A metal-enhanced fluorescence sensing platform for selective detection of picric acid in aqueous medium

Abstract

Apart from national security and military purposes, it is also of great importance to detect picric acid (PA) in aqueous solution for pollution control. Herein, we report a gold nanoparticle (AuNP)-based sensor for detection of PA in aqueous condition, based on metal-enhanced fluorescence (MEF) of poly(allylamine)hydrochloride (PAH). Notable enhancement in fluorescence intensity is observed when PAH is incubated with [email protected]2 nanoparticles, where silica shell controls the distance between gold core and PAH. Almost ∼ 280 fold enhancement is recorded when PAH is incubated with ∼ 45 nm diameter Au nanoparticles. A significant reduction in excited state lifetime followed the enhancement in fluorescence intensity, identifying the mechanism to be primarily obtained from the intrinsic radiative decay rate enhancement of PAH. The MEF sensor shows excellent selectivity for detection of PA in water, among similar electron deficient compounds via fluorescence quenching. The detection limit of the sensor is calculated to be 79 nM, in the linear range. Detection of PA is demonstrated in simulated water samples, where matrix effects are taken into account to assess the efficacy of the sensor.

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Contents lists available at ScienceDirect
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journal homepage: http://ees.elsevier.com
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Department of Chemistry, Birla Institute of Technology and Science (BITS) Pilani, Hyderabad Campus, Jawahar Nagar, Kapra Mandal, Hyderabad, 500078, India
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1. Introduction
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UNCORRECTED PROOF
S. Kaja et al. / Analytica Chimica Acta xxx (xxxx) 1–11
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2. Materials and methods
2.1. Chemicals
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L=EH=J9LMJ= 0@=Q O=J= MK=< 9K K==<K OAL@AF  @ 0@= ?=F=J9D E=L@G<
>GJ ?JGOAF? K==<K AK 9K >GDDGOK =JL9AF 9EGMFL G> K==<K O9K <ADML=< LG
 ED 9F< HD9;=< AF 9 LOG F=;C=< JGMF< :GLLGE=< Z9KC 0@=F LG L@AK
 ED G> KGDMLAGF  9F<  =9;@ O=J= 9<<=< K=H9J9L=DQ GN=J 9 H=JAG< G>
 EAF MF<=J NA?GJGMK KLAJJAF? (9L=J L@= EAPLMJ= O9K C=HL MF<=J :GAD
AF? >GJ  EAF "AF9DDQ L@= KGDMLAGF O9K 9DDGO=< LG ;GGD <GOF 9F< MK=<
>GJ >MJL@=J KLM<A=K )=9FO@AD= KGDMLAGF  O9K HJ=H9J=< :Q <ADMLAF? DAL
LD= 9EGMFL G>  ON $MDX$+ LG  ED /GDMLAGF  O9K E9<=
:Q <ADMLAF? 9 EAPLMJ= G>  ON K;GJ:A; 9;A< 9F<  ON 0/ KLG;C
KGDMLAGF LG  ED 0@= ;GEH9J9LAN= NGDME= J9LAGK >GJ L@= EAPAF? O9K
9K >GDDGOAF? KGDMLAGF  K;GJ:A; 9;A< 0/   M*,K G> <A>>=J=FL
KAR=K O=J= KQFL@=KAR=< :Q N9JQAF? L@= 9EGMFL G> K==< <MJAF? L@= ?JGOL@
HJG;=KK
2.3. Synthesis of Au@SiO2core-shell nanoparticles
0G HJ=H9J= L@= ;GJ=K@=DD M/A+F9FGH9JLA;D=K O= MK=< 9 HJG;=
<MJ= 9K J=HGJL=< :Q #J9> =L 9D 78 JA=ZQ  ED G> KQFL@=KAR=< M*,K
O=J= <AKH=JK=< AF  ED G> =L@9FGD 0@=F L@= H$ O9K 9<BMKL=< LG  :Q
<JGHOAK= 9<<ALAGF G>  ) *9+$ 0G L@AK  μD 9EEGFA9 9F< N9JAGMK
9EGMFLK G> 0!+/  μD– μD O=J= 9<<=< 9F< KLAJJ=< >GJ  EAF
LG G:L9AF M/A+;GJ=K@=DD F9FGH9JLA;D=K OAL@ <A>>=J=FL KADA;9 D9Q=J
L@A;CF=KK 0@=Q O=J= D9L=J ;=FLJA>M?=< 9L  JHE >GJ  EAF 9F< L@=
KMH=JF9L9FL O9K J=B=;L=< 0@= H=DD=L O@A;@ ;GFL9AF=< M/A+O9K <AK
H=JK=< AF  ED G> =L@9FGD
2.4. Deposition of poly(allylamine)hydrochloride on Au@SiO2
"AF9DDQ L@= K=FKGJ O9K <=N=DGH=< 9>L=J L@= <=HGKALAGF G> ,$ GF
L@= KADA;9 KMJ>9;= :Q >GDDGOAF? 9 CFGOF HJG;=<MJ= 78 JA=ZQ LG L@=
KQFL@=KAR=< M/A+;GJ= K@=DD *,K  μ( G>  ,$ O9K 9<<=< 9F<
KLAJJ=< >GJ  EAF (9L=J L@AK O9K ;=FLJA>M?=< 9L  JHE >GJ  EAF
9F< KMH=JF9L9FL O9K J=B=;L=< 0@= G:L9AF=< H=DD=L O9K <AKH=JK=< AF
=L@9FGD 0@AK KGDMLAGF O9K MK=< >GJ 9DD L@= KLM<A=K 9F< O9K ;@9J9;L=JAR=<
L@GJGM?@DQ
2.5. Detection of PA
%F 9 LQHA;9D =PH=JAE=FL  μ( G> <A>>=J=FL ;GF;=FLJ9LAGF G> , O9K
9<<=< LG  E( G> K=FKGJ 9F< EAP=< O=DD %EE=<A9L=DQ ZMGJ=K;=F;=
E=9KMJ=E=FLK G> L@= KGDMLAGF O=J= H=J>GJE=< 9L JGGE L=EH=J9LMJ=
2.5.1. Detection of PA in real water samples
,GF< O9L=J 9F< D9C= O9L=J K9EHD=K O=J= ;GDD=;L=< >JGE 9 F=9J:Q
NADD9?= 9F< /@9EAJH=L D9C= F=9J %0/ ,AD9FA $Q<=J9:9< ;9EHMK J=KH=;
LAN=DQ DD L@= O9L=J K9EHD=K O=J= YJKL ;=FLJA>M?=< 9F< YDL=J=< L@JGM?@
9  μE E=E:J9F= 0@=F  μ( G> O9L=J K9EHD= O9K 9<<=< LG
 E( G> K=FKGJ 9F< ZMGJ=K;=F;= O9K ;GDD=;L=<
2.5.2. Detection of PA in soil samples
/GAD K9EHD=K O=J= ;GDD=;L=< >JGE L@= ?9J<=F G> L@= ;9EHMK  ?EK G>
?JGMF< YF= HGO<=J DAC= KGAD K9EHD= O9K HD9;=< AF YN= <A>>=J=FL H=LJA
<AK@=K *=PL  E?  E?  E? 9F<  E? G> , O9K 9<<=< LG >GMJ H=LJA
<AK@=K AF<ANA<M9DDQ 9F< EAP=< O=DD 0@= KGAD K9EHD= OAL@GML , O9K
MK=< 9K :D9FC "AF9DDQ  E? KGAD K9EHD= >JGE =9;@ O9K 9<<=< LG  E(
G> K=FKGJ KGDMLAGF 9F< ZMGJ=K;=F;= O9K ;GDD=;L=<
2.6. Instruments
QF9EA; DA?@L K;9LL=JAF?  (/ =PH=JAE=FLK 9F< R=L9 HGL=FLA9D E=9
KMJ=E=FLK O=J= H=J>GJE=< MKAF? )9DN=JF H9JLA;D= KAR= 9F9DQR=J6=L9

UNCORRECTED PROOF
S. Kaja et al. / Analytica Chimica Acta xxx (xxxx) 1–11 
KAR=J F9FG K=JA=K *9FG6/ 9L JGGE L=EH=J9LMJ= !PLAF;LAGF KH=;LJ9 G>
L@= M*,K 9F< 12–2AK 9:KGJHLAGF KH=;LJ9 G> ,$ O=J= J=;GJ<=< MK
AF? /@AE9<RM 12  HDMK KH=;LJGH@GLGE=L=J /L=9<Q KL9L= ZMGJ=K
;=F;= E=9KMJ=E=FLK O=J= ;9JJA=< GML :Q MKAF? $AL9;@A " /H=;
LJGZMGJGE=L=J (A>= LAE= E=9KMJ=E=FLK O=J= H=J>GJE=< MKAF? $GJA:9
=DL9 Z=P )G<MD9J ZMGJ=K;=F;= DA>=LAE= KQKL=E OAL@ >GDDGOAF? AFKLJM
E=FL9D H9J9E=L=JK  FE *9FG (! =P;AL9LAGF KGMJ;= 9F< H=9C HJ=
K=L  ;GMFLK  ;E H9L@ D=F?L@ -M9JLR ;MN=LL= O9K MK=< >GJ ZMG
J=K;=F;= E=9KMJ=E=FLK /!) AE9?=K O=J= J=;GJ<=< MKAF? 9 "!% HJ=G
 '2 Y=D< =EAKKAGF K;9FFAF? =D=;LJGF EA;JGK;GH= "!/!) 0@= K9E
HD=K O=J= <JGH;9KL=< GF 9 /A O9>=J 9F< <JA=< ;GEHD=L=DQ :=>GJ= L9CAF?
/!) AE9?=K M ?JA<K O=J= MK=< LG ;GDD=;L /0!) AE9?=K
2.7. Details of FDTD simulations
" 0 KAEMD9LAGFK O=J= H=J>GJE=< :Q MKAF? 9F< EG<A>QAF? L@= H9
J9E=L=JK G> 9 EG<=D =P9EHD= “"DMGJ=K;=F;= !F@9F;=E=FL”>JGE L@=
KG>LO9J= (ME=JA;9D /GDMLAGFK %F; 29F;GMN=J 9F9<9 N=JKAGF :
78 JA=ZQ M F9FGH9JLA;D= ;GN=J=< OAL@ KADA;9 O9K ;GFKA<=J=< 9K L@=
9FL=FF9 9F< 9 <AHGD= =EALL=J O9K HD9;=< 9L L@= LGH G> KADA;9 K@=DD 0@= <A
HGD= KGMJ;= O9K DG;9L=< 9L L@= =EALL=J HGKALAGF 9F< AF L@= " 0 KAEMD9
LAGF L@AK <AHGD= KGMJ;= EG<=D=< L@= J9<A9LAGF ;@9J9;L=JAKLA;K G> L@= =EAL
L=J 3@=J= L@= J9LAG G> γ<AHGD= LG γJ9<A9LAN= HJGNA<=< 9F AF<A;9LAGF 9:GML
L@= ZMGJ=K;=F;= =F@9F;=E=FL O@=J= γ<AHGD= 9F< γJ9<A9LAN= O=J= ‘LGL9D <=
;9Q J9L= AF HJ=K=F;= G> F9FGKLJM;LMJ=’9F< ‘J9<A9LAN= <=;9Q J9L= OAL@GML
L@= AFZM=F;= G> F9FGKLJM;LMJ=’G> L@= <AHGD= J=KH=;LAN=DQ 3= ;9D;MD9L=<
γ<AHGD=γJ9<A9LAN= >GJ L@= <AHGD= 9K 9 >MF;LAGF G> <AKL9F;= >JGE L@= KH@=J
A;9D E=L9DDA; KMJ>9;= 0@= KAEMD9LAGFK O=J= H=J>GJE=< 9L <A>>=J=FL <A
HGD=E=L9D <AKL9F;=K G>     9F<  FE E9L;@AF? OAL@
L@= =PH=JAE=FL9D ;GF<ALAGFK 9F< <A9E=L=J G> L@= ?GD< F9FGH9JLA;D= O9K
;GFKA<=J=< LG :=  FE 0@= <AHGD= GJA=FL9LAGF O9K ;GFKA<=J=< H=JH=F
<A;MD9J >JGE L@= E=L9D KMJ>9;= 9F< <AHGD= ;=FL=J G> L@= M F9FGH9JLA;D=
O=J= 9DGF? L@= R 9PAK θ V )=K@ KL=H O9K  FE 9F< E=K@ GJ<=J O9K
L9C=F 9K  >GJ 9DD L@= KAEMD9LAGFK H=J>GJE=<
3. Results and discussion
3.1. Characterization of the AuNPs and Au@SiO2nanoparticles
0@= KQFL@=KAR=< M*,K O=J= YJKL KLJM;LMJ9DDQ ;@9J9;L=JAR=< MKAF?
"!/!) L=;@FAIM= "A?  M*,K G> L@J== <A>>=J=FL 9N=J9?= KAR=K O=J=
HJ=H9J=< >GJ L@= KLM<Q KH=;A>A;9DDQ  FE  FE 9F<  FE "A? 9–;
K@GO L@= /!) AE9?=K G> M*,K 9F< L@= <AKLJA:MLAGF G> H9JLA;D= KAR=
AK K@GOF AF "A? / !/% 12–2AKA:D= KH=;LJGH@GLGE=LJQ O9K MK=< LG
;GDD=;L L@= =PLAF;LAGF KH=;LJ9 "A? < G> L@= M*,K KGDMLAGF %L O9K
=NA<=FL >JGE L@= Y?MJ= L@9L L@= E9PAE9 G> L@= HD9KEGFA; KH=;LJ9 G>
L@= M*,K EGN=< ;GFLAFM9DDQ LGO9J<K @A?@=J O9N=D=F?L@K OAL@ KDA?@L
:JG9<=FAF? 9K L@= KAR= G> L@= M*,K AF;J=9K=< >JGE  LG  FE 0@=
G:K=JN=< J=< K@A>L AF L@= =PLAF;LAGF KH=;LJ9 AF<A;9L=< 9:GML L@= HJG?J=K
KAN= AF;J=9K= AF KAR= >GJ L@= M*,K 0@= FME:=J <=FKALA=K H=J ED G> L@=
KQFL@=KAR=< M*,K O=J=  ]   ]  9F<  ]  >GJ  
9F<  FE J=KH=;LAN=DQ 9D;MD9LAGF / AF /% K== "A? 
>L=J L@= KQFL@=KAK 9F< ;@9J9;L=JAR9LAGF G> L@= M*,K O= KM:K=
IM=FLDQ HJ=H9J=< 9F< ;@9J9;L=JAR=< L@= M/A+;GJ=K@=DD F9FGH9JLA
;D=K OAL@ KADA;9 KH9;=J 0@= F9FGH9JLA;D=K OAL@ N9JAGMK KADA;9 K@=DD L@A;C
F=KK=K O=J= KQFL@=KAR=< L@JGM?@ L@= J=HGJL=< /LG:=J E=L@G< :Q N9JQAF?
L@= 9EGMFL G> 0!+/ 9<<=< "A?  9F< "A? / !/% 0@= =PLAF;LAGF ;G
=>Y;A=FL O9K >GMF< LG := DGO=J >GJ  FE M/A+ FE H9JLA;D=K
;GEH9J=< LG L@= :9J=  FE M*,K "A? < AF<A;9LAF? L@= HJ=K=F;=
G> KADA;9 D9Q=J M= LG L@= HJ=K=F;= G> L@= F=?9LAN= ;@9J?= GF ALK KMJ
>9;= 9 KADA;9 K@=DD ;9F G>>=J KH=;AY; :AF<AF? KAL= LG :AF< EGD=;MD=K DAC=
,$ NA9 =D=;LJGKL9LA; 9LLJ9;LAGF OAL@ L@= HGKALAN= 9EAF= ?JGMHK G> ,$
%F >9;L L@= R=L9 HGL=FLA9D E=9KMJ=E=FLK "A? / !/% ;GFYJE=< L@9L
L@= KMJ>9;= >GJ :GL@ >J== M*,K 9F< /A ;G9L=< M*,K O=J= F=?9LAN=DQ
;@9J?=< O@=J=9K M/A+KMJ>9;= <=N=DGH=< HGKALAN= ;@9J?= 9>L=J <=
HGKALAGF G> ,$ 0@= H$ G> L@= KGDMLAGF O9K >GMF< LG :=  L L@AK H$
9DCQD 9EAF=K =PAKL=< HJ=<GEAF9FLDQ 9K HGKALAN=DQ ;@9J?=< .–*$ /!)
AE9?=K HJGN=< L@9L MFA>GJE KADA;9 D9Q=JK G> <A>>=J=FL L@A;CF=KK=K O=J=
?JGOF GF L@= KMJ>9;= G> M*,K 3@AD= L@= ;@9F?= AF R=L9 HGL=FLA9D N9D
M=K 9F< %. <9L9 @9N= ;GFYJE=< L@= KM;;=KK>MD ,$ <=HGKALAGF GFLG L@=
KMJ>9;= G> ;GJ=K@=DD F9FGH9JLA;D=K
Fig. 1. 9 : 9F< ; 9J= "!/!) AE9?=K >GJ   9F<  FE M*,K J=KH=;LAN=DQ 9F< < AK L@= =PLAF;LAGF KH=;LJ9 G> L@= F9FGH9JLA;D=K

UNCORRECTED PROOF
S. Kaja et al. / Analytica Chimica Acta xxx (xxxx) 1–11
Fig. 2. 9JC Y=D< /0!) AE9?=K G>  FE M*,K ;G9L=< OAL@ 9  9F< :  μ( G> 0!+/ ;G9LAF?
3.1.1. FTIR studies
"0%. KH=;LJ9 O9K J=;GJ<=< >GJ ,$ M*,K M/A+9F<
M/A+,$ LG ;GFYJE L@= <=HGKALAGF G> KADA;9 D9Q=J 9K O=DD 9K ,$
9K K@GOF AF "A?  M*,K K@GO=< L@= >GDDGOAF? H=9CK AF %. +–$
KLJ=L;@ 9JGMF<  ;E−   + KLJ=L;@ 9JGMF<  ;E−9F< –+$
KLJ=L;@ 9JGMF<  ;E−78 0@= %. KH=;LJ9 G> M*,/A+K@GO=<
9 HJGFGMF;=< H=9C 9L  ;E−O@A;@ ;9F := 9K;JA:=< LG 9KQEE=L
JA; KLJ=L;@AF? G> /A–+–/A 0@= @MEH 9L  ;E−GJA?AF9L=< >JGE /A–+$
9KQEE=LJA; NA:J9LAGFK 78 0@= J=KMDLK AF<A;9L=< L@= KM;;=KK>MD >GJE9
LAGF G> ;GJ= K@=DD F9FGH9JLA;D=K 0@= 9<KGJHLAGF G> ,$ ;9F := ;GF
YJE=< :Q ;9J=>MD ;GEH9JAKGF G> >J== ,$ 9F< M/A+,$ "J==
,$ K@GO=< LOG AEHGJL9FL ;@9J9;L=JAKLA; H=9CK 9L  9F<  ;E−
O@A;@ ;9F := 9KKA?F=< 9K <=>GJE9LAGF NA:J9LAGFK G> *–$ :GF< 9F<
*–$ :=F<AF? J=KH=;LAN=DQ 3@=J=9K AF ;9K= G> M/A+
Fig. 3. "0%. KH=;LJ9 G> M*,K M*,/A+ M*,/A+,$ 9F< >J== ,$
,$ L@= H=9C 9L  ;E−K@A>L=< LG  ;E−9F< L@= H=9C 9L
 ;E−<AK9HH=9J=< ;GFYJEAF? L@= 9<KGJHLAGF G> ,$ GF ;GJ= K@=DD
M/A+F9FGH9JLA;D=K 78
3.2. MEF studies of PAH on Au@SiO2nanoparticles
0@= KLJM;LMJ= G> ,$ AK K@GOF AF "A? / !/% 0@= ZMGJ=K;=F;= AF
L=FKALQ G> >J== ,$ AF L@= :MDC 9IM=GMK ;GF<ALAGF O9K >GMF< LG := N=JQ
D=KK "A? / !/% 9F< ;9F := ;GFKA<=J=< 9K AFKA?FA>A;9FL O@=F =P;AL=<
9L  FE $GO=N=J LG GMJ KMJHJAK= ,$9<KGJ:=<  FE M/A+
F9FGH9JLA;D=K AF =L@9FGD K@GO=< 9 J=E9JC9:D= ZMGJ=K;=F;= =F@9F;=
E=FL ;GEH9J=< LG >J== ,$ "A? 9 3@=J=9K O= OALF=KK=< IM=F;@=<
ZMGJ=K;=F;= AFL=FKALQ O@=F ,$ O9K 9<KGJ:=< <AJ=;LDQ GF L@= K9E=
M*,K OAL@GML KADA;9 D9Q=J "A? / !/% K 9 ;GFLJGD =PH=JAE=FL O=
@9N= 9DKG G:K=JN=< L@9L M/A+ZMGJ=K;=F;= AK EM;@ D=KK ;GEH9J=< LG
M/A+,$ AF<A;9LAF? L@= AFKA?FA>A;9FL JGD= G> KADA;9 AF L@= G:K=JN=<
ZMGJ=K;=F;= AFL=FKALQ "A? / !/% 0@AK ;GFYJE=< L@9L L@= G:K=JN=<
=F@9F;=E=FL AF ZMGJ=K;=F;= G> ,$ OAL@  FE M/A+H9JLA;D=K O9K
;=JL9AFDQ 9 J=KMDL G> )!" AEHGK=< :Q L@= M*,K MF<=J 9F 9HHJGHJA9L=
;GJ=K@=DD 9JJ9F?=E=FL
%L AK O=DDCFGOF L@9L >GJ )!" L@= =F@9F;=E=FL G> ZMGJ=K;=F;=
AK @A?@DQ <=H=F<=FL GF <AKL9F;= :=LO==F L@= F9FGKLJM;LMJ= 9F< ZMG
JGH@GJ= 78 !9JDA=J *GNGLFQ 9F< ;GOGJC=JK J=HGJL=< IM=F;@AF?
G> EGD=;MD9J ZMGJ=K;=F;= O@=F EGD=;MD=?GD< <AKL9F;=K O=J= K@GJL=J
L@9F  FE 78 DKG AL O9K G:K=JN=< L@9L EGFGD9Q=J <=HGKALAGF G>
EGD=;MD=K <AJ=;LDQ GF KADN=J 9F< ?GD< KMJ>9;=K =P@A:AL=< KA?FA>A;9FL KMJ
>9;==F@9F;=< .9E9F K;9LL=JAF? OAL@ LGL9D IM=F;@AF? G> ZMGJ=K;=F;=
78 "A? 9 AF<A;9L=< L@9L 9K O= AF;J=9K=< L@= L@A;CF=KK G> /A
;G9LAF? L@= ZMGJ=K;=F;= AFL=FKALQ G> ,$9<KGJ:=<  FE M/A+
F9FGH9JLA;D=K 9DKG AF;J=9K=< 9L L@= :=?AFFAF? :ML >=DD G\ 9K L@= KH9;=J
L@A;CF=KK ;JGKK=< 9F GHLAEME N9DM= 0@AK AK 9?9AF ;D=9JDQ MF<=JKLGG<
O@=F O= HDGLL=< L@= =F@9F;=E=FL >9;LGJ !" G> ZMGJ=K;=F;= O@A;@ AK
L@= J9LAG G> L@= ZMGJ=K;=F;= AFL=FKALQ G> ,$ GF M/A+F9FGH9JLA
;D=K LG >J== ,$ 9K 9 >MF;LAGF G> KADA;9 L@A;CF=KK AF "A? : 0@= GH
LAEME <AKL9F;= >JGE L@= M KMJ>9;= O9K >GMF< LG :=  FE O@=J=
E9PAEME =F@9F;=E=FL G> S >GD< O9K J=;GJ<=< 0@= G:K=JN=< <=
H=F<=F;= G> )!" GF KADA;9 L@A;CF=KK ;GEH=DD=< MK LG :=DA=> L@9L DGKK
<M= LG FGFJ9<A9LAN= =F=J?Q LJ9FK>=J 9F< F=9JY=D< =F@9F;=E=FL NA9
HD9KEGFA; ;GMHDAF? EMKL := GH=J9LAN= 9K LOG ;GEH=LAF? HJG;=KK=K :=
LO==F ,$ 9F< M*,K 0@= GN=JD9H G> 9:KGJHLAGF 9F< =EAKKAGF KH=;
LJ9 G> ,$ OAL@ HD9KEGFA; H=9C G>  FE M*,K 9J= K@GOF AF "A?
/ !/% ,GKKA:DQ )!" AFALA9DDQ AF;J=9K=K 9K ,$ 9HHJG9;@=K ;DGK=J LG
M KMJ>9;= :ML KL9JLK LG <=;J=9K= GF;= L@= <AKL9F;= :=;GE=K D=KK L@9F
 FE <M= LG HGKKA:D= FGFJ9<A9LAN= DGKK 0@= L@=GJ=LA;9D " 0 KAE
MD9LAGF J=KMDLK 9DKG K@GO=< N=JQ KAEAD9J LJ=F< "A? ; O@=F FGJE9D
AR=< <=;9Q J9L= G> 9 <AHGD= =EALL=J O=J= HDGLL=< 9L <A>>=J=FL <AKL9F;=K

UNCORRECTED PROOF
S. Kaja et al. / Analytica Chimica Acta xxx (xxxx) 1–11 
Fig. 4. 9 "DMGJ=K;=F;= AFL=FKALQ G> M/A+,$ F9FGH9JLA;D=K 9K 9 >MF;LAGF G> KH9;=J L@A;CF=KK 9F< : !F@9F;=E=FL >9;LGJ 9?9AFKL KH9;=J L@A;CF=KK >GJ  FE M*,K ; /AEMD9L=<
<=;9Q J9L= =F@9F;=E=FL G> 9 J=HJ=K=FL9LAN= ‘<AHGD=’ 9K 9 >MF;LAGF G> K=H9J9LAGF >JGE  FE M*, KMJ>9;=
G> L@= <AHGD= >JGE 9  FE M*, KMJ>9;= K ;9F := K==F AF "A? ;
L@= E9PAEME =F@9F;=E=FL AF L@= <=;9Q J9L= O9K >GMF< 9L  FE 9F<
L@= J9L= <JGHH=< KA?FA>A;9FLDQ 9>L=JO9J<K %L EMKL := FGL=< @=J= L@9L γ<A
HGD=γJ9<A9LAN= O9K ;9D;MD9L=< 9K 9 >MF;LAGF G> O9N=D=F?L@K "A? / !/%
>JGE O@A;@ "A? ; <=EGFKLJ9L=< L@= =F@9F;=E=FL GFDQ 9L  FE
3.3. Mechanism of MEF
L HJ=K=FL L@=J= 9J= LOG =KL9:DAK@=< E=;@9FAKEK >GJ )!" AF<M;=<
:Q F=9J Y=D< =F@9F;=E=FL +F= E=;@9FAKE AK 9KKG;A9L=< OAL@ L@= =F
@9F;=E=FL G> L@= DG;9D =D=;LJA; Y=D< :Q L@= F9FGH9JLA;D= AF O@A;@ L@=
=EALL=JK 9JGMF< L@= E=L9D F9FGH9JLA;D= ;9F =>Y;A=FLDQ 9:KGJ: EGJ= J9
<A9LAGF 0@AK ;9F AF;J=9K= L@= =P;AL9LAGF J9L= LG =F@9F;= L@= ZMGJ=K
;=F;= HJG;=KK :ML OAL@GML 9DL=JAF? L@= DA>=LAE= 9F< IM9FLME QA=D< G>
L@= ZMGJGH@GJ=K 0@= GL@=J E=;@9FAKE KL9L=K L@9L AF HJ=K=F;= G> E=L9D
DA; F9FGH9JLA;D=K L@= AFLJAFKA; J9<A9LAN= <=;9Q J9L= G> ZMGJGH@GJ=K AK
KLJ=F?L@=F=< <M= LG 9<<ALAGF9D J9<A9LAN= ;@9FF=D %F ;GFLJ9JQ LG L@= =>
>=;L ?MA<=< :Q DG;9D =D=;LJA; Y=D< O@=F =F@9F;=E=FL AF ZMGJ=K;=F;=
AFL=FKALQ AK ;GFLJGDD=< :Q L@= AFLJAFKA; J9<A9LAN= <=;9Q J9L= =>>=;L AL AK
9;;GEH9FA=< :Q 9F AF;J=9K= AF -5 9F< 9F MFMKM9D <=;J=9K= AF L@= DA>=
LAE= >GJ L@= =EALL=J 0@=J=>GJ= ZMGJ=K;=F;= DA>=LAE= @9K :==F J=;G?
FAR=< 9K 9F AEHGJL9FL ;@9J9;L=JAR9LAGF LGGD O@=J= 9 ;GFKA<=J9:D= <=
;J=9K= AF DA>=LAE= OAL@ ;GF;GEAL9FL =F@9F;=E=FL AF ZMGJ=K;=F;= OADD
HJ=<A;L L@= )!" E=;@9FAKE NA9 AF;J=9K= AF J9<A9LAN= <=;9Q J9L= 1K
AF? 9 &9:DGFKCA <A9?J9E 78 L@= ZMGJ=K;=F;= IM9FLME QA=D< - 9F<
L@= <=;9Q LAE= τ G> L@= =EALL=J ;9F := =PHJ=KK=< 9K >GDDGOAF? 3AL@
GML E=L9DK - ΓΓ CFJ  CI 9F< τ Γ CFJ  CI− O@=J=
Γ CFJ 9F< CI9J= L@= J9L= ;GFKL9FLK G> .9<A9LAN= <=;9Q *GF.9<A9LAN=
<=;9Q 9F< IM=F;@AF? HJG;=KK A> 9FQ J=KH=;LAN=DQ 3@=J=9K AF HJ=K
=F;= G> E=L9DK L@= EG<AY=< IM9FLME QA=D< -E 9F< L@= <=;9Q LAE=
τE :=;GE= -E ΓΓEΓΓE CFJ  CI 9F< τE Γ
ΓE CFJ  CI− O@=J= ΓE J9L= ;GFKL9FL G> 9<<ALAGF9D .9<A9LAN= <=
;9Q ;@9FF=D AF HJ=K=F;= G> M*,K
0G MF<=JKL9F< L@= E=;@9FAKE G> )!" AF GMJ KLM<Q O= ;GEH9J=<
L@= DA>=LAE= N9DM=K G> >J== ,$ OAL@ ,$9<KGJ:=<  FE M/A+
F9FGH9JLA;D=K G> <A>>=J=FL L@A;CF=KK=K "A? 9 9F< 09:D=  GEH9J=<
LG >J== ,$ O= G:K=JN=< 9 <=;J=9K= AF L@= KDGO=J ;GEHGF=FL G> L@= DA>=
LAE= 9K O=DD 9K AF L@= 9N=J9?= DA>=LAE= G> ,$ O@=F AL AK 9<KGJ:=< GF
M/A+F9FGH9JLA;D=K 0@= 9N=J9?= DA>=LAE= G> L@= =EALL=J O9K ;9D;M
D9L=< MKAF? L@= >GDDGOAF? =IM9LAGF 783@=J= τiAK L@= DA>=LAE= G> 9 H9J
LA;MD9J ;GEHGF=FL αiAK ;GFKA<=J=< 9K L@= ;GFLJA:MLAGF G> L@9L H9JLA;MD9J
;GEHGF=FL 9F< τfAK L@= 9N=J9?= DA>=LAE= $GO=N=J 09:D=  KM??=KLK
L@9L L@= DA>=LAE= G> ,$ <=;J=9K=K AF L@= :=?AFFAF? 9F< L@=F MFMKM9DDQ
AF;J=9K=K OAL@ AF;J=9K= AF KADA;9 KH9;=J ML O= @9N= K==F =9JDA=J AF "A?
 L@9L L@= ZMGJ=K;=F;= AFL=FKALQ AF;J=9K=K AFALA9DDQ 9F< L@=F <=;J=9K=
OAL@ KH9;=J L@A;CF=KK 0@=K= J=KMDLK ;JALA;9DDQ KM??=KL L@9L L@= =F@9F;=
E=FL G> ZMGJ=K;=F;= G> ,$ AK <AJ=;LDQ 9KKG;A9L=< OAL@ L@= <=;J=9K= G>
ALK ZMGJ=K;=F;= <=;9Q LAE= %F >9;L "A? : ;D=9JDQ K@GO=< L@AK 9FLA
;GJJ=D9L=< :=@9NAGJ G> ZMGJ=K;=F;= AFL=FKALQ 9F< ALK ;GJJ=KHGF<AF? DA>=
LAE= 9L <A>>=J=FL <AKL9F;=K >JGE L@= E=L9DDA; KMJ>9;= )9Q:= :=DGO 9F
GHLAEME <AKL9F;= L@= )!" <=;J=9K=K <M= LG ;GEH=LAF? ".!0 HJG;=KK 9L
K@GJL=J <AKL9F;=K  FE J=KMDLAF? AF AF;J=9K= AF DA>=LAE= $GO=N=J
AL E9Q := FGL=< L@9L 9L =N=JQ L@A;CF=KK G> L@= KADA;9 KH9;=J L@= DA>=LAE=
G> L@= 9<KGJ:=< ,$ AK KLADD D=KK L@9F L@= >J== ,$ 0@= J=KMDLK <=>AFAL=DQ
AF<A;9L=< L@9L L@= )!" G> ,$ >GDDGO=< L@= E=;@9FAKE G> L@= =F@9F;=
E=FL G> AFLJAFKA; J9<A9LAN= <=;9Q J9L=

UNCORRECTED PROOF
S. Kaja et al. / Analytica Chimica Acta xxx (xxxx) 1–11
Fig. 5. 9 (A>= LAE= G>  FE ,$9<KGJ:=< M/A+F9FGH9JLA;D=K OAL@ <A>>=J=FL KH9;=J L@A;CF=KK 9F< : FLA;GJJ=D9L=< :=@9NAGJ G> =F@9F;=E=FL >9;LGJ G> ,$ :DM= KIM9J=K 9F<
(A>= LAE= J=< ;AJ;D=K O@=F HDGLL=< 9K 9 >MF;LAGF G> KH9;=J L@A;CF=KK "GJ AFL=JHJ=L9LAGF G> L@= J=>=J=F;=K LG ;GDGMJ AF L@AK Y?MJ= D=?=F< L@= J=9<=J AK J=>=JJ=< LG L@= 3=: N=JKAGF G> L@AK
9JLA;D=
Table 1
0@= DA>=LAE= N9DM=K G> >J== ,$ OAL@ ,$9<KGJ:=<  FE M/A+F9FGH9JLA;D=K G> <A>>=J=FL L@A;CF=KK=K
/9EHD= τFK τFK τFK αααχN=J9?=DA>=LAE=FK
"J==,$        
3AL@ FEKH9;=J        
3AL@ FEKH9;=J        
3AL@ FEKH9;=J        
3AL@ FEKH9;=J        
3AL@ FEKH9;=J        
3.4. Discussion on dependence of MEF on size of AuNPs using Radiating
Plasmon model
0G =PHDGJ= @GO L@= KAR= G> L@= M*,K AFZM=F;= L@= GML;GE= G>
)!" KL=9<Q KL9L= ZMGJ=K;=F;= 9F< DA>=LAE= E=9KMJ=E=FLK O=J= 9DKG
H=J>GJE=< OAL@  9F<  FE M*,K 9F< L@= J=KMDLK O=J= ;GEH9J=<
OAL@  FE ;9K= >GJ 9 YP=< KADA;9 KH9;=J K ;9F := K==F >JGE "A?
9 L@= ZMGJ=K;=F;= =F@9F;=E=FL AK @A?@=KL >GJ  FE 9F< DGO=KL
OAL@  FE <A9E=L=J H9JLA;D=K )GJ=GN=J DA>=LAE= E=9KMJ=E=FLK ;GF
YJE=< L@9L =F@9F;=E=FL G> ZMGJ=K;=F;= G> ,$ O9K <AJ=;LDQ ;GFF=;L=<
OAL@ L@= <=;J=9K= G> ALK ZMGJ=K;=F;= <=;9Q LAE= "A? : 9F< 09:D=
 A= 9K =PH=;L=< O= G:K=JN=< DGO=KL 9F< @A?@=KL 9N=J9?= DA>=LAE=K
OAL@  FE 9F<  FE H9JLA;D=K J=KH=;LAN=DQ *GL GFDQ L@9L O= 9DKG
H=J>GJE=< L@= )!" KLM<A=K 9K 9 >MF;LAGF G> KH9;=J L@A;CF=KK >GJ 
9F<  FE M*,K "A?K / 9F< / !/% 3= G:K=JN=< KAEAD9J LJ=F<
9K  FE ;9K= L@9L OAL@ AF;J=9K= AF ZMGJ=K;=F;= AFL=FKALQ G> ,$ L@=J=
O9K 9 ;GF;GEAL9FL DGO=JAF? AF L@= <=;9Q LAE= >GJ ,$ "A?K / 9F<
/ !/%
3= @9N= MK=< L@= ‘.9<A9LAF? ,D9KEGF’., EG<=D AFLJG<M;=< =9JDA=J
:Q & (9CGOA;R AF  78 LG MF<=JKL9F< L@= <=H=F<=F;= G> )!" GF
L@= KAR= G> M*,K ;;GJ<AF? LG ., EG<=D <M= LG L@= ;GMHDAF? G> L@=
=EAKKAGF >JGE L@= =P;AL=< ZMGJGH@GJ= OAL@ L@= KMJ>9;= HD9KEGF G> L@=
E=L9DDA; F9FGKLJM;LMJ= KMJ>9;= HD9KEGF ;GMHD=< =EAKKAGF /,! AK G:
K=JN=< OAL@ =F@9F;=< AFL=FKALQ 9L L@= =EAKKAGF O9N=D=F?L@ G> L@= >J==
ZMGJGH@GJ= %L AK @QHGL@=KAR=< L@9L L@= AF<M;=< HD9KEGFK OADD J9<A9L=
EGJ= O@=F L@= K;9LL=JAF? ;GEHGF=FL G> L@= M*,K OGMD< := <GEAF9FL
;GEH9J=< LG L@= 9:KGJHLAGF ;GEHGF=FL G> L@= ;GDDGA< K L@= 9:KGJH
LAGF ;JGKK K=;LAGF E9AFDQ ;GFLJA:ML=K AF L@= IM=F;@AF? G> ZMGJ=K;=F;=
K 9 E9LL=J G> >9;L K;9LL=JAF? =>Y;A=F;A=K G> L@= M*,K 9J= <AJ=;LDQ HJG
Fig. 6. 9 "DMGJ=K;=F;= AFL=FKALQ 9F< : "DMGJ=K;=F;= <=;9Q ;MJN=K G> ,$ 9<KGJ:=< GFLG M/A+F9FGH9JLA;D=K G> K9E= KH9;=J D=F?L@ :ML <A>>=J=FL <A9E=L=J G> M*,K

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S. Kaja et al. / Analytica Chimica Acta xxx (xxxx) 1–11 
Table 2
0@= DA>=LAE= N9DM=K G> >J== ,$ 9F< ,$ 9<KGJ:=< GFLG M/A+F9FGH9JLA;D=K G> K9E= KH9;=J D=F?L@ :ML <A>>=J=FL <A9E=L=J G> M*,K
/9EHD= τFK τFK τFK αααχN=J9?=DA>=LAE=FK
"J==,$        
3AL@ FE        
3AL@ FE        
3AL@ FE        
HGJLAGF9D LG ALK <A9E=L=J KG L@= KAR= G> L@= E=L9DDA; F9FGH9JLA;D=K J=
E9AFK 9K 9 ;JM;A9D >9;LGJ >GJ G:K=JN=< )!" %F GJ<=J LG ?=L EGJ= AFKA?@L
G> L@= G:K=JN=< )!" =>>=;L O= @9N= L@=GJ=LA;9DDQ ;9D;MD9L=< "A? 
L@= 9:KGJHLAGF K;9LL=JAF? 9F< =PLAF;LAGF KH=;LJ9 G> L@= MK=< M*,K MK
AF? )A=,DGL KG>LO9J= 78 %L ;9F := ;D=9JDQ K==F >JGE "A?  L@9L
L@= 9:KGJHLAGF ;GEHGF=FL AK @A?@ >GJ KE9DD=J M*,K O@=J=9K K;9LL=JAF?
;GEHGF=FL AF;J=9K=K OAL@ AF;J=9K= AF KAR= 3= =PH=;L=< L@9L OAL@ EGJ=
K;9LL=JAF? ;GEHGF=FL D9J?=J F9FGH9JLA;D=K LG := :=LL=J ;9F<A<9L=K >GJ
)!" ML 9K K@GOF AF "A?  L@= 9;LM9D =PH=JAE=FL9D J=KMDL O9K ;GMF
L=JAFLMALAN= 9K @A?@=KL =F@9F;=E=FL O9K G:K=JN=< OAL@  FE H9JLA;D=K
O@AD=  FE HJG<M;=< L@= DGO=KL =F@9F;=E=FL
,GKKA:DQ L@= @A?@=KL )!" O9K 9KKG;A9L=< OAL@  FE 9K AL HGK
K=KK=< @A?@=J K;9LL=JAF? =>Y;A=F;Q 9F< DGO=J 9:KGJHLAGF =>Y;A=F;Q ;GE
H9J=< LG  FE H9JLA;D=K L L@AK HGAFL AL AK 9DKG LG := FGL=< L@9L L@=
DAF=OA<L@ G> L@= =PLAF;LAGF :9F< G> 9 F9FGKLJM;LMJ= AK <AJ=;LDQ 9KKG;A
9L=< LG L@=AJ 9:ADALQ LG ;GFYF= 9F< =F@9F;= L@= AF;A<=FL =D=;LJGE9?
F=LA; Y=D< 78 0@=J=>GJ= A> L@= DAF=OA<L@ >GJ 9 K;9LL=JAF? :9F< AK
>GMF< LG := :JG9< AL AK ;@9DD=F?AF? >GJ L@= H9JLA;MD9J F9FGKLJM;LMJ= LG
=F@9F;= L@= ZMGJ=K;=F;= 9F< K@GO <=KAJ=< )!" 9DL@GM?@ L@=GJ=LA;9D
K;9LL=JAF? =>Y;A=F;A=K 9J= KLADD @A?@ 0@AK O9K 9 HJG:9:D= J=9KGF L@9L
O= G:K=JN=< GFDQ 9 EG<=KL =F@9F;=E=FL OAL@ L@=  FE F9FGH9JLA;D=K
9K L@= HD9KEGFA; :9F< O9K >GMF< LG := :JG9< "A?K < 9F< < ;GE
H9J=< LG L@=  9F<  FE H9JLA;D=K
3.5. Detection of Picric acid via =uorescence quenching of PAH-adsorbed
Au@SiO2particles (sensor)
#=F=J9DDQ =D=;LJGF <=Y;A=FL EGD=;MD=K 9J= AF;DAF=< LGO9J<K AFL=J
9;LAGF OAL@ =D=;LJGFJA;@ EGD=;MD=K KM;@ 9K >J== 9EAF=K GJ 9JQD 9EAF=
?JGMHK 9K=< GF L@AK AF>GJE9LAGF K=N=J9D LQH= G> K=FKGJK 7–8 @9K
:==F <=N=DGH=< >GJ @A?@DQ =D=;LJGF <=Y;A=FL FALJG 9JGE9LA; ;GEHGMF<K
*K 0@MK @A?@ ZMGJ=K;=F;= AFL=FKALQ G> ,$ 9K 9 J=KMDL G> )!" @9K
=F;GMJ9?=< MK LG <=DN= AFLG ALK HJG:9:D= 9HHDA;9LAGF 9K 9 K=FKGJ >GJ FA
LJG 9JGE9LA; =PHDGKAN=K , AK 9 @A?@DQ =D=;LJGF <=Y;A=FL FALJG 9JGE9LA;
EGD=;MD= <M= LG HJ=K=F;= G> L@J== FALJG ?JGMHK 3= G:K=JN=< AEE=<A
9L= IM=F;@AF? G> ZMGJ=K;=F;= AFL=FKALQ G> L@=  FE M*, :9K=< K=F
KGJ GF 9<<ALAGF G> , 0G ;GEHJ=@=F< L@= IM=F;@AF? =>Y;9;Q G> K=F
KGJ LGO9J<K , ZMGJ=K;=F;= LALJ9LAGFK O=J= H=J>GJE=< OAL@ AF;J=9KAF?
L@= ;GF;=FLJ9LAGF G> , "A? 9 <=EGFKLJ9L=< 9 K=IM=FLA9D ‘LMJFG\’
:=@9NAGJ G> L@= K=FKGJ 9K O= G:K=JN=< 9 <=;J=9K= AF L@= =EAKKAGF G>
Fig. 7. 0@=GJ=LA;9D ePLAF;LAGF K;9LL=JAF? 9F< 9:KGJHLAGF KH=;LJ9 G> 9  :  9F< ;  FE M*,K AF /A+ <  ;GEH9JAKGF G> L@= K;9LL=JAF? ;GEHGF=FL G>   9F<  FE
M*,K

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Fig. 8. 9 -M=F;@AF? G> ZMGJ=K;=F;= AFL=FKALQ G> K=FKGJ GF 9<<ALAGF G> <A>>=J=FL 9EGMFL G> −) G> , AF O9L=J : /L=JF2GDE=J 9F9DQK=K G> L@= K=FKGJ 9L <A>>=J=FL ;GF;=FLJ9LAGFK G>
, L@= J=< <GLL=< DAF= K@GOAF? L@= DAF=9J J9F?= 9F< ; =L=;LAGF DAEAL ;9D;MD9LAGF G> L@= K=FKGJ >GJ , "GJ AFL=JHJ=L9LAGF G> L@= J=>=J=F;=K LG ;GDGMJ AF L@AK Y?MJ= D=?=F< L@= J=9<=J AK
J=>=JJ=< LG L@= 3=: N=JKAGF G> L@AK 9JLA;D=
L@= K=FKGJ GF 9<<ALAGF G> AF;J=9KAF? 9EGMFL G> , 0@= GML;GE=K 9;;GE
HDAK@=< >JGE ZMGJ=K;=F;= LALJ9LAGF O=J= MK=< LG <=L=JEAF= /L=JF2GDE=J
IM=F;@AF? ;GFKL9FL :=LO==F L@= AFL=J9;LAGF G> K=FKGJ 9F< ,
/L=JF2GDE=J HDGL %% NK ;GF;=FLJ9LAGF G> , >GJ L@= K=FKGJ O9K HJ=
K=FL=< AF "A? : O@=J= % 9F< %9J= L@= ZMGJ=K;=F;= AFL=FKALA=K G> K=F
KGJ AF HJ=K=F;= 9F< 9:K=F;= G> IM=F;@=J - 0@= HDGL AK G:L9AF=< 9K DAF
=9J 9L DGO=J ;GF;=FLJ9LAGFK G> , 9F< AL <=H9JLK >JGE DAF=9JALQ 9L @A?@=J
;GF;=FLJ9LAGFK 0@= /L=JF2GDE=J ;GFKL9FL '/2 O9K ;9D;MD9L=< AF L@= DAF
=9J J9F?= G> L@= ?J9H@ >JGE L@= J=D9LAGF    7-8 0@= N9DM=
O9K >GMF< LG :=  ] )− ;GEH9J9:D= LG =9JDA=J J=HGJL=< N9DM=K
78 %L AK 9HH9J=FL >JGE /L=JF 2GDE=J HDGL "A? : L@9L L@= HDGL
JAK=K =PHGF=FLA9DDQ OAL@ AF;J=9K= AF ;GF;=FLJ9LAGF G> , <=EGFKLJ9LAF?
9 KMH=J 9EHDAY=< IM=F;@AF? HJG;=KK 78 0@= FGFDAF=9J F9LMJ= G>
L@= HDGL KM??=KLK AFL=FKAY=< ZMGJ=K;=F;= IM=F;@AF? L@JGM?@ <QF9EA;
IM=F;@AF?
K K@GOF AF "A? ; 9 HDGL :=LO==F %E9P –%%E9P %EAF 2K DG?7,8
O9K G:L9AF=< 9F< L@= <=L=;LAGF DAEAL (+  O9K ;9D;MD9L=< >JGE L@=
4AFL=J;=HL G> L@= KLJ9A?@L DAF= 9K H=J KL9F<9J< HJG;=<MJ= 78 3@=J=
%E9P 9F< %EAF O=J= L@= E9PAEME 9F< EAFAEME AFL=FKALQ AF L@= K=D=;L=<
J9F?= G> ;GF;=FLJ9LAGFK 9F< % O9K L@= ZMGJ=K;=F;= AFL=FKALQ 9L L@9L H9J
LA;MD9J ;GF;=FLJ9LAGF 0@= <=L=;LAGF DAEAL G> L@AK )!" K=FKGJ >GJ , O9K
>GMF< LG :=  F)
3.6. Selectivity study of the detection and discussion on the mechanism
0G =N9DM9L= L@= K=D=;LANALQ G> GMJ )!" K=FKGJ >GJ , GN=J GL@=J AF
L=J>=JAF? 9F9DQL=K ZMGJ=K;=F;= IM=F;@AF? KLM<A=K O=J= 9DKG H=J>GJE=<
OAL@ KAEAD9J =D=;LJGF <=Y;A=FL FALJG 9JGE9LA;K DAC= EGFG FALJG LGDM=F=
)*0 LJA FALJG LGDM=F= 0*0 H@=FGD FALJG H@=FGD *, FA
LJG H@=FGD *, *ALJG :=FR=F= * *ALJG 9;=LGH@=FGF= * 9F<
*ALJG :=FRGA; 9;A< * 0@= J=KHGFK= G> L@= K=FKGJ O9K J=;GJ<=< 9F<
HDGLL=< AF "A? 9 >GJ 9DD G> L@= FALJG9JGE9LA;K K =PH=;L=< <A>>=J=FL
=PL=FLK G> ZMGJ=K;=F;= IM=F;@AF? O=J= G:K=JN=< GF 9<<ALAGF G> <A>>=J
=FL 9F9DQL=K G> K9E= ;GF;=FLJ9LAGF −) "GJ :=LL=J MF<=JKL9F<AF?
IM=F;@AF? =>Y;A=F;Q G> <A>>=J=FL 9F9DQL=K O=J= 9DKG ;9D;MD9L=< :Q MKAF?
L@= >GJEMD9 %–%% 9F< HDGLL=< O@=J= %9F< % O=J= L@= ;GJJ=
KHGF<AF? ZMGJ=K;=F;= AFL=FKALA=K G> L@= K=FKGJ :=>GJ= 9F< 9>L=J L@= 9<
<ALAGF G> <A>>=J=FL 9F9DQL=K "A? : K ;9F := K==F ;D=9JDQ 9DD L@= 9F
9DQL=K KD9C=< L@= ZMGJ=K;=F;= LG DALLD= =PL=FL :ML HA;JA; 9;A< @9K K@GOF
=PLJ=E=DQ FGL=OGJL@Q 9F< K=FKALAN= ZMGJ=K;=F;= IM=F;@AF? =>Y;A=F;Q G>
 1HGF N9JQAF? L@= H$ G> L@= E=<AME L@= IM=F;@AF? =>Y;A=F;Q G>
L@= K=FKGJ >GJ , O9K >GMF< LG := MF;@9F?=< AF L@= 9;A<A; H$ @GO=N=J
AL KDA?@LDQ <=;J=9K=< LG S AF L@= @A?@=J H$ 9:GN=  "A? / !/%
0@= @A?@ K=D=;LANALQ G> L@AK )!" K=FKGJ LGO9J<K , 9F< HJ=K=F;=
G> ;MJN9LMJ= AF L@= /L=JF 2GDE=J HDGL KM??=KL=< L@= ;GFLJA:MLAGF >JGE
:GL@ KL9LA; 9F< <QF9EA; IM=F;@AF? %F GJ<=J LG AFN=KLA?9L= A> L@=J=
O9K 9 HGKKA:ADALQ G> ZMGJ=K;=F;= J=KGF9F;= =F=J?Q LJ9FK>=J ".!0 >JGE
L@= K=FKGJ <GFGJ LG *K 9;;=HLGJ O= HDGLL=< L@= 9:KGJHLAGF KH=;
LJ9 G> *K 9DGF? OAL@ L@= ZMGJ=K;=F;= KH=;LJME G> L@= K=FKGJ %L AK
CFGOF L@9L L@= =PL=FL G> KH=;LJ9D GN=JD9H :=LO==F K=FKGJK =EAKKAGF 9F<
IM=F;@=JK 9:KGJHLAGF KH=;LJME <=L=JEAF=K L@= J9L= G> =F=J?Q LJ9FK>=J
"A? ; ;GFYJE=< 9 D9J?= GN=JD9H :=LO==F L@= ZMGJ=K;=F;= KH=;LJME
G> L@= )!" K=FKGJ 9F< 9:KGJHLAGF KH=;LJME G> , O@A;@ J=KMDL=< AF KA?
FA>A;9FL IM=F;@AF? AF ZMGJ=K;=F;= AF ;GFLJ9KL LG GL@=J *K OAL@ D=KK
GJ F=?DA?A:D= GN=JD9H 0G MF<=JKL9F< L@= =PL=FL G> GN=JD9H AF 9 IM9F
LAL9LAN= O9Q GN=JD9H AFL=?J9D N9DM=K &λ O=J= 9DKG ;9D;MD9L=< 09:D=
/ !/% &λO9K >GMF< LG := E9PAEME >GJ HA;JA; 9;A< O@=F ;GEH9J=<

UNCORRECTED PROOF
S. Kaja et al. / Analytica Chimica Acta xxx (xxxx) 1–11 
Fig. 9. 9 "DMGJ=K;=F;= IM=F;@AF? G> K=FKGJ AF HJ=K=F;= G> N9JAGMK 9F9DQL=K  μ( G> −) 9F9DQL= KGDMLAGF AF O9L=J O9K 9<<=< LG  ED G> K=FKGJ KGDMLAGF AF =9;@ ;9K= : -M=F;@AF?
=>Y;A=F;Q HDGL G> <A>>=J=FL 9F9DQL=K ; :KGJHLAGF KH=;LJ9 G> 9F9DQL=K 9F< L@=AJ GN=JD9H OAL@ =EAKKAGF KH=;LJ9 G> K=FKGJ < 0AE= J=KGDN=< ZMGJ=K;=F;= KH=;LJ9 G> K=FKGJ OAL@ AF;J=9KAF?
NGDME=K G> ,
LG GL@=J *K )GJ=GN=J 9 ;GEH9JAKGF KLM<Q G> L@= DA>=LAE= <=;9Q
;MJN=K "A? < 9F< DA>=LAE= ;GEHGF=FLK 09:D=  G> L@= K=FKGJ OAL@
AF;J=9KAF? 9EGMFL G> , ;D=9JDQ AF<A;9L=< L@= E=;@9FAKE G> L@= IM=F;@
AF? HJG;=KK %FALA9DDQ L@= 9N=J9?= DA>=LAE= G> L@= K=FKGJ <A< FGL 9DL=J >JGE
 FK LADD  μ( 9<<ALAGF G> , AF<A;9LAF? 9 HGKKA:D= KL9LA; IM=F;@AF?
$GO=N=J L@= 9N=J9?= DA>=LAE= <JGHH=< LG  FK OAL@ >MJL@=J 9<<ALAGF
G>  μ( G> , LG L@= K=FKGJ KGDMLAGF KM??=KLAF? <QF9EA; IM=F;@AF?
NA9 ".!0 0@AK AF<A;9L=< L@9L L@= <=;J=9K= G> ZMGJ=K;=F;= AFL=FKALQ G>
L@= K=FKGJ OAL@ , O9K 9F =P9EHD= G> ;GE:AF=< KL9LA; 9F< <QF9EA;
IM=F;@AF?
3.7. Detection of PA in real samples
0@= K=FKGJ O9K 9DKG =PHDGJ=< >GJ <=L=;LAGF G> , AF 9IM=GMK K9EHD=K
>JGE N9JAGMK KGMJ;=K LG 9KK=KK L@= =>Y;9;Q G> L@= HJGHGK=< E=L@G< AF
HJ=K=F;= G> AFL=J>=J=F;=K >JGE <A>>=J=FL E9LJAP /AF;= FG G:NAGMK , <=
L=;LAGF O9K FGLA;=< AF ;GDD=;L=< O9L=J K9EHD=K O= KM:K=IM=FLDQ KHAC=<
=9;@ K9EHD= OAL@ L@J== CFGOF ;GF;=FLJ9LAGFK G> ,   9F<  μ)
9F< L=KL=< >GJ J=;GN=JQ "A? / !/% K K@GOF AF 09:D= 
 L@= J=;GN=JA=K O=J= >GMF< LG := AF L@= J9F?= G> – 9F< L@= J=D9
LAN= KL9F<9J< <=NA9LAGF G> LJAHDA;9L=K O9K D=KK L@9F  HJGNAF? L@= >=9KA
:ADALQ G> K=FKGJ =N=F AF J=9D O9L=J K9EHD=K "MJL@=J O= 9DKG KLM<A=< L@=
=>Y;9;Q G> L@= K=FKGJ AF ;GEH=LALAN= =FNAJGFE=FL 9EGF?KL HGKKA:D= AGFA;
AFL=J>=J=F;=K AF 9IM=GMK E=<AME 3= ;9JJA=< GML L@= , <=L=;LAGF AF
HJ=K=F;= G> ;GEEGF ;9LAGFK *9 9 )? ' M 6F $?
*A "= 9F< 9FAGFK $+− +− D− J− %− /+− /− +;−
*+− HJ=K=FL AF O9L=J K K@GOF AF "A? / !/% O= <A< FGL G:K=JN=
9FQ FGL9:D= AFL=J>=J=F;= >JGE E=L9D AGFK GJ 9FAGFK AF<A;9LAF? L@9L L@=
K=FKGJ ;GMD< := MK=< >GJ <=L=;LAGF G> , =N=F AF O9L=J K9EHD=K G:L9AF=<
>JGE F9LMJ9D KGMJ;=K
K H9JL G> L@= GFKAL= <=L=;LAGF G> , O= =PL=F<=< GMJ 9F9DQKAK AF
KGAD K9EHD= K K@GOF AF "A?  L@= K=FKGJ KGDMLAGF OAL@  E? G>
KGAD :ML OAL@GML , K@GO=< MF;@9F?=< =EAKKAGF AFL=FKALQ MF<=J 12 =P
;AL9LAGF 9L  FE $GO=N=J 9<<LAGF G> K9E= 9EGMFL G> KGAD :ML EAP=<
OAL@ AF;J=9KAF? ;GF;=FLJ9LAGF G> , <=EGFKLJ9L=< AEE=<A9L= IM=F;@
AF? G> L@= AFL=FKALQ 3= G:K=JN=< KAEAD9J LJ=F< AF L@= IM=F;@AF? :=
@9NAGMJ O@=F O= J=;GJ<=< L@= ZMGJ=K;=F;= KH=;LJ9 G> L@= K9E= KG
DMLAGFK "A? / !/% !9;@ KGDMLAGF O9K YDL=J=< :=>GJ= L@= ZMGJ=K
Table 3
N=J9?= DA>= LAE= N9DM=K G> K=FKGJ GF 9<<ALAGF G> AF;J=9KAF? NGDME=K G> ,
/9EHD= τFK τFK τFK αααχN=J9?=DA>=LAE=FK
"J==,$        
/=FKGJ        
/=FKGJ μ( ,        
/=FKGJ μ( ,        
/=FKGJ μ( ,        
/=FKGJ μ( ,        

UNCORRECTED PROOF
 S. Kaja et al. / Analytica Chimica Acta xxx (xxxx) 1–11
Table 4
=L=;LAGF G> , AF KHAC=< O9L=J K9EHD=K
/9EHD=
<<=<
μ)
"GMF<
μ)
.=;GN=JQ

./

09HO9L=J    
   
   
,GF<O9L=J    
   
   
(9C=O9L=J    
   
   
Fig. 10. /=FKAF? G> , AF KGAD 9 GFDQ K=FKGJ : K=FKGJ OAL@  E? G> KGAD OAL@GML ,
; < = 9F< > K=FKGJ OAL@  E? G> KGAD ;GFL9AFAF?    9F<  E? G> , J=KH=;
LAN=DQ
;=F;= KH=;LJ9 O9K G:L9AF=< %L O9K G:K=JN=< L@= K9EHD= ;GFL9AFAF? GFDQ
K=FKGJ 9F< KGAD OAL@GML , K@GO=< @A?@ ZMGJ=K;=F;= AFL=FKALQ "A?
: AF<A;9LAF? L@= 9HHDA;9:ADALQ G> L@= HJGHGK=< E=L@G< >GJ NAKM9D <=
L=;LAGF G> , AF KGAD
4. Conclusions
0G L@= :=KL G> GMJ CFGOD=<?= YJKL LAE= M*,K :9K=< )!" K=FKGJ @9K
:==F MK=< LG <=L=;L HA;JA; 9;A< AF 9IM=GMK ;GF<ALAGF 0@= D=KKZMGJ=K;=FL
J=HGJL=J EGD=;MD= ,$ O@=F 9<KGJ:=< GF KADA;9 ;G9L=<  FE M*,K
O9K :=F=YLL=< OAL@ LJ=E=F<GMK S >GD< ZMGJ=K;=F;= =F@9F;=E=FL
;GEH9J=< LG >J== ,$ AF @GEG?=F=GMK =FNAJGFE=FL 0@= =F@9F;=E=FL
O9K >GMF< LG <=H=F< ;JM;A9DDQ GF L@= <AKL9F;= :=LO==F L@= E=L9D 9F<
L@= ZMGJGH@GJ= O@AD= S FE :=AF? L@= GHLAEME K=H9J9LAGF >GJ L@=
@A?@=KL =F@9F;=E=FL 0@= HJG:9:D= E=;@9FAKE >GJ L@= )!" H@=FGE
=F9 O9K 9LLJA:ML=< E9AFDQ <M= LG L@= =F@9F;=E=FL G> AFLJAFKA; J9<A9
LAN= <=;9Q J9L= 9K AF<A;9L=< :Q L@= J=<M;LAGF AF L@= ZMGJGH@GJ= DA>=LAE=
9DGF? OAL@ =F@9F;=E=FL EGF? <A>>=J=FL M*,K L@= @A?@=KL =F@9F;=
E=FL O9K 9;;GEHDAK@=< OAL@ L@= 9N=J9?= <A9E=L=J G>  FE O@=J=9K
 FE 9F<  FE H9JLA;D=K K@GO=< EG<=J9L= 9F< DGO=KL =F@9F;=E=FL
J=KH=;LAN=DQ "MJL@=J L@= ,$ 9<KGJ:=< ZMGJ=K;=FL F9FGH9JLA;D=K O=J=
<=EGFKLJ9L=< 9K 9 K=D=;LAN= ‘LMJFG\’K=FKGJ >GJ , AF O9L=J OAL@ 9 <=
L=;LAGF DAEAL G>  FE 0@= /L=JF2GDE=J HDGL 9F< L@= DA>=LAE= KLM<Q G>
L@= K=FKGJ ;GFYJE=< L@9L L@= ‘LMJFG\’<=L=;LAGF HJG;=KK G> , O9K 9
;GE:AF=< ;9K= G> KL9LA; 9F< <QF9EA; IM=F;@AF? "AF9DDQ L@= K=FKGJ O9K
KM;;=KK>MDDQ 9HHDA=< >GJ GFKAL= NAKM9D <=L=;LAGF , AF KGAD AF 9<<ALAGF LG
L@= <=L=;LAGF G> , AF 9IM=GMK K9EHD=K G:L9AF=< >JGE N9JAGMK F9LMJ9D
KGMJ;=
CRediT authorship contribution statement
Sravani Kaja: %FN=KLA?9LAGF 9L9 ;MJ9LAGF 3JALAF?  GJA?AF9D
<J9>L Deepthi Priyanka Damera: 9L9 ;MJ9LAGF Amit Nag: "MF<AF?
9;IMAKALAGF )=L@G<GDG?Q GF;=HLM9DAR9LAGF /G>LO9J= 3JALAF?  J=
NA=O  =<ALAF? /MH=JNAKAGF
Declaration of competing interest
0@= 9ML@GJK <=;D9J= L@9L L@=Q @9N= FG CFGOF ;GEH=LAF? YF9F;A9D AF
L=J=KLK GJ H=JKGF9D J=D9LAGFK@AHK L@9L ;GMD< @9N= 9HH=9J=< LG AFZM=F;=
L@= OGJC J=HGJL=< AF L@AK H9H=J
Acknowledgements
/' 9F< ,  L@9FC %0/ ,AD9FA >GJ L@= KMHHGJL AF >GJE G> J=K=9J;@
>=DDGOK@AHK ML@GJK 9J= ?J9L=>MD 9F< 9;CFGOD=<?= L@= KMHHGJL >JGE =
H9JLE=FL G> /;A=F;= 9F< 0=;@FGDG?Q %F<A9 >GJ HJGNA<AF? L@= "%/0 ?J9FL
/."/0/% =FLJ9D F9DQLA;9D (9:GJ9LGJQ G> %0/ ,AD9FA $Q
<=J9:9< 9EHMK AK 9;CFGOD=<?=< >GJ /!) 9F< ZMGJ=K;=F;= DA>=LAE=
E=9KMJ=E=FLK
Appendix A. Supplementary data
/MHHD=E=FL9JQ <9L9 LG L@AK 9JLA;D= ;9F := >GMF< GFDAF= 9L @LLHK<GA
GJ?B9;9
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78 ) /J== / @9J9LA  @9F<M / 2 .9G !PHDGKAN=K K=FKAF? MKAF? ? –M 9DDGQ
F9FGH9JLA;D=K KQFL@=KAR=< :Q >=ELGK=;GF< D9K=J 9:D9LAGF 9F< AJJ9<A9LAGF ./
<N   –
78 0 39F? * 6@9F? . 9A 5 9G ??J=?9LAGF=F@9F;=< ".!09;LAN= ;GFBM?9L=<
HGDQE=J F9FGH9JLA;D=K >GJ HA;JA; 9;A< K=FKAF? AF 9IM=GMK KGDMLAGF & )9L=J
@=E    –
78 / /9JC9J / MLL9 / @9CJ9:9JLA , 9AJA 0 ,9D .=<GPKOAL;@9:D= ;GHH=J%
E=L9DDG?=D 9 E=L9DGJ?9FA; E9L=JA9D >GJ K=D=;LAN= 9F< F9C=<=Q= K=FKAF? G>
HA;JA; 9;A< / HHD )9L=J %FL=J>9;=K   –
78  (A ( (A 6 (AF ( /GF? 6 39F? - @=F 0 59F? 0 59F? #M=KLAF<M;=<
J=N=JKA:D= KLJM;LMJ9D LJ9FKALAGFK 9F< ;GF;GEAL9FL GFG\ DMEAF=K;=F;= KOAL;@AF?
9HHDA;9LAGF AF <=L=;LAF? HA;JA; 9;A< *=O & @=E   –
78 0 (MG 5 (A 5 4M / 6@9F? 5 39F? 4 'GM 4AG .9HA< KQFL@=KAK G> F9FGK;9D=
L=J:AME:9K=< E=L9DGJ?9FA; >J9E=OGJCK :Q 9 ;GE:AF=< MDLJ9KGMF<N9HGMJ
H@9K= <A\MKAGF E=L@G< >GJ @A?@DQ K=D=;LAN= K=FKAF? G> HA;JA; 9;A< /=FK
;LM9LGJK    –
78 4 -A 5 &AF * (A 6 39F? ' 39F? - 6@9F?  DMEAF=K;=FL @=L=JGE=L9DDA;
E=L9DGJ?9FA; >J9E=OGJC >GJ L@= F9C=<=Q= <AK;JAEAF9LAGF G> FALJG9JGE9LA;
=PHDGKAN=K @=E GEEMF   –
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UNCORRECTED PROOF
S. Kaja et al. / Analytica Chimica Acta xxx (xxxx) 1–11 
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