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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
NASA NTRS1991

Optical properties of aggregate particles whose outer diameter is comparable to the wavelength

Results are described of numerical calculations of the optical properties (extinction efficiency, single-scattering albedo, phase function, and linear polarization) of aggregate particles whose outer diameter is comparable with the wavelength. Results are presented for two types of particle, one composed of monomers whose radius is small compared with the wavelength and a second containing monomers with larger radii. The shape of the forward-scattered lobe of the phase function is diagnostic of the mean projected area (but differs from that for an equal-area sphere), while the linear polarization, phase function at large scattering angles, and single-scattering albedo depend on the monomer diameter. The wavelength dependence of the extinction efficiency differs markedly from that for equal-area spheres. These results can be used to infer particle properties from remotely sensed data.

West, Robert A.↗
NASA NTRS1993

Compounds containing meta-biphenylenedioxy moieties and polymers therefrom

Two monomers containing meta-biphenylenedioxy moieties were prepared. One monomer, a diamine, is used to prepare polyimide, polyamide, and epoxy polymers. The other monomer, a dianhydride, was used to prepare polyimide polymers. These polymers are used to make films, coatings, and selective membranes.

St.clair, Terry L.↗
NASA NTRS1995

Proton affinity determinations and proton-bound dimer structure indications in C2 to C15, (alpha),(omega)-alkyldiamines

The 'kinetic method' was used to determine the proton affinity (PA) of a,coalkyldiamines from collision induced dissociation (CID) studies of protonated heterodimers. These PA values were consistently lower than those reported in the proton affinity scale. The apparent discrepancy was rationalized in terms of differences in the conformation of the protonated diamine monomers. The minimum energy species, formed by equilibrium proton transfer processes, have a cyclic conformation and the ion charge is shared by both amino-groups which are bridged by the proton. On the other hand, the species formed through dissociation of protonated dimers have a linear structure and the charge is localized on one of the amino-groups. Thus, the difference in the PA values obtained by both methods is a measure of the additional stability acquired by the protonated diamines through cyclization and charge delocalization. The major collision dissociation pathway of the protonated diamine monomers involved elimination of an ammonia moiety. Other reactions observed included loss of the second amino-group and several other bond cleavages. CID of the protonated dimers involved primarily formation of a protonated monomer through cleavage of the weaker hydrogen bond and subsequently loss of ammonia at higher collision energies. As observed from the CID studies, doubly charged ions were also formed from the diamines under conditions of the electrospray ionization.

Karpas, Z.↗
NASA NTRS1996

Kinetic Studies on Photodeposition of Polydiacetylene Thin Film from Solution: Preliminary Determination of the Rate Law

Preliminary kinetic studies were undertaken on the photodeposition of thin films of a polydiacetylene derivative of 2-methyl-4-nitroaniline from monomer solutions onto quartz substrates. Solutions of the monomer, DAMNA, in 1,2-dichloroethane at various concentrations were irradiated at 364 nm using an argon-ion laser at several intensities. It was found that the rate of polydiacetylene (PDAMNA) film photodeposition varies linearly with UV light intensity and as the square root of monomer concentration.

Paley, M. S.↗
NASA NTRS1997

New Fluorinated Polymers

This report summarizes progress during 1996 in our research effort along with a description of additional results associated with a TAG supplement to this grant (items 2 and 5 below). Progress is reported in five areas: 1) Polyamides Derived from [(p-HOOCC6H4)](sub 2)C(CF3)X (X= -CF3, OCH3, Cl); 2) Phosphorus-containing '12F-PEK' - Effect of Systematic Replacement of [(p-FC6H4COC6H4)](sub 2)C[(CF3)](sub 2) Monomer by [(p-FC6H4)](sub 2)(C6H5)PO; 3) Poly(ether ketone)s Derived from [(p-FC6H4COC6H4)](sub 2)(C6H5)PO; 4) New CF3-containing Organosilane Monomers and; 5) New Monomers for 12F-PEK Analogues with Improved Processability and Solubility.

Fitch, John W., III↗
NASA NTRS1997

Fabrication and Evaluation of Graphite Fiber-Reinforced Polyimide Composite Tube Forms Using Modified Resin Transfer Molding

The techniques necessary for the fabrication of a complex three-dimensional tubular form using a PMR-type resin have been developed to allow for the construction of several tubes with good physical and mechanical properties. Employing established resin transfer molding practices, the relatively non-hazardous AMB-21 in acetone formulation was used to successfully impregnate four layers of AS4 braided graphite fiber preform previously loaded around an aluminum cylindrical core in an enclosed mold cavity. Using heat and vacuum, the solvent was evaporated to form a prepreg followed by a partial imidization and removal of condensation products. The aluminum core was replaced by a silicone rubber bladder and the cure cycle continued to the final stage of 550 F with a bladder internal pressure of 200 lbs/sq in while simultaneously applying a strong vacuum to the prepreg for removal of any additional imidization products. A combination of several modifications to the standard resin transfer molding methodology enabled the mold to 'breathe', allowing the imidization products a pathway for escape. AMB-21 resin was chosen because of the carcinogenic nature of the primary commercial polyimide PMR-15. The AMB-21 resin was formulated using commercially available monomers or monomer precursors and dissolved in a mixture of methyl alcohol and acetone. The viscosity of the resulting monomer solution was checked by use of a Brookfield rheometer and adjusted by adding acetone to an easily pumpable viscosity of about 600 cP. In addition, several types of chromatographic and thermal analyses were of the braids, and excess handling of the preforms broke some of the microscopic fibers, needlessly decreasing the strength of the finished part. In addition, three dimensional braided preforms with fibers along the length of the tube will be significantly stronger in tension than the braided preforms used in this study.

Exum, Daniel B.↗
NASA NTRS1998

Modeling the Growth Rates of Tetragonal Lysozyme Crystal Faces

The measured macroscopic growth rates of the (110) and (101) faces of tetragonal lysozyme show an unexpectedly complex dependence on the supersaturation. The growth rates decay asymptotically to zero when the supersaturation is lowered to zero and increase rapidly when the supersaturation is increased. When supersaturations are increased still further the growth rates attain a maximum before starting to decrease. However, growth of these crystals is known to proceed by the classical dislocation and 2D nucleation growth mechanisms. This anomaly can be explained if growth is assumed to occur not by monomer units but by lysozyme aggregates. Analysis of the molecular packing of these crystals revealed that they were constructed of strongly bonded 4(sub 3) helices, while weaker bonds were responsible for binding the helices to each other. It follows that during crystal growth the stronger bonds are formed before the weaker ones. Thus, the growth of these crystals could be viewed as a two step process: aggregate growth units corresponding to the 4(sub 3) helix are first formed in the bulk solution by stronger intermolecular bonds and then attached to the crystal face by weaker bonds on dislocation hillocks or 2D islands. This will lead to a distribution of aggregates in the solution with monomers and lower order aggregates being predominant at low supersaturations and higher order aggregates being predominant at high supersaturations. If the crystal grows mostly by higher order aggregates, such as tetramers and octamers, it would explain the anomalous dependence of the growth rates on the supersaturation. Besides the analysis of molecular packing, a comprehensive analysis of the measured (110) and (101) growth rates was also undertaken in this study. The distribution of aggregates in lysozyme nutrient solutions at various solution conditions were determined from reversible aggregation reactions at equilibrium. The supersaturation was defined for each aggregate species with respect to its concentration at saturation in order to apply growth rate models to this process. The measured growth rates were then compared with the predicted ones from several dislocation and 2D nucleation growth models, employing tetramer and octamer growth units in polydisperse solutions and monomer units in monodisperse solutions. For the (110) face, the calculations consistently showed that the measured growth rates followed the expected model relations with octamer growth units. For the (101) face, it is not possible to obtain a clear agreement between the predicted and measured growth rates for a single growth unit as done for the (110) face. However, the calculations do indicate that the average size of the growth unit is between a tetramer and an octamer. This suggests that tetramers, octamers and other intermediate size growth units all participate in the growth process for this face. These calculations show that it is possible to model the macroscopic protein crystal growth rates if the molecular level processes can be account for, particularly protein aggregation processes in the bulk solution. Our recent investigations of tetragonal lysozyme crystals employing high resolution atomic force microscopy scans have further confirmed the growth of these crystals by aggregate growth units corresponding to 4(sub 3) helices.

Li, Meirong↗
NASA NTRS1998

Effects of Microheterogeneity in Hen Egg-White Lysozyme Crystallization

In earlier sodium dodecylsulfate polyacylamide gel electrophoresis (SDS-PAGE) studies it has been found that commonly utilized commercial hen egg-white lysozyme (HEWL) preparations contained 0.2-0.4 mol% covalently bound dimers. Here it is shown, using high-performance capillary electrophoresis (HPCE), that HEWL contains, in addition, two differently charged monomers in comparable amounts. To explore the origin of these microheterogeneous contaminants, purified HEWL (PHEWL) has been oxidized with hydrogen peroxide (0.0026-0.88 M) at various pH levels between 4.5 and 12.0. Optical densitometry of oxidized PHEWL (OHEWL) bands in SDS PAGE gels shows that hydrogen peroxide at 0.88 M in acetate buffer pH 4.5 increased the amount of dimers about sixfold over that in commercial HEWL. OHEWL had, in addition to one of the two monomer forms found in HEWL and PHEWL, three other differently charged monomer forms, each of them representing about 25% of the preparation. SDS-PAGE analysis of OHEWL yielded two closely spaced dimer bands with M(sub r) = 28 000 and 27 500. In addition, larger HEWL oligomers with M, = 1.7 million and 320 000 were detected by gel-filtration fast protein liquid chromatography with multiangle laser light scattering detection. Non-dissociating PAGE in large pore size gels at pH 4.5 confirmed the presence of these large oligomers in HEWL and OHEWL. Increased microheterogeneity resulted in substantial effects on crystal growth and nucleation rate. On addition of 10 microgram(exp -1) mg ml(exp -1) OHEWL to 32 mg ml(exp -1) HEWL crystallizing solutions, both the number and size of forming crystals decreased roughly proportionally to the concentration of the added microheterogeneity. The same effect was observed in HEWL solutions on addition of 0.03-9,3 M Hydrogen peroxide. Repartioning of the dimer during crystallzation aat various temperatures between 277 and 293 K was analyzed by SDS-PAGE. The crystals contained <= 25 % weight by volume of the oligomers in the solution, with no apparent temperature dependence of the repartioning.

Thomas, B. R.↗
NASA NTRS1998

Space Product Development of Commercial NLO Materials

Growth on selected substrates under various processing conditions have been useful for preparing highly oriented and otherwise promising films of organic compounds for optical thin films and waveguides. The significance of processing conditions to uniformity in thickness, degree of orientation, film quality, and optical properties for a specific processing technique is the general focus of work in this area. A study on the effect of processing conditions relevant to thin-film deposition by various techniques is particularly difficult because of the possibility that convection may play a major role in some cases. It is a goal of some researchers to produce good quality anisotropic films, therefore, an important, yet understudied, requirement should be to assess the role of gravity during certain processing methods. This may be particularly true for the vapor deposition of diacetylenes where subsequent polymerization in the crystal is topochemical and occurs readily only when neighboring monomer molecules are sufficiently close and suitably oriented. Likewise, this requirement is equally viable for the vapor deposition of certain materials such as Pcs in view of the results of microgravity experiments by 3M Corporation involving the preparation of thin films of copper Pc (CuPc). Microgravity-grown CuPc had several desirable features which indicate that the vapor growth of organic films in low-g may result in better quality films for optical and electrical applications. Indeed, other materials vapor deposited onto specific substrates in microgravity produce films potentially beneficial for electro-optic applications. A novel technique, recently discovered, for growing polydiacetylene thin films involves exposing a transparent substrate, in contact with diacetylene monomer solution, to ultraviolet (LTV) light. A polymer film deposits on the side of the substrate in contact with monomer in solution, and there are distinct gravitational effects, which influence film quality. Good quality thin films elude growth from solutions absent of uniform flow fields and homogeneous temperature distributions near the substrate surfaces. The flow fields and temperature distributions during the polymerization process by exposure to UV light details the nature of gravitational influences on this process.

Frazier, Donald O.↗
NASA NTRS2000

Photochemically and Thermally Cross-Linkable Polyconjugated Systems

This project focused on the synthesis and characterization of water soluble and/or water-borne electrically conducting polymer systems that could be cross-linked thermally or photochemically. The development of these materials was carried out so that they could be applied as metal and fabric coatings. Polyaniline and polypyrrole were the polymers under investigation. The main impediment preventing commercial development of these polymers is their inherent insolubility. Methods employed to enhance polymer solubility were monomer or polymer modifications. Some post-polymerization modifications were attempted to derivatize the parent polymers, These involved attachment of suitable pendant groups that would enhance polar solvent solubility. The pendant groups of these derivatized polymers were then further reacted to cross-link, rendering the polymer insoluble. The other modifications involved polymerization of monomers in the presence of polyelectrolytic polymers. The acid functionalities of the electrolyte served as a template/dopant for monomer alignment/complexation before polymerization, resulting in a water-borne composite or complex.

Source record↗
NASA NTRS2001

UV Curable Polyimides

The development of UV curable polyimides for high-temperature applications is a growing area of research activity. The objective of this technology is an attempt to bypass many of the issues associated with "typical" high-temperature polymers. For example, the use of toxic or mutagenic monomers (i.e., many aromatic diamines) can be prevented. Also, it proves to be a viable means in circumventing the problems associated with high-processing temperature of polymers, which cause thermally induced processing stresses (i.e., microcracking). The approach that we have been pursuing is Diels-Alder Polymerization. In this approach, we are generating dienes with light instead of heat. This process is called photoenolization. Several bismaleimides and bisacrylates are used as the dienophiles. The method is fairly general and a wide variety of diketones and bismaleimides can be used. UV curability processes are advantageous due to the following: (1) With such a wide variety of monomers, it allows for the use of nontoxic/nonmutagenic monomers; (2) Polyimides cure at room temperature, which reduces thermally induced stresses; (3) It reduces processing and tooling cost; (4) There are many potential applications for this technology, i.e., thin films as alignment layers for LC displays, photoresists, and photonic material as well as a potential market for use as adhesives.

Meador, Michael↗
NASA NTRS2003

Self-Propagating Frontal Polymerization in Water at Ambient Pressure

Advances in polymer chemistry have led to the development of monomers and initiation agents that enable propagating free-radical polymerization fronts to exist. These fronts are driven by the exothermicity of the polymerization reaction and the transport of heat from the polymerized product to the reactant monomer/solvent/initiator solution. The thermal energy transported to the reactant solution causes the initiator to decompose, yielding free radicals, which start the free radical polymerization process as discussed in recent reviews. The use of polymerization processes based on propagating fronts has numerous applications. Perhaps the most important of these is that it enables rapid curing of polymers without external heating since the polymerization process itself provides the high temperatures necessary to initiate and sustain polymerization. This process also enables more uniform curing of arbitrarily thick samples since it does not rely on heat transfer from an external source, which will necessarily cause the temperature history of the sample to vary with distance from the surface according to a diffusion-like process. Frontal polymerization also enables filling and sealing of structures having cavities of arbitrary shape without having to externally heat the structure. Water at atmospheric pressure is most convenient solvent to employ and the most important for practical applications (because of the cost and environmental issues associated with DMSO and other solvents). Nevertheless, to our knowledge, steady, self-propagating polymerization fronts have not been reported in water at atmospheric pressure. Currently, polymerization fronts require a high boiling point solvent (either water at high pressures or an alternative solvent such as dimethyl sulfoxide (DMSO) (boiling point 189 C at atmospheric pressure.) Early work on frontal polymerization, employed pressures up to 5000 atm in order to avoid boiling of the monomer/solvent/initiator solution. High boiling point solutions are needed because in order to produce a propagating front, a high front temperature is needed to produce sufficiently rapid decomposition of the free radical initiator and subsequent free radical polymerization and heat release at a rate faster than heat losses remove thermal energy from the system. (While the conduction heat loss rate increases linearly with temperature, the free radical initiator decomposition is a high activation energy process whose rate increases much more rapidly than linearly with temperature, thus as the temperature decreases, the ratio of heat loss to heat generation increases, eventually leading to extinction of the front if the temperature is too low.) In order to obtain atmospheric pressure frontal polymerization in water, it is necessary to identify a monomer/initiator combination that is water soluble and will not extinguish even when the peak temperature (T*) is less than 100 C. In this work acrylic acid (AA) was chosen as the monomer because is it one of the most reactive monomers and can polymerize readily at low temperatures even without initiators. Ammonium persulfate (AP) was chosen as the initiator because it decomposes readily at low temperatures, produces relatively few bubbles and is commercially available. The propagation rates and extinction conditions of the fronts are studied for a range of AA and AP concentrations. Small amounts of fumed silica powder (Cab-o-sil, Cabot Corporation) were added to the solutions to inhibit buoyancy induced convection in the solutions; future studies will investigate the effects of buoyant convection within the solutions.

Olten, Nesrin↗
NASA NTRS2000

Remote Enantioselection Transmitted by an Achiral Peptide Nucleic Acid Backbone

short homochiral segment of DNA into a PNA helix could have guaranteed that the next short segment of DNA to be incorporated would have the same handedness as the first. Once two segments of the same handedness were present, the probability that a third segment would have the same handedness would increase, and so on. Evolution could then slowly dilute out the PNA part. This scenario would ultimately allow the formation of a chiral oligonucleotide by processes that are largely resistant to enantiomeric crossinhibition. It is important to note that the ligation of homochiral dinucleotides on a nucleic acid template would probably be at least as enantiospecific as the reaction that we have studied. The disadvantage of using chiral monomers as components of a replicating system arises from the difficulty of generating a first long homochiral template from a racemic mixture of monomers, although results of experiments designed to overcome this difficulty by employing homochiral tetramers have been reported.l l The probability of obtaining a homochiral n-mer from achiral substrates is approximately 1P-I if the nontemplate-directed extension of the primer is not enantioselective. Hence, it would be very hard to get started with a homochiral 40-mer, for example. No such difficulty exists in a scenario that originates with an achiral genetic material and in which the incorporation of very few chiral monomers in this achiral background gradually progresses towards homochirality. It seems possible that some PNA sequences could act as catalysts, analogous to ribozymes, even though PNA lacks clear metal binding sites. Although such catalysts could not be enantioselective, the incorporation of as few as two chiral nucleotides could then impose chiral specificity on the system. Furthermore, such patch chimeras could help to bridge the gap in catalytic potential between PNA and RNA, while guaranteeing enantioselectivity.

Kozlov, Igor A.↗
NASA NTRS1998

[Synthesis and Characterization of a Sugar Based Electrolyte for Thin-film Polymer Batteries]

The work performed during the current renewal period, March 1,1998 focused primarily on the synthesis and characterization of a sugar based electrolyte for thin-film polymer batteries. The initial phase of the project involved developing a suitable sugar to use as the monomer in the polymeric electrolyte synthesis. The monomer has been synthesized and characterized completely. Overall the yield of this material is high and it can be produced in relatively large quantity easily and in high purity. The scheme used for the preparation of the monomer is outlined along with pertinent yields.

Source record↗
NASA NTRS2003

Functional nanocomposites prepared by self-assembly and polymerization of diacetylene surfactants and silicic acid

Conjugated polymer/silica nanocomposites with hexagonal, cubic, or lamellar mesoscopic order were synthesized by self-assembly using polymerizable amphiphilic diacetylene molecules as both structure-directing agents and monomers. The self-assembly procedure is rapid and incorporates the organic monomers uniformly within a highly ordered, inorganic environment. By tailoring the size of the oligo(ethylene glycol) headgroup of the diacetylene-containing surfactant, we varied the resulting self-assembled mesophases of the composite material. The nanostructured inorganic host altered the diacetylene polymerization behavior, and the resulting nanocomposites show unique thermo-, mechano-, and solvatochromic properties. Polymerization of the incorporated surfactants resulted in polydiacetylene (PDA)/silica nanocomposites that were optically transparent and mechanically robust. Molecular modeling and quantum calculations and (13)C spin-lattice relaxation times (T(1)) of the PDA/silica nanocomposites indicated that the surfactant monomers can be uniformly organized into precise spatial arrangements prior to polymerization. Nanoindentation and gas transport experiments showed that these nanocomposite films have increased hardness and reduced permeability as compared to pure PDA. Our work demonstrates polymerizable surfactant/silica self-assembly to be an efficient, general approach to the formation of nanostructured conjugated polymers. The nanostructured inorganic framework serves to protect, stabilize, and orient the polymer, mediate its performance, and provide sufficient mechanical and chemical stability to enable integration of conjugated polymers into devices and microsystems.

NASA Discipline Life Support Systems↗
NASA NTRS1991

Template-directed synthesis of oligonucleotides under eutectic conditions

One of the most important sets of model prebiotic experiments consists of reactions that synthesize complementary oligonucleotides from preformed templates under nonenzymatic conditions. Most of these experiments are conducted at 4 degrees C using 0.01-0.1 M concentrations of activated nucleotide monomer and template (monomer equivalent). In an attempt to extend the conditions under which this type of reaction can occur, we have concentrated the reactants by freezing at -18 degrees C, which is close to the NaCl-H2O eutectic at -21 degrees C. The results from this set of experiments suggest that successful syntheses can occur with poly(C) concentrations as low at 5 x 10(-4) M and 2MeImpG concentrations at 10(-3) M. It was also anticipated that this mechanism might allow the previously unsuccessful poly(A)-directed synthesis of oligo(U)s to occur. However, no template effect was seen with the poly(A) and ImpU system. The failure of these conditions to allow template-directed synthesis of oligo(U)s supports the previously proposed idea that pyrimidines may not have been part of the earliest genetic material. Because of the low concentrations of monomer and template that would be expected from prebiotic syntheses, this lower temperature could be considered a more plausible geologic setting for template-directed synthesis than the standard reaction conditions.

NASA Discipline Number 52-20↗
NASA NTRS2001

Self-assembly of mesoscopically ordered chromatic polydiacetylene/silica nanocomposites

Nature abounds with intricate composite architectures composed of hard and soft materials synergistically intertwined to provide both useful functionality and mechanical integrity. Recent synthetic efforts to mimic such natural designs have focused on nanocomposites, prepared mainly by slow procedures like monomer or polymer infiltration of inorganic nanostructures or sequential deposition. Here we report the self-assembly of conjugated polymer/silica nanocomposite films with hexagonal, cubic or lamellar mesoscopic order using polymerizable amphiphilic diacetylene molecules as both structure-directing agents and monomers. The self-assembly procedure is rapid and incorporates the organic monomers uniformly within a highly ordered, inorganic environment. Polymerization results in polydiacetylene/silica nanocomposites that are optically transparent and mechanically robust. Compared to ordered diacetylene-containing films prepared as Langmuir monolayers or by Langmuir-Blodgett deposition, the nanostructured inorganic host alters the diacetylene polymerization behaviour, and the resulting nanocomposite exhibits unusual chromatic changes in response to thermal, mechanical and chemical stimuli. The inorganic framework serves to protect, stabilize, and orient the polymer, and to mediate its function. The nanocomposite architecture also provides sufficient mechanical integrity to enable integration into devices and microsystems.

NASA Discipline Life Support Systems↗