Direct test of defect mediated laser induced melting theory for two dimensional solids

We investigate by direct numerical solution of appropriate renormalization flow equations, the validity of a recent dislocation unbinding theory for laser induced freezing/melting in two dimensions. The bare elastic moduli and dislocation fugacities which are inputs to the flow equations are obtained for three different 2-d systems (hard disk, inverse $12^{th}$ power and the Derjaguin-Landau-Verwey-Overbeek potentials) from a restricted Monte Carlo simulation sampling only configurations {\em without} dislocations. We conclude that (a) the flow equations need to be correct at least up to third order in defect fugacity to reproduce meaningful results, (b) there is excellent quantitative agreement between our results and earlier conventional Monte Carlo simulations for the hard disk system and (c) while the qualitative form of the phase diagram is reproduced for systems with soft potentials there is some quantitative discrepancy which we explain.Comment: 11 pages, 14 figures, submitted to Phys. Rev.

Micellization of Sliding Polymer Surfactants

Following up a recent paper on grafted sliding polymer layers (Macromolecules 2005, 38, 1434-1441), we investigated the influence of the sliding degree of freedom on the self-assembly of sliding polymeric surfactants that can be obtained by complexation of polymers with cyclodextrins. In contrast to the micelles of quenched block copolymer surfactants, the free energy of micelles of sliding surfactants can have two minima: the first corresponding to small micelles with symmetric arm lengths, and the second corresponding to large micelles with asymmetric arm lengths. The relative sizes and concentrations of small and large micelles in the solution depend on the molecular parameters of the system. The appearance of small micelles drastically reduces the kinetic barrier signifying the fast formation of equilibrium micelles.Comment: Submitted to Macromolecule

Self-assembly of telechelic tyrosine end-capped PEO and poly(alanine) polymers in aqueous solution

The self-assembly in aqueous solution of three novel telechelic conjugates comprising a central hydrophilic polymer and short (trimeric or pentameric) tyrosine end-caps has been investigated. Two of the conjugates have a central poly(oxyethylene) (polyethylene oxide, PEO) central block with different molar masses. The other conjugate has a central poly(l-alanine) (PAla) sequence in a purely amino-acid based conjugate. All three conjugates self-assemble into β-sheet based fibrillar structures, although the fibrillar morphology revealed by cryogenic-TEM is distinct for the three polymers—in particular the Tyr5-PEO6k-Tyr5 forms a population of short straight fibrils in contrast to the more diffuse fibril aggregates observed for Tyr5-PEO2k-Tyr5 and Tyr3-PAla-Tyr3. Hydrogel formation was not observed for these samples (in contrast to prior work on related systems) up to quite high concentrations, showing that it is possible to prepare solutions of peptide–polymer-peptide conjugates with hydrophobic end-caps without conformational constraints associated with hydrogelation. The Tyr5-PEO6k-Tyr5 shows significant PEO crystallization upon drying in contrast to the Tyr5-PEO2k-Tyr5 conjugate. Our findings point to the remarkable ability of short hydrophobic peptide end groups to modulate the self-assembly properties of polymers in solution in model peptide-capped “associative polymers”. Retention of fluidity at high conjugate concentration may be valuable in potential future applications of these conjugates as bioresponsive or biocompatible materials, for example exploiting the enzyme-responsiveness of the tyrosine end-group

Chiral organocatalysts based on lipopeptide micelles for aldol reactions in water

A comprehensive study of the self-assembly in water of a lipopeptide consisting of a sequence of L-proline, L-arginine and L-tryptophan with a hydrocarbon chain has been performed. Fluorescence assays were used to determine the critical aggregation concentration. In situ small-angle X-ray scattering (SAXS) and molecular dynamics simulations showed the presence of spherical micelles with diameters around 6 nm. In agreement with these results, cryo-TEM images showed globular aggregates with diameters ranging from ≈4 nm up to ≈9 nm. Furthermore, the lipopeptide catalytic activity has been tested for the direct aldol reaction between cyclohexanone and p-nitrobenzaldehyde, and we have observed that the self-association of the organocatalyst played a critical role in the enhanced activity. Water affects the selectivity, and poor results are obtained under neat reaction conditions. The location of the catalytic groups at the lipopetide/water solvent interface also endowed unusual selectivity in the catalyzed aldol reactions. Under optimized reaction conditions, high yields (up to >99%), good enantioselectivity (ee up to 85%) and high diastereoselectivity (ds up to 92 : 8) were obtained

Nanosheet formation by an anionic surfactant-like peptide and modulation of self-assembly through ionic complexation

The surfactant-like peptide (Ala)6-(Asp) (A6D) is shown to self-assemble into ultrathin (3 nm thick) nanosheets in aqueous solution above a critical aggregation concentration. A combination of circular dichroism and FTIR spectroscopy and X-ray diffraction shows that the nanosheets comprise interdigitated bilayers of the peptide with β-sheet conformation. The self-assembly can be modulated by addition of hexamethylenediamine which is expected to interact with the anionic C terminus (and C-terminal D residue) of the peptide. Multiple ordered nanostructures can be accessed depending on the amount of added diamine. Nanosheet and bicontinuous network structures were observed using cryogenic-TEM and small-angle X-ray scattering. Addition of hexamethylenediamine at a sufficiently large molar ratio leads to disruption of the ordered nanostructure and the formation of a solution of A6D–diamine molecular complexes with highly charged end groups. The multiple acid-functionalized nanostructures that are accessible in this system are expected to have many applications in the fabrication of new nanomaterials

Self-assembly of the toll-like receptor agonist macrophage-activating lipopeptide MALP-2 and of its constituent peptide

The self-assembly of the macrophage-activating lipopeptide MALP-2 in aqueous solution has been investigated and is compared to that of the constituent peptide GNNDESNISFKEK. MALP-2 is a toll-like receptor agonist lipopeptide with diverse potential biomedical applications and its self-assembly has not previously been examined. It is found to self-assemble, above a critical aggregation concentration (cac), into remarkable “fibre raft” structures, based on lateral aggregation of β-sheet based bilayer tapes. Peptide GNNDESNISFKEK also forms β-sheet structures above a cac, although the morphology is distinct, comprising highly extended and twisted tape structures. A detailed insight into the molecular packing within the MALP-2 raft and GNNDESNISFKEK nanotape structures is obtained through X-ray diffraction and small-angle X-ray scattering. These results point to the significant influence of the attached lipid chains on the self-assembly motif, which lead to the raft structure for the lipopeptide assemblies

Tuning chelation by the surfactant-like peptide A6H using predetermined pH values

We examine the self-assembly of a peptide A6H comprising a hexa-alanine sequence A6 with a histidine (H) “head group”, which chelates Zn2+ cations. We study the self assembly of A6H and binding of Zn2+ ions in ZnCl2 solutions, under acidic and neutral conditions. A6H self-assembles into nanotapes held together by a β-sheet structure in acidic aqueous solutions. By dissolving A6H in acidic ZnCl2 solutions, the carbonyl oxygen atoms in A6H chelate the Zn2+ ions and allow for β-sheet formation at lower concentrations, consequently reducing the onset concentration for nanotape formation. A6H mixed with water or ZnCl2 solutions under neutral conditions produces short sheets or pseudocrystalline tapes, respectively. The imidazole ring of A6H chelates Zn2+ ions in neutral solutions. The internal structure of nanosheets and pseudocrystalline sheets in neutral solutions is similar to the internal structure of A6H nanotapes in acidic solutions. Our results show that it is possible to induce dramatic changes in the self-assembly and chelation sites of A6H by changing the pH of the solution. However, it is likely that the amphiphilic nature of A6H determines the internal structure of the self-assembled aggregates independent from changes in chelation

Degradation versus self-assembly of block copolymer micelles

The stability of micelles self-assembled from block copolymers can be altered by the degradation of the blocks. Slow degradation shifts the equilibrium size distribution of block copolymer micelles and change their properties. Quasi-equilibrium scaling theory shows that the degradation of hydrophobic blocks in the core of micelles destabilize the micelles reducing their size, while the degradation of hydrophilic blocks forming coronas of micelles favors larger micelles and may, at certain conditions, induce the formation of micelles from individual chains.Comment: Published in Langmuir http://pubs.acs.org/doi/pdf/10.1021/la204625

Spin-Nematic Squeezed Vacuum in a Quantum Gas

Using squeezed states it is possible to surpass the standard quantum limit of measurement uncertainty by reducing the measurement uncertainty of one property at the expense of another complementary property. Squeezed states were first demonstrated in optical fields and later with ensembles of pseudo spin-1/2 atoms using non-linear atom-light interactions. Recently, collisional interactions in ultracold atomic gases have been used to generate a large degree of quadrature spin squeezing in two-component Bose condensates. For pseudo spin-1/2 systems, the complementary properties are the different components of the total spin vector , which fully characterize the state on an SU(2) Bloch sphere. Here, we measure squeezing in a spin-1 Bose condensate, an SU(3) system, which requires measurement of the rank-2 nematic or quadrupole tensor as well to fully characterize the state. Following a quench through a nematic to ferromagnetic quantum phase transition, squeezing is observed in the variance of the quadratures up to -8.3(-0.7 +0.6) dB (-10.3(-0.9 +0.7) dB corrected for detection noise) below the standard quantum limit. This spin-nematic squeezing is observed for negligible occupation of the squeezed modes and is analogous to optical two-mode vacuum squeezing. This work has potential applications to continuous variable quantum information and quantum-enhanced magnetometry

Supramolecular peptide nanofiber morphology affects mechanotransduction of stem cells

Chirality and morphology are essential factors for protein function and interactions with other biomacromolecules. Extracellular matrix (ECM) proteins are also similar to other proteins in this sense; however, the complexity of the natural ECM makes it difficult to study these factors at the cellular level. The synthetic peptide nanomaterials harbor great promise in mimicking specific ECM molecules as model systems. In this work, we demonstrate that mechanosensory responses of stem cells are directly regulated by the chirality and morphology of ECM-mimetic peptide nanofibers with strictly controlled characteristics. Structural signals presented on l-amino acid containing cylindrical nanofibers (l-VV) favored the formation of integrin β1-based focal adhesion complexes, which increased the osteogenic potential of stem cells through the activation of nuclear YAP. On the other hand, twisted ribbon-like nanofibers (l-FF and d-FF) guided the cells into round shapes and decreased the formation of focal adhesion complexes, which resulted in the confinement of YAP proteins in the cytosol and a corresponding decrease in osteogenic potential. Interestingly, the d-form of twisted-ribbon like nanofibers (d-FF) increased the chondrogenic potential of stem cells more than their l-form (l-FF). Our results provide new insights into the importance and relevance of morphology and chirality of nanomaterials in their interactions with cells and reveal that precise control over the chemical and physical properties of nanostructures can affect stem cell fate even without the incorporation of specific epitopes