Telechelic Research Articles

Synthesis and chemical recycling investigations of polythioureas

There is currently intensive research on the development of biobased polymers as potential alternatives to the environmentally hazardous isocyanate-based polyurethanes. In this context, polythioureas (PTUs) form a particularly attractive target because they can be synthesized by using isothiocyanates, a class of molecules that can be found in nature with expected low toxicity. Herein, a series of 16 PTUs with varied chemical structures, mostly being new polymers, have been synthesized and their possible chemical recycling pathways via thermally induced and acid-catalyzed depolymerizations have been investigated. The obtained PTUs showed a varied range of molecular weights (up to Mn ∼ 69.5 kDa), intrinsic viscosity (up to ∼6 dL/g), and glass transition temperatures (Tg ∼ 59–128 °C). Notably, we observed that the presence of aromatic segments lowered the thermal stability of the polymers, so they were generally easier to depolymerize (compared to those without aromatic groups), forming oligomers with controlled end-groups (i.e. telechelic polymers) that could be repolymerized. The obtained aliphatic PTUs were generally resistant against thermochemical depolymerizations, but they could be effectively depolymerized by sulfuric acid. The repolymerization methods depended on the end groups of the depolymerized products, which in this work included direct repolymerization of polythioureas (if the end groups contain ∼1:1 of isothiocyanates and amines) and copolymerizations with another monomer terephthaldehyde (if the end groups contain only amines). Our results provided a first comprehensive molecular insight into the synthetic and recycling possibilities of using isothiocyanates and polythioureas in the exploration of potential alternatives for isocyanates and polyurethanes.

Bottlebrush Midblocks Promote Colloidal Bridging of Telechelic Polymers.

Telechelic polymers are effective rheological modifiers that bridge between associative constituents to form elastic networks. The performance of linear telechelic chains, however, is controlled by entropic forces and thus suffers from an upper limit on bridge formation. This work overcomes this limitation by utilizing telechelic triblock copolymers containing bottlebrush midblocks. By comparing the rheological properties of emulsions linked by telechelic bottlebrush polymers to those containing linear chains, we determined that telechelic polymers with bottlebrush midblocks form elastic networks more efficiently. These enhanced rheological properties arise from the high stiffness of the bottlebrush midblocks, which offsets the entropic stretching penalty for bridge formation, enabling them to more readily form networks. This molecular-level control over polymer conformation in complex fluids opens avenues for designing highly elastic networks with minimal polymeric additives.

A General Strategy toward Enhanced Electrochemical and Mechanical Performance of Solid‐State Lithium Batteries through Constructing Covalently Bonded Electrode Materials/Electrolyte Interfaces

AbstractSolid‐state lithium batteries (SSLBs) offer inherent safety and high energy density for next‐generation energy storage, but the large interfacial resistance and poor physical connection between electrode materials and the solid electrolyte (SE) severely impede their practical applications. This work reports a general strategy to introduce covalent bonds between electrode materials and SE, not only reducing interfacial resistance but also enhancing electrochemical stability and mechanical robustness of SSLBs. The covalent bonding is accomplished by functionalizing electrode surfaces with C═C groups, enabling in situ copolymerization with telechelic polymers in the SE. This approach is applicable to various cathode/anode materials and SEs. Particularly, the SSLBs comprising LiFePO4 cathode, Li6.75La3Zr1.75Ta0.25O12/(polyethylene oxide (PEO)/lithium bis(trifluoromethylsulfonyl)imide (LiTFSI)/silk composite SE and metallic lithium anode exhibit a specific capacity of 158.4 mAh g−1 and can be cycled at 2 C for 2200 times with >80% retention. Additionally, the SSLBs containing the high nickel‐content LiNi0.96Co0.03Mn0.01O2 cathode can afford a high specific capacity of 201.8 mAh g−1. Comprehensive experimental examination and theoretical simulations confirm that the lowered interfacial resistance and intimately contacted electrode materials/electrolyte interfaces facilitate Li+ transport at different stages of charge. Furthermore, the covalently bonded electrode/electrolyte interfaces also endow SSLBs with outstanding mechanical stability, enabling flexible SSLB pouch cells to operate under various bending states without performance decay.

Thermal Solution Depolymerization of RAFT Telechelic Polymers.

Thermal solution depolymerization is a promising low-temperature chemical recycling strategy enabling high monomer recovery from polymers made by controlled radical polymerization. However, current methodologies predominantly focus on the depolymerization of monofunctional polymers, limiting the material scope and depolymerization pathways. Herein, we report the depolymerization of telechelic polymers synthesized by RAFT polymerization. Notably, we observed a significant decrease in the molecular weight (Mn) of the polymers during monomer recovery, which contrasts the minimal Mn shift observed during the depolymerization of monofunctional polymers. Introducing Z groups at the center or both ends of the polymer resulted in distinct kinetic profiles, indicating partial depolymerization of the bifunctional polymers, as supported by mathematical modeling. Remarkably, telechelic polymers featuring R-terminal groups showed up to 68% improvement in overall depolymerization conversion compared to their monofunctional analogues, highlighting the potential of these materials in chemical recycling and the circular economy.

Valence can control the nonexponential viscoelastic relaxation of multivalent reversible gels.

Gels made of telechelic polymers connected by reversible cross-linkers are a versatile design platform for biocompatible viscoelastic materials. Their linear response to a step strain displays a fast, near-exponential relaxation when using low-valence cross-linkers, while larger supramolecular cross-linkers bring about much slower dynamics involving a wide distribution of timescales whose physical origin is still debated. Here, we propose a model where the relaxation of polymer gels in the dilute regime originates from elementary events in which the bonds connecting two neighboring cross-linkers all disconnect. Larger cross-linkers allow for a greater average number of bonds connecting them but also generate more heterogeneity. We characterize the resulting distribution of relaxation timescales analytically and accurately reproduce stress relaxation measurements on metal-coordinated hydrogels with a variety of cross-linker sizes including ions, metal-organic cages, and nanoparticles. Our approach is simple enough to be extended to any cross-linker size and could thus be harnessed for the rational design of complex viscoelastic materials.

Structure-properties relationships of defined CNF single-networks crosslinked by telechelic PEGs

The high structural anisotropy and colloidal stability of cellulose nanofibrils' enable the creation of self-standing fibrillar hydrogel networks at very low solid contents. Adding methacrylate moieties on the surface of TEMPO oxidized CNFs allows the formation of more robust covalently crosslinked networks by free radical polymerization of acrylic monomers, exploiting the mechanical properties of these networks more efficiently. This technique yields strong and elastic networks but with an undefined network structure. In this work, we use acrylate-capped telechelic polymers derived from the step-growth polymerization of PEG diacrylate and dithiothreitol to crosslink methacrylated TEMPO-oxidized cellulose nanofibrils (MATO CNF). This combination resulted in flexible and strong hydrogels, as observed through rheological studies, compression and tensile loading. The structure and mechanical properties of these hydrogel networks were found to depend on the dimensions of the CNFs and polymer crosslinkers. The structure of the networks and the role of individual components were evaluated with SAXS (Small-Angle X-ray Scattering) and photo-rheology. A thorough understanding of hybrid CNF/polymer networks and how to best exploit the capacity of these networks enable further advancement of cellulose-based materials for applications in packaging, soft robotics, and biomedical engineering.

Interpenetrated and Bridged Nanocylinders from Self-Assembled Star Block Copolymers.

The design of functional polymeric materials with tunable response requires a synergetic use of macromolecular architecture and interactions. Here, we combine experiments with computer simulations to demonstrate how physical properties of gels can be tailored at the molecular level, using star block copolymers with alternating block sequences as a paradigm. Telechelic star polymers containing attractive outer blocks self-assemble into soft patchy nanoparticles, whereas their mirror-image inverted architecture with inner attractive blocks yields micelles. In concentrated solutions, bridged and interpenetrated hexagonally packed nanocylinders are formed, respectively, with distinct structural and rheological properties. The phase diagrams exhibit a peculiar re-entrance where the hexagonal phase melts upon both heating and cooling because of solvent-block and block-block interactions. The bridged nanostructure is characterized by similar deformability, extended structural coherence, enhanced elasticity, and yield stress compared to micelles or typical colloidal gels, which make them promising and versatile materials for diverse applications.

Shear thickening in suspensions of particles with dynamic brush layers.

Control of frictional interactions among liquid-suspended particles has led to tunable, strikingly non-Newtonian rheology via the formation of strong flow constraints as particles come into close proximity under shear. Typically, these frictional interactions have been in the form of physical contact, controllable via particle shape and surface roughness. We investigate a different route, where molecular bridging between nearby particle surfaces generates a controllable constraint to relative particle movement. This is achieved with surface-functionalized colloidal particles capable of forming dynamic covalent bonds with telechelic polymers that comprise the suspending fluid. At low shear stress this results in particles coated with a uniform polymer brush layer. Beyond an onset stress σ* the telechelic polymers become capable of bridging and generate shear thickening. Over the size range investigated, we find that the dynamic brush layer leads to dependence of σ* on particle diameter that closely follows a power law with exponent -1.76. In the shear thickening regime, we observe an enhanced dilation in measurements of the first normal stress difference N1 and reduction in the extrapolated volume fraction required for jamming, both consistent with an effective particle friction that increases with decreasing particle diameter. These results are discussed in light of predictions for suspensions of hard spheres and of polymer-grafted particles.

Understanding associative polymer self-assembly with shrinking gate fluorescence correlation spectroscopy.

The self-assembly of polymers is integral to their role in liquid formulations. In this study, we combine a dye whose lifetime is sensitive to the nanoviscosity of its local environment with shrinking gate fluorescence correlation spectroscopy (sgFCS) to study the self-assembly of a model telechelic polymer, hydrophobically modified ethoxylated urethane (HEUR). Fluorescence lifetime measurements show a monotonic increase in average lifetime with increasing HEUR concentration driven by a small fraction of dye (<1%) with long lifetimes strongly bound to HEUR. Despite this small fraction, sgFCS isolates the diffusional dynamics of the bound fraction with no a priori assumptions as to the distribution of lifetimes. Sensitivity is greatly enhanced compared to standard FCS, revealing micellar aggregates forming between 0.2 and 1 wt% followed by formation of a percolated network. This sgFCS approach, which we apply for the first time to polymers in this work, is readily extendable to any dye that changes lifetime on binding.

Phase Separation, Reaction Equilibrium, and Self-Assembly in Binary Telechelic Homopolymer Blends.

We study a binary blend of telechelic homopolymers that can form reversible AB-type bonds at the chain ends. Reversibly bonding polymers display novel material properties, including thermal tunability and self-healing, that are not found in conventional covalently bonded polymers. Previous studies of reversibly bonding polymer systems have been limited by the computational demand of accounting for an infinite number of possible reaction products in a spatially inhomogeneous, self-assembled structure. We demonstrate that newly developed theoretical models and numerical methods enable the simultaneous computation of phase equilibrium, reaction equilibrium, and self-assembly via self-consistent field theory. Phase diagrams are computed at a variety of physically relevant conditions and are compared with nonreactive analogues as well as previous experimental studies of telechelic polymer blends.

Synergistic Defect Healing and Device Encapsulation via Structure Regulation by Silicone Polymer Enables Durable Inverted Perovskite Photovoltaics with High Efficiency

AbstractPolymers play a crucial role in promoting the progress of high‐performance inverted perovskite solar cells (PSCs). However, few polymers have simultaneously achieved defect passivation and device encapsulation in PSCs. Herein, a telechelic silicone polymer (poly(dimethylsiloxane‐co‐methylsiloxane acrylate) [PDMA]) is introduced, which possesses crosslinking capability to enable structure regulation through a condensation reaction. By leveraging the advantages of the polymers before and after crosslinking, a synergistic strategy of defect healing and device encapsulation for PSCs is developed via the application of the targeted polymer. PDMA as additives anchors tightly at the grain boundaries (GBs) and bridges the perovskite grains, achieving defect passivation and GBs crosslinking, increasing the efficiency of inverted PSCs from 22.32% to 24.41%. Crosslinked PDMA (CPDMA) is used as an encapsulant to encapsulate the entire device, enabling non‐destructive encapsulation at room temperature and inhibiting perovskite degradation under photothermal aging. Remarkably, the PDMA‐modified device with CPDMA encapsulation maintains 98% of its initial efficiency after 1200 h under continuous illumination at 55 ± 5 °C and retains 95% of its original efficiency after 1000 h of damp heat testing, meeting one of the IEC61215:2016 standards.

Cocontinuous Nanostructures by Microphase Separation of Statistically Cross-Linked Polystyrene/Poly(2-vinylpyridine) Networks.

Cocontinuous polymeric nanostructures have drawn considerable attention due to their ability to combine distinct, percolation-dependent properties of two different polymer domains. Randomly end-linked copolymer networks (RECNs) have previously been shown to support the formation of disordered cocontinuous nanostructures across wide composition windows in a robust way. However, achieving highly efficient linking of telechelic polymers with excellent end-group fidelity often requires complex synthetic routes. As an alternative, we study here statistically cross-linked copolymer networks (SCCNs) composed of polystyrene and poly(2-vinylpyridine) (PS and P2VP) with cross-linkable allyl pendent groups that are conveniently synthesized by controlled radical copolymerization. Via selective extraction of P2VP, coupled with gravimetry, small-angle X-ray scattering, and electron microscopy, we find disordered cocontinuous phases across wide composition ranges (up to ≈ 35 wt %), approaching values previously determined for RECNs. Remarkably, even for samples that appear to exhibit full percolation, a substantial fraction of P2VP (≈ 20-30 wt %) cannot be removed, which we ascribe to short strands between nearby cross-linkers that are physically embedded within PS domains. The resulting PS porous monoliths with residual surface P2VP layers enable facile surface modification to resist protein adsorption and templating of porous gold nanostructures.

Thermoreversible Gelation with Supramolecularly Polymerized Cross-Link Junctions.

Structure and reversibility of cross-link junctions play pivotal roles in determining the nature of thermoreversible gelation and dynamic mechanical properties of the produced polymer networks. We attempt to theoretically explore new types of sol-gel transitions with mechanical sharpness by allowing cross-links to grow without upper bound. We consider thermoreversible gelation of the primary molecules R{Af} carrying the number f of low molecular weight functional groups (gelators) A. Gelators A are assumed to form supramolecular assemblies. Some examples are: telechelic polymers (f=2) carrying π-π stacking benzene derivatives at their both ends, and trifunctional star molecules (f=3) bearing multiple hydrogen-bonding gelators. The sol-gel transition of the primary molecules becomes sharper with the cooperativity parameter of the stepwise linear growth of the cross-links. There is a polymerization transition (crossover without singularity) of the junctions in the postgel region after the gel point is passed. If the gelator A tends to form supramolecular rings competitively with linear chains, there is another phase transition in the deep postgel region where the average molecular weight of the rings becomes infinite (Bose-Einstein condensation of rings). As a typical example of binary cross-links where gelators A and B form mixed junctions, we specifically consider metal-coordinated binding of ligands A by metal ions B. Two types of multi-nuclear supramolecular complexes are studied: (i) linear stacking (ladder) of the sandwich A2B units, and (ii) linear train of egg-box A4B units. To find the strategy towards experimental realization of supramolecular cross-links, the average molecular weight, the gel fraction, the average length of the cross-link junctions are numerically calculated for all of these models as functions of the functionality f, the concentration of the solute molecules, and the temperature. Potential candidates for the realization of these new types of thermoreversible gelation are discussed.

Colloidally Stable Graphite Oleogels by Pyrene-Functionalized Telechelic Polymers for Friction and Wear Reduction.

Although graphite derivatives, such as graphene, graphene oxide, and reduced graphene oxide, have been widely used as lubricating oil additives to reduce friction and wear, their synthesis either proceeds with complicated procedures in low yield, suffering from high cost, or involves the utilization of highly corrosive chemicals, raising safety and environmental concerns. Therefore, the direct use of pristine graphite as a lubricating oil additive is indispensable for practical tribological applications. However, the realization of this idea has been seriously hampered by the incompatibility of graphite with lubricating base oils. In this work, we report a rational strategy to directly disperse graphite in base oils in the form of oleogels assisted by pyrene functionalized telechelic polymers under mild condition. The resulting oleogels exhibit long-time colloidal stability for more than one year, wherein the graphite has been exfoliated to in situ form graphene through π-π interactions with the pyrene-containing telechelics. Moreover, compared with the base oil, the graphite-based oleogels are found to exhibit remarkable reductions in friction and wear by up to 52% and 97%, respectively. Significantly, such tribological performances are comparable to those of exfoliated graphite derivatives. Taken collectively, directly using pristine graphite as a lubricating oil additive with superior tribological properties represents a revolutionary approach to create low-cost, green, and high-performance lubricants just based on pristine layered materials without involving any pre-exfoliations.

Landscape of Network Connectivity in Transient Polymer Networks with Competing Homo- and Hetero-complementary Bonds

Polymer networks expose a wide range of mechanical properties depending on their microstructure and connectivity. Specifically, transient networks based on end-linking of mixed telechelic polymer precursors capable of forming competing homo- and hetero-complementary bonds demonstrate a wide range of network structures and consequently mechanical properties depending on the composition and reactivity of employed precursors. To address this gap, the Miller–Macosko’s recursive model is extended to tetra-arm polymer precursors capable of forming homo- and hetero-complementary bonds. As such, the composition and time evolution of n-fold network connectivities are visualized as a function of precursor composition and bond selectivity. The model potential is highlighted by confronting its predictions with the rheological behavior of transient metallo-supramolecular polymer networks (MSPNs) obtained by mixing tetra-arm poly(ethylene glycol) functionalized with either sterically demanding mesitylene-substituted phenanthroline or unsubstituted slim phenanthroline or terpyridine ligands. The former precursor is incapable of homoleptic complexation; however, in combination with the latter two, they can form a mixture of homo- and heteroleptic complexes, depending on the coordination geometry preference of the utilized metal ion. These results not only visualize the connectivity landscape that can be explored in transient polymer networks, even beyond MSPNs, but can also provide a selectivity index for competing transient bonds based on rheological properties.

Covalently Crosslinked Networks from Telechelic Polycyclooctene with Reinforced Properties

Comprehensive SummaryIntroducing covalently crosslinked network to telechelic polymers can enable the formation of advanced polymeric materials with enhanced material properties. In this contribution, well‐defined telechelic polymers bearing acetoacetate groups were synthesized via Ru‐catalyzed ring‐opening metathesis polymerization of cyclooctene in the presence of chain transfer agents. Given the unique feature of muti‐site reactive acetoacetate end groups, several crosslinked networks were constructed using different crosslinkers under mild conditions. In the Michael addition reaction system, the introduction of di/trifunctional aliphatic acrylate as crosslinkers significantly enhanced the mechanical properties of the generated crosslinked network (tensile strength up to 27 MPa, elongation at break up to 500%). On the other hand, vitrimers with dynamic covalent crosslinked networks were accessed via transamination of vinylogous urethane reaction using telechelic polymers and tris(2‐aminoethyl)amine. These vitrimers presented great mechanical properties and reprocessing properties. These strategies can be potentially applied to construct other types of high‐performance polymeric materials.

Toward high-performance lubricants: Rational design and construction of supramolecular oil gels by amphiphilic telechelic polymers to stabilize two-dimensional nanomaterials in base oils

Two-dimensional (2D) nanomaterials have long been promised as environment-friendly lubricant additives. However, their agglomeration in base oils have largely limited their practical applications. Here, we report the supramolecular oil gels constructed by amphiphilic telechelic polymers poly(2-hydroxyethyl methacrylate)-block-poly(stearyl methacrylate)-block-poly(2-hydroxyethyl methacrylate) in base oils. 2D nanomaterials GO, h-BN, and g-C3N4 can be homogeneously stabilized in the oil gels over one year, which are the most stable oil dispersions of the 2D nanomaterials reported to date. The oil gels demonstrate excellent lubricating performance, which could be attributed to the 60 − 90 nm thick tribofilms formed on the worn areas. These supramolecular oil gels not only represent an efficient and versatile platform for stabilizing 2D nanomaterials, but also a universal strategy to explore high-performance lubricants.

Low-Viscosity Polydimethylsiloxane Resin for Facile 3D Printing of Elastomeric Microfluidics.

Microfluidics is a rapidly advancing technology with expansive applications but has been restricted by slow, laborious fabrication techniques for polydimethylsiloxane (PDMS)-based devices. Currently, 3D printing promises to address this challenge with high-resolution commercial systems but is limited by a lack of material advances in generating high-fidelity parts with micron-scale features. To overcome this limitation, a low-viscosity, photopolymerizable PDMS resin was formulated with a methacrylate-PDMS copolymer, methacrylate-PDMS telechelic polymer, photoabsorber, Sudan I, photosensitizer, 2-isopropylthioxanthone, and a photoinitiator, 2,4,6-trimethyl benzoyl diphenylphosphine oxide. The performance of this resin was validated on a digital light processing (DLP) 3D printer, an Asiga MAX X27 UV. Resin resolution, part fidelity, mechanical properties, gas permeability, optical transparency, and biocompatibility were investigated. This resin produced resolved, unobstructed channels as small as 38.4 (±5.0) µm tall and membranes as thin as 30.9 (±0.5) µm. The printed material had an elongation at break of 58.6% ± 18.8%, Young's modulus of 0.30 ± 0.04 MPa, and was highly permeable to O2 (596 Barrers) and CO2 (3071 Barrers). Following the ethanol extraction of the unreacted components, this material demonstrated optical clarity and transparency (>80% transmission) and viability as a substrate for in vitro tissue culture. This paper presents a high-resolution, PDMS 3D-printing resin for the facile fabrication of microfluidic and biomedical devices.

Short-Loop Chemical Recycling via Telechelic Polymers for Biobased Polyesters with Spiroacetal Units

Spirocyclic acetal structures have recently received growing attention in polymer science due to their dual potential to raise the glass transition temperature (Tg) and enable chemical recycling of biobased polymers. In the present work, a vanillin-based diol with a spirocyclic acetal structure was incorporated in a series of rigid amorphous polyesters based on neopentyl glycol and dimethyl terephthalate (DMT). Up to 50 mol % of spirocyclic diol (with respect to DMT) could be incorporated in the copolyesters, but a reasonably high molecular weight was only achieved when ≤30 mol % of the spirocyclic diol was used. The presence of the spiroacetal units in the polyesters not only enhanced the Tg (up to 103 °C) and thermal stability (T5 ≥ 300 °C) but also the oxygen barrier of solution-cast films. We found that the acetal units in the copolyesters could be selectively hydrolyzed under acidic conditions while virtually retaining all of the ester bonds in the polymer backbone. After acidic hydrolysis, telechelic polymers exclusively terminated by two aldehyde end groups were obtained. In this work, we have demonstrated that these telechelic polyesters can be conveniently converted back into poly(acetal-ester)s via cycloacetalization reactions with pentaerythritol.

Brownian dynamics simulations of telechelic polymer - latex suspensions under steady shear.

We carry out coarse-grained Brownian dynamics simulations of shearing flow of a colloidal suspension bridged by telechelic polymers with "sticky" end groups and vary sticker strength ε over a range from 3 to 12 in units of kBT, motivated by an interest in simulating the rheology of latex paints. The most extensive results are obtained for dumbbells, but the trends are confirmed for 3-bead trumbbells and chains of up to 11 beads. The numbers of colloids and of polymers are also varied over a wide range to confirm trends established for smaller, more computationally affordable, systems. The dynamics are the result of an interplay of the shear rate and three different times scales: the time τBridge for a sticker on a bridging chain to be released from a particle surface, which scales as exp(0.77ε), the time for the polymer chain to relax, τR, which scales as the square of polymer chain length, and the time τD for a colloid to diffuse a distance comparable to its own radius, R, which scales as R3. The scalings of the bridge-to-loop and loop-to-bridge times namely τBL ∝ exp (0.75ε) and τLB ∝ exp (0.71ε), are similar to those of τBridge, for ε values above around 5 kBT, because of the relatively short chains considered here (i.e., 60 Kuhn steps). However, τR becomes more dominant for longer chains, as shown by Travitz and Larson. The zero-shear viscosity η0 is estimated from the Green-Kubo relation, and found to scale as exp (0.69ε), similar to that of τBridge. A weak influence of η0 on τD is observed, with the influence expected to become stronger when τD becomes larger, as shown previously by Wang and Larson. At shear rates in the nonlinear regime, shear-thinning is found with exponents ≈ -0.10 to -0.60, and the first normal stress difference is positive, consistent with some of the experimental data of Chatterjee et al. on model latex paint formulations. The weakness of the shear thinning, relative to that of hydrophobically modified ethoxylated urethane (HEUR) solutions without colloids, is likely due to the observed insensitivity of the loop-to-bridge and bridge-to-loop transition times to the imposed shear rate. This preliminary study provides the first mesoscale simulations of these suspensions, useful for assessing and improving both more accurate multi-scale models and eventually constitutive equations for these complex suspensions.