Thomas A. Everett

Direct observation of bis(dicarbollyl)nickel conformers in solution by fluorescence spectroscopy: an approach to redox-controlled metallacarborane molecular motors.

As a continuation of work on metallacarborane-based molecular motors, the structures of substituted bis(dicarbollyl)nickel complexes in Ni(III) and Ni(IV) oxidation states were investigated in solution by fluorescence spectroscopy. Symmetrically positioned cage-linked pyrene molecules served as fluorescent probes to enable the observation of mixed meso-trans/dl-gauche (pyrene monomer fluorescence) and dl-cis/dl-gauche (intramolecular pyrene excimer fluorescence with residual monomer fluorescence) cage conformations of the nickelacarboranes in the Ni(III) and Ni(IV) oxidation states, respectively. The absence of energetically disfavored conformers in solution--dl-cis in the case of nickel(III) complexes and meso-trans in the case of nickel(IV)--was demonstrated based on spectroscopic data and conformer energy calculations in solution. The conformational persistence observed in solution indicates that bis(dicarbollyl)nickel complexes may provide attractive templates for building electrically driven and/or photodriven molecular motors.

High-resolution direct-write multiphoton photolithography in poly(methylmethacrylate) films

Multiphoton photolithography in poly(methylmethacrylate) films is demonstrated. High-resolution structures of arbitrary geometry with edge sharpnesses as small as 120nm are produced using femtosecond pulses of 870nm light focused to a diffraction-limited spot in the films. The power dependence of etching and tests of different polymers prove that the process is nonlinear and involves excitation of the polymer’s chromophores. Atomic force microscopy images show that the vast majority of polymer is removed during etching. It is concluded that the etching mechanism involves depolymerization and thermal evaporation of the polymer. Application of this method in the fabrication of electrochemical microelectrodes is demonstrated.

Aggregation and its influence on macroscopic in-plane organization in thin films of electrostatically self-assembled perylene-diimide/polyelectrolyte nanofibers.

The influence of precursor aggregation on materials deposition efficiency, film morphology, and macroscopic in-plane organization is explored for electrostatically self-assembled perylene-diimide/polyelectrolyte (PDI/PE) composites. PDI/PE thin films are prepared from aqueous precursor solutions by sequential dip-coating methods. Three PDI dyes are employed to probe the influence of aggregation on electrostatic self-assembly (ESA) of the composites. These include a singly charged PDI, C(7)OPDI(+), and two doubly charged species, PDISO(3)(2-) and TAPDI(2+). Poly(diallyldimethylammonium) (PDDA(+)) chloride and sodium poly(acrylate) (PA(-)) are used as the PEs. UV-vis absorbance and fluorescence spectroscopies show that all three dyes are heavily aggregated in their respective aqueous solutions. Temperature-dependent fluorescence data and filtration studies show that C(7)OPDI(+) is most strongly associated and also forms the largest aggregates. Absorbance data obtained as a function of the number of deposition cycles employed in film preparation demonstrate that C(7)OPDI(+) is also most efficiently deposited. Atomic force microscopy (AFM) images show that all three PDI/PE films are comprised of similar serpentine nanofibers. Interestingly, bulk absorbance dichroism data and AFM images demonstrate that the C(7)OPDI(+)/PA(-) composites incorporate macroscopically oriented dye and aligned nanofibers. Dye and nanofiber alignment is found to be perpendicular and parallel, respectively, to the dipping direction. No such organization is observed for the other two composites. It is concluded that deposition is strongly influenced by the level of precursor aggregation and that macroscopic in-plane organization in the C(7)OPDI(+)/PA(-) composites results from flow-induced alignment of relatively large preformed C(7)OPDI(+) aggregates during deposition.

Electrostatic self-assembly of ordered perylene-diimide/polyelectrolyte nanofibers in fluidic devices: from nematic domains to macroscopic alignment.

Sequential deposition of nanofibrous composites of charged perylene diimide (PDI) dyes and oppositely charged polyelectrolyte (PE) is demonstrated within fluidic devices. The PDIs employed include an amphiphilic, singly charged PDI (C(7)OPDI(+)) and a doubly charged species (TAPDI(2+)). Anionic poly(acrylate) (PA(-), 5100 and 250K MW) is used as the PE. As previously demonstrated [Weitzel, C. R.; Everett, T. A.; Higgins, D. A. Langmuir, 2009, 25, 1188], dip-coated PDI/PE composites form nanofibrous films that exhibit flow-induced alignment due to gravitational draining of the dipping solution. In this study, the potential for producing patterned, flow-aligned PDI/PE composites by deposition using pressure-driven flow within fluidic channels is explored. The influence of flow profile, PE molecular weight (MW) and PDI structure on deposition efficiency, macroscopic and microscopic morphology, and the potential for nanofiber alignment are also investigated. Optical absorbance microscopy and tapping mode AFM data demonstrate that C(7)OPDI(+)/PA(-) deposition is controlled by PDI aggregation, while TAPDI(2+)/PA(-) composites are more dependent upon PE MW. Optical dichroism images show that C(7)OPDI(+)/PA(-) composites form serpentine, partially aligned nanofibers under all conditions explored, while TAPDI(2+)/PA(-) films incorporate more tightly packed nanofibers that form randomly oriented nematic-like domains when high MW PA(-) is employed. In-plane organization in C(7)OPDI(+)/PA(-) films is concluded to result from flow-induced alignment of solution-formed C(7)OPDI(+) aggregates, while the unaligned domains found in TAPDI(2+)/PA(-) films are concluded to form on the substrate surface by the complexation of small TAPDI(2+) aggregates or monomers with PE.

Validation and Comparison of the Therapeutic Efficacy of Boron Neutron Capture Therapy Mediated By Boron-Rich Liposomes in Multiple Murine Tumor Models

Boron neutron capture therapy (BNCT) was performed at the University of Missouri Research Reactor in mice bearing CT26 colon carcinoma flank tumors and the results were compared with previously performed studies with mice bearing EMT6 breast cancer flank tumors. Mice were implanted with CT26 tumors subcutaneously in the caudal flank and were given two separate tail vein injections of unilamellar liposomes composed of cholesterol, 1,2-distearoyl-sn-glycer-3-phosphocholine, and K[nido-7-CH3(CH2)15–7,8-C2B9H11] in the lipid bilayer and encapsulated Na3[1-(2`-B10H9)-2-NH3B10H8] within the liposomal core. Mice were irradiated 30 hours after the second injection in a thermal neutron beam for various lengths of time. The tumor size was monitored daily for 72 days. Despite relatively lower tumor boron concentrations, as compared to EMT6 tumors, a 45 minute neutron irradiation BNCT resulted in complete resolution of the tumors in 50% of treated mice, 50% of which never recurred. Median time to tumor volume tripling was 38 days in BNCT treated mice, 17 days in neutron-irradiated mice given no boron compounds, and 4 days in untreated controls. Tumor response in mice with CT26 colon carcinoma was markedly more pronounced than in previous reports of mice with EMT6 tumors, a difference which increased with dose. The slope of the dose response curve of CT26 colon carcinoma tumors is 1.05 times tumor growth delay per Gy compared to 0.09 times tumor growth delay per Gy for EMT6 tumors, indicating that inherent radiosensitivity of tumors plays a role in boron neutron capture therapy and should be considered in the development of clinical applications of BNCT in animals and man.