Analytical and Bioanalytical Chemistry - Current Research Articles
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Analytical and Bioanalytical Chemistry - published by Springer
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A microarray enables high-throughput interaction screening of numerous biomolecules; however, fabrication of a microarray
composed of cellular membrane components has proven difficult. We report fabrication of a liposomal glyco-microarray by using
an azide-reactive liposome that carries synthetic and natural glycolipids via chemically selective and biocompatible liposome
immobilization chemistry. Briefly, liposomes carrying anchor lipid dipalmitoylphosphatidylethanolamine (DPPE)–PEG2000–triphenylphosphine and ganglioside (GM1 or GM3) were prepared first and were then printed onto an azide-modified glass slide
so as to afford a liposomal glyco-microarray via Staudinger ligation. Fluorescent dye release kinetics and fluorescence imaging
confirmed successful liposome immobilization and specific protein binding to the intact arrayed glycoliposomes. The liposomal
glyco-microarray with different gangliosides showed their specific lectin and toxin binding with different binding affinity.
The azide-reactive liposome provides a facile strategy for fabrication of either a natural or a synthetic glycolipid-based
membrane-mimetic glycoarray. This liposomal glyco-microarray is simple and broadly applicable and thus will find important
biomedical applications, such as studying glycolipid–protein interactions and toxin screening applications.
Figure Liposome immobilization format provides a facile strategy for glycolipid-based membrane-mimetic glycoarray fabrication
Content Type Journal Article
Category Original Paper
Pages 1-8
DOI 10.1007/s00216-012-6096-2
Authors
Yong Ma, Department of Chemistry, Cleveland State University, 2121 Euclid Avenue SI 313, Cleveland, OH 44115, USA
Irena Sobkiv, Department of Chemistry, Cleveland State University, 2121 Euclid Avenue SI 313, Cleveland, OH 44115, USA
Valentinas Gruzdys, Department of Chemistry, Cleveland State University, 2121 Euclid Avenue SI 313, Cleveland, OH 44115, USA
Hailong Zhang, Department of Chemistry, Cleveland State University, 2121 Euclid Avenue SI 313, Cleveland, OH 44115, USA
Xue-Long Sun, Department of Chemistry, Cleveland State University, 2121 Euclid Avenue SI 313, Cleveland, OH 44115, USA
In recent years, bismuth has been promoted as a “green element” and is used as a substitute for the toxic lead in ammunition
and other applications. However, the bioavailability and toxicity of bismuth is still not very well described. Following a
hunting accident with bismuth-containing shots, a bioavailability study of bismuth from metal pellets inoculated into rat
limb muscles was carried out. Bismuth could be found in urine and blood of the animals. Bio-imaging using laser ablation ICP-MS
of thin sections of the tissue around the metal implant was carried out to find out more about the distribution of the metal
diffusing into the tissue. Two laser ablation systems with different ablation cell designs were compared regarding their analytical
performance. Low concentrations of bismuth showing a non-symmetrical pattern were detected in the tissue surrounding the metal
implant. This was partly an artefact from cutting the thin sections but also bio-mobilisation of the metals of the implant
could be seen. An accumulation of zinc around the implant was interpreted as a marker of inflammation. Challenges regarding
sample preparation for laser ablation and bio-imaging of samples of diverse composition became apparent during the analysis.
Figure ?
Content Type Journal Article
Category Original Paper
Pages 1-11
DOI 10.1007/s00216-012-6101-9
Authors
Dagmar S. Urgast, TESLA (Trace Element Speciation Laboratory), University of Aberdeen, College of Physical Sciences, Department of Chemistry, Meston Walk, Aberdeen, AB24 3UE Scotland, UK
Dag G. Ellingsen, National Institute of Occupational Health, P.O. Box 8149 Dep., 0033 Oslo, Norway
Balázs Berlinger, National Institute of Occupational Health, P.O. Box 8149 Dep., 0033 Oslo, Norway
Einar Eilertsen, National Institute of Occupational Health, P.O. Box 8149 Dep., 0033 Oslo, Norway
Grete Friisk, National Institute of Occupational Health, P.O. Box 8149 Dep., 0033 Oslo, Norway
Vidar Skaug, National Institute of Occupational Health, P.O. Box 8149 Dep., 0033 Oslo, Norway
Yngvar Thomassen, National Institute of Occupational Health, P.O. Box 8149 Dep., 0033 Oslo, Norway
John H. Beattie, Rowett Institute of Nutrition and Health, College of Life Sciences and Medicine, Micronutrients Group, University of Aberdeen, Greenburn Road, Bucksburn, Aberdeen, AB21 9SB Scotland, UK
In-Sook Kwun, Department of Food Science and Nutrition, Andong National University, Andong, Kyungpook 760-749, Republic of Korea
Jörg Feldmann, TESLA (Trace Element Speciation Laboratory), University of Aberdeen, College of Physical Sciences, Department of Chemistry, Meston Walk, Aberdeen, AB24 3UE Scotland, UK
Teaching bioanalytical methods in a BSc analytical chemistry course
Content Type Journal Article
Category ABCs of Teaching Analytical Science
Pages 1-3
DOI 10.1007/s00216-012-6081-9
Authors
G. Horvai, Department of Inorganic and Analytical Chemistry and HAS-BUTE Research Group of Technical Analytical Chemistry, Budapest University of Technology and Economics, Szt Gellert ter 4, 1111 Budapest, Hungary
In the present study, a new analytical method has been developed for the simultaneous quantification of 15 organophosphorus
pesticides, including some of their metabolites, (disulfoton-sulfoxide, ethoprophos, cadusafos, dimethoate, terbufos, disulfoton,
chlorpyrifos-methyl, malaoxon, fenitrothion, pirimiphos-methyl, malathion, chlorpyrifos, terbufos-sulfone, disulfoton-sulfone
and fensulfothion) in three different types of commercial cereal-based baby foods. Dispersive solid-phase extraction (dSPE)
with multi-walled carbon nanotubes (MWCNTs) was used together with gas chromatography with nitrogen phosphorus detection.
Most favorable conditions involved a previous ultrasound-assisted extraction of the sample with acetonitrile containing formic
acid. After evaporation of the extract and redissolution in water, a dSPE procedure was carried out with MWCNTs. The whole
method was validated in terms of repeatability, linearity, precision and accuracy and matrix effect was also evaluated. Absolute
recoveries were in the range 64–105 % with relative standard deviation values below 7.6 %. Limits of quantification achieved
ranged from 0.31 to 5.50 ?g/kg, which were lower than the European Union maximum residue limits for pesticide residues in
cereal-based baby foods.
Content Type Journal Article
Category Original Paper
Pages 1-14
DOI 10.1007/s00216-012-6103-7
Authors
Miguel Ángel González-Curbelo, Departamento de Química Analítica, Nutrición y Bromatología, Facultad de Química, Universidad de La Laguna (ULL), Avenida Astrofísico Francisco Sánchez, s/no. 38206, La Laguna, Tenerife, Spain
María Asensio-Ramos, Departamento de Química Analítica, Nutrición y Bromatología, Facultad de Química, Universidad de La Laguna (ULL), Avenida Astrofísico Francisco Sánchez, s/no. 38206, La Laguna, Tenerife, Spain
Antonio V. Herrera-Herrera, Departamento de Química Analítica, Nutrición y Bromatología, Facultad de Química, Universidad de La Laguna (ULL), Avenida Astrofísico Francisco Sánchez, s/no. 38206, La Laguna, Tenerife, Spain
Javier Hernández-Borges, Departamento de Química Analítica, Nutrición y Bromatología, Facultad de Química, Universidad de La Laguna (ULL), Avenida Astrofísico Francisco Sánchez, s/no. 38206, La Laguna, Tenerife, Spain
Methylmalonic acid (MMA) is a functional biomarker of vitamin B12 deficiency. Measurement of plasma MMA is challenging due
to its small molecular weight and hydrophilic nature. Several liquid chromatography-tandem mass spectrometry (LC-MS/MS) methods
have been developed for measuring plasma MMA. However, these methods involve lengthy sample preparation, long chromatographic
run time, inadequate sensitivity, or interference from succinic acid (SA). Here we report a novel LC-MS/MS method for quantitation
of underivatized MMA in serum or heparinized plasma with high sensitivity and selectivity. Sample preparation involved only
strong anion exchange solid phase extraction. The extract was purified by online turbulent flow and analyzed on an Organic
Acids column. MS/MS analysis was performed in negative electrospray mode, and the analytical time was 6 min. The use of ion
ratio confirmation in combination with chromatographic resolution from SA greatly enhanced the selectivity. No interference
was observed. This method was linear from 26.2 to 26,010.0 nM with an accuracy of 98–111 %. Total coefficient of variation
was less than 4.6 % for three concentration levels tested. Comparison with a reference laboratory LC-MS/MS method using leftover
patient serum specimens (n?=?48) showed a mean bias of ?2.3 nM (?0.61 %) with a Deming regression slope of 1.016, intercept of ?6.6 nM, standard error
of estimate of 25.3 nM, and a correlation coefficient of 0.9945. In conclusion, this LC-MS/MS method offers highly sensitive
and selective quantitation of MMA in serum and plasma with simple sample preparation.
Content Type Journal Article
Category Original Paper
Pages 1-8
DOI 10.1007/s00216-012-6099-z
Authors
Chao Yuan, Department of Clinical Pathology, Cleveland Clinic, LL3-129, 9500 Euclid Ave, Cleveland, OH 44195, USA
Jessica Gabler, Department of Clinical Pathology, Cleveland Clinic, LL3-129, 9500 Euclid Ave, Cleveland, OH 44195, USA
Joe M. El-Khoury, Department of Clinical Pathology, Cleveland Clinic, LL3-129, 9500 Euclid Ave, Cleveland, OH 44195, USA
Regina Spatholt, Department of Clinical Pathology, Cleveland Clinic, LL3-129, 9500 Euclid Ave, Cleveland, OH 44195, USA
Sihe Wang, Department of Clinical Pathology, Cleveland Clinic, LL3-129, 9500 Euclid Ave, Cleveland, OH 44195, USA
A new two-dimensional micro-flow magnetophoresis device was constructed in a superconducting magnet (10 T) using triangular
shaped pole pieces, which could apply a magnetic strength, B(dB/dx), in the range of ca. 0–14,000 T2 m?1 across a capillary cell. Polystyrene particles with diameters of 1, 3, and 6 ?m were used as test samples in a paramagnetic
medium of 1 M MnCl2 to evaluate the performance of this method. Microparticles migrated across the capillary along the edge of the pole pieces,
and then flowed through the gap in the pole piece at a position defined as the migration distance, depending on the magnetic
susceptibility and the size of particles as well as the flow rate. The most effective flow rate to exhibit the largest resolution
among the particles was theoretically predicted and experimentally confirmed. By this method, the magnetic susceptibilities
of individual deoxygenated and non-deoxygenated red blood cells were measured from the relative migration distance.
Figure Two-dimensional flow magnetophoresis of microparticles, e.g., red blood cells
Content Type Journal Article
Category Original Paper
Pages 1-9
DOI 10.1007/s00216-012-6016-5
Authors
Makoto Kawano, Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan
Hitoshi Watarai, Institute for NanoScience Design, Osaka University, Toyonaka, Osaka 560-8531, Japan
This paper describes the reversed-phase liquid chromatographic behaviour of the trypanocidal quaternary ammonium salt isometamidium
chloride and its related compounds on a range of liquid chromatographic phases possessing alkyl and phenyl ligands on the
same inert silica. In a parallel study with various extended polar selectivity phases which possessed different hydrophobic/silanophilic
(hydrogen bonding) activity ratios, the chromatographic retention/selectivities of the quaternary ammonium salts was shown
to be due to a co-operative mechanism between hydrophobic and silanophilic interactions. The highly aromatic and planar isometamidium
compounds were found to be substantially retained on stationary phases containing aromatic functionality via strong ?–? interactions.
The chemometric approach of principal component analysis was used to characterise the chromatographic behaviour of the isometamidium
compounds on the differing phases and to help identify the dominant retention mechanism(s). Two-dimensional (temperature/gradient)
retention modelling was employed to develop and optimise a rapid liquid chromatography method for the separation of the six
quaternary ammonium salts within 2.5 min which would be suitable for bioanalysis using liquid chromatography–mass spectrometry.
This is the first reported systematic study of the relationship between stationary phase chemistries and retention/selectivity
for a group of quaternary ammonium salts.
Fig. 1 Structure of isometamidium and related quaternary ammonium salts and their LC separation on a diverse range of RP columns.
Content Type Journal Article
Category Original Paper
Pages 1-17
DOI 10.1007/s00216-012-6105-5
Authors
Gesa J. Schad, Strathclyde Institute for Pharmacy and Biomedical Sciences, University of Strathclyde, 161 Cathedral Street, Glasgow, G4 0RE UK
Melvin R. Euerby, 1 The Markham Centre, Hichrom Ltd, Station Road, Theale, Reading, Berkshire RG7 4PE, UK
Graham G. Skellern, Strathclyde Institute for Pharmacy and Biomedical Sciences, University of Strathclyde, 161 Cathedral Street, Glasgow, G4 0RE UK
Justice N. A. Tettey, Strathclyde Institute for Pharmacy and Biomedical Sciences, University of Strathclyde, 161 Cathedral Street, Glasgow, G4 0RE UK
The chemical analysis of egg-based wall paintings—the mezzo fresco technique—is an interesting topic in the characterisation of organic binders. A revised procedure for a dot-enzyme-linked
immunosorbent assay (dot-ELISA) able to detect protein components of egg-based wall paintings is reported. In the new dot-ELISA
procedure we succeeded in maximizing the staining colour by adjusting the temperature during the staining reaction. Quantification
of the colour intensity by visible reflectance spectroscopy resulted in a straight line plot of protein concentration against
reflectance in the wavelength range 380–780 nm. The modified dot-ELISA procedure is proposed as a semi-quantitative analytical
method for characterisation of protein binders in egg-based paintings. To evaluate its performance, the method was first applied
to standard samples (ovalbumin, whole egg, egg white), then to model specimens, and finally to real samples (Giotto’s wall
paintings). Moreover, amino acid analysis performed by innovative ultra-performance liquid chromatography was applied both
to standards and to model samples and the results were compared with those from the dot-ELISA tests. In particular, after
protein hydrolysis (24 h, 114 °C, 6 mol L?1 HCl) of the samples, amino acid derivatization by use of 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate enabled reproducible analysis of amino acids. This UPLC amino acid analysis was rapid and reproducible
and was applied for the first time to egg-based paintings. Because the painting technique involved the use of egg-based tempera
on fresh lime-based mortar, the study enabled investigation of the effect of the alkaline environment on egg-protein detection
by both methods.
Figure Model wall paintings specimens and typical dot-ELISA stains for egg proteins.
Content Type Journal Article
Category Original Paper
Pages 1-11
DOI 10.1007/s00216-012-6049-9
Authors
Mariangela Potenza, Dipartimento di Chimica “Ugo Schiff”, Università degli Studi di Firenze, via della Lastruccia 3, 50019 Sesto Fiorentino, Firenze, Italy
Giuseppina Sabatino, Espikem srl, via F. Ferrucci 203/c, 59100 Prato, Italy
Francesca Giambi, Consorzio Interuniversitario CSGI, c/o Dipartimento di Chimica “Ugo Schiff”, Polo Scientifico e Tecnologico, Università degli Studi di Firenze, via della Lastruccia 13, 50019 Sesto Fiorentino, Firenze, Italy
Luca Rosi, Dipartimento di Chimica “Ugo Schiff”, Polo Scientifico e Tecnologico, Università degli Studi di Firenze, via della Lastruccia, 3/13, 50019 Sesto Fiorentino, Firenze, Italy
Anna Maria Papini, Laboratorio Interdipartimentale di Chimica e Biologia di Peptidi e Proteine, Polo Scientifico e Tecnologico, Università degli Studi di Firenze, via della Lastruccia 13, 50019 Sesto Fiorentino, Firenze, Italy
Luigi Dei, Dipartimento di Chimica “Ugo Schiff”, Polo Scientifico e Tecnologico, Università degli Studi di Firenze, via della Lastruccia, 3/13, 50019 Sesto Fiorentino, Firenze, Italy
In this work it was demonstrated that sample endogenous polyphenols are selectively driving the gold-nanoparticle (AuNPs)-formation
process when representative food samples were used as natural sources of reducing compounds. The process of AuNPs formation
was characterized by UV–visible spectroscopy and was described by a sigmoidal curve (R2???0.990) which gave information about the polyphenol concentration at which the localized surface plasmon resonance (LSPR)
absorption reached its half-value, Xc50, and about AuNPs production per polyphenol concentration unit, KAuNPs. The behavior of phenolic acids was different, with lower Xc50 and higher KAuNPs values than flavonoids. For the food samples tea, apple, pear, wine, and honey Xc50 values were 0.22, 7.3, 11.5, 20.4, 30.3, and 53.5 (mg mL?1) and KAuNPs values were 28.7, 0.70, 0.60, 0.20, 0.14, and 0.10 (mg?1 mL), respectively. Excellent correlation between KAuNPs and total phenolics (TP) was obtained (r?=?0.98, p-value?<?0.05), implying KAuNPs is a novel marker for evaluation of food sample antioxidant capacity in vitro. The KAuNPs values of samples indicated their antioxidant capacity was in the order: tea > apple > pear > wine > honey. The reproducibility
of the AuNPs formation approach was excellent, not only for polyphenol standards (RSD?<?6 % for Xc50 and RSD?<?11 % for KAuNPs) but also for food samples (RSD?<?9 % for Xc50 and RSD?<?15 % for KAuNPs). Transmission electronic microscopy (TEM) enabled confirmation of the formation of stabilized Au-nanospheres from endogenous
polyphenols with very well-defined sizes under 20 nm diameter for all the food samples investigated.
Figure Gold-nanosphere formation using food polyphenols for antioxidant activity assessment
Content Type Journal Article
Category Original Paper
Pages 1-9
DOI 10.1007/s00216-012-6084-6
Authors
Diana Vilela, Department of Analytical Chemistry and Chemical Engineering, University of Alcalá, 28871 Alcalá de Henares, Madrid, Spain
María Cristina González, Department of Analytical Chemistry and Chemical Engineering, University of Alcalá, 28871 Alcalá de Henares, Madrid, Spain
Alberto Escarpa, Department of Analytical Chemistry and Chemical Engineering, University of Alcalá, 28871 Alcalá de Henares, Madrid, Spain
The number of cases of invasive fungal infections (IFIs) has risen significantly in recent years; therefore, this study developed
a sensitive and effective sweeping-micellar electrokinetic chromatography (MEKC) method for the simultaneous determination
of the three most frequently used triazole antifungal drugs for the treatment of IFIs, which included voriconazole, itraconazole,
and posaconazole. Due to the diverse lipophilicity of the tested drugs, the analytical conditions that resulted in good resolution
between itraconazole and posaconazole caused the peak for voriconazole to split. The splitting phenomenon was resolved by
incorporating a high-salt stacking mechanism into the sweeping-MEKC method. The optimum background electrolyte was composed
of 25 mM phosphoric acid solution (pH 2.2), 100 mM sodium dodecyl sulfate, 13 % acetonitrile, and 13 % tetrahydrofuran. The
best peak shape of voriconazole was obtained when the conductivity ratio between the sample matrix and background electrolyte
was 2.3. Compared to the conventional MEKC mode, the enhancement factor of the sweeping-MEKC method was 66 for itraconazole,
55 for posaconazole, and 43 for voriconazole. The sweeping-MEKC method was validated in terms of precision, accuracy, linearity,
specificity, selectivity, and sensitivity. The linearity ranges of the method covered the commonly used therapeutic ranges
of the three drugs. The developed sweeping-MEKC method was successfully applied to the analysis of clinical samples, thus
demonstrating its applicability for clinical use.
Fig ?
Content Type Journal Article
Category Original Paper
Pages 1-12
DOI 10.1007/s00216-012-6087-3
Authors
Shu-Chiao Lin, School of Pharmacy, College of Medicine, National Taiwan University, 1, Section 1, Jen-Ai Road, Taipei, 100 Taiwan
Hsiang-Yin Liu, School of Pharmacy, College of Medicine, National Taiwan University, 1, Section 1, Jen-Ai Road, Taipei, 100 Taiwan
Shu-Wen Lin, School of Pharmacy, College of Medicine, National Taiwan University, 1, Section 1, Jen-Ai Road, Taipei, 100 Taiwan
Ming Yao, Division of Hematology, Department of Internal Medicine, National Taiwan University Hospital, Taipei, 100 Taiwan
Un-In Wu, Division of Infectious Diseases, Department of Internal Medicine, National Taiwan University Hospital, Taipei, 100 Taiwan
Hsiu-Po Kuo, Department of Chemical and Materials Engineering, Chang Gung University, Tao-Yuan, 333 Taiwan
Ching-Hua Kuo, School of Pharmacy, College of Medicine, National Taiwan University, 1, Section 1, Jen-Ai Road, Taipei, 100 Taiwan
A certified reference material (CRM) is a higher-order calibration material used to enable a traceable analysis. This paper
describes the development of a C-peptide CRM (NMIJ CRM 6901-a) by the National Metrology Institute of Japan using two independent
methods for amino acid analysis based on isotope-dilution mass spectrometry. C-peptide is a 31-mer peptide that is utilized
for the evaluation of ?-cell function in the pancreas in clinical testing. This CRM is a lyophilized synthetic peptide having
the human C-peptide sequence, and contains deamidated and pyroglutamylated forms of C-peptide. By adding water (1.00?±?0.01)
g into the vial containing the CRM, the C-peptide solution in 10 mM phosphate buffer saline (pH 6.6) is reconstituted. We
assigned two certified values that represent the concentrations of total C-peptide (mixture of C-peptide, deamidated C-peptide,
and pyroglutamylated C-peptide) and C-peptide. The certified concentration of total C-peptide was determined by two amino
acid analyses using pre-column derivatization liquid chromatography–mass spectrometry and hydrophilic chromatography–mass
spectrometry following acid hydrolysis. The certified concentration of C-peptide was determined by multiplying the concentration
of total C-peptide by the ratio of the relative area of C-peptide to that of the total C-peptide measured by liquid chromatography.
The certified value of C-peptide (80.7?±?5.0)?mg/L represents the concentration of the specific entity of C-peptide; on the
other hand, the certified value of total C-peptide, (81.7?±?5.1)?mg/L can be used for analyses that does not differentiate
deamidated and pyroglutamylated C-peptide from C-peptide itself, such as amino acid analyses and immunochemical assays.
Content Type Journal Article
Category Paper in Forefront
Pages 1-9
DOI 10.1007/s00216-012-6097-1
Authors
Tomoya Kinumi, Bio-Medical Standard Section, National Metrology Institute of Japan (NMIJ), National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Umezono, Tsukuba, Ibaraki 305-8563, Japan
Mari Goto, Bio-Medical Standard Section, National Metrology Institute of Japan (NMIJ), National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Umezono, Tsukuba, Ibaraki 305-8563, Japan
Sakae Eyama, Bio-Medical Standard Section, National Metrology Institute of Japan (NMIJ), National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Umezono, Tsukuba, Ibaraki 305-8563, Japan
Megumi Kato, Bio-Medical Standard Section, National Metrology Institute of Japan (NMIJ), National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Umezono, Tsukuba, Ibaraki 305-8563, Japan
Takeshi Kasama, Research Center for Medical and Dental Sciences, Tokyo Medical and Dental University, 1-5-45 Yushima, Bunkyo-ku, Tokyo 113-8510, Japan
Akiko Takatsu, Bio-Medical Standard Section, National Metrology Institute of Japan (NMIJ), National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Umezono, Tsukuba, Ibaraki 305-8563, Japan
Ischemia-mediated lipidomic changes in rat brains were explored by matrix-assisted laser desorption/ionization-mass spectrometry
(MALDI-MS) profiling and imaging after in situ desalting which drastically simplified the spectral presentation of tissue
lipids. Removal of interference from the massively changed cations in response to tissue damage permitted the revelation of
subtle yet important lipidomic changes. The identities of the detected lipids were confirmed by MALDI tandem mass spectrometry
(MALDI-MS/MS). The MALDI-MS imaging (MALDI-MSI) result of lysophosphatidylcholine 16:0 (LPC 16:0) in the desalted brain section
appeared essentially identical to that of sodiated LPC 16:0 in the adjacent undesalted section and verified the suitability
of the desalting method for the MALDI-MSI studies of lipids in tissue. Other than the consistently decreased phosphatidylcholine
(PC) 16:0/18:1, images of PCs containing all saturated, or combined saturated and monounsaturated fatty acyl (MUFA) residues
revealed their parenchymal increase by ischemia. Images of PCs containing polyunsaturated fatty acyl (PUFA) residues in normal
cortex showed laminated patterns similar to cortical lamina. Ischemia reduced the abundance of PC 16:0/20:4 and PC 16:0/22:6
and disrupted the laminated distribution of the former. However, ischemia increased the subcortical abundance of PUFA-PCs
containing stearoyl residue and confined their cortical increase within limited areas. Image of parenchymal sphingomyelin
18:0 (SM 18:0) showed its consistent decrease by ischemia that paralleled the increase of ceramide 18:0-H2O in region of moderate to high SM abundance. The above results presented the lipidomic changes largely different from previous
MALDI-MSI results and suggested a window of intervention that may benefit the management of cerebrovascular accident and other
brain injuries.
Content Type Journal Article
Category Original Paper
Pages 1-12
DOI 10.1007/s00216-012-6077-5
Authors
Hay-Yan J. Wang, Department of Biological Sciences, National Sun Yat-Sen University, 70 Lien-Hai Rd, Kaohsiung, 80424 Taiwan
Hsuan-Wen Wu, Department of Biological Sciences, National Sun Yat-Sen University, 70 Lien-Hai Rd, Kaohsiung, 80424 Taiwan
Ping-Ju Tsai, Department of Biological Sciences, National Sun Yat-Sen University, 70 Lien-Hai Rd, Kaohsiung, 80424 Taiwan
Cheng Bin Liu, Department of Biological Sciences, National Sun Yat-Sen University, 70 Lien-Hai Rd, Kaohsiung, 80424 Taiwan
There are a wide and growing variety of feedstocks for biodiesel fuel. Most commonly, these feedstocks contain triglycerides
which are transesterified into the fatty acid alkyl esters (FAAEs) which comprise biodiesel fuel. While the tranesterification
reaction itself is simple, monitoring the reaction progress and reaction products is not. Gas chromatography–mass spectrometry
is useful for assessing the FAAE products, but does not directly address either the tri-, di-, or monoglycerides present from
incomplete transesterification or the free fatty acids which may also be present. Analysis of the biodiesel reaction mixture
is complicated by the solubility and physical property differences among the components of the tranesterification reaction
mixture. In this contribution, we present a simple, rapid HPLC method which allows for monitoring all of the main components
in a biodiesel fuel transesterification reaction, with specific emphasis on the ability to monitor the reaction as a function
of time. The utilization of a relatively new, core-shell stationary phase for the HPLC column allows for efficient separation
of peaks with short elution times, saving both time and solvent.
Formaldehyde is a key fixation reagent. This review explores its application in combination with qualitative and quantitative
mass spectrometry (MS). Formalin-fixed and paraffin-embedded (FFPE) tissues form a large reservoir of biologically valuable
samples and their investigation by MS has only recently started. Furthermore, formaldehyde can be used to stabilise protein–protein
interactions in living cells. Because formaldehyde is able to modify proteins, performing MS analysis on these samples can
pose a challenge. Here we discuss the chemistry of formaldehyde cross-linking, describe the problems of and progress in these
two applications and their common aspects, and evaluate the potential of these methods for the future.
Content Type Journal Article
Category Review
Pages 1-11
DOI 10.1007/s00216-012-6065-9
Authors
Cordula Klockenbusch, The Biomedical Research Centre, University of British Columbia, 2222 Health Sciences Mall, Vancouver, BC V6T 1Z3, Canada
Jane E. O’Hara, The Biomedical Research Centre, University of British Columbia, 2222 Health Sciences Mall, Vancouver, BC V6T 1Z3, Canada
Juergen Kast, The Biomedical Research Centre, University of British Columbia, 2222 Health Sciences Mall, Vancouver, BC V6T 1Z3, Canada
Low-molecular-weight heparins (LMWHs) are produced from heparin by various depolymerization strategies, which result in a
reduction of the average molecular weight of the polysaccharide chains, a reduction of the anti-factor IIa activity (and a
concomitant increase in the anti-factor Xa/anti-factor IIa ratio), and introduction of process-related structural signatures.
Numerous techniques have been developed to characterize LMWHs and to measure the type and extent of structural modifications
that are introduced as a function of the depolymerization process. We present here an analysis of the tetrasaccharide pool
of enoxaparin sodium, a LMWH produced by chemical ?-elimination of heparin benzyl ester. We identify the predominant sequences
present within the tetrasaccharide pool and demonstrate that this pool provides a sensitive, specific readout of the physicochemical
process conditions used to generate enoxaparin sodium.
Content Type Journal Article
Category Original Paper
Pages 1-12
DOI 10.1007/s00216-012-6045-0
Authors
Jennifer Ozug, Momenta Pharmaceuticals, 675 West Kendall Street, Cambridge, MA 02142, USA
Steve Wudyka, Momenta Pharmaceuticals, 675 West Kendall Street, Cambridge, MA 02142, USA
Nur Sibel Gunay, Momenta Pharmaceuticals, 675 West Kendall Street, Cambridge, MA 02142, USA
Daniela Beccati, Momenta Pharmaceuticals, 675 West Kendall Street, Cambridge, MA 02142, USA
Jonathan Lansing, Momenta Pharmaceuticals, 675 West Kendall Street, Cambridge, MA 02142, USA
Jing Wang, Momenta Pharmaceuticals, 675 West Kendall Street, Cambridge, MA 02142, USA
Ishan Capila, Momenta Pharmaceuticals, 675 West Kendall Street, Cambridge, MA 02142, USA
Zachary Shriver, Momenta Pharmaceuticals, 675 West Kendall Street, Cambridge, MA 02142, USA
Ganesh V. Kaundinya, Momenta Pharmaceuticals, 675 West Kendall Street, Cambridge, MA 02142, USA
As recently reported, dried blood spot (DBS) analysis is an advantageous technique for doping control purposes due to the
minimal invasive sample collection, the simple and economic manner, as well as the low susceptibility to manipulation. Its
general applicability to the sports drug testing arena has been shown for analytes of various substance classes, all of which
comprise exclusively low molecular mass compounds. The aim of the present study was to investigate whether the technique of
DBS analysis is applicable also to (pegylated) peptides with relevance for doping controls. As target analyte, peginesatide
(Omontys, Hematide), a recently approved pegylated erythropoietin-mimetic peptide of approximately 45 kDa, tested for the
treatment of anaemia in patients with renal failure, was chosen, which has been prohibited in elite sports due to its assumed
endurance enhancing effects. Therefore, a detection method for peginesatide employing DBS was developed based on extraction,
proteolytic digestion and cation-exchange purification followed by liquid chromatography–tandem mass spectrometry analysis.
Eventually, the assay was validated for qualitative purposes and proved to be specific, sensitive (limit of detection, 10 ng/mL)
and precise (relative standard deviations below 18 %), demonstrating the general suitability of DBS analysis in sports drug
testing also for (pegylated) peptides.
Content Type Journal Article
Category Original Paper
Pages 1-10
DOI 10.1007/s00216-012-6043-2
Authors
Ines Möller, Institute of Biochemistry, Center for Preventive Doping Research, German Sport University Cologne, Am Sportpark Müngersdorf 6, 50933 Cologne, Germany
Andreas Thomas, Institute of Biochemistry, Center for Preventive Doping Research, German Sport University Cologne, Am Sportpark Müngersdorf 6, 50933 Cologne, Germany
Hans Geyer, Institute of Biochemistry, Center for Preventive Doping Research, German Sport University Cologne, Am Sportpark Müngersdorf 6, 50933 Cologne, Germany
Wilhelm Schänzer, Institute of Biochemistry, Center for Preventive Doping Research, German Sport University Cologne, Am Sportpark Müngersdorf 6, 50933 Cologne, Germany
Mario Thevis, Institute of Biochemistry, Center for Preventive Doping Research, German Sport University Cologne, Am Sportpark Müngersdorf 6, 50933 Cologne, Germany
Erratum to: Preparation and certification of Hijiki reference material, NMIJ CRM 7405-a, from the edible marine algae hijiki (Hizikia fusiforme)
Content Type Journal Article
Category Erratum
Pages 1-3
DOI 10.1007/s00216-012-5994-7
Authors
Tomohiro Narukawa, Environmental Standard Section, National Metrology Institute of Japan (NMIJ), National Institute of Advanced Industrial Science and technology (AIST), Tsukuba Central 3, 1-1-1 Umezono, Tsukuba, Ibaraki 305-8563, Japan
Kazumi Inagaki, Environmental Standard Section, National Metrology Institute of Japan (NMIJ), National Institute of Advanced Industrial Science and technology (AIST), Tsukuba Central 3, 1-1-1 Umezono, Tsukuba, Ibaraki 305-8563, Japan
Yanbei Zhu, Environmental Standard Section, National Metrology Institute of Japan (NMIJ), National Institute of Advanced Industrial Science and technology (AIST), Tsukuba Central 3, 1-1-1 Umezono, Tsukuba, Ibaraki 305-8563, Japan
Takayoshi Kuroiwa, Environmental Standard Section, National Metrology Institute of Japan (NMIJ), National Institute of Advanced Industrial Science and technology (AIST), Tsukuba Central 3, 1-1-1 Umezono, Tsukuba, Ibaraki 305-8563, Japan
Izumi Narushima, Environmental Standard Section, National Metrology Institute of Japan (NMIJ), National Institute of Advanced Industrial Science and technology (AIST), Tsukuba Central 3, 1-1-1 Umezono, Tsukuba, Ibaraki 305-8563, Japan
Koichi Chiba, Environmental Standard Section, National Metrology Institute of Japan (NMIJ), National Institute of Advanced Industrial Science and technology (AIST), Tsukuba Central 3, 1-1-1 Umezono, Tsukuba, Ibaraki 305-8563, Japan
Akiharu Hioki, Environmental Standard Section, National Metrology Institute of Japan (NMIJ), National Institute of Advanced Industrial Science and technology (AIST), Tsukuba Central 3, 1-1-1 Umezono, Tsukuba, Ibaraki 305-8563, Japan
Enantiomeric separations of 18 chiral polychlorinated biphenyls (PCBs) were investigated on three polysaccharide-type chiral
stationary phases (CSPs; Sino-Chiral OJ, Chiralpak IB, and Chiralcel OD) by supercritical fluid chromatography (SFC). With
these commonly used polysaccharide CSPs, 17 PCBs except PCB 135 (RS?=?0.81) were well resolved (RS?>?1.5) under appropriate mobile phases and temperatures. Using Sino-Chiral OJ, 14 PCBs could be baseline-separated, while
only one and nine PCBs could be completely separated using Chiralpak IB and Chiralcel OD, respectively. The influence of column
temperature was studied for the optimization of resolution, as well as for the type and percentage of organic modifier in
the mobile phase. The resolution decreased as the temperature increased in the range of 26–40 °C in which the enantiomeric
separations were an enthalpy-driven process. The addition of modifiers in the mobile phase decreased the resolution of the
PCB enantiomers, but it clearly shortened their retention time. These separation results indicate that SFC is a promising
chromatographic technique for chiral separation and enantiopure standard preparation.
Figure ?
Content Type Journal Article
Category Original Paper
Pages 1-8
DOI 10.1007/s00216-012-6063-y
Authors
Anping Zhang, College of Biological and Environmental Engineering, Zhejiang University of Technology, No. 18 Chaowang Road, Hangzhou, Zhejiang Province 310014, China
Weiliang Gao, College of Biological and Environmental Engineering, Zhejiang University of Technology, No. 18 Chaowang Road, Hangzhou, Zhejiang Province 310014, China
Binbin Ma, College of Biological and Environmental Engineering, Zhejiang University of Technology, No. 18 Chaowang Road, Hangzhou, Zhejiang Province 310014, China
Lixia Jin, College of Biological and Environmental Engineering, Zhejiang University of Technology, No. 18 Chaowang Road, Hangzhou, Zhejiang Province 310014, China
Chunmian Lin, College of Biological and Environmental Engineering, Zhejiang University of Technology, No. 18 Chaowang Road, Hangzhou, Zhejiang Province 310014, China
Alginate is an important medical and commercial product and currently is isolated from seaweeds. Certain microorganisms also
produce alginate and these polymers have the potential to replace seaweed alginates in some applications, mainly because such
production will allow much better and more reproducible control of critical qualitative polymer properties. The research conducted
here presents the development of a new approach to this problem by analysing a transposon insertion mutant library constructed
in an alginate-producing derivative of the Pseudomonas fluorescens strain SBW25. The procedure is based on the non-destructive and reagent-free method of Fourier transform infrared (FT-IR)
spectroscopy which is used to generate a complex biochemical infrared fingerprint of the medium after bacterial growth. First,
we investigate the potential differences caused by the growth media fructose and glycerol on the bacterial phenotype and alginate
synthesis in 193 selected P. fluorescens mutants and show that clear phenotypic differences are observed in the infrared fingerprints. In order to quantify the level
of the alginate we also report the construction and interpretation of multivariate partial least squares regression models
which were able to quantify alginate levels successfully with typical normalized root-mean-square error in predictions of
only approximately 14 %. We have demonstrated that this high-throughput approach can be implemented in alginate screens and
we believe that this FT-IR spectroscopic methodology, when combined with the most appropriate chemometrics, could easily be
modified for the quantification of other valuable microbial products and play a valuable screening role for synthetic biology.
Figure PLS regression coefficients (top) and FT-IR spectra of pure fructose, pure glycerol, and pure alginate (bottom)
Content Type Journal Article
Category Original Paper
Pages 1-9
DOI 10.1007/s00216-012-6068-6
Authors
Elon Correa, School of Chemistry, Manchester Interdisciplinary Biocentre, University of Manchester, 131 Princess Street, Manchester, M1 7ND UK
Håvard Sletta, Department of Biotechnology, SINTEF Materials and Chemistry, SINTEF, 7465 Trondheim, Norway
David I. Ellis, School of Chemistry, Manchester Interdisciplinary Biocentre, University of Manchester, 131 Princess Street, Manchester, M1 7ND UK
Sunniva Hoel, Department of Biotechnology, SINTEF Materials and Chemistry, SINTEF, 7465 Trondheim, Norway
Helga Ertesvåg, Department of Biotechnology, Norwegian University of Science and Technology (NTNU), Sem Sælandsvei 6/8, 7491 Trondheim, Norway
Trond E. Ellingsen, Department of Biotechnology, SINTEF Materials and Chemistry, SINTEF, 7465 Trondheim, Norway
Svein Valla, Department of Biotechnology, Norwegian University of Science and Technology (NTNU), Sem Sælandsvei 6/8, 7491 Trondheim, Norway
Royston Goodacre, School of Chemistry, Manchester Interdisciplinary Biocentre, University of Manchester, 131 Princess Street, Manchester, M1 7ND UK
Simultaneous determination of three herbicides (dicamba, 2,4-D, and atrazine) has been achieved by on-line solid-phase extraction
(SPE) coupled to multisyringe chromatography (MSC) with UV detection. The preconcentration conditions were optimized; a preconcentration
flow rate of 0.5 mL min?1 and elution at 0.8 mL min?1 were the optimum conditions. A C18 (8 mm i.d.) membrane extraction disk conditioned with 0.3 mol L?1 HCl in 0.5 % MeOH was used. A 3-mL sample was preconcentrated, then eluted with 0.43 mL 40:60 water–MeOH. A C18 monolithic column (25 mm?×?4.6 mm) was used for chromatographic separation. Separation of the three compounds was achieved
in 10 min by use of 0.01 % aqueous acetic acid–MeOH (60:40) as mobile phase at a flow rate of 0.8 mL min?1. The limits of detection (LOD) were 13, 57, and 22 ?g L?1 for dicamba, 2,4-D, and atrazine, respectively. The sampling frequency was three analyses per hour, and each analysis consumed
only 7.3 mL solvent. The method was applied to spiked water samples, and recovery between 85 and 112 % was obtained. Recovery
was significantly better than in the conventional HPLC–UV method. These results indicated the reliability and accuracy of
this flow-based method. This is the first time this family of herbicides has been simultaneously analyzed by on-line SPE–MSC
using a monolithic column.
Figure On-line solid phase extraction coupled to multisyringe chromatography
Content Type Journal Article
Category Original Paper
Pages 1-10
DOI 10.1007/s00216-012-6055-y
Authors
C. A. Chávez-Moreno, Facultad de Ciencias Químicas, Cd Universitaria, Universidad Autónoma de Nuevo León, UANL, San Nicolás de los Garza, Nuevo León C.P. 66451, Mexico
J. L. Guzmán-Mar, Facultad de Ciencias Químicas, Cd Universitaria, Universidad Autónoma de Nuevo León, UANL, San Nicolás de los Garza, Nuevo León C.P. 66451, Mexico
L. Hinojosa-Reyes, Facultad de Ciencias Químicas, Cd Universitaria, Universidad Autónoma de Nuevo León, UANL, San Nicolás de los Garza, Nuevo León C.P. 66451, Mexico
A. Hernández-Ramírez, Facultad de Ciencias Químicas, Cd Universitaria, Universidad Autónoma de Nuevo León, UANL, San Nicolás de los Garza, Nuevo León C.P. 66451, Mexico
L. Ferrer, Department of Chemistry, University of the Balearic Islands, 07122 Palma de Mallorca, Spain
V. Cerdà, Department of Chemistry, University of the Balearic Islands, 07122 Palma de Mallorca, Spain
Fluorescence recovery after photobleaching (FRAP) can help unveil subtle dynamical and biochemical properties of intracellular
components. A peculiar aspect of this method is that it is based on the change of optical properties only, whereas dynamics
and biochemistry of the molecules of interest are not perturbed. This makes FRAP particularly suitable for the study of protein
translocation, e.g., between nucleus and cytoplasm. Here we present a comprehensive theoretical treatment of FRAP applied
to protein nucleocytoplasmic translocation by passive diffusion and/or energy-driven processes across the nuclear envelope.
Our mathematical model is validated by experimental FRAP studies with functionalized fluorescent protein chimeras. Using this
approach we demonstrate that molecular crowding at the nuclear pore does not hamper passive diffusion and calculate the dimension
of the nuclear pore size (5.33 nm). Additionally, our FRAP analysis reveals the biochemical parameters (maximum translocation
rate and dissociation constant of the transport complex in cytoplasm) associated with the active import of a prototypical
nuclear localization sequence (NLS of SV40) and related mutants. We demonstrate that transportin binding and active import
into the nucleus are independent processes that can be separately modulated. The present results are discussed in light of
their potential to help in engineering sequences for intracellular targeted delivery of sensors and/or therapeutic compounds.
Finally, the limits of validity of our mathematical model are addressed.
Figure Nucleocytoplasmic translocation. Left: Pictorial description of translocation processes across the nuclear pore: passive diffusion
(up) and active transport (down). Right: time-lapse images of Fluorescence Recovery After Photobleaching (FRAP) technique
applied to monitor the dynamic nucleocytoplasmic exchange of fluorescent molecules
Content Type Journal Article
Category Original Paper
Pages 1-13
DOI 10.1007/s00216-012-6025-4
Authors
Ranieri Bizzarri, NEST, Scuola Normale Superiore and Istituto Nanoscienze – CNR, Piazza San Silvestro 12, 56127 Pisa, Italy
Francesco Cardarelli, Center for Nanotechnology Innovation @ NEST, Istituto Italiano di Tecnologia, Piazza San Silvestro 12, 56127 Pisa, Italy
Michela Serresi, Center for Nanotechnology Innovation @ NEST, Istituto Italiano di Tecnologia, Piazza San Silvestro 12, 56127 Pisa, Italy
Fabio Beltram, NEST, Scuola Normale Superiore and Istituto Nanoscienze – CNR, Piazza San Silvestro 12, 56127 Pisa, Italy
The determination of methylglyoxal (MG) concentrations in vivo is gaining increasing importance as high levels of MG are linked
to various health impairments including complications of diabetes. In order to standardize the measurements of MG in body
fluids, it is necessary to precisely determine the concentration of MG stock solutions used as analytical standards. The “gold
standard” method for the determination of MG concentration in the millimolar range is an enzyme-catalyzed endpoint assay based
on the glyoxalase I catalyzed formation of S-lactoylglutathione. However, as this assay used purified glyoxalase I enzyme, it is quite expensive. Another method uses
a derivation reaction with 2,4-dinitrophenylhydrazine, but this substance is explosive and needs special handling and storage.
In addition, precipitation of the product methylglyoxal-bis-2,4-dinitrophenylhydrozone during the reaction limits the reliability
of this method. In this study, we have evaluated a new method of MG determination based on the previously published fast reaction
between MG and N-acetyl-l-cysteine at room temperature which yields an easily detectable condensation product, N-?-acetyl-S-(1-hydroxy-2-oxo-prop-1-yl)cysteine. When comparing these three different assays for the measurement of MG concentrations,
we find that the N-acetyl-l-cysteine assay is the most favorable, providing an economical and robust assay without the need for the use of hazardous
or expensive reagents.
Figure Comparison of the three different spectrophotometrical methods of MG determination
Content Type Journal Article
Category Technical Note
Pages 1-5
DOI 10.1007/s00216-012-6086-4
Authors
Rebekka Wild, Department of Pharmacology, School of Medicine, University of Western Sydney, Locked Bag 1797, Penrith South DC, 1797 Australia
Lezanne Ooi, Department of Pharmacology, School of Medicine, University of Western Sydney, Locked Bag 1797, Penrith South DC, 1797 Australia
Velandai Srikanth, Department of Medicine, Monash University, Wellington Road, Clayon, VIC 3168, Australia
Gerald Münch, Department of Pharmacology, School of Medicine, University of Western Sydney, Locked Bag 1797, Penrith South DC, 1797 Australia
Commercially available polystyrene (PS) slides were plasma nanotextured (nano-roughened) through treatment in oxygen plasma
discharges to create substrates with increased surface area for microarray applications. Conditions of plasma treatment were
determined for maximum and uniform oligonucleotide immobilization on these nanotextured PS slides. Oligonucleotides were immobilized
onto the surface in the form of biotinylated oligonucleotide/streptavidin conjugates to take advantage of increased protein
binding capacity of the substrate. It was found that the amount of oligonucleotides that could be immobilized was increased
up to ten times on plasma treated as compared with untreated slides. The sensitivity of detection of labelled hybridized probes
was improved by a factor of 20. Optimized nanotextured PS slides were subsequently used to develop a microarray for the detection
of three deleterious BRCA1 gene mutations by immobilizing oligonucleotides corresponding to wild and mutant-type sequences.
The microarray developed on the nanotextured PS slides provided higher specific hybridization signal and discrimination ratios
as compared with flat untreated PS slides.
Figure The process of O2 plasma nanotexturing and biomolecule immobilization is shown. An image from the slide scanner showing bright spots is presented
together with an SEM image of the slide.
Content Type Journal Article
Category Original Paper
Pages 1-8
DOI 10.1007/s00216-012-6058-8
Authors
K. Tsougeni, Institute of Microelectronics, NCSR “Demokritos”, P.O. Box 60228, Aghia Paraskevi, 153 10 Attiki, Greece
G. Koukouvinos, Institute of Radioisotopes and Radiodiagnostic Products, NCSR “Demokritos”, P.O. Box 60228, Aghia Paraskevi, 153 10 Attiki, Greece
P. S. Petrou, Institute of Radioisotopes and Radiodiagnostic Products, NCSR “Demokritos”, P.O. Box 60228, Aghia Paraskevi, 153 10 Attiki, Greece
A. Tserepi, Institute of Microelectronics, NCSR “Demokritos”, P.O. Box 60228, Aghia Paraskevi, 153 10 Attiki, Greece
S. E. Kakabakos, Institute of Radioisotopes and Radiodiagnostic Products, NCSR “Demokritos”, P.O. Box 60228, Aghia Paraskevi, 153 10 Attiki, Greece
E. Gogolides, Institute of Microelectronics, NCSR “Demokritos”, P.O. Box 60228, Aghia Paraskevi, 153 10 Attiki, Greece
The Petasis reaction is the multi-component reaction of a carbonyl compound, amine, and arylboronic acid to form an ?-amino
acid or a ?-aminoalcohol. In this work, as the first analytical application of the Petasis reaction, a high-performance liquid
chromatographic (HPLC) method with fluorescence detection was developed for determination of glyoxylic acid. The glyoxylic
acid was derivatized with 1-pyreneboronic acid, as fluorescent arylboronic acid, in the presence of N-methylbutylamine, as amine, to give a fluorescent ?-amino acid. HPLC separation of the fluorescent derivative was performed
within 30 min on an octyl column eluted with a gradient prepared from acetonitrile and 50 mmol L?1 acetate buffer (pH 4.0). The detection limit (S/N=3) for glyoxylic acid was 5.0 nmol L?1 (20 fmol/injection). The method can be used to determine the concentration of glyoxylic acid in human urine without interference
from biological components.
Content Type Journal Article
Category Original Paper
Pages 1-6
DOI 10.1007/s00216-012-6036-1
Authors
Kohki Chihara, Graduate School of Biomedical Sciences, Course of Pharmaceutical Sciences, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki, 852-8521 Japan
Naoya Kishikawa, Graduate School of Biomedical Sciences, Course of Pharmaceutical Sciences, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki, 852-8521 Japan
Kaname Ohyama, Graduate School of Biomedical Sciences, Course of Pharmaceutical Sciences, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki, 852-8521 Japan
Kenichiro Nakashima, Graduate School of Biomedical Sciences, Course of Pharmaceutical Sciences, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki, 852-8521 Japan
Naotaka Kuroda, Graduate School of Biomedical Sciences, Course of Pharmaceutical Sciences, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki, 852-8521 Japan
Isobaric tagging has proven to be a popular quantitative proteomics tool and has been rapidly adopted to study a wide range
of biological questions in the few years since its commercialization. While the flexibility and multiplexing capacity afforded
by this technology are clear attractions, it is not without its shortcomings. As the speed and sensitivity of mass spectrometers
have improved and the application of isobaric tags to all manner of biological systems has increased, significant issues with
quantitative accuracy and precision have come to light. Here we review the issues associated with the use of isobaric tagging
methods and discuss the possible solutions which have been proposed to improve their precision and accuracy to approach the
levels required within quantitative proteomics.
Content Type Journal Article
Category Review
Pages 1-9
DOI 10.1007/s00216-012-6012-9
Authors
Andy L. Christoforou, Cambridge Centre for Proteomics, Cambridge Systems Biology Centre, Department of Biochemistry, University of Cambridge, Tennis Court Road, Cambridge, CB2 1QR UK
Kathryn S. Lilley, Cambridge Centre for Proteomics, Cambridge Systems Biology Centre, Department of Biochemistry, University of Cambridge, Tennis Court Road, Cambridge, CB2 1QR UK
Magnetic techniques based on the application of magnetic nanoparticles and microparticles and films have been successfully
used for the determination and detection of different types of xenobiotics (e.g. herbicides, insecticides, fungicides, aromatic
and polyaromatic hydrocarbons, pentachlorophenol and heavy metal ions) as well as viruses, microbial pathogens and protozoan
parasites in water samples. Preconcentration of xenobiotics from large volumes of samples can be performed using magnetic
solid-phase extraction, stir-bar sorptive extraction and related procedures. This review provides basic information about
these techniques. Published examples of successful applications document the importance of these simple and efficient procedures
employing magnetic materials.
Content Type Journal Article
Category Review
Pages 1-17
DOI 10.1007/s00216-012-6056-x
Authors
Ivo Safarik, Department of Nanobiotechnology, Institute of Nanobiology and Structural Biology of GCRC, Na Sadkach 7, 370 05 Ceske Budejovice, Czech Republic
Katerina Horska, Department of Nanobiotechnology, Institute of Nanobiology and Structural Biology of GCRC, Na Sadkach 7, 370 05 Ceske Budejovice, Czech Republic
Kristyna Pospiskova, Department of Biochemistry, Faculty of Science, Palacky University, Slechtitelu 11, 783 71 Olomouc, Czech Republic
Mirka Safarikova, Department of Nanobiotechnology, Institute of Nanobiology and Structural Biology of GCRC, Na Sadkach 7, 370 05 Ceske Budejovice, Czech Republic
Emerging contaminants are a broad category of chemicals, previously unknown or unrecognized as being of concern, but which,
because of their potential health effects associated with human exposure, are under increasing scrutiny. To accurately measure
their levels in biological matrices, specific and sensitive analytical methods have recently been developed. We have reviewed
here the methods used for analysis of selected emerging organic contaminants, for example metabolites of organophosphate triesters,
metabolites of new phthalates or phthalate substitutes, perchlorate, organic UV filters, and polycyclic siloxanes, in human
matrices. Although the use of new techniques and approaches has been emphasized, we also acknowledge methods previously used
for other contaminants and adapted for the emerging contaminants listed above. In all cases, chromatography and mass spectrometry
were the techniques of choice, because of their selectivity and sensitivity for measurements at ng g?1 levels. Critical issues and challenges have been discussed, together with recommendations for further improvement in particular
cases (e.g. metabolites of phthalates or their substitutes). In particular, the use of labeled internal standards, the availability
of certified reference materials, and the need for interlaboratory comparison exercises are key aspects of further development
of this field of research.
Figure Humans are daily exposed to a cocktail of chemicals, including new compounds
Content Type Journal Article
Category Review
Pages 1-27
DOI 10.1007/s00216-012-6053-0
Authors
Alin C. Dirtu, Toxicological Centre, University of Antwerp, Universiteitsplein 1, 2610 Wilrijk, Belgium
Nele Van den Eede, Toxicological Centre, University of Antwerp, Universiteitsplein 1, 2610 Wilrijk, Belgium
Govindan Malarvannan, Toxicological Centre, University of Antwerp, Universiteitsplein 1, 2610 Wilrijk, Belgium
Alin C. Ionas, Toxicological Centre, University of Antwerp, Universiteitsplein 1, 2610 Wilrijk, Belgium
Adrian Covaci, Toxicological Centre, University of Antwerp, Universiteitsplein 1, 2610 Wilrijk, Belgium
Perry G. Wang and Weixuan He (Eds.): Hydrophilic interaction liquid chromatography (HILIC) and advanced applications
Content Type Journal Article
Category Books and Software in Review
Pages 1-2
DOI 10.1007/s00216-012-6074-8
Authors
Pavel Jandera, Department of Analytical Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 573, 53210 Pardubice, Czech Republic
An immobilised enzyme reactor (IMER) in the form of capillary monolith was developed for a micro-liquid chromatography system.
The plain monolith was obtained by in situ thermal copolymerisation of glycidyl methacrylate and ethylene dimethacrylate in
a fused silica capillary (200?×?0.53 mm ID) by using n-propanol/1,4-butanediol as porogen. The enzyme, ?-chymotrypsin (CT), was covalently attached onto the monolith via triazole
ring formation by click-chemistry. For this purpose, the monolithic support was treated with sodium azide and reacted with
the alkyne carrying enzyme derivative. CT was covalently linked to the monolith by triazole-ring formation. The activity behaviour
of monolithic IMER was investigated in a micro-liquid chromatography system by using benzoyl-l-tyrosine ethyl ester (BTEE) as synthetic substrate. The effects of mobile-phase flow rate and substrate feed concentration
on the final BTEE conversion were investigated under steady-state conditions. In the case of monolithic IMER, the final substrate
conversion increased with increasing feed flow rate and increasing substrate feed concentration. Unusual behaviour was explained
by the presence of convective diffusion in the macropores of monolith. The results indicated that the monolithic-capillary
IMER proposed for micro-liquid chromatography had significant advantages with respect to particle-based conventional high-performance
liquid chromatography–IMERs.
Figure The variation of DAD signal and final BTEE conversion with the flow rate of substrate solution.
Content Type Journal Article
Category Original Paper
Pages 1-9
DOI 10.1007/s00216-012-6075-7
Authors
Bekir Çelebi, Chemical Engineering Department, Hacettepe University, 06532 Beytepe, Ankara, Turkey
Asl?han Bayraktar, Chemical Engineering Department, Hacettepe University, 06532 Beytepe, Ankara, Turkey
Ali Tuncel, Chemical Engineering Department, Hacettepe University, 06532 Beytepe, Ankara, Turkey
The plant Stevia rebaudiana accumulates a suite of diterpenoid metabolites that are natural sweeteners finding increased use as sugar substitutes. To
guide breeding of stevia plants that accumulate substances with desirable flavor in high yield, rapid and accurate methods
are needed to profile these substances in plant populations. This report describes an 8-min ultrahigh performance liquid chromatography–tandem
mass spectrometry method for separation and quantification of seven stevia glycosides including steviolbioside; stevioside;
rebaudiosides A, B, and C; rubusoside; and dulcoside as well as aglycones steviol and isosteviol. This negative mode electrospray
ionization/multiple reaction monitoring method yielded low limits of detection <1 ng/mL for steviol, 6 ng/mL for isosteviol,
and <15 ng/mL for all stevia glycosides. Stevioside and Reb A, B, and C were quantified in more than 1,100 extracts from stevia
leaves as part of a large-scale profiling exercise. Leaf tissue levels in this population spanned about two orders of magnitude
for stevioside (2–125 mg/g dry weight), Reb A (2.5–164 mg/g), Reb B (0.5–50 mg/g), and Reb C (1.5–125 mg/g), but levels of
individual metabolites exhibited independent variation. The wide spread of metabolite levels highlights the utility and importance
of performing targeted metabolic profiling for large plant populations.
Content Type Journal Article
Category Original Paper
Pages 1-8
DOI 10.1007/s00216-012-6071-y
Authors
Behnaz Shafii, Department of Chemistry, Michigan State University, East Lansing, MI 48824, USA
Ramin Vismeh, Department of Chemistry, Michigan State University, East Lansing, MI 48824, USA
Randy Beaudry, Department of Horticulture, Michigan State University, East Lansing, MI 48824, USA
Ryan Warner, Department of Horticulture, Michigan State University, East Lansing, MI 48824, USA
A. Daniel Jones, Department of Chemistry, Michigan State University, East Lansing, MI 48824, USA
The development and application of new separation mechanisms such as hydrophilic interaction chromatography (HILIC) is of
high importance for the simultaneous analysis of polar molecules such as primary metabolites. However the retention mechanism
in HILIC is not fully understood and as a result retention prediction tools are not at hand for this chromatographic approach.
In the present report we study the utility of a simple algorithm, based on a simple linear and/or a simple logarithmic retention
model, for retention prediction in HILIC gradient separation of a mixture of 23 selected compounds including (poly)amines,
amino acids, saccharides, and other molecules. Utilizing two types of gradient elution programs with or without an isocratic
part, retention data were collected in order to build prediction models. Starting from at least three gradient runs the prediction
of analyte retention was very satisfactory for all gradient programs tested, providing useful evidence of the value of such
retention time prediction methodologies.
Figure
Content Type Journal Article
Category Original Paper
Pages 1-9
DOI 10.1007/s00216-012-6015-6
Authors
Helen Gika, Department of Chemical Engineering, Aristotle University of Thessaloniki, 54124 Thessaloniki, Greece
Georgios Theodoridis, IASMA Research and Innovation Centre, Fondazione Edmund Mach, Food Quality and Nutrition Area, Via E. Mach 1, 38010 S. Michele all’Adige, Italy
Fulvio Mattivi, IASMA Research and Innovation Centre, Fondazione Edmund Mach, Food Quality and Nutrition Area, Via E. Mach 1, 38010 S. Michele all’Adige, Italy
Urska Vrhovsek, IASMA Research and Innovation Centre, Fondazione Edmund Mach, Food Quality and Nutrition Area, Via E. Mach 1, 38010 S. Michele all’Adige, Italy
Adriani Pappa-Louisi, Department of Chemistry, Aristotle University of Thessaloniki, 54124 Thessaloniki, Greece
To provide a new insight into the response of plants to abiotic stresses, the ionomic profiles of Nicotiana langsdorffii specimens have been determined before and after exposure to toxic metals (chromium) or drought conditions. The plants were
genetically transformed with the rat glucocorticoid receptor (GR) or the gene for Agrobacterium rhizogenes rolC, because these modifications are known to produce an imbalance in phytohormone equilibria and a significant change in
the defence response of the plant. Elemental profiles were obtained by developing and applying analytical procedures based
on inductively coupled plasma atomic emission and mass spectrometry (ICP–AES/MS). In particular, the removal of isobaric interferences
affecting the determination of Cr and V by ICP–MS was accomplished by use of a dynamic reaction cell, after optimization of
the relevant conditions. The combined use of ICP atomic emission and mass spectrometry enabled the determination of 29 major
and trace elements (Ba, Bi, Ca, Cd, Co, Cr, Cu, Eu, Fe, Ga, K, Li, Mg, Mn, Mo, Na, P, Pb, Pt, Rb, S, Sb, Sn, Sr, Te, V, W,
Y, and Zn) in different parts of the plants (roots, stems, and leaves), with high accuracy and precision. Multivariate data
processing and study of element distribution patterns provided new information about the ionomic response of the target organism
to chemical treatment or water stress. Genetic modification mainly affected the distribution of Bi, Cr, Mo, Na, and S, indicating
that these elements were involved in biochemical processes controlled by the GR or rolC genes. Chemical stress strongly affected
accumulation of several elements (Ba, Ca, Fe, Ga, K, Li, Mn, Mo, Na, P, Pb, Rb, S, Sn, Te, V, and Zn) in different ways; for
Ca, Fe, K, Mn, Na, and P the effect was quite similar to that observed in other studies after treatment with other transition
elements, for example Cu and Cd. The effect of water deficit was less evident, mainly consisting in a decrease of Ba, Cr,
Na, and Sr in roots.
Figure Roots, stems and leaves of different Nicotiana langsdorffii genotypes exposed to abiotic stresses were analysed by ICP-AES and ICP-MS, obtaining information on the distribution of 29
major and trace elements in the samples
Content Type Journal Article
Category Original Paper
Pages 1-13
DOI 10.1007/s00216-012-5997-4
Authors
Francisco Ardini, Department of Chemistry and Industrial Chemistry, University of Genoa, Via Dodecaneso 31, 16146 Genoa, Italy
Francesco Soggia, Department of Chemistry and Industrial Chemistry, University of Genoa, Via Dodecaneso 31, 16146 Genoa, Italy
Maria Luisa Abelmoschi, Department of Chemistry and Industrial Chemistry, University of Genoa, Via Dodecaneso 31, 16146 Genoa, Italy
Emanuele Magi, Department of Chemistry and Industrial Chemistry, University of Genoa, Via Dodecaneso 31, 16146 Genoa, Italy
Marco Grotti, Department of Chemistry and Industrial Chemistry, University of Genoa, Via Dodecaneso 31, 16146 Genoa, Italy
An LC–MS–MS-based procedure for determination in hair of 14 different drugs of abuse belonging to the classes cocaine, amphetamine-like
compounds, opiates, and hallucinogens has been developed. A pressurized-liquid extraction procedure was used and proved useful
for quantitative recovery of all the analytes tested. This procedure, in conjunction with a simple decontamination step, performed
to avoid false-positive samples, enabled the detection of all the analytes with LOQ ranging from 1.8 to 16 pg mg?1 and accuracy varying from 85 to 111 %. The procedure was validated in accordance with the SOFT/AAFS guidelines and seems
to be suitable for routine determination of the drugs tested in hair.
Content Type Journal Article
Category Original Paper
Pages 1-11
DOI 10.1007/s00216-012-6072-x
Authors
Manuel Sergi, Department of Food Science, University of Teramo, 64023 Teramo, Italy
Sabino Napoletano, Department of Chemistry, Sapienza University of Rome, 00185 Rome, Italy
Camilla Montesano, Department of Chemistry, Sapienza University of Rome, 00185 Rome, Italy
Roberto Iofrida, Department of Chemistry, Sapienza University of Rome, 00185 Rome, Italy
Roberta Curini, Department of Chemistry, Sapienza University of Rome, 00185 Rome, Italy
Dario Compagnone, Department of Food Science, University of Teramo, 64023 Teramo, Italy
Response to Letter to the Editor regarding “Determination of glyphosate in groundwater samples using an ultrasensitive immunoassay and confirmation by on-line solid phase extraction followed by liquid chromatography coupled to tandem mass spectrometry”
Content Type Journal Article
Category Letter to the Editor
Pages 1-2
DOI 10.1007/s00216-012-6048-x
Authors
Josep Sanchís, Institute of Environmental Assessment and Water Research (IDAEA-CSIC), C/Jordi Girona, 18-26, 08034 Barcelona, Spain
Lina Kantiani, Institute of Environmental Assessment and Water Research (IDAEA-CSIC), C/Jordi Girona, 18-26, 08034 Barcelona, Spain
Marta Llorca, Institute of Environmental Assessment and Water Research (IDAEA-CSIC), C/Jordi Girona, 18-26, 08034 Barcelona, Spain
Fernando Rubio, Abraxis LLC, 54 Steam Whistle Drive, Warminster, PA 18974, USA
Antoni Ginebreda, Institute of Environmental Assessment and Water Research (IDAEA-CSIC), C/Jordi Girona, 18-26, 08034 Barcelona, Spain
Josep Fraile, Catalan Water Agency, Provença 204-208, 08036 Barcelona, Spain
Teresa Garrido, Catalan Water Agency, Provença 204-208, 08036 Barcelona, Spain
Marinella Farré, Institute of Environmental Assessment and Water Research (IDAEA-CSIC), C/Jordi Girona, 18-26, 08034 Barcelona, Spain
The analytical performances of a novel DNA-ligand system using the time-resolved fluorescence (TRF) response of ochratoxin
A (OTA)–terbium–DNA aptamer interaction were tested for the quantitative determination of OTA in wheat. Wheat was extracted
with acetonitrile/water (60:40, v/v) followed by clean-up through affinity columns containing a DNA-aptamer-based oligosorbent.
Then, OTA was detected by TRF spectroscopy after reaction with a terbium fluorescent solution containing the DNA-aptamer probe.
The entire procedure was performed in less than 30 min, including sample preparation, and allowed analysis of several samples
simultaneously with a 96-well microplate reader. The average recovery from samples spiked with 2.5-25 ?g kg?1 OTA was 77 %, with a relative standard deviation lower than 6 % and a quantification limit of 0.5 ?g kg?1. Comparative analyses of 29 naturally contaminated (up to 14 ?g kg-1) wheat samples using the aptamer-affinity column/TRF method or the immunoaffinity column/high-performance liquid chromatography
method showed good correlation (r?=?0.985) in the range tested. The trueness of the aptamer-based method was additionally assessed by analysis of two quality
control wheat materials for OTA. The DNA-ligand system is innovative, simple and rapid, and can be used to screen large quantities
of samples for OTA contamination at levels below the EU regulatory limit with analytical performances satisfying EU criteria
for method acceptability.
Content Type Journal Article
Category Original Paper
Pages 1-8
DOI 10.1007/s00216-012-6076-6
Authors
Annalisa De Girolamo, Institute of Sciences of Food Production (ISPA), National Research Council of Italy, Via G. Amendola 122/O, 70126 Bari, Italy
Linda Le, NeoVentures Biotechnology Inc, 516 Colborne Street, London, ON N6B 2T5, Canada
In eukaryotic organisms, sphingolipids are major structural lipids of biological membranes and perform additional essential
functions as signalling molecules. While long-chain bases (LCB), the common precursor to all sphingolipid classes, is represented
by only one major molecular species in animals and fungi, up to nine LCB have been found in plants. In the absence of genuine
plant sphingolipid references required for proper quantification, we have reinvestigated and optimized a protocol destined
to the quantification of total plant LCB that relies on the use of gas chromatography-mass spectrometry (GC-MS). This rapid
three-step protocol sequentially involves (1) the release of LCB from biological samples using barium hydroxide solution,
(2) their oxidation into aldehydes by metaperiodate, and (3) the subsequent identification/quantification of these aldehydes
by GC-MS. It is simple and reliable and enables separation of aldehydes upon their stero-specificity. It further enables the
quantification of total LCB from a wide variety of samples including yeast and animal cell cultures.
Figure Rationale for rapid LCB analysis by GC-MS
Content Type Journal Article
Category Original Paper
Pages 1-11
DOI 10.1007/s00216-012-6060-1
Authors
Jean-Luc Cacas, Laboratoire de Biogenèse Membranaire, UMR 5200 CNRS-Université Victor Segalen Bordeaux 2, 146 rue Léo Saignat, 33076 Bordeaux, France
Su Melser, Laboratoire de Biogenèse Membranaire, UMR 5200 CNRS-Université Victor Segalen Bordeaux 2, 146 rue Léo Saignat, 33076 Bordeaux, France
Frédéric Domergue, Laboratoire de Biogenèse Membranaire, UMR 5200 CNRS-Université Victor Segalen Bordeaux 2, 146 rue Léo Saignat, 33076 Bordeaux, France
Jérôme Joubès, Laboratoire de Biogenèse Membranaire, UMR 5200 CNRS-Université Victor Segalen Bordeaux 2, 146 rue Léo Saignat, 33076 Bordeaux, France
Brice Bourdenx, Laboratoire de Biogenèse Membranaire, UMR 5200 CNRS-Université Victor Segalen Bordeaux 2, 146 rue Léo Saignat, 33076 Bordeaux, France
Jean-Marie Schmitter, Chimie Biologie des Membranes et Nanoobjets (CBMN)-UMR 5248, Centre de Génomique Fonctionnelle, Université de Bordeaux, BP 68, Université Bordeaux 2-Victor Segalen, 146 rue Léo Saignat, 33076 Bordeaux Cedex, France
Sébastien Mongrand, Laboratoire de Biogenèse Membranaire, UMR 5200 CNRS-Université Victor Segalen Bordeaux 2, 146 rue Léo Saignat, 33076 Bordeaux, France
Computational simulation and Doehlert experimental optimization were done for the rational design of a core–shell molecularly
imprinted polymer (CS-MIP) for use in the highly selective separation of Tanshinone IIA (TSIIA) from the crude extracts of
Salvia miltiorrhiza Bunge (SMB). The functional monomer layer of the polymer shells directed the selective occurrence of imprinting polymerization
at the surface of silica through the copolymerization of vinyl end groups with functional monomers and also drove TSIIA templates
into the formed polymer shells through the charge–transfer complex interactions between TSIIA and the functional monomer layer.
As a result, the maximum rebinding capacity was achieved with the use of optimal grafting ratio by the Doehlert design. The
CS-MIP exhibited high recognition selectivity and binding affinity to TSIIA. When the imprinted particles were used as dispersive
solid phase extraction sorbents, the recovery yield of TSIIA reached 93 % by a one-step extraction from the crude extracts
of SMB, and the purity of TSIIA was larger than 98 % by HPLC analysis. These results show the possibility of a highly selective
separation and enrichment of TSIIA from the SMB using the TSIIA-imprinted core–shell molecularly imprinted polymers.
Content Type Journal Article
Category Original Paper
Pages 1-13
DOI 10.1007/s00216-012-6078-4
Authors
Xianjun Jia, School of Pharmacy, Nanjing Medical University, Nanjing, 210029 China
Hong Li, School of Pharmacy, Nanjing Medical University, Nanjing, 210029 China
Jing Luo, School of Pharmacy, Nanjing Medical University, Nanjing, 210029 China
Qing Lu, School of Pharmacy, Nanjing Medical University, Nanjing, 210029 China
Yan Peng, School of Pharmacy, Nanjing Medical University, Nanjing, 210029 China
Liying Shi, School of Pharmacy, Nanjing Medical University, Nanjing, 210029 China
Liping Liu, School of Pharmacy, Nanjing Medical University, Nanjing, 210029 China
Shuhu Du, School of Pharmacy, Nanjing Medical University, Nanjing, 210029 China
Guijun Zhang, School of Chinese Material Medica, Beijing University of Chinese Medicine, Beijing, 100102 China
Lina Chen, School of Pharmacy, Nanjing Medical University, Nanjing, 210029 China
Letter to the editor regarding “Determination of glyphosate in groundwater samples using an ultrasensitive immunoassay and confirmation by on-line solid phase extraction followed by liquid chromatography coupled to tandem mass spectrometry”
Content Type Journal Article
Category Letter to the Editor
Pages 1-2
DOI 10.1007/s00216-012-6046-z
Authors
Marie-Anne Reding, Monsanto Europe SA/NV, Regulatory Affairs, Brussels, Belgium
Budesonide (BUD) is a glucocorticoid widely used for the treatment of asthma, rhinitis, and inflammatory bowel disease. Its
use in sport competitions is prohibited when administered by oral, intravenous, intramuscular, or rectal routes. However,
topical preparations are not prohibited. Strategies to discriminate between legal and forbidden administrations have to be
developed by doping control laboratories. For this reason, metabolism of BUD has been re-evaluated using liquid chromatography–tandem
mass spectrometry (LC-MS/MS) with different scan methods. Urine samples obtained after oral administration of 3 mg of BUD
to two healthy volunteers have been analyzed for metabolite detection in free and glucuronide metabolic fractions. Structures
of the metabolites have been studied by LC-MS/MS using collision induced dissociation and gas chromatography–mass spectrometry
(GC/MS) in full scan mode with electron ionization. Combination of all structural information allowed the proposition of the
most comprehensive picture for BUD metabolism in humans to this date. Overall, 16 metabolites including ten previously unreported
compounds have been detected. The main metabolite is 16?-hydroxy-prednisolone resulting from the cleavage of the acetal group.
Other metabolites without the acetal group have been identified such as those resulting from reduction of C20 carbonyl group,
oxidation of the C11 hydroxyl group and reduction of the A ring. Metabolites maintaining the acetal group have also been identified,
resulting from 6-hydroxylation (6? and 6?-hydroxy-budesonide), 23-hydroxylation, reduction of C6-C7, oxidation of the C11
hydroxyl group, and reduction of the C20 carbonyl group. Metabolites were mainly excreted in the free fraction. All of them
were excreted in urine during the first 24 h after administration, and seven of them were still detected up to 48 h after
administration for both volunteers.
Content Type Journal Article
Category Original Paper
Pages 1-16
DOI 10.1007/s00216-012-6037-0
Authors
Xavier Matabosch, Bioanalysis Research Group, IMIM, Institut de Recerca Hospital del Mar, Doctor Aiguader 88, 08003 Barcelona, Spain
Oscar J. Pozo, Bioanalysis Research Group, IMIM, Institut de Recerca Hospital del Mar, Doctor Aiguader 88, 08003 Barcelona, Spain
Clara Pérez-Mañá, Human Pharmacology and Neurosciences Research Group, IMIM and UCIEC-IMIM-CAIBER, Doctor Aiguader 88, 08003 Barcelona, Spain
Magi Farré, Human Pharmacology and Neurosciences Research Group, IMIM and UCIEC-IMIM-CAIBER, Doctor Aiguader 88, 08003 Barcelona, Spain
Josep Marcos, Bioanalysis Research Group, IMIM, Institut de Recerca Hospital del Mar, Doctor Aiguader 88, 08003 Barcelona, Spain
Jordi Segura, Bioanalysis Research Group, IMIM, Institut de Recerca Hospital del Mar, Doctor Aiguader 88, 08003 Barcelona, Spain
Rosa Ventura, Bioanalysis Research Group, IMIM, Institut de Recerca Hospital del Mar, Doctor Aiguader 88, 08003 Barcelona, Spain
Analytical Challenges in Environmental and Geosciences
Content Type Journal Article
Category Editorial
Pages 1-2
DOI 10.1007/s00216-012-6059-7
Authors
Christian Zwiener, Environmental Analytical Chemistry, Center for Applied Geoscience (ZAG), Eberhard Karls University, Tübingen, Hoelderlinstraße 12, 72074 Tübingen, Germany
The aim of this study was to characterize self-assembled structures of guanosine derivatives in aqueous solutions by vibrational
circular dichroism (VCD) and electronic circular dichroism (ECD). Three guanosine derivatives were studied [5?-guanosine monophosphate
(GMP), diphosphate (GDP), and triphosphate (GTP)] using a broad range of concentrations and various metal/guanosine ratios.
VCD was used for the first time in this field and showed itself to be a powerful method for obtaining specific structural
information in solution. It can also help to determine the impact that the cations have, when added to the solution, on the
versatile structures of guanine derivatives in terms of their association and disassociation. Based on the markedly different
intensities and signs of the VCD signals observed for different concentrations of guanosine derivatives, we propose various
structures based on guanine quartets for high guanosine concentrations and high K+/guanosine ratios (i.e., columnar helical organization of the quartets, which are rearranged into a continuous helix). We
performed a degenerate coupled oscillator (DCO) calculation to interpret the VCD spectra obtained and how they vary during
the assembly of guanosine derivatives. The calculations correctly predicted the VCD spectra and enabled us to identify the
structures of the metal cation/guanosine monophosphate aggregates. ECD in the ultraviolet region was used as a diagnostic
tool to characterize the studied systems and as a contact point between the previously defined structures of the guanine derivative
assemblies and the molecular systems studied here. These studies revealed that the VCD technique is a powerful new method
for determining the structures of optically active guanosine motifs.
Figure Proposed geometries of the guanosine adducts, the corresponding spectra calculated by the degenerate coupled oscillator method,
and experimental vibrational circular dichroism spectra
Content Type Journal Article
Category Original Paper
Pages 1-10
DOI 10.1007/s00216-012-6014-7
Authors
Iryna Goncharova, Department of Analytical Chemistry, Institute of Chemical Technology, Prague, Technická 5, 166 28 Prague, Czech Republic
Jana Novotná, Department of Analytical Chemistry, Institute of Chemical Technology, Prague, Technická 5, 166 28 Prague, Czech Republic
Marie Urbanová, Department of Physics and Measurements, Institute of Chemical Technology, Prague, Technická 5, 166 28 Prague, Czech Republic
Field-flow fractionation (FFF) separates analytes by use of an axial channel-flow and a cross-field. Its soft separation capability
makes it an ideal tool for initial fractionation of complex mixtures, but large elution volumes and high flow rates have limited
its applicability without significant user handling. Recent advances in instrumentation and miniaturization have successfully
reduced channel size and elution speed, and thus the volume of each fraction, making it possible to conveniently couple FFF
with orthogonal separation techniques for improved resolution. More detailed analysis can also be performed on the fractions
generated by FFF by use of diverse analytical techniques, including MS, NMR, and even X-ray scattering. These developmental
trends have given FFF more power in the analysis of different types of molecule, and will be the direction of choice for further
advances in FFF technology.
Content Type Journal Article
Category Trends
Pages 1-8
DOI 10.1007/s00216-012-6069-5
Authors
Samantha Schachermeyer, Department of Chemistry, University of California, Riverside, CA 92521, USA
Jonathan Ashby, Department of Chemistry, University of California, Riverside, CA 92521, USA
Wenwan Zhong, Department of Chemistry, University of California, Riverside, CA 92521, USA
Mass spectra were obtained to evaluate the use of numerous single-cation and dicationic ionic liquids as stationary liquid
phases in GC/MS at high temperature. Background mass spectra and product ion mass spectra of several ions in the background
spectrum were obtained. Fragmentation mechanisms were propounded, including the detailed fragmentation pathway of the 1,2-dimethyl-3-propylimidazole
cation. The relation between temperature and the main signals in the mass spectra of ILs was studied.
Content Type Journal Article
Category Original Paper
Pages 1-10
DOI 10.1007/s00216-012-6020-9
Authors
M. V. Shashkov, Boreskov Institute of Catalysis SB RAS, pr. Lavrentieva 5, 630090 Novosibirsk, Russia
V. N. Sidelnikov, Boreskov Institute of Catalysis SB RAS, pr. Lavrentieva 5, 630090 Novosibirsk, Russia
The specific interaction of peptides with proteins is often a key factor which determines biological activities. The determination
of Kd values of such interactions is commonly performed with fluorescence polarization. However, fluorescence polarization assays
are prone to false-positive results due to the potential for non-specific interactions and only afford very low signal-to-background
ratios. Here, we present as an alternative a fluorescence resonance energy transfer based quenching assay to measure peptide–protein
interactions in solution. In a test setup where antimicrobial peptides were tested for their affinity towards the protein
DnaK, the assay provided high specificity and good reproducibility and correlated with the results obtained by fluorescence
polarization methods. Furthermore, we established a fast prescreening method which will allow a highly efficient screening
of peptide libraries by reducing the amount of sample by 98 % compared to conventional fluorescence polarization assays.
Content Type Journal Article
Category Original Paper
Pages 1-7
DOI 10.1007/s00216-012-6050-3
Authors
K. Dobslaff, Institute of Bioanalytical Chemistry, Faculty of Chemistry and Mineralogy and Center of Biotechnology and Biomedicine, Universität Leipzig, Deutscher Platz 5, 04103 Leipzig, Germany
T. Kreisig, Institute of Bioanalytical Chemistry, Faculty of Chemistry and Mineralogy and Center of Biotechnology and Biomedicine, Universität Leipzig, Deutscher Platz 5, 04103 Leipzig, Germany
N. Berthold, Institute of Bioanalytical Chemistry, Faculty of Chemistry and Mineralogy and Center of Biotechnology and Biomedicine, Universität Leipzig, Deutscher Platz 5, 04103 Leipzig, Germany
R. Hoffmann, Institute of Bioanalytical Chemistry, Faculty of Chemistry and Mineralogy and Center of Biotechnology and Biomedicine, Universität Leipzig, Deutscher Platz 5, 04103 Leipzig, Germany
T. Zuchner, Institute of Bioanalytical Chemistry, Faculty of Chemistry and Mineralogy and Center of Biotechnology and Biomedicine, Universität Leipzig, Deutscher Platz 5, 04103 Leipzig, Germany
Persistent organic pollutants are widely distributed in the environment and lots of toxicological data are available. However,
little is known on the intracellular fate of such compounds. Here a method applying secondary ion mass spectrometry is described
that can be used to visualize cellular localization of halogenated compounds and to semi-quantitatively calculate concentrations
of such compounds. Of the model compounds tested, TBBPA was homogenously distributed in the cell membrane of the H295R cells
while PFOS accumulated in very distinct locations in the cell membrane. Relative intracellular concentrations of 4-OH-BDE69
and 4-OH-BDE121 in GH3.TRE were 61 % and 18 %, respectively, compared to the parent compounds. These differences may partly
explain that observed effect concentrations for 4-OH-BDEs in in vitro experiments are usually lower than what would be expected
based on receptor binding studies. NanoSIMS50 proved to be a powerful tool to describe the cellular distribution of halogenated
compounds. The semi-quantitative data that can be obtained may help to further explain results from in vitro or in vivo experiments.
Content Type Journal Article
Category Original Paper
Pages 1-6
DOI 10.1007/s00216-012-6066-8
Authors
Arno C. Gutleb, Department Environment and Agro-biotechnologies (EVA), Centre de Recherche Public—Gabriel Lippmann, 41, rue de Brill, 4422 Belvaux, Luxembourg
Jaime Freitas, Toxicology Section, Wageningen University, Tuinlaan 5, 6703 HE Wageningen, The Netherlands
Albertinka J. Murk, Toxicology Section, Wageningen University, Tuinlaan 5, 6703 HE Wageningen, The Netherlands
Steven Verhaegen, Norwegian School of Veterinary Science, 0033 Oslo, Norway
Erik Ropstad, Norwegian School of Veterinary Science, 0033 Oslo, Norway
Thomas Udelhoven, Department Environment and Agro-biotechnologies (EVA), Centre de Recherche Public—Gabriel Lippmann, 41, rue de Brill, 4422 Belvaux, Luxembourg
Lucien Hoffmann, Department Environment and Agro-biotechnologies (EVA), Centre de Recherche Public—Gabriel Lippmann, 41, rue de Brill, 4422 Belvaux, Luxembourg
Jean-Nicolas Audinot, Département Science et Analyse des Matériaux (SAM), Centre de Recherche Public—Gabriel Lippmann, 41, rue de Brill, 4422 Belvaux, Luxembourg
Anthelmintic drugs are used in clinical and veterinary practice for the treatment of infections caused by parasitic worms.
Their extensive use in food-producing animals can cause the presence of residues in food. For consumer protection it is necessary
to monitor the levels of anthelmintic residues to ensure that they remain within the legally permitted maximum acceptable
concentrations. For this purpose, the use of multiplex screening methods is advantageous. Biochip array technology allows
the simultaneous determination of multiple analytes from a single sample at a single point in time. This study reports the
development of an Evidence biochip array for the multiplex screening of anthelmintic drugs. Simultaneous competitive chemiluminescent
immunoassays are employed. The solid support and vessel is the biochip, which contains an array of discrete test sites. The
assays were applied to the semiautomated bench-top analyser Evidence Investigator. The aminobenzimidazoles assay detected
aminomebendazole, albendazole 2-aminosulphone and aminoflubendazole, the avermectins assay detected emamectin benzoate, eprinomectin,
abamectin, ivermectin and doramectin, the benzimidazoles assay detected albendazole sulphone, albendazole, albendazole sulphoxide,
oxibendazole, oxfendazole and flubendazole, the thiabendazole assay detected cambendazole, thiabendazole and 5-hydroxythiabendazole
and the triclabendazole assay detected ketotriclabendazole, triclabendazole and triclabendazole sulphoxide. The limits of
detection ranged from 0.3 ppb (aminobenzimidazoles) to 2.0 ppb (levamisole) in milk and from 0.15 ppb (aminobenzimidazoles)
to 6.5 ppb (levamisole) in tissue. The average recovery range was 71–135 %. This multianalytical approach on a biochip platform
is applicable to the screening of more than 20 anthelmintic drugs in different food matrices, leading to consolidation of
tests and enhancement of the test result output.
Content Type Journal Article
Category Original Paper
Pages 1-6
DOI 10.1007/s00216-012-5995-6
Authors
J. Porter, Randox Food Diagnostics, 55 Diamond Road, Crumlin, Co. Antrim BT29 4QY, UK
N. O’Loan, Randox Food Diagnostics, 55 Diamond Road, Crumlin, Co. Antrim BT29 4QY, UK
B. Bell, Randox Food Diagnostics, 55 Diamond Road, Crumlin, Co. Antrim BT29 4QY, UK
J. Mahoney, Randox Food Diagnostics, 55 Diamond Road, Crumlin, Co. Antrim BT29 4QY, UK
M. McGarrity, Randox Food Diagnostics, 55 Diamond Road, Crumlin, Co. Antrim BT29 4QY, UK
R. I. McConnell, Randox Food Diagnostics, 55 Diamond Road, Crumlin, Co. Antrim BT29 4QY, UK
S. P. Fitzgerald, Randox Food Diagnostics, 55 Diamond Road, Crumlin, Co. Antrim BT29 4QY, UK
We describe the use of hair roots as a matrix for detection of methamphetamine (MP) and 3,4-methylenedioxymethamphetamine
(MDMA) abuse. The concentration of drugs was determined in rat hair roots, hair shafts, and plasma after a single administration
of MP or MDMA, by use of an HPLC–peroxyoxalate chemiluminescence (PO-CL) method involving column switching. Plasma and hair
roots and shafts were collected from male Wistar rats before and after administration of MP (10 mg kg?1, i.p.). In addition, the roots and shafts of pigmented and non-pigmented hair of male Lister hooded rats were collected after
administration of MDMA (10 mg kg?1, i.p.). The concentrations of MP and MDMA in plasma and hair were determined by use of the HPLC–PO-CL method, with satisfactory
sensitivity and reproducibility. The concentration of MP in hair roots 1–14 days after administration ranged from 0.038 to
0.115 ng mg?1 (n?=?3). By use of the HPLC–PO-CL method, MP could be detected in hair roots for longer (up to 14 days) than it could be detected
in conventional biological specimens, for example plasma (~1 day), and MDMA was detected in hair roots from 1 to 10 days after
administration. The AUC1–10 (ng day mg?1) for MDMA in roots of non-pigmented and pigmented hair was comparable (4.93?±?2.09 vs. 6.67?±?1.28, n?=?3), whereas AUC1–14 for hair shafts differed significantly (1.86?±?0.93 vs. 4.58?±?0.63, P?<?0.05, n?=?3). The window for detecting MP (or MDMA) in hair roots under our conditions was 1–14 (or 1–10) days.
Content Type Journal Article
Category Short Communication
Pages 1-8
DOI 10.1007/s00216-012-6054-z
Authors
Mitsuhiro Wada, Graduate School of Biomedical Sciences, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki, 852-8521 Japan
Yuko Ochi, Graduate School of Biomedical Sciences, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki, 852-8521 Japan
Kumi Nogami, Graduate School of Biomedical Sciences, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki, 852-8521 Japan
Rie Ikeda, Graduate School of Biomedical Sciences, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki, 852-8521 Japan
Naotaka Kuroda, Graduate School of Biomedical Sciences, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki, 852-8521 Japan
Kenichiro Nakashima, Graduate School of Biomedical Sciences, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki, 852-8521 Japan
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