Low vaporization enthalpy of modified chitosan hydrogel for high performance solar evaporator.

The high vaporization enthalpy of water attributed to the strong hydrogen bonds between water molecules is limiting the performance of solar evaporators. This work demonstrates a deliberate attempt to significantly reduce the vaporization enthalpy of water through the introduction of weak water-amine hydrogen bond interactions in hydrogel evaporators. In this article, bio-based chitosan-agarose/multiwalled carbon nanotube hydrogel film evaporators (CAMFEs) exhibit larger vaporization enthalpy reduction with the presence of primary amine groups in chitosan. An interplay between vaporization enthalpy reduction and water diffusivity leads to an optimal ratio of chitosan to agarose = 7:1 (CAMFE7) showing an impressive evaporation rate of 4.13 kg m-2 h-1 under 1 sun irradiation. CAMFE7 also exhibits excellent salt resistance, with a stable water evaporation rate, using brine water of up to 10 % salinity under continuous 1 sun irradiation. The high mechanical robustness together with its scalability makes CAMFE7 a highly promising material for practical drinking water production.

Engineering Carbon Nanotube Yarns with Polyaniline Coating toward Enhanced Thermoelectric Performance.

The growing demand for wearable electronics has driven the development of flexible thermoelectric (TE) generators which can harvest waste body heat as a renewable power source. Despite carbon nanotube (CNT) yarns have attracted significant attention as a promising candidate for TE materials, challenges still exist in improving their TE efficiency for commercial applications. Herein, we developed high performance CNT/polyaniline (PANI) yarns by engineering the coating of polyaniline emeraldine base (PANIeb), in which CNT yarns were firstly coated by PANIeb layer and further doped by HCl vapor treatment. With the incorporation of PANIeb, σ and S were simultaneously increased to 1796 S cm-1 and 74.8 µV K-1 for CNT/PANIeb 4-2d fibers, respectively. Further HCl vapor treatment induced greatly increased σ to 3194 S cm-1, but maintained be 83 % value before doping, giving rise to the highest power factor of 1224 µW m-1K-2, higher than pristine CNT yarns of 576 µW m-1K-2. Combining outstanding high TE performance and bending durability, a flexible TE generator was constructed to deliver high out power of 187 nW with temperature gradients of about 30 K. These results demonstrate the potential promise of high-performance CNT/PANI-HCl yarns to harvest waste body heat for sustainable power supply.

Reprogrammable, Sustainable, and 3D-Printable Cellulose Hydroplastic.

Modern human societies are highly dependent on plastic materials, however, the bulk of them are non-renewable commodity plastics that cause pollution problems and consume large amounts of energy for their thermal processing activities. In this article, a sustainable cellulose hydroplastic material and its composites, that can be shaped repeatedly into various 2D/3D geometries using just water are introduced. In the wet state, their high flexibility and ductility make it conducive for the shaping to take place. In the ambient environment, the wet hydroplastic transits spontaneously into rigid materials with its intended shape in a short time of <30 min despite a thickness of hundreds of microns. They also possess humidity resistance and are structurally stable in highly humid environments. Given their excellent mechanical properties, geometry reprogrammability, bio-based, and biodegradable nature, cellulose hydroplastic poses as a sustainable alternative to traditional plastic materials and even "green" thermoplastics. This article also demonstrates the possibility of 3D-printing these hydroplastics and the potential of employing them in electronics applications. The demonstrated hydroshapable structural electronic components show capability in performing electronic functions, load-bearing ability and geometry versatility, which are attractive features for lightweight, customizable and geometry-unique electronic devices.

High-Performance Polyaniline-Coated Carbon Nanotube Yarns for Wearable Thermoelectric Generators.

Carbon nanotubes/polyaniline (CNTs/PANI) composites have attracted significant attention in thermoelectric (TE) conversion due to their excellent stability and easy synthesis. However, their TE performance is far from practical demands, and few flexible yarns/fibers have been developed for wearable electronics. Herein, we developed flexible CNTs/PANI yarns with outstanding TE properties via facile soaking of CNT yarns in a PANI solution, in which the PANI layer was coated on the CNT surface and served as a bridge to interconnect adjacent CNT filaments. With optimizing PANI concentration, immersing duration, and doping level of PANI, the power factor reached 1294 µW m-1 K-2 with a high electrical conductivity of 3651 S cm-1, which is superior to that of most of the reported CNTs/PANI composites and organic yarns. Combining outstanding TE performance with excellent bending stability, a highly integrated and flexible TE generator was assembled consisting of 40 pairs of interval p-n segments, which generate a high power of 377 nW at a temperature gradient of 10 K along the out-of-plane direction. These results indicate the promising application of CNTs/PANI yarns in wearable energy harvesting.

Entropically Toughened Robust Biodegradable Polymer Blends and Composites for Bone Tissue Engineering.

Biodegradable polymers and composites are promising candidates for biomedical implants in tissue engineering. However, state-of-the-art composite scaffolds suffer from a strength-toughness dilemma due to poor interfacial adhesion and filler dispersion. In this work, we propose a facile and scalable strategy to fabricate strong and tough biocomposite scaffolds through interfacial toughening. The immiscible biopolymer matrix is compatible by the direct incorporation of a third polymer. Densely entangled polymer chains lead to massive crazes and global shear yields under tension. Weak chemical interaction and high-shear melt processing create nanoscale dispersion of nanofillers within the matrix. The resultant ternary blends and composites exhibit an 11-fold increase in toughness without compromising stiffness and strength. At 70% porosity, three-dimensional (3D)-printed composite scaffolds demonstrate high compressive properties comparable to those of cancellous bones. In vitro cell culture on the scaffolds demonstrates not only good cell viability but also effective osteogenic differentiation of human mesenchymal stem cells. Our findings present a widely applicable strategy to develop high-performance biocomposite materials for tissue regeneration.

Negative Enthalpy Variation Drives Rapid Recovery in Thermoplastic Elastomer.

The mechanism behind the resilience of polymeric materials, typically attributed to the well-established entropy elasticity, often ignores the contribution of enthalpy variation (ΔH), because it is based on the assumption of an ideal chain. However, this model does not fully account for the reduced resilience of thermoplastic polyurethane (TPU) during long-range deformation, which is mainly caused by the dynamics of physical crosslink networks. Such reduction is undesirable for long-range stretchable TPU considering its wide application range. Therefore, a negative ΔH effect is established in this work to facilitate instant recovery in long-range stretchable TPU, achieved by constructing a reversible interim interface via strain-induced phase separation. Consequently, the newly constructed dual soft segmental TPU shows resilience efficiency exceeding 95%, surpassing many synthetic high-performance TPUs with typical efficiencies below 80%, and comparable to biomaterials. Moreover, a remarkable hysteresis loop with a ratio exceeding 50%, makes it a viable candidate for applications such as artificial ligaments or buffer belts. The research also clarifies structural factors influencing resilience, including the symmetry of the dual soft segments and the content of hard segments, offering valuable insights for the design of highly resilient long-range stretchable elastomers.

Bamboo-Inspired Crack-Face Bridging Fiber Reinforced Composites Simultaneously Attain High Strength and Toughness.

Biological strong and tough materials have been providing original structural designs for developing bioinspired high-performance composites. However, new synergistic strengthening and toughening mechanisms from bioinspired structures remain yet to be explored and employed to upgrade current carbon material reinforced polymer composites, which are keystone to various modern industries. In this work, from bamboo, the featured cell face-bridging fibers, are abstracted and embedded in a cellular network structure, and develop an epoxy resin/carbon composite featuring biomimetic architecture through a fabrication approach integrating freeze casting, carbonization, and resin infusion with carbon fibers (CFs) and carbon nanotubes (CNTs). Results show that this bamboo-inspired crack-face bridging fiber reinforced composite simultaneously possesses a high strength (430.8 MPa) and an impressive toughness (8.3 MPa m1/2 ), which surpass those of most resin-based nanocomposites reported in the literature. Experiments and multiscale simulation models reveal novel synergistic strengthening and toughening mechanisms arising from the 2D faces that bridge the CFs: sustaining and transferring loads to enhance the overall load-bearing ability and furthermore, incorporating CNTs pullout that resembles the intrinsic toughening at the molecular to nanoscale and strain delocalization, crack branching, and crack deflection as the extrinsic toughening at the microscale. These constitute a new effective and efficient strategy to develop simultaneously strong and tough composites through abstracting and implenting novel bioinspired structures, which contributes to addressing the long-standingly challenging attainment of both high strength and toughness for advanced structural materials.

General Entropy Approach Toward Ultratough Sustainable Plastics.

Entropy is a universal concept across the physics of mixtures. While the role of entropy in other multicomponent materials has been appreciated, its effects in polymers and plastics have not. In this work, it is demonstrated that the seemingly small mixing entropy contributes to the miscibility and performance of polymer alloys. Experimental and modeling studies on over 30 polymer pairs reveal a strong correlation between entropy, morphology, and mechanical properties, while elucidating the mechanism behind: in polymer blends with weak interactions, entropy leads to homogeneously dispersed nanosized domains stabilized by highly entangled chains. This unique microstructure promotes uniform plastic deformation at the interface, thus improving the toughness of conventional brittle polymers by 1-2 orders of magnitude without sacrificing other properties, analogous to high-entropy metallic alloys. The proposed strategy also applies to ternary polymer systems and copolymers, offering a new pathway toward the development of sustainable polymers.

Protein Nanotubes Assembled from Imidazole-Grafted Horseradish Peroxidase Nanogels.

Protein assembly, a common phenomenon in nature, plays an important role in the evolution of life. Inspired by nature, assembling protein monomers into delicate nanostructures has emerged as an attractive research area. However, sophisticated protein assemblies usually need complicated designs or templates. In this work, we successfully fabricated protein nanotubes in a facile way by coordination interactions between imidazole-grafted horseradish peroxidase (HRP) nanogels (iHNs) and Cu2+. The iHNs were synthesized by polymerization on the surface of HRP by employing vinyl imidazole as a comonomer. By direct addition of Cu2+ into iHN solution, protein tubes were therefore formed. The size of the protein tubes could be adjusted by changing the added Cu2+ amount, and the mechanism behind the formation of protein nanotubes was elucidated. Furthermore, a highly sensitive H2O2 detection system was established based on the protein tubes. This work provides a facile method to construct diverse sophisticated functional protein nanomaterials.

Modified staging system of positive lymph nodes based nomogram in intrahepatic cholangiocarcinoma.

BACKGROUND: Intrahepatic cholangiocarcinoma (iCCA) presents the similar trend and prevalence of lymph node metastasis to other biliary tract cancer. There is still a necessity and possibility for the current classification of lymph node in the 8th TNM of iCCA, which is the same as the criteria of hepatoma carcinoma (HCC), to further improve the prognostic capacity. We aim to explore the optimal positive lymph nodes cutoff value that could predict the survival outcomes of patients with iCCA and further establish a prognostic nomogram. METHOD: Clinical characteristics were retrospectively collected in 292 patients with iCCA from Sun Yat-sen University Cancer Center (SYSUCC) for preliminary analysis. A retrospective analysis of 107 patients with iCCA in the First Hospital of Dalian Medical University (FHDMU) was performed for verification. R software was used to determine the optimal cutoff value of positive lymph nodes (PLN) and further establish the nomogram with the Cox regression model in the primary cohort. RESULTS: In those patients who were graded into the N1 stage in 8th TNM staging system, the patients with PLN between 1 and 3 showed significantly better overall survival than those patients with more than 4 PLN (P < 0.0001). Moreover, there was a significant correlation between the new PLN classification and adverse clinical characteristic including Micro Invasion (P = 0.001), Lymph Vessel Invasion (P = 0.040), Satellite Sites (P < 0.001), and Tumor Size (P = 0.005). The PLN and ELN were both independent prognostic factors for survival outcomes in the multivariate analysis, and further showed large contribution to the nomogram. The nomogram achieved a satisfied C-index of 0.813 for overall survival (OS), 0.869 for progression-free survival (PFS) in the primary cohort, and 0.787 for OS, 0.762 for PFS in the validation cohort. CONCLUSION: The modified classification of PLN in iCCA could accurately stratify the N1 stage patients in 8th TNM staging system into two groups with significantly different overall survival. The development of this nomogram can offer new evidence to precisely post-operative management of iCCA patients.

An Amphiphilic Entangled Network Design Toward Ultratough Hydrogels.

Hydrogels find important roles in biomedicine, wearable electronics, and soft robotics, but their mechanical properties are often unsatisfactory. Conventional tough hydrogel designs are based on hydrophilic networks with sacrificial bonds, while the incorporation of hydrophobic polymers into hydrogels is less well understood. In this work, a hydrogel toughening strategy is demonstrated by introducing a hydrophobic polymer as reinforcement. Semicrystalline hydrophobic polymer chains are "woven" into a hydrophilic network via entropy-driven miscibility. In-situ-formed sub-micrometer crystallites stiffen the network, while entanglements between hydrophobic polymer and hydrophilic network enable large deformation before failure. The hydrogels are stiff, tough, and durable at high swelling ratios of 6-10, and the mechanical properties are tunable. Moreover, they can effectively encapsulate both hydrophobic and hydrophilic molecules.

Ionogels: recent advances in design, material properties and emerging biomedical applications.

Ionic liquid (IL)-based gels (ionogels) have received considerable attention due to their unique advantages in ionic conductivity and their biphasic liquid-solid phase property. In ionogels, the negligibly volatile ionic liquid is retained in the interconnected 3D pore structure. On the basis of these physical features as well as the chemical properties of well-chosen ILs, there is emerging interest in the anti-bacterial and biocompatibility aspects. In this review, the recent achievements of ionogels for biomedical applications are summarized and discussed. Following a brief introduction of the various types of ILs and their key physicochemical and biological properties, the design strategies and fabrication methods of ionogels are presented by means of different confining networks. These sophisticated ionogels with diverse functions, aimed at biomedical applications, are further classified into several active domains, including wearable strain sensors, therapeutic delivery systems, wound healing and biochemical detections. Finally, the challenges and possible strategies for the design of future ionogels by integrating materials science with a biological interface are proposed.

Presence, origins and effect of stable surface hydration on regenerated cellulose for underwater oil-repellent membranes.

HYPOTHESIS: Underwater oil-repellency of polyelectrolyte brushes has been attributed mainly to electric double-layer repulsion forces based on Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Many non-polyelectrolyte materials also exhibit oil-repellent behaviour, but it is not clear if there exist similar electric double-layer repulsion and if it is the sole mechanism governing their underwater oil-repellency. EXPERIMENTS/SIMULATIONS: In this article, the oil-repellency of highly amorphous cellulose exhibiting is investigated in detail, through experiments and molecular dynamics simulations (MDS). FINDINGS: It was found that the stable surface hydration on regenerated cellulose was due to a combination of long-range electrostatic repulsions (DLVO theory) and short-range interfacial hydrogen bonding between cellulose and water molecules (as revealed by MDS). The presence of a stable water layer of about 200 nm thick (similar to that of polyelectrolyte brushes) was confirmed. Such stable surface hydration effectively separates cellulose surface from oil droplets, resulting in extremely low adhesion between them. As a demonstration of its practicality, regenerated cellulose membranes were fabricated via electrospinning, and they exhibit high oil/water separation efficiencies (including oil-in-water emulsions) as well as self-cleaning ability.

Advancement of Polyaniline/Carbon Nanotubes Based Thermoelectric Composites.

Organic thermoelectric (TE) materials have been widely investigated due to their good stability, easy synthesis, and high electrical conductivity. Among them, polyaniline/carbon nanotubes (PANI/CNTs) composites have attracted significant attention for pursuing enhanced TE properties to meet the demands of commercial applications. In this review, we summarize recent advances in versatile PANI/CNTs composites in terms of the dispersion methods of CNTs (such as the addition of surfactants, mechanical grinding, and CNT functional group modification methods), fabrication engineering (physical blending and in-situ polymerization), post-treatments (solvent treatments to regulate the doping level and microstructure of PANI), and multi-components composites (incorporation of other components to enhance energy filtering effect and Seebeck coefficient), respectively. Various approaches are comprehensively discussed to illustrate the microstructure modulation and conduction mechanism within PANI/CNTs composites. Furthermore, we briefly give an outlook on the challenges of the PANI/CNTs composites for achieving high performance and hope to pave a way for future development of high-performance PANI/CNTs composites for sustainable energy utilization.

Nanoenzyme-chitosan hydrogel complex with cascade catalytic and self-reinforced antibacterial performance for accelerated healing of diabetic wounds.

The significant disability and fatality rate of diabetes chronic wounds necessitates the development of efficient diabetic wound healing techniques. The present oxygen treatments for wound healing is restricted by issues such as poor penetration, inadequate supply, and absorption difficulties as well as tanglesome diabetic wound microenvironment issues such as hyperglycemia, excessive reactive oxygen species (ROS), and hypoxia. Herein, we designed a multifunctional glucose oxidase (GOx) and catalase (CAT) nanoenzyme-chitosan (GCNC) hydrogel complex to improve the microenvironment of diabetic wounds and provide continuous oxygen delivery for efficient wound healing. By simultaneously forming the GOx-CAT nanoenzyme (GCNE) composite, the GCNC hydrogel complex could effectively reduce glucose and ROS (H2O2) concentrations in diabetic wounds through cascade catalytic reactions and achieve continuous oxygen supply, which promoted cell proliferation, migration, and angiogenesis, thereby accelerating diabetic wound healing. In addition, the byproduct gluconic acid produced by the cascade reaction can activate the amino group of chitosan to reinforce the antibacterial performance and prevent microbial infection. This multifunctional GCNC hydrogel complex with continuous oxygen supply, self-reinforcing antibacterial properties, and byproduct-free features provides a general strategy for repairing the extensive tissue damage in diabetes.

Self-Healing Approach toward Catalytic Soft Robots.

Soft robotics is a rapidly evolving research field that focuses on developing robots with bioinspired actuation/sensing mechanisms and highly flexible soft materials, some of which are similar to those found in living organisms. The hydrogel has the characteristics of excellent biocompatibility, softness, and elasticity, which makes it an ideal candidate material for the preparation of soft robots. Here we utilized a self-healing approach to develop a catalytically driven soft robot, which was constructed by dynamic imine bonds between modular hydrogels. One of the modules was a hydrogel formed by dynamic aldimine cross-linking of chitosan and glutaraldehyde, and the other module was a hydrogel embedded with catalase. The soft hydrogel robot moved because of catalytic reactions between the robot and environment [hydrogen peroxide (H2O2) fuel], giving rise to a fluidic release that supports propulsion, as inspired by the jet-propulsive mechanism in swimming dragonfly larvae. The speed of the soft robot can be mediated by adjusting the concentration of H2O2 and enable/disable movement based on the folding and unfolding of enzymes. In addition, the hydrogel formed by replacing glutaraldehyde with dialdehyde-functionalized PEG2000 had excellent elastic properties, and the soft robot based on PEG2000 had a higher movement speed than that based on glutaraldehyde under the same H2O2 concentration. Moreover, the addition of iron oxide nanoparticles can realize the magnetic guidance of the soft robot and the combination of different modules can realize different motion modes. The highly configurable self-healing catalytic soft robot holds great potential for a variety of interesting applications, including swimming robots, robot-assisted water treatment, and drug release.

An Inflammatory Response-Related Gene Signature Reveals Distinct Survival Outcome and Tumor Microenvironment Characterization in Pancreatic Cancer.

Background: Desmoplasia or rich fibrotic stroma is a typical property of pancreatic cancer (PC), with a significant impact on tumor progression, metastasis, and chemotherapy response. Unusual inflammatory responses are considered to induce fibrosis of tissue, but the expression and clinical significance of inflammatory response-related genes in PC have not been clearly elucidated. Methods: Prognosis-related differentially expressed genes (DEGs) between tumor and normal tissues were identified by comparing the transcriptome data of PC samples based on The Cancer Genome Atlas (TCGA) portal and the Genotype Tissue Expression (GTEx) databases. Samples from the ArrayExpress database were used as an external validation cohort. Results: A total of 27 inflammatory response-related DEGs in PC were identified. Least absolute shrinkage and selection operator (LASSO) analysis revealed three core genes that served as an inflammatory response gene signature (IRGS), and a risk score was calculated. The diagnostic accuracy of the IRGS was validated in the training (n = 176) and validation (n = 288) cohorts, which reliably predicted the overall survival (OS) and disease-free survival (DFS) of patients with PC. Furthermore, multivariate analysis identified the risk score as an independent risk factor for OS and DFS. The comprehensive results suggested that a high IRGS score was correlated with decreased CD8+ T-cell infiltration, increased M2 macrophage infiltration, increased occurrence of stroma-activated molecular subtype and hypoxia, enriched myofibroblast-related signaling pathways, and greater benefit from gemcitabine. Conclusion: The IRGS was able to promisingly distinguish the prognosis, the tumor microenvironment characteristics, and the benefit from chemotherapy for PC.

Progression Patterns and Post-Progression Survival in Recurred Intrahepatic Cholangiocarcinoma Patients: A Novel Prognostic Nomogram Based on Multicenter Cohorts.

Background: The post-progression survival (PPS) of recurred intrahepatic cholangiocarcinoma (iCCA) patients relates to the characteristics of tumor progression. Moreover, the prediction model of PPS in those patients has not been well established. This study aimed at developing a novel nomogram for predicting PPS in recurred iCCA patients. Method: Clinical characteristics were retrospectively collected in 396 patients diagnosed with iCCA from cohorts of Sun Yat-sen University Cancer Center (SYSUCC) and the First Hospital of Dalian Medical University (FHDMU). The PPS in patients with different progression patterns was investigated. The nomogram of PPS was established with the Cox regression model in the primary cohort. Then the nomogram was verified in the external validation cohort. Results: Liver progression was the commonest pattern (42.08%) in recurred iCCA patients, while patients with local LN progression had significantly better PPS than those with other patterns. The independent prognostic factors comprised elevated CEA levels, tumor differentiation, N stage 8th, adjuvant therapy, Local LN metastasis, Liver Metastasis only, and Multiple Metastasis. The nomogram constructed on these factors achieved satisfied C-indexes of 0.794 (95% CI 0.769-0.828) and 0.827 (0.779-0.876) for the training and validation cohorts, respectively. These values were significantly higher than those of the 8th TNM stage system (all p < 0.001). The recurred iCCA patients could be precisely classified into high- and low-risk groups according to the cutoff point of this nomogram (p < 0.01). Conclusion: The investigation of progression patterns and the development of this nomogram can offer new evidence to precisely postoperative and post-progression management of iCCA patients.

Fatty Acid-Based Coacervates as a Membrane-free Protocell Model.

Membrane-less scenarios that involve liquid-liquid phase separation (coacervation) provide clues for how protocells might emerge. Here, we report a versatile approach to construct coacervates by mixing fatty acid with biomolecule dopamine as the protocell model. The coacervate droplets are easily formed over a wide range of concentrations. The solutes with different interaction characteristics, including cationic, anionic, and hydrophobic dyes, can be well concentrated within the coacervates. In addition, reversible self-assemblies of the coacervates can be controlled by concentration, pH, temperature, salinity, and bioreaction realizing cycles between compartmentalization and noncompartmentalization. Through in situ dopamine polymerization, the stability of coacervate droplets is significantly improved, leading to higher resistance toward external factors. Therefore, the coacervates based on fatty acid and dopamine could serve as a bottom-up membrane-less protocell model that provides the links between the simple (small molecule) and complex (macromolecule) systems in the process of cell evolution.