Stabilization and Multiple-Responsive Recognition of Natural Base Pairs in Water by a Cationic Cage

Open AccessCCS ChemistryCOMMUNICATION5 Sep 2022Stabilization and Multiple-Responsive Recognition of Natural Base Pairs in Water by a Cationic Cage Lin Cheng, Ping Tian, Qingfang Li, Anyang Li and Liping Cao Lin Cheng College of Chemistry and Materials Science, Northwest University, Xi’an 710069 Google Scholar More articles by this author , Ping Tian College of Chemistry and Materials Science, Northwest University, Xi’an 710069 Google Scholar More articles by this author , Qingfang Li College of Chemistry and Materials Science, Northwest University, Xi’an 710069 Google Scholar More articles by this author , Anyang Li College of Chemistry and Materials Science, Northwest University, Xi’an 710069 Google Scholar More articles by this author and Liping Cao *Corresponding author: E-mail Address: [email protected] College of Chemistry and Materials Science, Northwest University, Xi’an 710069 Google Scholar More articles by this author https://doi.org/10.31635/ccschem.021.202101584 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail The hydrogen-bonded (H-bonded) base pairs, double H-bonded A•T and triple H-bonded G•C in DNA, are important units for storing, encoding, and expressing genetic information. Owing to the interference from water, however, the formation of H-bonded base pairs from short deoxynucleotide fragments such as mono- or di-deoxynucleotide are not easily achieved in aqueous solutions. Here, we report a host–guest strategy to stabilize H-bonded base pairs of monodeoxynucleotides by a tetraphenylethene (TPE)-based octacationic cage to form host–guest complexes in water. The X-ray structure of cage⊃base pair complex clearly shows the double hydrogen bonds between A and T can be stabilized inside the hydrophobic cavity of the cage to form a H-bonded base pair ( A•T) with the Hoogsteen pairing rule. Furthermore, the adaptive chirality of the cage with excess right-handed (P) rotational conformation of TPE units is triggered by two base pairs ( A•T and G•C) to exhibit differentiated multiple responses, including turn-on/turn-off fluorescence, negative circular dichroism, and negative circularly polarized luminescence in water. Download figure Download PowerPoint Introduction The research in supramolecular chemistry1 stemming from natural systems has mainly been focused on the synthetic mimicking of biological structures/processes to understand the mysteries of nature and then develop functional systems, such as biosensors, catalysts, drug delivery systems, and molecular machines.2–6 Compared to natural systems, these artificial supramolecular systems offer relatively simplified and representative models to uncover the intrinsic mechanisms or rules of molecular behavior in biological systems, such as the efficient synthesis of DNA in DNA polymerase, selective catalysis based on protein recognition, and controllable ion transmission through molecular channels.7 And all of these molecule behaviors—including substance transfer, catalysis, recognition, and self-assembly—occur in water, which is an important medium, essential to all life.8 On the other hand, compared to pure organic systems, aqueous reactions or assemblies have many more challenges, such as poor solubility of organic molecules in water, interference from water molecules due to strong hydrogen bonds or solvation, and a strong hydrophobic effect. To address these problems, supramolecular scientists try to study molecular recognition or self-assembly in aqueous environments by using water-soluble hosts such as clips, macrocycles, and cages through host–guest complexation.9–14 For example, Isaacs and coworker11 mimicked the supra strong binding between avidin and biotin (Ka ≈ 1015 M−1) to find a stronger binding pair of cucurbit[7]uril and the diamantane quaternary diammonium ion with an attomolar dissociation constant in water. Others have explored molecular behavior involving recognition, catalysis, and chirality based on host–guest recognition in aqueous systems.12–15 The water-soluble tetraphenylethene (TPE)-based octacationic cage ( 1) possesses remarkable absorption, excellent fluorescence, and adaptive chirality (Scheme 1a, top).16–20 Based on the left-handed (M) and right-handed (P) rotational conformation of two TPE units (Scheme 1a, bottom), in theory, 1 can have three conformational isomers. including mesomeric PM- 1 and a pair of racemic MM- 1 and PP- 1. The M-rotational conformation of TPE can exhibit positive circular dichroism (CD) and circularly polarized luminescence (CPL) signals, and P-rotational conformation of TPE can exhibit negative CD and CPL signals, which are ideal responses for chiral guests. This dynamically conformational chirality of the free cage cannot express any chiral signals when binding without any chiral guests in solution, because there is no preference between the racemic MM-/PP- and mesomeric MP-rotational conformation of two TPE units. However, this TPE-based achiral cage can preferentially adopt one of the chiral conformations (PP or MM) to exhibit adaptive chirality via efficient through-space chirality transfer between cage and guests when binding with chiral guests.19 Therefore, an achiral cage 1 with dynamically adaptive features could be an ideal host for recognizing chiral biomolecules or bioassemblies with chiroptical responses. Scheme 1 | Chemical structures of (a) 1 and its P-/M-rotational conformation of TPE unit, (b) deoxynucleotides (A, T, G, and C), and (c) possible H-bonded structures of base pairs (A•T and G•C) analyzed based on the data from the Cambridge Structural Database.b Download figure Download PowerPoint As basic units in DNA, deoxynucleotides ( A, T, C, and G; Scheme 1b) have received considerable attention because of the chirality and H-bonded heterodimerization of their base pairs ( A•T and G•C; Scheme 1c) in the double helix structure.21 Owing to the interference from water molecules, monodeoxynucleotides cannot form stable H-bonded base pairs in water, although recognition of their derivatives have been achieved in organic solvents.7,22 However, biological evolution processes provide a perfect solution to stabilize H-bonded base pairs through the hydrophobic pockets of enzymes in the duplication process of genetic information.23 The relatively hydrophobic cavity offers a comfortable environment (which is isolated from bulk water) to promote the formation of hydrogen bonds. Inspired by nature, hydrophobic proflavin molecule, micelle, or metal-organic framework serve as a platform for the recognition or formation of unnatural base pairs.24–26 Previously, Fujita and coworkers27,28 first reported the encapsulation of natural base pairs with anti-Hoogsteen H-bonds by metallacages in solution and in the crystalline state. In that case, the hydrogen-bonding groups were incorporated inside the hydrophobic cavity of the metallacage, which shielded the hydrogen bonds from outside water molecules. However, the chiral characterization or response with spectroscopic features for these base pairs by using supramolecular hosts through host–guest complexation in water still is a huge challenge. Therefore, development of chiral recognition with chiral signals such as CD and CPL for deoxynucleotide base pairs via a supramolecular approach is desired. Given the hydrophobic cavity, optical properties, and adaptive chirality of the TPE-based octacationic cage, herein we report the stabilization and adaptively chiral recognition of base pairs ( A•T and G•C) by 1 in water. The X-ray structure of cage⊃base pair complex confirms that this cage prefers to encapsulate and stabilize base pair A•T, which is assembled through double hydrogen bonds with the Hoogsteen pairing rule inside the cavity of the cage. Furthermore, excess P-rotational conformation of TPE units on the cage is triggered by base pairs in water to achieve differentiated multiple responses on fluorescence, CD, and CPL Results and Discussion The hydrophobic and rigid cavity of 1 is an ideal space in aqueous media for the formation of H-bonded base pairs between monodeoxynucleotides. The X-ray quality crystal of 1 (1.0 mM) with A (1.2 equiv) and T (1.2 equiv) was obtained by slow vapor diffusion of acetone into its aqueous solution at 10 °C (Figure 1 and Supporting Information Table S1).a In the host–guest complex, the chiral sugar units of base pairs create a chiral environment for the inside cavity of the cage, which compels TPE units to preferentially adopt P- or M-rotation conformation. In the X-ray structure of 1 with A and T, two TPE units of 1 show both PP-rotational conformation and MM-rotational conformation, which indicates that the chiral guests can induce the achiral MP -1 to the chiral MM-/PP -1 (Figure 1a). Base pair A 1 •T 1 in the cavity of the cage adopts the Hoogsteen pairing rule with a R22(9) H-bonded motif, in which the NH···O and CH···N distances are 2.09 and 2.47 Å, respectively (Figure 1b, top). The base units of A 1 and T 1 are not in the same geometric plane, and the dihedral angle between them is about 30.9° (Figure 1b, bottom). Notably, besides the base pair ( A 1 •T 1) in the cavity of the cage, another adenine A 2 contacts with A 1 •T 1 through CH···N (2.62 Å) and NH···O (2.63 Å) hydrogen bonds ( Supporting Information Figure S1). Furthermore, multiple noncovalent interactions (e.g., hydrogen bonds, CH∙∙∙π, and π∙∙∙π interactions) are found between host and guests. For example, the adenine or thymine units in the base pair are held within the cavity by multiple CH-π (2.52–2.83 Å) and π–π (3.87 Å) interactions ( Supporting Information Figures S2 and S3), while the CH-π interactions (2.30–3.48 Å) between adeninyl CH/thyminyl CH3 and p-xylylene rings at the surrounding pillar position also contribute to host–guest complexation ( Supporting Information Figure S4). At the same time, another host–guest complex also exists in which there are no obvious hydrogen bonds between A and T ( Supporting Information Figure S5). The X-ray structure of the chiral cage⊃base pair indicates that base pairs can induce the chiral conformation of a TPE-based cage to exhibit adaptive chirality. Figure 1 | X-ray structures of (a) PP-1⸧(A 1•T 1•A 2) and (b) H-bonded pattern of A 1•T 1•A 2 in the cavity. Counter ions Cl− are omitted for clarity. Only PP-rotational conformation of two TPE units is shown here. Download figure Download PowerPoint The 1H NMR titration experiment of 1 with the 1:1 mixture of A and T was employed to investigate the host–guest complexation in D2O (Figures 2a and 2b). For guests, the 1H NMR spectra of host–guest complex showed that the proton resonances for the adenine or thymine (H1′–H2′), ribodesose (H3′–H6′), and CH2 (H7′) exhibited upfield shifts when compared to free A and T, confirming that both A and T molecules were fully encapsulated inside the cavity of the cage. For the cage, the resonances (Ha′–Hc′) for the phenyl protons of TPE units showed large upfield shifts (ΔHa′ = −0.32 ppm and ΔHb′ = −0.12 ppm) at the ratio of 1:( A•T) = 1:1 caused by π-electron shielding of the adenine and thymine units of A•T, which indicates that the adenine and thymine units are located at the center of the hydrophobic cavity. In contrast, the proton resonances for the pyridinium (Hd′), CH2 (He′), and p-xylylene (Hf′) units, which are located at the edge of the cavity, displayed slight downfield shifts (ΔHc′ = 0.03 ppm, ΔHd′ = 0.14 ppm, ΔHe′ = 0.06 ppm, and ΔHf′ = 0.13 ppm), owing to the deshielding effects of the adenine and thymine units and the electrostatic interactions between the phosphate groups and the pyridinium cationic units. 1H NMR titration of 1 with the 1:1 mixture of C and G also showed similar chemical shifts to form the 1⊃( G•C) complex ( Supporting Information Figure S6). The step-by-step titrations of 1 by A/G firstly and then T/C, or T/C firstly and then A/G showed the same equilibrium state, indicating that these hetero host–guest systems have thermodynamic stability when compared with the corresponding homo host–guest systems ( Supporting Information Figures S7 and S8). Figure 2 | (a) Schematic representation for the formation of cage⊃base pairs. (b) 1H NMR spectra (400 MHz, 298 K, D2O) of 1 (0.4 mM) titrated with the 1:1 mixture of A and T (0–5.0 equiv). Primes (′) denote the resonances within the host–guest complex. Download figure Download PowerPoint Isothermal titration calorimetry (ITC) further gave the 1:1 stoichiometry between 1 and A•T/G•C with binding constants of Ka = (2.16 ± 0.05) × 104 M−1 for 1⊃( A•T) and Ka = (1.36 ± 0.21) × 105 M−1 for 1⊃( G•C) in H2O, respectively, which are consistent with the results from UV–vis titration ( Supporting Information Figures S9 and S10 and Table S2). Electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS) and Job plots by both NMR and UV-vis measurements indicated the 1:1 stoichiometry of the 1⊃( A•T) and 1⊃( G•C) complexes ( Supporting Information Figures S11–S14). Based on the above results, it is obvious that A•T and G•C base pairs can be stabilized through the hydrogen bonds between corresponding deoxynucleotide base pairs inside a hydrophobic cavity of the cage to form 1⊃( A•T) and 1⊃( G•C) host–guest complexes. In these complexes, the cage offers a hydrophobic cavity as a perfect shelter for promoting the formation of H-bonded base pairs in water. Given the photophysical property of the TPE-based cage, host–guest complexation endows 1⊃( A•T) and 1⊃( G•C) complexes with distinct photophysical responses, including UV/vis absorption (200–450 nm) and fluorescent emission (450–700 nm). In UV/vis titration experiments of 1 with the 1:1 mixture of A/T or G/C in water, the absorbance maximum of the host was slightly red-shifted with two clean isobestic points, respectively, confirming the charge-transfer interactions between the cage and the guests ( Supporting Information Figures S15 and S16). Interestingly, the fluorescence intensity at 550 nm of the supramolecular system increased, accompanying the formation of the 1⊃( A•T) complex (ΦF = 52.4%) when compared with free 1 (ΦF = 27.2%)16 (Figure 3a and Supporting Information Table S3). In contrast, the fluorescence intensity of the 1⊃( G•C) complex (ΦF = 7.7%) exhibited an obvious decrease (Figure 3b and Supporting Information Table S3). It is the result of equilibrium between the fluorescence enhancement mechanism restricting intramolecular rotation (RIR) based on the restriction of TPE units from the host–guest complex29,30 and the fluorescence-quenching mechanism of photoinduced electron transfer (PET) based on the charge-transfer interaction between the cage and the guests.31 G•C can induce strong PET between cage and guest because the higher tendency of guanine to donate electrons induces fluorescence quenching compared to the other bases,32 while both A•T and G•C in the cavity partially restrict RIR of two TPE units in the cage to increase fluorescence. Figure 3 | Fluorescence spectral response of 1 (10 μM) titrated with 1:1 mixture of (a) A and T or (b) G and C in water. λex = 410 nm, Ex/Em slit = 1.1 nm. Download figure Download PowerPoint The chiral recognition with both CD and CPL responses by a host has not yet been explored and applied for base pairs in aqueous solutions. Cage, deoxynucleotides, or 1:1 mixture of A/ T or G/ C did not exhibit any obvious Cotton effect in the long-wavelength (300–450 nm) region ( Supporting Information Figure S17). However, CD spectra of 1 (20 μM) titrated with the 1:1 mixture of A, and T showed two new negative CD signals centered at 330 nm (gabs ≈ −1.1 × 10−4) and 390 nm (gabs ≈ −8.8 × 10−5), and stronger negative/positive CD signals at 200–250 nm (gabs(240 nm) ≈ −2.4 × 10−4) and 250–300 nm (gabs(290 nm) ≈ 6.5 × 10−5) when compared with free guests (Figure 4a and Supporting Information Table S4). This strongly suggests that the adaptive chirality of 1 is induced by the chirality of A•T. Similarly, CD spectra of 1 (20 μM) with a 1:1 mixture of G and C also exhibited two new negative CD signals centered at 330 nm (gabs ≈ −2.7 × 10−4) and 395 nm (gabs ≈ –2.8 × 10−4), and stronger negative/positive CD signals at 200–250 nm (gabs(220 nm) ≈ −4.40 × 10−4) and 250–300 nm (gabs(280 nm) ≈ 1.8 × 10−4) when compared with free guests (Figure 4b and Supporting Information Table S4). Based on previous reports18–20,31,33,34 and theoretical calculations ( Supporting Information Figure S18), the negative Cotton effect in the 300–450 nm region is attributed to the P-rotational conformation of TPE units, strongly suggesting that P-rotational conformation of TPE units on the chiral host–guest complexes is preferential. Energy-minimized structures of possible chiral host–guest complexes show that the dynamic conformation transformation from MP- 1/MM- 1 to PP- 1 is an energy-favored process when a cage binds with base pairs ( Supporting Information Figure S19). We observe that CD spectra are continuously changing after the addition of more than 1.0 equiv of base pair, indicating that there are some extra interactions (e.g., π–π and electrostatic interactions) between cage and exo-guests (which like A2 make contact with the base pair through hydrogen bonds, in the same way as shown in the X-ray structure or which are located on the cationic surface of the cage35,36). In this case, the adaptive chirality of 1 is dynamic and reversible based on the recognition of chiral guests, which is an adaptively chiral recognition. As a result, it is difficult to precisely determine the proportion of P- and M-rotational conformation of TPE units on the host–guest complexes in solution, and the chiral response on CD is attributed to the excess P-rotational conformation of TPE units in three possible conformation isomers, MP- 1, MM- 1, and PP- 1. Figure 4 | CD spectral response of 1 titrated with 1:1 mixture of (a) A and T and (b) G and C in water. CPL spectral response of 1 titrated with 1:1 mixture of (c) A and T and (d) G and C in water. For CD, [1] = 20 μM; for CPL, [1] = 100 μM, [A] = [T] = [G] = [C] = 100 μM, λex = 350 nm, Ex/Em slit = 2000 μm. Download figure Download PowerPoint The adaptively chiral recognition endowed these chiral host–guest complexes with excellent fluorescence and the dynamically adaptive chirality of the TPE units, which achieve a perfect integration of emission and chirality. Therefore, the chiral recognition of base pairs by 1 in the ground state encouraged us to explore their CPL property, which is an extra signal of chiral recognition in the excited state. Free cage 1 does not display CPL; however, achiral 1 exhibits a negative CPL response when binding with A•T (glum(545 nm) = −3.8 × 10−4) and G•C (glum(545 nm) = −6.3 × 10−4), which is a result of P-rotational conformation of TPE units (Figures 4c and 4d). The correlation between CD and CPL signals reveals that the chiral host–guest complexes with negative Cotton effect in the 300–450 nm region display negative CPL.18–20,33,34 Therefore, P-rotational conformation of TPE units in the cage has a definite chirality relationship between the negative Cotton effect in the 300–450 nm region and the negative CPL centered at 550 nm. Conclusions In conclusion, we have developed a host–guest strategy to stabilize the H-bonded heterodimerization of natural base pairs inside the cavity of a TPE-based octacationic cage in water. The X-ray structure of the base pair A•T is successfully captured by the hydrophobic cavity of the cage from the bulk-water environment, which is solid X-ray evidence of natural monodeoxynucleotide base pairs with the Hoogsteen pairing rule. More interestingly, the cage exhibits adaptive chirality induced by base pairs to achieve a unique chiral recognition with multiple differentiated responses to fluorescence, CD, and CPL. In the future, this adaptively chiral recognition of the TPE-based cage for natural base pairs can be applied to determine base sequences of DNA by using the cage as a single-molecular probing mechanism. Footnote a CCDC 2100667 (the host–guest complexes of 1 with A and T) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif b Analysis of the heterodimeric H-bonded structures of adenine/thymine and guanine/cytosine units from CSD (see Supporting Information Figure S20 and Tables S5–S6). Supporting Information Supporting Information is available and includes experimental details about NMR, ITC, ESI-TOF-MS, UV–vis, fluorescence, CD and CPL data, and X-ray structure analysis of hydrogen-bonded dimers from CCD. Conflict of Interest There is no conflict of interest to report. Funding Information This work was supported by the National Natural Science Foundation of China (nos. 22122108, 21971208, and 21771145), the Natural Science Basic Research Plan for Distinguished Young Scholars in Shaanxi Province of China (no. 2021JC-37), the Fok Ying Tong Education Foundation (no. 171010), and the Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates (no. 2019B030301003) from South China University of Technology. References 1. Lehn J.-M.Supramolecular Chemistry—Scope and Perspectives Molecules, Supermolecules, and Molecular Devices (Nobel Lecture).Angew. Chem. Int. Ed.1988, 27, 89–112. Google Scholar 2. Bruns C. J.; Stoddart J. F.Rotaxane-Based Molecular Muscles.Acc. Chem. Res.2014, 47, 2186–2199. Google Scholar 3. Ma X.; Tian H.Bright Functional Rotaxanes.Chem. Soc. Rev.2010, 39, 70–80. Google Scholar 4. Persch E.; Dumele O.; Diederich F.Molecular Recognition in Chemical and Biological Systems.Angew. Chem. Int. Ed.2015, 54, 3290–3327. Google Scholar 5. Erbas-Cakmak S.; Leigh D. A.; McTernan C. T.; Nussbaumer A. L.Artificial Molecular Machines.Chem. Rev.2015, 115, 10081–10206. Google Scholar 6. Koumura N.; Zijlstra R. W. J.; van Delden R. A.; Harada N.; Feringa B. L.Light-Driven Monodirectional Molecular Rotor.Nature1999, 401, 152–155. Google Scholar 7. Philp D.; Stoddart J. F.Self-Assembly in Natural and Unnatural Systems.Angew. Chem. Int. Ed.1996, 35, 1154–1196. Google Scholar 8. Weaver R. F.Molecular Biology, 5th ed.; McGraw-Hill Companies, Inc.: New York, 2012. Google Scholar 9. Salonen L. M.; Ellermann M.; Diederich F.Aromatic Rings in Chemical and Biological Recognition: Energetics and Structures.Angew. Chem. Int. Ed.2011, 50, 4808–4842. Google Scholar 10. Biedermann F.; Nau W. M.; Schneider H.-J.The Hydrophobic Effect Revisited—Studies with Supramolecular Complexes Imply High-Energy Water as a Noncovalent Driving Force.Angew. Chem. Int. Ed.2014, 53, 11158–11171. Google Scholar 11. Cao L.; Sekutor M.; Zavalij P. Y.; Mlinaric-Majerski K.; Glaser R.; Isaacs L.Cucurbit[7]uril·Guest Pair with an Attomolar Dissociation Constant.Angew. Chem. Int. Ed.2014, 53, 988–993. Google Scholar 12. Davis A. P.Biomimetic Carbohydrate Recognition.Chem. Soc. Rev.2020, 49, 2531–2545. Google Scholar 13. Plajer A. J.; Percástegui E. G.; Santella M.; Rizzuto F. J.; Gan Q.; Laursen B. W.; Nitschke J. R.Fluorometric Recognition of Nucleotides within a Water-Soluble Tetrahedral Capsule.Angew. Chem. Int. Ed.2019, 58, 4200–4204. Google Scholar 14. Nian H.; Cheng L.; Wang L.; Zhang H.; Wang P.; Li Y.; Cao L.Hierarchical Two-Level Supramolecular Chirality of an Achiral Anthracene-Based Tetracationic Nanotube in Water.Angew. Chem. Int. Ed.2021, 60, 15354–15358. Google Scholar 15. Liu M.; Zhang L.; Wang T.Supramolecular Chirality in Self-Assembled Systems.Chem. Rev.2015, 115, 7304–7397. Google Scholar 16. Duan H.; Li Y.; Li Q.; Wang P.; Liu X.; Cheng L.; Yu Y.; Cao L.Host–Guest Recognition and Fluorescence of a Tetraphenylethene-Based Octacationic Cage.Angew. Chem. Int. Ed.2020, 59, 10101–10110. Google Scholar 17. Duan H.; Cao F.; Hao H.; Bian H.; Cao L.Efficient Photoinduced Energy and Electron Transfers in a Tetraphenylethene-Based Octacationic Cage Through Host–Guest Complexation.ACS Appl. Mater. Interfaces2021, 13, 16837–16845. Google Scholar 18. Li Y.; Li Q.; Miao X.; Qin C.; Chu D.; Cao L.Adaptive Chirality of an Achiral Cucurbit[8]uril-Based Supramolecular Organic Framework for Chirality Induction in Water.Angew. Chem. Int. Ed.2021, 60, 6744–6751. Google Scholar 19. Cheng L.; Liu K.; Duan Y.; Duan H.; Li Y.; Gao M.; Cao L.Adaptive Chirality of an Achiral Cage: Chirality Transfer, Induction, and Circularly Polarized Luminescence through Aqueous Host–Guest Complexation.CCS Chem.2020, 2, 2749–2751. Google Scholar 20. Zhang H.; Cheng L.; Nian H.; Du J.; Chen T.; Cao L.Adaptive Chirality of Achiral Tetraphenylethene-Based Tetracationic Cyclophanes with Dual Responses of Fluorescence and Circular Dichroism in Water.Chem. Commun.2021, 57, 3135–3138. Google Scholar 21. Saenger W.Principles of Nucleic Acid Structure; Springer: Berlin, 1984. Google Scholar 22. Sessler J. L.; Lawrence C. M.; Jayawickramarajah J.Molecular Recognition via Base-Pairing.Chem. Soc. Rev.2007, 36, 314–325. Google Scholar 23. Korostelev A.; Trakhanov S.; Laurberg M.; Noller H. F.Crystal Structure of a 70S Ribosome-tRNA Complex Reveals Functional Interactions and Rearrangements, Cell2006, 126, 1065–1077. Google Scholar 24. Nowick J. S.; Chen J. S.; Noronha G.Molecular Recognition in Micelles: The Roles of Hydrogen Bonding and Hydrophobicity in Adenine-Thymine Base-Pairing in SDS Micelles.J. Am. Chem. Soc.1993, 115, 7636–7644. Google Scholar 25. Nowick J. S.; Cao T.; Noronha G.Molecular Recognition between Uncharged Molecules in Aqueous Micelles.J. Am. Chem. Soc.1994, 116, 3285–3289. Google Scholar 26. Cai H.; Li M.; Lin X.-R.; Chen W.; Chen G.-H.; Huang X.-C.; Li D.Spatial, Hysteretic, and Adaptive Host–Guest Chemistry in a Metal–Organic Framework with Open Watson–Crick Sites.Angew. Chem. Int. Ed.2015, 54, 10454–10459. Google Scholar 27. Sawada T.; Yoshizawa M.; Sato S.; Fujita M.Minimal Nucleotide Duplex Formation in Water through Enclathration in Self-Assembled Hosts.Nat. Chem.2009, 1, 53–56. Google Scholar 28. Sawada T.; Fujita M.A Single Watson-Crick G · C Base Pair in Water: Aqueous Hydrogen Bonds in Hydrophobic Cavities.J. Am. Chem. Soc.2010, 132, 7194–7201. Google Scholar 29. Li J.; Wang J.; Li H.; Song N.; Wang D.; Tang B. Z.Supramolecular Materials Based on AIE Luminogens (AIEgens): Construction and Applications.Chem. Soc. Rev.2020, 49, 1144–1172. Google Scholar 30. Feng H.-T.; Yuan Y.-X.; Xiong J.-B.; Zheng Y.-S.; Tang B. Z.Macrocycles and Cages Based on Tetraphenylethylene with Aggregation-Induced Emission Effect.Chem. Soc. Rev.2018, 47, 7452–7476. Google Scholar 31. Cheng L.; Zhang H.; Dong Y.; Zhao Y.; Yu Y.; Cao L.Tetraphenylethene-Based Tetracationic Cyclophanes and Their Selective Recognition for Amino Acids and Adenosine Derivatives in Water.Chem. Commun.2019, 55, 2372–2375. Google Scholar 32. Lakowicz J. R.Principles of Fluorescence Spectroscopy, Chapter 9; Springer: Singapore, 2006, pp 331–348. Google Scholar 33. Qu H.; Wang Y.; Li Z.; Wang X.; Fang H.; Tian Z.; Cao X.Molecular Face-Rotating Cube with Emergent Chiral and Fluorescence Properties.J. Am. Chem. Soc.2017, 139, 18142–18145. Google Scholar 34. Xiong J. B.; Feng H. T.; Sun J. P.; Xie W. Z.; Yang D.; Liu M. H.; Zheng Y. S.The Fixed Propeller-Like Conformation of Tetraphenylethylene that Reveals Aggregation-Induced Emission Effect, Chiral Recognition, and Enhanced Chiroptical Property.J. Am. Chem. Soc.2016, 138, 11469–11472. Google Scholar 35. Duan H.; Cao F.; Zhang M.; Gao M.; Cao L.On-Off-On Fluorescence Detection for Biomolecules by a Fluorescent Cage through Host–Guest Complexation in Water.Chin. Chem. Lett.2021. doi: https://doi.org/10.1016/j.cclet.2021.11.010 Crossref, Google Scholar 36. Xu W.; Duan H.; Chang X.; Wang G.; Hu D.; Wang Z.; Cao L.; Fang Y.Polyanion and Anionic Surface Monitoring in Aqueous Medium Enabled by an Ionic Host–Guest Complex.Sens. Actuators B: Chem.2021, 340, 129916. Google Scholar Previous articleNext article FiguresReferencesRelatedDetails Issue AssignmentVolume 4Issue 9Page: 2914-2920Supporting Information Copyright & Permissions© 2021 Chinese Chemical SocietyKeywordstetraphenylethene-based cationic cagebase pairchiral recognitionhost–guest chemistryadaptive chirality Downloaded 1,249 times PDF DownloadLoading ...