Cation-Induced Pesticide Binding and Release by a Functionalized Calix[4]arene Molecular Host

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Received
2 November 2014

Accepted
6 February 2015

Published
11 March 2015

Correspondence and

requests for materials

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[H.L. (lhbing@mail.](mailto:lhbing@mail.ccnu.edu.cn)

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## Cation-Induced Pesticide Binding and Release by a Functionalized Calix[4]arene Molecular Host

Li Luo, Xiaoyan Zhang, Ningmei Feng, Demei Tian, Hongtao Deng & Haibing Li

Key Laboratory of Pesticide and Chemical Biology (CCNU), Ministry of Education, College of Chemistry, Central China Normal
University, Wuhan 430079 (P. R. China).

Ion-controlled switchable progress is very important in many biological behaviors. Here, we reported
K 1 -controlled switch, this switch system exhibited excellent carbaryl (G) binding/release by fluorescent
(FL), ultraviolet-visible (UV) spectrums and 1 H NMR spectroscopy. More importantly, the K 1 -controlled G
binding/release switch based on C4C5 not only in the solution, but also on the surface, promising for the
application for the pesticide controlled release.

on-controlled switchable process is very important in many biological behaviors, for example, metal iondirected protein folding and self-assembly, Ca 21 induced contraction or relaxation of the human heart and the
Na 1 stimulated nerve impulses 1–6 . Recently, those in which the binding substrate could be ‘‘on’’ or ‘‘off’’ by ion,
# I
have attracted great interest in host-guest complex 7–9, due to their extensive potential application not only in the
construction of artificial molecular machines but also in the development of sensing and controllable drugdelivery system 10–23 . For example, riptycene-derived containing two dibenzo-[18]-crown-6 interacted with paraquat derivatives which can be combined and released by Li 124 . To our knowledge, most biological ion-controlled
switches realize on the membrane interface, but the ion-controlled switch on the surface has been scarcely
reported.

Controlling surface wettability has attracted interest in recent years 25–28, as it is important for range of biological
and chemical application 29–30, thus, chemical, thermal, and pH-sensitive wettability changed have been reported.
These changes own to their inherent physicochemical properties under environmental conditions. These means
can provide a general method to realize ion-controlled switch between hydrophobicity and hydrophilicity. For
example, wettability provides a method for calix[4]azacrown modified Si-surface response to [C4min]Cl 31 .
Among of these, the design and synthesis of response molecules play an important role in constructing wettable
functional surface. As we all known, calixarene, because of its adjustable cavity and modifying substituents of the
upper and lower rims, have been a good choice of functional response molecules. Calixcrown make a family of
calixarenes that exhibit a superior recognition of organic molecules and metal ions via the cooperation of both the
calixarene and crown moieties 32–39 . Carbaryl (G) is a pesticide which have naphthalene group can interact with
calixarene through p-p stacking. Crown ether was employed to selectively bind K 1 in aqueous solution 40 . It was
known that 18C6 is a very strong sequestering agent for potassium ion 41–42, which has strong binding affinity
toward K 1 . Therefore, we designed a wettable responsive switch based on K 1 -controlled calixcrown binding/
release G. All were shown in the figure 1b. As a consequence of its outstanding properties, the K 1 -controlled
switch has formed attractive application in many fields, especially on a silicon surface.

Results
Synthesize of C4C5. Dialkyne 1 43–45 (0.5 g, 9.8 mmol) and NaH (0.067 g, 40 mmol) and OTS glycol (0.35 g,
10 mmol) were stirred in the anhydrous THF (70 mL), see in the figure 1a. The mixture reaction was stirred at
50uC for 15 h. When the flask was cooled to room temperature, methanol was added to remove the no reacting
NaH. The residue solvent was evaporated by suction filtration to give white powder C4C5 (0.45 g, 73%). The
structure and conformation of C4C5 were confirmed by 1 H NMR, 13 C NMR studies (Supplementary Fig. S1, Fig.
S2), elemental analyses and EI(1)MS spectra (Supplementary Fig. S3). All of these indicated the cone
conformation of C4C5 46–49 . Base on the interaction between the cavity of the C4C5 and naphthalene group,
we obtained [C4C51G] complex with a conjugation ratio of 151, by UV, 1 H NMR spectroscopy and density

Figure 1 | (a) The synthesis of C4C5. (b) The scheme of K 1 -controlled
binding/release G.

functional calculation studies. Further, in the situ [C4C51G]
complex was added K 1 . From fluorescence and 1H NMR
spectroscopy we found the C4C5 binding/release G was controlled
by K 1 . Even further, the K 1 -controlled G binding/release switch had
been successfully applied on the functional micro-silicon surface by
the simple click reaction. Moreover, the K 1 -controlled G binding/
release could act as a convenient and effective wettability switch by
contact angle (CA) measurement on the silicon surface.

The K 1 -controlled G binding/release in the solution. To provide
support for the K 1 -controlled binding/release G, some experiments
were done in the solution phase. First of all, a fluorescence
experiment of the C4C5 and G, K 1 were carried out using an
excitation wavelength of 280 nm. The fluorescence of G (1.0 3
10 25 M, 2.0 mL) enhanced with the addition of the C4C5 (1.0 3
10 23 M, 20 mL) in CH3CN because of their interaction. This

indicated the [C4C51G] complex was successfully obtained. To
further study of the C4C5 with G carried out by K 1, the same
equiv. of K 1 was added for the interaction with [C4C51G] which
showed fluorescence recovered (Fig. 2). Then, ultraviolet-visible
(UV) spectrums of C4C5, [C4C51G], [C4C51K 1 ] were also done
in CH3CN solution. From the spectrum of UV (Supplementary Fig.
S4), the absorption of C4C5 was increased when G added and
recovered when K 1 added. The fluorescence spectrum and UV
spectrum all demonstrated K 1 - controlled binding/ release G can
come true in the solution.

In order to illustrate the details of formation of [C4C51G] in the
solution, the binding stoichiometry of the complex formed between
C4C5 and G was 151 from Job’s plot by ultraviolet-visible (UV)
spectrum, which had a peak at 277.9 nm with a molar fraction of
0.5 (Supplementary Fig. S5). The binding stoichiometry of the complex formed between C4C5 and K 1 was also 151 from the Job’s plot.
The liner relationship between intensity of UV at 277.9 nm and
different concentration of G was carried (Supplementary Fig. S6).
We found the [C4C51K 1 ] binding stoichiometry was also 151
(Supplementary Fig. S6). The host C4C5 was 1 3 10 24 M, 2.0 mL
CH3CN solution and then the different amount of G (1 3 10 23 M,
CH3CN solution) was gradually adding into the host solution. At the
same time, the liner relationship between intensity of UV 277.9 nm
and different concentration of K 1 was also carried using the same
method (Supplementary Fig. S7). The association constant of C4C5
and G is 6.22 3 10 3 M 21, however, C4C5 and K 1 is 1.04 3 10 5 M 21,
these results clearly suggested the complex of [C4C51K 1 ] was much
stable than the complex of [C4C51G].

The K 1 -controlled G binding/release characterized by NMR. To
obtain insights into the mechanism, NMR experiments were carried
out, 6.0 mM C4C5 and 1.0 equiv. of G and K 1 in CD3CN, as showed
in Fig. 3. The protons of the napthalene in the G underwent upfield
shift of 0.05 ppm in the presence of C4C5. The result also indicated
that the [C4C51G] complex was successfully formed. When K 1

added, the protons of naphthalene underwent an upfield shift of
0.05 ppm and recovered to original chemical shift, moreover, the
protons of crown have underwent the protons of crown ether unit
of C4C5 Ha, Hb, Hc and Hd underwent downfield shift of 0.04 ppm,
0.18 ppm, 0.14 ppm and 0.17 ppm respectively. According to the
NMR, we deduced that before K 1 was added, the crown ring of
C4C5 was stretched, when K 1 added, K 1 entered into crown space,
which made the lower space of crown become smaller and this

Figure 2 | (a) Fluorescence intensity changes of G, binding G and release G in CH3CN upon irradiation with 334 nm light (lex 5 280 nm, black line
represents the fluorescence of G; red line represents binding G; green line represents release G). (b) FL variation [DI 5 (I-I0)] (I0 is the FL intensity of G)
histogram for the [C4C51G] complex and [C4C51G] with K 1 at 334 nm

Figure 3 | (a) Partial 1 H NMR spectroscopy of G (6.0 mM each, CD3CN, 400 MHz, 298 K). (b)Partial 1 H NMR spectroscopy of C4C5 reacted with G. (c)
1H NMR spectroscopy of K1 and C4C5, which indicated G release from the C4C5 by K1 interacted with crown ring with C4C5.

reaction has made the space of the upper of the C4C5 become bigger
and led to G released.

We also found the 18C6 was added (Supplementary Fig. S8e), the
chemical shifts of Ha, Hb, Hc, Hd recovered to original values, moreover there appeared a new in peak in the spectrum, we supposed the
new peak is the complex of 18C6 and K 1 . Based on above experiments, we have obtained the K 1 -controlled G binding/ release
switch.

The K 1 -controlled G binding/release characterized by ESI-MS. To
further verify the binding between C4C5 and G, the ESI-MS analysis
was carried out. The peak observed at m/z 5 1084.72 in the ESI mass
spectrum (Fig. 4a) can be attributed to [C4C51G] complex.
Furthermore, the peak observed at m/z 5 921.61 in the ESI mass
spectrum (Fig. 4b) can be attributed to [C4C51K 1 ] complex, we also
found m/z 5 883.58 in the ESI mass spectrum (Fig. S9) can be
attributed to K 1 released from C4C5. The whole ESI-MS study
fully explained the binding/release process and also confirmed the
151 complex formation C4C5 and G, C4C5 and K 1 .

The Gaussian calculation of C4C5, [C4C51G] and [C4C5 and
K 1 ]. Further, the binding of C4C5 and G, K 1 were also examined
by Gaussian03. The results were shown in Fig. 5. The host C4C5 was
yellow, the guest carbaryl was green, oxygen atoms were red, nitrogen
atoms were blue, hydrogen atoms were white, purple atom was
potassium. The structure of C4C5 and the complex of [C4C51G],

[C4C51K 1 ] have been optimized by going through a cascade process
starting from HF/3-21G R HF/6-31G R B3LYP/3-21G R B3LYP/631G. Meanwhile, the frequency analysis calculations were performed
and the absence of imaginary frequencies indicated the low energy
minimum of the structures obtained. All the energy were obtained by
the equation of DE (binding energy) 5 E (host 2 guest) 2 [(E (host)
1 E (guest)], [C4C51G] binding energy is 20.0014 a.u./mol,

[C4C51G1K 1 ] binding energy is 0.05789 a.u./mol, while [C4C51
K 1 ] is 20.9438 a.u./mol, comparing to these energy, which indicated
that [C4C51K 1 ] complex is much stable than [C4C51G] complex.
The space of [C4C51G] is 6.1A ˚, 7.1A ˚, while [C4C51K 1 ] is 6.4A ˚,
7.2A ˚, which indicated that K 1 interacted with C4C5 made the space of
become bigger and G can released from the space. These results of
molecular mechanics calculation were generally consistent with the

UV, 1 H NMR experimental results. All the calculation details were
shown in Supplementary Fig. S10, Fig. S11, Fig. S12.

K 1 - controlled G binding/release on the surface. More importantly,
the K 1 -controlled binding/release carbaryl switch had an important
and potential application by measurement of the contact angle (CA)
on a functional micro- silicon surface. Because micro-structured and
functional silicon surface can amplify the signal output with the respect
of wettability 50, it could reversibly switch between hydrophobic
character and a hydrophilic character. At first, the C4C5-SAMs (selfassembled monolayer) were established by click reaction between the
Si-N3 SAMs and C4C5 in CH3CN (Fig. 6).

Through the SEM (Supplementary Fig. S13), the rough substrate
exhibited a regular array of square silicon micro convexes (bright
squares), and then the C4C5-modified substrate showed a thin film
on the surface. Comparing SEM image of the rough surface before
and after modification with C4C5, these results indicated that C4C5
was successfully modified on the silicon surface. From XPS
(Supplementary Fig. S14), the concentration of carbon had a significant increase and the concentration of oxygen had an obvious
decrease. Moreover, the water-drop profiles showed a different CAs
on bare silicon surface. This also proved the above conclusion. The
silicon surface was immersed into G solution (1.0 3 10 23 M), after
15 min the silicon wafer was washed by little water to remove the
residue G, dried by nitrogen and measured. The results showed in
Figure 7a, C4C5 SAMs immersed into G the CA became from superhydrophobic to hydrophilic, which was only 22.8 6 3.0u, however,
when immersed into KClO3 solution (1.0 3 10 23 M) and 18C6 solution (1.0 3 10 23 M) respectively, the wettability of the surface recovered to their original values (150.0 6 3.0u). Because G interacted with
C4C5 and the group of CONH was exposed, which made the surface
become hydrophilicity, nevertheless, K 1 formed complex with C4C5
and made G released from the space and left the tertiary butyl, which
led to the surface become superhydrophility again. 18C6 interacting
with K 1 didn’t change the property of the upper rim of C4C5, so the
wettability remained superhydrophobicity (Supplementary Fig. S15).

Upon further treatment of the surface with water, then the silicon
was immersed into G, K 1 and 18C6 consecutively, the results
remained the same as the first time. A cycle experiment (Fig. 7b)
reflected a good reversibility for K 1 controlled G binding/release

Figure 4 | (a) G and C4C5 were mixed, there appeared m/z 5 1084.721 in the spectrum, which indicated [C4C51G] has formed. (b) [C4C51G] was
added into KClO4, there has appeared m/z 5 921.611 in the spectrum and m/z 5 1084.72 was disappeared, which indicated G was released from C4C5
and [C4C51K 1 ] was formed.

switch on the surface. According to above results, we found the
experiments were consistent with NMR and Gaussian calculation,
which confirmed K 1 -controlled and binding/release G based on the
surface wettability can be established by contact angle measurement.

Discussion
In conclusion, we found that the fluorescent intensity of C4C5 and G
increasing/decreased by K 1 . More interestingly, the application of
wettability can provide a general method to realize K 1 -controlled
switch between hydrophobicity and hydrophilicity. It is anticipated
that this research can be further extended to fabricate functional
surfaces for pesticide control release, intelligent microfluidic and
laboratory on chip devices

Methods
Materials and instruments. 1 H NMR and 13 C NMR were recorded on Varian
Mercury VX400 instrument at ambient temperature with TMS as the internal
standard. ESI-MS were recorded on a Finnigan LCQ-Advantage instrument. The
static water contact angle was measured at 25uC by means of an OCA 20 contact angle
system (Dataphysics, Germany). X-ray photoelectron spectroscopic (XPS) image was
gained by PHI Quantera SXM. The scanning electron microscope image was
measured at 25uC by means of a JSM-6700F HR-FESEM.

All chemicals were A.R. grade and were purified by standard procedures. Mill-Q
water was used to prepare all solutions in this study.

The synthesis of C4C5. Compound 1 (0.5 g, 9.8 mmol) and NaH (0.067 g, 40 mmol)
and OTS glycol (0.35 g, 10 mmol) were stirred in the anhydrous THF (70 mL). The
mixture reaction was stirred at 50uC for 15 h. When the flask was cooled to room
temperature, methanol was added to remove the no reacting NaH. The residue
solvent was evaporated by suction filtration to give white powder C4C5 (0 45 g 73%)

Figure 5 | (a) The side view on the optimized structure of [C4C51G]
complex, the binding energy was 20.0014 a.u./mol (in the C4C5 the
yellow atoms represent carbon, red atoms represent oxygen, blue atoms
represent nitrogen, white atom represents hydrogen; in the G, the cyan
atoms represent carbon, the blue atoms represent nitrogen, red atoms
represent oxygen). (b) The top view on the optimized structure of

[C4C51K 1 ], the binding energy was 20.9438 a.u./mol (the yellow atoms
represent carbon, red atoms represent oxygen, purple atom represents
potassium). Which demonstrated the complex of [C4C51K 1 ] was much
stable than [C4C51G]. The space of [C4C51K 1 ] is 6.4A ˚, 7.2A ˚, which is
much bigger than [C4C51G] and make G release from the space.

1H NMR (400 MHz, CH3CN): d 7.22 (4H, s, ArH), 6.95 (4H, s, ArH), 5.50 (4H, s,
CH2CCH), 4.48 (4H, d, J 5 11.5 Hz, ArCH2Ar), 3.97 (4H, s, OCH2), 3.78 (8H, d, J 5
10.7 Hz, OCH2CH2O), 3.68 (4H, s, OCH2CH2O), 3.23 (4H, d, J 5 12.3 Hz,
ArCH2Ar), 2.57 (2H, s, CCH), 1.27 (18H, s, C(CH3)3), 1.04 (18H, s, C(CH3)3).
ESI(1)MS calcd for C58H74O7Na [M1Na] 1 905.5 found: 906.0; calc. for
C58H74O7Na [M1Na1H] 1 906.5 found: 907. Anal. Calc. for C58H74O7: C, 78.74; H,
8. 38. Found: C, 78.66; H, 8.26%.

Fluorescence experiments. All experiments of fluorescence were carried out at an
excitation wavelength of 288.0 nm using a fluorescence spectrometer and a 1 cm
quartz cell. C4C5 solution (1.0 3 10 25 M) was made by dissolving C4C5 in CH3CN
(5.0 mL). G solution (1.0 3 10 23 M) was made by dissolving G in CH3CN (5.0 mL)
The K 1 solution was made at 1.0 3 10 23 M in CH3CN. The fluorescence was carried
at 288.0 nm after adding the appropriate volume (20 mL) of C4C5 solution to
measure the fluorescence. Then the K 1 solution (20 mL) was added to the above
mixed solution to measure the fluorescence, which showed a fluorescence recovery
after adding K 1 .

Figure 7 | (a) CA relationship images for C4C5 SAMs with G, K 1, 18C6.
(b) Cycling experiment of K 1 -ion controlled switch which indicate a good
reversibility between hydrophobicity and hydrophilicity.

Ultraviolet-visible experiments. All experiments of UV were carried out using a UV
spectrometer and a 1 cm quart cell. 1.0 mL1.0 3 10 24 C4C5 interacted with G
(100 mL, 1.0 3 10 23 M) and K 1 (100 mL, 1.0 3 10 23 M) CH3CN respectively. The
liner relationship between intensity of UV at 277.9 nm and different concentration of
G, K 1 were carried. The host was 1.0 3 10 24 M 2.0 mL CH3CN solution and then
different amount of G, K 1 were adding into the host solution. The added G, K 1 were 0,
20 40, 60, 80, 100, 120, 140, 160, 180, 200 mL, respectively.

DFT computational details. The calculations reported in this article were performed
using Gaussian03 program package. The structure of C4C5 and the complex of C4C5,
G and K 1 have been optimized by going through a cascade process starting from HF/
3-21G R HF/6-31G R B3LYP/3-21G R B3LYP/6-31G. The frequency analysis
calculations were performed and the absence of imaginary frequencies indicated the
low energy minimum of the structures obtained.

Preparation of the Si-N3-modified silicon substrates. Fabrication of the micro–Si
interface. A silicon wafer was used directly as the smooth substrate. The structured
silicon substrate was fabricated by the combination of photolithography and
inductively coupled plasma (ICP) deep etching techniques. The photolithography
and ICP techniques were used to obtain the patterned silicon micropillar structure on
the silicon wafer. A rough surface introduced geometrical structures with patterned

Figure 6 | The formation process of the functional C4C5 SAM which indicated that the C4C5 has successfully modified on the silicon surface

square pillars on a flat silicon wafer, 20 mm high, 9 mm long and with a spacing of
12 mm between the silicon pillars 51 .

Preparation of the Si-N3 -modified silicon substrates. Silicon substrates cut into 1 3
1 cm 2 square pieces were soaked in chromosulfuric acid solution for 30 minutes and
then rinsed with double distilled water and dried under a stream of N2 gas. Cleaned
wafers were immersed in aqueous NaOH (0.1 mol?L 21 ) for 6 minutes and subsequently in HNO3 (0.1 mol?L 21 ) for 12 minutes to generate surface hydroxyl groups.
Then the silicon substrates had been washed by an excess of double distilled water and
dried under N2 flow. After the silicon substrates had been washed with an excess of
water and dried under a stream of N2 flow, they were immersed in a refluxed solution
of 5 wt% Si-N3 in dry toluene (10 mL) at 110uC for 6 h. Then they were washed with
toluene and chloroform to remove excess Si-N3 and dried under a stream of N2 gas.

The click reaction between Si-N3 and C4C5 on silicon substrates. The silicon surfaces
modified Si-N3 were immersed in C4C5 solution in CH3CN at 10 23 M, then the
mixture of copper sulfate(10 26 M) and sodium ascorbate (10 27 M) were added into
this solution, and heated the solution at 75uC for 8 hours. Then the silicon wafer were
washed with little CH3CN and dried under a stream of N2 gas.

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Acknowledgments
This work was financially supported by the National Natural Science Foundation of China
(21372092, 21102051), Natural Science Foundation of Hubei Province (2013CFA112) and
Self-determined research funds of CCNU from the colleges’ basic research and operation of
MOE (CCNU13F005,CCNU14Z01001).

Author contributions
N.M.F., D.M.T., H.T.D. and H.B.L. designed research; L.L. and N.M.F. performed research;
N.M.F. synthesized compounds; L.L. and N.M.F. analysed data; L.L. done the calculation;
L L X Y Z and H B L wrote the paper

Additional information
[Supplementary information accompanies this paper at http://www.nature.com/](http://www.nature.com/scientificreports)
[scientificreports](http://www.nature.com/scientificreports)

Competing financial interests: The authors declare no competing financial interests.

How to cite this article: Luo, L. et al. Cation-Induced Pesticide Binding and Release by a
Functionalized Calix[4]arene Molecular Host. Sci. Rep. 5, 8982; DOI:10.1038/srep08982
(2015).

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