Ultra high performance liquid chromatography tandem mass spectrometry determination and profiling of prohibited steroids in human biological matrices. A review.

The use of doping agents, once restricted to professional athletes, has nowadays become a problem of public health, since it also concerns young people and non-competing amateurs in different sports. The use is also diffused in social life for improving physical appearance and enhancing performance and even dietary supplements assumed to improve performance often contain anabolic steroids. While decades ago the so-called "classical doping agents" (like stimulants and narcotics) were used, to-day anabolic steroids are more widely diffused.

Non-target screening of Allura Red AC photodegradation products in a beverage through ultra high performance liquid chromatography coupled with hybrid triple quadrupole/linear ion trap mass spectrometry.

The study deals with the identification of the degradation products formed by simulated sunlight photoirradiation in a commercial beverage that contains Allura Red AC dye. An UHPLC-MS/MS method, that makes use of hybrid triple quadrupole/linear ion trap, was developed. In the identification step the software tool information dependent acquisition (IDA) was used to automatically obtain information about the species present and to build a multiple reaction monitoring (MRM) method with the MS/MS fragmentation pattern of the species considered.

Identification of photodegradation products of Allura Red AC (E129) in a beverage by ultra high performance liquid chromatography-quadrupole-time-of-flight mass spectrometry.

The study deals with the identification of the degradation products formed by simulated sunlight photoirradiation in a beverage that contains Allura Red AC (E129) dye. An UHPLC-MS/MS method that makes use of high resolution quadrupole-time-of-flight mass spectrometer, was developed. For the identification of the degradation products the software tool Information Dependent Acquisition (IDA) was used to automatically obtain information about the high resolution MS and MS/MS spectra of the species present.

Simultaneous determination of sixteen underivatized biogenic amines in human urine by HPLC-MS/MS.

The broad group of biogenic amines includes polyamines and catecholamines, whose presence in human tissues and biological fluids can give important diagnostic information and act as marker of many pathologies. In particular, polyamines are involved in cancer cell growth while catecholamines act as neurotransmitters and hormones. Their simultaneous determination in biological tissues and fluids is therefore an important task.

Simultaneous determination of thirteen polycyclic aromatic hydrocarbons and twelve aldehydes in cooked food by an automated on-line solid phase extraction ultra high performance liquid chromatography tandem mass spectrometry.

An on-line solid phase extraction (SPE) ultra high performance liquid chromatography tandem mass spectrometry method has been developed for the simultaneous identification and determination of thirteen polycyclic aromatic hydrocarbons (PAHs) and twelve aldehydes (derivatized with 2,4-dinitrophenylhydrazine). The chromatographic conditions have been optimized to obtain the maximum of sensitivity and resolution taking into account the different retention interactions and the different ionization conditions of PAHs and derivatized aldehydes. LOD values ranging from 0.

Determination of perfluorochemicals in biological, environmental and food samples by an automated on-line solid phase extraction ultra high performance liquid chromatography tandem mass spectrometry method.

A rapid on-line solid phase extraction ultra high performance liquid chromatography tandem mass spectrometry method was developed for the identification and quantitation of nine perfluorinated compounds in matrices of environmental, biological and food interest. Pre-treatment, solid phase extraction, chromatographic and mass detection conditions were optimised, in order to apply the whole methodology to the analysis of different matrices. Particular attention was devoted to the evaluation of matrix effect and the correlated phenomena of ion enhancement or suppression in mass spectrometry detection.

Automated online solid phase extraction ultra high performance liquid chromatography method coupled with tandem mass spectrometry for determination of forty-two therapeutic drugs and drugs of abuse in human urine.

The study deals with a fast (analysis times of around 11 min) simultaneous identification and quantification in human urine of 42 drugs (21 therapeutic and 21 of abuse), through an automated online solid phase extraction ultra high performance liquid chromatography method coupled with tandem mass spectrometry (SPE UHPLC-MS/MS). In the method validation, particular attention was devoted to the matrix effect, through matrix-matched calibration in blank urine, suitably diluted. For all the abuse drugs investigated, the limit of quantitation (LOQ) values are lower than the legal threshold concentration levels, making the method suitable for routine control.

A new on-line solid phase extraction high performance liquid chromatography tandem mass spectrometry method to study the sun light photodegradation of mono-chloroanilines in river water.

The study investigates the natural photodegradation pathway of mono-chloroanilines in river waters, with the aim to identify the predominant photoproducts formed. At this purpose a new sensitive on-line SPE HPLC-MS/MS method has been developed with LOQ values equal or lower than the legal threshold concentration levels allowed for mono-chloroanilines in waters. The degradation processes of o-, m- and p-chloroaniline have been investigated subjecting their solutions, prepared both in ultrapure and in river water, to sun light irradiation simulated by a solar box system.

Signal suppression/enhancement in high-performance liquid chromatography tandem mass spectrometry.

The review discusses the pitfalls of the matrix effect in mass spectrometry detection hyphenated to liquid chromatography separation. Matrix effect heavily influences both qualitative and quantitative analyses, giving rise to suppression or enhancement of the signal. As generally recognised, the predominant cause is the presence of undesired components that co-elute in the chromatographic separation and alter the ionisation process.

High-performance liquid chromatography-ultraviolet detection method for the simultaneous determination of typical biogenic amines and precursor amino acids. Applications in food chemistry.

A reversed-phase high-performance liquid chromatography (HPLC) method was developed for the simultaneous determination in food of biogenic amines and their precursor amino acids after a precolumn derivatization with dansyl chloride. The chromatographic conditions, selected to be suitable for mass spectrometry detection, were optimized through experimental design and artificial neural networks. The HPLC-UV method was validated by comparing the separation results with those obtained through a HPLC method, working under the same chromatographic conditions but employing mass spectrometry detection.

Sun light degradation of 4-chloroaniline in waters and its effect on toxicity. A high performance liquid chromatography - Diode array - Tandem mass spectrometry study.

This paper studies the degradation reactions that 4-chloroaniline can naturally undergo in waters for the action of sun light. 10.00 mg L(-1) 4-chloroaniline aqueous solution, without any addition of organic solvent, are undergone to photoirradiation under conditions that simulate sun light.

Evaluation of signal and noise and identification of a suitable target function in the tuning of an ESI ion trap mass spectrometer by multivariate pattern recognition tools.

When mass spectrometry is not combined to separation techniques, the evaluation of signal and noise in a complex mass spectrum is not trivial. The tuning of the spectrometer based only on the increase of the signal of a selected number of m/z values does not ensure the achievement of the best experimental conditions: signal could improve and noise could increase as well. The scope of this work is the development of a function separating signal and noise (for evaluating the S/N) from complex mass spectra for potential use as target function for the automatic tuning of the instrument.

Monitoring of pigmented surfaces in accelerated ageing process by ATR-FT-IR spectroscopy and multivariate control charts.

This work is an extension of a method for monitoring the conservation state of pigmented surfaces presented in a previous paper. A cotton canvas painted with an organic pigment (Alizarin) was exposed to UV light in order to evaluate the effects of the applied treatment on the surface of the sample. The conservation state of the pigmented surface was monitored with ATR-FT-IR spectroscopy and multivariate control charts.

Monitoring of pigmented and wooden surfaces in accelerated ageing processes by FT-Raman spectroscopy and multivariate control charts.

Two of the most suitable analytical techniques used in the field of cultural heritage are NIR (near-infrared) and Raman spectroscopy. FT-Raman spectroscopy coupled to multivariate control charts is applied here for the development of a new method for monitoring the conservation state of pigmented and wooden surfaces. These materials were exposed to different accelerated ageing processes in order to evaluate the effect of the applied treatments on the goods surfaces.

Hydrolytic and photoinduced degradation of tribenuron methyl studied by HPLC-DAD-MS/MS.

The paper studies, with the help of HPLC-DAD-MS/MS technique, the hydrolytic and photoinduced degradation processes that take place in aqueous solutions of tribenuron methyl, both when preserved in the dark and when undergoing solar box irradiation under conditions that simulate sun light. The results indicate that the degradation products formed by hydrolysis alone and by photoirradiation are the same, but kinetics of the hydrolysis reaction is much slower. The degradation products are identified as 2-methoxy-4-methylamino-6-methyl-1,3,5-triazine (P1), methyl 2-aminosulfonylbenzoate (P2), and saccharin (P3) and quantified.

Sorption and desorption behavior of chloroanilines and chlorophenols on montmorillonite and kaolinite.

The bioavailability of pollutants, pesticides and/or their degradation products in soil depends on the strength of their sorption by the different soil components, particularly by the clay minerals. This study reports the sorption-desorption behavior of the environmentally hazardous industrial pollutants and certain pesticides degradation products, 3-chloroaniline, 3,4-dichloroaniline, 2,4,6-trichloroaniline, 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol on the reference clays kaolinite KGa-1 and Na-montmorillonite SWy-l. In batch studies, 2.

HPLC-MSn to investigate the oxidative destruction pathway of aromatic sulfonate wastes.

The article concerns the problem of destruction and remediation of industrial wastes containing aromatic sulfonates. The effects of an oxidation process induced by thermally activated persulfate in the degradation of 1,5-naphthalenedisulfonate (NDS) are investigated by the use of UV-Vis spectrophotometry, high performance liquid chromatography-mass spectrometry (HPLC-MS) and HPLC-MS(n) techniques. The results obtained indicated that thermal activation (80 degrees C) of a solution containing NDS and sodium persulfate in a molar ratio equal to 1 leads to the cleavage of the naphthalene structure.

HPLC-MS degradation study of E10 Sunset Yellow FCF in a commercial beverage.

Experimental evidence has shown that a beverage containing Sunset Yellow FCF (labelled as E110 in the European Union), when exposed to natural conditions of summer temperature and sunlight, losses its colour. To possibly identify the degradation pathway and collect information on the potential toxicity of the uncoloured species formed, different degradation conditions, under both oxidising and reducing environments, were simulated in laboratory. Experiments were carried out under the following conditions: (i) thermally induced degradation, (ii) visible photo induced degradation, (iii) UV-photo induced conditions in oxidising environment (addition of hydrogen peroxide, Fenton reaction) and (iv) UV-photo induced conditions in reducing environment (addition of sulphide and ascorbic acid, addition of ascorbic acid in the absence and in the presence of saccharose).

The state of conservation of painted surfaces in the presence of accelerated ageing processes monitored by use of FT-Raman spectroscopy and multivariate control charts.

A new method has been developed for monitoring the degradation of paintings. Two inorganic pigments (ultramarine blue and red ochre) were blended with linseed oil and spread on canvas. Each canvas was subjected to simulated accelerated ageing in the presence of typical degradation agents (UV radiation and acidic solution).

Miniaturised pressurised liquid extraction of chloroanilines from soil with subsequent analysis by large-volume injection-gas chromatography-mass spectrometry.

A number of chloroanilines were extracted from soil by means of miniaturised pressurised liquid extraction (PLE). The extraction procedure was optimised for both large-volume on-column (LV-OC) and programmed-temperature vaporisation (PTV) injections combined with GC-MS. Hexane was the only extraction solvent suited for LV-OC and hexane/acetone gave the best results when using a PTV.

Comparison of different calibration methods for the determination by FT-NIR spectroscopy of the hydroxyl number in polyester resins.

Different calibration methods have been applied for the determination of the Hydroxyl Number in polyester resins, namely Partial Least Squares (PLS), Principal Component Regression (PCR), Ordinary Least Squares with selection of the variables by genetic algorithm (OLS-GEN) and back-propagation Artificial Neural Networks (BP-ANN). The predictive ability of the regression models was estimated by splitting the dataset in training and test sets by application of the Kohonen self-organising maps. The linear methods (OLS-GEN, PLS and PCR) showed comparable results while artificial neural networks provided the best results both in fitting and prediction.

A method for monitoring the surface conservation of wooden objects by Raman spectroscopy and multivariate control charts.

The principles of quality control and multivariate statistical analysis were applied to the monitoring of the conservation state of wooden works of art. Three degradation processes (exposure to a wet atmosphere, to an acidic attack, and to UV light) were simulated on the surface of wooden boards of the XVI century and were monitored by the use of Raman spectroscopy. The resulting spectra were treated by principal component analysis, which allowed reduction of the system dimensionality.

Monitoring of an industrial process by multivariate control charts based on principal component analysis.

The control and monitoring of an industrial process is performed in this paper by the multivariate control charts. The process analysed consists of the bottling of the entire production of 1999 of the sparkling wine "Asti Spumante". This process is characterised by a great number of variables that can be treated with multivariate techniques.

Optimisation of the formulation of a bubble bath by a chemometric approach market segmentation and optimisation.

The optimisation of the formulation of a commercial bubble bath was performed by chemometric analysis of Panel Tests results. A first Panel Test was performed to choose the best essence, among four proposed to the consumers; the best essence chosen was used in the revised commercial bubble bath. Afterwards, the effect of changing the amount of four components (the amount of primary surfactant, the essence, the hydratant and the colouring agent) of the bubble bath was studied by a fractional factorial design.

Chemometric investigations on environmental data from Carlo Alberto irrigation canal (Alessandria, Piedmont, Italy).

The Carlo Alberto Canal connects Bormida and Tanaro rivers in Piedmont (ITALY). It was created for irrigation purposes but since its waters are suspected to be polluted, a sampling campaign was performed by the ARPA of Alessandria. The physico-chemical parameters analysed along 3 years (1998-2000) were investigated by multivariate chemometric methods.