Wholly Aromatic Ether-Imides as n-Type Semiconductors

Some wholly aromatic ether-imides consisting of rod-shaped, relatively-low-mass molecules that can form liquid crystals have been investigated for potential utility as electron-donor-type (ntype) organic semiconductors. It is envisioned that after further research to improve understanding of their physical and chemical properties, compounds of this type would be used to make thin film semiconductor devices (e.g., photovoltaic cells and field-effect transistors) on flexible electronic-circuit substrates. This investigation was inspired by several prior developments: Poly(ether-imides) [PEIs] are a class of engineering plastics that have been used extensively in the form of films in a variety of electronic applications, including insulating layers, circuit boards, and low-permittivity coatings. Wholly aromatic PEIs containing naphthalene and perylene moieties have been shown to be useful as electrochromic polymers. More recently, low-molecular-weight imides comprising naphthalene-based molecules with terminal fluorinated tails were shown to be useful as n-type organic semiconductors in such devices as field-effect transistors and Schottky diodes. Poly(etherimide)s as structural resins have been extensively investigated at NASA Langley Research Center for over 30 years. More recently, the need for multi-functional materials has become increasingly important. This n-type semiconductor illustrates the scope of current work towards new families of PEIs that not only can be used as structural resins for carbon-fiber reinforced composites, but also can function as sensors. Such a multi-functional material would permit so-called in-situ health monitoring of composite structures during service. The work presented here demonstrates that parts of the PEI backbone can be used as an n-type semiconductor with such materials being sensitive to damage, temperature, stress, and pressure. In the near future, multi-functional or "smart" composite structures are envisioned to be able to communicate such important parameters to the flight crew and provide vital information with respect to the operational status of their aircraft

Probing molecular ordering in the nematic phases of para-linked bimesogen dimers through NMR studies of flexible prochiral solutes

The quadrupolar splittings of perdeuteriated n-decane dissolved in nematic phases formed by mesogenic dimers of the CBnCB series, for n = 7,9,10,11, are measured throughout the entire temperature range of these phases. These results are reported together with related measurements using the common nematic phase of 5CB as a solvent for n-decane. The data obtained from the 13C spectra of the cyanobiphenyl mesogenic units of the monomeric and dimeric solvent molecules yield the order parameter of those units. The information obtained from this set of experiments is used to elucidate the structure of the low temperature (NX) and the high temperature (N) nematic phases of CBnCB dimers with n = 7,9,11. The polar twisted nematic (NPT) model is found to provide a consistent description not only of our experimental results but also of NMR measurements previously reported in the literature for these phases. These findings suggest that the high temperature nematic (N) is not a common, locally uniaxial and apolar nematic, but rather a nematic phase consisting of NPT clusters. The twist-bend (NTB) model, often identified with the NX phase, is shown to be inadequate to account even qualitatively for crucial features of the experimental findings

The Pursuit of a Scalable Nanofabrication Platform for Use in Material and Life Science Applications

In this Account, we describe the use of perfluoropolyether (PFPE)-based materials that are able to accurately mold and replicate micro- and nanosized features using traditional techniques such as embossing as well as new techniques that we developed to exploit the exceptional surface characteristics of fluorinated substrates. Because of the unique partial wetting and nonwetting characteristics of PFPEs, we were able to go beyond the usual molding and imprint lithography approaches and have created a technique called PRINT (Particle [or Pattern] Replication In Nonwetting Templates)

Remodeling of cortical bone allografts mediated by adherent rAAV-RANKL and VEGF gene therapy

Structural allograft healing is limited because of a lack of vascularization and remodeling. To study this we developed a mouse model that recapitulates the clinical aspects of live autograft and processed allograft healing. Gene expression analyses showed that there is a substantial decrease in the genes encoding RANKL and VEGF during allograft healing. Loss-of-function studies showed that both factors are required for autograft healing. To determine whether addition of these signals could stimulate allograft vascularization and remodeling, we developed a new approach in which rAAV can be freeze-dried onto the cortical surface without losing infectivity. We show that combination rAAV-RANKL- and rAAV-VEGF-coated allografts show marked remodeling and vascularization, which leads to a new bone collar around the graft. In conclusion, we find that RANKL and VEGF are necessary and sufficient for efficient autograft remodeling and can be transferred using rAAV to revitalize structural allografts

Self-Assembled α-Helical Polypeptide Films

Poly(γ-benzyl-L-glutamate) (PBLG) derivatized at its N-terminus with lipoic acid, a disulfide-containing moiety, self-assembles on gold from helicogenic solvents to give a thin film with the polypeptide α-helices orientation distribution different from the planar orientation in the unlabeled, physisorbed PBLG films (control) and Langmuir-Blodgett monolayers. The SA films were studied by angle-dependent XPS, reflection-absorption FTIR spectroscopy, and ellipsometry. The IR dichroic properties of the amide I and amide II bands were used to infer the orientational distribution of the helices in the self-assembled film and lead to two extreme pictures of the helix axis distribution function: (a) random (hemispherical distribution) and (b) perfect order with a tilt of 53° from the surface normal. Additional characterization is necessary to differentiate between these two distributions