FLUORESCENCE ENERGY TRANSFER BETWEEN DIMETHYLDIAZAPEROPYRENIUM DICATION AND ETHIDIUM INTERCALATED IN POLY d(A-T)

Dimethyldiazaperopyrenium is one of the largest known DNA intercalators. Fluorescence energy transfer occurred between dimethyldiazaperopyrenium (donor) and ethidium (acceptor) when these dyes were bound to a double-stranded polynucleotide such as poly d(A-T). The addition of increasing amounts of ethidium bromide led to a marked shortening of the fluorescence lifetime of the donor, whereas the excited state of the acceptor was progressively populated via energy transfer from the donor. Critical Förster distance between these two chromophores was calculated to be 3.8 nm. The observed transfer efficiency was lower than that calculated on the basis of this critical distance and a statistical distribution of bound drugs. These results are discussed taking into account the conformational change induced by intercalation of dimethyldiazaperopyrenium in the double-stranded polynucleotide.     

The interaction of vinyl monomers and poly (ethylene terephthalate) in the presence of various initiators produces a physical mixture,not a graft copolymer

The interaction between poly(ethylene terephthalate) and four vinyl monomers, methacrylic acid, methyl methacrylate, styrene, and vinyl acetate, has been studied using hydrogen peroxide, benzoyl peroxide, azobisisobutyronitrile, and cobalt acetylacetonate as initiators. The ease of addition of the monomer to the polymer follows the solubility of the monomer in the polymer film. No chemical interaction occurs between the PET film and the monomer; rather, the monomer is homopolymerized within the film and forms a semi-interpenetrating network so that the two homopolymers cannot be separated unless the PET matrix is destroyed. © 1995 John Wiley & Sons, Inc.     

Anion complexation via C-H...X interactions using a palladacyclic receptor

A novel organometallic receptor binds anions in solution and in the solid state, with complexes stabilised through a series of C-HX interactions, as evidenced by 1H NMR spectroscopy, X-ray crystallography and computational models.     

High‐throughput method for estimating the time to sustained ignition of polystyrene–clay nanocomposites based on thermogravimetric analysis

Polymer‐modified clay nanocomposites were prepared by melt blending and the time to ignition was measured by cone calorimetry at various heat fluxes. Based on these experimental results, a critical mass flux and critical percentage mass loss (pml_crit) for piloted ignition were identified and validated for both virgin polystyrene and its composites, across a wide range of heating fluxes. Based on the assumption that the polymer degradation kinetics in the heating segment of the cone calorimetry (up to the moment of ignition) and thermogravimetry experiments are similar, and using the pml_crit, we hypothesized that the onset degradation temperature of the TGA samples (defined here as the temperature at pml_crit) could be used to estimate the time to sustained ignition in cone calorimetry experiments. The onset degradation temperature and the time to sustained ignition showed a good correlation, regardless of the heating flux used in cone calorimetry experiments. Copyright © 2009 John Wiley & Sons, Ltd.     

Design, synthesis, structure and properties of an α-helix cap template derived from N-[(2S)-2-chloropropionyl]-(2S)-Pro-(2R)-Ala-(2S,4S)-4-thioPro-OMe which initiates α-helical structures

A strategy based upon removing the requirement for all of the carbonyl dipoles to align at the same time in the transition state leading to the cyclisation of N-[(2S)-2-chloropropionyl]-(2S)-Pro-(2R)-Ala-(2S,4S)-4-thioPro-OMe to a Zimm-Bragg type α-helix peptide intitator template was successful. Each amide bond of the 12-membered macrocyclic template existed in the trans-rotomeric form. Derivatives of the template were prepared by extending the C-terminus and these were characterised by NMR spectroscopy and restrained simulated annealing. In deuterochloroform solution at low temperature, separate sets of NMR signals were observed for two rapidly interconverting helical conformational isomers of the thioether macrocycle which possessed an appended trialkylammonium ion. A similar time-averaged conformation was also observed in aqueous solution. At −80 °C in d₂-dichloromethane the rate of conformational exchange was slowed sufficiently to obtain resonance assignments and NOE data separately for each isomer. In the minor isomer (40%), the four carbonyl oxygen hydrogen-bond acceptors of the template are aligned in an α-helical conformation and in the major conformer the Pro² carbonyl dipole was anti-aligned with the other three dipoles. Thus, the conformers differ in the orientation of one carbonyl group. Molecular modelling calculations showed that the minor isomer was stabilised by coulombic interactions between the trialkylammonium salt and the carbonyl group dipole moments.     

Kraus decomposition for chaotic environments including time-dependent subsystem Hamiltonians

We derive an exact and explicit Kraus decomposition for the reduced density of a quantum system simultaneously interacting with time-dependent external fields and a chaotic environment of thermodynamic dimension. We test the accuracy of the Kraus decomposition against exact numerical results for a CNOT gate performed on two qubits of an (N+2) qubit statically flawed isolated quantum computer. Here the N idle qubits comprise the finite environment. We obtain very good agreement even for small N.     

Influence of surface conditions on thermal positron reemission spectra from W(100)

Our measurements trace the temporal dependence of positron reemission spectral features, namely, the reemission intensity, energy and angular distributions with post-cleaning time and oxygen exposure. The unwanted inelastic component in the reemission spectra can be kept at less than 6 % of the total reemitted positrons during long and continuous operation by simply ensuring the cleanliness of the sample with better vacuum level. Simultaneously the other optimized spectral features of the beam can be maintained except for the reemission spectral intensity which decreased with increasing time after cleaning. Even though oxygen at high temperature is used normally in the cleaning process of the tungsten moderators, exposure of the sample to oxygen at room temperature caused an exponential reduction in the reemission yield with exposure time.     

Thermal stability and flammability characteristics of ethylene vinyl acetate (EVA) composites blended with a phenyl phosphonate-intercalated layered double hydroxide (LDH), melamine polyphosphate and/or boric acid

A phenyl phosphonate-intercalated MgAl-LDH (MgAl-PPh), melamine polyphosphate (MP), and boric acid (BA) were independently and concomitantly added to neat ethylene vinyl acetate (EVA) copolymer at loading fractions of 10% (w/w). The structural morphology of MgAl-PPh was established via powder X-ray diffraction (PXRD) and scanning electron microscopy (SEM) while the presence of phenyl phosphonate in the galleries was confirmed by Fourier transform infrared (FTIR). Thermogravimetric analysis (TGA) and cone calorimetry were used to evaluate the thermal stability and flammability behavior of EVA and its composites. While time-to-ignition is greatly reduced for EVA composites compared to the virgin polymer, there are remarkable reductions in the peak heat release rate (PHRR) which relates to a reduction in flame intensity. Synergistic effects were observed in cone calorimetry for the formulation containing MgAl-PPh, MP, and BA.