Preparation and characterization of polypropylene and waste tire powder modified by allylamine blends

Waste tire powder subjected to allylamine modification in the presence of ultraviolet (UV) radiation has been used to prepare polypropylene based thermoplastic vulcanizates with maleic anhydride polypropylene (MA‐PP) as compatibilizer. The effect of increasing the concentration of MA‐PP on performance characteristics like tensile strength, elongation and rheological properties have been investigated. X‐ray diffraction studies of the PP/waste tire powder blend indicate the disappearance of β crystalline peaks on addition of waste tire powder in the PP, whereas it is observed in the allylamine modified rubber powder loaded PP. Differential scanning calorimetry results further supported the above fact. The improvement in mechanical properties of the PP/allylamine modified rubber powder loaded thermoplastic vulcanizates has been explained in terms of βα transformation of PP crystals during straining of the samples and uniform dispersion of allylamine coated rubber powder in the PP matrix. The melt rheological properties of the thermoplastic vulcanizates loaded with modified rubber powder are higher than its counterpart due to the higher dispersion as a result of chemical interaction between the rubber powder surface with the MA‐PP. Copyright © 2008 John Wiley & Sons, Ltd.     

3,4-dimethylbenzyl radical formed in a corona discharge of 1,2,4-trimethylbenzene

A precursor, 1,2,4-trimethylbenzene, seeded in a large amount of an inert carrier gas, helium, was electrically discharged in a corona-excited supersonic expansion using a pinhole-type glass nozzle. The blue-green colored fluorescence emanating from the downstream jet was recorded with a long path monochromator to observe the vibronic emission spectrum of the benzyl-type radical formed. Analysis of the spectrum suggests that the most dominant product of the corona discharge is the 3,4-dimethylbenzyl radical formed by extracting a hydrogen atom from the methyl group at the 4-position. The electronic energies of the D1 and D2 states and the vibrational mode frequencies of the 3,4-dimethylbenzyl radical were accurately obtained for the first time by comparison with those from an ab initio calculation as well as those of the known vibrational mode frequencies of the precursor.     

Metal ion sensing novel calix[4]crown fluoroionophore with a two-photon absorption property

1,3-Alternate calix[4]arene-based fluorescent chemosensors bearing two-photon absorbing chromophores have been synthesized, and their sensing behaviors toward metal ions were investigated via absorption band shifts as well as one- and two-photon fluorescence changes. Free ligands absorb the light at 461 nm and weakly emit their fluorescence at 600 nm when excited by UV-vis radiation at 461 nm, but no two-photon excited fluorescence is emitted by excitation at 780 nm. Addition of an Al(3+) or Pb(2+) ion to a solution of the ligand causes a blue-shifted absorption and enhanced fluorescence due to a declined resonance energy transfer (RET) upon excitation by one- and two-photon processes. Addition of a Pb(2+) ion to a solution of 1.K(+) results in a higher fluorescence intensity than the original 1.Pb(2+) complex regardless of one- or two-photon excitation, due to the allosteric effect induced by the complexation of K(+) with a crown loop.     

Electrical conduction through linear porphyrin arrays

Electrical conduction measurements were made on two extreme types of directly linked porphyrin arrays by using nanoelectrodes. One type is the directly linked Zn(II)porphyrin arrays, consisting of 48 Zn(II)porphyrin moieties (Z48), and the other type is the completely flat, tape-shaped Zn(II)porphyrin arrays, consisting of eight Zn(II)porphyrin units (T8). The I-V curve for Z48 exhibits the diode-like behavior and the hysteresis depending on the voltage sweep direction presumably due to the conformational heterogeneity arising from the dihedral angle distribution in Z48. On the other hand, the I-V curve for T8 is nearly symmetric without any hysteresis, leading to the higher conductivity and the smaller band gap. These results illustrate that the stronger pi-electron conjugation in T8, as compared with that of Z48, results in better electrical conduction.     

Sensitivity analysis in vector optimization

For a vector optimization problem that depends on a parameter vector, the sensitivity analysis of perturbation, proper perturbation, and weak perturbation maps is dealth with. Each of the perturbation maps is defined as a set-valued map which associates to each parameter value the set of all minimal, properly minimal, and weakly minimal points of the perturbed feasible set in the objective space with respect to a fixed ordering cone. Using contingent cones in a finite-dimensional Euclidean space, we investigate the relationship between the contingent derivatives of the three types of perturbation maps and three types of minimal point sets for the contingent derivative of the feasible-set map in the objective space. These results provide quantitative informations on the behavior of the perturbation maps.The authors would like to thank the referees for their valuable comments and suggestions.     

A new catalyst layer based on in situ pore generation of sulfonated poly(ether ether ketone) for PEMFC

A new concept of in situ pore generation to reduce water flooding in cathode catalyst layer (CCL) of polymer electrolyte membrane fuel cell (PEMFC) is proposed with the introduction of water soluble poly(ethylene glycol) (PEG) as a porogen to CCL based on sulfonated poly(ether ether ketone) (sPEEK). In this new type of CCL, PEG is directly removed by water produced during the cathode reaction. The new CCL exhibited much higher cell performance especially in mass transport limitation region compared to the pristine sPEEK-CCL. In addition, the presence of PEG in the new CCL lowered the glass transition temperature of the sPEEK binder, and it could improve the transference of catalyst layer onto the polymer electrolyte membrane.     

Direct observation of localized defect States in semiconductor nanotube junctions

We report scanning tunneling microscopy of semiconductor-semiconductor carbon nanotube junctions with different band gaps. Characteristic features of the wave functions at different energy levels, such as a localized defect state, are clearly exhibited in the atomically resolved scanning tunneling spectroscopy. The peaks of the Van Hove singularity on each side penetrate and decay into the opposite side across the junction over a distance of approximately 2 nm. These experimental features are accounted for, with the help of tight-binding calculation, by the presence of pentagon-heptagon pair defects at the junction.     

Electronic properties of Gd@C<Subscript>82</Subscript> metallofullerene peapods: (Gd@C<Subscript>82</Subscript>)<Subscript>n</Subscript>@SWNTs

Electronic properties of Gd@C₈₂ metallofullerene peapods, (Gd@C₈₂)_n@SWNTs, were investigated by electron energy-loss spectroscopy (EELS), scanning tunneling microscopy and spectroscopy (STM/STS), and field-effect transistor (FET) transport measurements. The results indicate that the electronic structure of Gd@C₈₂ metallofullerene peapods is completely different from that of intact single-walled nanotubes (SWNTs). For example, Gd@C₈₂-peapod-FETs show ambipolar behavior which is not observed in the empty SWNT-FETs under our experimental conditions. Furthermore, in semiconducting nanotubes the band gap can be varied from ∼0.5 to ∼0.1 eV using inserted Gd@C₈₂ endohedral metallofullerenes with a spatial periodicity of 1.1 to 8.0 nm, depending on the density of the fullerenes. The present findings suggest that metallofullerene peapods may point the way toward novel electronic devices. Received: 6 September 2002 / Accepted: 25 October 2002 / Published online: 10 March 2003 RID="*" ID="*"Corresponding author. Fax: +81-52/789-1169, E-mail: noris@cc.nagoya-u.ac.jp     

An excimer-based, binuclear, on-off switchable calix[4]crown chemosensor

A new fluorescent chemosensor with two different types of cation binding sites on the lower rims of a 1,3-alternate calix[4]arene (1) is synthesized. Two pyrene moieties linked to a cation recognition unit composed of two amide groups form a strong excimer in solution. For 1, the excimer fluorescence is quenched by Pb2+, but revived by addition of K+ to the Pb2+ ligand complex. Thus, metal ion exchange produces an on-off switchable, fluorescent chemosensor. Computational results show that the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbitals (LUMO) of the two pyrene moieties interact under UV irradiation of 1 and its K+ complex, while such HOMO-LUMO interactions are absent in the Pb2+ complex.