Effect of three-dimensional to one-dimensional orientation of cellulose nanofiber sizing agents on carbon fibers under magnetic and electric fields on composite material properties.

Nanoparticle-containing sizing agents are essential for the overall performance of high-quality carbon fiber (CF) composites. However, the uneven dispersion of nanoparticles often leads to agglomeration on the surface of CF after sizing, consequently diminishing the material properties. In this study, the properties of cellulose nanofibers (CNFs) that can respond to magnetic and electric fields were utilized to achieve three-dimensional to one-dimensional orientations in CFs containing sizing agents. Cobalt ferrite (CoFe2O4) was utilized to enhance the response of CNFs to a magnetic field, and subsequently, it was combined with an electric field to attain a higher degree of orientation. The occurrence of nanoparticle agglomeration is diminished on CF surface, while establishing a structured network. The flexural strength and thermal conductivity of CF composites treated with CoFe2O4 self-assembled CNF sizing agent exhibit an increase of 54.23 % and 57.5 %, respectively, compared to those of desized CF composites, when subjected to magnetic and electric fields. Consequently, the approach can depolymerize the nano-fillers within the sizing agent and orient it into the carbon fiber under the influence of magnetic and electric fields, effectively improving the mechanical properties and thermal conductivity of the composite material.

Growth of ZnO nanorods/flowers on the carbon fiber surfaces using sodium alginate as medium to enhance the mechanical properties of composites.

The chemical inertness of the carbon fiber (CF) surface results in suboptimal mechanical properties of the prepared composites. To address this issue, we employed a combination of tannic acid and 3-aminopropyltriethoxysilane mixture (TA-APTES) grafted sodium alginate (SA) as a medium to enhance the interfacial properties of composites through the growth of ZnO nanoparticles on CF surfaces. ZnO nanolayers with rod-like and flower-like structures were obtained by adjusting the pH of the reaction system (pH = 10 and 12, respectively). Characterization results show that in comparison with the untreated CF composites, in the flexural strength, flexural modulus, interlaminar shear strength (ILSS) and interfacial shear strength (IFSS) of the as-prepared CF/TA-APTES/SA/ZnO10 (nanorods) composites were improved by 40.8 %, 58.4 %, 44.9 % and 47.8 %, respectively. The prepared CF/TA-APTES/SA/ZnO12 (nanoflowers) composite showed an increase in flexural strength, flexural modulus, ILSS and IFSS by 39.8 %, 63.6 %, 47.3 % and 48.2 %, respectively. These positive results indicate that the ZnO nanolayers increase the interfacial phase area and fiber surface roughness, thereby enhancing mechanical interlocking and load transfer between the fibers and resin matrix. This work provides a novel interfacial modification method for preparing CF composites used in longer and more durable wind turbine blades.

Fabrication of Porous Reduced Graphene Oxide Encapsulated Cu(OH)2 Core-shell Structured Carbon Fiber-Based Electrodes for High-Performance Flexible Supercapacitors.

To explore next-generation flexible supercapacitors, lightweight, superior conductivity, low cost, and excellent capacitance are the preconditions for practical use. However, subjected to unsatisfactory conductivity, limited surface areas, and poor porosity leading to long ion transport channels, carbon fiber (CF)-based flexible supercapacitors need to further boost the electrochemical properties. Hence, a porous reduced graphene oxide encapsulated Cu(OH)2 core-shell structured CF-based electrode was fabricated through a scalable approach. The inexpensive Cu(OH)2 nanoarrays were controllably grown in situ on a CF substrate, with residual Cu promoting conductivity. Porous graphene oxide (PrGO), which served as the shell, was realized by Ni nanoparticle etching, which not only provided more active sites for capacitance as well as shortened accessible pathways for the ion transport but also effectively alleviated the exfoliation of the internal active materials. Moreover, thanks to this distinctive core-shell architecture, the extra space between the outer PrGO layer and the internal ordered Cu(OH)2 nanoarrays provided increased space for capacitance storage. The assembled PrGO/Cu(OH)2/Cu@CF electrode exhibited an excellent areal capacitance, reaching up to 722 mF cm-2 at a current density of 0.5 mA cm-2, attributed to its superior structure and materials advantages. The resulting PrGO/Cu(OH)2/Cu@CF//AC//CF asymmetric flexible all-solid-state supercapacitor achieved a high energy density of 0.052 mWh cm-2 and exhibited long-term durability. This work proposes a low-cost and effective way to fabricate hierarchically structured electrodes for wearable CF-based supercapacitors.

Modulation of metal species as control point for Ni-catalyzed stereodivergent semihydrogenation of alkynes with water.

A base-assisted metal species modulation mechanism enables Ni-catalyzed stereodivergent transfer semihydrogenation of alkynes with water, delivering both olefinic isomers smoothly using cheap and nontoxic catalysts and additives. Different from most precedents, in which E-alkenes derive from the isomerization of Z-alkene products, the isomers were formed in orthogonal catalytic pathways. Mechanistic studies suggest base as a key early element in modulation of the reaction pathways: by adding different bases, nickel species with disparate valence states could be accessed to initiate two catalytic cycles toward different stereoisomers. The practicability of the method is showcased with nearly 70 examples, including internal and terminal triple bonds, enynes and diynes, affording semi-hydrogenated products in high yields and selectivity.

Improvement of Interfacial Properties and Bioactivity of CF/PEEK Composites by Rapid Biomineralization of Hydroxyapatite.

The carbon fiber/hydroxyapatite (CF/HA) reinforcement with a three-dimensional flower-like structure was rapidly fabricated with the biomimetic mineralization method to strengthen the interfacial performance and bioactivity of carbon fiber/polyether ether ketone (CF/PEEK) composites. Silk fibroin (SF), which can construct a robust interphase between CF and PEEK, supported an organic template to regulate the growth of inorganic HA. The interfacial properties were markedly enhanced through mechanical interlocking and interface adhesion induced by increasing roughness and surface energy of CF. Besides, the mineralization time was significantly reduced after the addition of cetyltrimethylammonium bromide to the simulated body fluid, and the prepared CF/HA possessed good bioactivity. In this study, the interlaminar shear strength (ILSS) and flexural strength of CF-HA/45/PEEK composites demonstrated an enhancement of 45.9% and 51.2%, respectively, compared to the untreated CF/PEEK composites. It is predicted that this strategy could provide a rapid and convenient route to ameliorate the interfacial performance and bioactivity of CF/PEEK composites simultaneously.

Divergent functionalization of α,ß-enones: catalyst-free access to ß-azido ketones and ß-amino α-diazo ketones.

A simple and practical method for the azidation of ß-fluoroalkyl α,ß-unsaturated ketones to access a wide variety of fluorinated nitrogenous carbonyl compounds is developed. Different from existing precedents, neither a metallic nor an organic catalyst was involved in our strategy. Judicious choice of solvents allows for the modulation of the reaction outcomes, delivering ß-azido ketones or ß-amino α-diazo ketones. The reaction system features environmental friendliness, mild conditions, simplicity and excellent functional group tolerance.

Ultra-stretchable, self-recovering, self-healing cationic guar gum/poly(stearyl methacrylate-co-acrylic acid) hydrogels.

Hydrogels that exhibit properties such as ultra-elongation, self-recovery, and self-healing have applications in sensors and many other fields. With these properties and applications in mind, we hypothesised that we could develop a strain-sensing hydrogel based on acrylic acid, stearyl methacrylate, cationic guar gum, and hexadecyl trimethyl ammonium bromide, without any covalent crosslinker. The hydrogels are instead held together by physical, non-covalent interactions such as ionic interactions, hydrogen bonding, and the hydrophobic effect, as suggested by spectroscopy and swelling experiments. The hydrogels exhibit many useful properties, such as: excellent stretching-up to 4267%-and almost complete reversion to their original state at a large strain of 500%, even after 20 successive cycles; temperature-dependent self-healing and self-recovery; and strain-sensitive conductivity that is attributable to the directional migration of ions. Because of these outstanding features, such as notch-insensitivity and the ability to withstand knotting under high strain, our hydrogels will be useful as flexible sensors.

Catalytic C-C Cleavage/Alkyne-Carbonyl Metathesis Sequence of Cyclobutanones.

A ring-opening/alkyne-carbonyl metathesis sequence of alkyne-tethered cyclobutanones catalyzed by AgSbF6 is realized for the first time to furnish multisubstituted naphthyl ketones under mild conditions. A range of substrates decorated with various substituents at different positions were all well accommodated. Preliminary mechanistic studies show that silver salt acted as a Lewis acid to facilitate both C-C cleavage of the cyclobutanone moiety and the subsequent metathesis between C═O and C≡C bonds.

Fabrication of microcapsule-type composites with the capability of underwater self-healing and damage visualization.

Inspired by biology, underwater self-healing polymer composites with damage-healing visible agents were successfully designed and prepared. The healing agents, same as epoxy resin matrices, were encapsulated and embedded into a matrix that contained fluorescent latent curing agents. The results of investigation on healing properties revealed that the fluorescent latent curing agents and the microcapsules in the matrix play two roles. First, the matrix could be self-healed via a crosslinking reaction between the amine group and epoxy resin, in which the amine group could be released from the fluorescent latent curing agents (FLCAs) after exposure to water. Second, the fluorescent dyes released under water could indicate the scratches and healing area visually. Embedding 15 mass% microcapsules and 6 mass% FLCAs in self-healing materials yielded a healing efficiency of 85.6% and the most efficient fluorescence detection. Self-healing materials can be repaired underwater and they show the location of damage, which is of great significance in applications such as water conservation engineering, environmental treatment engineering, ship engineering and ocean engineering.

Multiple dye-doped silica cross-linked micellar nanoparticles for colour-tuneable sensing of cysteine in an aqueous media and living cells.

This work demonstrated the design and synthesis of multiple dye-doped silica cross-linked micellar nanoparticles (MD-SCMNPs) by encapsulating three organic dyes (fluorescein derivative (FCD), coumarin derivative (HCE) and Rhodamine b (RhB)) in SCMNPs cores for colour-tuneable sensing of cysteine (Cys) in aqueous media and in living cells. In the presence of Cys, HCE exhibited blue emission, and RhB exhibited purple emission, while FCD reacted with Cys and exhibited green fluorescence "turn-on" in the core of MD-SCMNPs. This green-light-emitting sensing product may cause "step by step" fluorescent resonance energy transfer (FRET) from HCE to the sensing product and then to RhB. Based on the FRET process in the core, MD-SCMNPs can quantitatively detect Cys by a colour change with a low limit of detection (LOD) of 0.3 µM in living cells. Furthermore, MD-SCMNPs exhibited ultrasmall size (∼12 nm) and excellent dispersity and biocompatibility, which could potentially be used as a visualized Cys sensor for health monitoring and disease prediction in the human body.

Oriented Polyaniline Nanowire Arrays Grown on Dendrimer (PAMAM) Functionalized Multiwalled Carbon Nanotubes as Supercapacitor Electrode Materials.

At present, PANI/MWNT composites have been paid more attention as promising electrode materials in supercapacitors. Yet some shortcomings still limit the widely application of PANI/MWNT electrolytes. In this work, in order to improve capacitance ability and long-term stability of electrode, a multi-amino dendrimer (PAMAM) had been covalently linked onto multi-walled carbon nanotubes (MWNT) as a bridge to facilitating covalent graft of polyaniline (PANI), affording P-MWNT/PANI electrode composites for supercapacitor. Surprisingly, ordered arrays of PANI nanowires on MWNT (setaria-like morphology) had been observed by scanning electron microscopy (SEM). Electrochemical properties of P-MWNT/PANI electrode had been characterized by cyclic voltammetry (CV) and galvanostatic charge-discharge technique. The specific capacitance and long cycle life of P-MWNT-PANI electrode material were both much higher than MWNT/PANI. These interesting results indicate that multi-amino dendrimer, PAMAM, covalently linked on MWNT provides more reaction sites for in-situ polymerization of ordered PANI, which could efficiently shorten the ion diffusion length in electrolytes and lead to making fully use of conducting materials.

Hydrogen bond-induced bright enhancement of fluorescent silica cross-linked micellar nanoparticles.

This work demonstrated the synthesis and design of ultra-bright and ultra-small fluorescent nanoparticles, which were prepared by encapsulating 4-(diphenylamino)benzaldehyde (DPB) in silica cross-linked micellar nanoparticles (SCMNPs). The DPB-doped SCMNPs (DPB-SCMNPs) exhibited ultra-bright fluorescence in an aqueous medium that was 22 times brighter than that of free DPB molecules in an organic solvent. For the first time, density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations were used to confirm that the enhanced brightness of the DPB-SCMNPs was due to a hydrogen bond-induced mechanism. In addition, the 3D fluorescence spectra and the Commission Internationale de L'Eclairage (CIE) diagram were employed to determine the optical properties and emission colour of the DPB-SCMNPs. Moreover, the DPB-SCMNPs were water-soluble, monodisperse and ultra-small (∼12 nm) and should be robust and stable in aqueous media and biological systems.

Novel Schiff base (DBDDP) selective detection of Fe (III): Dispersed in aqueous solution and encapsulated in silica cross-linked micellar nanoparticles in living cell.

This work demonstrated the synthesis of (4E)-4-(4-(diphenylamino)benzylideneamino)-1,2-dihydro-1,5- dimethyl-2-phenylpyrazol-3-one (DBDDP) for Fe (III) detection in aqueous media and in the core of silica cross-linked micellar nanoparticles in living cells. The free DBDDP performed fluorescence enhancement due to Fe (III)-promoted hydrolysis in a mixed aqueous solution, while the DBDDP-doped silica cross-linked micellar nanoparticles (DBDDP-SCMNPs) performed an electron-transfer based fluorescence quenching of Fe (III) in living cells. The quenching fluorescence of DBDDP-SCMNPs and the concentration of Fe (III) exhibited a linear correlation, which was in accordance with the Stern-Volmer equation. Moreover, DBDDP-SCMNPs showed a low limit of detection (LOD) of 0.1 ppm and an excellent selectivity against other metal ions. Due to the good solubility and biocompatibility, DBDDP-SCMNPs could be applied as fluorescence quenching nanosensors in living cells.