Synthesis of some heterocyclic systems from nucleophilic substitution reactions with η6-o-dichlorobenzene-η5-cyclopentadienyliron hexafluorophosphate

A method for the synthesis of heterocylic systems related to 9,10-dihydroanthracene with two hetero-atoms at the 9,10-positions is described. It involves the nucleophilic substitution reaction of η⁶-o-dichlorobenzene-η⁵-cyclopentadienyliron hexafluorophosphate with two nucleophilic groups (OH, SH and/or NH₂) located in the 1,2-positions of a benzene ring to give a cyclopentadienyliron complexed heterocycle. Upon pyrolytic sublimation of the complex, the free heterocyclic compound is then obtained.     

Transformation of aminoacyl tRNAs for the in vitro selection of "drug-like" molecules

Evolutionary approaches are regularly used to isolate single molecules with desired activities from large populations of nucleic acids (approximately 10(15)). Several methods have also been developed to generate libraries of mRNA-encoded peptides and proteins for the in vitro selection of functional polypeptides. In principal, such mRNA encoding systems could be used with libraries of nonbiological polymers if the ribosome can be directed to polymerize tRNAs carrying unnatural amino acids. The fundamental problem is that current chemical aminoacylation systems cannot easily produce sufficient amounts of the numerous misacylated tRNAs required to synthesize a complex library of encoded polymers. Here, we show that bulk-aminoacylated tRNA can be transformed into N-monomethylated aminoacyl tRNA and translated. Because poly-N-methyl peptide backbones are refractory to proteases and are membrane permeable, our method provides an uncomplicated means of evolving novel drug candidates.     

Synthesis of some heterocyclic skeletons via organoiron complexes. Crystal and molecular structure of (5a,6,7,8,9,9a-η6-1,4-benzoxathiino[3,2-b]pyridine)(η5-cyclopentadienyl)iron hexafluorophosphate

Synthesis of the heterocyclic skeletons of some biologically active compounds from (η⁶-o-dichlorobenzene)(η⁵-cyclopentadienyrl)iron hexafluorophosphate in a two step procedure is described. Cyclopentadienyliron hexafluorophosphate complexes of 1,4-benzodioxino[2,3-b]pyridine, 1,4-benzoxathiino[3,2-b]pyridine, 10H-pyrido[3,2-b]benzoxazine, benzo[b]naphtho[2,3-e][1,4]dioxin, 4-methylbenzo[b]benzopyran-2-one[7,6-e][1,4]dioxin and benzo[b]anthracen-9,10-diono[1,2-e][1,4]dioxin were isolated and characterized. Upon pyrolytic sublimation of these complexes the free heterocycles were obtained and characterized. (η⁶-1,4-Benzoxathiino[3,2-b]pyridine)(η⁵-cyclopentadienyl)iron hexafluorophosphate crystalizes in the orthothombic system, space group Pbca; the dihedral angle between the planes of outer rings was found to be 176.8 (1).     

Superlight small bipolarons in the presence of a strong Coulomb repulsion

We study a lattice bipolaron on a staggered triangular ladder and triangular and hexagonal lattices with both long-range electron-phonon interaction and strong Coulomb repulsion using a novel continuous-time quantum Monte Carlo algorithm to solve the two-particle Coulomb-Fr?hlich model. The algorithm is preceded by an exact integration over phonon degrees of freedom, and as such is extremely efficient. The bipolaron effective mass and radius are computed. Bipolarons on lattices constructed from triangular plaquettes have a novel crablike motion, and are small but very light over a wide range of parameters. We discuss the conditions under which such particles may form a Bose-Einstein condensate with high transition temperature, proposing a route to room temperature superconductivity.     

Following the cat: A preface for the next three papers

The three papers to follow, by Chris Rasmussen and three of his students, build from a task design the authors of this note developed in the 1990s. To introduce these papers, which extend our prior work in new directions, we sketch some background here.     

Erratum to: Determination of metal ion content of beverages and estimation of target hazard quotients: a comparative study

This is a correction to the following paper: Hague T, Petroczi A, Andrews PR, Barker J, Naughton DP: Determination of metal ion content of beverages and estimation of target hazard quotients: a comparative study. Chem Central J 2008, 2:13.     

Connecting mem-models with classical theories

A family of mem-models, including the mem-dashpots, mem-springs, and most recently, mem-inerters, is emerging as a new and powerful way of capturing complex nonlinear behaviors of materials and systems under various types of dynamic loads involving different frequency, amplitude, and loading histories (e.g., hysteresis). Under the framework of nonlinear state-space representation and hybrid dynamical systems, mem-springs may be formulated to effectively represent an inherent degradation of material state. It is shown in this study, for the first time, how the absement (time integral of strain/displacement), a signature state variable for a mem-spring, can be connected with the damage variable, a key quantity in continuum damage mechanics. The generalized momentum (time integral of stress), on the other hand, is shown to be efficient in modeling strain ratcheting via the concept of mem-dashpot. It is also shown in this study, for the first time, how two formulations of the memcapacitive system models (for mem-springs) are special cases of the Preisach model.

     

Shape Matters: A Gold Nanoparticle Enabled Shape Memory Polymer Triggered by Laser Irradiation

With incorporation of gold nanoparticles, i.e., nanorods (AuNR) and nanospheres (AuNS), into a polyurethane‐based shape‐memory polymer (SMP) EG‐72D matrix, SMP nanocomposite films capable of being remotely triggered by low‐power laser are fabricated and characterized using UV‐vis‐NIR spectroscopy, X‐ray scattering, and dynamic mechanical analysis (DMA). It is demonstrated that, with incorporation of very low concentration of gold nanorods (≈0.1 wt%), the mechanically programmed EG‐72D/AuNR nanocomposite presents rapid response to low power laser irradiation (785 nm, ≈10 mW). Comparative studies on the laser irradiation response of EG‐72D/AuNS and EG‐72D/AuNR nanocomposite films suggest that AuNRs have significantly higher photothermal conversion efficiency than AuNS and on‐resonance laser irradiation, matching the wavelength of the incident laser with the longitudinal plasmon resonance of AuNR, is necessary to induce the fast response of gold nanoparticle enabled SMP nanocomposites.