CN100408994C - Apparatus for metering analytes contained in a liquid sample and related process - Google Patents
Apparatus for metering analytes contained in a liquid sample and related process Download PDFInfo
- Publication number
- CN100408994C CN100408994C CNB038156407A CN03815640A CN100408994C CN 100408994 C CN100408994 C CN 100408994C CN B038156407 A CNB038156407 A CN B038156407A CN 03815640 A CN03815640 A CN 03815640A CN 100408994 C CN100408994 C CN 100408994C
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- CN
- China
- Prior art keywords
- equipment
- sample
- reagent
- valve
- pipeline
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N35/00—Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
- G01N35/10—Devices for transferring samples or any liquids to, in, or from, the analysis apparatus, e.g. suction devices, injection devices
- G01N35/1095—Devices for transferring samples or any liquids to, in, or from, the analysis apparatus, e.g. suction devices, injection devices for supplying the samples to flow-through analysers
- G01N35/1097—Devices for transferring samples or any liquids to, in, or from, the analysis apparatus, e.g. suction devices, injection devices for supplying the samples to flow-through analysers characterised by the valves
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N35/00—Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
- G01N35/08—Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor using a stream of discrete samples flowing along a tube system, e.g. flow injection analysis
Abstract
Apparatus (1) for metering analytes in liquid samples apt to be used in underwater environment, comprising: a sampling unit (2) to allow the addition inside the apparatus itself of the liquid sample (C) to be analyzed; a unit (22) for the addition to the sample of reagents (R1, ..., Rn); a unit (28) for detecting the concentration of the analytes contained in the sample; a closed circuit (10) which connects the above mentioned units to allow the continuous and repeated circulation of the sample among them; and a peristaltic pump (29) arranged along the closed circuit, the arrangement being so that the reagent-inletting valves of the addition units are arranged along the closed circuit, implementing tracts with tortuous development of the latter and so that the mixing between sample and reagents takes place thanks to the turbulent motion which begins during the circulation of the sample inside the circuit.
Description
Technical field
The present invention relates to measure the equipment and relevant method of contained analyte in the liquid sample that is fit to underwater environment.Specifically, the present invention relates to such equipment, comprising: sampling unit, can add analyzed liquid sample at device interior; Adding device can add a kind of reagent at least in sample; Detecting unit is used for detecting the concentration of the contained analyte of sample; And pump arrangement, sample is circulated between different unit.
Background technology
In artificial practice, in order to carry out chemical analysis, at first need to determine reactive chemistry and its condition of carrying out, then, we add required reagent in analyzed sample.At last, the time that these compositions are mixed to reduce molecular diffusion also can make chemical reaction carry out apace.In case the generation chemical reaction, for example, we can utilize than colour pattern method check and analysis thing.Under the situation of this last type of analysis methodologies, the progress of chemical reaction relates to the transmission change of reaction product frequency spectrum, and transparency and/or the absorption band of this product on specific wavelength is relevant with the concentration of object being measured.
In nearest 50 years, people have set up the automated system that number of chemical is analyzed.Specifically.Can realize the such instrumentation of many method utilizations of this robotization, they are based on so-called " Continuous Flow Analysis " (C.F.A.), " FlowInjection Analysis " (F.I.A.) and " Discrete Analysis " (D.A.) analysis principle.
At clinical field, people have designed this automated system that belongs to prior art, but the restriction of its detectability is not enough to satisfy the analysis requirement in many fields.In addition, the analytical equipment of prior art has huge mechanical dimension, and it is not easy to transportation or is used as on-the site analysis.Because this shortcoming, described equipment is not suitable for environmental monitoring, for example, the ocean, the river, the lake, air and industrial discharge are because these use the system requirements height miniaturization to using.Another shortcoming of prior art equipment is, a large amount of consumption of reagent and electric energy, and it relates to the logistics support problem.
The shortcoming of above-mentioned prior art systems is overcome by the content of italian patent 1249433, and its author is the application's a same Applicant, and this patent is described the equipment that comprises closed fluid pressure line, and it makes the circulation repeatedly in equipment of analyzed sample.
Yet the equipment of described patent is not suitable for medium and the underwater environment of high depth very.In fact, this equipment provides based on sample and the reagent mix of using mixing chamber, sets up depression in mixing chamber circularly, and this mode of operation is not suitable for the pressure environment under the High Voltage.
In addition, we still need to make element miniaturization and the further use amount that reduces reagent more.
Summary of the invention
Technical matters of the present invention provides a kind of equipment and relevant method, and it can overcome the above-mentioned shortcoming relevant with prior art.
The equipment that is used for measuring the liquid sample analyte of the present invention can address this problem, and this equipment comprises:
Sampling unit is suitable for adding analyzed liquid sample in equipment;
Adding device is suitable for adding a kind of reagent selectively at least in sample, and this adding device comprises itself: the suction valve that at least one reagent hold-up vessel is relevant with at least one is drawn in the sample reagent;
Detecting unit is used for detecting the concentration of the contained analyte of sample;
Hydraulic pressure connects the device of each described unit, is suitable for forming closed hydraulic pressure mixed pipe line, and sample is circulated in described unit continuously and repeatedly; With
Pump arrangement, it is arranged on the described mixed pipe line and is suitable for determining the circulation of described sample,
This arrangement is such, at least one reagent suction valve of described adding device is inserted into described mixed pipe line, and by means of the action of described pump arrangement, reagent is directly entered in the described pipeline, and described at least one reagent suction valve forms the pipeline that described mixed pipe line complications are advanced, therefore, by means of the turbulent motion of setting up in the described pipeline, between described sample and described at least a reagent, mix.
The present invention also provides a kind of equipment set that is used for measuring the contained analyte of sample of underwater environment, comprising:
The described equipment that is used for measuring the liquid sample analyte, wherein said sampling unit are suitable for taking out liquid sample from underwater environment; With
Pressure compensator, portion installs described equipment and is suitable for making it to keep substantially invariable pressure within it, and this pressure equals the pressure of outside underwater environment substantially.
According to same inventive concept, the invention still further relates to a kind of method that is used for measuring the liquid sample analyte, comprise the steps:
In mixed pipe line, introduce analyzed liquid sample;
At least add a kind of reagent selectively in sample, it directly sucks the container in described pipeline separately;
The state of setting up turbulent motion in described pipeline is to realize mixing of described sample and described at least a reagent; With
Detect the concentration of contained analyte in the sample of mixing reagent along described mixed pipe line.
Term herein " valve " has wide significance, that is, it is meant and is applicable to that in pipeline permission/prevention introduces any device of reagent.
The present invention also has some important advantages.Main advantage is based on such fact, because the arrangement and the shape of reagent suction valve, by means of continuous circulation be under the turbulence state, every kind of reagent can mix with analyzing samples effectively and directly enters into mixed pipe line, therefore, the present invention does not need mixing chamber.With respect to prior art system, this can reduce required amount of reagent and realize further miniaturization.In addition, this is the air in the remover apparatus pipeline fully, so this equipment can be used for the pressure environment that pressure is several hectobars, therefore, it can finish chemical analysis effectively in the underwater environment at deep-sea.
Description of drawings
By following detailed description to some embodiment, these embodiment only as an example rather than restrictive, other advantages of the present invention, feature and application are conspicuous.We are with reference to following accompanying drawing, wherein:
Fig. 1 represents the equipment work scheme according to the embodiment of the invention; With
Fig. 2 represents to comprise according to the present invention factory's programme of work of equipment shown in Figure 1.
Embodiment
At first with reference to Fig. 1, the equipment integral of measuring analyte in the liquid is labeled as 1.
Equipment 1 comprises: a plurality of unit of hydraulic pressure connection are to form the fluid pressure line 10 that mixes mutually.
Specifically, equipment 1 comprises: sampling unit 2 is suitable for introducing analyzed liquid sample C at device interior.This sampling unit 2 at first comprises first T-valve 3, and specifically, it is a guide valve.Be labeled as 4 guides movable end the primary importance 5 and the second place 6 can be arranged; In primary importance 5, the adding liquid sample C that valve 3 allows in equipment specifically, is added in the fluid pressure line 10; In the second place 6, valve 3 and second T-valve 7 are set up liquid stream continuity.T-valve 7 also is a valve that guides 8 is arranged, and its end can be movable between the primary importance 9 and the second place 11.By first valve 3, pipeline 10 is communicated with the container 13 that comprises caliberator at 9, the second valves of primary importance 7.On the contrary, still allow in pipeline 10, to add cleaning fluid by first valve 3 at 11, the second valves 7 of the second place, for example, the water that comprises in the container 12.
Sampling unit 2 also comprises: the 3rd 2 * 3 logical valve 14 of two guidess arranged, and be inserted on the pipeline 10 with On/Off pipeline 10.This valve 14 is inserted on the pipeline 10, in order that be limited with the pipeline of zigzag path.Valve 14 has first threeway part 141 and second threeway part 142, and threeway part 141 comprises first guides 15, and threeway part 142 comprises second guides 19.
First guides 15 has movable end between the primary importance 16 and the second place 17; In primary importance 16, it sets up fluid path between pipeline 10 and first valve 3; In the second place 17, by means of passage 18, it sets up the fluid path with second portion 142, prevents sample to flow into liquid in the detergent line or caliberator.
Second guides 19 has movable end between the primary importance 20 and second vent position 21; In primary importance 20, by means of passage 18, it sets up the fluid path with first 141; In second vent position 21, its permission pipeline 10 is released outside the equipment 1.
Equipment 1 also comprises: adding device 22, be suitable for adding selectively sample, that is and, add plurality of reagents R according to controlled manner
1, R
2..., R
nFor every kind of reagent, unit 22 comprises: container 23 and relevant reagent suction valve 24, it is inserted on the pipeline 10 and limits the pipeline of its zigzag path.Each reagent suction valve 24 is suitable for making selectively relevant container 23 to be communicated with pipeline 10, is used for directly adding in pipeline 10 reagent.Specifically, in the present embodiment, valve 24 is threeway and guides type.Each guides 25 has movable end between the primary importance 26 and the second place 27; In primary importance 26, it allows relevant reagent to flow in pipeline 10; In the second place 27, it prevents described flowing.In this second place 27, valve 24 is set up hydraulic pressure and is connected between other unit of valve 14 and equipment 1, and these unit are inserted on the pipeline 10.
Equipment 1 also comprises: detecting unit 28, be used for detecting the concentration of the contained analyte of sample, for example, photometric detector, specifically, than colour pattern detecting device, fluorescence detector, ion is selected detecting device, electromotive force detecting device, or any other type detector of knowing of professional.
On pipeline 10, also arrange pump arrangement, specifically, the wriggling volume pump 29 of two-way type, it is suitable for making sample to circulate in pipeline 10.
At last, this equipment also comprises: all valves 24,14,3 and 7 control device (not shown), for example, it can be the electric control type, and the control device that comprises plurality of units and pump 29 in the equipment 1.
According to other schemes of this embodiment, equipment of the present invention can also comprise: one or more extra cells, it can with detecting unit 28 collaborative works, and be selected from following one group: reduction column, temperature adjustment serpentine, dialysis piece, still and ion exchange resin.
The mode of operation of present description equipment 1.
In order to implement to sample operation and utilize analyzing samples to be full of the whole volume of mixed pipe line 10, the guides 15 that we make valve 14 firsts 141 is in the position 16 and to make the guides 19 of valve 14 second portions 142 be in vent position 21.The guides 25 of valve 24 is the positions 27 at them.In this configuration, by the excitation of pump 29, equipment 1 can make the liquid sample of analysis enter into pipeline 10.The action of pump 29 can make sample enter pipeline 10 really, and makes sample be recycled to bleed outlet W from sampling unit 2 according to counter clockwise direction shown in Figure 1.After the suitable sample time, make sample fully be full of pipeline 10, then, pump 29 gets clogged, and to make first guides 15 of valve 14 be to be in primary importance 20 in the second place 17 and second guides 19.In this manner, pipeline 10 is closed with respect to the outside, specifically, and with respect to analyzed sample source with respect to bleed outlet W.In detecting unit 28 inside, can also find the sample that adds in the above step in the pipeline, wherein before injecting reagent, can estimate its feature.
In order to implement above this process, we make second guides 19 of valve 14 is in vent position 21, and makes a valve 24 be in configuration corresponding to guides 25 positions 26, and therefore, by means of the action of pump 29, relevant reagent can be called in the pipeline 10.The driving of pump has preset time, thereby can call amount of reagent (mean value is between 50 to 400 microlitres) in proportion.Because the configuration of valve 14 second portions 141, when some reagent were called in the pipeline 10, suitable sample size was driven into bleed outlet W.
When reagent inject to finish, pump 29 was de-energized, and made valve 24 and 14 enter into configuration corresponding to pipeline 10 closures, that is, guides 25 be in the position 27 and guides 19 be in the position 21.For reagent contained in the pipeline 10 is mixed with sample, pump 29 is at rotary state, in order that the sample of reagent is mixed in the circulation of vortex ground.After transmission was by valve 24 and valve 14, particular geometric configuration and arrangement by means of valve can produce very strong eddy current, and this eddy current can make sample mix completely with reagent formation.Therefore, because pump 29 produces continuously and the shuttling movement that repeats sample, the every bit in closed pipeline produces mixing between sample and the reagent substantially.
Certainly, for every kind of reagent, can repeat above-mentioned interpolation and mixed process.
In case finish reagent injection and with the mixing of sample, can detect the reaction product of formation by detecting unit 28.
For cleaning equipment 1 when mixing reagent and finish back and/or beginning at every turn, we make first guides 15 of valve 14 firsts 141 is in primary importance 16, the guides 4 of valve 3 be in the position 6 and the guides 8 of valve 7 be in the position 11.On the contrary, second guides 19 of valve 14 is in vent position 21.Then, pump 29 is driven so that cleaning fluid joins pipeline 10 and up to bleed outlet W, the required time is enough to remove reaction product.
Operation simulation proves, utilizes the equipment of present embodiment, the volume of used sample and reagent be about in the italian patent 1249433 the use equipment described volume required 1/4.With respect to prior art, this amount of releasing volume that relates to generation is reduced to 1/4 and the operation automation that increases system.
At this moment, we are appreciated that equipment of the present invention is the development to equipment in the above-mentioned italian patent 1 249433, wherein still keep the principle of closed pipeline operation.Yet the present invention is different from the injection way that above-mentioned equipment mainly is reagent, and it is not through fillup valve reagent to be injected in the pipeline by producing vacuum, but because the action of pump makes reagent " suction ".
Should be noted that equipment of the present invention does not have one or more hypobaric mixing chambers in the prior art equipment fully, this makes it go for the environment of High Voltage.
Be appreciated that the required device number of the basic structure of implementing present device is few.In addition, in the above-described embodiment, this equipment is applicable to lower cost solution.In addition, importantly, putting in order of element can change on the mixed pipe line 10 of described embodiment, and it can not influence the operation of equipment 1.For example, the order of adding device 22-pump 29-detecting unit 28 can be replaced as opposite order, that is, detecting unit 28-pump 29-adding device 22, it does not change the mode of operation of the said equipment 1 substantially.So equipment of the present invention has the simplicity of function and structure, can realize having several configurations of identical mode of operation, every kind of configuration is corresponding to the various combination and/or the arrangement of several elements.In other words, the invention provides a kind of equipment of dynamic-configuration.This feature is represented the additional differentiation of the present invention with respect to content in the above-mentioned italian patent 1 249 433.
Another difference is, opposite with system in the above-mentioned patent, equipment of the present invention is not limited to vertical orientated.In fact, pipeline of the present invention can have orientation arbitrarily, diversity that this helps using and various device in the space.
As mentioned above, owing to there is not air basically in mixed pipe line, equipment of the present invention is applicable to underwater environment.
Fig. 2 is illustrated in the equipment set 100 of mixing analyte in the liquid sample of underwater environment, comprising: according to equipment of the present invention, specifically, the equipment 1 in the foregoing description.In this application, by means of the sealed hydraulic system that utilizes conventional method to realize, sampling unit 2 is suitable for taking out liquid sample C from underwater environment.
In the present embodiment, compensation system is the hydraulic device.Specifically, this device comprises: the compensator 31 of deformable outer wall is arranged, and it is exposed to the underwater environment pressure external; With the shell 32 of place apparatus 1, shell 32 forms hydraulic communication with compensator 31.Be full of heavy oil in compensator 31 and the shell 32, for example, vaseline.
Because above-mentioned arrangement, equipment 1 is subjected to substantially invariable pressure, and this pressure equals the pressure of outside underwater environment substantially, and therefore, it has identical pressure with analyzed sample.In other words, factory 100 can make all liquid keep the pressure that equates, and utilizes equipment 1 under 6000 meters deep-sea, and it is equivalent to 600 crust.
Should be understood that the present invention is applicable to other schemes of describing outside the embodiment herein.
Description of the invention is with reference to preferred embodiment.This means, can also have other embodiment that belong to same concept of the present invention, yet all these is in the scope that following claims are protected.
Claims (22)
1. equipment that is used for measuring the liquid sample analyte comprises:
Sampling unit (2) is suitable for adding analyzed liquid sample (C) in equipment;
Adding device (22) is suitable for adding at least selectively a kind of reagent (R in sample
1..., R
n), this adding device comprises itself: the suction valve (24) that at least one reagent hold-up vessel (23) is relevant with at least one is drawn in the sample reagent;
Detecting unit (28) is used for detecting the concentration of the contained analyte of sample;
Hydraulic pressure connects the device of each described unit, is suitable for forming closed hydraulic pressure mixed pipe line (10), and sample is circulated in described unit continuously and repeatedly; With
Pump arrangement (29), it is arranged on the described mixed pipe line and is suitable for determining the circulation of described sample,
This arrangement is such, at least one reagent suction valve of described adding device is inserted into described mixed pipe line, and by means of the action of described pump arrangement, reagent is directly entered in the described pipeline, and described at least one reagent suction valve forms the pipeline that described mixed pipe line complications are advanced, therefore, by means of the turbulent motion of setting up in the described pipeline, between described sample and described at least a reagent, mix.
2. according to the equipment (1) of claim 1, wherein said at least one reagent suction valve (24) is a T-valve.
3. according to the equipment (1) of claim 1 or 2, wherein said at least one reagent suction valve (24) is a guide valve.
4. according to the equipment (1) of claim 1 or 2, wherein said adding device (22) comprising: a plurality of containers (23), each container are suitable for storing different reagent (R
1..., R
n); And to each container (23), relevant reagent suction valve (24) is inserted in the pipeline that its zigzag path was gone up and limited to described mixed pipe line (10).
5. according to the equipment (1) of claim 1 or 2, a wherein said sampling unit (2) comprises a sample suction valve (14) at least, and it is inserted on the described mixed pipe line (10), and forms the pipeline that the pipeline complications are advanced.
6. according to the equipment (1) of claim 5, wherein said at least one sample suction valve (14) is a T-valve.
7. according to the equipment (1) of claim 5, wherein said at least one sample suction valve (14) is a guide valve.
8. according to the equipment (1) of claim 1 or 2, wherein said detecting unit (28) comprising: be selected from photometric detector, and fluorescence detector, ion is selected detecting device, a detecting device in the electromotive force detecting device.
9. according to the equipment (1) of claim 8, wherein said detecting unit (28) comprising: the colorimetric detection device.
10. according to the equipment (1) of claim 1 or 2, wherein said pump arrangement (29) is the two-way type device.
11. according to the equipment (1) of claim 1 or 2, wherein said pump arrangement comprises: volume pump (29).
12. according to the equipment (1) of claim 1 or 2, wherein said pump arrangement comprises: peristaltic pump (29).
13. the equipment (1) according to claim 1 or 2 comprising: bleeder, be used to the analyzed sample of releasing, it comprises: valve separately (14) is suitable for described mixed pipe line of On/Off (10) and hydraulic pressure and is connected to bleed outlet (W).
14. according to the equipment (1) of claim 13, the described valve (14) of wherein said bleeder is inserted in described mixed pipe line (10) and goes up and form the pipeline that the pipeline complications are advanced.
15. according to the equipment (1) of claim 13, wherein said bleeder valve is a T-valve.
16. according to the equipment (1) of claim 13, wherein said bleeder valve is a guide valve.
17. the equipment (1) according to claim 1 or 2 comprising: one or more extra cells are suitable for and described detecting unit (28) collaborative work, and are selected from following one group: reduction column, temperature adjustment serpentine, dialysis piece, still and ion exchange resin.
18. an equipment set (100) that is used for measuring the contained analyte of sample of underwater environment comprising:
Claim 1 or 2 described equipment (1), wherein said sampling unit (2) are suitable for taking out liquid sample (C) from underwater environment; With
Pressure compensator, portion installs described equipment and is suitable for making it to keep substantially invariable pressure within it, and this pressure equals the pressure of outside underwater environment substantially.
19. equipment set (100) according to claim 18, wherein said pressure compensator is a hydraulic, comprise: compensator (31), its deformable outer wall is exposed to the pressure outside of underwater environment, and shell (32), place described equipment (1) in the enclosure, this shell and described compensator hydraulic communication, described compensator and shell are full of heavy oil.
20. a method that is used for measuring the liquid sample analyte comprises the steps:
In mixed pipe line (10), introduce analyzed liquid sample (C);
In sample, add a kind of reagent (R selectively at least
1..., R
n), it directly sucks the container (23) in described pipeline separately;
The state of setting up turbulent motion in described pipeline is to realize mixing of described sample and described at least a reagent; With
Detect the concentration of contained analyte in the sample of mixing reagent along described mixed pipe line.
21. according to the method for claim 20, wherein said step is carried out in the environment under water.
22. according to the method for claim 20 or 21, wherein said step is to carry out by means of the equipment according to claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITRM2002A000356 | 2002-07-03 | ||
| IT2002RM000356A ITRM20020356A1 (en) | 2002-07-03 | 2002-07-03 | EQUIPMENT FOR DOSING ANALYTES CONTAINED IN A LIQUID SAMPLE AND RELATED PROCEDURE. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1666098A CN1666098A (en) | 2005-09-07 |
| CN100408994C true CN100408994C (en) | 2008-08-06 |
Family
ID=11456387
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038156407A Expired - Fee Related CN100408994C (en) | 2002-07-03 | 2003-07-03 | Apparatus for metering analytes contained in a liquid sample and related process |
Country Status (4)
| Country | Link |
|---|---|
| CN (1) | CN100408994C (en) |
| AU (1) | AU2003281296A1 (en) |
| IT (1) | ITRM20020356A1 (en) |
| WO (1) | WO2004005893A2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100428183C (en) * | 2006-01-17 | 2008-10-22 | 奇奕国际股份有限公司 | Automated etching control system, equipment, and method |
| CN102095075A (en) * | 2010-12-17 | 2011-06-15 | 同济大学 | Circulating pipeline device |
| CN112378863A (en) * | 2020-09-30 | 2021-02-19 | 深圳市朗诚科技股份有限公司 | Water quality analysis method of water quality analyzer |
| CN116106574B (en) * | 2023-04-12 | 2023-09-08 | 深圳市帝迈生物技术有限公司 | Sample detection device and control method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3717078A (en) * | 1970-04-03 | 1973-02-20 | Fuji Photo Film Co Ltd | Pressure resistant underwater casing |
| US4181154A (en) * | 1978-02-27 | 1980-01-01 | Ara Services, Inc. | Deflector valve for fluids |
| GB2110501A (en) * | 1981-11-26 | 1983-06-15 | Frank Frungel | Housings for underwater measuring equipment |
| US5411708A (en) * | 1991-08-06 | 1995-05-02 | Moscetta; Pompeo | Apparatus for the determination of analytes in liquid samples |
| EP0848242A2 (en) * | 1996-12-12 | 1998-06-17 | Patrik Källback | Method of analysis and equipment therefore |
| US5840254A (en) * | 1995-06-02 | 1998-11-24 | Cdc Technologies, Inc. | Apparatus for mixing fluids for analysis |
| CN2354133Y (en) * | 1999-01-28 | 1999-12-15 | 宝山钢铁(集团)公司 | Continuous-flowing hydride generating apparatus |
-
2002
- 2002-07-03 IT IT2002RM000356A patent/ITRM20020356A1/en unknown
-
2003
- 2003-07-03 AU AU2003281296A patent/AU2003281296A1/en not_active Abandoned
- 2003-07-03 CN CNB038156407A patent/CN100408994C/en not_active Expired - Fee Related
- 2003-07-03 WO PCT/IB2003/002610 patent/WO2004005893A2/en not_active Application Discontinuation
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3717078A (en) * | 1970-04-03 | 1973-02-20 | Fuji Photo Film Co Ltd | Pressure resistant underwater casing |
| US4181154A (en) * | 1978-02-27 | 1980-01-01 | Ara Services, Inc. | Deflector valve for fluids |
| GB2110501A (en) * | 1981-11-26 | 1983-06-15 | Frank Frungel | Housings for underwater measuring equipment |
| US5411708A (en) * | 1991-08-06 | 1995-05-02 | Moscetta; Pompeo | Apparatus for the determination of analytes in liquid samples |
| US5840254A (en) * | 1995-06-02 | 1998-11-24 | Cdc Technologies, Inc. | Apparatus for mixing fluids for analysis |
| EP0848242A2 (en) * | 1996-12-12 | 1998-06-17 | Patrik Källback | Method of analysis and equipment therefore |
| CN2354133Y (en) * | 1999-01-28 | 1999-12-15 | 宝山钢铁(集团)公司 | Continuous-flowing hydride generating apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2004005893A2 (en) | 2004-01-15 |
| CN1666098A (en) | 2005-09-07 |
| ITRM20020356A0 (en) | 2002-07-03 |
| WO2004005893A3 (en) | 2004-08-12 |
| AU2003281296A1 (en) | 2004-01-23 |
| ITRM20020356A1 (en) | 2004-01-05 |
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