WO2004025272A1 - Pressurized fluid sample injector apparatus and method - Google Patents
Pressurized fluid sample injector apparatus and method Download PDFInfo
- Publication number
- WO2004025272A1 WO2004025272A1 PCT/US2003/028249 US0328249W WO2004025272A1 WO 2004025272 A1 WO2004025272 A1 WO 2004025272A1 US 0328249 W US0328249 W US 0328249W WO 2004025272 A1 WO2004025272 A1 WO 2004025272A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sample
- valve
- pressure
- aspirating needle
- loop
- Prior art date
- 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.)
- Ceased
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/10—Devices for withdrawing samples in the liquid or fluent state
- G01N1/14—Suction devices, e.g. pumps; Ejector devices
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/10—Devices for withdrawing samples in the liquid or fluent state
- G01N1/14—Suction devices, e.g. pumps; Ejector devices
- G01N2001/1418—Depression, aspiration
- G01N2001/1427—Positive displacement, piston, peristaltic
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/10—Devices for withdrawing samples in the liquid or fluent state
- G01N1/14—Suction devices, e.g. pumps; Ejector devices
- G01N2001/1445—Overpressure, pressurisation at sampling point
Definitions
- the present invention relates to sample handling and injection systems and in particular to apparatus and methods for increasing the speed of the injection cycle.
- liquid chromatography sample injection a sample is drawn into a needle or capillary and then loaded into a sample loop by pulling the fluid through the needle and any associated tubes into the sample loop.
- the sample loop is connected to an injection mechanism, such as a pump/detector system, that pushes the sample through a liquid chromatography column where a separation takes place.
- the sample can be pulled through the system of tubes at a flow rate that is directly related to the vapor pressure of the fluid. If the fluid is drawn through the tubing too quickly, the fluid can vaporize and cause undesirable results in sample integrity as well as sample positioning within the sample loop.
- sample loading speed is increased significantly by pressurizing the fluid system, thus avoiding vaporization of the fluid. This process allows the sample to be transported through the system faster than in a system that draws the sample into a sample loop without utilizing an elevated pressure. Ultimately, the faster sample loading time reduces the overall cycle time between sample injections.
- the invention embodies a pressurized sample injector system, which utilizes elevated pressure to aid sample delivery to a sample loop.
- the sample loop is connected across a multiport valve that allows the sample loop to be alternately connected to the sample loading mechanism and the separation mechanism.
- the sample loading mechanism consists of an aspirating needle, which has already aspirated a sample from a container, that is sealed to a pressure vessel for the loading operation.
- the aspirating needle is connected to one side of the sample loop through the multiport valve.
- a metering syringe is connected to the other side of the sample loop through the multiport valve.
- a sample is aspirated from a container holding the sample into the sample needle.
- the needle tip is then connected to the pressure vessel and the pressure assist pump and the fluid path is pressurized.
- the sample is transported from the aspirating needle to the sample loop by creating a pressure differential across the path from the pressure vessel to the metering syringe.
- the sample is moved from the sample loop to an analytical column by a gradient pump.
- the second position of the multiport valve disconnects the metering syringe and the aspirating needle from the sample loop and connects the aspirating needle directly to the metering syringe allowing wash cycle(s) to cleanse the flow path while the injection and separation are proceeding.
- Fig. 1 depicts part of the apparatus
- Fig. 2 depicts the steps of sample aspiration
- Fig. 3 depicts one embodiment of the apparatus during pressurization
- Fig. 4 depicts the pressurization of a sample
- Fig. 5 A depicts the apparatus during metering
- Fig. 5B depicts a partial loop sample in the sample loop after metering
- Fig. 5C depicts a full loop sample with overfill in the sample loop after metering
- Fig. 6 depicts one embodiment of the invention.
- Fig. 1 a simplified method of moving a sample quickly is illustrated.
- a quantity of sample 10 is held in a container 12.
- a sample loop 18 is in fluid communication with a first end of a sample loop 18 and the second end of the sample loop 18 is in fluid communication with a metering syringe 20.
- the fluid path from the needle 14 to the syringe 20 is filled with a solute.
- a second end of the aspirating needle 14 is placed in the sample 10 through a seal 7 that allows the sample 10 to be held under pressure.
- the entire fluid path from the sample 10 to the metering syringe 20 is under pressure.
- a pressure differential is established between the metering syringe 20 and the sample 10 which transports the sample liquid through the needle 14 and into the sample loop more swiftly than in a fluidic system that is not under pressure.
- the device of Fig. 1 When the needle is moved between successive sealed baths of fluid, the device of Fig. 1 is useful for loading a sequence of fluids into a lengthy loop.
- the handling of the samples could be simplified, the concentration of the samples can be made consistent and the amount of sample used can be minimized using air gaps between samples and by connecting the sample loop across the ports of a suitably configured multiport valve.
- the metered sample 11 is typically bracketed by air gaps within the aspirating needle.
- the aspirating needle starts filled with fluid 9 and, as shown in Fig. 2A, before aspiration the metering syringe (not shown) is drawn back to pull in a volume of air 13 at the tip of the aspirating needle 14.
- the aspirating needle 14 is placed into the sample 10 and the metering syringe is further pulled back a metered amount which draws a predetermined metered sample portion 11 into the aspirating needle 14.
- the aspirating needle 14 is then lifted from the sample 10 and a post-sample air gap 15 is drawn into the aspirating needle 14 by the metering syringe.
- Fig. 3 depicts an embodiment of the invention showing pressurization of the metered sample 11 while in the aspirating needle 14 and the use of a multiport valve 16.
- the apparatus is shown after aspiration of the metered sample 11.
- the aspirating needle 14 containing the metered sample 11 is placed in a pressurized fluid 28 held in a pressure vessel 42 adapted for this purpose.
- the aspirating needle 14 is sealed to the pressure vessel 42 by seal 32.
- a pressure assist pump 30 is in fluid communication with the pressure vessel 42 to pressurized fluid 28.
- All of the connections of the present invention substantially seal the sample path from ambient pressure.
- a relief flow means 36 may be used in conjunction with the pressure assist pump to further regulate the pressure on the pressurized fluid 28.
- a pressure monitor 38 may be connected to the pressurized fluid line for diagnostic and/or control purposes.
- Fig. 4 depicts the metered sample 11 , bracketed by air gaps, being pressurized in the aspirating needle 14 before being transported under pressure to the sample loop 18. i one embodiment, the aspirating needle 14 is sealed to the pressure vessel 42 by an O-ring 32. A lip seal or any other means for substantially sealing the aspirating needle 14 to the pressure vessel 42 is appropriate.
- the multiport valve 16 has two positions: in the first position (illustrated in Fig. 3) ports one and three, two and four, and five and six are fluidically connected; in the second position, ports one and two, three and five and four and six are fluidically connected.
- the aspirating needle 14 is connected to the first port 1.
- the sample loop 18 is connected across the multiport valve 16 utilizing ports 3 and 4.
- the metering syringe 20 is connected to the multiport valve 16 at port 2.
- a gradient pump (not shown) is connected to the multiport valve 16 at port 5 and an analytical column (not shown) is connected to the multiport valve 16 at port 6.
- the multiport valve is adapted to operate up to the pressures being provided by the pressure assist pump and/or the gradient pump.
- the gradient pump and column are maintained in fluid communication by the multiport valve 16 and the aspirating needle 14, sample loop 18 and metering syringe 20 are maintained in fluid communication by the multiport valve 16.
- the first position is also used to draw the metered sample 11 into the aspirating needle 14 before the transport operation depicted by Fig. 3.
- the multiport valve 16 maintains the gradient pump, sample loop 18 and analytic column in one fluidic path, while the aspirating needle 14 and metering syringe 20 are maintained in fluid communication in a separate fluidic path.
- This position allows the gradient pump to push the metered sample 11 from the sample loop 18 onto the analytic column while the rest of the device undergoes a cleaning operation.
- the metering syringe 20 is for drawing a metered amount of fluid through the sample path.
- the metering syringe 20 functions by creating a vacuum in the syringe.
- the vacuum creates a pressure differential between the aspirating needle 14 and the metering syringe 20 that pulls fluid toward the syringe.
- the device controls how far the leading edge of the metered sample 11 moves along the sample path.
- the metering syringe 20 can be any pump operating on this principle.
- Multiport valves having different numbers of ports may be utilized in the device. For instance, a four port valve with two positions could be used to draw the metered sample into a sample loop in one position and isolate the sample loop in the second position. Sample loops so filled could be disconnected and retained for further processing. Control means to position the aspirating needle, control the multiport valve and position the metering syringe are needed to coordinate the components.
- the pressure assist pump 30 is a wash syringe 34, which may also be used to supply wash fluid for cleansing the sample path.
- the metering syringe 20 is drawn back creating a pressure differential across the sample path.
- Fig. 5B illustrates a partial loop placement used to position the metered sample 11 in the sample loop 18 when very small quantities of sample 10 are available.
- the sample loop 18 extends from port 3 to port 4 of the multiport valve 16 and the metered sample 11 is centered in the loop 18.
- the metering syringe 20 when the metering syringe 20 is drawn back, it positions the metered sample 11 centered in the sample loop 18. Because the loop is overfilled, the metered sample 11 not only fills the sample loop 18 but also extends past the sample loop ports 3, 4, and usually past the connection port 1 for the aspirating needle 14 and the connection port 2 for the metering syringe 20. This positioning places the air gaps 13, 15 well beyond the sample loop 18.
- the advantage of the full loop with over fill is that it assures that a known quantity of full strength sample is injected into the analytical column from the sample loop 18 during the loading phase of the cycle.
- the metered sample 11 is not centered but rather is positioned with the trailing air gap 15 just before sample loop port 3.
- This embodiment takes account of the fact that sample near the leading air gap 13 may become diluted due to dispersion. Consistent concentration of sample is optimized by minimizing the amount of possibly diluted sample near the leading air gap 13 that is positioned in the sample loop 18, and maximizing the amount of concentrated sample near the trailing air gap 17 positioned in the sample loop 18. Since the metered sample 11 is pressurized within the sample path, the metered sample 11 does not vaporize when it is transported into the sample loop 18.
- Determination of the pressurization level for optimum performance takes the viscosity of the sample and other fluids, the desired positioning speed and the internal diameters (ID) of the sample needle, the interconnecting tubing, the multiport valve, and the metering syringe into account.
- ID the internal diameters
- sample movement speeds 600- 2000 ⁇ L/min were attained.
- This system exhibited a sample load time up to 10 times greater than could be achieved without pressurization. Pressures beyond 150 psig can be used, but the unpressurized air gap size must be increased significantly creating an undesirable effect on cycle time.
- Table 1 In the preferred embodiment depicted in Fig. 6, the apparatus is set up to operate in a cycle having two phases: one phase transports the metered sample 11 into the sample loop 18 and the second phase cleans the fluid path while the metered sample 11 is being pushed through the analytical column.
- the cleaning mechanism shown in the figure is representative only, as cleaning technology is well known in the art.
- a wash syringe pump is used to pressurize the fluid path during the sample transport phase of the cycle.
- the wash syringe 34 acting as the pressure assist pump 30, maintains a wash block 42, functioning as the pressure vessel, at the desired pressure.
- a pressure regulating vent 40 is used to maintain a substantially constant pressure while the aspirating needle 14is in the wash block 42.
- the wash block 42 is constructed so that excess fluid from the pressure regulating vent and the upper portion of a sealed chamber 29 is directed to a collection area 33 that drains into a waste container 41.
- the aspirating needle 14 is inserted in the O-ring 32 of the wash block 42 and the volume of fluid between the metering syringe 20 and the pressure assist pump 30 is pressurized to assist sample movement.
- Naive 44 at the head of the metering syringe 20, is set to provide connection between the multiport valve 16 and the metering syringe 20 during this part of the cycle. Pressure is created in the system by dispensing fluid from the pressure assist pump 30, here the wash syringe 34, and is held constant by the pressure regulating vent 40.
- the metering syringe 20 meters back a pre-determined volume in order to transport the metered sample 11 from the the aspirating needle 14 into the sample loop 18.
- the multiport valve 16 is actuated and the sample in the sample loop 18 is connected to the gradient pump and analytical column for injection into the analytical column.
- the apparatus changes to the cleaning phase.
- the aspirating needle 14 is withdrawn from the O-ring 32 and held above the collection area 33.
- Valve 46 changes state to allow the wash syringe to be recharged from a wash reservoir 48.
- Naive 44 changes state to allow wash fluid to be supplied from wash reservoir 48 to the line connected to multiport valve port 2, through the multiport valve 16 to the aspirating needle 14 where it is flushed into the waste 41.
- wash fluid typically supplied from wash reservoir 48 to the line connected to multiport valve port 2, through the multiport valve 16 to the aspirating needle 14 where it is flushed into the waste 41.
- the invention allows a sample to be transported into a sample loop in significantly less time than it takes at atmospheric pressure, where transport speed is constrained by the vapor pressure of the fluids transported. Sample positioning accuracy is also improved over other chromatography systems as well.
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- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Sampling And Sample Adjustment (AREA)
- Automatic Analysis And Handling Materials Therefor (AREA)
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004536388A JP4564356B2 (ja) | 2002-09-11 | 2003-09-10 | 加圧流体試料インジェクタおよび流体試料の射出方法 |
| DE10393201.1A DE10393201B4 (de) | 2002-09-11 | 2003-09-10 | Hochdruckfluidprobeninjektionsvorrichtung und Verfahren |
| DE10393201T DE10393201T5 (de) | 2002-09-11 | 2003-09-10 | Hochdruckfluidprobeninjektionsvorrichtung und Verfahren |
| AU2003268571A AU2003268571A1 (en) | 2002-09-11 | 2003-09-10 | Pressurized fluid sample injector apparatus and method |
| GB0502759A GB2408098B (en) | 2002-09-11 | 2003-09-10 | Pressurized fluid sample injector and method of injecting fluid samples |
| US11/072,906 US20050194298A1 (en) | 2002-09-11 | 2005-03-04 | Pressurized fluid sample injector and method of injecting fluid samples |
| US11/532,234 US7951597B2 (en) | 2002-09-11 | 2006-09-15 | Pressurized fluid sample injector and method of injecting fluid samples |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US40983602P | 2002-09-11 | 2002-09-11 | |
| US60/409,836 | 2002-09-11 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US11/072,906 Continuation US20050194298A1 (en) | 2002-09-11 | 2005-03-04 | Pressurized fluid sample injector and method of injecting fluid samples |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2004025272A1 true WO2004025272A1 (en) | 2004-03-25 |
Family
ID=31994012
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2003/028249 Ceased WO2004025272A1 (en) | 2002-09-11 | 2003-09-10 | Pressurized fluid sample injector apparatus and method |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20050194298A1 (https=) |
| JP (1) | JP4564356B2 (https=) |
| AU (1) | AU2003268571A1 (https=) |
| DE (2) | DE10393201T5 (https=) |
| GB (1) | GB2408098B (https=) |
| WO (1) | WO2004025272A1 (https=) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007109529A2 (en) | 2006-03-17 | 2007-09-27 | Waters Investments Limited | Device and methods for reducing pressure and flow perturbations in a chromatographic system |
| CN103675174A (zh) * | 2013-11-15 | 2014-03-26 | 国网山东省电力公司青岛供电公司 | 一种色谱分析仪 |
| WO2014085003A3 (en) * | 2012-11-30 | 2014-07-31 | Agilent Technologies, Inc. | Mixer bypass sample injection for liquid chromatography |
| CN105675776A (zh) * | 2016-04-07 | 2016-06-15 | 中科合成油技术有限公司 | 一种在线色谱稳定进样装置及方法 |
| US9435773B2 (en) | 2009-06-03 | 2016-09-06 | Agilent Technologies, Inc. | Sample injector with metering device balancing pressure differences in an intermediate valve state |
| US10386342B2 (en) | 2008-01-25 | 2019-08-20 | Dionex Softron Gmbh | Sample injector for liquid chromatography, particularly for high performance liquid chromatography |
| US10473631B2 (en) | 2015-06-25 | 2019-11-12 | Dionex Softron Gmbh | Sampler for liquid chromatography |
| EP3617701A1 (en) * | 2018-08-27 | 2020-03-04 | F. Hoffmann-La Roche AG | Sample injector with sample loop and buffer loop |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8241013B2 (en) * | 2005-10-27 | 2012-08-14 | Waters Technologies Corporation | Serial capillary pump |
| JP4955342B2 (ja) * | 2006-08-28 | 2012-06-20 | 株式会社日立ハイテクノロジーズ | 液体クロマトグラフ装置及び試料導入装置 |
| US8794052B2 (en) * | 2009-04-16 | 2014-08-05 | Shimadzu Corporation | Liquid chromatograph |
| JP5111476B2 (ja) * | 2009-10-26 | 2013-01-09 | 株式会社日立ハイテクノロジーズ | 液体試料分析装置及び液体試料導入装置 |
| JP5270771B2 (ja) * | 2012-02-03 | 2013-08-21 | 株式会社日立ハイテクノロジーズ | 液体クロマトグラフ装置及び試料導入装置 |
| AU2016228931B2 (en) * | 2015-03-06 | 2020-07-09 | Alcoa Of Australia Limited | Online sampling device |
| WO2018134662A1 (en) * | 2017-01-17 | 2018-07-26 | Waters Technologies Corporation | Systems, methods, and devices for providing pressurized solvent flow |
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- 2003-09-10 AU AU2003268571A patent/AU2003268571A1/en not_active Abandoned
- 2003-09-10 GB GB0502759A patent/GB2408098B/en not_active Expired - Lifetime
- 2003-09-10 DE DE10393201.1A patent/DE10393201B4/de not_active Expired - Lifetime
- 2003-09-10 WO PCT/US2003/028249 patent/WO2004025272A1/en not_active Ceased
- 2003-09-10 JP JP2004536388A patent/JP4564356B2/ja not_active Expired - Fee Related
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Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1996930A4 (en) * | 2006-03-17 | 2011-01-19 | Waters Technologies Corp | DEVICE AND METHOD FOR REDUCING THE PRESSURE AND SUPPRESSING RIVER FAILURES IN A CHROMATOGRAPHIC SYSTEM |
| US8312762B2 (en) | 2006-03-17 | 2012-11-20 | Waters Technologies Corporation | Device and methods for reducing pressure and flow perturbations in a chromatographic system |
| WO2007109529A2 (en) | 2006-03-17 | 2007-09-27 | Waters Investments Limited | Device and methods for reducing pressure and flow perturbations in a chromatographic system |
| EP1996930B1 (en) | 2006-03-17 | 2018-01-10 | Waters Technologies Corporation | Device and methods for reducing pressure and flow perturbations in a chromatographic system |
| US10386342B2 (en) | 2008-01-25 | 2019-08-20 | Dionex Softron Gmbh | Sample injector for liquid chromatography, particularly for high performance liquid chromatography |
| US12372500B2 (en) | 2008-01-25 | 2025-07-29 | Dionex Softron Gmbh | Sample injector for liquid chromatography, particularly for high performance liquid chromatography |
| US11802854B2 (en) | 2008-01-25 | 2023-10-31 | Dionex Softron Gmbh | Sample injector for liquid chromatography, particularly for high performance liquid chromatography |
| US11156589B2 (en) | 2008-01-25 | 2021-10-26 | Dionex Softron Gmbh | Sample injector for liquid chromatography, particularly for high performance liquid chromatography |
| US11519884B2 (en) | 2009-06-03 | 2022-12-06 | Agilent Technologies, Inc. | Sample injector with metering device balancing pressure differences in an intermediate valve state |
| US9435773B2 (en) | 2009-06-03 | 2016-09-06 | Agilent Technologies, Inc. | Sample injector with metering device balancing pressure differences in an intermediate valve state |
| US10209229B2 (en) | 2012-11-30 | 2019-02-19 | Agilent Technologies, Inc. | Mixer bypass sample injection for liquid chromatography |
| US9945820B2 (en) | 2012-11-30 | 2018-04-17 | Agilent Technologies, Inc. | Mixer bypass sample injection for liquid chromatography |
| WO2014085003A3 (en) * | 2012-11-30 | 2014-07-31 | Agilent Technologies, Inc. | Mixer bypass sample injection for liquid chromatography |
| CN103675174A (zh) * | 2013-11-15 | 2014-03-26 | 国网山东省电力公司青岛供电公司 | 一种色谱分析仪 |
| US11307178B2 (en) | 2015-06-25 | 2022-04-19 | Dionex Softron Gmbh | Sampler for liquid chromatography |
| US10473631B2 (en) | 2015-06-25 | 2019-11-12 | Dionex Softron Gmbh | Sampler for liquid chromatography |
| US11867669B2 (en) | 2015-06-25 | 2024-01-09 | Dionex Softron Gmbh | Sampler for liquid chromatography |
| CN105675776A (zh) * | 2016-04-07 | 2016-06-15 | 中科合成油技术有限公司 | 一种在线色谱稳定进样装置及方法 |
| CN110865132A (zh) * | 2018-08-27 | 2020-03-06 | 豪夫迈·罗氏有限公司 | 样品注射器 |
| US11408865B2 (en) | 2018-08-27 | 2022-08-09 | Roche Diagnostics Operations, Inc. | Sample injector |
| EP3617701A1 (en) * | 2018-08-27 | 2020-03-04 | F. Hoffmann-La Roche AG | Sample injector with sample loop and buffer loop |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4564356B2 (ja) | 2010-10-20 |
| GB2408098B (en) | 2006-03-22 |
| GB2408098A (en) | 2005-05-18 |
| US20050194298A1 (en) | 2005-09-08 |
| AU2003268571A1 (en) | 2004-04-30 |
| DE10393201B4 (de) | 2023-11-16 |
| JP2005538378A (ja) | 2005-12-15 |
| GB0502759D0 (en) | 2005-03-16 |
| DE10393201T5 (de) | 2005-09-01 |
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