Esr of pterin and lumazine radicals in solution

Cationic tetrahydrolumazine radicals and cationic tetrahydropterin radicals were detected by electron spin resonance when 5-alkyl-5,6,7,8-tetrahydrolumazines and 5-alkyl-5,6,7,8-tetrahydropterins were oxidized with hydrogen peroxide in formic acid. The hyperfine interactions of both types of radicals are essentially the same.Two consecutive radical species were observed during the oxidation of 3,5,8-trialkyl-5,6,7,8-tetrahydrolumazines in formic acid. They were identified as cationic tetrahydrolumazine radicals and cationic dihydrolumazine radicals.The ESR spectra of neutral trihydro- and monohydro-lumazine radicals, which have not been obtained before, were recorded during the oxidation of 5-alkyl-5,6,7,8-tetrahydrolumazines in chloroform. Starting from 5-butyl-1,3-dimethyl-5,6,7,8-tetrahydrolumazine three different radicals were observed.The spectra were interpreted in terms of hyperfine coupling constants and nuclear spins of the atoms involved.     

Photodynamic therapy with pyropheophorbide-a methyl ester in human lung carcinoma cancer cell: efficacy,localization and apoptosis

Pyropheophorbide-a methyl ester (MPPa) is a semisynthetic photosensitizer derived from chlorophyll a. The absorption peak of MPPa in organic solvent and in cells was at 667 and 674 nm, respectively. 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide reduction assay showed that MPPa had no dark cytotoxicity. In vitro photodynamic activity was extensively evaluated using a human lung carcinoma cancer cell line (NCI-h446). MPPa exhibited no genotoxicity, as assayed by single-cell gel electrophoresis. Using confocal laser scanning microscopy and organelle-specific fluorescent probes, MPPa was found to localize in the intracellular membrane system, namely the endoplasmic reticulum, Golgi apparatus, lysosomes and mitochondria, in the NCI-h446 cells. Furthermore, nuclear staining and DNA gel electrophoresis revealed that DNA condensation and fragmentation occurred post-photodynamic therapy, indicating the cell death was in the apoptotic mode.     

New liquid‐crystal alignment agents based on fluorinated polyimides with trifluoromethyl‐substituted benzene or diphenylether in the side chain

Fluorinated copolyimides derived from 4,4′‐oxydiphthalic anhydride (ODPA) with 4,4′‐oxydianline (ODA) and trifluoromethyl‐containing aromatic diamines have been synthesized and characterized. The trifluoromethyl‐containing diamines include 2,4‐diamino‐3′‐trifluoromethylazobenzene, 2,4‐diamino‐1‐[(4′‐trifluoromethylphenoxy) phenyl] aniline, 3,5‐diamino‐1‐[(4′‐trifluoromethylphenoxy) phenyl] benzamide, 3,5‐diamino‐1‐[(3′‐trifluoromethyl) phenyl] benzamide, 1,4‐bis(4′‐aminophenoxy)‐2‐(3′‐trifluoromethylphenyl) benzene, 3,5‐diaminobenzenetrifluoride, 4,4′‐diamino‐4″‐(p‐trifluoromethyl phenoxy) triphenylamine, and 4‐[(4′‐trifluoromethylphenoxy) phenyl]‐2,6‐bis(4″‐aminophenyl)pyridine. Strong and flexible copolyimide films, produced by casting the polyamic acid solution followed by thermal imidization, exhibited great thermal stability and high mechanical properties. The polyimides had an ultraviolet–visible absorption cutoff at 330–340 nm and pretilt angles as high as 20° for nematic liquid crystals, making them great potential candidates for advanced liquid‐crystal display applications. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1583–1593, 2002     

The glass transition time scale and configurational entropy in polymers: an experimental molecular view

We report direct experimental observation of local conformational dynamics in a polymer chain at the calorimetric glass transition temperature Tg. Variable-temperature two-dimensional (2D) solid-state exchange NMR, at natural abundance, reveals segmental dynamics in pure polyisobutylene (PIB) occurring on a time scale of several seconds over the Tg range observed by DSC (203-208 K). To our knowledge, this is the first direct observation of molecular-level conformer interchange (trans-trans/trans-gauche/gauche-gauche) at the caloric glass transition temperature. Our results provide a chronologically accurate and pedagogically advantageous demonstration of molecular processes during a polymer phase transition, relative to traditional bulk mechanical and calorimetric techniques. More importantly, we use a miscible blend to demonstrate a general strategy for quantitative evaluation of configurational entropy changes via combination of temperature-dependent 2D exchange NMR and Adams-Gibbs theory. Our results on the Tg time scale are directly relevant to fundamental understanding of the Tg length scale, i.e., the dimension of cooperatively rearranging regions.     

Influence of Light Scattering by Residual Alumina Nanoparticles on the Analysis of Surfactants Adsorption Using Spectroscopy

The adsorption of a surfactant mixture, based on an anionic surfactant, sodium dodecyl benzenesulfonate (SDBS) and a nonionic surfactant (Triton X-100, or TX100), on alumina nanoparticles was determined by solution depletion method combined with spectrometric measurement. It is shown that the light scattering, originated from the residual adsorbent alumina particles in the supernatant after centrifugation separation, interferes with the measurements of absorbance of the surfactant molecules, and therefore constitutes an error source for determination of the surfactant concentration in the supernatant by spectrometric means. The intensity of this light scattering, namely the influence of the residual alumina nanoparticles upon the surfactant adsorption, was related to the surfactant adsorption and its equilibrium concentration and varied among a batch. In this paper we report a Kalman filter method in order to eliminate the variational scattering background caused by non-separated residual alumina nanoparticles in each supernatant. This method is of interest as it is simple, easy to carry out and of high precision.     

HPLC of amino acids and oligopeptides by pre-column fluorescence derivatization with N-hydroxysuccinimidyl-α-(9-phenanthrene)-acetate

Summary A sensitive LC method for the detection of amino acids and oligopeptides with pre-column fluorescence derivatization has been developed. Glycine, glycylglycine, triglycine, glutathione, glutamic acid, and cysteine were separated on a reversed-phase C₁₈ column with methanol-water-triethylamine eluent, derivatization and chromatographic conditions were optimized. The six derivatives were eluted in 20 min with good reproducibility. The relative standard derviations (n=6) at an analytical concentration of 2×10⁻⁶ M are <5%. Detection limits (signal-to-noise ratio=3) for the six derivatives are 23–68 fmol.     

Quantitative and bioluminescent assay to measure efficacy of conventional and DNA vaccinations against Helicobacter pylori

Vaccination against Helicobacter pylori using DNA sequences encoding Urease A and B subunits was compared to immunization with urease antigen and MTP-PE in a liposome formulation. To determine the effectiveness of a vaccine against H. pylori in a mouse model it is essential to quantify the number of H. pylori remaining in the stomachs following challenge with an inoculum of live bacteria. Culture assays and enzymatic assays produce inconsistent results often unsuitable to conclude if vaccine candidates are protective. To overcome this problem, we developed two assays: 1) a competitive quantitative PCR using a colorimetric readout and 2) a non-competitive direct quantitative PCR using a highly sensitive bioluminescent readout. The competitive PCR requires coamplification of a segment of the urease C sequence and an internal control standard in a competitive manner using a single set of primers. PCR products were quantified colorimetrically by an enzyme-linked immunosorbent assay and compared with known quantities of the internal control standard added to the PCR reaction. The highly sensitive, bioluminescent assay measures the amplified DNA directly using a flash-type luminescent tag and a specific probe. The Sydney strain of H. pylori was used for the mouse infection model. Quantification of H. pylori by either the bioluminescent assay or the competitive PCR was reliable, specific and sensitive compared to quantitative growth assays which often gave false results. The bioluminescent assay was much more sensitive and less labor/time intensive than the competitive PCR. The bioluminescent assay was able to quantitate as few as 100 bacteria, while the competitive assay could not detect less than 10(3) bacteria per mouse stomach. Quantification of H. pylori by bioluminescent assay was superior to the competitive assay and may be used for research applications, such as the development of vaccines, pathogenesis of gastric disease and monitoring of antibiotic treatment.     

Determination of Cr(III) and Cr(VI) in environmental waters by derivative flame atomic absorption spectrometry using flow injection on-line preconcentration with double-microcolumn adsorption

The species of Cr(III) and Cr(VI) in water samples were determined by flow injection on-line preconcentration and separation on two-microcolumn system-derivative flame atomic absorption spectrometry during a collaborative analysis for certification. The Cr(III) and Cr(VI) in water samples were retained on two microcolumns with ion exchange resin and were eluted directly to nebulizer by 15% HNO³ and 8% NH⁴NO³, respectively. The characteristic concentration (at the sensitivity grade of 2 mV min^?1 for 1 min of preconcentration time) for Cr(III) and Cr(VI) were 0.130 and 0.0985 μg l^?1, in the order which were 332- and 431-fold better than those of FAAS, and 45- and 47-fold better than those of FI-FAAS, respectively. The relative standard deviations were 3.27% and 3.66% with corresponding detection limits (3σ) of 0.244 and 0.235 μg l^?1, respectively. The linear ranges of determinations for Cr(III) and Cr(VI) were 0～100 μgm l^?1 with correlation coefficients of 0.9984 to 0.9996. The satisfactory recovery of 94.4%～106% for Cr(III) and Cr(VI) could be obtained from water samples.