Application note Received: 4 August 2013
Revised: 14 November 2013
Accepted: 19 November 2013
Published online in Wiley Online Library
(wileyonlinelibrary.com) DOI 10.1002/jms.3315
Detection of histamine in beer by nano extractive electrospray ionization mass spectrometry Jiuxiao Cai,b Ming Li,a* Xingchuang Xiong,a* Xiang Fanga and Ruifeng Xua In this study, rapid quantitative detection of histamine in beer was achieved by using nano extractive electrospray ionization mass spectrometry (nano EESI-MS) coupling with standard addition method. Based on the MS2 experiment, histamine concentrations in three beer samples were determined to be 1.10 ± 0.12 μg/ml, 0.81 ± 0.09 μg/ml and 0.79 ± 0.09 μg/ml. The limit of detection for this method was calculated to be 0.02 μg/ml. These results show that this novel method can be used for direct, rapid and sensitive detection of histamine in beer without any tedious sample pretreatment. Copyright © 2014 John Wiley & Sons, Ltd. Keywords: histamine; beer; extractive electrospray ionization; mass spectrometry; ambient ionization
Introduction
J. Mass Spectrom. 2014, 49, 9–12
Experimental Reagents and instruments Histamine (A. R.), methanol (HPLC) and formic acid (A. R.) were bought from Sigma Aldrich Co., Ltd. The deionized water (18.2 Ω·cm) used was prepared with Milli-Q Direct water purification system (Millipore, USA). All the beer samples were bought from a local supermarket in China and directly analyzed without removing carbonation. All the chemicals were directly used without further treatment. Experiments were performed on an LTQ-Orbitrap Velos (Thermo Scientific Co. LTD.) coupled with a homemade nano EESI source. A schematic of nano EESI is shown in Fig. 1 and the principle of nano EESI is descripted elsewhere.[21–23] Briefly, nanoEESI is composed of a nanospray emitter for generating the primary ions and a disposable manual nebulizer for introducing the
* Correspondence to: Ming Li and Xingchuang Xiong, National Institute of Metrology, 100013 Beijing, China. E-mail: [email protected]; [email protected] a National Institute of Metrology, 100013 Beijing, China b Dalian Polytechnic University, 116034 Dalian, China
Copyright © 2014 John Wiley & Sons, Ltd.
9
Biogenic amine is a kind of low molecular weight compound with one or more amine group,[1] which is usually divided into single amine and polyamines. And it exists widely in food and beverage, such as aquatic product, meat and meat product, cheese, beer and soft drink. The concentration of biogenic amines (e.g. color amine, cadaverine and histamine) in food and beverage varies according to the storage time, storage condition and quality of raw materials. It is well known that consuming high amount of biogenic amines would cause allergic reaction accompanied with several clinical symptoms such as itch, nasal congestion, asthma, red eyes, hives, angioedema and anaphylaxis. Especially, high amount of histamine will trigger an inflammatory response[2,3] as histamine is involved in local immune responses regulating physiological function in the gut and acting as a neurotransmitter.[4] Histamine in beer has been considered as an important ‘indicator’ of microbial contamination during the brewing process. Therefore, it is highly required to develop an efficient method for the analysis of histamine in beer. In the past years, many analytical methods such as gas chromatography-mass spectrometry (GC-MS)[5] and liquid chromatography mass spectrometry (LC-MS)[6,7] have been developed for the determination of histamine in beer. However, these methods suffer several disadvantages such as time consuming and cost consuming because tedious sample pretreatments (e.g. liquid–liquid extraction, chromatographic separation) are needed prior to the sample analysis. Ambient mass spectrometry-based methods are potential tools for the direct detection of histamine, because the analytes can be easily ionized and introduced to a mass spectrometer under ambient conditions with no or minimal sample pretreatment. Ambient ionization was pioneered by Cooks’ desorption electrospray ionization (DESI),[8,9] which allows the direct determination of compounds on surfaces, by removing sample preparation steps such as chromatographic separation, solid phase micro extraction prior to the sample analysis. Many other techniques including direct-analysis-in-real-time (DART),[10,11] low temperature plasma (LTP),[12,13] electrospray assisted laser desorption/ionization (ELDI),[14,15] dielectric barrier discharge
ionization (DBDI),[16] extractive electrospray ionization (EESI),[17,18] paper spray[19] and easy ambient sonic ionization (EASI)[20] have been reported for rapid analysis of complex samples under ambient conditions with minimal or no sample pretreatment. Also, nano extractive electrospray ionization mass spectrometry (nano EESI-MS)[21–23] is a novel ambient ionization technology and it takes the outstanding advantages of readiness for miniaturization and integration, simple maintenance, easy operation and low cost. This new technique has been used for rapid detection of trace amount of cocaine in beverages,[22] such as PepsiTM, Coca-ColaTM, Red BullTM energy drinks and aerosol drug preparations[23] with high throughput and high sensitivity, etc. In this paper, a new approach based on nano EESI was developed for quantitative detection of histamine in beer.
J. Cai et al.
Figure 1. Schematic of the nano EESI setup.
neutral samples. The nanospray emitter was made of a commercial silica capillary nanoemitter (I.D. 5 ± 1 μm) (Pico Tip). The manual nebulizer is used for the generation of sample aerosol. The distance (a) between the nanospray emitter and the inlet of the mass spectrometer was set at 4 cm. The distance (b) between the manual nebulizer and the inlet of the mass spectrometer was optimized and chosen as 8 cm. The angle (α) formed between the nanospray emitter and the inlet of the mass spectrometer was 150°, and the angle (β) formed between the nanospray emitter and the sample nebulizer was 135°. A high voltage of 4.5 kV was supplied to the nanospray emitter. A mixture solution (50% methanol, 50% water, 0.1% formic acid) with a flow rate of 0.10 μl/min was used to generate the primary ions. The analytes in beer samples were ionized directly when the neutral sample plume was intersecting the primary ion beam, then the analyte ions were introduced to the mass spectrometer. The temperature of the inlet capillary was maintained at 180 °C during the analysis process. The ion injection time was set at 100 ms for the LTQ-MS instrument. To perform collision-induced dissociation (CID), ions of interest were isolated using an m/z window width of 1 unit. Helium was used as the collision gas, and the CID energy was set at 24% with a duration time of 30 ms for tandem mass spectrometry. The other parameters used in the experiment were the default values of the mass spectrometer. All the mass spectra were obtained using the Xcalibur® software.
Results and discussion
10
A standard histamine solution (0.5 μg/ml) was used to optimize the configuration of the nano EESI source and the parameters of the mass spectrometer. As shown in Fig. 2, the signal at m/z 112 corresponded to protonated histamine. Other signals such as m/z 123 in MS spectrum probably correspond to the some species in air, because the experiment was performed under ambient condition. The tandem mass spectrometry experiment was performed and a typical MS2 spectrum is shown in the inset of Fig. 2. In a histamine molecule, there are two possible lone pair electrons which can accept a proton; thus, two possible kinds of protonated histamine species (A and D as shown in Scheme 1) could be generated. During the CID process, the fragment ions of m/z 95 were generated from species A by loss of NH3, and the ions of m/z 69 were generated by further loss of C2H2. Alternatively, the fragment ions of m/z 83 were generated from species D by loss of CH2NH. This is in agreement with the results reported previously.[24,25] A beer sample was introduced to nano EESI-MS for the detection of histamine. As a result, a mass spectrum with a good
wileyonlinelibrary.com/journal/jms
Figure 2. A typical full MS spectrum of a standard histamine solution 2 (0.5 μg/ml) (inset shows MS spectrum of m/z 112).
Scheme 1. Two possible fragmentation pathways of the histamine precursor ions.
signal-to-noise (>120) was rapidly recorded without matrix cleaning up (as shown in Fig. 3). The signal at m/z 112 in the full MS spectrum corresponded to the protonated histamine, which was confirmed by the characteristic fragment ions of m/z 95, 69 and 83 in the MS2 spectrum (inset of Fig. 3). The limit of detection (S/N = 3) was evaluated to be 0.02 μg/ml. The accuracy of EESI technique has been validated by comparing the results from EESI and conventional spectrophotometric method.[26] Although external calibration method could be used for fast screening large numbers of beer samples. For accurately quantitative analysis, a standard addition method was used to avoid the matrix effect in this study. A serial of histamine stock solutions were spiked into one beer sample to increase the histamine level by 0.75, 1.50, 2.25 and 3.00 μg/ml, respectively. Then, the spiked samples were directly measured by using nano EESI with m/z 95 as the quantitative ions. The average of ten measurements for each sample was used as a final value and the standard addition curve was plotted (Fig. 4). As a result, the signal intensities (m/z 95) linearly responded to the histamine concentrations, providing a good correlation with a sound coefficient (R2 = 0.991) and acceptable relative standard deviation (RSD) values of 5.0%–11%. Consequently, the original concentration of the histamine in this beer sample was calculated to be 1.10 ± 0.12 μg/ml, which is lower than the suggested histamine limit (2–10 μg/ml)[27] in alcoholic beverages. This indicates that the new approach reported here is sensitive enough to detect histamine level in beer. In
Copyright © 2014 John Wiley & Sons, Ltd.
J. Mass Spectrom. 2014, 49, 9–12
Detection of histamine in beer by nano EESI
References
2
Figure 3. A typical MS spectrum of a beer sample (inset shows MS spectrum of m/z 112).
Figure 4. Standard addition curve for determination of histamine in one beer sample with transition ion pair m/z 112-95 as quantitative ions (Error bars designate the standard deviation for ten measurements).
addition, two another beer samples were also analyzed by using this method and the histamine concentrations were found to be 0.81 ± 0.09 μg/ml, and 0.79 ± 0.09 μg/ml, respectively. There results show that nano EESI can be used for used for direct, rapid and sensitive detection of histamine in beer without any tedious sample pretreatment.
Conclusion Rapid detection of histamine in beer sample was achieved based on nano EESI-MS without matrix cleaning up. Because the samples can be manually introduced by using a sample nebulizer and the primary ions are generated by a nanoESI emitter rather than a conventional ESI probe. Therefore, nebulizing gas or/and discharging gas is not required in this case. This significantly simplifies the instrument and the operation. This new approach has a potential for in situ detection of histamine in beer samples when nano EESI device is coupled with a portable mass spectrometer. Acknowledgements
J. Mass Spectrom. 2014, 49, 9–12
Copyright © 2014 John Wiley & Sons, Ltd.
wileyonlinelibrary.com/journal/jms
11
This work was jointly supported by the National Natural Science Foundation of China (No. 21005024) and the Ministry of Science and Technology of P. R. China (No. 2011YQ09000507, 2008FY130200). M.L. also thanks the Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry.
[1] P. Kalac, M. Krizek. A review of biogenic amines and polyamines in beer. J. Inst. Brew. 2003, 109, 123. [2] Y. Zhu. How does biogenic amine produce and method to control it in beer. Beer Sci. Tech. 2006, 7, 26. [3] X. Peng, C. Lin. Biogenic amine and polyamines in beer. Beer Sci. Tech. 2004, 2, 50. [4] C. Wackes, M. Herwald, H. Borck, E. Diel, L. Page, B. Horr, L. Rohn, F. Diel. Histamine in selected beer samples. Inflammation Res. 2006, 55, S67. [5] C. Almeida, J. O. Fernandes, S. C. Cunha. A novel dispersive liquidliquid microextraction (DLLME) gas chromatography-mass spectrometry (GC-MS) method for the determination of eighteen biogenic amines in beer. Food Control 2012, 25, 380. [6] R. L. Self, W.-H. Wu, H. S. Marks. Simultaneous quantification of eight biogenic amine compounds in tuna by Matrix Solid-Phase Dispersion followed by HPLC Orbitrap mass spectrometry. J. Agric. Food Chem. 2011, 59, 5906. [7] T. Tang, T. Shi, K. Qian, P. Li, J. Li, Y. Cao. Determination of biogenic amines in beer with pre-column derivatization by high performance liquid chromatography. J. Chromatogr. B 2009, 877, 507. [8] Z. Takats, J. M. Wiseman, B. Gologan, R. G. Cooks. Mass spectrometry sampling under ambient conditions with desorption electrospray ionization. Science 2004, 306, 471. [9] Z. Takats, J. M. Wiseman, R. G. Cooks. Ambient mass spectrometry using desorption electrospray ionization (DESI): instrumentation, mechanisms and applications in forensics, chemistry, and biology. J. Mass Spectrom. 2005, 40, 1261. [10] R. B. Cody, J. A. Laramée, H. D. Durst. Versatile new ion source for the analysis of materials in ppen air under ambient conditions. Anal. Chem. 2005, 77, 2297. [11] K. Kpegba, T. Spadaro, R. B. Cody, N. Nesnas, J. A. Olson. Analysis of self-assembled monolayers on gold surfaces using direct analysis in real time mass spectrometry. Anal. Chem. 2007, 79, 5479. [12] J. D. Harper, N. A. Charipar, C. C. Mulligan, X. Zhang, R. G. Cooks, Z. Ouyang. Low-temperature plasma probe for ambient desorption ionization. Anal. Chem. 2008, 80, 9097. [13] Y. Zhang, X. Ma, S. Zhang, C. Yang, Z. Ouyang, X. Zhang. Direct detection of explosives on solid surfaces by low temperature plasma desorption mass spectrometry. Analyst 2009, 134, 176. [14] C.-Y. Cheng, C.-H. Yuan, S.-C. Cheng, M.-Z. Huang, H.-C. Chang, T.-L. Cheng, C.-S. Yeh, J. Shiea. Electrospray-assisted laser desorption/ionization mass spectrometry for continuously monitoring the states of ongoing chemical reactions in organic or aqueous solution under ambient conditions. Anal. Chem. 2008, 80, 7699. [15] I. X. Peng, R. R. Ogorzalek Loo, J. Shiea, J. A. Loo. Reactiveelectrospray-assisted laser desorption/ionization for characterization of peptides and proteins. Anal. Chem. 2008, 80, 6995. [16] H. Chen, Y. Sun, A. Wortmann, H. Gu, R. Zenobi. Differentiation of maturity and quality of fruit using noninvasive extractive electrospray ionization quadrupole time-of-flight mass spectrometry. Anal. Chem. 2007, 79, 1447. [17] H. Chen, A. Venter, R. G. Cooks. Extractive electrospray ionization for direct analysis of undiluted urine, milk and other complex mixtures without sample preparation. Chem. Commun. 2006, 0, 2042. [18] H. Chen, B. Hu, Y. Hu, Y. Huan, Z. Zhou, X. Qiao. Neutral desorption using a sealed enclosure to sample explosives on human skin for rapid detection by EESI-MS. J. Am. Soc. Mass Spectrom. 2009, 20, 719. [19] H. Wang, J. J. Liu, R. G. Cooks, Z. Ouyang. Paper spray for direct analysis of complex mixtures using mass spectrometry. Angew. Chem.Int. Ed. 2010, 49, 877. [20] R. Haddad, R. R. Catharino, L. A. Marques, M. N. Eberlin. Perfume fingerprinting by easy ambient sonic-spray ionization mass spectrometry: nearly instantaneous typification and counterfeit detection. Rapid Commun. Mass Spectrom. 2008, 22, 3662. [21] M. Li, B. Hu, J. Li, R. Chen, X. Zhang, H. Chen. Extractive electrospray ionization mass spectrometry toward in situ analysis without sample pretreatment. Anal. Chem. 2009, 81, 7724. [22] B. Hu, X. Peng, S. Yang, H. Gu, H. Chen, Y. Huan, T. Zhang, X. Qiao. Fast quantitative detection of cocaine in beverages using nanoextractive electrospray ionization tandem mass spectrometry. J. Am. Soc. Mass Spectrom. 2010, 21, 290.
J. Cai et al. [23] H. Gu, B. Hu, J. Li, S. Yang, J. Han, H. Chen. Rapid analysis of aerosol drugs using nano extractive electrospray ionization tandem mass spectrometry. Analyst 2010, 135, 1259. [24] J. Koyama, S. Taga, K. Shimizu, M. Shimizu, I. Morita, A. Takeuchi. Simultaneous determination of histamine and prostaglandin D-2 using an LC-ESI-MS/MS method with positive/negative ionswitching ionization modes: application to the study of antiallergic flavonoids on the degranulation of KU812 cells. Anal. Bioanal. Chem. 2011, 401, 1385.
[25] M. D. Stanescu, F. Harja, C. Mosoarca, A. D. Zamfir. Biogenic amines fingerprints evidenced by performant MS analysis. Rev. Roum. Chim. 2010, 55, 1053. [26] X. Li, X. Fang, Z. Yu, G. Sheng, M. Wu, J. Fu, H. Chen. Direct quantification of creatinine in human urine by using isotope dilution extractive electrospray ionization tandem mass spectrometry. Anal. Chim. Acta 2012, 748, 53. [27] J. E. Stratton, R. W. Hutkins, S. L. Taylor. Biogenic amines in cheese and other fermented foods: a review. J. Food Prot. 1991, 64, 460.
12 wileyonlinelibrary.com/journal/jms
Copyright © 2014 John Wiley & Sons, Ltd.
J. Mass Spectrom. 2014, 49, 9–12
Revised: 14 November 2013
Accepted: 19 November 2013
Published online in Wiley Online Library
(wileyonlinelibrary.com) DOI 10.1002/jms.3315
Detection of histamine in beer by nano extractive electrospray ionization mass spectrometry Jiuxiao Cai,b Ming Li,a* Xingchuang Xiong,a* Xiang Fanga and Ruifeng Xua In this study, rapid quantitative detection of histamine in beer was achieved by using nano extractive electrospray ionization mass spectrometry (nano EESI-MS) coupling with standard addition method. Based on the MS2 experiment, histamine concentrations in three beer samples were determined to be 1.10 ± 0.12 μg/ml, 0.81 ± 0.09 μg/ml and 0.79 ± 0.09 μg/ml. The limit of detection for this method was calculated to be 0.02 μg/ml. These results show that this novel method can be used for direct, rapid and sensitive detection of histamine in beer without any tedious sample pretreatment. Copyright © 2014 John Wiley & Sons, Ltd. Keywords: histamine; beer; extractive electrospray ionization; mass spectrometry; ambient ionization
Introduction
J. Mass Spectrom. 2014, 49, 9–12
Experimental Reagents and instruments Histamine (A. R.), methanol (HPLC) and formic acid (A. R.) were bought from Sigma Aldrich Co., Ltd. The deionized water (18.2 Ω·cm) used was prepared with Milli-Q Direct water purification system (Millipore, USA). All the beer samples were bought from a local supermarket in China and directly analyzed without removing carbonation. All the chemicals were directly used without further treatment. Experiments were performed on an LTQ-Orbitrap Velos (Thermo Scientific Co. LTD.) coupled with a homemade nano EESI source. A schematic of nano EESI is shown in Fig. 1 and the principle of nano EESI is descripted elsewhere.[21–23] Briefly, nanoEESI is composed of a nanospray emitter for generating the primary ions and a disposable manual nebulizer for introducing the
* Correspondence to: Ming Li and Xingchuang Xiong, National Institute of Metrology, 100013 Beijing, China. E-mail: [email protected]; [email protected] a National Institute of Metrology, 100013 Beijing, China b Dalian Polytechnic University, 116034 Dalian, China
Copyright © 2014 John Wiley & Sons, Ltd.
9
Biogenic amine is a kind of low molecular weight compound with one or more amine group,[1] which is usually divided into single amine and polyamines. And it exists widely in food and beverage, such as aquatic product, meat and meat product, cheese, beer and soft drink. The concentration of biogenic amines (e.g. color amine, cadaverine and histamine) in food and beverage varies according to the storage time, storage condition and quality of raw materials. It is well known that consuming high amount of biogenic amines would cause allergic reaction accompanied with several clinical symptoms such as itch, nasal congestion, asthma, red eyes, hives, angioedema and anaphylaxis. Especially, high amount of histamine will trigger an inflammatory response[2,3] as histamine is involved in local immune responses regulating physiological function in the gut and acting as a neurotransmitter.[4] Histamine in beer has been considered as an important ‘indicator’ of microbial contamination during the brewing process. Therefore, it is highly required to develop an efficient method for the analysis of histamine in beer. In the past years, many analytical methods such as gas chromatography-mass spectrometry (GC-MS)[5] and liquid chromatography mass spectrometry (LC-MS)[6,7] have been developed for the determination of histamine in beer. However, these methods suffer several disadvantages such as time consuming and cost consuming because tedious sample pretreatments (e.g. liquid–liquid extraction, chromatographic separation) are needed prior to the sample analysis. Ambient mass spectrometry-based methods are potential tools for the direct detection of histamine, because the analytes can be easily ionized and introduced to a mass spectrometer under ambient conditions with no or minimal sample pretreatment. Ambient ionization was pioneered by Cooks’ desorption electrospray ionization (DESI),[8,9] which allows the direct determination of compounds on surfaces, by removing sample preparation steps such as chromatographic separation, solid phase micro extraction prior to the sample analysis. Many other techniques including direct-analysis-in-real-time (DART),[10,11] low temperature plasma (LTP),[12,13] electrospray assisted laser desorption/ionization (ELDI),[14,15] dielectric barrier discharge
ionization (DBDI),[16] extractive electrospray ionization (EESI),[17,18] paper spray[19] and easy ambient sonic ionization (EASI)[20] have been reported for rapid analysis of complex samples under ambient conditions with minimal or no sample pretreatment. Also, nano extractive electrospray ionization mass spectrometry (nano EESI-MS)[21–23] is a novel ambient ionization technology and it takes the outstanding advantages of readiness for miniaturization and integration, simple maintenance, easy operation and low cost. This new technique has been used for rapid detection of trace amount of cocaine in beverages,[22] such as PepsiTM, Coca-ColaTM, Red BullTM energy drinks and aerosol drug preparations[23] with high throughput and high sensitivity, etc. In this paper, a new approach based on nano EESI was developed for quantitative detection of histamine in beer.
J. Cai et al.
Figure 1. Schematic of the nano EESI setup.
neutral samples. The nanospray emitter was made of a commercial silica capillary nanoemitter (I.D. 5 ± 1 μm) (Pico Tip). The manual nebulizer is used for the generation of sample aerosol. The distance (a) between the nanospray emitter and the inlet of the mass spectrometer was set at 4 cm. The distance (b) between the manual nebulizer and the inlet of the mass spectrometer was optimized and chosen as 8 cm. The angle (α) formed between the nanospray emitter and the inlet of the mass spectrometer was 150°, and the angle (β) formed between the nanospray emitter and the sample nebulizer was 135°. A high voltage of 4.5 kV was supplied to the nanospray emitter. A mixture solution (50% methanol, 50% water, 0.1% formic acid) with a flow rate of 0.10 μl/min was used to generate the primary ions. The analytes in beer samples were ionized directly when the neutral sample plume was intersecting the primary ion beam, then the analyte ions were introduced to the mass spectrometer. The temperature of the inlet capillary was maintained at 180 °C during the analysis process. The ion injection time was set at 100 ms for the LTQ-MS instrument. To perform collision-induced dissociation (CID), ions of interest were isolated using an m/z window width of 1 unit. Helium was used as the collision gas, and the CID energy was set at 24% with a duration time of 30 ms for tandem mass spectrometry. The other parameters used in the experiment were the default values of the mass spectrometer. All the mass spectra were obtained using the Xcalibur® software.
Results and discussion
10
A standard histamine solution (0.5 μg/ml) was used to optimize the configuration of the nano EESI source and the parameters of the mass spectrometer. As shown in Fig. 2, the signal at m/z 112 corresponded to protonated histamine. Other signals such as m/z 123 in MS spectrum probably correspond to the some species in air, because the experiment was performed under ambient condition. The tandem mass spectrometry experiment was performed and a typical MS2 spectrum is shown in the inset of Fig. 2. In a histamine molecule, there are two possible lone pair electrons which can accept a proton; thus, two possible kinds of protonated histamine species (A and D as shown in Scheme 1) could be generated. During the CID process, the fragment ions of m/z 95 were generated from species A by loss of NH3, and the ions of m/z 69 were generated by further loss of C2H2. Alternatively, the fragment ions of m/z 83 were generated from species D by loss of CH2NH. This is in agreement with the results reported previously.[24,25] A beer sample was introduced to nano EESI-MS for the detection of histamine. As a result, a mass spectrum with a good
wileyonlinelibrary.com/journal/jms
Figure 2. A typical full MS spectrum of a standard histamine solution 2 (0.5 μg/ml) (inset shows MS spectrum of m/z 112).
Scheme 1. Two possible fragmentation pathways of the histamine precursor ions.
signal-to-noise (>120) was rapidly recorded without matrix cleaning up (as shown in Fig. 3). The signal at m/z 112 in the full MS spectrum corresponded to the protonated histamine, which was confirmed by the characteristic fragment ions of m/z 95, 69 and 83 in the MS2 spectrum (inset of Fig. 3). The limit of detection (S/N = 3) was evaluated to be 0.02 μg/ml. The accuracy of EESI technique has been validated by comparing the results from EESI and conventional spectrophotometric method.[26] Although external calibration method could be used for fast screening large numbers of beer samples. For accurately quantitative analysis, a standard addition method was used to avoid the matrix effect in this study. A serial of histamine stock solutions were spiked into one beer sample to increase the histamine level by 0.75, 1.50, 2.25 and 3.00 μg/ml, respectively. Then, the spiked samples were directly measured by using nano EESI with m/z 95 as the quantitative ions. The average of ten measurements for each sample was used as a final value and the standard addition curve was plotted (Fig. 4). As a result, the signal intensities (m/z 95) linearly responded to the histamine concentrations, providing a good correlation with a sound coefficient (R2 = 0.991) and acceptable relative standard deviation (RSD) values of 5.0%–11%. Consequently, the original concentration of the histamine in this beer sample was calculated to be 1.10 ± 0.12 μg/ml, which is lower than the suggested histamine limit (2–10 μg/ml)[27] in alcoholic beverages. This indicates that the new approach reported here is sensitive enough to detect histamine level in beer. In
Copyright © 2014 John Wiley & Sons, Ltd.
J. Mass Spectrom. 2014, 49, 9–12
Detection of histamine in beer by nano EESI
References
2
Figure 3. A typical MS spectrum of a beer sample (inset shows MS spectrum of m/z 112).
Figure 4. Standard addition curve for determination of histamine in one beer sample with transition ion pair m/z 112-95 as quantitative ions (Error bars designate the standard deviation for ten measurements).
addition, two another beer samples were also analyzed by using this method and the histamine concentrations were found to be 0.81 ± 0.09 μg/ml, and 0.79 ± 0.09 μg/ml, respectively. There results show that nano EESI can be used for used for direct, rapid and sensitive detection of histamine in beer without any tedious sample pretreatment.
Conclusion Rapid detection of histamine in beer sample was achieved based on nano EESI-MS without matrix cleaning up. Because the samples can be manually introduced by using a sample nebulizer and the primary ions are generated by a nanoESI emitter rather than a conventional ESI probe. Therefore, nebulizing gas or/and discharging gas is not required in this case. This significantly simplifies the instrument and the operation. This new approach has a potential for in situ detection of histamine in beer samples when nano EESI device is coupled with a portable mass spectrometer. Acknowledgements
J. Mass Spectrom. 2014, 49, 9–12
Copyright © 2014 John Wiley & Sons, Ltd.
wileyonlinelibrary.com/journal/jms
11
This work was jointly supported by the National Natural Science Foundation of China (No. 21005024) and the Ministry of Science and Technology of P. R. China (No. 2011YQ09000507, 2008FY130200). M.L. also thanks the Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry.
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