Gas-Fueled Non-Equilibrium Co-Assembly via C1 Catalytic Feedback for Gas-Encoded 4D Information Encryption

Gas-Fueled Non-Equilibrium Co-Assembly via C1 Catalytic Feedback for Gas-Encoded 4D Information Encryption | 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 Gas-Fueled Non-Equilibrium Co-Assembly via C1 Catalytic Feedback for Gas-Encoded 4D Information Encryption Qiang YAN, Yulian Zhang, Cuiqin Yang, Xin Liang, Jun Xiang This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4677523/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Dissipative self-assembly, which exploits energy inputs of chemical fuels to maintain the functional states far from equilibrium, is essential to the living systems. Among a variety of fuels, carbon dioxide (CO2) gas, as one of the most ubiquitous but original forms of fuel on which life depends, has yet been introduced in artificial dissipative materials. Here we describe a CO2-fueled non-equilibrium co-assembly system that couples with a C1 catalytic feedback path to drive fuel dissipation and function output. Using common frustrated Lewis pair (FLP) as precursors, CO2 can dynamically bridge between them to constitute metastable amphiphiles, which not only highly activate CO2 but also enable their co-assembly with substrates into a transient fibrillar gel. In turn, the feedback process is realized by cooperative C1 catalytic insertion owing to the proximity of substrate and activated CO2 species in the assembled state. This can boost the depletion of gas fuel and facilitate disassembly to sol. Moreover, tailoring the intrinsic substrate/FLP chemistries, as well as external cues, to shift the catalytic activity is accessible to regulate the period and lifetime of sol-gel-sol transition over a wide range. Based on the tunability in phase transition on a time scale, we develop time-dependent information encryption materials using the transient FLP array loaded gas-encoded substrates, and the correct information can be read only at a specified time window. This study provides inspiration on a new fuel paradigm for dissipative system and their intelligent material applications. Physical sciences/Materials science/Soft materials/Self-assembly Physical sciences/Chemistry/Supramolecular chemistry/Self-assembly Physical sciences/Chemistry/Materials chemistry/Soft materials/Gels and hydrogels Biological sciences/Systems biology/Dynamical systems Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Introduction Life works in order at a non-equilibrium state at the expense of energy, which is thermodynamic foundation for the maintenance of biological processes 1 , 2 . As exemplified by actin filaments and microtubules, they can exploit and convert chemical energy stored in ATP or GTP fuel to activate transient assembly, forming dynamic nanostructures 3 , 4 . In general, these living systems require a continuous consumption of fuels to sustain their high-energy biotic functions; once the fuel supply ceases the disassembly commences 5 . Such biologically dissipative phenomena have aroused mounting interest of chemists toward the development of artificial dissipative assemblies and materials 6 – 10 . Various forms of fuels, including chemicals and light, have been employed as the major energy inputs to drive the dissipative self-assembly 11 , 12 . Chemical fuels, such as alkylating agents 13 , carbodiimides 14 – 17 , redox 18 – 21 , and ATP 22 – 25 , have high efficiency in generating activated species, while their inadequacies in spatial control and chemical wastes impede their long-standing applications. Optically fueled systems are more spatiotemporally programmable and waste-free; however, they suffer from limited metastable speciation 12 . In view of these, the pursuit of new forms of energy (e.g. electric field and mechanical forces) 26 , 27 to orchestrate chemical reaction networks for creation of lifelike active materials have emerged as a challenge in systems chemistry. Gas substances, especially carbon dioxide (CO 2 ) gas, have been recognized as fundamental and primitive sources of energy on earth 28 . CO 2 is a necessary nutrient (fuel) for photosynthesis of plants and cyanobacteria, as well as a basic C1 feedstock for complex organics conversion under primordial chemistry 29 . As an ideal fuel candidate, not only CO 2 manifests benign, green, and clean merits, because excessive gas can escape from the system without residues, but also it is easy to operate in a spatiotemporal manner 30 . Currently, CO 2 -sensitive materials have been applied in broad fields of smart latexes, cell mimics, switchable surfaces, and gas therapy 31 , 32 . Yet, these materials all work in equilibrium state wherein CO 2 is only regarded as a trigger. Harnessing CO 2 as a fuel to direct non-equilibrium assembly has been unexplored. One major hurdle is difficult to establish a gas-involved reaction loop, where gas is required to play two opposite roles, both activating molecular precursors to drive an energetically uphill assembly process, and being consumed to deactivate the assembly and reboot the system. Moreover, such activation and deactivation should feature kinetic asymmetry ( k act > k deact ) to maintain the cycle 5 . As far as we know, gas reactions that can meet all these requirements at once are rare. To address these unmet challenges, our idea is to engineer a tri-component supramolecular reaction loop consisting of gas, precursor, and substrate, which should satisfy three prerequisites: (i) The precursor without gas lies dormant incapable of assembly. (ii) What needs to be stressed is that gas as a fuel could dynamically bind with the precursor, rather than a commonly covalent reaction. This would make the precursor structurally into an active gas-bound form, and further induce its co-assembly with substrate via synergy of noncovalent forces. (iii) In the assembled state, the activity of these discrete gas-bound species gets amplified, which would catalyze the proximal substrate to react with gas. This could serve as a feedback pathway for the depletion of gas fuel and breakup of assemblies (Fig. 1a). If the forward gas association is faster than the backward gas catalysis in kinetics, a non-equilibrium self-assembled system is accessible. As a proof of principle, in this study, we report a CO 2 -fueled non-equilibrium co-assembly system formed from frustrated Lewis pair (FLP) precursors and a benzoheterocyclic substrate. FLP refers to a pair of sterically encumbered Lewis acid and base that can prevent the formation of conventional Lewis adduct but close to each other to offer confined gap for binding small molecules, especially a range of gas molecules 33 . Previously, we have shown that CO 2 gas can enter this void, dynamically bridging two complementary FLPs to form adaptive materials 34 , in which such bound CO 2 species is of latent catalytic capacity because of the weakened C═O double bond 35 . With these in mind, the system reported here used a commercial tri(pentafluoro-phenyl)borane ( TB ) and a simple alkylated trimesitylphosphine ( C n TP , n = 0, 3, 7 and 11) as the bulky Lewis acidic and basic precursors, and different benzoheterocycles as the substrates ( S1‒S12 ). CO 2 fuel accesses the two FLPs to bind together via a dynamic gas bridge, and drives the dormant precursors to temporally co-assemble with the substrates into a fibrillar gel through consequent supramolecular synergy of polar‑π and π‑π interactions among them. By harvesting the gas binding energy, the assembly entry into a high-energy state unlocks the catalytic activity of CO 2 . At the meantime, the substrates and activated CO 2 -FLP complexes closely packed in the assemblies can induce a CO 2 insertion towards the substrate, conversely promoting the gel breakdown for the initial state recovery (Fig. 1b). Moreover, tailoring either FLP chemistry or substrate reactivity, as well as varying the environmental cues, is crucial to tuning the catalytic kinetics, which enables temporal control of the period and lifespan of this sol-gel-sol transition. Based on this feature, we encrypt time-dependent 4D information in an encoded FLP array of different longevities. CO 2 treatment causes each unit in the array to undergo transient gelation and dissociation with different times. Such a time-gated phase transition allows information to be identified on a time scale, and the correct ones can be decrypted at only a specified time and will self-erase after readout. Given that CO 2 could come from our breath, this gas-fueled non-equibrium system would inspire a facile, portable way for secure information materials. Results Precursor and substrate design. We adopted TB as a Lewis acid since not only the strong electron-withdrawing effect of perfluorophenyl group lifts the acidity of boron center for CO 2 capture 33 , 36 , but also it has a preferred stacking selectivity with electron-rich arene via polar-π interaction, which is conducive to its co-aggregation with the conjugated substrate 37 . As Lewis bases, C n TP s attached one alkyl tail of different lengths possess variable solvophobicity. This might become a key parameter to tune gelation kinetics and further impact the assembly cycle. On the other hand, the molecular series bearing benzoheterocyclic core ( S1-S12 ) were chosen as the substrates, in which the unsaturated C(sp 2 )‒H located next to the heteroatom is relatively weak, prone to be catalytially inserted by CO 2 (R-H to R-COOH). All the FLP precursors and substrates were confirmed by NMR and mass spectra in structure (Supplementary Figs. 1–10). CO 2 -fueled transient gelation. Our first target was to investigate whether the designed FLP precursors and substrate could be transiently gelated by CO 2 gas. Using C 11 TP/TB and S1 ( N -methyl benzimidazole) as representatives, their mixture can be completely dissolved in toluene. Adding 1 mM of S1 into the two precursors (4 mM), neither solution color nor state underwent an obvious change, suggesting their free-flowing sol form. However, after CO 2 was applied (1 mM, p = 1.0 bar, flow rate = 2.0 mL/s), the solution became a little viscous within 6 min (Fig. 2a) and then changed into a self-supporting gel within ca. 50 min (Fig. 2b). Interestingly, this gelation process did not maintain for long, but spontaneously returned to the sol state after a while (160 min, Fig. 2c), implying that the gel might stand on a short-lived yet high-energy assembled form. Turbidity test showed that the solution transmittance varied parabolically with time, which exactly corresponds to such sol-gel-sol phase transition (Supplementary Fig. 11) 14 . To visualize their morphological change at nanoscale, transmission electron microscopy (TEM) was employed. TEM image revealed that the precursors and substrate emerged aggregation just after the addition of CO 2 (6 min) and formed plenty of short fibrillar structures (Fig. 2d). Close inspection by atomic force microscopy (AFM) further exhibited that these nanofibrils have homogenous diameter and their contour lengths ranging from 20‒150 nm (Supplementary Fig. 12a). There were some entanglement and bundling existed among the fibrils, which should be the incentive for an uplifted solution viscosity. Each short fibril continued to grow along its 1D axial direction over time and intertwined into long fiber network (Fig. 2e and Supplementary Fig. 12b). Their radial widths remained constant but their average lengths extended to several microns with a high length-diameter ratio (> 500), tens of times more than that of the beginning, confirming a sort of fiber gel formed. The gel dissociation occurred after 160 min, as attested by the rupture of the fibrils (Fig. 2f and Supplementary Fig. 12c,13). From these results, we reasoned that CO 2 could activate the dormant FLP precursors and facilitate their transient co-assembly via possible gas binding. Simultanesouly, an underlying feedback pathway should be concealed in such system that is responsible to debind CO 2 for gel collapse and system recovery. On the other hand, we adopted rheological method to monitor the gel mechanical properties in real-time 14 , 15 . As shown in Fig. 2g, storage modulus ( G ′) of the system was less than its loss modulus ( G ″) within the initial 20 min; but subsequently, G ′ gave a rapid growth, higher than that of G ″, to reach a maximum of 58.2 kPa, followed by a gradual drop to its original value. This mechanical change coincides with the actual transition from rheological liquids to solids and back to liquids 16 . Furthermore, there are two cross-points existed in the G ′ and G ″ curves at 18 and 138 min, which means that this gelation is indeed transitory, with the lifetime of ~ 120 min. We further found that the gel lifetime is dependent on the amounts of fuel and substrate. Higher levels of fuel and substrate (1.0→4.0 mM) resulted in longer duration (120→262 min, column 3–5 in Fig. 2h) and preferable strength (58.2→122.6 kPa, Supplementary Fig. 14c-e), suggesting that more CO 2 cross-linking sites are formed in the molecular network that reinforce their mechanics. As control, blank samples lack of either gas fuel or substrate did not exhibit any gelling phenomenon (column 1–2 in Fig. 2h and Supplementary Fig. 14a,b). If we replaced CO 2 with other gases, such as more inert nitrogen (N 2 ), no gel produced as well (column 6 in Fig. 2h and Supplementary Fig. 14f). In striking contrast, when using diethyl azodicarboxylate (DEAD), a competing fuel that is of higher binding affinity to FLP 38 , instead of CO 2 , the gel could generate immediately and persist permanently (column 7 in Fig. 2h and Supplementary Fig. 14g). No spontaneous gel dissociation was seen since DEAD unlike CO 2 had no reactivity with the substrate. These findings point that CO 2 fuel is essential to underpin FLP precursors and substrate to form metastable gel networks. CO 2 -fueled non-equilibrium co-assembly mechanism. To unveil the transient mechanism driven by CO 2 , the spectrometric change of the co-assembly system was probed. Prior to CO 2 , the mixture solution ([ C 11 TP ]:[ TB ]:[ S1 ] = 1:1:1) showed a unimodal absorption at 266 nm, ascribed to the TP moiety (Fig. 3a, blue curve). Upon addition of CO 2 , however, this band was depressed until entire vanishment within 60 min, indicating CO 2 binding with FLP precursors to form typical gas-bridged bond 35 . Concomitantly, a new absorption emerged at 327 nm with elevated intensity (from 0 to 60 min, black solid lines between blue and green curves in Fig. 3a). Such a bathochromic shift hints that there are intermolecular charge-transfer interactions in the system 39 . Since TB is known to be a strong electron-deficient compound that can bind to electron-rich benzimidazole species via polar‑π interactions 37 , 40 , we thus speculated that this new peak should arise from the complexation between TB and S1 , and that it may act in concert with CO 2 -bridged linkages to lead the co-assembly. In the next period (from 60 to 200 min), the two absorptions at 266 and 327 nm returned to the original state whereas another new peak of 281 nm enhanced (black dash lines between green and orange curves in Fig. 3a). This means that both CO 2 linkages and polar‑π interactions that sustain the gel formation are dissociated, but a new species is yielded from the system, which we suspect is the product of S1 reaction with CO 2 . Furthermore, the change of diverse characteristic absorptions in intensity provided insight on the evolvement of different pathways in the system. From Fig. 3b, we found that the molar ratios of CO 2 -linkage (reflected by λ = 266 nm) and π-association (reflected by λ = 327 nm) follow a trend that first ascend and then fall off (blue and green curves), consistent with the rheological profile, which evidence that this sol-gel-sol transition is resulted from the transient co-assembly and reverse disassembly of FLP precursors and substrate fueled by CO 2 . The apparent rate coefficient of forward gas-binding ( k + app ) was evaluated to be 2.60 × 10 − 4 s − 1 , 2.5-fold faster than its backward debinding rate ( k − app = 1.04 × 10 − 4 s − 1 ). This kinetic discrepancy is the chemical basis to establish a gas-driven reaction cycle (Supplementary Fig. 15). In addition, NMR titration experiments confirmed the above results from the perspective of molecular structure. In the absence of CO 2 , 31 P NMR spectra gave a single signal at δ = -24.2 ppm (P α ), assigned to the triphenylphosphine group of free C 11 TP . Interestingly, after exposure to CO 2 , this peak was vastly suppressed in the first 60 min and then gradually recovered (blue peak in Fig. 3c), and concurrently, another P β peak, ascribed to four-coordination phosphine species 34 , 35 , 41 , appeared in the low-field region ( δ = 50.5 ppm) but with a opposite change (green peak in Fig. 3c), suggesting a short-lived complexation of CO 2 and phosphine but subsequent decomplexation. Similar phenomenon was observed in 11 B NMR spectra (Supplementary Fig. 16). These results indicate that CO 2 can bridge between C 11 TP and TB to form a P‒CO 2 ‒B structure (P‒CO 2 ‒B, inset in Fig. 3c), and this gas-bridge is dynamic that can be automatically disconnected and release the precursors. To figure out what is the hidden path that causes this reverse CO 2 dissociation in the system, we probed the structural conversion of substrate by 1 H NMR. Without CO 2 , S1 gave three groups of typical benzimidazole proton peaks with splitting (H a , δ = 8.03 ppm; H b , δ = 7.67 ppm; H c , δ = 7.42 ppm, blue peaks in Fig. 3d). However, after purged with CO 2 , H a continued to decline until disappearance, while H b and H c produced pronounced downfield shifts (H b’ , δ = 7.76 ppm; H c’ , δ = 7.55 ppm, green peaks in Fig. 3d). This result corresponds to the NMR data of benzo[d]imdiazole-2-carboxylic acid (Supplementary Fig. 17), indicating that CO 2 is indeed catalytically inserted into the unsaturated C(sp 2 )‒H site of S1 , leading to a carboxylated product (inset in Fig. 3d). Spectroscopic change also verified this continuous conversion (orange line in Fig. 3b). Exactly this catalytic process achieves the negative feedback, helping to use up CO 2 fuel and restart the system. According to these experimental results, the CO 2 -fueled transient gelation mechanism could be deduced. In the absence of CO 2 , FLP precursor and substrate exist free forms in the solution. When adding CO 2 , it associates with FLP pairs to constitute CO 2 -bridged amphiphiles ( C 11 TP ‒CO 2 ‒ TB ). This further induces a co-assembly with S1 substrate along 1D axis to form a fibril nanostructure, in which S1 is probably sandwiched between two neighboring FLP complexes through the synergy of polar‑π interactions with TB and π-π interactions with C 11 TP , and these π-stacked moieties together become the inner core of nanofibrils and the flexible alkyl chains as the outer layer (Fig. 3f). The proposed co-assembly model was validated by AFM analysis. Figure 3e disclosed that the gel is made up of fiber-like nanoobjects and the diameter of individual nanofibril is determined to be 4.9 nm (inset), corresponding to the total length of head-to-head arrangement of two FLP amphiphiles (49.6 Å). Molecular simulation further confirmed the co-aggregated molecular packing fashion and showed the parameters of cooperative interactions (Fig. 3g and Supplementary Fig. 18). The optimized length of each C 11 TP ‒CO 2 ‒ TB complex is about 22.9 Å bound by CO 2 bridge (P‒CO 2 ‒B spacing of 4.39 Å), while S1 species is located between the two complexes but is closer to TB (3.28 Å) than to the TP group (3.60 Å), meaning that polar‑π interactions are the main contribution to maintain the intermolecular co-assembly. It is worth mentioning that the distance of S1 and the adjacent CO 2 -bridged bond within this arrangement is only ~ 3.4 Å (green region in Fig. 3g), and such a short spacing may elicit a chemical proximal effect, which would become the structural basis for the catalysis of substrate in supramolecular level. On the other hand, in-solution small angle X-ray scattering (SAXS) and powder X-ray diffraction (PXRD) experimentally supported the above simulation. From SAXS profile, a diagnostic q − 1 decay at the Guinier region confirmed the presence of a solid cylinder nanostructure formed 42 , and two scattering peaks at 0.128 Å −1 and 0.270 Å −1 (Fig. 3h), corresponding to the d -spacing of 49.0 Å and 23.2 Å, in line with the sizes of fibril diameter (4.9 nm) and one CO 2 -bound FLP amphiphile (2.29 nm), respectively. On a smaller scale, XRD analysis presented a series of 2 θ peaks, among which three reflected the typical intermolecular interacting distances (3.26 Å, 3.58 Å, and 4.32 Å), in good accordance with the simulated spacings of polar‑π, π-π, and CO 2 -bridged bonds (Fig. 3i). These results together demonstrate the alternating-stack fashion of FLP precursors and substrate in a single nanofibril. Periodic behavior regulation of CO 2 -fueled transient gel. Like other dissipative systems, we wondered whether our FLP networks could manifest tunable phase transition behavior under control of internal or external factors. To elucidate this point, we studied the effects of precursor structure, substrate type and polarity on the periodicity and lifetime of transient gelation. First, when replacing TB precursor with fluorine-free triphenylborane ( TB F ), no aggregate can form at the same conditions (Fig. 4a). Even CO 2 fuel level was elevated by 10 times, it remained in a sol state ( G ′ < G ″) without any catalytic activity as compared to TB reference (columns 1–2 in Fig. 4c-d and Supplementary Fig. 19). The low gas binding ability is attributed to loss of Lewis acidity in TB F due to the removal of strong electron-withdrawing fluorine groups 36 . Second, we selected N -methylimidazole ( SC ), a similar counterpart but short of π-conjugated property, as the substrate to conduct the assembly. However, only small nanoparticles with a mean size of 20 nm were seized by TEM after CO 2 addition, and no fiber appeared (Fig. 4b). Moreover, although the sol viscosity increased, it was still insufficient to impel the formation of gel networks (column 3 in Fig. 4c-d and Supplementary Fig. 20). These indicated that SC can somewhat co-aggregate with CO 2 -bound FLPs; however, because of its weak aromaticity and less electronic delocalization, SC moieties are hard to stack with TB in long-range ordering, accordingly, no gel produced. Third, we also attempted to alter the polarity in assemblies by varying the tail length in Lewis base (Fig. 4e). Notably, the shorter the alkyl chain installed on TP moiety was, the weaker the strength of formed transient gel showed. In comparison to C 11 TP system ( G ′ = 58.2 kPa), the gel modulus in the presence of C 7 TP declined a half (22.8 kPa), while that in the case of C 3 TP less than one-tenth of the original (4.7 kPa, green columns 1–3 in Fig. 4f). As well, the backward catalytic reaction encountered lessened activity with the decrease of Lewis base in solvophobicity (orange columns 1–3 in Fig. 4f and Supplementary Fig. 21a-c). If the alkyl tail was absent ( C 0 TP ), it cannot support the gelation due to devoid of solvophobic effect to assist intermolecular aggregation (column 4 in Fig. 4f and Supplementary Fig. 21d). The aforesaid comparative tests illustrate that the chemical structure and property of FLP precursors and substrates have significant influence on their non-equilibrium co-assembly behavior. Considering that varying TP structure can shift the strength of formed transient gel and their catalytic capacity, we speculated that this factor could manipulate the non-equilibrium periodic behavior of such co-assembled system. To survey this tunability, upon batch addition of CO 2 fuel, we monitored the variation of gel modulus by rheology and the accumulative content of catalytic product by high performance liquid chromatography (HPLC) over time. Taking C 11 TP as a standard reference, its storage modulus first raised up to ~ 60 kPa within 60 min, and then spontaneously dropped down in another 140 min, corresponding to one round of sol-gel-sol transition. After resupplying of CO 2 , a new dissipative cycle can be continued. If we defined the difference between the maximal and minimal moduli as the amplitude, while the duration time from the beginning of modulus change until recovery as one complete period, the system still maintained the stable periodicity without obvious decay after operating in 3000 min (left y-axis, upper panel in Fig. 5a and Supplementary Fig. 22). Accompanied with the oscillating feature of gel mechanics, their feedback catalytic process presented a stepped curve, that is, the catalysis shut down and the conversion of products paused during the gel formation, whereas as soon as the gel started to collapse, the catalytic reaction switched on for a growing conversion (right y-axis, upper panel in Fig. 5a). In a similar way, other TP s were compared. As the alkyl group was shortened, the phase transition periods became slower ( C 7 TP , 308 min; C 3 TP , 410 min), with attenuated amplitude (middle and bottom panels in Fig. 5a and Supplementary Fig. 23–24). Furthermore, we noticed that when the alkyl chain length is less than a critical value of n = 2, the co-assembly was highly impeded and thus no periodic gelation phenomenon happened (Fig. 5e and Supplementary Fig. 25). Such a TP structure-dependent change in periodicity is explicable. The weaker the solvophobic effect of TP species have, the looser the molecules arrange inside the fibers, which means lower intermolecular interactions and subdued proximal effect. These would inhibit the cooperative catalysis and retard the backward reaction, leading to a longer sol-gel-sol transitional cycle. In addition to the TP structure, exterior parameters such as fuel concentration and temperature also had important regulatory effect on their transient process. Using TB (1 mM) and C 11 TP (1 mM) FLP precursors with excess of S1 substrate and batch addition of 1 mM CO 2 gas as a standard reference (saturated gas-bound state), a higher level of fuel supply (2 and 4 mM each batch) could reduce the total period from 210 min to 185 min and 156 min, respectively (upper and middle panels in Fig. 5b and Supplementary Fig. 26–27). Notably, the fuel increase speeded up the forward process (60 min→45 min and 23 min) but had negligible influence on their backward catalysis. This is because the gas binding kinetics is only related to the initial CO 2 concentration while the catalytic rate relies on the number of CO 2 -bridged sites. In contrast, if CO 2 level was unsaturated (0.5 mM), both period and amplitude were damped (bottom panel in Fig. 5b and Supplementary Fig. 28). The extension of period (210 min→300 min) is due to a substantial decrease in gas concentration and active sites, while the amplitude reduction (60 kPa→34 kPa) is originated from the incomplete gas bridging that depresses gel modulus. The critical limit of fuel level to maintain this cycle was determined to be ~ 0.3 mM, one-third of its saturated point (Fig. 5f and Supplementary Fig. 29). As well, temperature is a key factor in tuning the time-dependent behavior of gel. It is known that high temperature is favor of the kinetics of CO 2 catalytic insertion, but against the dynamic bridging between gas and FLP species 34 . Accordingly, elevating temperature (10 o C to 50 o C) could expedite the backward catalytic process but decelerate the forward CO 2 binding reaction, meanwhile, resulting in a decay in mechanical amplitude by nearly half (60 kPa→33 kPa) due to the promotion in thermally induced dissociation rate (Fig. 5c and Supplementary Fig. 30–32). Moreover, we found that this cyclical process has an optimal temperature window (5‒55 o C). Below 5 o C the formed gel is unable to spontaneously collapse since the feedback path of fuel consumption is blocked in low temperature; on the contrary, the gel cannot form above 55 o C because gas dissociation is predominated (Fig. 5g and Supplementary Fig. 33–34). We also interested in the effect of substrates on the periodic regulation. For this purpose, 12 commercially available N-heterocyclic chemicals were chosen for evaluation (Fig. 5h). Among them, when using benzoxazole-type compounds ( S2 ‒ S5 ) as substrates, the temporal period and mechanical amplitude of formed gels remained nearly unchanged, which mainly resulted from their similar chemical structure and activity to S1 . Typically, in the case of benzothiazole ( S3 ), its gel lifecycle lasted for 238 min and the extreme strength reached to ~ 52.4 kPa (upper panel in Fig. 5d and column 1–5 in Fig. 5i). However, if co-assembly was driven by quinoline-type substrates ( S6 ‒ S9 ), their lifecycles were generally extended to quite long time (350 ~ 700 min). A possible reason is that quinoline carrying one single nitrogen atom has a much lower acidity of C-H bond than that of benzoxazole ones with two electron-withdrawing heteroatoms, which retarded their catalytic processes (column 6–9 in Fig. 5i) 43 . For example, the transient gel in the presence of 7-methoxyquinoline ( S8 ) showed a periodic extremum (~ 700 min), especially in the process of backward catalysis (middle panel in Fig. 5d). We inferred that the electron-donating property of methoxy substituent causes this result because of its strong inhibition on the CO 2 insertion catalysis towards C-H bond. In striking contrast, the introduction of electron-withdrawing nitro-substituted quinoline ( S9 ) can effectively shorten this period to ~ 350 min. The fastest gel oscillation can be achieved using quinazoline-type substrates ( S10 ‒ S12 , column 10–12 in Fig. 5i). For the case of quinazoline ( S10 ), it appeared a dramatic acceleration in the spontaneous sol-gel-sol transition (~ 152 min, bottom panel in Fig. 5d) since it possesses much higher C-H bond acidity. On the whole, fine regulation of the internal and external variables of the FLP system in a preprogrammed manner can on-demand orchestrate the period of non-equilibrium gels, as well as their oscillating mechanical performance (Fig. 5e,f,g,i). As compared to dissipative systems powered by other chemical fuels 13–15,18−23 , this gas-driven one features a much longer operating life (> 3000 min over 15 cycles) and stable rhythmicity, with relatively low periodic fluctuation and amplitude decay. This is mostly derived from the low waste generation and accumulation. First, excess gas fuel can escape spontaneously away the co-assembled system in gaseous form. Second, the catalytic product (carboxylic acid) is of higher polarity than the assemblies, which makes it incompatible with the gel networks and easily excluded. Gas-encoded 4D information encryption. 4D information encryption technique is established on the conventional 3D encryption and furnishes an extra time dimension, which permits the ciphertext to change dynamically over time 44 . Only if decoding in a specified time window can obtain correct information, otherwise will show the false one in other time periods. This time-dependent encryption and decryption paves the way towards the requirements of higher level of information security. Up to now, most of 4D encryption techniques are based on the dynamic optical properties of fluorescent/phosphorescent molecules 45 – 48 . However, these materials still work in equilibrium state; exploiting dissipative materials for time-gated cryptograph remains rare 14 . As a proof of concept, we explored our gas-fueled non-equilibrium gels potential for creating 4D information materials encouraged by their tunable phase transition times according to the added substrate difference. Three kinds of substrates ( S10 , S1 and S8 ) were chosen owing to their distinct gelation windows (at 50 min, 80 min and 180 min, Fig. 6a). The FLP precursor sols with different substrates were edited as an encoded array. To distinguish easily, we added trace pH indicator (bromothymol blue, pH color range: 6.0 ~ 7.6) into each unit of the array to point the sol-gel transition (pH is ~ 7.8 in sol state, blue color; pH drops to ~ 6.3 in gel state due to the generation of carboxylic acids, yellow color). When decoder purged the array with CO 2 or directly blow the array with exhaled CO 2 , the sol unit doped with S10 would first turn into gel at the time of ~ 50 min, concomitant with the color change, to exhibit a false code pattern. The correct information can only be read out at ~ 80 min until the array units with S1 became gels. While the extension of time could lead to the phase transition occurred on the sols doped with S8 , as a result, concealing the previous correct codes (Fig. 6b). In the first example, we used a 96-well plate to encrypt the code array (Fig. 6c). After blowing CO 2 , the sol units loaded with S10 substrate changed color at an early stage and gave the unreal letter code pattern (FDU). If the decoding time was preset to 80 min, the correct pattern (P00) can be only decrypted until some units containing S1 were also gelated. Afterwards, the codes further transformed into an invalid mode because the sol units with S8 also underwent the phase transition and sheltered the correct codes. Such a time-dependent transient gelation process can be effectively used to time-gated information materials, and that the encrypted information can be expediently encoded by CO 2 gas. Moreover, the information complexity can be extended by introducing different substrates, and the improvement of information security can be achieved by fine-regulating the phase transition windows of the non-equilibrium gel. It is known that solid-phase information encryption is more portable and convenient than that of liquid phase systems. To achieve this, in the second example, we further attempted whether our non-equilibrium system could be applicable to QR code print test. Using the FLP precursor sols containing three different substrates as three types of inks, we printed them out on a grid paper (21 × 21 cells) according to the pre-coded pattern information (Fig. 6d, panel 1). Since the ink added trace amount of ferrous ion (Fe 2+ ) indicator, the paper printed became pale yellow color due to the weak metal-coordination with benzoheterocycle substrates (Supplementary Fig. 35) 49 . Interestingly, when the paper was treated by moist CO 2 , the color change occurred in sequence. The pattern regions printed by S10 ink altered color earliest because of its shortest sol-gel transition period. The formed quinazoline-2-carboxylic acid product is a multidentate ligand that can chelate with Fe 2+ to display the signature blue color. However, the code pattern obtained at this moment is incorrect (Fig. 6d, panel 2). Only waiting for a longer time, after the pattern regions encrypted by S1 ink turned color, a correct QR code could emerge by the smart phone scanning (Fig. 6d, panel 3). The true codes actually represent a position coordination (31.2419, 121.4952) that hints the Oriental Pearl Tower. Moreover, if continuing to prolong time, the code pattern would further change, which automatically covers the previous QR one and avoids the leakage of true information (Fig. 6d, panel 4). Discussion In conclusion, we have demonstrated a new paradigm of FLP-based dissipative co-assembly system powered by gas fuel, which shows CO 2 -induced transient sol-gel-sol phase transition behavior. The operation of non-equilibrium state is built on a gas-involved supramolecular loop, where CO 2 dynamically bridging FLP precursors serves as the forward pathway to activate the co-assembly with substrate, and the activated CO 2 species in assembled state in turn catalyzes the substrate as feedback pathway for fuel dissipation. The period, gel mechanical properties, and function are temporally regulated through varying the external parameters and tailoring the internal FLP chemistries. Particularly, the form of gas fuel results in a traceless waste in the system as excess gas can automatically escape out of the assemblies. This feature endows the transient gel networks with stable rhythmicity, long lifetime, and programmable function. The selection of substrate allows us to tune the transient period over a wide range. Relying on this periodic distinction, a time-dependent 4D information encryption application is achieved by fabricating encoded FLP array loaded with different substrates. Different array units undergo transient gelation at different time windows, which makes true code information be identified only at a specified time. Given that the decryption only requires CO 2 gas, even breathing CO 2 done, and the information can be carried in the solid phase, this will pave a way for creation of gas-encoded information materials and technology with portability, mobility and high-security. More importantly, FLPs have universal binding ability to a spectrum of gas substances (e.g. H 2 , CO, NO, N 2 O, SO 2 and C 2 H 4 ) 33 , we thus believe that the gas-fueled out-of-equilibrium system could serve as an inspiring starting point for development of gas-driven advanced materials. Methods Materials. Frustrated Lewis acids, tri(pentafluorophenyl)borane ( TB ) and triphenylborane ( TB F ), were purchased from Sigma-Aldrich. Frustrated Lewis bases ( C n TP , n = 0, 3, 7 and 11) were synthesized by n-alkyl bromide with various chain lengths and dimesitylphosphorus bromide according to the previous literature with modification 34 . The needed compounds, bromomethane, 1-bromobutane, 1-bromooctane, and 1-bromododecane were purchased from TCI and Adamas-beta. A series of substrates (S1-S12) were used commercially available products without any further purification. All solvents were reagent grade and were treated from Innovative Technologies Solvent Purification system. FLP precursor synthesis. Frustrated Lewis acids, TB and TB F , directly used the commercial products. Frustrated Lewis bases ( C n TP , n = 0, 3, 7 and 11) were prepared by two steps and the synthetic details were described in Supplementary Fig. S1 . Their molecular structures were determined using 1 H NMR, 31 P NMR, 11 B NMR spectroscopies, and electronic spray ionization (ESI) mass spectrometry, as shown in Supplementary Fig. S2-S10. Instruments and Characterization. Nuclear magnetic resonance (NMR) spectroscopy was measured on an AVANCE III HD 400 MHz of Bruker BioSpin International Instrument. Tetramethylsilane (TMS) was utilized as an internal standard, and CDCl 3 or d 8 -toluene were used as the NMR solvents to probe 1 H NMR (400MHz), 11 B NMR (128 MHz), 31 P NMR (162 MHz) spectra of all the frustrated Lewis acid and base. Electrospray ionization mass spectrometry (ESI-MS) was recorded on a Bruker McriOTOF11 ESI-TOF mass spectrometer equipped with an ESI interface and ion trap analyzer. UV-vis spectroscopy and turbidity test was conducted on an Agilent Cary-60 UV-vis spectrometry using a 1.0 mm cuvette. The spectral change of FLP sols fueled by CO 2 was monitored over time and the optical transmittance of FLP sol samples was probed at the wavelength of 600 nm. Atomic force microscope (AFM) was carried out on a Dimension-ICON Scanning probe Microscope (Bruker, Digital Instrument Co. Ltd.) equipped with a MikroMasch silicon cantilever, NSCII (radius < 10 nm, resonance frequency = 300 kHz, spring constant = 40 N/m) with tapping mode at room temperature. The sol state or gel state of FLP-based co-assemblies were drop casted onto the fresh exfoliated mica and allowed to adsorb for 1 min. After excess solution was wicked off with filter paper and the sample was dried for few hours in vacuum before AFM imaging. Transmission electron microscopy (TEM) was recorded on a FEI Tecnai G2-T20 S-TWIN instrument at 120 kV equipped with an AMT 16 megapixel in-line CCD camera. The sol or gel state of FLP-based co-assemblies in the absence or presence of CO 2 (10 µL) were taken out at given time and dropped onto a copper grid for 2 min and then blotted with filter paper to remove excess solution followed by drying overnight in vacuum oven before TEM observation. Small-angle X-ray scattering (SAXS) analysis was obtained on the diamond light source beam line I22 in the Shanghai Synchrotron Radiation Facility (SRF). The working voltage and current for the X-ray tube are 45 kV and 0.88 mA, and the wavelength of incident X-ray beam was 0.126 nm. The scattering vector ( q ) was calibrated using silver behenate with the primary reflection peak at q = 1.067 nm − 1 . X-ray diffraction (XRD) was conducted using an AXS D8 Advance (Bruker, Germany) diffractometer operated at 1,600 W power (40 kV, 40 mA) using Cu-Kα radiation. The FLP co-assembly samples in powder or xerogel (transient gel at ca. 60 min) were prepared by plunging in liquid nitrogen and drying by the process of lyophilization. The dried samples were then mounted on glass slides for diffraction and 2 θ was fixed at 5–50°. CO 2 -fueled gelation. C 11 TP and TB as the complementary FLP precursors were dissolved in toluene in glass vial, followed by addition of varying concentrations of S1 substrate. The final mixture solution was incubated for half an hour with stirring at room temperature. CO 2 gas was applied in the solution through a microflow-pump HRF 1425 − 580 (PraStar, Praxair Co.) connected to a standard gas cylinder (4 L). This equipment can tune the CO 2 pressure and flow rate to quantify the amount of gas aeration. The gas flow rate can be adjusted from 0.002 to 20 mL/s and the pressure can be adjusted from 0.01 to 10 bar. For the gas-FLP binding, the amount of CO 2 addition was set at the given concentrations (1 ~ 4 mM). Gel formation was monitored by inverting the glass vial and the apparent lifetimes of the gel state could be roughly determined. Rheology measurement. The rheological change of FLP-based transient gel networks over time was monitored in parallel plates using HAAKE Par Rotary Rheometer (HAAKE MARS III) with a 40 mm diameter cross-hatched tool. The frequency sweep experiments were performed as a function of angular frequency (0.1 to 100 Hz) at a fixed strain of 0.1% at given temperature, and the storage moduli ( G′ ) and the loss moduli ( G″ ) was plotted against time. Catalytic efficiency analysis. The catalytic ability of transient system was examined by analytical high-performance liquid chromatograph (HPLC) using Waters HPLC system (2535 quaternary pump) with 2489 UV-vis detector, and all compounds involved were separated using a linear gradient eluent toluene : chloroform from 95:5 to 60:40. At a fixed time interval (10 min), aliquots of gel suspension was taken out and injected to HPLC with dilution to in-situ monitor the evolution of the concentration of precursor, substrate and catalytic product. The increase of peak areas of catalytic product, benzo[d]imdiazole-2-carboxylic acid, reflects the catalytic kinetics. Calibration curves for substrate (λ = 220 nm) and product (λ = 281 nm) were performed in triplicate in order to quantify the compounds over time. MD simulation of co-assembly structure. The molecular packing mode of FLP precursor and substrate into fibrillar nanostructure was revealed by molecular dynamics (MD) simulations. The MD simulations employed AMBER force field after the structure optimization using M062x with 6-31g (d,p) basis set implanted in Gaussin09. Fabrication of time-gated 4D code pattern in solution state. FLP stock solutions were prepared by dissolving FLP precursors ( C 11 TP and TB , 1 mM) in toluene and added three types of substrates ( S1 , S8 or S10 , 1 mM) respectively. Trace amount of pH indicator (bromothymol blue, 1 mg) was added in each mixture solution. Upon introduction of the indicator, the stock solutions turned brilliant blue color because of the weak alkalinity of substrates. Afterwards, the three different types of FLP solutions were dropped into the 96-well plate (12 × 8 units) according to a preset pattern and each well unit contained 0.1 mL solution. Purging or blowing enough CO 2 gas (within 60 s) to the plate in a parallel mode and recording their time-dependent phase transition and concomitant color change. At a certain time window, when the sol in different well unit turned into gel state and its color changed from blue to slight yellow, we could read out the obtained pattern as the code information. Different time windows correspond to the different code pattern, and the correct one can be decrypted only at a specified time. QR code time-gated encryption in solid state. Printing tests were performed on a Canon inkjet printer (MG2400) and Canon PG-845 FINE cartridge, using paper (4 × 4 cm) without optical brightener. The original three kinds of inks (Cyan, Yellow and Blue) were replaced by our FLP sol inks. The FLP-based inks were the mixture of FLP precursor ( C 11 TP and TB , 1 mM) and substrate ( S1 , S8 or S10 , 1 mM), with trace amount of ferrous ion indicator, respectively. The code information was pre-encoded by FLP array in paper and printed. When exposing the paper to moist CO 2 gas for minutes, the FLP array began to occur transient gelling transition at a certain time window, which make the indicator show blue color. Consequently, the QR code could be seen and we could scan it by a commercially available smartphone APP. 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Angew Chem Int Ed 61:e202208460 Li SY, Tang YQ, Kang WX, Bisoyi HK, Guo JB, Li Q (2023) Photo-triggered full-color circularly polarized luminescence based on photonic capsules for multilevel information encryption. Nat Commun 14:3005 Nandanwar SK et al (2020) Cobalt(II) benzazole derivative complexes: synthesis, characterization, antibacterial and synergistic activity. Biol Chem Chem Biol 5:3471–3476 Additional Declarations There is NO Competing Interest. Supplementary Files CO2fueledtransientcoassemblyforgasencodeddynamicencryptionSI.pdf Cite Share Download PDF Status: Posted 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. 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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-4677523","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":327663318,"identity":"c88346d4-f5cc-46e4-acd8-3b79f3117ca0","order_by":0,"name":"Qiang 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04:30:09","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-4677523/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-4677523/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":60513567,"identity":"e0e3a76c-0e6c-41b9-b7f7-a282cb8ff191","added_by":"auto","created_at":"2024-07-17 15:00:59","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":815941,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eDesign rationale for a gas-fueled non-equilibrium co-assembly system.\u003c/strong\u003e \u003cstrong\u003ea.\u003c/strong\u003e Schematic illustration of gas-fueled transient co-assembly mechanism that couples gas-precursor dynamic interactions with reverse gas-substrate cooperative catalysis. \u003cstrong\u003eb.\u003c/strong\u003e Transient co-assembly of two complementary FLP precursors (\u003cstrong\u003eC\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003en\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eTP\u003c/strong\u003e and \u003cstrong\u003eTB\u003c/strong\u003e) and substrate (\u003cstrong\u003eS\u003c/strong\u003e) into nanofibrils driven by CO\u003csub\u003e2\u003c/sub\u003e gas and its catalytic feedback pathway for the consumption of CO\u003csub\u003e2\u003c/sub\u003e fuel.\u003c/p\u003e","description":"","filename":"image1.png","url":"https://assets-eu.researchsquare.com/files/rs-4677523/v1/527b33ed5d4d0c3924617993.png"},{"id":60513563,"identity":"f20c6454-a1f0-47c9-92e4-a15c49aea6df","added_by":"auto","created_at":"2024-07-17 15:00:58","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":896623,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eCO\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e-fueled transient gelation.\u003c/strong\u003e \u003cstrong\u003ea-c.\u003c/strong\u003e Vial images showing the sol-gel-sol transition of FLP precursors (\u003cstrong\u003eC\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e11\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eTP\u003c/strong\u003e and \u003cstrong\u003eTB\u003c/strong\u003e) with substrate (\u003cstrong\u003eS1\u003c/strong\u003e) in the presence of CO\u003csub\u003e2\u003c/sub\u003e under various time: \u003cstrong\u003ea.\u003c/strong\u003e 6 min, \u003cstrong\u003eb.\u003c/strong\u003e 50 min, and \u003cstrong\u003ec.\u003c/strong\u003e 160 min. \u003cstrong\u003ed-f.\u003c/strong\u003e TEM images tracking the co-assembly process of the ternary mixture (\u003cstrong\u003eC\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e11\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eTP-TB-S1)\u003c/strong\u003e after CO\u003csub\u003e2\u003c/sub\u003e treatment. \u003cstrong\u003eg.\u003c/strong\u003e Time-resolved rhelogical change of the transient gelation. The concentration of precursor mixiture was at 4.0 mM and \u003cstrong\u003eS1\u003c/strong\u003e of 1.0 mM. \u003cstrong\u003eh.\u003c/strong\u003e Lifetime of transient gels under different fuel and substrate conditions. *Fuel is replaced by N\u003csub\u003e2\u003c/sub\u003e with the same concentration. **Fuel is DEAD molecule with higher affinity to FLP units.\u003c/p\u003e","description":"","filename":"image2.png","url":"https://assets-eu.researchsquare.com/files/rs-4677523/v1/c590e5c9c9244d981ed81a02.png"},{"id":60513566,"identity":"53f8c1b8-1187-4a25-b263-018f5dc02ce6","added_by":"auto","created_at":"2024-07-17 15:00:59","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":665255,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eMonitoring of CO\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e-fueled non-equilibrium co-assembly process and proposed co-assembly molecular mechanism.\u003c/strong\u003e \u003cstrong\u003ea.\u003c/strong\u003e UV-Vis absorption change of FLP precursors (\u003cstrong\u003eC\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e11\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eTP\u003c/strong\u003e and \u003cstrong\u003eTB\u003c/strong\u003e) with substrate (\u003cstrong\u003eS1\u003c/strong\u003e) over time after treatment with CO\u003csub\u003e2\u003c/sub\u003e. Blue curve at 0 min, green curve at 60 min, and orange dash curve at 200 min; black solid lines representing 0‒60 min and black dash lines representing 60‒200 min. \u003cstrong\u003eb.\u003c/strong\u003e The molar ratios different binding structures formed in the system: blue line, CO\u003csub\u003e2\u003c/sub\u003e-linkages; green line, π-association; orange line, catalytic product. \u003cstrong\u003ec-d.\u003c/strong\u003e The spectral variation (0‒200 min) of \u003cstrong\u003ec.\u003c/strong\u003e \u003csup\u003e31\u003c/sup\u003eP NMR and \u003cstrong\u003ed.\u003c/strong\u003e partial \u003csup\u003e1\u003c/sup\u003eH NMR of FLP precursors and \u003cstrong\u003eS1\u003c/strong\u003e upon addition of CO\u003csub\u003e2\u003c/sub\u003e. \u003cstrong\u003ee.\u003c/strong\u003e AFM image and height analysis (inset) of the co-assembled nanofibril morphology. \u003cstrong\u003ef.\u003c/strong\u003e The proposed co-assembly model of FLP precursors and substrates driven by CO\u003csub\u003e2\u003c/sub\u003e-bridged linkages and intermolecular polar-π and π-π interactions. \u003cstrong\u003eg.\u003c/strong\u003e Simulated molecular arrangement of the individual nanofibril and its internal weak interacting parameters. \u003cstrong\u003eh.\u003c/strong\u003e Solution-phase SAXS and \u003cstrong\u003ei.\u003c/strong\u003e powder XRD analysis of the co-assembled nanofibrils.\u003c/p\u003e","description":"","filename":"image3.png","url":"https://assets-eu.researchsquare.com/files/rs-4677523/v1/6c0b8da15e4e87b5f9531b0c.png"},{"id":60513564,"identity":"69e87041-4dc9-4342-a7f3-3917236a266c","added_by":"auto","created_at":"2024-07-17 15:00:58","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":265727,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eTemporal regulation of gelation behavior by presetting the strucutural parameter of FLP precursors and substrates.\u003c/strong\u003e \u003cstrong\u003ea.\u003c/strong\u003e The co-assembly morphology using fluorine-free \u003cstrong\u003eTB\u003c/strong\u003e\u003csup\u003e\u003cstrong\u003eF\u003c/strong\u003e\u003c/sup\u003e as the intial Lewis acidic precursor. \u003cstrong\u003eb.\u003c/strong\u003e The co-assembly morphology using \u003cstrong\u003eSC\u003c/strong\u003e compound with low conjugated nature as the substrate. Histogram comparisons of \u003cstrong\u003ec.\u003c/strong\u003e the gel moduli (\u003cem\u003eG\u003c/em\u003e′ and \u003cem\u003eG\u003c/em\u003e″) and \u003cstrong\u003ed. \u003c/strong\u003ebackward catalytic activity with \u003cstrong\u003eTB\u003c/strong\u003e\u003csup\u003e\u003cstrong\u003eF\u003c/strong\u003e\u003c/sup\u003e precursor or \u003cstrong\u003eSC\u003c/strong\u003e substrate. \u003cstrong\u003ee.\u003c/strong\u003e Tuning the lengths of alkyl tails in \u003cstrong\u003eC\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003en\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eTP\u003c/strong\u003e precursor and \u003cstrong\u003ef.\u003c/strong\u003e Histogram comparison of the gel moduli (left y-axis) and backward catalytic activities (right y-axis) for different \u003cstrong\u003eC\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003en\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eTP\u003c/strong\u003e precursor (n = 0, 3, 7 and 11).\u003c/p\u003e","description":"","filename":"image4.png","url":"https://assets-eu.researchsquare.com/files/rs-4677523/v1/dcce89d5e732aabeddb5d1d5.png"},{"id":60514000,"identity":"47c88198-d3b2-4f2d-be6e-fe46b2cfc98c","added_by":"auto","created_at":"2024-07-17 15:08:59","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":895734,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eProgrammable periodic behavior of CO\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e-fueled transient gel system by interior or exterior factors.\u003c/strong\u003e \u003cstrong\u003ea-d.\u003c/strong\u003e Rheological monitoring of the rhythmic variation on gel modulus over time under different conditions. \u003cstrong\u003ea.\u003c/strong\u003e Varying the chain length of \u003cstrong\u003eC\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003en\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eTP\u003c/strong\u003e species: n = 11 (upper), n = 7 (middle), n = 3 (bottom); \u003cstrong\u003eb.\u003c/strong\u003e Varying CO\u003csub\u003e2\u003c/sub\u003e fuel concentration: each batch addition of 2 mM (upper), 4 mM (middle), 0.5 mM (bottom); \u003cstrong\u003ec.\u003c/strong\u003e Various external temperature: 10 \u003csup\u003eo\u003c/sup\u003eC (upper), 30 \u003csup\u003eo\u003c/sup\u003eC (middle), 50 \u003csup\u003eo\u003c/sup\u003eC (bottom); \u003cstrong\u003ed.\u003c/strong\u003e Introducing various structures of substrates: benzothiazole (\u003cstrong\u003eS3\u003c/strong\u003e, upper), 7-methoxyquinoline (\u003cstrong\u003eS8\u003c/strong\u003e, middle), quinazoline (\u003cstrong\u003eS10\u003c/strong\u003e, bottom). All the experiments fixed the concentration of FLP precursor at 1 mM and the arrows indicate the resupply of gas fuel in batchwise. \u003cstrong\u003ee-f.\u003c/strong\u003e Impacts of different interior and exterior factors on the regulation of periodicity, amplitude and lifecycle of transient gel. \u003cstrong\u003ee.\u003c/strong\u003e \u003cstrong\u003eC\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003en\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eTP\u003c/strong\u003e chain length, \u003cstrong\u003ef.\u003c/strong\u003e CO\u003csub\u003e2\u003c/sub\u003e fuel level, \u003cstrong\u003eg.\u003c/strong\u003e temperature. The color region represents the optimal window that is available to drive the periodic behavior of transient gel, while the white region represents the window that is unavailable to induce the periodic ones. The arrows indicate the critical points of different factors. \u003cstrong\u003eh.\u003c/strong\u003e The selection of diverse categories of substrates: \u003cstrong\u003eS1\u003c/strong\u003e-\u003cstrong\u003eS5\u003c/strong\u003e (benzoxazole-type), \u003cstrong\u003eS6\u003c/strong\u003e-\u003cstrong\u003eS9\u003c/strong\u003e (quinoline-type), and \u003cstrong\u003eS10\u003c/strong\u003e-\u003cstrong\u003eS12\u003c/strong\u003e (quinazoline-type). \u003cstrong\u003ei.\u003c/strong\u003e Histograms of the impacts of substrates on transient periodicity and mechanical amplitude.\u003c/p\u003e","description":"","filename":"image5.png","url":"https://assets-eu.researchsquare.com/files/rs-4677523/v1/00f3cc5b9c2f3b1315b8ffc6.png"},{"id":60513569,"identity":"15923c21-2310-46ff-8aed-4dffab70fa60","added_by":"auto","created_at":"2024-07-17 15:00:59","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":894453,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eGas-encoded 4D information encryption technique.\u003c/strong\u003e \u003cstrong\u003ea.\u003c/strong\u003e Distinct phase transition time windows of transient gels loaded with different substrates. \u003cstrong\u003eb.\u003c/strong\u003e Schematic representations of the FLP array pattern with pre-designed encoded substrates and their time-gated decryption after CO\u003csub\u003e2\u003c/sub\u003e treatment to collect correct code information at a specified time. \u003cstrong\u003ec.\u003c/strong\u003e Practical outputs (upper) and readout code patterns (bottom) of 4D information in gas-encoded FLP array. Using 96-well plate (12 × 8) to perform the test, each unit contains FLP precursors (trace indicator) and preset substrate. If the phase transition happens upon blowing CO\u003csub\u003e2\u003c/sub\u003e the sol changes color from blue to yellow, so the code pattern can be read out. \u003cstrong\u003ed.\u003c/strong\u003e Using FLP sols with different substrates as inks to print on paper to encrypt QR code pattern.\u003c/p\u003e","description":"","filename":"image6.png","url":"https://assets-eu.researchsquare.com/files/rs-4677523/v1/6e3c77eab5fb257907c75b7a.png"},{"id":63565570,"identity":"16a4a93c-2d26-45ee-a195-1181a42e4a50","added_by":"auto","created_at":"2024-08-29 15:49:35","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":5627437,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4677523/v1/bd53f5fd-c066-43af-82d7-d349605f874b.pdf"},{"id":60513568,"identity":"6385b885-a561-4a08-8830-15fdc2c5dd51","added_by":"auto","created_at":"2024-07-17 15:00:59","extension":"pdf","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":4866022,"visible":true,"origin":"","legend":"","description":"","filename":"CO2fueledtransientcoassemblyforgasencodeddynamicencryptionSI.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4677523/v1/368b10fa933b756d9ba8f005.pdf"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"\u003cp\u003eGas-Fueled Non-Equilibrium Co-Assembly via C1 Catalytic Feedback for Gas-Encoded 4D Information Encryption\u003c/p\u003e","fulltext":[{"header":"Introduction","content":"\u003cp\u003eLife works in order at a non-equilibrium state at the expense of energy, which is thermodynamic foundation for the maintenance of biological processes\u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e,\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e. As exemplified by actin filaments and microtubules, they can exploit and convert chemical energy stored in ATP or GTP fuel to activate transient assembly, forming dynamic nanostructures\u003csup\u003e\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e,\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e\u003c/sup\u003e. In general, these living systems require a continuous consumption of fuels to sustain their high-energy biotic functions; once the fuel supply ceases the disassembly commences\u003csup\u003e\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e\u003c/sup\u003e. Such biologically dissipative phenomena have aroused mounting interest of chemists toward the development of artificial dissipative assemblies and materials\u003csup\u003e\u003cspan additionalcitationids=\"CR7 CR8 CR9\" citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e–\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e\u003c/sup\u003e. Various forms of fuels, including chemicals and light, have been employed as the major energy inputs to drive the dissipative self-assembly\u003csup\u003e\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e,\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u003c/sup\u003e. Chemical fuels, such as alkylating agents\u003csup\u003e\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e\u003c/sup\u003e, carbodiimides\u003csup\u003e\u003cspan additionalcitationids=\"CR15 CR16\" citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e–\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u003c/sup\u003e, redox\u003csup\u003e\u003cspan additionalcitationids=\"CR19 CR20\" citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e–\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e\u003c/sup\u003e, and ATP\u003csup\u003e\u003cspan additionalcitationids=\"CR23 CR24\" citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e–\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e\u003c/sup\u003e, have high efficiency in generating activated species, while their inadequacies in spatial control and chemical wastes impede their long-standing applications. Optically fueled systems are more spatiotemporally programmable and waste-free; however, they suffer from limited metastable speciation\u003csup\u003e\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u003c/sup\u003e. In view of these, the pursuit of new forms of energy (e.g. electric field and mechanical forces)\u003csup\u003e\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e,\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e\u003c/sup\u003e to orchestrate chemical reaction networks for creation of lifelike active materials have emerged as a challenge in systems chemistry.\u003c/p\u003e\u003cp\u003eGas substances, especially carbon dioxide (CO\u003csub\u003e2\u003c/sub\u003e) gas, have been recognized as fundamental and primitive sources of energy on earth\u003csup\u003e\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e\u003c/sup\u003e. CO\u003csub\u003e2\u003c/sub\u003e is a necessary nutrient (fuel) for photosynthesis of plants and cyanobacteria, as well as a basic C1 feedstock for complex organics conversion under primordial chemistry\u003csup\u003e\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e\u003c/sup\u003e. As an ideal fuel candidate, not only CO\u003csub\u003e2\u003c/sub\u003e manifests benign, green, and clean merits, because excessive gas can escape from the system without residues, but also it is easy to operate in a spatiotemporal manner\u003csup\u003e\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e\u003c/sup\u003e. Currently, CO\u003csub\u003e2\u003c/sub\u003e-sensitive materials have been applied in broad fields of smart latexes, cell mimics, switchable surfaces, and gas therapy\u003csup\u003e\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e,\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e\u003c/sup\u003e. Yet, these materials all work in equilibrium state wherein CO\u003csub\u003e2\u003c/sub\u003e is only regarded as a trigger. Harnessing CO\u003csub\u003e2\u003c/sub\u003e as a fuel to direct non-equilibrium assembly has been unexplored. One major hurdle is difficult to establish a gas-involved reaction loop, where gas is required to play two opposite roles, both activating molecular precursors to drive an energetically uphill assembly process, and being consumed to deactivate the assembly and reboot the system. Moreover, such activation and deactivation should feature kinetic asymmetry (\u003cem\u003ek\u003c/em\u003e\u003csub\u003eact\u003c/sub\u003e \u0026gt; \u003cem\u003ek\u003c/em\u003e\u003csub\u003edeact\u003c/sub\u003e) to maintain the cycle\u003csup\u003e\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e\u003c/sup\u003e. As far as we know, gas reactions that can meet all these requirements at once are rare.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eTo address these unmet challenges, our idea is to engineer a tri-component supramolecular reaction loop consisting of gas, precursor, and substrate, which should satisfy three prerequisites: (i) The precursor without gas lies dormant incapable of assembly. (ii) What needs to be stressed is that gas as a fuel could dynamically bind with the precursor, rather than a commonly covalent reaction. This would make the precursor structurally into an active gas-bound form, and further induce its co-assembly with substrate via synergy of noncovalent forces. (iii) In the assembled state, the activity of these discrete gas-bound species gets amplified, which would catalyze the proximal substrate to react with gas. This could serve as a feedback pathway for the depletion of gas fuel and breakup of assemblies (Fig.\u0026nbsp;1a). If the forward gas association is faster than the backward gas catalysis in kinetics, a non-equilibrium self-assembled system is accessible.\u003c/p\u003e\u003cp\u003eAs a proof of principle, in this study, we report a CO\u003csub\u003e2\u003c/sub\u003e-fueled non-equilibrium co-assembly system formed from frustrated Lewis pair (FLP) precursors and a benzoheterocyclic substrate. FLP refers to a pair of sterically encumbered Lewis acid and base that can prevent the formation of conventional Lewis adduct but close to each other to offer confined gap for binding small molecules, especially a range of gas molecules\u003csup\u003e\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e\u003c/sup\u003e. Previously, we have shown that CO\u003csub\u003e2\u003c/sub\u003e gas can enter this void, dynamically bridging two complementary FLPs to form adaptive materials\u003csup\u003e\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e\u003c/sup\u003e, in which such bound CO\u003csub\u003e2\u003c/sub\u003e species is of latent catalytic capacity because of the weakened C═O double bond\u003csup\u003e\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e\u003c/sup\u003e. With these in mind, the system reported here used a commercial tri(pentafluoro-phenyl)borane (\u003cb\u003eTB\u003c/b\u003e) and a simple alkylated trimesitylphosphine (\u003cb\u003eC\u003c/b\u003e\u003csub\u003e\u003cb\u003en\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eTP\u003c/b\u003e, n = 0, 3, 7 and 11) as the bulky Lewis acidic and basic precursors, and different benzoheterocycles as the substrates (\u003cb\u003eS1‒S12\u003c/b\u003e). CO\u003csub\u003e2\u003c/sub\u003e fuel accesses the two FLPs to bind together via a dynamic gas bridge, and drives the dormant precursors to temporally co-assemble with the substrates into a fibrillar gel through consequent supramolecular synergy of polar‑π and π‑π interactions among them. By harvesting the gas binding energy, the assembly entry into a high-energy state unlocks the catalytic activity of CO\u003csub\u003e2\u003c/sub\u003e. At the meantime, the substrates and activated CO\u003csub\u003e2\u003c/sub\u003e-FLP complexes closely packed in the assemblies can induce a CO\u003csub\u003e2\u003c/sub\u003e insertion towards the substrate, conversely promoting the gel breakdown for the initial state recovery (Fig.\u0026nbsp;1b). Moreover, tailoring either FLP chemistry or substrate reactivity, as well as varying the environmental cues, is crucial to tuning the catalytic kinetics, which enables temporal control of the period and lifespan of this sol-gel-sol transition. Based on this feature, we encrypt time-dependent 4D information in an encoded FLP array of different longevities. CO\u003csub\u003e2\u003c/sub\u003e treatment causes each unit in the array to undergo transient gelation and dissociation with different times. Such a time-gated phase transition allows information to be identified on a time scale, and the correct ones can be decrypted at only a specified time and will self-erase after readout. Given that CO\u003csub\u003e2\u003c/sub\u003e could come from our breath, this gas-fueled non-equibrium system would inspire a facile, portable way for secure information materials.\u003c/p\u003e"},{"header":"Results","content":"\u003cp\u003e\u003cb\u003ePrecursor and substrate design.\u003c/b\u003e We adopted \u003cb\u003eTB\u003c/b\u003e as a Lewis acid since not only the strong electron-withdrawing effect of perfluorophenyl group lifts the acidity of boron center for CO\u003csub\u003e2\u003c/sub\u003e capture\u003csup\u003e\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e,\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e\u003c/sup\u003e, but also it has a preferred stacking selectivity with electron-rich arene via polar-π interaction, which is conducive to its co-aggregation with the conjugated substrate\u003csup\u003e\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e\u003c/sup\u003e. As Lewis bases, \u003cb\u003eC\u003c/b\u003e\u003csub\u003e\u003cb\u003en\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eTP\u003c/b\u003es attached one alkyl tail of different lengths possess variable solvophobicity. This might become a key parameter to tune gelation kinetics and further impact the assembly cycle. On the other hand, the molecular series bearing benzoheterocyclic core (\u003cb\u003eS1-S12\u003c/b\u003e) were chosen as the substrates, in which the unsaturated C(sp\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e)‒H located next to the heteroatom is relatively weak, prone to be catalytially inserted by CO\u003csub\u003e2\u003c/sub\u003e (R-H to R-COOH). All the FLP precursors and substrates were confirmed by NMR and mass spectra in structure (Supplementary Figs.\u0026nbsp;1–10).\u003c/p\u003e\u003cp\u003e\u003cb\u003eCO\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e-fueled transient gelation.\u003c/b\u003e Our first target was to investigate whether the designed FLP precursors and substrate could be transiently gelated by CO\u003csub\u003e2\u003c/sub\u003e gas. Using \u003cb\u003eC\u003c/b\u003e\u003csub\u003e\u003cb\u003e11\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eTP/TB\u003c/b\u003e and \u003cb\u003eS1\u003c/b\u003e (\u003cem\u003eN\u003c/em\u003e-methyl benzimidazole) as representatives, their mixture can be completely dissolved in toluene. Adding 1 mM of \u003cb\u003eS1\u003c/b\u003e into the two precursors (4 mM), neither solution color nor state underwent an obvious change, suggesting their free-flowing sol form. However, after CO\u003csub\u003e2\u003c/sub\u003e was applied (1 mM, \u003cem\u003ep\u003c/em\u003e = 1.0 bar, flow rate = 2.0 mL/s), the solution became a little viscous within 6 min (Fig.\u0026nbsp;2a) and then changed into a self-supporting gel within ca. 50 min (Fig.\u0026nbsp;2b). Interestingly, this gelation process did not maintain for long, but spontaneously returned to the sol state after a while (160 min, Fig.\u0026nbsp;2c), implying that the gel might stand on a short-lived yet high-energy assembled form. Turbidity test showed that the solution transmittance varied parabolically with time, which exactly corresponds to such sol-gel-sol phase transition (Supplementary Fig.\u0026nbsp;11)\u003csup\u003e\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u003c/sup\u003e. To visualize their morphological change at nanoscale, transmission electron microscopy (TEM) was employed. TEM image revealed that the precursors and substrate emerged aggregation just after the addition of CO\u003csub\u003e2\u003c/sub\u003e (6 min) and formed plenty of short fibrillar structures (Fig.\u0026nbsp;2d). Close inspection by atomic force microscopy (AFM) further exhibited that these nanofibrils have homogenous diameter and their contour lengths ranging from 20‒150 nm (Supplementary Fig.\u0026nbsp;12a). There were some entanglement and bundling existed among the fibrils, which should be the incentive for an uplifted solution viscosity. Each short fibril continued to grow along its 1D axial direction over time and intertwined into long fiber network (Fig.\u0026nbsp;2e and Supplementary Fig.\u0026nbsp;12b). Their radial widths remained constant but their average lengths extended to several microns with a high length-diameter ratio (\u0026gt; 500), tens of times more than that of the beginning, confirming a sort of fiber gel formed. The gel dissociation occurred after 160 min, as attested by the rupture of the fibrils (Fig.\u0026nbsp;2f and Supplementary Fig.\u0026nbsp;12c,13). From these results, we reasoned that CO\u003csub\u003e2\u003c/sub\u003e could activate the dormant FLP precursors and facilitate their transient co-assembly via possible gas binding. Simultanesouly, an underlying feedback pathway should be concealed in such system that is responsible to debind CO\u003csub\u003e2\u003c/sub\u003e for gel collapse and system recovery.\u003c/p\u003e\u003cp\u003eOn the other hand, we adopted rheological method to monitor the gel mechanical properties in real-time\u003csup\u003e\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e,\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003e. As shown in Fig.\u0026nbsp;2g, storage modulus (\u003cem\u003eG\u003c/em\u003e′) of the system was less than its loss modulus (\u003cem\u003eG\u003c/em\u003e″) within the initial 20 min; but subsequently, \u003cem\u003eG\u003c/em\u003e′ gave a rapid growth, higher than that of \u003cem\u003eG\u003c/em\u003e″, to reach a maximum of 58.2 kPa, followed by a gradual drop to its original value. This mechanical change coincides with the actual transition from rheological liquids to solids and back to liquids\u003csup\u003e\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u003c/sup\u003e. Furthermore, there are two cross-points existed in the \u003cem\u003eG\u003c/em\u003e′ and \u003cem\u003eG\u003c/em\u003e″ curves at 18 and 138 min, which means that this gelation is indeed transitory, with the lifetime of ~ 120 min. We further found that the gel lifetime is dependent on the amounts of fuel and substrate. Higher levels of fuel and substrate (1.0→4.0 mM) resulted in longer duration (120→262 min, column 3–5 in Fig.\u0026nbsp;2h) and preferable strength (58.2→122.6 kPa, Supplementary Fig.\u0026nbsp;14c-e), suggesting that more CO\u003csub\u003e2\u003c/sub\u003e cross-linking sites are formed in the molecular network that reinforce their mechanics. As control, blank samples lack of either gas fuel or substrate did not exhibit any gelling phenomenon (column 1–2 in Fig.\u0026nbsp;2h and Supplementary Fig.\u0026nbsp;14a,b). If we replaced CO\u003csub\u003e2\u003c/sub\u003e with other gases, such as more inert nitrogen (N\u003csub\u003e2\u003c/sub\u003e), no gel produced as well (column 6 in Fig.\u0026nbsp;2h and Supplementary Fig.\u0026nbsp;14f). In striking contrast, when using diethyl azodicarboxylate (DEAD), a competing fuel that is of higher binding affinity to FLP\u003csup\u003e\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e\u003c/sup\u003e, instead of CO\u003csub\u003e2\u003c/sub\u003e, the gel could generate immediately and persist permanently (column 7 in Fig.\u0026nbsp;2h and Supplementary Fig.\u0026nbsp;14g). No spontaneous gel dissociation was seen since DEAD unlike CO\u003csub\u003e2\u003c/sub\u003e had no reactivity with the substrate. These findings point that CO\u003csub\u003e2\u003c/sub\u003e fuel is essential to underpin FLP precursors and substrate to form metastable gel networks.\u003c/p\u003e\u003cp\u003e\u003cb\u003eCO\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e-fueled non-equilibrium co-assembly mechanism.\u003c/b\u003e To unveil the transient mechanism driven by CO\u003csub\u003e2\u003c/sub\u003e, the spectrometric change of the co-assembly system was probed. Prior to CO\u003csub\u003e2\u003c/sub\u003e, the mixture solution ([\u003cb\u003eC\u003c/b\u003e\u003csub\u003e\u003cb\u003e11\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eTP\u003c/b\u003e]:[\u003cb\u003eTB\u003c/b\u003e]:[\u003cb\u003eS1\u003c/b\u003e] = 1:1:1) showed a unimodal absorption at 266 nm, ascribed to the TP moiety (Fig.\u0026nbsp;3a, blue curve). Upon addition of CO\u003csub\u003e2\u003c/sub\u003e, however, this band was depressed until entire vanishment within 60 min, indicating CO\u003csub\u003e2\u003c/sub\u003e binding with FLP precursors to form typical gas-bridged bond\u003csup\u003e\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e\u003c/sup\u003e. Concomitantly, a new absorption emerged at 327 nm with elevated intensity (from 0 to 60 min, black solid lines between blue and green curves in Fig.\u0026nbsp;3a). Such a bathochromic shift hints that there are intermolecular charge-transfer interactions in the system\u003csup\u003e\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e\u003c/sup\u003e. Since \u003cb\u003eTB\u003c/b\u003e is known to be a strong electron-deficient compound that can bind to electron-rich benzimidazole species via polar‑π interactions\u003csup\u003e\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e,\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e\u003c/sup\u003e, we thus speculated that this new peak should arise from the complexation between \u003cb\u003eTB\u003c/b\u003e and \u003cb\u003eS1\u003c/b\u003e, and that it may act in concert with CO\u003csub\u003e2\u003c/sub\u003e-bridged linkages to lead the co-assembly. In the next period (from 60 to 200 min),\u003c/p\u003e\u003cp\u003ethe two absorptions at 266 and 327 nm returned to the original state whereas another new peak of 281 nm enhanced (black dash lines between green and orange curves in Fig.\u0026nbsp;3a). This means that both CO\u003csub\u003e2\u003c/sub\u003e linkages and polar‑π interactions that sustain the gel formation are dissociated, but a new species is yielded from the system, which we suspect is the product of \u003cb\u003eS1\u003c/b\u003e reaction with CO\u003csub\u003e2\u003c/sub\u003e. Furthermore, the change of diverse characteristic absorptions in intensity provided insight on the evolvement of different pathways in the system. From Fig.\u0026nbsp;3b, we found that the molar ratios of CO\u003csub\u003e2\u003c/sub\u003e-linkage (reflected by \u003cem\u003eλ\u003c/em\u003e = 266 nm) and π-association (reflected by \u003cem\u003eλ\u003c/em\u003e = 327 nm) follow a trend that first ascend and then fall off (blue and green curves), consistent with the rheological profile, which evidence that this sol-gel-sol transition is resulted from the transient co-assembly and reverse disassembly of FLP precursors and substrate fueled by CO\u003csub\u003e2\u003c/sub\u003e. The apparent rate coefficient of forward gas-binding (\u003cem\u003ek\u003c/em\u003e\u003csub\u003e+\u003c/sub\u003e \u003csup\u003eapp\u003c/sup\u003e) was evaluated to be 2.60 × 10\u003csup\u003e− 4\u003c/sup\u003e s\u003csup\u003e− 1\u003c/sup\u003e, 2.5-fold faster than its backward debinding rate (\u003cem\u003ek\u003c/em\u003e\u003csub\u003e−\u003c/sub\u003e \u003csup\u003eapp\u003c/sup\u003e = 1.04 × 10\u003csup\u003e− 4\u003c/sup\u003e s\u003csup\u003e− 1\u003c/sup\u003e). This kinetic discrepancy is the chemical basis to establish a gas-driven reaction cycle (Supplementary Fig.\u0026nbsp;15).\u003c/p\u003e\u003cp\u003eIn addition, NMR titration experiments confirmed the above results from the perspective of molecular structure. In the absence of CO\u003csub\u003e2\u003c/sub\u003e, \u003csup\u003e\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e\u003c/sup\u003eP NMR spectra gave a single signal at \u003cem\u003eδ\u003c/em\u003e = -24.2 ppm (P\u003csup\u003eα\u003c/sup\u003e), assigned to the triphenylphosphine group of free \u003cb\u003eC\u003c/b\u003e\u003csub\u003e\u003cb\u003e11\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eTP\u003c/b\u003e. Interestingly, after exposure to CO\u003csub\u003e2\u003c/sub\u003e, this peak was vastly suppressed in the first 60 min and then gradually recovered (blue peak in Fig.\u0026nbsp;3c), and concurrently, another P\u003csup\u003eβ\u003c/sup\u003e peak, ascribed to four-coordination phosphine species\u003csup\u003e\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e,\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e,\u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e\u003c/sup\u003e, appeared in the low-field region (\u003cem\u003eδ\u003c/em\u003e = 50.5 ppm) but with a opposite change (green peak in Fig.\u0026nbsp;3c), suggesting a short-lived complexation of CO\u003csub\u003e2\u003c/sub\u003e and phosphine but subsequent decomplexation. Similar phenomenon was observed in \u003csup\u003e\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e\u003c/sup\u003eB NMR spectra (Supplementary Fig.\u0026nbsp;16). These results indicate that CO\u003csub\u003e2\u003c/sub\u003e can bridge between \u003cb\u003eC\u003c/b\u003e\u003csub\u003e\u003cb\u003e11\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eTP\u003c/b\u003e and \u003cb\u003eTB\u003c/b\u003e to form a P‒CO\u003csub\u003e2\u003c/sub\u003e‒B structure (P‒CO\u003csub\u003e2\u003c/sub\u003e‒B, inset in Fig.\u0026nbsp;3c), and this gas-bridge is dynamic that can be automatically disconnected and release the precursors. To figure out what is the hidden path that causes this reverse CO\u003csub\u003e2\u003c/sub\u003e dissociation in the system, we probed the structural conversion of substrate by \u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eH NMR. Without CO\u003csub\u003e2\u003c/sub\u003e, \u003cb\u003eS1\u003c/b\u003e gave three groups of typical benzimidazole proton peaks with splitting (H\u003csub\u003ea\u003c/sub\u003e, \u003cem\u003eδ\u003c/em\u003e = 8.03 ppm; H\u003csub\u003eb\u003c/sub\u003e, \u003cem\u003eδ\u003c/em\u003e = 7.67 ppm; H\u003csub\u003ec\u003c/sub\u003e, \u003cem\u003eδ\u003c/em\u003e = 7.42 ppm, blue peaks in Fig.\u0026nbsp;3d). However, after purged with CO\u003csub\u003e2\u003c/sub\u003e, H\u003csub\u003ea\u003c/sub\u003e continued to decline until disappearance, while H\u003csub\u003eb\u003c/sub\u003e and H\u003csub\u003ec\u003c/sub\u003e produced pronounced downfield shifts (H\u003csub\u003eb’\u003c/sub\u003e, \u003cem\u003eδ\u003c/em\u003e = 7.76 ppm; H\u003csub\u003ec’\u003c/sub\u003e, \u003cem\u003eδ\u003c/em\u003e = 7.55 ppm, green peaks in Fig.\u0026nbsp;3d). This result corresponds to the NMR data of benzo[d]imdiazole-2-carboxylic acid (Supplementary Fig.\u0026nbsp;17), indicating that CO\u003csub\u003e2\u003c/sub\u003e is indeed catalytically inserted into the unsaturated C(sp\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e)‒H site of \u003cb\u003eS1\u003c/b\u003e, leading to a carboxylated product (inset in Fig.\u0026nbsp;3d). Spectroscopic change also verified this continuous conversion (orange line in Fig.\u0026nbsp;3b). Exactly this catalytic process achieves the negative feedback, helping to use up CO\u003csub\u003e2\u003c/sub\u003e fuel and restart the system.\u003c/p\u003e\u003cp\u003eAccording to these experimental results, the CO\u003csub\u003e2\u003c/sub\u003e-fueled transient gelation mechanism could be deduced. In the absence of CO\u003csub\u003e2\u003c/sub\u003e, FLP precursor and substrate exist free forms in the solution. When adding CO\u003csub\u003e2\u003c/sub\u003e, it associates with FLP pairs to constitute CO\u003csub\u003e2\u003c/sub\u003e-bridged amphiphiles (\u003cb\u003eC\u003c/b\u003e\u003csub\u003e\u003cb\u003e11\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eTP\u003c/b\u003e‒CO\u003csub\u003e2\u003c/sub\u003e‒\u003cb\u003eTB\u003c/b\u003e). This further induces a co-assembly with \u003cb\u003eS1\u003c/b\u003e substrate along 1D axis to form a fibril nanostructure, in which \u003cb\u003eS1\u003c/b\u003e is probably sandwiched between two neighboring FLP complexes through the synergy of polar‑π interactions with \u003cb\u003eTB\u003c/b\u003e and π-π interactions with \u003cb\u003eC\u003c/b\u003e\u003csub\u003e\u003cb\u003e11\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eTP\u003c/b\u003e, and these π-stacked moieties together become the inner core of nanofibrils and the flexible alkyl chains as the outer layer (Fig.\u0026nbsp;3f). The proposed co-assembly model was validated by AFM analysis. Figure\u0026nbsp;3e disclosed that the gel is made up of fiber-like nanoobjects and the diameter of individual nanofibril is determined to be 4.9 nm (inset), corresponding to the total length of head-to-head arrangement of two FLP amphiphiles (49.6 Å). Molecular simulation further confirmed the co-aggregated molecular packing fashion and showed the parameters of cooperative interactions (Fig.\u0026nbsp;3g and Supplementary Fig.\u0026nbsp;18). The optimized length of each \u003cb\u003eC\u003c/b\u003e\u003csub\u003e\u003cb\u003e11\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eTP\u003c/b\u003e‒CO\u003csub\u003e2\u003c/sub\u003e‒\u003cb\u003eTB\u003c/b\u003e complex is about 22.9 Å bound by CO\u003csub\u003e2\u003c/sub\u003e bridge (P‒CO\u003csub\u003e2\u003c/sub\u003e‒B spacing of 4.39 Å), while \u003cb\u003eS1\u003c/b\u003e species is located between the two complexes but is closer to \u003cb\u003eTB\u003c/b\u003e (3.28 Å) than to the \u003cb\u003eTP\u003c/b\u003e group (3.60 Å), meaning that polar‑π interactions are the main contribution to maintain the intermolecular co-assembly. It is worth mentioning that the distance of \u003cb\u003eS1\u003c/b\u003e and the adjacent CO\u003csub\u003e2\u003c/sub\u003e-bridged bond within this arrangement is only ~ 3.4 Å (green region in Fig.\u0026nbsp;3g), and such a short spacing may elicit a chemical proximal effect, which would become the structural basis for the catalysis of substrate in supramolecular level. On the other hand, in-solution small angle X-ray scattering (SAXS) and powder X-ray diffraction (PXRD) experimentally supported the above simulation. From SAXS profile, a diagnostic \u003cem\u003eq\u003c/em\u003e\u003csup\u003e− 1\u003c/sup\u003e decay at the Guinier region confirmed the presence of a solid cylinder nanostructure formed\u003csup\u003e\u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e\u003c/sup\u003e, and two scattering peaks at 0.128 Å\u003csup\u003e−1\u003c/sup\u003e and 0.270 Å\u003csup\u003e−1\u003c/sup\u003e (Fig.\u0026nbsp;3h), corresponding to the \u003cem\u003ed\u003c/em\u003e-spacing of 49.0 Å and 23.2 Å, in line with the sizes of fibril diameter (4.9 nm) and one CO\u003csub\u003e2\u003c/sub\u003e-bound FLP amphiphile (2.29 nm), respectively. On a smaller scale, XRD analysis presented a series of 2\u003cem\u003eθ\u003c/em\u003e peaks, among which three reflected the typical intermolecular interacting distances (3.26 Å, 3.58 Å, and 4.32 Å), in good accordance with the simulated spacings of polar‑π, π-π, and CO\u003csub\u003e2\u003c/sub\u003e-bridged bonds (Fig.\u0026nbsp;3i). These results together demonstrate the alternating-stack fashion of FLP precursors and substrate in a single nanofibril.\u003c/p\u003e\u003cp\u003e\u003cb\u003ePeriodic behavior regulation of CO\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e-fueled transient gel.\u003c/b\u003e Like other dissipative systems, we wondered whether our FLP networks could manifest tunable phase transition behavior under control of internal or external factors. To elucidate this point, we studied the effects of precursor structure, substrate type and polarity on the periodicity and lifetime of transient gelation. First, when replacing \u003cb\u003eTB\u003c/b\u003e precursor with fluorine-free triphenylborane (\u003cb\u003eTB\u003c/b\u003e\u003csup\u003e\u003cb\u003eF\u003c/b\u003e\u003c/sup\u003e), no aggregate can form at the same conditions (Fig.\u0026nbsp;4a). Even CO\u003csub\u003e2\u003c/sub\u003e fuel level was elevated by 10 times, it remained in a sol state (\u003cem\u003eG\u003c/em\u003e′ \u0026lt; \u003cem\u003eG\u003c/em\u003e″) without any catalytic activity as compared to \u003cb\u003eTB\u003c/b\u003e reference (columns 1–2 in Fig.\u0026nbsp;4c-d and Supplementary Fig.\u0026nbsp;19). The low gas binding ability is attributed to loss of Lewis acidity in \u003cb\u003eTB\u003c/b\u003e\u003csup\u003e\u003cb\u003eF\u003c/b\u003e\u003c/sup\u003e due to the removal of strong electron-withdrawing fluorine groups\u003csup\u003e\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e\u003c/sup\u003e. Second, we selected \u003cem\u003eN\u003c/em\u003e-methylimidazole (\u003cb\u003eSC\u003c/b\u003e), a similar counterpart but short of π-conjugated property, as the substrate to conduct the assembly. However, only small nanoparticles with a mean size of 20 nm were seized by TEM after CO\u003csub\u003e2\u003c/sub\u003e addition, and no fiber appeared (Fig.\u0026nbsp;4b). Moreover, although the sol viscosity increased, it was still insufficient to impel the formation of gel networks (column 3 in Fig.\u0026nbsp;4c-d and Supplementary Fig.\u0026nbsp;20). These indicated that \u003cb\u003eSC\u003c/b\u003e can somewhat co-aggregate with CO\u003csub\u003e2\u003c/sub\u003e-bound FLPs; however, because of its weak aromaticity and less electronic delocalization, \u003cb\u003eSC\u003c/b\u003e moieties are hard to stack with \u003cb\u003eTB\u003c/b\u003e in long-range ordering, accordingly, no gel produced. Third, we also attempted to alter the polarity in assemblies by varying the tail length in Lewis base (Fig.\u0026nbsp;4e). Notably, the shorter the alkyl chain installed on \u003cb\u003eTP\u003c/b\u003e moiety was, the weaker the strength of formed transient gel showed. In comparison to \u003cb\u003eC\u003c/b\u003e\u003csub\u003e\u003cb\u003e11\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eTP\u003c/b\u003e system (\u003cem\u003eG\u003c/em\u003e′ = 58.2 kPa), the gel modulus in the presence of \u003cb\u003eC\u003c/b\u003e\u003csub\u003e\u003cb\u003e7\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eTP\u003c/b\u003e declined a half (22.8 kPa), while that in the case of \u003cb\u003eC\u003c/b\u003e\u003csub\u003e\u003cb\u003e3\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eTP\u003c/b\u003e less than one-tenth of the original (4.7 kPa, green columns 1–3 in Fig.\u0026nbsp;4f). As well, the backward catalytic reaction encountered lessened activity with the decrease of Lewis base in solvophobicity (orange columns 1–3 in Fig.\u0026nbsp;4f and Supplementary Fig.\u0026nbsp;21a-c). If the alkyl tail was absent (\u003cb\u003eC\u003c/b\u003e\u003csub\u003e\u003cb\u003e0\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eTP\u003c/b\u003e), it cannot support the gelation due to devoid of solvophobic effect to assist intermolecular aggregation (column 4 in Fig.\u0026nbsp;4f and Supplementary Fig.\u0026nbsp;21d). The aforesaid comparative tests illustrate that the chemical structure and property of FLP precursors and substrates have significant influence on their non-equilibrium co-assembly behavior.\u003c/p\u003e\u003cp\u003eConsidering that varying \u003cb\u003eTP\u003c/b\u003e structure can shift the strength of formed transient gel and their catalytic capacity, we speculated that this factor could manipulate the non-equilibrium periodic behavior of such co-assembled system. To survey this tunability, upon batch addition of CO\u003csub\u003e2\u003c/sub\u003e fuel, we monitored the variation of gel modulus by rheology and the accumulative content of catalytic product by high performance liquid chromatography (HPLC) over time. Taking \u003cb\u003eC\u003c/b\u003e\u003csub\u003e\u003cb\u003e11\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eTP\u003c/b\u003e as a standard reference, its storage modulus first raised up to ~ 60 kPa within 60 min, and then spontaneously dropped down in another 140 min, corresponding to one round of sol-gel-sol transition. After resupplying of CO\u003csub\u003e2\u003c/sub\u003e, a new dissipative cycle can be continued. If we defined the difference between the maximal and minimal moduli as the amplitude, while the duration time from the beginning of modulus change until recovery as one complete period, the system still maintained the stable periodicity without obvious decay after operating in 3000 min (left y-axis, upper panel in Fig.\u0026nbsp;5a and Supplementary Fig.\u0026nbsp;22). Accompanied with the oscillating feature of gel mechanics, their feedback catalytic process presented a stepped curve, that is, the catalysis shut down and the conversion of products paused during the gel formation, whereas as soon as the gel started to collapse, the catalytic reaction switched on for a growing conversion (right y-axis, upper panel in Fig.\u0026nbsp;5a). In a similar way, other \u003cb\u003eTP\u003c/b\u003es were compared. As the alkyl group was shortened, the phase transition periods became slower (\u003cb\u003eC\u003c/b\u003e\u003csub\u003e\u003cb\u003e7\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eTP\u003c/b\u003e, 308 min; \u003cb\u003eC\u003c/b\u003e\u003csub\u003e\u003cb\u003e3\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eTP\u003c/b\u003e, 410 min), with attenuated amplitude (middle and bottom panels in Fig.\u0026nbsp;5a and Supplementary Fig.\u0026nbsp;23–24). Furthermore, we noticed that when the alkyl chain length is less than a critical value of n = 2, the co-assembly was highly impeded and thus no periodic gelation phenomenon happened (Fig.\u0026nbsp;5e and Supplementary Fig.\u0026nbsp;25). Such a \u003cb\u003eTP\u003c/b\u003e structure-dependent change in periodicity is explicable. The weaker the solvophobic effect of TP species have, the looser the molecules arrange inside the fibers, which means lower intermolecular interactions and subdued proximal effect. These would inhibit the cooperative catalysis and retard the backward reaction, leading to a longer sol-gel-sol transitional cycle.\u003c/p\u003e\u003cp\u003eIn addition to the \u003cb\u003eTP\u003c/b\u003e structure, exterior parameters such as fuel concentration and temperature also had important regulatory effect on their transient process. Using \u003cb\u003eTB\u003c/b\u003e (1 mM) and \u003cb\u003eC\u003c/b\u003e\u003csub\u003e\u003cb\u003e11\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eTP\u003c/b\u003e (1 mM) FLP precursors with excess of \u003cb\u003eS1\u003c/b\u003e substrate and batch addition of 1 mM CO\u003csub\u003e2\u003c/sub\u003e gas as a standard reference (saturated gas-bound state), a higher level of fuel supply (2 and 4 mM each batch) could reduce the total period from 210 min to 185 min and 156 min, respectively (upper and middle panels in Fig.\u0026nbsp;5b and Supplementary Fig.\u0026nbsp;26–27). Notably, the fuel increase speeded up the forward process (60 min→45 min and 23 min) but had negligible influence on their\u003c/p\u003e\u003cp\u003ebackward catalysis. This is because the gas binding kinetics is only related to the initial CO\u003csub\u003e2\u003c/sub\u003e concentration while the catalytic rate relies on the number of CO\u003csub\u003e2\u003c/sub\u003e-bridged sites. In contrast, if CO\u003csub\u003e2\u003c/sub\u003e level was unsaturated (0.5 mM), both period and amplitude were damped (bottom panel in Fig.\u0026nbsp;5b and Supplementary Fig.\u0026nbsp;28). The extension of period (210 min→300 min) is due to a substantial decrease in gas concentration and active sites, while the amplitude reduction (60 kPa→34 kPa) is originated from the incomplete gas bridging that depresses gel modulus. The critical limit of fuel level to maintain this cycle was determined to be ~ 0.3 mM, one-third of its saturated point (Fig.\u0026nbsp;5f and Supplementary Fig.\u0026nbsp;29).\u003c/p\u003e\u003cp\u003eAs well, temperature is a key factor in tuning the time-dependent behavior of gel. It is known that high temperature is favor of the kinetics of CO\u003csub\u003e2\u003c/sub\u003e catalytic insertion, but against the dynamic bridging between gas and FLP species\u003csup\u003e\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e\u003c/sup\u003e. Accordingly, elevating temperature (10 \u003csup\u003eo\u003c/sup\u003eC to 50 \u003csup\u003eo\u003c/sup\u003eC) could expedite the backward catalytic process but decelerate the forward CO\u003csub\u003e2\u003c/sub\u003e binding reaction, meanwhile, resulting in a decay in mechanical amplitude by nearly half (60 kPa→33 kPa) due to the promotion in thermally induced dissociation rate (Fig.\u0026nbsp;5c and Supplementary Fig.\u0026nbsp;30–32). Moreover, we found that this cyclical process has an optimal temperature window (5‒55 \u003csup\u003eo\u003c/sup\u003eC). Below 5 \u003csup\u003eo\u003c/sup\u003eC the formed gel is unable to spontaneously collapse since the feedback path of fuel consumption is blocked in low temperature; on the contrary, the gel cannot form above 55 \u003csup\u003eo\u003c/sup\u003eC because gas dissociation is predominated (Fig.\u0026nbsp;5g and Supplementary Fig.\u0026nbsp;33–34).\u003c/p\u003e\u003cp\u003eWe also interested in the effect of substrates on the periodic regulation. For this purpose, 12 commercially available N-heterocyclic chemicals were chosen for evaluation (Fig.\u0026nbsp;5h). Among them, when using benzoxazole-type compounds (\u003cb\u003eS2\u003c/b\u003e‒\u003cb\u003eS5\u003c/b\u003e) as substrates, the temporal period and mechanical amplitude of formed gels remained nearly unchanged, which mainly resulted from their similar chemical structure and activity to \u003cb\u003eS1\u003c/b\u003e. Typically, in the case of benzothiazole (\u003cb\u003eS3\u003c/b\u003e), its gel lifecycle lasted for 238 min and the extreme strength reached to ~ 52.4 kPa (upper panel in Fig.\u0026nbsp;5d and column 1–5 in Fig.\u0026nbsp;5i). However, if co-assembly was driven by quinoline-type substrates (\u003cb\u003eS6\u003c/b\u003e‒\u003cb\u003eS9\u003c/b\u003e), their lifecycles were generally extended to quite long time (350 ~ 700 min). A possible reason is that quinoline carrying one single nitrogen atom has a much lower acidity of C-H bond than that of benzoxazole ones with two electron-withdrawing heteroatoms, which retarded their catalytic processes (column 6–9 in Fig.\u0026nbsp;5i)\u003csup\u003e\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e\u003c/sup\u003e. For example, the transient gel in the presence of 7-methoxyquinoline (\u003cb\u003eS8\u003c/b\u003e) showed a periodic extremum (~ 700 min), especially in the process of backward catalysis (middle panel in Fig.\u0026nbsp;5d). We inferred that the electron-donating property of methoxy substituent causes this result because of its strong inhibition on the CO\u003csub\u003e2\u003c/sub\u003e insertion catalysis towards C-H bond. In striking contrast, the introduction of electron-withdrawing nitro-substituted quinoline (\u003cb\u003eS9\u003c/b\u003e) can effectively shorten this period to ~ 350 min. The fastest gel oscillation can be achieved using quinazoline-type substrates (\u003cb\u003eS10\u003c/b\u003e‒\u003cb\u003eS12\u003c/b\u003e, column 10–12 in Fig.\u0026nbsp;5i). For the case of quinazoline (\u003cb\u003eS10\u003c/b\u003e), it appeared a dramatic acceleration in the spontaneous sol-gel-sol transition (~ 152 min, bottom panel in Fig.\u0026nbsp;5d) since it possesses much higher C-H bond acidity.\u003c/p\u003e\u003cp\u003eOn the whole, fine regulation of the internal and external variables of the FLP system in a preprogrammed manner can on-demand orchestrate the period of non-equilibrium gels, as well as their oscillating mechanical performance (Fig.\u0026nbsp;5e,f,g,i). As compared to dissipative systems powered by other chemical fuels\u003csup\u003e13–15,18−23\u003c/sup\u003e, this gas-driven one features a much longer operating life (\u0026gt; 3000 min over 15 cycles) and stable rhythmicity, with relatively low periodic fluctuation and amplitude decay. This is mostly derived from the low waste generation and accumulation. First, excess gas fuel can escape spontaneously away the co-assembled system in gaseous form. Second, the catalytic product (carboxylic acid) is of higher polarity than the assemblies, which makes it incompatible with the gel networks and easily excluded.\u003c/p\u003e\u003cp\u003e\u003cb\u003eGas-encoded 4D information encryption.\u003c/b\u003e 4D information encryption technique is established on the conventional 3D encryption and furnishes an extra time dimension, which permits the ciphertext to change dynamically over time\u003csup\u003e\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e\u003c/sup\u003e. Only if decoding in a specified time window can obtain correct information, otherwise will show the false one in other time periods. This time-dependent encryption and decryption paves the way towards the requirements of higher level of information security. Up to now, most of 4D encryption techniques are based on the dynamic optical properties of fluorescent/phosphorescent molecules\u003csup\u003e\u003cspan additionalcitationids=\"CR46 CR47\" citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e–\u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e\u003c/sup\u003e. However, these materials still work in equilibrium state; exploiting dissipative materials for time-gated cryptograph remains rare\u003csup\u003e\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u003c/sup\u003e. As a proof of concept, we explored our gas-fueled non-equilibrium gels potential for creating 4D information materials encouraged by their tunable phase transition times according to the added substrate difference. Three kinds of substrates (\u003cb\u003eS10\u003c/b\u003e, \u003cb\u003eS1\u003c/b\u003e and \u003cb\u003eS8\u003c/b\u003e) were chosen owing to their distinct gelation windows (at 50 min, 80 min and 180 min, Fig.\u0026nbsp;6a). The FLP precursor sols with different substrates were edited as an encoded array. To distinguish easily, we added trace pH indicator (bromothymol blue, pH color range: 6.0 ~ 7.6) into each unit of the array to point the sol-gel transition (pH is ~ 7.8 in sol state, blue color; pH drops to ~ 6.3 in gel state due to the generation of carboxylic acids, yellow color). When decoder purged the array with CO\u003csub\u003e2\u003c/sub\u003e or directly blow the array with exhaled CO\u003csub\u003e2\u003c/sub\u003e, the sol unit doped with \u003cb\u003eS10\u003c/b\u003e would first turn into gel at the time of ~ 50 min, concomitant with the color change, to exhibit a false code pattern. The correct information can only be read out at ~ 80 min until the array units with \u003cb\u003eS1\u003c/b\u003e became gels. While the extension of time could lead to the phase transition occurred on the sols doped with \u003cb\u003eS8\u003c/b\u003e, as a result, concealing the previous correct codes (Fig.\u0026nbsp;6b).\u003c/p\u003e\u003cp\u003eIn the first example, we used a 96-well plate to encrypt the code array (Fig.\u0026nbsp;6c). After blowing CO\u003csub\u003e2\u003c/sub\u003e, the sol units loaded with \u003cb\u003eS10\u003c/b\u003e substrate changed color at an early stage and gave the unreal letter code pattern (FDU). If the decoding time was preset to 80 min, the correct pattern (P00) can be only decrypted until some units containing \u003cb\u003eS1\u003c/b\u003e were also gelated. Afterwards, the codes further transformed into an invalid mode because the sol units with \u003cb\u003eS8\u003c/b\u003e also underwent the phase transition and sheltered the correct codes. Such a time-dependent transient gelation process can be effectively used to time-gated information materials, and that the encrypted information can be expediently encoded by CO\u003csub\u003e2\u003c/sub\u003e gas. Moreover, the information complexity can be extended by introducing different substrates, and the improvement of information security can be achieved by fine-regulating the phase transition windows of the non-equilibrium gel.\u003c/p\u003e\u003cp\u003eIt is known that solid-phase information encryption is more portable and convenient than that of liquid phase systems. To achieve this, in the second example, we further attempted whether our non-equilibrium system could be applicable to QR code print test. Using the FLP precursor sols containing three different substrates as three types of inks, we printed them out on a grid paper (21 × 21 cells) according to the pre-coded pattern information (Fig.\u0026nbsp;6d, panel 1). Since the ink added trace amount of ferrous ion (Fe\u003csup\u003e2+\u003c/sup\u003e) indicator, the paper printed became pale yellow color due to the weak metal-coordination with benzoheterocycle substrates (Supplementary Fig.\u0026nbsp;35)\u003csup\u003e\u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e49\u003c/span\u003e\u003c/sup\u003e. Interestingly, when the paper was treated by moist CO\u003csub\u003e2\u003c/sub\u003e, the color change occurred in sequence. The pattern regions printed by \u003cb\u003eS10\u003c/b\u003e ink altered color earliest because of its shortest sol-gel transition period. The formed quinazoline-2-carboxylic acid product is a multidentate ligand that can chelate with Fe\u003csup\u003e2+\u003c/sup\u003e to display the signature blue color. However, the code pattern obtained at this moment is incorrect (Fig.\u0026nbsp;6d, panel 2). Only waiting for a longer time, after the pattern regions encrypted by \u003cb\u003eS1\u003c/b\u003e ink turned color, a correct QR code could emerge by the smart phone scanning (Fig.\u0026nbsp;6d, panel 3). The true codes actually represent a position coordination (31.2419, 121.4952) that hints the Oriental Pearl Tower. Moreover, if continuing to prolong time, the code pattern would further change, which automatically covers the previous QR one and avoids the leakage of true information (Fig.\u0026nbsp;6d, panel 4).\u003c/p\u003e"},{"header":"Discussion","content":"\u003cp\u003eIn conclusion, we have demonstrated a new paradigm of FLP-based dissipative co-assembly system powered by gas fuel, which shows CO\u003csub\u003e2\u003c/sub\u003e-induced transient sol-gel-sol phase transition behavior. The operation of non-equilibrium state is built on a gas-involved supramolecular loop, where CO\u003csub\u003e2\u003c/sub\u003e dynamically bridging FLP precursors serves as the forward pathway to activate the co-assembly with substrate, and the activated CO\u003csub\u003e2\u003c/sub\u003e species in assembled state in turn catalyzes the substrate as feedback pathway for fuel dissipation. The period, gel mechanical properties, and function are temporally regulated through varying the external parameters and tailoring the internal FLP chemistries. Particularly, the form of gas fuel results in a traceless waste in the system as excess gas can automatically escape out of the assemblies. This feature endows the transient gel networks with stable rhythmicity, long lifetime, and programmable function. The selection of substrate allows us to tune the transient period over a wide range. Relying on this periodic distinction, a time-dependent 4D information encryption application is achieved by fabricating encoded FLP array loaded with different substrates. Different array units undergo transient gelation at different time windows, which makes true code information be identified only at a specified time. Given that the decryption only requires CO\u003csub\u003e2\u003c/sub\u003e gas, even breathing CO\u003csub\u003e2\u003c/sub\u003e done, and the information can be carried in the solid phase, this will pave a way for creation of gas-encoded information materials and technology with portability, mobility and high-security. More importantly, FLPs have universal binding ability to a spectrum of gas substances (e.g. H\u003csub\u003e2\u003c/sub\u003e, CO, NO, N\u003csub\u003e2\u003c/sub\u003eO, SO\u003csub\u003e2\u003c/sub\u003e and C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003e)\u003csup\u003e\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e\u003c/sup\u003e, we thus believe that the gas-fueled out-of-equilibrium system could serve as an inspiring starting point for development of gas-driven advanced materials.\u003c/p\u003e"},{"header":"Methods","content":"\u003cp\u003e\u003cb\u003eMaterials.\u003c/b\u003e Frustrated Lewis acids, tri(pentafluorophenyl)borane (\u003cb\u003eTB\u003c/b\u003e) and triphenylborane (\u003cb\u003eTB\u003c/b\u003e\u003csup\u003e\u003cb\u003eF\u003c/b\u003e\u003c/sup\u003e), were purchased from Sigma-Aldrich. Frustrated Lewis bases (\u003cb\u003eC\u003c/b\u003e\u003csub\u003e\u003cb\u003en\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eTP\u003c/b\u003e, n = 0, 3, 7 and 11) were synthesized by n-alkyl bromide with various chain lengths and dimesitylphosphorus bromide according to the previous literature with modification\u003csup\u003e\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e\u003c/sup\u003e. The needed compounds, bromomethane, 1-bromobutane, 1-bromooctane, and 1-bromododecane were purchased from TCI and Adamas-beta. A series of substrates (S1-S12) were used commercially available products without any further purification. All solvents were reagent grade and were treated from Innovative Technologies Solvent Purification system.\u003c/p\u003e\u003cp\u003e\u003cb\u003eFLP precursor synthesis.\u003c/b\u003e Frustrated Lewis acids, \u003cb\u003eTB\u003c/b\u003e and \u003cb\u003eTB\u003c/b\u003e\u003csup\u003e\u003cb\u003eF\u003c/b\u003e\u003c/sup\u003e, directly used the commercial products. Frustrated Lewis bases (\u003cb\u003eC\u003c/b\u003e\u003csub\u003e\u003cb\u003en\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eTP\u003c/b\u003e, n = 0, 3, 7 and 11) were prepared by two steps and the synthetic details were described in Supplementary Fig. \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e. Their molecular structures were determined using \u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eH NMR, \u003csup\u003e\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e\u003c/sup\u003eP NMR, \u003csup\u003e\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e\u003c/sup\u003eB NMR spectroscopies, and electronic spray ionization (ESI) mass spectrometry, as shown in Supplementary Fig. S2-S10.\u003c/p\u003e\u003cp\u003e\u003cb\u003eInstruments and Characterization.\u003c/b\u003e Nuclear magnetic resonance (NMR) spectroscopy was measured on an AVANCE III HD 400 MHz of Bruker BioSpin International Instrument. Tetramethylsilane (TMS) was utilized as an internal standard, and CDCl\u003csub\u003e3\u003c/sub\u003e or \u003cem\u003ed\u003c/em\u003e\u003csub\u003e8\u003c/sub\u003e-toluene were used as the NMR solvents to probe \u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eH NMR (400MHz), \u003csup\u003e\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e\u003c/sup\u003eB NMR (128 MHz), \u003csup\u003e\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e\u003c/sup\u003eP NMR (162 MHz) spectra of all the frustrated Lewis acid and base. Electrospray ionization mass spectrometry (ESI-MS) was recorded on a Bruker McriOTOF11 ESI-TOF mass spectrometer equipped with an ESI interface and ion trap analyzer. UV-vis spectroscopy and turbidity test was conducted on an Agilent Cary-60 UV-vis spectrometry using a 1.0 mm cuvette. The spectral change of FLP sols fueled by CO\u003csub\u003e2\u003c/sub\u003e was monitored over time and the optical transmittance of FLP sol samples was probed at the wavelength of 600 nm. Atomic force microscope (AFM) was carried out on a Dimension-ICON Scanning probe Microscope (Bruker, Digital Instrument Co. Ltd.) equipped with a MikroMasch silicon cantilever, NSCII (radius \u0026lt; 10 nm, resonance frequency = 300 kHz, spring constant = 40 N/m) with tapping mode at room temperature. The sol state or gel state of FLP-based co-assemblies were drop casted onto the fresh exfoliated mica and allowed to adsorb for 1 min. After excess solution was wicked off with filter paper and the sample was dried for few hours in vacuum before AFM imaging. Transmission electron microscopy (TEM) was recorded on a FEI Tecnai G2-T20 S-TWIN instrument at 120 kV equipped with an AMT 16 megapixel in-line CCD camera. The sol or gel state of FLP-based co-assemblies in the absence or presence of CO\u003csub\u003e2\u003c/sub\u003e (10 µL) were taken out at given time and dropped onto a copper grid for 2 min and then blotted with filter paper to remove excess solution followed by drying overnight in vacuum oven before TEM observation. Small-angle X-ray scattering (SAXS) analysis was obtained on the diamond light source beam line I22 in the Shanghai Synchrotron Radiation Facility (SRF). The working voltage and current for the X-ray tube are 45 kV and 0.88 mA, and the wavelength of incident X-ray beam was 0.126 nm. The scattering vector (\u003cem\u003eq\u003c/em\u003e) was calibrated using silver behenate with the primary reflection peak at \u003cem\u003eq\u003c/em\u003e = 1.067 nm\u003csup\u003e− 1\u003c/sup\u003e. X-ray diffraction (XRD) was conducted using an AXS D8 Advance (Bruker, Germany) diffractometer operated at 1,600 W power (40 kV, 40 mA) using Cu-Kα radiation. The FLP co-assembly samples in powder or xerogel (transient gel at ca. 60 min) were prepared by plunging in liquid nitrogen and drying by the process of lyophilization. The dried samples were then mounted on glass slides for diffraction and 2\u003cem\u003eθ\u003c/em\u003e was fixed at 5–50°.\u003c/p\u003e\u003cp\u003e\u003cb\u003eCO\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e-fueled gelation. C\u003c/b\u003e \u003csub\u003e \u003cb\u003e11\u003c/b\u003e \u003c/sub\u003e \u003cb\u003eTP\u003c/b\u003e and \u003cb\u003eTB\u003c/b\u003e as the complementary FLP precursors were dissolved in toluene in glass vial, followed by addition of varying concentrations of \u003cb\u003eS1\u003c/b\u003e substrate. The final mixture solution was incubated for half an hour with stirring at room temperature. CO\u003csub\u003e2\u003c/sub\u003e gas was applied in the solution through a microflow-pump HRF 1425 − 580 (PraStar, Praxair Co.) connected to a standard gas cylinder (4 L). This equipment can tune the CO\u003csub\u003e2\u003c/sub\u003e pressure and flow rate to quantify the amount of gas aeration. The gas flow rate can be adjusted from 0.002 to 20 mL/s and the pressure can be adjusted from 0.01 to 10 bar. For the gas-FLP binding, the amount of CO\u003csub\u003e2\u003c/sub\u003e addition was set at the given concentrations (1 ~ 4 mM). Gel formation was monitored by inverting the glass vial and the apparent lifetimes of the gel state could be roughly determined.\u003c/p\u003e\u003cp\u003e\u003cb\u003eRheology measurement.\u003c/b\u003e The rheological change of FLP-based transient gel networks over time was monitored in parallel plates using HAAKE Par Rotary Rheometer (HAAKE MARS III) with a 40 mm diameter cross-hatched tool. The frequency sweep experiments were performed as a function of angular frequency (0.1 to 100 Hz) at a fixed strain of 0.1% at given temperature, and the storage moduli (\u003cem\u003eG′\u003c/em\u003e) and the loss moduli (\u003cem\u003eG″\u003c/em\u003e) was plotted against time.\u003c/p\u003e\u003cp\u003e\u003cb\u003eCatalytic efficiency analysis.\u003c/b\u003e The catalytic ability of transient system was examined by analytical high-performance liquid chromatograph (HPLC) using Waters HPLC system (2535 quaternary pump) with 2489 UV-vis detector, and all compounds involved were separated using a linear gradient eluent toluene : chloroform from 95:5 to 60:40. At a fixed time interval (10 min), aliquots of gel suspension was taken out and injected to HPLC with dilution to in-situ monitor the evolution of the concentration of precursor, substrate and catalytic product. The increase of peak areas of catalytic product, benzo[d]imdiazole-2-carboxylic acid, reflects the catalytic kinetics. Calibration curves for substrate (λ = 220 nm) and product (λ = 281 nm) were performed in triplicate in order to quantify the compounds over time.\u003c/p\u003e\u003cp\u003e\u003cb\u003eMD simulation of co-assembly structure.\u003c/b\u003e The molecular packing mode of FLP precursor and substrate into fibrillar nanostructure was revealed by molecular dynamics (MD) simulations. The MD simulations employed AMBER force field after the structure optimization using M062x with 6-31g (d,p) basis set implanted in Gaussin09.\u003c/p\u003e\u003cp\u003e\u003cb\u003eFabrication of time-gated 4D code pattern in solution state.\u003c/b\u003e FLP stock solutions were prepared by dissolving FLP precursors (\u003cb\u003eC\u003c/b\u003e\u003csub\u003e\u003cb\u003e11\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eTP\u003c/b\u003e and \u003cb\u003eTB\u003c/b\u003e, 1 mM) in toluene and added three types of substrates (\u003cb\u003eS1\u003c/b\u003e, \u003cb\u003eS8\u003c/b\u003e or \u003cb\u003eS10\u003c/b\u003e, 1 mM) respectively. Trace amount of pH indicator (bromothymol blue, 1 mg) was added in each mixture solution. Upon introduction of the indicator, the stock solutions turned brilliant blue color because of the weak alkalinity of substrates. Afterwards, the three different types of FLP solutions were dropped into the 96-well plate (12 × 8 units) according to a preset pattern and each well unit contained 0.1 mL solution. Purging or blowing enough CO\u003csub\u003e2\u003c/sub\u003e gas (within 60 s) to the plate in a parallel mode and recording their time-dependent phase transition and concomitant color change. At a certain time window, when the sol in different well unit turned into gel state and its color changed from blue to slight yellow, we could read out the obtained pattern as the code information. Different time windows correspond to the different code pattern, and the correct one can be decrypted only at a specified time.\u003c/p\u003e\u003cp\u003e\u003cb\u003eQR code time-gated encryption in solid state.\u003c/b\u003e Printing tests were performed on a Canon inkjet printer (MG2400) and Canon PG-845 FINE cartridge, using paper (4 × 4 cm) without optical brightener. The original three kinds of inks (Cyan, Yellow and Blue) were replaced by our FLP sol inks. The FLP-based inks were the mixture of FLP precursor (\u003cb\u003eC\u003c/b\u003e\u003csub\u003e\u003cb\u003e11\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eTP\u003c/b\u003e and \u003cb\u003eTB\u003c/b\u003e, 1 mM) and substrate (\u003cb\u003eS1\u003c/b\u003e, \u003cb\u003eS8\u003c/b\u003e or \u003cb\u003eS10\u003c/b\u003e, 1 mM), with trace amount of ferrous ion indicator, respectively. The code information was pre-encoded by FLP array in paper and printed. When exposing the paper to moist CO\u003csub\u003e2\u003c/sub\u003e gas for minutes, the FLP array began to occur transient gelling transition at a certain time window, which make the indicator show blue color. Consequently, the QR code could be seen and we could scan it by a commercially available smartphone APP. In a similar way, different time windows showed different QR codes, and the correct one can be identified only at a specified time.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eKarsenti E (2008) Self-organization in cell biology: a brief story. Nat Rev Mol Cell Biol 9:255\u0026ndash;262\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eGiuseppone N, Walther A (2021) Out-of-equilibrium (Supra)molecular Systems and Materials. Wiley-VCH., Weinheim\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eDominguez R, Holmes KC (2011) Actin structure and function. Annu Rev Biophys 40:169\u0026ndash;186\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eBrouhard GJ, Rice LM (2018) Microtubule dynamics: an interplay of biochemistry and mechanics. 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Biol Chem Chem Biol 5:3471\u0026ndash;3476\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":true,"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":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-4677523/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4677523/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"Dissipative self-assembly, which exploits energy inputs of chemical fuels to maintain the functional states far from equilibrium, is essential to the living systems. Among a variety of fuels, carbon dioxide (CO2) gas, as one of the most ubiquitous but original forms of fuel on which life depends, has yet been introduced in artificial dissipative materials. Here we describe a CO2-fueled non-equilibrium co-assembly system that couples with a C1 catalytic feedback path to drive fuel dissipation and function output. Using common frustrated Lewis pair (FLP) as precursors, CO2 can dynamically bridge between them to constitute metastable amphiphiles, which not only highly activate CO2 but also enable their co-assembly with substrates into a transient fibrillar gel. In turn, the feedback process is realized by cooperative C1 catalytic insertion owing to the proximity of substrate and activated CO2 species in the assembled state. This can boost the depletion of gas fuel and facilitate disassembly to sol. Moreover, tailoring the intrinsic substrate/FLP chemistries, as well as external cues, to shift the catalytic activity is accessible to regulate the period and lifetime of sol-gel-sol transition over a wide range. Based on the tunability in phase transition on a time scale, we develop time-dependent information encryption materials using the transient FLP array loaded gas-encoded substrates, and the correct information can be read only at a specified time window. This study provides inspiration on a new fuel paradigm for dissipative system and their intelligent material applications.","manuscriptTitle":"Gas-Fueled Non-Equilibrium Co-Assembly via C1 Catalytic Feedback for Gas-Encoded 4D Information Encryption","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-07-17 15:00:54","doi":"10.21203/rs.3.rs-4677523/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"bdea47f7-05f4-45da-ac01-a33c72478f1c","owner":[],"postedDate":"July 17th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[{"id":34746551,"name":"Physical sciences/Materials science/Soft materials/Self-assembly"},{"id":34746552,"name":"Physical sciences/Chemistry/Supramolecular chemistry/Self-assembly"},{"id":34746553,"name":"Physical sciences/Chemistry/Materials chemistry/Soft materials/Gels and hydrogels"},{"id":34746554,"name":"Biological sciences/Systems biology/Dynamical systems"}],"tags":[],"updatedAt":"2024-08-29T15:41:25+00:00","versionOfRecord":[],"versionCreatedAt":"2024-07-17 15:00:54","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-4677523","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4677523","identity":"rs-4677523","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}