Fullerenes separation with monomeric type C30 stationary phase in high-performance liquid chromatography

The temperature effect on the separation of fullerenes in LC was examined using monomeric type C30, C18 and C8 alkyl bonded stationary phases. It appears that the C30 phase exhibits superior separation ability for fullerenes. It is observed that the maximum retention temperature of fullerenes on the C30 phase is around 20 degrees C. A strong correlation between the changes in NMR spectra and the retention behavior of the solutes was found. The interpretation of the retention behavior of fullerenes on the alkyl bonded stationary phases, including the behavior in subambient temperature, is discussed using the information obtained by CP-MAS solid-state NMR spectroscopy and LC.     

Cu-Chelex as a selective adsorbent for o-nitroso derivatives of phenolic substances

Summary Chelex resins in several metal forms were tested for selective uptake of o-nitrosonaphthols and o-nitrosophenols from aqueous solution. Cu-Chelex was the most efficient resin over a wide pH range, and the taken-up nitroso compounds were effectively eluted with concentrated ammonia: acetonitrile (4:1, v/v) after washing the resin with acetonitrile to eliminate non-specific binding. The upper and lower limits of uptake capacity of the resin for 1-nitroso-2-naphthol were 0.5 mol/100 mg and 1.25 mol/100 mg, respectively. A preliminary recovery experiment using urine and cucumber juice showed that Cu-Chelex would be useful for screening of o-nitroso derivatives of phenolic substances in complicated samples such as biological fluids and foods.     

Singlet Oxygen–mediated Hydroxyl Radical Production in the Presence of Phenols: Whether DMPO–·OH Formation Really Indicates Production of ·OH?¶

The reaction of singlet oxygen (1O2) generated by ultraviolet-A (UVA)-visible light (lambda > 330 nm) irradiation of air-saturated solutions of hematoporphyrin with phenolic compounds in the presence of a spin trap, 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), gave an electron spin resonance (ESR) spectrum characteristic of the DMPO-hydroxyl radical spin adduct (DMPO-*OH). In contrast, the ESR signal of 5,5-dimethyl-2-pyrrolidone-N-oxyl, an oxidative product of DMPO, was observed in the absence of phenolic compounds. The ESR signal of DMPO-*OH decreased in the presence of either a *OH scavenger or a quencher of *O2 and under anaerobic conditions, whereas it increased depending on the concentration of DMPO. These results indicate both 1O2- and DMPO-mediated formation of free *OH during the reaction. When DMPO was replaced with 5-(diethoxyphosphoryl)-5-methyl-1-pyrroline-N-oxide (DEPMPO), no DEPMPO adduct of oxygen radical species was obtained. This suggests that 1O2, as an oxidizing agent, reacts little with DEPMPO, in which a strong electron-withdrawing phosphoryl group increases the oxidation potential of DEPMPO compared with DMPO. A linear correlation between the amounts of DMPO-*OH generated and the oxidation potentials of phenolic compounds was observed, suggesting that the electron-donating properties of phenolic compounds contribute to the appearance of *OH. These observations indicate that 1O2 reacts first with DMPO, and the resulting DMPO-1O2 intermediate is immediately decomposed/reduced to give *OH. Phenolic compounds would participate in this reaction as electron donors but would not contribute to the direct conversion of 1O2 to *OH. Furthermore, DEPMPO did not cause the spin-trapping agent-mediated generation of *OH like DMPO did.     

Slurry sampling techniques for the determination of lead in Bangladeshi fish samples by electrothermal atomic absorption spectrometry with a metal tube atomizer

Ultrasonic slurry sampling electrothermal atomic absorption spectrometry with a metal tube atomizer has been applied to the determination of lead in Bangladeshi fish samples. The slurry sampling conditions, such as slurry stabilizing agent, slurry concentration, pyrolysis temperature for the slurried fish samples, particle size and ultrasonic agitation time, were optimized for electrothermal atomic absorption spectrometry with the Mo tube atomizer. Thiourea was used as the chemical modifier for the interference of matrix elements. The detection limit was 53 fg (3S/N). The determined amount of lead in Bangladeshi fish samples was consistent with those measured in the dissolved acid-digested samples. The advantages of the proposed methods are easy calibration, simplicity, low cost and rapid analysis.     

High performance liquid chromatography with an electrochemical detector in the cathodic mode as a tool for the determination of p-nitrophenol and assay of acid phosphatase in urine samples

Utilizing a commercially available helium-purging device and PEEK tubes for all tubing, especially for connection between the mobile phase and pump, high performance liquid chromatography with an electrochemical detector (ECD/HPLC) at the cathodic mode is a simple and precise method for the determination of p-nitrophenol (NP). Studies with cyclic and hydrodynamic voltammetry indicated that 25% aqueous MeOH containing 0.1% (v/v) CF(3)CO(2)H and -0.8 V vs. Ag/AgCl are the best mobile phase and detection potential for cathodic ECD/HPLC. With the present system, the limits of detection and determination were 0.2 and 0.25 microM, respectively, and up to 50 microM, a linear calibration curve was afforded. Within-day precisions for the analysis of 5 and 50 microM NP were 0.8 and 0.7% (n=6), respectively, and between-day precisions (n=6) for these samples were 3.5 and 2.2%, respectively. Compared with the commonly used Bessey-Lowry-Brock method, cathodic ECD/HPLC was useful for the assay of acid phosphatase in urine samples with p-nitrophenyl phosphate disodium salt as a substrate.     

Facile synthesis of polyamide dendrimers from unprotected AB2 building blocks

[structure: see text]. A fast, inexpensive, and highly efficient synthesis of aromatic polyamide dendrimers without the need for protection and deprotection steps has been developed. Dendrons and third-generation polyamide dendrimers were easily prepared by a convergent approach involving activation of a focal point with thionyl chloride, followed by condensation with unprotected AB2 building blocks.     

Different reaction modes for the oxidative dimerization of epoxyquinols and epoxyquinones. Importance of intermolecular hydrogen-bonding

An oxidative dimerization reaction, involving the three successive steps of oxidation, 6 pi-electrocyclization, and Diels-Alder reaction, has been experimentally and theoretically investigated for the three 2-alkenyl-3-hydroxymethyl-2-cyclohexen-1-one derivatives epoxyquinol 3, epoxyquinone 6, and cyclohexenone 10. Of the sixteen possible modes of the oxidation/6 pi-electrocylization/Diels-Alder reaction cascade for the epoxyquinone 6, and eight for the cyclohexenone 10, only the endo-anti(epoxide)-anti(Me)-hetero and endo-anti(Me)-hetero modes are, respectively, observed, while both endo-anti(epoxide)-anti(Me)-hetero and exo-anti(epoxide)-anti(Me)-homo reaction modes occur with the epoxyquinol 3. Intermolecular hydrogen-bonding is found to be the key cause of formation of both epoxyquinols A and B with 3, although epoxyquinone 6 and cyclohexenone 10 both gave selectively only the epoxyquinol A-type product. In the dimerization of epoxyquinol 3, two monomer 2H-pyrans 5 interact with each other to afford intermediate complex 28 or 29 stabilized by hydrogen-bonding, from which Diels-Alder reaction proceeds. Theoretical calculations have also revealed the differences in the reaction profiles of epoxyquinone 6 and cyclohexenone 10. Namely, the rate-determining step of the former is the Diels-Alder reaction, while that of the latter is the 6 pi-electrocyclization.     

Determination of phosphorus in biological material using electrothermal atomisation atomic absorption spectrometry with a molybdenum tube atomiser

Phosphorus has been determined by electrothermal atomisation atomic absorption spectrometry with a molybdenum tube atomiser. The effects of interferents on the phosphorus signal have been investigated. Chemical interferences were eliminated by high-temperature pyrolysis. The detection limit for the molybdenum tube system was 2.3 ng (corresponding to 2.3 micrograms ml-1 when 1 microliter was injected into the atomiser) and the characteristic mass was 1.9 ng of phosphorus. A calibration graph method combined with high-temperature pyrolysis has been evaluated through the determination of phosphorus in biological materials. The sensitivity, accuracy and precision of the method were superior to or nearly equal to those of graphite furnace atomic absorption spectrometry. The advantages of the high-temperature pyrolysis method are its simplicity and low cost.