Amplification sensing manipulated by a sumanene-based supramolecular polymer as a dynamic allosteric effector

Amplification sensing manipulated by a sumanene-based supramolecular polymer as a dynamic allosteric effector | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Amplification sensing manipulated by a sumanene-based supramolecular polymer as a dynamic allosteric effector Gaku Fukuhara, Hiroaki Mizuno, Hironobu Nakazawa, Akihisa Miyagawa, and 2 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-3831095/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted You are reading this latest preprint version Abstract The synthesis of signal-amplifying chemosensors induced by various triggers is a major challenge for multidisciplinary sciences. In this study, a signal-amplification system that was flexibly manipulated by a dynamic allosteric effector (trigger) was developed. Herein, the focus was on using the behavior of supramolecular polymerization to control the degree of polymerization by changing the concentration of a functional monomer (seed). It was assumed that this control was facilitated by a gradually changing/dynamic allosteric effector. A curved-π buckybowl sumanene and a sumanene -based chemosensor ( SC ) were employed as the seed/allosteric effector and the molecular binder, respectively. The hetero-supramolecular polymer, ( SC •( sumanene ) n ), facilitated the manipulation of the degree of signal-amplification; this was accomplished by changing the sumanene seed concentration, which resulted in up to a 62.5-fold amplification of a steroid. The current results and the concept proposed herein provide an alternate method to conventional chemosensors and signal-amplification systems. Sumanene Supramolecular Polymer Allosterism Amplification Sensing Figures Figure 1 Figure 2 Figure 3 Figure 4 Introduction Chemical sensors (chemosensors), such as artificial receptors and supramolecular synthetic hosts, have rapidly developed in recent years as a multidisciplinary science, which incorporates mainly supramolecular and analytical chemistry 1–17 . Recently, smart chemosensors have been used for real-time apoptosis detection 18–20 , as well as basic molecular recognition. The range of applications of chemosensors is based on the lock-and-key principle (enzyme-substrate model) proposed by Emil Fischer 21 . However, further advancements are required to address the overwhelming of conventional chemosensors. Amplifying the signal is an effective solution for chemosensor overload because it minimizes the disadvantages of the lock-and-key model 22–24 , resulting in enhanced sensitivity. This has been demonstrated in Fig. 1 a, where the signals (blue curve) against the guest concentration exhibited a typical nonlinear least-square binding isotherm when the complexation type was 1:1; the blue slope represents sensitivity 25 . The enhancement of a binding constant ( K ), triggered by an amplifying mechanism, also amplified the signals (red curve) in the initial-to-middle section, resulting in increased sensitivity (red slope). Biological systems can amplify K through methods such as allosterism 26–32 . Hemoglobin is a well-known example of an allosteric system 33 . Once an O 2 molecule binds to hemoglobin, a conformational change is induced in the protein, enabling further addition of O 2 molecules. Homotropic allosterism is an allosteric system wherein the target molecule simultaneously functions as an effector (hemoglobin). By contrast, heterotropic allosterism is an allosteric system that requires a different effector to enhance the binding of the target molecule. Biological systems have shown that some contrivance can be applied to an allosteric effector. This resulted in exploring a nature-surpassed dynamic effector that can control and then suppress/promote a binding equilibration; that is, dynamic control of signal amplification. This effector can exploit supramolecular polymerization. Supramolecular polymers consist of a functional monomer (seed) that spontaneously stacks on each other through noncovalent interactions, such as p–p, hydrogen bonding, and electrostatic interactions 34–42 . Porphyrins 43 and perylene bisimides 44 have been widely used as p-plane seeds. Therefore, it was assumed that the degree of polymerization (DP) of the seed can be manipulated by changing the seed concentration. This will likely result in a gradual and dynamic change in the seed characteristics as an allosteric effector (monomer, dimer, trimer, •••, n -mer) (Fig. 1 b). In this study, a novel, nature-surpassed signal-amplification system was discovered. Within this system, dynamic changes in the allosteric effector occurred via supramolecular polymerization adjustments, which were for the first time achieved by using curved-p buckybowl sumanene 45 (Fig. 1 c) as the seed. A recent study showed that pristine sumanene spontaneously forms supramolecular polymers in solutions in an isodesmic manner 46 — K n (nucleation) = K e (elongation). Therefore, a sumanene -based chemosensor ( SC , Fig. 1 c) was constructed based on the guideline shown in Fig. 1 b. Pristine sumanene gradually stacks on the convex face of the chemosensor to form hetero-supramolecular polymers ( SC •( sumanene ) n ). The likelihood of the stacking- sumanene moieties in the hetero-supramolecular polymers perturbing the electronic properties of the molecular recognition sites in SC was high. Here, we report an unprecedented signal-amplification system based on the hetero-supramolecular polymers composed of SC as a molecular binder and sumanene as a dynamic allosteric effector. This concept resulted in a powerful, widely applicable chemosensor capable of manipulating signal amplification. Results and discussion Photophysical properties of SC The UV/vis absorption and fluorescence spectra, and fluorescence lifetime decays of SC in dichloromethane (CH 2 Cl 2 ) are shown in Fig. 2 and Supplementary Fig. S12 in Supplementary Information (SI). The maximum peak in the UV/vis absorption spectra of SC was observed at approximately 280 nm (Fig. 2 a), which was similar to the sum of sumanene and the indole reference compound ( ref , Fig. 1 c). However, new absorption bands at approximately 310 and 360 nm were observed after comparing the molar extinction coefficients of SC with those of sumanene and ref , suggesting that a p-conjugation extended from the sumanene core to the indole chromophore. An emission peak at 412 nm was observed in the fluorescence spectrum of SC (Fig. 2 b). Because of the appreciable bathochromic shift in SC compared with those of sumanene and ref , this peak may have originated from the p-extended indole- sumanene conjugation. The fluorescence decay profiles (Fig. 2 c) monitored at 392, 406, and 431 nm (l ex : 340 nm) were fitted to a sum of reasonable exponential functions to produce the first short-lived species (0.4 ns) at the shorter wavelength region, a major fluorescence species (2.6 ns) presented in the entire region, and the second short-lived species (0.3–0.4 ns) at the longer wavelength region (Supplementary Table S1 in SI). The major excited species (2.6 ns) was assigned to the fluorescent SC monomer. A titration of SC using triethylamine as an organic base (Supplementary Figs. S13–S14 and Supplementary Table S2–S3 in SI) showed the fluorescence quenching mainly involved the first short-lived species; this was assigned to a fluorescent anion species where protons dissociated from the indole moiety. A rise component with a negative A factor (relative abundance) was observed in the second short-lived species (Fig. 2 c, Supplementary Figs. S12c,d (SI), and Supplementary Table S1 (SI)). Density functional theory (DFT) calculations (function/basis set: ωB97X-D/6-311G(d,p)) of SC were performed to identify the rise component (Fig. 2 d). Three indole side chains aligned in a T-shape manner with a distance of 6.7 Å. The results of the DFT calculations suggested that the second short-lived species is originated from the frustrated (second) excimer formed via the intramolecular, T-shaped overlap of the indole side chains; this was observed in previous studies 47,48 . This interesting photochemical property was formed by the fixation of the fluorescent moieties on the sumanene scaffold. Sensing behavior of SC A series of benzene and cyclohexane derivatives were used as model guests for a proof of concept (Fig. 3 a). Thereafter, their sensing behaviors were investigated in CH 2 Cl 2 . Upon the gradual addition of MB , a wide range broadened peak was observed in the long wavelength region (> 355 nm) of the UV/vis absorption spectra for the titration of SC ⸦ MB (Supplementary Fig. S17a in SI). Efficient quenching was only observed when a new band emerged, and peak shifts were absent in the corresponding fluorescence spectra (Fig. 3 b and Supplementary Fig. S17b (SI)). Using this spectral change, K SC was estimated as 7 ± 1 M − 1 , assuming the formation of a 1:1 complexation (Fig. 3 c) wherein: ( 1 ) the stoichiometric analysis in Supplementary Fig. S20 in SI was discussed using the following anion system, and ( 2 ) the following 1:1 complex structure was provided in advance (Fig. 3 d). Subsequently, the anion sensing shown in Supplementary Figs. S18–S19 in SI was discussed. The UV/vis absorption spectra of SC ⸦ TBPB exhibited a similar broadened wavelength (> 355 nm); however, a hypochromic effect was observed at approximately 320–355 nm. During fluorescence titration, the peak maxima bathochromically shifted with appreciable quenching. The spectral differences between neutral MB and anionic TBPB were likely responsible for the different ground-state complexations based on the neutral- or anion- SC . Furthermore, the K SC value of anion- SC , assuming the complexation type was 1:1, was enhanced to 850 ± 10 M − 1 . Therefore, the spectroscopic behaviors were affected by the strength of the anion complexation. The interaction between SC and MB was further investigated using IR spectroscopy. The broad peak at 3303 cm − 1 , which was derived from the N–H stretching vibration in the indole ring, decreased in intensity as the higher wavenumber shifted to 3329 cm − 1 with increasing MB concentration (Fig. 3 e). Additionally, the ref compound can bind MB ( K ref = 4 ± 1 M − 1 ) and TBPB ( K ref = 4 ± 1 M − 1 ) with sufficient fluorescence quenching; this was also observed in SC (Supplementary Fig. S16 in SI). These results suggest that the hydrogen bonds formed via the carbonyl moiety of the guests and the dissociated N–H protons on the indole rings in SC are main recognition forces. This was consistent with the fluorescence quenching behavior observed after adding triethylamine ( vide supra ). The K SC value of SC ⸦ TBPB was enhanced by a factor of 213 compared with K ref of ref ⸦ TBPB , which was likely owing to a cooperative complexation through the octopus-like three indoles on the sumanene scaffold. Therefore, it was important to elucidate the thermodynamic parameters before applying the temperature-dependent van’t Hoff analysis of SC ⸦ TBPB at four temperatures from 5 to 35°C (Fig. 3 f and Supplementary Figs. S18–S19 (SI)). The van’t Hoff plot showed a straight line, indicating that the same complexation mechanism can be found in this temperature range (same heat capacity); Δ H ° and Τ Δ S ° were − 20.8 and − 4.2 kJ mol − 1 , respectively. The thermodynamic parameters exhibited enthalpy-driven complexation. Nevertheless, the observed entropy loss was relatively low despite the immobilization by three recognition sites, which was accounted for by the classical chelate effect 49 . Therefore, the high enthalpy gain and low entropy loss (the common cooperative manner) resulted in a higher and enhanced K SC (D G ° = -16.6 kJ mol − 1 ) based on the distinctive structural specificity. The sensing results of the eight guests by SC are listed in Table 1 and Supplementary Figs. S21–S23 (SI). First, the K SC values of SC against methyl esters were in the range of 7–28 M − 1 ; small but gradual increases in K SC were observed as the number of carboxylic groups increased. The K SC values for TT and TC were similar, indicating that the contribution of the benzene ring (p–p interaction) in supramolecular complexation was minimal. This reinforced the hydrogen bonding interactions as the main driving force. Subsequently, the K SC values of SC against anions were between 850–1940 M − 1 . These values exhibited a factor of 44–121 enhancement compared with the corresponding methyl esters. The marginal deviation in K SC as the number of carboxylates increased from two to three was likely owing to the bulkiness of the TBP cation (steric hindrance). Similar K SC values for TBPT and TBPC were observed, showing that the main complexation was derived from hydrogen bonding interactions and not p–p interactions. Hetero-supramolecular polymerization consisting of SC and sumanene Similar to a previous study on homo-supramolecular polymerization 46 , the formation of hetero-supramolecular polymers using SC and sumanene in CH 2 Cl 2 was investigated. No new absorption bands were observed in the UV spectra as sumanene was titrated against 128 µM of SC (Supplementary Fig. S25 in SI); these UV spectra were similar to the concentration-dependent UV spectra of sumanene . Nevertheless, the hetero-supramolecular polymerization behavior was elucidated by calculating the molar extinction coefficient of the sumanene skeleton in SC , e sumanene,(calcd.) . This provided the basis for the \(\stackrel{-}{\epsilon }\) value of the SC •( sumanene ) n hetero-supramolecular polymer, which was used to estimate a agg (Supplementary Fig. S25, Supplementary Table S5, and their relevant discussion in SI). Assuming that the model was isodesmic based on the similar curvature surfaces of SC (depth as 0.90 Å) and sumanene (depth as 0.89 Å) estimated using the DFT calculations, a K i value of 770 ± 120 M − 1 was determined after analyzing the molar extinction coefficient at 363 nm. Heteromer formation was further supported by the diffusion coefficient ( D ) obtained via NMR diffusion ordered spectroscopy (DOSY). The D value of a CD 2 Cl 2 mixture of SC (447 µM) and sumanene (9.09 mM) was 7.37 × 10 − 10 m 2 /s (Supplementary Figs. S26–S29 in SI). This value was subjected to the ellipsoid approximation model; a 4–5-mer was estimated (Supplementary Table S6 and its relevant discussion in SI). By contrast, the number-average DP value of the heteromer calculated using the assumption of the isodesmic model was 3.3, which was similar to the DOSY experiment (see structures in Supplementary Fig. S30 in SI). Amplification-sensing behavior using the hetero-supramolecular polymer Broad peaks were observed in the long wavelength region of the UV/vis absorption spectra of SC •( sumanene ) n ⸦ MB in CH 2 Cl 2 (Supplementary Fig. S35a in SI), which was similar to the peaks in the long wavelength region of the SC ⸦ MB spectra. A fluorescence quench was observed in the fluorescence spectra of SC •( sumanene ) n ⸦ MB (Fig. 4 a); this quench was similar to that observed in the SC ⸦ MB spectra. A new emission band was observed at the longer wavelength region (approximately 500 nm) in the normalized fluorescence spectra (Supplementary Fig. S35b in SI), indicating that supramolecular complexation of SC •( sumanene ) n ⸦ MB occurred. The fluorescence spectral changes at 399 nm were fitted (Fig. 4 b, red), assuming that the hetero-supramolecular polymer and the guest molecule form a 1:1 complex owing to the same recognition moiety (the SC starburst in the complex). The obtained apparent binding constant ( K SMP ) was 79 ± 6 M − 1 , which was 11.3-fold higher than the K SC of SC ⸦ MB (7 ± 1 M − 1 ). Table 1 shows the K SMP and K SC values of the eight guest molecules and the sensing behaviors of the hetero-supramolecular polymer and SC system. Large amplification ratios of 2.9–11.3 for esters with smaller K SC were observed, whereas amplification ratios of 1.1–2.5 for anions with relatively large K SC (Supplementary Figs. S36–S49 in SI). Therefore, signal-amplification sensing with sumanene supramolecular polymers may be useful for enhancing a low signal of a target molecule with a small K in the SC system. To elucidate the origin of the signal-amplification, DFT calculations (function/basis set: ωB97X-D/6-311G(d,p)) of SC , sumanene , and SC •( sumanene ) n were performed (Fig. 4 d). The LUMO energy of SC was 0.02 eV; this value remained constant even when a sumanene molecule stacked on SC (dimer formation). By contrast, stacking two or more sumanene molecules on SC resulted in the gradual reduction of LUMO energies to between − 0.02 ( SC •( sumanene ) 2 ) and − 0.09 eV ( SC •( sumanene ) 4 ). Furthermore, the LUMO energy of ( sumanene ) 5 was positive (0.45 eV). Therefore, the likelihood of the negative LUMO energy values being more electron-receptive was high 50 . This improved the acceptor properties of the SC binding site in the heteromer. Because the LUMO orbitals of SC •( sumanene ) n extended from the sumanene core in SC to the indole binding site, the formation of SC •( sumanene ) n influenced the electronic acceptor properties of the indole moiety—the origin of the signal-amplification. In addition, natural population analysis showed that the formation of hetero-supramolecular polymers caused the electron transfer from sumanene to SC , resulting in an anionic SC core in the charge-transfer (CT) complex (Supplementary Table S7 in SI). Therefore, the signals for the anions were not amplified because of electrostatic repulsion in the hetero-supramolecular polymer system; however, amplification was observed against the esters. Importantly, the experimental and theoretical findings showed that the number of stacks of sumanene played a critical role in signal amplification. The functionality of the conceptual mechanism shown in Fig. 1 b was assessed by sensing MB with varying concentrations of the sumanene seed in SC (Supplementary Figs. S31–S34 in SI). The ln K SMP value (= D G °) as a function of DP increased exponentially (Fig. 4 c); therefore, the behavior of sumanene was that of a dynamic allosteric effector . The conceptual illustration observed in this study (signal amplification) is shown in Fig. 4 e. Table 1 Binding constants (K) between guest molecules and ref, SC, or SC•(sumanene)n in CH2Cl2 at 25°Ca Guest K / M − 1 K SMP / K SC ref ( K ref ) SC ( K SC ) SC • ( sumanene ) n ( K SMP ) MB 4 ± 1 7 ± 1 79 ± 6 11.3 DI b 16 ± 2 46 ± 16 2.9 TT b 20 ± 2 78 ± 32 3.9 TC b 28 ± 8 102 ± 28 3.6 TBPB 4 ± 1 850 ± 10 2120 ± 310 2.5 TBPI b 1940 ± 140 3140 ± 680 1.6 TBPT b 1400 ± 90 1470 ± 100 1.1 TBPC b 1240 ± 80 1310 ± 110 1.1 testosterone b 34 ± 3 170 ± 17 5.0 corticosterone b 440 ± 10 530 ± 50 1.2 allylestrenol b 4 ± 0.3 250 ± 20 62.5 a [ ref ] = 1.35–1.36 mM, [ SC ] = 396–480 µM, [ SC •( sumanene ) n ] = 394–450 µM SC + 8.64–9.29 mM sumanene ; DP = 3.2–3.3. b Not determined. Steroid sensing: general validity and application using the hetero-supramolecular polymer To further generalize the current signal-amplification method and demonstrate its applicability in biologically important materials, steroids such as testosterone, corticosterone, and allylestrenol were selected as target molecules with lower donor characteristics (Fig. 4 f). The fluorescence spectral changes of SC •( sumanene ) n ⸦ allylstrenol exhibited distinctive fluorescence quenching similar to that of other sensing systems (Supplementary Figs. 50–54). A similar 1:1 fitting for the fluorescence changes at 409 nm resulted in a K SMP value of 250 ± 20 M − 1 , which was a 62.5-fold higher signal-amplification than K SC of SC ⸦ allylstrenol as 4 ± 0.3 M − 1 (Fig. 4 g). A lower K SC value in the SC system corresponded to a higher amplification of the K SMP in the hetero-supramolecular polymer system. It was concluded that the signal amplification by the sumanene -based hetero-supramolecular polymer was 62.5-fold higher than that of the other sensing systems. Conclusion A novel signal-amplification system was developed, wherein the curved-p sumanene seed for supramolecular polymerization functioned as a dynamic allosteric effector. This seed effector altered the DP to flexibly manipulate the electronic properties at the binding site (positive heterotopic allosterism), achieving an amplification that was up to 62.5-fold higher than other systems at sensing the biologically important steroid, allylestrenol. The sensing method and the conceptual guideline proposed herein facilitate the sensing of diverse guests that are difficult to signally recognize using the conventional lock-and-key type chemosensors. Methods Complexation studies A stock solution of SC was prepared by dissolving SC powder in CH 2 Cl 2, followed by sonication for 1 min. Unused stock solutions were stored in the freezer. Stored samples were warmed to room temperature and then sonicated for 1 min before use. The concentration was calculated from the absorbance of the solution. The CH 2 Cl 2 mixture of SC and sumanene was prepared by mixing ca. 600 µM SC solution and ca. 2–34 mM sumanene solution in a ratio of 8:3. The CH 2 Cl 2 solutions of the guest molecules were prepared at 50 mM to 8 M concentrations; thereafter, these solutions were titrated into SC or hetero-supramolecular polymer solutions using a micro-syringe injection. A preparation concentration of SC was used for the nonlinear least-squares fitting to determine the binding constants. IR spectra were measured on the plate by adding a few drops of CH 2 Cl 2 solution to the sample and then drying. Computational studies All chemosensors and supramolecular complexes were structurally optimized by the DFT calculations with the ωB97X-D/6-311G (d,p) level, and the most stable structures were used for discussions. Triethylene glycol chains in SC were changed to methoxy groups for simplicity. Declarations Data availability All results and supporting data are available within the main text and Supplementary Information. They can also be requested from the corresponding author. Acknowledgments G.F. appreciates the generous supports by Grant-in-Aid (No. 19H02746, 23H04020) from the Japan Society for the Promotion of Science (JSPS) and Tokuyama Science Foundation. H.M. acknowledges JSPS Fellowships for Young Scientists (No. 21J22528, 22KJ1283). H.S. appreciates the generous support by Grant-in-Aid (No. 26102002, 21H05233, 19H00912, 20H00400) from JSPS. H.N. acknowledges JSPS Fellowships for Young Scientists (No. 21J10937). We are grateful to Mr. Yu Fukunaga, Prof. Susumu Kawauchi, and Prof. Tetsuo Okada at Tokyo Institute of Technology and Assoc. Prof. Takashi Hirose at Kyoto University for their constructive discussions. Author contributions G.F. initiated and supervised the whole study. G.F. and H.S. designed the project and the experiments. H.M. synthesized chemosensors and carried out the experiments. H.N. prepared the sumanene seed and its triol derivative. Y.Y. and A.M. analyzed the data. All authors contributed to writing the manuscript. Competing interests The authors declare no competing interests. Additional information Supplementary information The online version contains supplementary material available at XXX. Correspondence and requests for materials should be addressed to Gaku Fukuhara. Reprints and permissions information is available at www.nature.com/reprints. References Wintner, E. A., Conn, M. M. & Rebek, Jr., J. Studies in molecular replication. Acc . Chem . 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Supplementary Files SumaneneSensorSI.docx Supplementary Information floatimage1.png Graphical abstract Cite Share Download PDF Status: Under Review Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-3831095","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":266687101,"identity":"15f56b3a-9b89-4e3b-a4db-d396e0344c83","order_by":0,"name":"Gaku Fukuhara","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA+0lEQVRIiWNgGAWjYFACNgaGDwwHwEwQmQBmSRDQwjgDrJiZ4cABYrUw80C1MMC14APy7sfSpG1q7sjpNvAfPPyhwi6Pgf3wAwbLHbi1GJ5JOyadc+yZsdkBkMPOJBcz8KQZMEiewaOlIb1NOrfhcOI2kJaDbQcSGxhyGBgk2/Bo6X/eJm3ZcLgeouUfUAv/G/xa5CWADmNsOJwAdtjBBqAWCQK2GEg8S7bsOXbYcNthZoMDZ44lJ7ZJPDM4gM8v8v1phjd+1ByWNzve+PhDRY1dYj9/8sPHknhCzOAAjMUMpYGpgeGwZAMeW7DKMX7Eo2UUjIJRMApGHAAAhhxYivkOq2gAAAAASUVORK5CYII=","orcid":"https://orcid.org/0000-0002-2189-8943","institution":"Tokyo Institute of Technology","correspondingAuthor":true,"prefix":"","firstName":"Gaku","middleName":"","lastName":"Fukuhara","suffix":""},{"id":266687102,"identity":"276fe414-eb13-492e-9bd4-687a7d48c766","order_by":1,"name":"Hiroaki Mizuno","email":"","orcid":"","institution":"Tokyo Institute of Technology","correspondingAuthor":false,"prefix":"","firstName":"Hiroaki","middleName":"","lastName":"Mizuno","suffix":""},{"id":266687103,"identity":"34f46214-7f6d-4332-87e0-7b95901dd8c2","order_by":2,"name":"Hironobu Nakazawa","email":"","orcid":"","institution":"Osaka University","correspondingAuthor":false,"prefix":"","firstName":"Hironobu","middleName":"","lastName":"Nakazawa","suffix":""},{"id":266687104,"identity":"58c6d5e8-a63e-4da0-aee4-ed9c0ee35d24","order_by":3,"name":"Akihisa Miyagawa","email":"","orcid":"","institution":"University of Tsukuba","correspondingAuthor":false,"prefix":"","firstName":"Akihisa","middleName":"","lastName":"Miyagawa","suffix":""},{"id":266687105,"identity":"7857d8bf-0933-4336-8579-c02708a38f8d","order_by":4,"name":"Yumi Yakiyama","email":"","orcid":"","institution":"Osaka University","correspondingAuthor":false,"prefix":"","firstName":"Yumi","middleName":"","lastName":"Yakiyama","suffix":""},{"id":266687106,"identity":"c333a18e-701e-4437-8781-dc559b602e09","order_by":5,"name":"Hidehiro Sakurai","email":"","orcid":"https://orcid.org/0000-0001-5783-4151","institution":"Osaka University","correspondingAuthor":false,"prefix":"","firstName":"Hidehiro","middleName":"","lastName":"Sakurai","suffix":""}],"badges":[],"createdAt":"2024-01-03 05:35:51","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-3831095/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-3831095/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":52410005,"identity":"3b218776-0100-4d1d-9632-9342f861c675","added_by":"auto","created_at":"2024-03-11 10:15:43","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":437959,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eConcept and design guidelines of the chemosensors. a\u003c/strong\u003e, Model titration curves, assuming the 1:1 stoichiometric complexation represents each nonlinear least-squares binding isotherm. The black arrow indicates signal amplification. \u003cstrong\u003eb\u003c/strong\u003e, Schematic of the concept for the dynamic allosteric effector that can flexiblymanipulate binding equilibria via supramolecular polymerization. \u003cstrong\u003ec\u003c/strong\u003e, Chemical structures of \u003cstrong\u003esumanene\u003c/strong\u003e as a seed for supramolecular polymers, \u003cstrong\u003eSC\u003c/strong\u003eas a chemosensor, and \u003cstrong\u003eref\u003c/strong\u003e as a reference compound, respectively.\u003c/p\u003e","description":"","filename":"floatimage2.png","url":"https://assets-eu.researchsquare.com/files/rs-3831095/v1/4d9c2870382d63e847396970.png"},{"id":52410004,"identity":"c20fafe3-dd4b-4c27-8bc0-4abcd77c698c","added_by":"auto","created_at":"2024-03-11 10:15:43","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":537377,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003ePhotophysical properties of SC.\u003c/strong\u003e \u003cstrong\u003ea\u003c/strong\u003e, UV/vis absorption spectra of \u003cstrong\u003eSC\u003c/strong\u003e (8.3 mM, black solid line), \u003cstrong\u003esumanene\u003c/strong\u003e (9.8 mM, green dotted line), and \u003cstrong\u003eref\u003c/strong\u003e (15.6 mM, purple dotted line, three times) in CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e at 25 °C. The red solid line represents the subtraction spectrum. \u003cstrong\u003eb\u003c/strong\u003e, Fluorescence spectra of \u003cstrong\u003eSC\u003c/strong\u003e (black, l\u003csub\u003eex\u003c/sub\u003e: 330 nm), \u003cstrong\u003esumanene\u003c/strong\u003e (red, l\u003csub\u003eex\u003c/sub\u003e: 351 nm), and \u003cstrong\u003eref\u003c/strong\u003e (blue, l\u003csub\u003eex\u003c/sub\u003e: 330 nm) in CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e at 25 °C, measured in a 1 cm cell. \u003cstrong\u003ec\u003c/strong\u003e, Fluorescence lifetime decays (l\u003csub\u003eex\u003c/sub\u003e: 340 nm) of \u003cstrong\u003eSC\u003c/strong\u003e monitored at 392 (black), 406 (brown), and 431 nm (red) in CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e at room temperature, measured in a 1 cm cell; the green dotted line represents instrument response function (IRF). \u003cstrong\u003ed\u003c/strong\u003e, Quantum chemistry calculation-based optimized structure of \u003cstrong\u003eSC\u003c/strong\u003e.\u003c/p\u003e","description":"","filename":"floatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-3831095/v1/08ff20f8828dd05bf6829e4f.png"},{"id":52410007,"identity":"df253af7-76e7-43ef-99af-1177f4ddb246","added_by":"auto","created_at":"2024-03-11 10:15:43","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":740904,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eSensing behavior of SC.\u003c/strong\u003e \u003cstrong\u003ea\u003c/strong\u003e, Chemical structures of model guests. \u003cstrong\u003eb\u003c/strong\u003e, Fluorescence spectra (l\u003csub\u003eex\u003c/sub\u003e: 351 nm) of \u003cstrong\u003eSC\u003c/strong\u003e (421 mM; black) showing the gradual addition of \u003cstrong\u003eMB\u003c/strong\u003e (18.0–575 mM; from brown to blue) in CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e at 25 °C, measured in a 1 mm cell; the excitation wavelength at which comparable absorbances were obtained was selected. \u003cstrong\u003ec\u003c/strong\u003e, Nonlinear least-squares fitting line (assuming the 1:1 stoichiometry with \u003cstrong\u003eSC\u003c/strong\u003e and \u003cstrong\u003eMB\u003c/strong\u003e monitored at 407 nm) to determine the binding constant at 25 °C. \u003cstrong\u003ed\u003c/strong\u003e, Optimized supramolecular complex structure of \u003cstrong\u003eSC\u003c/strong\u003e ⸦ trimesate (C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e3\u003c/sub\u003e(COO\u003csup\u003e-\u003c/sup\u003e)\u003csub\u003e3\u003c/sub\u003e); counter cations were omitted for clarity. \u003cstrong\u003ee\u003c/strong\u003e, IR spectra of \u003cstrong\u003eSC\u003c/strong\u003e (4.2 mM, black) showing the gradual addition of \u003cstrong\u003eMB\u003c/strong\u003e (40 mM–1.6 M, brown to pink) in CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e at room temperature, where the green dotted line represents \u003cstrong\u003eMB\u003c/strong\u003e (1.6 M) in CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e. \u003cstrong\u003ef\u003c/strong\u003e, van’t Hoff plot of the binding constants obtained from the complexation of \u003cstrong\u003eTBPB\u003c/strong\u003e with \u003cstrong\u003eSC\u003c/strong\u003e in CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e (\u003cem\u003er\u003c/em\u003e = 0.992).\u003c/p\u003e","description":"","filename":"floatimage4.png","url":"https://assets-eu.researchsquare.com/files/rs-3831095/v1/489cf81c5972417954f4f6c7.png"},{"id":52410009,"identity":"6191c441-0c23-4535-b8de-0ca80a82cc1c","added_by":"auto","created_at":"2024-03-11 10:15:44","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":1826221,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eSensing behavior of SC\u003c/strong\u003e•(\u003cstrong\u003esumanene\u003c/strong\u003e)\u003csub\u003e\u003cstrong\u003en\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e hetero-supramolecular polymer.\u003c/strong\u003e \u003cstrong\u003ea\u003c/strong\u003e, Fluorescence spectra (l\u003csub\u003eex\u003c/sub\u003e: 355 nm) of \u003cstrong\u003eSC \u003c/strong\u003e(445 mM) with \u003cstrong\u003esumanene\u003c/strong\u003e (8.87 mM, DP = 3.2, black) following the addition of \u003cstrong\u003eMB\u003c/strong\u003e (1.8–147 mM, from brown to blue) in CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e at 25 °C, measured in a 1 mm cell; the excitation wavelength at which comparable absorbances were obtained was selected. \u003cstrong\u003eb\u003c/strong\u003e, Normalized binding isotherms of \u003cstrong\u003eSC\u003c/strong\u003e•(\u003cstrong\u003esumanene\u003c/strong\u003e)\u003csub\u003en\u003c/sub\u003e (red) and \u003cstrong\u003eSC\u003c/strong\u003e (black) following the addition of \u003cstrong\u003eMB\u003c/strong\u003e at 25 °C. \u003cstrong\u003ec\u003c/strong\u003e, Plots of ln \u003cem\u003eK\u003c/em\u003e\u003csub\u003eSMP\u003c/sub\u003e between \u003cstrong\u003eSC\u003c/strong\u003e•(\u003cstrong\u003esumanene\u003c/strong\u003e)\u003csub\u003en\u003c/sub\u003e (n = 0~) and \u003cstrong\u003eMB\u003c/strong\u003e at 25 °C as a function of DP; the red line represents a fitting regression line (\u003cem\u003ey\u003c/em\u003e = 1.3498 e\u003csup\u003e0.33547\u003c/sup\u003e\u003csup\u003e\u003cem\u003ex\u003c/em\u003e\u003c/sup\u003e, \u003cem\u003er\u003c/em\u003e = 0.970). \u003cstrong\u003ed\u003c/strong\u003e, LUMO and the corresponding energy levels calculated from the optimized structures of \u003cstrong\u003eSC\u003c/strong\u003e, \u003cstrong\u003eSC\u003c/strong\u003e•(\u003cstrong\u003esumanene\u003c/strong\u003e)\u003csub\u003en\u003c/sub\u003e (n = 1–4), and (\u003cstrong\u003esumanene\u003c/strong\u003e)\u003csub\u003e5\u003c/sub\u003e. \u003cstrong\u003ee\u003c/strong\u003e, Conceptual illustration of “regular signal” (the common method) \u003cem\u003evs.\u003c/em\u003e “signal amplification” via a dynamic allosteric effector (this study). \u003cstrong\u003ef\u003c/strong\u003e, Chemical structures of steroids. \u003cstrong\u003eg\u003c/strong\u003e, Normalized binding isotherms of\u003cstrong\u003e SC\u003c/strong\u003e•(\u003cstrong\u003esumanene\u003c/strong\u003e)\u003csub\u003en\u003c/sub\u003e (red) and \u003cstrong\u003eSC\u003c/strong\u003e (black) upon the addition of \u003cstrong\u003eallylestrenol\u003c/strong\u003e at 25 °C.\u003c/p\u003e","description":"","filename":"floatimage5.png","url":"https://assets-eu.researchsquare.com/files/rs-3831095/v1/8a990a7bd2b48a034dd0dd7b.png"},{"id":52411808,"identity":"1df6a9c5-c1c3-49b6-84dc-617cf93d7ad6","added_by":"auto","created_at":"2024-03-11 10:23:44","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1084594,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-3831095/v1/fa2bb175-f3ee-445f-8054-fb3e34a01f31.pdf"},{"id":52410008,"identity":"1421350b-4ea1-4977-b16e-a7a62f8ade59","added_by":"auto","created_at":"2024-03-11 10:15:44","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":49860900,"visible":true,"origin":"","legend":"Supplementary Information","description":"","filename":"SumaneneSensorSI.docx","url":"https://assets-eu.researchsquare.com/files/rs-3831095/v1/45814a20b1e6decb4b0dd870.docx"},{"id":52410006,"identity":"de036eeb-ebe5-4c3e-b3ca-95ec85e57f8b","added_by":"auto","created_at":"2024-03-11 10:15:43","extension":"png","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":1477936,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eGraphical abstract\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"floatimage1.png","url":"https://assets-eu.researchsquare.com/files/rs-3831095/v1/9b5715c143b1878d1536b88f.png"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Amplification sensing manipulated by a sumanene-based supramolecular polymer as a dynamic allosteric effector","fulltext":[{"header":"Introduction","content":"\u003cp\u003eChemical sensors (chemosensors), such as artificial receptors and supramolecular synthetic hosts, have rapidly developed in recent years as a multidisciplinary science, which incorporates mainly supramolecular and analytical chemistry\u003csup\u003e1\u0026ndash;17\u003c/sup\u003e. Recently, smart chemosensors have been used for real-time apoptosis detection\u003csup\u003e18\u0026ndash;20\u003c/sup\u003e, as well as basic molecular recognition. The range of applications of chemosensors is based on the lock-and-key principle (enzyme-substrate model) proposed by Emil Fischer\u003csup\u003e21\u003c/sup\u003e. However, further advancements are required to address the overwhelming of conventional chemosensors.\u003c/p\u003e \u003cp\u003eAmplifying the signal is an effective solution for chemosensor overload because it minimizes the disadvantages of the lock-and-key model\u003csup\u003e22\u0026ndash;24\u003c/sup\u003e, resulting in enhanced sensitivity. This has been demonstrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea, where the signals (blue curve) against the guest concentration exhibited a typical nonlinear least-square binding isotherm when the complexation type was 1:1; the blue slope represents sensitivity\u003csup\u003e25\u003c/sup\u003e. The enhancement of a binding constant (\u003cem\u003eK\u003c/em\u003e), triggered by an amplifying mechanism, also amplified the signals (red curve) in the initial-to-middle section, resulting in increased sensitivity (red slope). Biological systems can amplify \u003cem\u003eK\u003c/em\u003e through methods such as allosterism\u003csup\u003e26\u0026ndash;32\u003c/sup\u003e. Hemoglobin is a well-known example of an allosteric system\u003csup\u003e33\u003c/sup\u003e. Once an O\u003csub\u003e2\u003c/sub\u003e molecule binds to hemoglobin, a conformational change is induced in the protein, enabling further addition of O\u003csub\u003e2\u003c/sub\u003e molecules. Homotropic allosterism is an allosteric system wherein the target molecule simultaneously functions as an effector (hemoglobin). By contrast, heterotropic allosterism is an allosteric system that requires a different effector to enhance the binding of the target molecule.\u003c/p\u003e \u003cp\u003eBiological systems have shown that some contrivance can be applied to an allosteric effector. This resulted in exploring a nature-surpassed dynamic effector that can control and then suppress/promote a binding equilibration; that is, dynamic control of signal amplification. This effector can exploit supramolecular polymerization. Supramolecular polymers consist of a functional monomer (seed) that spontaneously stacks on each other through noncovalent interactions, such as p\u0026ndash;p, hydrogen bonding, and electrostatic interactions\u003csup\u003e34\u0026ndash;42\u003c/sup\u003e. Porphyrins\u003csup\u003e43\u003c/sup\u003e and perylene bisimides\u003csup\u003e44\u003c/sup\u003e have been widely used as p-plane seeds. Therefore, it was assumed that the degree of polymerization (DP) of the seed can be manipulated by changing the seed concentration. This will likely result in a gradual and dynamic change in the seed characteristics as an allosteric effector (monomer, dimer, trimer, \u0026bull;\u0026bull;\u0026bull;, \u003cem\u003en\u003c/em\u003e-mer) (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb).\u003c/p\u003e \u003cp\u003eIn this study, a novel, nature-surpassed signal-amplification system was discovered. Within this system, dynamic changes in the allosteric effector occurred via supramolecular polymerization adjustments, which were for the first time achieved by using curved-p buckybowl \u003cb\u003esumanene\u003c/b\u003e\u003csup\u003e45\u003c/sup\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ec) as the seed. A recent study showed that pristine \u003cb\u003esumanene\u003c/b\u003e spontaneously forms supramolecular polymers in solutions in an isodesmic manner\u003csup\u003e46\u003c/sup\u003e\u0026mdash;\u003cem\u003eK\u003c/em\u003e\u003csub\u003en\u003c/sub\u003e (nucleation)\u0026thinsp;=\u0026thinsp;\u003cem\u003eK\u003c/em\u003e\u003csub\u003ee\u003c/sub\u003e (elongation). Therefore, a \u003cb\u003esumanene\u003c/b\u003e-based chemosensor (\u003cb\u003eSC\u003c/b\u003e, Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ec) was constructed based on the guideline shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb. Pristine \u003cb\u003esumanene\u003c/b\u003e gradually stacks on the convex face of the chemosensor to form hetero-supramolecular polymers (\u003cb\u003eSC\u003c/b\u003e\u0026bull;(\u003cb\u003esumanene\u003c/b\u003e)\u003csub\u003en\u003c/sub\u003e). The likelihood of the stacking-\u003cb\u003esumanene\u003c/b\u003e moieties in the hetero-supramolecular polymers perturbing the electronic properties of the molecular recognition sites in \u003cb\u003eSC\u003c/b\u003e was high. Here, we report an unprecedented signal-amplification system based on the hetero-supramolecular polymers composed of \u003cb\u003eSC\u003c/b\u003e as a molecular binder and \u003cb\u003esumanene\u003c/b\u003e as a dynamic allosteric effector. This concept resulted in a powerful, widely applicable chemosensor capable of manipulating signal amplification.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e"},{"header":"Results and discussion","content":"\u003cp\u003e \u003cb\u003ePhotophysical properties of SC\u003c/b\u003e \u003c/p\u003e \u003cp\u003eThe UV/vis absorption and fluorescence spectra, and fluorescence lifetime decays of \u003cb\u003eSC\u003c/b\u003e in dichloromethane (CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e) are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e and Supplementary Fig. S12 in Supplementary Information (SI). The maximum peak in the UV/vis absorption spectra of \u003cb\u003eSC\u003c/b\u003e was observed at approximately 280 nm (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea), which was similar to the sum of \u003cb\u003esumanene\u003c/b\u003e and the indole reference compound (\u003cb\u003eref\u003c/b\u003e, Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ec). However, new absorption bands at approximately 310 and 360 nm were observed after comparing the molar extinction coefficients of \u003cb\u003eSC\u003c/b\u003e with those of \u003cb\u003esumanene\u003c/b\u003e and \u003cb\u003eref\u003c/b\u003e, suggesting that a p-conjugation extended from the \u003cb\u003esumanene\u003c/b\u003e core to the indole chromophore. An emission peak at 412 nm was observed in the fluorescence spectrum of \u003cb\u003eSC\u003c/b\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb). Because of the appreciable bathochromic shift in \u003cb\u003eSC\u003c/b\u003e compared with those of \u003cb\u003esumanene\u003c/b\u003e and \u003cb\u003eref\u003c/b\u003e, this peak may have originated from the p-extended indole-\u003cb\u003esumanene\u003c/b\u003e conjugation. The fluorescence decay profiles (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec) monitored at 392, 406, and 431 nm (l\u003csub\u003eex\u003c/sub\u003e: 340 nm) were fitted to a sum of reasonable exponential functions to produce the first short-lived species (0.4 ns) at the shorter wavelength region, a major fluorescence species (2.6 ns) presented in the entire region, and the second short-lived species (0.3\u0026ndash;0.4 ns) at the longer wavelength region (Supplementary Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e in SI). The major excited species (2.6 ns) was assigned to the fluorescent \u003cb\u003eSC\u003c/b\u003e monomer. A titration of \u003cb\u003eSC\u003c/b\u003e using triethylamine as an organic base (Supplementary Figs. S13\u0026ndash;S14 and Supplementary Table S2\u0026ndash;S3 in SI) showed the fluorescence quenching mainly involved the first short-lived species; this was assigned to a fluorescent anion species where protons dissociated from the indole moiety. A rise component with a negative \u003cem\u003eA\u003c/em\u003e factor (relative abundance) was observed in the second short-lived species (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec, Supplementary Figs. S12c,d (SI), and Supplementary Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e (SI)). Density functional theory (DFT) calculations (function/basis set: ωB97X-D/6-311G(d,p)) of \u003cb\u003eSC\u003c/b\u003e were performed to identify the rise component (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ed). Three indole side chains aligned in a T-shape manner with a distance of 6.7 \u0026Aring;. The results of the DFT calculations suggested that the second short-lived species is originated from the frustrated (second) excimer formed via the intramolecular, T-shaped overlap of the indole side chains; this was observed in previous studies\u003csup\u003e47,48\u003c/sup\u003e. This interesting photochemical property was formed by the fixation of the fluorescent moieties on the \u003cb\u003esumanene\u003c/b\u003e scaffold.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e\n\u003ch3\u003eSensing behavior of SC\u003c/h3\u003e\n\u003cp\u003eA series of benzene and cyclohexane derivatives were used as model guests for a proof of concept (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea). Thereafter, their sensing behaviors were investigated in CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e. Upon the gradual addition of \u003cb\u003eMB\u003c/b\u003e, a wide range broadened peak was observed in the long wavelength region (\u0026gt;\u0026thinsp;355 nm) of the UV/vis absorption spectra for the titration of \u003cb\u003eSC\u003c/b\u003e ⸦ \u003cb\u003eMB\u003c/b\u003e (Supplementary Fig. S17a in SI). Efficient quenching was only observed when a new band emerged, and peak shifts were absent in the corresponding fluorescence spectra (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eb and Supplementary Fig. S17b (SI)). Using this spectral change, \u003cem\u003eK\u003c/em\u003e\u003csub\u003eSC\u003c/sub\u003e was estimated as 7\u0026thinsp;\u0026plusmn;\u0026thinsp;1 M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, assuming the formation of a 1:1 complexation (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ec) wherein: (\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e) the stoichiometric analysis in Supplementary Fig. S20 in SI was discussed using the following anion system, and (\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e) the following 1:1 complex structure was provided in advance (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ed). Subsequently, the anion sensing shown in Supplementary Figs. S18\u0026ndash;S19 in SI was discussed. The UV/vis absorption spectra of \u003cb\u003eSC\u003c/b\u003e ⸦ \u003cb\u003eTBPB\u003c/b\u003e exhibited a similar broadened wavelength (\u0026gt;\u0026thinsp;355 nm); however, a hypochromic effect was observed at approximately 320\u0026ndash;355 nm. During fluorescence titration, the peak maxima bathochromically shifted with appreciable quenching. The spectral differences between neutral \u003cb\u003eMB\u003c/b\u003e and anionic \u003cb\u003eTBPB\u003c/b\u003e were likely responsible for the different ground-state complexations based on the neutral- or anion-\u003cb\u003eSC\u003c/b\u003e. Furthermore, the \u003cem\u003eK\u003c/em\u003e\u003csub\u003eSC\u003c/sub\u003e value of anion-\u003cb\u003eSC\u003c/b\u003e, assuming the complexation type was 1:1, was enhanced to 850\u0026thinsp;\u0026plusmn;\u0026thinsp;10 M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Therefore, the spectroscopic behaviors were affected by the strength of the anion complexation.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe interaction between \u003cb\u003eSC\u003c/b\u003e and \u003cb\u003eMB\u003c/b\u003e was further investigated using IR spectroscopy. The broad peak at 3303 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, which was derived from the N\u0026ndash;H stretching vibration in the indole ring, decreased in intensity as the higher wavenumber shifted to 3329 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e with increasing \u003cb\u003eMB\u003c/b\u003e concentration (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ee). Additionally, the \u003cb\u003eref\u003c/b\u003e compound can bind \u003cb\u003eMB\u003c/b\u003e (\u003cem\u003eK\u003c/em\u003e\u003csub\u003eref\u003c/sub\u003e = 4 \u0026plusmn; 1 M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) and \u003cb\u003eTBPB\u003c/b\u003e (\u003cem\u003eK\u003c/em\u003e\u003csub\u003eref\u003c/sub\u003e = 4 \u0026plusmn; 1 M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) with sufficient fluorescence quenching; this was also observed in \u003cb\u003eSC\u003c/b\u003e (Supplementary Fig. S16 in SI). These results suggest that the hydrogen bonds formed via the carbonyl moiety of the guests and the dissociated N\u0026ndash;H protons on the indole rings in \u003cb\u003eSC\u003c/b\u003e are main recognition forces. This was consistent with the fluorescence quenching behavior observed after adding triethylamine (\u003cem\u003evide supra\u003c/em\u003e). The \u003cem\u003eK\u003c/em\u003e\u003csub\u003eSC\u003c/sub\u003e value of \u003cb\u003eSC\u003c/b\u003e ⸦ \u003cb\u003eTBPB\u003c/b\u003e was enhanced by a factor of 213 compared with \u003cem\u003eK\u003c/em\u003e\u003csub\u003eref\u003c/sub\u003e of \u003cb\u003eref\u003c/b\u003e ⸦ \u003cb\u003eTBPB\u003c/b\u003e, which was likely owing to a cooperative complexation through the octopus-like three indoles on the \u003cb\u003esumanene\u003c/b\u003e scaffold. Therefore, it was important to elucidate the thermodynamic parameters before applying the temperature-dependent van\u0026rsquo;t Hoff analysis of \u003cb\u003eSC\u003c/b\u003e ⸦ \u003cb\u003eTBPB\u003c/b\u003e at four temperatures from 5 to 35\u0026deg;C (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ef and Supplementary Figs. S18\u0026ndash;S19 (SI)). The van\u0026rsquo;t Hoff plot showed a straight line, indicating that the same complexation mechanism can be found in this temperature range (same heat capacity); Δ\u003cem\u003eH\u003c/em\u003e\u0026deg; and \u003cem\u003eΤ\u003c/em\u003eΔ\u003cem\u003eS\u003c/em\u003e\u0026deg; were \u0026minus;\u0026thinsp;20.8 and \u0026minus;\u0026thinsp;4.2 kJ mol\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, respectively. The thermodynamic parameters exhibited enthalpy-driven complexation. Nevertheless, the observed entropy loss was relatively low despite the immobilization by three recognition sites, which was accounted for by the classical chelate effect\u003csup\u003e49\u003c/sup\u003e. Therefore, the high enthalpy gain and low entropy loss (the common cooperative manner) resulted in a higher and enhanced \u003cem\u003eK\u003c/em\u003e\u003csub\u003eSC\u003c/sub\u003e (D\u003cem\u003eG\u003c/em\u003e\u0026deg; = -16.6 kJ mol\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) based on the distinctive structural specificity.\u003c/p\u003e \u003cp\u003eThe sensing results of the eight guests by \u003cb\u003eSC\u003c/b\u003e are listed in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e and Supplementary Figs. S21\u0026ndash;S23 (SI). First, the \u003cem\u003eK\u003c/em\u003e\u003csub\u003eSC\u003c/sub\u003e values of \u003cb\u003eSC\u003c/b\u003e against methyl esters were in the range of 7\u0026ndash;28 M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e; small but gradual increases in \u003cem\u003eK\u003c/em\u003e\u003csub\u003eSC\u003c/sub\u003e were observed as the number of carboxylic groups increased. The \u003cem\u003eK\u003c/em\u003e\u003csub\u003eSC\u003c/sub\u003e values for \u003cb\u003eTT\u003c/b\u003e and \u003cb\u003eTC\u003c/b\u003e were similar, indicating that the contribution of the benzene ring (p\u0026ndash;p interaction) in supramolecular complexation was minimal. This reinforced the hydrogen bonding interactions as the main driving force. Subsequently, the \u003cem\u003eK\u003c/em\u003e\u003csub\u003eSC\u003c/sub\u003e values of \u003cb\u003eSC\u003c/b\u003e against anions were between 850\u0026ndash;1940 M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. These values exhibited a factor of 44\u0026ndash;121 enhancement compared with the corresponding methyl esters. The marginal deviation in \u003cem\u003eK\u003c/em\u003e\u003csub\u003eSC\u003c/sub\u003e as the number of carboxylates increased from two to three was likely owing to the bulkiness of the TBP cation (steric hindrance). Similar \u003cem\u003eK\u003c/em\u003e\u003csub\u003eSC\u003c/sub\u003e values for \u003cb\u003eTBPT\u003c/b\u003e and \u003cb\u003eTBPC\u003c/b\u003e were observed, showing that the main complexation was derived from hydrogen bonding interactions and not p\u0026ndash;p interactions.\u003c/p\u003e\n\u003ch3\u003eHetero-supramolecular polymerization consisting of SC and sumanene\u003c/h3\u003e\n\u003cp\u003eSimilar to a previous study on homo-supramolecular polymerization\u003csup\u003e46\u003c/sup\u003e, the formation of hetero-supramolecular polymers using \u003cb\u003eSC\u003c/b\u003e and \u003cb\u003esumanene\u003c/b\u003e in CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e was investigated. No new absorption bands were observed in the UV spectra as \u003cb\u003esumanene\u003c/b\u003e was titrated against 128 \u0026micro;M of \u003cb\u003eSC\u003c/b\u003e (Supplementary Fig. S25 in SI); these UV spectra were similar to the concentration-dependent UV spectra of \u003cb\u003esumanene\u003c/b\u003e. Nevertheless, the hetero-supramolecular polymerization behavior was elucidated by calculating the molar extinction coefficient of the \u003cb\u003esumanene\u003c/b\u003e skeleton in \u003cb\u003eSC\u003c/b\u003e, \u003cem\u003ee\u003c/em\u003e\u003csub\u003esumanene,(calcd.)\u003c/sub\u003e. This provided the basis for the \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\stackrel{-}{\\epsilon }\\)\u003c/span\u003e\u003c/span\u003e value of the \u003cb\u003eSC\u003c/b\u003e\u0026bull;(\u003cb\u003esumanene\u003c/b\u003e)\u003csub\u003en\u003c/sub\u003e hetero-supramolecular polymer, which was used to estimate \u003cem\u003ea\u003c/em\u003e\u003csub\u003eagg\u003c/sub\u003e (Supplementary Fig. S25, Supplementary Table S5, and their relevant discussion in SI). Assuming that the model was isodesmic based on the similar curvature surfaces of \u003cb\u003eSC\u003c/b\u003e (depth as 0.90 \u0026Aring;) and \u003cb\u003esumanene\u003c/b\u003e (depth as 0.89 \u0026Aring;) estimated using the DFT calculations, a \u003cem\u003eK\u003c/em\u003e\u003csub\u003ei\u003c/sub\u003e value of 770\u0026thinsp;\u0026plusmn;\u0026thinsp;120 M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e was determined after analyzing the molar extinction coefficient at 363 nm. Heteromer formation was further supported by the diffusion coefficient (\u003cem\u003eD\u003c/em\u003e) obtained via NMR diffusion ordered spectroscopy (DOSY). The \u003cem\u003eD\u003c/em\u003e value of a CD\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e mixture of \u003cb\u003eSC\u003c/b\u003e (447 \u0026micro;M) and \u003cb\u003esumanene\u003c/b\u003e (9.09 mM) was 7.37 \u0026times; 10\u003csup\u003e\u0026minus;\u0026thinsp;10\u003c/sup\u003e m\u003csup\u003e2\u003c/sup\u003e/s (Supplementary Figs. S26\u0026ndash;S29 in SI). This value was subjected to the ellipsoid approximation model; a 4\u0026ndash;5-mer was estimated (Supplementary Table S6 and its relevant discussion in SI). By contrast, the number-average DP value of the heteromer calculated using the assumption of the isodesmic model was 3.3, which was similar to the DOSY experiment (see structures in Supplementary Fig. S30 in SI).\u003c/p\u003e\n\u003ch3\u003eAmplification-sensing behavior using the hetero-supramolecular polymer\u003c/h3\u003e\n\u003cp\u003eBroad peaks were observed in the long wavelength region of the UV/vis absorption spectra of \u003cb\u003eSC\u003c/b\u003e\u0026bull;(\u003cb\u003esumanene\u003c/b\u003e)\u003csub\u003en\u003c/sub\u003e ⸦ \u003cb\u003eMB\u003c/b\u003e in CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e (Supplementary Fig. S35a in SI), which was similar to the peaks in the long wavelength region of the \u003cb\u003eSC\u003c/b\u003e ⸦ \u003cb\u003eMB\u003c/b\u003e spectra. A fluorescence quench was observed in the fluorescence spectra of \u003cb\u003eSC\u003c/b\u003e\u0026bull;(\u003cb\u003esumanene\u003c/b\u003e)\u003csub\u003en\u003c/sub\u003e ⸦ \u003cb\u003eMB\u003c/b\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea); this quench was similar to that observed in the \u003cb\u003eSC\u003c/b\u003e ⸦ \u003cb\u003eMB\u003c/b\u003e spectra. A new emission band was observed at the longer wavelength region (approximately 500 nm) in the normalized fluorescence spectra (Supplementary Fig. S35b in SI), indicating that supramolecular complexation of \u003cb\u003eSC\u003c/b\u003e\u0026bull;(\u003cb\u003esumanene\u003c/b\u003e)\u003csub\u003en\u003c/sub\u003e ⸦ \u003cb\u003eMB\u003c/b\u003e occurred. The fluorescence spectral changes at 399 nm were fitted (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eb, red), assuming that the hetero-supramolecular polymer and the guest molecule form a 1:1 complex owing to the same recognition moiety (the \u003cb\u003eSC\u003c/b\u003e starburst in the complex). The obtained apparent binding constant (\u003cem\u003eK\u003c/em\u003e\u003csub\u003eSMP\u003c/sub\u003e) was 79\u0026thinsp;\u0026plusmn;\u0026thinsp;6 M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, which was 11.3-fold higher than the \u003cem\u003eK\u003c/em\u003e\u003csub\u003eSC\u003c/sub\u003e of \u003cb\u003eSC\u003c/b\u003e ⸦ \u003cb\u003eMB\u003c/b\u003e (7\u0026thinsp;\u0026plusmn;\u0026thinsp;1 M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e).\u003c/p\u003e \u003cp\u003eTable\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e shows the \u003cem\u003eK\u003c/em\u003e\u003csub\u003eSMP\u003c/sub\u003e and \u003cem\u003eK\u003c/em\u003e\u003csub\u003eSC\u003c/sub\u003e values of the eight guest molecules and the sensing behaviors of the hetero-supramolecular polymer and \u003cb\u003eSC\u003c/b\u003e system. Large amplification ratios of 2.9\u0026ndash;11.3 for esters with smaller \u003cem\u003eK\u003c/em\u003e\u003csub\u003eSC\u003c/sub\u003e were observed, whereas amplification ratios of 1.1\u0026ndash;2.5 for anions with relatively large \u003cem\u003eK\u003c/em\u003e\u003csub\u003eSC\u003c/sub\u003e (Supplementary Figs. S36\u0026ndash;S49 in SI). Therefore, signal-amplification sensing with \u003cb\u003esumanene\u003c/b\u003e supramolecular polymers may be useful for enhancing a low signal of a target molecule with a small \u003cem\u003eK\u003c/em\u003e in the \u003cb\u003eSC\u003c/b\u003e system.\u003c/p\u003e \u003cp\u003eTo elucidate the origin of the signal-amplification, DFT calculations (function/basis set: ωB97X-D/6-311G(d,p)) of \u003cb\u003eSC\u003c/b\u003e, \u003cb\u003esumanene\u003c/b\u003e, and \u003cb\u003eSC\u003c/b\u003e\u0026bull;(\u003cb\u003esumanene\u003c/b\u003e)\u003csub\u003en\u003c/sub\u003e were performed (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ed). The LUMO energy of \u003cb\u003eSC\u003c/b\u003e was 0.02 eV; this value remained constant even when a \u003cb\u003esumanene\u003c/b\u003e molecule stacked on \u003cb\u003eSC\u003c/b\u003e (dimer formation). By contrast, stacking two or more \u003cb\u003esumanene\u003c/b\u003e molecules on \u003cb\u003eSC\u003c/b\u003e resulted in the gradual reduction of LUMO energies to between \u0026minus;\u0026thinsp;0.02 (\u003cb\u003eSC\u003c/b\u003e\u0026bull;(\u003cb\u003esumanene\u003c/b\u003e)\u003csub\u003e2\u003c/sub\u003e) and \u0026minus;\u0026thinsp;0.09 eV (\u003cb\u003eSC\u003c/b\u003e\u0026bull;(\u003cb\u003esumanene\u003c/b\u003e)\u003csub\u003e4\u003c/sub\u003e). Furthermore, the LUMO energy of (\u003cb\u003esumanene\u003c/b\u003e)\u003csub\u003e5\u003c/sub\u003e was positive (0.45 eV). Therefore, the likelihood of the negative LUMO energy values being more electron-receptive was high\u003csup\u003e50\u003c/sup\u003e. This improved the acceptor properties of the \u003cb\u003eSC\u003c/b\u003e binding site in the heteromer. Because the LUMO orbitals of \u003cb\u003eSC\u003c/b\u003e\u0026bull;(\u003cb\u003esumanene\u003c/b\u003e)\u003csub\u003en\u003c/sub\u003e extended from the \u003cb\u003esumanene\u003c/b\u003e core in \u003cb\u003eSC\u003c/b\u003e to the indole binding site, the formation of \u003cb\u003eSC\u003c/b\u003e\u0026bull;(\u003cb\u003esumanene\u003c/b\u003e)\u003csub\u003en\u003c/sub\u003e influenced the electronic acceptor properties of the indole moiety\u0026mdash;the origin of the signal-amplification. In addition, natural population analysis showed that the formation of hetero-supramolecular polymers caused the electron transfer from \u003cb\u003esumanene\u003c/b\u003e to \u003cb\u003eSC\u003c/b\u003e, resulting in an anionic \u003cb\u003eSC\u003c/b\u003e core in the charge-transfer (CT) complex (Supplementary Table S7 in SI). Therefore, the signals for the anions were not amplified because of electrostatic repulsion in the hetero-supramolecular polymer system; however, amplification was observed against the esters.\u003c/p\u003e \u003cp\u003eImportantly, the experimental and theoretical findings showed that the number of stacks of \u003cb\u003esumanene\u003c/b\u003e played a critical role in signal amplification. The functionality of the conceptual mechanism shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb was assessed by sensing \u003cb\u003eMB\u003c/b\u003e with varying concentrations of the \u003cb\u003esumanene\u003c/b\u003e seed in \u003cb\u003eSC\u003c/b\u003e (Supplementary Figs. S31\u0026ndash;S34 in SI). The ln \u003cem\u003eK\u003c/em\u003e\u003csub\u003eSMP\u003c/sub\u003e value (=\u0026thinsp;D\u003cem\u003eG\u003c/em\u003e\u0026deg;) as a function of DP increased exponentially (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ec); therefore, the behavior of \u003cb\u003esumanene\u003c/b\u003e was that of a \u003cem\u003edynamic allosteric effector\u003c/em\u003e. The conceptual illustration observed in this study (signal amplification) is shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ee.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eBinding constants (K) between guest molecules and ref, SC, or SC\u0026bull;(sumanene)n in CH2Cl2 at 25\u0026deg;Ca\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"5\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003eGuest\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"3\" nameend=\"c4\" namest=\"c2\"\u003e \u003cp\u003e\u003cem\u003eK\u003c/em\u003e / M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003e\u003cem\u003eK\u003c/em\u003e\u003csub\u003eSMP\u003c/sub\u003e / \u003cem\u003eK\u003c/em\u003e\u003csub\u003eSC\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cb\u003eref\u003c/b\u003e (\u003cem\u003eK\u003c/em\u003e\u003csub\u003eref\u003c/sub\u003e)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003e\u003cb\u003eSC\u003c/b\u003e (\u003cem\u003eK\u003c/em\u003e\u003csub\u003eSC\u003c/sub\u003e)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003e\u003cb\u003eSC\u003c/b\u003e\u0026bull; (\u003cb\u003esumanene\u003c/b\u003e)\u003csub\u003en\u003c/sub\u003e (\u003cem\u003eK\u003c/em\u003e\u003csub\u003eSMP\u003c/sub\u003e)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eMB\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e4\u0026thinsp;\u0026plusmn;\u0026thinsp;1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e7\u0026thinsp;\u0026plusmn;\u0026thinsp;1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e79\u0026thinsp;\u0026plusmn;\u0026thinsp;6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e11.3\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eDI\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eb\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e16\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e46\u0026thinsp;\u0026plusmn;\u0026thinsp;16\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e2.9\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eTT\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eb\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e20\u0026thinsp;\u0026plusmn;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e78\u0026thinsp;\u0026plusmn;\u0026thinsp;32\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e3.9\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eTC\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eb\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e28\u0026thinsp;\u0026plusmn;\u0026thinsp;8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e102\u0026thinsp;\u0026plusmn;\u0026thinsp;28\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e3.6\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eTBPB\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e4\u0026thinsp;\u0026plusmn;\u0026thinsp;1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e850\u0026thinsp;\u0026plusmn;\u0026thinsp;10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e2120\u0026thinsp;\u0026plusmn;\u0026thinsp;310\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e2.5\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eTBPI\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eb\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1940\u0026thinsp;\u0026plusmn;\u0026thinsp;140\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e3140\u0026thinsp;\u0026plusmn;\u0026thinsp;680\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1.6\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eTBPT\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eb\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1400\u0026thinsp;\u0026plusmn;\u0026thinsp;90\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1470\u0026thinsp;\u0026plusmn;\u0026thinsp;100\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1.1\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eTBPC\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eb\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1240\u0026thinsp;\u0026plusmn;\u0026thinsp;80\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1310\u0026thinsp;\u0026plusmn;\u0026thinsp;110\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1.1\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003etestosterone\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eb\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e34\u0026thinsp;\u0026plusmn;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e170\u0026thinsp;\u0026plusmn;\u0026thinsp;17\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e5.0\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003ecorticosterone\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eb\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e440\u0026thinsp;\u0026plusmn;\u0026thinsp;10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e530\u0026thinsp;\u0026plusmn;\u0026thinsp;50\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1.2\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eallylestrenol\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eb\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e4\u0026thinsp;\u0026plusmn;\u0026thinsp;0.3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e250\u0026thinsp;\u0026plusmn;\u0026thinsp;20\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e62.5\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colspan=\"5\" nameend=\"c5\" namest=\"c1\"\u003e \u003cp\u003e\u003csup\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sup\u003e[\u003cb\u003eref\u003c/b\u003e]\u0026thinsp;=\u0026thinsp;1.35\u0026ndash;1.36 mM, [\u003cb\u003eSC\u003c/b\u003e]\u0026thinsp;=\u0026thinsp;396\u0026ndash;480 \u0026micro;M, [\u003cb\u003eSC\u003c/b\u003e\u0026bull;(\u003cb\u003esumanene\u003c/b\u003e)\u003csub\u003en\u003c/sub\u003e]\u0026thinsp;=\u0026thinsp;394\u0026ndash;450 \u0026micro;M \u003cb\u003eSC\u003c/b\u003e\u0026thinsp;+\u0026thinsp;8.64\u0026ndash;9.29 mM \u003cb\u003esumanene\u003c/b\u003e; DP\u0026thinsp;=\u0026thinsp;3.2\u0026ndash;3.3. \u003csup\u003e\u003cem\u003eb\u003c/em\u003e\u003c/sup\u003eNot determined.\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e\n\u003ch3\u003eSteroid sensing: general validity and application using the hetero-supramolecular polymer\u003c/h3\u003e\n\u003cp\u003eTo further generalize the current signal-amplification method and demonstrate its applicability in biologically important materials, steroids such as testosterone, corticosterone, and allylestrenol were selected as target molecules with lower donor characteristics (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ef). The fluorescence spectral changes of \u003cb\u003eSC\u003c/b\u003e\u0026bull;(\u003cb\u003esumanene\u003c/b\u003e)\u003csub\u003en\u003c/sub\u003e ⸦ \u003cb\u003eallylstrenol\u003c/b\u003e exhibited distinctive fluorescence quenching similar to that of other sensing systems (Supplementary Figs.\u0026nbsp;50\u0026ndash;54). A similar 1:1 fitting for the fluorescence changes at 409 nm resulted in a \u003cem\u003eK\u003c/em\u003e\u003csub\u003eSMP\u003c/sub\u003e value of 250\u0026thinsp;\u0026plusmn;\u0026thinsp;20 M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, which was a 62.5-fold higher signal-amplification than \u003cem\u003eK\u003c/em\u003e\u003csub\u003eSC\u003c/sub\u003e of \u003cb\u003eSC\u003c/b\u003e ⸦ \u003cb\u003eallylstrenol\u003c/b\u003e as 4\u0026thinsp;\u0026plusmn;\u0026thinsp;0.3 M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eg). A lower \u003cem\u003eK\u003c/em\u003e\u003csub\u003eSC\u003c/sub\u003e value in the \u003cb\u003eSC\u003c/b\u003e system corresponded to a higher amplification of the \u003cem\u003eK\u003c/em\u003e\u003csub\u003eSMP\u003c/sub\u003e in the hetero-supramolecular polymer system. It was concluded that the signal amplification by the \u003cb\u003esumanene\u003c/b\u003e-based hetero-supramolecular polymer was 62.5-fold higher than that of the other sensing systems.\u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eA novel signal-amplification system was developed, wherein the curved-p \u003cb\u003esumanene\u003c/b\u003e seed for supramolecular polymerization functioned as a dynamic allosteric effector. This seed effector altered the DP to flexibly manipulate the electronic properties at the binding site (positive heterotopic allosterism), achieving an amplification that was up to 62.5-fold higher than other systems at sensing the biologically important steroid, allylestrenol. The sensing method and the conceptual guideline proposed herein facilitate the sensing of diverse guests that are difficult to signally recognize using the conventional lock-and-key type chemosensors.\u003c/p\u003e"},{"header":"Methods","content":"\u003cp\u003e \u003cb\u003eComplexation studies\u003c/b\u003e \u003c/p\u003e \u003cp\u003eA stock solution of \u003cb\u003eSC\u003c/b\u003e was prepared by dissolving \u003cb\u003eSC\u003c/b\u003e powder in CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2,\u003c/sub\u003e followed by sonication for 1 min. Unused stock solutions were stored in the freezer. Stored samples were warmed to room temperature and then sonicated for 1 min before use. The concentration was calculated from the absorbance of the solution. The CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e mixture of \u003cb\u003eSC\u003c/b\u003e and \u003cb\u003esumanene\u003c/b\u003e was prepared by mixing ca. 600 \u0026micro;M \u003cb\u003eSC\u003c/b\u003e solution and ca. 2\u0026ndash;34 mM \u003cb\u003esumanene\u003c/b\u003e solution in a ratio of 8:3. The CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e solutions of the guest molecules were prepared at 50 mM to 8 M concentrations; thereafter, these solutions were titrated into \u003cb\u003eSC\u003c/b\u003e or hetero-supramolecular polymer solutions using a micro-syringe injection. A preparation concentration of \u003cb\u003eSC\u003c/b\u003e was used for the nonlinear least-squares fitting to determine the binding constants. IR spectra were measured on the plate by adding a few drops of CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e solution to the sample and then drying.\u003c/p\u003e\n\u003ch3\u003eComputational studies\u003c/h3\u003e\n\u003cp\u003eAll chemosensors and supramolecular complexes were structurally optimized by the DFT calculations with the ωB97X-D/6-311G (d,p) level, and the most stable structures were used for discussions. Triethylene glycol chains in \u003cb\u003eSC\u003c/b\u003e were changed to methoxy groups for simplicity.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eData availability\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAll results and supporting data are available within the main text and Supplementary Information. They can also be requested from the corresponding author.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgments\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eG.F. appreciates the generous supports by Grant-in-Aid (No. 19H02746, 23H04020) from the Japan Society for the Promotion of Science (JSPS) and Tokuyama Science Foundation. H.M. acknowledges JSPS Fellowships for Young Scientists (No. 21J22528, 22KJ1283). H.S. appreciates the generous support by Grant-in-Aid (No. 26102002, 21H05233, 19H00912, 20H00400) from JSPS. H.N. acknowledges JSPS Fellowships for Young Scientists (No. 21J10937). We are grateful to Mr. Yu Fukunaga, Prof. Susumu Kawauchi, and Prof. Tetsuo Okada at Tokyo Institute of Technology and Assoc. Prof. Takashi Hirose at Kyoto University for their constructive discussions.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eG.F. initiated and supervised the whole study. G.F. and H.S. designed the project and the experiments. H.M. synthesized chemosensors and carried out the experiments. H.N. prepared the \u003cstrong\u003esumanene\u003c/strong\u003e seed and its triol derivative. Y.Y. and A.M. analyzed the data. All authors contributed to writing the manuscript.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting interests\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare no competing interests.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAdditional information\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSupplementary information\u003c/strong\u003e The online version contains supplementary material available at XXX.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCorrespondence\u0026nbsp;\u003c/strong\u003eand requests for materials should be addressed to Gaku Fukuhara.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eReprints and permissions information\u003c/strong\u003e is available at www.nature.com/reprints.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eWintner, E. A., Conn, M. M. \u0026amp; Rebek, Jr., J. 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Chem.\u003c/em\u003e\u003cstrong\u003e19\u003c/strong\u003e, 522\u0026ndash;530 (2009).\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"nature-portfolio","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Nature Portfolio","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"ejp","reportingPortfolio":"","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Sumanene, Supramolecular Polymer, Allosterism, Amplification Sensing","lastPublishedDoi":"10.21203/rs.3.rs-3831095/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-3831095/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"The synthesis of signal-amplifying chemosensors induced by various triggers is a major challenge for multidisciplinary sciences. In this study, a signal-amplification system that was flexibly manipulated by a dynamic allosteric effector (trigger) was developed. Herein, the focus was on using the behavior of supramolecular polymerization to control the degree of polymerization by changing the concentration of a functional monomer (seed). It was assumed that this control was facilitated by a gradually changing/dynamic allosteric effector. A curved-π buckybowl \u003cb\u003esumanene\u003c/b\u003e and a \u003cb\u003esumanene\u003c/b\u003e-based chemosensor (\u003cb\u003eSC\u003c/b\u003e) were employed as the seed/allosteric effector and the molecular binder, respectively. The hetero-supramolecular polymer, (\u003cb\u003eSC\u003c/b\u003e•(\u003cb\u003esumanene\u003c/b\u003e)\u003csub\u003en\u003c/sub\u003e), facilitated the manipulation of the degree of signal-amplification; this was accomplished by changing the \u003cb\u003esumanene\u003c/b\u003e seed concentration, which resulted in up to a 62.5-fold amplification of a steroid. The current results and the concept proposed herein provide an alternate method to conventional chemosensors and signal-amplification systems.","manuscriptTitle":"Amplification sensing manipulated by a sumanene-based supramolecular polymer as a dynamic allosteric effector","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-03-11 10:15:38","doi":"10.21203/rs.3.rs-3831095/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"communications-chemistry","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"commschem","sideBox":"Learn more about [Communications Chemistry](http://www.nature.com/commschem/)","snPcode":"","submissionUrl":"","title":"Communications Chemistry","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Communications Series","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"18067015-266e-48dd-a6f9-9e43e9f3f935","owner":[],"postedDate":"March 11th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[],"tags":[],"updatedAt":"2024-04-05T09:44:24+00:00","versionOfRecord":[],"versionCreatedAt":"2024-03-11 10:15:38","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-3831095","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-3831095","identity":"rs-3831095","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}