Enhanced Selectivity by Passivation: Molecular Imprints for Viruses

Mar 5, 2018 - Batch rebinding studies were performed in both buffer and real-world matrix, and proved the high binding capability of these materials. ...
0 downloads 4 Views 3MB Size
Subscriber access provided by UNIV OF DURHAM

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

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 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

!

Enhanced Selectivity by Passivation: Molecular Imprints for Viruses with Exceptional Binding Properties "#$%&'#!(#)*+,!-*&.#$/&!012$&34,!5#3#'6!-78&94,!Paul Walther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`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a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

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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bB7'&@%'#3!B&B73?X!/)!/$*376%@&6!/$*7!*2&!>7'?B&3,!D2/@2! /)! $7D! @#>#8'&! 7.! 3&8/$6/$A! *2&! #$#'?*&! D/*2! #! @&3*#/$! 6&A3&&!7.!)&'&@*/E/*?F!=$!&))&$@&,!*2/)!>37@&))!/)!@7$)/6&3&6! #$#'7A7%)! *7! &$;?B&C)%8)*3#*&! 3&@7A$/*/7$c! *2&! %$/O%&! A&7B&*3/@! )*3%@*%3&! 7.! #$! #@*/E&! 8/$6/$A! )/*&! &$#8'&)! *2&! 3&@7A$/*/7$! 7.! #! )%8)*3#*&! D/*2! @733&)>7$6/$A! )2#>&! #$6! 6/)*3/8%*/7$! 7.! B7'&@%'#3! .%$@*/7$),! D2/'&! #$! /$@733&@*'?! )2#>&6! B7'&@%'&! /)! $7*! 3&@7A$/;&6,! #')7! @#''&6! b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d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

Page 2 of 12

H^QK-IUZ,!.'7D!@?*7B&*3?U[,!&$;?B&C'/$9&6!/BB%$7)738&$*! #))#?!HLJ=-MI]\,!#$6!O%#$*/*#*/E&!>7'?B&3#)&!@2#/$!3&#@*/7$! HOKPQI]+F! ^2&! >37@&6%3&! %)&6! 2&3&/$! /)! 6/E/6&6! /$*7! *23&&! )*&>)! 8&A/$$/$A! D/*2! #! @7E#'&$*! #$@273/$A! 7.! *2&! E/3#'! >#3*/@'&)! H/F&F! 2&3&,! #6&$7E/3%)I! #*! *2&! )%3.#@&! 7.! )/'/@#! B/@37B&*&3C )/;&6! >#3*/@'&)! .7''7D&6! 8?! *2&! A37D*2! 7.! #$! *2/$! '#?&3! 7.! )/'/@#!H)&&!./A%3&!-4I,!#$6!*2&!3&B7E#'!7.!*2&!*&B>'#*&!E/3%)F! =$! @7$*3#)*! *7! *2&! 3&)%'*)! 3&>73*&6! 8?! -2#2A#'6/#$! &*! #'F]4! #$6!M'*/$*#)!&*!#'F]S,!*2&!)*3#*&A/&)!/$!*2&!>3&)&$*!)*%6?!V!$&R*! *7!#!6/..&3&$*!@7B>7)/*/7$!7.!*2&!/B>3/$*/$A!'#?&3!3&)%'*/$A! .37B!*2&!>37*&/$!>#**&3$!7.!*2&!E/3%)!)2&''!V!.73!*2&!./3)*!*/B&! O%#$*/*#*/E&! KPQ! D#)! %)&6! .73! E/3%)! O%#$*/./@#*/7$! /$! *2/)! @7$*&R*F!e>7$!*2&)&!/$E&)*/A#*/7$)!D&!>3&)&$*!/$!*2/)!3&>73*,! 27D! *2&! )&'&@*/E/*?! 8&*D&&$! /B>3/$*&6! #$6! $7*! /B>3/$*&6! @7$*37'! >#3*/@'&)! @#$! 8&! >#3*/@%'#3'?! &$2#$@&6! 8?! >#))/E#*/7$! *237%A2! 8'7@9/$A! #A&$*)F! =$! #66/*/7$,! #! 8#*@2! 3&8/$6/$A! #))#?! /$! 3&#'CD736! )#B>'&! #$#'?)/)! #$6! @7B>&*/*/E&! )*%6/&)! D/*2! $7$C*&B>'#*&! "a"! E/3%)! D&3&! >&3.73B&6F!

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!

Synthesis of Silica Micrometer-Sized Particles.!-/'/@#! >#3*/@'&)! H-K)I! D&3&! >3&>#3&6! #@@736/$A! *2&! >3/$@/>'&! 7.! -*o8&3F]S! ^2&3&.73&,! [\! BJ! H4F4SS! B7'I! #BB7$/%B! 2?637R/6&! #$6! W\! B'! H+F\S! B7'I! &*2#$7'! D&3&! B/R&6! /$! #! 37%$6C87**7B! .'#)9,! D2&3&#*! *2&$! +\! BJ! HUUFYZ! BB7'I! ^L`-! D#)! #66&6,! #$6! *2&! B/R*%3&! D#)! )*/33&6! #*! 377B! *&B>&3#*%3&! %$6&3! B#A$&*/@! )*/33/$A! HW\\! 3>BI! .73! 4\! 27%3)F! ^2&! 78*#/$&6! B/'9?! )%)>&$)/7$! D#)! @&$*3/.%A&6! HW]\\!3>BI! .73! +\! B/$! #$6! *2&! 3&@&/E&6! -K! >&''&*! D#)! D#)2&6! 7$&! */B&! /$! &*2#$7'! #$6! *23&&! */B&)! /$! %'*3#>%3&! D#*&3F!N/$#''?,!*2&!-K)!D&3&!63/&6!#*!U\!pP!7E&3!$/A2*!*7!?/&'6! 4F4S!A!#$6!)*73&6!/$!#!A'#))!E/#'!#*!377B!*&B>&3#*%3&!%$*/'! .%3*2&3!%)&F!

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

!

Synthesis of Functionalized Silica ()*+,-./0. ^7! .%$@*/7$#'/;&! *2&! -K)! .73! *2&! 3&#@*/7$! D/*2! *2&! E/3%),! -K)! H\F\4! AqBJI! D&3&! )%)>&$6&6! 8?! %'*3#C)7$/@#*/7$! #$6! /$@%8#*&6! D/*2! MK^L-! H+F]! rB7'! q! BA! -KI! .73! S\! B/$! /$! D#*&3! %$6&3! B#A$&*/@! )*/33/$A! /$!#! 4\!BJ!A'#))! E/#'! H*7*#'! E7'%B&! +\! BJIF! M.*&3! @&$*3/.%A#*/7$! HW]\\! 3>BI! *2&! >#3*/@'&)! D&3&! D#)2&6! *23&&! */B&)! D/*2! %'*3#>%3&! D#*&3F! ^2&$!*2&!8)!D&3&!)%)>&$6&6!#$7*2&3!*/B&!8?!%'*3#)7$/@! *3&#*B&$*! /$! D#*&3! #$6! 3&#@*&6! D/*2! A'%*#3#'6&2?6&! /$! &R@&))!HY!rB7'!q!BA!-KI!.73!S\!B/$!/$!*&$!B/''/'/*&3!)7'%*/7$! %$6&3! B#A$&*/@! )*/33/$AF! M.*&3! D#)2/$A! *2&B! *23/@&! D/*2! %'*3#>%3&! D#*&3! *2&! 8)! D&3&! 63/&6! #*! U\! pP! 7E&3! $/A2*! #$6!)*73&6!#*!377B!*&B>&3#*%3&!%$*/'!.%3*2&3!%)&F!

Synthesis of Virus Imprinted Particles (VIPs). =$!#! *?>/@#'!/B>3/$*/$A!&R>&3/B&$*,!*2&!.%$@*/7$#'/;&6!>#3*/@'&)! D&3&! )%)>&$6&6! /$! K:-! HS! BA! -K!q! BJ! K:-I! 8?! %'*3#C )7$/@#*/7$! .73! S\! B/$F! M! *?>/@#'!E7'%B&!D#)! WFY! BJF! ^2&$! *2&!8)!D&3&!/$@%8#*&6!D/*2!*2&!E/3%)!H+F\\!+\W!=e!q!]!sJI! #$6! )2#9&$! 8?! SW\p! E&3*/@#'! 37*#*/7$)! HW\! 3>BI! .73! 7$&! 27%3F! T7! #66/*/7$#'! D#)2/$A! 73! @&$*3/.%A#*/7$! )*&>! .7''7D&6,! *7! #E7/6! 6&$#*%3#*/7$! 73! %$.7'6/$A! 7.! E/3#'! >#3*/@'&),! 7D/$A! *7! *2&! B&@2#$/@#'! )*3&))! #))7@/#*&6! D/*2! 3&)%)>&$)/7$! #$6! @&$*3/.%A#*/7$F! ^2&! >3&>#3#*/7$! 7.! a=KqT=K^MM!D#)!/B>'&B&$*&6!8?!#66/$A!]FW\!sB7'!^L`-!q! BA!-K,!\FZ]!sB7'!MK^L-!q!BA!-K!#$6!+F+]!sB7'!MK^"-!q! BA!-K,!#$6!)2#9/$A!*2&!B/R*%3&!.73!4\!2!#*!+\!pP!#$6!Y\\! 3>BF!M.*&3!>#))/$A!*2&!>7'?B&3/;#*/7$!*/B&!*2&!)%)>&$)/7$! D#)!D#)2&6!*23&&!*/B&)!D/*2!K:-!HW!BJIF!M''!*2&!D#)2/$A! )*&>)! D&3&! >&3.73B&6! 8?! @&$*3/.%A#*/7$! #*! +]\\! 3>B! .73! ./E&! B/$F! OKPQ! B&#)%3&B&$*)! D&3&! >&3.73B&6! 7%*! 7.! *2&! 3&B#/$/$A!)%>&3$#*#$*!#.*&3!*2&!/B>3/$*/$A!>37@&6%3&F!T=K)! H$7*!/B>3/$*&6!>#3*/@'&)I!D&3&!>376%@&6!/$!#!)/B/'#3!D#?!8?! 7B/**/$A!*2&!E/3%)!#66/*/7$!)*&>F! Virus Removal. ^7!3&B7E&!*2&!E/3%)!.37B!*2&!8)!#! B/R*%3&! 7.! 2?637@2'73/6&! #@/6! H+! "I! D/*2! ^3/*7$! hC+\\! H\F\+!fI!D#)!%*/'/;&6F!=*!D#)!%)&6!S\\!sJ!3&B7E#'!)7'%*/7$! >&3!BA!-KF!^2&!8)!D&3&!)%)>&$6&6!/$!*2&!B&6/%B!#$6! *2&! )%)>&$)/7$! D#)! )2#9&$! .73! S\! B/$! 8?! SW\p! E&3*/@#'! 37*#*/7$),! .7''7D&6! 8?! #! +]CB/$%*&C'7$A! %'*3#)7$/@! *3&#*B&$*F! M.*&3D#36),! *2&! 8)! D&3&! @&$*3/.%A&6! H+]\\! 3>B,! ]! B/$FI! #$6! D#)2&6! *23/@&! D/*2! S\\!sJ! K:-! >&3! B/''/A3#B!8F Rebinding Studies. N73! #! *?>/@#'! 8/$6/$A! #))#?,! /B>3/$*&6,! '?)&6!#$6! D#)2&6! >#3*/@'&)!D&3&! )%)>&$6&6! /$! K:-!73!#>>37>3/#*&!PP-!6/'%*/7$)!D/*2!#!./$#'!@7$@&$*3#*/7$! 7.! W! BA! q! BJF! -%8)&O%&$*'?! UZ\! rA! H&FAF! Z\! rJI! 7.! *2&)&! 8)!D&3&!*3#$).&33&6!/$!#!\F]!rJ!L>>&$673.!*%8&,!B/R&6! D/*2!YY!rA!:-M!#$6!*2&!#))7@/#*&6!#B7%$*!7.!*#3A&*!H%)%#''?! 3#$A/$A! 8&*D&&$!+F\\! L]CLW! =eI,!#$6! /$! >#3*/@%'#3! )*%6/&)! D/*2! $7$C*&B>'#*&! E/3%)! H"a",! +LS! =eI,!3&)>&@*/E&'?F! ^2&! ./$#'!E7'%B&!D#)!#6d%)*&6!*7!+\]!rJ!D/*2!K:-qPP-!#$6!*2&! 3&#@*/7$!3%8&!D#)!)2#9&$!8?!SW\p!E&3*/@#'!37*#*/7$)F!M.*&3! *2&!6&)/3&6!@7$*#@*!*/B&,!*2&!*%8&!D#)!@&$*3/.%A&6!#*![\\\! 3>B!.73!7$&!B/$%*&!#$6!#!E7'%B&!7.!./E&!B/@37'/*&3)!7.!*2&! )%>&3$#*#$*! D#)! @7''&@*&6! .73! *2&! E/3%)! O%#$*/./@#*/7$! 8?! %)&!7.!OKPQF!

Scanning Electron Microscopy Studies. N73! *2&!

5/*#@2/! -C]4\\! P3?7C-@#$$/$ACL'&@*37$C"/@37)@7>&! H5/*#@2/,!t#>#$I!D#)!%)&6F!-#B>'&)!D&3&!./R&6!7$!#!>/$F!N73! *2&! 8'#$9! -K)! $7! #66/*/7$#'! >3&*3&#*B&$*! D#)! $&@&))#3?F! K#3*/@'&)!*2#*!@#B&!/$!@7$*#@*!D/*2!E/3%),!D&3&!./R&6!D/*2!#! ./R#*/7$!B&6/%B!V!@7$*#/$/$A!]!f!A'%*#3#'6&2?6&!#$6!U!f! >#3#.73B#'6&2?6&!/$!#$!\F+!"!>27)>2#*&!@#@76?'#*&!8%..&3! #*! >5! YFS! /$!#66/*/7$! 7.! )%@37)&F! K#3*/@'&)! D&3&! ./R&6! 7$! #! )/'/@#!D#.&3!#$6!D#)2&6!D/*2!K:-F!N7''7D/$A!*2/),!7)B/%B! *&*3#C7R/6&! D#)! #>>'/&6F! :&! 3/$)/$A! *2&! )#B>'&)! /$! /$@3&#)/$A!#'@727'!@7$@&$*3#*/7$),!*2&!3&B#/$/$A!D#*&3!D#)! 3&B7E&6F!^2&$!*2&!)#B>'&)!D&3&!.3&&;&C63/&6,!.7''7D&6!8?! #!>'#*/$%B!6&>7)/*/7$!7$!*2&!8)F!

TaqMan primer pair and probe.!K3&3&O%/)/*&)! .73!#! )%@@&)).%'!OKPQ!/$@'%6&!6&)/A$!7.!7>*/B#'!>3/B&3!>#/3),!%)&! 7.!#>>37>3/#*&!>3/B&3!@7$@&$*3#*/7$,!#)!D&''!#)!*2&!@733&@*! )*73#A&! 7.! >3/B&3! #$6! >378&! )7'%*/7$)F! ^2&! )>&@/./@! KPQ! >3/B&3! >#/3! #$6! >378&! D&3&! 6&)/A$&6! /$! #A3&&B&$*! D/*2! E/3#'! )&O%&$@&! 7.! *2&! TP:=X)! HT#*/7$#'! P&$*&3! .73! :/7*&@2$7'7A?! =$.73B#*/7$,! e-MI! $7$C3&6%$6#$*! >37*&/$! )&O%&$@&! 6#*#8#)&)! HM6a! Q&.&3&$@&! -&O%&$@&c! MPu\\\\\ZF+v! "a"! Q&.&3&$@&! -&O%&$@&c! TPu\\+]+\F+I! %)/$A! *2&! >3/B&3! 6&)/A$/$A! )7.*D#3&! K3/B&3! LR>3&))l! -7.*D#3&! ESF\F+! HM>>'/&6! :/7)?)*&B),! N7)*&3! P/*?,! PMIF! M.*&3D#36),! *7! &$)%3&! *2&! )>&@/./@/*?! >3/73! *7! >3#@*/@#'! #>>'/@#*/7$! #$! '$" %'.'0*! #$#'?)/)! D#)! >&3.73B&6! %)/$A! *2&! TP:=! :JM-^w! >37A3#B! /$! 736&3! *7! @7B>#3&! 27B7'7A7%)! )&O%&$@&)! #$6! &R@'%6&! %$)>&@/./@! #B>'/./@#*/7$,! 3&)>&@*/E&'?F!! ^2&! E/3#'! */*&3)! D&3&! 6&*&3B/$&6! 8?! O%#$*/*#*/E&! 3&#'C */B&! KPQ! HOKPQI! %)/$A! #! -*&>! `$&! K'%)! Q&#'C^/B&! KPQC -?)*&B! .37B! M>>'/&6! :/7)?)*&B)! #$6! *2&! -7.*D#3&! -*&>`$&k!E4FSF!M6&$7E/3%)!!>3/B&3)!D&3&!6&)/A$&6!.73!*2&! #B>'/./@#*/7$! 7.! #! ]]! 8>! .3#AB&$*! H.73D#36! >3/B&3! ]XC (^PPM^(((P(PMP^PMCSX,! 3&E&3)&! >3/B&3! ]XC ((P((M(^^((P(^M(M(MC^M(CSXIF! ^2&! 6&*&@*/7$! 7.! *2&! KPQ! >376%@*! D#)! >&3.73B&6! %)/$A! ]XCWCNM"C MPP^(((PPMMMMPC"(:CSX! #)! 6&*&@*/7$! >378&F! N73! *2&! #B>'/./@#*/7$! 7.! ][! 8>! )/;&6! "a"! .3#AB&$*! .7''7D/$A! >3/B&3)! #$6! >378&! D&3&! %)&6! H.73D#36! >3/B&3! ]XC! ((M((M^^^(M(M(P(^(P^^CSX,! 3&E&3)&! >3/B&3! ]XC (P((P^P(P^(MM(^P^^^C^M(CSX,! >378&! ]XCa=PC ^(P((MMPP(^^(MMC"(:CSXI! Rapid determination of adenovirus titers. N73! *2&! O%#$*/./@#*/7$! 7.! E/3#'! */*&3)! /$! /B>3/$*/$A! &R>&3/B&$*)! #! )*#$6#36! @%3E&! H+R+\4! V! +R+\Y! =e! q! ]! r'I! D#)! &)*#8'/)2&6! %)/$A! #$! #6&$7E/3%)! )*7@9! )7'%*/7$F! M'/O%7*)! H]! r'I! 7.! *2&! #6&$7E/3%)! )*7@9! )7'%*/7$! 73! )#B>'&)! @7$*#/$/$A! #6&$7E/3%)!D&3&!6/3&@*'?!#66&6!*7!*2&!KPQ!B#)*&3!B/R!H+]! r'I!D/*27%*!#!jTM!/)7'#*/7$!>37@&6%3&F!N73!*2&!#B>'/./@#*/7$! 7.! E/3#'! jTM! *2&! ^#O"#$! (&$&! LR>3&))/7$! "#)*&3! "/R! H^2&3B7!N/)2&3I!D#)!%)&6!#)!3&@7BB&$6&6!8?!*2&!)%>>'/&3F! M.*&3!#$!/$/*/#'!6&$#*%3#*/7$!#*![]!pP!.73!+\!B/$,!U\!@?@'&)! H[]! pP! .73! +]! )&@,! W\! pP! .73! U]! )&@I! D&3&! >&3.73B&6F! ^2&! &../@/&$@?! 7.! *2&! OKPQ! D#)! @#'@%'#*&6! 8?! *2&! .7''7D/$A! &O%#*/7$c!L!f!x!H+\!C+q)'7>&!C+Iy+\\F RESULTS -/'/@#!"/@37B&*&3C-/;&6!K#3*/@'&)F!->2&3/@#'!)/'/@#!B/@37C >#3*/@'&)!V!>376%@&6!%)/$A!*2&!-*o8&3]S!B&*276!V!)&3E&6!#)! @#33/&3! B#*&3/#'! *7! 6&)/A$! *2&! E/3%)! /B>3/$*&6! >#3*/@'&)! Ha=K)IF!^2&)&!>#3*/@'&)!2#E&!#!2/A2!)%3.#@&C#3&#C*7CE7'%B&!

@2#3#@*&3/;#*/7$! 7.! >#3*/@'&! )/;&,! )2#>&! #$6! )%3.#@&! B73>27'7A?! #$6! *2&! E/)%#'/;#*/7$! 8?! &'&@*37$! B/@37@7>?! /B#A&)! #! 5&'/7)! 5&'/7)! T#$7J#8k! W\\! HNL=,! e-MI! #$6! #! ! 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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

Page 4 of 12

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denovirus.!5%B#$!#6&$7E/3%)&)!73/A/$#''?!>%3@2#)&6! .37B!M^PP!HaQC],!(&3B#$?I!D&3&!)&'&@*&6!#)!*#3A&*!)>&@/&),! #)!*2&?!>37E/6&!#!$7$C&$E&'7>&6!>)&%67!^x4]!/@7)#2&63#'! )%3.#@&! '#**/@&! B73>27'7A?F! ^2/)! A&7B&*3?! /)! #B7$A! *2&! B7)*! >3&E#'&$*! @7$.73B#*/7$)! /$! $#*%3&,! )/$@&! *2&! @#>)/6! >37*&/$! #))&B8'?! B/$/B/;&)! *2&! .3&&! &$&3A?F! G/*2! *2/)! )?BB&*3?,! #')7! *2&! $%B8&3! 7.! >7))/8'&! 73/&$*#*/7$)! 7$@&! /BB78/'/;&6! #*! *2&! -K! D#)! 3&6%@&6F! ^2&! E/3%)! 8&'7$A)! *7! A37%>!=!7.!*2&!:#'*/B73&!@'#))/./@#*/7$,!8#)&6!7$!*2&!6)CjTMF! ^2&!)2&''!6/#B&*&3!3#A&)!.37B!Y\!*7!+\\!$BFUS,UU! N73!*2&!/BB78/'/;#*/7$,!*2&!E/3%)!)7'%*/7$!D#)!#66&6!*7! *2&!)%)>&$6&6!8)!#$6!B/R&6!E/#!SW\p!E&3*/@#'!37*#*/7$)F! ^2%),! #! 27B7A&$&7%)! 6/)*3/8%*/7$! 7$! -K)! #$6! E/3%)! >#3*/@'&)! D&3&! &$)%3&6F! M.*&3! *2&! /BB78/'/;#*/7$! )*&>,! $7! .%3*2&3! D#)2/$A! )*&>)! .7''7D&6! )/$@&! B&@2#$/@#'! )*3&))! /$6%@&6!E/#!@&$*3/.%A#*/7$!7.!*2&!8)!#$6!3&C)%)>&$)/7$! 7.! *2&! -K! >&''&*! @7%'6! >7*&$*/#''?! '! *7! 6&$#*%3#*/7$! #$6q73!%$.7'6/$A!7.!*2&!#6&$7E/3%)!*&B>'#*&)F!

!

!

! 1,23*/4564(*7-/0048*794+:/483;-+,7;).,,.,IF!P37))'/$9/$A!7.!*2&! #B/$7CB76/./&6!-K)!D/*2!A'%*#3#'6&2?6&!HB/66'&IF!P7%>'/$A!7.!*2&!E/3%)!*7!*2&!B76/./&6!-K)!E/#!.73B#*/7$!7.!#$!/B/$&!87$6!H87**7BIF!

!

Virus Imprinting. M.*&3! A3#.*/$A! *2&! E/3#'! >#3*/@'&)! 7$*7!

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aragon Plus Environment

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

! E/3%)!>#3*/@'&),!D2/'&!@7E#'&$*'?!8/$6/$A!*7!*2&!-K!)%3.#@&F][V W+! ^2&)&! >37>&3*/&)! )27%'6! &$#8'&! .#@/'&! E/3%)! 3&B7E#'! D/*27%*! 6&)*37?/$A! 73! 3&B7E#'! 7.! *2&! >7'?B&3! #.*&3! /B>3/$*/$AF! ^7! @7B>#3&! *2&! >&3.73B#$@&! 7.! a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`-! H*&*3#&*2?'73*27)/'/@#*&I,! MK^L-! HHSC#B/$7>37>?'IC *3/&*27R?)/'#$&I,! #$6! MK^"-! HHSC#B/$7>37>?'IC *3/B&*27R?)/'#$&I! H/F&F! /$! *2&! .7''7D/$A! $#B&6! b^MM! B/R*%3&XIF!^2&!@27/@&!7.!MK^L-!#$6!MK^"-!D#)!./3)*'?!8#)&6! 7$!*2&!.#@*!*2#*!*2&?!B/B/@!*2&!'#*&3#'!#B/$7!#@/6!@2#/$)!7.! '?)/$&!3&)/6%&)!#*!*2&!#6&$7E/3%)!>37*&/$!)2&'',!D2/@2!.#E73)! *2&/3! /$*&3#@*/7$F! -&@7$6'?,! *2&?! #3&! #**3/8%*&6! #! @#*#'?*/@! &..&@*!*2#*!)%>>73*)!*2&!2?637'?)/)!7.!*2&!73A#$7)/'#$&)!E/#! *2&/3!>3/B#3?!#B/$&!A37%>F!M''!)&'&@*&6!73A#$7)/'#$&)!D&3&! 2?637'?)#8'&! /$! D#*&3,! D2&3&8?! A&$*'&! >7'?B&3/;#*/7$! @7$6/*/7$)! D&3&! &$)%3&6F! ^2&! 3#*/7! 7.! *2&! ^MM! B/R*%3&! @7B>7$&$*)! %)&6! .73! *2&! )?$*2&)/)! D#)! /$E&)*/A#*&6! &B>/3/@#''?F!

->&@/./@/*?! )*%6/&)! D&3&! >&3.73B&6! #.*&3! /$@%8#*/7$! 7.! a=K)! 73! T=K)! H/F&F! @7$*37'! >#3*/@'&)I! D/*2! *2&! #6&$7E/3%)! .7''7D&6! 8?! @&$*3/.%A#*/7$! #$6! %)/$A! #$! #'/O%7*! 7.! *2&! )%>&3$#*#$*!.73!#$#'?)/)!E/#!OKPQ,!/$!736&3!*7!6&*&3B/$&!*2&! #B7%$*!7.!87%$6!E/3%)F!

Batch Rebinding Assays Protein Blocking Agents for Suppressing NonSpecific Virus Binding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

! 1,23*/4A64#-:/9)+,-4,..30+*)+,7;4784+:/4,9B*,;+,;24B*7-/C3*/64 4

^2&!78*#/$&6!3&)%'*)!HN/A%3&!S#I!)%AA&)*!*2#*!/$!#8)&$@&! 7.!:-M!*2&!6/..&3&$@&!/$!8/$6/$A!8&2#E/73!8&*D&&$!a=K!#$6! T=K! /)! $7*! &R@&>*/7$#''?! 2/A2F! M.*&3! 7>*/B/;#*/7$,! /*! D#)! )27D$! *2#*! *2&! 3/A2*! @7$@&$*3#*/7$! 7.! :-M! 63#B#*/@#''?! /$@3&#)&6!*2&!6/..&3&$@&!/$!8/$6/$A!8&*D&&$!a=K)!#$6!T=K)! *7D#36)! #6&$7E/3%)F! ^2&! 78*#/$&6! 3&)%'*)! )%AA&)*! *2&! 2?>7*2&)/)!*2#*!:-M,!#)!#!A'78%'#3!>37*&/$!D/*2!2?637>2/'/@! #$6! 2?637>278/@! )%8A37%>)! /)! #6)738&6! #*! '7D! @7$@&$*3#*/7$)!*7!*2&!>37*&/$)!7.!*2&!E/3%)!#$6!*%8&!D#''),! #$6!*2%)!>37*&@*)!.37B!8/$6/$A!*7!7*2&3!>37*&/$),!@2#3A&6! !

)%3.#@&),!#$6!*2&!>7'?B&3F!57D&E&3,!*2&)&!/$*&3#@*/7$)!#3&! D ! /$! $#*%3&,! #$6! *2%),! E/3%)&)! B#?! )*/''! 8/$6! *7! *2&! /B>3/$*&6! B7/&*/&)! #*! *2&! a=K! E/#! )/A$/./@#$*'?! )*37$A&3! -@2/..! 8#)&! /$*&3#@*/7$),! 7$@&! /$! >37R/B/*?! 7.! *2&! 8)F! P7$)&O%&$*'?,! A/E&$! *2&! 3/A2*! 8#'#$@&! 7.! :-M! E)F! E/3%)! E)F! a=K,!:-M!B7'&@%'&)!#3&!#>>#3&$*'?!6/)>'#@&6,!27D&E&3,!7$'?! .73! E/3%)&)! 8/$6/$A! *7! 2/A2'?! )>&@/./@! 8/$6/$A! )/*&)F! `>*/B/;&6!3&)%'*)!D&3&!78*#/$&6!8?!#66/$A!#$!#B7%$*!7.!YY! rA!:-MF!!

ACS Paragon Plus Environment

Analytical Chemistry ! N/A%3&!S8!)27D)!*2&!@7B>#3/)7$!7.!3&8/$6/$A!&R>&3/B&$*)! %)/$A! A&'#*/$! #)! 8'7@9/$A! #A&$*F! j/..&3&$@&)! 8&*D&&$! a=K! #$6! T=K! @#$! 8&! #@2/&E&6! #A#/$! 8?! A&'#*/$! @7$@&$*3#*/7$! 7>*/B/;#*/7$F!57D&E&3,!*2&! A3&#*! 6/..&3&$@&)! 8&*D&&$!a=K! #$6! T=K! /$! @7$*3#)*! *7! :-M! @#$$7*! 8&! 3&#@2&6F! =$! #! *2/36! )*%6?!B/'9!>37*&/$)!D&3&!%)&6!#)!8'7@9/$A!#A&$*F!M)!N/A%3&! S@! /$6/@#*&)! /)! /*)! %)#A&! .73! *2/)! >%3>7)&! /$#6&O%#*&F! ^2&! 78*#/$&6! 3&)%'*)! 6&B7$)*3#*&! *2#*! /$! #8)&$@&! 7.! 8'7@9/$A! #A&$*)! 7$'?! #! B/$%*&! 6/..&3&$@&! 8&*D&&$! a=K! #$6! T=K! /)! &E/6&$*F! 57D&E&3,! /$! *2&! >3&)&$@&! 7.! *2&! 8&)*C&R#B/$&6! 8'7@9/$A! 3&#A&$*! :-M,! *2&! E/3%)! 87%$6! )&'&@*/E&'?! 7$'?! *7! *2&!a=KF!!

()*+,-./+01-2-345

P)Q4 &!! %! $! #! "!

M)! #! )/6&! $7*&,! /*! D#)! )27D$! /$! #66/*/7$! *2#*! %)/$A! )B#''! E/#')!&$2#$@&6!*2&!3&8/$6/$A!&../@/&$@?!6%&!*7!*2&!3&6%@&6! )%3.#@&! #3&#! 7.! *2&! *%8&F! P7$)&O%&$*'?,! '&))! $7$C)>&@/./@! >37*&/$C)%3.#@&!/$*&3#@*/7$)!/$@3&#)&6!*2&!#B7%$*!7.!*#3A&*! E/3%)!#E#/'#8'&!.73!8/$6/$A!*7!*2&!>#3*/@'&)F!=$!)%BB#3?,!7$&! B#?! @7$@'%6&! *2#*! 7$'?! 8?! *2&! 6&E&'7>&6! b>#))/E#*/7$X! )*3#*&A?!2/A2'?!)>&@/./@!8/$6/$A!)/*&)!#*!a=K!>#3*/@'&)!.73!*2&! *&B>'#*&! E/3%)! #3&! /$! .#@*! b#@*/E#*&6X,! /F&F,! >3&67B/$#$*'?! 3&)>7$)/8'&!.73!)&'&@*/E&!/$*&3#@*/7$F! !

Rebinding Kinetics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

!

'!

&!!

&'!

"!!

"'!

67/+08-9:;-2-3Q4 &!! %! $!

@K LK a=K

HK

T=K

AK K K

#! "! ! !

'! &!! &'! "!! 67/+08-=>?68)0-2-37/$*)! H! ! I! 3&>3&)&$*! *2&! E#'%&)! .73! T=K^MM,! D2/'&! *2&! 8'%&! >7/$*)!H! !I!/$6/@#*&!3&)%'*)!78*#/$&6!.73!a=K^MMF!LR>&3/B&$*)! D&3&! >&3.73B&6! D/*2! >#3*/@'&)! /B>3/$*&6! D/*2! ^L`-,!MK^L-,! #$6!MK^"-!#*!#!B7'#3!3#*/7!7.!4\cScUF!Q&>'/@#*&!B&#)%3&B&$*)! D&3&! >&3.73B&6! #*! '&#)*! *23&&! */B&),! &#@2! B&#)%3&B&$*! /$! 6%>'/@#*&F! M''! E#'%&)! #3&! >3&)&$*&6! #)! >&3@&$*#A&! E)F! *2&! /$/*/#''?!#66&6!#B7%$*!7.!*#3A&*!E/3%)F!

!

()*+,-./+01-2-345

!

()*+,-./+01-2-345

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

Page 6 of 12

5K

AK DK HK +,9/4M4N9,;O

?K

LK !

1,23*/4 H64 $,9/4 /=7.3+,7;4 784 )4 >,;C,;24 )00)G4 87*4 IJ(0! H/B>3/$*&6! D/*2! ^L`-,! MK^L-! #$6! MK^"-! z! B7'#3! 3#*/7! 4\cScUIF!-#B>'&)!D&3&!@7''&@*&6!#.*&3!+,!],!+\,!4\,!S\,!W\!B/$!7.! /$@%8#*/7$!*/B&F!^2&!3&8/$6/$A!)7'%*/7$!H./$#'!E7'%B&!+\]!rJI! @7$*#/$&6! UZ\!rA! >#3*/@'&),! YY! rA! :-M,! #$6! +F\\! L]! =e! #6&$7E/3%)F!"&#)%3&B&$*)!D&3&!>&3.73B&6!#*!'&#)*!*23&&!*/B&),! #$6!&#@2!B&#)%3&B&$*!D#)!>&3.73B&6!/$!6%>'/@#*&F!M''!E#'%&)!#3&! $73B#'/;&6! #$6! 3&>3&)&$*&6! #)! >&3@&$*#A&! 7.! .3&&! E/3%)! 3&B#/$/$A!/$!*2&!)%>&3$#*#$*!

Reusability of Imprinted Particles. -/$@&!#!>7*&$*/#'! #>>'/@#*/7$! 7.! *2&! 6&E&'7>&6! a=K)! /)! *2&! )&>#3#*/7$! 7.! E/3%)&)! /$! 8/7*&@2$7'7A/@#'! #$6! 8/7>2#3B#@&%*/@#'! >37@&))&),! /$! #! ./$#'! )&*! 7.! &R>&3/B&$*)! *2/)! >7*&$*/#'! )@#E&$A&3! B#*&3/#'! D#)! *&)*&6! .73! 3&%)#8/'/*?F! K#3*/@'&)! /B>3/$*&6! D/*2! *2&! ^MM! B/R*%3&! a=K^MM! #$6! T=K^MM! D&3&! %)&6!6%3/$A!B%'*/>'&!3&8/$6/$A!#$6!3&A&$&3#*/7$!@?@'&)F!N73! *2#*! >%3>7)&,! #'/O%7*)! 7.! /B>3/$*&6! #$6! $7$C/B>3/$*&6! 8)! D&3&! )%)>&$6&6! /$! K:-,! #$6! :-M! #$6! #6&$7E/3%)! D&3&!#66&6F!^2&!*7*#'!E7'%B&!D#)!#A#/$!#6d%)*&6!*7!+\]!rJ,! #$6! #$! 7>*/B/;&6! /$@%8#*/7$! */B&! 7.! S\! B/$! D#)! #>>'/&6F! -#B>'&)! .73! 6&*&3B/$/$A! 3&B#/$/$A! E/3%)! D&3&! @7''&@*&6! #.*&3!@&$*3/.%A#*/7$! .37B! *2&! )%>&3$#*#$*F!M.*&3D#36),! *2&! 8)!D&3&!'?)&6!D/*2!#!B/R*%3&!7.!5P'!#$6!^3/*7$!hC+\\F! ^2&$,!*2&!8)!D&3&!D#)2&6!#$6!/$@%8#*&6!#A#/$!%)/$A!*2&! )#B&! #B7%$*! 7.! :-M! #$6! E/3%)! /$! &O%#'! E7'%B&)F! ^2/)! >37@&))!D#)!3&>&#*&6!./E&!*/B&)!Ha=KqT=K+C]IF!M)!)27D$!/$! N/A%3&! ]! *2&! 6&E&'7>&6! 8)! #3&! /$6&&6! %)#8'&! 6%3/$A! )&E&3#'! @?@'&)! D/*2! *2&! 3&8/$6/$A! E#'%&)! 7.! *2&! a=K)!

ACS Paragon Plus Environment

Page 7 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

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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a=K!>#3*/@'&)!D&3&!#8'&! *7!8/$6!*2&!*#3A&*!D/*2!7%*)*#$6/$A!8/$6/$A!@#>#@/*?!H/F&F!%>! *7![Y!f!7.!*2&!/$@%8#*&6!E/3%)&)I,!D2/'&!*2&!$7*!/B>3/$*&6! >#3*/@'&)!87%$6!'&))!*2#$!]!f!E/3%)!#*!*2&!)#B&!@7$6/*/7$)! #$6! /$/*/#'! E/3%)! @7$@&$*3#*/7$F! e)/$A! :-M! /$! @7$*3#)*! *7! 7*2&3! 8'7@9/$A! #A&$*)! &$2#$@&)! *2&! >&3.73B#$@&! 7.! 2/A2C )&'&@*/E/*?! 8/$6/$A! )/*&)F! N%3*2&3B73&,! *2&! 3&8/$6/$A! 9/$&*/@)! D&3&! )*%6/&6! /$! 6&*#/'! $&R*! *7! @7$./3B/$A! 3&%)#8/'/*?! 7.! *2&! >376%@&6! 8)! 6%3/$A! ./E&! @7$)&@%*/E&! 3&8/$6/$A! &R>&3/B&$*)F! =$! #66/*/7$,! )%@@&)).%'! 8#*@2! 3&8/$6/$A! )*%6/&)! /$! 3&#'CD73'6! B#*3/@&)! D&3&! >&3.73B&6! #$6! *2&! )&'&@*/E/*?! *7D#36)! $7$C*#3A&*! E/3%)! H"a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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

Page 10 of 12

!

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! !

H4ZI!! a#)#>7''7,! (Fv! -7'&,! QF!jFv! "&3A7'#,!JFv!J#;;7/,!"F!QFv! -@#36/$7,!MFv!-@733#$7,!-Fv!"&'&,!(F!#$&D"VD"E*.D"P0'D!AK55,! !A,!][\ZV][U]F! H4[I!! •&,! JF! =$! E*.)0(.-6" #5R6'$&'$I" ;" S6'$0'R.)%" -$1" ,RR.'0-&'*$%" *+" E'06*;" -$1" ]-$*%&6(0&(6)1" S*./5)6%v! K#$!-*#$.736!K%8'/)2/$A!K*&F!J*6Fc!-/$A#>73&,!4\+SF! HS\I!! 5#%>*,!0F!,$-./%&!AKK5,!!A[,!YUYVY]WF! HS+I!! 5#%>*,!0Fv!"7)8#@2,!0F!34)5D"O)9D!AKKK,!!??,!4U[]V 4]\UF! HS4I!! K'%2#3,!:Fv!"/;#/97..,!:F!E-06*5*.D"2'*%0'D!AK5?,!!U,! +]\YV+]++F! HSSI!! ^/D#3/,! MF,! =$! ,19-$0)1" J)-.&40-6)" E-&)6'-.%v! -@3/E&$&3!K%8'/)2/$AqG/'&?c!:&E&3'?,!"M,!4\+UF! HSUI!! "#**/#))7$,! :F,! •&,! JF,! =$! E*.)0(.-6./" #5R6'$&)1" S*./5)6%" '$" 2'*&)04$*.*I/! C! M6E#$@&)! /$! 8/7@2&B/@#'! &$A/$&&3/$A,!8/7*&@2$7'7A?v!->3/$A&3c!P2#B,!4\+]F! HS]I!! (&33#36,! tF! MF,! =$" E)&4*1%" '$" 5*.)0(.-6" :'*.*I/" `" S6*&)'$" ]-$*&)04$*.*I/Q" S6*&*0*.%7" #$%&6(5)$&-&'*$7" -$1" ,RR.'0-&'*$%,! 4$6! &6Fv! 5%B#$#! K3&))•c! ->3/$A&3c! T&D!•739,!4\+SF! HSWI!! "7'/$&''/,! MF! JF,! (&73A/#! =$)*/*%*&! 7.! ^&@2$7'7A?,! 4\\UF! HSYI!! €#2&6/,! KFv! €/#&&,! "Fv! M867%)),! "Fv! N#3#;/$,! MFv! "/;#/97..,! :F! S*./5D" ,19D" X)04$*.D! AK5L,! AW,! ++4UV ++U4F! HSZI!! :7'/)#?,!JF!jFv! P%'E&3,! tF! TFv! 07./$#),!KF! 2'*5-&)6'-.%! AKKL,!AW,!U+W]VU+WZF! HS[I!! :7))/,! MFv! :7$/$/,! NFv! ^%3$&3,! MF! KF! NFv! K/'&*)9?,! -F! MF! 2'*%)$%D"2'*).)0&6*$D!AKKU,!AA,!++S+V++SYF! HU\I!! K/@27$,!aFv!P2#>%/)C5%A7$,!NF!,$-.D"34'5D",0&-!AKK@,! [AA,!UZVW+F! HU+I!! K%7@/,!NFv!P/3/''7,!(Fv!P%3@/7,!"Fv!=&BB#,!NFv!->/;;/33/,! eF!(Fv!K/@@/,!TF!,$-.D"34'5D",0&-!AKKU,!U>\,!+WUV+Y\F! HU4I!! :#AA/#$/,! PFv! M$.7))/,! JFv! (/7E#$$7'/,! PF! ,$-.D" 34'5D" ,0&-!AKKU,!U>!,!4[VS[F! HUSI!! -?973#,!-Fv!P%B87,!MFv!:&''/7*,!(Fv!K7*2/&3,!KFv!M3$#',! PFv! j%6#',! •Fv! P73E/$/,! KF! NFChFv! -2#2A#'6/#$,! KF! 34)5D" 3*55($D!AK5?,!U!,!44]WV44]ZF! HUUI!! Q&&6,!JF,!tFv!"%&$@2,!5F!,5"V"J/I!5YD@,!AW,!U[SVU[YF! HU]I!! 5#3*,!5Fv!Q&/6,!0Fv!5#3*,!GF!Y*Z"P-$ID!5YYD,![K,!Z4V ZZF! HUWI!! `X(3#6?,!tFv!J7)/97..,!MFv!K7/'&?,!tFv!N/@9&**,!jFv!`'/E&3,! PF!C)9D"2'*.D"P&-$1D!5YYL,!==,!S+[VS4WF! HUYI!! "‚$6&;Ca/'#),! MFv! jƒ#;,! tF,! =$! E'06*%0*R/Q" P0')$0)7" X)04$*.*I/7" ,RR.'0-&'*$%" -$1" >&3,!-F!JF!VD"Y'6*.D" E)&4*1%!5Y@L,!!K,![[V+\[F! H]+I!! G#*;/$A&3,!NFv!L8$&3,!0Fv!J/7$,!^F!E*.D",%R)0&%"E)1D! AKKL,!AW,!4]UV4[ZF! H]4I!! -2#2A#'6/#$,! KFv! P%B87,! MFv! P73E/$/,! G`q4\+4q\SU[UW,!4\+4F! H]SI!! -*o8&3,!GFv!N/$9,!MFv!:72$,!LF!VD"3*..*'1"#$&)6+-0)"P0'D! 5YL@,!A[,!W4VW[F! H]UI!! :7%'#$A&3,! KF! MFv! t#%B&,! NFv! N'#B&$@7%3*,! KFv! :/)&3*&,!(F!VD"Y'6*.D!5YUK,!U,!+\[V++SF! H]]I!! j#E/6,!MF!LF,!e$/E&3)/*?!7.!"#3?'#$6,!4\\UF!

ACS Paragon Plus Environment

Page 11 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

! H]WI!! "/A$&#%'*,! =Fv! j#3*/A%&$#E&,! PFv! :&3*3#$6,! "F! tFv! G#'637$,! 0F! PF! 2'*X)04$'T()%! AKKH,! \W,! Y[\VY[W,! Y[ZVZ\4F! H]YI!! ^%3$&3,!TF!GFv!t&#$),!PF!GFv!:3#/$,!0F!QFv!M''&$6&3,!PF! tFv!5'#6?,!aFv!:3/**,!jF!GF!2'*&)04$*.D"S6*ID!AKKL,!AA,! +UYUV+UZ[F! H]ZI!! (#)*,!"Fv!012$&3,!-Fv!-78&9,!5Fv!"/;#/97..,!:F!,$-./%&! AK5U,!#@@&>*&6F! H][I!! 0&)9/$,! `Fv! (%3)7?,! MFv! "#,! :Fv! T%))/$7E,! QF! 34)5D" O)9D!AKK@,!!?=,!+44]V+4UUF! HW\I!! 6&'! a#67,! "F! MF! (Fv! L@2&E#33ƒ#,! (F! QFv! :'#$@7,! tF! -Fv! :'#$@7,!NF!(F!VD"E*.D"3-&-.D"34)5D!5YYU,!!!=,!4+V4WF!

!

HW+I!! P'#@9)7$,! ^Fv! G&''),! tF! MF! P0')$0)! 5YY?,! A[W,! SZSV SZWF! HW4I!! P%B87,!MFv!J738&3,! :Fv!P73E/$/,! KF!NFChFv! "&/&3,!GFv! -2#2A#'6/#$,!KF!]-&"3*55($!AK5D,!K,!+]\SF! HWSI!! J/,! -F,! =$! E*.)0(.-6./" #5R6'$&)1" P)$%*6%! +)*! &6Fv! L')&E/&3,!`R.736,!4\+4F! HWUI!! "73&$D&/)&3,!QF!@)$)"X4)6D!AKK?,!!A,!+\SV++\F! HW]I!! P2#>B#$,!"F!-Fv!MA8#$6d&C"@9&$$#,!"F,!=$!,&*5'0" P&6(0&(6)"*+"Y'6-."S-6&'0.)%";"S-69*9'6(%)%v!PQP!K3&))c! T&D!•739,!4\\WF! !

!

!

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 12 of 12