A record-high EQE of 7.65%@3300 cd m-2 achieved in non-doped near-ultraviolet OLEDs based on novel D'-D-A type bipolar fluorophores upon molecular configuration engineering.

Developing a high-performance near-ultraviolet (NUV) material and its simple non-doped device with a small efficiency roll-off and good color purity is a promising but challenging task. Here, we proposed a novel donor'-donor-acceptor (D'-D-A) type molecular strategy to largely solve the intrinsic contradictions among wide-bandgap NUV emission, fluorescence efficiency, carrier injection and transport. An efficient NUV fluorophore, 3,6-mPPICNC3, exhibiting a hybridized local and charge-transfer state, is achieved through precise molecular configuration engineering, realizing similar hole and electron mobilities at both low and high electric fields. Moreover, the planarized intramolecular charge transfer excited state and steric hindrance effect endow 3,6-mPPICNC3 with a considerable luminous efficiency and good color purity in the aggregation state. Consequently, the non-doped device emitting stable NUV light with Commission Internationale de l'Eclairage (CIE) coordinates of (0.160, 0.032) and a narrow full width at half maximum of 44 nm exhibits a state-of-the-art external quantum efficiency (EQE) of 7.67% and negligible efficiency roll-off over a luminance range from 0 to 3300 cd m-2. This is a record-high efficiency among all the reported non-doped NUV devices. Amazingly, an EQE of 7.85% and CIE coordinates of (0.161, 0.025) are achieved in the doped device. This demonstrates that the D'-D-A-type molecular structure has great potential for developing high-performance organic light-emitting materials and their optoelectronic applications.

The Shear-Accelerated II-I Phase Transition of Isotactic Poly(1-Butene).

The II-I phase transition of isotactic poly(1-butene) (iPBu) leads to improved mechanical performance. However, this will take several weeks and increase storage and processing costs. In this work, shear forces are introduced into the supercooled iPBu melt, and the effects of isothermal crystallization temperature (Tc) and shear temperature (Tshear) on crystallization and phase transition are explored. Shear-induced transcrystalline morphology of Form II with a significantly shortened crystallization induction period can be observed at relatively high Tc (105 °C). Besides, the shear-induced Form II can transit to Form I faster than the unsheared one. In addition, the phase transition rate increases as the Tshear decreases, with the fastest rate occurring at Tshear of 120 °C. The half transition time (t1/2) is measured as 6.3 h when Tc = 105 °C, Tshear = 120 °C, which is much shorter than the 20.7 h required for unsheared samples. The accelerated phase transition of iPBu can be attributed to the stretching of molecular chains, resulting from shear treatment. This study provides a quantitative analysis of the influence of the shear treatment and the Tshear on the II-I phase transition rate. It also presents a cost-effective and straightforward approach for expediting the phase transition process.

Enhancing Light-Emitting Efficiency of Blue Through-Space Charge Transfer Emitters via Fixing Configuration Induced by Intramolecular Hydrogen Bonding.

Closely aligned configuration of the donor (D) and acceptor (A) is crucial for the light-emitting efficiency of thermally activated delayed fluorescence (TADF) materials with through-space charge transfer (TSCT) characteristics. However, precisely controlling the D-A distance of blue TSCT-TADF emitters is still challenging. Herein, an extra donor (D*) located on the side of the primary donor (D) is introduced to construct the hydrogen bonding with A and thus modulate the distance of D and A units to prepare high-efficiency blue TSCT emitters. The obtained "V"-shaped TSCT emitter presents a minimal D-A distance of 2.890 Å with a highly parallel D-A configuration. As a result, a high rate of radiative decay (>107 s-1) and photoluminescence quantum yield (nearly 90%) are achieved. The corresponding blue organic light-emitting diodes show maximum external quantum efficiencies (EQEmax) of 27.9% with a Commission Internationale de L'Eclairage (CIE) coordinate of (0.16, 0.21), which is the highest device efficiency of fluorene-based blue TSCT-TADF emitters. In addition, the TSCT-TADF emitter-sensitized OLEDs also achieve a high EQEmax of 29.3% with a CIE coordinate of (0.12, 0.16) and a narrow emission.

High Mobility Emissive Excimer Organic Semiconductor Towards Color-Tunable Light-Emitting Transistors.

Organic light-emitting transistors (OLETs) are highly integrated and minimized optoelectronic devices with significant potential superiority in smart displays and optical communications. To realize these various applications, it is urgently needed for color-tunable emission in OLETs, but remains a great challenge as a result of the difficulty for designing organic semiconductors simultaneously integrating high carrier mobility, strong solid-state emission, and the ability for potential tunable colors. Herein, a high mobility emissive excimer organic semiconductor, 2,7-di(2-anthryl)-9H-fluorene (2,7-DAF) was reasonably designed by introducing a rotatable carbon-carbon single bond connecting two anthracene groups at the 2,7-sites of fluorene, and the small torsion angles simultaneously guarantee effective conjugation and suppress fluorescence quenching. Indeed, the unique stable dimer arrangement and herringbone packing mode of 2,7-DAF single crystal enables its superior integrated optoelectronic properties with high carrier mobility of 2.16 cm2 ⋅ V-1 ⋅ s-1 , and strong excimer emission with absolute photoluminescence quantum yield (PLQY) of 47.4 %. Furthermore, the voltage-dependent electrically induced color-tunable emission from orange to blue was also demonstrated for an individual 2,7-DAF single crystal based OLETs for the first time. This work opens the door for a new class of high mobility emissive excimer organic semiconductors, and provides a good platform for the study of color-tunable OLETs.

Epitaxy-Directed Self-Assembly of Copolymers and Polymer Blends.

Directed self-assembly of materials into patterned structures is of great importance since the performance of them depends remarkably on their multiscale hierarchical structures. Therefore, purposeful structural regulation at different length scales through crystallization engineering provides an opportunity to modify the properties of polymeric materials. Here, an epitaxy-directed self-assembly strategy for regulating the pattern structures including phase structure as well as crystal modification and orientation of each component for both copolymers and polymer blends is reported. Owing to the specific crystallography registration between the depositing crystalline polymers and the underlying crystalline substrate, not only order phase structure with controlled size at nanometer scale but also the crystal structure and chain orientation of each component within the separated phases for both copolymers and polymer blend systems can be precisely regulated.

Adjusting the Electron-Withdrawing Ability of Acceptors in Thermally Activated Delayed Fluorescence Conjugated Polymers for High-Performance OLEDs.

Constructing high-performance solution-processed organic light-emitting diodes (OLEDs) based on thermally activated delayed fluorescence (TADF) conjugated polymers remains a challenging issue. The electron-withdrawing ability of acceptors in TADF units significantly affects the TADF properties of the conjugated polymers. Herein, we have designed three TADF conjugated polymers, in which phenoxazine donors and anthracen-9(10H)-one acceptors are incorporated into the polymeric backbones and side chains, respectively, and the carbazole derivative is copolymerized as the host. By incorporating different heteroatoms, such as nitrogen, oxygen, or sulfur, with slightly different electronegativities into anthracen-9(10H)-one, the effect of the electron-withdrawing ability of the acceptor on the performance of conjugated TADF polymer-based OLEDs is thus systematically studied. It is found that the introduction of a nitrogen atom can enhance the spin-orbital coupling and RISC process due to the modulated energy levels and nature of the excited states. As a result, the solution-processed OLEDs based on the prepared polymer p-PXZ-XN display an excellent comprehensive performance with an EQEmax of 17.6%, a low turn-on voltage of 2.8 V, and a maximum brightness of 14750 cd m-2. Notably, the efficiency roll-off is quite low, maintaining 15.1% at 1000 cd m-2, 12.1% at 3000 cd m-2, and 6.1% at 10000 cd m-2, which ranks in the first tier among the reported TADF conjugated polymers. This work provides a guideline for constructing high-efficiency TADF polymers.

Unravelling the Superiority of Nonbenzenoid Acepleiadylene as a Building Block for Organic Semiconducting Materials.

Acepleiadylene (APD), a nonbenzenoid isomer of pyrene, exhibits a unique charge-separated character with a large molecular dipole and a small optical gap. However, APD has never been explored in optoelectronic materials to take advantage of these appealing properties. Here, we employ APD as a building block in organic semiconducting materials for the first time, and unravel the superiority of nonbenzenoid APD in electronic applications. We have synthesized an APD derivative (APD-IID) with APD as the terminal donor moieties and isoindigo (IID) as the acceptor core. Theoretical and experimental investigations reveal that APD-IID has an obvious charge-separated structure and enhanced intermolecular interactions as compared with its pyrene-based isomers. As a result, APD-IID displays significantly higher hole mobilities than those of the pyrene-based counterparts. These results imply the advantages of employing APD in semiconducting materials and great potential of nonbenzenoid polycyclic arenes for optoelectronic applications.

Regulating the Nature of Triplet Excited States of Thermally Activated Delayed Fluorescence Emitters.

ConspectusCharacterized by the reverse intersystem crossing (RISC) process from the triplet state (T1) to the singlet state (S1), thermally activated delayed fluorescence (TADF) emitters, which produce light by harvesting both triplet and singlet excitons without noble metals, are considered to be third-generation organic electroluminescent materials. Rapid advances in molecular design criteria, understanding the photophysics underlying TADF, and applications of TADF materials as emitters in organic light-emitting diodes (OLEDs) have been achieved. Theoretically, enhanced spin-orbit coupling (SOC) between singlet and triplet states can result in a fast RISC process and thus a high light-emitting efficiency according to Fermi's golden rule. Therefore, regulating the nature of triplet excited states by elaborate molecular design to improve SOC is an effective approach to high-efficiency TADF-based OLEDs. Generally, on one hand, the increased local excited (LE) populations of the excited triplet state can significantly improve the nature flips between S1 and T1. On other hand, the reduced energy gap between S1 and the lowest triplet with a charge transfer (CT) characteristic can also enhance their vibronic coupling. Consequently, it is vital to determine how to regulate the nature of triplet excited states by molecular design to guide the material synthesis, especially for polymeric emitters.In this Account, we focus on modulating the strategy of triplet excited states for TADF emitters and an in-depth understanding of the photophysical processes, leading to optimized OLED device performance. We include several kinds of strategies to control the nature of triplet excited states to guide the synthesis of small-molecule and polymer TADF emitters: (1) Modulating the electronic distribution of conjugated polymeric backbones by copolymerizing the electron-donating host: accordingly, the nature of excited states can be changed, especially for triplets. Meanwhile, the utilization of excitons can be systematically improved by adjusting the electronic structure of triplet states with long-range distribution in the conjugated polymeric backbones. (2) Halogenating acceptors of TADF units: the introduced halogen atoms would reestablish the electronic distribution of the triplet and relocate the hole orbits, resulting in a CT and LE hybrid nature of a triplet transformed into a LE-predominant state, which favors the RISC process. (3) Stereostructure regulation: by constructing a diverse arrangement of three-dimensional spatial configurations or conjugated architectures, the nature of the triplet can also be finely tuned, such as hyperbranched structures with multiple triplet-singlet vibration couplings, half-dendronized-half-encapsulated asymmetric systems, trinaphtho[3,3,3] propeller-based three-dimensional spatial interspersed structures, intramolecular close-packed donor-acceptor systems, and so on. We hope that this Account will provide insights into new structures and mechanisms for achieving high-performance OLEDs based on regulating the nature of triplet excited states.

Strain-induced 3D-oriented crystallites in natural rubber/chitin nanofiber composites.

Natural rubber (NR) composites containing bio-based chitin nanofibers (ChNFs) exhibit a wide range of mechanical properties - from rubber to plastic behavior - with increasing chitin contents. A constrained 3-dimensional network can be formed by mixing natural rubber latex and a modified zwitterionic rigid chitin counterpart. By inclusion of highly anisotropic chitin nanofibers (30 wt%), strain-induced NR crystallization occurs at a much lower strain of 50%. More intriguingly, 2D-WAXD results reveal that the strain-induced crystallization of NR/ChNFs composites show 3-dimensionally oriented crystallite formation behaving similar to "3D-single crystals orientation" when the content of ChNFs is over 5 wt%. It is suggested that not only c-axis (NR chains) orients along the stretching direction, but also the a- and b-axes deliberately arrange along the normal direction and transverse direction, respectively. Structure and morphology in 3-dimensional spaces after strain-induced crystallization of the NR/ChNFs30 composite are investigated in detail. Therefore, this study might pave a new way to enhance mechanical properties by incorporation of ChNFs, obtaining 3-dimensionally oriented crystallites of novel multifunctional NR/ChNFs composite with shape memory ability.

Flame-Retardant and Smoke-Suppressant Flexible Polyurethane Foams Based on Phosphorus-Containing Polyester Diols and Expandable Graphite.

A liquid-phosphorus-containing polyester diol, PPE, was prepared via condensation polymerization using commercial reactive flame retardant 9,10-dihydro-10-[2,3-di(hydroxycarbonyl)propyl]-10-phospha-phenanthrene-10-oxide, adipic acid, ethylene glycol, and 1,4-butanediol. PPE and/or expandable graphite (EG) were then incorporated into phosphorus-containing flame-retardant polyester-based flexible polyurethane foams (P-FPUFs). The structure and properties of the resultant P-FPUFs were characterized using scanning electron microscopy tensile measurements, limiting oxygen index (LOI), vertical burning tests, cone calorimeter tests, thermogravimetric analysis coupled with Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy. Unlike the FPUF prepared using regular polyester polyol (R-FPUF), PPE increased the flexibility and elongation at break of the resultant forms. More importantly, the peak heat release rate (PHRR) and total heat release (THR) of P-FPUF were reduced by 18.6% and 16.3%, respectively, via gas-phase-dominated flame-retardant mechanisms, compared with those of R-FPUF. The addition of EG further reduced the peak smoke production release (PSR) and total smoke production (TSP) of the resultant FPUFs while increasing the LOI and char formation. Interestingly, it was observed that EG noticeably improved the residual quantity of phosphorus in the char residue. When the EG loading was 15 phr, the resulting FPUF (P-FPUF/15EG) attained a high LOI value (29.2%) and exhibited good anti-dripping performance. Meanwhile, the PHRR, THR, and TSP of P-FPUF/15EG were significantly decreased by 82.7%, 40.3%, and 83.4%, respectively, compared with those of P-FPUF. This superior flame-retardant performance can be attributed to the combination of the bi-phase flame-retardant behavior of PPE and condensed-phase flame-retardant characteristics of EG.

Hyperbranched Conjugated Polymer with Multiple Charge Transfer Enables High-Efficiency Nondoped Red Electroluminescence with Low Driving Voltage.

Conjugated polymers featuring thermally activated delayed fluorescence (TADF) attract tremendous attention in both academic and industry communities due to their easy solution processing for fabricating large-area and low-cost high-performance polymer light-emitting diodes (PLEDs). However, current nondoped solution-processed PLEDs frequently encounter significant efficiency roll-offs and unreasonably high operating voltages at high brightness, especially for red-emitting polymers. Herein, we design hyperbranched conjugated polymers (HCPs) with D-A-D type TADF characteristics for high-performance red-emitting PLEDs. Multiple intramolecular charge transfer (ICT) channels induced by quasi-equivalent donors of the TADF core strongly boost the reverse intersystem crossing (RISC) process and singlet excitons radiative transition. Coupling with the efficient energy transfer process generated by structure advantages of HCPs, the strongly electron-withdrawing oxygen atoms located on the TADF cores further accelerate hole transportation from the host chains to the TADF cores. Under a rational regulation of the TADF core ratio, the related nondoped red-emitting device performs an outstanding performance with an EQEmax of 8.39% and exhibits no roll-off while the luminance is less than 100 cd/m2 and only 3.3% decrease at 500 cd/m2. Simultaneously, the EQE can maintain 7.4% under 1000 cd/m2. Furthermore, the corresponding nondoped device exhibits a low turn-on voltage of around 2.5 V and achieves a luminance of 500 cd/m2 at 3.5 V and even 1000 cd/m2 at 3.9 V. To our knowledge, this is the best performance among all nondoped red PLEDs with high brightness obtained at low operating voltage.

Structurally Regulated Carbazole-Pyridine Derivatives Based on Space-Crowded Theory for Efficient Narrowband Ultraviolet Nondoped Organic Light-Emitting Diodes from the High-Lying Reverse Intersystem Crossing Process.

Achieving ultraviolet and narrowband emission simultaneously in nondoped organic light-emitting diodes (OLEDs) remains a tremendous challenge. Here, a "space-crowded donor-acceptor-donor" molecular design strategy is proposed for developing ultraviolet pure organic fluorophores by the nearby substituted positions at the phenyl linker between carbazole and pyridine units. Benefitting from the large steric hindrance effect, multiple intramolecular interactions, and low-frequency vibronic coupling dominated excited state property, all the emitters exhibit excellent fluorescence efficiencies at the solid state as well as the narrow full width at half maximums (FWHMs). Moreover, the effect of different substitution positions of pyridine on the structure-property relationship is also revealed. Consequently, the nondoped OLEDs exhibit an electroluminescence emission peak of 397 nm with FWHMs of 17 and 22 nm. Due to the high-lying reverse intersystem crossing process, external quantum and exciton utilization efficiencies of 3.6 and 54.55%, respectively, have been achieved based on the emitter with para-linkage. These findings may pave an avenue for the development of high-performance narrowband ultraviolet materials and OLEDs.

Temperature-Dependent Polymorphism and Phase Transformation of Friction Transferred PLLA Thin Films.

Poly(L-lactic acid) (PLLA) thin films with a highly oriented structure, successfully prepared by a fast friction transfer technique, were investigated mainly on the basis of synchrotron radiation wide-angle X-ray diffraction (WAXD) and Fourier transform infrared spectroscopy (FTIR). The crystalline structure of the highly oriented PLLA film was remarkably affected by friction transfer temperatures, which exhibited various crystal forms in different friction temperature regions. Interestingly, metastable ß-form was generated at all friction transfer temperatures (70-140 °C) between Tg and Tm, indicating that fast friction transfer rate was propitious to the formation of ß-form. Furthermore, the relative content among ß-, α'-, and α-forms at different friction temperatures was estimated by WAXD as well as FTIR spectroscopy. In situ temperature-dependent WAXD was applied to reveal the complicated phase transition behavior of PLLA at a friction transfer temperature of 100 °C. The results illustrated that the contents of ß- and α'-forms decreased in turn, whereas the α-form increased in content due to partially melt-recrystallization or crystal perfection. Moreover, by immersing into a solvent of acetone, ß-, α'-form were transformed into stable α-crystalline form directly as a consequence. The highly oriented structure was maintained with the chain perfectly parallel to friction transfer direction after acetone treatment, evidenced by polarized FTIR and polarized optical microscopy (POM) measurements.

Constructing high-efficiency orange-red thermally activated delayed fluorescence emitters by three-dimension molecular engineering.

Preparing high-efficiency solution-processable orange-red thermally activated delayed fluorescence (TADF) emitters remains challenging. Herein, we design a series of emitters consisting of trinaphtho[3,3,3]propellane (TNP) core derivatized with different TADF units. Benefiting from the unique hexagonal stacking architecture of TNPs, TADF units are thus kept in the cavities between two TNPs, which decrease concentration quenching and annihilation of long-lived triplet excitons. According to the molecular engineering of TADF and host units, the excited states can further be regulated to effectively enhance spin-orbit coupling (SOC) processes. We observe a high-efficiency orange-red emission at 604 nm in one instance with high SOC value of 0.862 cm-1 and high photoluminescence quantum yield of 70.9%. Solution-processable organic light-emitting diodes exhibit a maximum external quantum efficiency of 24.74%. This study provides a universal strategy for designing high-performance TADF emitters through molecular packing and excited state regulation.

Spatially Confined Fabrication of Polar Poly(Vinylidene Fluoride) Nanotubes.

Polar poly(vinylidene fluoride) (PVDF) nanotubes have attracted significant attention due to their excellent piezoelectric and ferroelectric properties, yet a tunable fabrication of homogeneous polar PVDF nanotubes remains a challenge. Here, a simple method is reported to fabricate polar PVDF nanotubes using anodize aluminum oxide (AAO) membranes as templates that are removed by etching in a potassium hydroxide (KOH) solution and then ageing at room temperature. PVDF nanotubes originally crystallized in the AAO membrane are pure α-crystals with very low crystallinity, yet after being released from the templates, the crystallinity of the nanotubes markedly increases with ageing at room temperature, leading to the formation of ß-PVDF crystals in a very short time, with the formation of γ crystals after longer ageing times. A large amount of γ crystals formed when the released PVDF nanotubes are heated to ≈130 °C. The formation of polar PVDF nanotubes released from the AAO templates treated with higher concentrations of alkaline solution results from the reaction of the surface of the PVDF nanotubes with the alkaline solution and structure reorganization under confined conditions. This large-scale preparation of ß- and γ-PVDF opens a new pathway to produce polar PVDF nanomaterials.

Correction: Synthesis and properties of siloxane modified perylene bisimide discotic liquid crystals.

Correction for 'Synthesis and properties of siloxane modified perylene bisimide discotic liquid crystals' by Tingjie Zhang et al., Soft Matter, 2013, 9, 10739-10745, https://doi.org/10.1039/C3SM52054D.

Advances and Challenges of Self-Healing Elastomers: A Mini Review.

In the last few decades, self-healing polymeric materials have been widely investigated because they can heal the damages spontaneously and thereby prolong their service lifetime. Many ingenious synthetic procedures have been developed for fabricating self-healing polymers with high performance. This mini review provides an impressive summary of the self-healing polymers with fast self-healing speed, which exhibits an irreplaceable role in many intriguing applications, such as flexible electronics. After a brief introduction to the development of self-healing polymers, we divide the development of self-healing polymers into five stages through the perspective of their research priorities at different periods. Subsequently, we elaborated the underlying healing mechanism of polymers, including the self-healing origins, the influencing factors, and direct evidence of healing at nanoscopic level. Following this, recent advance in realizing the fast self-healing speed of polymers through physical and chemical approaches is extensively overviewed. In particular, the methodology for balancing the mechanical strength and healing ability in fast self-healing elastomers is summarized. We hope that it could afford useful information for research people in promoting the further technical development of new strategies and technologies to prepare the high performance self-healing elastomers for advanced applications.

Facile fabrication of ferroelectric poly(vinylidene fluoride) thin films with pure γ phase.

A simple heating-cooling procedure is employed to make pure polar γ-PVDF thin films. By controlling the relaxation state of the crystals, pure γ crystals are induced by two kinds of mechanism including self-seeding and self-nucleation upon cooling within 30 min. The methodology paves a new way for PVDF homopolymers in flexible ferroelectric device applications.

Tuning Intramolecular Stacking of Rigid Heteroaromatic Compounds for High-Efficiency Deep-Blue Through-Space Charge-Transfer Emission.

A series of ultrapure-blue thermally activated delayed fluorescence (TADF) emitters featuring through-space charge transfer (TSCT) have been constructed by close stacking between the donor and acceptor moieties in rigid heteroaromatic compounds. The obviously accelerated radiative transition of singlet excitons, the diminished vibrionic relaxation of ground and excited states, and the consequent reduced Stokes shift and the narrow emission are evident. The corresponding organic light-emitting diodes (OLEDs) based on AC-BO realize the best performance among all deep-blue TSCT-TADF emitters, with an external quantum efficiency (EQEmax ) of 19.3 %. Furthermore, the OLEDs based on QAC-BO display an EQEmax of 15.8 %, and achieve the first high-efficiency ultrapure-blue TSCT-TADF material with an excellent Commission Internationale de L'Eclairage coordinate (CIE) of (0.145, 0.076) which perfectly matches the ultrapure-blue CIE requirements (0.14, 0.08) defined by the National Television System Committee.

Printable hydrogels based on starch and natural rubber latex with high toughness and self-healing capability.

Fully bio-based hydrogels with printability, high toughness, self-healing, robust mechanical property and conductivity are highly desired but now remain a huge challenge. In this work, inspired by preparation of "Liangpi" (cold noodles, a traditional Chinese food), a satisfactory hydrogel was constructed using starch and natural rubber latex through a simple heating process. Benefitting from the physical dual cross-linked network, the resultant composite hydrogels exhibited high mechanical properties (ultimate tensile stress of 1.01 MPa with a failure strain of 1500 %, high toughness of 6.28 MJ m-3), good self-healing ability and 3D printability. Moreover, a conductive hydrogel can be easily obtained by in-situ silver mirror reaction during the heating process, which enable the hydrogel to be used as a wearable sensor to monitor human motions with high gauge factor of 2.027 and good durability (1000 cycles). Taking the advantage of its printability, electronic glove (E-glove) has been easily prepared by printing the precursor sol directly on the glove and successfully used to detect the hand motions exactly. This work provides a new route for the fabrication of multifunctional hydrogels with high performance and opens a new road for designing complex wearable sensors to monitor human motions.