The thermal degradation of the aliphatic polyamides 6 and 66 was investigated by means of the combined techniques TA-MS and TA-FTIR. The analyses were performed in three different devices. Sample mass ranged from 13 mg to 1 g and heating rates of 2.6 and 10 K min–1 were used in both air and nitrogen atmospheres. The most important decomposition products were caprolactam for PA 6 and cyclopentanone for PA 66. Evolution of NH3 and HCN was registered. The findings of the two hyphenated techniques led to the same results and complemented each other well. The evolved products were captured and analyzed off-line by GC/MS for further confirmation of results.
Authors:M. Saraji-Bozorgzad, R. Geißler, T. Streibel, M. Sklorz, E. Kaisersberger, T. Denner, and R. Zimmermann
The potential of hyphenating thermogravimetry (TG) and soft photo ionisation mass spectrometry (EBEL-SPI-MS) for fundamental
and applied research and material analysis has been demonstrated by a newly developed TG-SPI quadrupole MS coupling (TG-SPI-QMS).
Thermal decomposition of three common plastics, polyethylene (PE), polystyrene (PS) and polyvinylchloride (PVC) has been studied.
While the decomposition of PE and PS in inert atmosphere takes place in a one step process (main mass loss at about 490 and
420 °C, respectively), PVC decomposes in a two step mechanism. The organic signature of the PE decomposition shows homologous
series of alkenes and polyenes, while PS is forming mainly styrene mono- and oligomers. In the PVC decomposition, firstly
hydrogen chloride (HCl) is eliminated in a hydro-dechlorination reaction (1st mass loss step: 285–305 °C), this is accompanied
by the emission of the carbon skeletons of small aromatics (predominately benzene and naphthalene). In the second step (2nd
mass loss step: 490–510 °C), the residual cross-linked polyolefin moieties decompose under release of heavily alkylated aromatics,
including larger PAH. Chlorinated aromatics are formed only in trace levels.
Authors:K. Shanker, M. Singh, V. Srivastava, R. K. Verma, A. K. Gupta, and M. M. Gupta
An online-hyphenated high-performance liquid chromatography-photodiode array-mass spectrometry (HPLC-PDA-MS) analytical method was developed for the simultaneous determination of six lignans of therapeutic importance in four Phyllanthus spp. (P. amarus, P. maderaspatensis, P. urinaria, and P. virgatus). HPLC with monolithic reverse phase silica column (4.6 × 100 mm) and simple isocratic elution of methanol-water mixed with dioxane facilitated the separation of lignans of diverse nature such as diarylbutyrolactone, tetrahydrofuran, isomeric aryltetralin, and diarylbutane type for quantitative analysis. Targeted lignans viz. heliobuphthalmin lactone (1), virgatusin (2), hypophyllanthin (3), phyllanthin (4), nirtetralin (5), and niranthin (6) were confirmed unambiguously in four Phyllanthus species by their abundant molecular adduct ions, retention time, UV, and mass spectra as compared with those of reference compounds. Advantages and limitations of both detection techniques for qualitative (fingerprinting) and quantitative analysis of the above mentioned lignans in four Phyllanthus spp. are discussed. The method was validated following international guidelines. The described method can be utilized for assays and stability tests of P. amarus extracts as well as traditional Indian medicine based on Phyllanthus herb.
Authors:Emil Mincsovics, Katalin Pápai, Krisztina Ludányi, Ádám Dávid, Marianna Budai, István Antal, and Imre Klebovich
The newly developed experimental OPLC separation unit 100 (OSU 100) has been used for fully on-line multiple hyphenation using the one-channel flowing eluent wall (FEW) arrangement at the inlet. OSU 100-UV and OSU 100-DAD-ESI-MS with manual injector or autosampler were used to test the connected systems (OPLC-UV; OPLC-DAD-ESI-MS), using xanthine standards (caffeine, theophylline, theobromine) and green tea leaf extract as model compounds. The mobile phase chloroform-trifluoroacetic acid-acetonitrile-methanol, 76:4:6.67:13.33 (
) is suitable for rapid and selective separation, DAD, and ESI-MS of xanthines. The detection sensitivity of OPLC-UV or OPLC-DAD was increased by hyphenation with ESI-MS coupled in series. In contrast with DAD, the extracted ion chromatogram (
= 181.1 Da) after background subtraction yields readily measurable peaks from the small amounts of theophylline and theobromine in tea leaf extract. Analysis of xanthines was achieved within 10 min with less than 2 mL mobile phase. Owing to the openable adsorbent layer in OPLC the bed conditions can, moreover, be checked off-line after single or multiple fully online separations.
Authors:Christian Mattle, Nico Heigl, Gudrun Abel, Günther Bonn, and Christian Huck
By use of near infrared (NIR) spectroscopy hyphenated to thinlayer chromatography (TLC) for analysis of methoxylated flavones in a phytomedicine we sought to achieve two objectives: first, to establish a method for rapid, qualitative identification of five methoxylated flavones, denoted G1, G2, G3, G4, and G5, in order of their RF values in normal-phase TLC, and, second, to produce a quantitative model for analysis of G4 (3′,4′,5′-trimethoxyflavone), the compound most representative of Primula veris flowers in phytomedicine. To provide appropriate reference analytical data for building the multivariate cluster and partial least-squares regression (PLS) model, TLC was performed on alumina with n-hexane-ethyl acetate 70:30 (v/v) as mobile phase. Forty-four spectra of eleven independent phytomedicine samples were analyzed with five scans to generate a qualitative cluster model based on PCA (principle-components analysis) that enabled differentiation between G1-G5 on the basis of their methoxylation pattern. This PLS model, in the calibration range between 0 and 1000 mg L−1, enabled quantification of G4 with a standard error of cross validation (SECV) ,54.61 mg L−1. The possibility of conducting qualitative and quantitative analysis simultaneously by use of this method revealed NIRS to be an efficient alternative to conventional modes of detection used for analysis of G1-G5, especially in phytomedicines.
Conventional calorimetry has always the difficulty of choosing between near to equilibrium working conditions and high thermal
ramp rates. Thus, either the transport phenomena and sample homogeneities are good but the signals become weak due to thermal
losses, or the signals are sharp, but strong gradients across the sample lead to chemical and thermal heterogeneities. The
described pulsed fluidized bed technique, by strongly stirring the sample, allows good sample homogeneities even at high ramp
rates. Moreover, the permanently regenerated cover gas allows as well a good heat transfer towards the thermocouples as a
constant atmosphere composition leading to very precise onset temperatures.
Authors:L. Pérez-Maqueda, J. Poyato, and J. Pérez-Rodríguez
The thermal decomposition of the ammonium exchanged vermiculite takes place in three steps. A strong correlation exists between
the mass loss of ammonia and water suggesting a simultaneous release. It is proposed that proton transfer from the ammonium
ion to the hydroxyl units results in this simultaneous release. This behaviour could be explained by a mechanism where a resulting
proton, produced by the release of ammonia out of ammonium cation, combines with a structural hydroxyl to form water. Sonication
produces a substantial reduction in the particle size of the vermiculite sample. Thus, the macroscopic particle size of the
untreated material is drastically reduced to the micrometers range while the structure as assayed by XRD remains unchanged.
The particle size reduction produced by the sonication treatment modifies the thermal decomposition profile, mainly the mass
percentages of the different steps.
Authors:A. Hardy, H. Van den Rul, M. Van Bael, and J. Mullens
High-temperature X-ray diffraction, absorption–reflection infrared spectrometry and thermal analysis coupled on-line to mass
spectrometry, were applied to citratoperoxo precursor gels and films of (Bi,Nd)4Ti3O12 (BNdT). A slow heating rate resulted in secondary phases (Bi2Ti2O7 and Bi2O3) while a high rate yielded phase pure layered perovskite BNdT. Comparison of the evolved gas profiles from the bulk gel and
thin film, showed complete decomposition of the film at lower temperature than expected from thermogravimetric and evolved
gas analysis of the bulk gel. Thermal methods adapted to thin films, therefore are crucial for understanding and controlling
the oxide formation in the film.
, Basic Principles of Planar Chromatography and its Potential for Hyphenated Techniques , in: M.M. Srivastava (ed.) High-Performance Thin-Layer Chromatography (HPTLC) , Springer-Verlag , Berlin