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.

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).

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.

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.

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.

Comparative pharmacokinetic studies of 14C-octamethylcyclotetrasiloxane (14C-D4) in Fischer 344 and Sprague Dawley CD rats after single and repeated inhalation exposure.

Octamethylcyclotetrasiloxane (D4) is a high production volume chemical that has been subject to thorough toxicological investigations. Animal studies with the substance were conducted with either Fischer 344 or Sprague Dawley CD rats. While the pharmacokinetic fate of D4 in Fischer rats is well understood, little information exists on Sprague Dawley CD rats, where reproductive effects have been demonstrated. The objective of this study was to explore the pharmacokinetic behavior in both rats, and to identify potential strain-specific differences. Fischer and Sprague Dawley CD rats were exposed for six hours to 700 ppm of 14C-D4 vapor either with or without preceding 14-day exposure to non-radiolabeled D4. Time-course data in blood, tissues and excreta were obtained through 168 h post-exposure and analyzed for both total radioactivity and parent D4. The data confirm that repeated exposure results in increased metabolism in both rat strains, confirming the findings of earlier studies of auto-induction of CYP2B1/2 by D4. The results also indicate that D4 is subject to strain-specific pharmacokinetic behavior, and that Fischer rats appear to metabolize D4 to a greater extent than Sprague Dawley CD rats.

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.

Self-Healing, High-Strength, and Antimicrobial Polysiloxane Based on Amino Acid Hydrogen Bond.

Recent years have witnessed the rapid development of self-healing and recyclable materials because they can extend the life of the material. For polysiloxane materials, exploring polysiloxanes with high-strength and self-healing properties remains a challenge. In this work, a high-strength and self-healing polysiloxane containing N-acetyl-L-cysteine (NACL) side groups is prepared. The NACL is used to form strong hydrogen bonds to build a self-healing network. Molecular simulations help explain the reasons and processes for the repair of modified polysiloxanes. On the one hand, the obtained modified polysiloxanes have good self-healing properties. The self-healing efficiency of modified polysiloxane can reach 96.9%. As the number of NACL increases, the tensile strength of the modified polysiloxane increases. For PMVS-30%NACL, the tensile strength can reach 4.36 MPa, and the strain can reach 586%. On the other hand, modified polysiloxane has an apparent inhibitory effect on Staphylococcus aureus. With the increase in the number of NACL, the antibacterial effect of modified polysiloxane is more obvious. Furthermore, NACL is a bio-based amino acid with excellent biocompatibility. This work expands the idea of designing and synthesizing high-strength polysiloxanes with antibacterial properties. It has great potential in the field of polysiloxane antimicrobial coatings.

Some Theoretical and Experimental Evidence for Particularities of the Siloxane Bond.

The specific features of the siloxane bond unify the compounds based on it into a class with its own chemistry and unique combinations of chemical and physical properties. An illustration of their chemical peculiarity is the behavior of 1,3-bis(2-aminoethylaminomethyl)tetramethyldisiloxane (AEAMDS) in the reaction with carbonyl compounds and metal salts, by which we obtain the metal complexes of the corresponding Schiff bases formed in situ. Depending on the reaction conditions, the fragmentation of this compound takes place at the siloxane bond, but, in most cases, it is in the organic moieties in the ß position with respect to the silicon atom. The main compounds that were formed based on the moieties resulting from the splitting of this diamine were isolated and characterized from a structural point of view. Depending on the presence or not of the metal salt in the reaction mixture, these are metal complexes with organic ligands (either dangling or not dangling silanol tails), or organic compounds. Through theoretical calculations, electrons that appear in the structure of the siloxane bond in different contexts and that lead to such fragmentations have been assessed.

Polysiloxane-Based Polyurethanes with High Strength and Recyclability.

Polysiloxanes have attracted considerable attention in biomedical engineering, owing to their inherent properties, including good flexibility and biocompatibility. However, their low mechanical strength limits their application scope. In this study, we synthesized a polysiloxane-based polyurethane by chemical copolymerization. A series of thermoplastic polysiloxane-polyurethanes (Si-TPUs) was synthesized using hydroxyl-terminated polydimethylsiloxane containing two carbamate groups at the tail of the polymer chains 4,4'-dicyclohexylmethane diisocyanate (HMDI) and 1,4-butanediol as raw materials. The effects of the hard-segment content and soft-segment number average molecular weight on the properties of the resulting TPUs were investigated. The prepared HMDI-based Si-TPUs exhibited good microphase separation, excellent mechanical properties, and acceptable repeatable processability. The tensile strength of SiTPU-2K-39 reached 21.5 MPa, which is significantly higher than that of other flexible polysiloxane materials. Moreover, the tensile strength and breaking elongation of SiTPU-2K-39 were maintained at 80.9% and 94.6%, respectively, after three cycles of regeneration. The Si-TPUs prepared in this work may potentially be used in gas separation, medical materials, antifouling coatings, and other applications.

Metallacyclosilanes of Calcium, Yttrium, and Iron.

Utilizing a choice of α,ω-oligosilanylene diides, it is possible to synthesize a number of heterocyclosilanes with heteroelements of calcium, yttrium, and iron by metathesis reactions with respective metal halides CaI2, YCl3, and FeBr2. 29Si NMR spectroscopic analysis of the calcacyclosilanes suggests that these compounds retain a strong oligosilanylene dianion character, which is more pronounced than in the analogous magnesacyclosilanes. As the electronegativity of calcium lies between potassium and magnesium, silyl calcium reagents should be considered as building blocks with an attractive reactivity profile. Reaction of a 1,4-oligosilanylene diide with YCl3 gave the five-membered yttracyclosilane as an ate-complex with two chlorides still attached to the yttrium atom. Reaction of the obtained compound with two equivalents of NaCp led to another five-membered yttracyclosilane ate-complex with an yttracene fragment. When using a dianionic oligosilanylene ligand containing a siloxane unit, the siloxane oxygen acted as an additional coordination site for Ca and Y. When the same ligand was used to prepare a cyclic 1-ferra-4-oxatetrasilacyclohexane, an analogous transannular interaction between the iron and oxygen atoms is missing.

Effects chemical disinfectants on surface roughness of conventional impression materials used for dental prosthetic procedures.

Background to Aim: To compare the effects of disinfectants on surface roughness of the conventional impression materials following chemical disinfection procedures. Materials and Methods: Equal numbers (65 for each impression material) of disc-shaped (15 × 3 mm) samples (Total n = 195) were fabricated from polyvinyl siloxane (Zhermack Elite), polyether (3M Impregum Penta Soft), and vinyl siloxane ether (Kettenbach Identium Lightbody) impression materials. Each impression material group was divided into five subgroups including one control group (n = 13). Impression material samples were immersed in CaviCide for 3 min, Zeta 7 solution for 10 min, and 5.25% sodium hypochlorite solution for 3 and 10 min. Surface roughness (Ra) was measured using a profilometer (Mitutoyo-SJ 410, Mitutoyo Corp.). The study data were analyzed statistically. Results: A statistically significant difference was found among impression materials and disinfectants in terms of surface roughness (P < 0.05). Polyvinyl siloxane material showed a lower Ra value compared to Polyether and VSE materials; while polyether material showed a significantly lower Ra value compared to VSE material. Ra values of the control group were significantly lower than the disinfectant group immersed in 5.25% NaOCl solution for 10 min. Conclusion: Among all impression materials, polyvinyl siloxane showed the least surface roughness following disinfection procedures. Impression disinfectants that are specially designed for disinfecting dental impressions resulted in less surface roughness in all impression materials. With this study, it was aimed to obtain a smooth and clear model for the production of correct and compatible prostheses in the laboratory while at the same time purifying the impressions from microorganisms.

Optically Triggering and Monitoring Single-Cell-Level Metabolism Using Ormosil-Decorated Ultrathin Fibers.

The integration of biological components and artificial devices requires a bio-machine interface that can simultaneously trigger and monitor the activities in biosystems. Herein, we use an organically modified silicate (ormosil) composite coating containing a light-responsive nanocapsule and a fluorescent bioprobe for reactive oxygen species (ROS) to decorate ultrathin optical fibers, namely, ormosil-decorated ultrathin fibers (OD-UFs), and demonstrate that these OD-UFs can optically trigger and monitor the intracellular metabolism activities in living cells. The sizes and shapes of UF tips were finely controlled to match the dimension and mechanical properties of living cells. The increased elasticity of the ormosil coating of OD-UFs reduces possible mechanical damage during the cell membrane penetration. The light-responsive nanocapsule was physically absorbed on the surface of the ormosil coating and could release a stimulant to trigger the metabolism activities in cells upon the guided laser through OD-UFs. The fluorescent bioprobe was covalently linked with the ormosil matrix for monitoring the intracellular ROS generation, which was verified by the in vitro experiments on the microdroplets of a hydrogen peroxide solution. Finally, we found that the living cells could maintain most of their viability after being inserted with OD-UFs, and the intracellular metabolism activities were successfully triggered and monitored at the single-cell level. The OD-UF provides a new platform for the investigation of intracellular behaviors for drug stimulations and represents a new proof of concept for a bio-machine interface based on the optical and chemical activities of organic functional molecules.

Study of microheterogeneity of silatrane-based silica surface bonding chemistry and its optimization for the synthesis of chiral stationary phases for enantioselective liquid chromatography.

The present work systematically investigates the chemical microheterogeneity as part of the optimization of a single-step surface bonding chemistry of 3-mercaptopropylsilatrane (MPS) on mesoporous silica gel in comparison to the state-of-the-art silane chemistry with 3-mercaptopropyltrimethoxysilane (MPTMS). MPS functionalization turns out to be a favourable chemistry for the further use in thiol-ene click reactions such as the immobilization of chiral selectors, herein tert-butylcarbamoylquinine (tBuCQN), for the synthesis of chiral stationary phases (CSPs). MPS has higher reactivity than MPTMS and prefers the formation of trifunctional siloxane bondings unlike MPTMS which favours difunctional siloxane bonds to silica, as investigated by solid-state cross-polarization/magic angle spinning (CP/MAS) NMR (29Si and 13C nuclei). Reaction conditions (ternary mixtures of methanol, water and toluene; with and without acid; prewetting of silica; HCl pretreatment of silica) were evaluated with the aim to find conditions which promote the formation of a horizontal siloxane polymer layer on top of the silica surface. Silanization reaction times could be reduced to 2 h. The 29Si NMR signal corresponding to trifunctional siloxane bonding could be increased to 60% with no T1 signal that refers to monofunctional siloxane bonding in spite of water in the ternary reaction mixture. Furthermore, no significant disulfide bridges were formed in this approach, leading to high selector loadings. The thiol and selector coverage reached up to 4.6 and 1.4 µmol/m2, respectively. With the preferred CSP, the enantioselectivity could be increased for a chiral probe (FMOC-Phe) and the mass transfer resistance (C-term) bisected compared to the corresponding CSP prepared from benchmark MPTMS-modified silica (2.54 vs 5.72 ms). It is demonstrated that the fine-tuning of the microstructure on the silica surface can have a significant influence on enantioselectivity and mass transfer kinetics of the resultant CSPs.

Comparison of the Hardness of Novel Experimental Vinyl Poly Siloxane (VPS) Impression Materials with Commercially Available Ones.

PURPOSE: To determine the hardness and Young's moduli of both commercial and experimental vinyl poly siloxane (VPS). METHODS: The purpose of this study was to develop a medium-bodied experimental (Exp-I, II, III, IV, and V) VPS impression materials and to analyse their effects on hardness and Young's modulus and compare them with three commercial VPS materials (Aquasil, Elite, and Extrude) using Shore A hardness tester. Measurements were recorded after 1, 24, 72, and 168 hours of mixing. The results were analysed with one-way ANOVA and post hoc Tukey's test using the SPSS PASW statistical 22 software. RESULTS: Commercial and experimental vinyl polysiloxane exhibited higher Shore A hardness values with time (i.e., 1 hour after mixing, 24 hours after mixing, 72 hours after mixing, and 1 week after mixing). All Comml and Exp VPS demonstrated a significant increase (ANOVA, p < 0.05) in hardness at increasing time points. Generally, all commercial VPS exhibited significantly higher values for Shore A hardness compared to all Exp formulations. For commercial products, Elt M presented significantly highest values at all-time points followed by Aq M then Extr M. Exp-I was significantly harder than all other Exp VPS at all-time points. Young's modulus values were directly related to Shore A hardness; materials with higher Shore A hardness values had higher Young's moduli. CONCLUSION: Continued polymerisation of elastomeric impression materials results in increased hardness over time. Hardness, Young's moduli, and rigidity of the set commercial and experimental VPS materials were within the required limits. Shore A hardness and Young's moduli were directly proportional to each other, and commercial and experimental materials had enough rigidity to contain the stone during pouring.

Producing Fluorine- and Lubricant-Free Flexible Pathogen- and Blood-Repellent Surfaces Using Polysiloxane-Based Hierarchical Structures.

High-touch surfaces are known to be a major route for the spread of pathogens in healthcare and public settings. Antimicrobial coatings have, therefore, garnered significant attention to help mitigate the transmission of infectious diseases via the surface route. Among antimicrobial coatings, pathogen-repellent surfaces provide unique advantages in terms of safety in public settings such as instant repellency, affordability, biocompatibility, and long-term stability. While there have been many advances in the fabrication of biorepellent surfaces in the past two decades, this area of research continues to suffer challenges in scalability, cost, compatibility with high-touch applications, and performance for pathogen repellency. These features are critical for high-touch surfaces to be used in public settings. Additionally, the environmental impact of manufacturing repellent surfaces remains a challenge, mainly due to the use of fluorinated coatings. Here, we present a flexible hierarchical coating with straightforward and cost-effective manufacturing without the use of fluorine or a lubricant. Hierarchical surfaces were prepared through the growth of polysiloxane nanostructures using n-propyltrichlorosilane (n-PTCS) on activated polyolefin (PO), followed by heat shrinking to induce microscale wrinkles. The developed coatings demonstrated repellency, with contact angles over 153° and sliding angles <1°. In assays mimicking touch, these hierarchical surfaces demonstrated a 97.5% reduction in transmission of Escherichia coli (E.coli), demonstrating their potential as antimicrobial coatings to mitigate the spread of infectious diseases. Additionally, the developed surfaces displayed a 93% reduction in blood staining after incubation with human whole blood, confirming repellent properties that reduce bacterial deposition.