`Say et al.
`
`54 ELECTROCHEMICAL ANALYTE
`75 Inventors: James Say, Alameda; Michael F.
`Tomasco, Cupertino, both of Calif.;
`Adam Heller, Austin, Tex.; Yoram
`Gal, Kibbutz Yagur, Israel; Behrad
`Aria, Alameda, Calif.; Ephraim Heller,
`Oakland, Calif.; Phillip John Plante,
`Sunnyvale, Calif.; Mark S. Vreeke
`Alameda Calif s
`s
`s
`73 Assignee: E. Heller & Company, Alameda, Calif.
`
`21 Appl. No.: 09/034,372
`22 Filed:
`Mar. 4, 1998
`7
`51) Int. Cl.' ........................................................ A61B 5/05
`52 U.S. Cl. ............................................. 600/345; 600/309
`58 Field of Search ..................................... 600/306, 308,
`600/309, 345, 346, 347, 348, 352, 354,
`357, 358, 365, 372, 382, 384, 3.
`s
`
`56)
`
`Ref
`
`Cited
`CS
`
`U.S. PATENT DOCUMENTS
`
`Re. 32,947 6/1989 Dormer et al..
`3.260,656 7/1966 Ross, Jr..
`i. E.
`J
`I
`3,776.832 3. 973 b y, Jr.
`3837,339 o/1974 XEN "tal
`3,926,760 12f1975 Allen et
`2 - 1 - 2
`(List continued on next page.)
`FOREIGN PATENT DOCUMENTS
`
`0 010 375 A1 4/1980 European Pat. Off..
`0 026.995 A1 4/1981 European Pat. Off..
`0 048 090 A2 3/1982 European Pat. Off..
`g
`A.
`E. E. Eas s
`O 127958 A2 3. 984 EVEN E. off.
`0 136 362 A1 4/1985 European Pat. Off..
`(List continued on next page.)
`
`US006134461A
`Patent Number:
`11
`(45) Date of Patent:
`
`6,134,461
`Oct. 17, 2000
`
`OTHER PUBLICATIONS
`Abruna, H. D. et al., “Rectifying Interfaces Using
`Two-Layer Films of Electrochemically Polymerized
`Vinylpyridine and Vinylbipyridine Complexes of Ruthe
`nium and Iron on Electrodes,” J. Am. Chem. Soc.,
`()
`(an '98).
`Albery, W.J. et al., “Amperometric enzyme electrodes. Part
`II. Conducting Salts as electrode materials for the oxidation
`of glucose oxidase,” J. Electroanal. Chem. Interfacial Elec
`trochem., 194(2) (1 page-Abstract only) (1985).
`Albery, W. J. et al., “Amperometric Enzyme Electrodes,”
`Phil. Trans. R. Soc. Lond. B316:107–119 (1987).
`Alcock, S.J. et al., “Continuous Analyte Monitoring to Aid
`Clinical Practice.” IEEE Engineering in Medicine and Biol
`ogy, 319-325 (1994).
`Anderson, L. B. et al., “Thin-Layer Electrochemistry:
`Steady-State Methods of Studying Rate Processes,” J. Elec
`troanal. Chem., 10:295-395 (1965).
`(List continued on next page.)
`Primary Examiner-Cary O’Connor
`ASSistant Examiner Navin Natnithithadha
`Attorney, Agent, or Firm-Merchant & Gould P.C.
`y, Ag
`57
`ABSTRACT
`An electrochemical analyte Sensor formed using conductive
`traces on a Substrate can be used for determining and/or
`monitoring a level of analyte in in vitro or in Vivo analyte
`containing fluids. For example, an implantable Sensor may
`be used for the continuous or automatic monitoring of a level
`of an analyte, Such as glucose, lactate, or oxygen, in a
`patient. The electrochemical analyte Sensor includes a Sub
`Strate and conductive material disposed on the Substrate, the
`conductive material forming a working electrode. In Some
`Sensors, the conductive material is disposed in recessed
`channels formed in a Surface of the Sensor. An electron
`transfer agent and/or catalyst may be provided to facilitate
`the electrolysis of the analyte or of a Second compound
`whose level depends on the level of the analyte. A potential
`is formed between the working electrode and a reference
`electrode or counter/reference electrode and the resulting
`current is a function of the concentration of the analyte in the
`body fluid.
`
`29 Claims, 8 Drawing Sheets
`
`55
`- - - -
`85 -
`
`
`
`/
`-
`
`52
`
`O -
`
`o
`
`Y-50
`
`- 49
`
`Y-57
`
`Page 1 of 86
`
`
`
`U.S. PATENT DOCUMENTS
`
`3,972,320
`3,979,274
`4,008,717
`4,016,866
`4,055,175
`4,059,406
`4,076,596
`4,098,574
`4,100,048
`4,151,845
`4,168.205
`4,172,770
`4,178,916
`4,206,755
`4,224,125
`4,240,438
`4,247.297
`4,340.458
`4,352,960
`4,356,074
`4,365,637
`4,366,033
`4,375,399
`4,384,586
`4,390,621
`4,401,122
`4,404,066
`4,418,148
`4,427,770
`4,431,004
`4,436,094
`4,440,175
`4,450.842
`4,458,686
`4,461,691
`4,469,110
`4,477,314
`4,484.987
`4,522,690
`4,524,114
`4,526,661
`4,534,356
`4,538,616
`4,543,955
`4,545.382
`4,552,840
`4,560,534
`4,571,292
`4,573.994
`4,581,336
`4,595,011
`4,619,754
`4,627,445
`4,627,908
`4,633,878
`4,637,403
`4,650,547
`4,654,197
`4,655,880
`4,655,885
`4,671,288
`4,679,562
`4,680,268
`4,682,602
`4,684,537
`4,685,463
`4,703,756
`4,711.245
`4,717.673
`4,721,601
`
`8/1976
`9/1976
`2/1977
`4/1977
`10/1977
`11/1977
`2/1978
`7/1978
`7/1978
`5/1979
`9/1979
`10/1979
`12/1979
`6/1980
`9/1980
`12/1980
`1/1981
`7/1982
`10/1982
`10/1982
`12/1982
`12/1982
`3/1983
`5/1983
`6/1983
`8/1983
`9/1983
`11/1983
`1/1984
`2/1984
`3/1984
`4/1984
`5/1984
`7/1984
`7/1984
`9/1984
`10/1984
`11/1984
`6/1985
`6/1985
`7/1985
`8/1985
`9/1985
`10/1985
`10/1985
`11/1985
`12/1985
`2/1986
`3/1986
`4/1986
`6/1986
`10/1986
`12/1986
`12/1986
`1/1987
`1/1987
`3/1987
`3/1987
`4/1987
`4/1987
`6/1987
`7/1987
`7/1987
`7/1987
`8/1987
`8/1987
`11/1987
`12/1987
`1/1988
`1/1988
`
`Kalman.
`Newman.
`Kowarski.
`Lawton.
`Clemens et al. .
`Fleet.
`Connery et al. .
`Dappen.
`Pompei et al..
`Clemens.
`Danninger et al. .
`Semersky et al. .
`McNamara.
`Klein.
`Nakamura et al. .
`Updike et al..
`Berti et al. .
`Lerner et al. .
`Dormer et al. .
`Johnson.
`Johnson.
`Richter et al. .
`Havas et al. .
`Christiansen.
`Bauer.
`Clark, Jr. .
`Johnson.
`Oberhardt.
`Chen et al. .
`Bessman et al. .
`Cerami.
`Wilkins.
`Zick et al. .
`Clark, Jr. .
`Frank.
`Slama.
`Richter et al. .
`Gough.
`Venkatasetty .
`Samuels et al. .
`Steckhan et al. .
`Papadakis.
`Rogoff.
`Schroeppel.
`Higgins et al. .
`Riffer.
`Kung et al. .
`Liu et al. .
`Fischell et al. .
`Malloy et al..
`Phillips.
`Niki et al. .
`Garcia et al. .
`Miller.
`Bombardieri.
`Garcia et al. .
`Gough.
`Lilja et al. .
`Liu .
`Hill et al. .
`Gough.
`Luksha.
`Clark, Jr. .
`Prohaska.
`Graetzel et al. .
`Williams.
`Gough et al. .
`Higgins et al. .
`Wrighton et al. .
`Wrighton et al. .
`
`6,134,461
`Page 2
`
`4,721,677
`4,726,378
`4,726,716
`4,757,022
`4,758,323
`4,759,371
`4,759,828
`4,764,416
`4,776.944
`4,781,798
`4,784,736
`4,795.707
`4,796,634
`4,805,624
`4,813,424
`4,815,469
`4.820,399
`4,822,337
`4,830.959
`4,832,797
`4,840,893
`4,848,351
`4,871,351
`4,871,440
`4,874,500
`4,890,620
`4,894,137
`4,897,162
`4,897,173
`4909,908
`4,911,794
`4,917,800
`4.919,141
`4.919,767
`4923,586
`4,927,516
`4,934,369
`4,935,105
`4,935,345
`4,938.860
`4,944.299
`4.950,378
`4,953,552
`4.954,129
`4.969,468
`4970,145
`4,974,929
`4,986,271
`4,994,167
`5,001,054
`5,058,592
`5,070,535
`5,082.550
`5,082,786
`5,089,112
`5,095,904
`5,101,814
`5,108,564
`5,109,850
`5,120,420
`5,126,034
`5,133,856
`5,135,003
`5,141,868
`5,161,532
`5,165,407
`5,174,291
`5,190,041
`5,192,416
`5,198.367
`5,202.261
`5,205,920
`
`1/1988
`2/1988
`2/1988
`7/1988
`7/1988
`7/1988
`7/1988
`8/1988
`10/1988
`11/1988
`11/1988
`1/1989
`1/1989
`2/1989
`3/1989
`3/1989
`4/1989
`4/1989
`5/1989
`5/1989
`6/1989
`7/1989
`10/1989
`10/1989
`10/1989
`1/1990
`1/1990
`1/1990
`1/1990
`3/1990
`3/1990
`4/1990
`4/1990
`4/1990
`5/1990
`5/1990
`6/1990
`6/1990
`6/1990
`7/1990
`7/1990
`8/1990
`9/1990
`9/1990
`11/1990
`11/1990
`12/1990
`1/1991
`2/1991
`3/1991
`10/1991
`12/1991
`1/1992
`1/1992
`2/1992
`3/1992
`4/1992
`4/1992
`5/1992
`6/1992
`6/1992
`7/1992
`8/1992
`8/1992
`11/1992
`11/1992
`12/1992
`3/1993
`3/1993
`3/1993
`4/1993
`4/1993
`
`Clark, Jr. .
`Kaplan.
`McGuire .
`Shults et al. .
`Davis et al. .
`Franetzki.
`Young et al. .
`Ueyama et al. .
`Janata et al. .
`Gough.
`Lonsdale et al. .
`Niiyama et al. .
`Huntsman et al. .
`Yao et al. .
`Wilkins.
`Cohen et al. .
`Senda et al. .
`Newhouse et al. .
`McNeil et al. .
`Vadgama et al. .
`Hill et al. .
`Finch.
`Feingold.
`Nagata et al..
`Madou et al. .
`Gough.
`Takizawa et al. .
`Lewandowski et al. .
`Nankai et al. .
`Ross et al. .
`Parce et al. .
`Lonsdale et al. .
`Zier et al. .
`Vadgama et al. .
`Katayama et al. .
`Yamaguchi et al. .
`Maxwell.
`Churchouse.
`Guibeau et al. .......................... 435/14
`Wogoman.
`Silvian.
`Nagata.
`DeMarzo.
`Giuliani et al. .
`Byers et al. .
`Bennetto et al. .
`Curry.
`Wilkins.
`Shults et al. .
`Wagner.
`Whisler.
`Hochmair et al. .
`Rishpon et al. .
`Nakamoto.
`Skotheim et al. .
`Seligman et al. .
`Palti.
`Szuminsky et al. .
`Blanco et al. .
`Nankai et al. .
`Carter et al. .
`Yamaguchi et al. .
`Souma.
`Shanks et al. .
`Joseph.
`Wilson et al. .
`Schoonen et al. .
`Palti.
`Wang et al..
`Aizawa et al. .
`Musho et al. .
`Oyama et al..
`
`Page 2 of 86
`
`
`
`6,134,461
`Page 3
`
`5,208,154 5/1993 Weaver et al..
`5,209.229 5/1993 Gilli.
`5,217,595 6/1993 Smith et al.
`5,229.282 7/1993 Yoshioka et al..
`5,250,439 10/1993 Musho et al.
`5,262,035 11/1993 Gregg et al..
`5,262,305 11/1993 Heller et al. .
`5,264,103 11/1993 Yoshioka et al..
`5,264,104 11/1993 Gregg et al..
`5,264,106 11/1993 McAleer et al..
`5,271,815 12/1993 Wong.
`5,279.294
`1/1994 Anderson et al..
`5,286.362 2/1994 Hoenes et al..
`5,286.364 2/1994 Yacynych et al..
`5,288,636 2/1994 Pollmann et al..
`5,293.546 3/1994 Tadros et al..
`5,320,098 6/1994 Davidson.
`5,320,725 6/1994 Gregg et al..
`5,322,063
`6/1994 Allen et al..
`5,336,388 8/1994 Leader et al..
`5,337.747 8/1994 Neftel.
`5,352,348 10/1994 Young et al. .
`5,356,786 10/1994 Heller et al..
`5,368,028 11/1994 Palti.
`5,372,133 12/1994 Hogen Esch.
`5,376,251 12/1994 Kaneko et al..
`5,378,628
`1/1995 Grätzel et al..
`5,387.327 2/1995 Khan.
`5,390,671
`2/1995 Lord et al..
`5,391,250 2/1995 Cheney, II et al..
`5,395,504 3/1995 Saurer et al..
`5,403.462 4/1995 Lev et al..
`5,411,647 5/1995 Johnson et al..
`5,437,999 8/1995 Diebold et al..
`5,469,846 11/1995 Khan.
`5,494,562 2/1996 Maley et al..
`5,496,453 3/1996 Uenoyama et al..
`5,497,772 3/1996 Schulman et al..
`5,509,410 4/1996 Hill et al. ................................ 600/345
`5,531,878 7/1996 Vadgama et al..
`5,545,191
`8/1996 Mann et al..
`5,560,357 10/1996 Faupel et al..
`5,565,085 10/1996 Ikeda et al..
`5,567,302 10/1996 Song et al..
`5,568.806 10/1996 Cheney, II et al..
`5,569,186 10/1996 Lord et al..
`5,582,184 12/1996 Erickson et al..
`5,582,697 12/1996 Ikeda et al..
`5,582,698 12/1996 Flaherty et al. .
`5,586,553 12/1996 Halili et al..
`5,589,326 12/1996 Deng et al..
`5,593,852
`1/1997 Heller et al..
`5,596,150
`1/1997 Arndt et al..
`5,617,851
`4/1997 Lipkovker.
`5,628,890 5/1997 Carter et al..
`5,651,869 7/1997 Yoshioka et al..
`5,660,163 8/1997 Schulman et al..
`5,670,031
`9/1997 Hintsche et al..
`5,680.858 10/1997 Hansen et al..
`5,682,233 10/1997 Brinda.
`5,695,623 12/1997 Michel et al..
`5,708.247
`1/1998 McAleer et al..
`5,711,861
`1/1998 Ward et al. ............................. 204/403
`5,711,862
`1/1998 Sakoda et al..
`5,727,548 3/1998 Hill et al. ................................ 600/345
`5,741.211
`4/1998 Renirie et al..
`5,807.375 9/1998 Gross et al..
`5,820,551 9/1998 Hill et al. ................................ 600/345
`5,822,715 10/1998 Worthington et al. .
`5,840,020 11/1998 Heinonen et al..
`5,842,983 12/1998 Abel et al. .............................. 600/345
`5,954,685 9/1999 Tierney ..................................... 604/20
`
`
`
`FOREIGN PATENT DOCUMENTS
`
`O 170 375 A2 2/1986 European Pat. Off.
`O 177 743 A2 4/1986 European Pat. Off..
`O 080304 B1 5/1986 European Pat. Off.
`0 184909 A2 6/1986 European Pat. Off..
`O 206 218 A2 12/1986 European Pat. Off.
`O 230 472 A1 8/1987 European Pat. Off..
`0 241 309 A3 10/1987 European Pat. Off..
`0 245 073 A2 11/1987 European Pat. Off..
`0 278 647 A2 8/1988 European Pat. Off..
`0.359 831 A1 3/1990 European Pat. Off..
`O 368 209 A1 5/1990 European Pat. Off..
`O 390 390 A1 10/1990 European Pat. Off..
`O 400 918 A1 12/1990 European Pat. Off..
`O 453 283 A1 10/1991 European Pat. Off..
`O 470 290 A1 2/1992 European Pat. Off..
`0 127958 B2 3/1992 European Pat. Off..
`0 255 291 B1 6/1992 European Pat. Off..
`0 078 636 A1 5/1993 European Pat. Off..
`227 029 A3 9/1985 German Dem. Rep. .
`29 03 216 8/1979 Germany.
`3934299 10/1990 Germany.
`54-41191
`4/1979 Japan.
`55-10581
`1/1980 Japan.
`55-10583
`1/1980 Japan.
`55-10584 1/1980 Japan.
`55-12406
`1/1980 Japan.
`56-163447 12/1981 Japan.
`57-70448 4/1982 Japan.
`58-194748 11/1983 Japan.
`60-173457 9/1985 Japan.
`60-173458 9/1985 Japan.
`60-173459 9/1985 Japan.
`61-90050 5/1986 Japan.
`62-85855 4/1987 Japan.
`62-114747 5/1987 Japan.
`63-58149 3/1988 Japan.
`63-139246 6/1988 Japan.
`63-294799 12/1988 Japan.
`63-317757 12/1988 Japan.
`63-317758 12/1988 Japan.
`1-114746 5/1989 Japan.
`1-114747 5/1989 Japan.
`1-124060 5/1989 Japan.
`1-134244 5/1989 Japan.
`1-156658 6/1989 Japan.
`2-62958 3/1990 Japan.
`2-120655 5/1990 Japan.
`2-287.145 11/1990 Japan.
`2-310457 12/1990 Japan.
`3-26956 2/1991 Japan.
`3-28752 2/1991 Japan.
`3-202764 9/1991 Japan.
`5-72171 3/1993 Japan.
`5-196595 8/1993 Japan.
`6-190050 7/1994 Japan.
`7-55757 3/1995 Japan.
`7-72585 3/1995 Japan.
`8-285814 11/1996 Japan.
`8-285815 11/1996 Japan.
`9-21778 1/1997 Japan.
`9-101280 4/1997 Japan.
`9-285459 11/1997 Japan.
`63-128252 5/1998 Japan.
`10-170471 6/1998 Japan.
`1281988 A1 1/1987 U.S.S.R. .
`1394.171
`5/1975 United Kingdom.
`1599241 9/1981 United Kingdom.
`2 073891 10/1981 United Kingdom.
`2 154 003 2/1988 United Kingdom.
`2 204 408 11/1988 United Kingdom.
`
`Page 3 of 86
`
`
`
`6,134,461
`Page 4
`
`2 254 436 10/1992
`WO 85/05119 11/1985
`WO 89/08713 9/1989
`WO 90/O5300 5/1990
`WO 90/O5910 5/1990
`WO 91/O1680 2/1991
`WO 91/04704 4/1991
`WO 91/15993 10/1991
`WO 92/13271 8/1992
`WO 94/20602 9/1994
`WO 94/27140 11/1994
`WO 96/30431. 10/1996
`WO 97/02847
`1/1997
`WO 97/19344 5/1997
`WO 97/42882 11/1997
`WO 97/42883 11/1997
`WO 97/42886 11/1997
`WO 97/42888 11/1997
`WO 97/43962 11/1997
`
`United Kingdom.
`WIPO.
`WIPO.
`WIPO.
`WIPO.
`WIPO.
`WIPO.
`WIPO.
`WIPO.
`WIPO.
`WIPO.
`WIPO.
`WIPO.
`WIPO.
`WIPO.
`WIPO.
`WIPO.
`WIPO.
`WIPO.
`
`OTHER PUBLICATIONS
`Bartlett, P. N. et al., “Covalent Binding of Electron Relays
`to Glucose Oxidation,” J. Chem. Soc. Chem. Commun.,
`1603–1604 (1987).
`Bartlett, P. N. et al., “Modification of glucose oxidase by
`tetrathiafulvalene,” J. Chem. Soc., Chem. Commun., 16 (1
`page-Abstract only) (1990).
`Bartlett, P. N. et al., “Strategies for the Development of
`Amperometric Enzyme Electrodes,” BioSensors, 3:359-379
`(1987/88).
`Bindra, D.S. et al., “Design and in Vitro Studies of a
`Needle-Type Glucose Sensor for Subcutaneous Monitor
`ing", Anal. Chem. 63(17): 1692–1696 (Sep. 1, 1991).
`Bobbioni-Harsch, E. et al., “Lifespan of subcutaneous glu
`coSe Sensors and their performances during dynamic gly
`caemia changes in rats,” J. Biomed. Eng. 15:457-463
`(1993).
`Brandt, J. et al., “Covalent attachment of proteins to
`polysaccharide carriers by means of benzoquinone,” Bio
`chim. Biophys. Acta, 386(1) (1 page Abstract only) (1975).
`Brownlee, M. et al., “A Glucose-Controlled Insulin-Deliv
`ery System: Semisynthetic Insulin Bound to Lectin”, Sci
`ence, 206(4423): 1190–1191 (Dec. 7, 1979).
`Cass, A.E.G. et al., “Ferricinum Ion AS An Electron Accep
`tor for Oxido-Reductases,” J. Electroanal. Chem.,
`190:117-127 (1985).
`Cass, A.E.G. et al., “Ferrocene-Mediated Enzyme Electrode
`for Amperometric Determination of Glucose', Anal. Chem.,
`56(4):667-671 (Apr. 1984).
`Castner, J. F. et al., “Mass Transport and Reaction Kinetic
`Parameters Determined Electrochemically for Immobilized
`Glucose Oxidase,” Biochemistry, 23(10):2203-2210 (1984).
`Claremont, D.J. et al., “BioSensors for Continuous. In Vivo
`Glucose Monitoring”, IEEE Engineering in Medicine and
`Biology Society 10th Annual International Conference, New
`Orleans, Louisiana, 3 pgs. (Nov. 4–7, 1988).
`Clark, L.C. et al., “Differential Anodic Enzyme Polarogra
`phy for the Measurement of Glucose”, Oxygen Transport to
`Tissue. Instrumentation, Methods, and Physiology, 127-132
`(1973).
`Clark, L.C., Jr. et al., “Electrode Systems for Continuous
`Monitoring in Cardiovascular Surgery,” Annals New York
`Academy of Sciences, pp. 29-45 (1962).
`Clark, L.C. et al., “Long-term Stability of Electroenzymatic
`Glucose Sensors Implanted in Mice,” Trans. Am. Soc. Artif
`Inter. Organs, XXXIV:259-265 (1988).
`
`Clarke, W. L., et al., “Evaluating Clinical Accuracy of
`Systems for Self-Monitoring of Blood Glucose,” Diabetes
`Care, 10(5):622-628 (Sep.-Oct. 1987).
`Csóregi, E. et al., “Design, Characterization, and One-Point
`in Vivo Calibration of a Subcutaneously Implanted Glucose
`Electrode,” Anal. Chem. 66(19):3131-3138 (Oct. 1, 1994).
`Csóregi, E. et al., “Design and Optimization of a Selective
`Subcutaneously Implantable Glucose Electrode Based on
`“Wired” Glucose Oxidase,” Anal. Chem. 67(7): 1240–1244
`(Apr. 1, 1995).
`Csóregi, E. et al., “On-Line Glucose Monitoring by Using
`Microdialysis Sampling and Amperometric Detection Based
`on “Wired” Glucose Oxidase in Carbon Paste,” Mikrochim.
`Acta. 121:31-40 (1995).
`Davis, G., “Electrochemical Techniques for the Develop
`ment of Amperometric Biosensors”, BioSensors, 1:161-178
`(1985).
`Degani, Y. et al., “Direct Electrical Communication between
`Chemically Modified Enzymes and Metal Electrodes. 1.
`Electron Transfer from Glucose Oxidase to Metal Electrodes
`via Electron Relays, Bound Covalently to the Enzyme,” J.
`Phys. Chem., 91(6):1285–1289 (1987).
`Degani, Y. et al., “Direct Electrical Communication between
`Chemically Modified Enzymes and Metal Electrodes. 2.
`Methods for Bonding Electron-Transfer Relays to Glucose
`Oxidase and D-Amino-Acid Oxidase,” J. Am. Chem. Soc.,
`110(8):2615–2620 (1988).
`Degani, Y. et al., “Electrical Communication between Redox
`Centers of Glucose Oxidase and Electrodes via Electrostati
`cally and Covalently Bound Redox Polymers,” J. Am. Chem.
`Soc., 111:2357-2358 (1989).
`Denisevich, P. et al., “Unidirectional Current Flow and
`Charge State Trapping at Redox Polymer Interfaces on
`Bilayer Electrodes: Principles, Experimental Demonstra
`tion, and Theory,” J. Am. Chem. Soc., 103(16):4727-4737
`(1981).
`Dicks, J. M., “Ferrocene modified polypyrrole with immo
`bilised glucose oxidase and its application in amperometric
`glucose microbiosenors,” Ann. Biol. clin., 47:607-619
`(1989).
`Engstrom, R. C., “Electrochemical Pretreatment of Glassy
`Carbon Electrodes”, Anal. Chem., 54(13):2310-2314 (Nov.
`1982).
`EngStrom, R.C. et al., “Characterization of Electrochemi
`cally Pretreated Glassy Carbon Electrodes', Anal. Chem.,
`56(2): 136–141 (Feb. 1984).
`Ellis, C. D., “Selectivity and Directed Charge Transfer
`through an Electroactive Metallopolymer Film,” J. Am.
`Chem. Soc., 103(25):7480–7483 (1981).
`Feldman, B.J. et al., “Electron Transfer Kinetics at Redox
`Polymer/Solution Interfaces Using Microelectrodes and
`Twin Electrode Thin Layer Cells”, J. Electroanal. Chem.,
`194(1):63–81 (Oct. 10, 1985).
`Fischer, H. et al., “Intramolecular Electron Transfer Medi
`ated by 4,4'-Bipyridine and Related Bridging Groups', J.
`Am. Chem. Soc., 98(18):5512-5517 (Sep. 1, 1976).
`Foulds, N.C. et al., “Enzyme Entrapment in Electrically
`Conducting Polymers,” J. Chem. Soc., Faraday Trans 1.,
`82:1259–1264 (1986).
`Foulds, N.C. et al., “Immobilization of Glucose Oxidase in
`Ferrocene-Modified Pyrrole Polymers,” Anal. Chem.,
`60(22):2473–2478 (Nov. 15, 1988).
`Frew, J.E. et al., “Electron-Transfer Biosensors”, Phil.
`Trans. R. Soc. Lond, B316:95-106 (1987).
`
`Page 4 of 86
`
`
`
`6,134,461
`Page 5
`
`Gorton, L. et al., “Selective detection in flow analysis based
`on the combination of immobilized enzymes and chemically
`modified
`electrodes,”
`Analytica
`Chimica
`Acta.,
`250:203–248 (1991).
`Gregg, B. A. et al., “CroSS-Linked Redox Gels Containing
`Glucose Oxidase for Amperometric BioSensor Applica
`tions.” Analytical Chemistry, 62(3):258-263 (Feb. 1, 1990).
`Gregg, B. A. et al., “Redox Polymer Films Containing
`Enzymes. 1. A Redox-Conducting Epoxy Cement: Synthe
`sis, Characterization, and Electrocatalytic Oxidation of Hyd
`roquinone,” J. Phys. Chem., 95(15):5970-5975 (1991).
`Hale, P.D. et al., “A New Class of Amperometric Biosensor
`Incorporating a Polymeric Electron-Transfer Mediator,” J.
`Am. Chem. Soc., 11(9):3482-3482 (1989).
`Harrison, D.J. et al., “Characterization of Perfluorosulfonic
`Acid Polymer Coated Enzyme Electrodes and a Miniatur
`ized Integrated Potentiostat for Glucose Analysis in Whole
`Blood”, Anal. Chem., 60(19):2002–2007 (Oct. 1, 1988).
`Hawkridge, F. M. et al., “Indirect Coulometric Titration of
`Biological Electron Transport Components.” Analytical
`Chemistry, 45(7):1021–1027 (Jun. 1973).
`Heller, A., “Amperometric biosensors based on three-di
`mensional hydrogel-forming epoxy networks, SensOrS and
`Actuators B, 13–14:180–183 (1993).
`Heller, A., “Electrical Connection of Enzyme Redox Centers
`to Electrodes,” J. Phys. Chem., 96(9):3579–3587 (1992).
`Heller, A., “Electrical Wiring of Redox Enzymes,” Acc.
`Chem. Res., 23(5):129-134 (1990).
`Ianniello, R.M. et al. “Immobilized Enzyme Chemically
`Modified Electrode as an Amperometric Sensor”, Anal.
`Chem., 53(13):2090–2095 (Nov. 1981).
`Ianniello, R.M. et al., “Differential Pulse Voltammetric
`Study of Direct Electron Transfer in Glucose Oxidase
`Chemically Modified Graphite Electrodes”, Anal. Chem.,
`54:(7):1098–1101 (Jun. 1981).
`Ikeda, T. et al., “Glucose oxidase-immobilized benzoquino
`ne-carbon past electrode as a glucose Sensor,” Agric. Biol.
`Chem., 49(2) (1 page-Abstract only) (1985).
`Ikeda, T. et al., “Kinetics of Outer-Sphere Electron Trans
`fers Between Metal Complexes in Solutions and Polymeric
`Films on Modified Electrodes', J. Am. Chem. Soc.,
`103(25):7422–7425 (Dec. 16, 1981).
`Johnson, J. M. et al., “Potential-Dependent Enzymatic
`Activity in an Enzyme Thin-Layer Cell,” Anal. Chem.
`54:1377–1383 (1982).
`Johnson, K.W., “Reproducible Electrodeposition of Biomol
`ecules for the Fabrication of Miniature Electroenzymatic
`Biosensors’, Sensors and Atuators B Chemical, B5:85-89
`(1991).
`Jönsson, G. et al., “An Amperometric Glucose Sensor Made
`by Modification of a Graphite Electrode Surface With
`Immobilized Glucose Oxidase and Adsorbed Mediator',
`Biosensors, 1:355-368 (1985).
`Josowicz, M. et al., “Electrochemical Pretreatment of Thin
`Film Platinum Electrodes', J.
`Elecrochem. Soc.,
`135(1):112–115 (Jan. 1988).
`Katakis, I. et al., “Electrostatic Control of the Electron
`Transfer Enabling Binding of Recombinant Glucose Oxi
`dase and Redox Polyelectrolytes,” J. Am. Chem. Soc.,
`116(8):3617-3618 (1994).
`Katakis, I. et al., “L-O-Glycerophosphate and L-Lactate
`Electrodes Based on the Electrochemical “Wiring” of Oxi
`dases,” Analytical Chemistry, 64(9): 1008-1013 (May 1,
`1992).
`
`Kenausis, G. et al., “Wiring of glucose oxidase and lactate
`oxidase within a hydrogel made with poly(Vinyl pyridine)
`complexed with
`Os(4,4'-dimethoxy-2,2'-bipyridine)
`Cl’,” J. Chem. Soc., Faraday Trans., 92(20):4131–4136
`(1996).
`Koudelka, M. et al., “In-Vivo Behaviour of Hypodermically
`Implanted Microfabricated Glucose Sensors”, BioSensors &
`Bioelectronics, 6(1):31-36 (1991).
`KulyS, J. et al., “Mediatorless peroxidase electrode and
`preparation of bienzyme Sensors, Bioelectrochemistry and
`Bioenergetics, 24:305-311 (1990).
`Lager, W. et al., “Implantable Electrocatalytic Glucose Sen
`sor.” Horm. Metab. Res., 26:526-530 (Nov. 1994).
`Lindner, E. et al. "Flexible (Kapton-Based) Microsensor
`Arrays of High Stability for Cardiovascular Applications”, J.
`Chem. Soc. Faraday Trans., 89(2):361-367 (Jan. 21, 1993).
`Maidan, R. et al., “Elimination of Electrooxidizable Inter
`ferant-Produced Currents in Amperometric Biosensors.”
`Analytical Chemistry, 64(23):2889–2896 (Dec. 1, 1992).
`Mastrototaro, J.J. et al., “An Electroenzymatic Glucose
`Sensor Fabricated on a Flexible Substrate’, Sensors and
`Biosensors B Chemical, B5:139-144 (1991).
`McNeil, C. J. et al., “Thermostable Reduced Nicotinamide
`Adenine Dinucleotide Oxidase: Application to Amperomet
`ric Enzyme Assay,” Anal. Chem., 61(1):25-29 (Jan. 1,
`1989).
`Miyawaki, O. et al., “Electrochemical and Glucose Oxidase
`Coenzyme Activity of Flavin Adenine Dinucleotide
`Covalently Attached to Glassy Carbon at the Adenine Amino
`Group”, Biochimica et Biophysica Acta, 838:60-68 (1985).
`Moatti-Sirat, D. et al., “Evaluating in vitro and in vivo the
`interference of ascorbate and acetaminophen on glucose
`detection by a needle-type glucose Sensor, BioSensOrS &
`Bioelectronics, 7(5):345-352 (1992).
`Moatti-Sirat, D. et al., “Reduction of acetaminophen inter
`ference in glucose Sensors by a composite Nafion mem
`brane: demonstration in rats and man,” Diabetologia, 37(6)
`(1 page-Abstract only) (Jun. 1994).
`Moatti-Sirat, D. et al., “Towards continuous glucose moni
`toring: in Vivo evaluation of a miniaturized glucose Sensor
`implanted for Several days in rat Subcutaneous tissue,”
`Diabetologia, 35(3) (1 page-Abstract only) (Mar. 1992).
`Nagy, G. et al., “A New Type of Enzyme Electrode: The
`Ascorbic Acid Eliminator Electrode,” Life Sciences,
`31(23):2611–2616 (1982).
`Nakamura, S. et al., “Effect of Periodate Oxidation on the
`Structure and Properties of Glucose Oxidase,” Biochinica et
`Biophysica Acta., 445:294-308 (1976).
`NaraZimhan, K. et al., “p-Benzoquinone activation of metal
`oxide electrodes for attachment of enzymes, Enzyme
`Microb. Technol, 7(6) (1 page-Abstract only) (1985).
`Ohara, T. J. et al., “Glucose Electrodes Based on
`Cross-Linked
`Os(bpy)CI'"
`Complexed
`Poly(1-vinylimadazole) Films,” Analytical Chemistry,
`65(23):3512–3516 (Dec. 1, 1993).
`Ohara, T. J., “Osmium Bipyridyl Redox Polymers Used in
`Enzyme Electrodes.” Platinum Metals Rev., 39(2):54-62
`(Apr. 1995).
`Ohara, T.J. et al., “Wired” Enzyme Electrodes for Ampero
`metric Determination of Glucose or Lactate in the Presence
`of Interfering
`Substances,” Analytical
`Chemistry,
`66(15):2451–2457 (Aug. 1, 1994).
`Olievier, C. N. et al., “In Vivo Measurement of Carbon
`Dioxide Tension with a Miniature Electrode, Pflugers Arch.
`373:269-272 (1978).
`
`Page 5 of 86
`
`
`
`6,134,461
`Page 6
`
`Paddock, R. et al., “Electrocatalytic reduction of hydrogen
`peroxide Via direct electron transfer from pyrolytic graphite
`electrodes to irreversible adsorbed cytochrome c peroxi
`dase,” J. Electroanal. Chem., 260:487–494 (1989).
`Paleschi, G. et al., “A Study of Interferences in Glucose
`Measurements in Blood by Hydrogen Peroxide Based Glu
`cose Probes", Anal. Biochem., 159:114-121 (1986).
`Pankratov, I. et al., “Sol-gel derived renewable-surface
`biosensors,” Journal of Electroanalytical Chemistry,
`393:35-41 (1995).
`Pathak, C. P. et al., “Rapid Photopolymerization of Immu
`noprotective Gels in Contact with Cells and Tissue,” J. Am.
`Chem. Soc., 114(21):8311-83.12 (1992).
`Pickup, J., “Developing glucose Sensors for in Vivo use,”
`Tibtech, 11:285–289 (Jul 1993).
`Pickup, J. C. et al., “In Vivo molecular Sensing in diabetes
`mellitus: an implantable glucose Sensor with direct electron
`transfer.” Diabetologia, 32(3):213–217 (1989).
`Pickup, J. et al., “Potentially-implantable, amperometric
`glucose Sensors with mediated electron transfer improving
`the operating stability,” BioSensors, 4(2) (1 page-Abstract
`only) (1989).
`Pishko, M.V. et al., “Amperometric Glucose Microelec
`trodes Prepared Through Immobilization of Glucose Oxi
`dase in Redox Hydrogels”, Anal. Chem., 63(20):2268-2272
`(Oct. 15, 1991).
`Poitout, V. et al., “A glucose monitoring System for on line
`estimation in man blood glucose concentration using a
`miniaturized glucose Sensor implanted in the Subcutaneous
`tissue and a wearable control unit,” Biabetolgia, 36(7) (1
`page-Abstract only) (Jul. 1993).
`Poitout, V. et al., “Calibration in dogs of a subcutaneous
`miniaturized glucose Sensor using a glucose meter for blood
`glucose determination,
`BioSensOrS & Bioelectronics,
`7:587-592 (1992).
`Poitout, V. et al., “In vitro and in vivo evaluation in dogs of
`a miniaturized glucose sensor,” ASAIO Transactions, 37(3)
`(1 page-Abstract only) (Jul.-Sep. 1991).
`Pollak, A. et al., “Enzyme Immobilization by Condensation
`Copolymerization into Cross-Linked Polyacrylamide Gels,”
`J. Am. Chem. Soc., 102(20):6324–6336 (1980).
`Reach, G. et al., “Can Continuous Glucose Monitoring Be
`Used for the Treatment of Diabetes?” Analytical Chemistry,
`64(6):381–386 (Mar. 15, 1992).
`Rebrin, K. et al., “Automated Feedback Control of Subcu
`taneous Glucose Concentration in Diabetic Dogs”, Diabe
`tologia, 32(8):573–576 (Aug. 1989).
`Sakakida, M. et al., “Ferrocene-mediate needle-type glu
`coSe Sensor covered with newly designed biocompatible
`membrane,” Sensors and Actuators B, 13-14:319-322
`(1993).
`Samuels, G. J. et al., “An Electrode-Supported Oxidation
`Catalyst Based on Ruthenium (IV). pH “Encapsulation” in
`a Polymer Film,” J. Am. Chem. Soc., 103(2):307-312
`(1981).
`Sasso, S. V. et al., “Electropolymerized 1,2-Diaminoben
`Zene as a Means to Prevent Interferences and Fouling and to
`Stabilize Immobilized Enzyme in Electrochemical Biosen
`sors”, Anal. Chem., 62(11): 1111-1117 (Jun. 1, 1990).
`Scheller, F. et al., “Enzyme electrodes and their application,”
`Phil. Trans. R. Soc. Lond, B 316:85–94 (1987).
`Schmehl, R.H. et al., “The Effect of Redox Site Concentra
`tion on the Rate of Mediated Oxidation of Solution Sub
`strates by a Redox Copolymer Film, J. Electroanal. Chem.,
`152:97–109 (Aug. 25, 1983).
`
`Shichiri, M. et al., “Glycaemic Control in Pancreatetomized
`Dogs with a Wearable Artificial Endocrine Pancreas”, Dia
`betologia, 24(3):179–184 (Mar. 1983).
`Sittampalam, G. et al., “Surface-Modified Electrochemical
`Detector for Liquid Chromatography', Anal. Chem.,
`55(9):1608–1610 (Aug. 1983).
`Soegijoko, S. et al., Horm. Metabl. Res., Suppl. Ser, 12 (1
`page-Abstract only) (1982).
`Sprules, S. D. et al., “Evaluation of a New Disposable
`Screen-Printed Sensor Strip for the Measurement of NADH
`and Its Modification to Produce a Lactate Biosensor
`Employing
`Microliter
`Volumes,”
`Electroanalysis,
`8(6):539–543 (1996).
`Sternberg, F. et al., “Calibration Problems of Subcutaneous
`Glucosensors when Applied "In-Situ” in Man,” Horm.
`metabl. Res, 26:524–525 (1994).
`Sternberg, R. et al., “Covalent Enzyme Coupling on Cellu
`lose Acetate Membranes for Glucose Sensor Development,”
`Analytical Chemistry, 60(24):2781-2786 (Dec. 15, 1988).
`Sternberg, R. et al., “Study and Development of Multilayer
`Needle-type Enzyme-based Glucose Microsensors,” Bio
`sensors, 4:27-40 (1988).
`Suekane, M., “Immobilization of glucose isomerase,”
`Zeitschrift fir Allgemeine Mikrobiologie, 22(8):565-576
`(1982).
`Tajima, S. et al., “Simultaneous Determination of Glucose
`and 1.5-Anydroglucitol”, Chemical Abstracts, 111(25):394
`111:228556g (Dec. 18, 1989).
`Tarasevich, M.R. “Bioelectrocatalysis”, Comprehensive
`Treatise of Electrochemistry, 10 (Ch. 4):231-295 (1985).
`Tatsuma, T. et al., “Enzyme Monolayer- and Bilayer-Modi
`fied Tin Oxide ELectrodes for the Determination of Hydro
`gen
`Peroxide
`and
`Glucose.”
`Anal.
`Chem.,
`61(21):2352–2355 (Nov. 1, 1989).
`Taylor, C. et al., “Wiring of glucose oxidase within a
`hydrogel made with polyvinyl imidazole complexed with
`(OS-4,4'-dimethoxy-2,2'-bipyridine)C1''",” Journal of
`Electroanalytical Chemistry, 396:511–515 (1995).
`Trojanowicz, M. et al., “Enzyme Entrapped Polypyrrole
`Modified Electrode for Flow-Injection Determination of
`Glucose,” Biosensors & Bioelectronics, 5:149-156 (1990).
`Turner, A.P.F. et al., “Diabetes Mellitus: Biosensors for
`Research and Management”, BioSensors, 1:85-115 (1985).
`Turner, R. F. B. et al., “A Biocompatible Enzyme Electrode
`for Continuous in vivo Glucose Monitoring in Whole
`Blood.” Sensors and Actuators, B1(1-6):561-564 (Jan.
`1990).
`Tuzhi, P. et al., “Constant Potential Pretreatment of Carbon
`Fiber Electrodes for In Vivo Electrochemistry”, Analytical
`Letters, 24(6):935–945 (1991).
`Umaha, M., “Protein-Modifeid Electrochemically Active
`Biomaterial Surface,” U.S. Army Research Office Report,
`(12 pages) (Dec. 1988).
`Urban, G. et al., “Miniaturized Thin-Film Biosensors. Using
`Covalently Immobilized Glucose Oxidase”, BioSensors &
`Bioelectronics, 6(7):555-562 (1991).
`Velho, G. et al., “In Vitro and In Vivo Stability of Electrode
`Potentials in Needle-Type Glucose Sensors”, Diabetes,
`38(2):164–171 (Feb. 1989).
`Velho, G. et al., “Strategies for calibrating a Subcutaneous
`glucose sensor,” Biomed. Biochin. Acta, 48(11/12):957-964
`(1989).
`Von Woedtke, T. et al., “In Situ Calibration of Implanted
`Electrochemical Glucose Sensors,” Biomed Biochim. Acta,
`48(11/12): 943–952 (1989).
`
`Page 6 of 86
`
`
`
`6,134,461
`Page 7
`
`Vreeke, M. S. et al., “Chapter 15: Hydrogen Peroxide
`Electrodes Based on Electrical Connection of Redox Centers
`of Various Peroxidases to Electrodes through a Three-Di
`mensional Electron-Relaying Polymer Network, Diagnos
`tic BioSensor Polymers, 7 pgs. (Jul 26, 1993).
`Vreeke, M. et al., “Hydrogen Peroxide and B-Nicotinamide
`Adenine Dinucleotide Sensing Amperometric Electrodes
`Based on Electrical Connection of Horseradish Per