Biomedical subjects

Carlo Crescenzi

Publications and source records attributed to Carlo Crescenzi.

8 recordsLinked to original sources

PubMed2006

Air sampling with Empore solid phase extraction membranes and online single-channel desorption/liquid chromatography/mass spectrometry analysis: determination of volatile and semi-volatile organophosphate esters.

A method for determining organophosphate esters in air samples using C8 Empore solid phase extraction (SPE) membranes has been developed. After the sampling the analytes trapped in the membrane are completely desorbed with methanol, using an extraction cell connected online to the organic modifier channel of a HPLC gradient pump. The addition of water to the mobile phase prior to analytical chromatography ensures that the analytes are refocused and efficiently separated. Sampling with Empore SPE membranes enables the collection of analytes in both the vapour phase and particulate matter. During the air sampling procedure no losses were observed after 24 h of sampling, yielding a total volume of 14.4 m3, even for the most volatile compound used in this investigation (trimethylphosphate). Complete desorption was observed for all the organophosphate esters and recoveries were greater than 95%, with a relative standard deviation of less than 8%. The limits of detection ranged between 0.4 and 19 pg/m3. The effect of particulate matter on the extraction efficiency was investigated in detail by spiking the membranes with reference standard material. It was also found that the SPE membranes could be stored for at least 5 days at room temperature without any evidence of loss. The efficacy of the method was verified using real samples from different common indoor environments. Interestingly, significant quantities of several phosphate esters were found in a NIST standard reference material (urban dust, SRM 1649a).

Air Pollutants↗

PubMed2005

Determination of the flame retardant tetrabromobisphenol A in air samples by liquid chromatography-mass spectrometry.

An original method based on LC-MS for determination of the flame retardant tetrabromobisphenol A (TBBPA) in air is presented, as an alternative to the traditionally used GC-MS. The soft ionization in LC-MS makes it possible to monitor the intact molecule and to use 13C-labelled TBBPA as an internal surrogate standard, two features that improve both accuracy and precision of the analyses. Comparison of different acquisition modes in electrospray ionization showed that the lowest detections limit, 3.1 pg TBBPA injected, was obtained in SIM monitoring the molecular ions 542.7/544.7. A fragmentation pathway of TBBPA in LC-ESI-MS is suggested. The only sample clean-up steps required are solvent reduction and filtration of the sample extract. Recoveries were 93% at a 30 ng level and 75% at 3 ng. The new method was tested by analyses of air samples collected at a recycling plant for electronic equipment. The amount of TBBPA found was 13.8 ng/m3 with an RSD of 5.9%. Furthermore, it was found that TBBPA in a standard solution could be partially debrominated, if not carefully protected from light during storage.

Chromatography, Liquid↗

PubMed2005

Determination and characterization of organic explosives using porous graphitic carbon and liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

A new LC-MS method for the determination and characterization of three groups of commonly used organic explosives (nitroaromatic compounds, cyclic nitroamines and nitrate esters) was developed using a porous graphitic carbon (PGC) (Hypercarb) column. Twenty-one different explosive-related compounds--including 2,4,6-trinitrotoluene, its by-products and its degradation products--were chromatographically separated in a single analysis. This efficient separation facilitates the identification of the manufacturer of the explosive using the identified analytes as a fingerprint. A final, conclusive identification of the analytes can be obtained using LC-MS equipped with an atmospheric pressure chemical ionization (APCI) interface. Solvent effects on chromatographic behaviour were investigated, as were the effects of solvent mixtures and mobile phase additives. The number and the relative positions of the nitro groups within analyte molecules influence their order of elution; these effects were investigated. The data thus generated can be interpreted to support a hypothesis concerning the retention mechanism of nitro-containing compounds when using PGC. Limits of detection ranged from 0.5 to 41.2 ng. The new methodology described herein improves the sensitivity and selectivity of explosive detection. The effectiveness of the method is demonstrated by the analysis of soil samples containing explosives residue from test fields in Sweden and Afghanistan.

Atmospheric Pressure↗

PubMed2004

Investigation of matrix effects of urine on a molecularly imprinted solid-phase extraction.

This study investigates matrix effects on a molecularly imprinted solid-phase extraction (MISPE) method developed for the clean-up of diphenyl phosphate (a hydrolysis product of the commonly used flame retardant and plasticizer, triphenyl phosphate) in urine samples. The influence of potentially interfering compounds that naturally occur in urine was examined with respect to extraction recovery, repeatability and selectivity. The components tested were NaCl, urea, creatinine and hippuric acid. The imprinted polymer was prepared using 2-vinylpyridine as the functional monomer, ethylene glycol dimethacrylate as crosslinker and a structural analogue of the analyte as the template molecule. The recovery of diphenyl phosphate from water standards was over 90% using MISPE, compared to less than 25% using a non-imprinted SPE (NISPE) counterpart. The selectivity of MISPE compared to NISPE was achieved in a wash step with a basic modifier in methanol. The recovery and repeatability of the MISPE method were affected most by NaCl in the tested concentrations, while urea, creatinine and hippuric acid had no significant influence. NaCl most likely weakens the binding during the loading of the sample. This effect could be suppressed by diluting the sample with a citrate buffer at pH 4.0.

Creatinine↗

PubMed2003

Determination of a flame retardant hydrolysis product in human urine by SPE and LC-MS. Comparison of molecularly imprinted solid-phase extraction with a mixed-mode anion exchanger.

Diphenyl phosphate is a hydrolysis product and possible metabolite of the flame retardant and plasticiser additive triphenyl phosphate. A molecularly imprinted polymer solid-phase extraction (MISPE) method for extracting diphenyl phosphate from aqueous solutions has been developed and compared with SPE using a commercially available mixed-mode anion exchanger. The imprinted polymer was prepared using 2-vinylpyridine (2-Vpy) as the functional monomer, ethylene glycol dimethacrylate (EGDMA) as the cross-linker, and a structural analogue of the analyte as the template molecule. The imprinted polymer was evaluated for use as a SPE sorbent, in tests with both aqueous standards and spiked urine samples, by comparing recovery and breakthrough data obtained using the imprinted form of the polymer and a non-imprinted form (NIP). Extraction from aqueous solutions resulted in more than 80% recovery. Adsorption by the molecularly imprinted polymer (MIP) was non-selective, but selectivity was achieved by selective desorption in the wash steps. Diphenyl phosphate could also be selectively extracted from urine samples, although the urine matrix reduced the capacity of the MISPE cartridges. Recoveries from urine extraction were higher than 70%. It was important to control pH during sample loading. The MISPE method was found to yield a less complex LC-ESI-MS chromatogram of the urine extracts compared with the mixed-mode anion-exchanger method. An LC-ESI-MS method using a Hypercarb LC column with a graphitised carbon stationary phase was also evaluated for organophosphate diesters. LC-ESI-MS using negative-ion detection in selected ion monitoring (SIM) mode was shown to be linear for diphenyl phosphate in the range 0.08-20 ng microL(-1).

Anion Exchange Resins↗

PubMed2003

Feasibility of an on-line restricted access material/liquid chromatography/tandem mass spectrometry method in the rapid and sensitive determination of organophosphorus triesters in human blood plasma.

A rapid on-line solid phase extraction/liquid chromatography/tandem mass spectrometry (SPE/LC/MS/MS) method using restricted access material (RAM) was developed for the simultaneous determination of eight organophosphorus triesters in untreated human blood plasma. In a process involving column-switching techniques, the analytes were enriched on the RAM column, separated using a C-18 analytical column and detected with LC/MS. Tandem mass spectrometry was used to characterize and quantify the analytes. To elucidate the fragmentation pathway of a number of the analytes, MS3 experiments using an ion trap mass spectrometer were performed. The matrix effects associated with using APCI and ESI interfaces were investigated. The recoveries obtained were in the range 60-92% (R.S.D.<6%), with estimated detection limits between 0.2 and 1.8 ng/ml of plasma, and the total analysis time was 27 min.

Chromatography, Liquid↗

PubMed2003

Enhanced detection of nitroaromatic explosive vapors combining solid-phase extraction-air sampling, supercritical fluid extraction, and large-volume injection-GC.

A complete method for sampling and analyzing of energetic compounds in the atmosphere is described. The method consists of the hyphenation of several techniques: active air sampling using a solid-phase extraction cartridge to collect the analytes, extraction of the sorbed analytes by toluene/methyl tert-butyl ether modified supercritical fluid extraction (SFE), and analysis of the extract by large-volume injection GC-nitrogen/phosphorus detection. The GC system is equipped with a loop-type injection interface with an early solvent vapor exit, a utilizing concurrent solvent evaporation technique. Chemometric approaches, based on a Plackett-Burman screening design and a central composite design for response surface modeling, were used to determine the optimum SFE conditions. The relative standard deviations of the optimized method were determined to be 4.3 to 7.7%, giving raise to method detection limits ranging from 0.06 to 0.36 ng in the sampling cartridge, equivalent to 6.2-36.4 pg/L in the atmosphere, standard sampling volume 10 L. The analytical method was applied to characterize headspace composition above military grade trinitrotoluene (TNT). Results confirm that 2,4-dinitrotoluene (DNT) and 1,3-dinitrobenzene (DNB) constitute the largest vapor flux, but TNT, 2,6-DNT, and trinitrobenzene TNB were also consistently detected in all the samples.

Journal Article↗

PubMed2002

On-line coupling of supercritical fluid extraction with high-performance liquid chromatography for the determination of explosives in vapour phases.

An analytical method for determining nitroaromatic explosives in vapour phases is presented. Samples were collected by pumping air through glass fibre filters and polyurethane foam adsorbents, and an on-line extraction system combining supercritical fluid extraction (SFE) and high-performance liquid chromatography (HPLC) was developed. This allows analytes to be transferred from the adsorbent to the HPLC system via a porous graphitic carbon trap. When using gradient elution with a suitable mobile phase, most of the nitroaromatic isomers tested were separated. The proposed method is fully automated, allows a complete analysis to be processed in less than 30 min, and it is compatible with most of the organic solvents commonly used as SFE modifiers or additives. The method has been applied to the analysis of real samples obtained from headspace sampling of military-grade 2,4,6-trinitrotoluene and has been shown to constitute a promising alternative for assessing whether areas are mined in landmine-clearing operations.

Chromatography, High Pressure Liquid↗