Analytical and Bioanalytical Chemistry - Aktuelle Forschungsartikel
Aktuelle Forschungsartikel: Analytische Chemie
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Hier aufgeführte Forschungsartikel:
Analytical and Bioanalytical Chemistry - Verlag: Springer
ABC ist eine internationale Zeitschrift mit dem Auftrag, exzellente Forschungsarbeiten aus allen Bereichen der analytischen und bioanalytischen Wissenschaft zu veröffentlichen.
A time-resolved inverse spatially offset Raman spectrometer was constructed for depth profiling of Raman-active substances
under both the lab and the field environments. The system operating principles and performance are discussed along with its
advantages relative to traditional continuous wave spatially offset Raman spectrometer. The developed spectrometer uses a
combination of space- and time-resolved detection in order to obtain high-quality Raman spectra from substances hidden behind
coloured opaque surface layers, such as plastic and garments, with a single measurement. The time-gated spatially offset Raman
spectrometer was successfully used to detect concealed explosives and drug precursors under incandescent and fluorescent background
light as well as under daylight. The average screening time was 50 s per measurement. The excitation energy requirements were
relatively low (20 mW) which makes the probe safe for screening hazardous substances. The unit has been designed with nanosecond
laser excitation and gated detection, making it of lower cost and complexity than previous picosecond-based systems, to provide
a functional platform for in-line or in-field sensing of chemical substances.
Content Type Journal Article
Category Original Paper
Pages 1-9
DOI 10.1007/s00216-012-5792-2
Authors
Biju Cletus, Chemistry Discipline, Faculty of Science and Technology, Queensland University of Technology, 2 George St., Brisbane, QLD 4001, Australia
William Olds, Chemistry Discipline, Faculty of Science and Technology, Queensland University of Technology, 2 George St., Brisbane, QLD 4001, Australia
Emad L. Izake, Chemistry Discipline, Faculty of Science and Technology, Queensland University of Technology, 2 George St., Brisbane, QLD 4001, Australia
Shankaran Sundarajoo, Chemistry Discipline, Faculty of Science and Technology, Queensland University of Technology, 2 George St., Brisbane, QLD 4001, Australia
Peter M. Fredericks, Chemistry Discipline, Faculty of Science and Technology, Queensland University of Technology, 2 George St., Brisbane, QLD 4001, Australia
Esa Jaatinen, Physics Discipline, Faculty of Science and Technology, Queensland University of Technology, 2 George St., Brisbane, QLD 4001, Australia
Over the past two decades there have been great advances in biotechnology, including use of nucleic acids, proteins, and whole
cells to develop a variety of molecular analytical tools for diagnostic, screening, and pharmaceutical applications. Through
manipulation of bacterial plasmids and genomes, bacterial whole-cell sensing systems have been engineered that can serve as
novel methods for analyte detection and characterization, and as more efficient and cost-effective alternatives to traditional
analytical techniques. Bacterial cell-based sensing systems are typically sensitive, specific and selective, rapid, easy to
use, low-cost, and amenable to multiplexing, high-throughput, and miniaturization for incorporation into portable devices.
This critical review is intended to provide an overview of available bacterial whole-cell sensing systems for assessment of
a variety of clinically relevant analytes. Specifically, we examine whole-cell sensing systems for detection of bacterial
quorum sensing molecules, organic and inorganic toxic compounds, and drugs, and for screening of antibacterial compounds for
identification of their mechanisms of action. Methods used in the design and development of whole-cell sensing systems are
also reviewed.
Content Type Journal Article
Category Review
Pages 1-13
DOI 10.1007/s00216-012-5756-6
Authors
Nilesh Raut, Department of Chemistry, University of Kentucky, Lexington, KY 40506, USA
Gregory O’Connor, Department of Biochemistry and Molecular Biology, Miller School of Medicine, University of Miami, Miami, FL 33136, USA
Patrizia Pasini, Department of Biochemistry and Molecular Biology, Miller School of Medicine, University of Miami, Miami, FL 33136, USA
Sylvia Daunert, Department of Chemistry, University of Kentucky, Lexington, KY 40506, USA
The purpose of this review is to investigate the feasibility of bioaerosol fingerprinting based on current understanding of
cellular debris (with emphasis on human-emitted particulates) in aerosols and arguments regarding sampling, sensitivity, separations,
and detection schemes. Target aerosol particles include cellular material and proteins emitted by humans, animals, and plants
and can be regarded as information-rich packets that carry biochemical information specific to the living organisms present
where the sample is collected. In this work we discuss sampling and analysis techniques that can be integrated with molecular
(e.g. protein)-detection procedures to properly assess the aerosolized cellular material of interest. Developing a detailed
understanding of bioaerosol molecular profiles in different environments suggests exciting possibilities of bioaerosol analysis
with applications ranging from military defense to medical diagnosis and wildlife identification
Figure Feasibility of identifying humans via bioaerosols is examined.
Content Type Journal Article
Category Review
Pages 1-12
DOI 10.1007/s00216-012-5725-0
Authors
Josemar A. Castillo, Department of Chemistry and Biochemistry, Arizona State University, Physical Science Building, PO Box 871604, Tempe, 85287 AZ, USA
Sarah J. R. Staton, Department of Chemistry and Biochemistry, Arizona State University, Physical Science Building, PO Box 871604, Tempe, 85287 AZ, USA
Thomas J. Taylor, Department of Mathematics and Statistical Sciences, Arizona State University, Physical Science Building, PO Box 871604, Tempe, 85287 AZ, USA
Pierre Herckes, Department of Chemistry and Biochemistry, Arizona State University, Physical Science Building, PO Box 871604, Tempe, 85287 AZ, USA
Mark A. Hayes, Department of Chemistry and Biochemistry, Arizona State University, Physical Science Building, PO Box 871604, Tempe, 85287 AZ, USA
The strontium isotope ratio (87Sr/86Sr) in beef, derived from 206 European cattle, has been measured. These cattle were located in 12 different European regions
within France, Germany, Greece, Ireland, Italy, Spain and the UK. As animal protein is known to be a difficult material on
which to conduct Sr isotope analysis, several investigations were undertaken to develop and improve the sample preparation
procedure. For example, Sr isotope analysis was performed directly on freeze-dried meat and defatted dry mass from the same
samples. It was found that enormous differences—sometimes exceeding the measurement uncertainty—could occur between the fractions
and also within one sample even if treated in the same manner. These variations cannot be definitely allocated to one cause
but are most likely due to inhomogeneities caused by physiological and biochemical processes in the animals as post mortem
contamination during analytical processing could be excluded. For further Sr isotope measurements in meat, careful data handling
is recommended, and for the authentic beef samples within this project, it was decided to use only freeze-dried material.
It can be demonstrated, however, that Sr isotope measurements in beef proteins are a valuable tool for authentication of geographic
origin. Although partly overlapping, some of the European sampling sites could be discriminated even by only using 87Sr/86Sr.
Figure Box plot diagram displaying 87Sr/86Sr in authentic beef samples ordered by Trace sampling sites
Content Type Journal Article
Category Original Paper
Pages 1-12
DOI 10.1007/s00216-012-5759-3
Authors
S. Rummel, BSPG (Bayerische Staatssammlung für Paläontologie und Geologie), Richard-Wagner-Str. 10, 80333 München, Germany
C. H. Dekant, BSPG (Bayerische Staatssammlung für Paläontologie und Geologie), Richard-Wagner-Str. 10, 80333 München, Germany
S. Hölzl, BSPG (Bayerische Staatssammlung für Paläontologie und Geologie), Richard-Wagner-Str. 10, 80333 München, Germany
S. D. Kelly, FERA (Food and Environment Research Agency), North Yorkshire, YO41 1LZ UK
M. Baxter, FERA (Food and Environment Research Agency), North Yorkshire, YO41 1LZ UK
N. Marigheto, The Institute of Food Research, Norwich Research Park, Norwich, NR4 7UA UK
C. R. Quetel, EC-JRC-IRMM (European Commission-Joint Research Centre-Institute for Reference Materials and Measurements), 2440 Geel, Belgium
R. Larcher, IASMA (Fondazione E. Mach-Istituto Agrario di San Michele all’Adige), 38010 San Michele all’Adige, Italy
G. Nicolini, IASMA (Fondazione E. Mach-Istituto Agrario di San Michele all’Adige), 38010 San Michele all’Adige, Italy
H. Fröschl, Seibersdorf Labor GmbH, 2444 Seibersdorf, Austria
H. Ueckermann, Centre for Forensic Provenancing University of East Anglia, Norwich, NR4 7TJ UK
J. Hoogewerff, Oritain Global Limited, 8 Pacific Street, 9010 Dunedin, New Zealand
In vivo endocannabinoid (EC) microdialysis has only seldom been performed, mostly in rodent brain tissue. Low solubility in
aqueous media, adsorption to surfaces, and instability with co-present human serum albumin (HSA) are the major obstacles in
EC microdialysis. The addition of hydroxypropyl-ß-cyclodextrine (HPCD) to the perfusion fluid has been previously described
to facilitate lipid microdialysis, but the general biophysical properties of HPCD, especially with respect to peripheral EC
microdialysis, have not been described before. We report on the characterization of EC microdialysis using an in vitro system
using Ringer’s solution with 10% HPCD as the perfusion fluid and with fatty acid-free HSA as the matrix fluid. The endocannabinoids
anandamide (AEA) and 2-arachidonoyl glycerol (2AG) were measured using LC-MS/MS. AEA was stable in the perfusion and matrix
fluids, whereas 2AG was only stable in the perfusion fluid. In the matrix fluid, 2AG underwent rapid isomerization to 1-arachidonoyl
glycerol. A relative recovery of 3.5% for AEA was found with 10% HPCD in the perfusion fluid and a flow rate of 1 ?L/min.
For 2AG, a similar relative recovery of 3.5% was estimated. Since 2AG was found unstable in the matrix fluid, a reliable calculation
of the relative recovery rates was not possible. Delivery and recovery experiments revealed unequal inward and outward EC
transport across the microdialysis membrane. Contrary to usual microdialysis findings, we observed increasing recovery rates
for AEA with increasing flow rates. Long equilibration times of several hours were necessary to obtain constant relative recovery
rates. In a proof-of-concept study in humans, we collected AEA from subcutaneous abdominal adipose tissue employing the described
methodology. Our study suggests that the microdialysis technique is not suitable for the exact quantification of tissue EC
concentrations, but it allows for their rough estimation.
Figure Microdialysis of peripheral endocannabinoids, especially anandamide (AEA).
Content Type Journal Article
Category Original Paper
Pages 1-9
DOI 10.1007/s00216-012-5729-9
Authors
Alexander A. Zoerner, Institute for Clinical Pharmacology, Hannover Medical School, Carl-Neuberg-Straße 1, 30625 Hannover, Germany
Christin Rakers, Institute for Clinical Pharmacology, Hannover Medical School, Carl-Neuberg-Straße 1, 30625 Hannover, Germany
Stefan Engeli, Institute for Clinical Pharmacology, Hannover Medical School, Carl-Neuberg-Straße 1, 30625 Hannover, Germany
Sandor Batkai, Institute for Clinical Pharmacology, Hannover Medical School, Carl-Neuberg-Straße 1, 30625 Hannover, Germany
Marcus May, Institute for Clinical Pharmacology, Hannover Medical School, Carl-Neuberg-Straße 1, 30625 Hannover, Germany
Jens Jordan, Institute for Clinical Pharmacology, Hannover Medical School, Carl-Neuberg-Straße 1, 30625 Hannover, Germany
Dimitrios Tsikas, Institute for Clinical Pharmacology, Hannover Medical School, Carl-Neuberg-Straße 1, 30625 Hannover, Germany
A method to detect the presence of common wheat in durum wheat flour samples was developed and tested. Flour samples, or ground
wheat samples, were digested by pepsin and chymotrypsin, and the peptide mixture obtained was analyzed by LC/ESI-MS and LC/ESI-MS/MS,
which led to the identification of two marker peptides. One peptide was coded only in the DD genome, and thus present only
in common wheat; the second was present in all wheat samples (both common and durum), so it was used as marker of the total
wheat content. The ratio of the chromatographic areas of these two peptides, as determined by LC/ESI-MS, was related to the
proportion of common wheat in the sample using a calibration curve that was constructed with standards of known composition.
The proportions of common wheat in samples obtained by mixing different common and durum wheat varieties were accurately determined
by this method. Finally, the method was applied in a survey of several durum wheat flour brands present on the Italian market.
The results of the survey revealed that contamination of durum wheat flour with common wheat is commonplace.
Content Type Journal Article
Category Original Paper
Pages 1-6
DOI 10.1007/s00216-012-5731-2
Authors
Barbara Prandi, Department of Organic and Industrial Chemistry, University of Parma, Parco Area delle Scienze 17A, 43124 Parma, Italy
Mariangela Bencivenni, Department of Organic and Industrial Chemistry, University of Parma, Parco Area delle Scienze 17A, 43124 Parma, Italy
Tullia Tedeschi, Department of Organic and Industrial Chemistry, University of Parma, Parco Area delle Scienze 17A, 43124 Parma, Italy
Rosangela Marchelli, Department of Organic and Industrial Chemistry, University of Parma, Parco Area delle Scienze 17A, 43124 Parma, Italy
Arnaldo Dossena, Department of Organic and Industrial Chemistry, University of Parma, Parco Area delle Scienze 17A, 43124 Parma, Italy
Gianni Galaverna, Department of Organic and Industrial Chemistry, University of Parma, Parco Area delle Scienze 17A, 43124 Parma, Italy
Stefano Sforza, Department of Organic and Industrial Chemistry, University of Parma, Parco Area delle Scienze 17A, 43124 Parma, Italy
A continuous leaching method coupled online with inductively coupled plasma mass spectrometry (ICP-MS) detection was used
to assess the maximum bioaccessibility of arsenic (As) in seafood samples. The method simulates continuous-flow digestion
by successively pumping artificial saliva, gastric and intestinal juices through a mini-column of powdered sample directly
connected to the nebuliser of an ICP-MS instrument. The method allows the real-time measurement of As being released by a
given reagent. Because the analyte is continuously removed from the system, in contrast to batch methods, the dissolution
equilibrium is driven to the right, hence quickly providing information about the worst-case scenario. Following consecutive
leaching by the digestive reagents, the leachates were subject to speciation analysis by ion-exchange chromatography with
ICP-MS detection to determine the arsenic species released. Finally, the remaining residue from the mini-column was fully
digested to verify mass balance. The method was used to determine the bioaccessibility of total As and As species in four
certified reference materials and in several real seafood samples. The mass balance was verified in each case. Generally speaking,
the non-toxic form was easily released whereas the inorganic forms were poorly bioaccessible.
Content Type Journal Article
Category Original Paper
Pages 1-11
DOI 10.1007/s00216-012-5774-4
Authors
Axelle Leufroy, Agence nationale de sécurité sanitaire de l’alimentation, de l’environnement et du travail, Laboratoire de Sécurité des Aliments de Maisons-Alfort, unité des Contaminants Inorganiques et Minéraux de l’Environnement, ANSES, 23, Avenue du général de Gaulle, Maisons-Alfort, 94706 Paris, France
Laurent Noël, Agence nationale de sécurité sanitaire de l’alimentation, de l’environnement et du travail, Laboratoire de Sécurité des Aliments de Maisons-Alfort, unité des Contaminants Inorganiques et Minéraux de l’Environnement, ANSES, 23, Avenue du général de Gaulle, Maisons-Alfort, 94706 Paris, France
Diane Beauchemin, Department of Chemistry, Queen’s University, 90 Bader Lane, Kingston, ON K7L 3N6, Canada
Thierry Guérin, Agence nationale de sécurité sanitaire de l’alimentation, de l’environnement et du travail, Laboratoire de Sécurité des Aliments de Maisons-Alfort, unité des Contaminants Inorganiques et Minéraux de l’Environnement, ANSES, 23, Avenue du général de Gaulle, Maisons-Alfort, 94706 Paris, France
Erratum to: A review of recent developments in the speciation and location of arsenic and selenium in rice grain
Content Type Journal Article
Category Erratum
Pages 1-1
DOI 10.1007/s00216-012-5786-0
Authors
Anne-Marie Carey, Institute of Biological and Environmental Sciences, University of Aberdeen, Cruickshank Building, St Machar Drive, Aberdeen, AB24 3UU UK
Enzo Lombi, Centre for Environmental Risk Assessment and Remediation, University of South Australia, Building X, Mawson Lakes Campus, Mawson Lakes, South Australia 5095, Australia
Erica Donner, Centre for Environmental Risk Assessment and Remediation, University of South Australia, Building X, Mawson Lakes Campus, Mawson Lakes, South Australia 5095, Australia
Martin D. de Jonge, Australian Synchrotron, X-ray Fluorescence Microscopy, 800 Blackburn Road, Clayton, Victoria 3168, Australia
Tracy Punshon, Department of Biological Sciences, Dartmouth College, Hanover, NH 03755, USA
Brian P. Jackson, Department of Biological Sciences, Dartmouth College, Hanover, NH 03755, USA
Mary Lou Guerinot, Department of Biological Sciences, Dartmouth College, Hanover, NH 03755, USA
Adam H. Price, Institute of Biological and Environmental Sciences, University of Aberdeen, Cruickshank Building, St Machar Drive, Aberdeen, AB24 3UU UK
Andrew A. Meharg, Institute of Biological and Environmental Sciences, University of Aberdeen, Cruickshank Building, St Machar Drive, Aberdeen, AB24 3UU UK
Stationary-phase evaluation in reversed-phase liquid chromatography (RP-LC) is not a straightforward process. A number of
tests to characterize and classify stationary phases have been suggested. The results of these various tests, however, do
not always describe the real properties of the stationary phase. This study critically compares several tests for RP-LC stationary
phases, including the Engelhardt, Tanaka, and SRM 870 tests, as well as an in-house test, with emphasis on the stationary-phase
descriptors of hydrophobicity and silanol activity. The stationary phases were prepared by thermal immobilization of poly(methyloctylsiloxane)
onto silica. Hydrophobicity data from the tests were generally good and interchangeable between the several tests. In contrast,
the silanol activity results of the various tests differ significantly. As a consequence, stationary phase classification
with respect to silanol activity depends considerably on the test method applied. A new classification method for silanol
activity is proposed.
Content Type Journal Article
Category Original Paper
Pages 1-18
DOI 10.1007/s00216-012-5752-x
Authors
Endler M. Borges, Faculdade de Engenharia de Alimentos, Departamento de Ciência de Alimentos, Universidade Estadual de Campinas, Rua Monteiro Lobato 80 (Cidade Universitária Zeferino Vaz), P.O. Box 6121, 13083-970 Campinas, SP, Brazil
Melvin R. Euerby, Hichrom Ltd, 1 The Markham Centre, Station Road, Theale, Reading, Berkshire RG7 4PE, UK
Carol H. Collins, Institute of Chemistry, University of Campinas, P.O. Box 6154, 13083-970 Campinas, SP, Brazil
A UPLC-ESI-MS/MS method has been developed and validated for the determination of larotaxel in beagle dog plasma. After addition
of the internal standard, plasma samples were extracted by liquid–liquid extraction with methyl tert-butyl ether and separated
on a 50?×?2.1 mm ACQUITY 1.7 ?m C18 column (Waters, USA), with acetonitrile and 5 mM ammonium acetate as mobile phase, within a runtime of 3.0 min. The analytes
were detected without interference in Multiple Reaction Monitoring mode with positive electrospray ionization. The linear
range was 2.5–5,000 ng/mL. The intra-day and inter-day precisions (relative standard deviation, RSD, %) were within 9.3% and
10.2%, respectively, and the accuracy (relative error, RE, %) was less than 11.5%. The validated method was successfully applied
to a pharmacokinetic study of larotaxel in beagle dogs after intravenous administration of larotaxel-loaded lipid microsphere
with different doses of 0.4, 0.8, and 1.6 mg/kg. The area under the concentration–time curve and the peak concentration of
larotaxel seemed to increase with increasing dose proportionally, suggesting linear pharmacokinetics.
Figure The concentration–time curves of larotaxel in beagle dog plasma after intravenous administration of LTX-LM at different doses
of 0.4, 0.8, and 1.6 mg/kg
Content Type Journal Article
Category Original Paper
Pages 1-8
DOI 10.1007/s00216-012-5763-7
Authors
Zhenzhen Liu, School of Pharmacy, Shenyang Pharmaceutical University, 103 Wenhua Road, Shenyang, 110016 China
Bo Zhang, School of Pharmacy, Liaoning University of Traditional Chinese Medicine, Shenyang, 110032 China
Zhihong Liu, School of Pharmacy, Shenyang Pharmaceutical University, 103 Wenhua Road, Shenyang, 110016 China
Song Li, School of Pharmacy, Shenyang Pharmaceutical University, 103 Wenhua Road, Shenyang, 110016 China
Guofei Li, School of Pharmacy, Shenyang Pharmaceutical University, 103 Wenhua Road, Shenyang, 110016 China
Lulu Geng, School of Pharmacy, Shenyang Pharmaceutical University, 103 Wenhua Road, Shenyang, 110016 China
Xu Zhao, School of Pharmacy, Shenyang Pharmaceutical University, 103 Wenhua Road, Shenyang, 110016 China
Kaishun Bi, School of Pharmacy, Shenyang Pharmaceutical University, 103 Wenhua Road, Shenyang, 110016 China
Xing Tang, School of Pharmacy, Shenyang Pharmaceutical University, 103 Wenhua Road, Shenyang, 110016 China
Xiaohui Chen, School of Pharmacy, Shenyang Pharmaceutical University, 103 Wenhua Road, Shenyang, 110016 China
One of the limits of current electrochemical biosensors is a lack of methods providing stable and highly efficient junctions
between biomaterial and solid-state devices. This paper shows how laser-induced forward transfer (LIFT) can enable efficient
electron transfer from photosynthetic biomaterial immobilized on screen-printed electrodes (SPE). The ideal pattern, in terms
of photocurrent signal of thylakoid droplets giving a stable response signal with a current intensity of approximately 335?±?13 nA
for a thylakoid mass of 28?±?4 ng, was selected. It is shown that the efficiency of energy production of a photosynthetic
system can be strongly enhanced by the LIFT process, as demonstrated by use of the technique to construct an efficient and
sensitive photosynthesis-based biosensor for detecting herbicides at nanomolar concentrations.
Content Type Journal Article
Category Original Paper
Pages 1-8
DOI 10.1007/s00216-012-5771-7
Authors
Eleftherios Touloupakis, Institute of Crystallography, National Research Council, Via Salaria Km 29.300, Monterotondo Scalo, 00015 Rome, Italy
Christos Boutopoulos, Department of Physics, National Technical University of Athens, Iroon Polytehneiou 9, Zografou, 15780 Athens, Greece
Katia Buonasera, Institute of Crystallography, National Research Council, Via Salaria Km 29.300, Monterotondo Scalo, 00015 Rome, Italy
Ioanna Zergioti, Department of Physics, National Technical University of Athens, Iroon Polytehneiou 9, Zografou, 15780 Athens, Greece
Maria Teresa Giardi, Institute of Crystallography, National Research Council, Via Salaria Km 29.300, Monterotondo Scalo, 00015 Rome, Italy
This critical review describes a class of polymers prepared by electrochemical polymerization that employs the concept of
molecular imprinting for chemical sensing. The principal focus is on both conducting and nonconducting polymers prepared by
electropolymerization of electroactive functional monomers, such as pristine and derivatized pyrrole, aminophenylboronic acid,
thiophene, porphyrin, aniline, phenylenediamine, phenol, and thiophenol. A critical evaluation of the literature on electrosynthesized
molecularly imprinted polymers (MIPs) applied as recognition elements of chemical sensors is presented. The aim of this review
is to highlight recent achievements in analytical applications of these MIPs, including present strategies of determination
of different analytes as well as identification and solutions for problems encountered.
Content Type Journal Article
Category Review
Pages 1-28
DOI 10.1007/s00216-011-5696-6
Authors
Piyush S. Sharma, Department of Physical Chemistry of Supramolecular Complexes, Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland
Agnieszka Pietrzyk-Le, Department of Physical Chemistry of Supramolecular Complexes, Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland
Francis D’Souza, Department of Chemistry, University of North Texas, 1155 Union Circle, # 305070, Denton, TX 76203-5017, USA
Wlodzimierz Kutner, Department of Physical Chemistry of Supramolecular Complexes, Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland
Compound-specific stable-isotope analysis (CSIA) has greatly facilitated assessment of sources and transformation processes
of organic pollutants. Multielement isotope analysis is one of the most promising applications of CSIA because it even enables
distinction of different transformation pathways. This review introduces the essential features of continuous-flow isotope-ratio
mass spectrometry (IRMS) and highlights current challenges in environmental analysis as exemplified for the isotopes of nitrogen,
hydrogen, chlorine, and oxygen. Strategies and recent advances to enable isotopic measurements of polar contaminants, for
example pesticides or pharmaceuticals, are discussed with special emphasis on possible solutions for analysis of low concentrations
of contaminants in environmental matrices. Finally, we discuss different levels of calibration and referencing and point out
the urgent need for compound-specific isotope standards for gas chromatography–isotope-ratio mass spectrometry (GC–IRMS) of
organic pollutants.
Figure Compound-specific isotope analysis of environmental contaminants: chromatographic separation is followed by online conversion
to a suitable measurement gas (M) and subsequent isotope ratio mass spectrometry. Current challenges in the field concern
the analysis of multiple elements (C, H, N, O, Cl) in polar compounds, at low concentrations and in the presence of matrix
interferences. An urgent need exists for contaminant-specific reference materials.
Content Type Journal Article
Category Review
Pages 1-21
DOI 10.1007/s00216-011-5683-y
Authors
Martin Elsner, Helmholtz Zentrum München, Institute of Groundwater Ecology, Ingolstädter Landstr. 1, 85764 Neuherberg, Germany
Maik A. Jochmann, Instrumental Analytical Chemistry, University Duisburg-Essen, Universitätsstr. 5, 45141 Essen, Germany
Thomas B. Hofstetter, Eawag, Swiss Federal Institute of Aquatic Science and Technology, Überlandstr. 133, 8600 Dübendorf, Switzerland
Daniel Hunkeler, University of Neuchâtel, Centre for Hydrogeology, Rue Emile Argand 11, 2009 Neuchâtel, Switzerland
Anat Bernstein, Zuckerberg Institute for Water Research, Department of Environmental Hydrology and Microbiology, Ben-Gurion University of the Negev, Sede Boqer Campus, 84990 Negev, Israel
Torsten C. Schmidt, Instrumental Analytical Chemistry, University Duisburg-Essen, Universitätsstr. 5, 45141 Essen, Germany
Arndt Schimmelmann, Department of Geological Sciences, Indiana University, Bloomington, IN 47405-1405, USA
Miniaturization continues to be one of the leading trends in analytical chemistry and one that brings advantages that can
be particularly beneficial in biochemical research. Use of a miniaturized scale enables efficient analysis in a short time
and requires very small amounts of samples, solvents, and reagents. This can result in a remarkable decrease in costs of enzyme
kinetics studies, especially when expensive or rare enzymes and/or substrates are involved. Free zone electrophoresis is without
a doubt the most common microscale separation technique for capillary and on-chip enzyme assays. Progress and applications
in this field are reviewed frequently whereas other modes of separation, although successfully applied, receive only marginal
interest in such publications. This review summarizes applications of less common modes of separation in capillary or chip
formats, namely micellar electrokinetic chromatography, liquid chromatography, gel electrophoresis, isoelectric focusing,
and isotachophoresis. Because these techniques are based on separation mechanisms different from those of free zone electrophoresis,
they can be, and have been, successfully used in cases where zone electrophoresis fails. Advantages and drawbacks of these
alternative separation techniques are discussed, as also are the difficulties encountered most often and solutions proposed
by different research groups.
Content Type Journal Article
Category Review
Pages 1-11
DOI 10.1007/s00216-012-5744-x
Authors
Tomáš K?ížek, Faculty of Science, Department of Analytical Chemistry, Charles University in Prague, Hlavova 8, 128 43 Prague 2, Czech Republic
Anna Kubí?ková, Faculty of Science, Department of Analytical Chemistry, Charles University in Prague, Hlavova 8, 128 43 Prague 2, Czech Republic
The use of Fourier transform infrared spectromicroscopy and mass spectrometry (MS) allowed us to characterize the composition
of polar and non-polar binders present in sporadic wall paint fragments taken from Pompeii’s archaeological excavation. The
analyses of the polar and non-polar binder components extracted from paint powder layer showed the presence of amino acids,
sugars, and fatty acids but the absence of proteinaceous material. These results are consistent with a water tempera painting
mixture composed of pigments, flours, gums, and oils and are in agreement with those obtained from a simulated wall paint
sample made for mimicking an ancient “a secco” technique. Notably, for the first time, we report the capability to discriminate
by tandem MS the presence of free amino acids in the paint layer.
Content Type Journal Article
Category Technical Note
Pages 1-6
DOI 10.1007/s00216-012-5746-8
Authors
Gaetano Corso, Dipartimento di Biochimica e Biotecnologie Mediche, Università di Napoli Federico II, Via S. Pansini, 5-80131 Napoli, Italy
Monica Gelzo, Dipartimento di Biochimica e Biotecnologie Mediche, Università di Napoli Federico II, Via S. Pansini, 5-80131 Napoli, Italy
Carmen Sanges, Dipartimento di Biochimica e Biotecnologie Mediche, Università di Napoli Federico II, Via S. Pansini, 5-80131 Napoli, Italy
Angela Chambery, Dipartimento di Scienze per la Vita, Seconda Università di Napoli, Via Vivaldi 43, 81100 Caserta, Italy
Antimo Di Maro, Dipartimento di Scienze per la Vita, Seconda Università di Napoli, Via Vivaldi 43, 81100 Caserta, Italy
Valeria Severino, Dipartimento di Scienze per la Vita, Seconda Università di Napoli, Via Vivaldi 43, 81100 Caserta, Italy
Antonio Dello Russo, Dipartimento di Biochimica e Biotecnologie Mediche, Università di Napoli Federico II, Via S. Pansini, 5-80131 Napoli, Italy
Ciro Piccioli, Accademia di Belle Arti di Napoli, Via Costantinopoli, 107-80138 Napoli, Italy
Paolo Arcari, Dipartimento di Biochimica e Biotecnologie Mediche, Università di Napoli Federico II, Via S. Pansini, 5-80131 Napoli, Italy
The degradation of two ?-blockers (atenolol and propranolol) and one ?-receptor agonist (salbutamol) during water chlorination
was investigated by liquid chromatography–mass spectrometry (LC-MS). An accurate-mass quadrupole time-of-flight system (QTOF)
was used to follow the time course of the pharmaceuticals and also used in the identification of the by-products. The degradation
kinetics of these drugs was investigated at different concentrations of chlorine, bromide and sample pH by means of a Box–Behnken
experimental design. Depending on these factors, dissipation half-lives varied in the ranges 68–145 h for atenolol, 1.3–33 min
for salbutamol and 42–8362 min for propranolol. Normally, an increase in chlorine dosage and pH resulted in faster degradation
of these pharmaceuticals. Moreover, the presence of bromide in water samples also resulted in a faster transformation of atenolol
at low chlorine doses. The use of an accurate-mass high-resolution LC-QTOF-MS system permitted the identification of a total
of 14 by-products. The transformation pathway of ?-blockers/agonists consisted mainly of halogenations, hydroxylations and
dealkylations. Also, many of these by-products are stable, depending on the chlorination operational parameters employed.
Content Type Journal Article
Category Original Paper
Pages 1-11
DOI 10.1007/s00216-011-5707-7
Authors
José Benito Quintana, Department of Analytical Chemistry, Nutrition and Food Science, IIAA—Institute for Food Analysis and Research, University of Santiago de Compostela, 15782 Santiago de Compostela, Spain
Rosario Rodil, Department of Analytical Chemistry, Nutrition and Food Science, IIAA—Institute for Food Analysis and Research, University of Santiago de Compostela, 15782 Santiago de Compostela, Spain
Rafael Cela, Department of Analytical Chemistry, Nutrition and Food Science, IIAA—Institute for Food Analysis and Research, University of Santiago de Compostela, 15782 Santiago de Compostela, Spain
At least one third of all proteins are thought to require a metal ion co-factor for their function. Recognition of the importance
of metals in biological systems and major advances in analytical instrumentation and technology have led to the emergence
of the new research area of metalloproteomics in recent years. Despite this progress, the experimental determination of in-vivo
metal cofactors has remained challenging, because this requires elucidation of protein interactions with non-covalently bound
metal ions. This critical review highlights current methodological approaches, focusing, in particular, on issues relating
to the fractionation and separation of the metalloproteome, including recent experience with metalloproteomics for marine
cyanobacteria in our laboratory. Metalloproteomics promises to deliver novel insights into fundamental biological processes
in the future, but it is clear that further methodological advances are necessary to exploit the full potential of this emerging
research area.
Figure ?
Content Type Journal Article
Category Review
Pages 1-12
DOI 10.1007/s00216-012-5743-y
Authors
James P. Barnett, Department of Chemistry, University of Warwick, Coventry, CV4 7AL UK
David J. Scanlan, School of Life Sciences, University of Warwick, Coventry, CV4 7AL UK
Claudia A. Blindauer, Department of Chemistry, University of Warwick, Coventry, CV4 7AL UK
Mass spectrometry: Fifth meeting of the Spanish Society of Mass Spectrometry (SEEM)
Content Type Journal Article
Category Editorial
Pages 1-2
DOI 10.1007/s00216-011-5690-z
Authors
José M. Vadillo, Department of Analytical Chemistry, University of Málaga, 29071 Málaga, Spain
Damià Barceló, Catalan Institute for Water Research (ICRA), Parc Cientific i Tecnològic de la Universitat de Girona, Pic de Peguera 15, 17003 Girona, Spain
Clinical and forensic toxicology and doping control deal with hundreds or thousands of drugs that may cause poisoning or are
abused, are illicit, or are prohibited in sports. Rapid and reliable screening for all these compounds of different chemical
and pharmaceutical nature, preferably in a single analytical method, is a substantial effort for analytical toxicologists.
Combined chromatography–mass spectrometry techniques with standardised reference libraries have been most commonly used for
the purpose. In the last ten years, the focus has shifted from gas chromatography–mass spectrometry to liquid chromatography–mass
spectrometry, because of progress in instrument technology and partly because of the polarity and low volatility of many new
relevant substances. High-resolution mass spectrometry (HRMS), which enables accurate mass measurement at high resolving power,
has recently evolved to the stage that is rapidly causing a shift from unit-resolution, quadrupole-dominated instrumentation.
The main HRMS techniques today are time-of-flight mass spectrometry and Orbitrap Fourier-transform mass spectrometry. Both
techniques enable a range of different drug-screening strategies that essentially rely on measuring a compound’s or a fragment’s
mass with sufficiently high accuracy that its elemental composition can be determined directly. Accurate mass and isotopic
pattern acts as a filter for confirming the identity of a compound or even identification of an unknown. High mass resolution
is essential for improving confidence in accurate mass results in the analysis of complex biological samples. This review
discusses recent applications of HRMS in analytical toxicology.
Content Type Journal Article
Category Review
Pages 1-18
DOI 10.1007/s00216-012-5726-z
Authors
Ilkka Ojanperä, Hjelt Institute, Department of Forensic Medicine, Forensic Toxicology Division, University of Helsinki, P.O. Box 40, 00014 Helsinki, Finland
Marjo Kolmonen, Hjelt Institute, Department of Forensic Medicine, Forensic Toxicology Division, University of Helsinki, P.O. Box 40, 00014 Helsinki, Finland
Anna Pelander, Hjelt Institute, Department of Forensic Medicine, Forensic Toxicology Division, University of Helsinki, P.O. Box 40, 00014 Helsinki, Finland
Triclosan, an antibacterial and antifungal agent, is widely used in household and personal care products, processed foods
and food packaging, etc., and thus also released into the environment. Triclosan is acutely and chronically toxic to aquatic
organisms and bioaccumulates in fish tissue. Here, we propose a new miniaturized triclosan extraction method for aqueous and
fish roe samples, based on the use of a vortex mixer and an ultrasonic probe, respectively, and useful for triclosan determination
by gas chromatography coupled to a micro electron capture detector. Different solvents for extraction and sorbents for clean-up
purposes were tested. Multivariate optimization of the variables affecting ultrasonic extraction (ultrasound radiation amplitude,
sonication time, sample temperature, and the ratio of sample amount and extracting volume) was carried out. Solvent extraction
using ethyl acetate and further clean-up with mixed bed cartridges with two layers of Florisil® and Florisil® impregnated
with 10% sulfuric acid only for fish roe samples was finally selected. Extraction efficiencies of up to 95% and 90%, and detection
limits of 0.165 ng ml?1 and 2.7 ng g?1 for aqueous and fish roe samples were obtained, respectively. The optimized method was used in bioconcentration studies with
zebrafish larvae (Danio rerio), as an alternative method to the Organization for Economic Cooperation and Development technical guideline 305. Bioconcentration
values, BCF?=?2,630 and 2,018 at exposure concentrations of 30 and 3 ?g L?1, respectively, were assessed. These results are in agreement with those reported in the literature, showing the feasibility
of the method for estimation of toxicokinetic parameters and bioconcentration factors using zebrafish larvae instead of adult
fishes, reducing considerable animal testing, as suggested by the European legislation.
Content Type Journal Article
Category Original Paper
Pages 1-11
DOI 10.1007/s00216-012-5713-4
Authors
R. Gonzalo-Lumbreras, Department of Analytical Chemistry, Faculty of Chemistry, Universidad Complutense Madrid, Ciudad Universitaria, 28040 Madrid, Spain
J. Sanz-Landaluze, Department of Analytical Chemistry, Faculty of Chemistry, Universidad Complutense Madrid, Ciudad Universitaria, 28040 Madrid, Spain
J. Guinea, Zf BioLabs, Ronda de Valdecarrizo 41º B. 28760. Tres Cantos, Madrid, Spain
C. Cámara, Department of Analytical Chemistry, Faculty of Chemistry, Universidad Complutense Madrid, Ciudad Universitaria, 28040 Madrid, Spain
Traditional activity-guided fractionation of natural products is a time-consuming, labor intensive, and expensive strategy,
which cannot compete with high-throughput and rapid screening of natural products. Therefore, more efficient approaches are
necessary for searching active compounds from natural products. Three main methods based on high-performance liquid chromatography
(HPLC) analysis combined with 2,2?-diphenyl-1-picrylhydrazyl (DPPH) assay, DPPH spiking HPLC analysis, on-line post-column
HPLC-DPPH analysis, and HPLC-based DPPH activity profiling, were then developed for the rapid screening of antioxidants from
complex mixtures. In the present study, a comparative study of these three methods has been conducted to identify antioxidants
from an ethyl acetate fraction of Pueraria lobata flowers. The parameters in HPLC analysis and DPPH assay were optimized. The results indicated that all three methods could
achieve similar information with regard to antioxidants, without the need for preparative isolation techniques. However, there
were differences in instrumental set-up, sensitivity, and efficiency. DPPH spiking HPLC analysis seemed to be more sensitive
and effective with simpler instrumental set-up and easier operation, which could also detect the total antioxidant capacity
of color complexes. Eighteen antioxidants were tentatively screened and identified from P. lobata flowers by DPPH spiking HPLC-MS/MS. Among them, ten compounds including one new compound were first isolated from P. lobata flowers, and the DPPH radical scavenging activity of the new compound was reported for the first time.
Content Type Journal Article
Category Original Paper
Pages 1-12
DOI 10.1007/s00216-012-5722-3
Authors
Yu-Ping Zhang, State Key Laboratory of Powder Metallurgy, Central South University, Changsha, 410083 China
Shu-Yun Shi, State Key Laboratory of Powder Metallurgy, Central South University, Changsha, 410083 China
Xiang Xiong, State Key Laboratory of Powder Metallurgy, Central South University, Changsha, 410083 China
Xiao-Qing Chen, School of Chemistry and Chemical Engineering, Central South University, Changsha, 410083 China
Mi-Jun Peng, Key Laboratory of Hunan Forest Products and Chemical Industry Engineering, Jishou University, Zhangjiajie, 427000 China
A fast, easy-to-handle and cost-effective analytical method for 11 mycotoxins currently regulated in maize and other cereal-based
food products in Europe was developed and validated for maize. The method is based on two extraction steps using different
acidified acetonitrile–water mixtures. Separation is achieved using ultrahigh-performance liquid chromatography (UHPLC) by
a linear water–methanol gradient. After electrospray ionisation, tandem mass spectrometric detection is performed in dynamic
multiple reaction monitoring mode. Since accurate mass spectrometric quantification is hampered by matrix effects, uniformly
[13C]-labelled mycotoxins for each of the 11 compounds were added to the sample extracts prior to UHPLC-MS/MS analysis. Method
performance parameters were obtained by spiking blank maize samples with mycotoxins before as well as after extraction on
six levels in triplicates. The twofold extraction led to total recoveries of the extraction steps between 97% and 111% for
all target analytes, including fumonisins. The [13C]-labelled internal standards efficiently compensated all matrix effects in electrospray ionisation, leading to apparent
recoveries between 88% and 105% with reasonable additional costs. The relative standard deviations of the whole method were
between 4% and 11% for all analytes. The trueness of the method was verified by the measurement of several maize test materials
with well-characterized concentrations. In conclusion, the developed method is capable of determining all regulated mycotoxins
in maize and presuming similar matrix effects and extraction recovery also in other cereal-based foods.
Content Type Journal Article
Category Paper in Forefront
Pages 1-12
DOI 10.1007/s00216-012-5757-5
Authors
Elisabeth Varga, Christian Doppler Laboratory for Mycotoxin Metabolism and Center for Analytical Chemistry, Department for Agrobiotechnology (IFA-Tulln), University of Natural Resources and Life Sciences Vienna, Konrad Lorenz Str. 20, 3430 Tulln, Austria
Thomas Glauner, Chemical Analysis Group, Agilent Technologies Sales & Services GmbH & Co. KG, Hewlett-Packard-Str. 8, 76337 Waldbronn, Germany
Robert Köppen, Division 1.2 Organic Chemical Analysis, Reference Materials, Federal Institute for Materials Research and Testing, Richard-Willstätter-Str. 11, 12489 Berlin, Germany
Katharina Mayer, Christian Doppler Laboratory for Mycotoxin Metabolism and Center for Analytical Chemistry, Department for Agrobiotechnology (IFA-Tulln), University of Natural Resources and Life Sciences Vienna, Konrad Lorenz Str. 20, 3430 Tulln, Austria
Michael Sulyok, Christian Doppler Laboratory for Mycotoxin Metabolism and Center for Analytical Chemistry, Department for Agrobiotechnology (IFA-Tulln), University of Natural Resources and Life Sciences Vienna, Konrad Lorenz Str. 20, 3430 Tulln, Austria
Rainer Schuhmacher, Christian Doppler Laboratory for Mycotoxin Metabolism and Center for Analytical Chemistry, Department for Agrobiotechnology (IFA-Tulln), University of Natural Resources and Life Sciences Vienna, Konrad Lorenz Str. 20, 3430 Tulln, Austria
Rudolf Krska, Christian Doppler Laboratory for Mycotoxin Metabolism and Center for Analytical Chemistry, Department for Agrobiotechnology (IFA-Tulln), University of Natural Resources and Life Sciences Vienna, Konrad Lorenz Str. 20, 3430 Tulln, Austria
Franz Berthiller, Christian Doppler Laboratory for Mycotoxin Metabolism and Center for Analytical Chemistry, Department for Agrobiotechnology (IFA-Tulln), University of Natural Resources and Life Sciences Vienna, Konrad Lorenz Str. 20, 3430 Tulln, Austria
Erratum to: HS-SPME-GC×GC-qMS volatile metabolite profiling of Chrysolina herbacea frass and Mentha spp. leaves
Content Type Journal Article
Category Erratum
Pages 1-2
DOI 10.1007/s00216-012-5745-9
Authors
Chiara Cordero, Dipartimento di Scienza e Tecnologia del Farmaco, Università degli Studi di Torino, Via Pietro Giuria n°9, 10125 Torino, Italy
Simon Atsbaha Zebelo, Unità di Fisiologia Vegetale, Dipartimento di Biologia Vegetale, Università degli Studi di Torino, Centro della Innovazione, Via Quarello 11/A, 10135 Torino, Italy
Giorgio Gnavi, Unità di Fisiologia Vegetale, Dipartimento di Biologia Vegetale, Università degli Studi di Torino, Centro della Innovazione, Via Quarello 11/A, 10135 Torino, Italy
Alessandra Griglione, Dipartimento di Scienza e Tecnologia del Farmaco, Università degli Studi di Torino, Via Pietro Giuria n°9, 10125 Torino, Italy
Carlo Bicchi, Dipartimento di Scienza e Tecnologia del Farmaco, Università degli Studi di Torino, Via Pietro Giuria n°9, 10125 Torino, Italy
Massimo E. Maffei, Unità di Fisiologia Vegetale, Dipartimento di Biologia Vegetale, Università degli Studi di Torino, Centro della Innovazione, Via Quarello 11/A, 10135 Torino, Italy
Patrizia Rubiolo, Dipartimento di Scienza e Tecnologia del Farmaco, Università degli Studi di Torino, Via Pietro Giuria n°9, 10125 Torino, Italy
The antibody specific for the malaria protein, Rhop-3, and FL-Rhop-3, were immobilized on the surface of a gold electrode
modified with cysteamine. Colloidal gold was used to enhance the detection signal for Rhop-3 antigens. The Rhop-3 antibody
was also immobilized on gold electrodes preactivated with dithiobis(succinimidyl proprionate) (DSP). Immobilization was performed
at room temperature and at 37 °C. Cyclic voltammetry (CV) was used to monitor the interaction between the immobilized antibody
and its cognate antigen in solution, using ferricyanide, K3Fe(CN)6, as reporting electroactive probe. Tests indicate recognition of Rhop-3 protein by the immobilized antibody. Antigen recognition
was enhanced by incubation at 37 °C compared with room-temperature incubation. Our results suggest that an immunosensor can
be developed and optimized to aid detection of Rhop-3 antigens in samples from malaria patients. As far as we are aware, this
is the first amperometric immunosensor targeting Rhop-3 antigen as a malaria biomarker.
Content Type Journal Article
Category Short Communication
Pages 1-6
DOI 10.1007/s00216-012-5735-y
Authors
Salaam Saleh, Department of Biological, Geological, and Environmental Sciences, College of Science and Health Professions, Cleveland State University, Cleveland, OH 44115, USA
Susan Moreno-Molek, Department of Biological, Geological, and Environmental Sciences, College of Science and Health Professions, Cleveland State University, Cleveland, OH 44115, USA
Indika Perera, Department of Chemistry, College of Science and Health Professions, Cleveland State University, Cleveland, OH 44115, USA
Alan Riga, Department of Chemistry, College of Science and Health Professions, Cleveland State University, Cleveland, OH 44115, USA
Tobili Sam-Yellowe, Department of Biological, Geological, and Environmental Sciences, College of Science and Health Professions, Cleveland State University, Cleveland, OH 44115, USA
Mekki Bayachou, Department of Chemistry, College of Science and Health Professions, Cleveland State University, Cleveland, OH 44115, USA
Nucleic acid biosensors have a growing number of applications in genetics and biomedicine. This contribution is a critical
review of the current state of the art concerning the use of nucleic acid analogues, in particular peptide nucleic acids (PNA)
and locked nucleic acids (LNA), for the development of high-performance affinity biosensors. Both PNA and LNA have outstanding
affinity for natural nucleic acids, and the destabilizing effect of base mismatches in PNA- or LNA-containing heterodimers
is much higher than in double-stranded DNA or RNA. Therefore, PNA- and LNA-based biosensors have unprecedented sensitivity
and specificity, with special applicability in DNA genotyping. Herein, the most relevant PNA- and LNA-based biosensors are
presented, and their advantages and their current limitations are discussed. Some of the reviewed technology, while promising,
still needs to bridge the gap between experimental status and the harder reality of biotechnological or biomedical applications.
Content Type Journal Article
Category Review
Pages 1-19
DOI 10.1007/s00216-012-5742-z
Authors
Carlos Briones, Department of Molecular Evolution, Centro de Astrobiología (INTA-CSIC), Carretera de Ajalvir, Km 4. Torrejón de Ardoz, Madrid, Spain
Miguel Moreno, Department of Molecular Evolution, Centro de Astrobiología (INTA-CSIC), Carretera de Ajalvir, Km 4. Torrejón de Ardoz, Madrid, Spain
A label-free electrochemical biosensor for detecting DNA hybridisation was developed by monitoring the change in the voltammetric
activity of ferrocenecarboxylic acid at the biosensor–solution interface. The biosensor was constructed by initially immobilising
on a glassy carbon electrode an anchoring layer consisting of chitosan, carboxyl group functionalised carbon nanofibres and
glutaraldehye. Chitosan acted as an adhering agent and carbon nanofibres were strategically used to provide a large surface
area with binding points for DNA immobilisation, while glutaraldehye was a linker for DNA probes on the electrode surface.
Based on a two-factorial design, cyclic voltammetry of [Fe(CN)6]3?/4? was performed to optimise the composition of the anchoring layer. Next, a 17-base pair DNA probe was attached to the anchoring
layer, followed by its complementary target. Zr(IV) ion, known to exhibit affinity for oxygen-containing electroactive markers,
for example, ferrocenecarboxylic acid, was then coordinated in the DNA duplex. In this way, ferrocenecarboxylic acid was attracted
towards the biosensor for oxidation. A change in the voltammetric oxidation current of ferrocenecarboxylic acid pre- and post-hybridisation
was used to provide an indication of hybridisation. A linear dynamic range between 0.5 and 40 nM and a detection limit of
88 pM of DNA target were then achieved. In addition, the biosensor exhibited good selectivity, repeatability and stability
for the determination of DNA sequences.
Content Type Journal Article
Category Original Paper
Pages 1-10
DOI 10.1007/s00216-012-5733-0
Authors
Patoommarn Wipawakarn, Department of Chemistry and Biomolecular Sciences, Macquarie University, Sydney, NSW 2109, Australia
Huangxian Ju, Key Laboratory of Analytical Chemistry for Life Science (Ministry of Education of China), Department of Chemistry, Nanjing University, Nanjing, 210093 China
Danny K. Y. Wong, Department of Chemistry and Biomolecular Sciences, Macquarie University, Sydney, NSW 2109, Australia
The sizes of certain types of lipoprotein particles have been associated with an increased risk of cardiovascular disease.
However, there is currently no gold standard technique for the determination of this parameter. Here, we propose an analytical
procedure to measure lipoprotein particles sizes using diffusion-ordered nuclear magnetic resonance spectroscopy (DOSY). The
method was tested on six lipoprotein fractions, VLDL, IDL, LDL1, LDL2, HDL2, and HDL3, which were obtained by sequential ultracentrifugation from four patients. We performed a pulsed-field gradient experiment
on each fraction to obtain a mean diffusion coefficient, and then determined the apparent hydrodynamic radius using the Stokes–Einstein
equation. To validate the hydrodynamic radii obtained, the particle size distribution of these lipoprotein fractions was also
measured using transmission electron microscopy (TEM). The standard errors of duplicate measurements of diffusion coefficient
ranged from 0.5% to 1.3%, confirming the repeatability of the technique. The coefficient of determination between the hydrodynamic
radii and the TEM-derived mean particle size was r2?=?0.96, and the agreement between the two techniques was 85%. Thus, DOSY experiments have proved to be accurate and reliable
for estimating lipoprotein particle sizes.
Figure
Content Type Journal Article
Category Original Paper
Pages 1-9
DOI 10.1007/s00216-011-5705-9
Authors
Roger Mallol, Department of Electronic Engineering, Universitat Rovira i Virgili, Avinguda Països Catalans 26, 43007 Tarragona, Spain
Miguel A. Rodríguez, Metabolomics Platform, IISPV, Universitat Rovira i Virgili, Avinguda Països Catalans 26, 43007 Tarragona, Spain
We report herein a new class of metal ion chemosensors and give the first example of a metal-dependent peptidase chemosensor
for metal ions. The chemosensor contains the basic specific Ni(II)-dependent peptide bond hydrolysis sequence (Gly-Ala-Ser-Arg-His-Trp-Lys-Phe-Lys).
The substrate was labeled with a fluorophore at the N-terminal and a quencher at the C-terminal Lys side chain. Initially,
the MOCAc ((7-methoxycoumarin-4-yl)acetyl-) emission was quenched by the nearby quencher. In the presence of Ni(II), the substrate
was irreversibly cleaved at the cleavage site, leading to a 20-fold increase in fluorescence intensity. The chemosensor combines
the high selectivity of a peptidase (at least greater than tenfold for Ni(II) over other metal ions) with the high sensitivity
of fluorescence detection limit of 50 nM and can be applied for the quantitative detection of Ni(II) over a concentration
range of three orders of magnitude. Given this degree of selectivity and sensitivity, our molecular engineering design may
prove useful in the future development of other peptidase-based probes for different metal ions in toxicological and environmental
monitoring.
Figure The chemosensor peptidase was coordinated and cleaved by Ni(II), leading to its increased fluorescence intensity
Content Type Journal Article
Category Technical Note
Pages 1-4
DOI 10.1007/s00216-012-5734-z
Authors
Xiao-Li Lv, Beijing Key Laboratory of Bioprocess, College of Life Science and Technology, Beijing University of Chemical Technology, Beijing, 100029 China
Shi-Zhong Luo, Beijing Key Laboratory of Bioprocess, College of Life Science and Technology, Beijing University of Chemical Technology, Beijing, 100029 China
Petra Dittrich, Laboratory of Organic Chemistry, Swiss Federal Institute of Technology, Wolfgang-Pauli-Str. 10, 8093 Zürich, Switzerland
Detlef Günther, Laboratory of Inorganic Chemistry, Swiss Federal Institute of Technology, Wolfgang-Pauli-Str. 10, 8093 Zürich, Switzerland
Gérard Hopfgartner, Life Sciences Mass Spectrometry, University of Geneva, University of Lausanne, Quai Ernest Ansermet 30, CH-1211 Geneva, Switzerland
Renato Zenobi, Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology, 8093 Zürich, Switzerland
Aberrant protein glycosylation may be closely associated with cancer pathology. To measure the abundance of protein glycoforms
with a specific glycan structure in plasma samples, we developed a lectin-coupled multiple reaction monitoring (MRM)-based
mass spectrometric method. It was confirmed that the method could provide reproducible results with precision sufficient to
distinguish differences in the abundance of protein glycoforms between individuals. Plasma samples prepared from hepatocellular
carcinoma (HCC) patients without immuno-depletion of highly abundant plasma proteins were fractionated by use of fucose-specific
aleuria aurantia lectin (AAL) immobilized on magnetic beads by use of a biotin–streptavidin conjugate. The lectin-captured
fractions were digested by trypsin and profiled by tandem mass spectrometry. From the proteomic profiling data, target glycoproteins
were selected and analyzed quantitatively by MRM-based analysis. The reproducibility of MRM-based quantification of
the selected target proteins was reliable, with precision (CV; ?14% for batch-to-batch replicates and ?19% for replicates
over three days) sufficient to distinguish differences in the abundance of AAL-captured glycoforms between individual plasma
samples. This lectin-coupled, MRM-based method, measuring only lectin-captured glycoforms of a target protein rather than
total target protein, is a tool for monitoring differences between individuals by measuring the abundance of aberrant glycoforms
of a target protein related to a disease. This method may be further applied to rapid verification of biomarker candidates
involved in aberrant protein glycosylation in human plasma.
Figure A lectin-coupled, MRM-based approach for quantitative analysis of plasma glycoproteins
Content Type Journal Article
Category Original Paper
Pages 2101-2112
DOI 10.1007/s00216-011-5646-3
Authors
Yeong Hee Ahn, Division of Mass Spectrometry, Korea Basic Science Institute, 804-1 Yangcheong-Ri, Ochang-Eup, Cheongwon-Gun, 363-883 Republic of Korea
Park Min Shin, Division of Mass Spectrometry, Korea Basic Science Institute, 804-1 Yangcheong-Ri, Ochang-Eup, Cheongwon-Gun, 363-883 Republic of Korea
Eun Sun Ji, Division of Mass Spectrometry, Korea Basic Science Institute, 804-1 Yangcheong-Ri, Ochang-Eup, Cheongwon-Gun, 363-883 Republic of Korea
Hoguen Kim, Department of Pathology, Yonsei Medical Center, Yonsei University, Seoul, 120-752 Republic of Korea
Jong Shin Yoo, Division of Mass Spectrometry, Korea Basic Science Institute, 804-1 Yangcheong-Ri, Ochang-Eup, Cheongwon-Gun, 363-883 Republic of Korea
The preparation and characteristics of a disposable amperometric magnetoimmunosensor, based on the use of functionalized magnetic
beads (MBs) and gold screen-printed electrodes (Au/SPEs), for the specific detection and quantification of Staphylococcal
protein A (ProtA) and Staphylococcus aureus (S. aureus) is reported. An antiProtA antibody was immobilized onto ProtA-modified MBs, and a competitive immunoassay involving ProtA
antigen labelled with HRP was performed. The resulting modified MBs were captured by a magnetic field on the surface of tetrathiafulvalene-modified
Au/SPEs and the amperometric response obtained at ?0.15 V vs the silver pseudo-reference electrode of the Au/SPEs after the
addition of H2O2 was used as transduction signal. The developed methodology showed very low limits of detection (1 cfu S. aureus/mL of raw milk samples), and a good selectivity against the most commonly involved foodborne pathogens originating from milk.
These features, together with a short analysis time (2 h), the simplicity, and easy automation and miniaturization of the
required instrumentation make the developed methodology a promising alternative in the development of devices for on-site
analysis.
Figure Schematic display of the developed S. aureus amperometric magnetoimmunosensor
Content Type Journal Article
Category Original Paper
Pages 1-9
DOI 10.1007/s00216-012-5738-8
Authors
Berta Esteban-Fernández de Ávila, Departamento de Química Analítica, Facultad de CC. Químicas, Universidad Complutense de Madrid, 28040 Madrid, Spain
María Pedrero, Departamento de Química Analítica, Facultad de CC. Químicas, Universidad Complutense de Madrid, 28040 Madrid, Spain
Susana Campuzano, Departamento de Química Analítica, Facultad de CC. Químicas, Universidad Complutense de Madrid, 28040 Madrid, Spain
Vanessa Escamilla-Gómez, Departamento de Química Analítica, Facultad de CC. Químicas, Universidad Complutense de Madrid, 28040 Madrid, Spain
José M. Pingarrón, Departamento de Química Analítica, Facultad de CC. Químicas, Universidad Complutense de Madrid, 28040 Madrid, Spain
Quorum sensing (QS) allows bacteria to communicate with one another by means of QS signaling molecules and control certain
behaviors in a group-based manner, including pathogenicity and biofilm formation. Bacterial gut microflora may play a role
in inflammatory bowel disease pathogenesis, and antibiotics are one of the available therapeutic options for Crohn’s disease.
In the present study, we employed genetically engineered bioluminescent bacterial whole-cell sensing systems as a tool to
evaluate the ability of antibiotics commonly employed in the treatment of chronic inflammatory conditions to interfere with
QS. We investigated the effect of ciprofloxacin, metronidazole, and tinidazole on quorum sensing. Several concentrations of
individual antibiotics were allowed to interact with two different types of bacterial sensing cells, in both the presence
and absence of a fixed concentration of N-acylhomoserine lactone (AHL) QS molecules. The antibiotic effect was then determined by monitoring the biosensor’s bioluminescence
response. Ciprofloxacin, metronidazole, and tinidazole exhibited a dose-dependent augmentation in the response of both bacterial
sensing systems, thus showing an AHL-like effect. Additionally, such an augmentation was observed, in both the presence and
absence of AHL. The data obtained indicate that ciprofloxacin, metronidazole, and tinidazole may interfere with bacterial
communication systems. The results suggest that these antibiotics, at the concentrations tested, may themselves act as bacterial
signaling molecules. The beneficial effect of these antibiotics in the treatment of intestinal inflammation may be due, at
least in part, to their effect on QS-related bacterial behavior in the gut.
Content Type Journal Article
Category Original Paper
Pages 1-10
DOI 10.1007/s00216-012-5710-7
Authors
Anjali K. Struss, Department of Chemistry, University of Kentucky, Lexington, KY 40506, USA
Patrizia Pasini, Department of Chemistry, University of Kentucky, Lexington, KY 40506, USA
Deborah Flomenhoft, Division of Gastroenterology and Nutrition, Department of Pediatrics, University of Kentucky, Lexington, KY 40506, USA
Harohalli Shashidhar, Division of Gastroenterology and Nutrition, Department of Pediatrics, University of Kentucky, Lexington, KY 40506, USA
Sylvia Daunert, Department of Chemistry, University of Kentucky, Lexington, KY 40506, USA
Membrane-assisted solvent extraction coupled to large volume injection in a programmable temperature vaporisation injector
using gas chromatography–mass spectrometry analysis was optimised for the simultaneous determination of a variety of endocrine
disrupting compounds in environmental water samples (estuarine, river and wastewater). Among the analytes studied, certain
hormones, alkylphenols and bisphenol A were included. The nature of membranes, extraction solvent, extraction temperature,
solvent volume, extraction time, ionic strength and methanol addition were evaluated during the optimisation of the extraction.
Matrix effects during the extraction step were studied in different environmental water samples: estuarine water, river water
and wastewater (influent and effluent). Strong matrix effects were observed for most of the compounds in influent and effluent
samples. Different approaches were studied in order to correct or minimise matrix effects, which included the use of deuterated
analogues, matrix-matched calibration, standard addition calibration, dilution of the sample and clean-up of the extract using
solid-phase extraction (SPE). The use of deuterated analogues corrected satisfactorily matrix effect for estuarine and effluent
samples for most of the compounds. However, in the case of influent samples, standard addition calibration and dilution of
the sample were the best approaches. The SPE clean-up provided similar recoveries to those obtained after correction with
the corresponding deuterated analogue but better chromatographic signal was obtained in the case of effluent samples. Method
detection limits in the 5–54 ng L?1 range and precision, calculated as relative standard deviation, in the 2–25% range were obtained.
Content Type Journal Article
Category Original Paper
Pages 1-11
DOI 10.1007/s00216-012-5717-0
Authors
Arantza Iparraguirre, Department of Analytical Chemistry, University of the Basque Country (UPV/EHU), P.K. 644, 48080 Bilbao, Spain
Patricia Navarro, Department of Analytical Chemistry, University of the Basque Country (UPV/EHU), P.K. 644, 48080 Bilbao, Spain
Ailette Prieto, Department of Analytical Chemistry, University of the Basque Country (UPV/EHU), P.K. 644, 48080 Bilbao, Spain
Rosario Rodil, Department of Analytical Chemistry, University of Santiago de Compostela, Constantino Candeira s/n, 15782 Santiago de Compostela, Spain
Maitane Olivares, Department of Analytical Chemistry, University of the Basque Country (UPV/EHU), P.K. 644, 48080 Bilbao, Spain
Luis-Ángel Fernández, Department of Analytical Chemistry, University of the Basque Country (UPV/EHU), P.K. 644, 48080 Bilbao, Spain
Olatz Zuloaga, Department of Analytical Chemistry, University of the Basque Country (UPV/EHU), P.K. 644, 48080 Bilbao, Spain
A flow injection analyser coupled with a gas diffusion membrane and a conductometric microdetector was adapted for the field
analysis of natural concentrations of free dissolved CO2 and dissolved inorganic carbon in natural waters and used in a number of field campaigns for marine water monitoring. The
dissolved gaseous CO2 presents naturally, or that generated by acidification of the sample, is separated by diffusion using a hydrophobic semipermeable
gas porous membrane, and the permeating gas is incorporated into a stream of deionised water and measured by means of an electrical
conductometric microdetector. In order to make the system suitable and easy to use for in-field measurements aboard oceanographic
ships, the single components of the analyser were compacted into a robust and easy to use system. The calibration of the system
is carried out by using standard solutions of potassium bicarbonate at two concentration ranges. Calibration and sample measurements
are carried out inside a temperature-constant chamber at 25 °C and in an inert atmosphere (N2). The detection and quantification limits of the method, evaluated as 3 and 10 times the standard deviation of a series of
measurements of the matrix solution were 2.9 and 9.6 ?mol/kg of CO2, respectively. Data quality for dissolved inorganic carbon was checked with replicate measurements of a certified reference
material (A. Dickson, Scripps Institution of Oceanography, University of California, San Diego), both accuracy and repeatability
were ?3.3% and 10%, respectively. Optimization, performance qualification of the system and its application in various natural
water samples are reported and discussed. In the future, the calibration step will be operated automatically in order to improve
the analytical performance and the applicability will be increased in the course of experimental surveys carried out both
in marine and freshwater ecosystems. Considering the present stage of development of the method, it can only be applied for
studying of the carbon cycle in oxic environments.
Content Type Journal Article
Category Original Paper
Pages 1-11
DOI 10.1007/s00216-012-5762-8
Authors
Valter Martinotti, RSE SpA—Environment and Sustainable Development Department, Via Rubattino 54, 20134 Milan, Italy
Marcella Balordi, RSE SpA—Environment and Sustainable Development Department, Via Rubattino 54, 20134 Milan, Italy
Giovanni Ciceri, RSE SpA—Environment and Sustainable Development Department, Via Rubattino 54, 20134 Milan, Italy
A rapid microfluidic based capillary electrophoresis immunoassay (CEIA) was developed for on-line monitoring of glucagon secretion
from pancreatic islets of Langerhans. In the device, a cell chamber containing living islets was perfused with buffers containing
either high or low glucose concentration. Perfusate was continuously sampled by electroosmosis through a separate channel
on the chip. The perfusate was mixed on-line with fluorescein isothiocyanate-labeled glucagon (FITC-glucagon) and monoclonal
anti-glucagon antibody. To minimize sample dilution, the on-chip mixing ratio of sampled perfusate to reagents was maximized
by allowing reagents to only be added by diffusion. Every 6 s, the reaction mixture was injected onto a 1.5-cm separation
channel where free FITC-glucagon and the FITC-glucagon–antibody complex were separated under an electric field of 700 V cm?1. The immunoassay had a detection limit of 1 nM. Groups of islets were quantitatively monitored for changes in glucagon secretion
as the glucose concentration was decreased from 15 to 1 mM in the perfusate revealing a pulse of glucagon secretion during
a step change. The highly automated system should be enable studies of the regulation of glucagon and its potential role in
diabetes and obesity. The method also further demonstrates the potential of rapid CEIA on microfluidic systems for monitoring
cellular function.
Content Type Journal Article
Category Original Paper
Pages 1-7
DOI 10.1007/s00216-012-5755-7
Authors
Jonathan G. Shackman, Department of Chemistry, University of Michigan, Ann Arbor, MI 48109-1055 USA
Kendra R. Reid, Department of Chemistry, University of Michigan, Ann Arbor, MI 48109-1055 USA
Colleen E. Dugan, Department of Chemistry, University of Michigan, Ann Arbor, MI 48109-1055 USA
Robert T. Kennedy, Department of Chemistry, University of Michigan, Ann Arbor, MI 48109-1055 USA
A design of experiement approach is described for the optimization of the microscopic morphology of macro-mesoporous titania
monoliths that were elaborated for the chromatographic enrichment of phosphorylated compounds. The monolithic titania gels
were formed via an alkoxy-derived sol–gel route in association with a phase separation mechanism. The synthesis was performed
at mild temperatures of gelation using starting mixtures of titanium n-propoxide, hydrochloric acid, N-methylformamide, water,
and poly (ethylene oxide). The gelation temperature and the chemical compositions of N-methylformamide, water, and poly (ethylene
oxide) were chosen as the most relevant experimental factors of the sol–gel process. Using the sizes of the skeletons and
macropores as morphological descriptors of the dried porous monoliths, the statistical analyses simultaneously revealed the
effects and interactions between the different factors. Crack-free TiO2 monolithic rods of 8 to 10 cm long with well-defined co-continuous macropores and micro-structured skeletons were obtained
after selection of the sol–gel parameters and optimization of the drying and heat-treatment steps of the gels. The bimodal
texture of the rods exhibited macropores of 1.5 ?m and mesopores centered at 5.2 nm with a total surface area of 140 m2 g?1. The ability of the macro-mesoporous titania rods to selectively bind phosphorylated compounds was demonstrated for O-phosphoamino
acids (P-Ser, P-Thr, P-Tyr).
Content Type Journal Article
Category Original Paper
Pages 1-11
DOI 10.1007/s00216-012-5761-9
Authors
Maguy Abi Jaoudé, Institut des Sciences Analytiques, Université Claude Bernard Lyon 1, Université de Lyon, 69622 Villeurbanne Cedex, France
Jérôme Randon, Institut des Sciences Analytiques, Université Claude Bernard Lyon 1, Université de Lyon, 69622 Villeurbanne Cedex, France
Claire Bordes, Institut des Sciences Analytiques, Université Claude Bernard Lyon 1, Université de Lyon, 69622 Villeurbanne Cedex, France
Pierre Lanteri, Institut des Sciences Analytiques, Université Claude Bernard Lyon 1, Université de Lyon, 69622 Villeurbanne Cedex, France
Laurence Bois, Laboratoire des Multimatériaux et Interfaces, Université Claude Bernard Lyon 1, Université de Lyon, 69622 Villeurbanne Cedex, France
Choline is a quaternary amine that is synthesized in the body or consumed through the diet. Choline is critical for cell membrane
structure and function and in synthesis of the neurotransmitter acetylcholine. Although the human body produces this micronutrient,
dietary supplementation of choline is necessary for good health. The major challenge in the analysis of choline in foods and
dietary supplements is in the extraction and/or hydrolysis approach. In many products, choline is present as choline esters,
which can be quantitated individually or treated with acid, base, or enzymes in order to release choline ions for analysis.
A critical review of approaches based on extraction and quantitation of each choline ester as well as hydrolysis-based methods
for determination of total choline in foods and dietary supplements is presented.
Content Type Journal Article
Category Review
Pages 1-10
DOI 10.1007/s00216-011-5652-5
Authors
Melissa M. Phillips, Analytical Chemistry Division, Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD 20899, USA
In this paper, an electrochemical magneto-immunosensor for the detection of human growth hormone (hGH) is described for the
first time. The immunosensor involves the use of tosyl-activated magnetic microparticles (TsMBs) to covalently immobilize
a monoclonal mAbhHG antibody. A sandwich-type immunoassay with a secondary pAbhGH antibody and anti-IgG labelled with alkaline
phosphatase (anti-IgG-AP) was employed. TsMBs–mAbhGH–hGH–pAbhGH–anti-IgG-AP conjugates were deposited onto the surface of
a screen-printed gold electrode using a small neodymium magnet, and electrochemical detection was performed by square-wave
voltammetry upon the addition of 4-aminophenyl phosphate as the AP substrate. All the variables involved in the preparation
of immunoconjugates and in the immunoassay protocol were optimized. A calibration curve for hGH was constructed with a linear
range between 0.01 and 100 ng/mL (r?=?0.998) and a limit of detection of 0.005 ng/mL. This value is nearly three orders of magnitude lower than that obtained
using surface plasmon resonance (Treviño et al., Talanta 78:1011–1016, 2009). Furthermore, good repeatability, with RSD?=?3% (n?=?10) at the 1-ng/mL hGH level, was obtained. Cross-reactivity studies with other hormones demonstrated good selectivity.
The magneto-immunosensor was applied to the analysis of human serum spiked with hGH at the 4- and 0.1-ng/mL levels. Mean recoveries
of 96?±?6% and 99?±?2%, respectively, were obtained.
Content Type Journal Article
Category Original Paper
Pages 1-8
DOI 10.1007/s00216-012-5753-9
Authors
V. Serafín, Department of Analytical Chemistry, Faculty of Chemistry, University Complutense of Madrid, 28040 Madrid, Spain
N. Úbeda, Department of Analytical Chemistry, Faculty of Chemistry, University Complutense of Madrid, 28040 Madrid, Spain
L. Agüí, Department of Analytical Chemistry, Faculty of Chemistry, University Complutense of Madrid, 28040 Madrid, Spain
P. Yáñez-Sedeño, Department of Analytical Chemistry, Faculty of Chemistry, University Complutense of Madrid, 28040 Madrid, Spain
J. M. Pingarrón, Department of Analytical Chemistry, Faculty of Chemistry, University Complutense of Madrid, 28040 Madrid, Spain
An improved selectivity method for the simultaneous determination of four benzotriazoles (benzotriazole, 4-methylbenzotriazole,
5-methylbenzotriazole, and 5,6-dimethyl-1H-benzotriazole) and six benzothiazoles (benzothiazole, 2-hydroxybenzothiazole, 2-benzothiazolamine, mercaptobenzothiazole,
2-methylbenzothiazole, and 2-methylthiobenzothiazole) in aqueous matrices has been developed. Under optimal conditions, analytes
are concentrated using a MAX solid-phase extraction (SPE) cartridge, based on divinylbenzene-N-vinylpyrrolidone functionalized with quaternary amine groups, which allows reversed-phase interactions in combination with
ionic exchange. Selected compounds are recovered with methanol–acetone 7:3 (v/v) whereas acidic interferences remained attached to the sorbent, and as determined by liquid chromatography coupled to tandem
mass spectrometry (LC-MS/MS), LOQs for surface, urban and industrial wastewater are in the range of 0.002–0.29 ng/mL. Figures
of merit of the method revealed good precision (RSD% <12%), linearity (R2?>?0.99) and accuracy (%R?=?80–100%) for surface waters and effluents allowing direct external standard quantification. For more complex samples, such
as urban and industrial raw wastewater, either the standard addition method or pseudo-external standard calibration using
matrix matched standards are recommended. Analysis of different real samples, surface, urban wastewater and, for the first
time, metal industry wastewater, reflected concentrations up to 310 ng/mL. The methylbenzotriazole isomers ratio was also
determined.
Content Type Journal Article
Category Technical Note
Pages 1-8
DOI 10.1007/s00216-012-5718-z
Authors
I. Carpinteiro, Instituto de Investigación e Análisis Alimentarias (IIAA). Departamento de Química Analítica, Nutrición e Bromatoloxía, Universidade de Santiago de Compostela, 15782 Santiago de Compostela, Spain
B. Abuin, Instituto de Investigación e Análisis Alimentarias (IIAA). Departamento de Química Analítica, Nutrición e Bromatoloxía, Universidade de Santiago de Compostela, 15782 Santiago de Compostela, Spain
M. Ramil, Instituto de Investigación e Análisis Alimentarias (IIAA). Departamento de Química Analítica, Nutrición e Bromatoloxía, Universidade de Santiago de Compostela, 15782 Santiago de Compostela, Spain
I. Rodríguez, Instituto de Investigación e Análisis Alimentarias (IIAA). Departamento de Química Analítica, Nutrición e Bromatoloxía, Universidade de Santiago de Compostela, 15782 Santiago de Compostela, Spain
R. Cela, Instituto de Investigación e Análisis Alimentarias (IIAA). Departamento de Química Analítica, Nutrición e Bromatoloxía, Universidade de Santiago de Compostela, 15782 Santiago de Compostela, Spain
Glycoproteins secreted or expressed on the cell surface at specific pathophysiological stages are well-recognized disease
biomarkers and therapeutic targets. While mapping of specific glycan structures can be performed at the level of released
glycans, site-specific glycosylation and identification of specific protein carriers can only be determined by analysis of
glycopeptides. A key enabling step in mass spectrometry (MS)-based glycoproteomics is the ability to selectively or non-selectively
enrich for the glycopeptides from a total pool of a digested proteome for MS analysis since the highly heterogeneous glycopeptides
are usually present at low abundance and ionize poorly compared with non-glycosylated peptides. Among the most common approaches
for non-destructive and non-glycan-selective glycopeptide enrichment are strategies based on various forms of hydrophilic
interaction liquid chromatography (HILIC). We present here a variation of this method using amine-derivatized Fe3O4 nanoparticles, in concert with in situ peptide N-glycosidase F digestion for direct matrix-assisted laser desorption/ionization–mass
spectrometry analysis of N-glycosylation sites and the released glycans. Conditions were also optimized for efficient elution
of the enriched glycopeptides from the nanoparticles for on-line nanoflow liquid chromatography–MS/MS analysis. Successful
applications to single glycoproteins as well as total proteomic mixtures derived from biological fluids established the unrivaled
practical versatility of this method, with enrichment efficiency comparable to other HILIC-based methods.
Content Type Journal Article
Category Original Paper
Pages 1-12
DOI 10.1007/s00216-012-5724-1
Authors
Chu-Wei Kuo, NRPGM Core Facilities for Proteomics and Institute of Biological Chemistry, Academia Sinica, 128, Academia Road, Sec 2, Nankang, Taipei 11529, Taiwan
I-Lin Wu, NRPGM Core Facilities for Proteomics and Institute of Biological Chemistry, Academia Sinica, 128, Academia Road, Sec 2, Nankang, Taipei 11529, Taiwan
He-Hsuan Hsiao, NRPGM Core Facilities for Proteomics and Institute of Biological Chemistry, Academia Sinica, 128, Academia Road, Sec 2, Nankang, Taipei 11529, Taiwan
Kay-Hooi Khoo, NRPGM Core Facilities for Proteomics and Institute of Biological Chemistry, Academia Sinica, 128, Academia Road, Sec 2, Nankang, Taipei 11529, Taiwan
We report the development of a surface plasmon resonance sensor based on the silver ion (Ag+)-induced conformational change of a cytosine-rich, single-stranded DNA for the detection of Ag+ and cysteine (Cys) in aqueous solutions. In the free state, single-stranded oligonucleotides fold into double-helical structures
through the addition of Ag+ to cytosine–cytosine (C–C) mismatches. However, in the presence of Cys, which competitively binds to Ag+, the formation of the C–Ag+–C assembly is inhibited, resulting in free-state, single-stranded oligonucleotides. To enhance sensitivity, the DNA intercalator,
daunorubicin, was employed to achieve signal enhancement. The detection limit for Ag+ was 10 nM with a measurement range of 50–2,000 nM, and the detection limit for Cys was 50 nM with a measurement range of
50–2,000 nM. This simple assay was also used to individually determine the spiked Ag+ concentration in water samples and Cys concentrations in biological fluid samples.
Content Type Journal Article
Category Original Paper
Pages 1-9
DOI 10.1007/s00216-012-5720-5
Authors
Chia-Chen Chang, Institute of Biomedical Engineering, National Taiwan University, Taipei, 10617 Taiwan
Shenhsiung Lin, Department of Medicine, National Yang-Ming University, Taipei, 11221 Taiwan
Shih-Chung Wei, Institute of Biomedical Electronic and Bioinformatics, National Taiwan University, Taipei, 10617 Taiwan
Yu Chu-Su, Institute of Biomedical Engineering, National Taiwan University, Taipei, 10617 Taiwan
Chii-Wann Lin, Institute of Biomedical Engineering, National Taiwan University, Taipei, 10617 Taiwan
Despite the importance of stating the measurement uncertainty in chemical analysis, concepts are still not widely applied
by the broader scientific community. The Guide to the expression of uncertainty in measurement approves the use of both the partial derivative approach and the Monte Carlo approach. There are two limitations to the partial
derivative approach. Firstly, it involves the computation of first-order derivatives of each component of the output quantity.
This requires some mathematical skills and can be tedious if the mathematical model is complex. Secondly, it is not able to
predict the probability distribution of the output quantity accurately if the input quantities are not normally distributed.
Knowledge of the probability distribution is essential to determine the coverage interval. The Monte Carlo approach performs
random sampling from probability distributions of the input quantities; hence, there is no need to compute first-order derivatives.
In addition, it gives the probability density function of the output quantity as the end result, from which the coverage interval
can be determined. Here we demonstrate how the Monte Carlo approach can be easily implemented to estimate measurement uncertainty
using a standard spreadsheet software program such as Microsoft Excel. It is our aim to provide the analytical community with
a tool to estimate measurement uncertainty using software that is already widely available and that is so simple to apply
that it can even be used by students with basic computer skills and minimal mathematical knowledge.
Content Type Journal Article
Category Technical Note
Pages 1-7
DOI 10.1007/s00216-011-5698-4
Authors
Gina Chew, NUS Graduate School for Integrative Sciences and Engineering, National University of Singapore (NUS), Singapore, 119077 Singapore
Thomas Walczyk, NUS Graduate School for Integrative Sciences and Engineering, National University of Singapore (NUS), Singapore, 119077 Singapore
A sensitive and accurate method utilizing ultra-high performance liquid chromatography (U-HPLC) coupled to high resolution
mass spectrometry based on orbitrap technology (orbitrapMS) for the analysis of nine 3-chloropropane-1,2-diol (3-MCPD) diesters
in vegetable oils was developed. To remove the interfering triacylglycerols that induce strong matrix effects, a clean-up
step on silica gel column was used. The quantitative analysis was performed with the use of deuterium-labeled internal standards.
The lowest calibration levels estimated for the respective analytes ranged from 2 to 5 ?g kg?1. Good recovery values (89–120%) and repeatability (RSD 5–9%) was obtained at spiking levels of 2 and 10 mg kg?1. As an alternative, a novel ambient desorption ionization technique, direct analysis in real time (DART), hyphenated with
orbitrapMS, was employed for no separation, high-throughput, semi-quantitative screening of 3-MCPD diesters in samples obtained
by chromatographic fractionation. Additionally, the levels of 3-MCPD diesters measured in real-life vegetable oil samples
(palm oil, sunflower oil, rapeseed oil) using both methods are reported. Relatively good agreement of the data generated by
U-HPLC-orbitrapMS and DART-orbitrapMS were observed. With regard to a low ionization yield achieved for 3-MCPD monoesters,
the methods presented in this paper were not yet applicable for the analysis of these contaminants at the naturally occurring
levels.
Content Type Journal Article
Category Original Paper
Pages 1-13
DOI 10.1007/s00216-012-5732-1
Authors
Eliska Moravcova, Department of Food Chemistry and Analysis, Institute of Chemical Technology, Prague, Technicka 3, 16628 Prague 6, Czech Republic
Lukas Vaclavik, Department of Food Chemistry and Analysis, Institute of Chemical Technology, Prague, Technicka 3, 16628 Prague 6, Czech Republic
Ondrej Lacina, Department of Food Chemistry and Analysis, Institute of Chemical Technology, Prague, Technicka 3, 16628 Prague 6, Czech Republic
Vojtech Hrbek, Department of Food Chemistry and Analysis, Institute of Chemical Technology, Prague, Technicka 3, 16628 Prague 6, Czech Republic
Katerina Riddellova, Department of Food Chemistry and Analysis, Institute of Chemical Technology, Prague, Technicka 3, 16628 Prague 6, Czech Republic
Jana Hajslova, Department of Food Chemistry and Analysis, Institute of Chemical Technology, Prague, Technicka 3, 16628 Prague 6, Czech Republic
Thermoresponsive microgels have been shown to be an excellent platform for designing sensor materials. Recently, poly (N-isopropylacrylamide)-co-acrylic acid (pNIPAm-co-AAc) microgel based etalon materials have been described as direct sensing materials that can be designed to have a single,
unique color. These color tunable materials show immense promise for sensing due to their spectral sensitivity and bright
visual color. Here, we describe a proof-of-concept for etalon sensing of glucose. We found that aminophenylboronic acid (APBA)-functionalized pNIPAm-co-AAc microgels in an etalon respond to 3 mg/mL glucose concentrations by red shifting their reflectance peaks by 110 nm up
to 150 nm. Additionally, APBA-functionalized pNIPAm-co-AAc microgels have a depressed volume phase transition temperature at 18–20 °C, which shifts to 24–26 °C after glucose binding.
We also demonstrate that these materials show a marked visual color change, which is a first step towards developing direct
read-out sensor devices.
Figure Glucose sensitive, pNIPAm microgel-based etalons exhibit both a shift of the peaks in the reflectance spectrum, and a visual
color change, upon exposure to biologically relevant concentrations of glucose.
Content Type Journal Article
Category Short Communication
Pages 1-9
DOI 10.1007/s00216-012-5736-x
Authors
Courtney D. Sorrell, Department of Chemistry, University of Alberta, 11227 Saskatchewan Drive, Edmonton, Alberta, Canada T6G 2G2
Michael J. Serpe, Department of Chemistry, University of Alberta, 11227 Saskatchewan Drive, Edmonton, Alberta, Canada T6G 2G2
Surface-enhanced Raman scattering (SERS) spectroscopy and surface-enhanced infrared absorption (SEIRA) spectroscopy are analytical
tools suitable for the detection of small amounts of various analytes adsorbed on metal surfaces. During recent years, these
two spectroscopic methods have become increasingly important in the investigation of adsorption of biomolecules and pharmaceuticals
on nanostructured metal surfaces. In this work, the adsorption of B-group vitamins pyridoxine, nicotinic acid, folic acid
and riboflavin at electrochemically prepared gold and silver substrates was investigated using Fourier transform SERS spectroscopy
at an excitation wavelength of 1,064 nm. Gold and silver substrates were prepared by cathodic reduction on massive platinum
targets. In the case of gold substrates, oxidation–reduction cycles were applied to increase the enhancement factor of the
gold surface. The SERS spectra of riboflavin, nicotinic acid, folic acid and pyridoxine adsorbed on silver substrates differ
significantly from SERS spectra of these B-group vitamins adsorbed on gold substrates. The analysis of near-infrared-excited
SERS spectra reveals that each of B-group vitamin investigated interacts with the gold surface via a different mechanism of
adsorption to that with the silver surface. In the case of riboflavin adsorbed on silver substrate, the interpretation of
surface-enhanced infrared absorption (SEIRA) spectra was also helpful in investigation of the adsorption mechanism.
Content Type Journal Article
Category Original Paper
Pages 1-9
DOI 10.1007/s00216-011-5704-x
Authors
A. Kokaislová, Department of Analytical Chemistry, Institute of Chemical Technology Prague, Technicka 5, 166 28 Prague 6, Czech Republic
P. Mat?jka, Department of Analytical Chemistry, Institute of Chemical Technology Prague, Technicka 5, 166 28 Prague 6, Czech Republic
A novel, automatic on-line sequential injection dispersive liquid–liquid microextraction (SI-DLLME) method, based on 1-hexyl-3-methylimidazolium
hexafluorophosphate ([Hmim][PF6]) ionic liquid as an extractant solvent was developed and demonstrated for trace thallium determination by flame atomic absorption
spectrometry. The ionic liquid was on-line fully dispersed into the aqueous solution in a continuous flow format while the
TlBr4? complex was easily migrated into the fine droplets of the extractant due to the huge contact area of them with the aqueous
phase. Furthermore, the extractant was simply retained onto the surface of polyurethane foam packed into a microcolumn. No
specific conditions like low temperature are required for extractant isolation. All analytical parameters of the proposed
method were investigated and optimized. For 15 mL of sample solution, an enhancement factor of 290, a detection limit of 0.86 ?g L?1 and a precision (RSD) of 2.7% at 20.0 ?g L?1 Tl(I) concentration level, was obtained. The developed method was evaluated by analyzing certified reference materials while
good recoveries from environmental and biological samples proved that present method was competitive in practical applications.
Figure An automatic sequential injection dispersive liquid-liquid microextraction (SI-DLLME) system for thallium determination
Content Type Journal Article
Category Original Paper
Pages 1-7
DOI 10.1007/s00216-011-5700-1
Authors
Aristidis N. Anthemidis, Laboratory of Analytical Chemistry, Department of Chemistry, Aristotle University, 54124 Thessaloniki, Greece
Kallirroy-Ioanna G. Ioannou, Laboratory of Analytical Chemistry, Department of Chemistry, Aristotle University, 54124 Thessaloniki, Greece
A microfluidic chip based nano-HPLC coupled to tandem mass spectrometry (nano-HPLC-Chip-MS/MS) has been developed for simultaneous
measurement of abused drugs and metabolites: cocaine, benzoylecgonine, cocaethylene, norcocaine, morphine, codeine, 6-acetylmorphine,
phencyclidine, amphetamine, methamphetamine, MDMA, MDA, MDEA, and methadone in the hair of drug abusers. The microfluidic
chip was fabricated by laminating polyimide films and it integrated an enrichment column, an analytical column and a nanospray
tip. Drugs were extracted from hairs by sonication, and the chromatographic separation was achieved in 15 min. The drug identification
and quantification criteria were fulfilled by the triple quardropule tandem mass spectrometry. The linear regression analysis
was calibrated by deuterated internal standards with all of the R2 at least over 0.993. The limit of detection (LOD) and the limit of quantification (LOQ) were from 0.1 to 0.75 and 0.2 to
1.25 pg/mg, respectively. The validation parameters including selectivity, accuracy, precision, stability, and matrix effect
were also evaluated here. In conclusion, the developed sample preparation method coupled with the nano-HPLC-Chip-MS/MS method
was able to reveal the presence of drugs in hairs from the drug abusers, with the enhanced sensitivity, compared with the
conventional HPLC-MS/MS.
Content Type Journal Article
Category Original Paper
Pages 1-11
DOI 10.1007/s00216-012-5711-6
Authors
Kevin Y. Zhu, Division of Life Science, and Center for Chinese Medicine, The Hong Kong University of Science and Technology, Clear Water Bay Road, Hong Kong
K. Wing Leung, Division of Life Science, and Center for Chinese Medicine, The Hong Kong University of Science and Technology, Clear Water Bay Road, Hong Kong
Annie K. L. Ting, Division of Life Science, and Center for Chinese Medicine, The Hong Kong University of Science and Technology, Clear Water Bay Road, Hong Kong
Zack C. F. Wong, Division of Life Science, and Center for Chinese Medicine, The Hong Kong University of Science and Technology, Clear Water Bay Road, Hong Kong
Winki Y. Y. Ng, Division of Life Science, and Center for Chinese Medicine, The Hong Kong University of Science and Technology, Clear Water Bay Road, Hong Kong
Roy C. Y. Choi, Division of Life Science, and Center for Chinese Medicine, The Hong Kong University of Science and Technology, Clear Water Bay Road, Hong Kong
Tina T. X. Dong, Division of Life Science, and Center for Chinese Medicine, The Hong Kong University of Science and Technology, Clear Water Bay Road, Hong Kong
Tiejie Wang, Division of Life Science, and Center for Chinese Medicine, The Hong Kong University of Science and Technology, Clear Water Bay Road, Hong Kong
David T. W. Lau, Division of Life Science, and Center for Chinese Medicine, The Hong Kong University of Science and Technology, Clear Water Bay Road, Hong Kong
Karl W. K. Tsim, Division of Life Science, and Center for Chinese Medicine, The Hong Kong University of Science and Technology, Clear Water Bay Road, Hong Kong
The general population is exposed to acrylamide (AA) mainly through food and tobacco smoke. AA is classified as probably carcinogenic
to humans. Glycidamide (GA), as the primary oxidative metabolite, was identified to be the ultimate genotoxic agent. This
warrants full investigation of the oxidative pathway in AA metabolism and the share of the oxidative compared to the reductive
pathway. 2,3-Dihydroxy-propionamide (OH-PA) as the direct hydrolysis product of GA has been shown to be a major urinary oxidative
metabolite in human AA metabolism. We developed an analytical method to reliably quantify OH-PA in urine by GC-MS after a
multistep procedure including “stripping” on a solid phase material, lyophilization, silylation and re-extraction. With a
detection limit of 1 ?g/L, our method is sensitive enough to quantify OH-PA in all urine samples of the general population.
Within and between series precisions were between 1.9% and 8.2% and mean recoveries between 97% and 101%. We applied this
method to 30 urine samples from the general population. In all the samples, OH-PA was present in concentrations between 6.8
and 109.4 ?g/L (median, 49.7 ?g/L) with no difference between smokers and non-smokers. OH-PA concentrations were approximately
ten times higher than expected from the metabolism of AA via GA. Currently, we cannot confirm OH-PA to be a specific biomarker
of the oxidative pathway of AA metabolism. Other sources than AA respectively GA might need to be considered for the formation
of OH-PA.
Content Type Journal Article
Category Original Paper
Pages 1-8
DOI 10.1007/s00216-011-5692-x
Authors
Julia M. Latzin, Institute for Prevention and Occupational Medicine of the German Social Accident Insurance, Institute of the Ruhr Universität Bochum (IPA), Bürkle-de-la-Camp-Platz 1, 44789 Bochum, Germany
Birgit K. Schindler, Institute for Prevention and Occupational Medicine of the German Social Accident Insurance, Institute of the Ruhr Universität Bochum (IPA), Bürkle-de-la-Camp-Platz 1, 44789 Bochum, Germany
Tobias Weiss, Institute for Prevention and Occupational Medicine of the German Social Accident Insurance, Institute of the Ruhr Universität Bochum (IPA), Bürkle-de-la-Camp-Platz 1, 44789 Bochum, Germany
Jürgen Angerer, Institute for Prevention and Occupational Medicine of the German Social Accident Insurance, Institute of the Ruhr Universität Bochum (IPA), Bürkle-de-la-Camp-Platz 1, 44789 Bochum, Germany
Holger M. Koch, Institute for Prevention and Occupational Medicine of the German Social Accident Insurance, Institute of the Ruhr Universität Bochum (IPA), Bürkle-de-la-Camp-Platz 1, 44789 Bochum, Germany
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