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At least 91 records · Page 5

LARC-TPI 1500 series controlled molecular weight polyimide

LARC-TPI, a linear high temperature thermoplastic polyimide, was developed several years ago at NASA Langley Research Center. This material has been commercialized by Mitsui Toatsu Chemicals, Inc., Tokyo, Japan, as a varnish and powder. More recently, a melt-extruded film of a controlled molecular weight of this same polymer has been supplied to NASA Langley Research Center for evaluation. This new form, called LARC-TPI 1500 series, has been prepared in three molecular weights - high, medium and low flow polymers. The subject of this investigation deals with the rheological properties of the high and medium flow powders and the adhesive properties of the medium flow melt-extruded film. Rheological studies indicate that the high and medium flow forms of the polymer fall in the flow range of injection moldable materials. Adhesive data generated on the medium flow extruded film shows this form to be well suited for structural adhesive bonding. The data are as good or better than that for LARC-TPI data of previous studies.

Progar, Donald↗

Selective Depolymerization for Sculpting Polymethacrylate Molecular Weight Distributions

Chain-end reactivation of polymethacrylates generated by reversible-deactivation radical polymerization (RDRP) has emerged as a powerful tool for triggering depolymerization at significantly milder temperatures than those traditionally employed. In this study, we demonstrate how the facile depolymerization of poly(butyl methacrylate) (PBMA) can be leveraged to selectively skew the molecular weight distribution (MWD) and predictably alter the viscoelastic properties of blended PBMA mixtures. By mixing polymers with thermally active chain ends with polymers of different molecular weights and inactive chain ends, the MWD of the blends can be skewed to be high or low by selective depolymerization. This approach leads to the counterintuitive principle of the “destructive strengthening” of a material. As a result, we demonstrate, as a proof of concept, the encryption of information within polymer mixtures by linking Morse code with the MWDs before and after selective depolymerization, allowing for the encoding of data within blends of synthetic macromolecules.

36 MATERIALS SCIENCE↗

Population balance models for polymer upcycling: signatures of the mechanism in the molecular weight evolution

Chemical and catalytic upcycling processes could help realize a circular plastics economy, but current models for testing mechanistic hypotheses and designing catalysts remain primitive. This work shows how proposed catalytic mechanisms can be incorporated into population balance models to predict the time evolution of molecular weight distributions. We develop models for homogeneous and heterogeneous catalysts, including catalysts that cut at chain ends and catalysts that cut at random locations. For heterogeneous catalysts, we illustrate the effect of adsorption constants that depend on polymer chain length. Here, we discuss ongoing efforts and challenges in measuring and modeling the time evolving molecular weight distributions in polymer upcycling processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ultra-high molecular weight silphenylene-siloxane polymers

Silphenylene-siloxane copolymers with molecular weights above one million were prepared using a two stage polymerization technique. The technique was successfully scaled up to produce 50 grams of this high polymer in a single run. The reactive monomer approach was also investigated using the following aminosilanes: bis(dimethylamino)dimethylsilane, N,N-bis(pyrrolidinyl)dimethylsilane and N,N-bis(gamma-butyrolactam)dimethylsilane). Thermal analyses were performed in both air and nitrogen. The experimental polymers decomposed at 540 to 562 C, as opposed to 408 to 426 C for commercial silicones. Differential scanning calorimetry showed a glass transition (Tg) at -50 to -55 C for the silphenylene-siloxane copolymer while the commercial silicones had Tg's at -96 to -112 C.

Patterson, W. J.↗

A Hybrid Structural Method for Investigating Low Molecular Weight Oligomeric Structures of Amyloid Beta

Spurred in part by the failure of recent therapeutics targeting amyloid β plaques in Alzheimer's Disease (AD), attention is increasingly turning to the oligomeric forms of this peptide that form early in the aggregation process. However, while numerous amyloid β fibril structures have been characterized, primarily by NMR spectroscopy and cryo-EM, obtaining structural information on the low molecular weight forms of amyloid β that presumably precede and/or seed fibril formation has proved challenging. Furthermore, these transient forms are heterogeneous, and depend heavily on experimental conditions such as buffer, temperature, concentration, and degree of quiescence during measurement. Here, we present the concept for a new approach to delineating structural features of early-stage low molecular weight amyloid β oligomers, using a solvent accessibility assay in conjunction with simultaneous fluorescence measurements.

60 APPLIED LIFE SCIENCES↗

Effect Of Molecular Weight On Adhesive Properties Of The Phenylethynyl-Terminated Polyimide LARC(sup TM)-PETI-5

Future civilian aircraft will require the use of advanced adhesive systems with high temperature capabilities. One such material has been developed at the NASA Langley Research Center, a phenylethynyl-terminated polyimide given the designation LARC(sup TM)-PETI-5. Recent work has shown the advantages of similar phenylethynyl-terminated polyimides as films, moldings, adhesives, and composite matrix resins. Phenylethynyl-terminated oligomers provide greater processing windows than materials which incorporate simple ethynyl endcaps. Since these low molecular weight, low melt viscosity oligomers thermally cure without the evolution of volatile by-products, they provide an excellent means of producing polymers with high glass transition temperatures, excellent solvent resistance, and high mechanical properties. Three different versions of LARC(sup TM)-PETI-5 with theoretical number average molecular weights (M(sub n)s) of 250, 5000, and 10000 g/mol were synthesized in this work. Differential Scanning Calorimetry (DSC) measurements were performed on the dry powder form of these materials to establish cure conditions which result in high glass transition temperatures (T(sub g)s). Lap shear specimens were prepared from adhesive tape made from each material and with the thermal cure conditions determined from the DSC data. The tensile shear data established processing conditions which provided the best adhesive strengths. Further testing was performed to establish the properties of LARC(sup TM)-PETI-5 as an adhesive material and to determine its solvent resistance.

Cano, Roberto J.↗

Electrodeposition of Zinc in Aqueous Electrolytes Containing High Molecular Weight Polymers

Strong polarization of the ion distribution in liquid electrolytes subjected to potential differences exceeding the thermal voltage, V T = kT/e, produces a hydrodynamic instability termed electroconvection at ion-selective interfaces. Electroconvection is desirable in some situations (e.g., electrodialysis) because it promotes mixing in a stagnant electrolyte layer, enhancing the ion flux at a fixed potential difference. It is undesirable in others (e.g., electrodeposition of metals) where early experiments show that convective fluid rolls associated with hydrodynamic instability in bounded electrolytes produce preferential metal deposition at localized regions on an electrode. Such localized deposition drives the family of morphological instabilities loosely termed dendritic electrodeposition. We experimentally investigate the effect of ultrahigh molecular weight polymer additives on the onset conditions and physical characteristics of both instabilities. Direct observations of electrodeposit morphology and tracer particle motions used in tandem with indirect electrokinetic measurements reveal that even at moderate concentrations, the polymer additives have a large beneficial effect in extending the range of electric potentials where stable electrodeposition is observed. Additionally, we report that at polymer concentrations above the entanglement threshold, high molecular weight polymers impart elasticity to liquid electrolytes which dampen electroconvective flow at a cation-selective interface but have at most a minimal effect on the bulk ionic conductivity of the liquid.

25 ENERGY STORAGE↗

High molecular weight polysaccharide that binds and inhibits virus

This invention provides a high molecular weight polysaccharide capable of binding to and inhibiting virus and related pharmaceutical formulations and methods of inhibiting viral infectivity and/or pathogenicity, as well as immunogenic compositions. The invention further includes methods of inhibiting the growth of cancer cells and of ameliorating a symptom of aging. Additionally, the invention provides methods of detecting and/or quantifying and/or isolating viruses.

Konowalchuk, Thomas W.↗

High molecular weight polysaccharide that binds and inhibits virus

This invention provides a high molecular weight polysaccharide capable of binding to and inhibiting virus and related pharmaceutical formulations and methods of inhibiting viral infectivity and/or pathogenicity, as well as immunogenic compositions. The invention further includes methods of inhibiting the growth of cancer cells and of ameliorating a symptom of aging. Additionally, the invention provides methods of detecting and/or quantifying and/or isolating viruses.

Konowalchuk, Thomas W.↗

Permethylation as a strategy for high–molecular–weight polysaccharide structure analysis by nuclear magnetic resonance—Case study of Xylella fastidiosa extracellular polysaccharide

Current practices for structural analysis of extremely large-molecular-weight polysaccharides via solution-state nuclear magnetic resonance (NMR) spectroscopy incorporate partial depolymerization protocols that enable polysaccharide solubilization in suitable solvents. Non-specific depolymerization techniques utilized for glycosidic bond cleavage, such as chemical degradation or ultrasonication, potentially generate structural fragments that can complicate complete and accurate characterization of polysaccharide structures. Utilization of appropriate enzymes for polysaccharide degradation, on the other hand, requires prior structural knowledge and optimal enzyme activity conditions that are not available to an analyst working with novel or unknown compounds. Herein, we describe an application of a permethylation strategy that allows the complete dissolution of intact polysaccharides for NMR structural characterization. This approach is utilized for NMR analysis of Xylella fastidiosa extracellular polysaccharide (EPS), which is essential for the virulence of the plant pathogen that affects multiple commercial crops and is responsible for multibillion dollar losses each year.

13C↗

A study of the damage tolerance enhancement of carbon/epoxy laminates by utilizing an outer lamina of ultra high molecular weight polyethylene

The damage tolerance of carbon/epoxy was examined when an outer layer of ultra high molecular weight polyethylene (Spectra) material was utilized on the specimen. Four types of 16 ply quasi-isotropic panels, (0,+45,90,-45)s2 were tested. The first contained no Spectra, while the others had one lamina of Spectra placed on either the top (impacted side), bottom or both surfaces of the composite plate. A range of impact energies up to approximately 8.5 Joules (6.3 ft-lbs) was used to inflict damage upon these specimens. Glass/Phenolic honeycomb beams with a core density of 314 N/m3 (2.0 lb/ft3) and 8 ply quasi-isotropic facesheets were also tested for compression-after-impact strength with and without Spectra at impact energies of 1,2,3 and 4 Joules (.74, 1.47, 2.21 and 2.95 ft-lbs). It was observed that the composite plates had little change in damage tolerance due to the Spectra, while the honeycomb panels demonstrated a slight increase in damage tolerance when Spectra was added, the damage tolerance level being more improved at higher impact energies.

Nettles, Alan T.↗

A low molecular weight artificial RNA of unique size with multiple probe target regions

Artificial RNAs (aRNAs) containing novel sequence segments embedded in a deletion mutant of Vibrio proteolyticus 5S rRNA have previously been shown to be expressed from a plasmid borne growth rate regulated promoter in E. coli. These aRNAs accumulate to high levels and their detection is a promising tool for studies in molecular microbial ecology and in environmental monitoring. Herein a new construct is described which illustrates the versatility of detection that is possible with aRNAs. This 3xPen aRNA construct carries a 72 nucleotide insert with three copies of a unique 17 base probe target sequence. This aRNA is 160 nucleotides in length and again accumulates to high levels in the E. coli cytoplasm without incorporating into ribosomes. The 3xPen aRNA illustrates two improvements in detection. First, by appropriate selection of insert size, we obtained an aRNA which provides a unique and hence, easily quantifiable peak, on a high resolution gel profile of low molecular weight RNAs. Second, the existence of multiple probe targets results in a nearly commensurate increase in signal when detection is by hybridization. These aRNAs are naturally amplified and carry sequence segments that are not found in known rRNA sequences. It thus may be possible to detect them directly. An experimental step involving RT-PCR or PCR amplification of the gene could therefore be avoided.

Non-NASA Center↗

Ultra-High-Molecular-Weight Silphenylene/Siloxane Elastomers

Elastomers enhance thermal and mechancial properties. Capable of performing in extreme thermal/oxidative environments and having molecular weights above 10 to the sixth power prepared and analyzed in laboratory experiments. Made of methylvinylsilphenylene-siloxane terpolymers, new materials amenable to conventional silicone-processing technology. Similarly formulated commercial methyl-vinyl silicones, vulcanized elastomers exhibit enhance thermal/oxidative stability and equivalent or superior mechanical properties.

Hundley, N. H.↗