Application of an Antibacterial Coating Layer via Amine-Terminated Hyperbranched Zirconium-Polysiloxane for Stainless Steel Orthodontic Brackets.

The massive growth of various microorganisms on the orthodontic bracket can form plaques and cause diseases. A novel amine-terminated hyperbranched zirconium-polysiloxane (HPZP) antimicrobial coating was developed for an orthodontic stainless steel tank (SST). After synthesizing HPZP and HPZP-Ag coatings, their structures were characterized by nuclear magnetic resonance spectroscopy, scanning electron microscopy, thickness measurement, contact angle detection, mechanical stability testing, and corrosion testing. The cell toxicity of the two coatings to human gingival fibroblasts (hGFs) and human oral keratinocytes (hOKs) was detected by cell counting kit eight assays, and SST, HPZP@SST, and HPZP-Ag@SST were cocultured with Staphylococcus aureus, Escherichia coli, and Streptococcus mutans for 24 hr to detect the antibacterial properties of the coatings, respectively. The results show that the coatings are about 10 µm, and the water contact angle of HPZP coating is significantly higher than that of HPZP-Ag coating (P < 0.01). Both coatings can be uniformly and densely distributed on SST and have good mechanical stability and corrosion resistance. The cell counting test showed that HPZP coating and HPZP-Ag coating were less toxic to cells compared with SST, and the toxicity of HPZP-Ag coating was greater than that of HPZP coating, with the cell survival rate greater than 80% after 72 hr cocultured with hGFs and hOKs. The antibacterial test showed that the number of bacteria on the surface of different materials was ranked from small to large: HPZP@SST < HPZP-Ag@SST < SST and 800 µg/mL HPZP@SST showed a better bactericidal ability than 400 µg/mL after cocultured with S. aureus, E. coli, and S. mutans, respectively (all P < 0.05). The results showed that HPZP coating had a better effect than HPZP-Ag coating, with effective antibacterial and biocompatible properties, which had the potential to be applied in orthodontic process management.

Assessment of dimensional stability of novel VPES impression material at different time intervals with standard disinfectants.

BACKGROUND: Vinyl polyether silicone (VPES) is a novel impression biomaterial made of a combination of vinyl polysiloxane (VPS) and polyether (PE). Thus, it is significant to assess its properties and behaviour under varied disinfectant test conditions. This study aimed to assess the dimensional stability of novel VPES impression material after immersion in standard disinfectants for different time intervals. METHODS: Elastomeric impression material used -medium body regular set (Monophase) [Exa'lence GC America]. A total of 84 Specimens were fabricated using stainless steel die and ring (ADA specification 19). These samples were distributed into a control group (n=12) and a test group (n=72). The test group was divided into 3 groups, based on the type of disinfectant used - Group-A- 2% Glutaraldehyde, Group-B- 0. 5% Sodium hypochlorite and Group-C- 2% Chlorhexidine each test group was further divided into 2 subgroups (n=12/subgroup) based on time intervals for which each sample was immersed in the disinfectants - subgroup-1- 10 mins and Subgroup 2- 30 mins. After the impression material was set, it was removed from the ring and then it was washed in water for 15 seconds. Control group measurements were made immediately on a stereomicroscope and other samples were immersed in the three disinfection solutions for 10 mins and 30 mins to check the dimensional stability by measuring the distance between the lines generated by the stainless steel die on the samples using a stereomicroscope at x40 magnification. RESULTS: The distance measured in the control group was 4397.2078 µm and 4396.1571 µm; for the test group Group-A- 2% Glutaraldehyde was 4396.4075 µm and 4394.5992 µm; Group-B- 0. 5% Sodium hypochlorite was 4394.5453 µm and 4389.4711 µm Group-C- 2% Chlorhexidine was 4395.2953 µm and 4387.1703 µm respectively for 10 mins and 30 mins. Percentage dimensional change was in the range of 0.02 - 0.25 for all the groups for 10 mins and 30 mins. CONCLUSIONS: 2 % Glutaraldehyde is the most suitable disinfectant for VPES elastomeric impression material in terms of dimensional stability and shows minimum dimensional changes as compared to that of 2% Chlorhexidine and 0.5% Sodium hypochlorite.

Preparation and characterization of stationary phase gradients on C8 liquid chromatography columns.

Continuous C8 stationary phase gradients are created on commercial Waters Symmetry Shield RP8 columns by strategically cleaving the C8 moieties in a time-dependent fashion. The method relies on the controlled infusion of a trifluoroacetic acid/water/acetonitrile solution through the column to cleave the organic functionality (e.g., C8) from the siloxane framework. The bond cleavage solution is reactive enough to cleave the functional groups, even with polar groups embedded within the stationary phase to protect the silica. Both the longitudinal and radial heterogeneity were evaluated by extruding the silica powder into polyethylene tubing and evaluating the percent carbon content in the different sections using thermogravimetric analysis (TGA). TGA analysis shows the presence of a stationary phase gradient in the longitudinal direction but not in the radial direction. Two different gradient profiles were formed with good reproducibility by modifying the infusion method: one exhibited an 'S'-shaped gradient while the other exhibited a steep exponential-like gradient. The gradients were characterized chromatographically using test mixtures, and the results showed varied retention characteristics and an enhanced ability to resolve nicotine analytes.

Positional accuracy of a single implant analog in additively manufactured casts in biobased model resin.

OBJECTIVES: To evaluate the positional accuracy of implant analogs in biobased model resin by comparing them to that of implant analogs in model resin casts and conventional analogs in dental stone casts. METHODS: Polyvinylsiloxane impressions of a partially edentulous mandibular model with a single implant were made and poured in type IV dental stone. The same model was also digitized with an intraoral scanner and additively manufactured implant casts were fabricated in biobased model resin (FotoDent biobased model) and model resin (FotoDent model 2 beige-opaque) (n = 8). All casts and the model were digitized with a laboratory scanner, and the scan files were imported into a 3-dimensional analysis software (Geomagic Control X). The linear deviations of 2 standardized points on the scan body used during digitization were automatically calculated on x-, y-, and z-axes. Average deviations were used to define precision, and 1-way analysis of variance and Tukey HSD tests were used for statistical analyses (α = 0.05). RESULTS: Biobased model resin led to higher deviations than dental stone (all axes, P ≤ 0.031) and model resin (y-axis, P = 0.015). Biobased model resin resulted in the lowest precision of implant analog position (P ≤ 0.049). The difference in the positional accuracy of implant analogs of model resin and stone casts was nonsignificant (P ≥ 0.196). CONCLUSIONS: Implant analogs in biobased model resin casts mostly had lower positional accuracy, whereas those in model resin and stone casts had similar positional accuracy. Regardless of the material, analogs deviated more towards mesial, while buccal deviations in additively manufactured casts and lingual deviations in stone casts were more prominent.

Functionalization of Siloxanes with Arynes Generated from o-Triazenylarylboronic Acids.

Herein, we report the functionalization of polyhedral oligosilsesquioxanes (POSS) and related siloxanes with arynes. Using o-triazenylarylboronic acids as aryne precursors and silica gel as the activator, the transformation of siloxane bearing various arynophilic moieties on the side chains was achieved with high yields without touching the siloxane core. This method was applied to the conjugation of POSS and pharmaceutical cores using an aryne derived from the synthetic intermediate of cabozantinib. Furthermore, orthogonal dual functionalization of POSS was realized by combining the aryne reaction with Huisgen cyclization.

Digital Evaluation of Trueness and Precision of Modern Impression Materials in Implant- Retained Mandibular Overdentures.

INTRODUCTION: The purpose of this in vitro study was to evaluate the dimensional accuracy, trueness, and precision of vinyl siloxane ether (VSXE) and polyvinylsiloxane (PVS) impression materials using different impression techniques. MATERIAL AND METHODS: A three-dimensional (3D) printed mandibular model with implants and metal rods served as the reference model. Impressions were taken in custom trays, resulting in four groups: PVS-closed-tray, VSXE-closed-tray, PVS-open-tray, and VSXE-open-tray. The reference model and impressions were scanned and analyzed using 3D analysis software to assess the trueness and precision within each group. RESULTS: There was significant difference in trueness between the groups, with PVS closed tray showing a higher deviation than VSXE-closed-tray and PVS-open-tray. VSXE-open-tray had the lowest deviation, which was statistically significant. In terms of precision, PVS-closed-tray showed the highest deviation, while no significant differences were found among the other groups. CONCLUSIONS: VSXE impression material with an open tray technique consistently demonstrated the highest levels of accuracy and precision. Conversely, PVS impression material with a closed tray technique yielded less favorable results. CLINICAL RELEVANCE: Better understanding of trueness and precision of new impression materials with new impression techniques will increase their clinical effectiveness.

Interference of the gas chromatography- mass spectrometry instrumental background on the determination of trace cyclic volatile methylsiloxanes and exclusion of it by delayed injection.

Cyclic volatile methylsiloxanes (cVMS) have been widely found in various types of environmental media and attracted increasing attention as new pollutants. However, there is still a great challenge in the accurate quantification of trace cVMS, due to their volatility, and the high background originating from GC/MS accessories and surroundings. In this work, the main sources of the high background were investigated in detail for octamethylcyclotetrasiloxane (D4), decmethylcyclopentasiloxane (D5) and dodecmethylcyclohexosiloxane (D6). Several effective measures were employed to minimize these backgrounds, including the delayed injection method to minimize the interference from the injection septum. Then, a GC-MS method was developed for the accurate determination of D4, D5 and D6, with a linear range of 2 - 200 µg/L. The coefficient of determination was 0.9982-0.9986, the limit of detection (LOD) was 0.40-0.52 µg/L, and the quantitative range was 1.88-190 µg/L. Good reproducibility and recovery were obtained, indicating the reliability of the established analytical method.

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.

Refractive-index and density-matched emulsions with programmable DNA interactions.

Emulsion droplets on the colloidal length scale are a model system of frictionless compliant spheres. Direct imaging studies of the microscopic structure and dynamics of emulsions offer valuable insights into fundamental processes, such as gelation, jamming, and self-assembly. A microscope, however, can only resolve the individual droplets in a densely packed emulsion if the droplets are closely index-matched to their fluid medium. Mitigating perturbations due to gravity additionally requires the droplets to be density-matched to the medium. Creating droplets that are simultaneously index-matched and density-matched has been a long-standing challenge for the soft-matter community. The present study introduces a method for synthesizing monodisperse micrometer-sized siloxane droplets whose density and refractive index can be precisely and independently tuned by adjusting the volume fraction of three silane precursors. A systematic optimization protocol yields fluorescently labeled ternary droplets whose densities and refractive indexes match, to the fourth decimal place, those of aqueous solutions of glycerol or dimethylsiloxane. Because all of the materials in this system are biocompatible, we functionalize the droplets with DNA strands to endow them with programmed inter-droplet interactions. Confocal microscopy then reveals both the three-dimensional structure and the network of droplet-droplet contacts in a class of self-assembled droplet gels, free from gravitational effects. This experimental toolbox creates opportunities for studying the microscopic mechanisms that govern viscoelastic properties and self-assembly in soft materials.

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.

Directed evolution for Si-C bond cleavage of volatile siloxanes in glass bioreactors.

Volatile methylsiloxanes (VMS) are a class of non-biodegradable anthropogenic compounds with propensity for long-range transport and potential for bioaccumulation in the environment. As a proof-of-principle for biological degradation of these compounds, we engineered P450 enzymes to oxidatively cleave Si-C bonds in linear and cyclic VMS. Enzymatic reactions with VMS are challenging to screen with conventional tools, however, due to their volatility, poor aqueous solubility, and tendency to extract polypropylene from standard 96-well deep-well plates. To address these challenges, we developed a new biocatalytic reactor consisting of individual 2-mL glass shells assembled in conventional 96-well plate format. In this chapter, we provide a detailed account of the assembly and use of the 96-well glass shell reactors for screening biocatalytic reactions. Additionally, we discuss the application of GC/MS analysis techniques for VMS oxidase reactions and modified procedures for validating improved variants. This protocol can be adopted broadly for biocatalytic reactions with substrates that are volatile or not suitable for polypropylene plates.

New Ethynylphenylborasilsesquioxanes-Their Reactivity and Behavior during Thermal Decomposition.

In this paper, a new type of borasilsesquioxanes was synthesized through a condensation process, and its reactivity in catalytic hydrosilylation reactions with silanes, siloxanes, and silsesquioxanes was investigated. The obtained compounds were mostly obtained in >90% yield. They were fully characterized using spectroscopic (1H, 13C, 29Si NMR) and spectrometric (MALDI-TOF-MS) methods. The next stage of the research involved studying the thermogravimetric properties of the borasilsesquioxanes. By analyzing the different stages of decomposition using spectroscopic techniques (NMR, ATR-FTIR, Raman) and microscopic imaging, it was found that the structure of the borasilsesquioxanes changed during the pyrolysis process and polymer compounds were formed.

Are Si-C bonds formed in the environment and/or in technical microbiological systems?

Organosiloxanes are industrially produced worldwide in millions of tons per annum and are widely used by industry, professionals, and consumers. Some of these compounds are PBT (persistent, biaccumulative and toxic) or vPvB (very persistent and very bioaccumulative). If organosiloxanes react at all in the environment, Si-O bonds are hydrolyzed or Si-C bonds are oxidatively cleaved, to result finally in silica and carbon dioxide. In strong contrast and very unexpectedly, recently formation of new Si-CH3 bonds from siloxanes and methane by the action of microorganisms under mild ambient conditions was proposed (in landfills or digesters) and even reported (in a biotrickling filter, 30 °C). This is very surprising in view of the harsh conditions required in industrial Si-CH3 synthesis. Here, we scrutinized the pertinent papers, with the result that evidence put forward for Si-C bond formation from siloxanes and methane in technical microbiological systems is invalid, suggesting such reactions will not occur in the environment where they are even less favored by conditions. The claim of such reactions followed from erroneous calculations and misinterpretation of experimental results. We propose an alternative explanation of the experimental observations, i.e., the putative observation of such reactions was presumably due to confusion of two compounds, hexamethyldisiloxane and dimethylsilanediol, that elute at similar retention times from standard GC columns.

Comparison of the elastic recovery and strain-in-compression of commercial and novel vinyl polysiloxane impression materials incorporating a novel crosslinking agent and a surfactant.

This study aims to formulate experimental vinylpolysiloxane (VPS) impression materials and compare their elastic recovery and strain-in-compressions with three commercial VPS materials (Aquasil, Elite, and Extrude). Five experimental materials (Exp), two hydrophobic (Exp-I and II) and three hydrophilic (Exp-III, IV and V) were developed. Exp 1 contained vinyl-terminated poly-dimethyl siloxane and a conventional cross-linking agent (poly methylhydrosiloxane), while Exp- II contained a novel cross-linking agent that is tetra-functional dimethyl-silyl-ortho-silicate (TFDMSOS). Exp III-V (hydrophilic materials) were formulated by incorporating different concentrations of non-ionic surfactant (Rhodasurf CET-2) into Exp II formulation. Measurement of elastic recovery and strain-in-compression for commercial and experimental materials were performed according to ISO4823 standard using the calibrated mechanical testing machine (Tinius Olsen). One-way analysis of variance (one-way ANOVA) and Tukey's post-hoc (HSD) test were used for statistical analysis and a p-value of ≤ 0.05 was considered significant. Exp-I has statistically similar values to commercial VPS. The Exp-II showed the highest elastic recovery, while % elastic recovery was reduced with the addition of the non-ionic surfactant (Rhodasurf CET-2). The % reduction was directly related to the concentration of Rhodasurf CET-2. In addition, Exp II had significantly higher strain-in-compression values compared to Exp-I and commercial materials. These values were further increased with the addition of a non-ionic surfactant (Rhodasurf CET-2) was added (Exp-III, IV and V).

Fabrication of Highly Thermally Resistant and Self-Healing Polysiloxane Elastomers by Constructing Covalent and Reversible Networks.

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.

Synthesis of Siloxane Derivatives of Phenylboronic Acids of Different Structures.

The synthesis of a storage-stable organosilicon modifier with a dioxaborolane-protecting group is described. Its high reactivity and selective anti-Markovnikov addition in hydrosilylation reactions to afford siloxanes of various structures are shown. The possibility of deprotection of both the initial modifier and its siloxane derivatives under mild conditions using water in yields up to 96% is demonstrated. The existence of an equilibrium between the organosilicon derivatives of phenylboronic acids and their cyclic six-membered boroxines was confirmed by 1H NMR spectroscopy and X-ray diffraction analysis data. The use of siloxane derivatives of phenylboronic acids in Suzuki-Miyaura and Chan-Lam cross-coupling reactions was studied. All synthesized compounds were characterized by NMR (1H, 11B, 13C, and 29Si), IR spectroscopy, and high-resolution mass spectrometry.

Supramolecular Elastomers with Excellent Dielectric Properties and High Recyclability Based on the Coordinative Bond.

The enhancement in dielectric properties and self-healing ability for dielectric materials has been a challenging subject these years. Herein, a series of self-healed dielectric elastomers by combining the ferric ions and carboxyl-containing poly(sulfone siloxane)s is reported. Experimental results indicate the excellent dielectric properties of obtained elastomers, as the dielectric constant up to 12.8. SEM micrographs exhibit that carboxyl groups and ferric ions can aggregate together to generate clusters, which further result in interfacial polarization. Besides, high polarity dipole units including sulfonyl units and carboxyl groups contribute to dipole polarization. The overlay of the two mentioned polarization eventually results in the high dielectric property. The dielectric constant obviously increases with the contents of carboxyl groups and ferric ions. Moreover, the samples are feasible for recycling and reprocessing with high self-healing efficiency, owing to the reversibility of the coordination bond. A self-healing efficiency of 92.1% in tensile strength of the obtained samples can be reached after 2 h treatment at 60 °C. And the elastomers can also conveniently recover most mechanical properties after solution treatment. This work may offer a promising method for preparing dielectric elastomers with high dielectric properties and self-healing ability.

Occurrence of methylsiloxanes in indoor store dust in China and potential human exposure.

Methylsiloxanes are synthetic molecules with versatile and extensive applications. Because of their volatile properties, they are easily released from manufactured products and contaminate indoor environments, causing high human exposure. However, available information on their presence in specific microenvironments, and on the related potential risks for human health, is limited. We conducted a survey of sixteen methylsiloxanes species, including three cyclic (D4-D6) and thirteen linear (L4-L16) chemicals, in indoor dust samples from twenty-eight stores representative of six store categories in Beijing, China. Total methylsiloxane concentrations in store dust were 176-54,825 ng/g, depending on the store, with a median of 2196 ng/g. Linear chemicals represented a median proportion of 90.8% of total methylsiloxanes. The measured methylsiloxane concentrations in this study were marginally higher than those reported previously for standard living and working environments. The highest linear and total methylsiloxane concentrations were measured in electronic stores, while the highest cyclic methylsiloxane concentrations were measured in department stores. The presence of methylsiloxanes in the store dust samples was attributed mainly to their release from chemical additives in marketed products. Estimated median total exposure doses under normal and worst-case exposure scenarios were 0.237 and 0.888 ng/kg bw/d, respectively. Further investigation is needed to characterize methylsiloxane distribution in other microenvironments and to evaluate the associated health risks.