EP0377721B1 - Verfahren zur Durchführung von Reaktionen mit geringsten Mengen von fluiden Proben - Google Patents
Verfahren zur Durchführung von Reaktionen mit geringsten Mengen von fluiden Proben Download PDFInfo
- Publication number
- EP0377721B1 EP0377721B1 EP89907732A EP89907732A EP0377721B1 EP 0377721 B1 EP0377721 B1 EP 0377721B1 EP 89907732 A EP89907732 A EP 89907732A EP 89907732 A EP89907732 A EP 89907732A EP 0377721 B1 EP0377721 B1 EP 0377721B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- sample
- receiving tube
- end part
- lid
- insert
- 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.)
- Expired - Lifetime
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 39
- 239000012530 fluid Substances 0.000 title claims abstract description 4
- 238000000034 method Methods 0.000 title claims description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000007789 sealing Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 2
- 210000003141 lower extremity Anatomy 0.000 abstract 1
- 239000000523 sample Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 238000013459 approach Methods 0.000 description 4
- 239000011324 bead Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
- B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
- B01L3/508—Containers for the purpose of retaining a material to be analysed, e.g. test tubes rigid containers not provided for above
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
- B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
- B01L3/508—Containers for the purpose of retaining a material to be analysed, e.g. test tubes rigid containers not provided for above
- B01L3/5082—Test tubes per se
- B01L3/50825—Closing or opening means, corks, bungs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L7/00—Heating or cooling apparatus; Heat insulating devices
Definitions
- the invention relates to a method for carrying out reactions at temperatures above 50 ° C. of components to be heated, which emit components that evaporate when heated, in particular fluid samples.
- reaction In particular in molecular biological work, reactions often have to be carried out at temperatures above 50 (up to 100 ° C.) (heat inactivation of proteins, denaturation of nucleic acids, restriction digestion with Taq I and the like). It is common to carry out these reactions in standard reaction vessels that are used in preheated water baths or in bores of heated metal blocks.
- the volumes of the reaction solutions are usually between 10 and 50 ⁇ l, the volumes of the reaction vessels between about 1000 and 2500 ⁇ l.
- the reaction vessels therefore contain a large excess of volume, in which water evaporates from the reaction solutions and is deposited on the inside of the lid. This increases the concentration in the reaction solution, which can sometimes lead to the sample completely drying out. This is extremely cumbersome for the examinations and treatments and can only be prevented by special measures, such as repeated centrifugation of the reaction vessels or overlaying the reaction solution with oil.
- the object of the invention is to provide a method of the type mentioned, in which on the one hand the handling of the reaction vessel is ensured by a sufficiently voluminous design, but on the other hand one substantial concentration or even drying out of the sample is avoided during the reaction.
- the procedure according to the invention ensures that the gas volume with the part of the reaction vessel filled with the reaction solution or the like is reduced so much that it is no longer possible to evaporate the reaction solution into larger spaces above it, so that the sample dries out heat treatment is effectively avoided.
- the volume within the reaction vessel which is not required for receiving the sample, is reduced to such an extent that the evaporation space is as small as possible above the sample, which limits the evaporation of liquid from the sample.
- the approach ensures as close as possible above the sample arranged in the sample receiving tube that all-round sealing is ensured in such a way that the remaining volume above the sealing area is separated from the actual reaction space in which the sample is located in a gas-tight manner. In this way, the resulting steam is limited to the relatively small reaction space.
- a major problem is to make the seal between the neck and the sample tube so that when the neck is inserted into the sample tube, as little as possible and if possible no pressure is built up in the reaction space. This is important on the one hand, because otherwise the insertion of the approach into the sample tube is only possible with increased effort. It could also build up pressure in the reaction space be harmful to the sample or the tests to be performed.
- a pressure build-up when inserting the approach into the sample tube can be avoided particularly advantageously by the features of claim 2.
- a container made of thermoplastic material with a lid having an extension and a second closure is known from CH-A-330 179; a spoon for receiving a stool sample or the like is provided at the bottom of the second closure, which is introduced into the container after the stool sample has been taken and is closed off from the outside twice by the lid and the second closure.
- the method carried out with this container thus consists in enclosing a stool sample taken with a spoon separated from the environment by a double lock and then transporting it to the site of the examination.
- a reaction is to be carried out in a sample collection tube.
- a sample receiving tube 11 provided with a circular cross section has a region 11 '''' which widens conically upwards above a rounded-off tip which is formed as a rounded tip, followed by a relatively short circular-cylindrical region 11 ''', followed by a short extension section 11 '' and finally an upper circular cylindrical section 11 ', which is relatively long and has the largest diameter relative to the other parts. Its upper end represents the upper open end of the sample tube 11.
- An external thread 26 is provided on the outer wall of the sample receiving tube 11, onto which a screw cap 12 provided with an internal thread 27 is screwed.
- the cover 12 On its inside, the cover 12 has a circular cylindrical recess 28 which is open at the bottom and which is concentric with the central axis 23 and into which a hollow cylindrical extension 24 is inserted from below in a sliding or preferably clamped fit.
- the attachment 14 could also be fixed in the recess 28 by suitable fastening means, for example adhesive.
- the extension 14 can be pulled out again when the cover 12 is unscrewed, so that replacement is possible.
- the circumferential flange 29 forming the recess 28 is radially outside a slight distance 30 from the inner wall 15 of the sample tube 11, so that in a state between the upper end wall 31 and a lower ring wall 32 of the lid 12 there remains a clearance 33 when fully screwed on adjoins a lateral vent opening 25 in the threaded peripheral edge 34 of the cover 12. In this way, a pressure equalization can take place between the interior 13 of the sample receiving tube 11 and the atmosphere.
- the hollow-cylindrical extension 14 has a slightly smaller outer diameter than the circular-cylindrical region 11 ′′ ′′ and merges at the lower end into an end part 20 that tapers slightly downwards and has a bottom wall 17 at its lower end.
- the conical end part 20 is in a sealing connection 35 with the inner wall 15 of the sample receiving tube 11, which also tapers downward in this area, within the area 11 ''''.
- the end part 20 with the bottom wall 17 at the lower end of the sample tube 11 separates a reaction space 19 into which a sample 18 is filled, which is to be subjected to heat treatment by inserting the sample tube 11 into a heating apparatus.
- the attachment 14 could be replaced by an attachment 14 which is somewhat longer and has a narrower end part 20 at the bottom, which is indicated by dashed lines in FIG. 1. In this way, a substantially smaller reaction space 19 'could be separated from the total internal volume of the sample receiving tube 11.
- attachment 14 Due to the interchangeability of the attachment 14, one and the same cover 12 could be provided with attachments 14 of different lengths and different sizes of reaction spaces.
- a corrugation 21 which facilitates unscrewing and screwing is provided on the outer periphery of the screw cap 12.
- a further corrugation 36 is located on the outer circumference of the upper region 11 'of the sample receiving tube 11 in order to also provide increased resistance when unscrewing the other hand.
- the method according to the invention can be carried out as follows: With the cover 12 unscrewed and the extension 14 removed, the sample 18 is first filled into the sample tube 11 in the desired amount. Then, depending on the amount filled in, a suitable length 14 is selected and inserted into the screw cap 12 from below. Then the neck 14 is inserted into the interior of the sample tube 11 until finally the lid 12 can be screwed onto the external thread 26.
- the lid 12 must have sufficient freedom of movement in the axial direction so that the conical end part 20 of the attachment 14 comes into contact with the inner wall of the conical part 11 '''' of the sample tube 11 and by turning the lid 12 further in the closing direction the lower wall 37 of the cover 12 and the upper end edge 38 of the extension 14 a sufficient axial force in the direction of the arrow can be generated for the production of the sealing connection 35.
- a labeling insert 40 is inserted into an upper recess 39 of the cover 12.
- the entire lower conical end part 20 of the projection 14 does not abut the conical inner wall 15 of the region 11 '' '', but only a circumferential bead 20 'provided in the region of the bottom wall 17.
- both the end part 20 and the circumferential bead 20 have a clear distance from the inner wall 15 when the extension 14 is pushed in from above until it comes into engagement with it, this can be immediate venting of the reaction chamber 19 takes place before the sealing connection 35 is produced, as a result of which a substantial pressure build-up in the reaction chamber 19 is avoided when the sealing connection 35 is being produced.
- an inwardly projecting ring step 22 is provided at the lower end of the circular cylindrical region 11 ′′ ′′, with which the conical end part 20 of the projection 14 cooperates like a plug. This also makes it possible to separate the reaction space 19 in a gas-tight manner from the residual volume above it.
- FIG. 4 differs from that of FIG. 1 in that instead of the hollow cylindrical extension 14, a relatively thin rod-shaped extension 14 'made of solid material is provided, which carries at its lower end a sealing plate 17' forming the end part, which at Screwing on the cover 12 comes into sealing engagement 35 with the inner wall of the conical region 11 ''''.
- the rod-shaped extension 14 ' can also be separated from the cover 12 by pulling it out and replaced, for example, by a longer or shorter extension 14'.
- ventilation is carried out in the exemplary embodiment according to FIG. 1 through a transverse bore 25 in the cover 12, in the exemplary embodiment according to FIG. 4 a groove 25 'is provided on the internal thread 26, which via the clearance 33 and the circumferential gap 30 is used to vent the interior 13 guaranteed.
- a ring step 22 can also be provided at the lower end of the circular cylindrical region 11 ′′ ′′ when using a rod-shaped extension 14 ′, which cooperates with a stopper 20 ′′ forming the end part and attached to the lower end of the rod-shaped extension 14 ′.
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Clinical Laboratory Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Hematology (AREA)
- Sampling And Sample Adjustment (AREA)
- Devices For Use In Laboratory Experiments (AREA)
- Apparatus Associated With Microorganisms And Enzymes (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE8808738U | 1988-07-07 | ||
DE8808738U DE8808738U1 (de) | 1988-07-07 | 1988-07-07 | Gefäß zur Druchführung von Reaktionen bei erhöhter Temperatur |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0377721A1 EP0377721A1 (de) | 1990-07-18 |
EP0377721B1 true EP0377721B1 (de) | 1993-09-15 |
Family
ID=6825755
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89907732A Expired - Lifetime EP0377721B1 (de) | 1988-07-07 | 1989-07-07 | Verfahren zur Durchführung von Reaktionen mit geringsten Mengen von fluiden Proben |
Country Status (4)
Country | Link |
---|---|
US (1) | US5167929A (es) |
EP (1) | EP0377721B1 (es) |
DE (2) | DE8808738U1 (es) |
WO (1) | WO1990000442A1 (es) |
Families Citing this family (50)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6703236B2 (en) | 1990-11-29 | 2004-03-09 | Applera Corporation | Thermal cycler for automatic performance of the polymerase chain reaction with close temperature control |
KR100236506B1 (ko) * | 1990-11-29 | 2000-01-15 | 퍼킨-엘머시터스인스트루먼츠 | 폴리머라제 연쇄 반응 수행 장치 |
DE4139810C2 (de) * | 1991-12-03 | 1995-03-09 | Eppendorf Geraetebau Netheler | Deckelgefäß |
US5725832A (en) * | 1992-03-25 | 1998-03-10 | Gundelsheimer; Peter | Laboratory test tubes for the dosing of liquids |
CA2094317C (en) * | 1993-04-19 | 2003-01-07 | Victor Daykin | Biological specimen collection system |
JP3347824B2 (ja) * | 1993-06-30 | 2002-11-20 | 株式会社シゲミ | 核磁気共鳴装置用試料管の製造方法 |
US5620662A (en) * | 1993-08-23 | 1997-04-15 | Brandeis University | Temporary liquid storage cavities in a centrifuge tube lid |
US5823379A (en) * | 1993-10-20 | 1998-10-20 | Amersham International Plc | Sealed container for hazardous material |
US5871700A (en) * | 1993-12-21 | 1999-02-16 | C.A. Greiner & Sohne Gesellschaft M.B.H. | Holding device with a cylindrical container and blood sampling tube with such a holding device |
DE4412286A1 (de) * | 1994-04-09 | 1995-10-12 | Boehringer Mannheim Gmbh | System zur kontaminationsfreien Bearbeitung von Reaktionsabläufen |
US5458113A (en) * | 1994-08-12 | 1995-10-17 | Becton Dickinson And Company | Collection assembly |
GB2292737B (en) * | 1994-09-02 | 1998-01-07 | Huang Yu Hwei | Personal perfume carrier |
US5750075A (en) * | 1996-02-15 | 1998-05-12 | Sun International Trading , Ltd. | Chromotography vial |
US5785925A (en) * | 1996-08-29 | 1998-07-28 | Saigene Corporation | Centrifuge tube phase separation plug |
US5795784A (en) | 1996-09-19 | 1998-08-18 | Abbott Laboratories | Method of performing a process for determining an item of interest in a sample |
US5856194A (en) | 1996-09-19 | 1999-01-05 | Abbott Laboratories | Method for determination of item of interest in a sample |
US6312886B1 (en) | 1996-12-06 | 2001-11-06 | The Secretary Of State For Defence In Her Brittanic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Reaction vessels |
GB9716052D0 (en) | 1996-12-06 | 1997-10-01 | Secr Defence | Reaction vessels |
US5853102A (en) * | 1997-01-27 | 1998-12-29 | Jarrett; Guy R. | Insert for spray gun paint cups |
US5915583A (en) * | 1997-05-21 | 1999-06-29 | Abbott Laboraties | Container |
US5882601A (en) * | 1997-06-18 | 1999-03-16 | Merck & Co., Ltd. | Deflected septum seal access port |
US6179787B1 (en) | 1997-09-12 | 2001-01-30 | Becton Dickinson And Company | Collection container assembly |
US5955032A (en) * | 1997-09-12 | 1999-09-21 | Becton Dickinson And Company | Collection container assembly |
US6612997B1 (en) | 1997-09-12 | 2003-09-02 | Becton, Dickinson And Company | Collection container assembly |
US5924594A (en) * | 1997-09-12 | 1999-07-20 | Becton Dickinson And Company | Collection container assembly |
US5938621A (en) * | 1997-09-12 | 1999-08-17 | Becton Dickinson And Company | Collection container assembly |
US5975343A (en) * | 1997-09-12 | 1999-11-02 | Becton Dickinson And Company | Collection container assembly |
US5948365A (en) * | 1997-09-12 | 1999-09-07 | Becton Dickinson And Company | Collection container assembly |
DE19748749A1 (de) * | 1997-11-05 | 1999-05-06 | Roche Diagnostics Gmbh | Gefäßverschluß mit Mitteln zur Vermeidung eines Austrages beim Öffnen |
AU2666299A (en) * | 1998-02-10 | 1999-08-23 | Nl Technologies, Ltd. | Housing for receptacle filling |
DE10080524D2 (de) * | 1999-03-08 | 2002-08-29 | Evotec Ag | Probenaufnahmevorrichtung |
US6221307B1 (en) | 1999-11-10 | 2001-04-24 | Becton Dickinson And Company | Collection container assembly |
WO2003004596A1 (fr) * | 2001-07-06 | 2003-01-16 | Precision System Science Co., Ltd. | Recipient de reaction et dispositif de reaction |
AU2003225552A1 (en) * | 2002-02-05 | 2003-09-02 | Genome Therapeutics Corporation | Seal for microtiter plate and methods of use thereof |
EP1541668A4 (en) * | 2002-06-17 | 2008-08-06 | Prec System Science Co Ltd | REACTION TANK AND REACTION PRODUCT RETRIEVAL DEVICE |
US7959866B2 (en) * | 2002-09-04 | 2011-06-14 | Becton, Dickinson And Company | Collection assembly |
GB0226863D0 (en) * | 2002-11-19 | 2002-12-24 | Biogene Ltd | Improvements in and relating to reaction vessels and reaction apparatus for use with such vessels |
GB0229410D0 (en) * | 2002-12-17 | 2003-01-22 | Molecular Sensing Plc | Sample vessel |
DE102004005381B4 (de) * | 2003-02-03 | 2012-10-18 | Becton Dickinson And Co. | Behälteranordnung und Verfahren zur Herstellung dieser Anordnung |
JP4645040B2 (ja) * | 2003-05-05 | 2011-03-09 | ベクトン・ディキンソン・アンド・カンパニー | 容器アセンブリとアセンブリの作製方法 |
US20040258563A1 (en) | 2003-06-23 | 2004-12-23 | Applera Corporation | Caps for sample wells and microcards for biological materials |
US7823745B2 (en) * | 2004-05-18 | 2010-11-02 | The Automation Partnership (Cambridge) Limited | Tube, cap and rack for automatic handling of samples |
US20060018799A1 (en) * | 2004-07-21 | 2006-01-26 | Wong Cai Ne W | Universal tissue homogenizer device and methods |
US7722822B2 (en) * | 2006-03-23 | 2010-05-25 | Agilent Technologies, Inc. | Sample tube and vial processing system, and method for processing the sample |
US20090165574A1 (en) * | 2007-12-27 | 2009-07-02 | Finnzymes Instruments Oy | Instrument and method for nucleic acid amplification |
CA2662546A1 (en) * | 2009-04-15 | 2010-10-15 | Spartan Bioscience Inc. | Tube for dna reactions |
US9180461B2 (en) | 2012-10-22 | 2015-11-10 | Qiagen Gaithersburg, Inc. | Condensation-reducing incubation cover |
USD735881S1 (en) | 2012-10-22 | 2015-08-04 | Qiagen Gaithersburg, Inc. | Tube strip holder for automated processing systems |
CN111801148B (zh) * | 2018-03-19 | 2022-12-02 | 株式会社村田制作所 | 过滤装置 |
CN111077108B (zh) * | 2019-12-31 | 2020-08-25 | 中国科学院地质与地球物理研究所 | 一种适用于深空探测的激光样品室 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
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DE330179C (de) * | 1919-01-30 | 1920-12-10 | Otto Menn | Fraesmaschine mit waehrend der Leerlaufszeit des Arbeitstisches selbsttaetig erhoehter Drehgeschwindigkeit zum Fraesen von Zahnsegmenten nach dem Abwaelzverfahren |
CH330179A (de) * | 1954-12-13 | 1958-05-31 | Paul Dr Med Boettger | Verfahren zum Verpacken von medizinischem Untersuchungsmaterial sowie Behälter zur Durchführung des Verfahrens |
US3005564A (en) * | 1959-10-12 | 1961-10-24 | Biolog Res Inc | Laboratory equipment |
DE1865710U (de) * | 1962-07-24 | 1963-01-17 | Irma Dorothee Lautenschlaeger | Verschluss fuer reagenzglaeser. |
DE1275795B (de) * | 1963-01-28 | 1968-08-22 | Eppendorf Geraetebau Netheler | Reaktionsgefaess fuer kleine Fluessigkeitsmengen |
DE6927506U (de) * | 1969-07-09 | 1969-12-18 | Sarstedt W | Reagiergefaess fuer medizinisch-technische untersuchungen von fluessigkeiten. |
DE2355511A1 (de) * | 1973-11-07 | 1975-05-22 | Milchzentrale Mannheim Heidelb | Verschlusskappe fuer bakteriologische zwecke |
WO1983000386A1 (en) * | 1981-07-20 | 1983-02-03 | American Hospital Supply Corp | Container for small quantities of liquids |
US4599315A (en) * | 1983-09-13 | 1986-07-08 | University Of California Regents | Microdroplet test apparatus |
US4634676A (en) * | 1984-06-06 | 1987-01-06 | Becton, Dickinson And Company | Replica plating device |
US4683058A (en) * | 1986-03-20 | 1987-07-28 | Costar Corporation | Filter for centrifuge tube |
JPS62273454A (ja) * | 1986-04-28 | 1987-11-27 | アイ・シー・アイ・オーストラリヤ・リミテツド | 反応のための方法及びその装置 |
-
1988
- 1988-07-07 DE DE8808738U patent/DE8808738U1/de not_active Expired
-
1989
- 1989-07-07 EP EP89907732A patent/EP0377721B1/de not_active Expired - Lifetime
- 1989-07-07 WO PCT/EP1989/000786 patent/WO1990000442A1/de active IP Right Grant
- 1989-07-07 DE DE89907732T patent/DE58905630D1/de not_active Expired - Fee Related
- 1989-07-07 US US07/466,359 patent/US5167929A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
DE58905630D1 (de) | 1993-10-21 |
EP0377721A1 (de) | 1990-07-18 |
US5167929A (en) | 1992-12-01 |
DE8808738U1 (de) | 1988-09-01 |
WO1990000442A1 (de) | 1990-01-25 |
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