A new colorimetric and fluorescent probe with a large stokes shift for rapid and specific detection of biothiols and its application in living cells

Article abstract of DOI:10.1039/c7tb02323e

In this work, a new reversible colorimetric and fluorescent probe for sequential recognition of copper ions and biothiols is synthesized easily. Based on the chelation-enhanced fluorescence quenching (CHEQ) effect, this probe shows high sensitivity and selectivity towards Cu²⁺, which can be detected by the naked eye. And this experimental phenomenon can also be realised upon addition of biothiols, restoring their initial fluorescence intensity. This probe also features a very high response speed (less than 5 seconds) and a large stokes shift (178 nm) toward Cu²⁺ and biothiols. Moreover, the detection limit for Cu²⁺ and biothiols is as low as 7.34 nM and 10.3 nM, respectively. Additionally, this ON-OFF-ON-type fluorescence recognition cycle can be repeated more than 5 times by addition of Cu²⁺ and biothiols in turn. Particularly, this 1-Cu²⁺ ensemble is further successfully applied for GSH detection in living cells.

Full text of DOI:10.1039/c7tb02323e

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ISSN 2050-750X
PAPER
Guoping Chen et al.
Regulating the stemness of mesenchymal stem cells by tuning
micropattern features
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A new colorimetric and fluorescent probe with a large stokes shift
for rapid and specific detection of biothiols and its application in
livingcells
MengꢀZhaoZhanga,HaiꢀHaoHana,ShaoꢀZeZhangb, ChengꢀYunWanga,*,YunꢀXiangLub andWeiꢀ
HongZhua,*
Received 00th January 20xx,
Accepted 00th January20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
In this work, a new reversible colorimetric and fluorescent probe for sequential recognition of copper ions and biothiols is
synthesized easily. Based on the chelation–enhanced fluorescence quenching (CHEQ) effect, this probe shows high
sensitivity and selectivity towards Cu2+, which can be detected by naked eyes. And this experimental phenomenon can be
recovered upon addition of biothiols, restoring its initial fluorescence intensity. This probe also features a very high response
speed (less than 5 seconds) and a large stokes shift (178 nm) toward Cu2+ and biothiols. Moreover, the detection limit for
Cu2+ and biothiols are as low as 7.34 nM and 10.3 nM, respec8vely. Addi8onally, this ON−OFF−ON–type fluorescence
recognition circle can be repeated more than 5 times by addition of Cu2+ and biothiols in turn. Particularly, this 1−Cu2+
ensemble is further successfully applied for GSH detection in living cells.
sensitivity, selectivity, simplicity and realꢀtime detection.[22ꢀ26] To
date, a number of fluorescent probes have been developed for
distinguishing biothiols from other amino acids. These probes are
Introduction
Biological thiols, such as glutathione (GSH), cysteine (Cys) and
homocysteine (Hcy), play critical roles in physiological and
pathological processes.[1ꢀ5] While abnormal levels of these biothiols
have been shown to be associated with various human diseases.[6] For
example, elevated Cys is known to be associated with many
syndromes such as retarded growth, hair depigmentation edema,
lethargy and liver damage[7]; elevated Hcy might cause Alzheimer's,
cardiovascular diseases, neural tube effect, inflammatory bowel
disease, and osteoporosis.[8] Specifically, GSH is the most abundant
cellular thiol, it plays an essential role in maintaining biological redox
homeostasis.[9,10] In light of the aforementioned examples, efficient
monitoring of biothiols in live cells is crucial for identifying abnormal
biological processes and risk towards diseases.[11] Therefore, an
efficient method for selective discrimination of biothiols in biological
systems is urgently required for better physiological and pathological
analysis and early diagnostics.[12]
mainly based on five types of reactions: (1) cleavage of
sulfonamide/sulfonate ester by biothiols[27,28]
(2) Michael
;
addition[29,30]; (3) cyclization with aldehyde[31,32]; (4) cleavage of
disulfide by thiols[33ꢀ35]; (5) intramolecular elimination[36,37]. To best
of our knowledge, most organic reaction based fluorescent probes
suffered two main shortages: required strictly conditions and time–
consuming, thus limited the application of theseprobes.[38]
Due to its excellent features in donorꢀπꢀacceptor (DꢀπꢀA) structure,
near infrared emission wavelength and large Stokes shift[39,40]
,
dicyanoisophorone based dyes are well known in Dyeꢀsensitized solar
cells[41,42] and organic nonlinear optical crystals[43ꢀ45]. Our group had
longꢀstanding exploration for the synthesis and application of this
kind of fluorescence materials.[23] In this work, we synthesized a new
biothiols fluorescence probe (Compound 1) based on
dicyanoisophorone fluorescent dye (Scheme 1). As expected,
Compound 1 could coordinated with Cu2+ through hydroxyl group to
form 1–Cu2+ and the subsequent complex 1–Cu2+ could be developed
as a platform for biothiols real–time detection. This probe exhibited
excellent sensing properties, high sensitivity and selectivity for
biothiols with remarkable fluorescence enhancement and a large
Stokes shift (λem – λabs = 178 nm). Additionally, the potential utility of
this ON−OFF−ON and colorimetric fluorescence probe was
successfully used to detect biothiols in living cells.
Some methods have been attempted to discriminate biothiols, such
as high–performance liquid chromatography (HPLC)[13], UV–vis
absorption spectrophotometry[14]
,
capillary electrophoresis[15]
,
potentiometry[16] mass spectrometry (MS)[17] and fluorescent
,
technique[18–21]. Among these various analytical methods that are
available, fluorescent probes possess innate advantages owing to its
a.Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of
Chenmistry and Malecular Engineering, East China University of Science and
Technology, 130 Meilong Road, Shanghai 200237, PR China. Eꢀmail:
Experimental
cywang@ecust.edu.cn (CꢀY Wang); whzhu@ecust.edu.cn (WꢀH Zhu).
Synthesis of Compound 2
b. Department of Chemistry, School of Chemistry and Molecular Engineering, East
China University of Science & Technology, 130 Meilong Road, Shanghai 200237,
3,5,5ꢀTrimethylꢀ2ꢀcyclohexenꢀ1ꢀone (3.0 g, 21.7 mmol),
malononitrile (1.72 g, 26.0 mmol) and piperidine (0.3 g, 2.9 mmol)
were dissolved in absolute EtOH (50.0 mL). The mixture was heated
P.
R.
China.
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
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at 90 °C for 13 h under N2 atmosphere. After the mixture was cooled stained with Hoechst 33342 (5 ꢁg mL–1) at 37 °C for 5 min. Then,
and the solvent was removed, then the residue was dissolved in cells were washed with PBS (phosphate buffered saline) three times,
CH2Cl2, washed with water, and dried over Na2SO4. Finally, the recorded using an Operetta high content imaging system (Perkinelmer,
solvent was concentrated by rotary evaporation to obtain the raw US) at an excitation wavelength of 460–490 nm and an emission
product, which was purified by silica chromatography wavelength of 560–630 nm, quantified and plotted by columbus
(Petroleum/Ethyl acetate = 3/1) (2.88 g, 61%, Mp: 73ꢀ75 °C). 1H–
NMR (400 MHz, CDCl3): δ = 6.62(s, 1H), 2.52 (s, 2H), 2.18 (s, 2H),
2.03 (s, 3H), 1.00 (s, 6H) (Fig. S1). 13C–NMR (100 MHz, CDCl3): δ
= 170.24, 156.72, 147.93, 145.56, 138.74, 127.64, 126.16, 121.25,
120.95, 115.80, 114.71, 114.17, 113.31, 74.54, 42.30, 38.16, 31.63,
27.41. (Fig. S2).
analysis system (Perkinelmer, US).
Cell viabilityassay
The HepG2 cells were cultured according to previously report.[48]
Briefly, the cells were plated on 96–well plates at 8000 cells per well
in growth medium. The cells were incubating for 24 h upon addition
of 100 ꢁL of serum–free DMEM to 10 ꢁL per well of MTS/PMS (20:1,
Promega Corp) solution. After incubation at 37 °C under 5% CO2 for
2ꢀ4 h, the absorbance was recorded at 490 nm by M5 microplate
reader (Molecular Device, USA).
Synthesis of Compound 1
Compound 2 (500 mg, 2.7 mmol), 3,4–dihydroxybenzaldehyde
(320 mg, 2.7 mmol) and five drops of piperidine were dissolved in 30
mL of acetonitrile. The mixture was heated to reflux for 9 h under N2
atmosphere, and the solvent was removed by rotary evaporation. The
resulting residue was dissolved in dichloromethane, then washed with
water and dried over anhydrous MgSO4. The crude product was
purified by silica chromatography (eluted with Petroleum/Ethyl
acetate = 5/2, v/v) to afford an orange solid (610 mg, 77% yield, Mp:
186ꢀ188 °C). 1H NMR (400 MHz, DMSO–d6): δ = 9.61 (s, 1H), 9.08
(s, 1H), 7.13 (m, 3H), 7.03 (d, J =8 Hz, 1H), 6.80 (s, 1H), 6.75 (d, J=
8 Hz, 2H), 2.60 (s, 2H), 2.52 (s, 2H), 1.01 (s, 6H). (Fig. S3) 13C NMR
(100 MHz, d6–DMSO, Me4Si) δ (ppm) 170.24, 156.32, 147.92,
145.57, 138.74, 127.65, 126.17, 121.26, 120.95, 115.81, 114.71,
114.17, 113.31, 74.55, 42.31, 38.17, 31.63, 21.42. (Fig. S4)ESI–MS:
calculated [C19H18N52O2 –H]+ 305.1290; found 305.1287 (Fig. S5).
Resultanddiscussion
Synthesis route
This probe was easily synthesized with high yields in two steps
(Scheme 1), the detailed characterization dates were presented in the
Supporting information.
Absorption and emission properties about Compound 1 and Cu2+
Fig. 1 showed the absorbance and fluorescence spectra of
Compound 1 upon addition of Cu2+ in HEPES bu er solution
(containing 10% DMSO, pH = 7.4, 50 mM). Compound 1 showed
intense absorption band centered around 429 nm (ε = 2.3 × 104 M–1
cm–1, Φa = 0.062, Table S2) and strong emission peak centered around
607 nm (Fig. 1A and 1B). After addition of Cu2+ (20 ꢁM) lead to a
decrease in absorption band at 429 nm, at the same time, a new growth
of absorbance band at 505 nm formed (ε = 1.6 × 104 M–1cm–1, Φa =
0.012, ꢂλabs = 76 nm, Table S2). Additionally, a considerable color
change from yellow to pink was obvious to be detected by the naked
eyes. This could be explained by the stabilization of charge in the
excited state after the formation of 1–Cu2+ complex which enhanced
the ICT mechanism and gave a red shift.[42] At the same time, the
fluorescence emission band at 607 nm decreased sharply (Fig. 1B).
What’s more, both absorbance and fluorescence spectra kept stable
within 5 s, which was much faster than most of the previous reports
(Fig. S6, Table S1).
To further evaluate the Cu2+–responsive sensitivity of Compound 1,
the fluorescence titration experiments in HEPES bu er solution
(containing 10% DMSO, pH = 7.4, 50 mM) was investigated. The
absorbance ratio A505/A429 before adding Cu2+ was 0.13, however it
was increased to 2.06 when the concentration of Cu2+ was 20 ꢁM (Fig.
2). And the fluorescence intensity at 607 nm before adding Cu2+ was
737.26, but it was decreased to 69.69 when the concentration of Cu2+
was 20 ꢁM (quenching e ciency (I0 – I)/I0 × 100% = 90.6%). The
corresponding signal to background ratio of absorbance and
fluorescence spectra were calculated to be 15.85 and 32.68,
Characterization
All chemical reagents and solvents were analytical grade and
purchased from commercial suppliers.1H NMR and 13C NMRspectra
were collect in CDCl3 and DMSO–d6 on Bruker AM400 NMR
spectrometer. HRMS spectra analyses were carried out with Waters
LCT Premier XE spectrometer. Absorption spectra was recorded on a
Varian Cary 500 spectrophotometer, and fluorescence spectra was
performed on F97profluorospectrophotometer.
DFT calculations
At the method level of B3LYP/cc–Pvdz, the geometries of the
isolated molecule and coordination complex were fully
optimized.[47,48] No symmetry or geometry constraint was imposed
during the optimizations. Frequency calculations were implemented
at the same theoretical levels to corroborate that all the structures were
genuine minima on the potential energy surface. Then, the molecular
orbital analyses were performed by Multiwfn program.[49,50] The
color–filled isosurfaces of highest occupied molecular orbitals
(HOMOs) and lowest unoccupied molecular orbitals (LUMOs) were
visualized by means of the VMD package.
Cell culture
HepG2 was incubated in a Dulbecco’s Modified Eagle’s Medium
(Invitrogen, Carlsbad, CA, USA) supplemented with 10% fetal bovine
serum (Gibco, Gland Island, NY, USA). The HepG2 cells were
cultured according to previously report.[51] Briefly, the cells were
incubated with Compound 1 for 15 min, then incubated with Cu2+ for
30 min, finally incubated GSH for 30 min. After that, the cells were
Scheme 1. Synthetic route of Compound 1
2
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results demonstrated that Compound 1 and 1–Cu2+ can be employed
to visualize Cu2+ and GSH in living cells, respectively.
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Conclusions
In summary, we have reported a new fluorescent probe basedon
the displacement approach, which showed significant change in the
absorbance (ꢂλabs = 76 nm) and emission spectral behavior in the
presence of copper ions in HEPES buffer. The probe showed high
sensitivity toward copper ions with a low detection limit (7.34 nM),
which served as an ON–OFF type probe. Complex formation of
Compound 1 and Cu2+ was confirmed by DFT calculation and binding
studies. The product of the 1–Cu2+ ensemble was an excellent probe
for biothiols and constructed an ON−OFF−ON−type fluorescence
detection system. Moreover, 1–Cu2+ showed a very high response
speed (lower than 5s), low detection limit (10.3 nM) and a large
Stokes shift (178 nm) toward biothiols. Additionally, this 1–Cu2+
ensemble had been applied to image GSH in living cells successfully.
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The authors are grateful to financial support from Natural Science
Foundation of Shanghai (No. 16ZR1408000), the National Key
Program of China (No. 2016YFA0200302) and the Fundamental
Research Funds for the Central Universities. And the authors would
like to thank Dr XiaoꢀPeng He for living cells experiment.
–
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Graphical Abstract:
A new colorimetric and fluorescent probe with a large stokes
shift for rapid and specific detection of biothiols and its
application in living cells