Synergistic chemiluminescence nanoprobe: Au clusters-Cu2+-induced chemiexcitation of cyclic peroxides and resonance energy transfer

Article abstract of DOI:10.1039/d0cc00313a

An interesting chemiluminescence (CL) phenomenon of cyclic peroxides originating from tetrahydrofuran hydrogen peroxide (THF-HPO) in the presence of BSA-stabilized Au NCs (Au?BSA NCs) was found for the first time. In this CL system, Au?BSA NCs can greatly accelerate the decomposition of THF-HPO, and then chemiluminescence resonance energy transfer (CRET) occurs between excited dioxetane derivatives and the Au?BSA NCs, yielding enhanced CL emission which can be further enhanced more than 10 times by the addition of copper ions. Based on this, a synergistic CL nanoprobe with a special signal amplification strategy was developed.

Full text of DOI:10.1039/d0cc00313a

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Synergistic chemiluminescence nanoprobe: Au clusters-Cu2+-
induced chemiexcitation of cyclic peroxides and resonance energy
transfer
Received 00th January 20xx,
Accepted 00th January 20xx
Kexin Zhang,a Mingxia Sun, b Hongjie Song,a Yingying Sub and Yi Lv* ab
DOI: 10.1039/x0xx00000x
An interesting chemiluminescence (CL) phenomenon of cyclic become an intractable problem.7 In this case, nanomaterials
peroxides originated from Tetrahydrofuran hydrogen peroxide and semiconducting polymer dots are currently attracting
(THF-HPO) in the presence of BSA-stabilized Au NCs (Au@BSA NCs) considerable attention as an excellent candidate in CRET
was found for the first time. In this CL system, Au@BSA NCs can process.8
greatly accelerate the decomposition of THF-HPO, and then
Nanoclusters, designed with the protection groups, has large
chemiluminescence resonance energy transfer (CRET) occurs specific surface area and extraordinary optical property.
between excited dioxetane derivatives and Au@BSA NCs, yielding Accordingly, nanoclusters is regarded as an excellent enzymatic
enhanced CL emission which can be futher enhanced more than 10 catalyst and luminophore to amplify the CL and imaging.9 Lin's
times by the adding of copper ions. Based on this, a synergistic CL group observed a significantly enhancement induced by the
nanoprobe with
developed.
a
special signal amplification strategy was catalysis and unique the surface plasmon coupled of
Zn/Cu@BSA NCs in the NaHCO3-H2O2 system.10 Lu's group
exploited Au NCs as CL luminophores in the Bis(2,4,6-
Chemiluminescence (CL), deriving from chemiexcitation process trichlorophenyl) Oxalate (TCPO)-H2O2 system, which exhibited a
in special chemical reaction, has been an attractive topic of remarkable enhancement due to the aggregation.11 Taking into
intensive research due to its extremely low background signal. account these merits of nanoclusters, a novel nanoclusters
However, for diverse analytical applications, improving based CL system with greatly signal amplification can be
sensitivity and stability of CL is still an ongoing challenge.1 Thus, developed by coalescing the above effects. Herein, we reported
nanoparticle-assisted novel CL system2 and signal amplification Au clusters-induced synergistic enhanced chemiluminescence
technique3 have become growing areas of interest in recent nanoprobe with a double signal amplification strategy. Firstly,
years because of their powerful contribution to the excellent BSA-stabilized Au NCs could greatly promote the
sensitivity and stability for CL methods.
chemiexcitation of cyclic peroxides which were produced from
A cyclic peroxide species, an unstable unit, subsequently the decomposition of Tetrahydrofuran hydrogen peroxide (THF-
forms intermediate with high energy, which emits blue light.4 HPO).12 Simultaneously, with the large Stokes shifts and greatly
Furthermore, as a source of excited products, cyclic peroxide energy-transfer efficiency of Au@BSA NCs, CRET occurred
species can tune the emission color by energy transfer to between excited dioxetane derivatives and Au@BSA NCs,
suitable acceptor and induce CL amplification. Based on this, yielding enhanced CL emission. Surprisingly, it was further
Shabat and his coworkers developed a kind of dioxetane − enhanced by copper ions.
fluorogenic dye conjugates which was successfully applied to
The Au@BSA NCs was synthesized via a facile method as
bioimaging.5 Afterwards, stimuli-responsive self-immolative reported. As shown in Fig. S1, the optical spectrum, XPS, Fourier
polymers which innately assimilated chemiexcitation in a transform infrared (FTIR), and far-UV circular dichroism (CD)
domino-like fragmentation to produce amplified CL was analysis strongly suggested the formation of Au@BSA NCs,
developed by them.6 Unfortunately, most of the cyclic peroxide which were accordant with the previously reported results.13
based CL probes need complex synthesis due to instability.
A new CL phenomenon was illustrated in Fig. 1A, upon
More importantly, due to aggregation-caused CL quenching and injecting Au@BSA NCs solution into THF solution containing
small Stokes shift, fluorescent dyes as CL energy acceptors THF-HPO, without any external light excitation, an evident
luminescence signal was obtained, and the intensity was
pronouncedly intensified more than ten times when adding
copper ions. Interestingly, the signal peak was rapidly produced
in several seconds until it reached a maximum value, and the
emission could last for a long time over 600 s (Fig. 1B).
Meanwhile, the CL of the above mixture system was dependent
a. Key Laboratory of Green Chemistry & Technology, Ministry of Education, College
of chemistry, Sichuan university, Chengdu, Sichuan, 610064, China.
b. Analytical & Testing Center, Sichuan University, Chengdu 610064, China. E-mail:
lvy@scu.edu.cn; Fax: +86-28-85412798; Tel: +86-28-85412798.
†Electronic Supplementary Information (ESI) available: Preparation methods,
spectrum and analytical performance. See DOI: 10.1039/x0xx00000x
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DOI: 10.1039/D0CC00313A
Fig. 1 (A)Replicate CL signals of the THF- Au@BSA NCs–Cu2+ (blank), THF-HPO - Cu2+
(red),and THF-HPO -BSA–Cu2+(blue curve), THF-HPO- Au@BSA NCs ( dark green curve)
and THF-HPO - Au@BSA NCs–Cu2+ (purple curve) systems. (B)Kinetic curves of CL of THF-
HPO - Au@BSA NCs and THF-HPO- Au@BSA NCs–Cu2+ systems. The inset of (B) displayed
the CL spectrum of the above systems. (C) The CL signals of THF-HPO with different kinds
of gold nanoparticles. The inset of (C) was the FL spectrum of gold nanoparticles. (D) XPS
spectra of Au 4f for Au@BSA NCs after the reaction with THF-HPO. The insert of (D) was
the XPS spectra of Au@BSA NCs before the reaction.
Fig. 2 Evaluation of •OH and 1O2 production in the CL reactions. (A and C) ESR spectra
and the absorbance of DPBF to study the 1O2 generated in the Au@BSA NCs-THF-HPO
and Au@BSA NCs-THF-HPO-Cu2+ system. (B) Effects of thiourea as •OH scavenger on the
Au@BSA NCs-THF-HPO-Cu2+ system. The insert of(B) is the ESR spectra of •OH generated
in the CL systems. (D) MB trapping measurements of •OH generated in the Au@BSA NCs-
THF-HPO and Au@BSA NCs- THF-HPO -Cu2+ system. Conditions: DMPO 50 mM, TEMP 100
mM, DPBF 5 mg L-1, MB 5 mg L-1, Au@BSA NCs 0.04 mM, THF-HPO 1 mM, Cu2+ 2×10-4
M.
of pH (Fig. S3D). It suggested that this system had a highest CL Fig.S3B. These results seemed to be consistent with the
in acidic condition (pH=2). Under the same condition, a control previous reports.14 Simultaneously, the decreased fluorescence
experiment was performed. As shown in Fig. 1A, THF-HPO-Cu2+ intensity of the Au@BSA NCs after reacting with THF-HPO, and
and BSA-THF-HPO-Cu2+ systems both have an ultra-weak CL, X-ray photoelectron spectroscopy data all indicated that the Au
Au@BSA NCs-THF-Cu2+ has almost no CL signal compared with centers was oxidized. As shown in Fig. 1D, in the presence of the
Au@BSA NCs-THF-HPO-Cu2+ system. Meanwhile, no similar CL THF-HPO, the ratio of the Au4f7/2 peaks at 85.0 eV and 84.0 eV,
signal was recorded when gold nanoparticles with different which corresponded to Au (1) and Au (0), was increased than
active sites and FL intensity (Fig.1C). All these results indicated that of original Au nanoclusters.15 All of these characteristic
that Au@BSA NCs and THF-HPO played important roles in the results indicated that there was an oxidation reaction between
CL phenomenon. This conclusion could also be demonstrated by the Au@BSA NCs and THF-HPO.
altering the mixing orders of reagents (Fig. S2A). The highest CL
Generally, the active oxygen radicals were easily produced
intensity created with the injection of the mixture of Au@BSA from the unstable peroxides in the presence of Au
NCs and Cu2+ into THF-HPO by contrast to that the lowest CL nanoparticles.16 According to the previous reports, we
intensity was detected after adding Cu2+ to the mixture of THF- wondered whether the CL phenomenon was induced from the
HPO and Au@BSA NCs, and a slight weaker signal was obtained reactive oxygen species. Firstly, the relations between dissolved
when Cu2+ was added before Au@BSA NCs into THF-HPO. oxygen and the CL reaction was investigated. The solution of CL
Subsequently, we measured the CL wavelength of Au@BSA system was bubbled with N2 or O2 for 30 min before the CL
NCs-THF-HPO and Au@BSA NCs-Cu2+-THF-HPO systems by a reaction, respectively, Fig. S4 showed there was slightly
fluorescence spectrophotometer with the excitation lamp was decreased after bubbled with O2, which reflected that the
off. As shown in the insert of Fig. 1B, there was only one peak dissolved oxygen did not implicated the CL emission. Then, we
and the maximum emission was located at 650 nm, which was studied the effects of different active oxygen radical scavengers
overlapped with the FL spectrum of the Au@BSA NCs. The on the CL emission.17 As shown in Fig. S5, the CL intensity
overlapping nature of the spectra confirmed that the reaction obviously decreased and even totally quenched when
of Au@BSA NCs-THF-HPO and Au@BSA NCs-Cu2+-THF-HPO eliminated 1O2 , •OH, and •O2 , respectively. Likewise, electron
−
system could generate excited-state Au@BSA NCs.
spin resonance (ESR) spectroscopy and UV-vis absorption were
To elucidate the influence of Au@BSA NCs on CL reaction, the employed to investigate whether or not there were1O2 and •OH
optical properties and morphology of Au@BSA NCs after the CL radicals in this CL system. 2,2,6,6-Tetramethyl-4-Piperidoe
process (Fig. S3) were investigated. The UV-vis absorption (TEMP) and 1,3-diphenylisobenzofuran (DPBF) were usually
spectrum was measured to identify the conformational used to verify the existence of 1O2.18 TEMP could capture 1O2 to
behavior of BSA in Au NCs after CL reaction, which showed that generate nitroxide radical (TEMPO), which has a typical
there was an evident change in absorption intensity in system. spectrum. According to Fig. 2A, there were significant ESR
The same result was also confirmed by the DLS measures in
signals corresponding to TEMPO in the Au@BSA NCs-THF-HPO
and Au@BSA NCs-THF-HPO-Cu2+ system. Moreover, the
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increasing intensity of TEMPO verified that more 1O2 were obtained when 1O2 was introduced into Au@BSA NCs-Cu2+
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2+
produced when adding Cu2+ in the CL system. This was possibly system, but the same phenomenon arose from BSA-Cu . From
DOI: 10.1039/D0CC00313A
−
because Cu2+ could easily promote the formation of •O2 , and the above, the proposed system exhibited no emission with
-
1
•O2 was unstable in aqueous solution to convert to O2. DPBF individual free radicals. Besides, the CL signal of Au@BSA NCs in
could react with 1O2 undergoing a Diels-Alder 1,4-cycloaddition, the existence of •OH mixed with •O2 was studied. In the
−
which was used as probe molecule to identify 1O2 generated in control system, H2O2, ONOO- and tert-Butyl hydroperoxide
the CL process.19 From the UV-vis analysis (Fig. 2C), a strong (TBHP) were performed as a source of •OH and •O2 . The
−
−
absorption peak around 410 nm, ascribed to the unique existence of •O2 and •OH radicals in these reactions were
absorption of DPBF, was observed when adding DPBF into the monitored by the UV - vis absorption. The results pointed out
Au@BSA NCs-THF-HPO and Au@BSA NCs-THF-HPO-Cu2+ that the similar equivalent of radicals was generated in these
system. And it was consistent with the results of EPR that the systems (Fig. S6). Unfortunately, no similar CL curve was
increasing absorption peak at 410 nm in the presence of detected after adding Au@BSA NCs into the above peroxides,
Au@BSA NCs. At the same time, thiourea as a frequently •OH which firmly illustrated that the commonly radicals could not
radical inhibitor was added into the CL system, and the CL induce Au@BSA NCs emitted and the CL emission could not be
intensity even totally quenched (Fig. 2B). In particular, due to derived from the electron-hole recombination CL process.
the super oxidation capacity of THF-HPO, the strong 1:1:1 triplet
Based on the previous reports, peroxides can oxidize any
signal assigned to the oxidation peak of DMPO was clearly tryptophan metabolites to produce an emission species with
displayed in the insert of Fig.2B. The generation of •OH was also the CL peak centered at 558 nm.10 In the view of such results,
affirmed by spectrophotometry when methylene blue was we speculated chemiluminescence resonance energy transfer
served as indicator.20 When methylene blue reacted with •OH might occur a from the tryptophan residue luminophore to the
to form hydroxylated methylene blue, the absorption peak at Au@BSA NCs receptors. Considering this possibility, various
620 nm was decreased in the CL system (Fig. 2D). Therefore, the oxidizing agents instead of THF-HPO applied in the CL reaction
1
above experiments proved that •OH and O2 were present in were investigated. However, very weak emission was recorded
this CL system and had an important effect on the CL emission. while other oxidizing agents were used in the presence of the
We further analyzed whether the active species trigged the Au@BSA NCs, depicted as in Fig. S7. Furthermore, the
CL reaction. As shown in Fig. 3A, the various active species synchronous fluorescence spectrum of tryptophan before and
1
−
including O2, •OH, •O2 , RO• and ClO− were used to confirm after CL reactions was monitored to substantiate the above. The
the speculation. However, no obvious signal could be initiated changes of tryptophan in the existence of H2O2 or THF-HPO
−
by •O2 , •OH or ClO−. The relatively obvious emission was
were displayed in Fig. S8, which implied that the similar
equivalent of tryptophan was consumed in the reactions and
could not occur the CRET. Interestingly, similar CL phenomena
were observed when Au@BSA NCs reacted with other ether
peroxides (Fig. S9). According to the above data, the CL system
might have special reactive intermediates which dominated the
CL emission.
In order to further study the probable mechanism of the CL
system, •O2− acted as the reactant for the THF-HPO with a static
injection system and the emitters were investigated using high-
energy cutoff filters. It could be seen from Fig. 3B that only one
peak at 425 nm was detected, which was identical to the
intermediate (C2O4*) of TCPO-H2O2 system.21 Surprisingly, it had
been reported that the 2,3-Dihydrofuran could react with 1O2 to
form the dioxetane derivatives, which decomposed to emit
around 420 nm.21, 22 Therefore, we presumed that the similar
emitters might generate in such CL system, and it further
happened CRET from the intermediate to the Au@BSA NCs. To
further verify the validity of CRET, we investigated the CL
emission of 2,3-Dihydrofuran-1O2-Au@BSA NCs. As expected,
this system enabled successful CRET. As illustrated in Fig. 3C,
upon adding only 0.4 μM Au@BSA NCs into the 2,3-
Dihydrofuran-1O2 system, an obviously increased CL intensity
was detected. The same result was obtained in the 1,4-
butyrolactone-1O2 system(Fig. 3D). In addition, HPLC and FT-IR
were applied to study the feature of the THF-HPO. After the CL
reaction, the obvious absorption peak at about 1780 cm-1
assigned to C=O was appeared in FT-IR, which indicated the
product had carbonyl groups. The similar phenomenon was
Fig. 3 (A) The CL intensity of Au@BSA NCs towards different kinds of ROS. (B) CL
spectra of THF-HPO-•O2− systems. The CL curve of (C) the 2,3-Dihydrofuran-1O2-
Au@BSA NCs and (D) 1,4-butyrolactone-1O2-Au@BSA NCs system. Conditions: H2O2 and
NaClO 10 mM, (C) Au@BSA NCs 0.4 μM, (D) Au@BSA NCs 4 μM.
Fig. 4 Proposed CL mechanism of the Au@BSA NCs-THF-HPO-Cu2+ system.
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verified by the GC-MS (Fig. S10C). At about 2.315 min and
12.563 min, peaks belonged to 2,3-Dihydrofuran and 1,4-
butyrolactone were observed, respectively. All data manifested
the Au@BSA NCs induced the dioxetane derivatives generation,
which further trigged CRET to amplification.
Notes and references
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On the basis of the above results, a proposed CL mechanism
was illustrated as described in Fig. 4. The active sites of Au@BSA
NCs promoted the decomposition of THF-HPO to generate •OH,
−
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simultaneously from the combination of •OH and •O2 . When
introducing Cu2+, Cu2+ cooperated with Au@BSA NCs and broke
up THF-HPO specifically to produce more •O2−,23 and unstable
•O2− in aqueous solution converted into 1O2. Then, 1O2 reacted
with 1,4-butyrolactone and 2,3-Dihydrofuran to produce the
excited dioxetane derivatives. Particularly, this special excited
intermediate was formed on the surface of Au@BSA NCs and
could trigger the highly efficient collision, which promoted the
decomposition and light emission at 425 nm. This process could
persistently generate excited intermediate. Meanwhile, the
emitters transfer energy to the Au@BSA NCs equipped with
prolong fluorescence to generated excited-state nanoclusters.
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nm was generated due to the energy release of excited-state
Au@BSA NCs (Fig. S11). Considering the superior analytical
performance of the CL system, we explored it as a CL probe for
the quantitative analysis of THF-HPO. The CL responses of the
proposed probe toward THF-HPO with different concentrations
were tested under the optimal conditions. As illustrated in Fig.
S12, there was linear correlation between the CL signals and the
concentration of THF-HPO from 500 nM to 20 μM and from 40
μM to 3.5 mM. The limit of detection (LOD) for THF-HPO was
37.71 nM (S/N = 3). Meanwhile, the CL response to Cu2+ was
examined in the CL system.
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Conclusions
In conclusion, we describe a synergistic chemiluminescence
phenomenon of Au@BSA NCs-Cu2+ and cyclic peroxides
originated from THF-HPO. First, Au@BSA NCs-Cu2+ was utilized
to stimulate the decomposition of ether peroxides to generate
excited dioxetane derivatives, accompanied by light emission.
Then CRET occurs between excited dioxetane derivatives and
Au@BSA NCs-Cu2+, yielding greatly enhanced CL emission. With
the special signal amplification strategy, a highly sensitive and
selective CL nanoprobe towards ether peroxides was
constructed. We postulate the special signal amplification
strategy could be extended to more CL systems to design new
nanoprobes with high sensitivity.
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The authors gratefully acknowledge financial support from the
National Natural Science Foundation of China (No. 21874094 &
21405107). We also thank Dr. Shuguang Yan in Analytical &
Testing Center of Sichuan University for technical assistance.
Conflicts of interest
There are no conflicts to declare.
22 H. M. A. N. Masakatsu Matsumoto, Chem. Commun., 1998,
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2018, 33, 1268-1274; N. S. A. S. Shinji MURAi, 1963, 36, 527-
530.
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Graphical Abstract
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