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101.
Maria Chiara Pietrogrande Giulia Basaglia Francesco Dondi 《Journal of separation science》2009,32(9):1249-1261
This paper discusses the development of a comprehensive method for the simultaneous analysis of personal care products (PCPs) based on SPE and GC‐MS. The method was developed on 29 target compounds to represent PCPs belonging to different chemical classes: surfactants in detergents (alkyl benzenes), fragrances in cosmetics (nitro and polycyclic musks), antioxidants and preservatives (phenols), plasticizers (phthalates) displaying a wide range of volatility, polarity, water solubility. In addition to the conventional C18 stationary phase, a surface modified styrene divinylbenzene polymeric phase (StrataTM X SPE cartridge) has been investigated as suitable for the simultaneous extraction of several PCPs with polar and non‐polar characteristics. For both sorbents different solvent compositions and eluting conditions were tested and compared in order to achieve high extraction efficiency for as many sample components as possible. Comparison of the behavior of the two cartridges reveals that, overall, Strata‐X provides better efficiency with extraction recovery higher than 70% for most of the PCPs investigated. The best results were obtained under the following operative conditions: an evaporation temperature of 40°C, elution on Strata‐X cartridge using a volume of 15 mL of ethyl acetate (EA) as solvent and operating with slow flow rate (–10 KPa). In addition to the conventional method based on peak integration, a chemometric approach based on the computation of the experimental autocovariance function (EACVFtot) was applied to the complex GC‐MS signal: the percentage recovery and information on peak abundance distribution can be evaluated for each procedure step. The PC‐based signal processing proved very helpful in assisting the development of the analytical procedure, since it saves labor and time and increases result reliability in handling GC complex signals. 相似文献
102.
Flavio Granato Andrea Bianco Chiara Bertarelli Giuseppe Zerbi 《Macromolecular rapid communications》2009,30(6):453-458
Conductive Polyamide 6 (PA‐6) nanofibers were prepared by making a conductive polypyrrole coating obtained by a polymerization of pyrrole molecules directly on the fiber surface. A solution of PA‐6 added with ferric chloride in formic acid has been electrospun and the fibers obtained showed an average diameter of 260 nm with a smooth surface. The fibers have been then exposed to pyrrole vapours and a compact coating of polypyrrole was formed on the fiber surface. The growth of the coating was monitored by measuring the increment of the fiber diameter and by FT‐IR spectroscopy. The same technique was used to study the interaction between the ferric chloride and the polyamide chains. The polypyrrole coating on the fibers turned out to be conductive with a pure resistive characteristic and the stability of the conductivity was evaluated in air at room temperature.
103.
104.
Cabras T Boi R Pisano E Iavarone F Fanali C Nemolato S Faa G Castagnola M Messana I 《Journal of separation science》2012,35(9):1079-1086
This study describes the characterization of the glycan moieties and the peptide backbone of six glycoforms of IB-8a CON1(+), a basic proline-rich protein present in human saliva. MS analyses on the intact glycoproteins before and after N-deglycosylation with PNGase F and high-resolution MS/MS sequencing by LTQ Orbitrap XL of peptides and glycopeptides from tryptic digests allowed the structural characterization of the glycan moieties and the polypeptide backbone, as well as to establish the glycosylation site at the asparagine residue at 98th position. Five of the glycoforms carry a biantennary N-linked glycan fucosylated in the innermost N-acetylglucosamine of the core and showing from zero to four additional fucoses in the antennal region. The sixth glycoform carries a monoantennary monofucosylated oligosaccharide. The glycoform cluster was detected on 28 of 71 adult saliva specimens. Level of fucosylation showed interindividual variability with the major relative abundance for the trifucosylated glycoform. Nonglycosylated IB-8a CON1(+) and the variant IB-8a CON1(-), lacking of the glycosylation site, have been also detected in human saliva. 相似文献
105.
Optimization of a SPME/GC/MS Method for the Simultaneous Determination of Pharmaceuticals and Personal Care Products in Waters 总被引:2,自引:0,他引:2
A headspace solid phase microextraction (HS-SPME) method coupled with gas chromatography and MS detection (GC/MS) was optimized for the simultaneous determination of 21 target Pharmaceuticals and Personal Care Products (PPCPs) in water samples. The analytes included fragrances, UV-filters, antiseptics, estrogens, anti-inflammatory drugs, and pesticides. An on-fiber SPME derivatization, using silyl reagents, was performed for the analysis of more polar acidic compounds. An experimental design approach was applied to systematically investigate and optimize the operative parameters affecting the extraction recovery, namely: extraction temperature and time, derivatization time, desorption temperature and time. The optimum operating conditions were: extraction time of 125?min at a temperature of 40?°C; derivatization time of 30.5?min; desorption time of 2?min at a temperature of 300?°C. Under these conditions, good reproducibility was assessed as RDS% values ≤10% for underivatized PPCPs and ≤20% for derivatized compounds. The method detection limits (LOD) were between 0.7 and 9.0?ng?L?1, with the highest values in the range 2.5–9.0?ng?L?1 for the derivatized analytes. Method accuracy was evaluated on spiked tap water samples: recoveries varied from 85 to 103% and from 75 to 110% for non-derivatized and derivatized compounds, respectively. 相似文献
106.
Dr. Delphine Crozet Dr. Aitor Gual Dr. David McKay Dr. Chiara Dinoi Dr. Cyril Godard Prof. Martine Urrutigoïty Dr. Jean‐Claude Daran Prof. Laurent Maron Prof. Carmen Claver Prof. Philippe Kalck 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(23):7128-7140
The reactivity of [Rh(CO)2{(R,R)‐Ph? BPE}]BF4 ( 2 ) toward amine, CO and/or H2 was examined by high‐pressure NMR and IR spectroscopy. The two cationic pentacoordinated species [Rh(CO)3{(R,R)‐Ph? BPE}]BF4 ( 4 ) and [Rh(CO)2(NHC5H10){(R,R)‐Ph‐BPE}]BF4 ( 8 ) were identified. The transformation of 2 into the neutral complex [RhH(CO)2{(R,R)‐Ph? BPE}] ( 3 ) under hydroaminomethylation conditions (CO/H2, amine) was investigated. The full mechanisms related to the formation of 3 , 4 and 8 starting from 2 are supported by DFT calculations. In particular, the pathway from 2 to 3 revealed the deprotonation by the amine of the dihydride species [Rh(H)2(CO)2{(R,R)‐Ph? BPE}]BF4 ( 6 ), resulting from the oxidative addition of H2 on 2 . 相似文献
107.
This survey critically discusses high-concentration-capacity (HCC) headspace (HS) techniques applied to sample the volatile fraction of matrices of interest in the flavors and fragrance fields. In particular, the advantages, limits, and fields of application of HS solid-phase microextraction (SPME), high-capacity HS sorptive extraction (HSSE) and HS solid-phase dynamic extraction (SPDE) are evaluated. These techniques are discussed in view of the peculiar characteristic of HCC-HS techniques, from the standpoint that these techniques are a bridge between static (S-HS) and dynamic HS (D-HS) because they are as simple, fast, easy to automate, and reliable as S-HS, yet afford analyte concentration factors comparable to those of D-HS. Moreover, the different degree of their development is a consequence of the different times in which they were introduced into the market, because the potential of HS-SPME is now well known, having been introduced approximately 12 years ago, but that of HSSE has still to be fully explored, and HS-SPDE still has to be investigated because it is very recent. 相似文献
108.
The development and in-house testing of a method for the detection and quantification of cocoa butter equivalents in cocoa butter and plain chocolate is described. A database consisting of the triacylglycerol profile of 74 genuine cocoa butter and 75 cocoa butter equivalent samples obtained by high-resolution capillary gas liquid chromatography was created, using a certified cocoa butter reference material (IRMM-801) for calibration purposes. Based on these data, a large number of cocoa butter/cocoa butter equivalent mixtures were arithmetically simulated. By subjecting the data set to various statistical tools, reliable models for both detection (univariate regression model) and quantification (multivariate model) were elaborated. Validation data sets consisting of a large number of samples (n = 4050 for detection, n = 1050 for quantification) were used to test the models. Excluding pure illipé fat samples from the data set, the detection limit was determined between 1 and 3% foreign fat in cocoa butter. Recalculated for a chocolate with a fat content of 30%, these figures are equal to 0.3-0.9% cocoa butter equivalent. For quantification, the average error for prediction was estimated to be 1.1% cocoa butter equivalent in cocoa butter, without prior knowledge of the materials used in the blend corresponding to 0.3% in chocolate (fat content 30%). The advantage of the approach is that by using IRMM-801 for calibration, the established mathematical decision rules can be transferred to every testing laboratory. 相似文献
109.
An analytical procedure is described to study GC-MS isothermal chromatograms simulating those recovered from space missions: in fact GC plays a predominant role in space missions devoted to characterizing the chemical composition of extra-terrestrial atmospheres. SIM (selected ion monitoring) detection was used for monitoring selected chemical classes: a simplified chromatogram can be obtained giving information on the chemical composition of the complex mixture. Since only isothermal GC chromatograms are allowed by flight constraints, a time axis transformation is required to make them homogeneous: i.e., constant retention increments for CH2 additions in terms of a homologous series. The order in the linearized chromatogram can be simply singled out with a chemometric approach based on the study of the Autocovariance Function (ACVF) computed on the digitized chromatogram: the plot of the experimental autocorrelation function (EACF) shows well-shaped peaks if constant interdistances are repeated in different regions of the chromatogram. The method was applied to standard mixtures representative of planetary atmospheres--hydrocarbons, nitriles and oxygenated compounds with between 3 and 12 carbon atoms--analyzed in flight simulating conditions. The coupling of the selectivity of SIM detection with the interpretation power of the EACF procedure proves to be a powerful tool for interpreting data recovered from space missions: the chemical composition of the mixture can be identified by handling the raw SIM chromatograms. 相似文献
110.
Alberto Milani Jacopo Zanetti Chiara Castiglioni Elena Di Dedda Stefano Radice Giorgio Canil Claudio Tonelli 《European Polymer Journal》2012,48(2):391-403
Perfluoropolyether (PFPE) fluids constitute a class of polymers that fulfil a wide range of requirements for hi-tech applications, due to their pefluorinated backbone. For some of these applications they are requested to bear polar end groups, and the combination of a chemical inert backbone and a reactive end group can produce peculiar conformations and supramolecular structures. The molecular structure and the vibrational properties of the ethoxyl-terminated PFPE FLUOROLINK®E10H in solution are here investigated by means of IR spectroscopy. It is shown that the complex spectral features of the OH-stretching region cannot be explained without a thorough computational study, involving the investigation of the conformational space of an isolated model molecule by means of semiempirical AM1 calculations and DFT calculations. The most relevant conformers were singled out, showing a high degree of conformational disorder for FLUOROLINK®E10H. Furthermore, it is shown that intra- and intermolecular H-bonding affects significantly the molecular structure and the vibrational spectrum. Several interactions are shown to be relevant, such as OH…F interactions and complexes with residual water. Theoretical values of the absolute intensities of OH stretching IR bands, relevant for the analytical applications, are obtained. 相似文献