Ionization Polarity as a Cause of Matrix Effects, its Removal and Estimation in ESI-LC-MS/MS Bio-analysis

Ghosh, Chinmoy; Shinde, Chandrakant P.; Chakraborty, Bhaswat S.

doi:10.4172/2155-9872.1000106

Cited by 19 publications

(15 citation statements)

References 28 publications

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“…Ghosh et al (2010) demonstrated this by investigating the role of ionization polarity on matrix effects. They analyzed enalapril and its metabolite enalaprilat in positive and negative polarity by using ESI-LC-MS/MS.…”

Section: Matrix Effects In Liquid Chromatography-mass Spectrometrymentioning

confidence: 98%

“…Plasma was used as the working matrix. The results showed approximately 30-35% ion suppression in positive polarity for both analytes, but approximately 20% ion suppression for enalapril and 10% ion enhancement for enalaprilat in negative polarity (Ghosh, Shinde et al 2010). A lesser degree of matrix effects in negative polarity may be explained by the fact that there are a fewer number of compounds forming negative ions in the negative mode, in comparison to in the positive mode, thus reducing the competition among ions to receive charge (Antignac, de Wasch et al 2005).…”

Section: Matrix Effects In Liquid Chromatography-mass Spectrometrymentioning

confidence: 99%

See 1 more Smart Citation

Biological Matrix Effects in Quantitative Tandem Mass Spectrometry-Based Analytical Methods: Advancing Biomonitoring

Panuwet

Hunter

DʼSouza

et al. 2015

Critical Reviews in Analytical Chemistry

289

190

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The ability to quantify levels of target analytes in biological samples accurately and precisely, in biomonitoring, involves the use of highly sensitive and selective instrumentation such as tandem mass spectrometers and a thorough understanding of highly variable matrix effects. Typically, matrix effects are caused by co-eluting matrix components that alter the ionization of target analytes as well as the chromatographic response of target analytes, leading to reduced or increased sensitivity of the analysis. Thus, before the desired accuracy and precision standards of laboratory data are achieved, these effects must be characterized and controlled. Here we present our review and observations of matrix effects encountered during the validation and implementation of tandem mass spectrometry-based analytical methods. We also provide systematic, comprehensive laboratory strategies needed to control challenges posed by matrix effects in order to ensure delivery of the most accurate data for biomonitoring studies assessing exposure to environmental toxicants.

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Section: Matrix Effects In Liquid Chromatography-mass Spectrometrymentioning

confidence: 98%

Section: Matrix Effects In Liquid Chromatography-mass Spectrometrymentioning

confidence: 99%

Biological Matrix Effects in Quantitative Tandem Mass Spectrometry-Based Analytical Methods: Advancing Biomonitoring

Panuwet

Hunter

DʼSouza

et al. 2015

Critical Reviews in Analytical Chemistry

289

190

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show abstract

“…The evaluation of the method was performed using a dilute acid pretreated biomass hydrolysate containing a complex mixture of innumerable compounds [ 8 , 9 ]. Co-eluting compounds can potentially cause signal suppression or enhancement [ 41 ] and influence the detection and quantification of the organic acids. It is known that dilute acid hydrolysate in general is rich, for example, in monosaccharides and their degradation products as well as acetic acid; these compounds can exceed the concentrations of the other organic acids by a factor of up to 1,000.…”

Section: Resultsmentioning

confidence: 99%

“…A higher analyte signal compared to the calibration sample is referred to as “ion enhancement” and is a matrix effect caused by co-eluting compounds influencing the ionization of the compound in the MS ion source. A possible cause for ion enhancement is, for example, if the standard/calibration mixture contains a larger number (or larger amount) of co-eluting compounds than the sample [ 41 ] (thus, ionization is enhanced in the “cleaner” sample matrix). In the case of hydrolysate, this was excluded, since glyoxylic acid, malic acid, and malonic acid elute in a region where the most abundant hydrolysate component (xylose) also appears.…”

Section: Resultsmentioning

confidence: 99%

Analytical method for the determination of organic acids in dilute acid pretreated biomass hydrolysate by liquid chromatography-time-of-flight mass spectrometry

Ibáñez

Bauer

2014

Biotechnol Biofuels

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BackgroundFor the development of lignocellulosic biofuels a common strategy to release hemicellulosic sugars and enhance the enzymatic digestibility of cellulose is the heat pretreatment of biomass with dilute acid. During this process, fermentation inhibitors such as 5-hydroxymethylfurfural, furfural, phenolics, and organic acids are formed and released into the so-called hydrolysate. The phenolic inhibitors have been studied fairly extensively, but fewer studies have focused on the analysis of the organic acids profile. For this purpose, a simple and fast liquid chromatography/mass spectrometry (LC/MS) method for the analysis of organic acids in the hydrolysate has been developed using an ion exchange column based on a polystyrene-divinylbenzene polymer frequently used in biofuel research. The application of the LC/MS method to a hydrolysate from Miscanthus has been evaluated.ResultsThe presented LC/MS method involving only simple sample preparation (filtration and dilution) and external calibration for the analysis of 24 organic acids present in dilute acid pretreated biomass hydrolysate is fast (12 min) and reasonably sensitive despite the small injection volume of 2 μL used. The lower limit of quantification ranged from 0.2 μg/mL to 2.9 μg/mL and the limit of detection from 0.03 μg/mL to 0.7 μg/mL. Analyte recoveries obtained from a spiked hydrolysate were in the range of 70 to 130% of the theoretical yield, except for glyoxylic acid, malic acid, and malonic acid, which showed a higher response due to signal enhancement. Relative standard deviations for the organic acids ranged from 0.4 to 9.2% (average 3.6%) for the intra-day experiment and from 2.1 to 22.8% (average 8.9%) for the inter-day (three-day) experiment.ConclusionWe have shown that the analysis of the profile of 24 organic acids present in biomass hydrolysate can be achieved by a simple LC/MS method applying external calibration and minimal sample preparation. The organic acids eluted within only 12 min by isocratic elution, enabling high sample throughput. Repeatability (precision and accuracy) and recovery were sufficiently accurate for most of the organic acids tested, making the method suitable for their fast determination in hydrolysate. We envision that this method can be further expanded to a larger number of organic acids, including phenolic acids such as p-coumaric acid and ferulic acid and other molecules depending on the researchers’ needs.

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“…Já o LD se refere à quantidade mínima em que o analíto pode ser detectado em uma análise, inequivocadamente, enquanto que o LQ é a menor concentração em que este pode ser quantificado, considerando a exatidão e a precisão aceitáveis (ANVISA, 2003).A exatidão é o parâmetro que indica o quanto o valor medido se aproxima da concentração verdadeira, sendo associada com a recuperação do analíto pelo método utilizado(FAO, 1997), enquanto que, a precisão mede o quanto os resultados de uma amostra analisada repetidas vezes (num curto intervalo de tempo) se aproximam entre si. Entre algumas das consequências do efeito matriz sobre a análise estão a imprecisão dos resultados, aumento da linha de base e aumento ou decréscimo de sensibilidade(GHOSH et al, 2010).…”

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Validação de metodologia para a quantificação de metanol em glicerina bruta utilizada na alimentação animal

Nazato¹

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Ionization Polarity as a Cause of Matrix Effects, its Removal and Estimation in ESI-LC-MS/MS Bio-analysis

Cited by 19 publications

References 28 publications

Biological Matrix Effects in Quantitative Tandem Mass Spectrometry-Based Analytical Methods: Advancing Biomonitoring

Biological Matrix Effects in Quantitative Tandem Mass Spectrometry-Based Analytical Methods: Advancing Biomonitoring

Analytical method for the determination of organic acids in dilute acid pretreated biomass hydrolysate by liquid chromatography-time-of-flight mass spectrometry

Validação de metodologia para a quantificação de metanol em glicerina bruta utilizada na alimentação animal

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