Photophysical properties of oligo(2,3-thienyleneethynylene)s

Photophysical properties of oligo(2,3-thienyleneethynylene)s (nTE, n denotes the number of thiophene rings, n = 2, 3) in benzene were investigated using steady-state, time-resolved fluorescence, and transient absorption spectroscopies. For 2TE, generation of the radiative S2 and nonradiative S1 states was confirmed. Upon excitation, the S2 state was initially generated and deactivated to the S1 state within 10 ps. The S1 state exhibited the transient absorption band at 470 nm, of which the lifetime was estimated to be 5.3 ns. In the case of 3TE, on the other hand, it was revealed that the radiative S1 state with a transient absorption peak at 650 nm was generated upon excitation. The T1 states of nTE were generated from the S1 states. The quantum yields were estimated to be 0.52 and 0.54 for 2TE and 3TE, respectively. Extremely fast reactions in the higher triplet excited state were indicated for both 2TE and 3TE.     

Alkane Oxidation with Molecular Oxygen Using a New Efficient Catalytic System: N-Hydroxyphthalimide (NHPI) Combined with Co(acac)(n)() (n = 2 or 3)

A novel class of catalysts for alkane oxidation with molecular oxygen was examined. N-Hydroxyphthalimide (NHPI) combined with Co(acac)(n)() (n = 2 or 3) was found to be an efficient catalytic system for the aerobic oxidation of cycloalkanes and alkylbenzenes under mild conditions. Cycloalkanes were successfully oxidized with molecular oxygen in the presence of a catalytic amount of NHPI and Co(acac)(2) in acetic acid at 100 degrees C to give the corresponding cycloalkanones and dicarboxylic acids. Alkylbenzenes were also oxidized with dioxygen using this catalytic system. For example, toluene was converted into benzoic acid in excellent yield under these conditions. Ethyl- and butylbenzenes were selectively oxidized at their alpha-positions to form the corresponding ketones, acetophenone, and 1-phenyl-1-butanone, respectively, in good yields. A key intermediate in this oxidation is believed to be the phthalimide N-oxyl radical generated from NHPI and molecular oxygen using a Co(II) species. The isotope effect (k(H)/k(D)) in the oxidation of ethylbenzene and ethylbenzene-d(10) with dioxygen using NHPI/Co(acac)(2) was 3.8.     

Intramolecular Stacking in Ternary Complexes Containing Uridine 5′-Triphosphate, 2,2′-Bipyridyl,and a Divalent Metal Ion

The stability constants of the ternary complexes containing UTP, 2,2′-bipyridyl (bipy), and Co²⁺, Ni²⁺, Cu²⁺, or Zn²⁺ (M²⁺) have been determined by potentiometric titrations (Table 1). Changes in stability are quantified by Δlog K_M = log K–log K. For the Co²⁺, Ni²⁺, Cu²⁺, and Zn²⁺ systems Δlog K_M is 0.10, ?0.13, 0.36, and 0.15, respectively. All these ternary complexes are considerably more stable than would be expected on statistical grounds; indeed, for Co²⁺, Cu²⁺, and Zn²⁺, UTP^4? binds more tightly to M (bipy)²⁺ than to M²⁺. An UV. difference spectroscopic study suggests that stacked adducts between bipyridyl and the pyrimidine moiety of uridine are formed. ¹H-NMR. studies of the bipy/uridine, bipy/UTP, and bipy/UTP/Zn²⁺ systems (Figs. 1 and 2) confirm the presence of stacking in the binary adducts and in the ternary complex. There is also evidence for the existence of the stacked protonated complex, Zn(bipy) (HUTP)^?, with the proton at the γ-phosphate group. The acidity constant of this ternary complex has been measured (Fig. 3). The observed stability enhancement of stacked adducts by the formation of a metal ion bridge is discussed (Fig. 4) and biological implications are indicated.     

Isomerization of aldehyde-2,4-dinitrophenylhydrazone derivatives and validation of high-performance liquid chromatographic analysis

The most widely used method for qualitative and quantitative analysis of carbonyl compounds is the 2,4-dinitrophenylhydrazine method through the formation of 2,4-dinitrophenylhydrazone derivatives. However, this method may cause an analytical error because 2,4-dinitrophenylhydrazones have both E- and Z-stereoisomers. Purified aldehyde-2,4-dinitrophenylhydrazone demonstrated only the E-isomer. However under UV irradiation and the addition of acid, both E- and Z-isomers were seen. The spectral patterns of Z-isomers were different from those of E-isomers and the absorption maximum wavelengths were shifted towards shorter wavelengths by 5-8 nm. An equilibrium Z/E isomer ratio was observed in 0.02-0.2% (v/v) phosphoric acid solutions. In the case of acetaldehyde- and propanal-2,4-dinitrophenylhydrazones, the equilibrium Z/E isomer ratios were 0.32 and 0.14, respectively. However, when irradiated with ultraviolet light at 364 nm, the isomer ratios were increased beyond this constant ratio and reached 0.55 and 0.33, respectively. Zero-order rates for decreases of aldehyde derivatives were observed under UV irradiation (364 nm), however the decreases of concentration were not observed in phosphoric acid solutions. The best method for the determination of aldehyde-2,4-dinitrophenylhydrazones by HPLC is to add phosphoric acid to both the sample and the standard solution, to form a 0.02-1% acid solution.     

Large-scale separation of metallic and semiconducting single-walled carbon nanotubes

In the applications of single-walled carbon nanotubes (SWNTs), it is extremely important to separate semiconducting and metallic SWNTs. Although several methods have been reported for the separation, only low yields have been achieved at great expense. We show a separation method involving a dispersion-centrifugation process in a tetrahydrofuran solution of amine, which makes metallic SWNTs highly concentrated to 87% in a simple way.     

Synthesis, structure and magnetic properties of new vanadate PbCo2V2O8

A new vanadate PbCo₂V₂O₈ was obtained through the study of PbO-CoO-V₂O₅ ternary system. The crystal structure was determined by Rietveld method, indicating that PbCo₂V₂O₈ has a tetragonal structure of space group I41cd with a spiral chain along the c-axis. Magnetic properties of the titled compound were investigated by means of susceptibility, magnetization, and heat capacity measurements. The results show that PbCo₂V₂O₈ is a quasi-one-dimensional canted antiferromagnet with Neel temperature of ∼4 K, being consistent with its crystal structure.     

Analysis of conjugated linoleic acids as 9-anthrylmethyl esters by reversed-phase high-performance liquid chromatography with fluorescence detection

A simple and highly sensitive method for determining the fatty acid composition of food lipids containing conjugated linoleic acid (CLA) is described. The method is based on the separation of the 9-anthrylmethyl ester derivatives of saturated and unsaturated (conjugated and non-conjugated) fatty acids by reversed-phase high-performance liquid chromatography with fluorescence detection. Just like the other fatty acids, CLA reacts readily with 9-anthryldiazomethane at room temperature to produce 9-anthrylmethyl esters without isomerization and decomposition of the conjugated double bonds. Clear resolution of the individual fatty acids as their 9-anthrylmethyl esters is achieved on a highly efficient octadecylsilylated silica column (150- x 3-mm i.d., 3-microm particle size) using a stepwise gradient elution with methanol-water. The method is standardized with commercially available CLA isomers (cis-9, trans-11 and trans-10, cis-12-octadecadienoic acids, and their cis,cis and trans,trans isomers) and applied for determination of the fatty acid compositions of milk and sdairy products.