Planar and twisted molecular structure leads to the high brightness of semiconducting polymer nanoparticles for NIR-IIa fluorescence imaging

Article abstract of DOI:10.1021/jacs.0c07193

Semiconducting polymer nanoparticles (SPNs) emitting in the second near-infrared window (NIR-II, 1000-1700 nm) are promising materials for deep-tissue optical imaging in mammals, but the brightness is far from satisfactory. Herein, we developed a molecular design strategy to boost the brightness of NIR-II SPNs: structure planarization and twisting. By integration of the strong absorption coefficient inherited from planar π-conjugated units and high solid-state quantum yield (φPL) from twisted motifs into one polymer, a rise in brightness was obtained. The resulting pNIR-4 with both twisted and planar structure displayed improved φPL and absorption when compared to the planar polymer pNIR-1 and the twisted polymer pNIR-2. Given the emission tail extending into the NIR-IIa region (1300-1400 nm) of the pNIR-4 nanoparticles, NIR-IIa fluorescence imaging of blood vessels with enhanced clarity was observed. Moreover, a pH-responsive poly(β-amino ester) made pNIR-4 specifically accumulate at tumor sites, allowing NIR-IIa fluorescence image-guided cancer precision resection. This study provides a molecular design strategy for developing highly bright fluorophores.

Full text of DOI:10.1021/jacs.0c07193

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Article
Planar plus twisted molecular structure leads to high brightness of
semiconducting polymer nanoparticles for NIR-IIa fluorescence imaging
Shunjie Liu, Hanlin Ou, Yuanyuan Li, Haoke Zhang, Junkai Liu, Xuefeng
Lu, Ryan T. K. Kwok, Jacky W. Y. Lam, Dan Ding, and Ben Zhong Tang
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.0c07193 • Publication Date (Web): 05 Aug 2020
Downloaded from pubs.acs.org on August 6, 2020
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ACS Paragon Plus Environment

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Journal of the American Chemical Society
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DIV9TS D2HH&HH&K , !%5! k 28 R;SR.SQP ' @2-TS >@TS ,F [RQ #@( =!%-& F!& &@%HH%2# D&,3 -2>,F&K ,F hSSSd
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:!%H E&H"-F %#K%>,F&K F!,F F!& DE&H&#>& 28 F=%HF&K :YA "#%F >2"-K !,EK-1 E&HFE%>F F!& DE&K2@%#,F&K
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!&X1- "#%F H%5#%8%>,#F-1 K%HF2EF&K F!& M,>3M2#&( ,H E&8-&>F&K 8E2@ F!& , -,E5& K%!&KE,- K&5E&& 28 ^];Zo ,#K
ZP;Zo _f%5"E& PK`; :!& M,>3M2#& K%HF2EF%2# ME23& F!& >2#$"5,F%2# E&H"-F%#5 %# M-"&TH!%8F&K ,MH2EDF%2# _RQQ
#@` ,#K &@%HH%2# _SQSQ #@` _f%5"E& P&`; :2 2"E K&-%5!F( F!& DIV9Td H!2=&K , F1D%>,- AVJ >!,E,>F&E =%F!
F!& Y' %#F&#H%F1 %#>E&,H%#5 =%F! =,F&E 8E,>F%2#( 5%L%#5 ,# pAVJ _Y' %#F&#H%F1 E,F%2 28 WQi =,F&E 8E,>F%2# F2
F!,F 28 D"E& :+f` j P;] _f%5"E& P8`; I2F,M-1( DIV9Td K%HD-,1&K , Y' 28 P;di _f%5"E& ^(Z`( =!%>! %H !%5!&E
F!,# DE&L%2"H E&D2EFH _:,M-& S`(^d( ^WTZQ 2=%#5 F2 F!& &88%>%&#F !%#KE,#>& 28 %#F&Ee%#FE,@2-&>"-,E %#F&E,>F%2#H;
+2=&L&E( F!& F=%HF&K ,E>!%F&>F"E& K,@,5&K F!& ,MH2EDF%2# >2&88%>%&#F( 5%L%#5 , -2= k 28 P;d].SQP ' @2-TS
>@TS ,F RQQ #@;^P :!& c",#F"@ &88%>%&#>1 L,-"& gJ =,H 2#-1 SQ^; .# F!& 2F!&E !,#K( M1 >!,#5%#5 F!&
@2-&>"-,E E2F2E 8E2@ F!& FE%D!&#1-,@%#& _:YA` "#%F F2 :YJ( D2-1@&E DIV9TP HF%-- ,K2DF&K , F=%HF&K
M,>3M2#& _K%!&KE,- K&5E&& 28 ^R;]o ,#K ZQ;Zo` _f%5"E& P5`; :!& ,MH2EDF%2# ,#K &@%HH%2# D&,3 28 D2-1@&E
DIV9TP M-"&TH!%8F&K F2 ]]P ,#K WQR #@( E&HD&>F%L&-1( 2=%#5 F2 F!& =&,3&E &-&>FE2#TK2#,F%#5 ,M%-%F1 28 :YJ
_f%5"E& P!`; I&L&EF!&-&HH( DIV9TP K%HD-,1&K D,EF 28 AGg >!,E,>F&E =%F! ,# pAVJ 28 Q;P( D2HH%M-1 2=%#5 F2
F!& ,>F%L& %#FE,@2-&>"-,E @2F%2# 28 :YJ "#%FH =%F!%# IYH _f%5"E& P%`;Pd Y2-1@&E DIV9TP !,K , !%5! k 28
S;Q].SQ^ ' @2-TS >@TS ,F ]]P #@ =%F! , 8-"2E&H>&#F Y' 28 S;Wi; A&HD%F& , E&-,F%L&-1 !%5! gJ _dQS`( F!&
8-"2E&H>&#F &@%HH%2# =,H @,%#-1 %# F!& IV9TV E,#5& _RQQTWZQ #@`( =!%>! @%5!F &#>2"#F&E -%5!F H>,FF&E%#5
,#K ,FF&#",F%2# =%F! %@DE2L&K %@,5%#5 K&DF!;d V# D2-1@&E DIV9T^( F!& K%HF%#>F K%!&KE,- ,#5-&H 28 d;Ro ,#K
^W;Wo K&@2#HFE,F&K F!,F F!& M,>3M2#& ,K2DF&K , D-,#,E D-"H F=%HF&K HFE">F"E& _f%5"E& P$`; G2@D,E&K F2
>2@D-&F& F=%HF%#5 DIV9Td( D2-1@&E DIV9T^ H!2=&K , E&KH!%8F %# M2F! ,MH2EDF%2# _RQW #@` ,#K &@%HH%2#
_ME2,K D&,3a SQSdhSQ[Q #@` _f%5"E& P3`; DIV9T^ D2HH&HH&K ,# &#!,#>&K k 28 Z;RP.SQP ' @2-TS >@TS ,F RQW
#@ =%F! , !%5! Y' 28 d;d^i; I2F,M-1( F!& gJ 28 DIV9T^ E&,>!&K "D F2 Sd[( @">! !%5!&E F!,# F!& >2@D-&F&
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HFE,F&51; :!& Y' %#F&#H%F1 28 DIV9T^ K&>E&,H&K 8%EHF ,#K F!&# %#>E&,H&K =%F! F!& %#>E&,H& 28 =,F&E 8E,>F%2#
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%#FE,@2-&>"-,E >!,E5& FE,#H8&E _:VG:` HF,F&( =!2H& DE&K2@%#,F&K #2#E,K%,F%L& K&>,1 c"&#>!&K F!&
&@%HH%2#;ZS f"EF!&E %#>E&,H& 28 =,F&E 8E,>F%2# FE%55&E&K F!& AVJ @&>!,#%H@ L%, E&HFE%>F%2# 28 %#FE,@2-&>"-,E
@2F%2#H( 5%L%#5 ,# pAVJ 28 d;Q; :!& D!2F2D!1H%>,- DE2D&EF%&H 28 ,M2L& >2#$"5,F&K D2-1@&EH ,E& H"@@,E%U&K
%# :,M-& d; .L&E,--( &#!,#>&K ME%5!F#&HH >,# M& 2MF,%#&K M1 %#F&5E,F%2# D-,#,E ,#K F=%HF&K HFE">F"E& %#F2
2#& D2-1@&E;
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ACS Paragon Plus Environment

Journal of the American Chemical Society
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ACS Paragon Plus Environment

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Journal of the American Chemical Society
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F!& %# L%FE2 8-"2E&H>&#>& %@,5%#5; :2 &#K2= &X>&--&#F =,F&E K%HD&EH%F1( DIV9T^ =,H 82E@"-,F&K %#F2 IYH
F!E2"5! F!& #,#2DE&>%D%F,F%2# @&F!2K M1 F!& ,HH%HF,#>& 28 ,@D!%D!%-%> D2-1@&E A YJTYJ\dQQQ _f%5"E& ^,`;
:!& K1#,@%> -%5!F H>,FF&E%#5 ,#K FE,#H@%HH%2# &-&>FE2# @%>E2H>2D1 E&H"-FH H"55&HF&K , !1KE2K1#,@%>
K%,@&F&E 28 hSQQ #@ 82E HD!&E%>,- DIV9T^ IYH _f%5"E& ]`; :!& DIV9T^ IYH H!2=&K , F1D%>,- IV9TV
,MH2EDF%2# ,F RZQ #@ =%F! , F,%- &XF&#K%#5 F2 WQQ #@( =!%>! >2"-K D&#&FE,F& @">! K&&D&E F%HH"&H ,#K FE%55&E
-&HH D!2F2K,@,5& _f%5"E& ^M`; .# F!& 2F!&E !,#K( F!& &@%HH%2# DE28%-& 28 DIV9T^ IYH =,H @,X%@%U&K ,F
hSQ^Q #@( =%F! ,# 2ML%2"H F,%- HFE&F>!%#5 F2 S^QQ #@( =!%>! H!2=&K D2F&#F%,- 82E IV9TVV, M%2%@,5%#5; :2
K&@2#HFE,F& F!& ,KL,#F,5&H 28 IV9TVV, %@,5%#5( DIV9TP IYH =%F! IV9TV &@%HH%2# _WdZ #@` ,#K #&5-%5%M-&
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IYH _f%5"E& R`( DE2L%K%#5 , D-,F82E@ 82E c",#F%F,F%L& ,#,-1H%H; N2E&2L&E( DIV9T^ IYH K%HD-,1&K &X>&--&#F
D!2F2HF,M%-%F1( =!%>! =,H 28 L%F,- %@D2EF,#>& 82E DE,>F%>,- ,DD-%>,F%2#H _f%5"E& [`;
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:2 %#L&HF%5,F& F!& 8&,H%M%-%F1 28 DIV9T^ IYH ,H IV9TVV, DE2M& %# L%L2( F!& %@,5&H 28 F!& @2"H& ME,%#
,#K !%#K-%@M L,H>"-,F"E&H =&E& @2#%F2E&K M1 %#FE,L&#2"H %#$&>F%2# _f%5"E& Z,`; V# >2#FE,HF F2 H!,ED&E ,#K
!%5!&E E&H2-"F%2# %@,5&H K&F&>F&K %# F!& IV9TVV, E&5%2# _SPSW #@ 'Y`( F!& L,H>"-,F"E&H -223&K M-"EE1 %#
F!& IV9TVV E&5%2# _SQQQ #@ 'Y`( K&@2#HFE,F%#5 F!& @&E%F 28 IV9TVV, %@,5%#5; VF H!2"-K M& #2F&K F!,F DIV9T
^ IYH >,##2F D&#&FE,F& F!& M-22KTME,%#TM,EE%&E ,>>2EK%#5 F2 F!&%E F%HH"& K%HFE%M"F%2# _f%5"E& W`; IV9TVV,
%@,5%#5 =%F! DIV9TP IYH DE2L%K&K F!& %#82E@,F%2# 28 @,%# L&HH&-H F!,F =&E& !,EK F2 K%H>&E# _f%5"E& ZM`;
V# >2#FE,HF( K&F,%-&K H@,-- >,D%--,E%&H >2"-K M& H&&# M1 DIV9T^ IYH %# F!& IV9TVV, E&5%2# =%F! !%5! >-,E%F1(
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FE,K%F%2#,- IV9TVV %@,5%#5;
ACS Paragon Plus Environment

Journal of the American Chemical Society
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ACS Paragon Plus Environment

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Journal of the American Chemical Society
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DIV9^TYAJ IYH ,F F"@2E H%F&H _f%5"E& SS`;]d :2 >2#8%E@ F!& D+TE&HD2#H%L&#&HH 28 DIV9^TYAJ IYH(
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%F >,# M& L%H",-%U&K M1 , >2#82>,- @%>E2H>2D&; A8F&E , d ! %#>"M,F%2# =%F! YJ\ IYH ,#K YAJ IYH ,F D+
R;^ ,#K ];Z( E&HD&>F%L&-1( , ME%5!F&HF E&K H%5#,- =,H K&F&>F&K %# F!& +&D\d >&--H %#>"M,F&K =%F! YAJ IYH
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D2H%F%L&-1T>!,E5&K IYH ,F D+ j ];Z =%-- HFE&#5F!&# F!&%E %#F&E,>F%2# =%F! F"@2E >&--H ,#K &#!,#>& F"@2E
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F!,F 28 DIV9^TYJ\ IYH %# H"M>"F,#&2"H F"@2ETM&,E%#5 @%>& _f%5"E& SR`; :!&E&82E&( F!& DIV9^TYAJ IYH
F!,F >,# M& ,>F%L,F&K F2 M& D2H%F%L&-1 >!,E5&K %# F"@2E @%>E2&#L%E2#@&#F =&E& %#F&E#,-%U&K &88%>%&#F-1 M1
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Y&E%F2#&,- >,E>%#2@,F2H%H %H "H",--1 E&-,F&K =%F! , -2= 2L&E,-- H"EL%L,- E,F& ,#K %FH DE&2D&E,F%L&
,HH&HH@&#F ,#K %#FE,2D&E,F%L& %@,5%#5 ,E& L&E1 >!,--&#5%#5 K"& F2 F!& K%HD&EH%2# 28 -,E5& ,@2"#FH 28 F"@2E
#2K"-&H =%F! K%,@&F&EH qS @@ H>,FF&E&K %# F!& D&E%F2#&,- >,L%F1;]PT]^ :!&H& F%#1 F"@2E #2K"-&H F!,F ,E& !,EK
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>,E>%#2@,F2H%HTM&,E%#5 @%>& F2 ,HH&HH =!&F!&E DIV9^TYAJ IYH >,# ,HH%HF F!& H"E5%>,- K%H>E%@%#,F%2# ,#K
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Journal of the American Chemical Society
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Journal of the American Chemical Society
Page 18 of 19
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ACS Paragon Plus Environment

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Journal of the American Chemical Society
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ACS Paragon Plus Environment