Javelin-, Hockey Stick-, and Boomerang-Shaped Liquid Crystals. Structural Variations on <i>p</i>-Quinquephenyl^†

The ramifications of changing molecular geometry in a series of all-aromatic liquid crystals derived from p-quinquephenyl are reported. Substituting heterocyclic rings such as thiophene, oxadiazole, oxazole, or 1,3-phenylene into the p-quinquephenylene core affects molecular shape changes via the substituent's exocyclic bond angle. In general, we found that introducing nonlinearity into molecules depresses the melting transition temperature. The symmetric (boomerang-shaped) molecules, 2,5-bisbiphenyl-4-yl-1,3,4-oxadiazole, 2,5-bisbiphenyl-4-yl-oxazole, and 1,3-bisbiphenyl-4-yl-benzene, melt into isotropic phases showing small monotropic mesophases. By contrast, the asymmetric (hockey stick-shaped) mesogens, 2-terphenyl-4-yl-5-phenyl thiophene and 2-terphenyl-4-yl-5-phenyl-1,3,4-oxadiazole, exhibit more stable enantiotropic liquid crystalline phases. The hockey stick-shaped mesogens exhibit a smectic phase as well as a nematic phase. High-temperature X-ray determination of the smectic layer spacing gives an unambiguous picture of interdigitated, bilayerlike supramolecular architecture in the smectic phase. There are associated changes in the mesogen's electrostatic profile when a heterocycle is introduced into the quinquiphenylene framework (e.g., conjugation is perturbed). Our findings suggest that steric packing considerations dominate the phase preferences (nematic versus smectic phases). However, electronic considerations (conjugation) appear to control the range of mesomorphism in this new family of nonlinear liquid crystals

Structure of Hydrated Poly(d,l-lactic acid) Studied with X-ray Diffraction and Molecular Simulation Methods

The effect of hydration on the molecular structure of amorphous poly­(d,l-lactic acid) (PDLLA) with 50:50 L-to-D ratio has been studied by combining experiments with molecular simulations. X-ray diffraction measurements revealed significant changes upon hydration in the structure functions of the copolymer. Large changes in the structure functions at ∼10 days of incubation coincided with the large increase in the water uptake from ∼1 to ∼40% and the formation of voids in the film. Computer modeling based on the recently developed TIGER2/TIGER3 mixed sampling scheme was used to interpret these changes by efficiently equilibrating both dry and hydrated models of PDLLA. Realistic models of bulk amorphous PDLLA structure were generated as demonstrated by close agreement between the calculated and the experimental structure functions. These molecular simulations were used to identify the interactions between water and the polymer at the atomic level including the change of positional order between atoms in the polymer due to hydration. Changes in the partial O–O structure functions, about 95% of which were due to water–polymer interactions, were apparent in the radial distribution functions. These changes, and somewhat smaller changes in the C–C and C–O partial structure functions, clearly demonstrated the ability of the model to capture the hydrogen-bonding interactions between water and the polymer, with the probability of water forming hydrogen bonds with the carbonyl oxygen of the ester group being about 4 times higher than with its ether oxygen

Molecular, Crystalline, and Lamellar Length-Scale Changes in the Poly(l‑lactide) (PLLA) during Cyclopentanone (CPO) Desorption in PLLA/CPO Cocrystals

Polymer–solvent complexes, poly­(l-lactide) (PLLA) with cyclopentanone (CPO), were studied at multiple length scales using differential scanning calorimetry, small-angle neutron scattering, Fourier transform infrared spectroscopy, and temperature-dependent wide- and small-angle X-ray scattering. PLLA crystallizes in the ε form when organic solvents such as CPO are incorporated into the crystal lattice at subambient temperatures. The transformation of this structure into the α form during solvent desorption and the accompanying changes in the lamellar structure were followed by various measurements on PLLA/CPO cocrystals. SANS data suggest that CPO is present stoichiometrically in the crystal lattice and as clusters in the interlamellar amorphous regions in the nominally dried samples. DSC thermogram showed a sharp endotherm during this ε to α transition. X-ray fiber diagrams showed that the ε form transforms to the α form over a temperature range (40–55 °C) as the solvent molecules are expelled from the crystalline lattice, while maintaining chain orientation. Infrared spectra showed the splitting of the CH₃ symmetric deformation band at 1383 cm^–1 into a doublet (1382 and 1386 cm^–1) at ε to α transition, indicating the desorption of CPO molecules from the crystal lattice. Changes in the invariant in SAXS data are interpreted as due to the migration of the solvent from the crystalline phase to the amorphous phase during the ε to α transition followed by the evaporation of the solvent from the entire polymer. During this transition, lamellae that are tilted in the presence of CPO in the crystal lattice become perpendicular to the chain axis. In addition, there are changes in long period, lamellar thickness, and amorphous thickness. Continuing the desorption to dryness by further heating results in the removal of the solvent molecules in the amorphous phase of the α form. This is accompanied by increased crystallinity. These studies show that the solvent desorption results in a precise sequence of quantifiable structural changes at multiple length scales

Temperature-Activated PEG Surface Segregation Controls the Protein Repellency of Polymers

Poly­(ethylene glycol) (PEG) is widely used to modulate the hydration states of biomaterials and is often applied to produce nonfouling surfaces. Here, we present X-ray scattering data, which show that it is the surface segregation of PEG, not just its presence in the bulk, that makes this happen by influencing the hydrophilicity of PEG-containing substrates. We demonstrate a temperature-dependent trigger that transforms a PEG-containing substrate from a protein-adsorbing to a protein-repelling state. On films of poly­(desaminotyrosyl-tyrosine-co-PEG carbonate) with high (20 wt %) PEG content, in which very little protein adsorption is expected, quartz crystal microbalance data showed significant adsorption of fibrinogen and bovine serum albumin at 8 °C. The surface became protein-repellent at 37.5 °C. When the same polymer was iodinated, the polymer was protein-adsorbent, even when 37 wt % PEG was incorporated into the polymer backbone. This demonstrates that high PEG content by itself is not sufficient to repel proteins. By inhibiting phase separation either with iodine or by lowering the temperature, we show that PEG must phase-separate and bloom to the surface to create an antifouling surface. These results suggest an opportunity to design materials with high PEG content that can be switched from a protein-attractant to a protein-repellent state by inducing phase separation through brief exposure to temperatures above their glass transition temperature

Structure of Biodegradable Films at Aqueous Surfaces: X‑ray Diffraction and Spectroscopy Studies of Polylactides and Tyrosine-Derived Polycarbonates

Three representative polymers of increasing modulus, poly­(d,l-lactic acid), PDLLA, poly­(desaminotyrosyl-tyrosine ethyl ester carbonate), PDTEC, and the same polymer with iodinated DTE segments, PI₂DTEC, were characterized by surface-pressure versus area (Π–<i>A</i>) isotherms and surface sensitive X-ray diffraction techniques. Films of 10–100 Å thickness were prepared for these studies by spreading dilute polymer solutions at air–water interfaces. The general properties of the isotherms and the Flory exponents, determined from the isotherms, vary in accordance with the increasing modulus of PDLLA, PDTEC, PI₂DTEC, respectively. The analysis of in situ X-ray reflectivity and grazing incidence X-ray diffraction (GIXD) measurements from films at aqueous surfaces provides a morphological picture that is consistent with the modulus of the polymers, and to a large extent, with their packing in their dry-bulk state. Large absorption of X-rays by iodine enabled X-ray spectroscopic studies under near-total-reflection conditions to determine the iodine distribution in the PI₂DTEC film and complement the structural model derived from reflectivity and GIXD. These structural studies lay the foundation for future studies of polymer–protein interactions at aqueous interfaces

Iodination of PEGylated Polymers Counteracts the Inhibition of Fibrinogen Adsorption by PEG

Poly(ethylene glycol), PEG, known to inhibit protein adsorption, is widely used on the surfaces of biomedical devices when biofilm formation is undesirable. Poly(desaminotyrosyl-tyrosine ethyl ester carbonate), PDTEC, PC for short, has been a promising coating polymer for insertion devices, and it has been anticipated that PEG plays a similar role if it is copolymerized with PC. Earlier studies show that no fibrinogen (Fg) is adsorbed onto PC polymers with PEG beyond the threshold weight percentage. This is attributed to the phase separation of PEG. Further, iodination of the PC units in the PC polymer, (I2PC), has been found to counteract this Fg-repulsive effect by PEG. In this study, we employ surface-sensitive X-ray techniques to demonstrate the surface affinity of Fg toward the air–water interface, particularly in the presence of self-assembled PC-based film, in which its constituent polymer units are assumed to be much more mobile as a free-standing film. Fg is found to form a Gibbs monolayer with its long axis parallel to the aqueous surface, thus maximizing its interactions with hydrophobic interfaces. It influences the amount of insoluble, surface-bound I2PC likely due to the desorption of the formed Fg–I2PC complex and/or the penetration of Fg onto the I2PC film. The results show that the phase behavior at the liquid–polymer interface shall be taken into account for the surface behavior of bulk polymers surrounded by tissue. The ability of PEG units rearranging into a protein-blocking layer, rather than its mere presence in the polymer, is the key to antifouling characteristics desired for polymeric coating on insertion devices

Wholly Aromatic Ether-imides. Potential Materials for n-Type Semiconductors

We report on the synthesis and characterization of a series of low molar mass, high aspect ratio ether-imide compounds. All ether-imides were obtained by terminating the appropriate dianhydride, that is, pyromellitic dianhydride (PMDA), 1,4,5,8-naphthalenetetra-carboxylic dianhydride (NDA), 3,3‘,4,4‘-biphenyltetracarboxylic dianhydride (BPDA), and 3,3‘,4,4‘-oxydiphthalic dianhydride (ODPA), with three flexible aryl-ether tails of different chain lengths. Increasing the number of meta-substituted aryl-ether units reduces the melt transition temperatures and at the same time increases the solubility of the ether-imides. When the flexibility of the dianhydride moiety increases, the thermal behavior of the compounds becomes significantly more complex:  The BPDA- and ODPA-based compounds form glasses and exhibit multiple crystal phases. Most compounds form isotropic melts upon heating; however, 2,7-bis(-4-phenoxy-phenyl)-benzo[lmn][3,8]phenanthroline-1,3,6,8-tetraone (NDA-n0) displays a smectic A (SA)-type texture when cooled from the isotropic phase, followed by what appears to be a smectic phase with a columnar arrangement of the mesogens inside the layers. Single-crystal X-ray diffraction analysis and cyclic voltammetry experiments indicate that the wholly aromatic ether-imides NDA and BPDA could be excellent candidates for n-type semiconductor applications

Self-Assembly of Left- and Right-Handed Molecular Screws

Stereoselectivity is a hallmark of biomolecular processes from catalysis to self-assembly, which predominantly occur between homochiral species. However, both homochiral and heterochiral complexes of synthetic polypeptides have been observed where stereoselectivity hinges on details of intermolecular interactions. This raises the question whether general rules governing stereoselectivity exist. A geometric ridges-in-grooves model of interacting helices indicates that heterochiral associations should generally be favored in this class of structures. We tested this principle using a simplified molecular screw, a collagen peptide triple-helix composed of either l- or d-proline with a cyclic aliphatic side chain. Calculated stabilities of like- and opposite-handed triple-helical pairings indicated a preference for heterospecific associations. Mixing left- and right-handed helices drastically lowered solubility, resulting in micrometer-scale sheet-like assemblies that were one peptide-length thick as characterized with atomic force microscopy. X-ray scattering measurements of interhelical spacing in these sheets support a tight ridges-in-grooves packing of left- and right-handed triple helices