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CN1657941A - Use of investigating multiple antigen label combined by antibody absorption surface material and mass spectrum - Google Patents

Use of investigating multiple antigen label combined by antibody absorption surface material and mass spectrum Download PDF

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Publication number
CN1657941A
CN1657941A CN 200410004403 CN200410004403A CN1657941A CN 1657941 A CN1657941 A CN 1657941A CN 200410004403 CN200410004403 CN 200410004403 CN 200410004403 A CN200410004403 A CN 200410004403A CN 1657941 A CN1657941 A CN 1657941A
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antibody
absorption surface
protein
mark
surface material
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许洋
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Abstract

This invention relates to a method which is through the antigen mark which is caught by the immune body adsorption surface matter on, and analyzes with the mass spectrum examines. Adsorbs the many kinds of antigen mark in on a many kinds of immune bodies adsorptions surface, and carries on the mass spectrum analysis to the capture antigen mark. May examine many antigen mark group. This method may use examining the antigen mark combination in the biological sample. Examines the measurement with these antigen mark combinations to be possible at the same time to distinguish the many kinds of diseases.This method is accurate, convenience also quickly.

Description

Purposes with antibody absorption surface material and the multiple antigenic mark of mass spectrum joint-detection
Technical field
The present invention relates to protein analysis method in a kind of new biological sample, a kind of biomarker of catching by antibody absorption surface material, and come the detection of biological mark with mass spectrophotometry.The present invention has been improved the immune analysis method means widely referred in this, and is more accurate than present routine biochemistry inspection (enzyme-linked method or fluorescence method).Say that more properly this invention relates to various ways biomarker (biomarkers) or antigenic mark, and these antigens or biomarker can be used to distinguish multiple disease marker is disposable with higher specificity and sensitivity.The present invention can be applied to clinical examination.
Background technology
No matter the normal function or the pathology characteristic that are cell all are somewhat dependent upon the expressed protein function of cell.Therefore, identify the difference of disease expressed protein in human body, can be used for medical diagnosis on disease and examination, and finally be used for drug development and disease treatment.And to carry out the differentiation analysis of protein expression and function, requirement can reach the degree of differentiating the complex mixture of molecule in the cell.But many materials often exist with trace in the cell, and the method that is used for analysing protein at present has limitation at above-mentioned everyway, is difficult to multiple disease is carried out qualitative evaluation and quantitative test simultaneously with these conventional meanses.
As, hospital requires to detect specifically the known mark of multiple common disease.But the reagent for preparing multiple specificity incorporation of markings and can identify mark in the potpourri of complexity needs the plenty of time, and this has hindered the development of this type of diagnostic method.At present, also there is not a kind of method four kinds of disease markers can be detected simultaneously.
ELISA (enzyme-linked immunosorbent assay) kit utilizes antibody and the reaction of enzyme mark can be used to detect a kind of disease marker.Utilize antibody and three fluorescence, can accomplish to detect three disease markers at most, but three above disease markers just can't detect simultaneously.Utilize antibody absorption surface material and antibody and mass spectrometer use in conjunction, promptly can solve the disease antigen mark of differentiating simultaneously more than three kinds.Say for example, to resist HBV (HBsAg) antibody, HCV antigen/antibody combination, anti-HIV p24 antigen (Ribas SG et al.Performance of a quantitative humanimmunodeficiency virus type 1 p24 antigen assay on various HIV-1 subtypes for thefollow-up of human immunodeficiency type 1 seropositive individuals.J Virol Methods2003; 113:29-34) and anti-syphilis antibody (anti-treponemal 17 kDa protein) (George R et al.Ananalysis of the value of some antigen-antibody interactions used as diagnosticindicators in a treponemal Western blot (TWB) test for syphilis.J Clin Lab Immunol1998; Antibody combined being tagged on Protein A or the G antibody absorption surface material such as 50:27-44).Because the molecular weight of every kind of sick viral antigen of special body antibody capture is different, so when Protein A/G-antibody and mass spectrometer use in conjunction, mass spectrometer has just separated multiple antigen easily simultaneously.Reasoning thus, if select multiple specific antibody simultaneously, and the antigen molecular of these antibody institute combinations is different, then the present invention can distinguish countless versions disease antigen mark simultaneously.
Summary of the invention
The objective of the invention is to set up a kind of purposes that in biological sample, detects multiple disease biomarker or antigenic mark.This invention relates to biomarker (biomarkers), and these biomarkers can be distinguished multiple disease simultaneously by the higher specificity and the mass spectrum of sensitivity.
The present invention relates to a kind of mark specific antibody that passes through to antibody absorption surface material (Protein A and G or Mercapto-Ethyl-Pyridine), and detect multiple disease biomarker simultaneously with mass spectrophotometry.
Biomarker among the present invention is to utilize a mass spectrometer to do last evaluation.The exactness high in quality of this equipment is about+and/-0.1%.
Antibody absorption surface material: with Protein A and G antibody absorption surface material is representative (Protein A and G has capture antibody Fc section function).Protein A and G base and antibodies with absorbing agent function, biomarker/antigen protein in the antibodies serum.Through one section time enough, biomarker/antigen can be combined with antibody-ProteinA/G.The material that the base flush away does not adsorb.
Biomarker at first can be had the special antibody-Protein A and G absorption surface material that can combine with biomarker catches, and non-adsorbate can be from wash-out on the absorption surface material.Add reductive agent then, antigen is separated with antibody, the supernatant that will contain antigen is detected in flight mass spectrometer.The source takes place by ion in biomarker, as laser, is ionized, and the ion of generation is experienced the collector collection by an ion, and mass analyzer is analyzed those ions that passes through then.Afterwards, detecting device is a mass-to-charge ratio with the ion information translation that detects.The detection of biomarker is significantly with relevant with the detection of signal intensity.Like this, the quantity of biomarker and quality can be detected.
Flight mass spectrum generates time of flight spectrum to the analysis of analysans.The independent pulse signal that sample of ionization energy attack produces is not represented in the final analysis of this time of flight spectrum, but the signal sum of a series of pulses.Reduce interference like this, and increased dynamic range.These flight time data are subjected to the influence of data processing software.Data processing mainly comprises conversion flight time and mass-to-charge ratio and produces mass spectrum in the software, reduces baseline and reduces the side-play amount of instrument and filtration high frequency noise and alleviate high frequency noise.
Can utilize the DAP of computing machine to analyze by the data that the detection to biomarker produces.These data of this computer program analysis to be showing the quantity of detected label, and the intensity of shows signal and determine the molecular weight of each detected biomarker.Data analysis can also comprise the signal intensity of a series of definite biomarker and correct data departing from predetermined statistical distribution state.For example, by the height of calculating with each peak value of some parameter correlation, but the peak value that standard is measured.This parameter may be the interference that is produced by chemical constitutions such as instrument and similar energy absorption molecules, and this can be provided with zeroing.
Computing machine can convert computational data to various forms and show.Its standard spectrum can be expressed as two kinds: in a kind of form, have only peak height and quality information to keep in bands of a spectrum, produce one and scheme, and make more clearly to have easier the manifesting of biomarker of molecular weight much at one.In another form, two or more spectrums relatively are convenient to highlight the unique biological label and are higher or lower than the biomarker of calibration sample with those.
Analysis generally comprises the evaluation at peak the collection of illustrative plates of the signal that displaying obtains from analysans.The peak can be selected by view, and software is available, and it is detected peaks automatically.Generally speaking, this software is tested and appraised signal and has signal to noise ratio (S/N ratio) and be higher than one and select threshold value and mark in the such mode of quality at the peak at the barycenter place of peak-to-peak signal to operate.In an effective program, more many spectral lines appear in the mass spectrum some same in a certain selected scope peaks with identification.A version of this software is assembled all peaks that appear at each the bar spectrum in definite mass range, near all peaks quality of appointment (mass-to-charge ratio) quality (mass-to-charge ratio) intermediate value bunch.
The multiple disease biomarker that uses in the invention is caught by multiple special antibody.These biomarkers are by measuring its different molecular weight by mass spectrum (mass spectrometry).
On the adsorption site that a sample need be placed on the detection of biomarker, then clean.On adsorption site, add SINAPINIC acid and allow its drying.Then, with mass spectroscopy it is analyzed, and a legacy figure who has shown protein molecule will generate, this figure is on the basis of the quality-charge ratio of protein molecule, shows with the form of the peak figure that is separated from each other.
Because the biomarker in this invention identifies by quality and antibody, thereby they can detect by mass spectroscopy and directly know the identity that they are specific.This method than antibody be the basis ELISA and immunofluorescence technique more accurate.Yet if necessary, these biomarkers also can pass through, such as, determine that amino acid sequence of polypeptide differentiates.For example, a biomarker can be depicted with many enzymes, for example V8 proteinase (V8 protease) or trypsase, and digestion fragment (digestion fragments), claim the polypeptide fingerprint again, molecular weight can be used to search sequence in database, these sequences match with the molecular weight of the digestion segment that is generated by plurality of enzymes.Perhaps, if this biomarker is not the protein molecule in the given data storehouse, on the basis of the N of biomarker utmost point amino acid sequence (N-terminal AminoAcid Sequence), can use the degraded probe, then, these probes can be used to describe by genome that sample generated that has detected biomarker or cDNA storehouse.At last, protein biomarker available protein scalariform ranking method (protein ladder sequencing) sorts.By after molecule being broken into fragment and the method that fragment can be in order removed a single amino acids molecule from the fragment end with enzymolysis or other being handled, can generate protein gradient (protein ladders).Then, with mass spectrum this gradient is analyzed.Stepped fragment (ladder fragments) can identify the amino acid that is removed from molecular end in qualitative difference.Therefore, the present invention can be used for the goldstandard that multiple disease marker is identified.Say that for example if with anti-syphilis antibody (catching specificity syphilis 17kDa albumen), mass spectrogram shows a 17kDa albumen, we can diagnose syphilis; If a 10kDa albumen then may be syphilis 17kDa protein degradation product; If a 30kDa albumen then may be nonspecific proteins.At this moment just can do amino acid sequence with mass spectrum identifies: i.e. the most accurate discriminating (goldstandard).
Embodiment
The differentiation of embodiment 1 normal person and multiple disease antigenic mark in blood
(1) experimental technique
One, material
1. sample is originated: the blood serum sample of collecting the clinical diagnosis patient.50 routine control groups (normal person, known human chorionic gonadtropin, alpha-fetoglobulin, thyrotropic hormone, lactic dehydrogenase, creatine kinase isozyme, the L-aminobutanedioic acid transferase, transferrins, fibrinogen are all normal); The concurrent thyroid gland of 15 routine pregnant woman is hyperfunction, heart failure or infraction (known human chorionic gonadtropin, alpha-fetoglobulin, thyrotropic hormone, lactic dehydrogenase, creatine kinase isozyme, L-aminobutanedioic acid transferase, transferrins, fibrinogen all raises); 16 routine infractions (only lactic dehydrogenase, creatine kinase isozyme raise); The hyperfunction patient of 14 routine thyroid glands (only thyrotropic hormone, transferrins raise); 12 routine normal pregnancies (only human chorionic gonadtropin rising); 15 routine hepatocarcinoma patients (fibrinogen raises for alpha-fetoglobulin only, L-aminobutanedioic acid transferase).
2. reagent: Protein A and G, hcg antibody, alpha-fetoglobulin antibody, thyrotropic hormone antibody, lactate dehydrogenase antibody, creatine kinase isozyme antibody, L-aminobutanedioic acid transferase antibody, transferrins antibody, fibrin original antibody, acetonitrile, trifluoroacetic acid, SINAPINIC acid (Sinapinic acid) are all available from Sigma company or give.
Two, method
1. the collection of sample: draw serum after the whole blood collection, place-80 ℃ of preservations;
2. the preparation of sample: normal human serum; The concurrent thyroid gland of pregnant woman is hyperfunction, heart failure or infraction positive serum; The infraction positive serum; The hyperfunction patient's positive serum of thyroid gland; The normal pregnancies positive serum; The hepatocarcinoma patient positive serum.
3. The pretreatment: earlier 8 kinds of antibody are bonded to simultaneously a Protein A pillar (Column) and go up (the multiple antibody of pillar), then 100 μ l diluted sample are loaded in the pillar and slightly shook at ambient temperature 0.5 hour.From pillar, remove damping fluid (pH7.0-7.4).The same binding buffer liquid of 200 μ l is added in each pillar and concussion was washed 5 minutes.Repeated washing.Removing damping fluid and adding reductive agent (pH3.0-5.0) makes antigen separate from pillar.Get SINAPINIC acid (5mg/mL 50% acetonitrile that supernatant (containing antigen) adds 0.5 μ l; 0.5% trifluoroacetic acid), the drying of giving free rein to.
4. sample detection: sample is put into mass spectrum, will generate flight time mass spectrum.The outside peptide molecule quality standard of using is come the correction mass accuracy.
(2) experimental result
Analyze the composition of protein in 72 routine patients and 50 routine control group (normal person) serum, found that the antigenic mark that 8 protein are formed can divide into groups control group (normal person) with the patient accurately.
Predictablity rate: in statistical analysis and double blinding analysis, the result shows: the antigenic mark of forming with these 8 protein detects, and finds that 72 routine patients and 50 routine control groups (normal person) are correctly divided into groups, and accuracy rate is 100% (122/122).Sensitivity is 100%, and (the concurrent thyroid gland of 15/15 routine pregnant woman is hyperfunction, heart failure or infraction; 16/16 routine infraction; The hyperfunction patient of 14/14 routine thyroid gland; 12/12 routine normal pregnancies; 15/15 routine hepatocarcinoma patient; Correctly divided into groups); Specificity was 100% (50/50 routine control group normal person is correctly divided into groups).
(3) conclusion
To compare from sample with statistical significance patient group and control group (normal specimens), 5 kinds of diseases can be differentiated simultaneously with 8 kinds of serum antigen marks that specific antibody absorption surface material is caught, promptly multiple disease can be differentiated simultaneously with the Mass Spectrometer Method method of these antigenic mark combinations.
In theory, when the specific antibody amount that is added on the antibody absorption surface material ad infinitum increases, the antigenic mark molecule of measuring or biomarker also can correspondingly increase, promptly detect the biomarker more than three kinds simultaneously.On the absorption surface of a multiple antibody, catch multiple antigenic mark, and the antigenic mark of catching is carried out mass spectrophotometry, can detect a plurality of or multiple antigenic mark group simultaneously.

Claims (10)

1. catch the protein analysis method of antigenic mark in the biological sample with antibody absorption surface material for one kind, it is characterized in that adopting mass spectrophotometry that protein group in the sample is differentiated detection.
2. the described protein analysis method of claim 1, the method that wherein said discriminating detects protein group is a mass spectroscopy.
3. the described protein analysis method of claim 1, used antibody absorption surface material is any material that can combine with antibody selectivity or specificity, as albumin A and G (Protein A and Protein G).
4. the described antibody absorption surface of claim 3 material is monoclonal or the polyclonal antibody that is used for the capture antigen mark.
5. the described protein analysis method of claim 1, used antibody absorption surface material is in conjunction with a plurality of or organize monoclonal antibody more and remove to catch a plurality of or multiple biomarker (antigenic mark), can increase the monoclonal antibody group endlessly and reach and detect a plurality of or multiple biomarker or antigenic mark endlessly.
6. the described protein analysis method of claim 1, the analyte that used antibody absorption surface material is caught is biological sample-blood, body fluid, secretion, cytolysate, histolysate and organ dissolved matter.
In the methods analyst biological sample with claim 6 special biomarker to detect the purposes of multiple disease antigen mark.
8. with claim 7, can detect the authentication method of the antigenic mark more than three kinds simultaneously.
9. the described biomarker of claim 5 derives from blood, body fluid, secretion, cytolysis thing, histolysate and organ dissolved matter.
10. the holder of antibody absorption surface material can be sheet metal, glass sheet, potsherd, ceramic bead, magnetic particle or polymer in the claim 1.
CN 200410004403 2004-02-19 2004-02-19 Use of investigating multiple antigen label combined by antibody absorption surface material and mass spectrum Pending CN1657941A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008043256A1 (en) * 2006-10-08 2008-04-17 Yang Xu Test kit for detecting variant or modified biomarker groups with antibody groups and mass spectrometry, and method thereof
CN105209907A (en) * 2013-06-05 2015-12-30 Dh科技发展私人贸易有限公司 SWATH™ Data Independent Acquisition Technology for Detection of Host Cell Protein Contaminants in Biotherapeutic Protein Products

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008043256A1 (en) * 2006-10-08 2008-04-17 Yang Xu Test kit for detecting variant or modified biomarker groups with antibody groups and mass spectrometry, and method thereof
CN101158666B (en) * 2006-10-08 2012-06-27 许洋 Antibody group and mass spectrometric detection variation or modifying biological indication marks group kit and method
CN105209907A (en) * 2013-06-05 2015-12-30 Dh科技发展私人贸易有限公司 SWATH™ Data Independent Acquisition Technology for Detection of Host Cell Protein Contaminants in Biotherapeutic Protein Products
CN105209907B (en) * 2013-06-05 2019-08-16 Dh科技发展私人贸易有限公司 SWATH™ Data Independent Acquisition Technology for Detection of Host Cell Protein Contaminants in Biotherapeutic Protein Products

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