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At least 433 records · Page 24

Network stability of FKM rubber compounds under hydrogen pressure

Fluorocarbon-based rubber (FKM) compounds are typically utilized in the aeronautical industry due to its exceptional chemical and thermal resistance and recently has drawn significant interest from the hydrogen community for various hydrogen applications, but there exists little data evaluating its hydrogen compatibility. In this paper, a formulated FKM compound was exposed to ultrahigh hydrogen pressure (90 MPa) and analyzed by attenuated total reflectance Fourier-transform infrared (ATR-FTIR) spectroscopy and crosslinking densities by solvent swelling measurement. ATR-FTIR spectroscopic data demonstrated that high-pressure hydrogen not only caused cleavages in polymer backbone and cross linkages, but also induced additional degradation of FKM compounds by breaking intermolecular hydrogen bonding between carboxylic acids, which were produced during rubber molding and post curing processes. This hydrogen pressure-driven degradation was significantly higher towards the core of the material than at the surface due to its weaker bonding between polymers and fillers.

Polymers, hydrogen, stability, degradation, Charac↗

A two-component protein condensate of the EGFR cytoplasmic tail and Grb2 regulates Ras activation by SOS at the membrane

We reconstitute a phosphotyrosine-mediated protein condensation phase transition of the ~200 residue cytoplasmic tail of the epidermal growth factor receptor (EGFR) and the adaptor protein, Grb2, on a membrane surface. The phase transition depends on phosphorylation of the EGFR tail, which recruits Grb2, and crosslinking through a Grb2-Grb2 binding interface. The Grb2 Y160 residue plays a structurally critical role in the Grb2-Grb2 interaction, and phosphorylation or mutation of Y160 prevents EGFR:Grb2 condensation. By extending the reconstitution experiment to include the guanine nucleotide exchange factor, SOS, and its substrate Ras, we further find that the condensation state of the EGFR tail controls the ability of SOS, recruited via Grb2, to activate Ras. These results identify an EGFR:Grb2 protein condensation phase transition as a regulator of signal propagation from EGFR to the MAPK pathway.

59 BASIC BIOLOGICAL SCIENCES↗

A bioactive supramolecular and covalent polymer scaffold for cartilage repair in a sheep model

Regeneration of hyaline cartilage in human-sized joints remains a clinical challenge, and it is a critical unmet need that would contribute to longer healthspans. Injectable scaffolds for cartilage repair that integrate both bioactivity and sufficiently robust physical properties to withstand joint stresses offer a promising strategy. We report here on a hybrid biomaterial that combines a bioactive peptide amphiphile supramolecular polymer that specifically binds the chondrogenic cytokine transforming growth factor β-1 (TGFβ-1) and crosslinked hyaluronic acid microgels that drive formation of filament bundles, a hierarchical motif common in natural musculoskeletal tissues. The scaffold is an injectable slurry that generates a porous rubbery material when exposed to calcium ions once placed in cartilage defects. The hybrid material was found to support in vitro chondrogenic differentiation of encapsulated stem cells in response to sustained delivery of TGFβ-1. Using a sheep model, we implanted the scaffold in shallow osteochondral defects and found it can remain localized in mechanically active joints. Evaluation of resected joints showed significantly improved repair of hyaline cartilage in osteochondral defects injected with the scaffold relative to defects injected with the growth factor alone, including implantation in the load-bearing femoral condyle. These results demonstrate the potential of the hybrid biomimetic scaffold as a niche to favor cartilage repair in mechanically active joints using a clinically relevant large-animal model.

Science & Technology - Other Topics↗

Modification of Wool Fibers via Base/Cationic Detergent Pretreatment and Transglutaminase-mediated Reaction of Keratin

The surface modification of wool fibers is an important part of the textile industry to add functionality and stability to wool products. In this study, we developed a process utilizing a base/cationic surfactant solution pretreatment followed by an enzyme-mediated keratin crosslinking reaction to modify the wool fibers. Changes in water contact angle demonstrated the successful transformation of the hydrophobic wool surface to a more hydrophilic one after soaking in sodium carbonate solution containing hexadecyltrimethylammonium bromide (CTAB). The treated fabrics were further characterized by colorimetry and fluorescent spectrometry. Results showed that the pretreatment increased the yellowness of fabrics and caused some structural changes among certain amino acids, such as tryptophan and cystine. Keratin extracted from coarse wool fibers was further applied on pretreated fabrics through a microbial transglutaminase (mTGase) mediated reaction under mild conditions. Morphological characterization via SEM demonstrated the effective coverage of keratin on the scales of wool. The current method may provide an alternative processing protocol to modify wool fibers and improve the quality and performance of wool products.

36 MATERIALS SCIENCE↗

Cytogenetic follow-up studies on humans with internal and external exposure to ionizing radiation

Cells exposed to ionizing radiation have a wide spectrum of DNA lesions that include DNA single-strand breaks, DNA double-strand breaks (DSBs), oxidative base damage and DNA-protein crosslinks. Among them, DSB is the most critical lesion, which when mis-repaired leads to unstable and stable chromosome aberrations. Currently, chromosome aberration analysis is the preferred method for biological monitoring of radiation-exposed humans. Here, stable chromosome aberrations, such as inversions and balanced translocations, persist in the peripheral blood lymphocytes of radiation-exposed humans for several years and, therefore, are potentially useful tools to prognosticate the health risks of radiation exposure, particularly in the hematopoietic system. In this review, we summarize the cytogenetic follow-up studies performed by REAC/TS (Radiation Emergency Assistance Center/Training site, Oak Ridge, USA) on humans exposed to internal and external radiation. In the light of our observations as well as the data existing in the literature, this review attempts to highlight the importance of follow-up studies for predicting the extent of genomic instability and its impact on delayed health risks in radiation-exposed victims.

61 RADIATION PROTECTION AND DOSIMETRY↗

Freestanding high-aspect-ratio gold masks for low-energy, phase-based x-ray microscopy

High-resolution, x-ray phase contrast microscopy, a key technique with promising potential in biomedical imaging and diagnostics, is based on narrow-slit high-aspect-ratio gold gratings. Here we present the development, fabrication details, and experimental testing of the freestanding 10 μm thick gold membrane masks with an array of 0.9–1.5 μm void slit apertures for a novel low-energy x-ray microscope. The overall mask size is 4 mm × 4 mm, with a grating pitch of 7.5 μm, 6.0–6.6 μm wide gold bars are supported by 3 μm wide crosslinks at 400 μm intervals. The fabrication process is based on gold electroplating into a silicon mold coated with various thin films to form a voltage barrier, plating base, and sacrificial layer, followed by the mold removal to obtain the freestanding gold membrane with void slit apertures. We discuss key aspects for the materials and processes, including gold structures homogeneity, residual stresses, and prevention of collapsing of the grid elements. We further demonstrate the possibility to obtain high-resolution, high contrast 2D images of biological samples using an incoherent, rotating anode x-ray tube.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Thermal and Electrical Properties of Isocyanate Derived Organic Aerogels for Cryogenic Insulation Applications

The use and storage of cryogens such as liquefied nitrogen, helium, hydrogen among others requires reliable and efficient thermal insulation systems. Passive insulation from high performance materials that are well-known for their inherent low thermal conductivity would reduce the overall costs involved in design, manufacture and maintenance of such systems. One such class of materials are referred to as aerogels. These materials are known for their low density, high mesoporosity, high surface areas, low thermal conductivity and high acoustic impedance. Aerogels were invented by S.S. Kistler in 1931 and the most common type are those made of silica. However, the inherent fragility of silica aerogels makes them hard to mass produce, and therefore applications have been limited. A major breakthrough was introduced by our team almost 20 years ago with the invention of polymer crosslinked silica aerogels. Those materials shifted attention to all-polymer aerogels that have overcome all fragility issues associated with their inorganic counterparts. This study focuses on such polymeric aerogels that can be mass produced as large monoliths while maintaining the low thermal conductivity of traditional silica aerogels over a wide temperature range. Manufacturing flexibility of polymeric aerogels allows fabrication of blocks and sheets that can be applied in various configurations to insulate cryogenic and superconducting devices. The thermal conductivity with 80 K and room temperature boundary are reported as well as other properties (electrical), that need to be considered when designing devices for cryogenic applications.

Churu, Gitogo↗

Interactions that define the arrangement of sugar-binding sites in BDCA-2 and dectin-2 dimers

The sugar-binding receptors dectin-2 and blood dendritic cell antigen 2 (BDCA-2) bind oligosaccharide ligands through extracellular carbohydrate-recognition domains (CRDs) and initiate intracellular signaling through Fc receptor γ adapters (FcRγ). Dectin-2 stimulates macrophages in response to pathogen binding while BDCA-2 modulates cytokine production in plasmacytoid dendritic cells. The oligomeric states of these receptors and the orientations of their CRDs have been investigated by analysis of a naturally occurring disulfide-bonded variant of BDCA-2 and by replacement of transmembrane domains with N-terminal dimerization domains to create extracellular domain dimers of both dectin-2 and BDCA-2. Analysis of these constructs, as well as previously described crystal structures of the CRDs from these proteins and a novel structure of an extended version of the extracellular domain of dectin-2, showed that there is only limited interaction of the CRDs in the dimers, but interactions can be stabilized by the presence of the neck region. The resulting orientation of sugar-binding sites in the dimers would favor crosslinking of multiple dimers by oligosaccharide ligands, causing clustering of FcRγ to initiate signaling.

carbohydrate-binding protein↗

Molecular basis of crosstalk in nuclear receptors: heterodimerization between PXR and CAR and the implication in gene regulation

The 48 human nuclear receptors (NRs) form a superfamily of transcription factors that regulate major physiological and pathological processes. Emerging evidence suggests that NR crosstalk can fundamentally change our understanding of NR biology, but detailed molecular mechanisms of crosstalk are lacking. Here, we report the molecular basis of crosstalk between the pregnane X receptor (PXR) and constitutive androstane receptor (CAR), where they form a novel heterodimer, resulting in their mutual inhibition. PXR and CAR regulate drug metabolism and energy metabolism. Although they have been broadly perceived as functionally redundant, a growing number of reports suggests a mutual inhibitory relation, but their precise mode of coordinated action remains unknown. Using methods including RNA sequencing, small-angle X-ray scattering and crosslinking mass spectrometry we demonstrate that the mutual inhibition altered gene expression globally and is attributed to the novel PXR–CAR heterodimerization via the same interface used by each receptor to heterodimerize with its functional partner, retinoid X receptor (RXR). These findings establish an unexpected functional relation between PXR, CAR and RXR, change the perceived functional relation between PXR and CAR, open new perspectives on elucidating their role and designing approaches to regulate them, and highlight the importance to comprehensively investigate nuclear receptor crosstalk.

59 BASIC BIOLOGICAL SCIENCES↗

The plant cell wall—dynamic, strong, and adaptable—is a natural shapeshifter

Mythology is replete with good and evil shapeshifters, who, by definition, display great adaptability and assume many different forms—with several even turning themselves into trees. Cell walls certainly fit this definition as they can undergo subtle or dramatic changes in structure, assume many shapes, and perform many functions. In this review, we cover the evolution of knowledge of the structures, biosynthesis, and functions of the 5 major cell wall polymer types that range from deceptively simple to fiendishly complex. Along the way, we recognize some of the colorful historical figures who shaped cell wall research over the past 100 years. The shapeshifter analogy emerges more clearly as we examine the evolving proposals for how cell walls are constructed to allow growth while remaining strong, the complex signaling involved in maintaining cell wall integrity and defense against disease, and the ways cell walls adapt as they progress from birth, through growth to maturation, and in the end, often function long after cell death. We predict the next century of progress will include deciphering cell type–specific wall polymers; regulation at all levels of polymer production, crosslinks, and architecture; and how walls respond to developmental and environmental signals to drive plant success in diverse environments.

59 BASIC BIOLOGICAL SCIENCES↗

Mass spectrometry-based technologies for probing the 3D world of plant proteins

Abstract Over the past two decades, mass spectrometric (MS)-based proteomics technologies have facilitated the study of signaling pathways throughout biology. Nowhere is this needed more than in plants, where an evolutionary history of genome duplications has resulted in large gene families involved in posttranslational modifications and regulatory pathways. For example, at least 5% of the Arabidopsis thaliana genome (ca. 1,200 genes) encodes protein kinases and protein phosphatases that regulate nearly all aspects of plant growth and development. MS-based technologies that quantify covalent changes in the side-chain of amino acids are critically important, but they only address one piece of the puzzle. A more crucially important mechanistic question is how noncovalent interactions—which are more difficult to study—dynamically regulate the proteome’s 3D structure. The advent of improvements in protein 3D technologies such as cryo-electron microscopy, nuclear magnetic resonance, and X-ray crystallography has allowed considerable progress to be made at this level, but these methods are typically limited to analyzing proteins, which can be expressed and purified in milligram quantities. Newly emerging MS-based technologies have recently been developed for studying the 3D structure of proteins. Importantly, these methods do not require protein samples to be purified and require smaller amounts of sample, opening the wider proteome for structural analysis in complex mixtures, crude lysates, and even in intact cells. These MS-based methods include covalent labeling, crosslinking, thermal proteome profiling, and limited proteolysis, all of which can be leveraged by established MS workflows, as well as newly emerging methods capable of analyzing intact macromolecules and the complexes they form. In this review, we discuss these recent innovations in MS-based “structural” proteomics to provide readers with an understanding of the opportunities they offer and the remaining challenges for understanding the molecular underpinnings of plant structure and function.

Plant Sciences↗

Investigation of Inverse Temperature Effects During Thermal-Radiation Aging of Semicrystalline Cable Insulation

Inverse temperature effects were observed for semi-crystalline polymers subjected to combined thermal and irradiation aging. The mechanical durability of materials aged at low temperatures degrades with dose faster than at high temperatures. In this paper, two crosslinked polyethylene (XLPE) and two ethylene propylene rubber (EPR) type nuclear cable insulations were exposed to thermal-radiation aging at 100Gy/h up to 30Mrad and three temperatures (26°C, 50°C, 90°C). Their mass change and color change after aging were analyzed.

Ni, Yelin↗

Dose Rate Effects in the Aging of Nuclear Cable Insulation Subjected to Gamma Radiation

In nuclear power plants (NPPs), the aging of polymer-based electrical cable insulation must be effectively monitored to ensure the safe and reliable operation of NPPs. Gamma radiation is one of the main environmental stressors causing degradation of cable insulation. For a given total dose of absorbed gamma radiation, damage due to gamma irradiation may be dose rate dependent. The purpose of this work is to confirm whether a dose rate effect exists for the cable insulation made by crosslinked polyethylene (XLPE) and ethylene propylene rubber (EPR), quantify the relationship between degradation rate and dose rate, and explore the correlation of different measured properties. The dose rate effects at 1800 Gy/h, 200 Gy/h, and 100 Gy/h using 60Co gamma irradiation on cable aging was studied. Different types of cable insulation, including two XLPEs and one EPR, were irradiated at the different dose rates with a total dose around 300 kGy at 26 °C. The properties of unirradiated and irradiated samples were characterized by mass change, yellowness index, and other ongoing measurements. Dose rate effects were observed for mass change data of XLPE and EPR.

Li, Donghui↗

Field-Aged Glass/Backsheet and Glass/Glass PV Modules: Encapsulant Degradation Comparison

Ethylene vinyl acetate (EVA) is the predominant encapsulant in crystalline-silicon photovoltaic (PV) modules; however, its degradation is a subject of major concern, which causes significant power loss under field conditions. This article presents a comparison of EVA degradation in field-aged PV modules with glass/backsheet (G/B) and glass/glass (G/G) architectures. Modulelevel characterization included UV fluorescence imaging and I-V measurements. Material analytical techniques, including colorimetry, differential scanning calorimetry, thermogravimetric analysis, Fourier transform infrared spectroscopy, and Raman spectroscopy, were performed to correlate the module performance parameters with EVA material properties. An intense EVA discoloration in G/G modules was observed, which was corroborated by higher module Isc and Pmax degradation rates compared with its counterpart G/B modules. Higher power degradation was accompanied by a significant increase in EVA crosslinking, vinyl acetate content, yellowness index, and presence of functional groups containing unsaturated moieties that are linked to degradation products of photothermal reaction, and a higher decrease in the degree of crystallinity. The absence of a polymeric backsheet in hermetically sealed G/G modules, which restricts photobleaching and enhances the entrapment of volatile acetic acid and other degradation by-products, plays a major role in causing higher EVA degradation in G/G modules. This article concludes that EVA might have been a good choice of an encapsulant for the G/B modules over the decades, but it may prove to be an inappropriate choice for the G/G modules because of potential degassing, corrosion, and/or discoloration issues. Ionomers or polyester-based encapsulants like polyolefins could be best suited for G/G modules as it appears to be a current trend in the industry.

14 SOLAR ENERGY↗

Thermal Properties of Sodium Borosilicate Glasses as a Function of Sulfur Content

SO3 additions, up to 3.0 wt%, were systematically investigated for effects on the physical properties of sodium borosilicate glass melted in air, with a sulfur-free composition of 50SiO2-10Al2O3-12B2O3-21Na2O-7CaO (wt%). Solubility measurements, using electron microscopy chemical analysis, determined the maximum loading to be ~1.5 wt% SO3. It was found that sulfur (here as sulfate) in this glass increased the glass transition temperature, thermal diffusivity, heat capacity, and thermal conductivity, and decreased the mass density. Structural analysis, performed with Raman spectroscopy, indicated that the borosilicate network polymerized with sulfur additions, presumably due to Na2O being required to charge compensate the ionic SO42- additions, thus becoming unavailable to form non-bridging oxygen in the silicate network. It is postulated that this increased crosslinking of the borosilicate backbone lead to a structure with higher dimensionality and average bond energy. This increased the mean free paths and vibration frequency of the phonons, which resulted in the observed increase in thermal properties.

Thermal properties, Borosilicate glass, Sulfur sol↗

Hydrolytic Aging in Rubber-Like Materials: A Micro-Mechanical Approach to Modeling

Abstract The effect of hydrolytic aging on mechanical responses of Rubber likes materials, in particular, Mullins effect and the permanent set has been modeled. Hydrolytic aging is considered as the result of the competition between two phenomena (1) chain scission and (2) cross-link scission/reformation. Both phenomena were modeled and thus, the strain energy of the polymer matrix is written with respect to three independent mechanisms; i) the shrinking original matrix which has not been attacked by water, ii) conversion of the first network to a new network due to the reduction of the crosslinks, and iii) energy loss from network degradation due to water attacks to ester groups. The model is validated with respect to a set of experimental data. Besides accuracy, the simplicity and few numbers of fitting parameters make the model a good choice for further implementations.

Bahrololoumi, Amir↗

Experimental Investigation on the Performance Loss of Cross-Linked Polymers During Photo-Oxidative Aging

Abstract Polymeric substances have seen an unprecedented integration in countless applications and fields of life, subjecting them to a broad range of environmental conditions, which can cause a form of damage to the structural and mechanical properties of these components known as aging. In this study we investigate the effects of the degradation of polymeric materials due to the extended exposure to sunlight, which can be simulated through controlled photo-oxidative aging using ultraviolet (UV) radiation as the main catalyst of this phenomenon. The effects on mechanical behavior and chemical properties of four polymeric materials with different mechanical characteristics was accordingly monitored throughout the study. The materials range in hardness with the polyurethane adhesive being the hardest and acting plastically, followed by an acrylic which exhibits greater hardening with time, a polyurethane sealant, which behaves in an elastomeric manner, and a silicon sealant, which is the softest of the set. Samples were prepared and subjected to UV radiation at three different temperatures namely 45, 60 and 80°C, for different aging periods ranging from 1 day for higher temperatures to 150 days for lower ones. The samples were then subjected to the Fourier transform Infrared spectroscopy (FTIR) test to monitor the change in the chemical composition of the materials along the aging durations and conditions. The materials were then subjected to mechanical testing along two modes of mechanical loading, which are a simple tension until failure and a double-cyclic test with progressively increasing strain limits after every two successful cycles until the sample reaches failure. The samples are loaded at constant strain rates throughout both tests. These tests revealed the change of behavior of our materials along the aging periods and conditions. The changes in mechanical behavior vary across each individual material depending on the aging temperature and period, with the changes ranging from hardening to softening, embrittlement or an increase in the maximum strain the material can endure before failure. A general trend would be that most materials become harder after photo-oxidation, however due to the range of temperatures in the aging conditions, thermo-oxidation, which causes softening in some of the polymers, has an increasingly notable effect at higher temperatures. A visible correlation can be noted between the change in mechanical behavior and a change in absorbance of Infrared Radiation (IR) in the FTIR spectrum, as the greater the crosslinking throughout the polymer matrix, the lower the absorbance of IR radiation due to the increased stiffness of the overall macro-molecular structure.

Korayem, Abd-Elrahman↗

Independence of Environmental and Mechanical Damages on Silicone Adhesive Stored in a Thermo-Oxidative Environment

Abstract Elastomeric polymer materials hold a special place in today’s industrial sectors with respect to structural application needs. Low quality materials are detrimental to industries like aerospace, and automotive engineering. Assessment of the durability of elastomers for structural applications has been of much interest among the literary circles for decades and new materials keep outperforming the existing ones. Polymeric adhesives are one of the most abundantly used materials in these industries. All polymeric materials get damaged when in contact with aggressive environments in presence of high temperature and oxygen. Commonly referred to as thermo-oxidation, this environment exposes the material to heat and oxidation reactions in presence of oxygen. Resultantly, during service life, the damage to the polymer matrix is primarily caused by two factors: mechanical damage and environmental aging. Environmental aging is an irreversible phenomenon caused by changes in the molecular structure while mechanical damage maintains the shape of the polymer matrix, and the deterioration is mostly due to polymer chain mobility. Environmental aging can be caused by a single environmental agent or by a synergized impact of several environmental elements. Increasing temperature is found to be proportional to decreasing tensile strength and toughness of material. The rate and extent of degradation can be accessed by scrutinizing the changes in constitutive behavior of material through mechanical and chemical properties. Accelerated thermal aging is among the most common modes of process related degradation, leading generally to chain scission, and crosslinking phenomena and reduced resistance to fracture stress, and strain. In this experimental study, our goal is to separate the environmental degradation from mechanical damage. A silicone-based adhesive was aged in thermo-oxidative at (0%RH) aging environment. The damage and decay mechanisms have been used to draw a distinction between environmental degradation and mechanical damage. Material characterization included uniaxial tensile test (failure and cyclic) and scanning electron microscopy (SEM) tests on as-received and aged samples. Aging was conducted at three different temperatures (60°C, 80°C and 95°C) and six different exposure durations (1, 3, 10, 30, 90 and 200 days). This work confirms that environmental damage is superposed on top of the mechanical damage, and thus, they are separable. The total mechanical and environmental damage is a synergized effect of all exposure conditions and parameters involved i.e., aging time, temperature, and oxygen. The chemistry and mechanics of the polymer degradation were found to be in good agreement with each other.

Alazhary, Sharif↗