A spin-dependent Popov-Fedotov trick and a new loop expansion for the strong coupling negativeU Hubbard model

We calculate fluctuation effects on Bose condensation type superconductivity in the strong coupling negative U Hubbard model by means of a new loop expansion. Our method is based on a spin-dependent modification of the Popov-Fedotov trick. We replace the Popov-Fedotov chemical potential by a fictitious imaginary magnetic field. This field is absorbed in spindependent semionic Matsubara frequencies, which allows for a mixed statistics representation of the anisotropic quantum spin 1/2 Heisenberg model. We report results at one loop order for the superconducting order parameter , for the critical temperature, for the chemical potential, and for the excitation spectra both above and belowT _c. We identify mean field results in zeroth loop order and we find both dimensional and filling (v-)depending singularities in interaction fluctuations at one loop order. Renormalization of dimensional singularities is carried out in 4 dimensions. Divergencies withv (1–v)0 in the dilute limits indicate the breakdown of mean field solutions, but superconductivity persists for arbitrarily smallv(1–v) if our loop expansion is interpreted by exponential behaviour as it is suggested by the abelian nonlinear sigma model.     

Linear dichroism and fluorescence polarization of diphenyl polyenes in stretched polyethylene films

A study of the linear diehroism and fluorescence polarization of diphenylpolyenes (C₆H₅—(CH=CH)_n—C₆H₅) with n = 1,2,3,4,6,8 in stretched polyethylene films shows that the polyenes orient in the anisotropic matrix with their transition dipole (emission and absorption, π → π^*) aligned with the direction of stretch. The maximum dichroic ratio is observed for 1,6-diphenyl-1,3,5-hexatriene (DPH), with n = 3, whereas the values are substantially lower for n < 3 or n > 3. The high orientation of DPH and poor alignment of the higher polyenes may be accounted for in terms of the growing flexibility of the polyene chains with increasing chain length. The results justify the use of DPH as a convenient fluorescence probe for biological and synthetic membranes.     

Surface modification of mesoporous, macroporous, and amorphous silica with catalytically active polyoxometalate clusters

Transition-metal-substituted polyoxometalates (TMSP) of the type [MII(H2O)PW11O39]5- (M = Co, Zn) and [SiW9O37(CoII(H2O))3]10- have been chemically anchored to modified macroporous (400 nm pores), mesoporous (2.8 nm pores), and amorphous silica surfaces. The materials were characterized by solid-state 31P MAS NMR, UV-vis, FT-IR spectroscopy, and N2 adsorption experiments to verify cluster attachment and the structure of the TMSP on the support. On the basis of the spectroscopic evidence, clusters were attached datively to the surface, and the integrity of the [CoPW11] cluster was maintained for nonaqueous impregnation with TBA5[CoPW11]; partial degradation of the cluster occurred when it was impregnated from aqueous solution using the K5[CoPW11] salt. Both the amine surface groups and the cobalt centers in the clusters were found to be necessary to prevent cluster loss during washing or reaction processes. The catalytic activities of the supported TMSP clusters were tested by the epoxidation of cyclohexene to cyclohexene oxide in the presence of isobutyraldehyde. The percent conversion of the substrate and the amount of product formed per unit time were similar for [CoPW11] clusters on each of the three silica supports, but slightly lower than for purely homogeneous reactions. [SiW9Co3] clusters with three available cobalt centers exhibited higher catalytic activity with nearly identical performance on a silica support or in homogeneous solution.     

Poly-N-hydroxyethylacrylamide as a novel, adsorbed coating for protein separation by capillary electrophoresis.

We present the polymer poly-N-hydroxyethylacrylamide (PHEA) (polyDuramide) as a novel, hydrophilic, adsorbed capillary coating for electrophoretic protein analysis. Preparation of the PHEA coating requires a simple and fast (30 min) protocol that can be easily automated in capillary electrophoresis instruments. Over the pH range of 3-8.4, the PHEA coating is shown to reduce electroosmotic flow (EOF) by about 2 orders of magnitude compared to the bare silica capillary. In a systematic comparative study, the adsorbed PHEA coating exhibited minimal interactions with both acidic and basic proteins, providing efficient protein separations with excellent reproducibility on par with a covalent polyacrylamide coating. Hydrophobic interactions between proteins and a relatively hydrophobic poly-N,N-dimethylacrylamide (PDMA) adsorbed coating, on the other hand, adversely affected separation reproducibility and efficiency. Under both acidic and basic buffer conditions, the adsorbed PHEA coating produced an EOF suppression performance comparable to that of covalent polyacrylamide coating and superior to that of adsorbed PDMA coating. The protein separation performance in PHEA-coated capillaries was retained for 275 consecutive protein separation runs at pH 8.4, and for more than 800 runs at pH 4.4. The unique and novel combination of hydrophilicity and adsorptive coating ability of PHEA makes it a suitable wall coating for automated microscale analysis of proteins by capillary array systems.     

On the thermal behavior of 4-(o-carboranyl)-1-butylmethyl siloxane–dimethyl siloxane copolymers

Polysiloxanes containing carboranylbutyl and methyl pendant groups were investigated, to determine their resistance to thermal decomposition when heated in air. Results indicate that the copolymers degrade through Si? C as well as Si? O bond rupture. At 300°C. thermooxidative scission of pendant groups was the predominant reaction. whereas Si? O and Si? C bond rupture occurred at 500°C. Variations in the behavior of the copolymers studied suggest that the carborane nucleus provides some inhibiting influence on their thermal decomposition. This is mainly attributed to steric hindrance effects rather than polarity factors. Chain extension with tin octoate caused a reduction of thermal stability, probably because of the addition of Sn? O bonds to the molecules.     

Production of vector and tensor mesons in proton-proton collisions at\sqrt s = 52.5 GeV

Inclusive production of ?⁰,f, andg ⁰ mesons and ofK _s ⁰ ,K ^*0 (892), ? andK ^*0(1430)mesons has been measured at <y>～2.6 and <p _T >～1.1 GeV/c in proton-proton interactions at \(\sqrt s = 52.5\) GeV. The negative particle from the two-body decays of these resonances were identified by a threshold Cerenkov counter and used for triggering. Starting from the measured differential cross section, total inclusive cross sections for the vector and tensor mesons were determined using various parametrizations for they andp _T dependence of the differential cross section. The experimental results are discussed in the framework of production models based on the parton picture. The strangeness suppresion factor λ=(0.30±0.10) due toSU(3) symmetry breaking of the quark sea is derived.     

Facile Phenylphosphinidene Transfer Reactions from Carbene–Phosphinidene Zinc Complexes

Phosphinidenes [R-P] are convenient P₁ building blocks for the synthesis of a plethora of organophosphorus compounds. Thus far, transition-metal-complexed phosphinidenes have been used for their singlet ground-state reactivity to promote selective addition and insertion reactions. One disadvantage of this approach is that after transfer of the P₁ moiety to the substrate, a challenging demetallation step is required to provide the free phosphine. We report a simple method that enables the Lewis acid promoted transfer of phenylphosphinidene, [PhP], from NHC=PPh adducts (NHC=N-heterocyclic carbene) to various substrates to produce directly uncoordinated phosphorus heterocycles that are difficult to obtain otherwise.