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1.
The derivatization of cysteine-containing peptides with benzoquinone compounds is rapid, quantitative and specific in acidic
media. The conversion of cysteines into hydrophobic benzoquinone-adducted residues in peptides is used here to alter the chromatographic
properties of cysteinyl peptides during liquid chromatography separation. The benzoquinone derivatization is shown to allow
the accurate selection of cysteine-containing peptides of bovine serum albumin tryptic digest by diagonal reversed-phase chromatography,
which consists of one primary and a series of secondary identical liquid chromatographic separations, before and after a cysteinyl-targeted
modification of the peptides by benzoquinone compounds.
Figure Diagonal chromatographic selection of cysteinyl peptides modified with benzoquinones
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
2.
Zaher M Ravelet C Baussanne I Ravel A Grosset C Décout JL Peyrin E 《Analytical and bioanalytical chemistry》2009,393(2):655-660
In this paper, we describe the preparation and the evaluation of a porous graphitic carbon (PGC) column coated with a new
dinaphthyl derivative of neamine for chiral ligand-exchange (LE) chromatography. It was shown that the graphitic surface/dinaphthyl
anchor system efficiently (1.15 μmol/m2) and stably (three months of intensive use) adsorbs the neamine template onto the chromatographic support. The resulting
coated PGC stationary phase showed appreciable LE-based enantioselective properties towards several native amino acids.
Chromatographic separation of methionine enantiomers using a dinaphtyl neamine-based ligand-exchange chiral stationary phase 相似文献
3.
Highly efficient analysis of underivatized carbohydrates using monolithic-silica-based capillary hydrophilic interaction (HILIC) HPLC 总被引:1,自引:1,他引:0
Ikegami T Horie K Saad N Hosoya K Fiehn O Tanaka N 《Analytical and bioanalytical chemistry》2008,391(7):2533-2542
A polyacrylamide (PAAm)-modified monolithic silica capillary column of increased phase ratio, 200T-PAAm, for hydrophilic interaction
liquid chromatography (HILIC) was prepared. The column showed high separation efficiency, with a theoretical plate height
H = 7–20 μm at a linear velocity, u = 1–7 mm/s. From a kinetic plot analysis, it was expected that the monolithic column could provide three times faster separation
than particle-packed HILIC columns under a pressure limit at 20 MPa. HILIC coupled with electrospray ionization (ESI)–mass
spectrometry (HILIC-ESI-MS) using the 200T-PAAm column was employed for the analysis of underivatized carbohydrates to achieve
fast and efficient separations of mixtures containing mono-, di-, and trisaccharides within 5 min. Under single MS full scan
mode, 200 pg of oligosaccharides was detected by the system. The limit of detection (LOD) of the LC-ESI-MS/MS system was determined
using selected reaction monitoring (SRM) to be as low as 3.2 ng/mL (attomol level) for nonreducing saccharides. The system
was successfully applied to the detection of disaccharides in extracts of plant, such as corn, soybean, and Arabidopsis thaliana.
Figure HILIC-ESI-MS provides a high-efficiency separation and sensitive detection of underivatized carbohydrate oligomers, e.g.,
the homologs of glucose (1) up to maltoheptaose (7) 相似文献
4.
Pérez Pavón JL García Pinto C Guerrero Peña A Moreno Cordero B 《Analytical and bioanalytical chemistry》2008,391(2):599-607
In the present work we report the results obtained with a methodology based on direct coupling of a headspace generator to
a mass spectrometer for the identification of different types of petroleum crudes in polluted soils. With no prior treatment,
the samples are subjected to the headspace generation process and the volatiles generated are introduced directly into the
mass spectrometer, thereby obtaining a fingerprint of volatiles in the sample analysed. The mass spectrum corresponding to
the mass/charge ratios (m/z) contains the information related to the composition of the headspace and is used as the analytical signal for the characterization
of the samples. The signals obtained for the different samples were treated by chemometric techniques to obtain the desired
information. The main advantage of the proposed methodology is that no prior chromatographic separation and no sample manipulation
are required. The method is rapid, simple and, in view of the results, highly promising for the implementation of a new approach
for oil spill identification in soils.
Figure PCA score plots illustrate clear discrimination of types of crude oil in polluted soil samples (e.g. results are shown for
vertisol) 相似文献
5.
Christian V. Hoffmann Michael Lämmerhofer Wolfgang Lindner 《Analytical and bioanalytical chemistry》2009,393(4):1257-1265
A recently reported chiral strong cation exchanger (cSCX) type stationary phase was investigated for the LC separation of
a series of Cinchona alkaloids and synthetic derivatives thereof to test its usefulness as alternative methodology for the separation of those
important pharmaceuticals. The cSCX column-packing material was qualitatively compared on the one hand against a commercially
available non-enantioselective SCX-material, PolySulfoethyl-A, and, on the other hand, against a modern C18 reversed-phase
stationary phase which is commonly employed for Cinchona alkaloid analysis. Both SCX columns showed no pronounced peak-tailing phenomena which typically hamper Cinchona alkaloid RP analysis and require specific optimization. Thus, the cSCX-based assay provided new feasibilities for the separation
of the Cinchona alkaloids in polar organic mode as opposed to conventional reversed-phase methodologies. In particular, a method for the
simultaneous determination of eight Cinchona alkaloids (quinine, quinidine, cinchonine, cinchonidine, and their corresponding dihydro analogs) using the cSCX column in
HPLC has been developed and exemplarily applied to impurity profiling of a commercial alkaloid sample. Furthermore, both SCX
materials allowed successful separation of C9-epi and 10,11-didehydro derivatives from their respective educts in an application
in synthetic Cinchona alkaloid chemistry.
Figure An alternative separation principle - HPLC separation of strongly basic natural Cinchona alkaloids and synthetic derivatives thereof by means of a strong cation-exchanger type chiral stationary phase 相似文献
6.
Playing tag with quantitative proteomics 总被引:1,自引:0,他引:1
There is steady need for new proteomic strategies on quantitative measurements that provide essential components for detailing
dynamic changes in many cellular functions and processes. Stable isotope labeling is a rapidly evolving field, which can be
used either after protein extraction with chemical labeling, or in cell culture with metabolic incorporation. In this review,
we explore the most frequently utilized quantitation techniques with particular attention paid to chemical labeling using
different isotopic tags, including a recent labeling strategy—soluble polymer-based isotopic labeling (SoPIL)—that achieves
efficient labeling in homogeneous conditions. Special care should be devoted to the selection of appropriate quantitation
approaches according to the needs of the sample and overall experimental design. We evaluate recent advances in quantitative
proteomics using stable isotope labeling and their applications to current insightful biological inquiries.
Figure Chemical modules of isotopic tags for quantitative proteomics. 相似文献
7.
The use of polymers in microchip fabrication affords new opportunities for the development of powerful, miniaturized separation
techniques. One method in particular, the use of phase-changing sacrificial layers, allows for simplified designs and many
additional features to the now standard fabrication of microchips. With the possibility of adding a third dimension to the
design of separation devices, various means of enhancing analysis now become possible. The application of phase-changing sacrificial
layers in microchip analysis systems is discussed, both in terms of current uses and future possibilities.
Figure Phase-changing sacrificial materials enable multilayer microfluidic device layouts 相似文献
8.
A rapid and effective method was developed for the chiral separation of raltitrexed (RD) enantiomers by carboxymethyl-beta-cyclodextrin
(CM-β-CD)-modified micellar electrokinetic chromatography (MEKC). Optimization of conditions including the type and concentration
of the chiral selector, concentration of sodium dodecyl sulfate (SDS), pH and concentration of the background electrolyte
(BGE), capillary temperature, and applied voltage was investigated. The enantiomers of raltitrexed could be separated with
satisfactory resolution and linear response by using 75 mM Tris-phosphate at pH 8.0 containing 30 mM SDS and 8 mM CM-β-CD
as buffer system. Furthermore, the usefulness of this method was demonstrated in a purity test of a real synthetic drug sample.
Figure Chiral separation of raltitrexed by CM-β-CD MEKC was optimized and applied to test the purity of a synthetic drug sample 相似文献
9.
Raczyńska ED Gal JF Maria PC Zientara K Szelag M 《Analytical and bioanalytical chemistry》2007,389(5):1365-1380
Fourier transform ion cyclotron resonance mass spectrometry, combined with modern ionization (fast atom bombardment , electrospray
ionization, matrix-assisted laser desorption–ionization), fragmentation (collision-induced dissociation, surface-induced dissociation,
one-photon ultraviolet photodissociation, infrared multiphoton dissociation, blackbody infrared radiative dissociation, electron-capture
dissociation), and separation (high-performance liquid chromatography, liquid chromatography, capillary electrophoresis) techniques
is now becoming one of the most attractive and frequently used instrumental platforms for gas-phase studies of biomolecules
such as amino acids, bioamines, peptides, polypeptides, proteins, nucleobases, nucleosides, nucleotides, polynucleotides,
nucleic acids, saccharides, polysaccharides, etc. Since it gives the possibilities to trap the ions from a few seconds up
to thousands of seconds, it is often applied to study ion/molecule reactions in the gas phase, particularly proton-transfer
reactions which provide important information on acid–base properties. These properties determine in part the three-dimensional
structure of biomolecules, most of their intramolecular and intermolecular interactions, and consequently their biological
activity. They also indicate the form (unionized, zwitterionic, protonated, or deprotonated) which the biomolecule may take
in a nonpolar environment.
Figure Biomolecules in the gas-phase acidity-basicity scale 相似文献
10.
András Gergely Péter Horváth György Szász Gábor Veress 《Analytical and bioanalytical chemistry》2009,394(8):2105-2109
A three-step gradient reversed-phase high-performance liquid chromatography (RP-HPLC) method was developed for the separation
of dehydroepiandrosterone (DHEA), its sulfate ester (DHEA-S), its three C7-oxidized metabolites (7αOH-DHEA, 7βOH-DHEA, 7-keto-DHEA),
and its biosynthetic congeners (androstenedione, testosterone, estradiol, pregnenolone). This new method allows the quantitative
characterization of DHEA metabolism and biosynthetic transformation under given physiological, pathological, or therapeutically
influenced circumstances. Tetrahydrofuran probably acts as a proton acceptor coadsorbent, while isopropanol behaves as a proton
donor during the separation of testosterone, estradiol, and the stereoisomers of 7-OH-DHEA.
Figure Optimized gradient RP-HPLC results in full separation of DHEA from its biosynthetic congeners and metabolites 相似文献
11.
Two-dimensional liquid chromatography of synthetic polymers 总被引:2,自引:0,他引:2
Dušan Berek 《Analytical and bioanalytical chemistry》2010,396(1):421-441
Two-dimensional liquid chromatography, 2D-LC of synthetic polymers is critically assessed. Similarities and differences of
2D-LC of low-molecular-mass and polymeric substances are reviewed. The rationale of application of 2D-LC to macromolecular
substances is discussed. Basic information on retention mechanisms in liquid chromatography of synthetic polymers is furnished.
The principles, reasons, and significance of coupling of retention mechanisms are explained. The resulting separation processes
are elucidated, and the technical concepts of the corresponding experimental arrangements are described. The benefits of 2D-LC
are demonstrated together with numerous problems and shortcomings of the method.
相似文献
12.
Kallio M Jussila M Raimi P Hyötyläinen T 《Analytical and bioanalytical chemistry》2008,391(6):2357-2363
A previously constructed semi-rotating cryogenic modulator was modified for comprehensive two-dimensional gas chromatography
(GC×GC). The retention time repeatability was improved by replacing the modulator control program unit with a new system.
Peak widths obtained with the modified modulator were comparable with those obtained with the previous modulator and other
modulator types. The modulator was easy to construct and it can be installed in any commercial GC system. The constructed
GC×GC–FID system and data obtained by gas chromatography–mass spectrometry (GC–MS) were used for identification of unknowns
in forest aerosol samples.
Figure A semi-rotating cryogenic modulator in which modulation is based on two-step cryogenic trapping with continuously flowing
carbon dioxide has been developed for comprehensive two-dimensional gas chromatography 相似文献
13.
Kang DY Kim MJ Kim ST Oh KS Yuk SH Lee S 《Analytical and bioanalytical chemistry》2008,390(8):2183-2188
Asymmetrical flow field-flow fractionation (AsFlFFF) was used to determine the size distribution of drug-loaded core/shell
nanoparticles which have a lipid core of lecithin and a polymeric shell of a Pluronic. AsFlFFF provided separation of the
drug-loaded core/shell nanoparticles from smaller coreless polymeric micelles, thus allowing accurate size analysis of the
drug-loaded nanoparticles without interference by the coreless micelles. It was found from AsFlFFF that the drug-loaded nanoparticles
have broad size distributions ranging from 100 to 600 nm in diameter. It was also found that, after the nanoparticles had
been stored for 70 days, they disappeared as a result of self-degradation. Being a separation technique, AsFlFFF seems to
be more useful than transmission electron microscopy or dynamic light scattering for size analysis of core/shell nanoparticles,
which have broad and bimodal size distributions.
Figure Separation by AsFlFFF 相似文献
14.
Brambilla R Pinto CF Miranda MS dos Santos JH 《Analytical and bioanalytical chemistry》2008,391(7):2673-2681
A series of octadecylsilane-modified silicas were prepared by sol-gel and grafting methods. Carbon contents and octadecyl
chain conformations were shown to depend on the preparative route. Grafting engenders a low carbon content and a liquid-like
chain conformation, while the sol-gel method affords a much higher carbon content and a crystalline conformation. The relationships
between the toluene adsorption of the hybrid silicas and their chain conformations, their carbon contents and their textural
characteristics are discussed. These sorbents, when used in combination with ultraviolet diffuse reflectance spectroscopy
(UV DRS), can be employed as a rapid screening method for detection of aromatic compounds in water and air environmental matrices.
Figure Octadecylsilane-modified silicas in the adsorption of toluene 相似文献
15.
A novel on-column sequential preconcentration method based on the combination of field-amplified sample injection induced
by acetonitrile and pseudo isotachophoresis (ITP)–acid stacking is developed for simply but efficiently concentrating alkaloid
cations in a high-salt sample matrix in capillary electrophoresis. Acetonitrile (70%) added to a sample solution with a high-salt
sample matrix not only induces field-amplified sample stacking by decreasing conductivity but also acts as a termination reagent
in the succeeding pseudo ITP. After sample injection had been completed, a plug of H+ was injected electrokinetically and a neutralization reaction between H+ and tartrate from the buffer solution produced a low conductivity zone, in which the injected analyte cations were further
concentrated. With the sequential preconcentration method, a 3 orders of magnitude detection sensitivity (1,400-fold) increase
could be observed compared with the conventional electrokinetic injection method, without compromising separation efficiency
and peak shape, and detection limits of 0.1 ng/mL for myosmine and 0.3 ng/mL for anabasine with the conditions selected were
achieved. The calibration curves demonstrated good linearity in the concentration ranges 1.3–600 ng/mL for myosmine and 4.9–900 ng/mL
for anabasine, respectively. The proposed method has been used to analyze successfully trace alkaloids in cigarette samples.
Figure Sequential preconcentration processes: a sample injection; b introduction of HCl; c capillary zone electrophoresis separation. A
−
tartrate, white circles acetonitrile, black circles Na+, sample zone, myosmine, anabasine 相似文献
16.
Rosenberg E 《Analytical and bioanalytical chemistry》2008,391(1):33-57
This review discusses the characterisation of natural organic dyestuffs of historical interest by liquid chromatography–mass
spectrometry. The structures of the most important natural organic dyestuffs traditionally used are presented and discussed
from the perspective of their analytical chemical determination. The practical aspects of the determination of this inhomogeneous
range of compounds with different structures, such as anthraquinones, flavonoids, indigoids or tannins, are discussed with
their implications for sample preparation, liquid chromatographic separation and mass spectrometric detection. The particular
focus of this review is the discussion of the mass spectral fragmentation patterns of the different classes of natural organic
dyestuffs, which in the ideal case allow the identification of the dyestuff actually used, and thereby provide a key to the
better characterisation and understanding of historical objects dyed with natural organic dyestuffs.
Figure LC-MS allows characterisation of natural dyestuff constituents: the MS spectrum of alizarin is superimposed over a photo of
a textile coloured using this red dye 相似文献
17.
Bai LP Cai Z Zhao ZZ Nakatani K Jiang ZH 《Analytical and bioanalytical chemistry》2008,392(4):709-716
Spectrofluorometric titration, electrospray ionization time-of-flight mass spectrometric and UV melting methods were employed
to study the binding of chelerythrine and sanguinarine to bulged DNA. The results showed that both alkaloids bind specifically
to single pyrimidine (C, T) bulge sites. The ability of sanguinarine to bind to both regular and bulged hairpins was found
to be stronger than that of chelerythrine, but the binding selectivity of chelerythrine toward single-base bulges was much
larger than that of sanguinarine.
Figure Association constants for chelerythrine and sanguinarine toward regular and single-base bulged hairpins obtained from fluorometric
analysis 相似文献
18.
The membrane proteomes of a wild-type Corynebacterium glutamicum and an L-lysine-producing strain were quantitatively analyzed by two complementary proteomics techniques—anion exchange chromatography
AIEC/SDS-PAGE and 16BAC-PAGE/SDS-PAGE—and the results were compared. Although both techniques allow for the fast screening
of differences in protein abundance, AIEC/SDS-PAGE was superior to 16BAC-PAGE/SDS-PAGE with respect to protein separation,
it was more suitable for relative protein quantification, and allowed more differentially regulated proteins to be detected
(the succinate dehydrogenase complex, an ABC-type cobalamin/Fe3+ siderophore transport system, the maltose binding protein, and a subunit of the cytochrome bc-aa3 supercomplex were upregulated, while a periplasmic component of an ABC-type transporter and an iron-regulated ABC-type transporter
were downregulated in the producer). The results indicate the important role of tricarboxylic acid cycle enzymes as well as
the adaptation of transport processes in L-lysine-producing cells. Since the only genetic differences between the wild type and the L-lysine producer occur between four central metabolic enzymes in the cytoplasm, our study illustrates the complex effects
of metabolic engineering on cell physiology and the power of the new AIEC/SDS-PAGE proteomics approach to detect these effects.
相似文献
19.
Webb A 《Analytical and bioanalytical chemistry》2007,388(3):525-528
Figure Schematic diagram of a typical arrangement used for hyphenating chemical microseparations (e.g. capillary HPLC, CE, or CEC)
with microcoil NMR detection 相似文献