Fluorescent Recognition of 1,3-Diaminopropane in the Fluorous Phase – Greatly Enhanced Sensitivity and Selectivity

Article abstract of DOI:10.1002/ejoc.201701703

A 1,1′-binaphthyl-based dialdehyde, which is soluble in the fluorous phase, is synthesized. The fluorescence of this compound is greatly enhanced by 1,3-diaminopropane (DAP) in perfluorohexane (FC-72) but not by other amines and diamines. Thus, this compound can be used as a fluorescent sensor for the detection of the biologically important DAP at submicromolar concentrations. The selectivity and sensitivity of this fluorescent probe in this fluorous solvent are much greater than those in the common organic solvent dichloromethane.

Full text of DOI:10.1002/ejoc.201701703

DOI: 10.1002/ejoc.201701703
Full Paper
Fluorescent Sensors | Very Important Paper |
Fluorescent Recognition of 1,3-Diaminopropane in the Fluorous
Phase – Greatly Enhanced Sensitivity and Selectivity
Dan Shi,[a] Xinjing Wang,[a] Shanshan Yu,*[a] Feng Zhao,[a] Yachen Wang,[a] Jun Tian,[a]
Lingling Hu,[a] Xiaoqi Yu,*[a] and Lin Pu*[a,b]
Abstract: A 1,1′-binaphthyl-based dialdehyde, which is soluble the detection of the biologically important DAP at submicro-
in the fluorous phase, is synthesized. The fluorescence of this
compound is greatly enhanced by 1,3-diaminopropane (DAP) in
perfluorohexane (FC-72) but not by other amines and diamines.
Thus, this compound can be used as a fluorescent sensor for
molar concentrations. The selectivity and sensitivity of this fluo-
rescent probe in this fluorous solvent are much greater than
those in the common organic solvent dichloromethane.
Introduction
related with cell death and protection from cell stress.[7,8] Ow-
ing to the important roles of polyamines, a variety of methods
have been developed for their analysis. Fluorescence has been
investigated as a simple and effective real-time analytical
method for the detection of amines, diamines, and poly-
amines.[9] However, fluorescent sensors capable of discrimina-
ting various polyamine molecules are rare. Among the poly-
amines, DAP is the product of the oxidation of spermidine and
spermine by polyamine oxidases.[7] The selective fluorescent
recognition of DAP should provide a useful method to investi-
gate the biological functions of these polyamines. Recently, we
found that the fluorescence of certain aromatic aldehydes can
be enhanced by DAP because of the selective formation of six-
membered aminal rings.[10] In this paper, we report the synthe-
Perfluorocarbon-based molecules and structural units exhibit
unique hydrophobic and lipophobic properties as well as re-
markable affinities with each other, a property that is termed
fluorophilicity. In the past two decades, these properties of per-
fluorocarbon-based materials have been utilized to develop
new separation techniques.[1–3] For example, the fluorous bi-
phasic liquid–liquid extraction (F-LLE) and fluorous solid-phase
extraction (F-SPE) techniques have been conventionally used
for enrichment and purification in the synthesis of organic bio-
molecules.[4] Despite these developments, very little work has
been devoted to the application of fluorous chemistry in molec-
ular sensing.[5,6] In our laboratory, we are interested in the utili-
zation of fluorous-phase-based separation to develop fluores-
cent sensors for molecular recognition.[6] It is proposed that
fluorescence measurements conducted in the fluorous phase
could minimize the interference of other substances on the spe-
cific interactions between the sensors and their substrates; thus,
the sensitivity and selectivity of the sensor would be enhanced.
Polyamines such as 1,3-diaminopropane (DAP), putrescine
(1,4-diaminobutane), cadaverine (1,5-diaminopentane), sperm-
idine, and spermine are distributed widely in nature and are
present in all living organisms.[7,8] In biological systems, these
polyamines exist as protonated polycations and bind with DNA
and RNA. They are important for gene expression and also cor-
sis of
a perfluoroalkyl-substituted 1,1′-bi-2-naphthol-based
(BINOL-based) dialdehyde and its use for the fluorescent recog-
nition of DAP in the fluorous phase. We have demonstrated
that the fluorescent recognition of DAP in the fluorous phase
exhibits greatly increased sensitivity and selectivity over that in
a common organic solvent.
Results and Discussion
The BINOL-based aldehyde 1 is readily prepared from the
methoxymethyl-protected (S)-BINOL by ortho-metalation with
nBuLi followed by the addition of N,N-dimethylformamide
(DMF) and then acidic hydrolysis (Scheme 1).[11] It shows very
weak fluorescence and minimal fluorescence response toward
various primary amines and diamines in the absence of ZnII
ions.[12] This compound cannot be used directly for the fluores-
cent recognition of these substrates. The treatment of 1 with 3-
(perfluorooctyl)propyl iodide in the presence of K2CO3 in DMF
at 80 °C gave the dialkylated product 2 in 88 % yield.[13] The
two perfluoroalkyl units of 2 ensure that this compound is solu-
ble in perfluorohexane (FC-72). It is also soluble in common
organic solvents such as dichloromethane (DCM), methanol,
ethanol, tetrahydrofuran, and acetonitrile.
[a] Key Laboratory of Green Chemistry and Technology, Ministry of Education,
College of Chemistry,
Sichuan University, Chengdu, 610064, China
E-mail: xqyu@scu.edu.cn
yushanshan@scu.edu.cn
http://chem.scu.edu.cn/En/XiaoqiYu
http://chem.scu.edu.cn/En/ShanshanYu
[b] Department of Chemistry, University of Virginia,
McCormick Rd, Charlottesville VA 22904, USA
E-mail: lp6n@virginia.edu
http://chem.virginia.edu/faculty-research/faculty/lin-pu/
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under https://doi.org/10.1002/ejoc.201701703.
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In FC-72, the fluorescence of 2 is very weak (Figures 2 and
S1 in the Supporting Information). When 2 (1.0 × 10–5
M
) was
treated with 4–9 (2.0 × 10–4
M) in FC-72 (containing 3 % CH2Cl2
to dissolve the amines), it exhibited minimal fluorescence re-
sponse toward these primary, secondary, and tertiary mono-
amines (Figure 2a and b). Under the same conditions, the ali-
phatic 1,2-, 1,3-, 1,4-, and 1,5-diamines 10–13 were also added
to 2. Minimal fluorescence responses were observed except in
the presence of DAP (11), with which 2 showed greatly en-
hanced fluorescence at λ = 345 nm with I/I0 = 2343! In addition,
the fluorescence enhancement of 2 by DAP was mostly main-
tained even in the presence of other amines. As shown in Fig-
ure 2c and d, although the amines and diamines 4–10, 12, and
13 do not enhance the fluorescence of 2, their 1:1 mixtures
with DAP still greatly increased the fluorescence of 2. Thus, 2
exhibits very high sensitivity and selectivity for the fluorescent
recognition of DPA in the fluorous phase. We found that the
fluorescence enhancement of 2 reached saturation after 2 h
Scheme 1. Synthesis of 2.
We studied the interactions of 2 with the structurally diverse
amines listed in Figure 1, including the primary monoamines
4–7, the secondary amine 8, the tertiary amine 9, and the di-
amines 10–13.
Figure 1. Structures of the amines investigated.
Figure 2. (a) Fluorescence spectra of 2 (1.0 × 10–5
M
) in the presence of amines 4–13 (2.0 × 10–4
) with 20 equiv. of DAP mixed with 20 equiv. of other amines and diamines (4–13,
). (d) The fluorescence intensity ratio I345/I0 for 2 in the presence of 20 equiv. of DAP mixed with 20 equiv. of other amines and diamines (4–13,
). Reaction time: 3 h. Solvent: 3 % DCM/FC-72. λex = 290 nm. Slit widths: Ex/Em = 5 nm/5 nm.
M). (b) The fluorescence intensity ratio I345/I0 for 2 in the
presence of amines 4–13. (c) Fluorescence spectra of 2 (1.0 × 10–5
M
2.0 × 10–4
2.0 × 10–4
M
M
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Figure 3. (a) Fluorescence spectra of 2 (1.0 × 10–5
M
) in the presence of DAP at 0 to 3.0 × 10–4
M. (b) Plots of the fluorescence intensity I345 of 2 vs. DAP
concentration. Reaction time: 3 h. Solvent: 3 % DCM/FC-72. λex = 290 nm. Slit widths: Ex/Em = 5 nm/5 nm. The error bars were obtained with three
independent measurements.
with 20 equiv. of DAP and after 3 h with 5 equiv. of DAP (Fig-
ure S4).
The fluorescence spectra of 2 in the presence of 0 to
30 equiv. of DAP are shown in Figure 3, and the fluorescence
intensity at λ = 345 nm is plotted against the concentration
of DAP in Figure 3b. As shown in Figure 3b, the fluorescence
enhancement versus the concentration was greater when the
concentration of DAP was less than 8.0 × 10–5
when the concentration was greater than 8.0 × 10–5
Figure S2). The limit of detection (LOD) of 2 for DAP was found
to be 8.2 × 10–9
(see Figure S3).
The UV/Vis absorption spectrum of 2 (1.0 × 10–5
M
and decreased
(see also
M
M
Figure 4. UV/Vis absorption spectra of 2 in the presence of varying concentra-
tions of DAP in 3 % DCM/FC-72.
M
in FC-72)
is shown in Figure 4, and λmax (ε) = 245 (100900) and 290 nm
(13400). When 2 was titrated with DAP, the absorption at λ =
245 and 290 nm decreased, and a new absorption band ap- between the hydroxy and aldehyde groups of 1 that quenches
peared at λ = 224 nm. There are no isosbestic points in the its fluorescence.[14] When both compounds were treated with
spectra in Figure 4; therefore, multiple intermediates and prod- 20 equiv. of DAP, 2 exhibited fluorescence enhancement at λ =
ucts form.
We compared the fluorescence responses of 1 and 2 toward
amines in the common organic solvent dichloromethane. The
352 nm with I/I0 = 38, but little response was observed for 1
(Figure 5b).
The fluorescence responses of 2 toward other amines in di-
fluorescence spectra of 1 and 2 in dichloromethane are shown chloromethane are shown in Figure 6. Except for DAP and 10
in Figure 5a. Compound 2 shows weak emission at λ = 435 nm, (ethylenediamine, to a much smaller degree), most of the
and 1 only shows an extremely weak signal at λ = 352 nm. The amines (20 equiv.) did not cause much change to the fluores-
much lower fluorescence intensity of 1 relative to that of 2 cence of 2. A comparison of the fluorescence responses of 2 in
can be attributed to an excited-state proton-transfer process the fluorous phase (Figure 2) with those in dichloromethane
Figure 5. (a) Fluorescence spectra of 1 and 2 in CH2Cl2 (both at 1.0 × 10–5
M M) in the
). (b) Fluorescence spectra of 1 and 2 in CH2Cl2 (both at 1.0 × 10–5
presence of DAP (2.0 × 10–4
M). Reaction time: 3 h. λex = 290 nm. Slit widths: Ex/Em = 5 nm/5 nm.
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Figure 6. (a) The fluorescence intensity ratios I352/I0 for 2 in the presence of amines 4–13 (2.0 × 10–4
presence of amines 4–13 (2.0 × 10–4
M
). (b) Fluorescence spectra of 2 (1.0 × 10–5
M) in the
M
). Reaction time: 3 h. Solvent: dichloromethane. λex = 290 nm. Slit widths: Ex/Em = 5 nm/5 nm.
(Figure 6) demonstrates that the fluorescent recognition in the 14 in comparison with that of 1 is attributed to the stronger
fluorous phase has much greater sensitivity and selectivity.
To understand the dramatic difference in the fluorescence
responses of 1 and 2 toward DAP, we analyzed their reactions
intramolecular hydrogen bonding with the more basic imine
nitrogen atoms in 14. This is consistent with previous reports
for a similar macrocycle.[11a] When additional DAP was added,
as shown in Figure 7d–g, a new product with sharp signals
formed. The mass spectrum of the reaction mixture of 1 with
10 equiv. of DAP showed a signal at m/z = 455.239 (Figure S9),
which corresponds to the acyclic bisimine product 15 (calcd.
for [M + H]+ 455.244). The two sharp singlets at δ = 8.62 and
7.91 ppm in Figure 7g can be assigned to the imine protons
and 4,4′-binaphthyl protons of 15, respectively. The disappear-
ance of the signal at δ = 13.22 ppm could be attributed to
the fast exchange of the acidic protons catalyzed by the amine
groups.
1
with DAP through H NMR spectroscopy and mass spectrome-
try. As shown in Figure 7a–c, when 1 was treated with 1 equiv.
of DAP, its aldehyde signal at δ = 10.19 ppm disappeared com-
pletely. The mass spectrum of the reaction mixture of 1 with
1 equiv. of DAP showed a signal at m/z = 783.295 (Figure S8),
which corresponds to the macrocyclic structure 14 (calcd. For
[M + Na]+ 783.294) shown in Scheme 2. The formation of similar
macrocyclic structures was observed previously for the reac-
tions of 1 with diamines.[11a,15] The 1H NMR spectrum in Fig-
ure 7c shows a broad signal at δ = 8.62 ppm, which can be
assigned to the imine protons of 14. The broad 1H NMR signals
of 14 suggest that there should be slow interconversion be-
tween the various conformations of this macrocycle. A broad
downfield signal at δ = 13.22 ppm in Figure 7c can be assigned
to the intramolecularly hydrogen-bonded hydroxy protons in
14. The much more downfield signal of the hydroxy protons of
Scheme 2. Reaction of 1 with DAP.
The 1H NMR spectra of 2 in the presence of various amounts
of DAP are shown in Figure 8. As for the reaction of 1 with
1 equiv. of DAP, the treatment of 2 with 1 equiv. of DAP resulted
in a large reduction of the aldehyde signal (Figure 8c). The mass
spectrum of the reaction mixture of 2 with 1 equiv. of DAP
showed a signal at m/z = 2601.356 (Figure S7), which can be
assigned to macrocycle 16 (calcd. for [M + H]+ 2601.360). The
1H NMR signals of this macrocycle are much sharper than those
of 14. The broad signals of the macrocycle 14 could be attrib-
uted to its intramolecular hydrogen bonding, which could re-
strict the bond rotation and slow the interconversion of its vari-
Figure 7. 1H NMR spectra (CDCl3) of 1 with 0, 0.5, 1.0, 2.0, 3.0, 5.0, and
10.0 equiv. of DAP (the details of NMR sample preparation are provided in
the Supporting Information).
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ous conformations. In 16, however, there are no intramolecular sor toward DAP than a previously reported example, as it shows
hydrogen bonds like those in 14. That is, there should be much more than a 2000-fold fluorescence enhancement for 20 equiv.
faster interconversion between the various conformations of 16 of DAP.[10]
and, thus giving sharp 1H NMR signals. The singlet at δ =
In the reaction of 1 with DAP, the resulting product 15 does
8.78 ppm can be assigned to the imine protons of 16. The
further addition of DAP converted the macrocycle 16 to a major
product with a new peak at δ = 4.95 ppm (Figure 8d–g). This
signal suggests the formation of 17 with a six-membered
aminal ring, as shown in Scheme 3.[10] The mass spectrum of
the reaction mixture of 2 with 10 equiv. of DAP showed a signal
at m/z = 1375.360 (Figure S6), which corresponds to the major
product 17 (calcd. for [M +H]+ 1375.268).
not undergo cyclization to form a compound with a six-mem-
bered aminal ring like those in 17. This is attributed to the
enhanced stability of the imine structure of 15 owing to the
intramolecular hydrogen bonding between the hydroxy groups
and the imine nitrogen atoms. That is, 1 and 2 react with DAP
to give very different products; thus, their fluorescence re-
sponses are dramatically different.
We conducted density functional calculations on the molec-
ular structures of two analogs of 2 and 17 with the Spartan
program (ωB97X-D, 6-31G*), and the results are shown in Fig-
ures 9 and 10. The highest occupied molecular orbital (HOMO)
and lowest unoccupied molecular orbital (LUMO) of an analog
of 2 with methyl groups bound to the two central oxygen at-
oms instead of the long carbon chains are shown in Figure 9.
The HOMO is located on the methoxynaphthalene unit, but the
LUMO is extended to the aldehyde unit. These orbitals indicate
that 2 should form a charge-transfer state upon excitation ow-
ing to the electron-donating alkoxy group and the electron-
withdrawing aldehyde group. This charge-transfer transition
should be responsible for the quenching of the fluorescence of
the naphthalene ring of 2. As 2 is symmetric, the same HOMO
and LUMO are found for the upper naphthyl unit.
Figure 8. 1H NMR spectra (CDCl3) of 2 with 0, 0.5, 1.0, 2.0, 3.0, 5.0, and
10.0 equiv. of DAP (the details of the NMR sample preparation are in the
Supporting Information).
Figure 9. HOMO and LUMO of an analog of 2.
Scheme 3. Reaction of 2 with DAP.
Compounds 14 and 15 generated from the reaction of 1
with DAP are both expected to have very weak fluorescence
because of the imine units, as we demonstrated previously.[16]
This is consistent with the observed minimal fluorescence re-
sponse of 1 toward DAP. In the reaction of 2 with DAP, although
Figure 10. HOMO and LUMO of an analog of 17.
The HOMO and LUMO of an analog of 17 with methyl groups
the macrocycle 16 is also expected to show minimal fluores- bound to the two central oxygen atoms instead of the long
cence because of its imine bonds, the aminal product 17 should carbon chains are shown in Figure 10. If the aldehyde groups
contribute to the greatly enhanced fluorescence. Compound 2 of 2 are converted into the six-membered aminal rings of 17,
in the fluorous phase is a much more sensitive fluorescent sen- the LUMO and HOMO are both located on the naphthalene
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The DMF was removed by vacuum distillation, and the residue was
poured into cold water (10 mL). After acidification with concen-
trated HCl, the aqueous mixture was extracted with Et2O (3 ×
10 mL). The extracts were washed with water (2 × 20 mL) and dried
with MgSO4. The removal of the solvent in vacuo followed by the
purification of the residue by silica gel flash chromatography eluted
with dichloromethane/hexane (1:3) gave the product 2 as a white
solid in 87.7 % yield (309.9 mg). 1H NMR (400 MHz, CDCl3): δ =
10.46 (s, 2 H), 8.59 (s, 2 H), 8.08 (d, J = 8.2 Hz, 2 H), 7.53 (t, J =
7.5 Hz, 2 H), 7.44 (t, J = 7.6 Hz, 2 H), 7.21 (d, J = 8.4 Hz, 2 H), 3.98–
3.91 (m, 2 H), 3.55 (td, J = 8.6, 3.9 Hz, 2 H), 1.64 (m, 2 H), 1.53 (t, J =
13.1 Hz, 4 H), 1.25 (dd, J = 13.7, 10.2 Hz, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 188.5, 153.6, 135.6, 132.8, 129.4, 129.0, 128.9,
127.7, 125.4, 124.5, 107.2–117.0 (m), 72.9, 26.0 (t, JC,F = 22 Hz), 25.7,
19.8 ppm. 19F NMR (400 MHz, CDCl3): δ = –80.8 (3 F), –114.9 (2 F),
–122.0 (6 F), –122.8 (2 F), –123.5 (2 F), –126.1 (2 F) ppm. HRMS:
calcd. for C44H24F34O4Na [M + Na]+ 1285.1024; found 1285.1019.
[α]D = 4.001 (c = 1.0 mg/mL, CHCl3).
ring, and a charge-transfer state cannot be generated. Thus, the
fluorescence of the naphthalene unit is turned on.
As shown in Figure 5, when 2 was treated with 20 equiv. of
DAP in dichloromethane, two emission signals were observed
at λ = 435 and 352 nm. The long-wavelength emission at
435 nm can be attributed to the charge-transfer state of 2, and
the short-wavelength emission at λ = 352 nm can be attributed
to the naphthalene unit. As shown in Figure 5a, in the absence
of DAP, only the emission of the charge-transfer state of 2 was
observed. However, in the fluorous solvent, 2 did not show the
long-wavelength emission in the absence or presence of DAP
(Figures 2 and S1). That is, the charge-transfer state of 2 cannot
undergo irradiative decay in the fluorous solvent; thus the fluo-
rescence sensitivity of 2 toward DAP in the fluorous phase is
greatly increased relative to that in dichloromethane.
Preparation of the Samples for the Fluorescence Measurement
of 1 and 2 in the Presence of the Diamines and Monoamines:
Conclusions
Stock solutions of 1.0 m
prepared for each measurement. For the fluorescence enhancement
study, solutions of 1 or 2 (10–5
, 1.0 mL) were mixed with various
solutions of the di- or monoamine (10.0 m in CH2Cl2) in 10.0 mL
test tubes. The resulting solutions were left at room temperature
for 3 h, and the fluorescence spectra were recorded within 2 h.
M
1 (in CH2Cl2) and 2 (in FC-72) were freshly
We have discovered the first fluorous-phase-based fluorescent
probe (2) for the selective detection of the biologically signifi-
cant DAP. This molecular probe exhibits a large fluorescence
enhancement (more than 2300-fold) in the presence of DAP in
the fluorous phase, whereas other monoamines and diamines
cause minimal fluorescence responses. The sensitivity and se-
lectivity of 2 for the fluorescent recognition of DAP in the fluor-
ous phase are also much greater than those in the common
organic solvent DCM. Thus, if fluorescent recognition is con-
ducted in the fluorous phase, the nonspecific interactions of
substances other than the designated substrate with the sensor
can be minimized, and the sensitivity and selectivity can be
enhanced.
M
M
Preparation of the Samples for the UV/Vis Spectroscopy of 2 in
the Presence of Varying Concentrations of DAP: Stock solutions
of 1.0 m
For the UV/Vis spectroscopy study, solutions of 2 (10–5
were mixed with various solutions of DAP (10.0 m in CH2Cl2) in
M
2 in FC-72 were freshly prepared for each measurement.
M, 1.0 mL)
M
10.0 mL test tubes. The resulting solutions were left at room tem-
perature for 3 h, and the UV/Vis spectra were recorded within 2 h.
The 1H NMR spectroscopy and mass spectrometry studies
revealed remarkable differences between the reactions of the
BINOL dialdehyde 1 and the alkylated derivative 2 with DAP.
Compound 1 with free hydroxy groups forms stable imine prod-
ucts with DAP owing to strong intramolecular hydrogen bond-
ing, which results in minimal fluorescence response. However,
the imine intermediates from the reaction of 2 with DAP were
unstable without the intramolecular hydrogen bonding with
the hydroxy groups, and a product with a six-membered aminal
ring forms. This removes the charge-transfer state of 2, and the
fluorescence is greatly enhanced. Thus, the alkylation of the
hydroxy groups of 1 converts this non-fluorescent-responsive
compound to a highly sensitive and selective fluorescent sensor
for DAP.
Acknowledgments
This work was financially supported by the National Natural Sci-
ence Foundation of China (grant nos. 21502127 and J1310008)
and the National Program on Key Basic Research Project of
China (973 Program, 2013CB328905). L. P. is grateful for the
partial support of the US National Science Foundation (CHE-
1565627).
Keywords: Fluorescence · Sensors · Perfluorinated
solvents · Aldehydes · Amines
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Received: December 7, 2017
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