Search Results (19)

Polysiloxanes are unique polymers used in medicine and materials science and are ideal for various modifications. Classic functionalization methods involve a covalent approach, but finer tuning of the properties of the final polymers can also be achieved through sub-sequent noncovalent modifications. This study introduces a fundamentally new approach to polysiloxane functionalization by incorporating cooperative noncovalent interaction centers: selenium-based chalcogen bonding donors and polyfluoroaromatic π-hole acceptors into a single polymer platform. We developed an efficient nucleophilic substitution strategy using poly((3-chloropropyl)methylsiloxane) as a platform for introducing Se-containing groups with polyfluoroaromatic substituents. Three synthetic approaches were evaluated; only direct modification of Cl-PMS-2 proved successful, avoiding catalyst poisoning and crosslinking issues. The optimized methodology utilizes mild conditions and achieved high substitution degrees (74–98%) with isolated yields of 60–79%. Comprehensive characterization using ¹H, ¹³C, ¹⁹F, ⁷⁷Se, and ²⁹Si NMR, TGA, and contact angle measurements revealed significantly enhanced properties. Modified polysiloxanes demonstrated improved thermal stability (up to 37 °C higher decomposition temperatures, 50–60 °C shifts in DTG maxima) and increased hydrophobicity (water contact angles from 69° to 102°). These systems potentially enable chalcogen bonding and arene–perfluoroarene interactions, providing foundations for materials with applications in biomedicine, electronics, and protective coatings. This dual-functionality approach opens pathways toward adaptive materials whose properties can be tuned through supramolecular modification while maintaining the inherent advantages of polysiloxane platforms—flexibility, biocompatibility, and chemical inertness. Full article

The present study determined the distribution of fifteen methylsiloxane compounds (total methylsiloxanes, TMSs), including four cyclic (CMSs) and eleven linear (LMSs), in the marine surface sediment of Masan Bay, Korea, in 2018. The levels ranged from 76.6 to 2320 (median 264 ± 680), 5.00 to 3570 (median 359 ± 1310), and 81.6 to 5890 (median 607 ± 1940) ng/g-dw., in ΣCMSs, ΣLMSs, and ΣTMSs, respectively. The CMSs: LMSs ratio was 34:66, and the most dominant compound was D5 (27%), followed by L11 (22%) and L12 (20%). Principal component and cluster analyses categorized the ten sampling points into four groups based on the point sources: Group A (MS1) representing the industrial wastewater from the Changwon National Industrial complex; Group B (MS2) representing the ship movements; and Groups C (MS3, MS5, MS6, and MS7) and D (MS4, MS8, MS9, and MS10) representing the organic carbons. The present study hypothesized that the missing link between the methylsiloxane levels in 2013 and 2021 was due to the considerable industry recession in the bay. This was verified by positive correlations between the median ΣCMSs and the monthly production, the median ΣLMSs and ΣTMSs and the monthly employment in the complex. However, the hypothesis should be supplemented with the following perspectives: (1) selecting the sampling areas representing only the industrial wastewater, (2) considering the seasonal fluctuations, (3) estimating half-lives, and (4) investigating time series. This study is the first to link methylsiloxane levels and social issues in the bay, providing insights into illuminating the distribution characteristics of various pollutants. Full article

The automotive industry needs to improve energy efficiency rapidly to achieve carbon neutrality while creating a safe, secure, and comfortable driving environment for customers. Porous sound-absorbing materials and porous thermal insulators are typically used to satisfy these requirements despite limitations in mass and space. While these porous materials are similar, the microstructures they offer for high performance differ in the size and connectivity of their fluid phases, which enhances the difficulty of achieving excellent sound absorption and thermal insulation in the same material. In this study, a hydrophobic cellulose nanofiber–poly(methylsiloxane) xerogel composite was developed using computational microstructure modeling. This porous material has high porosity and excellent thermal insulation and sound absorption properties. Full article

A total of 8 mechanically ventilated residential buildings and 8 naturally ventilated residential buildings were selected to analyze the pollution characteristics of indoor VOCs under different ventilation modes in the severe cold area of northeast China. On typical meteorological days in each season, VOCs were detected on site, and ventilation modes were investigated by long-term online monitoring. The test results showed that the TVOC (total volatile organic compounds) concentrations varied greatly in different seasons or different functional rooms, and the TVOC concentration was the highest in winter, with a value of 0.994 mg/m³. The kitchen was the place with the most serious VOC pollution, and the TVOC concentration could reach 1.403 mg/m³. Benzene series and methylsiloxane had the highest detection rates, but the detected concentrations were low, and the average concentrations were 0.025 mg/m³ and 0.013 mg/m³ respectively. Among the VOC types with a detection rate greater than 50%, the average proportions of aldehydes, alkanes, and benzene series were 18.7%, 15.39%, and 14.38%, respectively. And their mass ratios were also high, which were 14.90%, 30.85%, and 15.70%, respectively. The annual daily average ventilation duration of mechanically ventilated residential buildings was 7.84 h longer than that of naturally ventilated residential buildings. The median TVOC concentrations of mechanically ventilated residential buildings and naturally ventilated residential buildings were 0.621 mg/m³ and 0.707 mg/m³, respectively. The fresh air system was applicable in the severe cold area of northeast China. Full article

Hydrogen sulphide (H₂S) and volatile methylsiloxanes (VMSs) are key pollutants from the point of view of the operators of biogas plants. H₂S poses corrosive hazards, while VMSs transform into difficult-to-remove deposits, reducing the availability and yield of biogas combustion equipment. This study provides a critical overview and evaluation (so-called SWOT analysis) of implemented and promising methods to reduce the content of the above pollutants in biogas, with particular emphasis on biological techniques. The aim of the analyses was to develop an innovative concept for a hybrid biological method for the combined removal of H₂S and VMSs using the same device, i.e., a two-phase biotrickling filter (BTF), in which the organic phase that intensifies the mass transfer of VMSs is in the form of a low-viscosity methyl silicone oil. The finally developed technological schematic diagram includes the basic devices and media streams. The concept is characterized by closed media circuits and comprehensively solves the problem of purifying biogas from sewage sludge. In conclusion, key issues requiring further research are identified. Full article

Methylsiloxanes (MSs), used in industrial production and personal care products, are released in various environmental media. In this study, we combined monitoring and modeling to investigate the occurrence and behavior of MSs in the urban environment in China. MSs were widely found in the air, water, soil and sediment of four cities in China. The concentrations of MSs in all four environmental media of Zhangjiagang were higher than those in the other three cities (Beijing, Kunming and Lijiang), indicating that the siloxane production plant had a significant impact on the pollution level of MSs in the surrounding environment. The samples with high MS concentrations were all from the sample sites near the outlet of the WWTPs, which showed that the effluent of the WWTPs was the main source of MS pollution in the surrounding environment. The modeling results of the EQC level III model showed that D4 discharged into the environment was mainly distributed in the air, while D5 and D6 were mainly distributed in the sediment. CMSs (D4–D6) discharged into various environmental media could exist in the urban environment for a long time with low temperatures in cities. When the temperature was 0 °C, the residence time of D5 and D6 could be 68.1 days and 243 days in the whole environmental system in Beijing. This study illustrates the importance of CMSs (D4–D6) in low-temperature environments and the potential environmental risks that they may pose. Full article

The branching and cross-linking of siloxane polymers are important processes in silicone technology. A new type of such a process has been developed, which is a self-restructuring of linear polyhydromethylsiloxane (PHMS). This process involves the reorganization of the PHMS to form a highly branched siloxane polymer or finally a cross-linked siloxane network. It occurs through the transfer of a hydride ion between silicon atoms catalyzed by tris(pentafluoromethyl)borane. Its advantage over existing branching and cross-linking reactions is that it runs at room temperature without a low-molecular-weight cross-linker in the absence of water, silanol groups, or other protic compounds and it does not use metal catalysts. The study of this process was carried out in toluene solution. Its course was followed by ¹H NMR, ²⁹Si NMR and FTIR, SEC, and gas chromatography. A general mechanism of this new self-restructuring process supported by quantum calculations is proposed. It has been shown that a linear PHMS self-restructured to a highly branched polymer can serve as a pure methylsiloxane film precursor. Full article

In this work, the synthesis of a new polysiloxane, poly {dimethylsiloxane-co-[4-(2,3-difluoro-4-hydroxyphenoxy) butyl] methylsiloxane} (dubbed PMFOS), is presented. This polymer exhibits high hydrogen bond acidity and was designed to be used as a sensor layer in gas sensors. The description of the synthetic route of the PMFOS has been divided into two main stages: the synthesis of the functional substituent 4-(but-3-en-1-yloxy)-2,3-difluorophenol, and the post-polymerization functionalization of the polysiloxane chain (methylhydrosiloxane-dimethylsiloxane copolymer) via hydrosilylation. The synthesized material was subjected to instrumental analysis, which confirmed its structure. The performed thermal analysis made it possible to determine some properties important for the sensor application, such as glass transition temperature and decomposition temperature. The results showed that PMFOS meets the requirements for materials intended for use in gas sensors based on acoustoelectric transducers. Full article

Microalgae are widely used in the bioremediation of wastewaters due to their efficient removal of pollutants such as nitrogen, phosphorus, and contaminants of emerging concern (CECs). Siloxanes are CECs that reach wastewater treatment plants (WWTPs), leading to the production of biogas enriched with these compounds, associated with the breakdown of cogeneration equipment. The biological removal of siloxanes from wastewaters could be a sustainable alternative to the costly existing technologies, but no investigation has been performed using microalgal cultures for this purpose. This study evaluated the ability of Chlorella vulgaris to bioremediate primary (PE) and secondary (SE) urban effluents and remove volatile methylsiloxanes (VMSs). C. vulgaris grew successfully in both effluents, and approximately 86% of nitrogen and 80% of phosphorus were efficiently removed from the PE, while 52% of nitrogen and 87% of phosphorus were removed from the SE, and the presence of VMSs does not seem to have a negative influence on nutrient removal. Three out of the seven of the analysed VMSs were detected in the microalgal biomass at the end of the PE assay. However, dodecamethylcyclohexasiloxane (D6) was the one that accumulated to a greater extent, since 48% of the initial mass of D6 was detected in the biomass samples. D6 is one of the most lipophilic VMSs, which might contribute to the higher adsorption onto the surface of microalgae. Overall, the results indicate C. vulgaris’ potential to remove specific VMSs from effluents. Full article

Developing self-healing silicone elastomers are highly significant because of their promising applications. Herein, we present novel self-healing disulfide-linked silicone elastomers (SEs) based on thiol-terminated sulfur-containing heterochain polysiloxanes (P-SHs) and three thiol-containing crosslinkers, including pentaerythritol tetrakis(β-mercaptopropionate) (PETMP), octa(3-mercaptopropyl)silsesquioxane (POSS-SH), and poly[(mercaptopropyl)methylsiloxane] (PMMS), via the thiol oxidation coupling reactions. The construction of these SEs can rapidly proceed at room temperature. The effects of crosslinker species and amounts on the formability and mechanical properties were investigated. The silicone elastomers can be self-healed by heating at 150 °C for 2 h or under UV radiation for 30 min after cutting them into pieces and the self-healing efficiency is >70%. Moreover, they can be utilized as adhesives for bonding glass sheets, which can hold a 200 g weight. The bonding is reversible and can repeatedly proceed many times, indicating that these materials can promisingly be applied as reversible adhesives. These results indicate that a thiol oxidation coupling reaction is a simple and effective strategy for the construction of self-healing disulfide-linked elastomers. Under this strategy, more disulfide-linked organic elastomers with self-healing properties can be designed and constructed and their applications can be further explored. Full article

This work investigates the possibility of using thiolated silicone oils as new components in protective creams and their impact on the efficacy of these products. Thiolated silicone oils were synthesized by amide bond formation between primary amino groups of poly17dimethylsiloxane-co-(3-aminopropyl)-methylsiloxane] and carboxylic groups of thiol ligand (3-mercaptopropionic acid) with carbodiimide as a coupling agent. To evaluate and compare the properties of these kinds of thiomers, three different emulsion o/w types were obtained. Emulsion E1 contained methyl silicone oil, E2 poly[dimethylsiloxane-co-(3-aminopropyl)-methylsiloxane], and E3 thiolated silicone oil (silicone-MPA), respectively. Physicochemical properties, including pH, conductivity, droplet size distribution, viscosity, and stability, were assessed. The efficacy of barrier creams in the prevention of occupational skin diseases depends on their mechanical and rheological properties. Thus, the method which imitates the spreadability conditions on the skin and how structure reconstruction takes places was performed. We also investigated textural profile, bioadhesion, protection against water and detergents, and water vapor permeability. Emulsion E3 was characterized by beneficial occlusion, spreadability, and adhesion properties. These features with prolonged residence time on the skin can make designed barrier creams more preferable for consumers. Full article

Volatile methylsiloxanes (VMSs) constitute a group of compounds used in a great variety of products, particularly personal care products. Due to their massive use, they are continually discharged into wastewater treatment plants and are increasingly being detected in wastewater and in the environment at low concentrations. The aim of this work was to develop and validate a fast and reliable methodology to screen seven VMSs in water samples, by headspace solid-phase microextraction (HS-SPME) followed by gas chromatography with flame ionization detection (GC-FID). The influence of several factors affecting the extraction efficiency was investigated using a design of experiments approach. The main factors were selected (fiber type, sample volume, ionic strength, extraction and desorption time, extraction and desorption temperature) and optimized, employing a central composite design. The optimal conditions were: 65 µm PDMS/Divinylbenzene fiber, 10 mL sample, 19.5% NaCl, 39 min extraction time, 10 min desorption time, and 33 °C and 240 °C as extraction and desorption temperature, respectively. The methodology was successfully validated, showing low detection limits (up to 24 ng/L), good precision (relative standard deviations below 15%), and accuracy ranging from 62% to 104% in wastewater, tap, and river water samples. Full article

Silicon oxynitrides (SiO_xN_y) have many advantageous properties for modern ceramic applications that justify a development of their new and efficient preparation methods. In the paper, we show the possibility of preparing amorphous SiO_xN_y-based materials from selected liquid organosilicon compounds, methyltrimethoxysilane CH₃Si(OCH₃)₃ and methyltriethoxysilane CH₃Si(OC₂H₅)₃, by a convenient spray pyrolysis method. The precursor mist is transported with an inert gas or a mixture of reactive gases through a preheated tube reactor to undergo complex decomposition changes, and the resulting powders are collected in the exhaust filter. The powders are produced in the tube at temperatures of 1200, 1400, and 1600 °C under various gas atmosphere conditions. In the first option, argon Ar gas is used for mist transportation and ammonia NH₃ gas serves as a reactive medium, while in the second option nitrogen N₂ is exclusively applied. Powder X-Ray Diffraction (XRD) results confirm the highly amorphous nature of all products except those made at 1600 °C in nitrogen. SEM examination shows the spheroidal particle morphology of powders, which is typical for this method. Fourier Transform Infrared (FT-IR) spectroscopy reveals the presence of Si–N and Si–O bonds in the powders prepared under Ar/NH₃, whereas those produced under N₂ additionally contain Si–C bonds. Raman spectroscopy measurements also support some turbostratic free carbon C in the products prepared under nitrogen. The directly determined O- and N-contents provide additional data linking the process conditions with specific powder composition, especially from the point of view of oxygen replacement in the Si–O moieties formed upon initial precursor decomposition reactions by nitrogen (from NH₃ or N₂) or carbon (from the carbonization of the organic groups). Full article

Biogas, a product of anaerobic digestion process that consists mainly of methane and carbon dioxide is a suitable alternative fuel if unwanted impurities are removed as they have a negative impact on the equipment. The most significant technologically troublesome trace compounds that must be removed are siloxanes since they are converted into silica on gas surface engines and turbines resulting in equipment damage. The quality of the gas is certainly improved by reducing the amount of impurities and the end use determines the extent of biogas cleaning needed. The major aim of this study was to compile information that can assist researchers or even designers in selecting a suitable technology to remove siloxanes. Siloxane removal definitely can be achieved using different methods and the effectiveness of each method relies on careful consideration of the characteristics of both biogas and siloxane, as well as the technological aspects of the method. Herein, we review on different cleaning techniques for siloxanes in raw biogas, the negative effects they have, their levels and technologies to reduce their concentrations. This review also incorporates the sources of the siloxanes, the progress to date on their removal and possible ways of regenerating adsorbents. The reviewed literature suggests that biogas upgrading technology should be promoted and encouraged especially in siloxane removal as it has detrimental effects on engines. The parameters and effectiveness of adsorption processes are discussed, and individual adsorbents are compared. Full article

Cyclic methylsiloxanes D4, D5, D6 (also called cyclic silicones) are widely used in various dermatological products and cosmetics, both for children and adults. As a result of their unique physicochemical properties, the production of cyclic methylsiloxanes has greatly increased over the last few years, which has resulted in increased exposure to mankind. The validated quantitative for gas chromatography-flame ionization detector (GC-FID) analysis with using the transdermal diffusion system with vertical Franz cells demonstrated that ex vivo human skin is not a barrier to cyclic siloxanes. D4, D5, and D6 have a specific affinity to stratum corneum (SC) (especially D6), and can even diffuse into the deeper layers of the skin (epidermis (E) and dermis (D)), or into the receptor fluid as well. An important achievement of this work was the observation of the characteristic ratio partitioning D4, D5, and D6 in skin layers and receptor fluid (RF). The studies have shown that, in order to thoroughly understand the mechanism, it is important to determine not only the differences in the amounts of cumulated doses in total in all skin layers and receptor fluid, but also the mutual ratios of analyte concentrations existing between matrices. For example, in the case of the stratum corneum, the cumulative doses of D4, D5, and D6 were 27.5, 63.9, and 67.2 µg/cm²/24 h, respectively, and in the epidermis, they were 6.9, 29.9, and 10.7 µg/cm²/24 h, respectively, which confirmed the highest affinity of D6 to stratum corneum as the amount diffused into the epidermis was 2.8 times smaller compared to D5. The calculated epidermis-to-stratum corneum ratios of analyte concentrations also confirm this. The largest ratio was identified for D5 (E/SC = 47), followed by D4 (E/SC = 25), and finally by D6 (E/SC = 16). The analysis of the next stage of diffusion from epidermis to dermis revealed that in dermis the highest cumulative dose was observed for D5 (13.9 µg/cm²/24 h), while the doses of D4 and D6 were similar (5.1 and 5.3 µg/cm²/24 h). Considering the concentration gradient, it can be concluded that the diffusion of D5 and D6 occurs at a similar level, while D4 diffuses at a much higher level. These observations were also confirmed by the dermis-to-epidermis concentration ratios. The final stage of diffusion from dermis to the receptor fluid indicated that D4 was able to permeate easily, while D5 exhibited a difficult diffusion and the diffusion of D6 was limited. The receptor fluid-to-dermis concentration ratios (RF/D) were calculated for D4, D5, and D6: 80, 53, and 17, respectively. Our results also revealed the increased risk of D4 and D5 absorption into the blood and lymphatic systems, whereas D6 demonstrated the lowest risk. Therefore, we can argue that, among the three tested compounds, D6 is the safest one that can be used in dermatological, cosmetic, and personal care products. This study demonstrates that the stratum corneum, epidermis, and dermis can be also considered reservoirs of cyclic methylsiloxanes. Therefore, these compounds can demonstrate potential long-term bioaccumulation, and can be absorbed to the bloodstream in a long-term and uncontrolled process. Full article