CN105259292B - Method for measuring paralysis shellfish poison in aquatic products - Google Patents
Method for measuring paralysis shellfish poison in aquatic products Download PDFInfo
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- CN105259292B CN105259292B CN201510772443.7A CN201510772443A CN105259292B CN 105259292 B CN105259292 B CN 105259292B CN 201510772443 A CN201510772443 A CN 201510772443A CN 105259292 B CN105259292 B CN 105259292B
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Abstract
The invention provides a method for measuring paralysis shellfish poison in aquatic products. The method comprises the steps of extraction, freezing, redissolving, purification and liquid chromatography-tandem mass spectrometer detection. The method has the advantages that sample pretreatment is simple, quick and economical, and sensitivity and recovery rate are high. The method is suitable for simultaneous, qualitative and quantitative detection of multiple kinds of paralysis shellfish poison in aquatic products, and provides effective technical support for guaranteeing quality safety of shellfish aquatic products in China.
Description
Technical field
The present invention relates to aquatic products detection field, determines paralytic shellfish poisoning (PSP) in aquatic products more particularly to a kind of
Method.
Background technology
Paralytic shellfish poisoning (PSP) (PSTs) is extremely strong little of planktonic algae or microorganism are produced in water body a class water solublity
Molecule secondary metabolite.Its basic structure be two guanidine radicals four aquation purine more fold hexatomic ring.According to substituted radical not
Together, four classes are broadly divided into：1. carbamate toxoid (Carbamate toxins), including saxitoxin
(Saxitoxin, STX), N-STX (neoSTX, NEO) and GTX1-4 (Gonyautoxins, GTXl-4)；
2. N- sulphonyl carbamyl toxoid (N-sulfocarbamoyl toxins), including GTX5 (B1), GTX6 (B2) and C1-C4；
3. deamination formoxyl toxoid (Decarbamoyl toxins), including dcSTX, dcneoSTX, dcGTX1-4；4. deoxidation deamination
Formoxyl toxoid (Deoxydecarb-amoyl toxins), including doSTX, doneoSTX and doGTX1 etc., wherein, amino
Formate ester toxin is a more important toxoid.
PSTs is the efficient sodium-ion channel neurotoxin of a class.After human body has taken in the marine product polluted by PSTs,
The clinical initial stage is mainly shown as that mouth, lip, tongue are numb, and paralysis symptom occur in extremity, feels exception occur, and people becomes weak and mixed
Disorderly；Later stage is mainly shown as nausea, vomiting, rapid breathing, headache fever, and consciousness occur in dysphagia, dysarteriotony, severe patient
It is fuzzy or even dead.Wherein, carbamate toxoid distribution most wide, toxicity is most strong, and its Typical Representative STX accounts for PSTs distributions
More than 85%.Although itself toxicity of N- sulphonyl carbamyl toxoids is less, easily turned by biological in vivo
Sulfonyl is sloughed in change and carbamic acid ester chain generates the very strong STX of toxicity and deamination formoxyl toxoid.In addition, newest biology
Transformation experiment finds and confirms there is a class C1/C2 toxin in shellfish body.
For ensureing that the public is not threatened by PSTs, world many countries, area and related international organization are all to shellfish
Aquatic products carry out strict control and control, and have formulated the PSTs limit standards of corresponding shellfish aquatic products and its product.It is different
The toxin standard substance toxicity assessments of itself is built upon in the safety evaluatio of other toxin, the limit standard of PSTs is based on dynamic
The toxicological evaluation of thing laboratory method.
PSTs limit standards are the United Nations's health organizations (WHO) according to mouse test method to biology current at present in vivo
(MBA) obtain.The LOD value of the method and the minimum virulence for pathological characteristicses occur are 80 μ g STXeq/100g, i.e. 400MU,
MBA is also determined as the standard method of PSTs safety evaluatios.This standard is included China and is adopted in interior most countries
With being also considered as the minimum standardss of PSTs safety problems.Research shows, although in the natural environment and single creature body simultaneously
Not comprising all PSTs (be currently known a kind of biology and at most detect 5-10 kinds PSTs in vivo) being currently known, but for certain
This toxoid having found a bit, we are unclear for its property, are also just difficult to carry out safety and toxicity assessment to which.Additionally, not
Same PSTs has different toxicity, although some toxin such as itself toxicity of N- sulphonyl carbamyl toxoid is relatively low,
Can pass through the molecular conformation that environmental induction or bioconversion form high poison, and this conversion is very in environmental and biological materials
It is common.Therefore, because the characteristics of PSTs has toxicity multiformity and changeableness so that for the accurate quantification of this toxoid is detected
Occur in that no small difficulty.Although MBA methods are at present general standard detecting methods, but its sensitivity is low and accuracy official post
Obtain this analysis method and endure dispute to the fullest extent.2009, EFSA's suggestion controlled PSTs Limited Doses in 7.5 μ gSTXeq/
Within 100g, well below the LOD of MBA.Therefore, it is necessary to find the suitable detection method for possessing more high sensitivity and accuracy replace
For MBA, means and premise are provided for PSTs Research on Safety Assessment.
At present, MBA and HPLC-FLD methods have become FSA (FSA), AOAC, U.S.'s shellfish administration of health
The standards setting organizations such as plan (NSSP) are defined as the standard detecting method of PSTs, have built up the monitoring system of relative maturity.
The appearance of LC-MS methods is considered as the suitable replacer of MBA and HPLC-FLD methods, because which is time-consuming to HPLC-FLD methods and it is difficult to operate
Spend big two big shortcomings and do obvious improvement.Certain deficiency is still suffered from for the LC-MS detection methods of PSTs in the world at present, such as
The response rate of pretreatment mode contratoxin each component is widely different, and no suitable purification method is limiting matrix effect well
Impact to compound mensuration etc..
It is therefore desirable to the quantitative detecting method for establishing a set of multicomponent PSTs of system, to guarantee that aquatic product quality is pacified
Entirely.
The content of the invention
It is an object of the invention to provide a kind of method for determining paralytic shellfish poisoning (PSP) in aquatic products, the method specifically wraps
Include following steps：
(1) sample after smashing to pieces is weighed, is added and is extracted solution, be centrifuged after vortex and supersound extract, supernatant merges
After freezing, take out lower floor's lyophilization and do near；
(2) redissolve, purified with adsorbent, vortex oscillation centrifugation, upper liquid filter membrane are to be analyzed；
(3) analyte sample fluid carries out the qualitative and quantitative analysis of paralytic shellfish poisoning (PSP) by Liquid Chromatography-Tandem Mass Spectrometry instrument.
Wherein described sample can be the shellfish aquatic products such as scallop, Carnis Mactrae, mussel；
Extraction solution described in step (1) is the acetonitrile solution (second containing 0.1% (mass percent concentration) formic acid
Nitrile：Water=80：20, volume ratio)；
In step (2), purifying adsorbent is C18 silica gel and acidic alumina, and the weight ratio of the two is 1：1；
In step (3), surveyed paralytic shellfish poisoning (PSP) is：Saxitoxin (STX), N-STX (neoSTX), knee joint
Ditch Algae toxins 1-4 (GTX1-4), N- sulphonyl carbamyls gonyatoxin -2 (C1) and N- sulphonyl carbamyl gonyatoxins -
3(C2)；
Liquid phase analysis condition in step (3) is specific as follows：
Chromatographic column：The hydrophilic posts of TSK-gel Amide-80 (150 × 2mm, 3 μm)；Column temperature：30℃；Flow velocity：0.3mL/min；
Sample size：5μL；
Mobile phase：A phases：Acetonitrile；B phases：3.6mM formic acid, 2mM formic acid aqueous ammoniums (pH 3.5)
Gradient elution program：0min, 15%B；0-10min, 45%B；10-11min, 45%B；11-14min, 15%B,
14-19, min 15%B；
Mass spectral analyses condition used in step (3) is specific as follows：
Ion source module：Positive ion mode (ESI+)；Spray voltage：4.0kv(ESI+)；Heating deblocking temperature：300℃；From
Sub- transfer tube temperature：350℃；Sheath gas：Nitrogen, flow 35arb；Auxiliary gas：Nitrogen, flow 20arb；Collision gas：Argon, collision
Pressure 1.5mTorr.
Specifically, in a kind of measure aquatic products of the invention paralytic shellfish poisoning (PSP) method, comprise the steps：
(1) the shellfish biological sample for collecting is washed, and is taken out soft tissue, is smashed to pieces, take in being put into tissue mashing machine
Sample adds the acetonitrile solution (80 containing 0.1% formic acid:20, v/v) extracted, surpassed under frozen water state after vortex oscillation 1min
Sound extracts 10min, and below 15 DEG C of 4500rpm is centrifuged 10min；The supernatant that will be obtained after centrifugation, freezes 4h under the conditions of -20 DEG C,
Discarded after taking-up rapidly upper organic phase (<1min), lower floor's lyophilization is done near；
Wherein the ratio of the acetonitrile solution containing 0.1% formic acid and sample is 1-3：1(ml：g)；
(2) redissolved and constant volume with the formic acid water that mass percent concentration is 0.1%, add mass ratio to be 1：1 C18 and acid
Property aluminium oxide which is purified as adsorbent, vortex oscillation 1min, less than 15 DEG C 4500rpm are centrifuged 10min, and upper liquid crosses 0.22
μm nylon leaching film is to be analyzed；
(3) detected sample that step (2) is obtained is analyzed by Liquid Chromatography-Tandem Mass Spectrometry instrument, obtains 8 respectively
Plant the testing result of paralytic shellfish poisoning (PSP).
The invention provides the liquid phase tandem mass spectrum that a kind of pre-treating method simple economy is quick, sensitivity and accuracy are high
Method determines the plain detection method of 8 kinds of paralytics shellfish poison in aquatic products.
The present invention a kind of measure aquatic products in paralytic shellfish poisoning (PSP) method compared with prior art, with following skill
Art advantage and effect：Pre-treatment using improved method it is more simple and efficient, save the time of sample treatment and cost, reduction
The consumption of organic solvent.Sample after processing simultaneously is very clean, and sensitivity after continuous sample introduction does not have significant change.This
In inventive method, different quantitative limit of the toxin in different substrates are respectively：STX,0.33-1.65μg/kg；NEO,0.69-2.59
μg/kg；GTX1,4.14-5.52 μ g/kg；GTX4,2.70-6.08μg/kg；GTX2,2.01-2.82μg/kg；GTX3,1.60-
4.79μg/kg；C1,2.27-3.33μg/kg；C1,1.35-2.69μg/kg；The response rate between 81.52%～116.50%,
Relative standard deviation is respectively less than 19.10%.As can be seen here, sensitivity and precision can meet detection by quantitative requirement.
Description of the drawings
Fig. 1 is Selective reaction monitoring (SRM) collection of illustrative plates (the wherein each component standard of 8 kinds of paralytic shellfish poisoning (PSP) standard solution
The concentration of solution is respectively：STX：39.69μg/mL；NEO：41.37μg/mL；GTX2：90.29μg/mL；GTX3：38.31μg/
mL；GTX1：49.69μg/mL；GTX4：16.21μg/mL；C1：107.82μg/mL；C2；32.23μg/mL.)；
Specific embodiment
The present invention is further illustrated for example given below.The present invention is described with reference to most preferred embodiment
, but after present example is read, those skilled in the art can appreciate the fact that and make many change in disclosed enforcement also may be used
Same or similar result is obtained, the spirit and scope of the present invention are belonged to.In particular, the alternative this paper institutes of some reagents
Disclosed reagent and obtain same or like result.All similar replacements or modification are all considered to design and the model of the present invention
Enclose, all above-mentioned equivalent form of values belong to the scope of claims of the present invention restriction.
Embodiment 1
1st, materials and methods
1.1 key instruments and reagent
Liquid Chromatography-Tandem Mass Spectrometry instrument:The triple level Four bar mass spectrometers of Thermo TSQ Quantum Ultra, EFI
Mist ion source (ESI) (Thermo Fisher Scientific, USA)；
Liquid-phase chromatographic column：The hydrophilic posts of TSK-gel Amide-80 (150 × 2mm, 3 μm)：
Tissue mincer：IKA T-18 (IKA, Germany)；
Vortex instrument：Its Lindberg Optic Design A/S of Haimen；
Ultrasonator：Ningbo Xin Zhi companies；
Refrigerated centrifuger：Heraeus Multifuge 1L-R (Thermo Fisher Scientific, Germany)；
Freezer dryer：Heto Power Dry LL3000, Shanghai Hui Fen Electronic Science and Technology Co., Ltd.s；
Nitrogen evaporator：HGC-24 Xi'an Jing great testing equipments company limited；
Ultrasonic washing instrument：Shanghai High Kudos Science Instrument Co., Ltd.；
Ultrapure water machine：Milli-Q, German Millipore companies；
1.2 standard substance and reagent
8 kinds of standard substance toxin (STX, NEO, GTX1/4, GTX2/3, C1/C2) are purchased from Canadian NRC sea
Foreign life science institute；Formic acid, acetonitrile, C18, acidic alumina and dSPE adsorption stuffings are purchased from the limited public affairs of traditional Chinese medicines chemical reagent
Department.
2nd, experimental technique
2.1 sample-pretreating method
(1) market collects scallop, Carnis Mactrae, mussel samples with water are cleaned, and are taken out soft tissue, are put into tissue mashing machine
In smash to pieces, take 1g ± 0.01g shellfish meats add 2mL containing 0.1% formic acid acetonitrile water (80:20, v/v) extracting solution, vortex oscillation
Supersound extraction 10min under frozen water state after 1min, below 15 DEG C of 4500rpm are centrifuged 10min.Extract 2 times repeatedly, after being centrifuged
The supernatant that obtains merges, and freezes 4h under the conditions of -20 DEG C, discarded after taking-up rapidly upper organic phase (<1min), lower floor's freezing is dry
It is dry near dry.
(2) 1mL is redissolved and is settled to 0.1% formic acid water, adds 50mg C18 and 50mg acidic alumina adsorbents pair
Its purification, vortex oscillation 1min, less than 15 DEG C 4500rpm are centrifuged 10min, and it is to be analyzed that upper liquid crosses 0.22 μm of nylon leaching film.
(3) detected sample for obtaining is analyzed by Liquid Chromatography-Tandem Mass Spectrometry instrument, obtains carbamate respectively
The result of toxoid and N- sulphonyl carbamyl toxoid residual quantities.
2.2 liquid chromatography mass conditions
(1) liquid-phase condition：
Chromatographic column：The hydrophilic posts of TSK-gel Amide-80 (150 × 2mm, 3 μm)；Column temperature：30℃；
Flow velocity：0.3mL/min；Sample size：5μL；
Mobile phase：A phases：Acetonitrile；B phases：3.6mM formic acid, 2mM formic acid aqueous ammoniums (pH 3.5)
Gradient elution program：0min, 15%B；0-10min, 45%B；10-11min, 45%B；11-14min, 15%B,
14-19, min 15%B.
(2) Mass Spectrometry Conditions：
Ion source module：Positive ion mode (ESI+)；Spray voltage：4.0kv(ESI+)；Heating deblocking temperature：300℃；From
Sub- transfer tube temperature：350℃；Sheath gas：Nitrogen, flow 35arb；Auxiliary gas：Nitrogen, flow 20arb；Collision gas：Argon, collision
Pressure 1.5mTorr.
The SRM collection of illustrative plates of the standard solution obtained under above-mentioned condition is shown in Fig. 1.
The mass spectrometry parameters of 8 kinds of paralytic shellfish poisoning (PSP)s are shown in Table 1.
The mass spectrometry parameters of 1 each toxin of table
* quantitative fragment ion, does not mark then excluding in table for the alternative ion of the qualitative ion of auxiliary for *
3rd, result and discussion
There is very high extraction efficiency to PSTs not only using acetonitrile/water system, and can preferably precipitate shellfish group
Protein in knitting so that sample is effectively purified.
3.1 linear relationships and detection limit, quantitative limit
The standard working solution of 8 kinds of paralytic shellfish poisoning (PSP)s is configured with bare substrate (scallop, Carnis Mactrae, mussel).Prepare mark
Quasi- product solution concentration is as follows：STX：39.69μg/mL；NEO：41.37μg/mL；GTX2：90.29μg/mL；GTX3：38.31μg/
mL；GTX1：49.69μg/mL；GTX4：16.21μg/mL；C1：107.82μg/mL；C2；32.23μg/mL.Investigate the range of linearity
Linear degree (R2) and quantitative limit (LOD), detection limit (LOQ), dependent linearity scope and LOD, LOQ value are shown in Table 2.As a result show
The detection method of the present embodiment is feasible.
The linear relationship of 8 kinds of paralytic shellfish poisoning (PSP)s and detection limit, quantitative limit in 2 different substrates of table
3.2nd, the response rate and Precision Experiment
Before extract after substrate mark-on and purification by the way of substrate mark-on, both ratio as classical prescription method post processing obtain
The response rate for arriving.Three groups of suitable addition concentration, per group of 6 parts of Duplicate Samples are selected to carry out in a few days repeated (Intra-day) and day
Between repeatability (Inter-day) determine, evaluated as standard with the response rate and its RSD values, the results are shown in Table 3.As a result explanation is originally
The repeatability of detection method is preferable.
4th, conclusion
The present invention uses improved sample-pretreating method and liquid phase tandem mass spectrometry to determine 8 kinds of paralysis in aquatic products simultaneously
Property saxitoxin content method, sensitivity and stability is high, solves technical barrier of the prior art, is to ensure China's water
Product quality and safety provides preferable technical support.
Claims (2)
1. it is a kind of determine aquatic products in paralytic shellfish poisoning (PSP) method, it is characterised in that the method specifically includes following steps：
(1) sample after smashing to pieces is weighed, is added and is extracted solution, be centrifuged after vortex and supersound extract, extract 2 times repeatedly, will
After the supernatant obtained after centrifugation merges freezing, take out lower floor's lyophilization and do near；
(2) redissolved with 0.1% formic acid water, purified with adsorbent, vortex oscillation centrifugation, upper liquid filter membrane are to be analyzed；
(3) analyte sample fluid carries out the qualitative and quantitative analysis of paralytic shellfish poisoning (PSP) by Liquid Chromatography-Tandem Mass Spectrometry instrument；
The solution that extracts wherein described in step (1) is the acetonitrile solution containing 0.1% formic acid；
In step (2), purifying adsorbent is C18 silica gel and acidic alumina, and the weight ratio of the two is 1：1；
In step (3), surveyed paralytic shellfish poisoning (PSP) is：Saxitoxin, N-STX, GTX1-4, N- sulphurs
Acyl carbamyl gonyatoxin -2 and N- sulphonyl carbamyls gonyatoxin -3.
2. it is according to claim 1 determine aquatic products in paralytic shellfish poisoning (PSP) method, it is characterised in that
Liquid phase analysis condition in step (3) is specific as follows：
Chromatographic column：The hydrophilic posts of TSK-gel Amide-80；Column temperature：30℃；Flow velocity：0.3mL/min；Sample size：5μL；
Mobile phase：A phases：Acetonitrile；B phases：PH is 3.5 formic acid-formic acid aqueous ammonium, wherein the concentration of formic acid be 3.6mM, formic acid
The concentration of ammonium is 2mM；
Gradient elution program：0min, 15%B；0-10min, 45%B；10-11min, 45%B；11-14min, 15%B, 14-
19min, 15%B；
Mass spectral analyses condition used in step (3) is specific as follows：
Ion source module：Positive ion mode ESI+；Spray voltage：4.0kv；Heating deblocking temperature：300℃；Ion transfer tube temperature：
350℃；Sheath gas：Nitrogen, flow 35arb；Auxiliary gas：Nitrogen, flow 20arb；Collision gas：Argon, impact pressure 1.5mTorr.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106324154B (en) * | 2016-09-05 | 2018-07-03 | 大连理工大学 | A kind of analysis method of molecular engram solid phase extraction-LC-MS detection gonyatoxin |
| CN106706829B (en) * | 2016-12-08 | 2018-05-22 | 浙江省海洋水产研究所 | The method that affine in immunity purification-Liquid Chromatography-Tandem Mass Spectrometry measures research of diarrhetic shellfish poisons in shellfish |
| CN107941951A (en) * | 2017-11-28 | 2018-04-20 | 安徽农业大学 | A kind of method of Quercetin in efficient detection dendrobium candidum |
| CN108469480A (en) * | 2018-03-20 | 2018-08-31 | 上海泰坦科技股份有限公司 | A kind of detection method of saxitoxin and its application |
| CN108507854A (en) * | 2018-04-12 | 2018-09-07 | 绿城农科检测技术有限公司 | The pre-treating method of multicomponent agricultural and veterinary chemicals residual quantity in a kind of measurement shellfish samples |
| CN108977506B (en) * | 2018-08-08 | 2022-03-25 | 浙江海洋大学 | Method for rapidly screening microbial strains generating gonyautoxin and digoxin labeled DNA probe used in method |
| CN112110930B (en) * | 2020-09-16 | 2022-03-29 | 中国水产科学研究院东海水产研究所 | Method for extracting neosaxitoxin from toxic shell |
| CN112379015A (en) * | 2020-10-30 | 2021-02-19 | 深圳市疾病预防控制中心（深圳市卫生检验中心、深圳市预防医学研究所） | Liquid chromatography-tandem mass spectrometry detection method for paralytic shellfish toxins in shellfish |
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| CA2007696A1 (en) * | 1990-01-12 | 1991-07-12 | Philip M. Townsley | Method and apparatus for the detection of paralytic shellfish poisons |
| JPH09133669A (en) * | 1995-11-07 | 1997-05-20 | Shimadzu Corp | Method for determining paralytic shell poison |
| JP4289694B2 (en) * | 1998-04-03 | 2009-07-01 | 正昭 児玉 | Novel saxitoxin derivative and method for producing the same |
| ES2155809B1 (en) * | 1999-10-15 | 2001-12-01 | Univ Santiago Compostela | QUANTIFICATION OF PARALYZING TOXINS (PSP) BY FLUORIMETRY IN EXCITABLE CELLS. |
| EP2638908A1 (en) * | 2012-03-16 | 2013-09-18 | Phytotox SpA | Paralytic Shellfish Poison |
| CN102928528B (en) * | 2012-10-15 | 2014-01-22 | 中国水产科学研究院黄海水产研究所 | High performance liquid chromatography-mass spectrometry detecting method of 16 fat soluble saxitoxins in shellfish meet |
| CN104876939A (en) * | 2014-02-28 | 2015-09-02 | 中国农业科学院原子能利用研究所 | Method for extracting paralytic shellfish toxins from shell raw materials |
| CN104198536A (en) * | 2014-07-30 | 2014-12-10 | 浙江大学 | Method for detecting paralytic shellfish poisoning |
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