Article pubs.acs.org/Langmuir
Janus Nanofilms Yara E. Ghoussoub and Joseph B. Schlenoff* Department of Chemistry and Biochemistry, The Florida State University, Tallahassee, Florida 32306-4390, United States S Supporting Information *
ABSTRACT: To make a two-dimensional Janus object, the perfluorinated anionic polyelectrolyte Nafion was adsorbed to the surface of ultrathin films of polyelectrolyte complex. Nafion changed the wetting characteristics of the polyelectrolyte multilayer (PEMU) of poly(diallyldimethylammonium) and poly(styrenesulfonate) from hydrophilic to hydrophobic. PEMUs assembled on aluminum substrates and terminated with Nafion could be released by exposure to alkali solution, producing free-floating films in the 100 nm thickness regime. Water contact angle measurements showed a strong difference in hydrophilicity between the two sides of this Janus film, which was further characterized using atomic force microscopy and Xray photoelectron spectroscopy (XPS). XPS revealed different fluorine contents on both sides of the PEMU, which could be translated to a Nafion gradient through the film. Fourier transform infrared spectroscopy showed the Nafion-containing films were much more resistant to decomposition by high salt concentration.
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INTRODUCTION A Janus particle has anisotropic surface properties, usually a well-defined direction of hydrophilicity, that mimic classical surfactants but on a larger scale.1−3 Nanoparticles with these amphiphilic properties assemble at interfaces,4−7 or selfassemble to yield interesting structures.8−11 Several strategies are available to make Janus nanoparticles: they may form spontaneously from block copolymers,12−14 or they may be prepared by more labor-intensive methods, such as deposition of isotropic particles on hard substrates followed by modification of exposed areas (masking).15−17 Self-assembly at the interface of emulsions stabilized by nanoparticles (Pickering emulsions)18,19 offers higher throughput than stepwise construction at planar interfaces. The various geometries of Janus architectures include disks,20,21 cylinders,22−24 and matchsticks.25 At first glance, films on the nanometer scale with Janus properties appear to be common. For example, monolayers organized at the liquid/air or liquid/liquid interface by the Langmuir−Blodgett technique have a high degree of structural regularity and polarity.26−28 However, amphiphilic films of small molecules require an interface to prevent collapse and spontaneous aggregation into micelles. Alternatively, gradients in hydrophobicity must be eliminated by organizing films of amphiphiles into bilayers, as seen in the cell membrane. Thus, the two-dimensional equivalent of Janus nanoparticles, rugged films on the nanometer scale with strongly amphiphilic faces, are much less common. Different approaches have been employed to synthesize Janus sheets.20,29−31 Dorvee et al. described a technique of etching silicon and fracturing the resulting thin film with © XXXX American Chemical Society
ultrasound to obtain micron sized sheets with Janus properties.32 More recently, Liang et al. described a higher-throughput method of making Janus nanosheets by crushing hollow silica shells with hydrophobic inner surfaces and hydrophilic exteriors.33 Asymmetric brushes were subsequently polymerized from these micrometer-diameter nanosheets.34,35 Kai et al. used an interfacial click reaction between hydrophilic and lipophilic polymers at the interface between oil and water to give porous films of ca. 30 μm thickness.29 Rugged, unsupported amphiphilic nanofilms of larger dimensions from all-polymer components would be an interesting material for promoting certain types of self-assembly. A Janus nanofilm would spontaneously organize small or large amphiphilic molecules or particles, maintain them in close proximity and keep their orientations polarized. In the present work, we exploit a recently developed method of producing free ultrathin films of polyelectrolyte complex made by the so-called polyelectrolyte multilayering, or layer-by-layer, method.36 The current strategy requires adding a hydrophobic polyelectrolyte as the last “layer” of a multilayer made from hydrophilic components poly(diallyldimethylammonium), PDADMA, and poly(styrenesulfonate), PSS, then releasing the film while adjusting the conditions to maximize the hydrophobicity of the “top” face of the film without allowing the hydrophobic polymer to break through to the “bottom” face. Received: February 21, 2016 Revised: March 25, 2016
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DOI: 10.1021/acs.langmuir.6b00672 Langmuir XXXX, XXX, XXX−XXX
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RESULTS AND DISCUSSION The surface properties of a polyelectrolyte multilayer were modified by the addition of a layer of hydrophobic polymer following the buildup of the PEMU. The initial film consisted of 19.5 bilayers, (PDADMA/PSS)19PDADMA, assembled on glass or silicon wafer using the layer-by-layer technique.37,38 A terminating Nafion layer (see Figure 1) was subsequently
increased gradually from 83° to 95° after 20 min in Nafion at 45 °C. Note that the change in surface wettability was not caused by the 2,2,2-trifluoroethanol (TFE) solvent: a film exposed to TFE only at 45 °C for 20 min exhibited a contact angle of 49° confirming that the increase in contact angle on exposure to Nafion solution resulted from the deposition of the fluorinated polymer. Dynamic contact angles were determined before and after 20 min of treatment with Nafion solution. The advancing and receding water contact angles of Si/(PDADMA/ PSS)19PDADMA were 50° and 32° respectively, whereas those of Si/(PDADMA/PSS)19PDADMA/Nafion films were 115° and 78° (see Figure 2B). Further evidence of Nafion sorption was provided by FTIR. Figure 2C depicts the IR spectra of (PDADMA/ PSS)19PDADMA before and after Nafion deposition. Interactive subtraction of Si/(PDADMA/PSS)19PDADMA from the Si/(PDADMA/PSS)19PDADMA/Nafion spectrum displays a band around 1350−1100 cm−1, corresponding to Nafion, as illustrated by the pure component spectrum of Nafion in Figure 2C. Thickness and surface morphology were obtained using atomic force microscopy. The added Nafion increased the thickness of the PDADMA-ending film from about 552 (±13) to 588 (±27) nm with no significant change of surface roughness. Figure 2D shows the topography of Si/(PDADMA/ PSS)19PDADMA before and after the Nafion treatment. Despite the thickness increase, the roughness of both Si/ (PDADMA/PSS)19PDADMA and Si/(PDADMA/ PSS)19PDADMA/Nafion were close (Rq = 22 and 23 nm and Rt = 144 and 163 nm, respectively). It has been reported that the hydrophobicity of a surface, as reflected by the contact angle, can be substantially increased by increasing its roughness.39−41 However, the result in Figure 2D shows that the hydrophobic behavior of the surface capped with Nafion is not caused by surface roughness. Films were treated at 45 °C in TFE in the absence of polymers to investigate the effect of the unusual solvent on the PEMU surface. The roughness was found to drop significantly from 22 to 4 nm (see Figure 2D) suggesting solvent-induced smoothing of the surface. When
Figure 1. Structures of the polyelectrolytes used.
applied on top of the Si/(PDADMA/PSS)19PDADMA PEMU by exposure to a 1 mM Nafion solution at 45 °C for various times. To confirm the adsorption of the fluorinated polymer and reveal the effect of the new added layer on the surface wettability, contact angle measurements were obtained using water. As shown in Figure 2A, the static contact angle of the films increased from 38° to 83° after 5 min of treatment due to the hydrophobic nature of Nafion. Nafion was also deposited on the surface of the PEMU at room temperature but the use of slightly warmer conditions was found to promote additional hydrophobicity. The hydrophobicity of the surface increased at longer exposure times. Specifically, the water contact angle
Figure 2. (A) Static contact angles of Si/(PDADMA/PSS)19PDADMA (39 L), Si/(PDADMA/PSS)19PDADMA soaked in TFE at 45 °C for 20 min, Si/(PDADMA/PSS)19PDADMA soaked in Nafion (1 mM) at 45 °C for 5, 10, 15, and 20 min. (B) Static, advancing and receding contact angles of Si/(PDADMA/PSS)19PDADMA and Si/(PDADMA/PSS)19PDADMA soaked in Nafion (1 mM) at 45 °C for 20 min. (C) FTIR transmission spectra of (a) Si/(PDADMA/PSS)19PDADMA (b) Si/(PDADMA/PSS)19PDADMA/Nafion (39 L/Nafion); (c) resulting spectrum from subtracting (a) from (b); and (d) Nafion. (D) AFM 3D images (5 × 5 μm) and rms roughness (Rq) of Si/(PDADMA/PSS)19PDADMA, Si/ (PDADMA/PSS)19PDADMA soaked in TFE at 45 °C for 20 min and Si/(PDADMA/PSS)19PDADMA/Nafion. Error bars represent the standard deviation from the average value. B
DOI: 10.1021/acs.langmuir.6b00672 Langmuir XXXX, XXX, XXX−XXX
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Langmuir Scheme 1. Release of Al/(PDADMA/PSS)19PDADMA/Nafion Films from an Aluminum Substrate in 0.1 M NaOHa
a
The multilayers are recovered “face up” or “flipped”.
Figure 3. (A) Static contact angle (θ) of Si/(PDADMA/PSS)19PDADMA, Si/(PDADMA/PSS)19PDADMA/Nafion, Si/(PDADMA/ PSS)19PDADMA/Nafion soaked in 0.1 M NaOH for 15 min, Al/(PDADMA/PSS)19PDADMA/Nafion released face up, and Al/(PDADMA/ PSS)19PDADMA/Nafion released flipped. The shaded area highlights data for the two sides of the free Janus film. (B) RMS roughness (Rq) of Si/ (PDADMA/PSS)19PDADMA, Si/(PDADMA/PSS)19PDADMA/Nafion soaked in 0.1 M NaOH for 15 min, and Al/(PDADMA/PSS)19PDADMA/ Nafion released “face up”. (C) AFM 3D (5 × 5 μm) images corresponding to the samples in panel B. Error bars represent the standard deviation from the mean value of the data.
detected except for a slight decrease in the peak area of PDADMA (see Supporting Information Figure S1). Contact angle measurements were then carried out on both faces of the released films. The upper- and substrate-side water contact angles were markedly different with 94° for the film recovered face up and 34° for the flipped one (see Figure 3A). The change in contact angle suggests a gradient of hydrophobicity within the PEMU equivalent to 1.02 × 106 degrees/ cm (assuming a linear gradient). These thin films were termed “Janus” due to their amphiphilic properties. IR spectra of the control films on silicon and those released from aluminum (see Supporting Information Figure S2) showed bands around 1047−993 cm−1 attributed to PSS and a band at 1513−1427 cm−1 corresponding to PDADMA. The area ratio of the two bands gave the relative amounts of PSS to PDADMA. A slight increase in the area ratio was observed for the released Al/(PDADMA/PSS)19PDADMA and Al/(PDADMA/PSS)19PDADMA/Nafion films compared to their untreated controls built on silicon, suggesting a loss of PDADMA during the release process. On the other hand, multilayers with Nafion on top showed slightly lower PSS/PDADMA ratios compared to the 39-layer films, possibly caused by a displacement of PSS by Nafion as it pairs with PDADMA. The control film assembled on a glass substrate with Nafion on top and treated in 0.1 M NaOH showed only minor topographical changes after exposure to NaOH for 15 min. The surface was slightly smoother with an average rms roughness of 16 nm (Rt = 116 nm) compared to 22 nm before treatment. Similarly, the PEMU built on aluminum and recovered face up
hydrated, the PSS/PDADMA complex is known to undergo a transition in modulus, possibly a glass transition, at around 35 °C. In contrast, dry PEMUs do not exhibit such a transition under accessible temperatures.42 The surface plasticization by TFE is an indication that this solvent is one of the few that can actually swell the PEMU to some extent, unlike many more common solvents.43 It has been shown that temperature promotes polymer chains mobility44 and layer interdiffusion,45 which explains the substantial decrease in surface roughness. After analyzing the substrate-bound multilayers, PEMUs were assembled on a pH-sensitive substrate (in this case aluminum) and subsequently released by exposure to 0.1 M NaOH as detailed in a recent study.36 Specifically, the gentle dissolution of the aluminum under basic conditions helped free the films from their substrate. Films were then recovered “flipped” where the film/substrate interface (initially in contact with the aluminum surface) became the upper side, or “face up” where the original solution/film interface was exposed (see Scheme 1), allowing further investigation of both sides of the multilayer. Control experiments were first conducted to verify the stability of the films at high pH. Si/(PDADMA/ PSS)19PDADMA/Nafion PEMUs built on glass substrates were treated with the alkali solution for 15 min and the water contact angle of the surface was determined. Despite the treatment at pH = 11, the multilayers essentially preserved contact angles with a slight decrease of 5° (from 95° to 90°) as shown in Figure 3A. No significant IR spectral changes were C
DOI: 10.1021/acs.langmuir.6b00672 Langmuir XXXX, XXX, XXX−XXX
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Figure 4. (A) Relative surface atomic percentage of N, S, and F in Si/(PDADMA/PSS)19 PDADMA, Si/(PDADMA/PSS)19PDADMA control soaked in TFE at 45 °C for 20 min (showing no detectable F), Si/(PDADMA/PSS)19PDADMA/Nafion, Al/(PDADMA/PSS)19PDADMA/Nafion released face up, and Al/(PDADMA/PSS)19PDADMA/Nafion released flipped obtained by XPS. Prior work shows that no Al is deposited on either side of the released PEMUs.36 (B) Fluorine gradient (atom % fluorine) in the Janus multilayer.
and θ2 are the contact angles of a Nafion film and a PDADMA/ PSS film. Assumptions are that the static contact angle is an equilibrium property (probably not true as seen from the difference between advancing and receding angles, that is, hysteresis47) and that the length scales of surface heterogeneity is fine enough to provide the weighted average described by eq 1.48 The Nafion composition according to this equation decreased from 80% at the film/solution interface to 6% at the film/substrate interface. It is well established that the pairing between oppositely charged polyelectrolyte repeat units can be broken by competing salt counterions.49,50 Under the right conditions, at sufficiently high salt concentration the polymer chains are completely dissociated leading to the disintegration of the PEMU. In the case of PSS and PDADMA complexation, this dissolution point has been established to be 1.80 M KBr in water at room temperature.51 The stability of the PEMUs in high ionic strength solution was studied by a postassembly exposure to a 2.5 M KBr solution. Immersion of (PDADMA/ PSS)19PDADMA built on silicon in the KBr solution resulted in complete dissolution of the multilayered film within 3 s, verified by the loss of all IR signals after treatment (see Figure 5A). Interestingly, films capped with Nafion undergo a much slower salt-induced dissociation when immersed in 2.5 M KBr. Figure 5B shows the IR spectra of the Si/(PDADMA/ PSS)19PDADMA/Nafion film before and after immersion in
had a roughness of 16 nm (Rt = 123 nm) (see Figure 3B,C) suggesting that the treatment at pH = 11 induces only minor changes in topography. To gain more insight on the surface composition, N(1s), S(2p), and F(1s) were investigated using XPS (see Figure 4A and Supporting Information Figure S3). Prior to Nafion addition, the film terminated with PDADMA had 63% N and 37% S (relative atomic percent, with N + S + F set to 100%) with no detectable fluorine. The excess nitrogen detected on top of the film is expected for a PDADMA-dominated surface.36 For the Si/(PDADMA/PSS)19PDADMA/Nafion films, a strong fluorine peak was observed around 690 eV. The relative atomic percentages reflected a substantial change in surface composition after treatment with the perfluorinated polyelectrolyte. Fluorine (97 atom %) along with 2% of nitrogen and sulfur were detected on the surface of the multilayer, confirming the postassembly deposition of a Nafion layer. To verify that the fluorine content is the result of the adsorption of Nafion, a PEMU treated with TFE only at 45 °C for 20 min was investigated with XPS, revealing no alteration in the surface composition (no F) compared to the untreated PEMU. Likewise, the Al/(PDADMA/PSS)19PDADMA/Nafion film released face up presented a strong fluorine peak and a relative atomic percentage of 97% F with 3% S and N, which is in agreement with the surface composition of the film built on Si with a terminating layer of Nafion. The substrate side of the PEMU had 42% N, 41% S, and 17% F. It has been suggested that higher temperature induces polymer chain mobility promoting layer interpenetration.46 The observation of fluorine on the bottom side of the film shows that the Nafion was not confined to the surface, but instead diffused into the bulk of the PEMU creating a smooth gradient of fluorine (see Figure 4B) decreasing from 97% F on the upper side to 17% F on the bottom side. Although the percentage of fluorine appears to be significant on the film/substrate interface it only corresponds to approximately 0.5% Nafion along with 50.5% PDADMA and 49% PSS because the perfluorinated polymer with a molecular weight of 1100 per repeat unit in Figure 1 contains so much F, that is, the Nafion has barely broken through the film/substrate interface. The film/solution interface is predominantly composed of Nafion with 97% fluorine. For comparison, the equation of Cassie and Baxter40 was used to obtain the surface composition from the observed contact angle cos θ = x1 cos θ1 + x 2 cos θ2
Figure 5. FTIR transmission spectra of (A) Si/(PDADMA/ PSS)19PDADMA before KBr and after 1 and 3 s in 2.5 M KBr. (B) Si/(PDADMA/PSS)19PDADMA/Nafion before KBr and after 12 and 15 h in 2.5 M KBr. (C) (a) PSS; (b) PDADMA; (c) Si/(PDADMA/ PSS)19PDADMA; (d) Si/(PDADMA/PSS)19PDADMA/Nafion; (e) Nafion; (f) Al/(PDADMA/PSS)19PDADMA/Nafion released and soaked in KBr for 6 h.
(1)
where θ is the contact angle of the surface, x1 and x2 are the area fractions of Nafion and PDADMA/PSS complex, and θ1 D
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Multilayer Assembly. Prior to multilayer assembly, silicon substrates were cleaned in piranha solution for 15 min, rinsed with 18 MΩ water, and dried with N2. PDADMA/PSS multilayers were built using a robot (StratoSequence V, nanoStrata Inc.) by alternately dipping the substrate (silicon or aluminum) in 10 mM PDADMA and PSS solutions (concentration based on the monomer repeat unit) in 1.0 M NaCl. The substrates were mounted face-down on the robot shafts and rotated at a speed of 300 rpm. The exposure time for the polymers was set to 5 min followed by three water rinses for 1 min each. The multilayers were subsequently exposed to 1 mM Nafion solution (in TFE) at 45 °C for 20 min, rinsed with TFE for 5 s and left to dry in air. Substrate/(PDADMA/PSS)x notation is used for the nomenclature of the PEMUs, where “x” denotes the number of bilayers of PDADMA and PSS, starting with PDADMA. Control PEMUs ((PDADMA/PSS)19PDADMA)) assembled on aluminum substrates were released in 0.1 M NaOH within 45 s with the aid of polypropylene tweezers and recovered on a clean silicon wafer. Multilayers terminating with a Nafion layer ((PDADMA/PSS)19 PDADMA/Nafion) were immersed in sodium hydroxide for 2 min. All films were recovered face up or flipped (where the bottom side became the upper side) as described previously.36 PEMUs were then rinsed with water and dried with nitrogen. Contact Angles. A contact angle meter (CAM-100) from KSV instruments was employed to determine the static and dynamic water contact angles of the PEMUs. Images were processed using CAM 2008 software by fitting a curve to the shape of the drop. Static contact angles were determined using the sessile drop technique by measuring the angle formed between the tangent to a drop (of volume 5 μL) and the baseline. During the advancing and receding contact angle measurements, the needle remained attached to the drop while the volume changed. The advancing contact angle was obtained after the deposition of a 5 μL drop on the surface. The volume was increased to 10 μL then decreased to 5 μL to measure the receding contact angle. Measurements were obtained for at least three films at two different locations each. Error bars represent the standard deviation from the average value. Imaging. Surface roughness and topography were obtained by atomic force microscopy, AFM, (MFP-3D AFM coupled to an ARC2 controller, Asylum Research Inc., Santa Barbara, CA) using NCHV tips from Veeco (tip radius = 10 nm, spring constant 20−80 N m−1) under the AC (intermittent contact) mode. The 5 × 5 μm images were recorded at different positions with a scan rate of 0.5 Hz. RMS surface roughness (Rq) and maximum peak to valley height (Rt) were obtained on 5 × 5 μm regions from 20 × 20 μm images. Each data point is the average of 20 values obtained from 2 different samples. Dry thicknesses were obtained by gently scratching the PEMUs to avoid damaging the underlying silicon substrate and measuring the step height. Data analysis was performed using Igor Pro software. IR Spectroscopy. Transmission FTIR spectroscopy was employed to study the composition of PEMUs. Spectra were collected with a Thermo Nicolet Avatar 360 FTIR equipped with a DTGS detector purged with N2 and data was analyzed using EZ-OMNIC software. Multilayers studied by FTIR were built on double-side polished Si 100 wafers with a bare Si wafer as a background. Each spectrum was obtained by averaging 100 scans with a resolution of 4 cm−1. X-ray Photoelectron Spectroscopy. Surface elemental composition was characterized using a PerkinElmer (PHI) 5100 XPS with a noncollimated Mg Kα X-ray source (hν = 1253.6 eV). The takeoff angle between the surface and the analyzer was set to 45° and the pass energy was 89.45 eV. Twenty scans for each of the elements (N (1s), S (2p), and F(1s)) were acquired at a speed of 0.5 eV s−1 and averaged.
KBr. A decrease in the peak areas of both PDADMA and PSS was observed after 12 h of treatment and 15 h were needed to completely dissolve the film. The remarkable resistance of Nafion capped films to high ionic strength solutions (2.5 M KBr) suggests that the fluorinated layer protected the multilayer and preserved its integrity. Nafion-capped multilayers were then exposed to 2.5 M KBr after being freed from the aluminum substrate. The Janus films were left floating in the salt solution for 6 h allowing direct access to both faces of the film. Polymer loss was evaluated by FTIR and thickness measurements. The film recovered after 6 h consisted predominantly of Nafion, as shown by the broad peak around 1350−1100 cm−1 (Figure 5C) with small amounts of PDADMA and PSS, suggesting that the PSS/PDADMA component of the PEMU was selectively dissociated by the salt leaving a Nafion layer floating in solution. The area under each of the PDADMA and PSS peaks was integrated and the ratio of PDADMA/PSS was determined to be 1.25:1 before treatment and 1.4:1 after soaking in KBr. The excess of PDADMA observed in the treated films, suggests that the remaining positive polyelectrolyte is paired to the negatively charged Nafion. Interestingly, the recovered film was thin enough to spontaneously fold during recovery mimicking a lipid bilayer. The dissociation of the multilayer led to a decrease of the film thickness from 588 nm before treatment to 47 nm after, close to the 40 nm increase originally observed when Nafion was added to the PSS/PDADMA multilayer.
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CONCLUSIONS The suite of Janus objects, those with close regions of strongly differing hydrophilicity, has been extended to include macroscopic films. Janus films with amphiphilic properties were obtained by the adsorption of perfluorinated Nafion to the solution/film interface of polyelectrolyte multilayers. Intrafilm diffusion created a gradient of hydrophobicity in the nanomembrane crossing from hydrophobic at the solution/film interface to hydrophilic at the substrate/film interface. The PSS/PDADMA component of Janus PEMUs treated at high salt concentration was substantially dissociated due to the disruption of polymer−polymer ion pairs by counterions, resulting in ultrathin nanosheets of thickness ca. 50 nm. The polyelectrolyte complex making up the bulk of the 400 nm Janus films was stiff enough (modulus ca. 10 MPa52) to prevent self-association of hydrophobic regions but the salt-thinned films spontaneously folded. The minimum thickness that would prevent self-association is a parameter of interest for future work.
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MATERIALS AND METHODS
Materials. Poly(4-styrenesulfonic acid sodium salt) (PSS, molecular weight = 7.5 × 104 g mol−1) (Scientific Polymer Products, Inc.), poly(diallyldimethylammonium chloride) (PDADMAC, molecular weight = 40 × 104 to 50 × 104 g mol−1), Nafion (5 wt % in lower aliphatic alcohols/H2O mix), 2,2,2-trifluoroethanol (TFE) and sodium hydroxide (1 and 0.1 M) (Sigma-Aldrich) were used as received. “Piranha” solution was prepared from sulfuric acid, 98% (J. T. Baker), and hydrogen peroxide, 30% (Macron) (7:3 by volume H2SO4/H2O2; caution: piranha is a strong acid and oxidizer and should not be stored in sealed containers). The ionic strength of the polyelectrolytes solutions was adjusted using sodium chloride (Fisher). Single and double-side-polished silicon 100 wafers (thickness = 381 ± 25 μm) were obtained from Okmetic. All polymer solutions (except Nafion) were prepared using deionized water (Barnstead, 18 MΩ E-pure).
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ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.langmuir.6b00672. FTIR spectra and peak areas and XPS raw data. (PDF) E
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AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS This work was supported by grant DMR-1207188 from National Science Foundation.
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