In operando visualization of redox flow battery in membrane-free microfluidic platform.

Redox flow batteries (RFBs) are attractive large-scale energy storage techniques, achieving remarkable progress in performance enhancement for the last decades. Nevertheless, an in-depth understanding of the reaction mechanism still remains challenging due to its unique operation mechanism, where electrochemistry and hydrodynamics simultaneously govern battery performance. Thus, to elucidate the precise reactions occurring in RFB systems, an appropriate analysis technique that enables the real-time observation of electrokinetic phenomena is indispensable. Herein, we report in operando visualization and analytical study of RFBs by employing a membrane-free microfluidic platform, that is, a membrane-free microfluidic RFB. Using this platform, the electrokinetic investigations were carried out for the 5,10-bis(2-methoxyethyl)-5,10-dihydrophenazine (BMEPZ) catholyte, which has been recently proposed as a high-performance multiredox organic molecule. Taking advantage of the inherent colorimetric property of BMEPZ, we unravel the intrinsic electrochemical properties in terms of charge and mass transfer kinetics during the multiredox reaction through in operando visualization, which enables theoretical study of physicochemical hydrodynamics in electrochemical systems. Based on insights on the electrokinetic limitations in RFBs, we verify the validity of electrode geometry design that can suppress the range of the depletion region, leading to enhanced cell performance.

NO2-Affinitive Conjugated Polymer for Selective Sub-Parts-Per-Billion NO2 Detection in a Field-Effect Transistor Sensor.

Conjugated polymers (CPs) have provided versatile semiconducting implements for the development of soft electronic devices. When three CPs with the same conjugated framework but different side chains were adopted in the field-effect transistor (FET) sensor for NO2 detection, the response to NO2 showed an opposite tendency to the charge carrier mobility of each CP. Morphological and structural characterizations revealed that the flexible glycol side chain enhances NO2 affinity as well as prevents the formation of lamellar stacking of the CP chains, thereby providing routes for the facile diffusion of NO2. Additionally, theoretical calculations for CP-NO2 complex formation at the molecular level support the relatively low energy barrier for inter-chain transition of NO2 between the glycol-based conjugated frameworks, which implies the spontaneous internal diffusion of NO2 to the semiconductor-dielectric interface in the FET-based sensor. As a result, the CP with a NO2-affinitive morphology exhibited an exceptional sensitivity of 13.8%/ppb upon NO2 (100 ppb) exposure for 50 s and provided excellent selectivity to the FET-based sensor toward other environmentally abundant harmful gases, such as SO2, CO2, and NH3. In particular, the theoretic limit of detection reached down to 0.24 ppb, which is the lowest value ever reported for organic FET-based NO2 gas sensors.

Designing Nonfullerene Acceptors with Oligo(Ethylene Glycol) Side Chains: Unraveling the Origin of Increased Open-Circuit Voltage and Balanced Charge Carrier Mobilities.

Despite the recent rapid development of organic solar cells (OSCs), the low dielectric constant (ϵr =3-4) of organic semiconducting materials limits their performance lower than inorganic and perovskite solar cells. In this work, we introduce oligo(ethylene glycol) (OEG) side chains into the dicyanodistyrylbenzene-based non-fullerene acceptors (NIDCS) to increase its ϵr up to 5.4. In particular, a NIDCS acceptor bearing two triethylene glycol chains (NIDCS-EO3) shows VOC as high as 1.12 V in an OSC device with a polymer donor PTB7, which is attributed to reduced exciton binding energy of the blend film. Also, the larger size grain formation with well-ordered stacking structure of the NIDCS-EO3 blend film leads to the increased charge mobility and thus to the improved charge mobility balance, resulting in higher JSC , FF, and PCE in the OSC device compared to those of a device using the hexyl chain-based NIDCS acceptor (NIDCS-HO). Finally, we fabricate NIDCS-EO3 devices with various commercial donors including P3HT, DTS-F, and PCE11 to show higher photovoltaic performance than the NIDCS-HO devices, suggesting versatility of NIDCS-EO3.

Redox Potential Tuning of s-Tetrazine by Substitution of Electron-Withdrawing/Donating Groups for Organic Electrode Materials.

Herein, we tune the redox potential of 3,6-diphenyl-1,2,4,5-tetrazine (DPT) by introducing various electron-donating/withdrawing groups (methoxy, t-butyl, H, F, and trifluoromethyl) into its two peripheral benzene rings for use as electrode material in a Li-ion cell. By both the theoretical DFT calculations and the practical cyclic voltammetry (CV) measurements, it is shown that the redox potentials (E1/2) of the 1,2,4,5-tetrazines (s-tetrazines) have a strong correlation with the Hammett constant of the substituents. In Li-ion coin cells, the discharge voltages of the s-tetrazine electrodes are successfully tuned depending on the electron-donating/withdrawing capabilities of the substituents. Furthermore, it is found that the heterogeneous electron transfer rate (k0) of the s-tetrazine molecules and Li-ion diffusivity (DLi) in the s-tetrazine electrodes are much faster than conventional electrode active materials.

Improvement of Electrical Conductivity in Conjugated Polymers through Cascade Doping with Small-Molecular Dopants.

Doping capability is primitively governed by the energy level offset between the highest occupied molecular orbital (HOMO) of conjugated polymers (CPs) and the lowest unoccupied molecular orbital (LUMO) of dopants. A poor doping efficiency is obtained when doping directly using NOBF4 forming a large energy offset with the CP, while the devised doping strategy is found to significantly improve the doping efficiency (electrical conductivity) by sequentially treating the NOBF4 to the pre-doped CP with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquino-dimethane (F4TCNQ), establishing a relatively small energy level offset. It is verified that the cascade doping strategy requires receptive sites for each dopant to further improve the doping efficiency, and provides fast reaction kinetics energetically. An outstanding electrical conductivity (>610 S cm-1 ) is achieved through the optimization of the devised doping strategy, and spectroscopy analysis, including Hall effect measurement, supports more efficient charge carrier generation via the devised cascade doping.

Mellitic Triimides Showing Three One-Electron Redox Reactions with Increased Redox Potential as New Electrode Materials for Li-Ion Batteries.

The mellitic triimide (MTI) bearing three imide groups on a benzene core with C3 symmetry is proposed as a new building block for organic electrode materials in lithium-ion batteries. MTI was anticipated to deliver a higher theoretical specific capacity of up to 282 mAh g-1 with increased reduction potentials compared with the well-known pyromellitic diimide building block bearing two imide groups because the additional imide group can accept one more electron and provide an electron-withdrawing effect. A model compound, ethyl-substituted mellitic triimide (ETTI), shows three well distinguished and reversible one-electron redox reactions at -0.97, -1.62, and -2.34 V versus Ag/Ag+ in 0.1 m tetrabutylammonium hexafluorophosphate electrolyte, but the redox potentials were increased in 2 m lithium bis(trifluoromethanesulfonyl)imide electrolyte: -0.60 V, -0.86 V, and -1.42 V vs. Ag/Ag+ . The DFT calculations revealed that the unique C3 symmetric structural design leads to the higher reduction potential of MTI in the Li-based electrolyte by formation of a stable 7-membered ring with a Li ion and the two carbonyl oxygen atoms from the adjacent imide groups. In a Li-ion coin cell, the ETTI electrode delivered a specific capacity of 176 mAh g-1 , corresponding to 81 % of capacity utilization, with three clear voltage plateaus. The higher average discharge voltage (2.41 V vs. Li/Li+ ) of ETTI allows it to deliver one of the highest specific energies (421 Wh kg-1 ) among reported diimide-based electrode materials. Finally, its redox mechanism was investigated by ex situ FTIR measurements and DFT calculations.

Anchored Mediator Enabling Shuttle-Free Redox Mediation in Lithium-Oxygen Batteries.

Redox mediators (RMs) are considered an effective countermeasure to reduce the large polarization in lithium-oxygen batteries. Nevertheless, achieving sufficient enhancement of the cyclability is limited by the trade-offs of freely mobile RMs, which are beneficial for charge transport but also trigger the shuttling phenomenon. Here, we successfully decoupled the charge-carrying redox property of RMs and shuttling phenomenon by anchoring the RMs in polymer form, where physical RM migration was replaced by charge transfer along polymer chains. Using PTMA (poly(2,2,6,6-tetramethyl-1-piperidinyloxy-4-yl methacrylate)) as a polymer model system based on the well-known RM tetramethylpiperidinyloxyl (TEMPO), it is demonstrated that PTMA can function as stationary RM, preserving the redox activity of TEMPO. The efficiency of RM-mediated Li2 O2 decomposition remains remarkably stable without the consumption of oxidized RMs or degradation of the lithium anode, resulting in an improved performance of the lithium-oxygen cell.

Dual-color fluorescent nanoparticles showing perfect color-specific photoswitching for bioimaging and super-resolution microscopy.

Dual-emissive systems showing color-specific photoswitching are promising in bioimaging and super-resolution microscopy. However, their switching efficiency has been limited because a delicate manipulation of all the energy transfer crosstalks in the systems is unfeasible. Here, we report a perfect color-specific photoswitching, which is rationally designed by combining the complete off-to-on fluorescence switching capability of a fluorescent photochromic diarylethene and the frustrated energy transfer to the other fluorescent dye based on the excited-state intramolecular proton transfer (ESIPT) process. Upon alternation of UV and visible light irradiations, the system achieves 100% switching on/off of blue emission from the diarylethene while orange emission from the ESIPT dye is unchanged in the polymer film. By fabricating this system into biocompatible polymer nanoparticles, we demonstrate microscopic imaging of RAW264.7 macrophage cells with reversible blue-color specific fluorescence switching that enables super-resolution imaging with a resolution of 70 nm.

Characterization of food waste-driven carbon dot focusing on chemical structural, electron relaxation behavior and Fe3+ selective sensing.

In the study, carbon dot (CD) with high fluorescence properties was obtained via one-step hydrothermal carbonization of food model and sandwich leftover, respectively. The data in the article represent the change of the chemical structure and PL properties of the food waste-driven carbon dot (FWCDs). In higher carbonization temperature, pyridinic N and graphitic N were increased while amino N and pyrrolic N was decreased. The lifetime was increased with the increase of temperature. The CD prepared from sandwich leftover showed the dependency of the emission on the exciting wavelength and excellent Fe3+ sensitivity without significant change of lifetime. It also had a pH-sensitive fluorescence feature and good stability in NaCl solutions. For more insight, please see Food waste-driven N-doped carbon dots: Applications for Fe3+ sensing and cell imaging Ahn et al., 2019.

Food waste-driven N-doped carbon dots: Applications for Fe3+ sensing and cell imaging.

We report highly fluorescent N-doped carbon dots (CDs) synthesized from food waste via one-step hydrothermal carbonization. To study the chemical transition of carbon dots from food wastes, the cat feed stocks driven from food waste were used as the waste model. In the model study, the core of the CDs was successfully self N-doped without extra pre- or post-treatments. The experimental results reveal that the nitrogen in the waste model played an important role in the formation of graphitic N and pyridinic N in the core and functional groups on the surface. Especially, high process temperature (≥180 °C) resulted in high quantum yield as 23% of the CDs from the waste model. To demonstrate the conversion of real food waste into CDs, the hamburger sandwich leftover was used as a precursor for CDs. The food waste driven CDs had similar chemical and fluorescent properties to that of the waste model, having quantum yield of 28%. This study exhibits the food waste driven carbon dots are excellent candidates for fluorescence probe to Fe3+ with high selectivity even under the interference of other metal, and for bio-imaging material with good cell viability over 80%.

s-Tetrazines as a New Electrode-Active Material for Secondary Batteries.

Because of the limitations of conventional metal-oxide-based electrodes, studies on organic redox-active materials as alternative electrodes for secondary batteries are emerging. However, reported organic electrode materials are still limited to a few kinds of organic redox groups. Therefore, the development of new redox-active groups for high-performance electrode materials is indispensable. Here, we evaluate s-tetrazine derivatives as a new electrode material in Li-ion batteries and study their charge/discharge mechanisms by ex situ XPS measurements. The porous carbon CMK-3 was introduced to encapsulate the s-tetrazines, which allowed 100 % utilization of the theoretical capacity and stable cycle performance of the s-tetrazines by preventing dissolution of the molecules into the electrolytes. This new class of redox-active group can pave the way for the next-generation of energy storage systems.

Instantaneous Detection of Trichlorinated Carbon via Photo-Induced Electron Transfer toward Chemosensor for Toxic Organochlorides.

Despite the usefulness of organochlorides as raw materials for organic synthesis, they cause several issues in the human body, such as hepatic dysfunction, tumor, and heavy damage to the central nervous system. Especially when organochlorides contain three or more chlorinated carbons, they tend to be more toxic to the human body possibly owing to relatively high reactivity. Several electron donors (TPCAs) are designed to devise a novel detection system for toxic organochlorides containing trichlorinated carbons, and the detection mechanism of the devised sensor system is systematically identified by EPR measurement and the analysis of the solution after the detection of chloroform, which is used as a model compound. Since the detection system simultaneously utilizes the radical-generation capability and the low LUMO level of the trichlorinated carbon, it provides high selectivity against most of the common organic compounds including other organochlorides containing mono- or dichlorinated carbons, and the outstanding selectivity of the designed sensor has been verified with Mirex composed of numerous chlorinated carbons. In addition, the detection system exhibits immediate sensing capability because only electron transfer and radical reaction are involved in the detection process. Finally, when diphosgene is detected with the devised sensing platform, a noticeable change in fluorescence intensities can be identified within 5 s even for a diphosgene concentration of less than 1 ppm.

An exotic band structure of a supramolecular honeycomb lattice formed by a pancake π-π interaction between triradical trianions of triptycene tribenzoquinone.

A supramolecular honeycomb lattice was successfully formed by using triradical trianion species of triptycene tribenzoquinone (TT) which forms strong intermolecular π-π pancake bonds toward three directions. The crystal structure of Rb3TT·2H2O belongs to the hexagonal P6/m space group, the tight-binding band calculation of which reveals Dirac cones and flat bands.

Signal-amplifying nanoparticle/hydrogel hybrid microarray biosensor for metal-enhanced fluorescence detection of organophosphorus compounds.

In this study, we developed an enzyme-based miniaturized fluorescence biosensor to detect paraoxon, one of the most well-known neurotoxic organophosphorus compounds. The biosensor was fabricated with poly(ethylene glycol) (PEG) hydrogel microarrays that entrapped acetylcholinesterase (AChE) and quantum dots (QDs) as fluorescence reporters. Metal-enhanced fluorescence (MEF) was utilized to amplify the fluorescence signal, which was achieved by decorating QDs on the surface of silica-coated silver nanoparticles (Ag@Silica). The MEF effects of Ag@Silica were optimized by tuning the thickness of the silica shells, and under the optimized conditions, the fluorescence intensity was shown to be increased 5 fold, compared with the system without MEF. PEG hydrogel microarray entrapping QD-decorated Ag@Silica and AChE was prepared via photopatterning process. The entrapped AChE hydrolyzed paraoxon to produce p-nitrophenol within the hydrogel microstructure, which subsequently quenched the fluorescence of the QDs on the surface of Ag@Silica. The MEF-assisted fluorescence detection resulted in a significant enhancement of paraoxon detection. The detection limit was approximately 1.0 × 10-10 M and 2.0 × 10-7 M for sensing with and without MEF, respectively. The successful integration of a hydrogel microarray system with a microfluidic system was demonstrated to be a potential application for the MEF-based micro-total-analysis-system.

Structure-Property Correlation in Luminescent Indolo[3,2-b]indole (IDID) Derivatives: Unraveling the Mechanism of High Efficiency Thermally Activated Delayed Fluorescence (TADF).

A series of indolo[3,2-b]indole (IDID) derivatives are designed as a novel structural platform for thermally activated delayed fluorescence (TADF) emitters. Intramolecular charge transfer (ICT)-type molecules consisting of IDID donor (D) and various acceptor (A) moieties are synthesized and characterized in the protocol of the systematical structure-property correlation. IDID derivatives exhibit high efficiency, prompt fluorescence as well as TADF with emission ranges tuned by the chemical structure of the acceptor units. Interestingly, almost all of the IDID derivatives show an identical energy level of the lowest triplet excited state (T1) attributed to the locally excited triplet state of the IDID backbone (3LEID), while that of their lowest singlet excited state (S1) is largely tuned by varying the acceptor units. Thus, we demonstrate the underlying mechanism in terms of the molecular engineering. Among the compounds, Tria-phIDID and BP-phIDID generate efficient delayed fluorescence based on the small energy gap between the lowest singlet and triplet excited states (ΔEST) and mediation of the 3LEID state. Organic light-emitting diodes with these Tria-phIDID and BP-phIDID as a dopant in the emitting layer show highly efficient electroluminescence with maximum external quantum efficiencies of 20.8% and 13.9%, respectively.

Highly Luminescent 2D-Type Slab Crystals Based on a Molecular Charge-Transfer Complex as Promising Organic Light-Emitting Transistor Materials.

A new 2:1 donor (D):acceptor (A) mixed-stacked charge-transfer (CT) cocrystal comprising isometrically structured dicyanodistyrylbenzene-based D and A molecules is designed and synthesized. Uniform 2D-type morphology is manifested by the exquisite interplay of intermolecular interactions. In addition to its appealing structural features, unique optoelectronic properties are unveiled. Exceptionally high photoluminescence quantum yield (ΦF ≈ 60%) is realized by non-negligible oscillator strength of the S1 transition, and rigidified 2D-type structure. Moreover, this luminescent 2D-type CT crystal exhibits balanced ambipolar transport (µh and µe of ≈10-4 cm2 V-1 s-1 ). As a consequence of such unique optoelectronic characteristics, the first CT electroluminescence is demonstrated in a single active-layered organic light-emitting transistor (OLET) device. The external quantum efficiency of this OLET is as high as 1.5% to suggest a promising potential of luminescent mixed-stacked CT cocrystals in OLET applications.

Smart Fluorescent Nanoparticles in Water Showing Temperature-Dependent Ratiometric Fluorescence Color Change.

We synthesized two different amphiphilic small molecules 1 and 2 by attaching the same oligo(ethylene glycol) (OEG) unit to the same dicyanodistyrylbenzene (DCS) fluorophore but at different positions. These molecules self-assemble into nanoparticles in water and show lower critical solution temperature (LCST) at 26 and 58 °C, respectively. Upon heating, the transition of hydrophilic coils to hydrophobic globules of the OEG unit leads to the change in the stacking structure of the luminescent DCS cores. As a result, it shows significant ratiometric fluorescence color changes from excimeric yellow emission to monomer-dominated green emission. Interestingly, the coassembly of 1 and 2 exhibits single transition temperature between the transition temperatures of the two components. Moreover, it is demonstrated that the transition temperature of the coassembly is delicately tuned over 26-58 °C by varying the molar mixing ratio of them.

Stimuli-Responsive Reversible Fluorescence Switching in a Crystalline Donor-Acceptor Mixture Film: Mixed Stack Charge-Transfer Emission versus Segregated Stack Monomer Emission.

We report on a molecularly tailored 1:1 donor-acceptor (D-A) charge-transfer (CT) cocrystal that manifests strongly red-shifted CT luminescence characteristics, as well as noteworthy reconfigurable self-assembling behaviors. A loosely packed molecular organization is obtained as a consequence of the noncentrosymmetric chemical structure of molecule A1, which gives rise to considerable free volume and weak intermolecular interactions. The stacking features of the CT complex result in an external stimuli-responsive molecular stacking reorganization between the mixed and demixed phases of the D-A pair. Accordingly, high-contrast fluorescence switching (red↔blue) is realized on the basis of the strong alternation of the electronic properties between the mixed and demixed phases. A combination of structural, spectroscopic, and computational studies reveal the underlying mechanism of this stimuli-responsive behavior.

Excited State Features and Dynamics in a Distyrylbenzene-Based Mixed Stack Donor-Acceptor Cocrystal with Luminescent Charge Transfer Characteristics.

Combined structural, photophysical, and quantum-chemical studies at the quantum mechanics/molecular mechanics (QM/MM) level precisely reveal the structure-property relationships in a mixed-stack donor-acceptor cocrystal, which displays vibronically structured fluorescence, strongly red-shifted against the spectra of the parent donor and acceptor, with high quantum yield despite the pronounced CT character of the emitting state. The study elucidates the reasons for this unusual combination, quantifies the ordering and nature of the collective excited singlet and triplet state manifold, and details the deactivation pathways of the initially created Franck-Condon state.

Excimer formation in organic emitter films associated with a molecular orientation promoted by steric hindrance.

White emission with two sharp strong peaks - a molecular emission peak at 455 nm and an excimer emission peak at 591 nm - was obtained by introducing a terphenyl group into a highly twisted core chromophore, which promoted a molecular orientation in the film state suitable for excimer formation.