Peroxidase-like activity and mechanism of gold nanoparticle-modified Ti3C2 MXenes for the construction of H2O2 and ampicillin colorimetric sensors.

Transition metal carbides modified by Au nanoparticles (Au/Ti3C2) were synthesized and developed as a colorimetric sensor for the determination of H2O2 and ampicillin. The surface electrical properties of Ti3C2 were changed, and Au nanoparticles (AuNPs) and gold growth solution were synthesized simultaneously. Au/Ti3C2 was obtained by seed growth method with AuNPs modified on the surface of transition metal carbides, nitrides or carbon-nitrides (Ti3C2 MXenes). The synthesized AuNPs and Ti3C2 had no peroxidase-like activity, but Au/Ti3C2 had. The peroxidase catalytic mechanism was due to electron transfer. The peroxidase activity of Au/Ti3C2 can be utilized for the determination of H2O2. The linear range of Au/Ti3C2 for H2O2 was 1-60 µM, and the detection limit was 0.12 µM (S/N = 3). A colometric sensor for ampicillin detection based on Au/Ti3C2 was further constructed since S in ampicillin formed an Au-S bond with Au/Ti3C2, leading to the weakening of its peroxidase-like property. The change of peroxidase-like property attenuated oxidation of TMB, and the ampicillin content was inversely proportional to the concentration of oxidized TMB, and the blue color of solution faded, which enabled the determination of ampicillin. The linear range for ampicillin was 0.005-0.5 µg mL- 1, and the detection limit was 1.1 ng mL- 1 (S/N = 3). The sensor was applied to the detection of ampicillin in milk and human serum.

Covalent Bonding of MXene/COF Heterojunction for Ultralong Cycling Li-Ion Battery Electrodes.

Covalent organic frameworks (COFs) have emerged as promising renewable electrode materials for LIBs and gained significant attention, but their capacity has been limited by the densely packed 2D layer structures, low active site availability, and poor electronic conductivity. Combining COFs with high-conductivity MXenes is an effective strategy to enhance their electrochemical performance. Nevertheless, simply gluing them without conformal growth and covalent linkage restricts the number of redox-active sites and the structural stability of the composite. Therefore, in this study, a covalently assembled 3D COF on Ti3C2 MXenes (Ti3C2@COF) is synthesized and serves as an ultralong cycling electrode material for LIBs. Due to the covalent bonding between the COF and Ti3C2, the Ti3C2@COF composite exhibits excellent stability, good conductivity, and a unique 3D cavity structure that enables stable Li+ storage and rapid ion transport. As a result, the Ti3C2-supported 3D COF nanosheets deliver a high specific capacity of 490 mAh g-1 at 0.1 A g-1, along with an ultralong cyclability of 10,000 cycles at 1 A g-1. This work may inspire a wide range of 3D COF designs for high-performance electrode materials.

Growth Factor-Decorated Ti3 C2 MXene/MoS2 2D Bio-Heterojunctions with Quad-Channel Photonic Disinfection for Effective Regeneration of Bacteria-Invaded Cutaneous Tissue.

Phototherapy has recently emerged as a competent alternative for combating bacterial infection without antibiotic-resistance risk. However, owing to the bacterial endogenous antioxidative glutathione (GSH), the exogenous reactive oxygen species (ROS) generated by phototherapy can hardly behave desired antibacterial effect. To address the daunting issue, a quad-channel synergistic antibacterial nano-platform of Ti3 C2 MXene/MoS2 (MM) 2D bio-heterojunctions (2D bio-HJs) are devised and fabricated, which possess photothermal, photodynamic, peroxidase-like (POD-like), and glutathione oxidase-like properties. Under near-infrared (NIR) laser exposure, the 2D bio-HJs both yield localized heating and raise extracellular ROS level, leading to bacterial inactivation. Synchronously, Mo4+ ions can easily invade into ruptured bacterial membrane, arouse intracellular ROS, and deplete intracellular GSH. Squeezed between the "ROS hurricane" from both internal and external sides, the bacteria are hugely slaughtered. After being further loaded with fibroblast growth factor-21 (FGF21), the 2D bio-HJs exhibit benign cytocompatibility and boost cell migration in vitro. Notably, the in vivo evaluations employing a mouse-infected wound model demonstrate the excellent photonic disinfection towards bacterial infection and accelerated wound healing. Overall, this work provides a powerful nano-platform for the effective regeneration of bacteria-invaded cutaneous tissue using 2D bio-HJs.

A turn-on-type fluorescence resonance energy transfer aptasensor for vibrio detection using aptamer-modified polyhedral oligomeric silsesquioxane-perovskite quantum dots/Ti3C2 MXenes composite probes.

A pair of composite probes based on aptamer modified polyhedral oligomeric silsesquioxane-perovskite quantum dots (POSS-PQDs-Apt) as signal probe and titanium carbide (Ti3C2) MXenes as quencher were prepared for the first time. They were employed to fabricate one turn-on-type aptasensor relying on fluorescence resonance energy transfer (FRET) for Vibrio parahaemolyticus (VP) determination. The POSS-PQDs-Apt can be adsorbed on the MXenes nanosheets, and its fluorescence was quenched due to the FRET. After the composite probes were incubated with VP for 50 min, the POSS-PQDs-Apt binding with VP can be released from the surface of MXenes, and the signal recovered due to its higher affinity to the VP than MXenes. The fluorescence intensity from 519 nm emission of the system was measured at 480 nm excitation. Under In optimized conditions, the assay can determine VP in the concentration range 102 - 106 cfu/mL, and the detection limit (LOD) was 30 cfu/mL using fluorescence detection. The LOD is still 100 cfu/mL by naked eye detection which is proper for on-line monitoring VP in aquaculture water. This method was also used to detect VP in actual samples of seawater, the recovery of spiked samples was between 93% and 106%, and relative standard deviation (RSD) was between 2.7% and 6.7%. The result is consistent with the plate count. Therefore, this assay could provide a candidate platform for screening VP in aquaculture industry.

Methyl orange as a novel colorimetric iodide indicator with in situ generation of H2O2 by etching uncoated Ag-Ti3C2 nanohybrids.

Iodine intake remains a major public health concern, as both iodine excess and deficiency are related to adverse effects on health. Therefore, developing simple and economical methods to detect I- is still in great demand. Herein, we constructed a visual I- sensing platform based on the uncoated Ag-Ti3C2 nanohybrids using methyl orange (MO) as a colorimetric indicator. Plasmonic nanostructures are frequently employed in colorimetric analysis, but uncoated Ag nanoparticles (NPs) are unstable because their surface energies are usually high. Considering that Ag NPs can be etched by I- via forming Ag-I bond, we introduce Ag-Ti3C2 nanohybrids because uncoated Ag NPs with immaculate surfaces are more conducive to binding with I- and being etched. Dissolved O2 molecules adsorbed on Ti3+ of Ti3C2 MXenes enable the in situ generation of H2O2 by iodine-etching of uncoated Ag-Ti3C2 nanohybrids. ∙OH radicals promote the degradation of MO through a self-driven Fenton-like process, exhibiting the color variation from orange to transparent. Under optimal conditions, the absorbance of MO at 465 nm decreases linearly with the concentration of I- in the range of 0.5-300 µM, with a limit of detection as low as 0.31 µM. This work opens the feasibility of iodine-etching of Ag in developing novel probes for facile colorimetric determination of I-.

Transformation from Electromagnetic Inflection to Absorption of Silicone Rubber and Accordion-Shaped Ti3C2MXene Composites by Highly Electric Conductive Multi-Walled Carbon Nanotubes.

Electromagnetic (EM) pollution becomes more penetrating in daily life and work due to more convenience provided by multi-electrical devices, as does secondary pollution caused by electromagnetic reflection. EM wave absorption material with less reflection is a good solution to absorb unavoidable EM radiation or reduce it from the source. Filled with two-dimensional Ti3SiC2MXenes, silicone rubber (SR)composite demonstrated a good electromagnetic shielding effectiveness of 20 dB in the X band by melt-mixing processes for good conductivity of more than 10-3 S/cm and displayed dielectric properties and a low magnetic permeability; however, the reflection loss was only -4 dB. By the combination of one-dimensional highly electric conductive multi-walled carbon nanotubes (HEMWCNTs) and MXenes, the composites achieved the transformation from electromagnetic inflection to an excellent absorbing performance to reach a minimum reflection loss of -30.19 dB due to electric conductivity of above 10-4 S/cm, a higher dielectric constant, and more loss in both dielectric and magnetic properties. Ni-added multi-walled carbon nanotubes were not able to achieve the transformation. The as-prepared SR/HEMWCNT/MXene composites have potential application prospects in protective layers, which can be used for electromagnetic wave absorption, electromagnetic interference suppression of devices, and stealth of the equipment.

Titanium carbide nanosheets with defect structure for photothermal-enhanced sonodynamic therapy.

Sonodynamic therapy (SDT) has attracted widespread interest in biomedicine, owing to its novel and noninvasive therapeutic method triggered by ultrasound (US). Herein, the Ti3C2 MXene nanosheets (Ti3C2 NSs) are developed as good sonosensitizers via a two-step method of chemical exfoliation and high-temperature treatment. With the high-temperature treatment, the oxygen defect of Ti3C2 MXene nanosheets (H-Ti3C2 NSs) is greatly increased. Therefore, the electron (e-) and hole (h+) generated by US can be separated faster due to the improved degree of oxidation, and then the recombination of e--h+ can be prevented with the abundant oxygen defect under US irradiation, which induced the sonodynamic efficiency greatly to improve around 3.7-fold compared with Ti3C2 NSs without high-temperature treatment. After PEGylation, the H-Ti3C2-PEG NSs show good stability and biocompatibility. In vitro studies exhibit that the inherent property of mild photothermal effect can promote the endocytosis of H-Ti3C2-PEG NSs, which can improve the SDT efficacy. In vivo studies further display that the increased blood supply by the mild photothermal effect can significantly relieve hypoxia in the tumor microenvironment, showing photothermal therapy (PTT) enhanced SDT. Most importantly, the H-Ti3C2-PEG NSs can be biodegraded and excreted out of the body, showing no significant long-term toxicity. Our work develops the defective H-Ti3C2 NSs as high-efficiency and safe sonosensitizers for photothermal-enhanced SDT of cancer, extending the biomedical application of MXene-based nanoplatforms.

Ti3C2 MXene Membranes for Gas Separation: Influence of Heat Treatment Conditions on D-Spacing and Surface Functionalization.

Two-dimensional (2D) MXene materials have recently been the focus of membrane research due to their unique properties, such as their single-atomic-layer thickness, flexibility, molecular filtration abilities and microstructural similarities with graphene, which is currently the most efficient precursor material for gas separation applications. In addition, the potential to process nanoscale channels has motivated investigations of parameters which can improve membrane permeability and selectivity. Interlayer spacing and defects, which are still challenging to control, are among the most crucial parameters for membrane performance. Herein, the effect of heat treatment on the d-spacing of MXene nanosheets and the surface functionalization of nanolayers was shown regarding its impact on the gas diffusion mechanism. The distance of the layers was reduced by a factor of over 10 from 0.345 nm to 0.024 nm, the defects were reduced, and the surface functionalization was maintained upon treatment of the Ti3C2 membrane at 500 °C under an Ar/H2 atmosphere as compared to 80 °C under vacuum. This led to a change from Knudsen diffusion to molecular sieving, as demonstrated by single-gas permeation tests at room temperature. Overall, this work shows a simple and promising way to improve H2/CO2 selectivity via temperature treatment under a controlled atmosphere.

MXene coupled graphitic carbon nitride nanosheets based plasmonic photocatalysts for removal of pharmaceutical pollutant.

The continuous rise in the amount of industrial and pharmaceutical waste in water sources is an alarming concern. Effective strategies should be developed for the treatment of pharmaceutical industrial waste. Hence the alternative renewable source of energy, such as solar energy, should be utilized for a sustainable future. Herein, a series of Au plasmonic nanoparticle decorated ternary photocatalysts comprising graphitic carbon nitride and Ti3C2 MXene has been designed to degrade colourless pharmaceutical pollutants, cefixime under visible light irradiation. These photocatalysts were synthesized by varying the amount of Ti3C2 MXene, and their catalytic potential was explored. The optimized photocatalyst having 3 wt% Ti3C2 MXene achieved 64.69% removal of the pharmaceutical pollutant, cefixime within 105 min of exposure to visible light. The presence of the Au nanoparticles and MXene in the nanocomposite facilitates the excellent charge carrier separation and increased the number of active sites due to the formation of interfacial contact with graphitic carbon nitride nanosheets. Besides, the plasmonic effect of the Au nanoparticles improves the absorption of light causing enhanced photocatalytic performance of the nanocomposite. Based on the obtained results, a plausible mechanism has been formulated to understand the contribution of different components in photocatalytic activity. In addition, the optimized photocatalyst shows excellent activity and can be reused for up to three cycles without any significant loss in its photocatalytic performance. Overall, the current work provides deeper physical insight into the future development of MXene graphitic carbon nitride-based plasmonic ternary photocatalysts.

Using a Self-Assembled Two-Dimensional MXene-Based Catalyst (2D-Ni@Ti3C2) to Enhance Hydrogen Storage Properties of MgH2.

In this work, we report the remarkable catalytic effects of a novel Ti3C2 MXene-based catalyst (Ni@Ti-MX), which was prepared via self-assembling of Ni nanoparticles onto the surface of exfoliated Ti3C2 nanosheets. The resultant Ni@Ti-MX catalyst, characterized by ultradispersed Ni nanoparticles being anchored on the monolayer Ti3C2 flakes, was introduced into MgH2 through ball milling. In situ transmission electron microscopy (TEM) analysis revealed that a synergetic catalytic effect of multiphase components (Mg2Ni, TiO2, metallic Ti, etc.) derived in the MgH2 + Ni@Ti-MX composite exhibits remarkable improvements in the hydrogen sorption kinetics of MgH2. In particular, the MgH2 + Ni@Ti-MX composite can absorb 5.4 wt % H2 in 25 s at 125 °C and release 5.2 wt % H2 in 15 min at 250 °C. Interestingly, it can uptake 4 wt % H2 in 5 h even at room temperature. Furthermore, the dehydrogenation peak temperature of the MgH2 + Ni@Ti-MX composite is about 221 °C, which is 50 and 122 °C lower than that of MgH2 + Ti-MX and MgH2, respectively. The excellent hydrogen sorption properties of the MgH2 + Ni@Ti-MX composite are primarily attributed to the peculiar core-shell nanostructured MgH2@Mg2NiH4 hybrid materials and the interfacial coupling effects from different catalyst-matrix interfaces. The results obtained in this study demonstrate that using self-assembling of transition-metal elements on two-dimensional (2D) materials as a catalyst is a promising approach to enhance the hydrogen storage properties of MgH2.

Highly electrically conductive two-dimensional Ti3C2 Mxenes-based 16S rDNA electrochemical sensor for detecting Mycobacterium tuberculosis.

Tuberculosis is one of the life-threatening infectious diseases caused by the obligate pathogenic bacterium Mycobacterium tuberculosis (M. tuberculosis). The current M. tuberculosis detection approaches cannot satisfy the requirement for early clinical diagnosis because of long detection time as well as low specificity. In our study, an electrochemical M. tuberculosis sensor was constructed by using specific fragment of 16S rDNA of M. tuberculosis H37Ra as target biomarker, peptide nucleic acid (PNA) as capture probe and highly conductive two-dimensional Ti3C2 MXenes as the signal amplified transduction material. After the hybridization between PNA and the specific fragment of 16S rDNA on the substrate of PNA-AuNPs nanogap network electrode, the target fragments were directly linked with conductive Ti3C2 MXenes by strong interactions between zirconium-cross-linked Ti3C2 MXenes and phosphate groups of the target fragments. The linking of Ti3C2 MXenes to the hybridized target fragments would bridge the gaps of the interrupted AuNPs in the nanogap network electrode and forming the conductive connection to cause the change in conductance between the electrodes. This conductance change could be used for M. tuberculosis detection. The limit of detection (LOD) of proposed method was 20 CFU mL-1, and detection time was 2 h. Proposed method would find potential application in rapid detection of M. tuberculosis.

Protein-Inspired Self-Healable Ti3C2 MXenes/Rubber-Based Supramolecular Elastomer for Intelligent Sensing.

Progress toward the integration of electronic sensors with a signal processing system is important for artificial intelligent and smart robotics. It demands mechanically robust, highly sensitive, and self-healable sensing materials which could generate discernible electric variations responding to external stimuli. Here, inspired by the supramolecular interactions of amino acid residues in proteins, we report a self-healable nanostructured Ti3C2MXenes/rubber-based supramolecular elastomer (NMSE) for intelligent sensing. MXene nanoflakes modified with serine through an esterification reaction assemble with an elastomer matrix, constructing delicate dynamic supramolecular hydrogen bonding interfaces. NMSE features desirable recovered toughness (12.34 MJ/m3) and excellent self-healing performance (∼100%) at room temperature. The NMSE-based sensor with high gauge factor (107.43), low strain detection limit (0.1%), and fast responding time (50 ms) can precisely detect subtle human motions (including speech, facial expression, pulse, and heartbeat) and moisture variations even after cut/healing processes. Moreover, NMSE-based sensors integrated with a complete signal process system show great feasibility for speech-controlled motions, which demonstrates promising potential in future wearable electronics and soft intelligent robotics.

Ti3C2 MXenes nanosheets catalyzed highly efficient electrogenerated chemiluminescence biosensor for the detection of exosomes.

Exosomes have been reported to play an important role in the anti-tumor immune response, tumor diagnosis and other processes, and are promising biomarkers for early cancer diagnosis. In this work, a sensitive electrogenerated chemiluminescence (ECL) biosensor was developed for detection of exosomes using aptamer modified two-dimensional material Ti3C2 MXenes nanosheets as the ECL nanoprobe because of its large surface area, the excellent conductivity and catalytic properties. The exosomes can be high efficiently captured onto the electrode surface by an EpCAM protein recognized aptamer modified on the electrode surface. In addition, the ECL nanoprobe can also recognize the exosomes, and significantly enhanced the ECL signals of luminol. Based on this strategy, a highly sensitive ECL biosensor for MCF-7 exosomes detection was obtained. The detection limit is 125 particles µL-1, which was over 100 times lower than that of conventional ELISA method. The as prepared ECL biosensor was performed successfully for MCF-7 exosomes detection in the serum. This strategy provided a feasible, sensitive and reliable tool for the exosomes detection in exosomes-related clinical diagnostics.