Formation of supramolecular ionic liquid (IL) gels (ionogels) induced by low-molecular-mass gelators (LMMGs) is an efficient strategy to confine ILs, and the negligible influence of LMMGs on the electrochemical properties of ILs makes ionogels ideal quasisolid electrochemical materials. Furthermore, the stimuli-responsive and self-healing characters of the supramolecular gel can be utilized for the potential development of smart electrochemical materials. However, the poor mechanical properties of supramolecular ionogels reported so far limit their practical applications. Herein, we investigated a series of efficient d-gluconic acetal-based gelators (Gn, PG16, and B8) that can harden a wide variety of ILs at low concentrations. It was shown that both alkyl chain length and the number of hydrogen bonding sites of a certain gelator, as well as the nature of the IL anion, significantly influenced the gelation abilities. The resulting ionogels were thermally reversible, and most of them were stable at room temperature. Interestingly, a PG16-based supramolecular ionogel showed rapid self-healing properties upon mechanical damage. Furthermore, the PG16-based ionogel demonstrated unprecedented performances including the favorable ionic conductivity, excellent mechanical strength, and enhanced viscoelasticity, which make it a great self-healing electrochemical material. The ionogel formation mechanism was proposed based on the analysis of Fourier transform infrared, HNMR, and X-ray diffraction, indicating that a combination of hydrogen bonding, π-π stacking, and interactions between alkyl chains was responsible for the self-assembly of gelators in ILs. Overall, our present studies on exploring the structure-property relationship of gelators for the formation of practically useful supramolecular ionogels shed light for future development of more functionalized ionogels.
Self-healing ionogel is a promising smart material because of its high conductivity and reliable stimuli responsiveness upon mechanical damage. However, self-healing ionogels possessing rapid, complete recovery properties and multifunctionality are still limited. Herein, we designed a new d-gluconic acetal-based gelator (PB8) bearing a urea group in the alkyl side chain. Interestingly, the balance between hydrophilicity and hydrophobicity of the molecule is achieved. Thus, PB8 could form transparent ionogels because of its excellent affinity to ionic liquids (ILs), which exhibited appropriate mechanical strength, high viscoelasticity, and efficient self-healing properties. The presence of synergistic effects from hydrogen bonding, π–π stacking, and interactions between the urea-containing side chains was responsible for the self-assembly of gelators in ILs and the self-healing property mainly related to the side chains of PB8. Interestingly, the transparent PB8-IL4 ionogel possessed high conductivity and mechanical strength, moldable and injectable properties, and rapid and complete self-healing characteristics (complete recovery within 14 min), which showed excellent performance as a smart ionic conductor. Furthermore, the self-healing PB8-based ionogels with anticorrosion properties are a remarkable lubricating material in the steel–steel contact and exhibited excellent lubricating performances. Overall, an efficient PB8-based ionogel with self-healing properties has been developed for potential use both as a smart electrical conductor and as a high-performance lubricating material. The unique structure of PB8 bearing a urea group in the side chain is found to be responsible for the multifunctional ionogel formation.
Intrahepatic cholangiocarcinoma (ICC) and hepatocellular carcinoma (HCC) are the most prevalent histologic types of primary liver cancer (PLC). Although ICC and HCC share similar risk factors and clinical manifestations, ICC usually bears poorer prognosis than HCC. Confidently discriminating ICC and HCC before surgery is beneficial to both treatment and prognosis. Given the lack of effective differential diagnosis biomarkers and methods, construction of models based on available clinicopathological characteristics is in need. Nomograms present a simple and efficient way to make a discrimination. A total of 2894 patients who underwent surgery for PLC were collected. Of these, 1614 patients formed the training cohort for nomogram construction, and thereafter, 1280 patients formed the validation cohort to confirm the model's performance. Histopathologically confirmed ICC was diagnosed in 401 (24.8%) and 296 (23.1%) patients in these two cohorts, respectively. A nomogram integrating six easily obtained variables (Gender, Hepatitis B surface antigen, Aspartate aminotransferase, Alpha‐fetoprotein, Carcinoembryonic antigen, Carbohydrate antigen 19‐9) is proposed in accordance with Akaike's Information Criterion (AIC). A score of 15 was determined as the cut‐off value, and the corresponding discrimination efficacy was sufficient. Additionally, patients who scored higher than 15 suffered poorer prognosis than those with lower scores, regardless of the subtype of PLC. A nomogram for clinical discrimination of ICC and HCC has been established, where a higher score indicates ICC and poor prognosis. Further application of this nomogram in multicenter investigations may confirm the practicality of this tool for future clinical use.
haloperoxidases. [15,16] This kind of natural enzymes can catalyze the two-electron oxidation of halides to microbicidal hypohalous acids (HOX, X: Cl − , Br − , I − ) or analogous oxidized halide species in the presence of hydrogen peroxide (H 2 O 2 ). [17][18][19] Such natural biofilm inhibition utilizing naturally occurring reagents (halide and H 2 O 2 ) represents a promising and environmentally friendly antibiofilm strategy. Nevertheless, natural enzymes often suffer from intrinsic drawbacks such as highcost, poor operational stability, and recyclability. Artificial nanozymes, one kind of nanomaterials combining nanoscale and enzyme-like catalytic functionalities, exhibit advantages such as low-cost and high durability. [20][21][22][23][24] Interestingly, some nanomaterials (e.g., vanadium pentoxide and ceria) have been explored as haloperoxidase-mimicking nanozymes. [25][26][27][28][29] Although high catalytic activity, the carcinogenicity and mutagenicity of vanadium pentoxide could hinder their large-scale application in marine environment. As a heterogeneous metal oxide nanozyme, mixed-valency nanoceria exhibited significantly enhanced catalytic activity towards haloperoxidase-like reaction in contrast to bulk ceria, [28] highlighting that high surface-to-volume ratio and surface geometric effect could strongly affect the activity of a nanozyme. Nevertheless, the haloperoxidase-like performance of nanoceria is relatively low. From a structural perspective, downsizing ceria to nanocluster scale is of significance for maximizing active component utilization and achieving better haloperoxidase-mimicking performance. Unfortunately, most nanomaterials have large particles owing to the natural tendency of agglomeration.Nanostructured materials involving highly dispersed subnanocluster species on supports have been shown to be crucial for enabling heterogeneous catalysts with high intrinsic activity and unexpected selectivity. [30][31][32][33] Nevertheless, stabilizing goaloriented high-density ultrasmall nanoclusters on solid substrates with uniform size and dispersion has been challenged by the thermodynamic instability of nanocluster, poor interfacial hybrid interaction, as well as chemical synthesis. [34][35][36] Herein we propose a fabrication strategy to fabricate hybrid CeO 2 @ ZrO 2 where high-density ultrasmall ceria clusters (≈0.8 nm) are stabilized on zirconia substrates. This unique feature of heterografting CeO 2 @ZrO 2 nanozyme enabled superior and stable haloperoxidase-mimicking performance in selectively catalyzing the oxidation of bromide with H 2 O 2 to hypobromousThe generation of undesired biofouling in medical and engineering applications results in a reduction in function and durability. Copying functionalities of natural enzymes to combat biofouling by artificial nanomaterials is highly attractive but still challenged by the inferior catalytic activity and specificity principally because of low densities of active sites. Here, an innovate strategy is demonstrated to stabilize high-density ...
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