On Nested Chain Decompositions of Normalized Matching Posets of Rank 3

In 1975, J. Griggs conjectured that a normalized matching rank-unimodal poset possesses a nested chain decomposition. This elegant conjecture remains open even for posets of rank 3. Recently, Hsu, Logan, and Shahriari have made progress by developing techniques that produce nested chain decompositions for posets with certain rank numbers. As a demonstration of their methods, they prove that the conjecture is true for all rank 3 posets of width at most 7. In this paper, we present new general techniques for creating nested chain decompositions, and, as a corollary, we demonstrate the validity of the conjecture for all rank 3 posets of width at most 11.     

3-Helix micelles stabilized by polymer springs

Despite increasing demands to employ amphiphilic micelles as nanocarriers and nanoreactors, it remains a significant challenge to simultaneously reduce the particle size and enhance the particle stability. Complementary to covalent chemical bonding and attractive intermolecular interactions, entropic repulsion can be incorporated by rational design in the headgroup of an amphiphile to generate small micelles with enhanced stability. A new family of amphiphilic peptide-polymer conjugates is presented where the hydrophilic headgroup is composed of a 3-helix coiled coil with poly(ethylene glycol) attached to the exterior of the helix bundle. When micelles form, the PEG chains are confined in close proximity and are compressed to act as a spring to generate lateral pressure. The formation of 3-helix bundles determines the location and the directionalities of the force vector of each PEG elastic spring so as to slow down amphiphile desorption. Since each component of the amphiphile can be readily tailored, these micelles provide numerous opportunities to meet current demands for organic nanocarriers with tunable stability in life science and energy science. Furthermore, present studies open new avenues to use energy arising from entropic polymer chain deformation to self-assemble energetically stable, single nanoscopic objects, much like repulsion that stabilizes bulk assemblies of colloidal particles.     

Supramolecular Materials Comprising Nucleic Acid Biopolymers

We have generated a supramolecular self-assembling film by exchanging the counter-ions of the phosphate moieties in nucleic acid with those of cationic amphiphiles as didodecyldimethylammonium bromide (or DDAB). SAXS and WAXS data for all film samples showed similar harmonic peaks suggesting a lamellar multilayer structure with layers of nucleic acids being separated by lipid bilayers of DDAB. AFM height images also showed that double stranded nucleic acid film can form the step or plateau type of structure and shorter nucleic acid film showed shorter step feature. Moreover, the length and the molecular structure of DNA and RNA can be used to manipulate the mechanical properties of these self-assembled films.     

Brush‐first and Click: Efficient Synthesis of Nanoparticles that Degrade and Release Doxorubicin in Response to Light

New strategies for the synthesis of multifunctional particles that respond to external stimuli and release biologically relevant agents will enable the discovery of new formulations for drug delivery. In this article, we combine two powerful methods: brush‐first ring‐opening metathesis polymerization and copper‐catalyzed azide–alkyne cycloaddition click chemistry, for the synthesis of a novel class of brush‐arm star polymers (BASPs) that simultaneously degrade and release the anticancer drug doxorubicin (DOX) in response to 365 nm light. In vitro cell viability studies were performed to study the toxicity of azide‐ and DOX‐loaded BASPs. The former were completely nontoxic. The latter showed minimal toxicity in the absence of light; UV‐triggered DOX release led to IC₅₀ values that were similar to that of free DOX.     

Self-association and membrane-binding behavior of melittins containing trifluoroleucine

We have investigated the effect of trifluoroleucine substitution on the membrane-binding and tetramerization behavior of melittin. Analogues were synthesized in which Leu 9, Leu 13, and all four intrinsic leucine residues of melittin were replaced by 5,5,5-trifluoroleucine. Both the mono- and tetra-substituted melittins were found to exhibit stronger self-association and enhanced affinity for lipid bilayer membranes, compared to the wild-type peptide. The extent of the observed effects depends on the site of introduction of trifluoroleucine and, in the case of substitution at position 13, on the stereochemistry of the trifluoroleucine side chain. Analysis of the membrane association isotherms is consistent with aggregation of fluorinated melittins within the lipid bilayer. These results suggest that fluorocarbon-hydrocarbon separation, in addition to an increase in hydrophobic character, contributes to enhanced membrane binding.     

A molecular orbital study of the interactions of acrylic polymers with aluminum: Implications for adhesion

We present results of molecular orbital thory calculations of the interactions of acrylic polymers with aluminum, with a view toward understanding the nature of chemical bonding at the corresponding polymer-metal interfaces. The reported results are for the interactions of polymer model compounds with metal atoms (as opposed to our ongoing studies with metal surfaces). As such, the results relate to experimental studies where small dosages of metal atoms are evaporated onto polymer surfaces in pristine high vacuum environments. Our studies have been conducted within the theoretical framework of Hartree-Fock molecular orbital theory. We find that aluminum atoms interact primarily with the carbonyl group of acrylic polymers. The reaction proceeds by the metal atoms interacting with both the carbon and the oxygen atoms of the carbonyl functionality. This weakens the C?O bond. Finally, the carbonyl bond loses double bond character, and strong AL—O bonds are formed. Our results are compared to experimental data, and the implications of the detailed nature of bonding for adhesion applications are discussed.     

Polymerized vesicles containing molecular recognition sites

Vesicles are prepared from diacetylenic peptide amphiphiles that expose a molecular recognition site at the surface. The amphiphiles can be polymerized using UV light, and the resulting polymeric vesicles exhibit interesting chromatic responses that can be used for label-free detection of the interaction with a distinct protein in solution.     

Directing the phase behavior of polyelectrolyte complexes using chiral patterned peptides

Polyelectrolyte complexes (PECs) have a broad range of promising applications as soft materials due to their self-assembly and diversity of structure and chemical composition. Peptide polymer PECs are highly biocompatible and biodegradable, making them particularly useful for encapsulation of food additives and flavors, micellar drug delivery, medical and underwater adhesives, fetal membrane patches, and scaffolds for cell growth in tissue engineering. While parameters affecting PEC formation and stability in regards to charge effects are well researched, little is known about the effects of van der Waals interactions, hydrogen bonding, and secondary structure in these materials. Peptide chirality provides a unique opportunity to manipulate PEC phase to modulate the amount of solid-like (precipitate) or liquid-like (coacervate) character by influencing hydrogen bonding interactions among peptide chains. In previous work, we showed that chiral peptides form solid complexes, while complexes with even one racemic peptide were fluid. This raised the interesting question of how long a homochiral sequence must be to result in solid phase formation. In this work, we designed chiral patterned peptides of polyglutamic acid and polylysine ranging from 50 to 90% L-chiral residues with increasing numbers of sequential L-chiral residues before a chirality change. These polymers were mixed together to form PECs. We observed that 8 or more sequential L-chiral residues are necessary to achieve both the appearance of a precipitate phase and sustained β-sheets in the complex, as determined by optical imaging and FTIR Spectroscopy. Less homochiral content results in formation of a coacervate phase. Thus, we show that chiral sequence can be used to control the phase transition of PECs. Understanding how to manipulate PEC phase using chiral sequence as presented here may enable tuning of the material properties to achieve the desired mechanical strength for coatings and polymer brushes, or the most effective molecular release kinetics for drug delivery applications, for example.