`US010407458B2
`
`c12) United States Patent
`Ju et al.
`
`US 10,407,458 B2
`(IO) Patent No.:
`*Sep.10,2019
`(45) Date of Patent:
`
`(54) MASSIVE PARALLEL METHOD FOR
`DECODING DNA AND RNA
`
`(71) Applicant: The Trustees of Columbia University
`in the City of New York, New York,
`NY (US)
`
`(72)
`
`Inventors: Jingyue Ju, Englewood Cliffs, NJ (US);
`Zengmin Li, Flushing, NY (US); John
`Robert Edwards, St. Louis, MO (US);
`Yasuhiro Itagaki, New York, NY (US)
`
`(73) Assignee: THE TRUSTEES OF COLUMBIA
`UNIVERSITY IN THE CITY OF
`NEW YORK, New York, NY (US)
`
`( *) Notice:
`
`Subject to any disclaimer, the term ofthis
`patent is extended or adjusted under 35
`U.S.C. 154(b) by O days.
`
`This patent is subject to a terminal dis(cid:173)
`claimer.
`
`(2018.01)
`(2006.01)
`
`C12Q 116876
`C40B 40/00
`(52) U.S. Cl.
`CPC ............. C07H 19114 (2013.01); C07H 19110
`(2013.01); C07H 21100 (2013.01); C12Q 1168
`(2013.01); C12Q 11686 (2013.01); C12Q
`116869 (2013.01); C12Q 116872 (2013.01);
`C12Q 116874 (2013.01); C12Q 116876
`(2013.01); C07B 2200111 (2013.01); Cl2Q
`25251117 (2013.01); Cl2Q 2525/186
`(2013.01); Cl2Q 2535/101 (2013.01); Cl2Q
`2535/122 (2013.01); Cl2Q 2563/107
`(2013.01); Cl2Q 2565/501 (2013.01); C40B
`40/00 (2013.01)
`
`(58) Field of Classification Search
`CPC .............................. C07H 19/04; C12Q 1/6869
`USPC ............................................. 536/4.1; 435/6.1
`See application file for complete search history.
`
`(56)
`
`References Cited
`
`U.S. PATENT DOCUMENTS
`
`(21) Appl. No.: 16/149,098
`
`(22) Filed:
`
`Oct. 1, 2018
`
`(65)
`
`Prior Publication Data
`
`US 2019/0031704 Al
`
`Jan. 31, 2019
`
`(60)
`
`Related U.S. Application Data
`
`Continuation of application No. 15/915,983, filed on
`Mar. 8, 2018, which is a continuation of application
`No. 14/670,748, filed on Mar. 27, 2015, which is a
`continuation of application No. 13/959,660, filed on
`Aug. 5, 2013, now Pat. No. 9,133,511, which is a
`continuation of application No. 13/672,437, filed on
`Nov. 8, 2012, now abandoned, which
`is a
`continuation of application No. 13/339,089, filed on
`Dec. 28, 2011, now abandoned, which
`is a
`continuation of application No. 12/804,284, filed on
`Jul. 19, 2010, now Pat. No. 8,088,575, which is a
`continuation of application No. 11/810,509, filed on
`Jun. 5, 2007, now Pat. No. 7,790,869, which is a
`continuation of application No. 10/702,203, filed on
`Nov. 4, 2003, now Pat. No. 7,345,159, which is a
`division of application No. 09/972,364, filed on Oct.
`5, 2001, now Pat. No. 6,664,079, which is a
`continuation-in-part of application No. 09/684,670,
`filed on Oct. 6, 2000, now abandoned.
`
`(60)
`
`Provisional application No. 60/300,894, filed on Jun.
`26, 2001.
`
`(51)
`
`Int. Cl.
`C07H 19114
`C12Q 1168
`C07H 21100
`C12Q 11686
`C12Q 116874
`C12Q 116872
`C12Q 116869
`C07H 19110
`
`(2006.01)
`(2018.01)
`(2006.01)
`(2018.01)
`(2018.01)
`(2018.01)
`(2018.01)
`(2006.01)
`
`4,711,955 A
`4,772,691 A
`4,804,748 A
`4,824,775 A
`4,863,849 A
`4,888,274 A
`5,043,272 A
`5,047,519 A
`5,118,605 A
`5,151,507 A
`5,174,962 A
`5,175,269 A
`
`12/1987 Ward et al.
`9/1988 Herman
`2/1989 Seela
`4/1989 Dattagupta et al.
`9/1989 Melamede
`12/1989 Radding et al.
`8/1991 Hartley
`9/1991 Hobbs, Jr. et al.
`6/1992 Urdea
`9/1992 Hobbs, Jr. et al.
`12/1992 Brennan
`12/1992 Stavrianopoulos
`(Continued)
`
`FOREIGN PATENT DOCUMENTS
`
`CA
`CA
`
`4/2002
`2425112
`11/2002
`2408143
`(Continued)
`
`OTHER PUBLICATIONS
`
`Aug. 19, 2013 Petition 2 of 2 for Inter Partes Review of U.S. Pat.
`No. 7,566,537, issued Aug. 19, 2013.
`(Continued)
`
`Jezia Riley
`Primary Examiner -
`(74) Attorney, Agent, or Firm -
`Dunham LLP
`
`John P. White; Cooper &
`
`ABSTRACT
`(57)
`This invention provides methods for attaching a nucleic acid
`to a solid surface and for sequencing nucleic acid by
`detecting the identity of each nucleotide analog after the
`nucleotide analog is incorporated into a growing strand of
`DNA in a polymerase reaction. The invention also provides
`nucleotide analogs which comprise unique labels attached to
`the nucleotide analog through a cleavable linker, and a
`cleavable chemical group to cap the -OH group at the
`3'-position of the deoxyribose.
`
`2 Claims, 28 Drawing Sheets
`Specification includes a Sequence Listing.
`
`Page 1
`
`Illumina Ex. 1001
`IPR Petition - USP 10,435,742
`
`
`
`US 10,407,458 B2
`Page 2
`
`(56)
`
`References Cited
`
`U.S. PATENT DOCUMENTS
`
`5,242,796 A
`5,302,509 A
`5,308,990 A
`5,328,824 A
`5,332,666 A
`5,383,858 A
`5,424,186 A
`5,436,143 A
`5,437,975 A
`5,449,767 A
`5,476,928 A
`5,516,664 A
`5,534,424 A
`5,547,839 A
`5,547,859 A
`5,556,748 A
`5,599,675 A
`5,602,000 A
`5,614,365 A
`5,637,469 A
`5,654,419 A
`5,658,736 A
`5,709,999 A
`5,714,330 A
`5,728,528 A
`5,763,594 A
`5,770,365 A
`5,770,367 A
`5,789,167 A
`5,798,210 A
`5,804,386 A
`5,808,045 A
`5,814,454 A
`5,821,356 A
`5,834,203 A
`5,844,106 A
`5,849,542 A
`5,853,992 A
`5,856,104 A
`5,858,671 A
`5,869,255 A
`5,872,244 A
`5,876,936 A
`5,885,775 A
`5,885,813 A
`5,908,755 A
`5,945,283 A
`5,948,648 A
`5,952,180 A
`5,959,089 A
`5,962,228 A
`6,001,566 A
`6,001,611 A
`6,008,379 A
`6,013,445 A
`6,028,190 A
`6,046,005 A
`6,074,823 A
`6,087,095 A
`6,111,116 A
`6,136,543 A
`6,175,107 Bl
`6,197,557 Bl
`6,207,831 Bl
`6,210,891 Bl
`6,214,987 Bl
`6,218,118 Bl
`6,218,530 Bl
`6,221,592 Bl
`6,232,465 Bl
`6,242,193 Bl
`6,245,507 Bl
`6,248,884 Bl
`6,255,083 Bl
`6,255,475 Bl
`
`9/1993 Prober et al.
`4/1994 Cheeseman
`5/1994 Takahashi et al.
`7/1994 Ward et al.
`7/1994 Prober et al.
`1/1995 Reilly et al.
`6/1995 Fodor et al.
`7/1995 Hyman
`8/1995 McClelland et al.
`9/1995 Ward et al.
`12/1995 Ward et al.
`5/1996 Hyman
`7/1996 Uhlen et al.
`8/1996 Dower et al.
`8/1996 Goodman et al.
`9/1996 Douglas
`2/1997 Brenner
`2/1997 Hyman
`3/1997 Tabor et al.
`6/1997 Wilding et al.
`8/1997 Mathies et al.
`8/1997 Wong
`1/1998 Shattuck-Eidens et al.
`2/1998 Brenner et al.
`3/1998 Mathies et al.
`6/1998 Hiatt et al.
`6/1998 Lane et al.
`6/1998 Southern et al.
`8/1998 Konrad
`8/1998 Canard et al.
`9/1998 Ju
`9/1998 Hiatt et al.
`9/1998 Ju
`10/1998 Khan et al.
`11/1998 Katzir et al.
`12/1998 Seela et al.
`12/1998 Reeve et al.
`12/1998 Glazer et al.
`1/1999 Chee et al.
`1/1999 Jones
`2/1999 Mathies et al.
`2/1999 Hiatt et al.
`3/1999 Ju
`3/1999 Haff et al.
`3/1999 Davis et al.
`6/1999 Kumar et al.
`8/1999 Kwok et al.
`9/1999 Khan et al.
`9/1999 Ju
`9/1999 Hannessian
`10/1999 Brenner
`12/1999 Canard
`12/1999 Will
`12/1999 Benson et al.
`1/2000 Albrecht et al.
`2/2000 Mathies et al.
`4/2000 Ju et al.
`6/2000 Koster
`7/2000 Rosenthal et al.
`8/2000 Benson et al.
`10/2000 Anazawa et al.
`1/2001 Juvinall
`3/2001 Makarov et al.
`3/2001 Auer et al.
`4/2001 Nyren et al.
`4/2001 Hiatt et al.
`4/2001 Sampson et al.
`4/2001 Rothschild et al.
`4/2001 Schwartz et al.
`5/2001 Hiatt et al.
`6/2001 Anazawa et al.
`6/2001 Bogdanov
`6/2001 Lam et al.
`7/2001 Williams
`7/2001 Kwiatkowski
`
`6,274,320 Bl
`6,277,607 Bl
`6,287,821 Bl
`6,294,324 Bl
`6,309,829 Bl
`6,309,836 Bl
`6,312,893 Bl
`6,316,230 Bl
`6,335,155 Bl
`6,361,940 Bl
`6,380,378 Bl
`6,432,360 Bl
`6,495,680 Bl
`6,524,829 Bl
`6,555,349 Bl
`6,613,508 Bl
`6,613,513 Bl
`6,627,436 B2
`6,627,748 Bl
`6,632,655 Bl
`6,639,088 B2
`6,664,079 B2
`6,664,399 Bl
`6,713,255 Bl
`6,780,591 B2
`6,787,308 B2
`6,818,395 Bl
`6,833,246 B2
`6,858,393 Bl
`6,864,052 Bl
`6,911,345 B2
`6,934,636 Bl
`6,982,146 Bl
`7,037,687 B2
`7,056,661 B2
`7,056,666 B2
`7,057,026 B2
`7,057,031 B2
`7,074,597 B2
`7,078,499 B2
`7,105,300 B2
`7,270,951 Bl
`7,279,563 B2
`7,329,496 B2
`7,345,159 B2
`7,393,533 Bl
`7,414,116 B2
`7,427,673 B2
`7,459,275 B2
`7,541,444 B2
`7,566,537 B2
`7,622,279 B2
`7,635,578 B2
`7,713,698 B2
`7,771,973 B2
`7,785,790 Bl
`7,790,869 B2
`7,883,869 B2
`7,982,029 B2
`8,088,575 B2
`8,158,346 B2
`8,298,792 B2
`8,399,188 B2
`8,796,432 B2
`8,889,348 B2
`9,115,163 B2
`9,133,511 B2
`9,159,610 B2
`9,175,342 B2
`9,255,292 B2
`9,297,042 B2
`9,708,358 B2
`9,718,852 B2
`9,719,139 B2
`9,725,480 B2
`9,868,985 B2
`2002/0012966 Al
`2002/0168642 Al
`2003/0008285 Al
`
`8/2001 Rothberg et al.
`8/2001 Tyagi et al.
`9/2001 Shi et al.
`9/2001 Bensimon et al.
`10/2001 Livak et al.
`10/2001 Kwiatkowski
`11/2001 Van Ness et al.
`11/2001 Egholm et al.
`1/2002 Wells et al.
`3/2002 Van Ness et al.
`4/2002 Kitamura et al.
`8/2002 Church
`12/2002 Gong
`2/2003 Seeger
`4/2003 O'Donnell
`9/2003 Ness et al.
`9/2003 Paree et al.
`9/2003 Sorge et al.
`9/2003 Ju et al.
`10/2003 Mehta et al.
`10/2003 Kwiatkowski
`12/2003 Ju et al.
`12/2003 Sabesan
`3/2004 Makino et al.
`8/2004 Williams et al.
`9/2004 Balasubramanian et al.
`11/2004 Quake et al.
`12/2004 Balasubramanian
`2/2005 Anderson et al.
`3/2005 Drmanac et al.
`6/2005 Quake et al.
`8/2005 Skierczynski et al.
`1/2006 Schneider et al.
`5/2006 Williams et al.
`6/2006 Korlach et al.
`6/2006 Dower et al.
`6/2006 Barnes et al.
`6/2006 Olejnik et al.
`7/2006 Ju
`7/2006 Odedra et al.
`9/2006 Paree et al.
`9/2007 Stemple et al.
`10/2007 Kwiatkowski
`2/2008 Dower et al.
`3/2008 Ju et al.
`7/2008 Crotty et al.
`8/2008 Milton et al.
`9/2008 Balasubramanian et al.
`12/2008 Dower et al.
`6/2009 Milton et al.
`7/2009 Balasubramanian et al.
`11/2009 Ju
`12/2009 Ju et al.
`5/2010 Ju et al.
`8/2010 Milton et al.
`8/2010 Church et al.
`9/2010 Ju et al.
`2/2011 Ju et al.
`7/2011 Ju et al.
`1/2012 Ju et al.
`4/2012 Balasubramanian et al.
`10/2012 Ju et al.
`3/2013 Zhao et al.
`8/2014 Ju et al.
`11/2014 Ju
`8/2015 Ju et al.
`9/2015 Ju et al.
`10/2015 Zhang et al.
`11/2015 Ju et al.
`2/2016 Ju et al.
`3/2016 Ju et al.
`7/2017 Ju et al.
`8/2017 Ju et al.
`8/2017 Ju et al.
`8/2017 Ju et al.
`1/2018 Ju et al.
`1/2002 Shi et al.
`11/2002 Drukier
`1/2003 Fischer
`
`Page 2
`
`
`
`US 10,407,458 B2
`Page 3
`
`(56)
`
`References Cited
`
`U.S. PATENT DOCUMENTS
`
`2003/0022225 Al
`2003/0027140 Al
`2003/0044871 Al
`2003/0054360 Al
`2003/0099972 Al
`2003/0166282 Al
`2003/0180769 Al
`2003/0186256 Al
`2003/0190680 Al
`2003/0198982 Al
`2004/0014096 Al
`2004/0096825 Al
`2005/0032081 Al
`2005/0170367 Al
`2005/0239134 Al
`2006/0003352 Al
`2006/0057565 Al
`2006/0105461 Al
`2006/0160081 Al
`2006/0160113 Al
`2006/0240439 Al
`2006/0252038 Al
`2007/0166705 Al
`2009/0088332 Al
`2009/0240030 Al
`2010/0159531 Al
`2010/0323350 Al
`2011/0014611 Al
`2011/0124054 Al
`2012/0052489 Al
`2012/0142006 Al
`2013/0264207 Al
`2014/0315191 Al
`2015/0037788 Al
`2015/0080232 Al
`2015/0111759 Al
`2015/0119259 Al
`2015/0197800 Al
`2015/0368710 Al
`2016/0024570 Al
`2016/0024574 Al
`2016/0041179 Al
`2016/0090621 Al
`2016/0264612 Al
`2017 /0088574 Al
`2017/0088575 Al
`2017 /0088891 Al
`2017 /0313737 Al
`2018/0201642 Al
`
`1/2003 Monforte et al.
`2/2003 Ju et al.
`3/2003 Cutsforth et al.
`3/2003 Gold et al.
`5/2003 Olejnik et al.
`9/2003 Brown et al.
`9/2003 Metzker
`10/2003 Fischer
`10/2003 Rothschild et al.
`10/2003 Seela et al.
`1/2004 Anderson et al.
`5/2004 Chenna et al.
`2/2005 Ju et al.
`8/2005 Quake et al.
`10/2005 Gorenstein et al.
`1/2006 Lipkin et al.
`3/2006 Ju et al.
`5/2006 Tom-Moy et al.
`7/2006 Milton et al.
`7/2006 Korlach et al.
`10/2006 Smith et al.
`11/2006 Ju
`7/2007 Milton et al.
`4/2009 Ju et al.
`9/2009 Ju et al.
`6/2010 Gordon et al.
`12/2010 Gordon et al.
`1/2011 Ju et al.
`5/2011 Olejnik et al.
`3/2012 Gordon et al.
`6/2012 Ju et al.
`10/2013 Ju et al.
`10/2014 Ju et al.
`2/2015 Ju
`3/2015 Ju et al.
`4/2015 Ju et al.
`4/2015 Ju et al.
`7/2015 Ju et al.
`12/2015 Fuller et al.
`1/2016 Ju et al.
`1/2016 Ju et al.
`2/2016 Ju et al.
`3/2016 Ju et al.
`9/2016 Ju et al.
`3/2017 Ju et al.
`3/2017 Ju et al.
`3/2017 Ju et al.
`11/2017 Ju et al.
`7/2018 Ju et al.
`
`FOREIGN PATENT DOCUMENTS
`
`DE
`DE
`DE
`EP
`EP
`EP
`EP
`EP
`EP
`EP
`EP
`EP
`GB
`GB
`GB
`GB
`GB
`WO
`WO
`WO
`WO
`WO
`WO
`
`4141178
`20122767
`112007002932.3
`0251786 Bl
`0995804
`1182267
`1291354
`0808320
`1337541 Bl
`1218391
`0992511
`2209911 Bl
`2000 0013276
`2001 0029012
`2446083
`2446084
`2457402
`WO 1989/09282
`WO 89/10977
`WO 1989/11548
`WO 1990/13666
`WO 91/06678
`WO 1991/06678
`
`6/1993
`8/2007
`8/2015
`11/1994
`4/2000
`2/2002
`3/2003
`4/2003
`3/2007
`4/2007
`3/2009
`10/2013
`6/2000
`12/2001
`3/2011
`3/2011
`9/2011
`10/1989
`11/1989
`11/1989
`11/1990
`5/1991
`5/1991
`
`WO
`WO1992/10587
`WO
`WO 1993/05183
`WO
`WO 93/12340
`WO
`WO 1993/21340
`WO
`WO 1994/14972
`WO
`WO 1996/07669
`WO
`WO 96/23807
`WO
`WO 1996/23807
`WO
`WO 96/27025
`WO
`WO 1996/27025
`WO
`WO 1997/08183
`WO
`WO 1997/27317
`WO
`WO 1997/35033
`WO
`WO 1998/30720
`WO
`WO 98/33939
`WO
`WO 1998/33939
`WO
`WO 1998/44151
`WO
`WO 98/53300
`WO
`WO 1999/05315
`WO
`WO 1999/49082
`WO
`WO 1999/57321
`WO
`WO 2000/02895
`WO
`WO 2000/06770
`WO
`WO 2000/09753
`WO
`WO 2000/15844
`WO
`WO 2000/18956
`WO
`WO 2000/21974
`WO
`WO 2000/50172
`WO
`WO 2000/50642
`WO
`WO 00/53812
`WO
`WO 2000/53805
`WO
`WO 2000/53812
`WO
`WO 2000/70073
`WO
`WO 2001/16375
`WO
`WO 2001/23610
`WO
`WO 2001/25247
`WO
`WO 2001/27625
`WO
`WO 2001/32930
`WO
`WO 2001/57248
`WO
`WO 2001/57249
`WO
`WO 01/92284
`WO
`WO 2001/92284
`WO
`WO 2002/02813
`WO
`WO 02/21098
`WO
`WO 2002/22883
`WO
`WO 02/29003
`WO
`WO 2002/29003
`WO
`WO 2002/72892
`WO WO 2002/079519
`WO
`WO 2002/88381
`WO
`WO 2002/88382
`WO
`WO 2003/02767
`WO
`WO 2003/20968
`WO
`WO 2003/48178
`WO
`WO 2003/48387
`WO
`WO 2003/85135
`WO
`WO 04/18493
`WO
`WO 04/18497
`WO
`WO 2004/18493
`WO WO 2004/018493
`WO WO 2004/018497
`WO
`WO 2004/18497
`WO WO 2004/055160
`WO WO 2005/084367
`WO
`WO 2006/73436
`WO WO 2007 /002204
`WO
`WO 2007/62105
`WO WO 2008/069973
`WO WO 2012/083249
`WO WO 2012/162429
`WO WO 2013/154999
`WO WO 2013/191793
`WO WO 2014/144883
`WO WO 2014/144898
`WO WO 2015/123430
`
`6/1992
`3/1993
`10/1993
`10/1993
`7 /1994
`3/1996
`8/1996
`8/1996
`9/1996
`9/1996
`3/1997
`7 /1997
`9/1997
`7 /1998
`8/1998
`8/1998
`10/1998
`11/1998
`2/1999
`9/1999
`11/1999
`1/2000
`2/2000
`2/2000
`3/2000
`4/2000
`4/2000
`8/2000
`8/2000
`9/2000
`9/2000
`9/2000
`11/2000
`3/2001
`4/2001
`4/2001
`4/2001
`5/2001
`8/2001
`8/2001
`12/2001
`12/2001
`1/2002
`3/2002
`3/2002
`4/2002
`4/2002
`9/2002
`10/2002
`11/2002
`11/2002
`1/2003
`3/2003
`6/2003
`6/2003
`10/2003
`3/2004
`3/2004
`3/2004
`3/2004
`3/2004
`3/2004
`7/2004
`9/2005
`7/2006
`1/2007
`5/2007
`6/2008
`6/2012
`11/2012
`10/2013
`12/2013
`9/2014
`9/2014
`8/2015
`
`Page 3
`
`
`
`US 10,407,458 B2
`Page 4
`
`(56)
`
`References Cited
`
`FOREIGN PATENT DOCUMENTS
`
`WO
`WO
`
`WO 2015/148402
`WO 2015/179284
`
`10/2015
`11/2015
`
`OTHER PUBLICATIONS
`
`Aug. 16, 2013 Declaration of Dr. Bruce Branchaud (Exhibit 1015,
`filed Aug. 19, 2013 in connection with IPR2013-00518).
`Excerpts from the '537 Patent file History (Exhibit 1016, filed Aug.
`19, 2013 in connection with IPR2013-00518).
`Excerpts from the file history of European Patent Application No.
`02781434.2 (Exhibit 1017, filed Aug. 19, 2013 in connection with
`IPR2013-00518).
`Feb. 13, 2014 Decision of Institution of Inter Partes Review
`IPR2013-00518.
`May 5, 2014 Patentee Request for Adverse Judgment in IPR2013-
`00518.
`May 6, 2014 Decision of Adverse Judgment in IPR2013-00518.
`Krecmerova (1990) "Synthesis of 5'-O-Phosphonomethyl Deriva(cid:173)
`tives of Pyrimidine 2'-Deoxynucleosides." Coll. Czech. Chem.
`Commun., 55:2521-2536.
`Kurata et al. (2001) "Fluorescent quenching-based quantitative
`detection of specific DNA/RNA using BODIPY® FL-labeled probe
`of primer," Nucleic Acids Research, vol. 29, No. 6, p. e34.
`Kvam et al., (1994) "Characterization of singlet oxygen-induced
`guanine residue damage after photochemical treatment of free
`nucleosides and DNA," Biochemica et Biophysica Acta., 1217:9-
`15.
`Lee, L.G., et al. (1992) "DNA sequencing with dye labeled termi(cid:173)
`nators and T7 DNA polymerase effect of dyes and dNTPs on
`incorporation of dye terminators and probability analysis of termi(cid:173)
`nation fragments," Nucleic Acids Res. 20:2471-2483.
`Lee L.G. et al, (1997) "New energy transfer dyes for DNA sequenc(cid:173)
`ing," Nucleic Acids Res. 25:2816-2822.
`Leroy, E.M. et al. (2000) "Diagnosis of Ebola Haemorrhagic Fever
`by RT-PCR in an Epidemic Setting," Journal of Medical Virology
`60:463-467.
`Lewis et al. (2002) "Click Chemistry in Situ: Acetylcholinesterase
`as a Reaction Vessel for the Selective Assembly of a Femtomolar
`Inhibitor from an Array of Building Blocks," Angew. Chem. Int. Ed.
`41(6): 1053-1057.
`Li, J. (1999) "Single Oligonucleotide Polymorphism Determination
`Using Primer Extension and Time-of-Flight Mass Spectrometry,"
`Electrophoresis 20: 1258-1265.
`Li et al. (2003) "A photocleavable Fluorescent Nucleotide for DNA
`Sequencing and Analysis," PNAS 100(2):414-419.
`Liu, H. et al. (2000) "Development of Multichannel Devices with an
`Array of Electrospray Tips for High-Throughput Mass Spectrom(cid:173)
`etry," Anal. Chem. 72:3303-3310.
`Loubinoux, B. et al. "Protection Des Phenols Par Le Groupement
`Azidomethylene Application A La Synthese De Phenols Instables,"
`Tetrahedron, 1998, 44(19): 6055 (English Abstract Only).
`Lu, G. and Burgess, K. (2006) "A Diversity Oriented Synthesis of
`3'-O-Modified Nucleoside Triphosphates for DNA 'Sequencing by
`Synthesis"' Bioorg. Med. Chem. Lett., 16:3902-3905.
`Lyamichev, V. et al. (1999) "Polymorphism Identification and
`Quantitative Detection of Genomic DNA by Invasive Cleavage of
`Oligonucleotide Probes," Nat. Biotech 17:292-296.
`Maier et al. (1995) "Synthesis and Properties of New Fluorescein(cid:173)
`Labeled Oligonucleotides," Nucleosides and Nucleotides, 14:961-
`965.
`Margulies, M.; Egholm, M.; Altman, W. E.(2005) "Genome Sequenc(cid:173)
`ing in Microfabricated High-Density Picolitre Reactors." Nature,
`437:376-380.
`Markiewicz et al. (1997) "Anew method of synthesis offluorescently
`labeled oligonucleotides and their application in DNA sequencing,"
`Nucleic Acids Research, 25:3672-3690.
`
`Marquez et al. (2003) "Selective Fluorescence Quenching of 2,3-
`Diazabicyclo[2.2.2]oct-2-ene by Nucleotides," Organic Letters, 5:3911-
`3914.
`Mathews C.K. et al. (1985) "Chemical Synthesis of Oligonucle(cid:173)
`otides," Biochemistry, 2nd Edition, pp. 127-128.
`Meng et al. (2006) "Design and Synthesis of a Photocleavable
`Fluorescent Nucleotide 3'-O-Allyl-dGTP-PC-Biodipy-FL-510 as a
`Reversible Terminator for DNA Sequencing by Synthesis," J. Org.
`Chem 71 :3248-3252.
`Metzker, M.L. et al. (1994) "Termination of DNA synthesis by
`novel 3' modified deoxyribonucleoside 5' triphosphates," Nucleic
`Acids Res. 22: 4259-4267.
`Metzker M.L. (2005) "Emerging Technologies in DNA Sequenc(cid:173)
`ing." Genome Res., 15:1767-1776.
`Mitra, R. D.; Shendure J.; Olejnik, J.; et al. (2003) "Fluorescent in
`situ sequencing on polymerase colonies." Anal. Biochem. 320:55-
`65.
`Monforte, J.A. and Becker, C.H. (1997) "High-throughput DNA
`analysis by time-of-flight mass spectrometry," Nat. Med. 3(3):360-
`362.
`Nazarenko et al. (2002) "Effect of primary and secondary structure
`of oligodeoxyribonucleotides on the fluorescent properties of con(cid:173)
`jugated dyes," Nucleic Acids Research, 30:2089-2095.
`Nickel et al. (1992) "Interactions of Azidothymidine triphosphate
`with the Cellular DNA polymerases alpha, delta, and episilon and
`with DNA Primase," J. Biol. Chem. 267(2):848-854.
`Nielsen et al. (2004) "Multiplexed Sandwich Assays in Microarray
`Format," Journal oflmmunological Methods, vol. 290, pp. 107-120.
`Nishino et al. (1991) "Efficient Deanilidation of Phosphoranilidates
`by the Use of Nitrites and Acetic Anhydride." Heteroatom Chem(cid:173)
`istry, vol. 2, pp. 187-196.
`Olejnik, J. et al. (1995) "Photocleavable biotin derivatives: a
`versatile approach for the isolation of biomolecules," Proc. Natl.
`Acad. Sci. USA. 92:7590-7594.
`Olejnik, J. et al. (1999) "Photocleavable peptide DNA conjugates:
`synthesis and applications to DNA analysis using MALDI MS,"
`Nucleic Acids Res. 27:4626-4631.
`Pastinen et al. (1997) "Minisequencing: A Specific Tool for DNA
`Analysis and Diagnostics on Oligonucleotide Arrays," Genomic
`Res., 7:606-614.
`Pelletier, H. et al. (1994) "Structures of ternary complexes of rat
`DNA polymerase fl, a DNA template-primer, and ddCTP," Science
`264:1891-1903.
`Prober, J.M. et al. (1987) "A system for rapid DNA sequencing with
`fluorescent chain-terminating dideoxynucleotides," Science 238:336-
`341.
`Quaedflieg et al. (1992) "An Alternative Approach Toward the
`Synthesis of (3'->5') Methylene Acetal Linked Dinucleosides."
`Tetrahedron Letters, vol. 33, pp. 3081-3084.
`Rao et al. (2001) "Four Color FRET Dye Nucleotide Terminators
`For DNA Sequencing," Nucleosides, Nucleotides and Nucleic Acids,
`20:673-676.
`Rasolonjatovo et al. ( 1998) "6-N-(N-Methylantluanylamido )-4-Oxo(cid:173)
`Hexanoic Acid: A New Fluorescent Protecting Group Applicable to
`a New DNA Sequencing Method," Nucleosides and Nucleotides,
`17:2021-2025.
`Ronaghi, (1998) "PCR-Introduced Loop Structure as Primer in
`DNA Sequencing." BioTechniques, 25:876.
`Ronaghi, M., Uhlen, M., and Nyren, P. (1998) "A Sequencing
`Method Based on Real-time Pyrophosphate," Science 281 :364-365.
`Rosenblum, B.B. et al. (1997) "New dye-labeled terminators for
`improved DNA sequencing patterns," Nucleic Acids Res. 25:4500-
`4504.
`Roskey, M.T., Juhasz, P., Smirnov, LP., Takach, E.J., Martin, S.A.,
`and Haff, L.A. (1996) "DNA sequencing by delayed extraction(cid:173)
`matrix-assisted laser desorption/ionization time of flight mass spec(cid:173)
`trometry," Proc. Natl. Acad. Sci. USA. 93:4724-4729.
`Ross, P.L. et al. (1997) "Discrimination of Single-Nucleotide Poly(cid:173)
`morphism in Human DNA Using Peptide Nucleic Acid Probes
`Detected by MALDI-TOF Mass Spectrometry," Anal. Chem. 69:4197-
`4202.
`Ross, P. et al. (1998) High Level Multiplex Genotyping by MALDI(cid:173)
`TOF Mass Spectrometry. Nat. Biotech 16:1347-1351.
`
`Page 4
`
`
`
`US 10,407,458 B2
`Page 5
`
`(56)
`
`References Cited
`
`OTHER PUBLICATIONS
`
`Ruparel et al. (2005) "Design and Synthesis of a 3'-O-Allyl Photocleav(cid:173)
`able Fluorescent Nucleotide as a Reversible Terminator for DNA
`Sequencing by Synthesis," PNAS 102(17):5932-5937.
`Sarfati et al., (1995) "Synthesis of fluorescent derivatives of 3'-O(cid:173)
`(6-arninohexanoyl)-pyrimidine nucleosides 5'-triphosphates that act
`as DNA polymerase substrates reversibly tagged at C-3'," JCS
`Perkin Trans, 1163-1171.
`Saxon, E. and Bertozzi, C.R. (2000) "Cell surface engineering by a
`modified Staudinger reaction," Science 287:2007-2010.
`Schena, M., Shalon, D. and Davis, R. Brown P.O. (1995) "Quan(cid:173)
`titative monitoring of gene expression patterns with a cDNA
`microarray," Science 270: 467-470.
`Seeger (1998) "Single Molecule Fluorescence: High-Performance
`Molecular Diagnosis and Screening," Bioforurn, Git Verlag, Darmstadt,
`DE vol. 21, (German text).
`Seo et al. (2003) "Click Chemistry to Construct Fluorescent Oli(cid:173)
`gonucleotides for DNA Sequencing," J. Org. Chem. 68:609-612.
`Seo et al. (2004) "Photocleavable Fluorescent Nucleotides for DNA
`Sequencing on a Chip Constructed by Site-Specific Coupling Chem(cid:173)
`istry," PNAS 101(15):5488-5493.
`Seo et al. (2005) "Four-Color DNA Sequencing by Synthesis on a
`Chip Using Photocleavable Fluorescent Nucleotides," PNAS
`102( 17): 5926-593.
`Shendure, J.; Porreca, G. J.; Reppas, N.B.; et al. (2005) "Accurate
`Multiplex Polony Sequencing of an Evolved Bacterial Genome."
`Science 309: 1728-1732.
`Smith, L.M., Sanders, J.Z., Kaiser, R.J., et al. (1986) "Fluorescence
`Detection in Automated DNA Sequence Analysis," Nature 321 :674-
`679.
`Speicher, M.R., Ballard, S.G., and Ward, D.C. (1996) "Karyotyping
`human chromosomes by combinatorial multi-fluor FISH," Nature
`Genetics 12: 368-375.
`Stoerker, J. et al. (2000) "Rapid Genotyping by MALDI-monitored
`nuclease selection from probe Libraries," Nat. Biotech 18: 1213-
`1216.
`Tang, K., Fu, D.J., Julien, D., Braun, A., Cantor, C.R., and Koster,
`H. (1999) "Chip-based genotyping by mass spectrometry," Proc.
`Natl. Acad. Sci. USA. 96:10016-10020.
`Tong, X. and Smith, L.M. (1992) "Solid-Phase Method for the
`Purification of DNA Sequencing Reactions," Anal. Chem. 64:2672-
`2677.
`Torimura et al. (2001) "Fluorescence-Quenching Phenomenon by
`Photoinduced Electron Transfer between a Fluorescent Dye and
`Nucleotide Base," Analytical Sciences, 17: 155-160.
`Tuncel et al. ( 1999) "Catalytically Self-Threading Polyrotaxanes,"
`Chem. Comm. 1509-1510.
`Veeneman et al. ( 1991) "An Efficient Approach to the Synthesis of
`Thymidine Derivatives containing Phosphate-Isoteric Methylene
`Acetyl Linkages," Tetrahedron, 47:1547-1562.
`Wada et al. (2001) "2-(Azidomethyl)benzoyl as a new protecting
`group in nucleosides," Tetrahedron Letters, 42:1069-1072.
`Weiss (1999) "Fluorescent Spectroscopy of Single Biomolecules."
`Science, 283:1676.
`Welch et al. (1999) "Synthesis ofNucleosides Designed for Combinato(cid:173)
`rial DNA Sequencing," Chemistry, European Journal, 5:951-960.
`Welch MB, Burgess K, (1999) "Synthesis of fluorescent, photolabile
`3'-O-protected nucleoside triphosphates for the base addition sequenc(cid:173)
`ing scheme," Nucleosides and Nucleotides 18:197-201.
`Wendy, Jen. Et al. (2000) "New Strategies for Organic Catalysis:
`The First Enantioselective Orgacnocatalytic 1,3-Dipolar Cycload(cid:173)
`dition," J. Am. Chem. Soc. 122:9874-9875.
`Woolley, A. T. et al. (1997) "High-Speed DNA Genotyping Using
`Microfabricated Capillary Array Electrophoresis Chips," Anal. Chem.
`69:2181-2186.
`Yamashita et al. (1987) "Studies on Antitumor Agents VII. Antitu(cid:173)
`mor Activities of O-Alkoxyalkyl Derivatives of 2'Deoxy-5-
`trifluoromethyluridine." Chem Pharm. Bull., vol. 35, pp. 2373-
`2381.
`
`Zavgorodny, S. et al. ( 1991) "1-Alkylthioalkylation of Nucleoside
`Hydroxyl Functions and Its synthetic Applications: A New Versatile
`Method in Nucleoside Chemistry," Tetrahedron Letters, 32(51):
`7593-7596.
`Zavgorodny et al. (2000) "S,X-Acetals in Nucleoside Chemistry.
`III. Synthesis of 2'- and 3'-O-Azidomethyl Derivatives of
`Ribonucleosides" Nucleosides, Nucleotides and Nucleic Acids,
`19( 10-12): 1977-1991.
`Zhang et al. (2002) "Synthesis of Releasable Electrophore Tags for
`Applications in Mass Spectrometry," Bioconjugate Chem., vol. 13,
`pp. 1002-1012.
`Zhu, Z., Chao, J., Yu, H, et al. (1994) "Directly Labeled DNA
`Probes Using Fluorescent Nucleotides with Different Length Link(cid:173)
`ers," Nucleic Acids Res., 22:3418-3422.
`Jun. 4, 2013 Petition for Inter Partes Review of U.S. Pat. No.
`7,057,026.
`J. Meinwald, An Approach to the Synthesis of Pederin, 49 Pure and
`Appl. Chem. 1275 (1977) (Exhibit 1004, filed Jun. 4, 2013 in
`connection with IPR2013-00324).
`Takeshi Matsumoto et al., A Revised Structure of Pederin, 60
`Tetrahedron Letters 6297 (1968) (Exhibit 1005, filed Jun. 4, 2013 in
`connection with IPR2013-00324).
`Jun. 4, 2013 Declaration of Dr. Bruce Branchaud (Exhibit 1009,
`filed Jun. 4, 2013 in connection with IPR2013-00324).
`Excerpts from the '026 Patent File History (Exhibit 1010, filed Jun.
`4, 2013 in connection with IPR2013-00324).
`Excerpts from the file history of European Patent Application No.
`02781434.2 (Exhibit 1011, filed Jun. 4, 2013 in connection with
`IPR2013-00324).
`Nov. 21, 2013 Decision Denying Institution of Inter Partes Review
`of U.S. Pat. No. 7,057,026 in connection with IPR2013-00324.
`Trustees of Columbia University in the City of New Yorkv. Illumina,
`Inc., Nos. 2014-1547, 2014-1548, and2014-1550 (Fed. Cir. Jul. 17,
`2015).
`Illumina Cambridge Ltd. v. Intelligent Bio-Systems, Inc., Nos. 167.
`2015-1123 and 2015-1243 (Fed. Cir. Jan. 29, 2016).
`Intelligent Bio-Systems, Inc. v. Illumina Cambridge Ltd., No.2015-
`1693 (Fed. Cir. May 9, 2016).
`Declaration of Michael Metzker in Opposition to Plaintiffs' Motion
`for Preliminary Injunction, Illumina, Inc. v. Qiagen, N V, No.
`3:16-cv-02788-WHA(N.D. Cal. Jul. 25, 2016) (Doc. 76), first made
`publicly available Aug. 25, 2016.
`Notice of Motion to Stay Injunction Pending Appeal or, Alterna(cid:173)
`tively, Pending Decision by the Federal Circuit on Stay Pending
`Appeal, Illumina, Inc. v. Qiagen, NV, No. 3: 16-cv-02788-WHA
`(N.D. Cal. Sep. 15, 2016)(Doc. 122) (Redacted Version of Docu(cid:173)
`ment Sought to be Sealed), first made publicly available Sep. 22,
`2016.
`Sep. 23, 2016 Response to May 24, 2016 Communication Pursuant
`to Article 94 (3) EPC filed with the European Patent Office in
`connection with European Patent Application No. 15195765.1.
`Patent Owner Preliminary Response filed by The Trustees of
`Columbia University in the City of New York Mar. 27, 2018, in
`connection with Case No. IPR2018-00291.
`Patent Owner Preliminary Response filed by The Trustees of
`Columbia University in the City of New York Apr. 9, 2018, in
`connection with Case No. IPR2018-00318.
`Patent Owner Preliminary Response filed by The Trustees of
`Columbia University in the City of New York Apr. 9, 2018, in
`connection with Case No. IPR2018-00322.
`Patent Owner Preliminary Response filed by The Trustees of
`Columbia University in the City of New York May 4, 2018, in
`connection with Case No. IPR2018-00385.
`Patent Owner Preliminary Response filed by The Trustees of
`Columbia University in the City of New York Jul. 6, 2018, in
`connection with Case No. IPR2018-00797.
`Excerpts from the Prosecution History of U.S. Pat. No. 9,718,852
`not included in Ex-1009 (Exhibit 2005 filed by The Trustees of
`Columbia University in the City ofNewYork with the Patent Owner
`Preliminary Response, in connection with Case No. IPR2018-
`00291).
`Excerpts from the Prosecution History of U.S. Pat. No. 9,725,480
`not included in Ex-1038 (Exhibit 2006 filed by The Trustees of
`
`Page 5
`
`
`
`US 10,407,458 B2
`Page 6
`
`(56)
`
`References Cited
`
`OTHER PUBLICATIONS
`
`Columbia University in the City of New York with the Patent Owner
`Preliminary Response, in connection with Case Nos. IPR2018-
`00291, IPR2018-00318, and IPR2018-00322).
`IPR2013-00517, Ex. 2011, Declaration of Floyd Romesberg, Ph.D.
`(May 5, 2014) (Exhibit 2007 filed by The Trustees of Columbia
`University in the City of New York with the Patent Owner Prelimi(cid:173)
`nary Response, in connection with Case Nos. IPR2018-00291,
`IPR2018-00318, IPR2018-00322, IPR2018-00385, and IPR2018-
`00797).
`IPR2013-00 517, Paper 3 2, Illumina' s Patent Owner Response (May
`5, 2014) (Exhibit 2008 filed by The Trustees of Columbia Univer(cid:173)
`sity in the City of New York with the Patent Owner Preliminary
`Response, in connection with Case Nos. IPR2018-00291, IPR2018-
`00318, IPR2018-00322, IPR2018-00385, and IPR2018-00797).
`Excerpts from the Ex Parte Reexamination History of U.S. Pat. No.
`5,808,045 (Exhibit 2009 filed by The Trustees of Columbia Uni(cid:173)
`versity in the City of New York with the Patent Owner Preliminary
`Response, in connection with Case Nos. IPR2018-00291, IPR2018-
`00318, IPR2018-00322, IPR2018-00385, and IPR2018-00797).
`Assignment data in connection with U.S. Pat. No. 5,808,045 (Exhibit
`2010 filed by The Trustees of Columbia University in the City of
`New York with the Patent Owner Preliminary Response, in con(cid:173)
`nection with Case Nos.IPR2018-00291, IPR2018-00318, IPR2018-
`00322, IPR2018-00385, and IPR2018-00797).
`Metzker, et al., "Elimination of Residual Natural Nucleotides from
`3'-O-Modified-dNTP Syntheses by Enzymatic Mop-Up,"
`BioTechniques, 25:814-817 (1998) (Exhibit 2012 filed by The
`Trustees of Columbia University in the City of New York with the
`Patent Owner Preliminary Response, in connection with Case Nos.
`IPR2018-00291, IPR2018-00318, IPR2018-00322, IPR2018-
`00385, and IPR2018-00797).
`PCT International Application Publication No. WO 00/53805, ASM
`Scientific, Inc., published Sep. 14, 2000 ("Stemple") (Exhibit 2013
`filed by The Trustees of Columbia University in the City of New
`York with the Patent Owner Preliminary Response, in connection
`with Case Nos. IPR2018-00291, IPR2018-00318, IPR2018-00322,
`IPR2018-00385, and IPR2018-00797).
`Metzker, et al., "Stop-Start DNA Synthesis in the Base Addition
`Sequencing Scheme (BASS)," Genome Mapping & Sequencing
`(1994) (Exhibit 2014 filed by The Trustees of Columbia University
`in the City of New York with the Patent Owner Preliminary
`Response, in connection with Case Nos. IPR2018-00291, IPR2018-
`00318, IPR2018-00322, IPR2018-00385, and IPR2018-00797).
`Boons, et al., "A New Procedure for the Isomerisation of Substituted
`and Unsubstituted Ally! Ethers of Carbohydrates," Chemical Com(cid:173)
`munications, 141-142 (1996) (Exhibit 2018 filed by The Trustees of
`Columbia University in the City of New York with the Patent Owner
`Preliminary Response, in connection with Case Nos. IPR2018-
`00291, IPR2018-00318, IRP2018-00322, IPR2018-00385, and
`IPR2018-00797).
`Ochiai, et al., "Hypervalent (tert-Butylperoxy)iodanes Generate
`Iodine-Centered Radicals at Room Temperature in Solution: Oxi(cid:173)
`dation and Deprotection of Benzyl and Ally! Ethers, and Evidence
`for