DOI: 10.1002/slct.

201702999 Full Papers

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2 z Organic & Supramolecular Chemistry
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Switching the Ion Selectivity from Fe3 + to Al3 + by a
6 Triazole-Appended Calix[4]arene-Based Amphiphile†
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8 Rahul Nag,[a] Manu Vashishtha,[b] and Chebrolu Pulla Rao*[a]
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11 A triazole appended benzaldehydic lower rim derivative of calix transferred onto H-terminated Si-wafer and characterized using
12 [4]arene (L) has been synthesized and was thoroughly charac- Atomic Force Microscopy, contact angle, Grazing Incidence
13 terized. In CH3CN solution, the L showed greater sensitivity for Fourier Transform Infrared Spectrscopy and X-ray Photoelectron
14 Fe3 + by a 5-fold increase in the absorbance and 37% quenching Spectroscopy. The study resulted selective binding of Al3 + to
15 in the fluorescence intensity, by forming a 1:1 complex. The the Langmuir film of L among the nine metal ions studied.
16 Fe3 + induces aggregation in L as studied by microscopy. The Thus, the calix[4]arene-conjugate L is sensitive and selective to
17 Langmuir film formed at the air-water interface was charac- Fe3 + in acetonitrile solution whereas to Al3 + in Langmuir film
18 terized by pressure-area isotherm and Brewster angle micro- and hence acts as an ion switch depending upon the physical
19 graphs, both in the presence and absence of metal ions. The state of L.
20 Langmuir films of pure L, {L + Al3 + } and {L + Zn2 + } were
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well as gas[36–37] sensing because of its supramolecular nature.
23 Introduction
The corresponding selectivity studies of the conjugates of
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Conjugates of calix[n]arenes, in particular, the calix[4]arene, calixarenes at air-water interface is limited[38] and hence
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have been studied for their ion and molecular sensing aspects deserves greater attention. In order to study the ion sensing at
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in solution owing to the ease of controlled derivatization of the air-water interface, the receptor L, given in Figure 1, was
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platforms both at lower and upper rims.[1–15] Variations in the
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induced supramolecular aggregation of the conjugates of calix
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[4]arenes by an ion or a molecule have been reported.[16–18]
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Orientation, thickness and the concentration gradient of these
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conjugates are important during the device fabrication. The
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Langmuir films[19] are already graduated systems from such
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aspects since the molecular alignment in the film is highly
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ordered and oriented.[20] In addition, the ease of making,
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transferring and characterization are some additional features
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of Langmuir films. In the literature, the Langmuir-Blodgett (LB)
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method has been further used in making magnetic monolayer,
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in electrical device fabrication, in sensors and in several other
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applications.[19] Since the conjugates of calix[4]arenes possesses
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both hydrophobic and hydrophilic regions, these are well
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suited to make Langmuir films[21] and hence can be used for
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the study of ion and molecular sensing on any substrate by
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using its functional moieties. The studies on Langmuir films of
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calixarenes are primarily focused on molecular,[22–25] ion[26–35] as
45
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47 [a] R. Nag, Prof. C. P. Rao
Department of Chemistry
48 Department of Chemical Engineering
49 Indian Institute of Technology Bombay
50 Powai, Mumbai-400076, India
51 Tel: + 91-22-25767162
E-mail: cprao@iitb.ac.in Figure 1. Design of L.
52 [b] Dr. M. Vashishtha
53 Department of Chemical Engineering
54 Indian Institute of Technology Bombay
Powai, Mumbai-400076, India designed in the light of the following aspects: (i) The calix[4]
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Supporting information for this article is available on the WWW under arene core is required for the presence of arene compartment
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https://doi.org/10.1002/slct.201702999 and also to provide a platform in order to build the arms with
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Scheme 1. Synthesis of L and its precursors. Reagents and conditions: (a) NaH, dry-N,N-DMF, 90 8C, 3 days. (b) CuSO4.5H2O, sodium ascorbate, t-butanol: CH2Cl2:
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H2O (1:1:2), RT, 1.5 days.
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ion binding core. (ii) The terminals of two of the arms are Ion sensing in solution
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decorated with polar as well as ion binding groups (such as
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-OH & -CHO). The other two arms are attached with dodecyl As two arms of the lower rim derivative of calix[4]arene (L)
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moiety. (iii) The triazole units would contribute to the polarity provides binding centers to metal ions, its affinity for ion
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of the arm while providing a coordinating ‘N’-center. As a result binding was studied both by absorption and emission spectro-
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of all such synthetic modifications, the conjugate, L will act as scopy in CH3CN using Mg2 +, Al3 +, Mn2 +, Fe2 +, Fe3 +, Co2 +, Ni2 +,
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an amphiphile which will yield Langmuir film easily. Cu2 + and Zn2 + ions (Supporting Information, S02). The L
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Therefore, in this paper we report the synthesis and exhibits primarily three absorption bands at 258, 284 and
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characterization of a triazole-appended benzaldehydic deriva- 333 nm. When incremental concentrations of ions were added
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tive of calix[4]arene (L), its Langmuir film at air-water interface to L, the absorption spectra of L exhibited either no change
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and the film transferred on to HSi-wafer. The ion selectivity (Mg2 +, Ni2 +, Mn2 + and Co2 +) or marginal changes (Al3 +, Fe2 +,
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studies were performed in solution as well as at air-water Cu2 + and Zn2 +) or large changes (Fe3 +) depending upon the
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interface. While L is selective to Fe3 + in solution, its selectivity is metal ion (Figure 2a,b and Supporting Information, Figure S5).
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switched to Al3 + in the film. In case of Fe3 +, the absorbance of 333 nm band increases by 5
37
fold as compared to L and the band is red shifted to 336 nm
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(Figure 2b). Similar calix[4]arene derivatives reported earlier by
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Results and discussion us showed selectivity towards Zn2 + without the involvement of
40
the triazole moiety.[39–40] The Job plot for the titration of L by
41 Synthesis and characterization of L
Fe3 + yields 1:1 complex (Figure 2c). Based on the absorption
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The receptor molecule, L has been synthesized starting from p- titration data, the binding constant for Fe3 + to L was derived to
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tert-butylcalix[4]arene followed by P1 and P2, and finally using a have Ka of (2.04  0.69) 3 104 M1 (Supporting Information,
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click reaction between P2 with P3 as given in Scheme 1. The Figure S6).
45
precursors and the final product were well characterized and In the fluorescence spectra, the L exhibits an emission band
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the corresponding data appears in the supporting information at 311 nm (lex = 284 nm). The fluorescence intensity is
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(S01; Figure S1-S4, Supporting information file). quenched as a function of the concentration of Fe3 + added
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The cone conformation of L was confirmed from 1H NMR by (Figure 2d). While the quenching is 37% in case of Fe3 +, this is
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the presence of AB type peak pattern observed for bridge -CH2 only 20% in case of Cu2 + (Figure 2e). However, the fluorescence
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(4.22 & 2.93 ppm and 4.19 & 2.89 ppm) and also by the intensity changes are not significant enough in case of, Al3 +,
51
presence of the bridge -CH2 peaks at 33.9 and 32.1 ppm in Ni2 +, Mg2 +, Mn2 +, Zn2 +, Fe2 + and Co2 +. Thus the spectral
52 13
C NMR. Since the L has metal ion binding sites, its ion binding titration data is more sensitive towards Fe3 + for L in CH3CN as
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was studied both in the solution state (non-oriented) and in compared to all the other ions studied. On the other hand,
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the oriented Langmuir films (at air-water interface). Differential when the terminal group is imino-phenolic core rather than
55
binding aspects of L in these two forms have been addressed aldehydic group, fluorescence enhancement was observed in
56
in this paper. presence of Mg2 + as reported by us recently.[41] All this supports
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26 Figure 2. (a) Absorption spectral traces obtained during the titration of L with different concentrations of Fe3 +. The inset corresponds to the plot of absorbance
27 at 333 nm vs. [Fe3 + ]/[L] mole ratio. (b) A-A0 plot at 333 nm for the titration of L with different metal ions. (c) Job plot for absorption titration of L with Fe3 +. (d)
28 Emission spectral traces obtained during the titration of L with different concentrations of Fe3 +. The inset corresponds to the plot of emission intensity at
311 nm vs. [Fe3 + ]/[L] mole ratio. (e) Plot of % change in the emission intensity at 311 nm for the titration of L with different metal ions. (f) 1H NMR spectral
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traces obtained during the titration of L with Fe3 + in CD3CN.
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that the presence of aldehydic moiety in place of the
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iminophenol would affect the ion sensitivity and selectivity. The
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binding of Fe3 + to L in solution was further confirmed from the
36 1
H NMR spectral changes observed with the benzaldehydic
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-CHO and -OH peak (Figure 2f).
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The complex formed between L and Fe(ClO4)3 was studied
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by ESI-MS spectrum and the peak observed at 1682.1 is
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assigned to [(L-2H + Fe + ClO4) + H] +. The peak thus observed
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for the 1:1 complex of L vs. Fe3 + was confirmed based on the
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isotopic peak pattern observed for iron as given under
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Figure 3.
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46 Studies on spin-coated film
Figure 3. Experimental isotopic peak pattern of {(L-2H + Fe + ClO4) + H} + in
47 ESI-MS. The inset shows the calculated one.
The spin-coated film of L on HSi-wafer was studied by
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microscopy and spectroscopy both in the absence and in the
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presence of metal ions, viz., Fe3 +, Al3 +, Cu2 + and Zn2 +. In
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presence of Fe3 +, the AFM (Figure 4a,b) showed increased spin-coated film was validated by analyzing the GIFTIR
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particle size due to the ion induced aggregation. However, the measured, which showed characteristic vibrational bands of L
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aggregation is not considerable in case of other three ions (Supporting information, Figure S8a,b and Table S1). The con-
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(Supporting information, Figure S7). Comparison of the TEM tact angle measurement of the spin-coated film showed 91.5 
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micrographs (Figure 4c,d) for L and {L + Fe3 + } reveal that the 0.68 and 95.3  0.88 respectively for L and {L + Fe3 + }, suggesting
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flower like morphology was observed in the presence of Fe3 + that the films are hydrophobic in nature.
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which was not seen with the simple L. Presence of L on the
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Fe3 + in the spin coated film of {L + Fe3 + } was confirmed by the
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Fe 2p XPS spectra (Figure 4h).
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4 Studies using Langmuir film
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Pressure-area (P-A) isotherm of L was measured and the same
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is depicted in Figure 5a. The L forms a stable film, with a well-
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defined phase transition from the gaseous to liquid-like at 1.04
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mN/m with 264 Å2 of mean molecular area (MMA), and liquid
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to solid-like state at ~ 12 mN/m with MMA of 211 Å2/molecule.
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Thus the collapse pressure (Pc) is ~ 13.2 mN/m for L. The
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Langmuir films of L were prepared in presence of metal ion in
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the solution and the corresponding data is plotted as isotherms
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in Figure 5a for all the nine metal ions, viz., Mg2 +, Al3 +, Mn2 +,
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Fe2 +, Fe3 +, Co2 +, Ni2 +, Cu2 + and Zn2 +, studied. The nature of the
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isotherm remains the same for all these ions, however, the
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MMA and Pc differ depending upon the metal ion. The
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quantitative measure of these parameters is given as histo-
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grams in Figure 5b and c.
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While Fe2 + shows negligible change in MMA, the Mg2 +,
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Ni , Cu2 + and Zn2 + shows a decrease with an order, Cu2 + >
2+
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Mg2 + > Zn2 + > Ni2 +, and the ions, such as, Mn2 +, Co2 +, Fe3 +
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and Al3 + shows increase in MMA in the order, Co2 + < Mn2 + <
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Fe3 + < Al3 +. Thus, the changes observed in MMA are
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considerable in case of most of the metal ions studied,
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however, is dramatic in case of Al3 +. In terms of Pc (Figure 5c),
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a decrease in collapse pressure was observed with Zn2 + while
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incremental changes were seen with Co2 +, Mn2 +, Mg2 +, Fe2 +,
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Fe3 +, Cu2 + and Al3 + with a trend of Co2 + < Mn2 + < Mg2 + <
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Cu2 + < Fe3 + < Fe2 + < Al3 +, however, Ni2 + showed no
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considerable change in Pc. Thus, the presence of Al3 + shows
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highest value in MMA and Pc, where these parameters increase
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by 148% and 251% respectively as compared to simple L. These
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results comply well with the smaller size and greater charge of
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Al3 + as compared to all other ions studied. If the metal ion
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were to occupy the cavity of calixarene, only minor changes are
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expected in the MMA/molecule,[29] but, appreciable changes are
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expected when the metal ion binds to the arms (Figure 5d),
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which is the case here. Specific binding and or complexation
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can bring major changes in the nature of the isotherm. Thus,
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the maximum changes observed for Al3 + shows that the L is
41 Figure 4. AFM micrograph (area: 2 mm 3 2 mm) of the spin-coated films of, (a)
selective towards Al3 + among all the ions studied.
42 L and (b) {L + Fe3 + }. TEM micrograph of (c) L and (d) {L + Fe3 + }. XPS spectra
of (e) C 1s, (f) O 1s, (g) N 1s, (h) Fe 2p of the spin-coated films. Colour code The excess Gibbs free energy (~Gdiff) is negative in case of
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for all: L (black) and {L + Fe3 + } (blue). Cu , Ni2 +, Zn2 + and Mg2 +, and is positive in case of Fe2 + /3 +,
2+
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Co2 +, Mn2 + and Al3 +; highest ~Gdiff is observed in case of Al3 +
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(Figure 5e). In the literature, the ~Gdiff results have been used
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to establish the selectivity of Cs + and guanidinium ion towards
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The XPS spectra measured of the spin coated L shows that different calix[6]arene derivatives.[30] In our study this plot
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the Fe3 + interacts with the benzaldehydic part present at the clearly shows that L is selective to Al3 +. This is in agreement
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lower rim of L. Both C 1s and O 1s spectra support the with the changes observed in P-A isotherm parameters of Al3 +.
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interaction of Fe3 + and L. While no change was observed for In order to show the involvement of the binding core in the
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CC bond region in the C 1s spectrum, 0.6 eV shift was seen in Langmuir film, a precursor of L, i. e., P2 not possessing such
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the C=O region (Figure 4e). The O 1s spectra supports this by binding core has been subjected to similar study and the
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showing a shift of ~ 0.2 eV for CO region and 0.4 eV in the C= corresponding P-A isotherms are given in Figure 5f as controls
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O region (Figure 4f). N 1s spectra too show changes in its for comparison. Thus simple P2 as well as {P2 + Al3 + /Zn2 + } does
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corresponding N-Csp3 and N-Csp2 region (Figure 4g). Presence of not form any P-A isotherm suggesting that the triazole-
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46 Figure 5. (a) P-A isotherm of L in presence of different metal ions. (b) Bar diagram showing % change in the mean molecular area (MMA). (c) Bar diagram
47 showing the % change in Pc. (d) Schematic representation of L at air-water interface in presence of Al3 +. (e) Plot of ~Gdiff for L in the presence of different
metal ions. (f) Comparison of P-A isotherm of L and P2 in presence of Al3 + and Zn2 +. The P-A Isotherms for P2, P2 + Al3 + and P2 + Zn2 + lie at the baseline. (g)
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Plot of MMA vs. [Mn + ]. (h) P-A isotherm of L: (i) at air-water interface, (ii) in presence of Zn2 +, (iii) in presence of 1:1 mixture of Al3 + and Zn2 +, (iv) in presence of
49 Al3 +.
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appended benzaldehydic moiety is important for the formation from Figure 5g and the Supporting Information, Figure S9. The
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of the Langmuir film as well as for the metal ion interaction. values of MMA are greater in presence of Al3 + (283 Å2) than
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As the concentration of the metal ion (viz., Al3 +, Mn2 +, Zn2 +) that of pure L (211 Å2) and this increases with increase in [Al3 + ]
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in the aqueous sub-phase is increased from 12.3 ! 16.4 ! in the order, 283 ! 300 ! 311 Å2/molecule due to the
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25 mM, constant changes were observed in MMA as evident generation of greater number of charged residues. On the
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Figure 6. BAM micrographs (scale bar = 2600 mm 3 3500 mm) of L at different surface pressures: (a, b, c) are for pure L at 0, 8 and 14 mN/m respectively; (e, f, g)
33 are for {L + Al3 + } at 0, 15 and 30 mN/m respectively; and (i, j, k) are for {L + Zn2 + } at 0, 13.7 and 14.3 mN/m respectively. 2D- images of LB films from AFM (area:
34 2 mm 3 2 mm): (d) L, (h) {L + Al3 + } and (l) {L + Zn2 + } on H-terminated Si-wafer.
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contrary, the compressibility does not change in a similar order at 10 mN/m shows spherical-particle like morphology which is
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with increasing [Al3 + ]. Initially the compressibility decreases on quite similar to the BAM micrograph of L. The topography of L
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going from 12.3 ! 16.4 mM and then increases on going is similar to that reported for calixarene derivatives by
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further from 16.4 ! 25 mM. However, the behavior is different possessing low-roughness and nanometer level height (Sup-
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in case of Mn2 + and Zn2 +, while the changes are major with porting Information, Figure S12).[21,37] The BAM Micrograph at
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Al3 + (Figure 5g). The P-A isotherm studies carried out in the starting of compression (0 mN/m) for {L + Al3 + } as well as
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presence of equimolar concentration of Al3 + /Zn2 + and Al3 + {L + Zn2 + } are quite similar to that of pure L (Figure 6e and 6i).
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/Mn2 + supported strong binding as well as selectivity of Al3 + to However, at a surface pressure of 15 mN/m in case of {L +
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L (Figure 5h, Supporting Information, Figure S10). Similar results Al3 + } (Figure 6f), the nature of the film varies largely from that
46
were reported for the selectivity of Cs + over Na + at the air- observed in simple water. With increase of surface pressure, the
47
water interface in case of a calix[6]arene derivative.[26] isolated particle like morphology of L changed to an
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The films were captured at air-water interface using BAM aggregated type in presence of Al3 + (Figure 6e-g) and this is
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and after transferring on to HSi-wafer using AFM. The BAM reflected as an increase in the particle density in AFM
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micrographs of L show liquid-expanded state at the starting of (Figure 6h). Similar results were reported in case of HgCl2, NiCl2,
51
compression (0 mN/m) (Figure 6a) on pure water. As the surface MnCl2 and CoCl2 with two different calix[4]arene deriva-
52
pressure increases, brighter domains are formed within the tives.[31,34] However, the micrographs observed for L in the
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darker ones (Figure 6a-c and Supporting Information, Fig- presence of Zn2 + showed only marginal changes (Figure 6i–k,
54
ure S11). This supports the co-existence of both the liquid- 6l). Thus, L is selective for sensing Al3 + in the Langmuir film as
55
expanded and liquid condensed states together. The AFM compared to all the other eight metal ions studied.
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micrograph of transferred LB film of L on Si-surface (Figure 6d)
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12 Figure 7. XPS spectra for (a) Al 2p, (b) C 1s, (c) O 1s and (d) N 1s. These correspond to the LB films of L (black) and {L + Al3 + } (red).
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42 Scheme 2. Comparison of the data based on L and {L + Mn + } in solution (under the left column) and on Langmuir film (under the right column). The middle
43 column shows schematic pictures corresponding to the solution, in the Langmuir film and on HSi wafer.
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The LB film of L on HSi-wafer has also been characterized the presence of metal ions owing to the ion induced
47
using GIFTIR (Supporting Information, Figure S8c and Table S1). aggregation of L.
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The contact angle data showed marginal decrease in the The XPS studies were carried out to confirm the binding of
49
hydrophobicity of the LB film of L on H-terminated Si-wafer metal ion in the binding core region of L and the presence of
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(79.1  1.58) as compared to the corresponding control, i. e., metal ion in the film. The Figure 7 shows XPS data of LB films
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bare H-terminated Si-wafer (83.8  0.88). The hydrophobicity of of L and {L + Al3 + } transferred on to H-terminated Si-wafer. As
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the film of L is marginally decreased in presence of Al3 + (71.7  evident from Figure 7a, Al3 + ion was detected in case of the
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1.88). A simple calix[4]arene film showed contact angle of 808 film prepared using {L + Al3 + } while it is absent in the film of L
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as reported in the literature[37] and is similar to that we found alone. The peak observed at 74.8 eV corresponds to Al 2p. The
55
for L. Thus the hydrophobicity of L was not affected even in XPS spectra of C 1s, O 1s and N 1s are given in Figure 7b, c, d.
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In the C 1s spectrum, the regions corresponding to CO and
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C=O binding were shifted in presence of Al3 +. The shifts are interface. All these aspects can be noticed easily from
1
0.178 and 0.28 eV respectively for C-O and C = O. These shifts Scheme 2. Thus the ion sensing of L switches from Fe3 + to Al3 +
2
are further supported by the O 1s spectrum to an extent of on going from solution phase to the Langmuir film at the air-
3
0.16 and 0.10 eV respectively for -C-O and -C = O in presence of water interface due to the orientation of L in the film. All this is
4
Al3 +. The N 1s spectrum also shows peak shift. Thus the XPS due to the variation in the coordination and or solvation
5
results show the presence of Al3 + in the corresponding film behaviour of Al3 + vs. Fe3 + and as a result this is reflected in
6
and its interaction with benzaldehydic binding motif present at their interaction with L. Thus L can be used as a dual sensor
7
the lower rim of L. depending upon the phase in which the studies are carried
8
out.
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10 Conclusions and comparisons
11 Acknowledgements
A triazole-appended benzaldehydic lower rim derivative of calix
12
[4]arene (L) has been synthesized as per the steps given in CPR thanks the DST (SERB, EMR/2014/000985) and CSIR for
13
Scheme 1 and was characterized by 1H, 13C NMR, ESI-MS and financial support and DST/SERB for JC Bose National Fellowship
14
FTIR. The presence of cone conformation in L has been (SB/S2/JCB/066/2015) and IIT Bombay for Chair Professorship. RN
15
supported by 1H & 13C NMR spectroscopy. Metal ion binding acknowledges CSIR for the fellowship. We acknowledge the
16
ability of the triazole appended benzaldehydic moiety on the services provided by the central facilities of IIT Bombay (AFM, XPS)
17
lower rim of L has been explored by absorption and emission and those at the Centre for Excellence in Nanoelectronics, and
18
studies in CH3CN using nine different metal ions. Major changes Prof. V.A. Juvekar for providing access to Langmuir film studies.
19
were observed mainly in case of Fe3 +. In presence of Fe3 +, a 5-
20
fold increase in the absorbance at the lmax = 333 nm and a 37%
21 Conflict of Interest
quenching in emission intensity were observed. The 1:1
22
complex formed between L and Fe3 + was derived based on the The authors declare no conflict of interest.
23
absorption data using Job plot as well as identified by ESI-MS
24
observed at m/z = 1682.1 assigned to [(L-2H + Fe + ClO4) + H] +. Keywords: Air-water interface · Calixarenes · Ion sensing ·
25
Microscopy studies on spin-coated film showed Fe3 + induced Langmuir-Blodgett film · Pressure-area isotherm
26
aggregation of L favourably. The binding of Fe3 + in the lower
27
rim of L through aldehydic, phenolic and triazole unit is further
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ChemistrySelect 2018, 3, 1248 – 1256 1256  2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Wiley VCH
1804 / 105882
Montag, 29.01.2018
[S. 1256/1256] 1