Article Cite This: Langmuir 2019, 35, 8383−8388
pubs.acs.org/Langmuir
Gemini-Type Supramolecular Amphiphile Based on a Water-Soluble Pillar[5]arene and an Azastilbene Guest and Its Application in Stimuli-Responsive Self-Assemblies Xiaoqing Lv,†,‡ Danyu Xia,*,† Ying Zuo,† Xiaoqin Wu,† Xuehong Wei,*,†,‡ and Pi Wang*,§ †
Scientific Instrument Center, Shanxi University, Taiyuan 030006, P. R. China School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, P. R. China § Ministry of Education Key Laboratory of Interface Science and Engineering in Advanced Materials, Research Center of Advanced Materials Science and Technology, Taiyuan University of Technology, Taiyuan 030024, P. R. China
Downloaded via NOTTINGHAM TRENT UNIV on August 17, 2019 at 03:31:25 (UTC). See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.
‡
S Supporting Information *
ABSTRACT: Supramolecular amphiphiles are a type of intriguing building blocks to fabricate self-assembled nanostructures that can be applied in diverse fields. Gemini-type supramolecular amphiphiles, containing two hydrophobic tails and two hydrophilic head groups linked by a spacer, are good candidates to fabricate many advanced materials that are able to apply in surface modification, drug/gene delivery, and solubilization. Pillararenes, the fifth generation of macrocyclic host molecules, have been used to fabricate many supramolecular amphiphiles that played important roles in biomedical fields and materials science. However, compared with single-chain and bolatype supramolecular amphiphiles, the studies of gemini-type supramolecular amphiphiles based on pillararenes are very rare. Herein, a new strategy to prepare gemini-type supramolecular amphiphiles was reported. A new acidresponsive host−guest recognition motif in water on the basis of a 4,4′azastilbene derivative (G1) and a water-soluble pillar[5]arene (WP5) was fabricated. The gemini-type supramolecular amphiphile was constructed by an azastilbene amphiphilic guest (G2) and WP5. Then its application in stimuli-responsive selfassemblies was investigated. G2 self-assembled into nanoribbons in water. Upon addition of WP5, the gemini-type supramolecular amphiphile formed, leading to the formation of disklike micelles. After further addition of hydrochloric acid, the morphology changed into nanosheets.
■
INTRODUCTION Supramolecular amphiphiles, a type of basic building blocks, are being widely and actively explored to prepare selfassembled nanostructures that can be used in diverse fields, for example, drug delivery systems, bioimaging, fluorescent sensing, multidrug resistance treatment, photodynamic therapy, and so on.1−5 Different kinds of supramolecular amphiphiles, including single-chain, bola-type, and geminitype supramolecular amphiphiles, have been investigated.6,7 Among them, gemini-type supramolecular amphiphiles, containing two hydrophobic tails and two hydrophilic head groups linked by a spacer, display higher surface activities, making them good candidates in various areas, such as surface modification, drug/gene delivery, and solubilization.8−11 Usually, a gemini amphiphile interacting with a suitable organic counterion can form a gemini-type supramolecular amphiphile.6,12 In addition, with befitting molecular design, proper building blocks can be used to construct gemini-type supramolecular amphiphiles by using noncovalent interactions.6,9 However, how the organic counterion and noncovalent interactions influence the construction and selfassembly of gemini-type supramolecular amphiphiles is difficult © 2019 American Chemical Society
to research. Thereupon, gemini-type supramolecular amphiphiles have not been that widely studied as the other two types. Therefore, it is important to explore different ways to construct gemini-type supramolecular amphiphiles. Various noncovalent interactions, including electrostatic interactions, macrocycle-based host−guest interactions, charge-transfer interactions, and π−π interactions, have been used to build supramolecular amphiphiles.13−18 Among them, macrocycle-based host−guest interactions played significant roles in preparing supramolecular amphiphiles because of their high binding abilities, abundant stimuli-responsiveness, controllable complexation, and so on.14,19−24 Pillararenes, the fifth generation of macrocyclic host molecules, have been studied intensively since 2008.25−27 Because of their symmetrical and rigid structure, pillararenes have displayed interesting host− guest recognition properties with different types of guests.28−32 Based on the established recognition motifs, many supramolecular amphiphiles have been fabricated to extend the Received: April 23, 2019 Revised: May 24, 2019 Published: May 28, 2019 8383
DOI: 10.1021/acs.langmuir.9b01188 Langmuir 2019, 35, 8383−8388
Article
Langmuir
Scheme 1. (a) Chemical Structures of WP5, WP5H, G1, G1′, G2, and G2′ and Schematic Illustration of the Acid-Responsive Host−Guest Recognition between WP5 and G1; (b) Chemical Structures of G2 and G2′ and Schematic Illustration of the Gemini-Type Supramolecular Amphiphile WP5⊃3G2; and (c) Schematic Illustration of the Acid-Responsive Self-Assembly of G2 and the Gemini-Type Supramolecular Amphiphile WP5⊃3G2
applications of pillararenes in diverse fields, such as drug delivery systems, bacterial cell agglutination, and artificial lightharvesting systems.16,21,33−38 However, compared with singlechain and bola-type supramolecular amphiphiles, the studies of gemini-type supramolecular amphiphiles based on pillararenes are very rare. It is essential to explore new host−guest systems to fabricate pillararene-based gemini-type supramolecular amphiphiles. Herein, a new gemini-type supramolecular amphiphile was fabricated by a single-chain amphiphile and a water-soluble pillar[5]arene (WP5). First, methyl-4,4′-azastilbene iodide (G1) was used as a guest to fabricate a new host− guest recognition motif with WP5. Then, a single-chain amphiphile, a 4,4′-azastilbene-containing molecule (G2), was synthesized to fabricate a gemini-type supramolecular amphiphile with WP5 driven by host−guest interaction and cation−π interaction. The acid-responsive self-assembly behavior of these amphiphiles was investigated. The amphiphile G2 self-assembled into nanoribbons. After addition of WP5, the gemini-type supramolecular amphiphile formed, resulting in the formation of disklike micelles. Upon addition of hydrochloric acid, the morphology of the self-assembled aggregates changed into nanosheets (Scheme 1).
■
concentration (CAC) values was carried out on a FE38-Standard Bench Instrument. Transmission electron microscopy (TEM) investigations were performed with a JEM-2100 or a JEM-1200EX instrument. Atomic force microscopy (AFM) experiments were performed by a Bruker Multi-Mode 8.0 instrument. The data of the single crystal structure were collected on a Bruker APEX-II CCD Xray diffractometer and processed using Bruker SAINT v8.37A. The crystal structures were solved by SHELXT42 and refined by SHELXL.43
■
RESULTS AND DISCUSSION
First, the single crystal structure of compound G1 was obtained by slow diffusion of 1,4-dioxane vapor into water solutions. As shown in Figure 1, G1 formed an antiparallel stacking structure by cation−π interaction between pyridinium
EXPERIMENTAL SECTION
All reagents were commercially available and used as supplied without further purification. Compounds WP5,39 G1,40 and G241 were synthesized according to published procedures. NMR spectra were obtained by a Bruker Avance DMX 600 spectrophotometer. Isothermal titration calorimetric (ITC) measurements were carried out on a MicroCal ITC200 instrument. High-resolution mass spectrometry experiments were performed with a Waters UPLC HClass QDA instrument. The determination of the critical aggregation
Figure 1. Ball−stick view of the crystal structure of G1. color code: C, red; N, blue. Iodide counterions, solvent molecules, and hydrogen atoms were omitted for clarity. Blue dashed lines indicate cation−π interactions (A, B). Cation−π interaction parameters are presented as follows: centroid−centroid distance (Å), dihedral angles (deg): A, 3.80; 15.3; B, 3.66, 8.85. 8384
DOI: 10.1021/acs.langmuir.9b01188 Langmuir 2019, 35, 8383−8388
Article
Langmuir
and pyridyl groups of the adjacent molecules,44 with the closest centroid−centroid distances of 3.80 and 3.66 Å, respectively. 1 H NMR spectroscopy experiments were carried out to study the host−guest recognition between WP5 and G1. As shown in Figure 2a−c, after addition of equimolar WP5 to the solution of G1 in deuterium oxide, the signals corresponding to the protons Ha−Hf on G1 shifted upfield, the signals for the proton Hg on G1 shifted downfield, and all of the signals became broad compared to those for free G1. In addition, the peaks corresponding to the proton H1 on WP5 became broad and protons H2 and H3 splitted compared to those for free WP5 because the protons H2 and H3 are different environments due to asymmetric guest threaded into the cavity of WP5.45 These results indicated the host−guest interaction between WP5 and G1. Next, a two-dimensional (2D) Nuclear Overhauser effect spectroscopy (NOESY) experiment was performed to investigate the relative locations of the components in WP5⊃G1 (Figure S1). NOE correlation signals were observed between proton Hb of G1 and proton H3 of WP5 (Figure S1A), between protons Hc, Hd, and Hf of G1 and protons H2 and H3 of WP5 (Figure S1B,C), indicating that G1 threaded into the cavity of WP5 to form an inclusion complex. These results confirmed the 1H NMR spectroscopy results. In addition, ITC was performed to ascertain the stoichiometry and association constant (Ka) of the host−guest complexation between WP5 and G1. As shown in Figure S2, the stoichiometry was calculated to be 1:1 and the Ka value was estimated to be (1.10 ± 0.24) × 107 M−1 for WP5⊃G1. These results proved the host−guest complexation between WP5 and G1. The complexation between WP5 and G1 in water not only showed high association constant but also acid-responsive property. As shown in the 1H NMR spectra (Figure 2c,d), when deuterium chloride was added to the solution of G1, the peaks corresponding to all of the protons of G1 shifted downfield. In addition, the signals for protons Ha and Hb merged and the two peaks of protons Hd and Hf changed from doublet to one singlet, indicating that the pyridyl group of G1 protonated to the pyridinium group to become compound G1′. Meanwhile, when the solution of equimolar WP5 and G1 was added with deuterium chloride (Figure 2b,e), the signals for the protons of WP5 disappeared in the 1H NMR spectrum and only the signals for the protons of G1′ existed, suggesting that the host−guest complexation between the host and G1 was broken. The reason is that WP5 changed into WP5H by protonation of the carboxylic groups to carboxylic acid groups and precipitated from water46 and G1 transformed into G1′. These results provided sufficient evidence for the acidresponsive complexation between WP5 and G1. In addition, the acid-responsive host−guest recognition motif based on WP5 and G1 was used to fabricate supramolecular amphiphiles. A trans-4,4′-azastilbene bromide-containing amphiphile, trans-N-n-dodecyl-4,4′-azastilbene iodide G2, was synthesized according to published procedures.41 According to previously reported supramolecular amphiphiles, the head group parts of the amphiphiles thread into the cavity of pillararene hosts to form host−guest complexes in a 1:1 manner.14,47−49 The complexes can act as supramolecular amphiphiles in which WP5 plays the role of the hydrophilic part and the alkyl chains of the guests served as the hydrophobic part. However, the host−guest recognition behavior of WP5 and G2 is quite different. First, 1H NMR titration experiments were performed to investigate the
Figure 2. Partial 1H NMR spectra (D2O, 293 K, 600 MHz): (a) WP5 (2.50 mM); (b) WP5 (2.50 mM) and G1 (2.50 mM); (c) G1 (2.50 mM); (d) after addition of deuterium chloride of (c); and (e) after addition of deuterium chloride of (b).
Figure 3. Partial 1H NMR spectra (D2O, 293 K, 600 MHz): (a) G2 (2.50 mM); (b) WP5 (2.50 mM); (c) after addition of 1.0 mol equiv of G2 to (b); (d) after addition of 2.0 mol equiv of G2 to (b); (e) after addition of 3.0 mol equiv of G2 to (b); and (f) after addition of 4.0 mol equiv of G2 to (b); (g) after addition of 5.0 mol equiv of G2 to (b). The peaks related the protons of uncomplexed WP5 were marked.
Figure 4. TEM images: (a) G2 (1.00 × 10−4 M) aggregates in water; (b) enlarged image of (a); (c) WP5 (3.30 × 10−5 M) and G2 (1.00 × 10−4 M) aggregates in water; (d) enlarged image of (c); (e) TEM image of (a) after addition of hydrochloric acid; (f) enlarged image of (e); (g) TEM image of (c) after addition of hydrochloric acid; and (h) enlarged image of (g). 8385
DOI: 10.1021/acs.langmuir.9b01188 Langmuir 2019, 35, 8383−8388
Article
Langmuir
Figure 5. AFM images: (a) G2 (1.00 × 10−4 M) in water; (b) after addition of hydrochloric acid of (a); (c) WP5 (3.30 × 10−5 M) and G2 (1.00 × 10−4 M) in water; (d) after addition of hydrochloric acid of (c); (e) measured thickness of (a); (f) measured thickness of (b); (g) measured thickness of (c); and (h) measured thickness of (d).
shown in Figure 4, amphiphile G2 self-assembled into nanoribbons in water (Figure 4a,b), and after addition of hydrochloric acid, they changed into nanosheets as G2 turned into G2′ (Figure 4c,d). After the addition of equimolar WP5 to the solution of G2, the gemini-type supramolecular amphiphile WP5⊃3G2 formed and the self-assembled aggregates turned into diskike micelles (Figure 4e,f). After the addition of hydrochloric acid WP5⊃3G2 solution, geminitype supramolecular amphiphile turned into single-chain amphiphile G2′, leading to the formation of nanosheets. Furthermore, AFM was also performed to study the structure of the aggregates self-assembled from these amphiphiles. As shown in Figure 5, amphiphile G2 selfassembled into nanoribbons in water (Figure 5a), confirming the TEM results. The thickness of the nanoribbons was estimated to be around 13.17 nm (Figure 5e). The extended length of G2 was calculated to be 2.385 nm by a DFToptimized structure in water (Figure S7), suggesting that the nanoribbons had a multilayered structure. In addition, the morphology of the self-assembled structure obtained by G2′ was confirmed by AFM, as shown in Figure 5b,f; nanosheets were observed and the thickness was around 3.944 nm, which was between one and two extended lengths of G2, suggesting that the nanosheets had a bilayered structure by antiparallel packing of G2′ in water. Moreover, the morphology of the disklike micelles formed by WP5⊃3G2 was also confirmed by AFM. As shown in Figure 5c,g, disklike micelles were observed, the thickness was around 7.286 nm, which was about two extended lengths of the gemini-type supramolecular amphiphile (Figure S8), indicating that the disklike micelles had a tetralayered structure by antiparallel packing of WP5⊃3G2 in water.1 Analogously, after addition of hydrochloric acid, the disklike micelles changed into nanosheets with a thickness of around 3.915 nm, indicating their bilayered structure (Figure 5d,h). A possible theory is put forward to explain the morphological changes of the acid-responsive self-assemblies. The amphiphilic guest G2 formed multilayered nanoribbons in water driven by hydrophobic interaction and cation−π interaction.44,49 When the solution of G2 was added with acid, G2 turned into G2′, which bears two positively charged pyridinium groups, and the cation−π interaction was destroyed. Therefore, the multilayered nanoribbons changed into bilayered nanosheets driven by hydrophobic interaction
formation of the complex. As shown in Figure 3, when G2 was gradually added to the solution of WP5, the uncomplexed WP5 disappeared when the molar ration of G2/WP5 reached 3:1. As shown in Figure 3a,c,g, compared to those of free G2 and WP5, the peaks related to the protons Hb and He on the pyridyl part of G2 shifted downfield. The peaks corresponding to the protons Ha and Hc on the pyridinium part of G2 and protons Hg, Hh, and Hi on the alkyl part of G2 shifted upfield. In addition, the chemical shift changes of Ha, Hg, Hh, and Hi were remarkable. These results suggested that the pyridinium and alkyl part of G2 was accommodated within the cavity of WP5. The 2D NOESY experiment was performed to confirm the phenomenon. As shown in Figure S3, NOE correlation signals were found between protons Hi, Hh, and Hg of G2 and proton H1 of WP5 (Figure S3A−C), between protons Hi and Hh of G2 and proton H2 of WP5 (Figure S3D,E), between proton Hi of G2 and protons H3 of WP5 (Figure S3F), confirming that the pyridium and alkyl part of G2 threaded into the cavity of WP5. Moreover, from the results of the ITC experiment (Figure S4), the stoichiometry of G2 to WP5 was 2.72:1 (approximately 3:1) and Ka was estimated to be (3.90 ± 0.56) × 106 M−1. High-resolution mass spectrometry results also confirmed the 3:1 molar ratio of G2 to WP5 (Figure S5). Due to the size of the cavity of pillar[5]arene and the size of G2,27,50 three G2 molecules all threaded into the cavity of WP5 is unreasonable. Therefore, according to the packing model of G1, a possible complexation mode was proposed. As shown in Scheme 1b, on one of the three G2 molecules, the alkyl chain next to the pyridinium part threaded into the cavity of WP5 and the other two G2 molecules both antiparallel packed to the first G2 molecules due to the cation−π interactions among the three G2 molecules. This kind of complexation behavior gave rise to the gemini-type supramolecular amphiphile WP5⊃3G2. Then, self-assembly behavior of the gemini-type supramolecular amphiphile in water was investigated. First, the CAC of the amphiphiles was determined using the concentrationdependent conductivity experiments. As shown in Figure S6, the CAC values of the amphiphiles G2 and G2′ and the gemini-type supramolecular amphiphile WP5⊃3G2 were measured to be 2.27 × 10−5, 3.46 × 10−5, and 7.17 × 10−5 M, respectively. The self-assembly behaviors of these amphiphiles in water were then investigated via TEM. As 8386
DOI: 10.1021/acs.langmuir.9b01188 Langmuir 2019, 35, 8383−8388
Langmuir
■
and the electrostatic repulsive interactions between the positively charged pyridinium groups.51 Upon addition of WP5 to the solution of G2, G2 and WP5 formed a gemini-type supramolecular amphiphile WP5⊃3G2,13 resulting in the formation of tetralayered disklike micelles because of electrostatic repulsion and steric hindrance between the supramolecular amphiphiles and hydrophobic interactions.46,52 Upon adding acid, complex WP5⊃3G2 disassociated, leading to the formation of the bilayered nanosheets formed by G2′.
CONCLUSIONS In conclusion, an acid-responsive host−guest recognition motif in water based on a monofunctionalized 4,4′-azastilbene derivative (G1) and a water-soluble pillar[5]arene (WP5) was investigated. A new strategy to construct gemini-type supramolecular amphiphile was achieved by a 4,4′-azastilbenecontaining amphiphile (G2) and WP5. Then, it was applied in stimuli-responsive self-assemblies. G2 self-assembled into multilayered nanoribbons in water. Upon addition of WP5, the gemini-type supramolecular amphiphile formed, leading to the formation of tetralayered disklike micelles. After further addition of hydrochloric acid, the morphology changed into bilayered nanosheets. This work suggested a new method to construct gemini-type supramolecular amphiphiles that can be used in diverse fields, such as nanoreactors, drug delivery systems, and bioimaging. ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.langmuir.9b01188. NMR spectra, ITC data, 2D NOESY spectra, ITC data, CAC data, DFT-optimized structure, and other materials (PDF) The single crystal data of G1 (CIF)
■
REFERENCES
(1) Wang, C.; Chen, Q.; Xu, H.; Wang, Z.; Zhang, X. Photoresponsive Supramolecular Amphiphiles for Controlled Self-Assembly of Nanofibers and Vesicles. Adv. Mater. 2010, 22, 2553−2555. (2) Zuo, M.; Qian, W.; Xu, Z.; Shao, W.; Hu, X.-Y.; Zhang, D.; Jiang, J.; Sun, X.; Wang, L. Multiresponsive Supramolecular Theranostic Nanoplatform Based on Pillar[5]arene and Diphenylboronic Acid Derivatives for Integrated Glucose Sensing and Insulin Delivery. Small 2018, 14, No. e1801942. (3) Zhou, J.; Yu, G.; Huang, F. Supramolecular Chemotherapy Based on Host-Guest Molecular Recognition: A Novel Strategy in the Battle Against Cancer with a Bright Future. Chem. Soc. Rev. 2017, 46, 7021−7053. (4) Cao, Y.; Hu, X.-Y.; Li, Y.; Zou, X.; Xiong, S.; Lin, C.; Shen, Y.-Z.; Wang, L. Multistimuli-Responsive Supramolecular Vesicles Based on Water-Soluble Pillar[6]arene and SAINT Complexation for Controllable Drug Release. J. Am. Chem. Soc. 2014, 136, 10762−10769. (5) Yu, G.; Zhou, J.; Shen, J.; Tang, G.; Huang, F. Cationic Pillar[6]arene/ATP Host-Guest Recognition: Selectivity, Inhibition of ATP Hydrolysis, and Application in Multidrug Resistance Treatment. Chem. Sci. 2016, 7, 4073−4078. (6) Zhang, X.; Wang, C. Supramolecular Amphiphiles. Chem. Soc. Rev. 2011, 40, 94−101. (7) Kang, Y.; Liu, K.; Zhang, X. Supra-Amphiphiles: A New Bridge Between Colloidal Science and Supramolecular Chemistry. Langmuir 2014, 30, 5989−6001. (8) Wang, G.; Kang, Y.; Tang, B.; Zhang, X. Tuning the Surface Activity of Gemini Amphiphile by the Host-Guest Interaction of Cucurbit[7]uril. Langmuir 2015, 31, 120−124. (9) Chi, X.; Yu, G.; Shao, L.; Chen, J.; Huang, F. A DualThermoresponsive Gemini-Type Supra-amphiphilic Macromolecular [3]Pseudorotaxane Based on Pillar[10]arene/Paraquat Cooperative Complexation. J. Am. Chem. Soc. 2016, 138, 3168−3174. (10) Rodrigues, M.; Calpena, A. C.; Amabilino, D. B.; GarduñoRamírez, M. L.; Pérez-García, L. Supramolecular Gels Based on a Gemini Imidazolium Amphiphile as Molecular Material for Drug Delivery. J. Mater. Chem. B 2014, 2, 5419−5429. (11) Zhai, X.; Zhang, L.; Liu, M. Supramolecular Assemblies between a New Series of Gemini-Type Amphiphiles and TPPS at the Air/Water Interface: Aggregation, Chirality, and Spacer Effect. J. Phys. Chem. B 2004, 108, 7180−7185. (12) Oda, R.; Huc, I.; Schmutz, M.; Candau, S. J.; MacKintosh, F. C. Tuning Bilayer Twist Using Chiral Counterions. Nature 1999, 399, 566−569. (13) Wang, C.; Wang, Z.; Zhang, X. Amphiphilic Building Blocks for Self-Assembly: From Amphiphiles to Supra-amphiphiles. Acc. Chem. Res. 2012, 45, 608−618. (14) Yu, G.; Jie, K.; Huang, F. Supramolecular Amphiphiles Based on Host-Guest Molecular Recognition Motifs. Chem. Rev. 2015, 115, 7240−7303. (15) Jeon, Y. J.; Bharadwaj, P. K.; Choi, S.; Lee, J. W.; Kim, K. Supramolecular Amphiphiles: Spontaneous Formation of Vesicles Triggered by Formation of a Charge-Transfer Complex in a Host. Angew. Chem., Int. Ed. 2002, 41, 4474−4476. (16) Yu, G.; Li, J.; Yu, W.; Han, C.; Mao, Z.; Gao, C.; Huang, F. Carbon Nanotube/Biocompatible Bola-Amphiphile Supramolecular Biohybrid Materials: Preparation and Their Application in Bacterial Cell Agglutination. Adv. Mater. 2013, 25, 6373−6379. (17) Chen, G.; Jiang, M. Cyclodextrin-Based Inclusion Complexation Bridging Supramolecular Chemistry and Macromolecular SelfAssembly. Chem. Soc. Rev. 2011, 40, 2254−2266. (18) Wang, S.-P.; Lin, W.; Wang, X.; Cen, T.-Y.; Xie, H.; Huang, J.; Zhu, B.-Y.; Zhang, Z.; Song, A.; Hao, J.; Wu, J.; Li, S. Controllable Hierarchical Self-Assembly of Porphyrin-Derived Supra-Amphiphiles. Nat. Commun. 2019, 10, No. 1399. (19) Yang, L. P.; Jia, F.; Zhou, Q. H.; Pan, F.; Sun, J. N.; Rissanen, K.; Chung, L. W.; Jiang, W. Guest-Induced Folding and Self-Assembly of Conformationally Adaptive Macrocycles into Nanosheets and Nanotubes. Chem. - Eur. J. 2017, 23, 1516−1520.
■
■
Article
The checkif report of the single crystal data of G1 (PDF)
AUTHOR INFORMATION
Corresponding Authors
*E-mail:
[email protected] (D.X.). *E-mail:
[email protected] (X.W.). *E-mail:
[email protected] (P.W.). ORCID
Danyu Xia: 0000-0001-6575-6448 Xiaoqin Wu: 0000-0002-4230-6644 Xuehong Wei: 0000-0002-9490-7265 Pi Wang: 0000-0002-8803-7953 Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS The authors gratefully acknowledge support from the National Science Foundation for Young Scientists of China (21704073), the Natural Science Foundation for Young Scientists of Shanxi Province, China (201701D221031, 201801D221078), and the high performance computing platform of Shanxi University. 8387
DOI: 10.1021/acs.langmuir.9b01188 Langmuir 2019, 35, 8383−8388
Article
Langmuir
10-methylacridinium Iodide Molecular Recognition. Chem. Commun. 2014, 50, 5064−5067. (40) Coe, B. J.; Foxon, S. P.; Harper, E. C.; Helliwell, M.; Raftery, J.; Swanson, C. A.; Brunschwig, B. S.; Clays, K.; Franz, E.; Garín, J.; Orduna, J.; Horton, P. N.; Hursthouse, M. B. Evolution of Linear Absorption and Nonlinear Optical Properties in V-Shaped Ruthenium(II)-Based Chromophores. J. Am. Chem. Soc. 2010, 132, 1706−1723. (41) El’chishcheva, N. V.; Shklyaev, Y. V.; Vnutskikh, Z. A.; Odegova, T. F.; Chekryshkin, Y. S.; Dubrovina, S. S. Synthesis and Antimicrobial Activity of New Mono-and Biquaternized Dipyridylethanes and Dipyridylethylenes. Pharm. Chem. J. 2010, 44, 251−253. (42) Sheldrick, G. Crystal Structure Refinement with SHELXL. Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 2015, 71, 3−8. (43) Sheldrick, G. A Short History of SHELX. Acta Crystallogr., Sect. A: Cryst. Phys., Diffr., Theor. Gen. Crystallogr. 2008, 64, 112−122. (44) Zhang, Y. J.; Chen, C.; Tan, B.; Cai, L. X.; Yang, X. D.; Zhang, J. A Dual-Stimuli Responsive Small Molecule Organic Material with Tunable Multi-State Response Showing Turn-on Luminescence and Photocoloration. Chem. Commun. 2016, 52, 2835−2838. (45) Zhang, C. F.; Li, S. H.; Zhang, C. C.; Liu, Y. Molecular Binding Behaviors and Thermodynamics of Ferrocenyl Dimethylaminium Derivatives by Anionic Pillar[5]arene. Org. Biomol. Chem. 2015, 13, 10808−10812. (46) Yu, G.; Xue, M.; Zhang, Z.; Li, J.; Han, C.; Huang, F. A WaterSoluble Pillar[6]arene: Synthesis, Host−Guest Chemistry, and Its Application in Dispersion of Multiwalled Carbon Nanotubes in Water. J. Am. Chem. Soc. 2012, 134, 13248−13251. (47) Xia, D.; Wang, P.; Shi, B. Controlling the Photochemical Reaction of an Azastilbene Derivative in Water Using a Water-Soluble Pillar[6]arene. Org. Biomol. Chem. 2017, 15, 7618−7622. (48) Li, Z.; Yang, J.; Yu, G.; He, J.; Abliz, Z.; Huang, F. Synthesis of a Water-Soluble Pillar[9]arene and Its pH-Responsive Binding to Paraquat. Chem. Commun. 2014, 50, 2841−2843. (49) Yu, G.; Zhou, X.; Zhang, Z.; Han, C.; Mao, Z.; Gao, C.; Huang, F. Pillar[6]arene/Paraquat Molecular Recognition in Water: High Binding Strength, pH-Responsiveness, and Application in Controllable Self-Assembly, Controlled Release, and Treatment of Paraquat Poisoning. J. Am. Chem. Soc. 2012, 134, 19489−19497. (50) Yu, G.; Han, C.; Zhang, Z.; Chen, J.; Yan, X.; Zheng, B.; Liu, S.; Huang, F. Pillar[6]arene-Based Photoresponsive Host−Guest Complexation. J. Am. Chem. Soc. 2012, 134, 8711−8717. (51) Song, B.; Wang, Z.; Chen, S.; Zhang, X.; Fu, Y.; Smet, M.; Dehaen, W. The Introduction of π−π Stacking Moieties for Fabricating Stable Micellar Structure: Formation and Dynamics of Disklike Micelles. Angew. Chem., Int. Ed. 2005, 44, 4731−4735. (52) Yan, Q.; Yuan, J.; Kang, Y.; Yin, Y. Dynamic Supramacromolecular Self-Assembly: Deformable Polymer Fabricated Nanostructures through a Host-Controlled Approach. Polym. Chem. 2010, 1, 423−425.
(20) Xia, D.; Li, Y.; Jie, K.; Shi, B.; Yao, Y. A Water-Soluble Cyclotriveratrylene-Based Supra-amphiphile: Synthesis, pH-Responsive Self-Assembly in Water, and Its Application in Controlled Drug Release. Org. Lett. 2016, 18, 2910−2913. (21) Zhu, H.; Shangguan, L.; Shi, B.; Yu, G.; Huang, F. Recent Progress in Macrocyclic Amphiphiles and Macrocyclic Host-Based Supra-Amphiphiles. Mater. Chem. Front. 2018, 2, 2152−2174. (22) Zhou, J.; Yang, J.; Zhang, Z.; Yu, G. A Cationic Water-Soluble Biphen[3]arene: Synthesis, Host−Guest Complexation and Fabrication of a Supra-Amphiphile. RSC Adv. 2016, 6, 77179−77183. (23) Zhou, J.; Yu, G.; Shao, L.; Hua, B.; Huang, F. A Water-Soluble Biphen[3]arene: Synthesis, Host-Guest Complexation, and Application in Controllable Self-Assembly and Controlled Release. Chem. Commun. 2015, 51, 4188−4191. (24) Wang, M.; Zhou, J. Discovery of Non-Classical Complex Models between a Cationic Water-Soluble Pillar[6]arene and Naphthalenesulfonate Serivatives and Their Self-Assembling behaviors. Soft Matter 2019, 15, 4127−4131. (25) Ogoshi, T.; Kanai, S.; Fujinami, S.; Yamagishi, T.-a.; Nakamoto, Y. para-Bridged Symmetrical Pillar[5]arenes: Their Lewis Acid Catalyzed Synthesis and Host−Guest Property. J. Am. Chem. Soc. 2008, 130, 5022−5023. (26) Sathiyajith, C.; Shaikh, R. R.; Han, Q.; Zhang, Y.; Meguellati, K.; Yang, Y.-W. Biological and Related Applications of Pillar[n]arenes. Chem. Commun. 2017, 53, 677−696. (27) Xue, M.; Yang, Y.; Chi, X.; Zhang, Z.; Huang, F. Pillararenes, A New Class of Macrocycles for Supramolecular Chemistry. Acc. Chem. Res. 2012, 45, 1294−1308. (28) Wang, Y.; Ping, G.; Li, C. Efficient Complexation between Pillar[5]arenes and Neutral Guests: from Host-Guest Chemistry to Functional Materials. Chem. Commun. 2016, 52, 9858−9872. (29) Ogoshi, T.; Yamagishi, T.-a.; Nakamoto, Y. Pillar-Shaped Macrocyclic Hosts Pillar[n]arenes: New Key Players for Supramolecular Chemistry. Chem. Rev. 2016, 116, 7937−8002. (30) Li, B.; Meng, Z.; Li, Q.; Huang, X.; Kang, Z.; Dong, H.; Chen, J.; Sun, J.; Dong, Y.; Li, J.; Jia, X.; Sessler, J. L.; Meng, Q.; Li, C. A pH Responsive Complexation-Based Drug Delivery System for Oxaliplatin. Chem. Sci. 2017, 8, 4458−4464. (31) Sun, Y.; Zhang, F.; Quan, J.; Zhu, F.; Hong, W.; Ma, J.; Pang, H.; Sun, Y.; Tian, D.; Li, H. A Biomimetic Chiral-Driven Ionic Gate Constructed by Pillar[6]arene-Based Host−Guest Systems. Nat. Commun. 2018, 9, No. 2617. (32) Zhou, T.; Song, N.; Yu, H.; Yang, Y.-W. Pillar[5,6]areneFunctionalized Silicon Dioxide: Synthesis, Characterization, and Adsorption of Herbicide. Langmuir 2015, 31, 1454−1461. (33) Zhang, H.; Liu, Z.; Zhao, Y. Pillararene-Based Self-Assembled Amphiphiles. Chem. Soc. Rev. 2018, 47, 5491−5528. (34) Duan, Q.; Cao, Y.; Li, Y.; Hu, X.; Xiao, T.; Lin, C.; Pan, Y.; Wang, L. pH-Responsive Supramolecular Vesicles Based on WaterSoluble Pillar[6]arene and Ferrocene Derivative for Drug Delivery. J. Am. Chem. Soc. 2013, 135, 10542−10549. (35) Yao, Y.; Chi, X.; Zhou, Y.; Huang, F. A Bola-Type SupraAmphiphile Constructed from a Water-Soluble Pillar[5]arene and a Rod-coil Molecule for Dual Fluorescent Sensing. Chem. Sci. 2014, 5, 2778−2782. (36) Xia, D.; Yu, G.; Li, J.; Huang, F. Photo-Responsive SelfAssembly Based on a Water-Soluble Pillar[6]arene and an Azobenzene-Containing Amphiphile in Water. Chem. Commun. 2014, 50, 3606−3608. (37) Yang, K.; Chang, Y.; Wen, J.; Lu, Y.; Pei, Y.; Cao, S.; Wang, F.; Pei, Z. Supramolecular Vesicles Based on Complex of Trp-Modified Pillar[5]arene and Galactose Derivative for Synergistic and Targeted Drug Delivery. Chem. Mater. 2016, 28, 1990−1993. (38) Guo, S.; Song, Y.; He, Y.; Hu, X.-Y.; Wang, L. Highly Efficient Artificial Light-Harvesting Systems Constructed in Aqueous Solution Based on Supramolecular Self-Assembly. Angew. Chem., Int. Ed. 2018, 57, 3163−3167. (39) Wang, P.; Yao, Y.; Xue, M. A Novel Fluorescent Probe for Detecting Paraquat and Cyanide in Water Based on Pillar[5]arene/ 8388
DOI: 10.1021/acs.langmuir.9b01188 Langmuir 2019, 35, 8383−8388
