preparation-of-homogeneous-maldi-samples-for-quantitative-applications

Preparation of Homogeneous MALDI Samples for Quantitative Applications

This protocol demonstrates a simple sample preparation to reduce spatial heterogeneity in ion signals during matrix-assisted laser desorption/ionization ...

an-efficient-sample-preparation-method-to-enhance-carbohydrate-ion

An Efficient Sample Preparation Method to Enhance Carbohydrate Ion Signals in Matrix-assisted Laser Desorption/Ionization Mass Spectrometry

Sample preparation is a critical process in mass spectrometry (MS) analysis of carbohydrates. Although matrix-assisted laser desorption/ionization (MALDI) ...

A method for the rapid screening and determination of amphetamine-type designer drugs in saliva by a novel nib-assisted paper spray-mass spectrometry procedure is described. Under optimized conditions, the limit of detections for amphetamine derivatives (model samples: o-, m-, p-chloroamphetamine and o-, m-, p-fluoroamphetamine, respectively) were determined to 0.1 μg/mL by the nib-assisted paper spray-mass spectrometry method. This method is easier and has a higher sensitivity than similar methodologies, including atmospheric pressure/matrix-assisted laser desorption ionization mass spectrometry and electrospray-assisted laser desorption ionization/mass spectrometry. Data obtained using more classical separation methods, including liquid chromatography and capillary electrophoresis, are also reported.

Rapid screening and determination of designer drugs in saliva by a nib-assisted paper spray-mass spectrometry and separation technique.

A novel drug-screening system, consisting of paper spray-MS (PS-MS) and a CE-ESI-MS method was developed. This system can be easily switched either to PS-MS for rapidly screening samples or to the traditional CE-ESI-MS method for separation and to obtain detailed mass spectral information, while sharing the same mass spectrometer. In the former case, when a sharp (15°-tip) chromatography paper was used, the optimized distance from the paper tip to the mass inlet was 7.7 mm, whereas the optimized distance for the CE-ESI tip was ∼13.5 mm. Using 4-chloroamphetamine as a model compound, the LODs for PS-MS and CE-ESI-MS were determined to ∼0.1 and 0.25 ppm, respectively. Comparisons of results obtained using PS-MS and CE-ESI-MS and the experimental conditions are described.

Rapid screening and determination of 4-chloroamphetamine in saliva by paper spray-mass spectrometry and capillary electrophoresis-mass spectrometry.

Diamond nanoparticles (DNPs) were incorporated into matrix-assisted laser desorption/ionization (MALDI) samples to enhance the sensitivity of the mass spectrometer to carbohydrates. The DNPs optimize the MALDI sample morphology and thermalize the samples for thermally labile compounds because they have a high thermal conductivity, a low extinction coefficient in UV-vis spectral range, and stable chemical properties. The best enhancement effect was achieved when matrix, DNP, and carbohydrate solutions were deposited and vacuum-dried consecutively to form a trilayer sample morphology. It allows the direct identification of underivatized carbohydrates mixed with equal amount of proteins because no increase in the ion abundance of proteins was achieved. For dextran with an average molecular weight of 1500, the trilayer method typically improves the sensitivity by 79- and 7-fold in comparison to the conventional dried-droplet and thin-layer methods, respectively.

Selective enhancement of carbohydrate ion abundances by diamond nanoparticles for mass spectrometric analysis.

A microwave-assisted fluorescence labeling method for use in CE-LIF (capillary electrophoresis-laser induced fluorescence) is described. Six amphetamine-like designer drugs, namely, o-, m-, p-chloro- and o-, m-, p-fluoro-amphetamine derivatives, were synthesized and used as model compounds. FITC (fluorescein isothiocyanate isomer I) and a blue-laser were used as the fluorescent labeling reagent and excitation source, respectively. When a microwave oven was used, the reaction was complete within ∼5 min, while the classical method required at least 20 h (usually, an overnight reaction). A mimic oral fluid sample was obtained by spiking oral fluid from a volunteer with the six standards, and after liquid-liquid extraction and microwave-derivatization, it was possible to process the analytes by CE-LIF within a period of ∼10 min; the wavelength of the blue-laser used was 473 nm. For comparison, data obtained using classical methods, including CZE-UV (capillary zone electrophoresis-UV absorbance detection), sweeping-MEKC-UV (micellar electrokinetic chromatography-UV absorbance detection) and LC-Q-TOFMS (liquid chromatography/electrospray ionization quadrupole time-of-flight mass spectrometry) are also reported.

A microwave-assisted fluorescent labeling method for the separation and detection of amphetamine-like designer drugs by capillary electrophoresis.

This work demonstrates a method to prepare homogeneous distributions of analytes to improve data reproducibility in matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS). Natural-air drying processes normally result in unwanted heterogeneous spatial distributions of analytes in MALDI crystals and make quantitative analysis difficult. This study demonstrates that inducing Marangoni flows within drying droplets can significantly reduce the heterogeneity problem. The Marangoni flows are accelerated by changing substrate temperatures to create temperature gradients across droplets. Such hydrodynamic flows are analyzed semi-empirically. Using imaging mass spectrometry, changes of heterogeneity of molecules with the change of substrate temperature during drying processes are demonstrated. The observed heterogeneities of the biomolecules reduce as predicted Marangoni velocities increase. In comparison to conventional methods, drying droplets on a 5 °C substrate while keeping the surroundings at ambient conditions typically reduces the heterogeneity of biomolecular ions by 65%-80%. The observation suggests that decreasing substrate temperature during droplet drying processes is a simple and effective means to reduce analyte heterogeneity for quantitative applications. Graphical Abstract ᅟ.

Reducing Spatial Heterogeneity of MALDI Samples with Marangoni Flows During Sample Preparation.

Carbohydrate analysis is challenging due to lack of sensitive detection and efficient separation methods. Although matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) is a sensitive tool, the low ionization efficiency of carbohydrates makes mass analyses inefficient. This work systematically examines the correlation between MALDI-MS sensitivity and carbohydrate sample morphology. Depending on the properties of the matrix used, the morphology changes through sample recrystallization after drying or imposition of hydrodynamic flows during droplet drying. Observation shows that amorphous solids and finer crystals offer higher carbohydrate sensitivity and spatial homogeneity than larger crystals. Clear evidences of an inverse correlation between sensitivity and crystal size are obtained when various kinds of carbohydrates are mixed with different matrixes. Similar experiments on proteins and peptides showed a negative or negligible effect. The result serves as a general guideline for improving efficiency in routine carbohydrate analysis.

ArticleTotal : 2	Year
Publication title Cited by 8	2016
Publication title Cited by 3	2018

Article	Year
Rapid screening and determination of designer drugs in saliva by a nib-assisted paper spray-mass spectrometry and separation technique. Journal of separation science\| PubMed ID: 22949336	2012
Rapid screening and determination of 4-chloroamphetamine in saliva by paper spray-mass spectrometry and capillary electrophoresis-mass spectrometry. Electrophoresis\| PubMed ID: 23002016	2012
Selective enhancement of carbohydrate ion abundances by diamond nanoparticles for mass spectrometric analysis. Analytical chemistry\| PubMed ID: 23496007	2013
A microwave-assisted fluorescent labeling method for the separation and detection of amphetamine-like designer drugs by capillary electrophoresis. Forensic science international\| PubMed ID: 23597745	2013
Reducing Spatial Heterogeneity of MALDI Samples with Marangoni Flows During Sample Preparation. Journal of the American Society for Mass Spectrometry\| PubMed ID: 27126469	2016
Enhancing carbohydrate ion yield by controlling crystalline structures in matrix-assisted laser desorption/ionization mass spectrometry. Analytica chimica acta\| PubMed ID: 29126468	2017

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