A comparative in vitro analysis of various temporization materials with respect to pulp chamber temperature changes during polymerization.

AIM: (1) To compare the temperature rise in the pulp chamber with different resin materials used for making provisional fixed partial dentures in anterior and posterior region while using Polyvinylsiloxane impression materials as matrix. (2) To identify a superior provisionalization material based on the amount of heat dissipated suitable for anterior and posterior provisional fixed partial denture fabrication. SETTINGS AND DESIGN: Temporary crowns and bridges are integral to Fixed Prosthodontics. It has been observed that conventional fixed prosthesis temporisation materials release heat due to the exothermic polymerisation reaction. When such a provisional material is directly let to set on a vital tooth, the heat transfer causes irreversible changes in the pulp tissue depending of the degree of change. Hence, this study observes amount of heat generation in various materials during temporisation procedure, by simulating similar conditions. MATERIALS AND METHODS: Two Models were fabricated, one simulating missing lateral incisor (Model A) and another simulating missing first molar (Model B). Intact maxillary central incisors and canine for Model A and intact mandibular Second Premolar and Second Molar were selected to act as abutments. These abutment teeth were fitted with the tip of a K-type Thermocouple inside their pulp chambers and these were connected to a digital thermometer. Five temporisation materials were chosen for fabrication of temporary crowns through Direct technique. (1) polymethy methacrylate (Self Cure acrylic), (2) bisacryl composite (Protemp 4), (3) visible light cure urethane dimethacrylate (Revotec LC), (4) barium glass and fumed silica infused methacrylate (Dentsply Integrity) and (5)nano-hybrid composite (VOCO Structur 3). Ten observations were made for each provisional material on each model. During each observation, temperature rise was recorded at 30s interval from the time of application, through the peak and till a decrease in temperature is observed. Polyvinyl siloxane was used as matrix for all except light cure resin, where polypropylene sheet was used. STATISTICAL ANALYSIS USED: Anova test used for statistical. RESULTS: ANOVA test revealed that there was a significant difference in the temperature changes associated with the provisional restorative materials used. Among the five, polymethy methacrylate (self cure resin) showed the maximum rise in temperature, followed by bisacryl composite (Protemp 4), visible light cure urethane dimethacrylate (Revotec LC), barium glass and fumed silica infused methacrylate (Dentsply Integrity) and nano-hybrid composite (VOCO Structur 3). There was no comparable difference between Model A and B but an overall reduction of temperature rise was observed in model B. CONCLUSION: VOCO Structur 3 showed the least temperature rise in the pulp chamber, and overall temperature rise was less for model B which can be attributed to the residual dentin thickness.

Polymers from Plant Oils Linked by Siloxane Bonds for Programmed Depolymerization.

The increased production of plastics is leading to the accumulation of plastic waste and depletion of limited fossil fuel resources. In this context, we report a strategy to create polymers that can undergo controlled depolymerization by linking renewable feedstocks with siloxane bonds. α,ω-Diesters and α,ω-diols containing siloxane bonds were synthesized from an alkenoic ester derived from castor oil and then polymerized with varied monomers, including related biobased monomers. In addition, cyclic monomers derived from this alkenoic ester and hydrosiloxanes were prepared and cyclized to form a 26-membered macrolactone containing a siloxane unit. Sequential ring-opening polymerization of this macrolactone and lactide afforded an ABA triblock copolymer. This set of polymers containing siloxanes underwent programmed depolymerization into monomers in protic solvents or with hexamethyldisiloxane and an acid catalyst. Monomers afforded by the depolymerization of polyesters containing siloxane linkages were repolymerized to demonstrate circularity in select polymers. Evaluation of the environmental stability of these polymers toward enzymatic degradation showed that they undergo enzymatic hydrolysis by a fungal cutinase from Fusarium solani. Evaluation of soil microbial metabolism of monomers selectively labeled with 13C revealed differential metabolism of the main chain and side chain organic groups by soil microbes.

Microaeration promotes volatile siloxanes conversion to methane and simpler monomeric products.

The ubiquitous use of volatile siloxanes in a myriad of product formulations has led to a widespread distribution of these persistent contaminants in both natural ecosystems and wastewater treatment plants. Microbial degradation under microaerobic conditions is a promising approach to mitigate D4 and D5 siloxanes while recovering energy in wastewater treatment plants. This study examined D4/D5 siloxanes biodegradation under both anaerobic and microaerobic conditions ( [Formula: see text]  = 0, 1, 3 %) using wastewater sludge. Results show that the use of microaeration in an otherwise strictly anaerobic environment significantly enhances siloxane conversion to methane. 16S rRNA gene sequencing identified potential degraders, including Clostridium lituseburense, Clostridium bifermentans and Synergistales species. Furthermore, chemical analysis suggested a stepwise siloxane conversion preceding methanogenesis under microaerobic conditions. This study demonstrates the feasibility of microaerobic siloxane biodegradation, laying groundwork for scalable removal technologies in wastewater treatment plants, ultimately highlighting the importance of using bio-based approaches in tackling persistent pollutants.

Studies of thermoluminescence properties of liquid crystalline N-phenyl substituted phenyl polysiloxane hydroxamic acids.

The investigation of thermoluminescence (TL) glow curves in liquid crystalline side chain N-phenyl-substituted phenyl polysiloxane hydroxamic acids (PHAs) has yielded significant insights. These polymers demonstrated TL behavior when exposed to ß-radiation between 0 and 220°C, indicating inherent luminescent properties when irradiated. Notably, a dose-dependent relationship was observed in reported derivatized polymers; this study elucidates the diverse TL characteristics exhibited by various liquid crystalline side chain N-phenyl-substituted phenyl PHAs when exposed to ß-radiation. Understanding these dose-dependent and dose-independent behaviors enhances the knowledge of their luminescent properties and potential applications in radiation detection.

Polymeric microenvironment enhancing polarity response sensitivity for discriminating lipid droplets in cancer cells.

Cellular micro-environment analysis via fluorescence probe has become a powerful method to explore the early-stage cancer diagnosis and pathophysiological process of relevant diseases. The polarity change of intracellular lipid droplets (LDs) is closely linked with disorders or diseases, which result in various physiological and pathological processes. However, the efficient design strategy for lipid droplet polarity probes with high sensitivity is lacking. To overcome this difficulty, two kinds of LDs-targeting and polarity-sensitive fluorescent probes containing carbazole and siloxane groups were rationally designed and synthesized. With the carbazole-based rotor and bridge-like siloxanes, two probes (P1 and P2) behave high sensitivity to polarity changes and show different fluorescent intensity in normal and cancer cells. Notably, polysiloxanes groups promoted the response sensitivity of the probes dramatically for the polymeric microenvironment. In addition, due to the polarity changes of LDs in cancer cells, the distinct fluorescent intensities in different channels of laser scanning confocal microscope were observed between NHA cell and U87 cells. This work could offer an opportunity to monitor the dynamic behaviors of LDs and further provide a powerful tool to be potentially applied in the early-stage diagnosis of cancer.

Contamination Profile of Different Formulations of Silicone Oil Tamponade Before and After Intraocular Permanence for Rhegmatogenous Retinal Detachment.

Purpose: The purpose of this study was to search for contaminants in silicone oil tamponades removed from eyes treated for retinal detachment, and to correlate chemical results with some clinical/functional parameters of the considered eyes. Methods: We examined a sequential cohort of eyes grouped according to the tamponade received: (1) Siluron2000 (S2), (2) RS-OIL ECS5000 (S5), and (3) Densiron Xtra (DX). Samples were collected at the beginning of the scheduled removal and analyzed by untargeted headspace gas-chromatography mass spectrometry (HS-GC-MS). Visual acuity and optic coherence tomography assessments were obtained before and after the tamponade removal. Results: Forty-one samples were analyzed: 22 belonging to the DX group, 13 to the S2 group, and 6 to the S5 group. For each group, a mixture of uninjected commercial preparation was analyzed as the reference. Different siloxanes and fluorinated compounds including perfluorodecalin (PFCL) were the most prevalent chemicals, found in 55% to 100% of the intraocular samples of the 3 groups. Some siloxanes were present also in the control matrices, whereas PFCL was only in the extracted tamponades. In the DX group, the concentration of hexamethylcyclotrisiloxane showed an inverse correlation trend with the duration of its permanence inside the eye (P = 0.054). Different alkanes, propanol, and acetaldehyde were identified only in the control matrices. Conclusions: Several contaminants including siloxanes were identified in the intraocular samples and in the control matrices. A time-related ocular uptake of some of these is conceivable. PFCL was also highly present but only in intraocular samples. Translational Relevance: After intraocular permanence silicone oils (SOs) have various unlabeled contaminants with some relevant differences with the commercial formulation chemical profile.

Two-year evaluation of a nano-hybrid and a bulk-fill resin composite: a randomized, double-blind split-mouth clinical study.

OBJECTIVES: The aim of this study was to compare the 2-year clinical performance of a bulk-fill composite resin and a nano-hybrid-filled composite resin in 6-12-year-old children in a split-mouth design. MATERIALS AND METHODS: This randomized, split-mouth, and double-blind study was conducted on 89 patients aged 6-12 years with caries on bilateral mandibular first molars. In a split-mouth design, restorations of mandibular permanent molars were completed with nano-hybrid organically modified ceramic (ORMOCER)-based bulk-fill composite resin Admira Fusion x-tra (Voco GmbH, Cuxhaven, Germany) and nano-hybrid composite Grandio (Voco, Cuxhaven, Germany). Futurabond U single dose (Voco, Cuxhaven, Germany) was used with selective enamel etching. The clinical success of the restorations was evaluated using USPHS and FDI criteria at 6, 12, and 24-month follow-up controls. RESULTS: In the 2-year follow-up, all restorations were clinically acceptable. Grandio was significantly worse than Admira Fusion x-tra in terms of surface luster and superficial change (p < 0.05). Surface staining and color match scores increased in Admira Fusion x-tra compared with Grandio significantly (p < 0.05). CONCLUSIONS: Although both materials showed acceptable clinical performance over 2 years, a significant difference was observed between the surface luster, surface staining, marginal adaptation, and staining of the nano-hybrid composite placed with the incremental technique and the bulk-fill ORMOCER-based composite resin. CLINICAL RELEVANCE: As an alternative to nano-hybrid composite resins, using bulk-fill restorative materials, which can be indicated in the proper case, may contribute to shortening treatment procedures and increasing patient and physician comfort, leading to clinical success.

Effect of Radiant Exposure on the Physical and Mechanical Properties of 10 Flowable and High-viscosity Bulk-fill Resin Composites.

OBJECTIVES: To evaluate the effect of the different radiant exposures from a multipeak light curing unit on the physical and mechanical properties of flowable and high-viscosity bulk-fill resin-based composites (RBC). METHODS: Five flowable bulk-fill RBCs (Tetric N-Flow Bulk-fill, Ivoclar Vivadent; Filtek Bulk Fill Flow, 3M Oral Care; Opus Bulk Fill Flow APS, FGM; Admira Fusion x-base, Voco and; and SDR Plus Bulk Fill Flowable, Dentsply Sirona) and five high-viscosity bulk-fill RBCs (Tetric N-Ceram Bulk-fill, Ivoclar Vivadent; Filtek One Bulk Fill, 3M Oral Care; Opus Bulk Fill APS, FGM; Admira Fusion x-tra, Voco; and SonicFill 2, Kerr) were photo-cured using a VALO Cordless light (Ultradent) for 10, 20, and 40 seconds at an irradiance of 1200, 800, or 400 mW/cm2, resulting in the delivery of 4, 8, 12, 16, 24, 32, or 48 J/cm2. Post-gel shrinkage (Shr) was calculated using strain-gauge test. The degree of conversion (DC, %) was calculated using FTIR. Knoop hardness (KH, N/mm2) and elastic modulus (E, MPa) were measured at the top and bottom surfaces. Logarithmic regressions between the radiant exposures and mechanical properties were calculated. Radiodensity was calculated using digital radiographs. Data of Shr and radiodensity were analyzed using two-way analysis of variance (ANOVA), and the DC, KH, and E data were analyzed with two-way ANOVA using split-plot repeated measurement tests followed by the Tukey test (a = 0.05). RESULTS: Delivering higher radiant exposures produced higher Shr values (p<0.001) and higher DC values (R2=0.808-0.922; R2=0.648-0.914, p<0.001), KH (R2=0.707-0.952; R2=0.738-0.919; p<0.001), and E (R2=0.501-0.925; R2=0.823-0.919; p<0.001) values for the flowable and high-viscosity RBCs respectively. Lower KH, E and Shr were observed for the flowable bulk-fill RBCs. All bulk-fill RBCs had a radiopacity level greater than the 4-mm thick aluminum step wedge. The radiant exposure did not affect the radiopacity. CONCLUSION: The Shr, DC, KH, and E values were highly correlated to the radiant exposure delivered to the RBCs. The combination of the higher irradiance for longer exposure time that resulted in radiant exposure between 24 J/cm2 to 48 J/cm2 produced better results than delivering 400 mW/cm2 for 40 s (16 J/cm2), and 800 mW/cm2 for 20 seconds (16 J/cm2) or 1200 mW/cm2 for 10 seconds (12 J/cm2). All the bulk-fill RBCs were sufficiently radiopaque compared to 4 mm of aluminum.

Dermal absorption of cyclic and linear siloxanes: a review.

Cyclic and linear siloxanes are compounds synthesized from silicon consisting of alternating atoms of silicone and oxygen [Si-O] units with organic side chains. The most common cyclic siloxanes are octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), while the most common linear siloxanes are high molecular weight polydimethylsiloxanes (PDMS) and low molecular weight volatile linear siloxanes known as hexamethyldisiloxane (L2), octamethyltrisiloxane (L3), decamethyltetrasiloxane (L4), dodecamethylpentasiloxane (L5). These compounds (1) exhibit low dermal toxicity, (2) are generally inert and non-reactive, and (3) are compatible with a wide range of chemicals offering beneficial chemical properties which include the following: wash-off or transfer resistance from the skin, sun protection factor (SPF) enhancement, emolliency in cleaning products). Because of these properties, these compounds are incorporated into multiple consumer products for use on the skin, such as cosmetics and health-care products, with over 300,000 tons annually sold into the personal care and consumer products sector. Because of their widespread use in consumer products and potential for human dermal exposure, a comprehensive understanding of the dermal absorption and overall fate of siloxanes following dermal exposure is important. This review summarizes available data associated with the dermal absorption/penetration as well as fate of the most commonly used siloxane substances.

Determination of solvation parameter model compound descriptors by gas chromatography.

The solvation parameter model uses five system independent descriptors to characterize compound properties defined as excess molar refraction, E, dipolarity/polarizability, S, hydrogen-bond acidity, A, hydrogen-bond basicity, B, and the gas-liquid partition constant at 25 °C on n-hexadecane, L, to model transfer properties in gas-condensed phase biphasic systems. The E descriptor for compounds liquid at 20 °C is available by calculation using a refractive index value while E for solid compounds at 20 °C and the S, A, B, and L descriptors are determined by experiment. As a single-technique approach, it is shown that with up to 20 retention factor measurements on four columns comprising a poly(siloxane) containing methyloctyl or dimethyldiphenylsiloxane monomers (SPB-Octyl or HP-5), a poly(siloxane) containing methyltrifluoropropylsiloxane monomers (Rtx-OPP or DB-210), a poly(siloxane) containing bis(cyanopropylsiloxane) monomers (HP-88 or SGE BPX-90), and a poly(ethylene glycol) stationary phase (DB-WAXetr or HP-INNOWAX) are suitable for assigning the S, A, and L descriptors. Using the descriptors in the updated WSU compound descriptor database as target values the average absolute error in the descriptor assignments for 52 varied compounds in the temperature range 60-140 °C was 0.072 for E, 0.016 for S, 0.008 for A, and 0.022 for L corresponding to 30 %, 3.5 %, and 0.6 % as a relative average absolute error for E, S, and L, respectively. For the higher temperature range of 160-240 °C and 34 varied compounds that are liquid at 20 °C the average absolute error for the S, A and L descriptors was 0.026, 0.020, and 0.031, respectively, with the largest relative average absolute error for S of 3.2 % (< 1 % for the L descriptor). For 35 varied compounds that are solid at 20 °C the relative absolute error for the E, S, A, and L descriptors in the higher temperature range was 0.068, 0.035, 0.020, and 0.020, respectively, with a relative average absolute error for E (6.5 %), S (3.5 %) and L (0.88 %). The S, A, and L descriptor can be accurately assigned on the four-column system over a wide temperature range. The E descriptor for solid compounds at 20 °C exhibits greater variability than desirable. The B descriptor cannot be assigned by the four-column system, which lack hydrogen-bond acid functional groups, and is only poorly assigned on the weak hydrogen-bond acid ionic liquid column SLB-IL100.

Occurrence and distribution of trisiloxane ethoxylates in citrus orchard soils in China: Analytical challenges.

Trisiloxane ethoxylates (TSEOn) are widely used as agricultural surfactants due to their significant synergism with the active ingredients of pesticides, generally, including three typical end groups which are hydroxyl (TSEOn-H), methoxy (TSEOn-CH3), and acetoxy (TSEOn-COCH3), respectively. However, the potential ecotoxicological and endocrine-disrupting risks of TSEOn congeners have recently attracted ever-growing concern. Above all, there is limited research on the concentration levels of TSEOn in agroecosystems. This study, simultaneous analysis of 39 TSEOn oligomers in citrus orchard soils in China was implemented by the modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) extraction coupled with ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The method detection limits (MDLs) and the method quantification limits (MQLs) for TSEOn were 0.003-0.07 µg/kg and 0.01-0.20 µg/kg, respectively. The recoveries for TSEOn oligomers in soils ranged from 81 % âˆ¼ 106 % with related standard deviations (RSDs) < 7 %. This newly developed UPLC-MS/MS method with high sensitivity and stability allows us to successfully trace the occurrence of TSEOn congeners in the citrus orchard soils from 3 provinces and 1 municipality in China. The detected concentrations of TSEOn-H oligomers in the sampled soils ranged from 0.02 to 0.288 µg/kg (dry weight). The congener profiles of TSEOn-H were dominated by TSEOn-H (n = 6- 8) in the soils. Additionally, the total concentrations of TSEOn-H congeners (ΣTSEOn-H) in the soils were in the range of 0.03 to 1.49 µg/kg. A comparison of ΣTSEOn-H distribution among the different citrus orchard soils indicated a higher level of ΣTSEOn-H in the soil samples collected from Zhejiang Province. Notably, TSEOn-CH3 or TSEOn-COCH3 oligomers were not detected in the tested soils. To the best of our knowledge, this is the first report on the occurrence and distribution of TSEOn congeners in agricultural soils.

Shape-Tunable Hollow Polysiloxane Nanoparticles Based on a Surfactant-Free Soft Templating Method and Their Application as a Drug Carrier.

A surfactant-free soft-templating method has been used to prepare polysiloxane hollow nanoparticles with a controllable shape. This method is simple and has the potential for large-scale preparation. For the first time, we successfully obtained hollow polysiloxane nanoparticles with different shapes, including eccentric hollow polysiloxane microspheres (EHPM), apple-like hollow polysiloxane microparticles (AHPM), and bowl-like hollow polysiloxane microparticles (BHPM), by simply changing the solvent. In this method, the hydrolyzed methyltriethoxysilane (MTES) not only stabilizes the system as a surfactant but also acts as a reactant for subsequent reactions, so no additional surfactant is needed. In addition, the formation mechanism of hollow polysiloxane microparticles with different shapes is also proposed: that is, MTES hydrolyzed under acidic conditions to form a surfactant, which changes the system from suspension to a stable oil-in-water emulsion. Then, under alkaline conditions, the hydrolyzed MTES polycondenses and nucleates at the oil-water interface. At the same time, with the process of polycondensation, the hydrolyzed MTES will migrate to the nucleation site driven by surface tension, thus forming an eccentric core/shell (solvent/polysiloxane) structure. Due to the different forces between hydrolyzed MTES and different solvents, the deviation degree of hollow in microspheres is different, thus forming particles with various morphologies. This synthesis method provides a new idea for the preparation of shapeable anisotropic hollow structures. Finally, we use AHPM to study the application of the drug load. The results show that the prepared hollow polysiloxane particles have a good drug loading capacity and release performance. It can be predicted that the shape-tunable hollow polysiloxane particles prepared by this method have broad application prospects in the field of drug delivery.

Properties of a novel composite elastomeric polymer vinyl polyether siloxane in comparison to its parent materials: a systemic review and meta-analysis.

BACKGROUND: The effectiveness of newly developed elastomeric polymer hybrid siloxane (PVES), which combines the properties of polyethylene (PE) and polyvinyl siloxane (PVS) elastomers, has been a subject of interest in recent studies. This study aimed to assess the physical properties of hybrid PVES materials by analyzing existing data from recent studies on this topic. METHODS: A systematic literature search was conducted to retrieve peer-reviewed articles published up to February 5, 2023. The population, intervention, comparison, and pertinent outcomes were specified under the PICO framework. The primary data analysis was performed in Microsoft Excel, while statistical analysis used Meta-Essentials. RESULTS: Of the 1152 articles assessed, 14 met the inclusion criteria. The meta-analysis of the selected studies indicated that polyether (PE) and polyvinyl siloxane (PVS) were highly correlated (two-tailed p-values of 0.000 and 0.001, respectively) with the improved tensile strength of vinyl polyether siloxane (PVES) with a significantly positive effect size. Similarly, the hydrophilic characteristics of PVES were significantly improved compared to those of PE and PVS. PE was a significant contributor to the hydrophilic characteristics of PVES, with a two-tailed p-value of 0.000. The effect size was highly positive for hydrophilicity but showed high heterogeneity. It was also observed that the dimensional accuracy of PVES was comparable to those of PE and PVS, with no statistically significant differences among the three materials. CONCLUSIONS: PVES showed promising features, with improved tensile strength and hydrophilic characteristics compared to those of PE and PVS.

In-vivo studies of targeted and localized cancer drug release from microporous poly-di-methyl-siloxane (PDMS) devices for the treatment of triple negative breast cancer.

Triple-negative breast cancer (TNBC) treatment is challenging and frequently characterized by an aggressive phenotype and low prognosis in comparison to other subtypes. This paper presents fabricated implantable drug-loaded microporous poly-di-methyl-siloxane (PDMS) devices for the delivery of targeted therapeutic agents [Luteinizing Hormone-Releasing Hormone conjugated paclitaxel (PTX-LHRH) and Luteinizing Hormone-Releasing Hormone conjugated prodigiosin (PG-LHRH)] for the treatment and possible prevention of triple-negative cancer recurrence. In vitro assessment using the Alamar blue assay demonstrated a significant reduction (p < 0.05) in percentage of cell growth in a time-dependent manner in the groups treated with PG, PG-LHRH, PTX, and PTX-LHRH. Subcutaneous triple-negative xenograft breast tumors were then induced in athymic female nude mice that were four weeks old. Two weeks later, the tumors were surgically but partially removed, and the device implanted. Mice were observed for tumor regrowth and organ toxicity. The animal study revealed that there was no tumor regrowth, six weeks post-treatment, when the LHRH targeted drugs (LHRH-PTX and LHRH-PGS) were used for the treatment. The possible cytotoxic effects of the released drugs on the liver, kidney, and lung are assessed using quantitative biochemical assay from blood samples of the treatment groups. Ex vivo histopathological results from organ tissues showed that the targeted cancer drugs released from the implantable drug-loaded device did not induce any adverse effect on the liver, kidneys, or lungs, based on the results of qualitative toxicity studies. The implications of the results are discussed for the targeted and localized treatment of triple negative breast cancer.

Investigating the Mobility-Compressibility Properties of Conjugated Polymers by the Contact Film Transfer Method with Prestrain.

Up to now, researches on the mobility-stretchability of semiconducting polymers are extensively investigated, but little attention was  paid to their morphology and field-effect transistor characteristics under compressive strains, which is equally crucial in wearable electronic applications. In this work, a contact film transfer method is applied to evaluate the mobility-compressibility properties of conjugated polymers. A series of isoindigo-bithiophene conjugated polymers with symmetric carbosilane side chains (P(SiSi)), siloxane-terminated alkyl side chains (P(SiOSiO)), and combined asymmetric side chains (P(SiOSi)) are investigated. Accordingly, a compressed elastomer slab is used to transfer and compress the polymer films by releasing prestrain, and the morphology and mobility evolutions of these polymers are tracked. It is found that P(SiOSi) outperforms the other symmetric polymers including P(Si─Si) and P(SiO─SiO), having the ability to dissipate strain with its shortened lamellar spacing and orthogonal chain alignment. Notably, the mechanical durability of P(SiOSi) is also enhanced after consecutive compress-release cycles. In addition, the contact film transfer technique is demonstrated to be applicable to investigate the compressibility of different semiconducting polymers. These results demonstrate a comprehensive approach to understand the mobility-compressibility properties of semiconducting polymers under tensile and compressive strains.

Polarity responsive polysiloxanes with twisting intramolecular charge transfer effect for monitoring lipophagy process and the detection of volatile organic compounds.

Polarity plays a critical role in biology and materials science, serving as a complex parameter. Imbalances in polarity within subcellular organelles are closely associated with various diseases. Moreover, volatile organic compounds (VOC) with low polarity pose significant health and safety risks, therefore, researchers have shown great interest in accurately detecting polarity. However, precise observation of polarity changes within organisms and identification of low-polarity volatile organic solvents are formidable challenges. To overcome these difficulties, we developed a versatile polymeric twisting intramolecular charge transfer (TICT) effect Polysiloxane-n (PDMS-n), utilizing polysiloxane molecular chains as "smart guides" to connect TICT molecules, inspired by the concept of "threading a needle." With the aid of PDMS-n, the process of polarity changes during cellular lipophagy was monitored in situ with high accuracy. Remarkably, the polarity changes of the local microstructure of the PDMS films were successfully visualized. PDMS-Films were also constructed, which enabled the recognition of Dichloromethane (DCM) gas during swelling. This work will contribute to the understanding of changes in cellular physiological processes, and facilitate the sensitive detection of VOCs.

Cyclic and linear siloxane contamination in sediment and invertebrates around a thermal power plant in Korea: Source impact, distribution, seasonal variation, and potential for bioaccumulation.

Siloxanes have been commonly used as additives in a variety of industrial and consumer products. Media and government investigations have revealed that defoamers containing siloxanes are used in the effluent of thermal power plants in Korea. However, investigations of the source impact of siloxane contamination from the discharge of thermal power plants into coastal environments are scarce. In this study, sediment and invertebrates were collected around a thermal power plant to assess source impact, seasonal variation, and a potential for bioaccumulation. Although siloxanes were detectable in sediment and invertebrates, the spatial distribution and composition (which differed between the siloxanes found in sediment and invertebrates and those in defoamer used in the plant) suggest they were likely transported by long-distance migration as well as the discharge of thermal power plant. Seasonal differences might affect sedimentary contamination and the bioaccumulation potential of siloxanes. Specifically, octamethylcyclotetrasiloxane (D4) may have limited adsorption capacity and potential for long-distance migration, as its contribution in sediment far from the coastline was greater than that of decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6). However, higher D5 accumulation in invertebrates, and D5 has a potential bioaccumulation. A molecular docking analysis showed that the binding affinity between D5 and the cytochrome enzyme in invertebrates was weaker than that with other siloxanes, which could lead to higher D5 accumulation in invertebrates.

Bioaccumulation of Linear Siloxanes in Fish.

The bioaccumulation behavior, including the uptake, internal distribution, depuration, and biotransformation rates, of three widely used linear methyl-siloxanes was investigated in rainbow trout. Dietary uptake efficiencies of octamethyltrisiloxane (L3), decamethyltetrasiloxane (L4), and dodecamethylpentasiloxane (L5) were 15% (3.3% standard error [SE]), 8.6% (1.4% SE), and 15% (1.8% SE), respectively, and for L3 and L4 were well below those of nonmetabolizable reference chemicals with similar octanol-water partition coefficients, suggesting significant intestinal biotransformation of L3 and L4. Somatic biotransformation rate constants were 0.024 (0.003 SE) day-1 for L3 and 0.0045 (0.0053 SE) day-1 for L4 and could not be determined for L5. Lipid-normalized biomagnification factors for L3, L4, and L5 were 0.24 (0.02 SE), 0.24 (0.01 SE), and 0.62 (0.05 SE) kg-lipid kg-lipid-1 , respectively. Bioconcentration factors standardized to a 5% lipid content fish for water in Canadian oligotrophic lakes with a dissolved organic carbon content of 7.1 mg L-1 were 2787 (354 SE) for L3, 2689 (312 SE) for L4, and 1705 (418 SE) L kg-wet weight-1 , respectively, and 3085 (392 SE) for L3, 4227 (490 SE) for L4, and 3831 (938 SE) L kg-wet weight-1 in water with a dissolved organic carbon content of 2.0 mg L-1 . A comparison of 238 bioaccumulation profiles for 166 different chemicals shows that the bioaccumulation profiles for L3, L4, and L5 are vastly different from those of other very hydrophobic compounds found in the environment. Environ Toxicol Chem 2024;43:42-51. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Factors determining contamination and time trends in cyclic and linear siloxanes in sediments from an industrialized lake in Korea.

Siloxanes, widely used in various consumer and industrial products, are emerging concerns of contaminants. Despite this, limited studies have been conducted on contamination and time trends on siloxanes in coastal environments. In the present study, four cyclic and 15 linear siloxanes were measured in sediments collected from an artificial saltwater lake in Korea during 2001-2016 to investigate contamination, time trends, and ecotoxicological concerns. Cyclic siloxanes were detected in all sediment samples, whereas linear siloxanes were not frequently detected. The highest siloxane concentrations were observed in creeks passing through various industrial complexes, indicating that industrial activities predominantly contributed to siloxane contamination in coastal environments. Decamethylcyclopentasiloxane (D5) and dodecylcyclohexasiloxane (D6) were predominant siloxanes in sediments over the last two decades. Siloxane concentrations significantly increased in creek sediments from 2008 to 2016, whereas those in inshore and offshore regions significantly decreased due to a strong dilution effect by the operation of tidal power plant. This suggests that consumption patterns and coastal development activities are crucial factors determining the contamination and time trends in the sedimentary siloxanes. The sedimentary concentrations of octamethylcyclotetrasiloxane (D4) and D5 exceeded several thresholds, raising the potentials for ecological risks to aquatic organisms.