Degradable, anti-swelling, high-strength cellulosic hydrogels via salting-out and ionic coordination.

Cellulosic hydrogels are widely used in various applications, as they are natural raw materials and have excellent degradability. However, their poor mechanical properties restrict their practical application. This study presents a facile approach for fabricating cellulosic hydrogels with high strength by synergistically utilizing salting-out and ionic coordination, thereby inducing the collapse and aggregation of cellulose chains to form a cross-linked network structure. Cellulosic hydrogels are prepared by soaking cellulose in an Al2(SO4)3 solution, which is both strong (compressive strength of up to 16.99 MPa) and tough (compressive toughness of up to 2.86 MJ/m3). The prepared cellulosic hydrogels exhibit resistance to swelling in different solutions and good biodegradability in soil. The cellulosic hydrogels are incorporated into strain sensors for human-motion monitoring by introducing AgNWs. Thus, the study offers a promising, simple, and scalable approach for preparing strong, degradable, and anti-swelling hydrogels using common biomass resources with considerable potential for various applications.

Facile synthesis of lignin-based Fe-MOF for fast adsorption of methyl orange.

To rapidly remove dyes from wastewater, iron-based metal-organic frameworks modified with phenolated lignin (NH2-MIL@L) were prepared by a one-step hydrothermal method. Analyses of the chemical structure and adsorption mechanism of the NH2-MIL@L proved the successful introduction of lignin and the enhancement of its adsorption sites. Compared with NH2-MIL-101-Fe without phenolated lignin, the modification with lignin increased the methyl orange (MO) adsorption rate of NH2-MIL@L. For the best adsorbent, NH2-MIL@L4, the MO adsorption efficiency in MO solution reached 95.09% within 5 min. NH2-MIL@L4 reached adsorption equilibrium within 90 min, exhibiting an MO adsorption capacity of 195.31 mg/g. The process followed pseudo-second-order kinetics and the Dubinin-Radushkevich model. MO adsorption efficiency of NH2-MIL@L4 was maintained at 89.87% after six adsorption-desorption cycles. In mixed solutions of MO and methylene blue (MB), NH2-MIL@L4 achieved an MO adsorption of 94.02% at 5 min and reached MO adsorption equilibrium within 15 min with an MO adsorption capacity of 438.6 mg/g, while the MB adsorption equilibrium was established at 90 min with an MB adsorption rate and capacity of 95.60% and 481.34 mg/g, respectively. NH2-MIL@L4 sustained its excellent adsorption efficiency after six adsorption-desorption cycles (91.2% for MO and 93.4% for MB). The process of MO adsorption by NH2-MIL@L4 followed the Temkin model and pseudo-second-order kinetics, while MB adsorption followed the Dubinin-Radushkevich model and pseudo-second-order kinetics. Electrostatic interactions, π-π interactions, hydrogen bonding, and synergistic interactions affected the MO adsorption process of NH2-MIL@L4.

Self-adhesive, freeze-tolerant, and strong hydrogel electrolyte containing xanthan gum enables the high-performance of zinc-ion hybrid supercapacitors.

Hydrogel electrolyte is an ideal candidate material for flexible energy storage devices due to its excellent softness and conductivity properties. However, challenges such as the inherent mechanical weakness, the susceptibility to be frozen in low-temperature environments, and the insufficiency of hydrogel-electrode contact persist. Herein, a "Multi in One" strategy is employed to effectively conquer these difficulties by endowing hydrogels with high strength, freeze-resistance, and self-adhesive ability. Multiple hydrogen bond networks and ion crosslinking networks are constructed within the hydrogel electrolyte (PVA/PAAc/XG) containing polyvinyl alcohol (PVA), acrylic acid (AAc), and xanthan gum (XG), promoting the enhanced mechanical property, and the adhesion to electrode materials is also improved through abundant active groups. The introduction of zinc ions provides the material with superior frost resistance while also promoting electrical conductivity. Leveraging its multifunction of superior mechanical strength, anti-freeze property, and self-adhesive characteristic, the PVA/PAAc/XG hydrogel electrolyte is employed to fabricate zinc ion hybrid supercapacitors (ZHS). Remarkably, ZHS exhibits outstanding electrochemical performance and cycle stability. A remarkable capacity retention rate of 83.86 % after 10,000 charge-discharge cycles can be achieved at high current densities, even when the operational temperature decreases to -60 °C, showing great potential in the field of flexible energy storage devices.

Fully Biobased Degradable Vitrimer Foams: Mechanical Robust, Catalyst-Free Self-Healing, and Shape Memory Properties.

Thermosetting foams have limited capabilities for recycling, reprocessing, or reshaping. Moreover, most of the foaming agents currently employed in these foams are derived from organic compounds sourced from petrochemicals, thereby posing a significant environmental threat due to heightened pollution. To solve these problems, a fully biobased degradable vitrimer foam (EPC-X) was fabricated using an environmentally friendly all-in-one foaming strategy by cross-linking epoxidized malepimaric anhydride (EMPA), 1,5-diaminopentane (PDA), and 1,5-diaminopentane carbamate (PDAC) as a latent curing-blowing agent. To our delight, the vitrimer foams exhibit excellent mechanical properties (2.86 ± 0.11 MPa compressive strength) owing to their unique rigid rosin backbone and cross-linking networks. The presence of dynamic ß-hydroxy ester bonds and the self-catalytic behavior of tertiary amine groups facilitate network rearrangement without requiring additional catalysts, thereby resulting in the development of EPC-X with rapid self-healing and shape memory properties. The self-healing foam could support a weight of 500 g (approximately 562 times its own mass). Moreover, these high-performance vitrimer foams can also be easily degraded in an ethanolamine (EA) or NaOH solution under mild conditions. Such a design strategy offers an alternative approach for developing superior degradable and thermal stimuli-responsive thermosetting foams.

CO2 responsive self-standing Pickering emulsion gel stabilized with rosin-based surfactant modified cellulose nanofibrils.

Emulsion gel was developed to provide desirable texture, palatability and functionality to food products. Tunable stability of emulsions is often desired, as in certain situations, the chemical content release usually relies on emulsion induced destabilization of the droplet. However, the destabilization for emulsion gel is difficult because of the formation of highly entangled networks. To address this issue, a fully biobased Pickering emulsion gel stabilized by cellulose nanofibrils (CNF) modified with a CO2 responsive rosin-based surfactant, maleopimaric acid glycidyl methacrylate ester 3-dimethylaminopropylamine imide (MPAGN) was reported. The emulsification/de-emulsification can be reversibly regulated because this surfactant has sensitive CO2 responsive property. MPAGN can be reversibly between active cationic (MPAGNH+) and inactive nonionic (MPAGN) responsive to CO2 and N2. The microstructure of the emulsion gel was observed and compared before and after the response. The rheological properties of emulsion gel stabilized by different concentrations of MPAGNH+ and different contents of CNF were studied separately. As 0.2 wt% CNF was dispersed in 1 mM MPAGNH+ solution, the obtained emulsion can be self-standing for long duration. The rheology study indicated that these emulsions show typical gel characteristics with shear-thinning behavior. The stabilization mechanism of these gel emulsion is a synergistic effect caused by the combination of CO2 responsive Pickering emulsion and intertwined network caused by the hydrogen-bond interaction among CNF.

Self-healing, EMI shielding, and antibacterial properties of recyclable cellulose liquid metal hydrogel sensor.

Flexible hydrogels are promising materials for the preparation of artificial intelligence electronics and wearable devices. Introducing a rigid conductive material into the hydrogels can improve their electrical conductivities. However, it may have poor interfacial compatibility with the flexible hydrogel matrix. Therefore, we prepared a hydrogel containing flexible and highly ductile liquid metal (LM). The hydrogel can be used as a strain sensor to monitor human motion. The hydrogel showed many properties (i.e., recyclability, EMI shielding properties (33.14 dB), antibacterial (100 %), strain sensitivity (gauge factor = 2.92), and self-healing) that cannot be achieved simultaneously by a single hydrogel. Furthermore, the recycling of LM and their application to hydrogel-based EMI shielding materials have not been investigated previously. Due to its excellent properties, the prepared flexible hydrogel has great potential for applications in artificial intelligence, personal healthcare, and wearable devices.

Strong, flexible and UV-shielding composite polyvinyl alcohol films with wood cellulose skeleton and lignin nanoparticles.

The development of high-performance composite films using biomass materials have become a sought-after direction. Herein, a green method to fabricate strong, flexible and UV-shielding biological composite film from wood cellulose skeleton (WCS), lignin nanoparticles (LNPs) and polyvinyl alcohol (PVA) was described. In the work, WCS and LNPs were prepared by chemical treatment of wood veneer and Enzymatic lignin, respectively. Then, WCS was infiltrated with the LNPs/PVA mixtures and dried to obtain composite films. WCS enhanced the mechanical properties of the composite films, the tensile stress reached to 85.8 MPa and the tensile strain reached to 6.39 %. The composite films with LNPs blocked over 98 % of UV-light, the water absorption decreased by 30 %, and the thermal stabilities were also improved. These findings would provide some references for exploring high quality biological composite films.

Fast and Reversible Photoresponsive Self-Assembly Behavior of Rosin-Based Amphiphilic Polymers.

Designing stimulus-responsive amphiphilic polymers with a fast photoresponsive self-assembly behavior remains a challenge. Two series of rosin-terminated and azobenzene-terminated amphiphilic polymers (PAMn and PMAn) with fast and reversible photoresponsive properties were prepared using rosin-based azobenzene groups and polyethylene glycol, respectively. Under 5-10 s of UV irradiation, the polymers showed trans-to-cis isomerization and reached a photosteady state. For the PAMn polymer, the absorbance of the absorption peak at 325 nm recovered to more than 95% of the initial value under visible light for 5-10 s, whereas that of the PMAn polymer recovered completely. Notably, the PAMn and PMAn polymers initially self-assembled to vesicles or spherical micelles, and various morphological changes were achieved by manipulating UV irradiation time, with the initial morphology again recovered under dark conditions or visible-light irradiation. Remarkably, vesicles of the PAM34 and PMA34 polymers presented an intermediate open-vesicle state before being completely deformed under UV irradiation because of the existence of a π-π interaction. Finally, the ability of PAM34 and PMA34 polymer vesicles to perform the controlled release and reversible loading of a fluorescent probe was evaluated.

Machine Learning Assisted Doppler Features for Enhancing Thyroid Cancer Diagnosis: A Multi-Cohort Study.

BACKGROUND: This pilot study aims at exploiting machine learning techniques to extract color Doppler ultrasound (CDUS) features and to build an artificial neural network (ANN) model based on these CDUS features for improving the diagnostic performance of thyroid cancer classification. METHODS: A total of 674 patients with 712 thyroid nodules (TNs) (512 from internal dataset and 200 from external dataset) were randomly selected in this retrospective study. We used ANN to build a model (TDUS-Net) for classifying malignant and benign TNs using both the automatically extracted quantitative CDUS features (whole ratio, intranodular ratio, peripheral ratio, and number of vessels) and gray-scale ultrasound (US) features defined by the American College of Radiology (ACR) Thyroid Imaging Reporting and Data System (TI-RADS). Then, we compared the diagnostic performance of the model, the performance of another ANN model based on the gray-scale US features alone (TUS-Net), and that of radiologists. RESULTS: The TDUS-Net (0.898, 95% CI: 0.868-0.922) achieved a higher area under the curve (AUC) than that of TUS-Net (0.881, 95% CI: 0.850-0.908) in the internal tests. Compared with radiologists, TDUS-Net (AUC: 0.925, 95% CI: 0.880-0.958) performed better than radiologists (AUC: 0.810, 95% CI: 0.749-0.862) in the external tests. CONCLUSIONS: Applying a machine learning model by combining both gray-scale US features and CDUS features can achieve comparable or even higher performance than radiologists in classifying TNs.

Cellulose-based polymeric emulsifier stabilized poly(N-vinylcaprolactam) hydrogel with temperature and pH responsiveness.

N-vinylcaprolactam (NVCL) is a temperature-responsive monomer, which is widely used for preparing responsive hydrogels. However, poor water solubility of NVCL necessitates the use of emulsifiers for better dispersion. Hydrolyzed epoxy soybean oil-grafted hydroxyethyl cellulose (H-ESO-HEC) polymeric emulsifier has excellent emulsifying properties, and the carboxyl groups afford pH-responsiveness to the hydrogels. A novel temperature- and pH-responsive cellulose-based hydrogel was prepared by combining NVCL and H-ESO-HEC. The hydrogel morphology, thermal stability, and swelling capacity were characterized, and it was also used as a dual-responsive drug preservative carrier. Scanning electron microscopy and thermogravimetric analysis confirmed the porous structure and good thermal stability, respectively, of the hydrogel. The hydrogel displayed a temperature- and pH-dependent swelling behavior and improved swelling capacity. The swelling behavior agreed well with the Korsmeyer-Peppas model and Schott's second-order kinetic model. The dual-responsive hydrogel has significant potential in the drug delivery systems owing to its biocompatibility and temperature and pH sensitivity.

Preparation and properties of room temperature vulcanized silicone rubber based on rosin-grafted polydimethylsiloxane.

Rosin-grafted polydimethylsiloxane (RGSO) was prepared via ring-opening reaction of glycidyl ester of rosin acid (ER) with hydroxy-terminated amino polydimethylsiloxane (PDMS). The structure of RGSO was confirmed by 1H and 13C NMR spectroscopy. The effects of ER on relative molecular weight and rheological properties of RGSO were studied by gel permeation chromatography and rotational rheometry. Then, room temperature vulcanized (RTV) silicone rubber modified with rosin was prepared using RGSO, hydroxy-terminated PDMS, tetraethoxysilane, and organotin catalyst. The structures and properties of RTV silicone rubbers were studied by scanning electron microscopy, thermogravimetric analysis, a universal testing machine and dynamic mechanical analysis. The rosin-modified silicone rubber showed remarkably improved thermal and mechanical properties. Temperatures corresponding to 10% weight loss and maximum rate of weight loss increased by 66 °C and 177 °C, respectively. Moreover, the tensile strength and elongation at break increased by 138% and 113%. The role of rosin structure in improvement of properties is discussed.

Oil-in-Water Emulsions Stabilized by Saponified Epoxidized Soybean Oil-Grafted Hydroxyethyl Cellulose.

An oil-in-water emulsion stabilized by saponified epoxidized soybean oil-grafted hydroxyethyl cellulose (H-ESO-HEC) was investigated. By using an ultrasonic method, oil-in-water emulsions were prepared by blending 50 wt % soybean oil and 50 wt % H-ESO-HEC aqueous suspensions. The influence of H-ESO-HEC concentrations on the properties of oil-in-water emulsions was examined. The H-ESO-HEC concentrations in the aqueous phase varied from 0.02 to 0.40 wt %. When the H-ESO-HEC concentration was 0.4 wt %, the emulsion remained stable for >80 days. The mean droplet sizes of the emulsions decreased by increasing the H-ESO-HEC concentration and extending the ultrasonic time. The adsorption amounts of H-ESO-HEC at the oil-water interface increased when the H-ESO-HEC concentrations in the aqueous phase increased. The rheological property revealed that the apparent viscosity of the H-ESO-HEC-stabilized oil-in-water emulsions increased when the H-ESO-HEC concentrations increased. Steady flow curves indicated an interfacial film formation in the emulsions. The evolution of G', G″, and tan η indicated the predominantly elastic behaviors of all the emulsions.

Preparation and Characterization of Polymeric Surfactants Based on Epoxidized Soybean Oil Grafted Hydroxyethyl Cellulose.

Epoxidized soybean oil (ESO) grafted hydroxyethyl cellulose (HEC) was prepared via ring-opening polymerization, in which the hydroxyl groups of HEC acted as initiators and the polymeric ESO were covalently bonded to the HEC. Hydrolysis of ESO-grafted HEC (ESO-HEC) was performed with sodium hydroxide, and the hydrolyzed ESO-HEC (H-ESO-HEC) products were characterized via Fourier transform infrared (FT-IR) and (1)H and (13)C nuclear magnetic resonance (NMR) spectroscopies, high-temperature gel permeation chromatography (HT-GPC), and differential scanning calorimetry (DSC). The results indicated that ring-opening polymerization of ESO occurred with the hydroxyl groups of HEC as initiators. The molecular weights of the H-ESO-HEC products were varied by adjusting the mass ratio of HEC and ESO. Through neutralizing the carboxylic acid of H-ESO-HEC with sodium hydroxide, novel polymeric surfactants (H-ESO-HEC-Na) were obtained, and the effects of polymeric surfactants on the surface tension of water were investigated as a function of concentration of H-ESO-HEC-Na. The H-ESO-HEC-Na was effective at lowering the surface tension of water to 26.33 mN/m, and the critical micelle concentration (CMC) value decreased from 1.053 to 0.157 g/L with increases in molecular weights of the polymeric surfactants. Rheological measurements indicated that the H-ESO-HEC-Na solutions changed from pseudoplastic property to Newtonian with increasing shear rate.