Basis set limit CCSD(T) harmonic vibrational frequencies

Benchmark, frozen-core CCSD(T) equilibrium harmonic vibrational frequencies of 12 closed-shell and five open-shell molecules are computed to within 1 cm-1 of the basis set limit using the explicitly correlated CCSD(T)-R12 method. The convergence of the standard CCSD(T) method with the one-particle basis sets of Dunning and co-workers is examined and found to be slow, with mean and maximum absolute errors of 1.3 and 3.5 cm-1 remaining at the cc-pV6Z level. Finite basis set effects do not appear to introduce systematic errors in equilibrium harmonic frequencies, and mean absolute errors reduce by a factor of 2 for each basis set cardinal number increment. The convergence of individual equilibrium harmonic frequencies is not guaranteed to be monotonic due to the associated shift in the equilibrium structure. The inclusion of computed scalar relativistic effects and previously available corrections for core-valence correlation and higher-order excitations in the cluster operator results in an agreement with experimentally derived harmonic frequencies of 0.1, 0.3, and -0.4 cm-1 for HF, N2, and CO, respectively. F2 continues to present a challenge to computational chemistry with an error of 3.2 cm-1, primarily resulting from the high basis set dependence of the quadruples contribution.     

Basis-set extrapolation techniques for the accurate calculation of molecular equilibrium geometries using coupled-cluster theory

To reduce remaining basis-set errors in the determination of molecular equilibrium geometries, a basis-set extrapolation (BSE) scheme is suggested for the forces used in geometry optimizations. The proposed BSE scheme is based on separating the Hartree-Fock and electron-correlation contributions and uses expressions obtained by straightforward differentiation of well established extrapolation formulas for energies when using basis sets from Dunning's hierarchy of correlation-consistent basis sets. Comparison with reference data obtained at the R12 coupled-cluster level [CCSD(T)-R12] demonstrates that BSE significantly accelerates the convergence to the basis-set limit, thus leading to improvements comparable to or even better than those obtained by increasing the cardinal number in the used basis set by one. However, BSE alone is insufficient to improve agreement with experiment, even after additional consideration of inner-shell correlation and quadruple-excitation effects (mean error and standard deviation with extrapolation are -0.014 and 0.047 pm in comparison with mean error and standard deviation of -0.002 and 0.036 pm without extrapolation). Improvement is obtained only when other contributions of similar magnitude as the BSE contributions (e.g., pentuple-excitation effects and relativistic effects) are also considered. A rather large discrepancy (of the order of a few tenths of a picometer) is observed for the F(2) molecule indicating an enhanced basis-set requirement for the various contributions in this case.     

Influence of lipid composition on membrane activity of antimicrobial phenylene ethynylene oligomers

Host defense peptides (HDPs), part of the innate immune system, selectively target the membranes of bacterial cells over that of host cells. As a result, their antimicrobial properties have been under intense study. Their selectivity strongly depends on the chemical and mostly structural properties of the lipids that make up different cell membranes. The ability to synthesize HDP mimics has recently been demonstrated. To better understand how these HDP mimics interact with bilayer membranes, three homologous antimicrobial oligomers (AMOs) 1-3 with an m-phenylene ethynylene backbone and alkyl amine side chains were studied. Among them, AMO 1 is nonactive, AMO 2 is specifically active, and AMO 3 is nonspecifically active against bacteria over human red blood cells, a standard model for mammalian cells. The interactions of these three AMOs with liposomes having different lipid compositions are characterized in detail using a fluorescent dye leakage assay. AMO 2 and AMO 3 caused more leakage than AMO 1 from bacteria membrane mimic liposomes composed of PE/PG lipids. The use of E. coli lipid vesicles gave the same results. Further changes of the lipid compositions revealed that AMO 2 has selectively higher affinity toward PE/PG and E. coli lipids than PC, PC/PG or PC/PS lipids, the major components of mammalian cell membranes. In contrast, AMO 3 is devoid of this lipid selectivity and interacts with all liposomes with equal ease; AMO 1 remains inactive. These observations suggest that lipid type and structure are more important in determining membrane selectivity than lipid headgroup charges for this series of HDP mimics.     

Water soluble poly(ethylene oxide) functionalized norbornene polymers

The synthesis of three different poly(ethylene oxide) macromonomers with a norbornene and oxanorbornene end group is presented. The macromonomers were polymerized to comb‐polymers by ring‐opening metathesis polymerization (ROMP) using Grubbs' Catalyst G3 to produce water soluble polymers with polydispersities between 1.04 and 1.30 and molecular weights between 14,000 and 50,000 g/mol. Characterization by static and dynamic light scattering reveals that the comb‐polymers with norbornene backbone are molecularly disperse in aqueous solution, while the oxanorbornene‐backbone polymers form small water‐soluble aggregates. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2640–2648, 2008     

Nanostructured block-random copolymers with tunable magnetic properties

It was recently shown that block copolymers (BCPs) produced room-temperature ferromagnetic materials (RTFMs) due to their nanoscopic ordering and the cylindrical phase yielded the highest coercivity. Here, a series of metal-containing block-random copolymers composed of an alkyl-functionalized homo block (C(16)) and a random block of cobalt complex- (Co) and ferrocene-functionalized (Fe) units was synthesized via ring-opening metathesis polymerization. Taking advantage of the block-random architecture, the influence of dipolar interactions on the magnetic properties of these nanostructured BCP materials was studied by varying the molar ratio of the Co units to the Fe units, while maintaining the cylindrical phase-separated morphology. DC magnetic measurements, including magnetization versus field, zero-field-cooled, and field-cooled, as well as AC susceptibility measurements showed that the magnetic properties of the nanostructured BCP materials could be easily tuned by diluting the cobalt density with Fe units in the cylindrical domains. Decreasing the cobalt density weakened the dipolar interactions of the cobalt nanoparticles, leading to the transition from a room temperature ferromagnetic (RTF) to a superparamagnetic material. These results confirmed that dipolar interactions of the cobalt nanoparticles within the phase-separated domains were responsible for the RTF properties of the nanostructured BCP materials.     

Biomimetic facially amphiphilic antibacterial oligomers with conformationally stiff backbones

A foldamer has been designed with a conformationally stiff backbone that is facially amphiphilic. The oligomer has excellent antimicrobial activity and was found to be 18 times more active toward bacterial cells than human red blood cells. The oligomer is built from arylamide bonds around a central 4,6-dicarboxy pyrimidine ring. The conformation was studied by X-ray crystallography and solution NMR spectroscopy. Density-functional (DFT) calculations were performed to guide the design. These calculations accurately predicted the overall conformation as well as NMR chemical shifts. Antibacterial activity was demonstrated against E. coli, a gram-negative strain, and B. subtilis, a gram-positive strain. The minimal inhibitory concentration is 0.8 microg/ml.     

Multiattribute electronic procurement using goal programming

One of the key challenges of current day electronic procurement systems is to enable procurement decisions transcend beyond a single attribute such as cost. Consequently, multiattribute procurement have emerged as an important research direction. In this paper, we develop a multiattribute e-procurement system for procuring large volume of a single item. Our system is motivated by an industrial procurement scenario for procuring raw material. The procurement scenario demands multiattribute bids, volume discount cost functions, inclusion of business constraints, and consideration of multiple criteria in bid evaluation. We develop a generic framework for an e-procurement system that meets the above requirements. The bid evaluation problem is formulated as a mixed linear integer multiple criteria optimization problem and goal programming is used as the solution technique. We present a case study for which we illustrate the proposed approach and a heuristic is proposed to handle the computational complexity arising out of the cost functions used in the bids.     

Atrp synthesis of abc lipophilic–hydrophilic–fluorophilic triblock copolymers

New ABC triblock copolymers that contain lipophilic, hydrophilic, and fluorophilic blocks are reported. These new block copolymers were synthesized via sequential controlled/living atom transfer radical polymerization. The formation of block copolymers was confirmed by size exclusion chromatography, ¹H, and ¹⁹F NMR. In direct comparison to the ABC copolymer, the corresponding ABA′ polymer did not produce a gel up to 45 wt % polymer. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2601–2608, 2007     

Gels based on cyclic polymers

Cyclic poly(5-hydroxy-1-cyclooctene) (PACOE) was synthesized by ring-expansion metathesis polymerization (REMP), and thiol-ene chemistry was used to cross-link the internal double bonds in the PACOE backbone. This created a novel network material (gels formed from cyclic polymers) with unique structural units, where the cyclic PACOE main chains, which serve as secondary topological cross-linkages, were connected by primary intermolecular chemical cross-linkages. The resulting properties were notably different from those of traditional chemically cross-linked linear PACOE gels, whose gel fraction (GF) and modulus (G) increased while the swelling ratio (Q) decreased with increasing initial polymer concentration in the gel precursor solution (C(0)). For the gels formed from cyclic polymers, however, the GF, Q, and G all simultaneously increased as C(0) increased at the higher range. Furthermore, at the same preparation state (same C(0)), the swelling ability and the maximum strain at break of the gels formed from cyclic polymers were always greater than those of the gels formed from linear polymers, and these differences became more pronounced as C(0) increased.