An effective and facile fluorescence sensing approach for the determination of 2,4,6-trinitrophenol (TNP) using the chemically oxidized and liquid exfoliated graphitic carbon nitride (g-C3N4) nanosheets was developed. The strong inner filter effect and molecular interactions (electrostatic, π-π, and hydrogen bonding interactions) between TNP and the g-C3N4 nanosheets led to the fluorescence quenching of the g-C3N4 nanosheets with efficient selectivity and sensitivity. Under optimal conditions, the limit of detection for TNP was found to be 8.2 nM. The proposed approach has potential application for visual detection of TNP in natural water samples for public safety and security.
Semiconducting polymeric carbon nitride (CN) has drawn wide attention ranging from photocatalysis to more recent biosensing owing to unique defect‐tolerated optoelectronic properties and being metal‐free, cheap, and highly stable. However, at the core of electrical–optical interconversion, the preparation of the CN photoelectrode is still challenging. Now, the growth of CN on electrodes is achieved simply by microwave‐assisted condensation in seconds. The ultrafast heating not only addressed the thermodynamic contradiction of precursor volatilization during polymerization but also led to strongly adhesive CN layer on electrodes with gradient carbon‐rich texture, greatly accelerating the electron–hole separation and mobility. Consequently, the CN photoelectrode exhibited a remarkable photocurrent and a record cathodic efficiency of electrochemiluminescence up to 7 times that of benchmark Ru(bpy)3Cl2 in aqueous solution.
Four-dimensional printing, a new process to fabricate active materials through three-dimensional (3D) printing developed by MIT's Self-Assembly Lab in 2014, has attracted more and more research and development interests recently. In this paper, a type of epoxy-acrylate hybrid photopolymer was synthesized and applied to fabricate shape memory polymers through a stereolithography 3D printing technique. The glass-to-rubbery modulus ratio of the printed sample determined by dynamic mechanical analysis is as high as 600, indicating that it may possess good shape memory properties. Fold-deploy and shape memory cycle tests were applied to evaluate its shape memory performance. The shape fixity ratio and the shape recovery ratio in ten cycles of fold-deploy tests are about 99 and 100%, respectively. The shape recovery process takes less than 20 s, indicating its rapid shape recovery rate. The shape fixity ratio and shape recovery ratio during 18 consecutive shape memory cycles are 97.44 ± 0.08 and 100.02 ± 0.05%, respectively, showing that the printed sample has high shape fixity ratio, shape recovery ratio, and excellent cycling stability. A tensile test at 62 °C demonstrates that the printed samples combine a relatively large break strain of 38% with a large recovery stress of 4.7 MPa. Besides, mechanical and thermal stability tests prove that the printed sample has good thermal stability and mechanical properties, including high strength and good toughness.
5Multifunctional self-healing hydrogel coatings based on dynamic disulfide exchange reaction were developed via surface-initiated thiol-ene photopolymerization. The functional monomers, (poly(ethylene glycol)methyl ether methacrylate (PEGMA), N-hydroxyethyl acrylamide (HEAA) and 2-(methacryloyloxy)ethyl trimethylammonium chloride (META)), and disulfide-containing crosslinker bis(2-methacryloyl)oxyethyl disulfide (BMOD) were employed for the preparation of antifouling, 10 antibacterial and self-healing hydrogel coatings. The hydrogel coatings reduced protein adsorption, as well as bacteria adhesion from Gram-negative Escherichia coli (E. coli). Moreover, the coatings exhibited good self-healing ability at moderate temperatures due to the dynamic disulfide exchange reaction. Introduction of self-healing ability provides a promising means for self-repairing of microcracks of functional polymer coatings and improving their stability and durability in the long-term applications as 15 biomaterials.
A series of photosensitive resins suitable for the production of silicone elastomers through digital light processing 3D printing are reported. Based on thiol− ene click reaction between a branched mercaptan-functionalized polysiloxane and different-molecular-weight vinyl-terminated poly(dimethylsiloxane), silicone elastomers with tunable hardness and mechanical properties are obtained. Printed elastomeric objects show high printing resolution and excellent mechanical properties. The break elongation of the silicone elastomers can get up to 1400%, which is much higher than the reported UV-cured elastomers and is even higher than the most stretchable thermocuring silicone elastomers. The superstretchable silicone elastomers are then applied to fabricate stretchable electronics with carbon nanotubes-doped hydrogel. The printable and processable silicone elastomers have great potential applications in various fields, including soft robotics, flexible actuators, and medical implants.
Classical pH test papers are widely used to measure the acid-base degree of media in a qualitative or semiquantitative manner. However, the extension of portable and inexpensive methods to a wide range of analytes so as to eliminate the tediousness of instrumental assays remains unsuccessful. Here, we report a novel kind of dual-colored carbon dot (CD) ratiometric fluorescent test paper for the semiquantitative assay of copper ions (Cu) by a dose-sensitive color evolution. The preparation of the test paper is based on the following two interesting findings: on the one hand, residual p-phenylenediamine at the surface of as-synthesized red CDs (r-CDs) efficiently binds Cu ions to produce a strong visible absorption that overlaps the emission of blue CDs (b-CDs); on the other hand, the Cu ions render the adsorption of small b-CDs onto the surface of larger r-CDs through their dual-coordinating interactions with the surface ligands of both r-CDs and b-CDs. These two mechanisms lead to a specific spectral energy transfer to quench the fluorescence of b-CDs with a sensitive detection limit of 8.82 nM Cu, whereas the red fluorescence of r-CDs is unaffected as a stable internal standard. Ratiometric fluorescent test papers have been prepared using a mixture of r-CDs and b-CDs (1:7) as ink by jetprinting on a piece of paper. With the addition of Cu ions, the blue test paper produces a consecutive wide-colored evolution from blue to orange-red, with a dose-discerning ability as low as 25 nM.
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