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1.
J Chromatogr A ; 1275: 70-7, 2013 Feb 01.
Article in English | MEDLINE | ID: mdl-23305856

ABSTRACT

This article analyses the interferences in the quantification of traces of bisphenol S in paper by applying the direct analytical method "analytical pyrolysis gas chromatography mass spectrometry" (Py-GC/MS) in conjunction with on-line derivatisation with tetramethylammonium hydroxide (TMAH). As the analytes are simultaneously analysed with the matrix, the interferences derive from the matrix. The investigated interferences are found in the analysis of paper samples, which include bisphenol S derivative compounds. As the free bisphenol S is the hydrolysis product of the bisphenol S derivative compounds, the detected amount of bisphenol S in the sample may be overestimated. It is found that the formation of free bisphenol S from the bisphenol S derivative compounds is enhanced in the presence of tetramethylammonium hydroxide (TMAH) under pyrolytic conditions. In order to avoid the formation of bisphenol S trimethylsulphonium hydroxide (TMSH) is introduced. Different parameters are optimised in the development of the quantification method with TMSH. The quantification method based on TMSH thermochemolysis has been validated in terms of reproducibility and accuracy.


Subject(s)
Gas Chromatography-Mass Spectrometry/methods , Paper , Phenols/analysis , Sulfones/analysis , Benzhydryl Compounds/analysis , Benzhydryl Compounds/chemistry , Calibration , Gas Chromatography-Mass Spectrometry/standards , Hot Temperature , Phenols/chemistry , Quaternary Ammonium Compounds/chemistry , Reproducibility of Results , Sulfones/chemistry , Sulfonium Compounds/chemistry
2.
Analyst ; 137(9): 2250-9, 2012 May 07.
Article in English | MEDLINE | ID: mdl-22428152

ABSTRACT

In this paper a simplified method based on analytical pyrolysis gas chromatography mass spectrometry (Py-GC/MS) for the detection and quantification of bisphenol A and bisphenol S in paper samples is presented. The method enables a direct analysis of the samples without tedious sample preparation. As the analytes are thermally desorbed, a solvent extraction is not needed. The method is applicable to small samples of ~120 µg. The limits of detection are below 1 mg kg(-1) for bisphenol A and for bisphenol S. The limits of quantification are about 1.3 mg kg(-1). Several validation characteristics of the method developed like standard error of calibration, limit of determination, linearity, and accuracy are given. To prove the accuracy of the method, interferences and matrix dependencies were also investigated. The influence of the pyrolysis crucibles, a special effect of analytical pyrolysis, was additionally investigated. It was found that the impact of the crucibles on the results is significant and one cause for matrix effects.

3.
Planta ; 235(2): 359-73, 2012 Feb.
Article in English | MEDLINE | ID: mdl-21909761

ABSTRACT

Constitutive expression of the FPF1 gene in hybrid aspen (Populus tremula L. × P. tremuloides Michx.) showed a strong effect on wood formation but no effect on flowering time. Gene expression studies showed that activity of flowering time genes PtFT1, PtCO2, and PtFUL was not increased in FPF1 transgenic plants. However, the SOC1/TM3 class gene PTM5, which has been related to wood formation and flowering time, showed a strong activity in stems of all transgenic lines studied. Wood density was lower in transgenic plants, despite significantly reduced vessel frequency which was overcompensated by thinner fibre cell walls. Chemical screening of the wood by pyrolysis GC/MS showed that FPF1 transgenics have higher fractions of cellulose and glucomannan products as well as lower lignin content. The latter observation was confirmed by UV microspectrophotometry on a cellular level. Topochemical lignin distribution revealed a slower increase of lignin incorporation in the developing xylem of the transgenics when compared with the wild-type plants. In line with the reduced wood density, micromechanical wood properties such as stiffness and ultimate stress were also significantly reduced in all transgenic lines. Thus, we provide evidence that FPF1 class genes may play a regulatory role in both wood formation and flowering in poplar.


Subject(s)
Arabidopsis Proteins/chemistry , Arabidopsis/genetics , Gene Expression Regulation, Plant , Populus/chemistry , Wood/physiology , Agrobacterium tumefaciens/chemistry , Agrobacterium tumefaciens/genetics , Arabidopsis Proteins/genetics , Cell Wall/chemistry , Cellulose/chemistry , Chimera/genetics , Chimera/physiology , DNA, Plant/genetics , Flowers/physiology , Gas Chromatography-Mass Spectrometry , Genes, Plant , Lignin/chemistry , Mannans/chemistry , Microspectrophotometry/methods , Plant Cells/chemistry , Plant Stems/chemistry , Plant Stems/genetics , Plant Stems/physiology , Plants, Genetically Modified/chemistry , Plants, Genetically Modified/genetics , Plants, Genetically Modified/physiology , Populus/genetics , Populus/physiology , Stress, Physiological , Surface Properties , Time Factors , Ultraviolet Rays , Wood/chemistry , Wood/genetics
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