Carbon Black Functionalized with Serinol Pyrrole to Replace Silica in Elastomeric Composites.

Elastomer composites for dynamic mechanical applications with a low dissipation of energy are of great importance in view of their application in tire compounds. In this work, furnace carbon black functionalized with 2-2,5-dimethyl-1H-pyrrol-1-yl-1,3-propanediol (SP) was used in place of silica in an elastomer composite based on poly(styrene-co-butadiene) from solution anionic polymerization and poly(1,4-cis-isoprene) from Hevea Brasiliensis. The traditional coupling agent used for silica was also used for the CB/SP adduct: 3,3'-bis(triethoxysilylpropyl)tetrasulfide (TESPT). The composite with the CB/SP + TESPT system revealed a lower Payne effect, higher dynamic rigidity, and lower hysteresis, compared to the composite with CB + TESPT, although the latter composite had a higher crosslinking density. The properties of the silica and the CB/SP + TESPT-based composites appear similar, though in the presence of slightly higher hysteresis and lower ultimate properties for the CB/SP-based composite. The use of CB in place of silica allows us to prepare lighter compounds and paves the way for the preparation of tire compounds with lower environmental impacts.

Bio-Based Pyrrole Compounds Containing Sulfur Atoms as Coupling Agents of Carbon Black with Unsaturated Elastomers.

In this work, the hysteresis of elastomer composites suitable for tire compounds was reduced by using CB functionalized with pyrrole compounds containing sulfur-based functional groups reactive with the elastomer chains. CB was functionalized with bio-based pyrrole compounds: 2-(2,5-dimethyl-1H-pyrrol-1-yl)ethane-1-thiol (SHP) and 1,2-bis(2-(2,5-dimethyl-1H-pyr-rol-1-yl)ethyl)disulfide (SSP), bearing an -SH and an -SS- functional group, respectively. SHP and SSP were synthesized via a one-pot two-step synthesis, with yields higher than 70%, starting from biosourced chemicals as follows: 2,5-hexanedione from 2,5-dimethylfuran, cysteine and cysteamine. The functionalization of CB was carried out by mixing the CB with PyC and heating, with quantitative yields ranging from 92 to 97%. Thus, the whole functionalization process was characterized by a high carbon efficiency. The formation of the covalent bond between SHP, SSP and CB, in line with the prior art of such a functionalization technology, was proven by means of extraction and TGA analyses. The reactivity of the sulfur-based functional groups with unsaturated polymer chains was demonstrated by using squalene as the model compound. Poly(styrene-co-butadiene) from solution anionic polymerization and poly(1,4-cis-isoprene) from Hevea Brasiliensis were the elastomers employed for the preparation of the composites, which were crosslinked with a sulfur-based system. Pristine CB was partially replaced with CB/SHP (33%) and CB/SSP (33% and 66%). The PyC resulted in better curing efficiency, an increase in the dynamic rigidity of approximately 20% and a reduction in the hysteresis of approximately 10% at 70 °C, as well as similar/better ultimate tensile properties. The best results were achieved with a 66% replacement of CB with CB/SSP. This new family of reactive carbon blacks paves the way for a new generation of 'green tires', reinforced by a CB reactive with the polymer chains, which provides high mechanical properties and low rolling resistance. Such a reactive CB eliminates the use of silica, and thus the ethanol emission resulting from the condensation of silane is used as a coupling agent. In addition, CB-based tires are characterized by a higher mileage, at a moment in which the reduction in tire wear has become a primary concern.

Adducts of Carbon Black with a Biosourced Janus Molecule for Elastomeric Composites with Lower Dissipation of Energy.

Elastomer composites with low hysteresis are of great importance for sustainable development, as they find application in billions of tires. For these composites, a filler such as silica, able to establish a chemical bond with the elastomer chains, is used, in spite of its technical drawbacks. In this work, a furnace carbon black (CB) functionalized with polar groups was used in replacement of silica, obtaining lower hysteresis. CBN326 was functionalized with 2-(2,5-dimethyl-1H-pyrrol-1-yl)-1,3-propanediol (serinol pyrrole, SP), and samples of CB/SP adducts were prepared with different SP content, ranging from four to seven parts per hundred carbon (phc). The entire process, from the synthesis of SP to the preparation of the CB/SP adduct, was characterized by a yield close to 80%. The functionalization did not alter the bulk structure of CB. Composites were prepared, based on diene rubbers-poly(1,4-cis-isoprene) from Hevea Brasiliensis and poly(1,4-cis-butadiene) in a first study and synthetic poly(1,4-cis-isoprene) in a second study-and were crosslinked with a sulfur-based system. A CB/silica hybrid filler system (30/35 parts) was used and the partial replacement (66% by volume) of silica with CB/SP was performed. The composites with CB/SP exhibited more efficient crosslinking, a lower Payne effect and higher dynamic rigidity, for all the SP content, with the effect of the functionalized CB consistently increasing the amount of SP. Lower hysteresis was obtained for the composites with CB/SP. A CB/SP adduct with approximately 6 phc of SP, used in place of silica, resulted in a reduction in ΔG'/G' of more than 10% and an increase in E' at 70 °C and in σ300 in tensile measurements of about 35% and 30%, respectively. The results of this work increase the degrees of freedom for preparing elastomer composites with low hysteresis, allowing for the use of either silica or CB as filler, with a potentially great impact on an industrial scale.

Hexagonal Boron Nitride as Filler for Silica-Based Elastomer Nanocomposites.

Two-dimensional hexagonal boron nitride (hBN) has attracted tremendous attention over the last few years, thanks to its stable structure and its outstanding properties, such as mechanical strength, thermal conductivity, electrical insulation, and lubricant behavior. This work demonstrates that hBN can also improve the rheological and mechanical properties of elastomer composites when used to partially replace silica. In this work, commercially available pristine hBN (hBN-p) was exfoliated and ball-mill treated in air for different durations (2.5, 5, and 10 h milling). Functionalization occurred with the -NH and -OH groups (hBN-OH). The functional groups were detected using Fourier-Transform Infrared pectroscopy (FT-IR) and were estimated to be up to about 7% through thermogravimetric analysis. The presence of an increased amount of oxygen in hBN-OH was confirmed using Scanning Electron Microscopy coupled with Energy-Dispersive X-ray Spectroscopy. (SEM-EDS). The number of stacked layers, estimated using WAXD analysis, decreased to 8-9 in hBN-OH (10 h milling) from about 130 in hBN-p. High-resolution transmission electron microscopy (HR-TEM) and SEM-EDS revealed the increase in disorder in hBN-OH. hBN-p and hBN-OH were used to partially replace silica by 15% and 30%, respectively, by volume, in elastomer composites based on poly(styrene-co-butadiene) from solution anionic polymerization (S-SBR) and poly(1,4-cis-isoprene) from Hevea Brasiliensis (natural rubber, NR) as the elastomers (volume (mm3) of composites released by the instrument). The use of both hBNs in substitution of 30% of silica led to a lower Payne effect, a higher dynamic rigidity, and an increase in E' of up to about 15% at 70 °C, with similar/lower hysteresis. Indeed, the composites with hBN-OH revealed a better balance of tan delta (higher at low temperatures and lower at high temperatures) and better ultimate properties. The functional groups reasonably promote the interaction of hBN with silica and with the silica's coupling agent, sulfur-based silane, and thus promoted the interaction with the elastomer chains. The volume of the composite, measured using a high-pressure capillary viscometer, increased by about 500% and 400% after one week of storage in the presence of hBN-p and hBN-OH. Hence, both hBNs improved the processability and the shelf life of the composites. Composites obtained using hBN-OH had even filler dispersion without the detachments of the filler from the elastomer matrix, as shown through TEM micrographs. These results pave the way for substantial improvements in the important properties of silica-based composites for tire compounds, used to reduce rolling resistance and thus the improve environmental impacts.

Influence of Carbon Nanotube-Pretreatment on the Properties of Polydimethylsiloxane/Carbon Nanotube-Nanocomposites.

Incorporating nanofillers into elastomers leads to composites with an enormous potential regarding their properties. Unfortunately, nanofillers tend to form agglomerates inhibiting adequate filler dispersion. Therefore, different carbon nanotube (CNT) pretreatment methods were analyzed in this study to enhance the filler dispersion in polydimethylsiloxane (PDMS)/CNT-composites. By pre-dispersing CNTs in solvents an increase in electrical conductivity could be observed within the sequence of tetrahydrofuran (THF) > acetone > chloroform. Optimization of the pre-dispersion step results in an AC conductivity of 3.2 × 10-4 S/cm at 1 Hz and 0.5 wt.% of CNTs and the electrical percolation threshold is decreased to 0.1 wt.% of CNTs. Optimum parameters imply the use of an ultrasonic finger for 60 min in THF. However, solvent residues cause a softening effect deteriorating the mechanical performance of these composites. Concerning the pretreatment of CNTs by physical functionalization, the use of surfactants (sodium dodecylbenzenesulfonate (SDBS) and polyoxyethylene lauryl ether ("Brij35")) leads to no improvement, neither in electrical conductivity nor in mechanical properties. Chemical functionalization enhances the compatibility of PDMS and CNT but damages the carbon nanotubes due to the oxidation process so that the improvement in conductivity and reinforcement is superimposed by the CNT damage even for mild oxidation conditions.

An In Vitro Barrier Model of the Human Submandibular Salivary Gland Epithelium Based on a Single Cell Clone of Cell Line HTB-41: Establishment and Application for Biomarker Transport Studies.

The blood-saliva barrier (BSB) consists of the sum of the epithelial cell layers of the oral mucosa and salivary glands. In vitro models of the BSB are inevitable to investigate and understand the transport of salivary biomarkers from blood to saliva. Up to now, standardized, cell line-based models of the epithelium of the submandibular salivary gland are still missing for this purpose. Therefore, we established epithelial barrier models of the submandibular gland derived from human cell line HTB-41 (A-253). Single clone isolation resulted in five different clones (B2, B4, B9, D3, and F11). Clones were compared to the parental cell line HTB-41 using measurements of the transepithelial electrical resistance (TEER), paracellular marker permeability assays and analysis of marker expression for acinar, ductal, and myoepithelial cells. Two clones (B9, D3) were characterized to be of acinar origin, one clone (F11) to be of myoepithelial origin and one isolation (B4) derived from two cells, to be presumably a mixture of acinar and ductal origin. Clone B2, presumably of ductal origin, showed a significantly higher paracellular barrier compared to other clones and parental HTB-41. The distinct molecular identity of clone B2 was confirmed by immunofluorescent staining, qPCR, and flow cytometry. Experiments with ferritin, a biomarker for iron storage, demonstrated the applicability of the selected model based on clone B2 for transport studies. In conclusion, five different clones originating from the submandibular gland cell line HTB-41 were successfully characterized and established as epithelial barrier models. Studies with the model based on the tightest clone B2 confirmed its suitability for transport studies in biomarker research.

Solution processable metal-organic frameworks for mixed matrix membranes using porous liquids.

The combination of well-defined molecular cavities and chemical functionality makes crystalline porous solids attractive for a great number of technological applications, from catalysis to gas separation. However, in contrast to other widely applied synthetic solids such as polymers, the lack of processability of crystalline extended solids hampers their application. In this work, we demonstrate that metal-organic frameworks, a type of highly crystalline porous solid, can be made solution processable via outer surface functionalization using N-heterocyclic carbene ligands. Selective outer surface functionalization of relatively large nanoparticles (250 nm) of the well-known zeolitic imidazolate framework ZIF-67 allows for the stabilization of processable dispersions exhibiting permanent porosity. The resulting type III porous liquids can either be directly deployed as liquid adsorbents or be co-processed with state-of-the-art polymers to yield highly loaded mixed matrix membranes with excellent mechanical properties and an outstanding performance in the challenging separation of propylene from propane. We anticipate that this approach can be extended to other metal-organic frameworks and other applications.

Characterization of Rough PTFE Surfaces by the Modified Wilhelmy Balance Technique.

The wetting of rough polymer surfaces is of great importance for many technical applications. In this paper, we demonstrate the relationship between the mean roughness values and the fractal dimension of rough and self-affine PTFE surfaces. We have used white light interferometry measurements to obtain information about the complex topography of the technical surfaces having different height distributions. Two different methods for the calculation of the fractal dimension were used: The height difference correlation function (HDC) and the cube counting method. It was demonstrated that the mean roughness value (Ra) correlates better with the fractal dimension Df determined by the cube counting method than with the Df values obtained from HDC calculations. However, the HDC values show a stronger dependency by changing the surface roughness. The advancing and receding contact angles as well as the contact angle hysteresis of PTFE samples of different roughness were studied by the modified Wilhelmy balance technique using deionized water as a liquid. The modified Wilhelmy balance technique enables the possibility for future analysis of very rough PTFE surfaces which are difficult to investigate with the sessile drop method.

Co-culture of osteochondral explants and synovial membrane as in vitro model for osteoarthritis.

The purpose of the current study was to establish an in vitro model for osteoarthritis (OA) by co-culture of osteochondral and synovial membrane explants. Osteochondral explants were cultured alone (control-1) or in co-culture with synovial membrane explants (control-2) in standard culture medium or with interleukin-1ß (IL1ß) and tumor necrosis factor (TNFα) added to the culture medium (OA-model-1 = osteochondral explant; OA-model-2 = osteochondroal-synovial explant). In addition, in OA-model groups a 2-mm partial-thickness defect was created in the centre of the cartilage explant. Changes in the expression of extracellular matrix (ECM) genes (collagen type-1 (Col1), Col2, Col10 and aggrecan) as well as presence and quantity of inflammatory marker genes (IL6, matrix metalloproteinase-1 (MMP1), MMP3, MMP13, a disintegrin and metalloproteinase with-thrombospondin-motif-5 (ADAMTS5) were analysed by immunohistochemistry, qPCR and ELISA. To monitor the activity of classically-activated pro-inflammatory (M1) versus alternatively-activated anti-inflammatory/repair (M2) synovial macrophages, the nitric oxide/urea ratio in the supernatant of osteochondral-synovial explant co-cultures was determined. In both OA-model groups immunohistochemistry and qPCR showed a significantly increased expression of MMPs and IL6 compared to their respective control group. ELISA results confirmed a statistically significant increase in MMP1and MMP3 production over the culturing period. In the osteochondral-synovial explant co-culture OA-model the nitric oxide/urea ratio was increased compared to the control group, indicating a shift toward M1 synovial macrophages. In summary, chemical damage (TNFα, IL1ß) in combination with a partial-thickness cartilage defect elicits an inflammatory response similar to naturally occurring OA in osteochondral explants with and without osteochondral-synovial explant co-cultures and OA-model-2 showing a closer approximation of OA due to the additional shift of synovial macrophages toward the pro-inflammatory M1 phenotype.

Polycyclic aromatic hydrocarbons in consumer goods made from recycled rubber material: A review.

Vast amounts of rubber waste are produced every year, where end-of-life tires (ELT) mount up the largest share with several million tonnes in the EU each year. This points up the necessity for reusing end-of-life rubber material. The recycled material shows nearly the same advantages like the origin materials. In consequence, the recycled material is predestined for the use in sport facilities, which explains that around half of the recycled ELTs are used to produce artificial turf, sports flooring and injury-prevention pavements on playgrounds. Since tires contain potentially toxic components, there is worry concerning the release of such chemical substances stemming from these products. As tires contain highly aromatic oils and carbon black, the presence of polycyclic aromatic hydrocarbons (PAH) and their carcinogenic properties are discussed controversially. This review issues a comprehensive overview of PAH release and a conclusive assessment on human health risk. Analytical studies dealing with the PAH content of consumer goods made from recycled rubber material and associated risk assessments are reviewed. In conclusion PAHs can be detected in consumer goods made from recycled rubber and are released into the environment. They reach humans via leaching (soil, ground water, rivers), oral intake, dermal exposure and inhalation. Thereby, dermal contact or inhalation is the primary route of exposure, whereas oral intake and environmental pollution are regarded as secondary risks. The amount of PAHs that could potentially harm humans is in the magnitude of urban pollution. Risk assessment studies reviewed in this article show no serious risk potential.

A novel glucokinase activator modulates pancreatic islet and hepatocyte function.

The glucose-sensing enzyme glucokinase (GK) plays a key role in glucose metabolism. We report here the effects of a novel glucokinase activator, LY2121260. The activator enhanced GK activity via binding to the allosteric site located in the hinge region of the enzyme. LY2121260 stimulated insulin secretion in a glucose-dependent manner in pancreatic beta-cells and increased glucose use in rat hepatocytes. In addition, incubation of beta-cells with the GK activator resulted in increased GK protein levels, suggesting that enhanced insulin secretion on chronic treatment with a GK activator may be due to not only changed enzyme kinetics but also elevated enzyme levels. Animals treated with LY2121260 showed an improved glucose tolerance after oral glucose challenge. These results support the concept that GK activators represent a new class of compounds that increase both insulin secretion and hepatic glucose use and in doing so may prove to be effective agents for the control of blood glucose levels in patients with type 2 diabetes.