Fabrication strategies and application fields of novel 2D Ti3C2Tx (MXene) composite hydrogels: A mini-review

Ti₃C₂T_x (MXene), a new kind of 2D ceramic nanosheets, is receiving more and more attention in the fields of medicine, biology, energy, electronics, etc. However, the preparation and application of MXene in hydrogel is still in its infancy period. Here, we review the latest progress (after 2018) related to MXene hydrogels in time. Aiming at the key issue of the dispersion stability of MXene in hydrogel systems, the preparation strategy, mechanism, advantages and disadvantages of MXene hydrogels are sorted out in detail, and the potential application prospects of MXene composite hydrogel are introduced. Finally, future viewpoints are put forward for the dispersion stability challenges that need solving in the design of MXene hydrogel.     

Preparation of one-dimensional polymer films by modification of a hydroxymethylbenzene self-assembled monolayer on iron with alkyltriethoxysilanes for preventing iron corrosion

A self-assembled monolayer (SAM) of p-hydroxymethylbenzene HOCH₂C₆H₄ - (HOMB) moiety adsorbed on iron by the formation of a covalent bond between carbon and iron atoms was prepared by electrochemical derivatization of an iron electrode with p-hydroxymethylbenzenediazonium tetrafluoroborate HOCH₂C₆H₄N₂BF₄. The electrode covered with the HOMB SAM was modified with alkyltriethoxysilanes C_nH_2n+1Si(OC₂H₅)₃ (C_nTES, n = 8 or 18) to prepare a film of one-dimensional polymer. The protective ability of the polymer film was determined by polarization measurement of the covered electrode in an aerated 0.5 M NaCl solution. The ability was enhanced by modification of the HOMB SAM with C_nTES markedly. The iron surface coated with the one-dimensional polymer film of the HOMB SAM modified with C₈TES was characterized by contact angle measurement and FTIR reflection and X-ray photoelectron spectroscopies. The persistence in the protective ability of the polymer film against iron corrosion in 0.5 M NaCl may be associated with the strong adsorption via the covalent bond, revealed by electron-probe microanalysis.     

Formation and surface modification of self-assembled films with acrylated hyperbranched poly(ester-amine) as the outmost layer

An acrylated hyperbranched poly(ester-amine) (HPEA) synthesized from piperazine and trimethylolpropanetriacrylate at a molar ratio of 1:1.42 was used as the polycation to form self-assembled films by layer-by-layer dipping with poly(sodium-p-styrenesulfonate) as the polyanion. The surface morphology and hydrophilicity of the films with HPEA as the outmost layer were controlled by adjusting the solution pH of HPEA. Due to the existence of many acrylate groups, the films with HPEA as the outmost layer were further reacted with a series of reagents, including piperazine, piperidine, laurylamine and p-phenylenediamine. The surface reactions of the films depended on both the nature of the reagents and the morphology of the initial surface. In the presence of the strong basic amines, piperazine and piperidine, the films dissolved extensively into the solution. In the case of laurylamine, a modified film with an opaque appearance was obtained due to the crystallization of long alkyl chains. With the weak basic amine p-phenylenediamine as the reactant, the film was effectively modified without any change in the surface morphology.     

A carboxyalkanethiol monolayer modified electrode for blocking of ascorbic acid oxidation and its application to a biosensor

Upon the application of amperometric biosensor to the biological fluid, ascorbic acid interferes the amperometric determination of analytes, because the oxidative potential of ascorbic acid is lower than that of electro active substances such as H₂O₂ produced by the enzymatic reaction. In this study we propose a method to block ascorbic acid based on the electrostatic interaction with self-assembled monolayer (SAM) and its application of the surface modified electrode to biosensor. In order to form SAM on the gold electrode with carboxyl group, 7-carboxy-heptanethiol (7-CHT) was used. The 7-CHT modified electrode did not show anodic response to ascorbic acid, but oxidized phenanthroline cobalt complex [Co(phen)₃²⁺], which can be used as a mediator of biosensor. Thus, the 7CHT-modified electrode was applied to biosensor mediated with Co(phen)₃²⁺. Fructose dehydrogenase (FDH) was immobilized to the 7-CHT modified electrode. Fructose was determined selectively with the FDH/7-CHT modified electrode at the range of 0.2-2 mM.     

Synthesis, structure and magnetic properties of β-MnO 2 nanorods

We present synthesis, structure and magnetic properties of structurally well-ordered single-crystalline β-MnO₂ nanorods of 50–100 nm diameter and several μm length. Thorough structural characterization shows that the basic β-MnO₂ material is covered by a thin surface layer (∼2.5 nm) of α-Mn₂O₃ phase with a reduced Mn valence that adds its own magnetic signal to the total magnetization of the β-MnO₂ nanorods. The relatively complicated temperature-dependent magnetism of the nanorods can be explained in terms of a superposition of bulk magnetic properties of spatially segregated β-MnO₂ and α-Mn₂O₃ constituent phases and the soft ferromagnetism of the thin interface layer between these two phases.     

Self-assembled monolayers of a disulphide-derivatised cobalt-porphyrin on gold

A self-assembled monolayer (SAM) of a novel cobalt(II)porphyrin disulphide derivative was prepared on flat gold(1 1 1) electrode. Evidence for surface modification was provided by electrochemical reductive desorption of the monolayer and ellipsometry, consistent with a coverage of 2.5 × 10⁻¹⁰ mol cm⁻² and a thickness of 13 Å, respectively. Both results support the presence of SAMs where the molecules share an intermediate position between perpendicular and flat orientation. Scanning tunnelling microscopy have also proven the formation of CoPSS SAMs, however high-resolution images could only be obtained when the CoPSS molecules were diluted in an hexanethiol SAM. The electrocatalytic activity of the surface confined Co-porphyrin was evaluated for the oxygen reduction. Voltammetric data indicate that reaction involves two electrons consistent with the formation of hydrogen peroxide. Under similar experimental conditions the data obtained for an iron-porphyrin analogue points for a full reduction of dioxygen to water.     

Photoelectric conversion of photosynthetic reaction center in multilayered films fabricated by layer-by-layer assembly

Multilayered protein films which contained ordered layers of photosynthetic reaction center (RC) from Rhodobacter Sphaeroides (RS601) were assembled by means of alternate electrostatic adsorption with positively charged poly(diallyldimethylammonium chloride) (PDDA). The assembly of RC was monitored by spectrometry and photocurrent measurement. Linear film growth was observed up to about 20 cycles of adsorption. For the monolayer film, the photocurrent was about 8.5 nA cm⁻². For the multilayered film, the total photocurrent was about 77 nA cm⁻² for the 24-layer RC film, while the average photocurrent increment per adsorption cycle was about 3.2 nA cm⁻². The overall light-to-electricity conversion efficiency for a 24-layer film was about eight times higher than that for the monolayer one. The effects of electrode potential and pH on the photocurrent were also measured to illustrate the light-to-electric converting mechanism.     

Characterization of self-assembled monolayers of iron and cobalt octaalkylthiosubstituted phthalocyanines and their use in nitrite electrocatalytic oxidation

Cobalt and iron phenylthiosubstituted phthalocyanines have been deposited on Au electrode surfaces through the self-assembled monolayer (SAM) technique. The so formed layers were studied using voltammetric and impedance techniques. These SAMs blocked a number of Faradic processes and electrocatalyzed the oxidation of nitrite. The electrocatalytic parameters of the cobalt and iron phenylthiosubstituted phthalocyanines deposited on Au electrodes in nitrite solution were studied. Nitrite overpotentials which are lower than ever reported were obtained in this work for the iron phenylthiosubstituted phthalocyanines with very high stability.     

Self-assembled monolayers of p-toluene and p-hydroxymethylbenzene moieties adsorbed on iron by the formation of covalent bonds between carbon and iron atoms for protection of iron from corrosion

An iron electrode was modified by electrolytic reduction in deaerated acetonitrile solution of p-toluenediazonium tetrafluoroborate CH₃C₆H₄N₂BF₄ (TDFB) or p-hydroxymethylbenzenediazonium tetrafluoroborate HOCH₂C₆H₄N₂BF₄ (HOTDFB) below 10 °C to form a self-assembled monolayer (SAM) of toluene CH₃C₆H₄- or hydroxymethylbenzene HOCH₂C₆H₄- (HOMB) moiety, probably adsorbed on the electrode by the formation of a covalent bond between carbon and iron atoms, as shown in references. The protective ability of the layer was examined by polarization measurement of the electrode in an aerated 0.5 M NaCl solution. The protective efficiencies of these two SAMs were not high, around 30%, a little higher than that of the toluenethiol CH₃C₆H₄SH SAM which was anchored on iron via a coordinate bond between sulfur and iron atoms. The iron surfaces modified with TDFB and HOTDFB were characterized by contact angle measurement, FTIR reflection spectroscopy and X-ray photoelectron spectroscopy. The persistence in protection of iron against corrosion by coverage with the HOMB SAM was confirmed by polarization measurements after immersion in 0.5 M NaCl for a long period of the time.     

A photoluminescence-based quantum semiconductor biosensor for rapid in situ detection of Escherichia coli

This work describes a novel method of detecting Escherichia coli using photoluminescence (PL) emission from III–V quantum semiconductor (QS) devices functionalized with two different antibody-based architectures. The first approach employed self-assembled monolayers of biotinylated polyethylene glycol thiols to immobilize biotinylated antibody via neutravidin. In the second approach, we used QS microstructures coated with a thin layer of Si₃N₄ allowing direct functionalization with E. coli antibodies through hydrofluoric acid etching and glutaraldehyde-based reticulation. Atomic force, optical and fluorescence microscopy measurements were used to assess the immobilization process. Depending on the biosensing architecture, density of the immobilized bacteria was observed in the range of 0.5–0.7 bacteria/100 μm². The detection of E. coli at 10⁴ CFU/ml was achieved within less than 120 min of the bacteria exposure. It is expected that an even better sensitivity threshold could be achieved following further optimization of the method.