A new issue of this journal has just
been published. To see abstracts of the papers it contains (with links through
to the full papers) click here:
Selected
papers from the latest issue:
Preparation of molecularly imprinted polymers for organophosphates and their application to the recognition of organophosphorus compounds and phosphopeptides
28 September 2012,
08:37:53
Publication year:
2012
Source:Analytica Chimica Acta, Volume 748
Jun Haginaka, Hiromi Tabo, Hisami Matsunaga
Monodisperse molecularly imprinted polymers (MIPs) for diphenyl phosphate (DPP) and 1-naphthyl phosphate (1-NapP) have been prepared by a multi-step swelling and polymerization method using 4-vinylpyridine as a functional monomer, glycerol dimethacrylate as a crosslinker and cyclohexanol or 1-hexanol as a porogen. The retention and molecular-recognition properties of these MIPs for organophosphorus compounds were evaluated by HPLC using a mixture of phosphate buffer and acetonitrile as an eluent. In addition to shape recognition, hydrogen bonding and hydrophobic interactions could play an important role in the retention and molecular recognition of DPP and 1-NapP. Furthermore, the MIPs were applied to the separation of adenosine and adenosine phosphates (AMP, ADP and ATP). These phosphates were retained on the MIPs according to the number of phosphate groups in the molecule and were well separated from one another. Hydrogen bonding and hydrophobic interactions seemed to affect the retention and recognition of adenosine phosphates in low acetonitrile content, while hydrophilic interactions affected these properties in high acetonitrile content. Finally, the MIPs were applied to the trapping of phosphopeptides. The MIPs non-selectively trapped phosphopeptides, which have phosphorylated tyrosine, serine or threonine in the sequences, and successfully trapped four phosphopeptides in tryptic digests of bovine α-casein.
Source:Analytica Chimica Acta, Volume 748
Jun Haginaka, Hiromi Tabo, Hisami Matsunaga
Monodisperse molecularly imprinted polymers (MIPs) for diphenyl phosphate (DPP) and 1-naphthyl phosphate (1-NapP) have been prepared by a multi-step swelling and polymerization method using 4-vinylpyridine as a functional monomer, glycerol dimethacrylate as a crosslinker and cyclohexanol or 1-hexanol as a porogen. The retention and molecular-recognition properties of these MIPs for organophosphorus compounds were evaluated by HPLC using a mixture of phosphate buffer and acetonitrile as an eluent. In addition to shape recognition, hydrogen bonding and hydrophobic interactions could play an important role in the retention and molecular recognition of DPP and 1-NapP. Furthermore, the MIPs were applied to the separation of adenosine and adenosine phosphates (AMP, ADP and ATP). These phosphates were retained on the MIPs according to the number of phosphate groups in the molecule and were well separated from one another. Hydrogen bonding and hydrophobic interactions seemed to affect the retention and recognition of adenosine phosphates in low acetonitrile content, while hydrophilic interactions affected these properties in high acetonitrile content. Finally, the MIPs were applied to the trapping of phosphopeptides. The MIPs non-selectively trapped phosphopeptides, which have phosphorylated tyrosine, serine or threonine in the sequences, and successfully trapped four phosphopeptides in tryptic digests of bovine α-casein.
Graphical abstract
Graphical abstract Highlights
► Monodisperse MIPs for organophosphates by multi-step swelling and polymerization. ► Application of MIPs to the separation of adenosine phosphates. ► Application of MIPs to the trapping of phosphopeptides in tryptic protein-digests.Application of semi-permeable membrane dialysis/ion trap mass spectrometry technique to determine polybrominated diphenyl ethers and polychlorinated biphenyls in milk fat
28 September 2012,
08:37:53
Publication year:
2012
Source:Analytica Chimica Acta, Volume 748
Marek Roszko, Małgorzata Rzepkowska, Arkadiusz Szterk, Krystyna Szymczyk, Renata Jędrzejczak, Marcin Bryła
Polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) are hazardous food contaminants, their maximum legally allowable levels in food and environment are in the low pgg−1 range. Therefore some highly selective and sensitive analytical methods must be used to determine them. The 96/23/EC Directive implemented by EC Decision of 12 August 2002 requires recovery rate of an analyte at a concentration below 1ngg−1 within the 50–120% range at relative standard deviation (RSD) as low as possible. A method to determine low level PCBs and PBDEs in milk fat based on the semi-permeable membrane dialysis/ion trap GC MS technique was developed. Validation experiments proved that the method performance was within bounds set by the currently standing UE regulations. Recovery rates calculated on the basis of labeled internal standards for majority of the studied indicator PCB congeners and PBDE congeners were close to 100% at RSD below 20%. Also, dioxin-like PCBs recovery rates were compatible with the 1883/2006 EC Regulation (80–120%, RSD below 15%). The developed method turned out to be linear within a far broader concentration range than the studied 0.0025–10pgμL−1 range entirely sufficient for analyses of PCB and PBDE in milk fat. Within that range coefficient of linear correlation (R 2) of calibration curves exceeded 0.98.
Source:Analytica Chimica Acta, Volume 748
Marek Roszko, Małgorzata Rzepkowska, Arkadiusz Szterk, Krystyna Szymczyk, Renata Jędrzejczak, Marcin Bryła
Polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) are hazardous food contaminants, their maximum legally allowable levels in food and environment are in the low pgg−1 range. Therefore some highly selective and sensitive analytical methods must be used to determine them. The 96/23/EC Directive implemented by EC Decision of 12 August 2002 requires recovery rate of an analyte at a concentration below 1ngg−1 within the 50–120% range at relative standard deviation (RSD) as low as possible. A method to determine low level PCBs and PBDEs in milk fat based on the semi-permeable membrane dialysis/ion trap GC MS technique was developed. Validation experiments proved that the method performance was within bounds set by the currently standing UE regulations. Recovery rates calculated on the basis of labeled internal standards for majority of the studied indicator PCB congeners and PBDE congeners were close to 100% at RSD below 20%. Also, dioxin-like PCBs recovery rates were compatible with the 1883/2006 EC Regulation (80–120%, RSD below 15%). The developed method turned out to be linear within a far broader concentration range than the studied 0.0025–10pgμL−1 range entirely sufficient for analyses of PCB and PBDE in milk fat. Within that range coefficient of linear correlation (R 2) of calibration curves exceeded 0.98.
Graphical abstract
Graphical abstract Highlights
► We have investigated the usefulness of SPM dialysis for determination of PCB/PBDE. ► The factors affecting the dialysis process were evaluated. ► The ion trap MS was optimized for determination of PCB/PBDE in milk fat. ► Described extraction/clean up method proves usefulness for the milk fat analysis.Determination of eight fluoroquinolones in groundwater samples with ultrasound-assisted ionic liquid dispersive liquid–liquid microextraction prior to high-performance liquid chromatography and fluorescence detection
28 September 2012,
08:37:53
Publication year:
2012
Source:Analytica Chimica Acta, Volume 748
M.M. Parrilla Vázquez, P. Parrilla Vázquez, M. Martínez Galera, M.D. Gil García
An ultrasound-assisted ionic liquid dispersive liquid–liquid microextraction (US-IL-DLLME) procedure was developed for the extraction of eight fluoroquinolones (marbofloxacin, norfloxacin, ciprofloxacin, lomefloxacin, danofloxacin, enrofloxacin, oxolinic acid and nalidixic acid) in groundwater, using high-performance liquid chromatography with fluorescence detection (HPLC-FD). The ultrasound-assisted process was applied to accelerate the formation of the fine cloudy solution using a small volume of disperser solvent (0.4mL of methanol), which increased the extraction efficiency and reduced the equilibrium time. For the DLLME procedure, the IL 1-octyl-3-methylimidazolium hexafluorophosphate ([C8MIM] [PF6]) and methanol (MeOH) were used as extraction and disperser solvent, respectively. By comparing [C8MIM] [PF6] with 1-hexyl-3-methylimidazolium hexafluorophosphate ([C6MIM] [PF6]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([C4MIM] [PF6]) as extraction solvents, it was observed that when using [C8MIM] [PF6] the cloudy solution was formed more readily than when using [C6MIM] [PF6] or [C4MIM] [PF6]. The factors affecting the extraction efficiency, such as the type and volume of ionic liquid, type and volume of disperser solvent, cooling in ice-water, sonication time, centrifuging time, sample pH and ionic strength, were optimised. A slight increase in the recoveries of fluoroquinolones was observed when an ice-water bath extraction step was included in the analytical procedure (85–107%) compared to those obtained without this step (83–96%). Under the optimum conditions, linearity of the method was observed over the range 10–300ngL−1 with correlation coefficient >0.9981. The proposed method has been found to have excellent sensitivity with limit of detection between 0.8 and 13ngL−1 and precision with relative standard deviation values between 4.8 and 9.4% (RSD, n =5). Good enrichment factors (122–205) and recoveries (85–107%) were obtained for the extraction of the target analytes in groundwater samples. This simple and economic method has been successfully applied to analyse real groundwater samples with satisfactory results.
Source:Analytica Chimica Acta, Volume 748
M.M. Parrilla Vázquez, P. Parrilla Vázquez, M. Martínez Galera, M.D. Gil García
An ultrasound-assisted ionic liquid dispersive liquid–liquid microextraction (US-IL-DLLME) procedure was developed for the extraction of eight fluoroquinolones (marbofloxacin, norfloxacin, ciprofloxacin, lomefloxacin, danofloxacin, enrofloxacin, oxolinic acid and nalidixic acid) in groundwater, using high-performance liquid chromatography with fluorescence detection (HPLC-FD). The ultrasound-assisted process was applied to accelerate the formation of the fine cloudy solution using a small volume of disperser solvent (0.4mL of methanol), which increased the extraction efficiency and reduced the equilibrium time. For the DLLME procedure, the IL 1-octyl-3-methylimidazolium hexafluorophosphate ([C8MIM] [PF6]) and methanol (MeOH) were used as extraction and disperser solvent, respectively. By comparing [C8MIM] [PF6] with 1-hexyl-3-methylimidazolium hexafluorophosphate ([C6MIM] [PF6]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([C4MIM] [PF6]) as extraction solvents, it was observed that when using [C8MIM] [PF6] the cloudy solution was formed more readily than when using [C6MIM] [PF6] or [C4MIM] [PF6]. The factors affecting the extraction efficiency, such as the type and volume of ionic liquid, type and volume of disperser solvent, cooling in ice-water, sonication time, centrifuging time, sample pH and ionic strength, were optimised. A slight increase in the recoveries of fluoroquinolones was observed when an ice-water bath extraction step was included in the analytical procedure (85–107%) compared to those obtained without this step (83–96%). Under the optimum conditions, linearity of the method was observed over the range 10–300ngL−1 with correlation coefficient >0.9981. The proposed method has been found to have excellent sensitivity with limit of detection between 0.8 and 13ngL−1 and precision with relative standard deviation values between 4.8 and 9.4% (RSD, n =5). Good enrichment factors (122–205) and recoveries (85–107%) were obtained for the extraction of the target analytes in groundwater samples. This simple and economic method has been successfully applied to analyse real groundwater samples with satisfactory results.
Graphical abstract
Graphical abstract Highlights
► A novel method by US-IL-DLLME-LC-FD for fluoroquinolones determination. ► Simple, rapid and efficient method for water samples. ► Advantages over conventional methods. ► Low detection limits.A new HPLC-DAD-MS/MS method for the simultaneous determination of major compounds in the crude extract of Lychnophora salicifolia Mart. (Brazilian arnicão) leaves: Application to chemical variability evaluation
28 September 2012,
08:37:53
Publication year:
2012
Source:Analytica Chimica Acta, Volume 748
Dayana Rubio Gouvea, Fernando Meloni, Arthur de Barros Bello Ribeiro, João Luis Callegari Lopes, Norberto Peporine Lopes
Lychnophora salicifolia Mart., which occurs in the Brazilian Cerrado in the states of Bahia and Minas Gerais as well as in the southeast of the state of Goiás, is the most widely distributed and also the most polymorphic species of the genus. This plant is popularly known to have anti-inflammatory and analgesic activities. In this work, we have studied the variation in terms of polar metabolites of ninety-three Lychnophora salicifolia Mart. specimens collected from different regions of the Brazilian Cerrado. Identification of the constituents of this mixture was carried out by analysis of the UV spectra and MS data after chromatographic separation. Twenty substances were identified, including chlorogenic acid derivatives, a flavonoid C-glucoside, and other sesquiterpenes. The analytical method was validated, and the reliability and credibility of the results was ensured for the purposes of this study. The concentration range required for analysis of content variability within the analyzed group of specimens was covered with appropriate values of limits of detection and quantitation, as well as satisfactory precision and recovery. A quantitative variability was observed among specimens collected from the same location, but on average they were similar from a chemical viewpoint. In relation to the study involving specimens from different locations, there were both qualitative and quantitative differences among plants collected from different regions of Brazil. Statistical analysis revealed that there is a correlation between geographical localization and polar metabolites profile for specimens collected from different locations. This is evidence that the pattern of metabolites concentration depends on the geographical distribution of the specimens.
Source:Analytica Chimica Acta, Volume 748
Dayana Rubio Gouvea, Fernando Meloni, Arthur de Barros Bello Ribeiro, João Luis Callegari Lopes, Norberto Peporine Lopes
Lychnophora salicifolia Mart., which occurs in the Brazilian Cerrado in the states of Bahia and Minas Gerais as well as in the southeast of the state of Goiás, is the most widely distributed and also the most polymorphic species of the genus. This plant is popularly known to have anti-inflammatory and analgesic activities. In this work, we have studied the variation in terms of polar metabolites of ninety-three Lychnophora salicifolia Mart. specimens collected from different regions of the Brazilian Cerrado. Identification of the constituents of this mixture was carried out by analysis of the UV spectra and MS data after chromatographic separation. Twenty substances were identified, including chlorogenic acid derivatives, a flavonoid C-glucoside, and other sesquiterpenes. The analytical method was validated, and the reliability and credibility of the results was ensured for the purposes of this study. The concentration range required for analysis of content variability within the analyzed group of specimens was covered with appropriate values of limits of detection and quantitation, as well as satisfactory precision and recovery. A quantitative variability was observed among specimens collected from the same location, but on average they were similar from a chemical viewpoint. In relation to the study involving specimens from different locations, there were both qualitative and quantitative differences among plants collected from different regions of Brazil. Statistical analysis revealed that there is a correlation between geographical localization and polar metabolites profile for specimens collected from different locations. This is evidence that the pattern of metabolites concentration depends on the geographical distribution of the specimens.
Graphical abstract
Graphical abstract Highlights
Statistical analysis revealed that there is a correlation between geographical localization of Lychnophora salicifolia samples and polar metabolites profile for specimens collected from different locations. ► A new HPLC-DAD-MS method for analysis of the crude extract of L. salicifolia leaves. ► Twenty substances were identified. ► Ninety-three wild specimens were analyzed. ► A correlation between geographic isolation and decrease of the chemical similarity. ► The pattern of metabolites depends on the geographical distribution of the specimens.Characterizing uranium oxide reference particles for isotopic abundances and uranium mass by single particle isotope dilution mass spectrometry
28 September 2012,
08:37:53
Publication year:
2012
Source:Analytica Chimica Acta, Volume 748
M. Kraiem, S. Richter, N. Erdmann, H. Kühn, M. Hedberg, Y. Aregbe
Uranium and plutonium particulate test materials are becoming increasingly important as the reliability of measurement results has to be demonstrated to regulatory bodies responsible for maintaining effective nuclear safeguards. In order to address this issue, the Institute for Reference Materials and Measurements (IRMM) in collaboration with the Institute for Transuranium Elements (ITU) has initiated a study to investigate the feasibility of preparing and characterizing a uranium particle reference material for nuclear safeguards, which is finally certified for isotopic abundances and for the uranium mass per particle. Such control particles are specifically required to evaluate responses of instruments based on mass spectrometric detection (e.g. SIMS, TIMS, LA-ICPMS) and to help ensuring the reliability and comparability of measurement results worldwide. In this paper, a methodology is described which allows quantifying the uranium mass in single micron particles by isotope dilution thermal ionization mass spectrometry (ID-TIMS). This methodology is characterized by substantial improvements recently achieved at IRMM in terms of sensitivity and measurement accuracy in the field of uranium particle analysis by TIMS. The use of monodisperse uranium oxide particles prepared using an aerosol generation technique developed at ITU, which is capable of producing particles of well-characterized size and isotopic composition was exploited. The evidence of a straightforward correlation between the particle volume and the mass of uranium was demonstrated in this study. Experimental results have shown that the uranium mass per particle can be measured via the ID-TIMS method to a relative expanded uncertainty of about 10% (coverage factor k =2). The availability of reliable and validated methods for the characterization of uranium particles is considered to be essential for the establishment of SI-traceable measurement results. It is therefore expected that the method developed in this study is valuable for the certification of particulate materials in which the isotopic composition and the content of uranium must be accurately known.
Source:Analytica Chimica Acta, Volume 748
M. Kraiem, S. Richter, N. Erdmann, H. Kühn, M. Hedberg, Y. Aregbe
Uranium and plutonium particulate test materials are becoming increasingly important as the reliability of measurement results has to be demonstrated to regulatory bodies responsible for maintaining effective nuclear safeguards. In order to address this issue, the Institute for Reference Materials and Measurements (IRMM) in collaboration with the Institute for Transuranium Elements (ITU) has initiated a study to investigate the feasibility of preparing and characterizing a uranium particle reference material for nuclear safeguards, which is finally certified for isotopic abundances and for the uranium mass per particle. Such control particles are specifically required to evaluate responses of instruments based on mass spectrometric detection (e.g. SIMS, TIMS, LA-ICPMS) and to help ensuring the reliability and comparability of measurement results worldwide. In this paper, a methodology is described which allows quantifying the uranium mass in single micron particles by isotope dilution thermal ionization mass spectrometry (ID-TIMS). This methodology is characterized by substantial improvements recently achieved at IRMM in terms of sensitivity and measurement accuracy in the field of uranium particle analysis by TIMS. The use of monodisperse uranium oxide particles prepared using an aerosol generation technique developed at ITU, which is capable of producing particles of well-characterized size and isotopic composition was exploited. The evidence of a straightforward correlation between the particle volume and the mass of uranium was demonstrated in this study. Experimental results have shown that the uranium mass per particle can be measured via the ID-TIMS method to a relative expanded uncertainty of about 10% (coverage factor k =2). The availability of reliable and validated methods for the characterization of uranium particles is considered to be essential for the establishment of SI-traceable measurement results. It is therefore expected that the method developed in this study is valuable for the certification of particulate materials in which the isotopic composition and the content of uranium must be accurately known.
Graphical abstract
Graphical abstract Highlights
► A method to quantify the U mass in single micron particles by ID-TIMS was developed. ► Well-characterized monodisperse U-oxide particles produced by an aerosol generator were used. ► A linear correlation between the mass of U and the volume of particle(s) was found. ► The method developed is suitable for determining the amount of U in a particulate reference material.A mass spectrometric method to determine activities of enzymes involved in polyamine catabolism
28 September 2012,
08:37:53
Publication year:
2012
Source:Analytica Chimica Acta, Volume 748
Shunsuke Moriya, Kaori Iwasaki, Keijiro Samejima, Koichi Takao, Kohfuku Kohda, Kyoko Hiramatsu, Masao Kawakita
An analytical method for the determination of three polyamines (putrescine, spermidine, and spermine) and five acetylpolyamines [N1-acetylspermidine (N1AcSpd), N8-acetylspermidine (N8AcSpd), N1-acetylspermine, N1,N8-diacetylspermidine, and N1,N12-diacetylspermine] involved in the polyamine catabolic pathway has been developed using a hybrid tandem mass spectrometer. Heptafluorobutyryl (HFB) derivatives of these compounds and respective internal standards labeled with stable isotopes were analyzed simultaneously by TOF MS, based on peak areas appearing at appropriate m/z values. The isomers, N1AcSpd and N8AcSpd were determined from their fragment ions, the acetylamidopropyl and acetylamidobutyl groups, respectively, using MS/MS with 13C2-N1AcSpd and 13C2-N8AcSpd which have the 13C2-acetyl group as an internal standard. The TOF MS method was successfully applied to measure the activity of enzymes involved in polyamine catabolic pathways, namely N1-acetylpolyamine oxidase (APAO), spermine oxidase (SMO), and spermidine/spermine N1-acetyltransferase (SSAT). The following natural substrates and products labeled with stable isotopes considering the application to biological samples were identified; for APAO, [4,9,12-15N3]-N1-acetylspermine and [1,4,8-15N3]spermidine (15N3-Spd), respectively; for SMO, [1,4,8,12-15N4]spermine and 15N3-Spd, respectively; and for SSAT, 15N3-Spd and [1,4,8-15N3]-N1-acetylspermidine, respectively.
Source:Analytica Chimica Acta, Volume 748
Shunsuke Moriya, Kaori Iwasaki, Keijiro Samejima, Koichi Takao, Kohfuku Kohda, Kyoko Hiramatsu, Masao Kawakita
An analytical method for the determination of three polyamines (putrescine, spermidine, and spermine) and five acetylpolyamines [N1-acetylspermidine (N1AcSpd), N8-acetylspermidine (N8AcSpd), N1-acetylspermine, N1,N8-diacetylspermidine, and N1,N12-diacetylspermine] involved in the polyamine catabolic pathway has been developed using a hybrid tandem mass spectrometer. Heptafluorobutyryl (HFB) derivatives of these compounds and respective internal standards labeled with stable isotopes were analyzed simultaneously by TOF MS, based on peak areas appearing at appropriate m/z values. The isomers, N1AcSpd and N8AcSpd were determined from their fragment ions, the acetylamidopropyl and acetylamidobutyl groups, respectively, using MS/MS with 13C2-N1AcSpd and 13C2-N8AcSpd which have the 13C2-acetyl group as an internal standard. The TOF MS method was successfully applied to measure the activity of enzymes involved in polyamine catabolic pathways, namely N1-acetylpolyamine oxidase (APAO), spermine oxidase (SMO), and spermidine/spermine N1-acetyltransferase (SSAT). The following natural substrates and products labeled with stable isotopes considering the application to biological samples were identified; for APAO, [4,9,12-15N3]-N1-acetylspermine and [1,4,8-15N3]spermidine (15N3-Spd), respectively; for SMO, [1,4,8,12-15N4]spermine and 15N3-Spd, respectively; and for SSAT, 15N3-Spd and [1,4,8-15N3]-N1-acetylspermidine, respectively.
No comments:
Post a Comment