Formation, isolation and characterization of an AB-biaryl atropisomer of oritavancin

Oritavancin is a semi-synthetic glycopeptide antibiotic which is structurally related to vancomycin. When oritavancin bisphosphate is dried in vacuo with heat, a new compound forms. This new compound is stable only in the solid state and reverts to oritavancin in solution. Highly enriched samples of this compound were obtained by preparative HPLC and the structure of this compound was elucidated by using one and two-dimensional (¹H and ¹³C) NMR spectroscopy in conjunction with computer-assisted molecular modeling. It has been determined that oritavancin adopts a conformation similar to that of vancomycin in solution, while the new compound is the unnatural R-AB-biaryl atropisomer of oritavancin. This is the first observation and isolation of an AB-biaryl atropisomer in an intact member of the vancomycin family of glycopeptide antibiotics.     

Ring resonators with N × M couplers

Multiple-zero multiple-pole optical filter transfer functions may be implemented more efficiently in an integrated optics architecture if higher order N × M optical couplers are utilized. For example, a coherent ring resonator made from two 3×3 couplers offers some advantages over the three mirror Fabry-Perot etalon, which is its analog. To this end we develop the formalism for obtaining the transfer functions and scattering matrices of ring resonators made from two N × M couplers. We then present a methodology for analyzing serial and parallel systems of N × M optical coupler ring resonators.     

Effect of reaction conditions on the molecular weight and polydispersity of linear poly(arylene ether phosphine oxide)s prepared from an AB monomer

A thorough study of the polymerization behavior of 4‐fluoro‐4′‐hydroxytriphenyl‐phosphine oxide, 2 , under nucleophilic aromatic substitution reactions has been carried out. The synthesis of 2 was achieved in excellent yields by the reaction of bis(4‐fluorophenyl)phenylphosphine oxide, 1 , with one equivalent of potassium hydroxide in DMSO/water. The structure and purity of 2 were confirmed via ¹H, ¹³C, and ³¹P NMR spectroscopy along with elemental analysis. Polymerization reactions of 2 in NMP or DMSO at 180 °C provided the corresponding linear poly(arylene ether phosphine oxide)s, PAEPOs, with number average molecular weights, M_n, ranging from 11,700 to 36,500 Da. All of the polymer samples were completely soluble in chloroform, tetrahydrofuran, DMSO, NMP, and DMAc. The polymerization reactions were accompanied by a competing intramolecular process that resulted in the formation of cyclic oligomeric species that were removed via a final precipitation from methanol. Analysis using ³¹P NMR spectroscopy and size exclusion chromatography (SEC) confirmed that the majority of the lower molecular weight cyclic species were removed via this process. The polymer samples formed tough films when chloroform solutions were slowly evaporated on a glass slide. The PAEPO samples prepared in this study exhibited excellent thermal stability with T_d (5%) values between 503 and 542 in air while the glass transition temperatures ranged from 223 to 237 °C. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2099–2106, 2006     

How electrons guard the space: shape optimization with probability distribution criteria

Efficient formulas for computing the probabilities of finding exactly electrons in an arbitrarily chosen volume ³ for Hartree–Fock wavefunctions are presented. These formulas allow the use of shape optimization techniques, such as level set methods, for optimizing with respect to various criteria involving such probabilities. The criterion defined as the difference between the Hartree–Fock and the independent-particle model probabilities of finding electrons in stresses the quantum effects due to the Pauli principle. We have implemented a 2D level set method for optimizing this criterion in order to study spatial separation of electron pairs in linear molecules. The method is described and the illustrative example of the BH molecule is reported.Contribution to the Jacopo Tomasi Honorary Issue     

Investigating the interface of superhydrophobic surfaces in contact with water

Neutron reflectivity (NR) is used to probe the solid, liquid, vapor interface of a porous superhydrophobic (SH) surface submerged in water. A low-temperature, low-pressure technique was used to prepare a rough, highly porous organosilica aerogel-like film. UV/ozone treatments were used to control the surface coverage of hydrophobic organic ligands on the silica framework, allowing the contact angle with water to be continuously varied over the range of 160 degrees (superhydrophobic) to <10 degrees (hydrophilic). NR shows that the superhydrophobic nature of the surface prevents infiltration of water into the porous film. Atomic force microscopy and density functional theory simulations are used in combination to interpret the NR results and help establish the location, width, and nature of the SH film-water interface.