CN101275885B - Analysis method of solid phase micro-extraction surface plasma resonance on-line joint use - Google Patents
Analysis method of solid phase micro-extraction surface plasma resonance on-line joint use Download PDFInfo
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- CN101275885B CN101275885B CN2007101913892A CN200710191389A CN101275885B CN 101275885 B CN101275885 B CN 101275885B CN 2007101913892 A CN2007101913892 A CN 2007101913892A CN 200710191389 A CN200710191389 A CN 200710191389A CN 101275885 B CN101275885 B CN 101275885B
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Abstract
An analysis method for online combination of a solid phase microextraction and surface plasma resonance of the invention, characterized in that the method connects the covering capillary for the extraction selected by the target analyzing object to the between the sample inlet joint of the surface plasma resonance sensor and the micro-fluid ejecting plate; then the method orderly connects the quantitative water sample and the single clone antibody solution to the online combined analysis device via the joint which can achieve the online analysis of the organic matter of the water special track quantity; then the method orderly connects the single clone antibody solution of the target analyzing object and the rebirth liquor to the online combined analysis device, namely removes the residual track quantity organic mater and achieve the rebirth of the chip. The invention can be used for the analysis and detection of the pesticide residue, phenol, polychlorinated biphenyls, polycyclic aromatic hydrocarbon, benzene series, fatty acid, amine, aldehydes, non-ion surface active agent and organic metal compound; the invention has the advantages of fast, high efficiency, high sensitivity, great reappearance, automation, which is a potential method for the online analyzing the organic matter in the water track quantity.
Description
Technical field:
The invention belongs to the environmental analysis technical field, particularly on-line coupling solid-phase microextraction and surface plasma resonance technology are to realize the separating of organic contaminant in the sample, enrichment, to go to disturb and quantitative detection method.
Background technology:
Organic contaminant residual quantity in environment is very low, often is low to moderate μ g/l even ng/l, and this has brought difficulty just for the detection of these organic micro-pollutants, research.As everyone knows, the preprocessing process of environmental sample is an important step, accounts for 2/3rds of whole analysis time.At present organic preconditioning technique in the water sample is mainly contained liquid-liquid extraction method, solid phase extraction, solid-phase microextraction method etc.Wherein Solid-Phase Extraction (SPE) technology realizes simply, efficiently, easily that because of it advantage such as the low consumption of robotization and organic solvent replaces traditional liquid-liquid extraction method (LLE) gradually, become the main method of sample pretreatment, be specially adapted to the detection and the analysis of trace organic substance in the environmental sample.Although SPE because of the extraction efficiency height, solvent-oil ratio is little, the enrichment multiple is big etc., and advantage has been widely used in the residual analysis of organic contaminant in the environmental sample, but when using SPE to handle the batch sample, still there is complex operation, introduces problems such as error easily, and still need to consume certain organic solvent.
Solid-phase microextraction (SPME) is a kind of based on the test substance abstraction technique that balance is distributed in sample and extraction coating what grow up on the solid phase extraction techniques basis, and its advantage is to have eliminated organic solvent fully.It is combined with technology such as gas chromatographies, can realize that extraction, preenrichment, sample introduction once finish, reduced analysis time, and easy and simple to handle, can realize automatic sampling, become the strong detection means of chemical analysis and instrumental analysis.But the analytical approach of present and SPME coupling is only applicable to analyze the organism of volatility and half volatile, and is powerless to the difficult volatile organic matter that occupies machine species 2/3.And, be difficult to the extract wash-out is detected with other off-line method again because the SPME enriching quantity is limited.
Surface plasma resonance (SPR) biology sensor is a kind of novel biochemical analytic system based on the physical optics principle.Compare with traditional transactional analysis technology, characteristics such as it has real-time monitoring, need not mark, consumption sample amount is few, simple to operate all have using value in all many-sides such as research intermolecular interaction, food analysis, environmental monitorings.But because organic contaminant mostly is micromolecule in the environment, make the application surface plasmon resonance biosensor generally adopt the method for indirect detection when micromolecule is detected, promptly in sample, add the quantitative big molecule (as monoclonal antibody) that combines with the organic contaminant specificity, by macromolecular quantitative test being realized detection to organic contaminant; In addition, the content of organic contaminant mostly is lower than the detectability of surface plasmon resonance biosensor in the environment, and this goes to toward utilizing off-line SPE that the organic contaminant in the sample is extracted and concentrates with regard to requiring to carry out sample detection at application SPR.Thereby traditional application SPR method of detecting organic micro-pollutant still exist complex operation, easily introduce error, reappearance is relatively poor and problem such as sensitivity deficiency.
Summary of the invention:
The invention provides the analytical approach of a kind of solid-phase microextraction and surface plasma resonance on-line joint use, overcoming the above-mentioned deficiency of prior art, realize fast, the automation process of organic contaminant in the efficient detection environment.
The analytical approach of solid-phase microextraction of the present invention and surface plasma resonance on-line joint use is utilized surface plasma resonance biological sensor and solid phase micro-extraction technique; It is characterized in that comprising the steps:
(1) foundation of on-line coupling analytical equipment
Select the coatings capillary pipe of respective type according to the target analysis properties, the coatings capillary pipe of this confession extraction usefulness is connected between the sample introduction joint and microjet chuck of surface plasma resonance biological sensor, be built into the on-line coupling analytical equipment: in this on-line coupling analytical equipment, the reagent bottle of splendid attire current-carrying liquid links to each other with sampling injector with the current-carrying syringe simultaneously; The current-carrying syringe by coupling assembling and microjet chuck, is crossed chip surface with the current-carrying liquid pump successively, and current-carrying liquid is flowed through sensing chip afterwards again by microjet chuck and coupling assembling, flows in the waste liquid bottle; Sample introduction joint in sampling injector, automatic sampler, the coupling assembling, coatings capillary pipe, microjet chuck link to each other successively, testing sample, antibody, regeneration damping fluid pump are successively crossed coatings capillary pipe and the sensing chip surface is detected; These reagent are flowed through sensing chip afterwards again by microjet chuck and coupling assembling, flow in the waste liquid bottle; The sensing chip one side is close together with the flow cell of microjet chuck, and another side and detecting device are close together, and when solution was surperficial by sensing chip, detecting device was collected signal and detected;
(2) the organic on-line analysis of underwater trace
Front and back at the automatic sampler sample introduction, surface plasma resonance biological sensor can feed the on-line coupling analytical equipment by the current-carrying syringe with the current-carrying inlet of the current-carrying liquid in the reagent bottle in coupling assembling automatically, to guarantee having flow of solution to cross the sensing chip surface always, at first, by sampling injector control automatic sampler, the monoclonal anti liquid solution that with 5-750 μ l water sample and 5-100 μ l concentration is the target analytes of 10 μ g/L-100mg/L successively feeds the on-line coupling analytical equipment from the sample introduction joint, target analytes in the water sample can be scribbled the coatings capillary pipe extraction that can extract this target analytes, and then the antibody that feeds combines with the target analytes that is extracted then, it is surperficial and detected that unconjugated antibody flows through sensing chip with solution through the microjet chuck, collects the on-line analysis that signal is promptly realized target analytes in the water sample this moment;
(3) regeneration of the removal of residual trace organic substance and chip
The monoclonal anti liquid solution and the 5-50 μ l regenerated liquid that with 5-325 μ l concentration are the target analytes of 10 μ g/L-100mg/L successively feed the on-line coupling analytical equipment from the sample introduction joint.
Described regenerated liquid is that 10-100mM NaOH and mass concentration are the mixed solution of 0.001%-0.5% sodium dodecylsulphonate.
When adopting the analytical approach of solid-phase microextraction of the present invention and surface plasma resonance on-line joint use to carry out analyzing and testing, by current-carrying syringe 2 the current-carrying inlet of the current-carrying liquid in the reagent bottle 1 in coupling assembling 5 fed the on-line coupling analytical equipment, to guarantee having flow of solution to cross chip 9 surfaces always; At first, by sampling injector 3 control automatic samplers 4, the sample introduction joint 6 of monoclonal anti liquid solution in coupling assembling 5 with water sample and target analytes feeds the on-line coupling analytical equipment successively, target analytes in the water sample can be scribbled coatings capillary pipe 7 extractions that can extract this target analytes, and then the antibody that feeds combines with the target analytes that is extracted then, it is surperficial and detected that unconjugated antibody flows through chip 9 with solution through microjet chuck 8, collects the on-line analysis that signal can be realized target analytes in the water sample this moment.At last, feed the solution of on-line coupling analytical equipment through microjet chuck 8 and coupling assembling 5 inflow waste liquid bottles 10.
Compared with prior art, the present invention has following outstanding advantage:
(1) since the present invention with solid-phase microextraction and surface plasma resonance technology on-line coupling, sample pre-treatments and detection are carried out synchronously, shortened analysis time, and operation is simple, favorable reproducibility has been avoided general off-line solid phase extraction complex operation, many, shortcoming such as solvent-oil ratio is big consuming time; Compare with existing SPME method for combined use, this method can be used to analyze difficult volatile organism.
(2) owing to the present invention analyzes the monoclonal antibody continuous sample introduction of water sample and binding target molecule, broken surface plasma resonance biological sensor and detected the traditional detection pattern of small-molecule substance, made organic separation in the sample, enrichment, go to disturb and detection by quantitative can be finished in continuous automatic sampling owing to need defectives such as easy introducing error that the monoclonal antibody of interpolation binding target molecule in the sample after extraction concentrates causes, sensitivity deficiency.
(3) coatings capillary pipe for extraction usefulness among the present invention is changed conveniently, can select dissimilar coatings capillary pipes according to the target analysis properties when practical application.
(4) owing to sample pre-treatments among the present invention is carried out synchronously with detecting, can be implemented in the concentration of line analysis or online detection object.
The inventive method has been broken the traditional detection pattern of surface plasma resonance biological sensor detection small-molecule substance, but having advantages such as quick, efficient, highly sensitive, favorable reproducibility robotization, is the organic method of a kind of quite potential on-line analysis underwater trace.The analytical approach of solid-phase microextraction of the present invention and surface plasma resonance on-line joint use is applicable to the analyzing and testing of residues of pesticides, phenols, polychlorinated biphenyl, palycyclic aromatic, benzene series thing, fatty acid, amine, aldehydes, non-ionic surfactant and organometallics etc.
Description of drawings:
Fig. 1 is the employed on-line coupling analytical equipment of a inventive method connected mode synoptic diagram.
Fig. 2 for solid phase micro-extraction surface plasma resonance on-line joint with analyzing the resonance signal curve that contains the standard solution of variable concentrations estradiol in embodiment 1 water sample;
Fig. 3 is the estradiol concentration done according to Fig. 2 analysis result among the embodiment 1 and the typical curve of resonance signal.
Embodiment:
Below in conjunction with embodiment the specific operation process of the inventive method is described in further detail.
Embodiment 1: the estradiol in the on-line analysis water
Fig. 1 has provided the employed on-line coupling analytical equipment of the inventive method connected mode synoptic diagram: this on-line coupling analytical equipment comprises the current-carrying syringe 2 of surface plasma resonance biological sensor, the automatic sampler 4 of sampling injector 3 and control thereof, coupling assembling 5, microjet chuck 8, chip 9, the coatings capillary pipe 7 of detecting device and confession extraction usefulness, wherein the inlet of the current-carrying in the coupling assembling links to each other with microjet chuck 8 respectively with waste liquid outlet, the other end of current-carrying inlet links to each other with current-carrying syringe 2, be connected by coatings capillary pipe 7 between sample introduction joint 6 in the coupling assembling and the microjet chuck 8 for extraction usefulness, chip simultaneously is fixed in the flow cell of microjet chuck, another side is fixed in detecting device, automatic sampler feeds microjet chuck 8 with sample solution through the sample introduction joint under the control of sampling injector, when solution flows through chip 9 surfaces by the microjet chuck, detecting device is collected signal, and solution flows out from the waste liquid outlet of microjet chuck 8 and coupling assembling 5 subsequently;
On-line coupling analysis to estradiol in the water in the present embodiment is undertaken by following step:
(1) foundation of on-line coupling analytical equipment
Select the coatings capillary pipe 7 of silicone rubber coating according to the character of the target analytes estradiol of present embodiment, the silicone rubber coating kapillary is connected between the sample introduction joint 6 and microjet chuck 8 of surface plasma resonance biological sensor.
(2) on-line analysis of estradiol in the water
Front and back at automatic sampler 4 sample introductions, surface plasma resonance biological sensor can feed the on-line coupling analytical equipment by current-carrying syringe 2 with the current-carrying inlet of the current-carrying liquid in the reagent bottle 1 in coupling assembling 5 automatically, to guarantee having flow of solution to cross chip 9 surfaces always.At first, by sampling injector 3 control automatic samplers 4, be the sample introduction joint 6 feeding on-line coupling analytical equipments of estradiol monoclonal anti liquid solution in coupling assembling 5 of 40 μ g/L with 100 μ l water samples and 30 μ l concentration successively, estradiol in the water sample can be by 7 extractions of silicone rubber coating kapillary, and then the antibody that feeds combines with the estradiol that is extracted then, it is surperficial and detected that unconjugated antibody flows through chip 9 with solution through microjet chuck 8, collects the on-line analysis that signal can be realized estradiol in the water sample this moment.At last, feed the solution of on-line coupling analytical equipment through microjet chuck 8 and coupling assembling 5 inflow waste liquid bottles 10.
(3) regeneration of the removal of residual estradiol and chip
With 50 μ l concentration be successively the estradiol monoclonal anti liquid solution of 40 μ g/L and 30 μ l to contain 50mM NaOH and mass concentration be that the mixed solution of 0.05% sodium dodecylsulphonate feeds the on-line coupling analytical equipment, promptly realize the removal of residual estradiol in the pipeline and the regeneration of chip surface.
Fig. 2 is the resonance signal curve of solid phase micro-extraction surface plasma resonance on-line joint with the standard solution that contains the variable concentrations estradiol in the analysis water-like.As can be seen from Figure 2, be that the estradiol standard solution of 0.625 (curve A), 1.25 (curve B), 2.5 (curve C), 5 (curve D) and 10 (curve E) μ g/L carries out on-line analysis respectively with concentration, collect signal and can obtain corresponding resonance signal curve; As shown in Figure 2, the concentration of estradiol is high more in the water sample, and the pairing resonance signal of feeding antibody-solutions is weak more.
By to concentration-resonance signal size mapping, just obtain the estradiol concentration shown in Figure 3 and the typical curve of resonance signal.As seen from Figure 3, in this concentration range, the resonance signal size is inversely proportional to estradiol concentration; By the resulting resonance signal size of the on-line analysis of water sample is calculated, just can learn the estradiol content in this water sample.
Embodiment 2: the estriol in the on-line analysis water
On-line coupling analysis to estriol in the water in the present embodiment is undertaken by following step:
(1) foundation of on-line coupling analytical equipment
Poly-dimethoxy silane coating kapillary is connected between the sample introduction joint and microjet chuck of surface plasma resonance biological sensor.
(2) on-line analysis of estriol in the water
Be the estriol monoclonal anti liquid solution feeding on-line coupling analytical equipment of 10 μ g/L with 5 μ l water samples and 5 μ l concentration successively, collect the on-line analysis that signal can be realized estriol in the water sample.
(3) regeneration of the removal of residual estriol and chip
With 5 μ l concentration be successively the estriol monoclonal anti liquid solution of 10 μ g/L and 5 μ l to contain 10mM NaOH and mass concentration be that the mixed solution of 0.001% sodium dodecylsulphonate feeds the on-line coupling analytical equipment, promptly realize the removal of residual estriol in the pipeline and the regeneration of chip surface.
Embodiment 3: the oestrone in the on-line analysis water
On-line coupling analysis to oestrone in the water in the present embodiment is undertaken by following step:
(1) foundation of on-line coupling analytical equipment
The silicone rubber coating kapillary is connected between the sample introduction joint and microjet chuck of surface plasma resonance biological sensor.
(2) on-line analysis of oestrone in the water
Be the oestrone monoclonal anti liquid solution feeding on-line coupling analytical equipment of 100mg/L with 750 μ l water samples and 100 μ l concentration successively, collect the on-line analysis that signal can be realized oestrone in the water sample.
(3) regeneration of the removal of residual oestrone and chip
With 325 μ l concentration be successively the oestrone monoclonal anti liquid solution of 100mg/L and 50 μ l to contain 100mM NaOH and mass concentration be that the mixed solution of 0.5% sodium dodecylsulphonate feeds the on-line coupling analytical equipment, promptly realize the removal of residual oestrone in the pipeline and the regeneration of chip surface.
The analytical approach of solid-phase microextraction of the present invention and surface plasma resonance on-line joint use is also applicable to the analyzing and testing of residues of pesticides, phenols, polychlorinated biphenyl, palycyclic aromatic, benzene series thing, fatty acid, amine, aldehydes, non-ionic surfactant and organometallics etc.
Claims (2)
1. the analytical approach of solid-phase microextraction and surface plasma resonance on-line joint use is utilized surface plasma resonance biological sensor and solid phase micro-extraction technique; It is characterized in that comprising the steps:
(1) foundation of on-line coupling analytical equipment
Select the coatings capillary pipe of respective type according to the target analysis properties, the coatings capillary pipe of this confession extraction usefulness is connected between the sample introduction joint and microjet chuck of surface plasma resonance biological sensor, be built into the on-line coupling analytical equipment: in this on-line coupling analytical equipment, the reagent bottle of splendid attire current-carrying liquid links to each other with sampling injector with the current-carrying syringe simultaneously; The current-carrying syringe by coupling assembling and microjet chuck, is crossed the sensing chip surface with the current-carrying liquid pump successively, and current-carrying liquid is flowed through sensing chip afterwards again by microjet chuck and coupling assembling, flows in the waste liquid bottle; Sample introduction joint in sampling injector, automatic sampler, the coupling assembling, coatings capillary pipe, microjet chuck link to each other successively, testing sample, antibody, regeneration damping fluid pump are successively crossed coatings capillary pipe and the sensing chip surface is detected; These reagent are flowed through sensing chip afterwards again by microjet chuck and coupling assembling, flow in the waste liquid bottle; The sensing chip one side is close together with the flow cell of microjet chuck, and another side and detecting device are close together, and when solution was surperficial by sensing chip, detecting device was collected signal and detected;
(2) the organic on-line analysis of underwater trace
Front and back at the automatic sampler sample introduction, surface plasma resonance biological sensor can feed the on-line coupling analytical equipment by the current-carrying syringe with the current-carrying inlet of the current-carrying liquid in the reagent bottle in coupling assembling automatically, to guarantee having flow of solution to cross the sensing chip surface always, at first, by sampling injector control automatic sampler, the monoclonal anti liquid solution that with 5-750 μ l water sample and 5-100 μ l concentration is the target analytes of 10 μ g/L-100mg/L successively feeds the on-line coupling analytical equipment from the sample introduction joint, target analytes in the water sample can be scribbled the coatings capillary pipe extraction that can extract this target analytes, and then the antibody that feeds combines with the target analytes that is extracted then, it is surperficial and detected that unconjugated antibody flows through sensing chip with solution through the microjet chuck, collects the on-line analysis that signal is promptly realized target analytes in the water sample this moment;
(3) regeneration of the removal of residual trace organic substance and chip
The monoclonal anti liquid solution and the 5-50 μ l regenerated liquid that with 5-325 μ l concentration are the target analytes of 10 μ g/L-100mg/L successively feed the on-line coupling analytical equipment from the sample introduction joint.
2. the analytical approach of solid-phase microextraction and surface plasma resonance on-line joint use according to claim 1 is characterised in that described regenerated liquid is that 10-100mM NaOH and mass concentration are the mixed solution of 0.001%-0.5% sodium dodecylsulphonate.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6194223B1 (en) * | 1997-04-14 | 2001-02-27 | Roche Diagnostics Gmbh | Method for the simultaneous determination of biomolecular interactions by means of plasmon resonance and fluoresence detection |
| CN1945332A (en) * | 2006-10-01 | 2007-04-11 | 中国科学技术大学 | Method for detecting pyrimidine dipolymer content on DNA chain |
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| US6194223B1 (en) * | 1997-04-14 | 2001-02-27 | Roche Diagnostics Gmbh | Method for the simultaneous determination of biomolecular interactions by means of plasmon resonance and fluoresence detection |
| CN1945332A (en) * | 2006-10-01 | 2007-04-11 | 中国科学技术大学 | Method for detecting pyrimidine dipolymer content on DNA chain |
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