Conjugated polymers in an arene sandwich

A series of poly(p-arylene butadiynylene)s containing zero, one, and two co-facial pi-pi interactions per repeat unit were synthesized and characterized. A surprisingly selective and high-yielding Diels-Alder cycloaddition of anthracene and nonsymmetric, sterically hindered anhydrides proved essential to generating the cofacial arene-containing monomers. Single-crystal X-ray structures display nearly parallel cofacial arenes that are within the van der Waals contact distances. The precursor molecules with cofacial arenes undergo reversible one- and two-electron oxidations to the radical cation and dication in CH2Cl2. The anhydrides were converted to N-alkyl imides to increase the solubility. High-molecular weight poly(p-arylene butadiynylene)s were prepared via Pd/Cu(I)/benzoquinone oxidative coupling of the diacetylene monomers. The resulting polymers are highly emissive in solution and thin films. The ionization potentials were measured using ultraviolet photoelectron spectroscopy with thin films. Last, fluorescence measurements of polymer thin films during continuous irradiation indicate that the most hindered polymer is more resistant to photobleaching.     

Induced P-wave superfluidity in asymmetric fermi gases

We show that two new intraspecies P-wave superfluid phases appear in two-component asymmetric Fermi systems with short-range S-wave interactions. In the BEC limit, phonons of the molecular BEC induce P-wave superfluidity in the excess fermions. In the BCS limit, density fluctuations induce P-wave superfluidity in both the majority and the minority species. These phases may be realized in experiments with spin-polarized Fermi gases.     

Vibrational frequencies and tuning of the African mbira

The acoustic spectrum of the mbira, a musical instrument from Africa that produces sound by the vibration of cantilevered metal rods, has been measured. It is found that the most prominent overtones present in the spectrum have frequencies that are approximately 5 and 14 times the lowest frequency. A finite-element model of the vibration of the key that takes into account the acoustic radiation efficiency of the various normal modes reveals that the far-field power spectrum is dominated by modes involving predominately transverse motion of the key. Modes involving longitudinal motion do not radiate efficiently, and therefore contribute little to the sound produced. The high frequencies of the dominant overtones relative to the fundamental make it unlikely that the tunings of the mbira that are used by expert musicians are determined by matching the fundamental frequencies of the upper keys with the overtones of the lower keys.     

Synthesis of nearly uniform single-walled carbon nanotubes using identical metal-containing molecular nanoclusters as catalysts

Uniform and small-diameter single-walled carbon nanotubes (SWNTs) have been produced using identical molecular nanoclusters containing Fe and Mo atoms with a defined molecular formula and a specific structure as catalysts in a chemical vapor deposition method. The average diameter of the SWNTs produced in these experiments is 1.0 nm with a standard deviation for the diameter distribution of 17%. The diameters of SWNTs were obtained by atomic force microscopy and Raman spectroscopy.     

Novel mixed ligand coordination compounds of some rare earth metal cations containing acesulfamato/N,N-diethylnicotinamide

The mixed ligand coordination compounds containing acesulfamato and N,N -diethylnicotinamide biomolecules of some rare earth metal cations (Eu³⁺, Tb³⁺, Ho³⁺, Er³⁺ and Yb³⁺) were synthesized, and their structural properties were investigated. Possible structural formulas have been proposed by determining the chemical composition of molecules (elemental analysis), binding properties (infrared spectroscopy, mass analysis, solid-state UV-vis spectroscopy), thermal degradation properties (TGA / DTA curves). Based on the data collected, it is suggested that rare earth metal cations with a 3+ oxidation state have sextet coordination. The geometries of the structures were thought to be distorted octahedral. The charge balance of the coordination sphere is balanced by a monoanionic acesulfamato located outside the coordination sphere. When the thermal behaviours of the complexes were examined, it was determined that the compounds with Eu³⁺, Tb³⁺, and Yb³⁺ metal cations contained one hydrate water outside the coordination sphere. Hydrate waters do not exist in the Ho³⁺ and Er³⁺ metal cation-centred complexes. At the end of the thermal decomposition analysis of all complex structures, it was determined that they leave the relevant metal oxides in the reaction vessels as final decomposition products.     

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.     

Self-amplification of coherent spontaneous emission in a cherenkov free-electron maser

Ultrashort pulses of microwave radiation have been produced in a dielectric-lined Cherenkov free-electron maser (FEM) amplifier. An intense initial seed pulse, due to coherent spontaneous emission (CSE), arises at the leading edge of the electron pulse. There is evidence to show that 3-4 cycle spikes are produced through the amplification of these seed pulses. A strong dependence of the start-up power on the rise time of the electron pulse has been found. The experimental results are verified by a theoretical analysis. Our study shows that amplification in a FEM amplifier is always initiated by CSE arising from the edge of the electron pulse when the rise time is comparable to the electromagnetic wave period.     

Nuclear magnetic resonance and relaxation in liquid zinc

Measurements of the Knight shift K and the nuclear spin-lattice relaxation rate $\text{(}\text{1}\text{T}{}_{\mathrm{l}}\text{)}$ of Zn⁶⁷ are reported for liquid Zn. Measurements of K extend from 409°C (supercooled) to 700°C; measurements of $\text{(}\text{1}\text{T}{}_{\mathrm{l}}\text{)}$ cover the range 425 – 620°C. The Knight shift shows a weak positive temperature dependence attributed to thermal expansion. The reciprocal enhancement factor of the Korringa relation K(α) is found to increase with temperature from .77 ± .04 to .82 ± .04 in the range 425 – 620°C. The quadrupolar contribution to the relaxation rate was concluded to be very small with an estimated upper limit given by $\text{(}\text{1}\text{T}{}_{\mathrm{l}}\text{)}{}_{\mathrm{Q}}\text{≤ 15 sec.}{}^{\mathrm{-l}}$