Improved sample pre-treatment for determination of caffeine in tea using a cartridge filled with polyvinylpolypyrroridone (PVPP)

We have improved sample pre-treatment for the effective removal of polyphenols and simple analysis of caffeine in tea using a cartridge filled with polyvinylpolypyrroridone (PVPP). Nearly 100% of catechins were removed from the green tea sample and caffeine was completely recovered in the range of 98.2-101.3% by sample pre-treatment with a PVPP cartridge. Reproducibility of preparing PVPP pre-treatment cartridges was sufficient for quantitative analysis, because RSDs of analytical values for caffeine obtained by using three individual pre-treatment cartridges filled with 10-200 mg PVPP were 0.60-2.8%. The PVPP pre-treatment cartridge also removed polyphenols perfectly and recovered caffeine faultlessly from oolong and black tea samples. Comparison with the conventional method without sample pre-treatment indicated that the present pre-treatment method with a PVPP cartridge was useful for the simple and precise analysis of caffeine in green, oolong and black tea samples.     

Design of a practical fluorescent probe for superoxide based on protection-deprotection chemistry of fluoresceins with benzenesulfonyl protecting groups

A strategy for designing probes based on protection-deprotection chemistry involving fluoresceins and their benzenesulfonyl (BES) derivatives has led to the development of a much more practical superoxide (O(2) (-.)) probe than the previously reported bis(2,4-dinitro-BES) tetrafluorofluorescein (6 a). Examination of various BES derivatives, developed from the starting point of the prototype probe 6 a, yielded 4,5-dimethoxy-2-nitro-BES tetrafluorofluorescein (BESSo; 7 j) as the optimal reagent. A microtiter plate assay with BESSo showed a tenfold improved detection limit for O(2) (-.) compared with such an assay based on 6 a. BESSo showed markedly better specificity for O(2) (-.) than for GSH or other reactive oxygen species, and this specificity was significantly higher than that of Fe(2+) and some reducing enzymes. These features have resulted in the development of an assay based on BESSo that is capable of providing more unambiguous results for O(2) (-.) release from neutrophils, with or without stimulation by phorbol myristate acetate, as compared with an assay based on 6 a. Intracellular generation of O(2) (-.) in human Jurkat T cells stimulated by butyric acid has been measured by using flow cytometry and fluorescence microscopy utilizing the acetoxymethyl derivative of BESSo.     

Stereochemical investigation on the construction of poly-functionalized bicyclo[3.3.1]nonenones by successive Michael reactions of 2-cyclohexenones

A method for the practical construction of poly-functionalized bicyclo[3.3.1]nonenones by successive Michael reactions of cyclohexenones with acrylates using K2CO3 and TBAB (n-Bu4N+ Br-) was developed. The construction could be carried out in both stepwise and one-pot reactions with similar tendencies in regioselectivity. The alpha-regioselectivity in the intramolecular Michael reaction agreed with that stereoelectronically expected in intermolecular reactions based upon consideration of the HOMO orbital profile of the enolate I, the precursor to ring-closure, although the reaction site was trisubstituted and prone to steric hindrance in most of the examples presented. For the acetoxymethylacrylates substituted at either the alpha or gamma position, steric hindrance of the substituents (R2 and R3) served as a controlling factor to induce high regiocontrol. Facial selection in the protonation of enolate II, formed upon ring-closure, was also affected by these substituents. In both the intramolecular Michael reaction and the protonation of enolate II, the ammonium counter cation played an important role.     

Enantioselective synthesis of endohedral metallofullerenes

Endohedral metallofullerenes are promising materials in biomedical and material sciences. In particular, they are of interest as agents for magnetic resonance imaging (MRI), photovoltaic devices, and semimetallic components. The synthesis of chiral endofullerenes represents one step further in the potential use of these carbon allotropes; however, this step has not been addressed so far. In this regard, enantiopure endofullerenes are expected to open new avenues in fields in which chirality is a key issue. Here, the synthesis and characterization of the first chiral endohedral metallofullerenes, namely, chiral bis-adducts of La@C(72), are reported. Eight optically active isomers were obtained by enantioselective 1,3-dipolar cycloaddition of a N-metalated azomethine ylide onto a non-isolated-pentagon rule metallofullerene derivative, La@C(72)(C(6)H(3)Cl(2)), catalyzed by a copper chiral complex. The chiral bis-adducts of La@C(72), isolated by nonchiral HPLC, showed optical purities as high as 98% as revealed by the remarkable positive or negative Cotton effects observed in the circular dichroic spectra.     

Experimental and analytical investigation of liquid sheet breakup characteristics

The main objective of this research is to study analytically and experimentally the liquid sheet breakup of a flat fan jet nozzle resulting from pressure-swirling. In this study the effects of nozzle shape and spray pressure on the liquid sheet characteristics were investigated for four nozzles with different exit widths (1.0, 1.5, 2.0 and 2.5 mm). The length of liquid sheet breakup, liquid sheet velocity and the size of formed droplets were measured by a digital high speed camera. The breakup characteristics of plane liquid sheets in atmosphere are analytically investigated by means of linear and nonlinear hydrodynamic instability analyses. The liquid sheet breakup process was studied for initial sinuous and also varicose modes of disturbance. The results presented the effect of the nozzle width and the spray pressure on the breakup length and also on the size of the formed droplets. Comparing the experimental results with the theoretical ones for all the four types of nozzles, gives a good agreement with difference ranges from 4% to 12%. Also, the comparison between the obtained results and the results due to others shows a good agreement with difference ranged from 5% to 16%. Empirical correlations have been deduced describing the relation between the liquid sheet breakup characteristics and affecting parameters; liquid sheet Reynolds number, Weber number and the nozzle width.     

Synthesis of γ-benzopyranone by TfOH-promoted regioselective cyclization of o-alkynoylphenols

Regioselective cyclization of o-alkynoylphenols forming γ-benzopyranones has been demonstrated. Trifluoromethanesulfonic acid (TfOH) induced 6-endo cyclization of o-alkynoylphenols without forming 5-exo cyclized benzofuranone derivatives to provide the corresponding γ-benzopyranones in high yields.