Rational Design of Stable Fluorescent and Hydrophobic Cellulose-based Film for Full-band UV-blocking by Surface Modification

doi:10.21203/rs.3.rs-1749439/v1

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Rational Design of Stable Fluorescent and Hydrophobic Cellulose-based Film for Full-band UV-blocking by Surface Modification

https://doi.org/10.21203/rs.3.rs-1749439/v1

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A novel fluorescent, hydrophobic cellulose-based UV-blocking film was developed via chemical surface modification. Cellulose acetoacetate (CAA) film was firstly regenerated by acetyl acetylation of cellulose in a homogeneous system. Based on this esterified film with acetoacetyl groups, both 1,4-dihydropyridine (DHP) fluorescent ring and hydrophobic octadecylamine (ODA) were bonded to cellulose chains through Hantzsch reaction and the formation of enamine bond, by using a one-pot process under room temperature. The resulting film exhibited bright fluorescent and excellent UV-blocking properties (shielding almost 100% UV), which are very stable even being exposed to long periods of UV radiation, harsh temperature treatment and different solvents. In addition, this film has good hydrophobic feature (the contact angle reach up to 112°). This work provided a facile and environmentally friendly strategy to fabricate multifunctional cellulose-based film, which had great application potential in the field of UV protection, fluorescent materials, packaging and cover materials for greenhouse.

cellulose

multi-functional film

fluorescent

hydrophobic

UV-blocking

The UVB (280–320 nm) and UVA (315–400 nm) are two most harmful to nature among UV classes, due to they are hardly absorbed by the ozone layer.(Fitsiou et al., 2021) Prolong exposure to UV radiation would cause serious damage to cells and skin of human.(Yamada et al., 2020) At the same time, it can lead to photodegradation of polymer materials, reducing the performance of them.(Niu et al., 2018) Therefore, the UV-blocking films were widely applied in various fields including food packaging, electronics, contact lenses and cover materials for either greenhouses or screenhouses.(Babaei-Ghazvini et al., 2018; Bisht et al., 2019; Gause et al., 2016; Shao et al., 2022; Shen et al., 2020) For example, Juho Antti Sirvio et el. developed surface-functionalized cellulose nanocrystals with high UV-absorption property, which demonstrated it was suitable for greenhouse to protect UV-induced plant damage.(Sirvio, et al., 2016)

Cellulose is the most abundant natural resources in the world.(Liu et al., 2021) It has been widely used in plentiful field such as biomedicine, construction, packaging, textiles, energy production etc. (Badulescu et al., 2008; Homaeigohar et al., 2020; Liu et al., 2021) However, cellulose itself could not resist UV radiation. Thus, the traditional cellulose-based UV-blocking film is fabricated through doping UV absorbers in the cellulose matrix,(Sun, et al., 2022) including inorganic oxides (e.g., nano-TiO₂, SiO₂, ZnO, etc.) and organic filters (e.g., benzophenone, benzotriazole, lignin etc.).(Mendoza et al., 2021) Although these cellulose films can act as UV-blocking to some extent, they still have some disadvantages, such as poor stability and nonuniformity of UV absorbents. What’s more, it is difficult to 100% shielding UVA for the cellulose film blending with inorganic nano particles, and the transparency of cellulose-based film decreased obviously at visible after doping organic absorbents.( Guo et al., 2017; Zhang et al., 2019)

Due to the large number of hydroxyl groups, cellulose-based UV absorbent can be fabricated by chemical functionalization modification.(Lu et al., 2018; Niu et al., 2018) For instance, Li et al. fabricated ethyl cellulose phenyl propylene ketone ethers with outstanding UV-shielding and fluorescent performance via click reaction.(Li et al., 2021) Zhang et al. developed a type of chitosan/curcumin grafted TEMPO-oxidized cellulose nanofiber composite film with excellent UV-blocking and antibacterial properties.(Zhang et al., 2021) However, these cellulose-based UV absorbents showed poor ability for film formation. Thus, the composite UV-blocking films were usually prepared by doping cellulose-based UV absorbents into other polymer matrixes (such as polyvinyl alcohol, chitosan, poly (lactic acid) etc.). (Arrieta et al., 2015) Additionally, it is unattainable to balance high transparency with preeminent UV-blocking property of the composite film. Previously, we developed a novel method to prepare cellulose-based fluorescent film with good UV-blocking performance based on cellulose acetoacetate (CAA) gel by using Hantzsch reaction.(Peng et al., 2022) Although great advancements on cellulose-based UV-blocking films have been achieved, the well hydrophilic feature may limit their practical application in fields such as packing and cover materials. In addition, UV transmittance at 400 nm is about 10–25% for these films, which means they are not 100% UV-blocking.

In this work, we aim to further improve the hydrophobic and UV-blocking properties of cellulose-based film. We found that CAA has plentiful carbonyl groups, which provides great potential for the preparation of multifunctional cellulose-based materials. Therefore, chemical surface modification of CAA films will be carried out to develop functional film. Cinnamyl aldehyde (CA) derived from plants is an acrolein derivative with a benzene ring, which makes it be naturally hydrophobic molecule and has specific UV absorption capacity. (Adzaly et al., 2015) It will be used as the aldehyde source to build 1,4-dihydropyridine (DHP) fluorescent ring by Hantzsch reaction in order to improve on UV-blocking performance of cellulose-based film. In addition, the hydrophobic long chain octadecylamine (ODA) molecule will be bonded to cellulose chains through the formation of enamine bond based on the surface of CAA film. The two reactions will be carried out by one-pot process. The structure and properties of resulting modified cellulose-based film will be comprehensively investigated.

2.1. Materials

Coniferous wood pulp was obtained from Shandong Daoxin New Material Co., LTD. N,N-Dimethylformamide (DMF, 99.9%), tert-butyl acetoacetate (t-BAA, 95%), cinnamyl aldehyde (CA, 98%), octadecylamine (ODA, 90%) ,and ammonium acetate (NH₄OAc, 99%) were purchased from Macklin Co., LTD. 1-allyl-3-methylimidazolium chloride (AMIMCl) was obtained from the Lanzhou institute of chemical physics. And all other chemicals were analytical grade without further purification.

2.2. The preparation of pure regenerated film

Dry coniferous wood pulp (4.0 g) was placed in a three-mouth flask with 76.0 g AMIMCl and 50 mL DMF were added to the reaction vessel. The mixture was stirred at 110°C until the wood pulp was fully dissolved. Then the mixture was cast in mold and soaked in ethanol. It was removed from ethanol and washed repeatedly with ethanol after the cellulose hydrogel was formed. Finally, the hydrogel was dried in a Fast Kaiser Method Sheet Forming Machine at 90°C at an applied pressure of about 0.8 bar for 10 min to obtain pure regenerated cellulose film.

2.3. The preparation of CAA film and CAA-CA-ODA film

Firstly, the cellulose acetoacetate (CAA) was obtained by previous method of the same research group.(Peng et al., 2022; Rong et al., 2019) That was to say, dry coniferous wood pulp (4.0 g) was placed in a three-mouth flask with 76.0 g AMIMCl. Then 50mL DMF were added to the reaction vessel. The mixture was stirred at 110°C until the wood pulp was fully dissolved. Then 12.33 t-BAA (molar ratio: AGU molar/t-BAA = 1/3) was gradually dropped into the reaction vessel and kept stirring for 4 h, after which the mixture was cast in mold and soaked in ethanol. It was removed and washed repeatedly with ethanol when the cellulose hydrogel was formed. CAA film was obtained after drying in a Fast Kaiser Method Sheet Forming Machine at 90°C at an applied pressure of about 0.8 bar. Secondly, the dry CAA film (1 g), NH₄OAc (200 mg) and CA (343 mg, molar ratio: NH₄OAc/CA = 1:1) was stirred with a beaker in 75% ethanol solution at room temperature for 24h. Then, ODA (3 g) was added to the reaction beaker and kept stirring for 12 h. The film was washed repeatedly with ethanol and was pressure-dried at 90°C for 5 min. The resulting film was named as CAA-CA-ODA film.

2.4. Characterization

The structure of samples was studied by Fourier transform infrared spectrometer (FT-IR) on Nicolet IS50-Nicolet Continuum (Thermo Fisher Scientific, USA) and X-ray photoelectron spectroscopy (XPS) on Thermo ESCALAB 250XI (Thermo Fisher Scientific, USA). The elemental analysis was performed with Vario EL cube (Elementar Germany). The morphology of samples was observed by scanning electron microscopy (SEM) on Merlin (Merlin, Zeiss, Germany). The property of cellulose film was measured on Cary 60 (Agilent, USA) (the UV-visible absorption spectra), Axios PW4400 (Panaco, Netherlands) (the PL spectra), OCA40 Micro (Germany) (the contact angle) respectively. Thermogravimetric analysis (TGA) was used to study the heat stability of cellulose film on TG209F1 (NETZSCH). And the samples were dealt with from 30°C to 700°C at a heating rate of 10°C under protection of nitrogen atmosphere.

X-ray diffraction data (XRD, X'pert Powder, PANalytical) was used to test the crystallinity of samples with a conventional wide-angle from 5°-60° at a scanning speed of 12°/min. All samples were measured in form of film, using the reflection mode. The films were cut into strips 7 mm long and 7 mm wide for measurements.

In order to investigate swelling ratio (SR) of the cellulose films, a pre-weighed film sample (2.5 cm*2.5 cm) was soaked in 20 mL different solvents for 24 h. Then they were taken out from solvents and weighed after removing surface liquid using a blotting paper. SR of the modified cellulose films were determined by following Eq. (1):

SR(%) = (W₂-W₁)/W₁ *100 (1)

Here W₁ and W₂ refer to the initial and final weights of the film samples respectively. And average of three parallel tests was recorded.

The pure regenerated cellulose film and modified films were investigated by tensile tests, which was carried out on INSTRON 5565, USA. Before test, the samples were disposed at 25°C and 55% relative humidity for 48 h. Each test sample was cut into a rectangle 10 cm long and 1.5 cm wide, and the stretching rate was 10 mm/min.

The air permeability of cellulose-based film was determined using L&W 166 (Sweden). Each sample was cut into 20 cm circles, and five different positions were tested for each sample. Then the average value was output.

3.1 Fabrication of cellulose-based films

As illustrated in Fig. 1a, CAA was firstly prepared by transesterification with tert-butylacetoacetate (t-BAA) under homogeneous condition according to our previous work.(Peng et al., 2022) The CAA film was obtained from CAA solution after regeneration in ethanol and drying. It was involved in Hantzsch reaction together with ammonium acetate and CA as a multi-functional group under the room temperature. At the same time, the ODA molecule was bonded to cellulose chains through the formation of enamine bond. That is, Hantzsch reaction and enamination modification were carried out through one-pot process without catalyst (Fig. 1.b).

Compared with in-situ chemical reaction on CAA gel, we directly grafted functional groups to the surface of CAA film, which was beneficial to improve the efficiency of modification, so as to achieve better UV-blocking and hydrophobic performances. Additionally, surface modification has no obvious effect on the surface morphology and structure of cellulose film in comparison to other methods to improve the hydrophobicity of cellulose film. (He, et al., 2013; Xu et al., 2019) This one-pot strategy is simple, safe and eco-friendly. The resulting modified cellulose-based films show highly transparent, remarkable UV-blocking, stable fluorescent and good hydrophobic features, which will be discussed in the following part.

3.2 Characterization of cellulose-based films

The chemical structure of as-prepared cellulose-based films were identified by the Fourier transform infrared (FT-IR) spectra and X-ray photoelectron spectroscopy (XPS) pattern. Based on previous work, (Guo et al., 2021) it was extremely clear that the acetoacetyl groups were successfully bonded to cellulose chains (Fig. 2a). The intensive peaks at 2921 cm^− 1 and 2857 cm^− 1 were mainly attributed to the long carbon chain skeleton of ODA. (Majdoub et al., 2021) In detail, the strong absorption peak at around 1597 cm^− 1, 1640 cm^− 1 were related to the –C-N bonds, indicating successful formation of DHP ring and enamine bonds.(Zeng et al., 2021) In addition, the XPS spectra of different cellulose-based films are presented in Fig. 2b. Compared with the pure regenerated cellulose film, the new peak of N1 was observed in the modified cellulose-based film spectra. The decomposition result of nitrogen displayed two obvious in 400 eV for C-N-C and 399.4 eV for N-H in Fig S1 b. Meanwhile, the typical peaks, C-O-C and C = O were exhibited in the spectra of deconvoluted oxygen (Fig S1a) and the bond of C-N, C-C, and C = O also emerged in the Fig. 2c. What’s more, as shown in the Table S1, the content of N increased gradually, which more verified the existence of DHP ring and enamine bonds. (Wang et al., 2022) The above results further confirmed that surface modification was successfully implemented on cellulose chain. Compared with CAA film, the microcosmic surface of CAA-CA-ODA film still exhibit flat and smooth after surface modification as revealed by SEM (Fig. 2d-f), which indicated the mild reaction caused little damage to surface of the cellulose film. The elemental mapping images (Fig. 2h-g) presented the independent distribution of C, N and O element respectively. It further suggested the surface modification was efficiently and homogenously performed on the cellulose-based film.

X-ray diffraction (XRD) are shown in Fig. 3a to gain insight into the change of crystalline phase in these samples. However, the characteristic peak (20.1°) of samples remained consistent after surface modification, revealing the crystalline morphology of CAA film was not destroyed in mild surface modification process. (Rong et al., 2019) In the thermogravimetry (TG) curves (Fig. 3b), main decomposition temperature of these cellulose-based films is concentrated at 200°C-500°C with the maximum of weight loss at 230°C, confirming that films had good thermal stability. The mechanical properties of different cellulose-based films were also studied (Fig. 3c-3d). The breaking stress and Young modulus of the resulting film was about 51.5 MPa and 2727.5 MPa. Compared with the pure regenerated cellulose film, the mechanical performance of CAA-CA-ODA film slightly decreased, ascribing to the surface modification that increased the distance between the cellulose chain and reduced the hydrogen bonding interactions. As summarized in Fig. 3e, in comparison to the pure regenerated cellulose film, the water contact angle (WCA) of the final film was significantly improved by long chain alkyl of ODA after surface modification, resulting in the WCA being 111.2°. For packing materials, applicable air permeability could prevent the accumulation of substances (O₂, CO_2, etc.) produced by the packaged something and improve the life of them. (Lai et al., 2021) As shown in Fig. 3f, there is no obvious difference between the pure regenerated film and the final cellulose-based film for air permeability after surface modification.

3.3 Transparency and fluorescence performance

In digital photos of Fig. 4a, we can see clearly the words “Cellulose SCUT”, suggesting the film had high transparency under visible light and the surface modification had little effect on the transparency of cellulose-based film. Moreover, CAA-CA and CAA-CA-ODA films emitted the bright blue when they were exposed to UV light (365 nm) while no fluorescence is observed on pure regenerated cellulose film (Fig. 4b), which was attributed to the successful formation of DHP ring via Hantzsch reaction. More importantly, the CAA-CA-ODA film still remained strong fluorescence after soaking in different solvents (DMSO, DMF, THF, water, ethyl alcohol, acetone) for 24 h, which reveals that the modified film has outstanding anti-solvent property (Fig. 4c). In addition, the swelling ratio of samples decreased gradually in strong polar solvents after surface modification, demonstrating the resulting film has extremely stable cross-linked structure (Table S2).

Meanwhile, the resulting film also exhibits fluorescence even after storing in harsh temperature and exposing to UV light (Fig. 4c). This result manifested the DHP ring was anchored firmly on cellulose chain. In the fluorescence spectra of samples (Fig. 4d), the maximum excitation wavelength of CAA-CA film is observed at 400 nm, and the broad emission spectrum appears at 400–550 nm with a maximum at 450 nm, which clearly indicates the conjugated structure of DHP ring could absorb UV radiation energy and convert it into visible fluorescence modality. The wide emission spectrum at 400–550 nm is also discovered in fluorescence spectra of CAA-CA-ODA film, suggesting the structure of DHP ring was not changed after formation of enamine bonds. Presumably, the unique structure of DHP ring by Hantzsch reaction could be regarded as the key to maintain fluorescent stability of CAA-CA-ODA film treated under different severe conditions (Fig S2 and Fig S3).

3.4 UV-blocking ability

UV-shielding could effectively prevent the degradation of polymer materials under the UV radiation. (Lu et al., 2021) As shown in the Fig. 5a, the pure regenerated cellulose film can only shield 200–238 nm UV light while the almost 100% UV-blocking ability was obtained for CAA-CA and CAA-CA-ODA films. Besides, the transmittance in 550 nm was 86%, which was similar to that of the pure regenerated cellulose film. After soaking in different solvents for 24 h, modified cellulose-based film still preserved excellent UV-shielding capacity, which demonstrated that this material had good anti-solvent performance (Fig. 5b). In addition, after freezing at -20°C for 24 h and heating at 110°C for 10 h (Fig. 5c), it still could shield all UVA and UVB spectrum. Even when the film was exposed to strong UV radiation for 240 h, the CAA-CA-ODA film could also completely shield UV light (Fig. 5d), further proving the film had stable UV-blocking property.

It has been reported that introducing the conjugated structure into materials was beneficial to improve the UV-blocking performance. (Zhang et al., 2019) Therefore, this excellent UV-blocking performance of CAA-CA-ODA film was mainly attributed to the absence of conjugated structure (O = C-C = C- and -C = C-C = C-) (Fig. 6a). For comparison, hexaldehyde was used to take part in Hantzsch reaction to prepare CAA-HEX film in the same way. It could only block UV light of 200–300 nm waveband (Fig. 6b). The UV transmittance at 400 nm is about 40% for CAA-HEX. In our previous work, similarly, the UV transmittance at 400 nm is 10–25% for those using aldehydes with benzene ring (such as BA, HBA, DBA). (Peng et al., 2022) That is, they cannot shield 100% UV light. Therefore, CA is further verified to be an efficient candidate to modify cellulose-based materials with superhigh UV-blocking property by Hantzsch reaction.

Additionally, cellulose-based UV-blocking films were compared and summarized in Fig. 6c and Table S3. Most of the reported cellulose-based films either exhibit poor UV-blocking performance or have low light transmittance. For example, although the CNF/LS/GaCl₂ could shield all UVA and UVB, the transmittance at 550 nm was extremely low, only about 5%.(Jancic et al., 2021) Moreover, TOCNF-MDF film had high transmittance at 550 nm while it can only block 52.8% of UVA.(Tan et al., 2022) However, in this work, the surface modification process not only preserves the high light transmittance (86% transmittance at 550 nm) of the film, but also render the material excellent UV-shielding ability (almost 100% UV-blocking) .

Chemical surface modification was demonstrated an efficient, mild, and eco-friendly way for the development of functional cellulose-based materials. The resulting films exhibited outstanding UV-blocking, fluorenscent, transparent and hydrophobic performances. The functional groups were covalently bonded to cellulose chains, which greatly improved the stability of the multifunctional cellulose-based film. Biconjugate structure leads to superhigh (nearly 100%) UV-blocking ability of the film. The WCA of CAA-CA-ODA film was significantly inceresed to 111.2° by grafting ODA molecules. It should be noted that the chemical surface modification has little effect on structure and morphology of cellulose-based film. The resulting CAA-CA-ODA film still has good transparency and mechanical property after chemical surface modification. In consideration of the mild and green chemical surface modification process based on CAA film, the strategy presented in this work has great potential for fabrication of multi-functional cellulose-based film, which can be employed in UV protection, fluorescent materials, packaging and cover materials for greenhouse.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influencethe work reported in this paper.

Acknowledgements

This work was financially supported by Guangdong Province Science Foundation (2017GC010429), Guangdong Basic and Applied Basic Research Foundation (2020A1515110594, 2022A1515010565).

CRediT authorship contribution statement

Changjing Qiu: Conceptualization, Methodology, Investigation, Data curation, Writing – original draft. Hongchen Liu: Conceptualization, Supervision, Writing – review & editing. Kaiyuan Shen: Methodology, Investigation, Data curation. Mengzhen Yuan: Methodology, Investigation, Data curation. Haisong Qi: Conceptualization, Supervision, Writing – review & editing.

Adzaly NZ, Jackson A, Villalobos-Carvajal R, Kang I, Almenar E (2015) Development of a novel sausage casing. J Food Eng 152:24–31
Arrieta MP, Fortunati E, Dominici F, Lopez J, Kenny JM (2015) Bionanocomposite films based on plasticized PLA-PHB/cellulose nanocrystal blends. Carbohydr Polym 121:265–275
Babaei-Ghazvini A, Shahabi-Ghahfarrokhi I, Goudarzi V (2018) Preparation of UV-protective starch/kefiran/ZnO nanocomposite as a packaging film: characterization. Food Packaging and Shelf Life 16:103–111
Badulescu R, Vivod V, Jausovec D, Voncina B (2008) Grafting of ethylcellulose microcapsules onto cotton fibers. Carbohydr Polym 71(1):85–91
Bisht A, Kumar V, Maity PC, Lahiri I, Lahiri D (2019) Strong and transparent PMMA sheet reinforced with amine functionalized BN nanoflakes for UV-shielding application. Compos Part B: Eng 176:1359–8368
Chen K, Yu J, Huang J, Tang Q, Li H, Zou Z (2021) Improved mechanical, water vapor barrier and UV-shielding properties of cellulose acetate films with flower-like metal-organic framework nanoparticles. Int J Biol Macromol 167:1–9
Fitsiou E, Pulido T, Campisi J, Alimirah F, Demaria M (2021) Cellular Senescence and the Senescence-Associated Secretory Phenotype as Drivers of Skin Photoaging. J Invest Dermatology 141(4S):1119–1126
Gause S, Chauhan A (2016) Incorporation of ultraviolet (UV) absorbing nanoparticles in contact lenses for Class 1 UV blocking. J Mater Chem B 4(2):327–339
Gomez-Hermoso-de-Mendoza J, Gutierrez J, Tercjak A (2020) Transparent and flexible cellulose triacetate–TiO₂ nanoparticles with conductive and UV-shielding properties. J Phys Chem C 124(7):4242–4251
Guo H, Klose D, Hou Y, Jeschke G, Burgert I (2017) Highly Efficient UV Protection of the Biomaterial Wood by A Transparent TiO2/Ce Xerogel. ACS Appl Mater Interfaces 9(44):39040–39047
Guo L, Liu H, Peng F, Qi H (2021) Efficient and portable cellulose-based colorimetric test paper for metal ion detection. Carbohydr Polym 274:118635
He M, Xu M, Zhang L (2013) Controllable stearic acid crystal induced high hydrophobicity on cellulose film surface. ACS Appl Mater Interfaces 5(3):585–591
Homaeigohar S, Boccaccini AR (2020) Antibacterial biohybrid nanofibers for wound dressings. Acta Biomater 107:25–49
Huang J, Lu Z, Li J, Ning D, Jin Z, Ma Q, Zhang M (2021) Improved mechanical and ultraviolet shielding performances of hydroxyethyl cellulose film by using aramid nanofibers as additives. Carbohydr Polym 255:117330
Jancic U, Bracic M, Ojstrsek A, Bozic M, Mohan T, Gorgieva S (2021) Consolidation of cellulose nanofibrils with lignosulphonate bio-waste into excellent flame retardant and UV blocking membranes. Carbohydr Polym 251:117126
Lai WF, Yip W, Wong WT (2021) UV-shielding and clusteroluminogenic cellulose‐based films with tuneable wettability and permeability for dually self‐Indicating food packaging. Adv Mater Technol 6(8):2100120
Li B, Xu C, Liu L, Yu J, Fan Y (2021) Facile and sustainable etherification of ethyl cellulose towards excellent UV blocking and fluorescence properties. Green Chem 23(1):479–489
Liu K, Du H, Zheng T, Liu H, Zhang M, Zhang R, Si C (2021) Recent advances in cellulose and its derivatives for oilfield applications. Carbohydr Polym 259:117740
Liu Y, Ahmed S, Sameen DE, Wang Y, Lu R, Dai J, Qin W (2021) A review of cellulose and its derivatives in biopolymer-based for food packaging application. Trends Food Sci Technol 112:532–546
Lu C, Yu J, Wang C, Wang J, Chu F (2018) Fabrication of UV-absorbent cellulose-rosin based thermoplastic elastomer via "graft from" ATRP. Carbohydr Polym 188:128–135
Lu J, Fang J, Li J, Zhu L (2021) Engineering highly transparent UV-shielding films with disassembled polydopamine oligomers as light adsorber. Appl Surf Sci 550:149284
Majdoub M, Essamlali Y, Amadine O, Ganetri I, Hafnaoui A, Khouloud M, Zahouily M (2021) Octadecylamine as chemical modifier for tuned hydrophobicity of surface modified cellulose: toward organophilic cellulose nanocrystals. Cellulose 28(12):7717–7734
Mendoza DJ, Browne C, Raghuwanshi VS, Mouterde LMM, Simon GP, Allais F, Garnier G (2021) Phenolic ester-decorated cellulose nanocrystals as UV-absorbing nanoreinforcements in polyvinyl alcohol films. ACS Sustain Chem Eng 9(18):6427–6437
Niu X, Liu Y, Fang G, Huang C, Rojas OJ, Pan H (2018) Highly transparent, strong, and flexible films with modified cellulose nanofiber bearing UV shielding property. Biomacromolecules 19(12):4565–4575
Peng F, Liu H, Xiao D, Guo L, Yue F, Würfe H, Qi H (2022) Green fabrication of high strength, transparent cellulose-based films with durable fluorescence and UV-blocking performance. J Mater Chem A 10(14):7811–7817
Rahman KU, Ferreira-Neto EP, Rahman GU, Parveen R, Monteiro AS, Rahman G, Ullah S (2021) Flexible bacterial cellulose-based BC-SiO₂-TiO₂-Ag membranes with self-cleaning, photocatalytic, antibacterial and UV-shielding properties as a potential multifunctional material for combating infections and environmental applications. J Environ Chem Eng 9(1):104708
Rong L, Zeng M, Liu H, Wang B, Mao Z, Xu H, Sui X (2019) Biginelli reaction on cellulose acetoacetate: a new approach for versatile cellulose derivatives. Carbohydr Polym 209:223–229
Roy S, Kim HC, Kim JW, Zhai L, Zhu QY, Kim J (2020) Incorporation of melanin nanoparticles improves UV-shielding, mechanical and antioxidant properties of cellulose nanofiber based nanocomposite films. Mater Today Commun 24:100984
Shao H, Zhang Y, Pan H, Jiang Y, Qi J, Xiao H, Xie J (2022) Preparation of flexible and UV-blocking films from lignin-containing cellulose incorporated with tea polyphenol/citric acid. Int J Biol Macromol 207:917–926
Shen X, Du J, Sun J, Guo J, Hu X, Wang C (2020) Transparent and UV blocking structural colored hydrogel for contact lenses. ACS Appl Mater Interfaces 12(35):39639–39648
Sirviö JA, Visanko M, Heiskanen JP, Liimatainen H (2016) UV-absorbing cellulose nanocrystals as functional reinforcing fillers in polymer nanocomposite films. J Mater Chem A 4(17):6368–6375
Sun L, Li L, An X, Qian X (2021) Nano-metal organic framework for enhanced mechanical, flame retardant and ultraviolet-blue light shielding properties of transparent cellulose-based bioplastics. Polym (Basel) 13(15):2433
Sun L, Qian X, An X (2022) Transparent and highly efficient full-band UV-shielding bioplastic designed by in-situ embedded metal-organic frameworks (MIL-68(In)-NH2) in cellulose matrix. Cellulose 29(2):1017–1034
Tan F, Zha L, Zhou Q (2022) Assembly of AIEgen-based Fluorescent Metal-Organic Framework Nanosheets and Seaweed Cellulose Nanofibrils for Humidity Sensing and UV-shielding.Advanced Materials, e2201470
Vázquez M, Velazquez G, Cazón P (2021) UV-Shielding films of bacterial cellulose with glycerol and chitosan. Part 2: Structure, water vapor permeability, spectral and thermal properties. CyTA - Journal of Food 19(1):115–126
Wang L, Hui L, Su W (2022) Superhydrophobic modification of nanocellulose based on an octadecylamine/dopamine system. Carbohydr Polym 275:118710
Xu L, Teng J, Li L, Huang HD, Xu JZ, Li Y, Li ZM (2019) Hydrophobic Graphene Oxide as a Promising Barrier of Water Vapor for Regenerated Cellulose Nanocomposite Films. ACS Omega 4(1):509–517
Yamada M, Prow TW (2020) Physical drug delivery enhancement for aged skin, UV damaged skin and skin cancer: Translation and commercialization. Adv Drug Deliv Rev 153:2–17
Zeng F, Jiang X, Zhang H, Chen M, Lu A, Yu A (2021) Multifunctional Dynamic Enamine-Based Hydrogels with On‐Demand Removability for Wound Healing. Adv Mater Interfaces 8(24):2101855
Zhang X, Li Y, Guo M, Jin TZ, Arabi SA, He Q, Liu D (2021) Antimicrobial and UV Blocking Properties of Composite Chitosan Films with Curcumin Grafted Cellulose Nanofiber. Food Hydrocolloids 112:106337
Zhang X, Liu W, Yang D, Qiu X (2019) Biomimetic supertough and strong biodegradable polymeric materials with improved thermal properties and excellent UV-blocking performance. Adv Funct Mater 29(4):1806912
Zhang XF, Song L, Wang Z, Wang Y, Wan L, Yao J (2020) Highly transparent graphene oxide/cellulose composite film bearing ultraviolet shielding property. Int J Biol Macromol 145:663–667

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Rational Design of Stable Fluorescent and Hydrophobic Cellulose-based Film for Full-band UV-blocking by Surface Modification

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Abstract

Figures

1. Introduction

2. Experimental Section

2.1. Materials

2.2. The preparation of pure regenerated film

2.3. The preparation of CAA film and CAA-CA-ODA film

2.4. Characterization

3. Result And Discussion

3.1 Fabrication of cellulose-based films

3.2 Characterization of cellulose-based films

3.3 Transparency and fluorescence performance

3.4 UV-blocking ability

4. Conclusion

Declarations

References

Supplementary Files

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