MXene Networks Research Articles

PVA/MB-ssDNA/MXene hydrogel synthesized by freeze thawing process with the effect of MB-ssDNA

Freeze-thawing plays a vital role in enhancing materials in medicines. Here, we describe the F-T process of synthesis of Poly (vinyl alcol)- Methylene blue single strand- Mxene (PVA–MB-ssDNA –Mxene), which may be effective for gen delivery applications. The PVA –MB-ssDNA –Mxene hydrogel was formed using 1,3,5 consecutive cycles. We also demonstrated that PVA –MB-ssDNA –Mxene hydrogel can be formed by the affection of DNA with PVA and the MXene network. The F-T process shows the new intra molecular bond of PVA-PVA, compared to the non F-T hydrogel which formed by a biologic crosslinking as MB-ssDNA. Scanning electron microscopy reported that the microstructure. The differential scan shows three endothermic peaks at 70, 180, and 300 ℃ for water loss and decomposition. The swelling behavior rapidly increased due to the PVA chains in the F-T methods and then became stable. With a high concentration of MB-DNA, the tensile strength was slightly high, and the swelling behavior was low. Our results indicated that the PVA –MB-ssDNA –Mxene hydrogel using F-T process would have more suitable structural features as gene hydrogel carrier which need greater mechanical strength and stability in body analyses.

Magnetic stirring hydroxylation for fabrication of a highly modulated Cu-intercalated 3D titanium aluminum carbide MXene network for efficient electrochemical detection of fluorouracil

With the growing incidence of cancer, cytostatic drugs that block the growth of cancer cells are being increasingly consumed, raising concerns regarding pharmaceutical pollutants. Halogen-containing antineoplastic fluorouracil (FLU) residues are continuously released into environmental water and soil surfaces, and upon entering the environment, they cause carcinogenic risks to environmental organisms and are hazardous to human health. Thus, on-site monitoring devices must be designed to prevent such hazardous pollutants from spreading to water, land, and ecosystems. We used erosion hydroxylation to fabricate a Cu-intercalated titanium aluminum carbide (TAC) MXene (Cu-Ti3Al1-xC2-OHx or Cu-TAC-3) for the on-site monitoring of cytotoxic FLU in environmental samples. The three-dimensional Cu-TAC-3 network was prepared using a simple, environmentally friendly magnetic stirring process, wherein Cu groups were intercalated into the hydroxylated TAC active sites to enhance the electrochemical properties. The physicochemical properties of Cu-TAC-3 were characterized spectroscopically. Furthermore, a Cu-TAC-3-modified glassy carbon electrode (GCE) was fabricated that could electrochemically detect FLU under various conditions, achieving a good sensitivity of 0.7033 μA/µM cm−2, linearity between 0.001 to83.76 μM, and a low limit of detection of 0.54 nM (70 ng mL−1). Cu-TAC-3/GCE demonstrated excellent electrochemical activity toward FLU even in real environmental samples, with a recovery of above 97 % from spiked samples. These sensors are therefore practical for the on-site electrochemical monitoring of FLU.

Large-Scale, Mechanically Robust, Solvent-Resistant, and Antioxidant MXene-Based Composites for Reliable Long-Term Infrared Stealth.

MXene-based thermal camouflage materials have gained increasing attention due to their low emissivity, however, the poor anti-oxidation restricts their potential applications under complex environments. Various modification methods and strategies, e.g., the addition of antioxidant molecules and fillers have been developed to overcome this, but the realization of long-term, reliable thermal camouflage using MXene network (coating) with excellent comprehensive performance remains a great challenge. Here, a MXene-based hybrid network comodified with hyaluronic acid (HA) and hyperbranched polysiloxane (HSi) molecules is designed and fabricated. Notably, the presence of appreciated HA molecules restricts the oxidation of MXene sheets without altering infrared stealth performance, superior to other water-soluble polymers; while the HSi molecules can act as efficient cross-linking agents to generate strong interactions between MXene sheets and HA molecules. The optimized MXene/HA/HSi composites exhibit excellent mechanical flexibility (folded into crane structure), good water/solvent resistance, and long-term stable thermal camouflage capability (with low infrared emissivity of ≈0.29). The long-term thermal camouflage reliability (≈8 months) under various outdoor weathers and the scalable coating capability of the MXene-coated textile enable them to disguise the IR signal of various targets in complex environments, indicating the great promise of achieved material for thermal camouflage, IR stealth, and counter surveillance.

Direct Assembly of Aerogel Micro‐Nanofiber/MXene Sponges with Dual‐Network Structures for All‐Day Personal Heating

AbstractMaintaining human body temperature under low temperature is crucial to human well‐being, thereby urgently requiring for high‐performance warmth retention materials. However, designing such materials with both mechanical robustness and warming up the human body under complex and changing outdoor environments remains challenging. Here, a dual‐network structured aerogel micro‐nanofiber/MXene sponge is directly synthesized by the synchronous occurrence of electrospinning and electrospraying. Tailoring phase inversion of the solution jet creates micro‐nanofibers with highly porous aerogel structures, which exhibit nanoscale aperture (30–60 nm) and high single fiber surface aera (56.5 m2 g−1). Under strong hydrogen bonding interaction, the dual‐network structures are constructed by chemical entanglement between aerogel micro‐nanofibers and self‐assembled MXene networks, achieving robust stretchable and compressible property. The nanopores of the single fiber cause the Knudsen effect to suppress the slippage of air molecules, thereby enhancing the unique capacity to block heat energy. Further integrating passive radiative heating and active heating performance of MXene networks, the as‐designed sponge offers an all‐day personal heating system to rise human skin temperature over 3.5 °C. This work may provide new candidates for the applications within aerospace, energy, transportation, and building.

Topological MXene Network Enabled Mixed Ion-Electron Conductive Hydrogel Bioelectronics.

Mixed ion-electron conductive (MIEC) bioelectronics has emerged as a state-of-the-art type of bioelectronics for bioelectrical signal monitoring. However, existing MIEC bioelectronics is limited by delamination and transmission defects in bioelectrical signals. Herein, a topological MXene network enhanced MIEC hydrogel bioelectronics that simultaneously exhibits both electrical and mechanical property enhancement while maintaining adhesion and biocompatibility, providing an ideal MIEC bioelectronics for electrophysiological signal monitoring, is introduced. Compared with nontopology hydrogel bioelectronics, the MXene topology increases the dynamic stability of bioelectronics by a factor of 8.4 and the electrical signal by a factor of 10.1 and reduces the energy dissipation by a factor of 20.2. Besides, the topology-enhanced hydrogel bioelectronics exhibits low impedance (<25 Ω) at physiologically relevant frequencies and negligible impedance fluctuation after 5000 stretch cycles. The creation of multichannel bioelectronics with high-fidelity muscle action mapping and gait recognition was made possible by achieving such performance.

Facile fabrication and characterization of MXene/cellulose composites for electrical properties, electric heating performance

AbstractDeveloping energy-efficient and multifunctional wearable electronic textiles (E-textiles) is a significant challenge. This study investigates MXene-coated cellulose hybrid fibers, focusing on their electrical properties, heating performance, and thermal stability. The fabrication process involves continuous dipping of cellulose fibers into an aqueous MXene solution, resulting in the creation of MXene-coated cellulose hybrid fibers. We confirm the uniform coating of MXene sheets on the cellulose fiber surfaces, with increasing content throughout the dip coating cycle, as evidenced by X-ray diffraction and scanning electron microscopy analysis. The high thermal conductivity of MXene acts as a heat source, impacting the thermal stability of cellulose fibers at lower temperatures. Additionally, the electrical properties of MXene/cellulose hybrid fiber composites are influenced at elevated temperatures. Remarkably, the longitudinal electrical conductivity of the MXene-coated cellulose fiber composites exhibits a notable increase of 0.06 S/cm after the final coating cycle, demonstrating the effective and conductive nature of the layer-by-layer MXene network formed on the cellulose fibers.

Porifera-Inspired Lightweight, Thin, Wrinkle-Resistance, and Multifunctional MXene Foam.

Transition metal carbides/nitrides (MXenes) demonstrate a massive potential in constructing lightweight, multifunctional wearable electromagnetic interference (EMI) shields for application in various fields. Nevertheless, it remains challenging to develop a facile, scalable approach to prepare the MXene-based macrostructures characterized by low density, low thickness, high mechanical flexibility, and high EMI SE at the same time. Herein, the ultrathin MXene/reduced graphene oxide (rGO)/Ag foams with a porifera-inspired hierarchically porous microstructure are prepared by combining Zn2+ diffusion induction and hard template methods. The hierarchical porosity, which includes a mesoporous skeleton and a microporous MXene network within the skeleton, not only exerts a regulatory effect on stress distribution during compression, making the foams rubber-like resistant to wrinkling but also provides more channels for multiple reflections of electromagnetic waves. Due to the interaction between Ag nanosheets, MXene/rGO, and porous structure, it is possible to produce an outstanding EMI shielding performance with the specific surface shielding effectiveness reaching 109152.4dBcm2 g-1 . Furthermore, the foams exhibit multifunctionalities, such as transverse Joule heating, longitudinal heat insulation, self-cleaning, fire resistance, and motion detection. These discoveries open up a novel pathway for the development of lightweight MXene-based materials with considerable application potential in wearable electromagnetic anti-interference devices.

Highly-confined, micro-Sb/C@MXene 3D architectures with strengthened interfacial bonding for high volumetric sodium-ion storage

High-theoretical-capacity antimony (Sb) anodes hold promise for high-performing sodium-ion storage, yet suffer from huge volume change. In solving this obstacle, traditional strategies normally incorporate nanosized Sb with low-density conductive materials, which, in turn, sacrifice volumetric performance. Here, we report micro-sized Sb particles (m-Sb) dually encapsulated in carbon layer and densely-packed Ti3C2Tx MXene network (m-Sb/C@MXene), forming a highly-confined composite with robust interfacial bonding of SbOC between m-Sb and the carbon layer, and COTi between the carbon layer and MXene. The m-Sb/C@MXene anode displays a high volumetric capacity of 482.6 mAh cm−3 and a high volumetric capacity retention of 407.1 mAh cm−3 after 100 cycles at 0.1 A/g. A high-rate capacity of 191.0 mAh cm−3 at 10 A/g has also been achieved. Such superior performance stems from its unique architecture highly confined by the conductive and elastic network, which can provide fast electron/ion transport and effectively buffer volume expansion. Furthermore, ex-situ X-ray diffraction reveals that this hierarchical structure not only stabilizes m-Sb but also enhances ion transport kinetics by promoting the amorphization of m-Sb, thus delivers the excellent capacity and rate performance. This work offers an effective design of high-volumetric-capacity anode materials for their practical applications in sodium-ion energy storage.

A Stretchable Electromagnetic Interference Shielding Fabric with Dual‐Mode Passive Personal Thermal Management

AbstractElectromagnetic interference (EMI) shielding fabrics are crucial in addressing the increasingly serious electromagnetic pollution. To meet wearable requirements, stretchability and thermal comfortability are often desired, but which still are challenging. Herein, a stretchable EMI shielding fabric is fabricated via electrospinning coupled with biaxial pre‐stretching spraying, in which a block stacking wrinkled silver nanowire (AgNW)/Ti3C2Tx MXene network is coated on one side of electrospun thermoplastic polyurethane (TPU)/polydimethylsiloxane (PDMS) fabric. As expected, the wrinkled structure protects conductive network from fracture during stretching process, so as to realize the strain‐invariant electrical conductivity. Thus, the fabric exhibits a stretchable EMI shielding performance of over 40 dB when subjected to 10–50% uniaxial strains or 21–125% biaxial strains. More importantly, the white TPU/PDMS side and the black AgNW/MXene side enable the fabric passive radiative cooling and heating, respectively. The cooling side exhibits high mid‐infrared emissivity (97.5%) and solar reflectance (90%), thus reducing the skin temperature by ≈4.9 °C. The heating side with high solar absorptivity (86.6%) and photothermal effect increased the skin temperature by ≈5 °C. Therefore, the fabirc with stretchable EMI shielding and Janus‐type dual‐mode personal passive thermal management is promising in future wearable products.

3D Assembly of MXene Networks using a Ceramic Backbone with Controlled Porosity.

Transition metal carbides (MXenes) are novel 2D nanomaterials with exceptional properties, promising significant impact in applications such as energy storage, catalysis, and energy conversion. A major barrier preventing the widespread use of MXenes is the lack of methods for assembling MXene in 3D space without significant restacking, which degrades their performance. Here, this challenge is successfully overcome by introducing a novel material system: a 3D network ofMXene formed on a porous ceramic backbone. The backbone dictates the network's 3D architecture while providing mechanical strength, gas/liquid permeability, and other beneficial properties. Freeze casting is used to fabricate a silica backbone with open pores and controlled porosity. Next, capilary flow is used to infiltrate MXene into the backbone from a dispersion. The system is then dried to conformally coat the pore walls with MXene, creating an interconnected 3D-MXene network. The fabrication approach is reproducible, and the MXene-infiltrated porous silica (MX-PS) system is highly conductive (e.g., 340 S m-1 ). The electrical conductivity of MX-PS is controlled by the porosity distribution, MXene concentration, and the number of infiltration cycles. Sandwich-type supercapacitors with MX-PS electrodes are shown to produce excellent areal capacitance (7.24 F cm-2 ) and energy density (0.32 mWh cm-2 ) with only 6% added MXene mass. This approach of creating 3D architectures of 2D nanomaterials will significantly impact many engineering applications.

Hierarchical assembly of NiFe-PB-derived bimetallic phosphides on 3D Ti3C2 MXene ribbon networks for efficient oxygen evolution

The development of MXene-based heterostructures for electrocatalysis has garnered significant attention owing to their potential as high-performance catalysts that play a pivotal role in hydrogen energy. Herein, we present a multistep strategy for the synthesis of a Ti3C2 MXene ribbon/NiFePx @graphitic N-doped carbon (NC) heterostructure that enables the formation of three-dimensional (3D) Ti3C2 MXene ribbon networks and bimetallic phosphide nanoarrays. With the assistance of HF etching and KOH shearing, the MXene sheets were successfully transformed into 3D MXene networks with interlaced MXene ribbons. Notably, a hydrothermal method, ion exchange route, and phosphorization process were used to anchor NiFePx@NC nanocubes derived from Ni(OH)2/NiFe-based Prussian blue (NiFe-PB) onto the MXene ribbon network. The resulting MXene ribbon/NiFePx@NC heterostructure demonstrated enhanced oxygen evolution reaction (OER) activity, characterized by a low overpotential (164 mV at a current density of 10 mA cm−2) and a low Tafel slope (45 mV dec−1). At the same time, the MXene ribbons/NiFePx@NC heterostructure exhibited outstanding long-term stability, with a 12 mV potential decay after 5000 cyclic voltammetry (CV) cycles. This study provides a robust pathway for the design of efficient MXene-based heterostructured electrocatalysts for water splitting.

Ultrarobust self-healing elastomers with hydrogen bonding connected MXene network for actuator applications

Self-healing ability is highly desired for flexible actuators that operate in dynamic and real-world environments, as these machines are vulnerable to mechanical damage. However, self-healing properties and mechanical strength are often difficult to combine at the same time. We report a synergistic enhancement strategy based on the ordered micro-nano structure and interfacial hydrogen bonding aggregation to achieve self-healing elastomer toughening. The hydrogen bonding interaction drives the MXene nanosheet to self-assemble into an interconnected network around the PU latex microsphere. Thanks to the synergy of dynamic physical networks and high-density interfacial hydrogen bonding, the composites with controllable room temperature self-healing efficiency (76.5–95.9%) and tensile strength (17.7–42.6 MPa). Furthermore, the MXene network structure of the composite endows the actuator with an efficient photothermal conversion efficiency, fast responsiveness, and even functional recovery. It is an effective strategy to achieve high-strength self-healing materials through hydrogen bonding connected MXene network and interfacial hydrogen bonding aggregation, which is expected to be applied to other flexible devices, such as flexible sensors and electromagnetic shielding.

Spiderweb-inspired fabrication of 3D MXene hybrid filler with multilayer and multiscale features for multifunctional polydimethylsiloxane composites

Polymer-based composite with high thermal conductivity and excellent fire safety is urgently desired and required in the field of thermal management of advanced electronic devices. In this study, inspired by the structure of a spiderweb, we reported a polymer composite with three-dimensional (3D) interconnected spiderweb-like structures by assembling adsorption of transition metal carbides/nitrides (MXene) and diethylenetriaminepenta(methylene-phosphonic acid) coordinated cobalt ions complex. In this composite, MXene combined with the coordination complex forms a 3D network structure with multi-layer/-scale features, which enables high cross-plane thermal conductivity (∼0.59 K w-1m−1) and excellent flame retardancy, especially including effective inhibition of toxic CO and asphyxiating CO2 production. Notably, the 3D MXene networks embedded in the polymer matrix impart the composite with an intelligent damage detection function that is able to detect the depth of cracks. This bioinspired strategy provides a promising approach to creating high-performance polymer-based composites.

Thick Electrodes of a Self‐Assembled MXene Hydrogel Composite for High‐Rate Energy Storage

Supercapacitors based on two‐dimensional MXene (Ti3C2Tz) have shown extraordinary performance in ultrathin electrodes with low mass loading, but usually there is a significant reduction in high‐rate performance as the thickness increases, caused by increasing ion diffusion limitation. Further limitations include restacking of the nanosheets, which makes it challenging to realize the full potential of these electrode materials. Herein, we demonstrate the design of a vertically aligned MXene hydrogel composite, achieved by thermal‐assisted self‐assembled gelation, for high‐rate energy storage. The highly interconnected MXene network in the hydrogel architecture provides very good electron transport properties, and its vertical ion channel structure facilitates rapid ion transport. The resulting hydrogel electrode show excellent performance in both aqueous and organic electrolytes with respect to high capacitance, stability, and high‐rate capability for up to 300 μm thick electrodes, which represents a significant step toward practical applications.

Nacre-inspired intumescent flame retardant bridging network for intelligent fire warning and prevention

MXene has proved a bright prospect for developing intelligent fire-warning sensors, which is an emerging field but suffers from poor thermal oxidation stability and low flame retardant efficiency. Herein, a nacre-inspired bridging network constructed by MXene and chitin nanocrystals (ChNCs) with early fire-warning and high fire prevention was fabricated through low-temperature evaporation assembly approach. When encountering a fire source, such insulated network can independently construct a conductive path and then trigger the fire-warning signal owing to the char-forming and bridging effect of ChNCs. Typically, the ChMXene network incorporated with 30 wt% of adenosine triphosphate (ATP) (ChMXene-30) exhibits an ultrafast fire alarm signal of only 0.78 s and an ideal response time of 290 s. The thermal oxidation resistance, insulation performance and fire protecting properties of the network were drastically enhanced by the synergistic intumescent flame retardant effect of ChNCs and ATP. The corresponding enhancement mechanism was ascribed to the quenching effect of phosphorus-based radicals and diluting effect of non-combustible gases in the gas phase, the barrier effect of intumescent char layers as well as the effect of blowing-out fire in the condensed phase. This work offers a novel strategy to achieving sensitive fire-warning and reliable thermal oxidation resistance of MXene network for protection applications in disparate major fire potential and related hazardous environments.

3D Porous Co3O4/MXene Foam Fabricated via a Sulfur Template Strategy for Enhanced Li/K-Ion Storage.

Co3O4 is a potential high-capacity anode material for lithium-ion batteries (LIBs) and potassium-ion batteries (PIBs), but the poor electrical conductivity and large volume fluctuations during long-term cycling severely limit its cycle durability and rate capabilities, especially for PIBs with large K-ion size. Here, we propose a sulfur template route to fabricate an integral 3D porous Co3O4/MXene (Ti3C2Tx) foam using simple vacuum co-filtrating an aqueous dispersion of Co3O4, S and MXene followed by calcining to remove the S template. The 3D porous structure can easily accommodate the large volume changes of Co3O4 while maintains electrode structural integrity, allowing to realize outstanding long-term cycle stability when tested as anodes for both LIBs (620.4 mA h g-1 after 1000 cycles at 1 A g-1) and PIBs (134.1 mA h g-1 after 1000 cycles at 0.5 A g-1). The high metallic conductivity of the 3D porous MXene network further facilitates the electron/ion transmission, resulting in an improved rate capability of 390 mA h g-1 at 13 A g-1 for LIBs and 125.3 mA h g-1 at 1 A g-1 for PIBs. The robust performance of the 3D porous Co3O4/MXene foam reflects its perspective as a high-performance anode material for both LIBs and PIBs.

A water-induced self-assembly approach to 3D hierarchical magnetic MXene networks for enhanced microwave absorption

A novel water-induced self-assembly method is developed for constructing ultrafine magnetic nanocrystal@carbon@MXene with continuous interfaces and high-density magnetic coupling networks.

Stretchable and Highly Sensitive Strain Sensor Based on a 2D MXene and 1D Whisker Carbon Nanotube Binary Composite Film.

We fabricate a 2D MXene and 1D whisker carbon nanotube (WCNT) binary composite, where the MXene layer was sandwiched between two WCNT films, and assemble a flexible resistive-type strain sensor using this composite film. The deformations of the conductive networks trigged by the external mechanical stimuli cause the variations of the number of effective conductive paths, which result in the changes of the electric resistance of composite films. The resistances of the MXene/WCNT composite films that carry the strain information about the external mechanical stimuli are monitored. In addition, we demonstrate the role of the conductive MXene networks and the WCNT networks in responding to the external mechanical stimuli. The MXene networks dominate the variations of the resistance of the strain sensors in the low strain range. In the middle strain range, the deformations of both the MXene networks and the WCNT networks are responsible for the variations of the resistance of the strain sensors. In the high strain range, an "island bridge" like conductive network forms, where MXenes act as islands and WCNTs connect the adjacent MXene islands like bridges. The multiple types of conductive networks lead to the high sensitivity of the MXene/WCNT-based strain sensors over a wide strain range and a wide response window. This stretchable strain sensor exhibits good performances in detecting human muscle motions with a wide strain range and has the potentials of being applicable to wearable electronics.

Bioinspired, stable adhesive Ti3C2Tx MXene-based coatings towards fire warning, smoke suppression and VOCs removal smart wood

Wood is an essential material widely used in a broad variety of daily life and industry. The development of an ecofriendly and smart wood towards potential environmental hazards such as fire hazards and air pollution still remains a huge challenge. Here, we report a bioinspired, stable adhesive, multifunctional coating for scalable construction of smart wood based on Ti3C2TX MXene network intercalated with cellulose nanocrystals (CNC). Polydopamine (PDA) is introduced as an intermediate adhesive bridge that possesses hydrogen bonds, van der Waals forces, and mechanical interlocking interactions to facilitate stable bonds of the MXene-based fire warning coating on wood surface. By constructing an intercalated architecture, CNC can not only solve the re-stacking of MXene nanosheets, but also serve as a thermoswitch that keep insulative mediator at room temperature, and promote the transport of electron triggered at higher temperature or on fires. During combustion, the MXene-based coating provides a denser, expanded physical barrier, captures the free radicals, and ultimately prevents the escape of smoke. Therefore, the optimized CNC/MXene coating exhibits high adhesion, sensitive fire response time (∼2.1 s), superior flame retardancy (LOI of 47.4 %, UL-94 V0 rate, and average heat release rate of 54.70 kW/m2), and excellent smoke suppression (total smoke rate of 119.9 m2/m2, peak CO2 production of 0.251 g/s, and peak CO production of 0.0037 g/s). In addition, smart wood has the potential photocatalysis oxidation capacity for volatile organic compounds (VOCs) removal (formaldehyde gas, 51 % removal rate within 60 min). This work puts forward a prospective strategy to fulfill multifunctional and high-performance coatings that simultaneously enhance the overall performance of wood, thus significantly contributing to expand its practical applications.

Organohydrogel based on cellulose-stabilized emulsion for electromagnetic shielding, flame retardant, and strain sensing

In the past, electromagnetic interference (EMI) shielding materials have achieved great breakthroughs, however, they still suffer from high reflectivity and poor environmental stability, resulting in detrimental secondary pollution and weak adaptability. Herein, an organohydrogel-based EMI shielding material was prepared through cellulose nanofibril-based Pickering emulsion, composed of an MXene network for electron conduction, encapsulated paraffin wax microspheres with MXene-Fe3O4 shells for multiple scattering of the incident wave, and MXene-CNF-Fe3O4-polyacrylamide hybrid interfaces for dielectric polarization. The EMI shielding performance of our organohydrogel shows an absorption-dominated feature. It can effectively shield 99.625 % electromagnetic wave, satisfying the requirement of commercial EMI shielding materials. Moreover, the organohydrogel possesses excellent flame retardancy properties and long-time environment properties to improve safety and reliability; and it also demonstrates sensitive deformation responses as an on-skin sensor. Therefore, our organohydrogel can simultaneously detect human motion and protect human from EMI radiation and accidental burn.