translocation rate of foliar-applied iodine to grains, which is required to increase the iodine density of staple grains effectively.

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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.

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The fabrication of self-healing elastomers with high thermal stability for use in extreme thermal conditions such as aerospace remains a major challenge. A strategy for preparing self-healing elastomers with stable covalent bonds and dynamic metal-ligand coordination interactions as crosslinking sites in polydimethylsiloxane (PDMS) is proposed. The added Fe (III) not only serves as the dynamic crosslinking point at room temperature which is crucial for self-healing performance, but also plays a role as free radical scavenging agent at high temperatures. The results show that the PDMS elastomers possessed an initial thermal degradation temperature over 380 °C and a room temperature self-healing efficiency as high as 65.7%. Moreover, the char residue at 800 °C of PDMS elastomer reaches 7.19% in nitrogen atmosphere, and up to 14.02% in air atmosphere by doping a small amount (i.e., 0.3 wt%) of Fe (III), which is remarkable for the self-healing elastomers that contain weak and dynamic bonds with relatively poor thermal stability. This study provides an insight into designing self-healing PDMS-based materials that can be targeted for use as high-temperature thermal protection coatings.

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Metal ions have significant roles in diagnosis, industry, human health, and the environment. To design and develop new lucid molecular receptors for the selective detection of metal ions is important for environmental and medical applications. In the present work, two-armed indole appended Schiff bases conjoined with 1,2,3-Triazole bis-organosilane and bis-organosilatrane skelton sensors for naked eye colorimetric and fluorescent detection sensors for Al(III) are developed. The introduction of Al(III) in sensor 4 and 5 show red shift in UV-visible spectra, changes in fluorescence spectra and immediate color change from colorless to dark yellow. Furthermore, the pH and time response studies were explored for both sensors 4 & 5. The sensors 4 and 5 exhibited significantly low detection limit (LOD) in nano-molar range 1.41 × 10-9 M and 0.17 × 10-9 M respectively from emission titration. The LOD form absorption titration was found to be 0.6 × 10-7 M for sensor 4 and 0.22 × 10-7 M for sensor 5. In addition, the sensing model is developed as paper based sensor for its practical applicability. The theoretical calculations were performed on Gaussian 03 program by relaxing the structures using Density functional theory.

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Efficient separation and enrichment of uranium from radioactive effluents is of strategic significance for sustainable development of nuclear energy and environmental protection. Macropore structure of adsorbent is conducive to accessibility of the pore and transport of the adsorbate during dynamic adsorption. However, the low specific surface area results in fewer ligand sites and subsequently reduces the adsorption capacity. Herein, we present a novel strategy for efficient dynamic uranium enrichment using polyphosphonate-segmented macroporous organosilicon frameworks (PMOFs). PMOFs are constructed through the copolymerization of diethyl vinylphosphonate and triethoxyvinylsilane, followed by hydrolysis and condensation of the oligomers. The introduction of polyphosphonate segments into the frameworks endows PMOFs with a macroporous structure (31 µm) and a high ligand content (up to 72 wt%). Consequently, the optimized PMOF-3 demonstrated an ultrahigh dynamic adsorption capacity of 114.8 mg/g among covalently conjugated silicon-based materials. Additionally, PMOF-3 achieves a high enrichment factor (120) in the dynamic enrichment of uranium on a fixed bed column, which can be in-situ regenerated with 1 M NaHCO3 as the eluent. This work presents a new strategy for efficient dynamic enrichment of nuclides, which can be extended to the separation of other specific pollutants, shedding new light on adsorbent design and technical innovation.

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Herein, a series of novel sulfur-containing functionalized disiloxanes based on a low-cost and commercially available material, i.e., 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, and various thiol compounds were prepared by thiol-epoxy click reaction. It was found that both lithium hydroxide (LiOH) and tetrabutylammonium fluoride (TBAF) have high catalytic activity after optimizing the reaction condition, and the reaction can be carried out with high yields, excellent regioselectivity, mild reaction condition, and good tolerance of functional groups. These compounds exhibit excellent nonconventional fluorescence due to the formation of coordination bonds between Si atoms and heteroatoms (e.g., S or N) and can emit blue fluorescence upon ultraviolet (UV) irradiation. These results demonstrate that the thiol-epoxy click reaction could promisingly act as an efficient organosilicon synthetic methodology to construct various organosilicon materials with novel structures and functionality, and thus their application scope will be significantly expanded.

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Investigations into C-H amidation reactions catalysed by cationic half-sandwich d6 metal complexes revealed that the indenyl-derived catalyst [Ind*RhCl2 ]2 significantly accelerated the directed ortho C-H amidation of benzoyl silanes using 1,4,2-dioxazol-5-ones. Ring slippage involving a haptotropic η5 to η3 rearrangement of the indenyl complex proposedly enables ligand substitution at the metal centre to proceed via associative, rather than dissociative pathways, leading to significant rate and yield enhancements. Intriguingly, this phenomenon appears specific for C-H amidation reactions involving weakly coordinating carbonyl-based directing groups with no acceleration observed for the corresponding reactions involving strongly coordinating nitrogen-based directing groups.