Oxidative degradation of dye pollutants over a broad pH range using hydrogen peroxide catalyzed by FePz(dtnCl2)4.

The oxidative degradation of rhodamine B (RhB) with hydrogen peroxide activated by iron(II) tetra-(5,6-dichloro-1,4-dithiin)-porphyrazine (abbreviated as FePz(dtnCl(2))(4)) was studied by means of UV-Vis spectra, GC-MS and TOC analysis, in which the effects of pH, light, concentration of hydrogen peroxide and the degraded products of the RhB were investigated. The results indicate that FePz(dtnCl(2))(4) was found to exhibit high catalytic activity to activate hydrogen peroxide for the oxidative degradation of RhB and good stability over a broad pH range under visible light irradiation (lambda>420 nm). The conversions of RhB in 80 min were 99%, 85%, 52% and the TOC removals in 240 min were 91%, 64%, 18% when the initial solutions pHs were 2, 7, 11, respectively. HO(.) radicals were testified to generate in the biomimetic catalytic system both at pH 2 and 7 by means of spin-trapping electron spin resonance. However, control experiment with scavenging of HO() radicals displayed the quite different results at pH 2 and 7. Based on experiment results together with theoretic deduction, a mechanism for RhB oxidation involving two kinds of reactive oxidizing species was proposed, the homolytic cleavage generating the HO(.) radicals and the heterolytic cleavage generating the Pz(.)(+)Fe(IV)=O radicals.

Analysis of fatty acids in sputum from patients with pulmonary tuberculosis using gas chromatography-mass spectrometry preceded by solid-phase microextraction and post-derivatization on the fiber.

A method based on solid-phase microextraction (SPME) and post-derivatization on the fiber coupled to gas chromatography-mass spectrometry (GC-MS) was developed for the analysis of fatty acids in sputum from patients with pulmonary tuberculosis. The sputum specimens were digested, hydrolyzed, extracted, derivertized, injected and analyzed without cultivation or isolation of the microorganism. Under optimized conditions, the relative standard deviations (RSD, n=5) for all analytes were below 17% and the limits of detection varied from 1.68 (C(24:0)) to 150.4 microg L(-1) (C(12:0)). Good linearity was observed for all the fatty acids studied except for C(12:0) within a wide concentration range of three orders of magnitudes with the correlation coefficients ranging from 0.91 (C(24:0)) to 0.99 (C(14:0)). Fatty acids in sputum specimens from 21 persons were directly analyzed using the proposed method. The results show that in all the sputum specimens from patients, who were clinically diagnosed with tuberculosis (TB), tuberculosis stearic acid (TBSA) was detected, while in all the sputum samples from persons without TB, TBSA was not found. The possibility of using the proposed method to detect mycobacterium tuberculosis (MTB) via the identification of TBSA in sputum was discussed. The comparison with other methods including sputum culture and microscopy of direct smears indicated that the proposed method is fast and sensitive for the analysis of fatty acids in sputum and offers an alternative for the detection of MTB in sputum.

Headspace solid-phase microextraction with novel sol-gel permethylated-beta-cyclodextrin/hydroxyl-termination silicone oil fiber for determination of polybrominated diphenyl ethers by gas chromatography-mass spectrometry in soil.

A simple, sensitive, and accurate method for determination of polybrominated diphenyl ethers (PBDEs) in soil has been developed based on headspace solid-phase microextraction (HS-SPME) followed by gas chromatography-mass spectrometry (GC-MS). Permethylated-beta-cyclodextrin/hydroxyl-termination silicone oil (PM-beta-CD/OH-TSO) fiber was first prepared by sol-gel technology and employed in SPME procedure. By exploiting the superiorities of sol-gel coating technique and the advantages of the high hydrophobic doughnut-shaped cavity of PM-beta-CD, the novel fiber showed desirable operational stability and extraction ability. After optimization on extraction conditions like water addition, extraction temperature, extraction time, salts effect, and solvents addition, the method was validated in soil samples, achieving good linearity (r>0.999), precision (R.S.D.<10%), accuracy (recovery>78%), and detection limits (S/N=3) raging from 13.0 to 78.3pg/g.

Analysis of fatty acids in lung tissues using gas chromatography-mass spectrometry preceded by derivatization-solid-phase microextraction with a novel fiber.

In this article, a laboratory-made sol-gel derived fiber with butyl methacrylate/hydroxy-terminated silicone oil (BMA/OH-TSO) coating was first used for headspace solid-phase microextraction (HS-SPME) of medium and long chain fatty acids after derivatization and applied to the analysis of fatty acids in lung tissues by coupling to gas chromatography-mass spectrometry (GC-MS). The experimental parameters for derivatization, HS-SPME and desorption were optimized. Fatty acids in cancerous lung tissues from five patients with lung cancer were determined under the optimized conditions. Normal lung tissues from the same five patients were used as controls. This fiber showed higher extraction efficiency for fatty acids after derivatization when compared with commercial polydimethylsiloxane (PDMS) and polydimethylsiloxane-divinylbenzene (PDMS/DVB) fibers due to the three-dimensional network in the coating. The method presented in this paper showed satisfactory precision, accuracy, linearity and limits of detection (LODs). The relative standard deviation values were below 13.3% (n=5) and the recoveries obtained ranged from 76.35% to 107.0%. The results obtained using the SPME method were also compared with those got by using liquid-liquid extraction (LLE) technique. It was found that the sensitivity could be enhanced by the SPME method. The analysis of the cancerous lung tissues and normal controls from five patients with lung cancer indicated that the main components of lung tissue were palmitic acid (C16:0), stearic acid (C18:0) and lignoceric acid (C24:0). A comparison between the levels of the fatty acids in cancerous lung tissues and normal controls from the same a patient with lung cancer shows that most of the saturated fatty acids showed higher levels in cancerous lung tissues, while unsaturated fatty acids showed higher levels in normal controls on the whole.