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Enhanced Selectivity by Passivation: Molecular Imprints for Viruses with Exceptional Binding Properties Manuela Gast, Stefanie Kuehner, Harald Sobek, Paul Walther, and Boris Mizaikoff Anal. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.analchem.7b05148 • Publication Date (Web): 05 Mar 2018 Downloaded from http://pubs.acs.org on March 10, 2018

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EXPERIMENTAL SECTION Materials. HSC#B/$7>37>?'IC*3/&*27R?)/'#$&! HMK^L-I! H[Z!fI! #$6! HSC#B/$7>37>?'IC*3/B&*27R?)/'#$&! HMK^"-I! H[Y! fI! D&3&! >%3@2#)&6! .37B! M'.#! M&)#3! H(&3B#$?IF! ^&*3#&*2?'73*27)/'/@#*&!H^L`-I!Hg[[!fI!#$6!^3/*7$!hC+\\!Hi! [\! fI! D&3&! #@O%/3&6! 8?! >%3@2#)&! .37B! "&3@9! 0(#M! H(&3B#$?IF! MBB7$/%B! 2?637R/6&! H4]! fI! #$6! &*2#$7'! H[[F]!fI!D&3&!>%3@2#)&6!.37B!aGQ!P2&B/@#')!H(&3B#$?IF! ('%*#36/#'6&2?6&!H]\!f!)7'%*/7$!/$!D#*&3I!D#)!>%3@2#)&6! .37B! "&3@9! -@2%@2#36*! `5(! H(&3B#$?I,! 87E/$&! )&3%B! #'8%B/$! H:-MI! Hi! [W! fI,! A&'#*/$! .37B! >73@/$&! )9/$! H.73! B/@378/7'7A?I,! j/.@7k! -9/B! "/'9! H.73! B/@378/7'7A?I! #$6! 2?637@2'73/@!#@/6!)7'%*/7$!H5P'I!H+!"I!.37B!-/AB#CM'63/@2l! H(&3B#$?IF! M''! @2&B/@#')! D&3&! %)&6! D/*27%*! .%3*2&3! >%3/./@#*/7$F! T#$7>%3&! D#*&3! D#)! >376%@&6!D/*2!#! "=JJ=C ml!"/''/>73&!)?)*&BF! M6&$7E/3%),!*?>&!],!/$/*/#''?!>%3@2#)&6!.37B!M^PPl!aQC]! H(&3B#$?I! #$6! "/$%*&! a/3%)! 7.! "/@&! H"a"I! .37B! M^PPl! aQC+SUW! D&3&! >37>#A#*&6! #$6! >%3/./&6! #)! >&3.73B&6! #*! J#873!j3F!"&39!n!07''&A&$!H(&3B#$?IF!K27)>2#*&C:%..&3&6! -#'/$&! HK:-I! #$6! @&''!@%'*%3&! )%>&3$#*#$*! HPP-I! .37B!P5`! @&'')!H+\R!@7$@&$*3#*&6!@&''C.3&&!@&''!@%'*%3&!.'%/6!/$!K:-!>5! YFUI! D#)! >%3@2#)&6! .37B! J#873! j3F! "&39! n! 07''&A&$! H(&3B#$?I! ^#O"#$l!(&$&!LR>3&))/7$!M))#?,!"#)*&3!"/R,!#)!D&''!#)! >3/B&3)! #$6! >378&! D&3&! >%3@2#)&6! .37B! ^2&3B7N/)2&3-@/&$*/./@^"!H(&3B#$?IF!

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ACS Paragon Plus Environment

Page 3 of 12 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Analytical Chemistry

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Scanning Electron Microscopy Studies. N73! *2&!

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Analytical Chemistry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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Page 4 of 12

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Page 5 of 12 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Analytical Chemistry

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ACS Paragon Plus Environment

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ACS Paragon Plus Environment

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Analytical Chemistry

ACS Paragon Plus Environment

Analytical Chemistry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Paragon Plus Environment

Page 8 of 12

Page 9 of 12 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Analytical Chemistry

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CONCLUSION P7B8/$/$A! #''! *2&)&! 3&)%'*),! 2&3&/$! #! )?$*2&*/@! )*3#*&A?! .73! #$! #6&$7E/3%)! @#>*%3&! B#*&3/#'! /)! >3&)&$*&6F! ^2&! 7>*/B/;&6! )7'CA&'! /B>3/$*/$A! B&*276! ./$#''?! ?/&'6&6! /$! !

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ASSOCIATED CONTENT Supporting Information ^2&!-%>>73*/$A!=$.73B#*/7$!/)!#E#/'#8'&!.3&&!7.!@2#3A&!7$!*2&! MP-!K%8'/@#*/7$)!D&8)/*&!#$6!/$@'%6&)c! ~C>7*&$*/#'! B&#)%3&B&$*),! E/3%)! 8/$6/$A! )*%6?! E/#! O%#$*/*#*/E&! KPQ,! #$6! 6&*&3B/$#*/7$! #$6! @7$*37''/$A! 7.! *2&! >7'?B&3!'#?&3!*2/@9$&))!HKjNI!

AUTHOR INFORMATION Corresponding Author
Author Contributions ^2&!B#$%)@3/>*!D#)!D3/**&$!*237%A2!@7$*3/8%*/7$)!7.!#''! #%*273)F!

Additional Information M6&$7E/3%)!/)!#!>#*27A&$!*2#*!/)!@#>#8'&!7.!A&$&3#*/$A! /$.'#BB#*73?!/BB%$&!3&)>7$)&)!/$!2%B#$F!"/$%*&!E/3%)!7.! B/@&!/)!7$&!7.!*2&!B7)*!.3&O%&$*!E/3#'!>#*27A&$)!/$!'#873#*73?! B/@&F!M''!D739!D/*2!#6&$7E/3%)!#*!B/$/B%B!3&O%/3&)!:-JC4! @7$*#/$B&$*F!5&$@&,!#''!&R>&3/B&$*)!/$E7'E/$A!#@*/E&! #6&$7E/3%)!#$6!"a"!D&3&!&R@'%)/E&'?!&R&@%*&6!#*!J#873!j3F! "&39!n!07''&A&$!(B85!&O%/>>&6!D/*2!*2&)&!.#@/'/*/&)F!!!

ACKNOWLEDGMENT This work has been supported by the Federal Ministry of Education and Research (BMBF) within the projects PROTSCAV I and II. The authors thank the Electron Microscopy facility and the Focused Ion Beam Center UULM at Ulm University for assistance during these studies.

ABBREVIATIONS KL(,! PP! >7'?&*2?'&$&! A'?@7'v! :-M,! PP! 87E/$&! )&3%B! #'8%B/$v! -M",! PP! )&'.C#))&B8'&6! B7$7'#?&3v! LJ=-M,! PP! &$;?B&C'/$9&6! /BB%$7)738&$*! #))#?v! OKPQ,! PP! O%#$*/*#*/E&! >7'?B&3#)&! @2#/$! 3&#@*/7$v! "=K,! B7'&@%'#3'?! /B>3/$*&6! >7'?B&3v! $7$C/B>3/$*&6! >#3*/@'&,! PP! T=Kv! ^L",! PP! *3#$)B/))/7$! &'&@*37$! B/@37)@7>?v! ^QK-,! PP! *%$#8'&! 3&)/)*/E&! >%')&! )&$)/$Av! a=K,! PP! E/3%)! /B>3/$*&6! >#3*/@'&v! -L",!PP!)@#$$/$A!&'&@*37$!B/@37)@7>?v!-K,!PP!)/'/@#!>#3*/@'&v! MK^L-,! PP! SC#B/$7>37>?'IC*3/&*27R?)/'#$&v! K:-,! PP! >27)>2#*&C8%..&3&6! )#'/$&v! ^L`-,! PP! *&*3#&*2?'73*27)/'/@#*&v! MK^"-,! PP! HSC#B/$7>37>?'IC *3/B&*27R?)/'#$&v! 5P',! PP! 2?637@2'73/@! #@/6v! M6a,! PP! M6&$7E/3%)v! "a",! PP! "/$%*&! a/3%)! 7.! "/@&v! K:-,! PP! K27)>2#*&C:%..&3&6! -#'/$&v! PP-,! PP! @&''! @%'*%3&! )%>&3$#*#$*F!

ACS Paragon Plus Environment

Analytical Chemistry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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REFERENCES H+I!! J&$)&$,!"F!PFv!-@2%'*&,!aF!MFv!j/&;,!"F!=$!2'*5-&)6'-.%";" S4/%'0%"-$1"34)5'%&6/v!=$^&@2c!J7$67$,!4\++v!>>!S[YV U+UF! H4I!! :3%/$)B#,! (F! "Fv! E#$! 6&3! "&/,! 5F! PFv! :%))@2&3,! 5F! tF! :#@*&3/#'!2'*5-&)6'-.%!AKK5,!AA!H4UI,!S4+YVS44UF! HSI!! ^/33&'',!"Fv!07997'/,!LFv!:/&)#')9/,!"F!P(6+D"P0'D!AKKA,!U??,! W+VZSF! HUI!! -2&$,! "Fv! G#A$&3,! "F! -Fv! P#)*$&3,! jF! (Fv! Q#*$&3,! :F! jFv! 5738&**,!^F!MF!B-$I5('6!AKKD,!!>,!+W[4V+W[[F! H]I!! Q7#@2,!KFv!N#33#3,!jFv!K&33?,!PF!PF!VD",5D"34)5D"P*0D!AKK?,! !AW,!Z+WZVZ+YSF! HWI!! P2#>B#$,!QF!(Fv!`)*%$/,!LFv!^#9#?#B#,!-Fv!57'B'/$,!QF!LFv! •#$,!JFv!G2/*&)/6&),!(F!"F!!VD",5D"34)5D"P*0D!AKKK,!!AA,! ZS\SVZS\UF! HYI!! P2&$A#,! (Fv! €2#$A#,! €Fv! P2&$#,! -Fv! :3?&3)8,! t#B&)! jF! 2'*5-&)6'-.%!AKKU,!A=,!U+[4VU+[[F! HZI!! Q7)@2&,! :Fv!J/,!hF!€Fv!5#%&3,! :Fv! -@2B/6,!MFv! :%&2'&3,! 0F! X6)$1%"2'*&)04$*.D!AKKY,!AW,!WSWVWUSF! H[I!! Q#*$&3,! :Fv! 57..B#$,! MFv! -@27&$,! NFv! J&B7$),! tFv! /$! 2'*5-&)6'-.%" P0')$0)Q" ,$" #$&6*1(0&'*$" &*" E-&)6'-.%" '$" E)1'0'$)v!Q#*$&3,!:F!jF,!L6Fv!M@#6&B/@!K3&))c!-#$!j/&A7,! +[[WF! H+\I!! 5'#6?,!aFv!:%/d),!tF!3(66D"LR'$D"2'*&)04$*.D!5YYL,!W,!Y4V YYF! H++I!! "39)/@2,!"F!34)5D"P*0D"O)9D!AKKK,!A>,!4WYV4YSF! H+4I!! `)*%$/,!LFv!P2#>B#$,!QF!(Fv!57'B'/$,!QF!LFv!^#9#?#B#,! -Fv!G2/*&)/6&),!(F!"F!B-$I5('6!AKK5,!!W,!]W\]V]W4\F! H+SI!! P2#$63#67)),!-F!jFv!5##A)B#,!MF!PFv!J&&,!•F!0Fv!5D#$A,! tFC5Fv!T#B,!tFC"Fv!t77,!PF!VD"Y'%D">,! U4ZUVU4Z[F! H4\I!! 5&?&),! PF! jFv! 078/*)9/,! MF! •Fv! MB/3A7%'7E#,! LF! aFv! T/&$2#%),! (F! eF! VD" S4/%D" 34)5D" 2! AKKH,! !?=,! +SSZYV +SS[UF! H4+I!! T/'))7$,!QFv!-doA3&$,!5F!`F!VD"#55($*.D"E)&4*1%!5Y@H,! [[,!+YV4]F! H44I!! j%'8&@@7,!QFv!a7A*,!"F!3*.1"PR6'$I"J-6:D"P/5RD"^(-$&D" 2'*.D!5Y?D,!!=,!4YSV4Y[F! H4SI!! G5`! C! G73'6! 5&#'*2! `3A#$/;#*/7$v! N#@*! )2&&*! TpS+\v!4\+UF! H4UI!! 0%'/@2,! KF! MFv! ^#?'73,! jF! JFv! MB&3/@#$! -7@/&*?! .73! "/@378/7'7A?F!X4)"#$+)0&'*$"S6)9)$&'*$'%&_%"@('1)"&*"&4)" B-:v!4\+4F! H4]I!! -*&>2&$)7$,! tF! QF,! G#3$&),! M! /$" C'-I$*%&'0"Y'6*.*I/" S6*&*0*.%,!4$6!&6Fv!->3/$A&3!>37*7@7')v!5%B#$#!K3&))c! T&D!•739,!4\++F! H4WI!! J&'#$6,! jF! -Fv! (/$7@@2/7,! PF! PF! 3.'$D" E'06*:'*.D" O)9D! AKKU,!A?,!U[VYZF! H4YI!! `E&38&3A2,!JFv!(/%'/&**/,!MFCKFv!a#'@9R,!jFv!"#*2/&%,!PF! =$! E*.)0(.-6" 1'-I$*%&'0%v! K#*3/$7),! (F! KF,! M$)73A&,! GF,! L6)Fv! L')&E/&3! M@#6&B/@! K3&))c! MB)*&36#B•v! :7)*7$,! 4\\]v!>>!+\[V+4WF! !

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