Conformational control via sequence for a heteropeptoid in water: coupled NMR and Rosetta modelling.

We report a critical advance in the generation and characterization of peptoid hetero-oligomers. A library of sub-monomers with amine and carboxylate side-chains are combined in different sequences using microwave-assisted synthesis. Their sequence-structure propensity is confirmed by circular dichroism, and conformer subtypes are enumerated by NMR. Biasing the ψ-angle backbone to trans (180°) in Monte Carlo modelling favors i to i + 3 naphthyl-naphthyl stacking, and matches experimental ensemble distributions. Taken together, high-yield synthesis of heterooligomers and NMR with structure prediction enables rapid determination of sequences that induce secondary structural propensities for predictive design of hydrophilic peptidomimetic foldamers and their future libraries.

Computational screening of organic polymer dielectrics for novel accelerator technologies.

The use of infrared lasers to power accelerating dielectric structures is a developing area of research. Within this technology, the choice of the dielectric material forming the accelerating structures, such as the photonic band gap (PBG) structures, is dictated by a range of interrelated factors including their dielectric and optical properties, amenability to photo-polymerization, thermochemical stability and other target performance metrics of the particle accelerator. In this direction, electronic structure theory aided computational screening and design of dielectric materials can play a key role in identifying potential candidate materials with the targeted functionalities to guide experimental synthetic efforts. In an attempt to systematically understand the role of chemistry in controlling the electronic structure and dielectric properties of organic polymeric materials, here we employ empirical screening and density functional theory (DFT) computations, as a part of our multi-step hierarchal screening strategy. Our DFT based analysis focused on the bandgap, dielectric permittivity, and frequency-dependent dielectric losses due to lattice absorption as key properties to down-select promising polymer motifs. In addition to the specific application of dielectric laser acceleration, the general methodology presented here is deemed to be valuable in the design of new insulators with an attractive combination of dielectric properties.

Morphological and performance measures of polyurethane foams using X-ray CT and mechanical testing.

Meso-scale structure in polymeric foams determines the mechanical properties of the material. Density variations, even more than variations in the anisotropic void structure, can greatly vary the compressive and tensile response of the material. With their diverse use as both a structural material and space filler, polyurethane (PU) foams are widely studied. In this manuscript, quantitative measures of the density and anisotropic structure are provided by using micro X-ray computed tomography (microCT) to better understand the results of mechanical testing. MicroCT illustrates the variation in the density, cell morphology, size, shape, and orientation in different regions in blown foam due to the velocity profile near the casting surface. "Interrupted" in situ imaging of the material during compression of these sub-regions indicates the pathways of the structural response to the mechanical load and the changes in cell morphology as a result. It is found that molded PU foam has a 6 mm thick "skin" of higher density and highly eccentric morphological structure that leads to wide variations in mechanical performance depending upon sampling location. This comparison is necessary to understand the mechanical performance of the anisotropic structure.

Shear-induced metastable states of end-grafted polystyrene.

The in situ molecular scale response of end-grafted polystyrene to shear against a deuterated polystyrene melt was investigated with neutron reflectometry. The derived grafted polystyrene density profiles showed that the grafted polystyrene was retained on the quartz wafer during the measurements. The profiles suggested that the end-grafted polystyrene response to shear results in a series of metastable states, rather than equilibrium states assumed in the current theory. Except for some possible extension and/or contraction of the grafted polystyrene with shear, there was no obvious correlation between the grafted polymer structure and the shear thinning behavior observed in these samples.

The Los Alamos Neutron Science Center neutron rheometer in the cone and plate geometry to examine tethered polymers/polymer melt interfaces via neutron reflectivity.

Although several other neutron rheometers have been built to study soft matter under nonequilibrium conditions, none of them have the ability to measure the structure and behavior of the polymeric interfacial regions in highly viscous polymer melts which require high torques/high strain rates and high temperatures. A neutron rheometer in the cone and plate geometry has been constructed at the Los Alamos Neutron Science Center to rectify this lack of experimental instrumentation. It is also the first-of-its-kind to perform neutron reflectivity studies concurrently with rheological measurements. The details of both the development and testing of the Los Alamos Neutron Science Center neutron rheometer in the cone and plate configuration are described. Proof of principle neutron reflectivity results of end-grafted polystyrene against an identical melt under shear are presented, showing qualitatively that the structural attributes of the end-grafted polymer change when exposed to shear.

The Couette configuration of the Los Alamos Neutron Science Center neutron rheometer for the investigation of polymers in the bulk via small-angle neutron scattering.

A neutron rheometer in the Couette geometry has been built at the Los Alamos Neutron Science Center to examine the molecular steady-state and dynamic responses of entangled polymeric materials in the bulk under the application of shear stress via small-angle neutron scattering. Although similar neutron rheometers have been fabricated elsewhere, this new design operates under the extreme conditions required for measuring the structure and behavior of high molecular weight polymer melts. Specifically, the rheometer achieves high torques (200 N m) and shear rates (865 s(-1)) simultaneously, never before attainable with other neutron rheometers at temperatures up to 240 degrees C under an inert gas environment. The design of the instrument is such that relatively small sample sizes are required. The testing of the Los Alamos Neutron Science Center Neutron Rheometer in the Couette design both as a rheometer and in the small-angle neutron optical configuration on highly viscous polystyrene is presented. The observed anisotropic neutron scattering pattern of the polystyrene melt at a molecular weight above entanglement provides evidence that the conformation of the polymer chains are elongated in the direction of the melt flow, in agreement with the current theories concerning linear polymers in the bulk.

Convenient synthesis of 6,6-bicyclic malonamides: a new class of conformationally preorganized ligands for f-block ion binding.

A general synthetic approach was developed for the preparation of a series of 6,6-bicyclic malonamides, a class of ligands that provide a preorganized binding site for f-block ions (particularly trivalent lanthanides). The approach described is convenient to introduce a variety of functional groups at the amide nitrogens to tune the properties of the ligand without altering the preorganized binding. Each of the ten derivatives (that represent a range of functionality, including R = alkyl, hydroxy, phenyl, ester, perfluorocarbon) reported here derives from a single, readily prepared dialdehyde intermediate. This intermediate is converted to the final products via reductive amination with an appropriately functionalized benzylamine, followed by hydrogenolysis and lactam formation. Because derivatization occurs late in the synthesis, the approach is general, requiring only modification of the purification procedures for each new derivative. To aid in the purification of the bicyclic malonamides, we report a novel complexation-based purification method that takes advantage of the high affinity of the ligand for f-block metals.

Solution and structural investigations of ligand preorganization in trivalent lanthanide complexes of bicyclic malonamides.

This report describes an investigation into the coordination chemistry of trivalent lanthanides in solution and the solid state with acyclic and preorganized bicyclic malonamide ligands. Two experimental investigations were performed: solution binding affinities were determined through single-phase spectrophotometric titrations and the extent of conformational change upon binding was investigated with single-crystal X-ray crystallography. Both experimental methods compare the bicyclic malonamide (BMA), which is designed to be preorganized for binding trivalent lanthanides, to an analogous acyclic malonamide. Results from the spectrophotometric titrations indicate that BMA exhibits a 10-100x increase in binding affinity to Ln(III) over acyclic malonamide. In addition, BMA forms compounds with high ligand-metal ratios, even when competing with water and nitrate ligands for binding sites. The crystal structures exhibit no significant differences in the nature of the binding between Ln(III) and the BMA or acyclic malonamide. These results support the conclusion that rational ligand design can lead to compounds that enhance the binding affinities within a ligand class.

Deliberate design of ligand architecture yields dramatic enhancement of metal ion affinity.

Evaluation of the malonamide substructure with respect to binding site preorganization and complementarity for lanthanide metal ions suggests a new ligand architecture specifically designed to enhance lanthanide ion affinity. Consideration of conformational reorganization, restricted bond rotation, and donor group orientation suggests that typical malonamide structures, for example, N,N,N'N'-tetrahexylpropane-1,3-diamide (1), N,N'-dibutyl-N,N'-dimethyl-2-tetradecylpropane-1,3-diamide (2), or N,N,N'N'-tetramethylpropane-1,3-diamide (6), are poorly organized for metal ion complexation. Molecular mechanics analyses show that the unfavorable enthalpic and entropic terms are eliminated by the use of the novel bicyclic architecture found in 3,9-diaza-3,9-dimethylbicyclo[4.4.0]decane-2,10-dione (7). Diamide 7 was prepared, and the X-ray crystal structure of the complex [Eu(7)(2)(NO(3))(3)] exhibits the same chelate conformation predicted by the molecular mechanics model. A hydrophobic derivative, 3,9-diaza-3,9-dioctylbicyclo[4.4.0]decane-2,10-dione (8), was prepared, and solvent extraction studies reveal that the preorganized architecture of 8 gives a dramatic enhancement in binding affinity, exhibiting Eu(3+) distribution coefficients that are 7 orders of magnitude larger than a typical malonamide ligand, 1.