The characterization of size-controlled nanocrystalline cellulose from soy hulls with ultrasonic assisted extraction

The characterization of size-controlled nanocrystalline cellulose from soy hulls with ultrasonic assisted extraction | 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 The characterization of size-controlled nanocrystalline cellulose from soy hulls with ultrasonic assisted extraction Kejin Yu, Lina Yang, Siyu Zhang, Ning Zhang, He Liu This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5667593/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Soybean is a crop of important economic significance and soy hull is the residual by-product of soybean processing industry. In this study, cellulose nanocrystals were extracted from soy hull using a combined acid hydrolysis-ultrasonic treatment process, and its structure, properties, and antimicrobial activity were investigated. Fourier-transform infrared spectroscopy revealed the presence of hydrogen and ester bonds in the soy hull nanocrystalline cellulose (SHNC), whereas scanning electron microscopy showed that the SHNC was globular or short-rod shaped with diameters in the range of 20–50 nm. The molecular weight of SHNC was 213,935 Da and the extraction yield was 11.42%. Meanwhile, SHNC also had high crystallinity (55.59%), thermal stability, transparency (80%), and UV resistance. Notably, SHNC exhibited an excellent bacteriostatic effect against Escherichia coli and Staphylococcus aureus , whose bacteriostatic percentage reached 69.33%. Meanwhile, this study provided a new idea for the high value utilization of waste soy hull. Nanocellulose Chemical structure Morphology Agroindustrial waste Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 1 Introduction Soybeans are an important component of grain in Northeast China and a large amount of by-products are produced during their production and processing. Soy hull is one of these by-products, which is usually used as animal feed, and represents a serious waste of this resource (Reichembach & de Oliveira Petkowicz, 2022). Recently, many researchers have extracted bioactive natural polymers such as polysaccharides and isoflavones from soy hull (Kim, Miller, Lee, & Kim, 2016 ; Reichembach & de Oliveira Petkowicz, 2022; Yang et al., 2019 ), providing a new direction for the high value utilization of soy hull. However, we have discovered that research on cellulose and its derivatives is scarce. Meanwhile, soy hull contains an abundant amount of cellulose, which has great potential as a source for developing high quality cellulose and its derivatives (Cai et al., 2022 ; Huang et al., 2024 ). Therefore, extracting cellulose and its derivatives from soy hull is of great significance. As a derivative of cellulose, nanocellulose has received widespread research attention in the fields of food, biomedical, and cosmetics due to its high crystallinity, large specific surface area, biocompatibility, hydrophilicity, non-toxicity, and environmental benefits (Grishkewich, Mohammed, Tang, & Tam, 2017 ; W. Li, Yue, & Liu, 2012 ). At present, there are several methods for preparing nanocellulose. For example, acid hydrolysis (H. Zhang et al., 2020 ), oxidation utilizing 2,2,6,6-tetramethylpyridine oxide (Tang & Huang, 2022 ), and biological methods (J. Wang, Tavakoli, & Tang, 2019 ). Among them, acid hydrolysis is the most well-known and widely used method because the disordered or amorphous regions of cellulose are preferentially hydrolyzed, while the crystalline regions have better acid resistance (Habibi, Lucia, & Rojas, 2010 ). Nanocellulose typically exhibits a specific morphology and properties after acid hydrolysis. For example, (Sumarago, dela Cerna, Leyson, Tan, & Magsico, 2024) extracted nanocellulose using sulfuric acid, which is short rod-shaped and exhibits excellent thermal stability. When compared with acid hydrolysis, ultrasonic treatment is a widely accepted mechanical extraction method that can effectively alter the morphology and properties of nanocellulose during the preparation process (Abral, Lawrensius, Handayani, & Sugiarti, 2018 ; Low et al., 2022 ). For example, (Chagas et al., 2023 ) revealed that ultrasonic treatment can transform large-sized microcrystalline cellulose into nanoscale rod-shaped cellulose nanocrystals. (Wong, Kasapis, & Huang, 2012 ) have also revealed that ultrasonic treatment can significantly reduce the molecular weight of bacterial and plant cellulose, and increase their crystallinity index. In addition, ultrasonic treatment can also affect the interfacial and thermal stability of nanocellulose (Meng et al., 2019 ; Xing et al., 2022 ). The changes in the morphology and properties of nanocellulose can be mainly attributed to the cavitation effect generated by ultrasound (Low et al., 2022 ). Recent studies have found that the combination of acid hydrolysis and ultrasonic treatment can achieve a smaller particle size, better performance, higher efficiency, and safer extraction of nanocellulose when compared to traditional methods (Karakehya & Bilgic, 2019 ; Low et al., 2022 ). For example, Lim et al. (Lim, Tang, Manickam, Yu, & Tan, 2024 ) successfully extracted mesh nanocellulost with a diameter of 18–26 nm from durian shells by acid hydrolyzation-ultrasonic combined treatment, and the lignin content inside was almost zero. Meanwhile, the nanocellulose also has excellent physical and chemical properties. Silva et al. (Silva, Silva, Assis, & Martelli-Tosi, 2024 ) successfully extracted nanocellulose from cherry by-product by acid hydrolyzation-ultrasonic treatment, and the yield of nanocellulose reached 69.9%, with high crystallinity (71.7%) and thermal stability. In addition, ultrasonic treatment helps to remove the non-cellulose components (Alanazi, 2022 ). Nanocellulose extracted using traditional methods (eg., ball-milling etc.) has low stability. In general, the stability of nanocellulose depends on the electrostatic interactions formed between the cellulose fibers, which can be enhanced by introducing negatively charged functional groups (Grishkewich et al., 2017 ). However, ultrasound can produce cavitation, which can break up nanocellulose in its amorphous regions and part of its crystalline areas, expose more surface charges, and improve its interface stability and gel performance (Abral et al., 2020 ). Therefore, it is of great research interest to extract nanocellulose from soybean seed coat using a combination of acid hydrolysis and ultrasonic treatment in order to reveal the changes in the morphology and properties of nanocellulose caused by their combined effect and further reveal the impact of these changes on the interfacial properties of nanocellulose. This study aimed to explore a green and environmentally friendly method for producing nanocellulose, providing the basis for the high value utilization of soy hull. Soy hull nanocrystalline cellulose (SHNC) was prepared using a combination of acid hydrolysis and ultrasonic treatment. The effect of the ultrasonic power on the composition and morphology of SHNC was investigated and the influence of ultrasonic power on the physicochemical properties of SNHC, including its thermal stability, hydrophilicity, and transparency, was analyzed. The results of this study can be used to improve the comprehensive utilization value of soy hull and lay a theoretical foundation for the comprehensive utilization of SHNC. 2 Materials and methods 2.1 Materials Soy hull was purchased from Yuwang Industry Co., Ltd. (Dezhou, China). Regular dialysis bags (14,000 Da) were purchased from Yuanye Biological Co., Ltd. (Shanghai, China). Escherichia coli and Staphylococcus aureus were purchased from Wuhan Punosai Life Technology Co., Ltd. (Wuhan, China). Brain heart infusion broth was purchased from Shunyou Biotechnology Co., Ltd. (Shanghai, China). Nutritional broth and agar were purchased from Haibo Biotechnology Co., Ltd. (Qingdao, China). Ethanol (analytical grade), sodium hydroxide (analytical grade), hydrochloric acid (analytical grade), acetic acid (analytical grade), vitriol (analytical grade), sodium chlorite (analytical grade), and sodium chloride (analytical grade) were purchased from Sinopharm Group Chemical reagent Co., Ltd. (Tianjin, China). Deionized water was used throughout the experiment. 2.2 Preparation of SHNC Soy hull was sifted through 20 mesh to remove any impurities and the soy hull crushed three times using a hammer stone cyclone mill (JXFM110, Shanghai, China) and then sifted through 60 mesh. Five g soy hull was placed in a beaker, 250 mL of deionized water added, and allowed to soak for 24 h. A total of 15 mL of 10% HCl was added to the beaker for acid hydrolysis and stirred at 170℃ for 2 h. A 3-fold excess of deionized water was used to terminate the reaction and the mixture allowed to cool to 25℃. The beaker was placed in the ultrasonic instrument (JY99-IIDN, Ningbo, China) for 120 min at 4℃ (0 W, 100 W, 200 W, and 300 W), centrifuged (Megafuge ST1 Plus, Thermo, USA) at 4,000 rpm in a 150-mL test tube for 15 min, the supernatant removed, and NaOH added to adjust the pH of the solution to 7. The solution was placed into a dialysis bag (Da = 14,000) for 3 d. The resulting solution was precipitated upon the slow addition of ethanol solution (95%, v/v) to dilute the concentrate at a ratio of 1:2 (v/v) with constantly stirring. The precipitate was stored at 4℃ for 24 h, the solution centrifuged at 4,000 rpm for 5 min, and the sediment was dried in a vacuum freeze dryer (SCIENTZ-10N/A, Ningbo, China) for 24 h to obtain the SHNC product. 2.3 Determination of the chemical composition The chemical composition of SHNC was determined using the method reported by (Sluiter et al., 2008 ) and (Chen, Lee, Juan, & Phang, 2016 ) with several improvements. Holocellulose and α-cellulose content: 2 g of SHNC was dispersed in 65 mL of deionized water and then treated with 1.5 g of NaClO 2 and 1 mL of CH 3 COOH for 4 h. The sample was rinsed until the pH was neutral, and dried. The remaining samples were treated with 17.5% NaOH for 30 min (25℃) and then soaked in 60 mL of deionized water for 30 min. The hemicellulose content was calculated using the difference between holocellulose and α-cellulose. Lignin content: 0.6 g of SHNC was dissolved in 6 mL of 72% concentrated H 2 SO 4 and hydrolyzed for 1 h, then 84 mL of deionized water was added and hydrolyzed at 121℃ for 1 h. The sample was then rinsed until the pH was neutral, and dried. Each experiment was repeated three times. 2.4 Scanning electron microscopy (SEM) A small amount of freeze-dried sample was attached to the platform with conductive adhesive, any excess sample was blown away with a dust ball, and the sample coated with a layer of gold. SEM (S-4800, Hitachi, Japan) was used to observe the morphology of the sample. The SEM parameters were set as follows: acceleration voltage of 10.0 kV and the normal mode amplification factor was ×50,000 and ×300,000 magnifications, respectively. Each experiment was repeated three times. 2.5 Fourier transform infrared (FT-IR) spectroscopy Freeze-dried samples and KBr powder were mixed in a 1:100 (w/w) ratio and the mixed powder was pressed into tablets. Prior to measurement, KBr was used as a blank correction to eliminate the interference of factors such as CO 2 and humidity in the air. The sample was then scanned using an FT-IR spectrometer (Agilent Technologies, Santa Clara, CA, USA) in the wavenumber range of 4000–400 cm –1 over 32 scans and resolution of 1 cm –1 . The data were processed and analyzed using Omnic software. Each experiment was repeated three times. 2.6 X-ray diffraction (XRD) measurements The crystalline structure of the SHNC was measured using XRD (D8 advance, Bruker, Germany) with Cu K α1 radiation at 40 kV and 40 mA. Briefly, after the lyophilized SHNC sample was crushed, it was poured into the groove of the sample rack, and then gently pressed with a slide to make the sample powder consistent with the frame level. The scanning rate was 0.209° s –1 with a step size of 0.0167°, and data were recorded over an angle range of 5−80°. The data was processed and analyzed using Jade software. The crystallinity index (CrI) of SHNC was calculated using the following formula: $$\:\text{C}\text{r}\text{I}\:\left(\text{%}\right)=\frac{{\text{I}}_{002}-\:{\text{I}}_{\text{a}\text{m}}}{{\text{I}}_{002}}\times\:100\text{%}\:\:\:\:\:\:\:\:\:\:\:\:\left(1\right)$$ where I 002 is the maximum intensity value of diffraction of the 002 lattice peak observed for crystalline cellulose at 2θ ~ 22°, while I am is the intensity value observed for amorphous cellulose at 2θ ~ 18°. Each experiment was repeated three times. 2.7 Thermogravimetric analysis (TGA) Taking a small amount of freeze-dried sample, the thermal stability of SHNC was investigated on a thermogravimetric analyzer (TGA500, SMS, UK). The instrument was operated under a nitrogen atmosphere over the temperature range of 30–800℃ at a heating rate of 10℃/min. Each experiment was repeated three times. 2.8 Water contact angle (WCA) The WCA of the sample was determined using the static solid/liquid-air contact method at room temperature (25℃). A 0.1 g sample of the freeze-dried powder was pressed into a cylindrical sheet with a diameter of 10 mm and thickness of 2 mm and placed on a slide. An automatic syringe was used to drop 5 µL of pure water on the surface of the sample. The image of the water drop was captured on a OCA20 video optical contact angle instrument (OCA20, Dataphysics, Germany) and the water contact angle (WCA) was calculated using the Laplace-Young equation. All measurements were repeated five times for each sample. 2.9 Antimicrobial properties The antimicrobial properties of SHNC were determined using the method reported by (Liu et al., 2020 ) with several improvements. Escherichia coli ( E. coli ) and Staphylococcus aureus ( S. aureus ) were cultured in brain heart infusion broth to achieve logarithmic growth with ~ 10 9 colony forming unit (CFU)/mL. One mL of 0.1% SHNC was added to 10 mL of the bacterial suspension. After 24 h, 0.1 mL of the bacterial suspension was placed into tubes containing 9.9 mL of 0.85% NaCl. The total number of remaining viable E. coli and S. aureus bacteria was calculated via a 10-fold gradient dilution method. Meanwhile, 10 µL of the bacterial suspension was coated onto an agar plate and the growth of E. coli and S. aureus observed after 24 h. Each experiment was repeated three times. 2.10 Statistical analysis The results were analyzed using Origin 2021 Pro software and one-way analysis of variance (ANOVA) using SPSS 26.0 software, and significance analysis ( P < 0.05) was performed using the Duncan test. Each experiment was repeated three times. 3 Results and discussion 3.1 Chemical composition Table 1 shows the chemical composition of SHNC treated with a combined acid and ultrasonic treatment process. The α-cellulose content in SHCN before ultrasonic treatment was 84.44%, the hemicellulose content was 1.32%, and the lignin content was 1.48%, which was consistent with those previously reported (Cui et al., 2021 ). Meanwhile, the cellulose content in SHNC was similar to that of bamboo (B. Wang et al., 2023 ) and poplar (J. Li et al., 2023 ) used as pulp materials. Ultrasound can be used to remove small molecular components, such as pectin and wax. After ultrasonic treatment, the total cellulose content in SHNC was significantly increased and the lignin content decreased from 1.48–0.51%. With a continuous increase in the ultrasound intensity, the total cellulose content increased to 95.23%. This indicated that substances such as lignin and pectin in SHNC were almost completely removed, while most of the cellulose and hemicellulose was retained. This can be attributed to the mechanical, acoustic cavitation, and shear effects generated by ultrasound, which causes cellulose to break at its amorphous regions and form small molecular substances, while substances with smaller molecular weights (such as glue) are removed via the dialysis process. After ultrasonic treatment, the total cellulose content was significantly increased and the anti-depolymerization barrier disrupted, which was beneficial for the subsequent hydrolysis reactions. The molecular weight of SHNC were further analyzed using gel chromatography and the results are shown in Fig. S1 . The gel chromatograph profile of SHNC exhibited two symmetrical single peaks, indicating that SHNC was a heterophasic cellulose (Arinaitwe & Pawlik, 2014 ). The relative molecular weight of SHNC was calculated to be 221,442 Da based on the retention times of the dextran standard samples. The absolute molecular weight of SHNC was calculated using GPC fitting. The results showed that the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of SHNC were 213,935 and 171,071 Da, respectively. Our results were consistent with the average molecular weight of SHNC. In addition, the Mw/Mn ratio of SHNC was 1.04, indicating that its molecular weight distribution had a high degree of homogeneity. Table 1 Chemical composition of different samples Sample Holocellulose/% α-cellulose/% Hemicellulose/% Lignin/% Ash/% Yield/% Optical image Soy hull 85.76 ± 1.43 d 84.44 ± 1.55 d 1.32 ± 0.41 a 1.48 ± 0.54 a 3.25 ± 0.97 a — 0W 89.62 ± 1.86 c 88.86 ± 2.87 c 0.76 ± 0.12 b 0.91 ± 0.14 b 1.29 ± 0.25 b 22.74 ± 2.38 a 100W 91.78 ± 2.21 bc 91.17 ± 1.92 b 0.61 ± 0.05 c 0.79 ± 0.04 c 0.93 ± 0.17 c 17.19 ± 1.49 b 200W 93.43 ± 0.51 ab 92.96 ± 2.65 ab 0.47 ± 0.06 d 0.67 ± 0.06 d 0.75 ± 0.12 d 13.25 ± 1.31 c 300W 95.23 ± 0.48 a 94.90 ± 3.21 a 0.33 ± 0.03 e 0.51 ± 0.05 e 0.62 ± 0.09 e 11.42 ± 0.79 d Note: All data were expressed as the mean ± SD (standard deviation) (n = 3). The different letters mean significant differences ( P < 0.05). 3.2 Chemical structure analysis The size and distribution of the average particle size of nanocellulose is crucial in terms of the stability of the system. The smaller the average particle size of nanocellulose and the more uniform its distribution, the more stable the system (Morais, de Freitas Rosa, Nascimento, Do Nascimento, & Cassales, 2013), as shown in Fig. 1 a. The average particle size of the SHNC suspension system was 420.2 nm when the ultrasonic power was 0 W. When the ultrasonic power reached 300 W, the average particle size of nanocellulose was 23.88 nm. With a gradual increase in the ultrasonic power, the average particle size of nanocellulose showed a gradual decrease. This indicated that ultrasound dissociated the cellulose and shifted the size distribution towards smaller diameters. This may be attributed to the mechanical and acoustic cavitation effects produced by ultrasound, which resulted in covalent bonds (i.e., the glycosidic linkage between glucose units) between the crystalline and amorphous regions within nanocellulose, and the hydrogen bonds between the broken chains will lead to the loosening of the amorphous regions, which may further break down the covalent linkage within the amorphous region. As a result, forming a smaller-sized nanocellulose. The variation in the zeta-potential of the SHNC suspension systems formed with different ultrasonic power is shown in Fig. 1 b. When the ultrasonic power was 0 W, the potential value of the SHNC suspension system was − 23.41 mV, and when the ultrasonic power reached 300 W, the potential value of nanocellulose suspension system was − 31.41 mV. The theory of DLVO colloidal solution showed that under certain conditions, the absolute value of the zeta-potential was positively correlated with the stability of the system and a decrease in the absolute value of the potential led to a decrease in the potential energy of the repulsive forces formed between the particles and the destabilization of the system (X. Wu et al., 2023 ). From our results, the absolute value of the potential of SHNC tended to gradually increase with an increase in the ultrasonic power. This may be attributed to the fact that ultrasonication reduced the agglomeration in nanocellulose and exposed more charge. At this time, the repulsive forces were greater than the attractive forces, and the SHNC system became more stable. The noncovalent interactions formed inside SHNC were characterized using FT-IR spectroscopy and the results shown in Fig. 1 c. The absorption peaks at 3100–3700, 2930, and 898 cm –1 in all of the spectra corresponded to the typical absorption peaks of cellulose structures (Abdelhameed, Abdel-Gawad, & Emam, 2021 ; Abdin, Mabrouk, et al., 2023 ; Hasanin, Abdelhameed, Dacrory, Abou-Yousef, & Kamel, 2021 ). The broad peak at 3100–3700 cm –1 was attributed to the stretching vibrations of the -OH groups in cellulose, hemicellulose, and lignin (Ren et al., 2023 ). Acid hydrolysis and ultrasonic treatment fully exposed the internal hydroxy groups in SHNC and the peak area and intensity gradually increased at 3100–3700 cm –1 , indicating a gradual increase in the internal hydroxy content (Samsalee, Meerasri, & Sothornvit, 2023 ). The absorption peak at 2930 cm –1 was the stretching vibrations of the saturated aliphatic methylene (-C-H) bonds in cellulose and hemicellulose (Mahur, Ahuja, Singh, Maji, & Rastogi, 2023 ; Ren et al., 2023 ). The absorption peak at 1720 cm –1 was caused by the stretching vibrations of -C = O, confirming the presence of carboxy groups. This was attributed to the presence of acidic monosaccharides such as galacturonic acid and glucuronic acid inside SHNC (Yang et al., 2020 ). The peak area and peak intensity gradually increased, indicating that the internal carboxy content gradually increased. This may be due to the ultrasonic waves causing the SHNC to break, fully exposing the carboxy groups, resulting in a gradual increase in the carboxy content. The absorption peaks at 1380 and 1240 cm –1 were derived from the stretching vibrations of C = O-O in the benzene ring skeleton and lignin (Mahur et al., 2023 ; S. Wu et al., 2021 ). As the ultrasound power increased, the peak intensity at this point gradually decreased, indicating that ultrasound removed the lignin from the interior of cellulose. All of the nanocellulose samples exhibited an absorption peak at 898 cm –1 , which was caused by the stretching vibrations of the β-glucosidic bonds in nanocellulose (Mirzaee, Nikzad, Battisti, & Araghi, 2023 ), indicating that acid hydrolysis and ultrasonic treatment did not change the structure of nanocellulose. The crystal structure of SHNC was studied using XRD, and the results shown in Fig. 1 d. SHNC exhibited a broad diffraction peak at 2θ = 21°, indicating that SHNC had a typical amorphous structure (Yu, Yang, Zhang, & Zhang, 2024 ). The diffraction peak at 2θ = 21° corresponded to the triple helix structure, which stimulated the formation of hydrogen bonds between H⋯OH and CH⋯O, internally forming a semi-crystalline structural domain. All of the samples exhibited diffraction peaks at 2θ = 15.2, 21, and 31.8°, which are typical cellulose type I structural peaks distributed in the (100), (200), and (004) crystal planes (Abdin, El-Beltagy, & Naeem, 2023 ; Emam, El-Shahat, & Abdelhameed, 2023 ; Shaheen, El-Shahat, & Abdelhameed, 2022 ), respectively, indicating that acid hydrolysis and ultrasound had no effect on the SHNC crystal structure. In addition, as the ultrasound power gradually increased, the crystallinity of SHNC gradually increased with SHNC-0W, SHNC-100W, SHNC-200W, and SHNC-300W being 37.18, 42.09, 48.12, and 55.59%, respectively. This was attributed to ultrasound causing the non-crystalline regions inside nanocellulose to break, allowing hydrogen ions to enter the cellulose, leading to the degradation of some lignin and hemicellulose. Meanwhile, the FT-IR spectra confirmed the presence of hemicellulose in SHNC. 3.3 Microstructure characterization The microstructure of SHNC was characterized using SEM and the results shown in Fig. 2 . After acid hydrolysis, cellulose showed aggregated, snowflake-like nanoparticles. This was due to the fact that acid hydrolysis removed most of the lignin, hemicellulose, and non-crystalline regions of the long cellulose chains (Kasiri & Fathi, 2018 ). Meanwhile, the movement of the cellulose molecular chains tended to be randomly entangled and twisted to form different cellulose bundles, and the connections between the fiber bundles form a snowflake-like network structure. In addition, the high specific surface area between nanocellulose and the hydrogen and ester bonds formed between the hydroxy and carboxy groups between the molecular chains made some positions of nanocellulose appear stacked and blocked (Chen, Lee, & Abd Hamid, 2017 ). With an increase in the ultrasound intensity, the degree of cellulose aggregation decreased and gradually dispersed, and the length of cellulose gradually decreased, transforming from long rod-shaped nanoparticles to spherical or short rod-shaped nanoparticles. This was attributed to the cavity effect of ultrasound, which provided acoustic energy to form, grow, and disintegrate in an aqueous solution (W. Li et al., 2012 ), while the violent rupture of the bubbles caused microjets and shockwaves on the suspended cellulose surface, which produced a fracture effect on the cellulose, and destroyed the van der Waals forces and hydrogen bonding interactions between the cellulose, leading to the disintegration of the cellulose to form nanoparticles (Shanmugam & Ashokkumar, 2014 ). Meanwhile, spherical and short rod-shaped nanocellulose with a high specific surface area facilitated its reactivity with polymers, enhancing the mechanical properties of polymer matrix (C. Zhang, Khorshidi, Najafi, & Ghasemi, 2023 ). 3.4 Physical properties of SHNC suspension 3.4.1 Water contact angle The water contact angle (WCA) is the characteristic angle between a liquid and solid surface, which is usually used to assess the wettability of a sample’s surface. Meanwhile, a smaller WAC indicates better wettability and hydrophilicity (Yu et al., 2024 ). The WAC of SHNC was 54.76 ± 0.46° when formed at an ultrasonic power of 0 W, while it was about 31.37 ± 0.24° at an ultrasonic power of 300 W. With a gradual increase in the ultrasonic power, the WAC of SHNC gradually decreased (Fig. 3 a), which indicated that the hydrophilicity of SHNC was gradually enhanced. This may be due to the fact that ultrasonication broke the hydrogen bonds formed between the cellulose molecules, forming smaller molecular weight nanocellulose, increasing its specific surface area, and exposing more hydrophilic groups. The WAC of all of the samples were < 90°, indicating that the SHNC samples were all highly hydrophilic, which may be due to the fact that soluble SHNC contained a large number of hydrophilic groups (e.g., hydroxy, carboxy, and amino groups) that allowed water binding to occur easily. 3.4.2 Thermal stability Thermal analysis techniques were used to analyze the stability of the samples under continuous heating conditions and determine the onset and maximum decomposition temperatures, as shown in Fig. 3 b. The thermal decomposition of SHNC was divided into three stages. The first stage was observed at 30–180°C, which exhibited a moderate mass loss due to the evaporation of water and volatile substances within SHNC (Ma et al., 2023 ). The second stage was 200–400°C, which exhibited a substantial mass loss due to the decomposition of hemicellulose and cellulose (Mudoi, Sinha, & Parthasarthy, 2022 ). The third stage was at 450–800°C, which was due to the gradual carbonization of the SHNC residues. Interestingly, a gradual rightward shift of the absorption peak of SHNC was seen in the DTG curves between 200–400°C, indicating a gradual increase in the decomposition temperature and thermal stability of SHNC. This may be related to the removal of the thermally unstable hemicellulose and pectin, a result that was consistent with the findings of Dominic et al. (Dominic et al., 2022 ). The onset degradation temperature (T onset ) and maximum degradation temperature (T max ) of the SHNC samples are summarized in Table 2 . At an ultrasound power of 0 W, SHNC decomposed at ~ 187.29°C, and the maximum degradation occurred at ~ 224.13°C. The T onset of SHNC was 180.38°C at an ultrasound intensity of 300 W, which was higher than that of SHNC at 0 W. This indicated that the thermal stability of SHNC was improved, and the higher initial degradation temperature, which was even higher than the melt softening temperature of general thermoplastic polymers, making it promising for use in polymer-reinforced composites. The initial degradation temperatures of the sonicated SHNC samples were all lower than those of the unsonicated SHNC, and the T max values showed the same trend, which was consistent with the findings reported in previous research studies (Dominic et al., 2022 ; Mirzaee et al., 2023 ). This may be related to the fact that ultrasonication breaks cellulose to form smaller-sized nanocellulose with high specific surface area and high crystallinity (Khanjanzadeh & Park, 2021 ; Mirzaee et al., 2023 ). (Ilyas, Sapuan, & Ishak, 2018 ) reported that the thermal stability of nanocellulose was positively correlated with its crystallinity, i.e., the higher the crystallinity, the higher the degradation temperature of the samples. In summary, SHNC had high thermal stability and had great potential for future applications in the field of nanomaterials. Table 2 Thermal properties of the different samples Sample T onset (℃) T Max (℃) 0W 187.29 ± 2.74 b 224.13 ± 3.65 c 100W 181.63 ± 3.31 c 250.48 ± 4.19 b 200W 202.22 ± 1.49 a 260.54 ± 2.43 a 300W 180.38 ± 2.37 c 262.75 ± 4.63 a Note: All data were expressed as the mean ± SD (standard deviation) (n = 3). The different letters mean significant differences ( P < 0.05). 3.4.3 Interfacial tension and pressure To investigate the effect of the ultrasound power on the oil-water interface properties (water droplet suspension in pure oil droplet in SHNC solution) of SHNC, the dynamic interfacial tension was monitored using an optical contact angle measuring instrument, and the results are shown in Fig. 4 a. The adsorption process of SHNC at the oil-water interface was divided into two stages. In the first stage, the nanoparticles quickly approached and adhered to the oil-water interface, exhibiting a rapid decrease in tension. During the second stage, the nanoparticles adsorbed at the oil-water interface were rearranged or even formed a viscoelastic film, exhibiting a slow decrease in the interfacial tension (Feng et al., 2021 ). (Q. Li, Chen, Li, Li, & Liu, 2020 ) also reported similar research results. Subsequently, by comparing the changes in the interfacial tension of SHNC formed under different ultrasonic powers, it was found that the larger the ultrasonic power, the smaller the interfacial tension value of the system. Among them, the interfacial tension of SHNC decreased from 13.86 to 3.4 mN/m, while the size of SHNC was the smallest at 300 W. This indicated that small-sized SHNC could more easily adsorb to the oil-water interface and reduce the interfacial tension of the system. This may be attributed to the cavitation effect generated by ultrasound, which caused the amorphous regions of SHNC to break and form short chain nanocellulose, while exposing more hydrophilic groups and enhancing the hydrophilic effect. Meanwhile, the specific surface area of nanocellulose increased, the intermolecular force increased, and the degree of cross-linking increased. The system gradually changed from a fluid state to a weak gel state, leading to an increase in the viscosity of the system, which further hindered the movement of nanocellulose molecules in the system. Therefore, the interface adsorption rate of SHNC gradually decreased and tended to flatten. Our results showed that SHNC exhibited excellent gelation properties. We further investigated the effect of different ultrasonic powers on the surface pressure at the gas/liquid interface of SHNC, as shown in Fig. 4 b. With an increase in the ultrasonic power, the interfacial pressure of SHNC showed a gradual increase with the adsorption time, indicating that the adsorption amount of SHNC at the gas/liquid interface gradually increased. Meanwhile, the higher the ultrasonic power, the higher the surface pressure of SHNC at the gas/liquid interface, which may be attributed to an increase in the interfacial tension due to the adsorption of SHNC at the gas/liquid interface via electrostatic action. 3.4.4 UV-visible transmittance Nanocellulose with excellent transparency and UV resistance is potentially more advantageous for the preparation of nanomaterials. The transparency of the SHNC suspension showed a gradual increase with an increase in the ultrasonic power (Fig. 4 c). At a wavelength of 600 nm, the transmittance of the SHNC suspension was > 73%. which was consistent with previous results (Cao, Ding, Yu, & Al-Deyab, 2012 ). This may be due to the fact that SHNC contains hydroxyl and carboxylic groups, which absorb ultraviolet light (Antunes et al., 2023 ). Meanwhile, SHNC contains some lignin, which is highly absorbable in the ultraviolet band, thus enhancing the ultraviolet light scattering and gradually reducing the ultraviolet absorption (Robles et al., 2020 ; Sadeghifar & Ragauskas, 2020 ). At wavelengths of 200–400 nm, the UV transmittance of SHNC dramatically decreased from 56.58% to almost zero, indicating that SHNC had excellent UV resistance. This may be attributed to the fact that the particle size of SHNC was smaller than the wavelength of UV light, the light scattering increased, and the UV absorption gradually decreased (Robles et al., 2020 ). The color of the SHNC suspension gradually changed from white to off-white due to the different proportions of lignin and hemicellulose in SHNC (Fig. 4 d) (Boufi & Chaker, 2016 ). Our results showed that SHNC had excellent transparency and UV resistance, which was expected to be widely used in transparent flexible electronic sensors, food packaging materials and other fields. 3.4.5 Shear viscosity Nanocellulose with high apparent viscosity is often more conducive to cross-linking, thus affecting the gelation self-assembly process (Abitbol, Kam, Levi-Kalisman, Gray, & Shoseyov, 2018 ). The shear viscosity scan curves of SHNC prepared under different ultrasonic intensities are shown in Fig. 4 e. All of the samples exhibited typical shear thinning behavior in their viscosity (Z. Li et al., 2018 ). When the shear rate increased from 0.1 to 1 s –1 , the viscosity of the SHNC suspension suddenly decreased, exhibiting pseudoplastic fluid behavior. Subsequently, as the shear rate gradually increased from 1 to 10 s –1 , the viscosity of the SHNC suspension tended to become smooth. The viscosity order at 0.1 s s –1 was: SHNC-300 W > SHNC-200 W > SHNC-100 W > SHNC-0 W. This may be due to the cavitation effect generated by ultrasound, where high energy sound energy promoted the disintegration of the microfiber structures, which was beneficial for preparing SHNCs with smaller particle size and higher surface charge, thereby increasing the effective volume fraction of SHNCs in the suspension, strengthening the hydrogen bonding interactions formed between the SHNCs and the solution, leading to an increase in viscosity. Our results showed that SHNC-300W had more advantages than SHNC-0W in terms of its gelation properties. 3.5 Antimicrobial properties of the SHNC suspension To explore the inhibitory effect of SHNC prepared under different ultrasonic powers, the inhibitory activity of the SHNC samples was analyzed by determining the number of remaining viable bacteria, as shown in Fig. 5 . With a gradual increase in the ultrasonic power, the inhibition rate of SHNC against E. coli and S. aureus gradually increased. At 0 W, the inhibition rate of SHNC against E. coli and S. aureus was 33.16 ± 1.04 and 45.01 ± 2.14%, respectively. This was due to the fact that SHNC contains glucuronic acid and glucosamine, which contained aldehyde, carboxy, and amino groups, which possessed great bacteriostatic properties. Specifically, the aldehyde groups underwent a nucleophilic addition reaction with the internal proteins of the bacteria, which caused the bacteria to lose their ability to replicate and cause disorders in their metabolic system (Balcerzak et al., 2023 ). The carboxy group combined with hydrogen ions to form a carboxylic acid, which acidified the bacterial growth environment, hindering bacterial adhesion, disrupting cell membranes, increasing the bacterial permeability, and causing the bacterial content to flow-out, leading to bacterial death (Jiang et al., 2024 ). Meanwhile, amino acids bound to negatively charged cell membranes or cell walls, leading to cell membrane disruption and cell death (Lan et al., 2023 ), achieving bacterial inhibition. The highest inhibition rate of SHNC against E. coli and S. aureus was achieved at 300 W with 61.13 ± 0.52 and 69.33 ± 1.52%, respectively. This was due to the fact that ultrasound caused the SHNC to break-up and form nanocellulose with smaller molecular weight, exposing more aldehyde, carboxy, and amino groups in SHNC, which increased the antibacterial effect of SHNC. Nanocellulose with excellent antimicrobial properties not only endowed the nanomaterials with antimicrobial properties, but also great biodegradability. 4 Conclusions In summary, an anionic nanocrystalline cellulose (Mw: 213,935 Da) has been extracted from discarded soy hull using a combined acid hydrolysis-ultrasonic treatment method, which contained a large number of hydrogen and ester bonds. The extraction rate of SHNC was higher (11.42%) and the whole cellulose content increased to > 95%. SHNC presented spherical or short rod-shaped nanoparticles with diameters in the range of 20–50 nm. Meanwhile, SHNC exhibited great crystallinity (55.59%), hydrophilicity, thermal stability, and transparency (80%). More importantly, SHNC had excellent bacteriostatic properties against E. coli and S. aureus with a high bacteriostatic rate of 69.33%. This study provided a new strategy for the high value utilization of discarded soy hull. Meanwhile, the high performance of SHNC will have excellent application prospects in the fields of food packaging, biomedicine, and tissue engineering. Declarations Author statement Kejin Yu: software, data curation, methodology, and writing the original draft. Lina Yang: conceptualization, methodology, writing the original draft, review & editing, and project administration. Siyu Zhang: software and data curation. Ning Zhang: software and data curation. 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(a) Particle size, (b) zeta-potential, (c) FT-IR spectrum, and (d) XRD of SHNC. All data are expressed as mean ± standard deviation (n = 3). The different letters represent significant differences (\u003cem\u003eP\u003c/em\u003e \u0026lt;0.05).\u003c/p\u003e","description":"","filename":"floatimage64.png","url":"https://assets-eu.researchsquare.com/files/rs-5667593/v1/5b4a255838a58563a27fce65.png"},{"id":72154091,"identity":"f735c08b-7629-4b81-a341-f39199e47cb0","added_by":"auto","created_at":"2024-12-23 08:39:21","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":3233756,"visible":true,"origin":"","legend":"\u003cp\u003eMicrostructure of SHNC. Each experiment was repeated three times.\u003c/p\u003e","description":"","filename":"floatimage73.png","url":"https://assets-eu.researchsquare.com/files/rs-5667593/v1/d5db053f0ff2d0999751f10e.png"},{"id":72154083,"identity":"1005a5c0-4ea9-4294-922f-c72f57770ba7","added_by":"auto","created_at":"2024-12-23 08:39:20","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":1239955,"visible":true,"origin":"","legend":"\u003cp\u003ePhysical properties of SHNC. (a) WCA, (b) TGA, and (c) DTG of SHNC. All data were expressed as the mean ± standard deviation (n = 3). The different letters represent significant differences (\u003cem\u003eP\u003c/em\u003e\u0026lt;0.05).\u003c/p\u003e","description":"","filename":"floatimage82.png","url":"https://assets-eu.researchsquare.com/files/rs-5667593/v1/d3b972404754f7eacd7c4991.png"},{"id":72154090,"identity":"95597c1a-cabe-430f-a060-50e3214c34a8","added_by":"auto","created_at":"2024-12-23 08:39:20","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":2574227,"visible":true,"origin":"","legend":"\u003cp\u003ePhysical properties of SHNC. (a) Interfacial tension, (b) interface pressure, (c-d) transparency, and (e) shear viscosity of SHNC. Each experiment was repeated three times.\u003c/p\u003e","description":"","filename":"floatimage91.png","url":"https://assets-eu.researchsquare.com/files/rs-5667593/v1/2f3642fc41f6f5c7a66b7ea4.png"},{"id":72154100,"identity":"1d2428e5-5835-4aed-aa32-be81a1ebd667","added_by":"auto","created_at":"2024-12-23 08:39:25","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":6602459,"visible":true,"origin":"","legend":"\u003cp\u003eAntimicrobial properties of SHNC. Antibacterial activity of SHNC against (a) \u003cem\u003eE. coli \u003c/em\u003eand (b) \u003cem\u003eS. aurus\u003c/em\u003e. All data were expressed as the mean ± standard deviation (n = 3). The different letters represent significant differences (\u003cem\u003eP\u003c/em\u003e \u0026lt;0.05).\u003c/p\u003e","description":"","filename":"floatimage101.png","url":"https://assets-eu.researchsquare.com/files/rs-5667593/v1/ecdded3774425a222980eab5.png"},{"id":75568123,"identity":"97c55796-5246-4416-80a9-f99bf3a2f70f","added_by":"auto","created_at":"2025-02-06 02:31:36","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":18433102,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5667593/v1/6e50be0b-3f51-4690-bad2-eebf2218644c.pdf"},{"id":72154092,"identity":"00ca2dc1-84c4-4ab1-9bdd-355801a9f43a","added_by":"auto","created_at":"2024-12-23 08:39:21","extension":"docx","order_by":0,"title":"","display":"","copyAsset":false,"role":"supplement","size":45083,"visible":true,"origin":"","legend":"","description":"","filename":"Supportinginformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-5667593/v1/8c5b41e184c3669f006f3135.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"The characterization of size-controlled nanocrystalline cellulose from soy hulls with ultrasonic assisted extraction","fulltext":[{"header":"1 Introduction","content":"\u003cp\u003eSoybeans are an important component of grain in Northeast China and a large amount of by-products are produced during their production and processing. Soy hull is one of these by-products, which is usually used as animal feed, and represents a serious waste of this resource (Reichembach \u0026amp; de Oliveira Petkowicz, 2022). Recently, many researchers have extracted bioactive natural polymers such as polysaccharides and isoflavones from soy hull (Kim, Miller, Lee, \u0026amp; Kim, \u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e2016\u003c/span\u003e; Reichembach \u0026amp; de Oliveira Petkowicz, 2022; Yang et al., \u003cspan citationid=\"CR62\" class=\"CitationRef\"\u003e2019\u003c/span\u003e), providing a new direction for the high value utilization of soy hull. However, we have discovered that research on cellulose and its derivatives is scarce. Meanwhile, soy hull contains an abundant amount of cellulose, which has great potential as a source for developing high quality cellulose and its derivatives (Cai et al., \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e2022\u003c/span\u003e; Huang et al., \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e2024\u003c/span\u003e). Therefore, extracting cellulose and its derivatives from soy hull is of great significance.\u003c/p\u003e \u003cp\u003eAs a derivative of cellulose, nanocellulose has received widespread research attention in the fields of food, biomedical, and cosmetics due to its high crystallinity, large specific surface area, biocompatibility, hydrophilicity, non-toxicity, and environmental benefits (Grishkewich, Mohammed, Tang, \u0026amp; Tam, \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; W. Li, Yue, \u0026amp; Liu, \u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e2012\u003c/span\u003e). At present, there are several methods for preparing nanocellulose. For example, acid hydrolysis (H. Zhang et al., \u003cspan citationid=\"CR66\" class=\"CitationRef\"\u003e2020\u003c/span\u003e), oxidation utilizing 2,2,6,6-tetramethylpyridine oxide (Tang \u0026amp; Huang, \u003cspan citationid=\"CR55\" class=\"CitationRef\"\u003e2022\u003c/span\u003e), and biological methods (J. Wang, Tavakoli, \u0026amp; Tang, \u003cspan citationid=\"CR57\" class=\"CitationRef\"\u003e2019\u003c/span\u003e). Among them, acid hydrolysis is the most well-known and widely used method because the disordered or amorphous regions of cellulose are preferentially hydrolyzed, while the crystalline regions have better acid resistance (Habibi, Lucia, \u0026amp; Rojas, \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e2010\u003c/span\u003e). Nanocellulose typically exhibits a specific morphology and properties after acid hydrolysis. For example, (Sumarago, dela Cerna, Leyson, Tan, \u0026amp; Magsico, 2024) extracted nanocellulose using sulfuric acid, which is short rod-shaped and exhibits excellent thermal stability. When compared with acid hydrolysis, ultrasonic treatment is a widely accepted mechanical extraction method that can effectively alter the morphology and properties of nanocellulose during the preparation process (Abral, Lawrensius, Handayani, \u0026amp; Sugiarti, \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e2018\u003c/span\u003e; Low et al., \u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). For example, (Chagas et al., \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2023\u003c/span\u003e) revealed that ultrasonic treatment can transform large-sized microcrystalline cellulose into nanoscale rod-shaped cellulose nanocrystals. (Wong, Kasapis, \u0026amp; Huang, \u003cspan citationid=\"CR58\" class=\"CitationRef\"\u003e2012\u003c/span\u003e) have also revealed that ultrasonic treatment can significantly reduce the molecular weight of bacterial and plant cellulose, and increase their crystallinity index. In addition, ultrasonic treatment can also affect the interfacial and thermal stability of nanocellulose (Meng et al., \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e2019\u003c/span\u003e; Xing et al., \u003cspan citationid=\"CR61\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). The changes in the morphology and properties of nanocellulose can be mainly attributed to the cavitation effect generated by ultrasound (Low et al., \u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e2022\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eRecent studies have found that the combination of acid hydrolysis and ultrasonic treatment can achieve a smaller particle size, better performance, higher efficiency, and safer extraction of nanocellulose when compared to traditional methods (Karakehya \u0026amp; Bilgic, \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e2019\u003c/span\u003e; Low et al., \u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). For example, Lim et al. (Lim, Tang, Manickam, Yu, \u0026amp; Tan, \u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e2024\u003c/span\u003e) successfully extracted mesh nanocellulost with a diameter of 18\u0026ndash;26 nm from durian shells by acid hydrolyzation-ultrasonic combined treatment, and the lignin content inside was almost zero. Meanwhile, the nanocellulose also has excellent physical and chemical properties. Silva et al. (Silva, Silva, Assis, \u0026amp; Martelli-Tosi, \u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e2024\u003c/span\u003e) successfully extracted nanocellulose from cherry by-product by acid hydrolyzation-ultrasonic treatment, and the yield of nanocellulose reached 69.9%, with high crystallinity (71.7%) and thermal stability. In addition, ultrasonic treatment helps to remove the non-cellulose components (Alanazi, \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). Nanocellulose extracted using traditional methods (eg., ball-milling etc.) has low stability. In general, the stability of nanocellulose depends on the electrostatic interactions formed between the cellulose fibers, which can be enhanced by introducing negatively charged functional groups (Grishkewich et al., \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). However, ultrasound can produce cavitation, which can break up nanocellulose in its amorphous regions and part of its crystalline areas, expose more surface charges, and improve its interface stability and gel performance (Abral et al., \u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). Therefore, it is of great research interest to extract nanocellulose from soybean seed coat using a combination of acid hydrolysis and ultrasonic treatment in order to reveal the changes in the morphology and properties of nanocellulose caused by their combined effect and further reveal the impact of these changes on the interfacial properties of nanocellulose.\u003c/p\u003e \u003cp\u003eThis study aimed to explore a green and environmentally friendly method for producing nanocellulose, providing the basis for the high value utilization of soy hull. Soy hull nanocrystalline cellulose (SHNC) was prepared using a combination of acid hydrolysis and ultrasonic treatment. The effect of the ultrasonic power on the composition and morphology of SHNC was investigated and the influence of ultrasonic power on the physicochemical properties of SNHC, including its thermal stability, hydrophilicity, and transparency, was analyzed. The results of this study can be used to improve the comprehensive utilization value of soy hull and lay a theoretical foundation for the comprehensive utilization of SHNC.\u003c/p\u003e"},{"header":"2 Materials and methods","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1 Materials\u003c/h2\u003e \u003cp\u003eSoy hull was purchased from Yuwang Industry Co., Ltd. (Dezhou, China). Regular dialysis bags (14,000 Da) were purchased from Yuanye Biological Co., Ltd. (Shanghai, China). \u003cem\u003eEscherichia coli\u003c/em\u003e and \u003cem\u003eStaphylococcus aureus\u003c/em\u003e were purchased from Wuhan Punosai Life Technology Co., Ltd. (Wuhan, China). Brain heart infusion broth was purchased from Shunyou Biotechnology Co., Ltd. (Shanghai, China). Nutritional broth and agar were purchased from Haibo Biotechnology Co., Ltd. (Qingdao, China). Ethanol (analytical grade), sodium hydroxide (analytical grade), hydrochloric acid (analytical grade), acetic acid (analytical grade), vitriol (analytical grade), sodium chlorite (analytical grade), and sodium chloride (analytical grade) were purchased from Sinopharm Group Chemical reagent Co., Ltd. (Tianjin, China). Deionized water was used throughout the experiment.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2 Preparation of SHNC\u003c/h2\u003e \u003cp\u003eSoy hull was sifted through 20 mesh to remove any impurities and the soy hull crushed three times using a hammer stone cyclone mill (JXFM110, Shanghai, China) and then sifted through 60 mesh. Five g soy hull was placed in a beaker, 250 mL of deionized water added, and allowed to soak for 24 h. A total of 15 mL of 10% HCl was added to the beaker for acid hydrolysis and stirred at 170℃ for 2 h. A 3-fold excess of deionized water was used to terminate the reaction and the mixture allowed to cool to 25℃. The beaker was placed in the ultrasonic instrument (JY99-IIDN, Ningbo, China) for 120 min at 4℃ (0 W, 100 W, 200 W, and 300 W), centrifuged (Megafuge ST1 Plus, Thermo, USA) at 4,000 rpm in a 150-mL test tube for 15 min, the supernatant removed, and NaOH added to adjust the pH of the solution to 7. The solution was placed into a dialysis bag (Da\u0026thinsp;=\u0026thinsp;14,000) for 3 d. The resulting solution was precipitated upon the slow addition of ethanol solution (95%, v/v) to dilute the concentrate at a ratio of 1:2 (v/v) with constantly stirring. The precipitate was stored at 4℃ for 24 h, the solution centrifuged at 4,000 rpm for 5 min, and the sediment was dried in a vacuum freeze dryer (SCIENTZ-10N/A, Ningbo, China) for 24 h to obtain the SHNC product.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3 Determination of the chemical composition\u003c/h2\u003e \u003cp\u003eThe chemical composition of SHNC was determined using the method reported by (Sluiter et al., \u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e2008\u003c/span\u003e) and (Chen, Lee, Juan, \u0026amp; Phang, \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e2016\u003c/span\u003e) with several improvements. Holocellulose and α-cellulose content: 2 g of SHNC was dispersed in 65 mL of deionized water and then treated with 1.5 g of NaClO\u003csub\u003e2\u003c/sub\u003e and 1 mL of CH\u003csub\u003e3\u003c/sub\u003eCOOH for 4 h. The sample was rinsed until the pH was neutral, and dried. The remaining samples were treated with 17.5% NaOH for 30 min (25℃) and then soaked in 60 mL of deionized water for 30 min. The hemicellulose content was calculated using the difference between holocellulose and α-cellulose. Lignin content: 0.6 g of SHNC was dissolved in 6 mL of 72% concentrated H\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e and hydrolyzed for 1 h, then 84 mL of deionized water was added and hydrolyzed at 121℃ for 1 h. The sample was then rinsed until the pH was neutral, and dried. Each experiment was repeated three times.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e2.4 Scanning electron microscopy (SEM)\u003c/h2\u003e \u003cp\u003eA small amount of freeze-dried sample was attached to the platform with conductive adhesive, any excess sample was blown away with a dust ball, and the sample coated with a layer of gold. SEM (S-4800, Hitachi, Japan) was used to observe the morphology of the sample. The SEM parameters were set as follows: acceleration voltage of 10.0 kV and the normal mode amplification factor was \u0026times;50,000 and \u0026times;300,000 magnifications, respectively. Each experiment was repeated three times.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003e2.5 Fourier transform infrared (FT-IR) spectroscopy\u003c/h2\u003e \u003cp\u003eFreeze-dried samples and KBr powder were mixed in a 1:100 (w/w) ratio and the mixed powder was pressed into tablets. Prior to measurement, KBr was used as a blank correction to eliminate the interference of factors such as CO\u003csub\u003e2\u003c/sub\u003e and humidity in the air. The sample was then scanned using an FT-IR spectrometer (Agilent Technologies, Santa Clara, CA, USA) in the wavenumber range of 4000\u0026ndash;400 cm\u003csup\u003e\u0026ndash;1\u003c/sup\u003e over 32 scans and resolution of 1 cm\u003csup\u003e\u0026ndash;1\u003c/sup\u003e. The data were processed and analyzed using Omnic software. Each experiment was repeated three times.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003e2.6 X-ray diffraction (XRD) measurements\u003c/h2\u003e \u003cp\u003eThe crystalline structure of the SHNC was measured using XRD (D8 advance, Bruker, Germany) with Cu K\u003csub\u003eα1\u003c/sub\u003e radiation at 40 kV and 40 mA. Briefly, after the lyophilized SHNC sample was crushed, it was poured into the groove of the sample rack, and then gently pressed with a slide to make the sample powder consistent with the frame level. The scanning rate was 0.209\u0026deg; s\u003csup\u003e\u0026ndash;1\u003c/sup\u003e with a step size of 0.0167\u0026deg;, and data were recorded over an angle range of 5\u0026minus;80\u0026deg;. The data was processed and analyzed using Jade software. The crystallinity index (CrI) of SHNC was calculated using the following formula:\u003cdiv id=\"Equa\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equa\" name=\"EquationSource\"\u003e\n$$\\:\\text{C}\\text{r}\\text{I}\\:\\left(\\text{%}\\right)=\\frac{{\\text{I}}_{002}-\\:{\\text{I}}_{\\text{a}\\text{m}}}{{\\text{I}}_{002}}\\times\\:100\\text{%}\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\:\\left(1\\right)$$\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003ewhere I\u003csub\u003e002\u003c/sub\u003e is the maximum intensity value of diffraction of the 002 lattice peak observed for crystalline cellulose at 2θ\u0026thinsp;~\u0026thinsp;22\u0026deg;, while I\u003csub\u003eam\u003c/sub\u003e is the intensity value observed for amorphous cellulose at 2θ\u0026thinsp;~\u0026thinsp;18\u0026deg;. Each experiment was repeated three times.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec9\" class=\"Section2\"\u003e \u003ch2\u003e2.7 Thermogravimetric analysis (TGA)\u003c/h2\u003e \u003cp\u003eTaking a small amount of freeze-dried sample, the thermal stability of SHNC was investigated on a thermogravimetric analyzer (TGA500, SMS, UK). The instrument was operated under a nitrogen atmosphere over the temperature range of 30\u0026ndash;800℃ at a heating rate of 10℃/min. Each experiment was repeated three times.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec10\" class=\"Section2\"\u003e \u003ch2\u003e2.8 Water contact angle (WCA)\u003c/h2\u003e \u003cp\u003eThe WCA of the sample was determined using the static solid/liquid-air contact method at room temperature (25℃). A 0.1 g sample of the freeze-dried powder was pressed into a cylindrical sheet with a diameter of 10 mm and thickness of 2 mm and placed on a slide. An automatic syringe was used to drop 5 \u0026micro;L of pure water on the surface of the sample. The image of the water drop was captured on a OCA20 video optical contact angle instrument (OCA20, Dataphysics, Germany) and the water contact angle (WCA) was calculated using the Laplace-Young equation. All measurements were repeated five times for each sample.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec11\" class=\"Section2\"\u003e \u003ch2\u003e2.9 Antimicrobial properties\u003c/h2\u003e \u003cp\u003eThe antimicrobial properties of SHNC were determined using the method reported by (Liu et al., \u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e2020\u003c/span\u003e) with several improvements. \u003cem\u003eEscherichia coli\u003c/em\u003e (\u003cem\u003eE. coli\u003c/em\u003e) and \u003cem\u003eStaphylococcus aureus\u003c/em\u003e (\u003cem\u003eS. aureus\u003c/em\u003e) were cultured in brain heart infusion broth to achieve logarithmic growth with ~\u0026thinsp;10\u003csup\u003e9\u003c/sup\u003e colony forming unit (CFU)/mL. One mL of 0.1% SHNC was added to 10 mL of the bacterial suspension. After 24 h, 0.1 mL of the bacterial suspension was placed into tubes containing 9.9 mL of 0.85% NaCl. The total number of remaining viable \u003cem\u003eE. coli\u003c/em\u003e and \u003cem\u003eS. aureus\u003c/em\u003e bacteria was calculated via a 10-fold gradient dilution method. Meanwhile, 10 \u0026micro;L of the bacterial suspension was coated onto an agar plate and the growth of \u003cem\u003eE. coli\u003c/em\u003e and \u003cem\u003eS. aureus\u003c/em\u003e observed after 24 h. Each experiment was repeated three times.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec12\" class=\"Section2\"\u003e \u003ch2\u003e2.10 Statistical analysis\u003c/h2\u003e \u003cp\u003eThe results were analyzed using Origin 2021 Pro software and one-way analysis of variance (ANOVA) using SPSS 26.0 software, and significance analysis (\u003cem\u003eP\u003c/em\u003e\u0026thinsp;\u0026lt;\u0026thinsp;0.05) was performed using the Duncan test. Each experiment was repeated three times.\u003c/p\u003e \u003c/div\u003e"},{"header":"3 Results and discussion","content":"\u003cdiv id=\"Sec14\" class=\"Section2\"\u003e\n \u003ch2\u003e3.1 Chemical composition\u003c/h2\u003e\n \u003cp\u003eTable \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e shows the chemical composition of SHNC treated with a combined acid and ultrasonic treatment process. The \u0026alpha;-cellulose content in SHCN before ultrasonic treatment was 84.44%, the hemicellulose content was 1.32%, and the lignin content was 1.48%, which was consistent with those previously reported (Cui et al., \u003cspan class=\"CitationRef\"\u003e2021\u003c/span\u003e). Meanwhile, the cellulose content in SHNC was similar to that of bamboo (B. Wang et al., \u003cspan class=\"CitationRef\"\u003e2023\u003c/span\u003e) and poplar (J. Li et al., \u003cspan class=\"CitationRef\"\u003e2023\u003c/span\u003e) used as pulp materials. Ultrasound can be used to remove small molecular components, such as pectin and wax. After ultrasonic treatment, the total cellulose content in SHNC was significantly increased and the lignin content decreased from 1.48\u0026ndash;0.51%. With a continuous increase in the ultrasound intensity, the total cellulose content increased to 95.23%. This indicated that substances such as lignin and pectin in SHNC were almost completely removed, while most of the cellulose and hemicellulose was retained. This can be attributed to the mechanical, acoustic cavitation, and shear effects generated by ultrasound, which causes cellulose to break at its amorphous regions and form small molecular substances, while substances with smaller molecular weights (such as glue) are removed via the dialysis process. After ultrasonic treatment, the total cellulose content was significantly increased and the anti-depolymerization barrier disrupted, which was beneficial for the subsequent hydrolysis reactions.\u003c/p\u003e\n \u003cp\u003eThe molecular weight of SHNC were further analyzed using gel chromatography and the results are shown in Fig. \u003cspan class=\"InternalRef\"\u003eS1\u003c/span\u003e. The gel chromatograph profile of SHNC exhibited two symmetrical single peaks, indicating that SHNC was a heterophasic cellulose (Arinaitwe \u0026amp; Pawlik,\u0026nbsp;\u003cspan class=\"CitationRef\"\u003e2014\u003c/span\u003e). The relative molecular weight of SHNC was calculated to be 221,442 Da based on the retention times of the dextran standard samples. The absolute molecular weight of SHNC was calculated using GPC fitting. The results showed that the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of SHNC were 213,935 and 171,071 Da, respectively. Our results were consistent with the average molecular weight of SHNC. In addition, the Mw/Mn ratio of SHNC was 1.04, indicating that its molecular weight distribution had a high degree of homogeneity.\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\u003eChemical composition of different samples\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003ccolgroup cols=\"8\"\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\u003eHolocellulose/%\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003e\u0026alpha;-cellulose/%\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eHemicellulose/%\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eLignin/%\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eAsh/%\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eYield/%\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eOptical image\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\u003eSoy hull\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e85.76\u0026thinsp;\u0026plusmn;\u0026thinsp;1.43\u003csup\u003ed\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e84.44\u0026thinsp;\u0026plusmn;\u0026thinsp;1.55\u003csup\u003ed\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1.32\u0026thinsp;\u0026plusmn;\u0026thinsp;0.41\u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1.48\u0026thinsp;\u0026plusmn;\u0026thinsp;0.54\u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e3.25\u0026thinsp;\u0026plusmn;\u0026thinsp;0.97\u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u0026mdash;\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cimg 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\"\u003e\u003cbr\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e200W\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e93.43\u0026thinsp;\u0026plusmn;\u0026thinsp;0.51\u003csup\u003eab\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e92.96\u0026thinsp;\u0026plusmn;\u0026thinsp;2.65\u003csup\u003eab\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e0.47\u0026thinsp;\u0026plusmn;\u0026thinsp;0.06\u003csup\u003ed\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e0.67\u0026thinsp;\u0026plusmn;\u0026thinsp;0.06\u003csup\u003ed\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e0.75\u0026thinsp;\u0026plusmn;\u0026thinsp;0.12\u003csup\u003ed\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e13.25\u0026thinsp;\u0026plusmn;\u0026thinsp;1.31\u003csup\u003ec\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cimg src=\"https://myfiles.space/user_files/127393_c7e80a1c9bb65875/127393_custom_files/img173494287586.png\"\u003e\u003cbr\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e300W\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e95.23\u0026thinsp;\u0026plusmn;\u0026thinsp;0.48\u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e94.90\u0026thinsp;\u0026plusmn;\u0026thinsp;3.21\u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e0.33\u0026thinsp;\u0026plusmn;\u0026thinsp;0.03\u003csup\u003ee\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e0.51\u0026thinsp;\u0026plusmn;\u0026thinsp;0.05\u003csup\u003ee\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e0.62\u0026thinsp;\u0026plusmn;\u0026thinsp;0.09\u003csup\u003ee\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e11.42\u0026thinsp;\u0026plusmn;\u0026thinsp;0.79\u003csup\u003ed\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e\u003cimg src=\"https://myfiles.space/user_files/127393_c7e80a1c9bb65875/127393_custom_files/img1734942875.png\"\u003e\u003cbr\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003ctfoot\u003e\n \u003ctr\u003e\n \u003ctd colspan=\"8\"\u003eNote: All data were expressed as the mean\u0026thinsp;\u0026plusmn;\u0026thinsp;SD (standard deviation) (n\u0026thinsp;=\u0026thinsp;3). The different letters mean significant differences (\u003cem\u003eP\u003c/em\u003e\u0026thinsp;\u0026lt;\u0026thinsp;0.05).\u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tfoot\u003e\n \u003c/table\u003e\n \u003c/div\u003e\n \u003cp\u003e\u003cbr\u003e\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec15\" class=\"Section2\"\u003e\n \u003ch2\u003e3.2 Chemical structure analysis\u003c/h2\u003e\n \u003cp\u003eThe size and distribution of the average particle size of nanocellulose is crucial in terms of the stability of the system. The smaller the average particle size of nanocellulose and the more uniform its distribution, the more stable the system (Morais, de Freitas Rosa, Nascimento, Do Nascimento, \u0026amp; Cassales, 2013), as shown in Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003ea. The average particle size of the SHNC suspension system was 420.2 nm when the ultrasonic power was 0 W. When the ultrasonic power reached 300 W, the average particle size of nanocellulose was 23.88 nm. With a gradual increase in the ultrasonic power, the average particle size of nanocellulose showed a gradual decrease. This indicated that ultrasound dissociated the cellulose and shifted the size distribution towards smaller diameters. This may be attributed to the mechanical and acoustic cavitation effects produced by ultrasound, which resulted in covalent bonds (i.e., the glycosidic linkage between glucose units) between the crystalline and amorphous regions within nanocellulose, and the hydrogen bonds between the broken chains will lead to the loosening of the amorphous regions, which may further break down the covalent linkage within the amorphous region. As a result, forming a smaller-sized nanocellulose.\u003c/p\u003e\n \u003cp\u003eThe variation in the zeta-potential of the SHNC suspension systems formed with different ultrasonic power is shown in Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003eb. When the ultrasonic power was 0 W, the potential value of the SHNC suspension system was \u0026minus;\u0026thinsp;23.41 mV, and when the ultrasonic power reached 300 W, the potential value of nanocellulose suspension system was \u0026minus;\u0026thinsp;31.41 mV. The theory of DLVO colloidal solution showed that under certain conditions, the absolute value of the zeta-potential was positively correlated with the stability of the system and a decrease in the absolute value of the potential led to a decrease in the potential energy of the repulsive forces formed between the particles and the destabilization of the system (X. Wu et al., \u003cspan class=\"CitationRef\"\u003e2023\u003c/span\u003e). From our results, the absolute value of the potential of SHNC tended to gradually increase with an increase in the ultrasonic power. This may be attributed to the fact that ultrasonication reduced the agglomeration in nanocellulose and exposed more charge. At this time, the repulsive forces were greater than the attractive forces, and the SHNC system became more stable.\u003c/p\u003e\n \u003cp\u003eThe noncovalent interactions formed inside SHNC were characterized using FT-IR spectroscopy and the results shown in Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003ec. The absorption peaks at 3100\u0026ndash;3700, 2930, and 898 cm\u003csup\u003e\u0026ndash;1\u003c/sup\u003e in all of the spectra corresponded to the typical absorption peaks of cellulose structures (Abdelhameed, Abdel-Gawad, \u0026amp; Emam, \u003cspan class=\"CitationRef\"\u003e2021\u003c/span\u003e; Abdin, Mabrouk, et al., \u003cspan class=\"CitationRef\"\u003e2023\u003c/span\u003e; Hasanin, Abdelhameed, Dacrory, Abou-Yousef, \u0026amp; Kamel, \u003cspan class=\"CitationRef\"\u003e2021\u003c/span\u003e). The broad peak at 3100\u0026ndash;3700 cm\u003csup\u003e\u0026ndash;1\u003c/sup\u003e was attributed to the stretching vibrations of the -OH groups in cellulose, hemicellulose, and lignin (Ren et al., \u003cspan class=\"CitationRef\"\u003e2023\u003c/span\u003e). Acid hydrolysis and ultrasonic treatment fully exposed the internal hydroxy groups in SHNC and the peak area and intensity gradually increased at 3100\u0026ndash;3700 cm\u003csup\u003e\u0026ndash;1\u003c/sup\u003e, indicating a gradual increase in the internal hydroxy content (Samsalee, Meerasri, \u0026amp; Sothornvit, \u003cspan class=\"CitationRef\"\u003e2023\u003c/span\u003e). The absorption peak at 2930 cm\u003csup\u003e\u0026ndash;1\u003c/sup\u003e was the stretching vibrations of the saturated aliphatic methylene (-C-H) bonds in cellulose and hemicellulose (Mahur, Ahuja, Singh, Maji, \u0026amp; Rastogi, \u003cspan class=\"CitationRef\"\u003e2023\u003c/span\u003e; Ren et al., \u003cspan class=\"CitationRef\"\u003e2023\u003c/span\u003e). The absorption peak at 1720 cm\u003csup\u003e\u0026ndash;1\u003c/sup\u003e was caused by the stretching vibrations of -C\u0026thinsp;=\u0026thinsp;O, confirming the presence of carboxy groups. This was attributed to the presence of acidic monosaccharides such as galacturonic acid and glucuronic acid inside SHNC (Yang et al., \u003cspan class=\"CitationRef\"\u003e2020\u003c/span\u003e). The peak area and peak intensity gradually increased, indicating that the internal carboxy content gradually increased. This may be due to the ultrasonic waves causing the SHNC to break, fully exposing the carboxy groups, resulting in a gradual increase in the carboxy content. The absorption peaks at 1380 and 1240 cm\u003csup\u003e\u0026ndash;1\u003c/sup\u003e were derived from the stretching vibrations of C\u0026thinsp;=\u0026thinsp;O-O in the benzene ring skeleton and lignin (Mahur et al., \u003cspan class=\"CitationRef\"\u003e2023\u003c/span\u003e; S. Wu et al., \u003cspan class=\"CitationRef\"\u003e2021\u003c/span\u003e). As the ultrasound power increased, the peak intensity at this point gradually decreased, indicating that ultrasound removed the lignin from the interior of cellulose. All of the nanocellulose samples exhibited an absorption peak at 898 cm\u003csup\u003e\u0026ndash;1\u003c/sup\u003e, which was caused by the stretching vibrations of the \u0026beta;-glucosidic bonds in nanocellulose (Mirzaee, Nikzad, Battisti, \u0026amp; Araghi, \u003cspan class=\"CitationRef\"\u003e2023\u003c/span\u003e), indicating that acid hydrolysis and ultrasonic treatment did not change the structure of nanocellulose.\u003c/p\u003e\n \u003cp\u003eThe crystal structure of SHNC was studied using XRD, and the results shown in Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003ed. SHNC exhibited a broad diffraction peak at 2\u0026theta;\u0026thinsp;=\u0026thinsp;21\u0026deg;, indicating that SHNC had a typical amorphous structure (Yu, Yang, Zhang, \u0026amp; Zhang, \u003cspan class=\"CitationRef\"\u003e2024\u003c/span\u003e). The diffraction peak at 2\u0026theta;\u0026thinsp;=\u0026thinsp;21\u0026deg; corresponded to the triple helix structure, which stimulated the formation of hydrogen bonds between H⋯OH and CH⋯O, internally forming a semi-crystalline structural domain. All of the samples exhibited diffraction peaks at 2\u0026theta;\u0026thinsp;=\u0026thinsp;15.2, 21, and 31.8\u0026deg;, which are typical cellulose type I structural peaks distributed in the (100), (200), and (004) crystal planes (Abdin, El-Beltagy, \u0026amp; Naeem, \u003cspan class=\"CitationRef\"\u003e2023\u003c/span\u003e; Emam, El-Shahat, \u0026amp; Abdelhameed, \u003cspan class=\"CitationRef\"\u003e2023\u003c/span\u003e; Shaheen, El-Shahat, \u0026amp; Abdelhameed, \u003cspan class=\"CitationRef\"\u003e2022\u003c/span\u003e), respectively, indicating that acid hydrolysis and ultrasound had no effect on the SHNC crystal structure. In addition, as the ultrasound power gradually increased, the crystallinity of SHNC gradually increased with SHNC-0W, SHNC-100W, SHNC-200W, and SHNC-300W being 37.18, 42.09, 48.12, and 55.59%, respectively. This was attributed to ultrasound causing the non-crystalline regions inside nanocellulose to break, allowing hydrogen ions to enter the cellulose, leading to the degradation of some lignin and hemicellulose. Meanwhile, the FT-IR spectra confirmed the presence of hemicellulose in SHNC.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec16\" class=\"Section2\"\u003e\n \u003ch2\u003e3.3 Microstructure characterization\u003c/h2\u003e\n \u003cp\u003eThe microstructure of SHNC was characterized using SEM and the results shown in Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e. After acid hydrolysis, cellulose showed aggregated, snowflake-like nanoparticles. This was due to the fact that acid hydrolysis removed most of the lignin, hemicellulose, and non-crystalline regions of the long cellulose chains (Kasiri \u0026amp; Fathi, \u003cspan class=\"CitationRef\"\u003e2018\u003c/span\u003e). Meanwhile, the movement of the cellulose molecular chains tended to be randomly entangled and twisted to form different cellulose bundles, and the connections between the fiber bundles form a snowflake-like network structure. In addition, the high specific surface area between nanocellulose and the hydrogen and ester bonds formed between the hydroxy and carboxy groups between the molecular chains made some positions of nanocellulose appear stacked and blocked (Chen, Lee, \u0026amp; Abd Hamid, \u003cspan class=\"CitationRef\"\u003e2017\u003c/span\u003e). With an increase in the ultrasound intensity, the degree of cellulose aggregation decreased and gradually dispersed, and the length of cellulose gradually decreased, transforming from long rod-shaped nanoparticles to spherical or short rod-shaped nanoparticles. This was attributed to the cavity effect of ultrasound, which provided acoustic energy to form, grow, and disintegrate in an aqueous solution (W. Li et al., \u003cspan class=\"CitationRef\"\u003e2012\u003c/span\u003e), while the violent rupture of the bubbles caused microjets and shockwaves on the suspended cellulose surface, which produced a fracture effect on the cellulose, and destroyed the van der Waals forces and hydrogen bonding interactions between the cellulose, leading to the disintegration of the cellulose to form nanoparticles (Shanmugam \u0026amp; Ashokkumar, \u003cspan class=\"CitationRef\"\u003e2014\u003c/span\u003e). Meanwhile, spherical and short rod-shaped nanocellulose with a high specific surface area facilitated its reactivity with polymers, enhancing the mechanical properties of polymer matrix (C. Zhang, Khorshidi, Najafi, \u0026amp; Ghasemi, \u003cspan class=\"CitationRef\"\u003e2023\u003c/span\u003e).\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec17\" class=\"Section2\"\u003e\n \u003ch2\u003e3.4 Physical properties of SHNC suspension\u003c/h2\u003e\n \u003cdiv id=\"Sec18\" class=\"Section3\"\u003e\n \u003ch2\u003e3.4.1 Water contact angle\u003c/h2\u003e\n \u003cp\u003eThe water contact angle (WCA) is the characteristic angle between a liquid and solid surface, which is usually used to assess the wettability of a sample\u0026rsquo;s surface. Meanwhile, a smaller WAC indicates better wettability and hydrophilicity (Yu et al., \u003cspan class=\"CitationRef\"\u003e2024\u003c/span\u003e). The WAC of SHNC was 54.76\u0026thinsp;\u0026plusmn;\u0026thinsp;0.46\u0026deg; when formed at an ultrasonic power of 0 W, while it was about 31.37\u0026thinsp;\u0026plusmn;\u0026thinsp;0.24\u0026deg; at an ultrasonic power of 300 W. With a gradual increase in the ultrasonic power, the WAC of SHNC gradually decreased (Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ea), which indicated that the hydrophilicity of SHNC was gradually enhanced. This may be due to the fact that ultrasonication broke the hydrogen bonds formed between the cellulose molecules, forming smaller molecular weight nanocellulose, increasing its specific surface area, and exposing more hydrophilic groups. The WAC of all of the samples were \u0026lt;\u0026thinsp;90\u0026deg;, indicating that the SHNC samples were all highly hydrophilic, which may be due to the fact that soluble SHNC contained a large number of hydrophilic groups (e.g., hydroxy, carboxy, and amino groups) that allowed water binding to occur easily.\u003c/p\u003e\n \u003c/div\u003e\n \u003cdiv id=\"Sec19\" class=\"Section3\"\u003e\n \u003ch2\u003e3.4.2 Thermal stability\u003c/h2\u003e\n \u003cp\u003eThermal analysis techniques were used to analyze the stability of the samples under continuous heating conditions and determine the onset and maximum decomposition temperatures, as shown in Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003eb. The thermal decomposition of SHNC was divided into three stages. The first stage was observed at 30\u0026ndash;180\u0026deg;C, which exhibited a moderate mass loss due to the evaporation of water and volatile substances within SHNC (Ma et al., \u003cspan class=\"CitationRef\"\u003e2023\u003c/span\u003e). The second stage was 200\u0026ndash;400\u0026deg;C, which exhibited a substantial mass loss due to the decomposition of hemicellulose and cellulose (Mudoi, Sinha, \u0026amp; Parthasarthy, \u003cspan class=\"CitationRef\"\u003e2022\u003c/span\u003e). The third stage was at 450\u0026ndash;800\u0026deg;C, which was due to the gradual carbonization of the SHNC residues. Interestingly, a gradual rightward shift of the absorption peak of SHNC was seen in the DTG curves between 200\u0026ndash;400\u0026deg;C, indicating a gradual increase in the decomposition temperature and thermal stability of SHNC. This may be related to the removal of the thermally unstable hemicellulose and pectin, a result that was consistent with the findings of Dominic et al. (Dominic et al., \u003cspan class=\"CitationRef\"\u003e2022\u003c/span\u003e).\u003c/p\u003e\n \u003cp\u003eThe onset degradation temperature (T\u003csub\u003eonset\u003c/sub\u003e) and maximum degradation temperature (T\u003csub\u003emax\u003c/sub\u003e) of the SHNC samples are summarized in Table \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e. At an ultrasound power of 0 W, SHNC decomposed at ~\u0026thinsp;187.29\u0026deg;C, and the maximum degradation occurred at ~\u0026thinsp;224.13\u0026deg;C. The T\u003csub\u003eonset\u003c/sub\u003e of SHNC was 180.38\u0026deg;C at an ultrasound intensity of 300 W, which was higher than that of SHNC at 0 W. This indicated that the thermal stability of SHNC was improved, and the higher initial degradation temperature, which was even higher than the melt softening temperature of general thermoplastic polymers, making it promising for use in polymer-reinforced composites. The initial degradation temperatures of the sonicated SHNC samples were all lower than those of the unsonicated SHNC, and the T\u003csub\u003emax\u003c/sub\u003e values showed the same trend, which was consistent with the findings reported in previous research studies (Dominic et al., \u003cspan class=\"CitationRef\"\u003e2022\u003c/span\u003e; Mirzaee et al., \u003cspan class=\"CitationRef\"\u003e2023\u003c/span\u003e). This may be related to the fact that ultrasonication breaks cellulose to form smaller-sized nanocellulose with high specific surface area and high crystallinity (Khanjanzadeh \u0026amp; Park, \u003cspan class=\"CitationRef\"\u003e2021\u003c/span\u003e; Mirzaee et al., \u003cspan class=\"CitationRef\"\u003e2023\u003c/span\u003e). (Ilyas, Sapuan, \u0026amp; Ishak, \u003cspan class=\"CitationRef\"\u003e2018\u003c/span\u003e) reported that the thermal stability of nanocellulose was positively correlated with its crystallinity, i.e., the higher the crystallinity, the higher the degradation temperature of the samples. In summary, SHNC had high thermal stability and had great potential for future applications in the field of nanomaterials.\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\u003eThermal properties of the different samples\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003ccolgroup cols=\"3\"\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\u003eT\u003csub\u003eonset\u003c/sub\u003e (℃)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eT\u003csub\u003eMax\u003c/sub\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\u003e0W\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e187.29\u0026thinsp;\u0026plusmn;\u0026thinsp;2.74\u003csup\u003eb\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e224.13\u0026thinsp;\u0026plusmn;\u0026thinsp;3.65\u003csup\u003ec\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e100W\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e181.63\u0026thinsp;\u0026plusmn;\u0026thinsp;3.31\u003csup\u003ec\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e250.48\u0026thinsp;\u0026plusmn;\u0026thinsp;4.19\u003csup\u003eb\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e200W\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e202.22\u0026thinsp;\u0026plusmn;\u0026thinsp;1.49\u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e260.54\u0026thinsp;\u0026plusmn;\u0026thinsp;2.43\u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e300W\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e180.38\u0026thinsp;\u0026plusmn;\u0026thinsp;2.37\u003csup\u003ec\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e262.75\u0026thinsp;\u0026plusmn;\u0026thinsp;4.63\u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003ctfoot\u003e\n \u003ctr\u003e\n \u003ctd colspan=\"3\"\u003eNote: All data were expressed as the mean\u0026thinsp;\u0026plusmn;\u0026thinsp;SD (standard deviation) (n\u0026thinsp;=\u0026thinsp;3). The different letters mean significant differences (\u003cem\u003eP\u003c/em\u003e\u0026thinsp;\u0026lt;\u0026thinsp;0.05).\u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tfoot\u003e\n \u003c/table\u003e\n \u003c/div\u003e\n \u003cp\u003e\u003cbr\u003e\u003c/p\u003e\n \u003c/div\u003e\n \u003cdiv id=\"Sec20\" class=\"Section3\"\u003e\n \u003ch2\u003e3.4.3 Interfacial tension and pressure\u003c/h2\u003e\n \u003cp\u003eTo investigate the effect of the ultrasound power on the oil-water interface properties (water droplet suspension in pure oil droplet in SHNC solution) of SHNC, the dynamic interfacial tension was monitored using an optical contact angle measuring instrument, and the results are shown in Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ea. The adsorption process of SHNC at the oil-water interface was divided into two stages. In the first stage, the nanoparticles quickly approached and adhered to the oil-water interface, exhibiting a rapid decrease in tension. During the second stage, the nanoparticles adsorbed at the oil-water interface were rearranged or even formed a viscoelastic film, exhibiting a slow decrease in the interfacial tension (Feng et al., \u003cspan class=\"CitationRef\"\u003e2021\u003c/span\u003e). (Q. Li, Chen, Li, Li, \u0026amp; Liu, \u003cspan class=\"CitationRef\"\u003e2020\u003c/span\u003e) also reported similar research results. Subsequently, by comparing the changes in the interfacial tension of SHNC formed under different ultrasonic powers, it was found that the larger the ultrasonic power, the smaller the interfacial tension value of the system. Among them, the interfacial tension of SHNC decreased from 13.86 to 3.4 mN/m, while the size of SHNC was the smallest at 300 W. This indicated that small-sized SHNC could more easily adsorb to the oil-water interface and reduce the interfacial tension of the system. This may be attributed to the cavitation effect generated by ultrasound, which caused the amorphous regions of SHNC to break and form short chain nanocellulose, while exposing more hydrophilic groups and enhancing the hydrophilic effect. Meanwhile, the specific surface area of nanocellulose increased, the intermolecular force increased, and the degree of cross-linking increased. The system gradually changed from a fluid state to a weak gel state, leading to an increase in the viscosity of the system, which further hindered the movement of nanocellulose molecules in the system. Therefore, the interface adsorption rate of SHNC gradually decreased and tended to flatten. Our results showed that SHNC exhibited excellent gelation properties.\u003c/p\u003e\n \u003cp\u003eWe further investigated the effect of different ultrasonic powers on the surface pressure at the gas/liquid interface of SHNC, as shown in Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003eb. With an increase in the ultrasonic power, the interfacial pressure of SHNC showed a gradual increase with the adsorption time, indicating that the adsorption amount of SHNC at the gas/liquid interface gradually increased. Meanwhile, the higher the ultrasonic power, the higher the surface pressure of SHNC at the gas/liquid interface, which may be attributed to an increase in the interfacial tension due to the adsorption of SHNC at the gas/liquid interface via electrostatic action.\u003c/p\u003e\n \u003c/div\u003e\n \u003cdiv id=\"Sec21\" class=\"Section3\"\u003e\n \u003ch2\u003e3.4.4 UV-visible transmittance\u003c/h2\u003e\n \u003cp\u003eNanocellulose with excellent transparency and UV resistance is potentially more advantageous for the preparation of nanomaterials. The transparency of the SHNC suspension showed a gradual increase with an increase in the ultrasonic power (Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ec). At a wavelength of 600 nm, the transmittance of the SHNC suspension was \u0026gt;\u0026thinsp;73%. which was consistent with previous results (Cao, Ding, Yu, \u0026amp; Al-Deyab, \u003cspan class=\"CitationRef\"\u003e2012\u003c/span\u003e).\u003c/p\u003e\n \u003cp\u003eThis may be due to the fact that SHNC contains hydroxyl and carboxylic groups, which absorb ultraviolet light (Antunes et al., \u003cspan class=\"CitationRef\"\u003e2023\u003c/span\u003e). Meanwhile, SHNC contains some lignin, which is highly absorbable in the ultraviolet band, thus enhancing the ultraviolet light scattering and gradually reducing the ultraviolet absorption (Robles et al., \u003cspan class=\"CitationRef\"\u003e2020\u003c/span\u003e; Sadeghifar \u0026amp; Ragauskas, \u003cspan class=\"CitationRef\"\u003e2020\u003c/span\u003e). At wavelengths of 200\u0026ndash;400 nm, the UV transmittance of SHNC dramatically decreased from 56.58% to almost zero, indicating that SHNC had excellent UV resistance. This may be attributed to the fact that the particle size of SHNC was smaller than the wavelength of UV light, the light scattering increased, and the UV absorption gradually decreased (Robles et al., \u003cspan class=\"CitationRef\"\u003e2020\u003c/span\u003e). The color of the SHNC suspension gradually changed from white to off-white due to the different proportions of lignin and hemicellulose in SHNC (Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ed) (Boufi \u0026amp; Chaker, \u003cspan class=\"CitationRef\"\u003e2016\u003c/span\u003e). Our results showed that SHNC had excellent transparency and UV resistance, which was expected to be widely used in transparent flexible electronic sensors, food packaging materials and other fields.\u003c/p\u003e\n \u003c/div\u003e\n \u003cdiv id=\"Sec22\" class=\"Section3\"\u003e\n \u003ch2\u003e3.4.5 Shear viscosity\u003c/h2\u003e\n \u003cp\u003eNanocellulose with high apparent viscosity is often more conducive to cross-linking, thus affecting the gelation self-assembly process (Abitbol, Kam, Levi-Kalisman, Gray, \u0026amp; Shoseyov, \u003cspan class=\"CitationRef\"\u003e2018\u003c/span\u003e). The shear viscosity scan curves of SHNC prepared under different ultrasonic intensities are shown in Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ee. All of the samples exhibited typical shear thinning behavior in their viscosity (Z. Li et al., \u003cspan class=\"CitationRef\"\u003e2018\u003c/span\u003e). When the shear rate increased from 0.1 to 1 s\u003csup\u003e\u0026ndash;1\u003c/sup\u003e, the viscosity of the SHNC suspension suddenly decreased, exhibiting pseudoplastic fluid behavior. Subsequently, as the shear rate gradually increased from 1 to 10 s\u003csup\u003e\u0026ndash;1\u003c/sup\u003e, the viscosity of the SHNC suspension tended to become smooth. The viscosity order at 0.1 s s\u003csup\u003e\u0026ndash;1\u003c/sup\u003e was: SHNC-300 W\u0026thinsp;\u0026gt;\u0026thinsp;SHNC-200 W\u0026thinsp;\u0026gt;\u0026thinsp;SHNC-100 W\u0026thinsp;\u0026gt;\u0026thinsp;SHNC-0 W. This may be due to the cavitation effect generated by ultrasound, where high energy sound energy promoted the disintegration of the microfiber structures, which was beneficial for preparing SHNCs with smaller particle size and higher surface charge, thereby increasing the effective volume fraction of SHNCs in the suspension, strengthening the hydrogen bonding interactions formed between the SHNCs and the solution, leading to an increase in viscosity. Our results showed that SHNC-300W had more advantages than SHNC-0W in terms of its gelation properties.\u003c/p\u003e\n \u003c/div\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec23\" class=\"Section2\"\u003e\n \u003ch2\u003e3.5 Antimicrobial properties of the SHNC suspension\u003c/h2\u003e\n \u003cp\u003eTo explore the inhibitory effect of SHNC prepared under different ultrasonic powers, the inhibitory activity of the SHNC samples was analyzed by determining the number of remaining viable bacteria, as shown in Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003e. With a gradual increase in the ultrasonic power, the inhibition rate of SHNC against \u003cem\u003eE. coli\u003c/em\u003e and \u003cem\u003eS. aureus\u003c/em\u003e gradually increased. At 0 W, the inhibition rate of SHNC against \u003cem\u003eE. coli\u003c/em\u003e and \u003cem\u003eS. aureus\u003c/em\u003e was 33.16\u0026thinsp;\u0026plusmn;\u0026thinsp;1.04 and 45.01\u0026thinsp;\u0026plusmn;\u0026thinsp;2.14%, respectively. This was due to the fact that SHNC contains glucuronic acid and glucosamine, which contained aldehyde, carboxy, and amino groups, which possessed great bacteriostatic properties. Specifically, the aldehyde groups underwent a nucleophilic addition reaction with the internal proteins of the bacteria, which caused the bacteria to lose their ability to replicate and cause disorders in their metabolic system (Balcerzak et al., \u003cspan class=\"CitationRef\"\u003e2023\u003c/span\u003e). The carboxy group combined with hydrogen ions to form a carboxylic acid, which acidified the bacterial growth environment, hindering bacterial adhesion, disrupting cell membranes, increasing the bacterial permeability, and causing the bacterial content to flow-out, leading to bacterial death (Jiang et al., \u003cspan class=\"CitationRef\"\u003e2024\u003c/span\u003e). Meanwhile, amino acids bound to negatively charged cell membranes or cell walls, leading to cell membrane disruption and cell death (Lan et al., \u003cspan class=\"CitationRef\"\u003e2023\u003c/span\u003e), achieving bacterial inhibition. The highest inhibition rate of SHNC against \u003cem\u003eE. coli\u003c/em\u003e and \u003cem\u003eS. aureus\u003c/em\u003e was achieved at 300 W with 61.13\u0026thinsp;\u0026plusmn;\u0026thinsp;0.52 and 69.33\u0026thinsp;\u0026plusmn;\u0026thinsp;1.52%, respectively. This was due to the fact that ultrasound caused the SHNC to break-up and form nanocellulose with smaller molecular weight, exposing more aldehyde, carboxy, and amino groups in SHNC, which increased the antibacterial effect of SHNC. Nanocellulose with excellent antimicrobial properties not only endowed the nanomaterials with antimicrobial properties, but also great biodegradability.\u003c/p\u003e\n\u003c/div\u003e"},{"header":"4 Conclusions","content":"\u003cp\u003eIn summary, an anionic nanocrystalline cellulose (Mw: 213,935 Da) has been extracted from discarded soy hull using a combined acid hydrolysis-ultrasonic treatment method, which contained a large number of hydrogen and ester bonds. The extraction rate of SHNC was higher (11.42%) and the whole cellulose content increased to \u0026gt;\u0026thinsp;95%. SHNC presented spherical or short rod-shaped nanoparticles with diameters in the range of 20\u0026ndash;50 nm. Meanwhile, SHNC exhibited great crystallinity (55.59%), hydrophilicity, thermal stability, and transparency (80%). More importantly, SHNC had excellent bacteriostatic properties against \u003cem\u003eE. coli\u003c/em\u003e and \u003cem\u003eS. aureus\u003c/em\u003e with a high bacteriostatic rate of 69.33%. This study provided a new strategy for the high value utilization of discarded soy hull. Meanwhile, the high performance of SHNC will have excellent application prospects in the fields of food packaging, biomedicine, and tissue engineering.\u003c/p\u003e "},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAuthor statement\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eKejin Yu: software, data curation, methodology, and writing the original draft.\u003c/p\u003e\n\u003cp\u003eLina Yang: conceptualization, methodology, writing the original draft, review \u0026amp; editing, and project administration.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eSiyu Zhang: software and data curation.\u003c/p\u003e\n\u003cp\u003eNing Zhang: software and data curation.\u003c/p\u003e\n\u003cp\u003eHe Liu: conceptualization, supervision, and resources.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eDeclarations of interest\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eNone.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis study was supported by the Liaoning Province Department of Education Fund (Grant No. LJKMZ20221489).\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eAbdelhameed, R. 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Carbohydrate polymers, 238, 116180.\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Nanocellulose, Chemical structure, Morphology, Agroindustrial waste","lastPublishedDoi":"10.21203/rs.3.rs-5667593/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-5667593/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eSoybean is a crop of important economic significance and soy hull is the residual by-product of soybean processing industry. In this study, cellulose nanocrystals were extracted from soy hull using a combined acid hydrolysis-ultrasonic treatment process, and its structure, properties, and antimicrobial activity were investigated. Fourier-transform infrared spectroscopy revealed the presence of hydrogen and ester bonds in the soy hull nanocrystalline cellulose (SHNC), whereas scanning electron microscopy showed that the SHNC was globular or short-rod shaped with diameters in the range of 20\u0026ndash;50 nm. The molecular weight of SHNC was 213,935 Da and the extraction yield was 11.42%. Meanwhile, SHNC also had high crystallinity (55.59%), thermal stability, transparency (80%), and UV resistance. Notably, SHNC exhibited an excellent bacteriostatic effect against \u003cem\u003eEscherichia coli\u003c/em\u003e and \u003cem\u003eStaphylococcus aureus\u003c/em\u003e, whose bacteriostatic percentage reached 69.33%. Meanwhile, this study provided a new idea for the high value utilization of waste soy hull.\u003c/p\u003e","manuscriptTitle":"The characterization of size-controlled nanocrystalline cellulose from soy hulls with ultrasonic assisted extraction","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-12-23 08:39:11","doi":"10.21203/rs.3.rs-5667593/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"d76f190a-c103-4b45-98b0-594926452cb1","owner":[],"postedDate":"December 23rd, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2025-02-06T02:23:14+00:00","versionOfRecord":[],"versionCreatedAt":"2024-12-23 08:39:11","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-5667593","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-5667593","identity":"rs-5667593","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}