Engineering topics
DiMasi, E
Publications and source records attributed to DiMasi, E.
The Stomatopod Dactyl Club: A Formidable Damage-Tolerant Biological Hammer
Nature has evolved efficient strategies to synthesize complex mineralized structures that exhibit exceptional damage tolerance. One such example is found in the hypermineralized hammer-like dactyl clubs of the stomatopods, a group of highly aggressive marine crustaceans. The dactyl clubs from one species, Odontodactylus scyllarus, exhibit an impressive set of characteristics adapted for surviving high-velocity impacts on the heavily mineralized prey on which they feed. Consisting of a multiphase composite of oriented crystalline hydroxyapatite and amorphous calcium phosphate and carbonate, in conjunction with a highly expanded helicoidal organization of the fibrillar chitinous organic matrix, these structures display several effective lines of defense against catastrophic failure during repetitive high-energy loading events.
The Role of Moderate Static Magnetic Fields on Biomineralization of Osteoblasts on Sulfonated Polystryene Films
We have investigated the effects of moderate static magnetic fields (SMFs) on murine MC3T3-E1 osteoblasts, and found that they enhance proliferations and promote differentiation. The increase in proliferation rates in response to SMFs was greater in cultures grown on partially sulfonated polytstyrene (SPS, degree of sulfonation: 33%) than in cultures grown on tissue culture plastic. We have previously shown that when the degree of sulfonation exceeded a critical value (12%) [1], spontaneous fibrillogenesis occured which allowed for direct observation of the ECM fibrillar organization under the influence of external fields. We found that the ECM produced in cultures grown on the SPS in the presence of the SMFs assembled into a lattice with larger dimensions than the ECM of the cultures grown in the absence of SMFs. During the early stages of the biomineralization process (day 7), the SMF exposed cultures also templated mineral deposition more rapidly than the control cultures. The rapid response is attributed to orientation of diamagnetic ECM proteins already present in the serum, which could then initiate further cellular signaling. SMFs also influenced late stage osteoblast differentiation as measured by the increased rate of osteocalcin secretion and gene expression beginning 15 days after SFM exposure. This correlated with a large increase in mineral deposition, and in cell modulus. GIXD and EDXS analysis confirmed early deposition of crystalline hydroxyapatite. Previous studies on the effects of moderate SMF had focused on cellular gene and protein expression, but did not consider the organization of the ECM fibers. Our ability to form these fibers has allowed us explore this additional effect and highlight its significance in the initiation of the biomineralization process.
Phase Diagrams of Electrostatically Self-Assembled Amphiplexes
We present the phase diagrams of electrostatically self-assembled amphiplexes (ESA) comprised of poly(acrylic acid) (PAA), cetyltrimethylammonium chloride (CTACl), dodecane, pentanol, and water at three different NaCl salt concentrations: 100, 300, and 500 mM. This is the first report of phase diagrams for these quinary complexes. Adding a cosurfactant, we were able to swell the unit cell size of all long-range ordered phases (lamellar, hexagonal, Pm3n, Ia3d) by almost a factor of 2. The added advantage of tuning the unit cell size makes such complexes (especially the bicontinuous phases) attractive for applications in bioseparation, drug delivery, and possibly in oil recovery.
Polythiophene-block-polyfluorene and Polythiophene-blockpoly(fluorene-co-benzothiadiazole): Insights into the Self-Assembly of All-Conjugated Block Copolymers
All-conjugated block copolymers have significant potential for solution-processed optoelectronic applications, in particular those relying on a p/n junction. Herein, we report the synthesis and structure of all-conjugated diblock copolymers poly(3-hexylthiophene)-block-poly(9,9-dioctylfluorene) and poly(3-hexylthiophene)-block-poly(9,9-dioctylfluorene-co-benzothiadiazole) in thin films and in the bulk. The diblock copolymers are prepared using a combination of Grignard metathesis polymerization and Suzuki polycondensation and characterized with NMR spectroscopy, size-exclusion chromatography, multiangle laser light scattering, and UV/vis spectroscopy. Structure in thin films and in the bulk is characterized using differential scanning calorimetry, X-ray diffraction, small-angle X-ray scattering, and atomic force microscopy. Diblock copolymer thin films self-assemble into a crystalline nanostructure with some long-range order after extended solvent annealing, and X-ray scattering measurements show that powder samples exhibit crystallinity throughout the bulk. By temperature dependent X-ray scattering measurements, we find that diblock copolymers self-assemble into crystalline nanowires with phase segregated block copolymer domains. These measurements show all-conjugated diblock copolymers may be useful for achieving solution-processed active layers in organic photovoltaics and light-emitting diodes with optimized structural and photophysical characteristics.
Polythiophene-block-polyfluorene and Polythiophene-blockpoly(fluorene-co-benzothiadiazole): Insights into the Self-Assembly of All-Conjugated Block Copolymers
All-conjugated block copolymers have significant potential for solution-processed optoelectronic applications, in particular those relying on a p/n junction. Herein, we report the synthesis and structure of all-conjugated diblock copolymers poly(3-hexylthiophene)-block-poly(9,9-dioctylfluorene) and poly(3-hexylthiophene)-block-poly(9,9-dioctylfluorene-co-benzothiadiazole) in thin films and in the bulk. The diblock copolymers are prepared using a combination of Grignard metathesis polymerization and Suzuki polycondensation and characterized with NMR spectroscopy, size-exclusion chromatography, multiangle laser light scattering, and UV/vis spectroscopy. Structure in thin films and in the bulk is characterized using differential scanning calorimetry, X-ray diffraction, small-angle X-ray scattering, and atomic force microscopy. Diblock copolymer thin films self-assemble into a crystalline nanostructure with some long-range order after extended solvent annealing, and X-ray scattering measurements show that powder samples exhibit crystallinity throughout the bulk. By temperature dependent X-ray scattering measurements, we find that diblock copolymers self-assemble into crystalline nanowires with phase segregated block copolymer domains. These measurements show all-conjugated diblock copolymers may be useful for achieving solution-processed active layers in organic photovoltaics and light-emitting diodes with optimized structural and photophysical characteristics.
Oriented hydroxyapatite in turkey tendon mineralized via the polymer-induced liquid-precursor (PILP) process
Bone is a hierarchically structured composite which imparts it with unique mechanical properties and bioresorptive potential. These properties are primarily influenced by the underlying nanostructure of bone, which consists of nanocrystals of hydroxyapatite embedded and uniaxially aligned within collagen fibrils. There is also a small fraction of non-collagenous proteins in bone, and these are thought to play an important role in bone's formation. In our in vitro model system of bone formation, polyanionic peptides are used to mimic the role of the non-collagenous proteins. In our prior studies, we have shown that intrafibrillar mineralization can be achieved in synthetic reconstituted collagen sponges using a polymer-induced liquid-precursor (PILP) mineralization process. This led to a nanostructured arrangement of hydroxyapatite crystals within the individual fibrils which closely mimics that of bone. This report demonstrates that biogenic collagen scaffolds obtained from turkey tendon, which consist of densely packed and oriented collagen fibrils, can also be mineralized by the PILP process. Synchrotron X-ray diffraction studies show that the mineralization process leads to a high degree of crystallographic orientation at the macroscale, thus emulating that found in the biological system of naturally mineralizing turkey tendon.
Bent core liquid crystal elastomers
Liquid crystal (LC) elastomers with bent-core side-groups incorporate the properties of bent-core liquid crystals in a flexible and self-supporting polymer network. Bent-core liquid crystal elastomers (BCEs) with uniform alignment were prepared by attaching a reactive bent-core LC to poly(hydrogenmethylsiloxane) and crosslinking with a divinyl crosslinker. Phase behavior studies indicate a nematic phase over a wide temperature range that approaches room temperature, and thermoelastic measurements show that these BCEs can reversibly change their length by more than a factor of two upon heating and cooling. Small-angle X-ray scattering studies reveal multiple, broad low-angle peaks consistent with short-range smectic C order of the bent-core side groups. A comparison of these patterns with predictions of a Landau model for short-range smectic C order shows that the length scale for smectic ordering in BCEs is similar to that seen in pure bent-core LCs. The combination of rubber elasticity and smectic ordering of the bent-core side groups suggests that BCEs may be promising materials for sensing, actuating, and other advanced applications.