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Journal: Journal of chromatography. A


A rapid thermal desorption-gas chromatography-electron ionization-mass spectrometry (TD-GC-EI-MS) method for airborne transfluthrin detection is studied. Active air sampling of 9 L over 1 h at 23 °C through a Tenax®-loaded tube resulted in efficient capture of airborne transfluthrin. Subsequent thermal desorption was employed to achieve an LOD of 2.6 ppqv (parts per quadrillion by volume). A minimum primary desorption temperature of 300 °C is necessary for optimal recovery of sample from the Tenax® adsorbent. The matrix effects of indoor air lead to an error of 10.9% and 10.5% recovery of sample (10 pg and 100 pg loaded tubes, respectively). The linear range was 74-74,000 ppqv with a correlation coefficient of 0.9981. Active air sampling of a novel passive release device revealed a ∼150 pg/L airborne concentration gradient over 1 m, providing spatial characterization of the device’s performance. This efficient method allows for the remote collection of samples and rapid analysis of airborne transfluthrin from industrial applications, optimization studies of commercial products as well as domestic/household monitoring.


A method for the rapid analysis of volatile organic compounds (VOCs) in smoke from tobacco and electronic cigarettes and in exhaled breath of users of these smoking systems has been developed. Both disposable and rechargeable e-cigarettes were considered. Smoke or breath were collected in Bio-VOCs. VOCs were then desorbed in Tenax cartridges which were subsequently analyzed by thermal desorption coupled to gas chromatography-mass spectrometry. The method provides consistent results when comparing the VOC compositions from cigarette smoke and the equivalent exhaled breath of the smokers. The differences in composition of these two sample types are useful to ascertain which compounds are retained in the respiratory system after tobacco cigarette or e-cigarette smoking. Strong differences were observed in the VOC composition of tobacco cigarette smoke and exhaled breath when comparing with those of e-cigarette smoking. The former involved transfers of a much larger burden of organic compounds into smokers, including benzene, toluene, naphthalene and other pollutants of general concern. e-Cigarettes led to strong absorptions of propylene glycol and glycerin in the users of these systems. Tobacco cigarettes were also those showing highest concentration differences between nicotine concentrations in smoke and exhaled breath. The results from disposable e-cigarettes were very similar to those from rechargeable e-cigarettes.

Concepts: Smoking, Tobacco, Tobacco smoking, Cigarette, Nicotine, Electronic cigarette, Propylene glycol, Glycerol


Static headspace - multi-capillary column - gas chromatography - ion mobility spectrometry (SHS-MCC-GC-IMS) has been applied to the analysis of malodour compounds from soiled clothing (socks and T-shirts), pre- and post washing, at low temperature (20°C). Six volatile compounds (VCs) (i.e. butyric acid, dimethyl disulfide, dimethyl trisulfide, 2-heptanone, 2-nonanone and 2-octanone) were identified. After sensory evaluation of soiled garments they were subjected to laundering with non-perfumed washing powder. The efficiency of the laundering process was evaluated by determining the reduction of each detected volatile compound (VC) post-wash (damp) for socks and T-shirts; VC concentration reductions of between 16 and 100% were noted, irrespective of sample type. Additionally the T-shirt study considered the change in VC concentration post-wash (dry) i.e. after the drying process at ambient temperature. Overall VC concentration reductions of between 25 and 98% were noted for T-shirt samples pre-wash to post-wash (dry). Finally, a potential biochemical metabolic pathway for the formation of malodour compounds associated with bacteria in axillary sweat is proposed.

Concepts: Bacteria, Metabolism, Mass spectrometry, Volatile organic compound, Volatile, Clothing, T-shirt, Laundry


Preparative high-speed counter-current chromatography (HSCCC) was successfully applied to the isolation and purification of two macrolactin antibiotics from marine bacterium Bacillus amyloliquefaciens for the first time using stepwise elution with a pair of two-phase solvent systems composed of n-hexane-ethyl acetate-methanol-water at (1:4:1:4, v/v) and (3:4:3:4, v/v). The preparative HSCCC separation was performed on 300mg of crude sample yielding macrolactin B (22.7mg) and macrolactin A (40.4mg) in a one-step separation, with purities over 95% as determined by HPLC. The structures of these compounds were identified by MS, (1)H NMR and (13)C NMR. Our results demonstrated that HSCCC was an efficient technique to separate marine antibiotics, which provide an approach to solve the problem of their sample availability for drug development.

Concepts: Bacteria, Chromatography, High performance liquid chromatography, Analytical chemistry, Gas chromatography, Bacillus, Bacillus amyloliquefaciens, Separation


Benazepril, an anti-hypertensive drug, was subjected to forced degradation studies. The drug was unstable under hydrolytic conditions, yielding benazeprilat, which is a known major degradation product (DP) and an active metabolite. It also underwent photochemical degradation in acid and neutral pH conditions, resulting in multiple minor DPs. The products were separated on a reversed phase (C18) column in a gradient mode, and subjected to LC-MS and LC-NMR studies. Initially, comprehensive mass fragmentation pathway of the drug was established through support of high resolution mass spectrometric (HR-MS) and multi stage tandem mass spectrometric (MS(n)) data. The DPs were also subjected to LC-MS/TOF studies to obtain their accurate masses. Along with, on-line H/D exchange data were obtained to ascertain the number of exchangeable hydrogens in each molecule. LC-(1)H NMR and LC-2DNMR data were additionally acquired in a fraction loop mode. The whole information was successfully employed for the characterization of all the DPs. A complete degradation pathway of the drug was also established.

Concepts: Fragmentation, Mass spectrometry, Mass, PH, Force, Prodrugs, Multiplication, Dissociation


Original mixed selectors were synthesized by coupling a single l-valine diamide moiety on permethylated β-cyclodextrin. The structures of the new selectors were designed to limit the interactions between the l-valine derivative and cyclodextrin by removing the amino acid moiety from the cyclodextrin cavity by means of an amide linkage on mono-6-amino permethylated β-CD or the insertion of a carboxymethyl group. The accessibility of the amino acid group moiety was thus facilitated. The new mixed selectors exhibited better enantioselectivity than Chirasil-l-Val for half (selector based on mono-6-amino permethylated β-CD) or more (selector with the carboxymethyl group) of the 41 amino acid derivatives. Molecular modeling confirmed that these results could be attributed to an increase in the distance between the chiral center of the amino acid and the cyclodextrin cavity allowing better access of the amino acid moiety. These new mixed chiral selectors demonstrated a novel enantioselective capability with the successful separation of more than 90 racemic mixtures among the 105 chiral compounds tested. These mixed selectors exhibited enhanced enantioselectivity in comparison to binary selectors previously described with respect to both enantiomer resolution and the number of separated chiral compounds. Moreover, an improvement of the enantioseparation factors compared to the corresponding ‘parent phases’ for the amino acid derivatives was observed in many cases. These mixed selectors should therefore be considered some of the most versatile selectors for chiral gas chromatography.

Concepts: Amino acid, Amine, Ammonia, Stereochemistry, Enantiomer, Chirality, Carboxylic acid, Racemic mixture


The separation of deuterated and non-deuterated compounds in gas liquid partitioning chromatography (GLC) on silicone type stationary phase usually results in the inverse isotope effect. With ionic liquids (ILs) as stationary phase, however, this may show a totally different nature. The inverse isotope effect, in which heavier (deuterated) isotopic compounds (isotopologues) elute earlier, is to be expected when van der Waals (London) dispersion forces play a dominant role in the solute-stationary phase interaction. Such (apolar) interactions seem to play only a minor role when ILs are the stationary phases, leading to only a marginal inverse isotope effect, e.g. for the separation of 2,4,6-trichloroanisole and its [(2)H(5)]-isotopologue on 1,12-di(tripropylphosphonium) dodecane bis(trifluoromethansulfonyl) amide (commercialized as SLB-IL59, Supelco). Indeed, with the most polar stationary phase available (commercialized as SLB-IL111; Supelco), this separation showed a normal isotope effect. Further examples are presented and the nature of the isotope effect observed is discussed.

Concepts: Chromatography, High performance liquid chromatography, Analytical chemistry, Gas chromatography, Isotope, Separation process, Separation processes, Chromatography software


The screening of plant material, the chemical composition, the abundance and the biological activity of triterpenoids are of a major economical importance. The classical analytical methods, such as TLC, GC, and HPLC are either little resolutive, or require derivatization steps, or fail in sensitivity. The supercritical fluid chromatography/evaporative light scattering detector (SFC/ELSD) coupling provides high resolution, fast analysis and higher responses for the analysis of triterpenoids. After the initial screening of seven stationary phases to select the well suited one, analytical conditions (modifier percentage, from 10 to 3%; backpressure (from 12 to 18MPa) and temperature (from 15 to 25°C) were studied to improve the separation, and ELSD detection of a standard mixture composed of 8 triterpenoids (oleanolic acid, erythrodiol, β-amyrin, ursolic acid, uvaol, betulinic acid, betulin, lupeol). Applied to apple pomace extracts, this method allows the separation of about 15 triterpenoid compounds, in less than 20min, with isocratic conditions. Moreover, the ELSD response is dramatically higher than the one provided by UV detection, and avoids derivatization steps. An attempt to identify some compounds was done by collecting chromatographic peaks and further analyzing them with mass spectrometry. Complete identification or molecular formula could be proposed for 11 compounds. However, due to the presence of position and orientation isomers the absolute identification remains difficult, despite some retention rules deduced from the standard analysis.

Concepts: Chromatography, Terpenes and terpenoids, Oleanolic acid, Medicinal triterpenes


A new, sensitive, and robust analytical method based on capillary zone electrophoresis with on-line capillary isotachophoresis sample pretreatment (ITP-CZE) using a column-coupling (CC) arrangement of automated capillary electrophoretic analyzer was developed for determination of bromate in different type of drinking water samples. Both columns were provided with contact-less conductivity detectors and in CZE step UV detection at 200nm wavelength was used. Electroosmotic flow of the buffer solutions was suppressed with the addition of 0.1% or 0.05% (m/v) methylhydroxyethylcellulose into the leading and terminating electrolyte, respectively. Hydrodynamic and electroosmotic flows of the buffer solutions were successfully suppressed and therefore, only the electrophoretic transport of ions was significant. Limit of detection for bromate approaching 0.6μg/L was achieved. Good repeatabilities of migration time (RSD less than 0.3%) and peak area (RSD less than 4.0%) at concentration level 1μg/L were obtained. Robustness of proposed ITP-CZE method and validation parameters were evaluated. Developed automated ITP-CZE method was applied to the determination of bromate in drinking water samples with different content of inorganic macroconstituents without the need of further sample preparation.

Concepts: Water, Gel electrophoresis, Capillary electrophoresis, Electrophoresis, Micellar electrokinetic chromatography, Affinity electrophoresis, Capillary fringe, Isotachophoresis


A comprehensive study on the enantioseparation of racemic bis[1-phenylethyl]amine (PEA) on a series of molecularly imprinted polymers (MIPs) prepared using the chiral functional monomer (S)-2-(2-methyl-acryloylamino)-3-phenyl propionic acid (MAPP) is reported. MIP-R, MIP-S and MIP-RS, were synthesized separately by imprinting the pure enantiomers (R-, S-PEA) and racemic PEA, respectively, MAPP, EDGMA as crosslinker and chloroform as the porogen. It was found that all MIPs prepared were able to resolve the PEA racemate. Residence times (t®) and enantioselectivity factors (α) were estimated from typical elution chromatography experiments. Frontal chromatography experiments were conducted to acquire the adsorption isotherms for both enantiomers on the different MIPs (and on the non-imprinted polymer, NIP). The adsorption isotherms were analyzed using the affinity spectrum (AS) and the expectation-maximization (EM) methods. The study also involved the theoretical evaluation of the MAPP/enantiomers interactions in the pre-polymer mixture. The EM method predicts mono- and bimodal distribution of affinity binding sites depending upon the polymer analyzed. Apparently, the enantioseparation process depends on relatively small differences in the stabilization of the diasteroisomeric ion-pairs PEA/MAPP complexes on the surface of the polymers.

Concepts: Protein, Stereochemistry, Polymer, Polymer chemistry, Adsorption, Enantiomer, Experiment, Racemic mixture