A simple and effective method for the accurate extraction of kinetic parameters using differential Tafel plots.

The practice of estimating the transfer coefficient ([Formula: see text]) and the exchange current ([Formula: see text]) by arbitrarily placing a straight line on Tafel plots has led to high variance in these parameters between different research groups. Generating Tafel plots by finding kinetic current, [Formula: see text] from the conventional mass transfer correction method does not guarantee an accurate estimation of the [Formula: see text] and [Formula: see text]. This is because a substantial difference in values of [Formula: see text] and [Formula: see text] can arise from only minor deviations in the calculated values of [Formula: see text]. These minor deviations are often not easy to recognise in polarisation curves and Tafel plots. Recalling the IUPAC definition of [Formula: see text] , the Tafel plots can be alternatively represented as differential Tafel plots (DTPs) by taking the first order differential of Tafel plots with respect to overpotential. Without further complex processing of the existing raw data, many crucial observations can be made from DTP which is otherwise very difficult to observe from Tafel plots. These for example include a) many perfectly looking experimental linear Tafel plots (R2 > 0.999) can give rise to incorrect kinetic parameters b) substantial differences in values of [Formula: see text] and [Formula: see text] can arise when the limiting current ([Formula: see text]) is just off by 5% while performing the mass transfer correction c) irrespective of the magnitude of the double layer charging current ([Formula: see text]), the Tafel plots can still get significantly skewed when the ratio of [Formula: see text] is small. Hence, in order to determine accurate values of [Formula: see text] and [Formula: see text], we show how the DTP approach can be applied to experimental polarisation curves having well defined [Formula: see text], poorly defined [Formula: see text] and no [Formula: see text] at all.

3D NiCo-Layered double Hydroxide@Ni nanotube networks as integrated free-standing electrodes for nonenzymatic glucose sensing.

Nickel cobalt layered double hydroxide (NiCo-LDH)-based materials have recently emerged as catalysts for important electrochemical applications. However, they frequently suffer from low electrical conductivity and agglomeration, which in turn impairs their performance. Herein, we present a catalyst design based on integrated, self-supported nickel nanotube networks (Ni-NTNWs) loaded with NiCo-LDH nanosheets, which represents a binder-free, hierarchically nanostructured electrode architecture combining continuous conduction paths and openly accessible macropores of low tortuosity with an ultrahigh density of active sites. Similar to macroscale metallic foams, the NTNWs serve as three-dimensionally interconnected, robust frameworks for the deposition of active material, but are structured in the submicron range. Our synthesis is solely based on scalable approaches, namely templating with commercial track-etched membranes, electroless plating, and electrodeposition. Morphological and compositional characterization proved the successful decoration of the inner and outer nanotube surfaces with a conformal NiCo-LDH layer. Ni-NTNW electrodes and hydroxide-decorated variants showed excellent performance in glucose sensing. The highest activity was achieved for the catalyst augmented with NiCo-LDH nanosheets, which surpassed the modification with pure Ni(OH)2. Despite its low thickness of 20 µm, the optimized catalyst layer provided an outstanding sensitivity of 4.6 mA mM-1 cm-2, a low detection limit of 0.2 µM, a fast response time of 5.3 s, high selectivity and stability, and two linear ranges covering four orders of magnitude, up to 2.5 mM analyte. As such, derivatized interconnected metal nano-networks represent a promising design paradigm for highly miniaturized yet effective catalyst electrodes and electrochemical sensors.

In Situ Transmission Electron Microscopy Analysis of Thermally Decaying Polycrystalline Platinum Nanowires.

Owing to their large surface area, continuous conduction paths, high activity, and pronounced anisotropy, nanowires are pivotal for a wide range of applications, yet far from thermodynamic equilibrium. Their susceptibility toward degradation necessitates an in-depth understanding of the underlying failure mechanisms to ensure reliable performance under operating conditions. In this study, we present an in-depth analysis of the thermally triggered Plateau-Rayleigh-like morphological instabilities of electrodeposited, polycrystalline, 20-40 nm thin platinum nanowires using in situ transmission electron microscopy in a controlled temperature regime, ranging from 25 to 1100 °C. Nanowire disintegration is heavily governed by defects, while the initially present, frequent but small thickness variations do not play an important role and are overridden later during reshaping. Changes of the exterior wire morphology are preceded by shifts in the internal nanostructure, including grain boundary straightening, grain growth, and the formation of faceted voids. Surprisingly, the nanowires segregate into two domain types, one being single-crystalline and essentially void-free, while the other preserves void-pinned grain boundaries. While the single-crystalline domains exhibit fast Pt transport, the void-containing domains are unexpectedly stable, accumulate platinum by surface diffusion, and act as nuclei for the subsequent nanowire splitting. This study highlights the vital role of defects in Plateau-Rayleigh-like thermal transformations, whose evolution not only accompanies but guides the wire reshaping. Thus, defects represent strong parameters for controlling the nanowire decay and must be considered for devising accurate models and simulations.

Dual Metastability in Electroless Plating: Complex Inertness Enabling the Deposition of Composition-Tunable Platinum Copper Alloy Nanostructures.

Autocatalytic deposition represents a facile, versatile, and scalable wet-chemical tool for nanofabrication. However, the intricate component interplay in plating baths containing multiple metal species impedes alloy deposition. We resolved this challenge in the bimetallic copper-platinum system by exploiting the kinetic stability of platinum complexes, which allows adjusting their ligand sphere and thus reactivity independently from the present copper ions in a preceding, thermally activated ligand exchange step. By using metastable PtIV precursors of varying degrees of complexation, copper-platinum alloys of adjustable atomic ratio were plated from solutions of identical composition and concentration, but differing local coordination environment. Due to its excellent conformity and nanoscale homogeneity, the reaction is compatible with ambitious 3D substrate morphologies, as demonstrated in the template-assisted fabrication of nanotubes with high aspect ratio. The ability to generate additional synthetic degrees of freedom by decoupling the metal complex speciation from the solution composition is of large interest for redox-chemical synthesis techniques, such as electrodeposition or nanoparticle colloid production.

Conformal Solution Deposition of Pt-Pd Titania Nanocomposite Coatings for Light-Assisted Formic Acid Electro-Oxidation.

Many nanofabrication processes require sophisticated equipment, elevated temperature, vacuum or specific atmospheric conditions, templates, and exotic chemicals, which severely hamper their implementation in real-world applications. In this study, we outline a fully wet-chemical procedure for equipping a 3D carbon felt (CF) substrate with a multifunctional, titania nanospike-supported Pt-Pd nanoparticle (Pt-Pd-TiO2@CF) layer in a facile and scalable manner. The nanostructure, composition, chemical speciation, and formation of the material was meticulously investigated, evidencing the conformal coating of the substrate with a roughened layer of nanocrystalline rutile spikes by chemical bath deposition from Ti3+ solutions. The spikes are densely covered by bimetallic nanoparticles of 4.4 ± 1.1 nm in size, which were produced by autocatalytic Pt deposition onto Pd seeds introduced by Sn2+ ionic layer adsorption and reaction. The as-synthesized nanocomposite was applied to the (photo)electro-oxidation of formic acid (FA), exhibiting a superior performance compared to Pt-plated, Pd-seeded CF (Pt-Pd@CF) and commercial Pt-C, indicating the promoting electrocatalytic role of the TiO2 support. Upon UV-Vis illumination, the performance of the Pt-Pd-TiO2@CF electrode is remarkably increased (22-fold), generating a current density of 110 mA cm-2, distinctly outperforming titania-free Pt-Pd@CF (5 mA cm-2) and commercial Pt-C (6 mA cm-2) reference catalysts. In addition, the Pt-Pd-TiO2@CF showed a much better stability, characterized by a very high poisoning tolerance for in situ-generated CO intermediates, whose formation is hindered in the presence of TiO2. This overall performance boost is attributed to a dual enhancement mechanism (∼30% electrocatalytic and ∼70% photoelectrocatalytic). The photogenerated electrons from the TiO2 conduction band enrich the electron density of the Pt nanoparticles, promoting the generation of active oxygen species on their surfaces from adsorbed oxygen and water molecules, which facilitate the direct FA electro-oxidation into CO2.

Electrical and thermal conductivities of polycrystalline platinum nanowires.

Understanding the electrical and thermal transport properties of polycrystalline metallic nanostructures is of great interest for applications in microelectronics. In view of the diverse experimental results in polycrystalline metallic nanowires and nanofilms, it is a long-standing question whether their electrical and thermal properties can be well predicted by a practical model. By eliminating the effects of electrical and thermal contact resistances, we measure the electrical and thermal conductivities of three different polycrystalline Pt nanowires. The electron scattering at the surface is found to be diffusive, and the charge reflection coefficient at grain boundaries is proved to be a function of the melting point. The Lorenz number is observed to be suppressed from the free-electron value by about 30%, which can be explained by introducing a thermal reflection coefficient in calculating the thermal conductivity to account for the small angle scattering effect involving phonons at the grain boundaries. Using this model, both the electrical and thermal conductivities of the polycrystalline Pt nanowires are calculated at different diameters and temperatures.

Data on peptidyl platform-based anticancer drug synthesis and triton-x-based micellar clusters (MCs) self-assembly peculiarities for enhanced solubilization, encapsulation of hydrophobic compounds and their interaction with HeLa cells.

The data presented here refer to a research article entitled "Self-Assembled Micellar Clusters Based on Triton-X-family Surfactants for Enhanced Solubilization, Encapsulation, Proteins Permeability Control, and Anticancer Drug Delivery" Solomonov et al., 2019. The present article provides the General Procedure for clusterization of Triton-X-based micelles and the effect of (i) metal ion, surfactant, and chelator concentration on the developed clusters formation, (ii) surfactant-chelator relation change, (iii) metal ion-micelles concertation ratio variation, (iv) metal ion replacement, (v) solvent replacement, (vi) kinetics of clusters formation, (vii) hydrophobic fluorescent dye (Coumarin 6) solubilization in aqueous MCs media, (viii) novel anticancer peptidyl drug synthesis and characterization and (ix) the viability of HeLa cells with and without the presence of drug-free Triton-X-based family MCs. These data provide additional insights useful for understanding all aspects of the micellar clusters formation, optimization, and control.

Self-assembled micellar clusters based on Triton-X-family surfactants for enhanced solubilization, encapsulation, proteins permeability control, and anticancer drug delivery.

Non-ionic surfactants have raised a considerable interest for solubilization, encapsulation, permeabilization and controlled release of various compounds due to their unique physicochemical properties. Nevertheless, it is still challenging to create convenient self-assembled multifunctional materials with high solubilization and encapsulation capacities by preserving their advanced capabilities to protect loaded cargos without altering their characteristics. In this work, we present an extended concept of micellar clusters (MCs) formation based on partial entrapment and stabilization of chelate ligands by hydrophobic forces found on the non-ionic surfactant micelle interface of the Triton-X family (TX-100/TX-114), followed by subsequent complexation of the preformed structures either by metal ions or a supporting chelator. The formation aspects, inner structure and the role of external factors such as the addition of competitive ligands have been extensively studied. MCs loaded by hydrophobic fluorescent compounds with high encapsulation efficiency demonstrate an excellent optical response in aqueous media without crystallization as well as sufficient increase in solubility of toxic hydrophobic compounds such as bilirubin (>50 times compared to pure surfactants). Furthermore, Triton-X-based MCs provide a unique feature of selective permeability to hydrophilic ligand-switching proteins such as UnaG and BSA demonstrating bright "turn-on" fluorescence signal either inside the cluster or on its interface via complexation. The proposed strategies allowed us to successfully encapsulate and visualize a newly synthesized, highly hydrophobic anticancer PTR-58-CLB-CAMP peptide drug, while MCs loaded by the drug exhibit a considerable antitumor activity against HeLa cells.

Shape-Selective Electroless Plating within Expanding Template Pores: Etching-Assisted Deposition of Spiky Nickel Nanotube Networks.

Nano-objects are favored structures for applications such as catalysis and sensing. Although they already provide a large surface-to-volume ratio, this ratio can be further increased by shape-selective plating of the nanostructure surfaces. This process combines the conformity of autocatalytic deposition with the defined nucleation and growth characteristics of colloidal nanoparticle syntheses. However, many aspects of such reactions are still not fully understood. In this study, we investigate in detail the growth of spiky nickel nanotubes in polycarbonate template membranes. One distinctive feature of our synthesis is the simultaneous growth of nanospikes on both the inside and outside of nanotubes while the tubes are still embedded in the polymer. This is achieved by combining the plating process with locally enhanced in situ etching of the poylmer template, for which we propose a theory. Electron microscopy investigations reveal twinning defects as the driving force for the growth of crystalline nanospikes. Deposit crystallinity is ensured by the reducing agent hydrazine. Iminodiacetic acid is not only used as a complexing agent during synthesis but apparently also acts as a capping agent and limits random nucleation on the spike facets. Finally, we apply our synthesis to templates with interconnected pores to obtain free-standing spiky nickel nanotube networks, demonstrating its ability to homogeneously coat substrates with extended inner surfaces and to operate in nanoscale confinement.

Empowering Electroless Plating to Produce Silver Nanoparticle Films for DNA Biosensing Using Localized Surface Plasmon Resonance Spectroscopy.

To facilitate the implementation of biosensors based on the localized surface plasmon resonance (LSPR) of metal nanostructures, there is a great need for cost-efficient, flexible, and tunable methods for producing plasmonic coatings. Due to its simplicity and excellent conformity, electroless plating (EP) is well suited for this task. However, it is traditionally optimized to produce continuous metal films, which cannot be employed in LSPR sensors. Here, we outline the development of an EP strategy for depositing island-like silver nanoparticle (NP) films on glass with distinct LSPR bands. The fully wet-chemical process only employs standard chemicals and proceeds within minutes at room temperature. The key step for producing spread-out NP films is an accelerated ripening of the silver seed layer in diluted hydrochloric acid, which reduces the nucleation density during plating. The reaction kinetics and mechanisms are investigated with scanning (transmission) electron microscopy (SEM/STEM), X-ray photoelectron spectroscopy (XPS), and UV-vis spectroscopy, with the latter enabling a convenient live monitoring of the deposition, allowing its termination at a stage of desired optical properties. The sensing capabilities of chemically deposited NP films as LSPR transducers are exemplified in DNA biosensing. To this end, a sensing interface is prepared using layer-by-layer (LbL) buildup of polyelectrolytes (PE), followed by adsorption and covalent immobilization of ssDNA. The obtained LSPR transducers demonstrate robustness and selectivity in sensing experiments with binding complementary and unrelated DNA strands.

Nucleation-Controlled Solution Deposition of Silver Nanoplate Architectures for Facile Derivatization and Catalytic Applications.

Due to their distinctive electronic, optical, and chemical properties, metal nanoplates represent important building blocks for creating functional superstructures. Here, a general deposition method for synthesizing Ag nanoplate architectures, which is compatible with a wide substrate range (flexible, curved, or recessed; consisting of carbon, silicon, metals, oxides, or polymers) is reported. By adjusting the reaction conditions, nucleation can be triggered in the bulk solution, on seeds and by electrodeposition, allowing the production of nanoplate suspensions as well as direct surface modification with open-porous nanoplate films. The latter are fully percolated, possess a large, easily accessible surface, a defined nanostructure with {111} basal planes, and expose defect-rich, particularly reactive edges in high density, making them compelling platforms for heterogeneous catalysis, and electro- and flow chemistry. This potential is showcased by exploring the catalytic performance of the nanoplates in the reduction of carbon dioxide, 4-nitrophenol, and hydrogen peroxide, devising two types of microreactors, and by tuning the nanoplate functionality with derivatization reactions.

Template-Free Electroless Plating of Gold Nanowires: Direct Surface Functionalization with Shape-Selective Nanostructures for Electrochemical Applications.

Metal nanowires (NWs) represent a prominent nanomaterial class, the interest in which is fueled by their tunable properties as well as their excellent performance in, for example, sensing, catalysis, and plasmonics. Synthetic approaches to obtain metal NWs mostly produce colloids or rely on templates. Integrating such nanowires into devices necessitates additional fabrication steps, such as template removal, nanostructure purification, or attachment. Here, we describe the development of a facile electroless plating protocol for the direct deposition of gold nanowire films, requiring neither templates nor complex instrumentation. The method is general, producing three-dimensional nanowire structures on substrates of varying shape and composition, with different seed types. The aqueous plating bath is prepared by ligand exchange and partial reduction of tetrachloroauric acid in the presence of 4-dimethylaminopyridine and formaldehyde. Gold deposition proceeds by nucleation of new grains on existing nanostructure tips and thus selectively produces curvy, polycrystalline nanowires of high aspect ratio. The nanofabrication potential of this method is demonstrated by producing a sensor electrode, whose performance is comparable to that of known nanostructures and discussed in terms of the catalyst architecture. Due to its flexibility and simplicity, shape-selective electroless plating is a promising new tool for functionalizing surfaces with anisotropic metal nanostructures.

Free-Standing Networks of Core-Shell Metal and Metal Oxide Nanotubes for Glucose Sensing.

Nanotube assemblies represent an emerging class of advanced functional materials, whose utility is however hampered by intricate production processes. In this work, three classes of nanotube networks (monometallic, bimetallic, and metal oxide) are synthesized solely using facile redox reactions and commercially available ion track membranes. First, the disordered pores of an ion track membrane are widened by chemical etching, resulting in the formation of a strongly interconnected pore network. Replicating this template structure with electroless copper plating yields a monolithic film composed of crossing metal nanotubes. We show that the parent material can be easily transformed into bimetallic or oxidic derivatives by applying a second electroless plating or thermal oxidation step. These treatments retain the monolithic network structure but result in the formation of core-shell nanotubes of altered composition (thermal oxidation: Cu2O-CuO; electroless nickel coating: Cu-Ni). The obtained nanomaterials are applied in the enzyme-free electrochemical detection of glucose, showing very high sensitivities between 2.27 and 2.83 A M-1 cm-2. Depending on the material composition, varying reactivities were observed: While copper oxidation reduces the response to glucose, it is increased in the case of nickel modification, albeit at the cost of decreased selectivity. The performance of the materials is explained by the network architecture, which combines the advantages of one-dimensional nano-objects (continuous conduction pathways, high surface area) with those of a self-supporting, open-porous superstructure (binder-free catalyst layer, efficient diffusion). In summary, this novel synthetic approach provides a fast, scalable, and flexible route toward free-standing nanotube arrays of high compositional complexity.

Self-Supporting Metal Nanotube Networks Obtained by Highly Conformal Electroless Plating.

We present a versatile approach for the fabrication of well-defined networks of interconnected metal nanotubes, which applies electroless plating to ion-track-etched polymer templates that enclose designed pore networks. In order to obtain self-supporting structures, the deposition reactions must be optimized to yield conformal nanoscale metal films on microstructured substrates possessing extensive inner surfaces. Using this route, gold, copper, silver, nickel, and platinum nanotube networks are synthesized. The resulting structures can be handled macroscopically and combine a large surface area with continuous mass transport and conduction pathways, rendering them promising for application in, for example, electrocatalysis and sensing. This potential is demonstrated by employing a gold nanotube network for the amperometric detection of hydrogen peroxide, in which excellent sensitivity, catalyst utilization, and stability is achieved.

Metal nanotubes and nanowires with rhombohedral cross-section electrolessly deposited in mica templates.

Electroless plating is a facile wet-chemical process for the creation of metal thin films on arbitrary substrates, which can be used to produce intricate nanomaterials. In this study, we demonstrate how nanotubes and nanowires can be electrolessly deposited in the rhombohedral pores of ion-track etched muscovite mica templates. Mutual optimization of the activation and plating reactions proved to be essential for the fabrication of well-defined nanostructures of an aspect ratio (length-to-diameter) of up to approximately 70. By repeating the activation procedure utilizing the redox couple Sn(II) and Ag(I), a high density of Ag nanoparticle seeds could be deposited on the template surface, which was required to initiate metal film nucleation with nanoscale homogeneity. Furthermore, it was necessary to adapt the plating reaction to ensure sufficient diffusion of the reagents into the depth of the template pores. To prove the flexibility of the process and to evaluate the effect of the intrinsic film morphology on the shape of the resulting nanostructures, three different plating reactions were applied (Ag, Au, Pt). If the size of the deposited metal particles approached the dimension of the template pores, only wire-like structures of moderate shape conformity were obtained. Electroless plating protocols which yield homogeneous deposits consisting of small nanoparticles allowed exact replication of the pore shape. Under consideration of the above-mentioned requirements, electroless plating displays an effective and versatile route toward the fabrication of parallel arrays of angular metal nanotubes and nanowires in the chemically and thermally robust mica templates. By simply immersing the templates in aqueous plating solutions for an appropriate time, well-defined metal nanomaterials for application in, for example, plasmonics, catalysis, or molecular separation are obtained.

Fabrication of single cylindrical Au-coated nanopores with non-homogeneous fixed charge distribution exhibiting high current rectifications.

We designed and characterized a cylindrical nanopore that exhibits high electrochemical current rectification ratios at low and intermediate electrolyte concentrations. For this purpose, the track-etched single cylindrical nanopore in polymer membrane was coated with a gold (Au) layer via electroless plating technique. Then, a non-homogeneous fixed charge distribution inside the Au-coated nanopore was obtained by incorporating thiol-terminated uncharged poly(N-isopropylacrylamide) chains in series to poly(4-vinylpyridine) chains, which were positively charged at acidic pH values. The functionalization reaction was checked by measuring the current-voltage curves prior to and after the chemisorption of polymer chains. The experimental nanopore characterization included the effects of temperature, adsorption of chloride ions, electrolyte concentration, and pH of the external solutions. The results obtained are further explained in terms of a theoretical continuous model. The combination of well-established chemical procedures (thiol and self-assembled monolayer formation chemistry, electroless plating, ion track etching) and physical models (two-region pore and Nernst-Planck equations) permits the obtainment of a new nanopore with high current rectification ratios. The single pore could be scaled up to multipore membranes of potential interest for pH sensing and chemical actuators.

Synthesis of nanoparticle/ligand composite thin films by sequential ligand self assembly and surface complex reduction.

Nanocomposite thin films consisting of ligand-connected metal nanoparticles were deposited by iteration of ligand assembly, surface complex formation and reduction. This novel and convenient approach combines characteristics of the layer-by-layer (LbL) and the successive ion layer adsorption and reaction (SILAR) techniques. In contrast to classical LbL assembly, the nanoparticle formation is performed in situ, avoiding separate reduction, protection and attachment steps. To demonstrate the versatility of the approach, different metal precursors (Pd, Ag and Au salts) and linkers (1,2-ethanedithiol, 1,4-benzenedithiol and polythiol) were applied. The formation of dithiol-linked nanoparticle films was confirmed by TEM and XPS. By combining the deposition protocol with ion track etched polycarbonate templates, nanotubes and nanowires with high aspect ratios of up to 300 could be fabricated.

Ligand-optimized electroless synthesis of silver nanotubes and their activity in the reduction of 4-nitrophenol.

A facile electroless plating procedure for the controlled synthesis of nanoscale silver thin films and derived structures such as silver nanotubes was developed and the products were characterized by SEM, TEM and EDS. The highly stable plating baths consist of AgNO(3) as the metal source, a suitable ligand and tartrate as an environmentally benign reducing agent. Next to the variation of the coordinative environment of the oxidizing component, the influence of the pH value was evaluated. These two governing factors strongly affect the plating rate and the morphology of the developing silver nanoparticle films and can be used to adapt the reaction to synthetic demands. The refined electroless deposition allows the fabrication of homogeneous high aspect-ratio nanotubes in ion track etched polycarbonate. Template-embedded metal nanotubes can be interpreted as parallelled microreactors. Following this concept, both the silver nanotubes and spongy gold nanotubes obtained by the use of the silver structures as sacrificial templates were applied in the reduction of 4-nitrophenol by sodium borohydride, proving to be extraordinarily effective catalysts.

4-(Dimethylamino)pyridine as a powerful auxiliary reagent in the electroless synthesis of gold nanotubes.

Gold nanotubes of small particle sizes down to 5 nm and high aspect ratios were synthesized in ion track etched polycarbonate following a rational reaction design. 4-(Dimethylamino)pyridine (DMAP) was employed to adjust the electroless deposition by interfering with the autocatalytically active gold surface. Modification of the pH value and DMAP concentration led to a wide range of products which were characterized by SEM, TEM, and EDS. Filigree nanotubes of 10-15 nm wall thickness and 5.0 ± 2.1 nm grain size were obtained as well as robust and free-standing structures proving homogeneous deposition along the whole template length of 30 µm. Template-supported gold nanotubes were applied in the UV-vis monitored reduction of 4-nitrophenol by sodium borohydride under pseudo-first-order conditions. They proved to be a reliable microfluidic system of excellent catalytic activity coming up with an apparent rate constant of 1.3 × 10(-2) s(-1). Despite a high flow rate, the reaction showed 99% conversion after a distance of just 60 µm.