Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Substituents”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
NASA NTRS1985

QSAR for cholinesterase inhibition by organophosphorus esters and CNDO/2 calculations for organophosphorus ester hydrolysis

Quantitative structure-activity relationships were derived for acetyl- and butyrylcholinesterase inhibition by various organophosphorus esters. Bimolecular inhibition rate constants correlate well with hydrophobic substituent constants, and with the presence or absence of catonic groups on the inhibitor, but not with steric substituent constants. CNDO/2 calculations were performed on a separate set of organophosphorus esters, RR'P(O)X, where R and R' are alkyl and/or alkoxy groups and X is fluorine, chlorine or a phenoxy group. For each subset with the same X, the CNDO-derived net atomic charge at the central phosphorus atom in the ester correlates well with the alkaline hydrolysis rate constant. For the whole set of esters with different X, two equations were derived that relate either charge and leaving group steric bulk, or orbital energy and bond order to the hydrogen hydrolysis rate constant.

Johnson, H.↗
NASA NTRS1985

QSAR for cholinesterase inhibition by organophosphorus esters and CNDO/2 calculations for organophosphorus ester hydrolysis

Quantitative structure-activity relationships were derived for acetyl- and butyrylcholinesterase inhibition by various organophosphorus esters. Bimolecular inhibition rate constants correlate well with hydrophobic substituent constants, and with the presence or absence of cationic groups on the inhibitor, but not with steric substituent constants. CNDO/2 calculations were performed on a separate set of organophosphorus esters, RR-primeP(O)X, where R and R-prime are alkyl and/or alkoxy groups and X is fluorine, chlorine or a phenoxy group. For each subset with the same X, the CNDO-derived net atomic charge at the central phosphorus atom in the ester correlates well with the alkaline hydrolysis rate constant. For the whole set of esters with different X, two equations were derived that relate either charge and leaving group steric bulk, or orbital energy and bond order to the hydrolysis rate constant.

Johnson, H.↗
NASA NTRS1991

Structure and functions of water-membrane interfaces and their role in proto-biological evolution

Among the most important developments in proto-biological evolution was the emergence of membrane-like structures. These are formed by spontaneous association of relatively simple amphiphilic molecules that would have been readily available in the primordial environment. The resulting interfacial regions between water and nonpolar interior of the membrane have several properties which made them uniquely suitable for promoting subsequent evolution. They can (1) selectively attract organic material and mediate its transport, (2) serve as simple catalysts for chemical reactions, and (3) promote the formation of trans-membrane electrical and chemical gradients which could provide energy sources for proto-cells. Understanding the structure of interfaces, their interactions with organic molecules and molecular mechanisms of their functions is an essential step to understanding proto-biological evolution. In our computer simulation studies, we showed that the structure of water at interfaces with nonpolar media is significantly different from that in the bulk. In particular, the average surface dipole density points from the vapor to the liquid. As a result, negative ions can approach the interface more easily than positive ions. Amphiphilic molecules composed of hydrocarbon conjugated rings and polar substituents (e.g., phenol) assume at the interface rigid orientations in which polar groups are buried in water while hydrocarbon parts are located in the nonpolar environment. These orientational differences are of special interest in connection with the ability of some of these molecules to efficiently absorb photons. Flexible molecules with polar substituents often adopt at interfaces conformations different from those in the bulk aquaeous solution and in the gas phase. As a result, in many instances both specificity and kinetics of chemical reactions in which these molecules can participate is modified by the presence of surfaces. Of special interest is the mechanism by which polar molecules are transferred across interface between water and a nonpolar medium. Our recent study showed that simple ionophores bind ions by the same mechanisms as ion channels and carriers from modern cells.

Pohorille, A.↗
NASA NTRS1992

Optical luminescence spectroscopy as a probe of the surface mineralogy of Mars

Optical luminescence (OpL) spectroscopy is an attractive use of a visible-near-IR spectrometer on a Mars lander because mineral products of atmosphere-surface interactions on Mars will probably have characteristic OpL spectra. Optical luminescence spectra would be taken at night, when a spectrometer might otherwise sit idle. Also needed would be a source of exciting radiation, which could be shared with other experiments. Optical luminescence is emission of nonthermal optical photons (near-UV through near-IR) as a response to energy input. On absorption of energy, an atom (or ion) will enter an excited state. The favored decay of many such excited states involving valence-band electrons is emission of an optical photon. Optical luminescence spectra can be useful in determining mineralogy and mineral composition. Optical luminescence in crystals can arise from essential elements (or ions), trace-element substituents (activators), or defects. Common activators in salts of alkali and alkaline earth elements include Mn(2+)(VI), other transition metals, the rare earths, and the actinides. Trace substituents of other species can enhance or quench OpL (e.g., Pb(2+) vs. Fe(3+)). Optical luminescence can also arise from defects in crystal structures, including those caused by radiation and shock.

Treiman, A. H.↗
NASA NTRS1997

Electron Affinity Calculations for Thioethers

Previous work indicated that polyphenyl thioethers possessed chemical properties, related to their electron affinities, which could allow them to function as vapor phase lubricants (VPL). Indeed, preliminary tribological tests revealed that the thioethers could function as vapor phase lubricants but not over a wide temperature and hertzian pressure range. Increasing the electron affinity of the thioethers may improve their VPL properties over this range. Adding a substituent group to the thioether will alter its electron affinity in many cases. Molecular orbital calculations were undertaken to determine the effect of five different substituent groups on the electron affinity of polyphenyl thioethers. It was found that the NO2, F, and I groups increased the thioethers electron affinity by the greatest amount. Future work will involve the addition of these groups to the thioethers followed by tribological testing to assess their VPL properties.

Sulton, Deley L.↗
NASA NTRS2000

Development of Highly Fluorescent Materials Based on Thiophenylimidazole Dyes

Organic fluorescent materials are expected to find many potential applications in optical devices and photo-functionalized materials. Although many investigations have been focused on heterocyclic compounds such as coumarins, bipyridines, rhodamines, and pyrrole derivatives, little is known for fluorescent imidazole materials. We discovered that one particular class of imidazole derivatives is highly fluorescent. A series of monomeric and polymeric based fluorescent dyes were prepared containing a thiophene unit at the second position of the imidazole ring. Dependence of fluorescence efficiency on parameters such as solvent polarity and substituent groups has been investigated. It was found that a formyl group at the 2-position of the thiophene ring dramatically enhance fluorescence properties. Ion recognition probes indicated their potential as sensor materials. These fluorophores have flexibility for introduction of versatile substituent groups that could improve the fluorescence efficiency and sensor properties.

Santos, Javier↗
NASA NTRS2003

Substitution Effects and Linear Free Energy Relationships During Reduction of 4- Benzoyl-n-(4-substituted Benzyl)pyridinium Cations

In analogy to 4-(para-substituted benzoyl)-N-methylpyridinium cations (1-X's), the title species (2-X's, -X = -OCH3, -CH3, -H, -Br, -COCH3, -NO2) undergo two reversible, well-separated (E(sub 1/2) greater than or equal to 650 mV) one-electron reductions. The effect of substitution on the reduction potentials of 2-X's is much weaker than the effect of the same substituents on 1-X's: the Hammett rho-values are 0.80 and 0.93 for the 1st- and 2nd-e reduction of 2-X's vs. 2.3 and 3.3 for the same reductions of 1-X's, respectively. Importantly, the nitro group of 2-NO2 undergoes reduction before the 2nd-e reduction of the 4-benzoylpyridinium system. These results suggest that the redox potentials of the 4-benzoylpyridinium system can be course-tuned via p-benzoyl substitution and fine-tuned via para-benzyl substitution. Introducing the recently derived substituent constant of the -NO2(sup)- group (sigma para-NO2(sup)- = -0.97) yields an excellent correlation for the 3rd-e reduction of 2- NO2 (corresponding to the reduction of the carbonyl group) with the 2nd-e reduction of the other 2-X's, and confirms the electron donating properties of -NO2(sup)-.

Leventis, Nicholas↗
NASA NTRS1986

Photoactivable analogs for labeling 25-hydroxyvitamin D3 serum binding protein and for 1,25-dihydroxyvitamin D3 intestinal receptor protein

3-Azidobenzoates and 3-azidonitrobenzoates of 25-hydroxyvitamin D3 as well as 3-deoxy-3-azido-25-hydroxyvitamin D3 and 3-deoxy-3-azido-1,25-dihydroxyvitamin D3 were prepared as photoaffinity labels for vitamin D serum binding protein and 1,25-dihydroxyvitamin D3 intestinal receptor protein. The compounds prepared were easily activated by short- or long-wavelength uv light, as monitored by uv and ir spectrometry. The efficacy of the compounds to compete with 25-hydroxyvitamin D3 or 1,25-dihydroxyvitamin D3 for the binding site of serum binding protein and receptor, respectively, was studied to evaluate the vitamin D label with the highest affinity for the protein. The presence of an azidobenzoate or azidonitrobenzoate substituent at the C-3 position of 25-OH-D3 significantly decreased (10(4)- to 10(6)-fold) the binding activity. However, the labels containing the azido substituent attached directly to the vitamin D skeleton at the C-3 position showed a high affinity, only 20- to 150-fold lower than that of the parent compounds with their respective proteins. Therefore, 3-deoxy-3-azidovitamins present potential ligands for photolabeling of vitamin D proteins and for studying the structures of the protein active sites.

NASA Discipline Musculoskeletal↗
NASA NTRS2002

Improved performance and safety of lithium ion cells with the use of fluorinated carbonate-based electrolytes

There has been increasing interest in developing lithium-ion electrolytes that possess enhanced safety characteristics, while still able to provide the desired stability and performance. Toward this end, our efforts have been focused on the development of lithium-ion electrolytes which contain partially and fully fluorinated carbonate solvents. The advantage of using such solvents is that they possess the requisite stability demonstrated by the hydrocarbon-based carbonates, while also possessing more desirable physical properties imparted by the presence of the fluorine substituents, such as lower melting points, increased stability toward oxidation, and favorable SEI film forming Characteristics on carbon. Specifically, we have demonstrated the beneficial effect of electrolytes which contain the following fluorinated carbonate-based solvents: methyl 2,2,2-trifluoroethyl carbonate (MTFEC), ethyl-2,2,2 trifluoroethyl carbonate (ETFEC), propyl 2,2,2-trifluoroethyl carbonate (PTFEC), methyl-2,2,2,2',2',2' -hexafluoro-i-propyl carbonate (MHFPC), ethyl- 2,2,2,2',2',2' -hexafluoro-i-propyl carbonate (EHFPC), and di-2,2,2-trifluoroethyl carbonate (DTFEC). These solvents have been incorporated into multi-component ternary and quaternary carbonate-based electrolytes and evaluated in lithium-carbon and carbon-LiNio.8Coo.202 cells (equipped with lithium reference electrodes). In addition to determining the charge/discharge behavior of these cells, a number of electrochemical techniques were employed (i.e., Tafel polarization measurements, linear polarization measurements, and electrochemical impedance spectroscopy (EIS)) to further characterize the performance of these electrolytes, including the SEI formation characteristics and lithium intercalatiodde-intercalation kinetics. In addition to their evaluation in experimental cells, cyclic voltammetry (CV) and conductivity measurements were performed on select electrolyte formulations to further our understanding of the trends in stability and ionic mobility imparted by different alkyl substituents in linear carbonates.

li-ion batteries fluorinated carbonate electrolyte↗
NASA NTRS2003

Two-photon or higher-order absorbing optical materials for generation of reactive species

Disclosed are highly efficient multiphoton absorbing compounds and methods of their use. The compounds generally include a bridge of pi-conjugated bonds connecting electron donating groups or electron accepting groups. The bridge may be substituted with a variety of substituents as well. Solubility, lipophilicity, absorption maxima and other characteristics of the compounds may be tailored by changing the electron donating groups or electron accepting groups, the substituents attached to or the length of the pi-conjugated bridge. Numerous photophysical and photochemical methods are enabled by converting these compounds to electronically excited states upon simultaneous absorption of at least two photons of radiation. The compounds have large two-photon or higher-order absorptivities such that upon absorption, one or more Lewis acidic species, Lewis basic species, radical species or ionic species are formed.

Cumpston, Brian↗
NASA NTRS2007

Two-photon or higher-order absorbing optical materials for generation of reactive species

Disclosed are highly efficient multiphoton absorbing compounds and methods of their use. The compounds generally include a bridge of pi-conjugated bonds connecting electron donating groups or electron accepting groups. The bridge may be substituted with a variety of substituents as well. Solubility, lipophilicity, absorption maxima and other characteristics of the compounds may be tailored by changing the electron donating groups or electron accepting groups, the substituents attached to or the length of the pi-conjugated bridge. Numerous photophysical and photochemical methods are enabled by converting these compounds to electronically excited states upon simultaneous absorption of at least two photons of radiation. The compounds have large two-photon or higher-order absorptivities such that upon absorption, one or more Lewis acidic species, Lewis basic species, radical species or ionic species are formed.

Cumpston, Brian↗
NASA NTRS2008

Fabricating Large-Area Sheets of Single-Layer Graphene by CVD

This innovation consists of a set of methodologies for preparing large area (greater than 1 cm(exp 2)) domains of single-atomic-layer graphite, also called graphene, in single (two-dimensional) crystal form. To fabricate a single graphene layer using chemical vapor deposition (CVD), the process begins with an atomically flat surface of an appropriate substrate and an appropriate precursor molecule containing carbon atoms attached to substituent atoms or groups. These molecules will be brought into contact with the substrate surface by being flowed over, or sprayed onto, the substrate, under CVD conditions of low pressure and elevated temperature. Upon contact with the surface, the precursor molecules will decompose. The substituent groups detach from the carbon atoms and form gas-phase species, leaving the unfunctionalized carbon atoms attached to the substrate surface. These carbon atoms will diffuse upon this surface and encounter and bond to other carbon atoms. If conditions are chosen carefully, the surface carbon atoms will arrange to form the lowest energy single-layer structure available, which is the graphene lattice that is sought. Another method for creating the graphene lattice includes metal-catalyzed CVD, in which the decomposition of the precursor molecules is initiated by the catalytic action of a catalytic metal upon the substrate surface. Another type of metal-catalyzed CVD has the entire substrate composed of catalytic metal, or other material, either as a bulk crystal or as a think layer of catalyst deposited upon another surface. In this case, the precursor molecules decompose directly upon contact with the substrate, releasing their atoms and forming the graphene sheet. Atomic layer deposition (ALD) can also be used. In this method, a substrate surface at low temperature is covered with exactly one monolayer of precursor molecules (which may be of more than one type). This is heated up so that the precursor molecules decompose and form one monolayer of the target material.

Bronikowski, Michael↗
NASA NTRS2013

High-Performance, Low-Temperature-Operating, Long-Lifetime Aerospace Lubricants

The synthesis and characterization of six new ionic liquids, with fluoroether moeties on the imidazolium ring, each with vapor pressures shown to be <10(exp -7 Torr at 25 C, have been demonstrated. Thermal stability of the ionic liquids up to 250 C was demonstrated. The ionic liquids had no measurable influence upon viscosity upon addition to perfluoropolyether (PFPE) base fluids. They also had no measureable influence upon corrosion on steel substrates upon addition to base fluids. In general, 13 to 34% lower COFs (coefficients of friction), and 30 to 80% higher OK load of base fluids upon addition of the ionic liquids was shown. The compound consists of a 1,3-disubstituted imidazolium cation. The substituents comprise perfluoroether groups. A bis(trifluoromethanesulfonyl) imide anion counterbalances the charge. The fluorinated groups are intended to enhance dispersion of the ionic liquid in the PFPE base fluid. The presence of weak Van der Waals forces associated with fluorine atoms will limit interaction of the substituents on adjacent ions. The longer interionic distances will reduce the heat of melting and viscosity, and will increase dispersion capabilities.

Bergeron, Bryan↗
NASA NTRS2013

Two-Photon or Higher-Order Absorbing Optical Materials for Generation of Reactive Species

Disclosed are highly efficient multiphoton absorbing compounds and methods of their use. The compounds generally include a bridge of pi-conjugated bonds connecting electron donating groups or electron accepting groups. The bridge may be substituted with a variety of substituents as well. Solubility, lipophilicity, absorption maxima and other characteristics of the compounds may be tailored by changing the electron donating groups or electron accepting groups, the substituents attached to or the length of the pi-conjugated bridge. Numerous photophysical and photochemical methods are enabled by converting these compounds to electronically excited states upon simultaneous absorption of at least two photons of radiation. The compounds have large two-photon or higher-order absorptivities such that upon absorption, one or more Lewis acidic species, Lewis basic species, radical species or ionic species are formed.

Cumpston, Brian↗
NASA NTRS1961

Kinetics of the Reaction Between Alcohols and Isocyanates Catalyzed by Ferric Acetylacetonate

The rate and temperature dependence of reaction for the ferric acetylacetonate catalyzed reaction between a-naphthyl, ortho-tolyl, and para-tolyl isocyanates and n-butyl alcohol are investigated. The effect of substituents on the reactivity of isocyanate and hydroxyl group are reported and for substituted isocyanates are correlated by means of the Hammett equation. Several metal chelates were studied and their catalytic activity was compared to that of ferric acetylacetonate. All rate data are interpreted in terms of a mechanism involving simultaneous second-order uncatalyzed and catalyzed reactions between alcohol and isocyanate.

ACETONE↗
NASA NTRS1971

Gas-phase basicities of amines.

Relative gas-phase basicities of some aliphatic amines have been determined by ion cyclotron resonance spectroscopy. It is found that increasing alkyl substitution increases basicity if similar substituents are compared, that increases in alkyl group size also increase basicity, and that increasing degree of substitution lowers the N-H bond dissociation energy in ammonium ions. Possible origins of these defects are discussed.

Brauman, J. I.↗
NASA NTRS1972

Development and characterization of lubricants for use near nuclear reactors in space vehicles

The synthesis and evaluation program was conducted to develop wide-temperature range lubricants suitable for use in space vehicles particularly in the vicinity of nuclear reactors. Synthetic approaches resulted in nonpolymeric, large molecular weight materials, all based on some combination of siloxane and aromatic groups. Evaluation of these materials indicated that certain tetramethyl and hexamethyl disiloxanes containing phenyl thiophenyl substituents are extremely promising with respect to radiation stability, wide temperature range, good lubricity, oxidation resistance and additive acceptance. The synthesis of fluids is discussed, and the equipment and methods used in evaluation are described, some of which were designed to evaluate micro-quantities of the synthesized lubricants.

Robinson, G. L.↗