Engineering topics

Tyson, Daniel S.

Publications and source records attributed to Tyson, Daniel S..

10 records

NASA NTRS2012

Fluorescent aromatic sensors and their methods of use

Aromatic molecules that can be used as sensors are described. The aromatic sensors include a polycyclic aromatic hydrocarbon core with a five-membered imide rings fused to the core and at least two pendant aryl groups. The aromatic sensor molecules can detect target analytes or molecular strain as a result of changes in their fluorescence, in many cases with on-off behavior. Aromatic molecules that fluoresce at various frequencies can be prepared by altering the structure of the aromatic core or the substituents attached to it. The aromatic molecules can be used as sensors for various applications such as, for example, the detection of dangerous chemicals, biomedical diagnosis, and the detection of damage or strain in composite materials. Methods of preparing aromatic sensor molecules are also described.

Meador, Michael A.↗

NASA NTRS2008

Aromatic Diimides - Potential Dyes for Use in Smart Films and Fibers

New aromatic diimide fluorescent dyes have been prepared with potential for use as chemical sensors and in chromogenic polymers. These dyes have been designed to utilize excited state electron transfer reactions as the means for sensing chemical species. For example, an aniline en-dcapped anthryl diimides functions effectively as an "on-off" sensor for pH and the detection of phosphoryl halide based chemical warfare agents, such as Sarin. In the absence of analytes, fluorescence from this dye is completely quenched by excited state electron transfer from the terminal amines. Reaction of these amines inhibits electron transfer and activates the fluorescence of the dye. Another substituted anthryl diimide is presented with the capability to detect pH and nitroaromatic compounds, such as TNT. Films prepared by doping small amounts (less than 0.1 weight percent) of several of these dyes in polymers such as linear low density polyethylene exhibit thermochromism. At room temperature, these films fluoresce reddish-orange. Upon heating, the fluorescence turns green. This process is reversible cooling the films to room temperature restores the orange emission.

Meador, Michael A.↗

NASA NTRS2008

Photochemically Synthesized Polyimides

An alternative to the conventional approach to synthesis of polyimides involves the use of single monomers that are amenable to photopolymerization. Heretofore, the synthesis of polyimides has involved multiple-monomer formulations and heating to temperatures that often exceed 250 C. The present alternative approach enables synthesis under relatively mild conditions that can include room temperature. The main disadvantages of the conventional approach are the following: Elevated production temperatures can lead to high production costs and can impart thermal stresses to the final products. If the proportions of the multiple monomeric ingredients in a given batch are not exactly correct, the molecular weight and other physical properties of the final material could be reduced from their optimum or desired values. To be useful in the alternative approach, a monomer must have a molecular structure tailored to exploit Diels-Alder trapping of a photochemically generated ortho-quinodimethane. (In a Diels-Alder reaction, a diene combines with a dienophile to form molecules that contain six-membered rings.) In particular, a suitable monomer (see figure) contains ortho-methylbenzophenone connected to a dienophile (in this case, a maleimide) through a generic spacer group. Irradiation with ultraviolet light gives rise to a photochemical intermediate the aforementioned ortho-quinodimethane from the ortho-methylbenzophenone. This group may react with the dienophile on another such monomer molecule to produce an oligomer that, in turn may react in a stepgrowth manner to produce a polyimide. This approach offers several advantages in addition to those mentioned above: The monomer can be stored for a long time because it remains unreactive until exposed to light. Because the monomer is the only active starting ingredient, there is no need for mixing, no concern for ensuring correct proportions of monomers, and the purity of the final product material is inherently high. The use of solvents is optional: The synthesis can be performed using the neat monomer or the monomer mixed with one or more solvent(s) in dilute or concentrated solution. The solubility of the monomer and the physical and chemical properties of the final polymer can be tailored through selection of the spacer group.

Meador, Michael A.↗

NASA NTRS2005

Synthesis and Near IR Photoluminescence of Os(II) Bis(2,2'-bipyridine) (3,8-Diarylethynyl-1,10-phemanthroline) Complexes: Anomalous Behavior of the 3,8-Dinitrophenylethynyl-substituted Homologue

A large bathochromic shift (50 nm) and emission in the near infrared is observed by attaching arylethynyl groups at the 3,8-positions of the 1,10-phenanthroline ligand (phen) of [Os(bipy)2(phen)]2+ (where bipy = 2,2'-bipyridine). Thus [Os(bipy)2(3,8-di-4-methoxyphenylethynyl-1,10-phenathroline)]2+ emits at 795 nm, while [Os(bipy)2(3,8-diphenylethynyl-1,10-phenanthroline)]2+ emits at 815 nm. According to this trend it would have been expected that [Os(bipy)2(3,8-di-4-nitrophenylethynyl-1,10-phenathroline)]2+ emits farther in the near infrared. Nevertheless, this complex is not photoluminescent because of intramolecular electron transfer quenching of the MLCT excited state by the nitroaromatic group. These results set structural and redox potential standards in the design of near infrared emitters based on [Os(bipy)2(phen)]2+ type complexes.

Yang, Jinhua↗

NASA NTRS2004

Synthesis and Luminescent Chemosensory Behavior of N,N'-bis(p-aminophenyl)-1,5-bis(p-(tetraethyleneglycoloxy)phenyl)anthracene-2,3,6,7-tetracarboxyl bisimide

We have utilized the photoenolization reaction of a dibenzoyl-p-xylene derivative to synthesize two new, highly substituted anthracene-based molecules. ABI-NO2 and ABI-NH2 maintained photostability with longer wavelength absorption and emission spectra as compared to unsubstituted anthracene. Conversion of the periphery nitro groups to amines created an internal photoinduced electron transfer scenario that quenched the luminescence of ABI-NH2. Reversible or irreversible reaction of the attached amines resulted in fluorescence recovery. Sensitivity, of ABI-NH2 and other potential derivatives, to toxic chemicals may prove useful for early detection systems.

Ilhan, Faysal↗

NASA NTRS2004

Diels-Alder Trapping of Photochemically Generated Dienes with Acrylic Esters: A Novel Approach to Photocured Polymer Film Development

Diels-Alder cycloadditions have often been utilized in polymer synthesis as an alternative to condensation reactions. In our earlier efforts, we developed a new method for the preparation of linear aromatic polyimides, which employs o-quionodimethanes (o-QDMs), generated by a well-known photochemical reaction: the photoenolization of o-methylphenyl ketones. Photolysis of o-methylbenzophenone 1 produces hydroxy-o-quino- diemthane 2, which can be trapped with dienophiles, such as dimethyl acetylenedicarboxylate, to efficiently yield the corresponding cycloadduct (Scheme 1). Here we extend this approach to a novel photocuring process for development of polymer films. We synthesized a series of molecules with multi o-mehtylphenyl ketone functionalities. We further investigated these molecules as photoreactive monomers to obtain polyester films through Diels-Alder cycloadditions.

Ilhan, Faysal↗

NASA NTRS2004

Synthesis, Characterization, and Optical Properties of a Cyano-Functionalized 4,5,9,10-tetraaryl-l,6-dioxapyrene

5,10-Di(4-cyanophenyl)-4,9-di(4-methylphenyl)-1,6-dioxapyrene ( CN-diox), a symmetrically substituted 4,5,9,10-tetraaryldioxapyrene, was synthesized in seven steps from 1,4-dihydroxynaphthalene. The synthetic methodology incorporated a base-catalyzed ring-closure process followed by dehydration to introduce the first tetraaryl- 1,6-dioxapyrene. Crystal structure and electrochemical analysis were performed to directly compare the properties of CN-diox to previously reported dioxapyrene derivatives, specifically 1,6-dioxapyrene (Diox) and 4,9-diethyl-2,7-dimethyl- 1,6-dioxapyrene (Alkyl-diox). Optical spectroscopy studies were performed to evaluate the potential of the 1,6-dioxapyrenes as fluorescent probes. CN-diox revealed a broad absorption centered near 450 nm (epsilon = 31,900/M/cm) in THF with a corresponding fluorescence at 619 nm (Phi(sub f) = 0.011). This was in sharp contrast to both Diox and Alkyl-diox which displayed broad absorption bands near 400 nm (epsilon approx. 5,000-10,000/M/cm) in THF with corresponding fluorescence near 500 nm (Phi(sub f) = 0.059 and 0.082 for Diox and Alkyl-diox, respectively). The luminescence of CN-diox was found to be solvatochromic (lambda(sub max) = 619 nm-644 nm) with single exponential lifetimes of less than 1.3 ns. Neither Diox nor Alkyl-diox showed solvatochromic properties.

Tyson, Daniel S.↗

NASA NTRS2004

Diels-Alder Trapping of Photochemically Generated o-Quinodimethane Intermediates: An Alternative Route to Photocured Polymer Film Development

Photolysis of o-methylphenyl ketones generates bis-o-quinodimethane intermediates that can be trapped in situ by dienophiles through Diels-Alder cycloadditions. This well-known photochemical process is applied to a series of six new photoreactive monomers containing bis-(o-methylphenyl ketone) functionalities combined with diacrylate and triacrylate ester monomers for the development of acrylic ester copolymer blends. Irradiation of cyclohexanone solutions of the bis-(o-methylphenyl ketone)s and acrylate esters produce thin polymer films. Solid state 13C NMR data indicated 47- 100% reaction of the bis-(o-methylphenyl ketone)s, depending on experimental conditions, to yield the desired products. DSC and TGA analyses were performed to determine the glass transition temperature, T,, and onset of decomposition, Td, of the resulting polymer films. A statistical Design of Experiments approach was used to obtain a systematic understanding of the effects of experimental variables on the extent of polymerization and the final polymer properties.

Tyson, Daniel S.↗

NASA NTRS2004

Arylethynyl Substituted 9,lO-Anthraquinones: Tunable Stokes Shifts by Substitution and Solvent Polarity

2-Arylethynyl- and 2,6- and 2,7-diarylethynyl-substituted 9,lO-anthraquinones were synthesized via Sonogashira coupling reactions of 2-bromo-, 2,6-dibromo-, and 2,7-dibromo-9,10- anthraquinone with para-substituted phenylacetylenes. While the redox properties of those compounds are almost insensitive to substitution, their absorption maxima are linearly related to the Hammett constants with different slopes for electron donors and electron acceptors. ABI compounds are photoluminescent both in solution (quantum yields of emission <= 6 %), and as solids. The emission spectra have the characteristics of charge-transfer bands with large Stokes shifts (100-250 nm). The charge-transfer character of the emitting state is supported by large dipole moment differences between the ground and the excited state as concluded on the basis of molecular modeling and Lippert-Mataga correlations of the Stokes shifts with solvent polarity. Maximum Stokes shifts are attained by both electron-donating and -withdrawing groups. This is explained by a destabilization of the HOMO by electron donors and a stabilization of the LUMO by electron acceptors. X-ray crystallographic analysis of, for example, 2,7-bisphenylethynfl- 9,lO-anthraquinone reveals a monoclinic P21In space group and no indication for pi-overlap that would promote quenching, thus explaining emission from the solid state. Representative reduced forms of the title compounds were isolated as stable acetates of the corresponding dihydrs-9,10- anthraquinones. The emission of these compounds is blue-shifted relative to the parent oxidized forms and is attributed to internal transitions in the dihydro-9,lO-anthraquinone core.

Yang, Jinhua↗

NASA NTRS2003

Efficient Synthesis of 4,8-Ditoluoyl-1,5-Dihydroxynaphthalene

4,8-Ditoluoyl-1,5-dihydroxynaphthalene was synthesized in quantitative yield from the corresponding methylenequinone via base-catalyzed hydration. Alkaline treatment gives the title compound in one step with a 99% yield, an improvement of 80% compared to the acidic, two step literature method for preparing 4,8-dibenzoyl-1,5-dihydroxynaphthalene.

Tyson, Daniel S.↗