Preparation of cellulose-based fluorescent elastomers via RAFT polymerization and lanthanide coordination

Preparation of cellulose-based fluorescent elastomers via RAFT polymerization and lanthanide coordination | 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 Research Article Preparation of cellulose-based fluorescent elastomers via RAFT polymerization and lanthanide coordination Rui Hu, Anjia Zheng, Cancan Zhang, Chuanxi Wang, Jiaming Zhang, and 4 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6671184/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 11 Oct, 2025 Read the published version in Cellulose → Version 1 posted 10 You are reading this latest preprint version Abstract High-performance sustainable elastomers with tunable fluorescent behavior designed via robust and facile strategies are highly pursued. In this work, cellulose- graft -poly(tetrahydrofurfuryl acrylate- co -2-(methacryloyloxy)ethyl acetoacetate) (Cell- g -P(THFA- co -AAEM)) copolymers with different compositions were prepared through homogeneous reversible addition-fragmentation chain transfer (RAFT) polymerization. In this design, cellulose acts as the backbone, while the hemicellulose derivative THFA and the petroleum-based monomer AAEM play the role of soft and rigid segments in the grafted side chains, respectively. By tuning the THFA/AAEM feed ratio and cellulose content, the mechanical and adhesion properties of these Cell- g -P(THFA- co -AAEM) copolymers were well manipulated. In addition, the b -diketone groups in THFA repeating units can be further used as the ligands to form dynamic networks in the copolymer matrix with terbium (Tb 3+ ) and europium (Eu 3+ ) ions via lanthanide coordination. The resulting coordinated Cell- g -P(THFA- co -AAEM) copolymers exhibit significantly improved tensile strength and tunable fluorescent colors by adjusting the Tb 3+ /Eu 3+ ratio. The combination of bio-based resources and lanthanide coordination can be further performed to achieve strong sustainable elastomers with improved macroscopic mechanical properties and unique fluorescent behavior. Cellulose Graft copolymers Mechanical properties Adhesion behavior Fluorescent performance Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Introduction Thermoplastic elastomers are essential engineering materials with outstanding stretchability and fantastic elasticity, which allows them to be used in automotive interior parts, seals, adhesives, sporting goods, medical devices, and electronics (Cater et al. 2024 ; Jiang et al. 2017 ; Liffland and Hillmyer 2021 ; Steube et al. 2022 ; Zanchin and Leone 2021 ). With the rapid development of the global economy, the demand for elastomer materials is continuously increasing (Burelo et al. 2024 ). However, traditional elastomers mostly rely on limited petroleum resources. In contrast, bio-based elastomers are made from sustainable biomass resources include corn, lignin, soybean, cellulose, rosin, chitin, and plant oils (Luo et al. 2024 ; Melendez-Zamudio et al. 2023 ; Wanamaker et al. 2007 ; Wang et al. 2020 ; Wang et al. 2017 ). These materials are widely available and renewable, effectively alleviating the pressure caused by the scarcity of petroleum resources and ensuring the long-term stable supply of elastomers. Sustainable elastomers, throughout their entire lifecycle, from production and use to disposal, can significantly reduce carbon dioxide emissions compared to traditional petroleum-based elastomers (Ge et al. 2025 ; Tang et al. 2022 ). The raw materials used in bio-based elastomers can absorb carbon dioxide from the atmosphere during their growth, thereby achieving carbon sequestration. This helps reduce greenhouse gas emissions and aligns with the low-carbon economy and sustainable development goals (Thomas et al. 2023 ). The achievement of bio-based elastomers can provide new opportunities and approaches for designing novel elastomer materials with unique properties and functions. In general, the mechanical properties of elastomers, such as tensile strength, extensibility, elasticity, and Youngʹs modulus, are primarily determined by the choice of monomers, compositions, architectures, microphase-separated morphologies, and network structures formed by the covalent/noncovalent interactions (Li et al. 2023 ; Wu et al. 2024 ; Wu et al. 2023 ). In recent years, sustainable polymers with linear and nonlinear topological structures have been reported as bio-based elastomers (Jeong et al. 2023 ; Liffland et al. 2023 ; Meier-Merziger et al. 2024 ; Odnoroh et al. 2024 ; Sun et al. 2025 ). It has been demonstrated that graft elastomers exhibit dramatically improved mechanical performance compared to their linear counterparts with similar compositions (Jiang et al. 2019 ; Jiang et al. 2013 ; Li et al. 2021 ; Wang et al. 2019 ). As the most promising natural biomacromolecule, cellulose offers the advantages of renewability, biodegradability, and excellent biocompatibility (Dang et al. 2024 ; Wang et al. 2024 ). Owing to the existence of plentiful hydroxyl groups, cellulose can be modified into various derivatives via different strategies conveniently, promoting the preparation of cellulose-based copolymers through controlled radical polymerization methods (Garcia-Valdez et al. 2018 ; Kumar et al. 2021 ; Wang et al. 2021 ). In recent years, renewable monomers derived from plant oils, lignin, rosin, and hemicellulose have been utilized to prepare cellulose graft copolymers with tunable properties (Cheng et al. 2019 ; Feng et al. 2024 ; Xu et al. 2025 ). Tetrahydrofurfuryl acrylate (THFA) is a typical polymerizable hemicellulose-derived monomer, which is an ideal candidate for soft petroleum-based segments in elastomers (Luo et al. 2025 ; Odnoroh et al. 2024 ). The integration of cellulose and sustainable monomers can inspire the further advancement of renewable elastomers with specific performance and application demands. Combining the excellent mechanical performance of elastomers and the fluorescence of chromophores under specific wavelengths of light, fluorescent elastomers are widely extensively used in the fields of fluorescence sensing, anti-counterfeiting, information encryption, and smart devices (Hu et al. 2024 ; Huang et al. 2024 ; Li et al. 2025 ; Lu et al. 2022 ; Zhou et al. 2025 ). Therefore, it is essential to produce fluorescent cellulose graft copolymer elastomers via rational design for advanced materials. Herein, sustainable cellulose- graft -poly(tetrahydrofurfuryl acrylate- co -2-(methacryloyloxy)ethyl acetoacetate) (Cell- g -P(THFA- co -AAEM)) copolymer elastomers were prepared as illustrated in Fig. 1 , where rubbery P(THFA- co -AAEM) side chains were grafted from rigid cellulose backbone by homogeneous reversible addition-fragmentation chain transfer (RAFT) polymerization. In this design, the cellulose backbone can act as multiple cross-linking points to prevent the side chains from flowing under external stress, while the AAEM repeating unit can play the role of ligand to coordinate lanthanide ions, such as terbium (Tb 3+ ) and europium (Eu 3+ ) ions, to provide additional physical cross-linked network structure as well as unique fluorescent property for the resultant elastomeric materials. We suppose the incorporation of Tb 3+ and Eu 3+ ions via lanthanide coordination can effectively improve the mechanical properties of cellulose-based copolymers and endow them with tunable fluorescent properties. This strategy combines renewable biomass and lanthanide coordination to achieve luminescent bio-based elastomers with tunable performance can accelerate the vigorous development of renewable polymeric materials. Materials and methods Materials Microcrystalline cellulose (Avicel PH-101) with a degree of polymerization of 128 was purchased from Sigma-Aldrich. 1-Allyl-3-methylimidazolium chloride (AMIMCl), N,N -dimethylformamide (DMF), 1,4-dioxane, dimethyl sulfoxide (DMSO), tetrahydrofurfuryl acrylate (THFA), 2-(methacryloyloxy)ethyl acetoacetate (AAEM), 2-bromoisobutyryl bromide, carbon disulfide, 1-butanethiol, triethylamine, 2,2ʹ-azobis(2-methylpropionitrile) (AIBN), terbium nitrate pentahydrate (Tb(NO 3 ) 3 ·5H 2 O), and europium nitrate hexahydrate (Eu(NO 3 ) 3 ·6H 2 O) were purchased from Aladdin (Shanghai, China). The inhibitors in THFA and AAEM were removed prior to use. Synthesis of cellulose-based macromolecular chain transfer agent (Cell-CTA) Microcrystalline cellulose (5.0 g, 30.9 mmol) and AMIMCl (100.0 g) were introduced into a flask (250 mL capacity) and stirred at 100 o C until cellulose was fully dissolved. DMF (50 mL) was added into the cellulose solution with stirring and cooled to room temperature. Then 2-bromoisobutyryl bromide (63.9 g, 277.9 mmol) was added dropwise to the cellulose solution in ice water. After 24 h reaction at room temperature, the resulting mixture was precipitated in deionized water (2 L). The cellulose-based macroinitiator (Cell-BiB) was collected, washed thoroughly with deionized water, and dried in vacuum at 60 o C until a constant weight was reached. To prepare Cell-CTA, Cell-BiB (4.9 g, 22.0 mmol of Br) was dispersed in 100 mL of DMSO with stirring at 40 o C to form a clear solution. 1-Butanethiol (0.50 g, 5.5 mmol) and triethylamine (0.56 g, 5.5 mmol) were mixed and stirred in DMSO (20 mL) for 30 min at room temperature, followed by the addition of carbon disulfide (1.26 g, 16.5 mmol). After 30 min, the solutions were mixed and reacted for 12 h at 40 o C. The solution was poured into deionized water (2 L) to precipitate Cell-CTA. The product was further dried at 60 o C for 12 h under vacuum. Synthesis of Cell- g -P(THFA- co -AAEM) copolymers Cell- g -P(THFA- co -AAEM) copolymers were prepared as follows. Cell-CTA (36.2 mg), THFA (1.64 g, 10.5 mmol), AAEM (1.0 g, 4.5 mmol), AIBN (0.4 mg, 0.0025 mmol), 1,4-dioxane (8 mL), DMF (2 mL), and a stirring bar were added into a 25 mL Schlenk flask. The flask was immersed in an oil bath preset at 70 o C after three freezing-vacuum-thawing cycles. After a certain time, the flask was taken out and the mixture was poured into methanol (150 mL). The precipitated product was collected, washed, and dried under vacuum at 60 o C overnight. Cell- g -P(THFA- co -AAEM) copolymers with varied AAEM/THFA feed ratios were prepared in the same way as summarized in Table 1 . Cell- g -P(THFA- co -AAEM) film was obtained by dissolving the sample in THF with a concentration of 10 wt% and evaporating the solvent in a Teflon mold in air. The resultant film was further dried in an oven under vacuum at 40 o C overnight. Preparation of fluorescent Cell- g -P(THFA- co -AAEM) copolymers Typically, Cell2.6-PAAEM180 (1.0 g) was dissolved in tetrahydrofuran (20 mL), and then Tb(NO 3 ) 3 ·5H 2 O (0.27 g, 0.62 mmol) was added and stirred for 12 h. The resultant solution was added into a Teflon mold and dried to obtain the free-standing film. The film was further dried in an oven under vacuum at 40 o C overnight. Films with varied Tb 3+ /Eu 3+ ratios were achieved similarly. Characterization The chemical structures of samples were examined by Nicolei 6670 Fourier transform infrared (FT-IR) spectrometer and Agilent DD2 600MHz nuclear magnetic resonance (NMR) spectrometer. A thermogravimetric analyzer (TGA 55, TA instruments) and differential scanning calorimeter (DSC 250, TA instruments) were used to investigate the thermal decomposition temperatures and glass transition temperatures of the samples. TGA curves were recorded from 40 to 700 o C under a nitrogen atmosphere with a heating rate of 10 o C/min. For DSC measurement, the T g value was determined using the heating curves from − 50 to 150 o C with a heating rate of 10 o C/min under a nitrogen atmosphere. Monotonic and cyclic stress-strain curves were recorded on a Suns UTM2502 universal testing machine. The tensile speed was set at 50 mm/min during the measurements. For adhesion tests, the specimens with a thickness of 0.15 nm were cut into sheets (25 mm × 12.5 mm) and then sandwiched between the steel plates. The steel plates were secured using dovetail clamps and heated at 150 o C for 3 h under vacuum in the oven. Small-angle X-ray scattering (SAXS) measurements were conducted at the synchrotron beamline BL16B1 with the X-ray wavelength of 0.124 nm at Shanghai Synchrotron Radiation Facility (SSRF), China. Hitachi F-7000 fluorescence spectrophotometer was used to investigate the fluorescent behavior of coordinated Cell- g -P(THFA- co -AAEM) copolymers. Results and discussion Preparation of Cell- g -P(THFA- co -AAEM) copolymers As depicted in Fig. 2 a, the FT-IR spectrum of Cell-BiB exhibits a distinct absorption band around 1740 cm -1 corresponding to the C = O groups. Meanwhile, it can be observed that the absorption band of hydroxyl groups on Cell-BiB becomes much weaker than that of pristine cellulose, suggesting the formation of ester bonds on cellulose. Cell-CTA shows a similar FT-IR spectrum to that of Cell-BiB, but the absorption bands ranging from 3000 to 2800 cm -1 corresponding to the C-H stretching vibration are more potent due to the incorporation of n -butyl groups. Figure 2 b displays the 1 H NMR spectrum of Cell-BiB in deuterated acetone, in which the signals located around 5.3 ppm and 1.9–1.6 ppm are assigned to the cellulose protons at the C1 position and methyl protons of 2-bromoisobutyrylate groups, respectively. As shown in Fig. 2 c, the new peaks appear at 1.0-0.8 ppm can be ascribed to the methyl protons of butyl groups. From the above 1 H NMR spectra, the degree of substitutions of Cell-BiB ( DS BiB ) and Cell-CTA ( DS CTA ) can be obtained according to the following equations $$D{S_{\text{B}\text{i}\text{B}}}=\frac{{{I_\text{b}}}}{{6{I_\text{a}}}}$$ 1 $$D{S_{\text{C}\text{T}\text{A}}}=\frac{{I\text{c}}}{{3{I_\text{a}}}}$$ 2 where I a , I b , and I c represent the integral areas of -CH protons of cellulose, methyl protons of 2-bromoisobutyrylate group, and methyl protons of butyl groups, respectively. Hence, the degree of substitutions of Cell-BiB and Cell-CTA are calculated to be 2.2 and 0.36, respectively. Cell- g -P(THFA- co -AAEM) copolymers with tunable compositions were synthesized through RAFT polymerization by changing the THFA/AAEM feed ratios. Figure 2 d plots the 1 H NMR spectrum of Cell2.6-PAAEM180, the signals located at 3.6 and 3.72 ppm are assigned to the CH 2 protons on AAEM and THFA repeating units, respectively, which can be further used to determine the PTHFA/PAAEM ratio in the copolymer. The detailed information for prepared Cell- g -P(THFA- co -AAEM) copolymers are listed in Table 1 . Table 1 Detailed information for prepared Cell- g -P(THFA- co -AAEM) copolymers. Sample a Feed ratio b Cellulose content (wt%) PTHFA content c (wt%) PAAEM content c (wt%) M n,th (grafts) c (kDa) T g d ( o C) Cell2.6-PAAEM60 1:540:60 2.6 82.7 14.7 74.1 -1.4 Cell2.6-PAAEM180 1:420:180 2.6 57.8 39.6 73.0 5.8 Cell5.3-PAAEM180 1:420:180 5.3 56.2 38.5 35.5 7.7 Cell11.9-PAAEM180 1:420:180 11.9 52.3 35.8 14.6 9.1 Cell2.6-PAAEM210 1:390:210 2.6 50.0 47.4 75.2 7.3 Cell2.6-PAAEM300 1:300:300 2.6 41.1 56.3 73.5 10.7 Cell2.7-PAAEM420 1:180:420 2.7 20.2 77.1 71.3 14.0 a The numbers after “Cell” and “AAEM” are the cellulose content and the molar ratio of the total amount of AAEM/monomers, respectively. b Feed ratio: Cell-CTA /AAEM/THFA. c Determined by 1 H NMR measurements. d Measured from DSC heat flow curves. Thermal properties of Cell- g -P(THFA- co -AAEM) copolymers The TGA and DTG curves for cellulose, Cell-BiB, Cell-CTA, and Cell2.6-PAAEM180 are shown in Fig. 3 a and 3 b. Pristine cellulose is thermally stable with an onset decomposition temperature ( T d 5% ) of 294°C and a maximum decomposition temperature ( T max ) of 319°C. Cell-BiB and Cell-CTA show reduced T d 5% and T max values after introducing unstable bromine and trithiocarbonate groups. The T d 5% and T max values for Cell-CTA are 243 o C and 275 o C, respectively, which are much lower than those of the pristine cellulose. Cell2.6-PAAEM180 exhibits a two-stage decomposition behavior with two T max values of 278 o C and 392 o C, respectively. As depicted in Fig. 3 c, when the AAEM/THFA feed ratio increases, the T g vale rises from − 1.4°C for Cell2.6-PAAEM60 to 14°C for Cell2.7-PAAEM420 due to the increased PAAEM content in the resultant copolymers. Figure 3 d displays the DSC curves of Cell- g -P(THFA- co -AAEM) copolymers synthesized with the same condition but different cellulose contents. Note that the T g value rises from 5.8°C for Cell2.6-PAAEM180 to 9.1°C for Cell11.9-PAAEM180 with the increase of cellulose content. It can be found that the rigid PAAEM content decreases from 57.8 wt% for Cell2.6-PAAEM180 to 56.2 wt% for Cell5.3-PAAEM180 and 52.3 wt% for Cell11.9-PAAEM180, respectively. Therefore, the increase of T g values for Cell2.6-PAAEM180, Cell5.3-PAAEM180, and Cell11.9-PAAEM180 is attributed to the higher cellulose content, which reduces the flexibility of P(AAEM- co -TFHA) side chains significantly. These findings indicate that the T g values of Cell- g -P(THFA- co -AAEM) copolymers can be facilely manipulated by tuning the THFA/AAEM feed ratio and cellulose content in the preparation process. Mechanical performance of Cell- g -P(THFA- co -AAEM) copolymers As shown in Fig. 3 a, the stress at break value rises sharply from 0.08 MPa for Cell2.6-PAAEM60 to 3.5 MPa for Cell2.7-PAAEM420, while the elongation decreases from 1417% for Cell2.6-PAAEM60 to 195% for Cell2.7-PAAEM420 when the THFA/AAEM feed ratio decreases. Figure 4 b indicates that the tensile toughness values for Cell2.6-PAAEM60, Cell2.6-PAAEM180, Cell2.6-PAAEM210, Cell2.6-PAAEM300, and Cell2.7-PAAEM420 are 2.7, 7.0, 12.0, 4.7, and 3.6 MJ/m³, respectively. Obviously, Cell2.6-PAAEM210 exhibits the highest tensile toughness by comprising tensile strength and extensibility. The increase of AAEM ratio in the feed monomers leads to higher PAAEM content in Cell- g -P(THFA- co -AAEM) copolymer, resulting in improved Youngʹs modulus as displayed in Fig. 4 c. Figure 4 d shows the monotonic stress-strain curves of Cell- g -P(THFA- co -AAEM) copolymers prepared in the same condition but varied cellulose contents. It can be found that the ultimate tensile strength grows from 0.5 MPa (Cell2.6-PAAEM180) to 6.0 MPa (Cell11.9-PAAEM180) as the cellulose content increases from 2.6 to 11.9 wt%, while the strain at break decreases from 1192% (Cell2.6-PAAEM180) to 303% (Cell11.9-PAAEM180). Both the tensile toughness and the Youngʹs modulus rise with increasing cellulose content as illustrated in Figs. 4 e and 4 f, indicating that higher cellulose content results in well-improved tensile strength, toughness, and Young's modulus. The detailed mechanical property parameters during monotonic tensile tests are listed in Table 2 . Table 2 Detailed mechanical property parameters for Cell- g -P(THFA- co -AAEM) copolymers Sample Stress at break (MPa) Strain at break (%) Tensile toughness (MJ/m 3 ) Youngʹs modulus (MPa) Cell2.6-PAAEM60 0.08 ± 0.01 1417 ± 149 2.7 ± 0.1 0.06 ± 0.01 Cell2.6-PAAEM180 0.5 ± 0.1 1192 ± 138 7.0 ± 0.3 0.2 ± 0.02 Cell5.3-PAAEM180 3.1 ± 0.3 415 ± 47 9.6 ± 0.6 1.9 ± 0.1 Cell11.9-PAAEM180 6.0 ± 0.5 303 ± 52 13.0 ± 0.8 4.3 ± 0.2 Cell2.6-PAAEM210 1.2 ± 0.2 1039 ± 58 12.0 ± 0.7 0.4 ± 0.03 Cell2.6-PAAEM300 2.6 ± 0.3 331 ± 32 4.7 ± 0.3 0.9 ± 0.05 Cell2.7-PAAEM420 3.5 ± 0.4 192 ± 14 3.7 ± 0.2 1.7 ± 0.1 Besides tensile tests, cyclic tensile tests were performed to reveal the elasticity and hysteresis behavior of Cell- g -P(THFA- co -AAEM) copolymers. During the cyclic tensile deformation, the film sample was stretched to 25% strain, 50% strain, and so on up to 200% strain at a 50 mm/min tensile speed. The stretching direction was reversed when the desired strain was reached, the film sample was released to zero stress with a 50 mm/min retraction speed. The cyclic stretching-retraction process was stopped when 200% strain was achieved. Figure 5 a-f exhibits the cyclic stress-strain curves of Cell- g -P(THFA- co -AAEM) copolymers. It should be noted that Cell2.6-PAAEM60 was too weak to perform stepwise cyclic tensile testing. Noticeably, the residual strain at zero stress during the retraction process increases with the maximum strain due to the presence of unrecoverable plastic deformation during the extension process. Both elastic and plastic deformations are present when the film sample is stretched, to evaluate the elasticity of Cell- g -P(THFA- co -AAEM) copolymers, the elastic recovery (ER) values during cyclic tensile tests are calculated as reported (Jiang et al. 2015 ). The evolutions of ER values during extension-retraction cycles for Cell- g -P(THFA- co -AAEM) copolymers are displayed in Fig. 5 g. Data show that the ER value in each cycle increases with the maximum strain and can even exceed 80% after several loading-unloading cycles, suggesting that the elasticity of Cell- g -P(THFA- co -AAEM) copolymers can be significantly improved by such kind of mechanical training strategy. Cell11.9-PAAEM180 shows the lowest ER values in the whole strain range on account of its highest cellulose content. The hysteresis loss (energy dissipation) value in each cycle can be measured by the integrated area of the hysteresis loop. The changes of hysteresis loss with the maximum strain are depicted in Fig. 5 h, which implies that the increase of PAAEM and cellulose contents leads to the dramatical increase of hysteresis loss due to the occurrence of chain friction during extension. As shown in Fig. 5 i, Cell11.9-PAAEM180 displays the highest hysteresis loss rate after two extension-retraction cycles, which means that higher cellulose content can promote more plastic deformation and energy dissipation, resulting in higher hysteresis loss rate. Overall, the macroscopic mechanical properties of Cell- g -P(THFA- co -AAEM) copolymers, including tensile strength, elongation, toughness, Youngʹs modulus, elasticity, and hysteresis loss, can be conveniently regulated by manipulating the compositions during polymerization. Morphology of Cell- g -P(THFA- co -AAEM) copolymers The microstructure of Cell- g -P(THFA- co -AAEM) copolymers was examined using SAXS measurements. Figure 6 shows the 2D SAXS patterns and corresponding intensity profiles of Cell2.6-PAAEM180, Cell5.3-PAAEM180, and Cell11.9-PAAEM180. Note that only weak and diffuse scattering patterns can be observed, illustrating the absence of microphase-separated structure in the graft copolymers. Although Cell11.9-PAAEM180 possesses the highest cellulose content of 11.9 wt%, the rigid cellulose chains are highly extended by the side chains, preventing the formation of well-ordered aggregates by cellulose in the matrix. Adhesion behavior of Cell- g -P(THFA- co -AAEM) copolymers For adhesives, their adhesion properties are strongly related to the cohesion and the interfacial interactions between adhesives and the interfaces. By tuning the adhesion performance, adhesives can find applications in glues, food packages, electronic devices, sticky notes, and automotive industries (Vahdati et al. 2023 ). To improve the adhesion behavior, nanofillers, nonlinear topologies, covalent bonds, and noncovalent interactions have been utilized to design strong adhesives. Cell- g -P(THFA- co -AAEM) copolymers have the advantages of branched architecture and renewability, they are excellent candidates for traditional petroleum-based adhesives. Figure 7 a displays the shear strength values of Cell- g -P(THFA- co -AAEM) copolymers prepared with different THFA/AAEM feed ratios, in which it can be found that Cell2.6-PAAEM210 shows the highest shear strength of 2.3 MPa. Figure 7 b exhibits the shear strength values of cellulose graft copolymers prepared in the same condition but varied cellulose contents, and Cell11.9-PAAEM180 possesses the highest shear strength of 2.5 MPa. The adhesion behavior of such kind of cellulose-based copolymers can be facilely adjusted by changing their compositions. As illustrated in Fig. 7 c, a weight of 5 kg can be easily lifted and sustained by the steel plates, proving the potential application in hot-melt adhesives. Preparation of fluorescent Cell- g -P(THFA- co -AAEM) copolymers via lanthanide coordination Lanthanide coordination was used to improve the mechanical performance and adjusting the fluorescent behavior of coordinated Cell- g -P(THFA- co -AAEM) copolymers, and thus Tb 3+ ion and Eu 3+ ions were selected to coordinate with the b -diketone groups in THFA repeating units. Different amounts of Tb 3+ and Eu 3+ ions were incorporated into Cell- g -P(THFA- co -AAEM) copolymers to form lanthanide coordination with b -diketone groups as summarized in Table 3 . It should be noted that the molar ratio between lanthanide (La 3+ ) ions and b -diketone groups in each sample was controlled to be 1/3. As shown in Fig. 8 a and Table 3 , the stress at break values of coordinated Cell2.6-PAAEM180 samples exhibit significantly enhanced tensile strength values compared to that of pristine Cell2.6-PAAEM180, which is only 0.5 MPa. As depicted in Fig. S1 , the T g values for coordinated Cell2.6-PAAEM180 samples are located in the range from 44.4 to 47.0 o C, which are much higher than that of Cell2.6-PAAEM180 (5.8 o C). In general, the T g value is determined by the flexibility of the polymer chains. In this case, the formation of lanthanide coordination between lanthanide ions and b -diketone groups can reduce the chain movement of the side chains, resulting in higher T g . However, as plotted in Fig. S2 , the SAXS results suggest that these coordinated Cell- g -P(THFA- co -AAEM) copolymers still show featureless structure without any distinct microphase-separated morphology, revealing that the improved mechanical properties of Cell- g -P(THFA- co -AAEM) copolymers are attributed to the coordinated networks and increased T g values. Figure 8 b shows the emission spectra of coordinated Cell2.6-PAAEM180 samples with different amounts of Tb 3+ and Eu 3+ ions excited at 254 nm, where the strong green and red emissions located at 547 nm and 620 nm are corresponding to the 5 D 4 - 7 F 5 deexcitation of Tb 3+ ions and 5 D 0 - 7 F 2 deexcitation of Eu 3+ ions, respectively. No emission signal can be observed for pristine Cell2.6-PAAEM180, indicating that the fluorescent performance is attributed to the incorporated Tb 3+ and Eu 3+ ions. To visually illustrate the fluorescent behavior of coordinated Cell- g -P(THFA- co -AAEM) copolymers, the film samples were cut into different shapes and assembled as shown in Fig. 8 c. Noticeably, all the films are transparent under ambient light without any color. When irradiated with UV light of 254 nm, the coordinated films exhibit varied luminescent colors depend on the amount of Tb 3+ and Eu 3+ ions, indicating extraordinary fluorescent performance. Table 3 Mechanical properties of coordinated Cell- g -P(THFA- co -AAEM) copolymers Sample Molar ratio of Tb 3+ /La 3+ Molar ratio of La 3+ / β -diketone groups Stress at break (MPa) Strain at break (%) Cell2.6-PAAEM180-C1 1.0 0.33 4.0 ± 0.3 410 ± 19 Cell2.6-PAAEM180-C2 0.75 0.33 4.2 ± 0.4 415 ± 28 Cell2.6-PAAEM180-C3 0.50 0.33 4.9 ± 0.5 341 ± 16 Cell2.6-PAAEM180-C4 0.25 0.33 4.7 ± 0.4 458 ± 35 Cell2.6-PAAEM180-C5 0 0.33 4.6 ± 0.4 502 ± 42 Conclusions In summary, sustainable Cell- g -P(THFA- co -AAEM) copolymers were synthesized by adjusting the compositions through RAFT polymerization. These Cell- g -P(THFA- co -AAEM) copolymers exhibit good thermal stability, outstanding mechanical properties, and excellent adhesion behavior. As expected, the introduction of Tb 3+ and Eu 3+ ions can form an additional dynamic network via lanthanide coordination to dramatically enhance the tensile strength of the Cell- g -P(THFA- co -AAEM) copolymers. Meanwhile, the fluorescent colors of resultant coordinated Cell- g -P(THFA- co -AAEM) copolymers can be systematically manipulated by adjusting the Tb 3+ /Eu 3+ ratio, enabling the wide applications in the fields of anti-counterfeiting, wearables devices, and smart labels. The marriage of different kinds of renewable resources and lanthanide coordination can inspire the development of fantastic sustainable elastomers with unique functions via elaborate molecular design. Declarations Acknowledgments This work was financially supported by the National Natural Science Foundation of China (Grants 51603199 and 32471428). We thank the Shanghai Synchrotron Radiation Facility (SSRF) of BL16B1 (https://cstr.cn/31124.02.SSRF.BL16B1) and the User Experiment Assist System for the assistance on SAXS measurements. Funding This work was financially supported by the National Natural Science Foundation of China (Grants 51603199 and 32471428). 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Carbohydr Polym:122385 Feng J, Xing Y, Yin C, Tang P, Jiang F (2024) Wholly sustainable graft copolymers derived from cellulose, lignin, and hemicellulose for high-performance elastomers, adhesives, and UV-blocking materials. Carbohydr Polym 326:121606 Garcia-Valdez O, Champagne P, Cunningham M F (2018) Graft modification of natural polysaccharides via reversible deactivation radical polymerization. Prog Polym Sci 76:151-173 Ge C, Hu R, Zhu J, Huang J, Zhang C, Zhang Y, Xing Y, Zhang B, Jiang F (2025) Combination of chitin, lignin, and plant oil for high-performance sustainable elastomers with UV-shielding and photothermal properties. Int J Biol Macromol 306:141553 Hu H, Cheng X, Wu Y, Chen M, Ma Z, Yang Q, Sijbesma R P, Ma Z (2024) Spirolactam and ESIPT in a double-network elastomer: multicolor mechanochromism and dual-ratiometric strain sensing in low and high tensile stress. 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Acc Chem Res 55:2291-2303 Luo T, Guo X, Qi J, Yu J, Lu C, Wang C, Chu F, Wang J (2024) Fabrication of liquid-free ionic conductive elastomer (ICE) from cellulose-rosin derived poly(esterimide) towards temperature-tolerant and solvent-resistant UV shadowless adhesive and sensor. Int J Biol Macromol 278:134921 Luo T, Qi J, Yu J, Wang C, Chu F, Wang J (2025) Lignin-based macromolecular photoinitiator for non‐migration, self‐adhesive, and water‐resistant eutectogels toward underwater reliable communication. Adv Funct Mater 35:2414481 Meier-Merziger M, Fotaras N, Tzourtzouklis I, Allouch C, Wagner M, Müller A H, Floudas G, Frey H (2024) One-step synthesis of fully biobased two-sided tapered ABA-type thermoplastic elastomers. ACS Sustainable Chem Eng Melendez-Zamudio M, Donahue-Boyle E, Chen Y, Brook M A (2023) Acrylated soybean oil: a key intermediate for more sustainable elastomeric materials from silicones. Green Chem 25:280-287 Odnoroh M, Ivanchenko O, Fleury G, Guerre M, Destarac M (2024) New generation of thermoplastic elastomers from narrowly dispersed all-(meth)acrylic ABA triblock copolymers made by RAFT. Macromolecules 57:9565-9575 Steube M, Johann T, Barent R D, Mueller A H, Frey H (2022) Rational design of tapered multiblock copolymers for thermoplastic elastomers. Prog Polym Sci 124:101488 Sun H, Wang X, Wang Z (2025) Grafting of nonpolar polyisoprene as midblock and polar polylactide as outer block onto cellulose to produce bio-based thermoplastic elastomers. Carbohydr Polym 348:122777 Tang S, Li J, Wang R, Zhang J, Lu Y, Hu G H, Wang Z, Zhang L (2022) Current trends in bio‐based elastomer materials. SusMat 2:2-33 Thomas J, Patil R S, Patil M, John J (2023) Addressing the sustainability conundrums and challenges within the polymer value chain. Sustainability 15:15758 Vahdati M, Hourdet D, Creton C (2023) Soft underwater adhesives based on weak molecular interactions. Prog Polym Sci 139:101649 Wanamaker C L, O'Leary L E, Lynd N A, Hillmyer M A, Tolman W B (2007) Renewable-resource thermoplastic elastomers based on polylactide and polymenthide. Biomacromolecules 8:3634-3640 Wang J, Zhang D, Chu F (2021) Wood‐derived functional polymeric materials. Adv Mater 33:2001135 Wang W, Lu W, Goodwin A, Wang H, Yin P, Kang N-G, Hong K, Mays J W (2019) Recent advances in thermoplastic elastomers from living polymerizations: Macromolecular architectures and supramolecular chemistry. Prog Polym Sci 95:1-31 Wang Z, Ganewatta M S, Tang C (2020) Sustainable polymers from biomass: Bridging chemistry with materials and processing. Prog Polym Sci 101:101197 Wang Z, Xu C, Qi L, Chen C (2024) Chemical modification of polysaccharides for sustainable bioplastics. Trends Chem 6:314-331 Wang Z, Yuan L, Tang C (2017) Sustainable elastomers from renewable biomass. Acc Chem Res 50:1762-1773 Wu X, Li M, Li H, Gao H, Wang Z, Wang Z (2024) Autonomous underwater self-healable adhesive elastomers enabled by dynamical hydrophobic phase-separated microdomains. Small 20:2311131 Wu X, Zhang J, Li H, Gao H, Wu M, Wang Z, Wang Z (2023) Dual-hard phase structures make mechanically tough and autonomous self-healable polyurethane elastomers. Chem Eng J 454:140268 Xu C, Yu J, Li B, Jia P, Lu C, Fan Y, Chu F (2025) Designing mechanically robust one-component nanocomposites via hyperbranched cellulose nanofibril grafted vegetable oil polymers. Carbohydr Polym 352:123131 Zanchin G, Leone G (2021) Polyolefin thermoplastic elastomers from polymerization catalysis: Advantages, pitfalls and future challenges. Prog Polym Sci 113:101342 Zhou Z, Shi B, Zhang C, Wang Y, Tang P, Feng J, Fan J, Jiang F, Ding Y (2025) High-performance sustainable polyester amide composites with persistent luminescence for multiple anti-counterfeiting. Chem Eng J 504:159007 Additional Declarations No competing interests reported. Cite Share Download PDF Status: Published Journal Publication published 11 Oct, 2025 Read the published version in Cellulose → Version 1 posted Editorial decision: Revision requested 19 Jun, 2025 Reviews received at journal 14 Jun, 2025 Reviews received at journal 13 Jun, 2025 Reviewers agreed at journal 05 Jun, 2025 Reviewers agreed at journal 05 Jun, 2025 Reviewers agreed at journal 04 Jun, 2025 Reviewers invited by journal 03 Jun, 2025 Editor assigned by journal 02 Jun, 2025 Submission checks completed at journal 16 May, 2025 First submitted to journal 15 May, 2025 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-6671184","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":467274503,"identity":"d42a0e17-8f03-4b2e-a56c-eb7500ee9d28","order_by":0,"name":"Rui Hu","email":"","orcid":"","institution":"Anhui Agricultural University","correspondingAuthor":false,"prefix":"","firstName":"Rui","middleName":"","lastName":"Hu","suffix":""},{"id":467274504,"identity":"027ddab3-ddf8-4455-bdad-0eecf4ee107f","order_by":1,"name":"Anjia Zheng","email":"","orcid":"","institution":"Anhui Agricultural University","correspondingAuthor":false,"prefix":"","firstName":"Anjia","middleName":"","lastName":"Zheng","suffix":""},{"id":467274505,"identity":"4fddecb6-0043-4281-9e44-6c4b95d8ab78","order_by":2,"name":"Cancan Zhang","email":"","orcid":"","institution":"Anhui Agricultural University","correspondingAuthor":false,"prefix":"","firstName":"Cancan","middleName":"","lastName":"Zhang","suffix":""},{"id":467274506,"identity":"24cf3cb9-9a90-4f01-9131-15cc779dc34f","order_by":3,"name":"Chuanxi Wang","email":"","orcid":"","institution":"Anhui Agricultural University","correspondingAuthor":false,"prefix":"","firstName":"Chuanxi","middleName":"","lastName":"Wang","suffix":""},{"id":467274507,"identity":"2c5af817-3095-4811-aeac-d72a04aef5ae","order_by":4,"name":"Jiaming Zhang","email":"","orcid":"","institution":"Anhui Agricultural University","correspondingAuthor":false,"prefix":"","firstName":"Jiaming","middleName":"","lastName":"Zhang","suffix":""},{"id":467274508,"identity":"5f306df4-0b2a-4089-adf7-117a54c28ddb","order_by":5,"name":"Chongxiao Ge","email":"","orcid":"","institution":"Anhui Agricultural University","correspondingAuthor":false,"prefix":"","firstName":"Chongxiao","middleName":"","lastName":"Ge","suffix":""},{"id":467274509,"identity":"5f32cdbe-6dd4-40f7-8a69-c3c72db896e4","order_by":6,"name":"Qing Li","email":"","orcid":"","institution":"Anhui Agricultural University","correspondingAuthor":false,"prefix":"","firstName":"Qing","middleName":"","lastName":"Li","suffix":""},{"id":467274510,"identity":"6ef09f64-80e2-4c83-ae8a-d6228ed72e99","order_by":7,"name":"Bin Zhang","email":"","orcid":"","institution":"Peking University","correspondingAuthor":false,"prefix":"","firstName":"Bin","middleName":"","lastName":"Zhang","suffix":""},{"id":467274511,"identity":"82b27397-b635-4511-89de-a0b062eecdc5","order_by":8,"name":"Feng Jiang","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA0UlEQVRIiWNgGAWjYBACxmYQaWPDYADmshGtJS2NBC0QkHaYBC3M7czPHn5JOC9vzn7GgOFD2WEG/tkNhBzGZm4sk3DbcGdPjgHjjHOHGSTuHCCkhcFMWvLHbcYNB3IMmHnbgC6USCCkhf2btETCOfsN598YMP8lTguPmeSHhAOJG24AbWEkUkuZNENCcvKGG88KDvacS+eRuEFAi2H/8W2SPxLsbDecT9744EeZtRz/DEJaGoABzQPlHABiHtxqoUAe5LgfBJWNglEwCkbBiAYAxGZCbAJML14AAAAASUVORK5CYII=","orcid":"","institution":"Anhui Agricultural University","correspondingAuthor":true,"prefix":"","firstName":"Feng","middleName":"","lastName":"Jiang","suffix":""}],"badges":[],"createdAt":"2025-05-15 09:38:33","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6671184/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6671184/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s10570-025-06809-z","type":"published","date":"2025-10-11T15:57:05+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":84083471,"identity":"29be2fcb-20cf-4c34-b34a-7bb83196b05b","added_by":"auto","created_at":"2025-06-06 14:29:56","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":304050,"visible":true,"origin":"","legend":"\u003cp\u003eScheme of the synthesis of fluorescent Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers through RAFT polymerization and lanthanide coordination.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-6671184/v1/c8c41354bc38366e61f2ab24.png"},{"id":84081817,"identity":"f996f9b9-dca3-420b-ac35-4bafd4d795c4","added_by":"auto","created_at":"2025-06-06 14:21:56","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":147052,"visible":true,"origin":"","legend":"\u003cp\u003e(a) FT-IR spectra of microcrystalline cellulose, Cell-BiB, Cell-CTA, and Cell2.6-PAAEM180. \u003csup\u003e1\u003c/sup\u003eH NMR spectra of (b) Cell-BiB, (c) Cell-CTA, and (d) Cell2.6-PAAEM180.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-6671184/v1/0c104188f7fcef1f0554adbe.png"},{"id":84081813,"identity":"12b42e84-0234-480d-9f08-30e222639423","added_by":"auto","created_at":"2025-06-06 14:21:56","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":166497,"visible":true,"origin":"","legend":"\u003cp\u003e(a)\u003cstrong\u003e \u003c/strong\u003eTGA and (b) DTG curves of microcrystalline cellulose, Cell-BiB, Cell-CTA, and Cell2.6-PAAEM180. DSC curves of Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers synthesized with (c) different THFA/AAEM feed ratios and (d) the same THFA/AAEM feed ratio.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-6671184/v1/ba3455b36661ca506ee744a3.png"},{"id":84083469,"identity":"714a3063-fab2-4c5b-a802-2f91354a0cf0","added_by":"auto","created_at":"2025-06-06 14:29:56","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":148641,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Monotonic stress-strain curves, (b) toughness, and (c) Youngʹs modulus of Cell2.6-PAAEM60, Cell2.6-PAAEM180, Cell2.6-PAAEM210, Cell2.6-PAAEM300, and Cell2.7-PAAEM420. (d) Monotonic stress-strain curves, (e) toughness, and (f) Youngʹs modulus of Cell2.6-PAAEM180, Cell5.3-PAAEM180, and Cell11.9-PAAEM180.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-6671184/v1/7b8b1ace405ec66123159288.png"},{"id":84081816,"identity":"be0f96d1-1c47-4bed-aa73-98dc6a2f5d9d","added_by":"auto","created_at":"2025-06-06 14:21:56","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":324005,"visible":true,"origin":"","legend":"\u003cp\u003eCyclic stress-strain curves of (a) Cell2.6-PAAEM180, (b) Cell2.6-PAAEM210, (c) Cell2.6-PAAEM300, (d) Cell2.7-PAAEM420, (e) Cell5.3-PAAEM180, and (f) Cell11.9-PAAEM180. Changes of (g) elastic recovery, (h) hysteresis loss, and (i) hysteresis loss ratio with strain during extension-retraction cycles.\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-6671184/v1/f1579526291e099f05cfcadd.png"},{"id":84083762,"identity":"37fc3ff1-5ad6-4c27-b231-2a7f7603fe2b","added_by":"auto","created_at":"2025-06-06 14:37:56","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":91136,"visible":true,"origin":"","legend":"\u003cp\u003e1D SAXS profiles and 2D SAXS patterns of Cell2.6-PAAEM180, Cell5.3-PAAEM180, and Cell11.9-PAAEM180.\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-6671184/v1/cbd39564af2c07c239d3bc1d.png"},{"id":84083473,"identity":"2121d646-5c40-458c-8df8-9c6cf3940f53","added_by":"auto","created_at":"2025-06-06 14:29:56","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":99609,"visible":true,"origin":"","legend":"\u003cp\u003eAdhesion values of Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers prepared with (a) different AAEM/THFA feed ratios and (b) the same condition. (c) Photograph of a lifted weight of 5 kg with two steel plates adhered by a thin Cell2.6-AAEM210 film. \u0026nbsp;Preparation of fluorescent Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers via lanthanide coordination\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-6671184/v1/214605888b7d0955364d2eb2.png"},{"id":84081830,"identity":"b900d7da-568d-49b8-8f0b-cfdef7016815","added_by":"auto","created_at":"2025-06-06 14:21:56","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":329287,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Monotonic stress-strain curves of coordinated Cell2.6-PAAEM180 samples. (b) Emission spectra of Cell2.6-PAAEM180 and corresponding coordinated counterparts excited at 254 nm. (c) Photographs of Cell2.6-PAAEM180 and corresponding coordinated counterpart films under ambient light and UV irradiation at 254 nm.\u003c/p\u003e","description":"","filename":"8.png","url":"https://assets-eu.researchsquare.com/files/rs-6671184/v1/d15392cce8ca91cffee11704.png"},{"id":93419719,"identity":"74622c3c-a1b2-44ea-9cb4-53da1c7c62b9","added_by":"auto","created_at":"2025-10-13 16:06:29","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2195438,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6671184/v1/cf052752-c9f0-4ba4-b39a-457e37b6af60.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"Preparation of cellulose-based fluorescent elastomers via RAFT polymerization and lanthanide coordination","fulltext":[{"header":"Introduction","content":"\u003cp\u003eThermoplastic elastomers are essential engineering materials with outstanding stretchability and fantastic elasticity, which allows them to be used in automotive interior parts, seals, adhesives, sporting goods, medical devices, and electronics (Cater et al. \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2024\u003c/span\u003e; Jiang et al. \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; Liffland and Hillmyer \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e2021\u003c/span\u003e; Steube et al. \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e2022\u003c/span\u003e; Zanchin and Leone \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). With the rapid development of the global economy, the demand for elastomer materials is continuously increasing (Burelo et al. \u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e2024\u003c/span\u003e). However, traditional elastomers mostly rely on limited petroleum resources. In contrast, bio-based elastomers are made from sustainable biomass resources include corn, lignin, soybean, cellulose, rosin, chitin, and plant oils (Luo et al. \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e2024\u003c/span\u003e; Melendez-Zamudio et al. \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; Wanamaker et al. \u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e2007\u003c/span\u003e; Wang et al. \u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e2020\u003c/span\u003e; Wang et al. \u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). These materials are widely available and renewable, effectively alleviating the pressure caused by the scarcity of petroleum resources and ensuring the long-term stable supply of elastomers. Sustainable elastomers, throughout their entire lifecycle, from production and use to disposal, can significantly reduce carbon dioxide emissions compared to traditional petroleum-based elastomers (Ge et al. \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e2025\u003c/span\u003e; Tang et al. \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). The raw materials used in bio-based elastomers can absorb carbon dioxide from the atmosphere during their growth, thereby achieving carbon sequestration. This helps reduce greenhouse gas emissions and aligns with the low-carbon economy and sustainable development goals (Thomas et al. \u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e2023\u003c/span\u003e). The achievement of bio-based elastomers can provide new opportunities and approaches for designing novel elastomer materials with unique properties and functions.\u003c/p\u003e \u003cp\u003eIn general, the mechanical properties of elastomers, such as tensile strength, extensibility, elasticity, and Youngʹs modulus, are primarily determined by the choice of monomers, compositions, architectures, microphase-separated morphologies, and network structures formed by the covalent/noncovalent interactions (Li et al. \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; Wu et al. \u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e2024\u003c/span\u003e; Wu et al. \u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e2023\u003c/span\u003e). In recent years, sustainable polymers with linear and nonlinear topological structures have been reported as bio-based elastomers (Jeong et al. \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; Liffland et al. \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; Meier-Merziger et al. \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e2024\u003c/span\u003e; Odnoroh et al. \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e2024\u003c/span\u003e; Sun et al. \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e2025\u003c/span\u003e). It has been demonstrated that graft elastomers exhibit dramatically improved mechanical performance compared to their linear counterparts with similar compositions (Jiang et al. \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e2019\u003c/span\u003e; Jiang et al. \u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e2013\u003c/span\u003e; Li et al. \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e2021\u003c/span\u003e; Wang et al. \u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e2019\u003c/span\u003e). As the most promising natural biomacromolecule, cellulose offers the advantages of renewability, biodegradability, and excellent biocompatibility (Dang et al. \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e2024\u003c/span\u003e; Wang et al. \u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e2024\u003c/span\u003e). Owing to the existence of plentiful hydroxyl groups, cellulose can be modified into various derivatives via different strategies conveniently, promoting the preparation of cellulose-based copolymers through controlled radical polymerization methods (Garcia-Valdez et al. \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e2018\u003c/span\u003e; Kumar et al. \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e2021\u003c/span\u003e; Wang et al. \u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). In recent years, renewable monomers derived from plant oils, lignin, rosin, and hemicellulose have been utilized to prepare cellulose graft copolymers with tunable properties (Cheng et al. \u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e2019\u003c/span\u003e; Feng et al. \u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e2024\u003c/span\u003e; Xu et al. \u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e2025\u003c/span\u003e). Tetrahydrofurfuryl acrylate (THFA) is a typical polymerizable hemicellulose-derived monomer, which is an ideal candidate for soft petroleum-based segments in elastomers (Luo et al. \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e2025\u003c/span\u003e; Odnoroh et al. \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e2024\u003c/span\u003e). The integration of cellulose and sustainable monomers can inspire the further advancement of renewable elastomers with specific performance and application demands. Combining the excellent mechanical performance of elastomers and the fluorescence of chromophores under specific wavelengths of light, fluorescent elastomers are widely extensively used in the fields of fluorescence sensing, anti-counterfeiting, information encryption, and smart devices (Hu et al. \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e2024\u003c/span\u003e; Huang et al. \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e2024\u003c/span\u003e; Li et al. \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e2025\u003c/span\u003e; Lu et al. \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e2022\u003c/span\u003e; Zhou et al. \u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e2025\u003c/span\u003e). Therefore, it is essential to produce fluorescent cellulose graft copolymer elastomers via rational design for advanced materials.\u003c/p\u003e \u003cp\u003eHerein, sustainable cellulose-\u003cem\u003egraft\u003c/em\u003e-poly(tetrahydrofurfuryl acrylate-\u003cem\u003eco\u003c/em\u003e-2-(methacryloyloxy)ethyl acetoacetate) (Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM)) copolymer elastomers were prepared as illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, where rubbery P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) side chains were grafted from rigid cellulose backbone by homogeneous reversible addition-fragmentation chain transfer (RAFT) polymerization. In this design, the cellulose backbone can act as multiple cross-linking points to prevent the side chains from flowing under external stress, while the AAEM repeating unit can play the role of ligand to coordinate lanthanide ions, such as terbium (Tb\u003csup\u003e3+\u003c/sup\u003e) and europium (Eu\u003csup\u003e3+\u003c/sup\u003e) ions, to provide additional physical cross-linked network structure as well as unique fluorescent property for the resultant elastomeric materials. We suppose the incorporation of Tb\u003csup\u003e3+\u003c/sup\u003e and Eu\u003csup\u003e3+\u003c/sup\u003e ions via lanthanide coordination can effectively improve the mechanical properties of cellulose-based copolymers and endow them with tunable fluorescent properties. This strategy combines renewable biomass and lanthanide coordination to achieve luminescent bio-based elastomers with tunable performance can accelerate the vigorous development of renewable polymeric materials.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e"},{"header":"Materials and methods","content":"\u003cp\u003eMaterials\u003c/p\u003e \u003cp\u003eMicrocrystalline cellulose (Avicel PH-101) with a degree of polymerization of 128 was purchased from Sigma-Aldrich. 1-Allyl-3-methylimidazolium chloride (AMIMCl), \u003cem\u003eN,N\u003c/em\u003e-dimethylformamide (DMF), 1,4-dioxane, dimethyl sulfoxide (DMSO), tetrahydrofurfuryl acrylate (THFA), 2-(methacryloyloxy)ethyl acetoacetate (AAEM), 2-bromoisobutyryl bromide, carbon disulfide, 1-butanethiol, triethylamine, 2,2ʹ-azobis(2-methylpropionitrile) (AIBN), terbium nitrate pentahydrate (Tb(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e\u0026middot;5H\u003csub\u003e2\u003c/sub\u003eO), and europium nitrate hexahydrate (Eu(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO) were purchased from Aladdin (Shanghai, China). The inhibitors in THFA and AAEM were removed prior to use.\u003c/p\u003e \u003cp\u003eSynthesis of cellulose-based macromolecular chain transfer agent (Cell-CTA)\u003c/p\u003e \u003cp\u003eMicrocrystalline cellulose (5.0 g, 30.9 mmol) and AMIMCl (100.0 g) were introduced into a flask (250 mL capacity) and stirred at 100 \u003csup\u003eo\u003c/sup\u003eC until cellulose was fully dissolved. DMF (50 mL) was added into the cellulose solution with stirring and cooled to room temperature. Then 2-bromoisobutyryl bromide (63.9 g, 277.9 mmol) was added dropwise to the cellulose solution in ice water. After 24 h reaction at room temperature, the resulting mixture was precipitated in deionized water (2 L). The cellulose-based macroinitiator (Cell-BiB) was collected, washed thoroughly with deionized water, and dried in vacuum at 60 \u003csup\u003eo\u003c/sup\u003eC until a constant weight was reached. To prepare Cell-CTA, Cell-BiB (4.9 g, 22.0 mmol of Br) was dispersed in 100 mL of DMSO with stirring at 40 \u003csup\u003eo\u003c/sup\u003eC to form a clear solution. 1-Butanethiol (0.50 g, 5.5 mmol) and triethylamine (0.56 g, 5.5 mmol) were mixed and stirred in DMSO (20 mL) for 30 min at room temperature, followed by the addition of carbon disulfide (1.26 g, 16.5 mmol). After 30 min, the solutions were mixed and reacted for 12 h at 40 \u003csup\u003eo\u003c/sup\u003eC. The solution was poured into deionized water (2 L) to precipitate Cell-CTA. The product was further dried at 60 \u003csup\u003eo\u003c/sup\u003eC for 12 h under vacuum.\u003c/p\u003e \u003cp\u003eSynthesis of Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers\u003c/p\u003e \u003cp\u003eCell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers were prepared as follows. Cell-CTA (36.2 mg), THFA (1.64 g, 10.5 mmol), AAEM (1.0 g, 4.5 mmol), AIBN (0.4 mg, 0.0025 mmol), 1,4-dioxane (8 mL), DMF (2 mL), and a stirring bar were added into a 25 mL Schlenk flask. The flask was immersed in an oil bath preset at 70 \u003csup\u003eo\u003c/sup\u003eC after three freezing-vacuum-thawing cycles. After a certain time, the flask was taken out and the mixture was poured into methanol (150 mL). The precipitated product was collected, washed, and dried under vacuum at 60 \u003csup\u003eo\u003c/sup\u003eC overnight. Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers with varied AAEM/THFA feed ratios were prepared in the same way as summarized in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) film was obtained by dissolving the sample in THF with a concentration of 10 wt% and evaporating the solvent in a Teflon mold in air. The resultant film was further dried in an oven under vacuum at 40 \u003csup\u003eo\u003c/sup\u003eC overnight.\u003c/p\u003e \u003cp\u003ePreparation of fluorescent Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers\u003c/p\u003e \u003cp\u003eTypically, Cell2.6-PAAEM180 (1.0 g) was dissolved in tetrahydrofuran (20 mL), and then Tb(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e\u0026middot;5H\u003csub\u003e2\u003c/sub\u003eO (0.27 g, 0.62 mmol) was added and stirred for 12 h. The resultant solution was added into a Teflon mold and dried to obtain the free-standing film. The film was further dried in an oven under vacuum at 40 \u003csup\u003eo\u003c/sup\u003eC overnight. Films with varied Tb\u003csup\u003e3+\u003c/sup\u003e/Eu\u003csup\u003e3+\u003c/sup\u003e ratios were achieved similarly.\u003c/p\u003e \u003cp\u003eCharacterization\u003c/p\u003e \u003cp\u003eThe chemical structures of samples were examined by Nicolei 6670 Fourier transform infrared (FT-IR) spectrometer and Agilent DD2 600MHz nuclear magnetic resonance (NMR) spectrometer. A thermogravimetric analyzer (TGA 55, TA instruments) and differential scanning calorimeter (DSC 250, TA instruments) were used to investigate the thermal decomposition temperatures and glass transition temperatures of the samples. TGA curves were recorded from 40 to 700 \u003csup\u003eo\u003c/sup\u003eC under a nitrogen atmosphere with a heating rate of 10 \u003csup\u003eo\u003c/sup\u003eC/min. For DSC measurement, the \u003cem\u003eT\u003c/em\u003e\u003csub\u003eg\u003c/sub\u003e value was determined using the heating curves from \u0026minus;\u0026thinsp;50 to 150 \u003csup\u003eo\u003c/sup\u003eC with a heating rate of 10 \u003csup\u003eo\u003c/sup\u003eC/min under a nitrogen atmosphere. Monotonic and cyclic stress-strain curves were recorded on a Suns UTM2502 universal testing machine. The tensile speed was set at 50 mm/min during the measurements. For adhesion tests, the specimens with a thickness of 0.15 nm were cut into sheets (25 mm \u0026times; 12.5 mm) and then sandwiched between the steel plates. The steel plates were secured using dovetail clamps and heated at 150 \u003csup\u003eo\u003c/sup\u003eC for 3 h under vacuum in the oven. Small-angle X-ray scattering (SAXS) measurements were conducted at the synchrotron beamline BL16B1 with the X-ray wavelength of 0.124 nm at Shanghai Synchrotron Radiation Facility (SSRF), China. Hitachi F-7000 fluorescence spectrophotometer was used to investigate the fluorescent behavior of coordinated Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers.\u003c/p\u003e"},{"header":"Results and discussion","content":"\u003cp\u003ePreparation of Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers\u003c/p\u003e\n\u003cp\u003eAs depicted in Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ea, the FT-IR spectrum of Cell-BiB exhibits a distinct absorption band around 1740 cm\u003csup\u003e-1\u003c/sup\u003e corresponding to the C\u0026thinsp;=\u0026thinsp;O groups. Meanwhile, it can be observed that the absorption band of hydroxyl groups on Cell-BiB becomes much weaker than that of pristine cellulose, suggesting the formation of ester bonds on cellulose. Cell-CTA shows a similar FT-IR spectrum to that of Cell-BiB, but the absorption bands ranging from 3000 to 2800 cm\u003csup\u003e-1\u003c/sup\u003e corresponding to the C-H stretching vibration are more potent due to the incorporation of \u003cem\u003en\u003c/em\u003e-butyl groups. Figure\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003eb displays the \u003csup\u003e1\u003c/sup\u003eH NMR spectrum of Cell-BiB in deuterated acetone, in which the signals located around 5.3 ppm and 1.9\u0026ndash;1.6 ppm are assigned to the cellulose protons at the C1 position and methyl protons of 2-bromoisobutyrylate groups, respectively. As shown in Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ec, the new peaks appear at 1.0-0.8 ppm can be ascribed to the methyl protons of butyl groups. From the above \u003csup\u003e1\u003c/sup\u003eH NMR spectra, the degree of substitutions of Cell-BiB (\u003cem\u003eDS\u003c/em\u003e\u003csub\u003eBiB\u003c/sub\u003e) and Cell-CTA (\u003cem\u003eDS\u003c/em\u003e\u003csub\u003eCTA\u003c/sub\u003e) can be obtained according to the following equations\u003c/p\u003e\n\u003cdiv id=\"Equ1\" class=\"Equation\"\u003e\n \u003cdiv class=\"mathdisplay\" id=\"FileID_Equ1\" name=\"EquationSource\"\u003e$$D{S_{\\text{B}\\text{i}\\text{B}}}=\\frac{{{I_\\text{b}}}}{{6{I_\\text{a}}}}$$\u003c/div\u003e\n \u003cdiv class=\"EquationNumber\"\u003e1\u003c/div\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Equ2\" class=\"Equation\"\u003e\n \u003cdiv class=\"mathdisplay\" id=\"FileID_Equ2\" name=\"EquationSource\"\u003e$$D{S_{\\text{C}\\text{T}\\text{A}}}=\\frac{{I\\text{c}}}{{3{I_\\text{a}}}}$$\u003c/div\u003e\n \u003cdiv class=\"EquationNumber\"\u003e2\u003c/div\u003e\n\u003c/div\u003e\n\u003cp\u003ewhere \u003cem\u003eI\u003c/em\u003e\u003csub\u003ea\u003c/sub\u003e, \u003cem\u003eI\u003c/em\u003e\u003csub\u003eb\u003c/sub\u003e, and \u003cem\u003eI\u003c/em\u003e\u003csub\u003ec\u003c/sub\u003e represent the integral areas of -CH protons of cellulose, methyl protons of 2-bromoisobutyrylate group, and methyl protons of butyl groups, respectively. Hence, the degree of substitutions of Cell-BiB and Cell-CTA are calculated to be 2.2 and 0.36, respectively. Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers with tunable compositions were synthesized through RAFT polymerization by changing the THFA/AAEM feed ratios. Figure \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ed plots the \u003csup\u003e1\u003c/sup\u003eH NMR spectrum of Cell2.6-PAAEM180, the signals located at 3.6 and 3.72 ppm are assigned to the CH\u003csub\u003e2\u003c/sub\u003e protons on AAEM and THFA repeating units, respectively, which can be further used to determine the PTHFA/PAAEM ratio in the copolymer. The detailed information for prepared Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers are listed in Table\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e.\u003c/p\u003e\n\u003cdiv class=\"gridtable\"\u003e\u0026nbsp;\u003ctable id=\"Tab1\" border=\"1\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eDetailed information for prepared Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers.\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003ccolgroup cols=\"7\"\u003e\u003c/colgroup\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eSample\u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eFeed ratio\u003csup\u003eb\u003c/sup\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eCellulose content (wt%)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003ePTHFA content\u003csup\u003ec\u003c/sup\u003e (wt%)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003ePAAEM content\u003csup\u003ec\u003c/sup\u003e (wt%)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e\u003cem\u003eM\u003c/em\u003e\u003csub\u003en,th\u003c/sub\u003e (grafts)\u003csup\u003ec\u003c/sup\u003e (kDa)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e\u003cem\u003eT\u003c/em\u003e\u003csub\u003eg\u003c/sub\u003e\u003csup\u003ed\u003c/sup\u003e (\u003csup\u003eo\u003c/sup\u003eC)\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCell2.6-PAAEM60\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1:540:60\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e2.6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e82.7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e14.7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e74.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e-1.4\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCell2.6-PAAEM180\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1:420:180\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e2.6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e57.8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e39.6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e73.0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e5.8\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCell5.3-PAAEM180\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1:420:180\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e5.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e56.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e38.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e35.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e7.7\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCell11.9-PAAEM180\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1:420:180\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e11.9\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e52.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e35.8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e14.6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e9.1\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCell2.6-PAAEM210\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1:390:210\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e2.6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e50.0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e47.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e75.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e7.3\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCell2.6-PAAEM300\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1:300:300\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e2.6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e41.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e56.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e73.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e10.7\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCell2.7-PAAEM420\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1:180:420\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e2.7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e20.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e77.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e71.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e14.0\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003c/table\u003e\n\u003c/div\u003e\n\u003cp\u003e\u003csup\u003ea\u003c/sup\u003e The numbers after \u0026ldquo;Cell\u0026rdquo; and \u0026ldquo;AAEM\u0026rdquo; are the cellulose content and the molar ratio of the total amount of AAEM/monomers, respectively.\u003c/p\u003e\n\u003cp\u003e\u003csup\u003eb\u003c/sup\u003e Feed ratio: Cell-CTA /AAEM/THFA.\u003c/p\u003e\n\u003cp\u003e\u003csup\u003ec\u003c/sup\u003e Determined by \u003csup\u003e1\u003c/sup\u003eH NMR measurements.\u003c/p\u003e\n\u003cp\u003e\u003csup\u003ed\u003c/sup\u003e Measured from DSC heat flow curves.\u003c/p\u003e\n\u003cp\u003eThermal properties of Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers\u003c/p\u003e\n\u003cp\u003eThe TGA and DTG curves for cellulose, Cell-BiB, Cell-CTA, and Cell2.6-PAAEM180 are shown in Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ea and \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003eb. Pristine cellulose is thermally stable with an onset decomposition temperature (\u003cem\u003eT\u003c/em\u003e\u003csub\u003ed 5%\u003c/sub\u003e) of 294\u0026deg;C and a maximum decomposition temperature (\u003cem\u003eT\u003c/em\u003e\u003csub\u003emax\u003c/sub\u003e) of 319\u0026deg;C. Cell-BiB and Cell-CTA show reduced \u003cem\u003eT\u003c/em\u003e\u003csub\u003ed 5%\u003c/sub\u003e and \u003cem\u003eT\u003c/em\u003e\u003csub\u003emax\u003c/sub\u003e values after introducing unstable bromine and trithiocarbonate groups. The \u003cem\u003eT\u003c/em\u003e\u003csub\u003ed 5%\u003c/sub\u003e and \u003cem\u003eT\u003c/em\u003e\u003csub\u003emax\u003c/sub\u003e values for Cell-CTA are 243 \u003csup\u003eo\u003c/sup\u003eC and 275 \u003csup\u003eo\u003c/sup\u003eC, respectively, which are much lower than those of the pristine cellulose. Cell2.6-PAAEM180 exhibits a two-stage decomposition behavior with two \u003cem\u003eT\u003c/em\u003e\u003csub\u003emax\u003c/sub\u003e values of 278 \u003csup\u003eo\u003c/sup\u003eC and 392 \u003csup\u003eo\u003c/sup\u003eC, respectively. As depicted in Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ec, when the AAEM/THFA feed ratio increases, the \u003cem\u003eT\u003c/em\u003e\u003csub\u003eg\u003c/sub\u003e vale rises from \u0026minus;\u0026thinsp;1.4\u0026deg;C for Cell2.6-PAAEM60 to 14\u0026deg;C for Cell2.7-PAAEM420 due to the increased PAAEM content in the resultant copolymers. Figure \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ed displays the DSC curves of Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers synthesized with the same condition but different cellulose contents. Note that the \u003cem\u003eT\u003c/em\u003e\u003csub\u003eg\u003c/sub\u003e value rises from 5.8\u0026deg;C for Cell2.6-PAAEM180 to 9.1\u0026deg;C for Cell11.9-PAAEM180 with the increase of cellulose content. It can be found that the rigid PAAEM content decreases from 57.8 wt% for Cell2.6-PAAEM180 to 56.2 wt% for Cell5.3-PAAEM180 and 52.3 wt% for Cell11.9-PAAEM180, respectively. Therefore, the increase of \u003cem\u003eT\u003c/em\u003e\u003csub\u003eg\u003c/sub\u003e values for Cell2.6-PAAEM180, Cell5.3-PAAEM180, and Cell11.9-PAAEM180 is attributed to the higher cellulose content, which reduces the flexibility of P(AAEM-\u003cem\u003eco\u003c/em\u003e-TFHA) side chains significantly. These findings indicate that the \u003cem\u003eT\u003c/em\u003e\u003csub\u003eg\u003c/sub\u003e values of Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers can be facilely manipulated by tuning the THFA/AAEM feed ratio and cellulose content in the preparation process.\u003c/p\u003e\n\u003cp\u003eMechanical performance of Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers\u003c/p\u003e\n\u003cp\u003eAs shown in Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ea, the stress at break value rises sharply from 0.08 MPa for Cell2.6-PAAEM60 to 3.5 MPa for Cell2.7-PAAEM420, while the elongation decreases from 1417% for Cell2.6-PAAEM60 to 195% for Cell2.7-PAAEM420 when the THFA/AAEM feed ratio decreases. Figure \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003eb indicates that the tensile toughness values for Cell2.6-PAAEM60, Cell2.6-PAAEM180, Cell2.6-PAAEM210, Cell2.6-PAAEM300, and Cell2.7-PAAEM420 are 2.7, 7.0, 12.0, 4.7, and 3.6 MJ/m\u0026sup3;, respectively. Obviously, Cell2.6-PAAEM210 exhibits the highest tensile toughness by comprising tensile strength and extensibility. The increase of AAEM ratio in the feed monomers leads to higher PAAEM content in Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymer, resulting in improved Youngʹs modulus as displayed in Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ec. Figure \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ed shows the monotonic stress-strain curves of Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers prepared in the same condition but varied cellulose contents. It can be found that the ultimate tensile strength grows from 0.5 MPa (Cell2.6-PAAEM180) to 6.0 MPa (Cell11.9-PAAEM180) as the cellulose content increases from 2.6 to 11.9 wt%, while the strain at break decreases from 1192% (Cell2.6-PAAEM180) to 303% (Cell11.9-PAAEM180). Both the tensile toughness and the Youngʹs modulus rise with increasing cellulose content as illustrated in Figs. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ee and \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ef, indicating that higher cellulose content results in well-improved tensile strength, toughness, and Young\u0026apos;s modulus. The detailed mechanical property parameters during monotonic tensile tests are listed in Table\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e.\u003c/p\u003e\n\u003cdiv class=\"gridtable\"\u003e\u0026nbsp;\u003ctable id=\"Tab2\" border=\"1\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eDetailed mechanical property parameters for Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003ccolgroup cols=\"5\"\u003e\u003c/colgroup\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eSample\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eStress at break (MPa)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eStrain at break\u003c/p\u003e\n \u003cp\u003e(%)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eTensile toughness (MJ/m\u003csup\u003e3\u003c/sup\u003e)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eYoungʹs modulus (MPa)\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCell2.6-PAAEM60\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.08\u0026thinsp;\u0026plusmn;\u0026thinsp;0.01\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1417\u0026thinsp;\u0026plusmn;\u0026thinsp;149\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e2.7\u0026thinsp;\u0026plusmn;\u0026thinsp;0.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.06\u0026thinsp;\u0026plusmn;\u0026thinsp;0.01\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCell2.6-PAAEM180\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.5\u0026thinsp;\u0026plusmn;\u0026thinsp;0.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1192\u0026thinsp;\u0026plusmn;\u0026thinsp;138\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e7.0\u0026thinsp;\u0026plusmn;\u0026thinsp;0.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.2\u0026thinsp;\u0026plusmn;\u0026thinsp;0.02\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCell5.3-PAAEM180\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e3.1\u0026thinsp;\u0026plusmn;\u0026thinsp;0.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e415\u0026thinsp;\u0026plusmn;\u0026thinsp;47\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e9.6\u0026thinsp;\u0026plusmn;\u0026thinsp;0.6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1.9\u0026thinsp;\u0026plusmn;\u0026thinsp;0.1\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCell11.9-PAAEM180\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e6.0\u0026thinsp;\u0026plusmn;\u0026thinsp;0.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e303\u0026thinsp;\u0026plusmn;\u0026thinsp;52\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e13.0\u0026thinsp;\u0026plusmn;\u0026thinsp;0.8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e4.3\u0026thinsp;\u0026plusmn;\u0026thinsp;0.2\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCell2.6-PAAEM210\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1.2\u0026thinsp;\u0026plusmn;\u0026thinsp;0.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1039\u0026thinsp;\u0026plusmn;\u0026thinsp;58\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e12.0\u0026thinsp;\u0026plusmn;\u0026thinsp;0.7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.4\u0026thinsp;\u0026plusmn;\u0026thinsp;0.03\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCell2.6-PAAEM300\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e2.6\u0026thinsp;\u0026plusmn;\u0026thinsp;0.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e331\u0026thinsp;\u0026plusmn;\u0026thinsp;32\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e4.7\u0026thinsp;\u0026plusmn;\u0026thinsp;0.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.9\u0026thinsp;\u0026plusmn;\u0026thinsp;0.05\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCell2.7-PAAEM420\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e3.5\u0026thinsp;\u0026plusmn;\u0026thinsp;0.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e192\u0026thinsp;\u0026plusmn;\u0026thinsp;14\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e3.7\u0026thinsp;\u0026plusmn;\u0026thinsp;0.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1.7\u0026thinsp;\u0026plusmn;\u0026thinsp;0.1\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003c/table\u003e\n\u003c/div\u003e\n\u003cp\u003eBesides tensile tests, cyclic tensile tests were performed to reveal the elasticity and hysteresis behavior of Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers. During the cyclic tensile deformation, the film sample was stretched to 25% strain, 50% strain, and so on up to 200% strain at a 50 mm/min tensile speed. The stretching direction was reversed when the desired strain was reached, the film sample was released to zero stress with a 50 mm/min retraction speed. The cyclic stretching-retraction process was stopped when 200% strain was achieved. Figure \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003ea-f exhibits the cyclic stress-strain curves of Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers. It should be noted that Cell2.6-PAAEM60 was too weak to perform stepwise cyclic tensile testing. Noticeably, the residual strain at zero stress during the retraction process increases with the maximum strain due to the presence of unrecoverable plastic deformation during the extension process. Both elastic and plastic deformations are present when the film sample is stretched, to evaluate the elasticity of Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers, the elastic recovery (ER) values during cyclic tensile tests are calculated as reported (Jiang et al. \u003cspan class=\"CitationRef\"\u003e2015\u003c/span\u003e). The evolutions of ER values during extension-retraction cycles for Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers are displayed in Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003eg. Data show that the ER value in each cycle increases with the maximum strain and can even exceed 80% after several loading-unloading cycles, suggesting that the elasticity of Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers can be significantly improved by such kind of mechanical training strategy. Cell11.9-PAAEM180 shows the lowest ER values in the whole strain range on account of its highest cellulose content. The hysteresis loss (energy dissipation) value in each cycle can be measured by the integrated area of the hysteresis loop. The changes of hysteresis loss with the maximum strain are depicted in Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003eh, which implies that the increase of PAAEM and cellulose contents leads to the dramatical increase of hysteresis loss due to the occurrence of chain friction during extension. As shown in Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003ei, Cell11.9-PAAEM180 displays the highest hysteresis loss rate after two extension-retraction cycles, which means that higher cellulose content can promote more plastic deformation and energy dissipation, resulting in higher hysteresis loss rate. Overall, the macroscopic mechanical properties of Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers, including tensile strength, elongation, toughness, Youngʹs modulus, elasticity, and hysteresis loss, can be conveniently regulated by manipulating the compositions during polymerization.\u003c/p\u003e\n\u003cp\u003eMorphology of Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers\u003c/p\u003e\n\u003cp\u003eThe microstructure of Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers was examined using SAXS measurements. Figure \u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003e shows the 2D SAXS patterns and corresponding intensity profiles of Cell2.6-PAAEM180, Cell5.3-PAAEM180, and Cell11.9-PAAEM180. Note that only weak and diffuse scattering patterns can be observed, illustrating the absence of microphase-separated structure in the graft copolymers. Although Cell11.9-PAAEM180 possesses the highest cellulose content of 11.9 wt%, the rigid cellulose chains are highly extended by the side chains, preventing the formation of well-ordered aggregates by cellulose in the matrix.\u003c/p\u003e\n\u003cp\u003eAdhesion behavior of Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers\u003c/p\u003e\n\u003cp\u003eFor adhesives, their adhesion properties are strongly related to the cohesion and the interfacial interactions between adhesives and the interfaces. By tuning the adhesion performance, adhesives can find applications in glues, food packages, electronic devices, sticky notes, and automotive industries (Vahdati et al. \u003cspan class=\"CitationRef\"\u003e2023\u003c/span\u003e). To improve the adhesion behavior, nanofillers, nonlinear topologies, covalent bonds, and noncovalent interactions have been utilized to design strong adhesives. Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers have the advantages of branched architecture and renewability, they are excellent candidates for traditional petroleum-based adhesives. Figure\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e7\u003c/span\u003ea displays the shear strength values of Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers prepared with different THFA/AAEM feed ratios, in which it can be found that Cell2.6-PAAEM210 shows the highest shear strength of 2.3 MPa. Figure\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e7\u003c/span\u003eb exhibits the shear strength values of cellulose graft copolymers prepared in the same condition but varied cellulose contents, and Cell11.9-PAAEM180 possesses the highest shear strength of 2.5 MPa. The adhesion behavior of such kind of cellulose-based copolymers can be facilely adjusted by changing their compositions. As illustrated in Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e7\u003c/span\u003ec, a weight of 5 kg can be easily lifted and sustained by the steel plates, proving the potential application in hot-melt adhesives.\u003c/p\u003e\n\u003cp\u003ePreparation of fluorescent Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers via lanthanide coordination\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eLanthanide coordination was used to improve the mechanical performance and adjusting the fluorescent behavior of coordinated Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers, and thus Tb\u003csup\u003e3+\u003c/sup\u003e ion and Eu\u003csup\u003e3+\u003c/sup\u003e ions were selected to coordinate with the \u003cem\u003eb\u003c/em\u003e-diketone groups in THFA repeating units. Different amounts of Tb\u003csup\u003e3+\u003c/sup\u003e and Eu\u003csup\u003e3+\u003c/sup\u003e ions were incorporated into Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers to form lanthanide coordination with \u003cem\u003eb\u003c/em\u003e-diketone groups as summarized in Table \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e. It should be noted that the molar ratio between lanthanide (La\u003csup\u003e3+\u003c/sup\u003e) ions and \u003cem\u003eb\u003c/em\u003e-diketone groups in each sample was controlled to be 1/3. As shown in Fig. \u003cspan class=\"InternalRef\"\u003e8\u003c/span\u003ea and Table \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e, the stress at break values of coordinated Cell2.6-PAAEM180 samples exhibit significantly enhanced tensile strength values compared to that of pristine Cell2.6-PAAEM180, which is only 0.5 MPa. As depicted in \u003cstrong\u003eFig. S1\u003c/strong\u003e, the \u003cem\u003eT\u003c/em\u003e\u003csub\u003eg\u003c/sub\u003e values for coordinated Cell2.6-PAAEM180 samples are located in the range from 44.4 to 47.0 \u003csup\u003eo\u003c/sup\u003eC, which are much higher than that of Cell2.6-PAAEM180 (5.8 \u003csup\u003eo\u003c/sup\u003eC). In general, the \u003cem\u003eT\u003c/em\u003e\u003csub\u003eg\u003c/sub\u003e value is determined by the flexibility of the polymer chains. In this case, the formation of lanthanide coordination between lanthanide ions and \u003cem\u003eb\u003c/em\u003e-diketone groups can reduce the chain movement of the side chains, resulting in higher \u003cem\u003eT\u003c/em\u003e\u003csub\u003eg\u003c/sub\u003e. However, as plotted in \u003cstrong\u003eFig. S2\u003c/strong\u003e, the SAXS results suggest that these coordinated Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers still show featureless structure without any distinct microphase-separated morphology, revealing that the improved mechanical properties of Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers are attributed to the coordinated networks and increased \u003cem\u003eT\u003c/em\u003e\u003csub\u003eg\u003c/sub\u003e values. Figure \u003cspan class=\"InternalRef\"\u003e8\u003c/span\u003eb shows the emission spectra of coordinated Cell2.6-PAAEM180 samples with different amounts of Tb\u003csup\u003e3+\u003c/sup\u003e and Eu\u003csup\u003e3+\u003c/sup\u003e ions excited at 254 nm, where the strong green and red emissions located at 547 nm and 620 nm are corresponding to the \u003csup\u003e5\u003c/sup\u003eD\u003csub\u003e4\u003c/sub\u003e-\u003csup\u003e7\u003c/sup\u003eF\u003csub\u003e5\u003c/sub\u003e deexcitation of Tb\u003csup\u003e3+\u003c/sup\u003e ions and \u003csup\u003e5\u003c/sup\u003eD\u003csub\u003e0\u003c/sub\u003e-\u003csup\u003e7\u003c/sup\u003eF\u003csub\u003e2\u003c/sub\u003e deexcitation of Eu\u003csup\u003e3+\u003c/sup\u003e ions, respectively. No emission signal can be observed for pristine Cell2.6-PAAEM180, indicating that the fluorescent performance is attributed to the incorporated Tb\u003csup\u003e3+\u003c/sup\u003e and Eu\u003csup\u003e3+\u003c/sup\u003e ions. To visually illustrate the fluorescent behavior of coordinated Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers, the film samples were cut into different shapes and assembled as shown in Fig. \u003cspan class=\"InternalRef\"\u003e8\u003c/span\u003ec. Noticeably, all the films are transparent under ambient light without any color. When irradiated with UV light of 254 nm, the coordinated films exhibit varied luminescent colors depend on the amount of Tb\u003csup\u003e3+\u003c/sup\u003e and Eu\u003csup\u003e3+\u003c/sup\u003e ions, indicating extraordinary fluorescent performance.\u003c/p\u003e\n\u003cdiv class=\"gridtable\"\u003e\u0026nbsp;\u003ctable id=\"Tab3\" border=\"1\" class=\"fr-table-selection-hover\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 3\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eMechanical properties of coordinated Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003ccolgroup cols=\"5\"\u003e\u003c/colgroup\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eSample\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eMolar ratio of Tb\u003csup\u003e3+\u003c/sup\u003e/La\u003csup\u003e3+\u003c/sup\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eMolar ratio of La\u003csup\u003e3+\u003c/sup\u003e/\u003cem\u003e\u0026beta;\u003c/em\u003e-diketone groups\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eStress at break\u003c/p\u003e\n \u003cp\u003e(MPa)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eStrain at break\u003c/p\u003e\n \u003cp\u003e(%)\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCell2.6-PAAEM180-C1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1.0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.33\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e4.0\u0026thinsp;\u0026plusmn;\u0026thinsp;0.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e410\u0026thinsp;\u0026plusmn;\u0026thinsp;19\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCell2.6-PAAEM180-C2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e0.75\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.33\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e4.2\u0026thinsp;\u0026plusmn;\u0026thinsp;0.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e415\u0026thinsp;\u0026plusmn;\u0026thinsp;28\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCell2.6-PAAEM180-C3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e0.50\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.33\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e4.9\u0026thinsp;\u0026plusmn;\u0026thinsp;0.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e341\u0026thinsp;\u0026plusmn;\u0026thinsp;16\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCell2.6-PAAEM180-C4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e0.25\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.33\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e4.7\u0026thinsp;\u0026plusmn;\u0026thinsp;0.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e458\u0026thinsp;\u0026plusmn;\u0026thinsp;35\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCell2.6-PAAEM180-C5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.33\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e4.6\u0026thinsp;\u0026plusmn;\u0026thinsp;0.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e502\u0026thinsp;\u0026plusmn;\u0026thinsp;42\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003c/table\u003e\n\u003c/div\u003e"},{"header":"Conclusions","content":"\u003cp\u003eIn summary, sustainable Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers were synthesized by adjusting the compositions through RAFT polymerization. These Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers exhibit good thermal stability, outstanding mechanical properties, and excellent adhesion behavior. As expected, the introduction of Tb\u003csup\u003e3+\u003c/sup\u003e and Eu\u003csup\u003e3+\u003c/sup\u003e ions can form an additional dynamic network via lanthanide coordination to dramatically enhance the tensile strength of the Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers. Meanwhile, the fluorescent colors of resultant coordinated Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers can be systematically manipulated by adjusting the Tb\u003csup\u003e3+\u003c/sup\u003e/Eu\u003csup\u003e3+\u003c/sup\u003e ratio, enabling the wide applications in the fields of anti-counterfeiting, wearables devices, and smart labels. The marriage of different kinds of renewable resources and lanthanide coordination can inspire the development of fantastic sustainable elastomers with unique functions via elaborate molecular design.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgments\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis work was financially supported by the National Natural Science Foundation of China (Grants 51603199 and 32471428). We thank the Shanghai Synchrotron Radiation Facility (SSRF) of BL16B1 (https://cstr.cn/31124.02.SSRF.BL16B1) and the User Experiment Assist System for the assistance on SAXS measurements.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding\u0026nbsp;\u003c/strong\u003eThis work was financially supported by the National Natural Science Foundation of China (Grants 51603199 and 32471428).\u003c/p\u003e\n\u003cp\u003eConflict of interest The authors declare no competing interests.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n \u003cli\u003eBurelo M, Mart\u0026iacute;nez A, Hern\u0026aacute;ndez-Varela J D, Stringer T, Ram\u0026iacute;rez-Melgarejo M, Yau A Y, Luna-B\u0026aacute;rcenas G, Trevi\u0026ntilde;o-Quintanilla C D (2024) Recent developments in synthesis, properties, applications and recycling of bio-based elastomers. 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Chem Eng J 504:159007\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"cellulose","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"cels","sideBox":"Learn more about [Cellulose](https://www.springer.com/journal/10570)","snPcode":"10570","submissionUrl":"https://submission.nature.com/new-submission/10570/3","title":"Cellulose","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Cellulose, Graft copolymers, Mechanical properties, Adhesion behavior, Fluorescent performance","lastPublishedDoi":"10.21203/rs.3.rs-6671184/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6671184/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eHigh-performance sustainable elastomers with tunable fluorescent behavior designed via robust and facile strategies are highly pursued. In this work, cellulose-\u003cem\u003egraft\u003c/em\u003e-poly(tetrahydrofurfuryl acrylate-\u003cem\u003eco\u003c/em\u003e-2-(methacryloyloxy)ethyl acetoacetate) (Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM)) copolymers with different compositions were prepared through homogeneous reversible addition-fragmentation chain transfer (RAFT) polymerization. In this design, cellulose acts as the backbone, while the hemicellulose derivative THFA and the petroleum-based monomer AAEM play the role of soft and rigid segments in the grafted side chains, respectively. By tuning the THFA/AAEM feed ratio and cellulose content, the mechanical and adhesion properties of these Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers were well manipulated. In addition, the \u003cem\u003eb\u003c/em\u003e-diketone groups in THFA repeating units can be further used as the ligands to form dynamic networks in the copolymer matrix with terbium (Tb\u003csup\u003e3+\u003c/sup\u003e) and europium (Eu\u003csup\u003e3+\u003c/sup\u003e) ions via lanthanide coordination. The resulting coordinated Cell-\u003cem\u003eg\u003c/em\u003e-P(THFA-\u003cem\u003eco\u003c/em\u003e-AAEM) copolymers exhibit significantly improved tensile strength and tunable fluorescent colors by adjusting the Tb\u003csup\u003e3+\u003c/sup\u003e/Eu\u003csup\u003e3+\u003c/sup\u003e ratio. The combination of bio-based resources and lanthanide coordination can be further performed to achieve strong sustainable elastomers with improved macroscopic mechanical properties and unique fluorescent behavior.\u0026nbsp; \u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u0026nbsp;\u003c/p\u003e","manuscriptTitle":"Preparation of cellulose-based fluorescent elastomers via RAFT polymerization and lanthanide coordination","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-06-06 14:21:51","doi":"10.21203/rs.3.rs-6671184/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-06-20T01:39:44+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-06-14T10:26:58+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-06-13T14:53:14+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"70032999520675302644413466257200059867","date":"2025-06-06T01:50:24+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"100256633969616537094608893395140507545","date":"2025-06-05T07:25:03+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"83019108115432257489939492107510572672","date":"2025-06-04T07:03:18+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-06-04T00:47:37+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-06-02T22:52:33+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-05-16T12:13:17+00:00","index":"","fulltext":""},{"type":"submitted","content":"Cellulose","date":"2025-05-15T09:28:32+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"cellulose","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"cels","sideBox":"Learn more about [Cellulose](https://www.springer.com/journal/10570)","snPcode":"10570","submissionUrl":"https://submission.nature.com/new-submission/10570/3","title":"Cellulose","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"31de98e3-ec9a-4875-a04c-96ebf037c000","owner":[],"postedDate":"June 6th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2025-10-13T16:01:04+00:00","versionOfRecord":{"articleIdentity":"rs-6671184","link":"https://doi.org/10.1007/s10570-025-06809-z","journal":{"identity":"cellulose","isVorOnly":false,"title":"Cellulose"},"publishedOn":"2025-10-11 15:57:05","publishedOnDateReadable":"October 11th, 2025"},"versionCreatedAt":"2025-06-06 14:21:51","video":"","vorDoi":"10.1007/s10570-025-06809-z","vorDoiUrl":"https://doi.org/10.1007/s10570-025-06809-z","workflowStages":[]},"version":"v1","identity":"rs-6671184","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6671184","identity":"rs-6671184","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}