Advanced Vitrimer with Spiropyran Beads: A Multi-Responsive, Shape Memory, Self-Healing, and Reprocessable Smart Material.

Thermosetting materials have limitations in terms of reshaping and recycling due to their irreversible bond structures, leading to significant plastic waste issues. Recently, epoxy vitrimers based on dynamic covalent bond exchange have been introduced as promising alternatives to traditional thermosets. Particularly, they demonstrate significant potential applications in the field of multi-responsive materials. In this research, a self-healable and mechano-responsive vitrimer (EB-V) is successfully prepared, incorporating epoxide spiropyran beads (ESP beads) derived from citric acid and epoxy derivatives. To enable self-reporting of cracks through color changes, ESP beads are covalently bonded to the vitrimer via an epoxy-carboxylic acid reaction. The photochromic properties of EB-V are demonstrated by color and fluorescence changes, and its tensile strength increased from 2.0 to 6.8 MPa compared to the control sample. Dynamic mechanical analysis confirmed the covalent exchange reaction of the vitrimer, revealing its reconfigurable behavior and stress relaxation at elevated temperatures. Furthermore, EB-V exhibited exceptional properties, including self-healing and reprocessability. As a smart material, it holds great promise for a wide range of applications, such as sensors, actuators, 4D printing, and industrial safety diagnostics.

Development and Optimization of Water-Soluble Double-Walled Carbon Nanotubes by Effective Surface Treatment of Inner Walls.

Carbon nanotubes are a significant class of nanomaterials with distinctive properties that have led to their application in a variety of fields, such as polymer composites, medicine, electronics, and material science. However, their nonpolar nature and insolubility in polar solvents limit their applications. To address this issue, highly functionalized and water-soluble double-walled carbon nanotubes (DWNTs) were developed by selectively oxidizing the inner walls of the DWNTs using oleum and nitric acid. The impact of reaction time on the chemical functionalization of DWNTs was investigated under two different reaction durations of 2 and 24 h. The presence of highly oxygenated functional groups resulted in high water solubility, which was confirmed by high- and low-frequency Raman spectroscopy, high-resolution transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET) method, and optical spectroscopy. The conductivity of highly water-soluble W-DWNTs (24 h) was 122.65 × 102 S cm-1. After annealing for 12 h at 140 °C, the W-DWNTs retained 72% of their conductivity (88.79 × 102 S cm-1).

Multiple Carbon Morphologies Derived from Polyion Complex-Based Double Hydrophilic Block Copolymers as Templates and Phenol as a Carbon Precursor.

This study demonstrates the multiple carbon morphology forming abilities of two dissimilar polyion complex (PIC)-based double hydrophilic block copolymers (DHBC) along with three different phenol concentrations when subjecting the blend in aqueous media via a hydrothermal-assisted carbonization strategy. The morphological transition from worm-like to spherical along with granular is found for the blend of oppositely charged poly(ethylene glycol) (PEG)-conjugated poly(amino acid) block copolymers, PEG-poly(l-lysine) (PEG-PLys) and PEG-poly(glutamic acid) (PEG-PGlu), along with three different concentrations of phenol. In contrast, after mixing the combination of PEG-PLys and PEG-poly(aspartic acid) (PEG-PAsp) separately with three different phenol contents, elliptical to irregular to spherical structural transition occurred. Fourier transform infrared and circular dichroism spectroscopic studies indicated that the formation of worm-like hybrid micellar structures is attributed to the presence of the ß-sheet structure, whereas spherical-shaped hybrid micellar structures are formed due to the existence of α-helix and random coil structures. We discuss the mechanism for the secondary structure-induced morphology formation based on the theory related to the packing parameter, which is commonly used for analyzing the shape of the micellar structures. Secondary structures of the PIC-based DHBC system are responsible for forming multiple carbon morphologies, whereas these structures are absent in the case of the amphiphilic block copolymer (ABC) system. Furthermore, ABC-based template methods require organic solvent, ultrasonication, and a prolonged solvent evaporation process to obtain multiple carbon morphologies. Scanning electron microscopy observations suggested there is no significant morphological change even after subjecting the hybrid micelles to carbonization at elevated temperatures. Raman scattering studies revealed that the degree of graphitization and the graphitic crystallite domain size of the carbonized sample depend on the phenol content. Carbon materials exhibited the highest specific surface area of 579 m2 g-1 along with a pore volume of 0.398 cc g-1, and this observation suggests that the prepared carbons are porous. Our findings illustrate the facile and effective strategy to fabricate the multiple carbon morphologies that can be used as potential candidates for energy storage applications.

Catheter detection by transthoracic echocardiography during placement of peripherally inserted central catheters: a real-time method for eliminating misplacement.

BACKGROUND: Although guidelines and protocols are available for central venous access, existing methods lack specificity and sensitivity, especially when placing peripherally inserted central catheters (PICCs). We evaluated the feasibility of catheter detection in the right atrial cavity using transthoracic echocardiography (TTE) during PICC placement. METHODS: This single-center, retrospective study included consecutive patients who underwent PICC placement between January 2022 and March 2023. TTE was performed to detect the arrival of the catheter in the right atrial cavity. Catheter misplacement was defined as an aberrant catheter position on chest x-ray (CXR). The primary endpoint was predicting catheter misplacement based on catheter detection in the right atrial cavity. The secondary endpoint was optimizing catheter placement and examining catheter-associated complications. RESULTS: Of the 110 patients identified, 10 were excluded because of poor echogenicity and vein access failure. The remaining 100 patients underwent PICC placement with TTE. The catheter was visualized in the right atrial cavity in 90 patients. CXR exams revealed catheter misplacement in seven cases. Eight patients with catheter misplacement underwent the same procedure in the other arm. In two patients, PICC placement failed due to anatomical reasons. Catheter misplacement was detected using TTE with sensitivity, specificity, positive predictive value, and negative predictive value of 97% confidence interval (CI; 91.31%-99.36%), 90% CI (55.50%-99.75%), 99%, and 75%, respectively. CONCLUSIONS: TTE is a reliable tool for detecting catheter misplacement and optimizing catheter tip positioning during PICC placement.

Revealing the Filler-Matrix Interfacial Interactions: Real-Time Observation with Mechano-Responsive Spiropyran Microbeads.

Interfacial interactions between polymers and fillers play a crucial role in determining the performance of composite materials. In this study, mechano-responsive spiropyran (SP) beads, which exhibit fluorescence changes under stress, serve as force probes to evaluate force transfer efficiency across two types of interfaces: noncovalent and covalent. These interfaces are engineered by respectively employing physical blending and grafting polymerization to integrate hydroxyl SP beads with a polyurethane (PU) matrix. A custom-built in situ opto-mechanical setup quantitatively assesses force transfer by monitoring changes in fluorescence intensity and peak wavelength during specimen stretching. The analysis reveals that the covalent interface significantly outperforms the noncovalent interface, demonstrating a 100% improvement in force magnitude and transfer rate from the PU matrix to the SP beads. Direct observation of SP beads within the PU matrix during tension unveils that enhanced force transfer efficiency is closely linked to changes in the SP beads' aspect ratio. Fluorescence changes in SP beads are solely a function of aspect ratio, making them effective independent force probes.

Clipless internal mammary artery harvesting for minimally invasive coronary artery bypass grafting using the shear-tip harmonic scalpel.

Background: The internal mammary artery (IMA) is the most commonly used graft in coronary artery bypass grafting (CABG) because of its superior long-term patency rate. However, its small diameter poses challenges in handling, and any vascular damage that may occur during harvesting can significantly affect surgical outcomes. The primary focus during IMA harvesting is to ensure safe and effective hemostasis without direct vascular injury, while ensuring secure and reliable ligation of the vascular branches. Various methods using multiple surgical instruments have been used for this purpose. Unlike traditional instruments, the shear-tip Harmonic scalpel offers more precise vessel branching control, while minimizing damage to surrounding tissues. In this study, we assessed the utility of the shear-tip Harmonic scalpel in patients undergoing minimally invasive coronary artery bypass grafting (MICABG). Methods: From April 2019 to May 2023, a total of 40 patients underwent MICABG. The IMA was harvested using the shear-tip Harmonic scalpel with a clipless skeletonized technique. In this cohort, 5 patients underwent complete endoscopic harvesting, while 34 patients underwent direct visualization harvesting through minimal thoracotomy. Graft patency was assessed by measuring a Doppler flowmeter in the bypass conduit. Results: Successful graft patency was achieved in all patients. The mean duration of IMA harvesting was 87 min. In total, 38 of the 40 patients underwent MICABG without the need for cardiopulmonary bypass, ensuring a stable procedure. There were no graft-related events or complications observed in any of the patients, and all were discharged without any issues. During a median follow-up period of 15.2 months, only one patient experienced graft occlusion necessitating intervention. Conclusions: The utilization of shear-tip Harmonic scalpel for IMA harvesting in MICABG is feasible and yields stable early results.

Challenge for Trade-Off Relationship between the Mechanical Property and Healing Efficiency of Self-Healable Polyimide.

Polyimide is actively applied in various industrial fields because of its strong mechanical properties, owing to the interactions between the polymer chains. Fully aromatic imide structures exhibit high glass-transition temperatures due to the strong interactions between their chains, which hinder chain mobility. Therefore, preparing a material that exhibits self-healing at a low temperature of ≤100 °C and good mechanical properties is challenging. Thus, we prepared imides with four-component semiaromatic structures by adjusting the contents of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride and 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride) to yield four-component self-healable colorless polyimides (f-SH-CPIs) with novel structures, flexibilities, good mechanical properties, and low healing temperatures. The flexibilities and distances between the polymer chains, as the basis of the trade-off relationship between the mechanical properties and healing efficiency, were controlled. These materials may be used as substrates in wearable devices and multilayer insulation that may protect from space dust, cosmic rays, and satellite fragments.

Manufacture of antibacterial carbon fiber-reinforced plastics (CFRP) using imine-based epoxy vitrimer for medical application.

An antibacterial carbon fiber-reinforced plastics (CFRP) was manufactured based on a vitrimer containing imine groups. A liquid curing agent was prepared to include an imine group in the matrix, and was synthesized without a simple mixing reaction and any purification process. The vitrimer used as the matrix for CFRP was prepared by reacting a commercial epoxy with a synthesized curing agent. The structural and thermal properties of the vitrimer were determined by Fourier transform-infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). In addition, the temperature-dependent behavior of the vitrimer was characterized by stress relaxation, reshaping, and shape memory experiments. The mechanical properties of composites fabricated using vitrimer were fully analyzed by tensile, flexural, short-beam strength, and Izod impact tests and had mechanical properties similar to reference material. Moreover, both the vitrimer and the vitrimer composites showed excellent antibacterial activity against Staphylococcus aureus and Escherichia coil due to the imine group inside the vitrimer. Therefore, vitrimer composites have potential for applications requiring antimicrobial properties, such as medical devices.

Fabrication of transparent, tough, and conductive shape-memory polyurethane films by incorporating a small amount of high-quality graphene.

We report a mechanically strong, electrically and thermally conductive, and optically transparent shape-memory polyurethane composite which was fabricated by introducing a small amount (0.1 wt%) of high-quality graphene as a filler. Geometrically large (≈4.6 µm(2)), but highly crystallized few-layer graphenes, verified by Raman spectroscopy and transmission electron microscopy, were prepared by the sonication of expandable graphite in an organic solvent. Oxygen- containing functional groups at the edge plane of graphene were crucial for an effective stress transfer from the graphene to polyurethane. Homogeneously dispersed few-layered graphene enabled polyurethane to have a high shape recovery force of 1.8 MPa cm(-3). Graphene, which is intrinsically stretchable up to 10%, will enable high-performance composites to be fabricated at relatively low cost and we thus envisage that such composites may replace carbon nanotubes for various applications in the near future.

Easy, Fast Self-Heating Polyurethane Nanocomposite with the Introduction of Thermally Annealed Carbon Nanotubes Using Near-Infrared Lased Irradiation.

In this study, high-crystallinity single walled carbon nanotubes (H-SWNTs) were prepared by high-temperature thermal annealing at 1800 °C and a self-heating shape memory polyurethane nanocomposite with excellent self-heating characteristics was developed within a few seconds by irradiation with near-infrared rays. With a simple method (heat treatment), impurities at the surface of H-SWNTs were removed and at the same time the amorphous structure converted into a crystalline structure, improving crystallinity. Therefore, high conductivity (electric, thermal) and interfacial affinity with PU were increased, resulting in improved mechanical, thermal and electric properties. The electrical conductivity of neat polyurethane was enhanced from ~10-11 S/cm to 4.72 × 10-8 S/cm, 1.07 × 10-6 and 4.66 × 10-6 S/cm, while the thermal conductivity was enhanced up to 60% from 0.21 W/mK, 0.265 W/mK and 0.338 W/mK for the composites of 1, 3 and 5 wt%, respectively. Further, to achieve an effective photothermal effect, H-SWNTs were selected as nanofillers to reduce energy loss while increasing light-absorption efficiency. Thereafter, near-infrared rays of 818 nm were directly irradiated onto the nanocomposite film to induce photothermal properties arising from the local surface plasmon resonance effect on the CNT surface. A self-heating shape memory composite material that rapidly heated to 270 °C within 1 min was developed, even when only 3 wt.% of H-SWNTs were added. The results of this study can be used to guide the development of heat-generating coating materials and de-icing materials for the wing and body structures of automobiles or airplanes, depending on the molding method.

Optically and biologically active mussel protein-coated double-walled carbon nanotubes.

A method of dispersing strongly bundled double-walled carbon nanotubes (DWNTs) via a homogeneous coating of mussel protein in an aqueous solution is presented. Optical activity, mechanical strength, as well as electrical conductivity coming from the nanotubes and the versatile biological activity from the mussel protein make mussel-coated DWNTs promising as a multifunctional scaffold and for anti-fouling materials.

Mass-produced multi-walled carbon nanotubes as catalyst supports for direct methanol fuel cells.

Commercially mass-produced multi-walled carbon nanotubes, i.e., VGNF (Showa Denko Co.), were applied to support materials for platinum-ruthenium (PtRu) nanoparticles as anode catalysts for direct methanol fuel cells. The original VGNFs are composed of high-crystalline graphitic shells, which hinder the favorable surface deposition of the PtRu nanoparticles that are formed via borohydride reduction. The chemical treatment of VGNFs with potassium hydroxide (KOH), however, enables highly dispersed and dense deposition of PtRu nanoparticles on the VGNF surface. This capability becomes more remarkable depending on the KOH amount. The electrochemical evaluation of the PtRu-deposited VGNF catalysts showed enhanced active surface areas and methanol oxidation, due to the high dispersion and dense deposition of the PtRu nanoparticles. The improvement of the surface deposition states of the PtRu nanoparticles was significantly due to the high surface area and mesorporous surface structure of the KOH-activated VGNFs.

Rapid and Local Self-Healing Ability of Polyurethane Nanocomposites Using Photothermal Polydopamine-Coated Graphene Oxide Triggered by Near-Infrared Laser.

In this study, we report the self-healing ability of polyurethane (PU) nanocomposites based on the photothermal effect of polydopamine-coated graphene oxide (PDA-rGO). Polydopamine (PDA) was coated on the graphene oxide (GO) surface, while simultaneously reducing GO by the oxidation of dopamine hydrochloride in an alkaline aqueous solution. The PDA-rGO was characterized by Fourier-transform infrared spectroscopy, X-ray diffraction, Raman spectroscopy, thermogravimetric analysis, and scanning electron microscopy-energy-dispersive X-ray analysis. PDA-rGO/PU nanocomposites with nanofiller contents of 0.1, 0.5 and 1 wt% were prepared by ex situ mixing method. The photothermal effect of the PDA-rGO in the PU matrix was investigated at 0.1 W/cm2 using an 808 nm near-infrared (NIR) laser. The photothermal properties of the PDA-rGO/PU nanocomposites were superior to those of the GO/PU nanocomposites, owing to an increase in the local surface plasmon resonance effect by coating with PDA. Subsequently, the self-healing efficiency was confirmed by recovering the tensile stress of the damaged nanocomposites using the thermal energy generated by the NIR laser.

Development of a Tough, Self-Healing Polyampholyte Terpolymer Hydrogel Patch with Enhanced Skin Adhesion via Tuning the Density and Strength of Ion-Pair Associations.

Polyampholyte (PA) hydrogels have great potential for biomedical applications, owing to their high toughness and good self-recovery and self-healing (SELF) behavior in addition to their physical properties similar to human tissue. However, their implementation as practical biomedical skin patches or wearable devices has so far been limited by their insufficient transdermal adhesion strength. In this work, a new polyampholytic terpolymer (PAT) hydrogel with enhanced skin adhesion was developed using a novel and simple strategy that tunes the structure of ion-pair associations (IPAs), acting as cross-links, in the hydrogel via adding an extra neutral monomer component into the network without changing the total charge balance. The PAT hydrogels were synthesized by the terpolymerization of the neutral monomer N,N-dimethylacrylamide (DMAAm) (or 2-hydroxyethyl methacrylate (HEMA)) as well as the cationic monomer 3-(methacryloylamino) propyl-trimethylammonium chloride (MPTC) and the anionic monomer sodium p-styrenesulfonate (NaSS). Their IPA, which determines their network structure, was modulated by varying the feed concentration of the neutral monomer, Cnm. An increase of Cnm within an optimized Cnm window (0.3-0.4 M) decreased the cross-linking density (strength and density of the IPAs) of the PAT hydrogels, reducing the softening temperature and Young's modulus, which increased compliance but maintained sufficient mechanical strength and thereby maximized the contact surface and enhanced skin adhesion. The DMAAm monomers, compared to the HEMA monomers, produced the higher skin adhesion of the PAT hydrogel, which was explained by the difference in their reactivity to the MPTC and NaSS. This study demonstrated this new method to develop the PAT hydrogels with excellent skin adhesion and biocompatibility while maintaining good toughness, compliance, and SELF behavior and the potential of the PAT hydrogels for biomedical skin patches and wearable devices.

Circulating Tumor Cell Detection in Lung Cancer Animal Model.

BACKGROUND: Metastasis and recurrence of primary cancer are the main causes of cancer mortality. Disseminated tumor cells refer to cancer cells that cause metastasis from primary cancer to other organs. Several recent studies have suggested that circulating tumor cells (CTCs) are associated with the clinical stage, cancer recurrence, cancer metastasis, and prognosis. There are several methods of isolating CTCs from whole blood; in particular, using a membrane filtration system is advantageous due to its cost-effectiveness and availability in clinical settings. In this study, an animal model of lung cancer was established in nude mice using the human large cell lung cancer cell line H460. METHODS: Six-week-old nude mice were used. The H460 lung cancer cell line was injected subcutaneously into the nude mice. Blood samples were obtained from the orbital area before cell line injection, 2 weeks after injection, and 2 weeks after tumor excision. Blood samples were filtered using a polycarbonate 12-well Transwell membrane (Corning Inc., Corning, NY, USA). An indirect immunofluorescence assay was performed with the epithelial cell adhesion molecule antibody. The number of stained cells was counted using fluorescence microscopy. RESULTS: The average size of the tumor masses was 35.83 mm. The stained cells were counted before inoculation, 2 weeks after inoculation, and 2 weeks after tumor excision. Cancer cells generally increased after inoculation and decreased after tumor resection. CONCLUSION: The CTC detection method using the commercial polycarbonate 12-well Transwell (Corning Inc.) membrane is advantageous in terms of cost-effectiveness and convenience.

Sensitive G-band Raman features for the electrical conductivity of multi-walled carbon nanotubes.

We have studied the structural parameters of catalytically grown highly disordered multi-walled carbon nanotubes that were heat treated at temperatures between 1200 degrees C and 2600 degrees C in an argon atmosphere. Rather than the interlayer spacing or the R value (the intensity of the D band divided by the intensity of the G band), we found that the half width at half maximum intensity of the G band was the most sensitive parameter that is correlated with the altered electrical conductivity of an individual carbon nanotube that had been heat treated at high temperatures. This is because one-dimensional nanocarbons exhibit a preference for two-dimensional structural development along the length of the tube due to the limited mobility of carbon atoms along the circumferential direction. Tubes heat treated at 2200 degrees C exhibited both a high electrical conductivity and an absence of lithium-ion intercalation, and thus are the best conductive filler for the active materials of lithium-ion batteries for long-term stability.

Application of shape memory polyurethane in orthodontic.

A shape memory polymer wire for orthodontic application was prepared by melt-spinning of polyurethane block copolymer (PU) which was synthesized in a two-step process from a reaction of 4,4'-methylene bis(phenylisocyanate), poly(ε-caprolactone)diol (PCL), and 1,4-butanediol. An orthodontic test using the PU wire was carried out in an orthodontic model with a metal bracket. High shape recovery force of 70 gf for PU wire at 40 wt% hard segment content could be preserved for even 1 month after a shape recovery force test at a constant temperature of 50°C. The shape recovery force decreased exponentially during the initial 2 h, but reached an equilibrium shape recovery force of 50 gf after about 20 days. It was found that this shape recovery force was sufficient to correct misaligned teeth in the orthodontic test. The shape memory PU wire possesses strong potential as a novel orthodontic appliance with esthetically appealing appearance.

Self-Healing EPDM Rubbers with Highly Stable and Mechanically-Enhanced Urea-Formaldehyde (UF) Microcapsules Prepared by Multi-Step In Situ Polymerization.

The mechanically-enhanced urea-formaldehyde (UF) microcapsules are developed through a multi-step in situ polymerization method. Optical microscope (OM) and field emission scanning electron microscope (FE-SEM) prove that the microcapsules, 147.4 µm in diameter with a shell thickness of 600 nm, are well-formed. From 1H-nuclear magnetic resonance (1H-NMR) analysis, we found that dicyclopentadiene (DCPD), a self-healing agent encapsulated by the microcapsules, occupies ca. 40.3 %(v/v) of the internal volume of a single capsule. These microcapsules are mixed with EPDM (ethylene-propylene-diene-monomer) and Grubbs' catalyst via a solution mixing method, and universal testing machine (UTM) tests show that the composites with mechanically-enhanced microcapsules has ca. 47% higher toughness than the composites with conventionally prepared UF microcapsules, which is attributed to the improved mechanical stability of the microcapsule. When the EPDM/microcapsule rubber composites are notched, Fourier-transform infrared (FT-IR) spectroscopy shows that DCPD leaks from the broken microcapsule to the damaged site and flows to fill the notched valley, and self-heals as it is cured by Grubbs' catalyst. The self-healing efficiency depends on the capsule concentration in the EPDM matrix. However, the self-healed EPDM/microcapsule rubber composite with over 15 wt% microcapsule shows an almost full recovery of the mechanical strength and 100% healing efficiency.

Wetting behavior of water and oil droplets in three-phase interfaces for hydrophobicity/philicity and oleophobicity/philicity.

Biomimetics, mimicking nature for engineering solutions, provides a model for the development of superhydrophobic/superoleophobic and self-cleaning surfaces. A number of biomimetic superhydrophobic surfaces have been developed by using a hydrophobic coating, surface roughness, and the ability to form air pockets between solid and water. Oleophobic surfaces that have the potential for self-cleaning and antifouling from biological and organic contaminants in both air and water need to be studied. The surface tension of oil and organic liquids is lower than that of water, so to create a superoleophobic surface, the surface energy of the solid surface in air should be lower than that of oil. The wetting behavior of water and oil droplets for hydrophobic/philic and oleophobic/philic surfaces in three-phase interfaces was studied. In order to make the surface oleophobic at a solid-air-oil interface, a material with a surface energy lower than that of oil was used. In underwater applications, the oleophobicity/philicity of an oil droplet in water was studied on the surfaces with different surface energies of various interfaces and contact angles of water and oil droplets in air. A model for predicting the contact angles of water and oil droplets was proposed. To validate the model, the wetting behavior of flat and micropatterned surfaces with varying pitch values were studied. Furthermore, the wetting behavior of the nano- and hierarchical structures found in Lotus plant surfaces and the shark skin replica as an example of aquatic animal were also studied. On the basis of the experimental data and the model, the trends were explained.

Optical spectroscopic studies of photochemically oxidized single-walled carbon nanotubes.

We examined the time-dependent changes in the optical properties of single-walled carbon nanotubes which were consecutively oxidized by irradiation with vacuum ultraviolet light. It is demonstrated that photochemical oxidation is a mild and controllable method for manipulating the surface of nanotubes in order to convert their affinity from hydrophobic to hydrophilic by controlling the density of functional groups on their sidewalls without destroying their tubular morphology.