The Mass-Balancing between Positive and Negative Electrodes for Optimizing Energy Density of Supercapacitors.

Supercapacitors (SCs) are some of the most promising energy storage devices, but their low energy density is one main weakness. Over the decades, superior electrode materials and suitable electrolytes have been widely developed to enhance the energy storage ability of SCs. Particularly, constructing asymmetric supercapacitors (ASCs) can extend their electrochemical stable voltage windows (ESVWs) and thus achieve high energy density. However, only full utilization of the electrochemical stable potential windows (ESPWs) of both positive and negative electrodes can endow the ASC devices with a maximum ESVW by using a suitable mass-ratio between two electrodes (the mass-balancing). Nevertheless, insufficient attention is directed to mass-balancing, and even numerous misunderstandings and misuses have appeared. Therefore, in this Perspective, we focus on the mass-balancing: summarize theoretic basis of the mass-balancing, derive relevant relation equations, analyze and discuss the change trends of the specific capacitance and energy density of ASCs with mass-ratios, and finally recommend some guidelines for the normative implementation of the mass-balancing. Especially, the issues related to pseudocapacitive materials, hybrid devices, and different open circuit potentials (OCPs) of the positive and negative electrodes in the mass-balancing are included and emphasized. These analyses and guidelines can be conducive to understanding and performing mass-balancing for developing high-performance SCs.

Activation and Inhibition of Isomerization of a Cationic Azobenzene Surfactant in the Large Void Space of Polyglycerol Dendron Micelles.

Owing to the unique geometric structure of dendritic amphiphiles with voluminous dendrons, their micelles can harbor a large void space, which provides a new research focus and approach for micellar functionalization. In this work, we used the void space to construct a UV responsive micelle system of the mixed dendritic amphiphile (C12-(G3)2) and cationic azobenzene surfactant (C4AzoTAB). The synthesized C12-(G3)2 that possesses double third generation polyglycerol (PG) dendrons and a single alkyl chain is expected to highlight the large void space within the inside of the micelles. Thus, the aims of this work are to achieve the isomerization of C4AzoTAB in situ and to deeply understand the intermolecular interaction in the mixed micelles. The effect of the large void room with a wall decorated with the ether oxygen atoms on the isomerization of C4AzoTAB was studied by isomerization kinetics, conductivity measurements, isothermal titration calorimetry (ITC), and 1H NMR and 2D NOESY spectroscopies. The isomerization behavior of C4AzoTAB in C12-(G3)2 micelles was presented in terms of its kinetic constant, counterionic association, interaction enthalpy, and position and orientation of C4AzoTAB. The results of NMR and conductivity show that the quaternary ammonium group of C4AzoTAB situates on the surface of the mixed micelles with C12-(G3)2 both before and after UV-irradiation, while the position of azobenzene group in C12-(G3)2 micelles depends on its conformation. The C12-(G3)2 micelles can inhibit the UV response of the trans-isomer and activate the thermal relaxation of the cis-isomer, which has a potential application in the field of light-controlled smart nanocarriers.

Supramolecular Vector/Drug Coassemblies of Polyglycerol Dendrons and Rutin Enhance the pH Response.

A coassembly strategy for a supramolecular vector/drug was proposed with a biocompatible ternary dodecyl-bi(third-generation polyglycerol (PG) dendrons) (C12-(G3)2) amphiphile, dodecyl sulfobetaine (SB3-12) surfactant, and poorly water-soluble drug rutin. C12-(G3)2 and rutin will mutually enhance their pH response by protonation and deprotonation of dendritic PG and rutin's ionization as the pH changes from the acidic gastric lumen to the weakly alkaline intestine. SB3-12 may increase the payload and bring about sustained release for rutin by intermolecular interactions. Self-assembling behaviors of C12-(G3)2, SB3-12, sodium dodecyl sulfate (SDS), and dodecyl trimethylammonium bromide (DTAB) and their hybrids with rutin were characterized by UV-vis spectroscopy, a fluorescence probe, and 1H NMR. UV-vis and 1H NMR were used to identify the position and orientation of rutin in the vectors. The functions of the vector/drug were confirmed by measuring the solubility and in vitro release of rutin. The ternary coassembling vector/drug easily imparted functions of pH-responsive and sustained release without complex synthetic processes. The nanocaves framed by PG dendrons in the micelles provide pH-responsive compartments for rutin and SB3-12 in the supramolecular vector/drug anchors that accommodate rutin by weak interactions. The finely matched supramolecular vector/drug coassemblies exhibit the pH-responsive function for a potential application in the treatment of inflammatory bowel disease.

Construction of Rich Conductive Pathways from Bottom to Top: A Highly Efficient Charge-Transfer System Used in Durable Li/Na-Ion Batteries at -20 °C.

The construction of potential electrode materials with wide temperature property for high-energy-density secondary batteries has attracted great interest in recent years. Herein, a hybrid electrode, consisting of a nitrogen-doped carbon/α-MnS/flake graphite composite (α-MnS@N-C/FG), is prepared through a post-sulfurization route. In the α-MnS@N-C/FG composite, α-MnS nanoparticles wrapped by the N-C layer are uniformly embedded onto FG, forming a novel nanofoam structure. The as-obtained α-MnS@N-C/FG shows excellent lithium/sodium storage performance, with a specific capacity of 712 mA h g-1 in the 700th cycle at 1.0 A g-1 or 186.4 mA h g-1 in the 100th cycle at 100 mA g-1 using lithium or sodium foil as the counter electrode, respectively. Moreover, even operated at -20 °C, the α-MnS@N-C/FG can still attain a high specific capacity of 350 mA h g-1 after 50 cycles at 100mA g-1 for LIBs. This exceptional electrochemical response is attributed to the synergetic effect of the smart design of a hybrid nanofoam structure, in which the FG skeleton and N-C coating layer can significantly enhance the conductivity of the whole electrode from bottom to top. Accordingly, the enhanced redox kinetics endow the electrode with pseudocapacitive-dominated electrochemical behavior, leading to fast electrode reactions and robust structural stability in the whole electrode.

Elemental-Sulfur-Incorporated Cyclizations of Pyrrolidines Leading to Thienopyrroles.

We report, herein, the synthesis of thieno[3,2-b]pyrroles from the direct oxidative [4 + 1] cyclization of 2-alkynyl pyrrolidines with elemental sulfur. This transformation likely originates from electrophilic attack at the ß-position of pyrrolidine followed by an intramolecular thienannulation to deliver the desired product. Mechanistic investigation suggests that the present reaction involves the formation of dihydrothieno[3,2-b]pyrrole as an intermediate.

Silanized carbon dot-based thermo-sensitive molecularly imprinted fluorescent sensor for bovine hemoglobin detection.

Using the surface molecular imprinting technique, a thermo-sensitive molecularly imprinted fluorescent sensor was constructed for bovine hemoglobin (BHb) detection with the silanized carbon dots (CD@SiO2) as fluorescent signal, N-isopropylacrylamide as monomer sensitive to temperature, and BHb as template. The silanized carbon dots coated by the molecularly imprinted polymer (CD@SiO2@MIP) were characterized by high-resolution transmission electron microscopy, Fourier transform infrared spectroscopy, and fluorescence spectroscopy. Owing to the combination of the strong fluorescence sensitivity of CDs and the high selectivity of the molecular imprinting shell, the prepared sensor showed good recognition and detection performance to the target protein BHb, with a linear range of 0.31-1.55 µM and a detection limit of 1.55 µM. Furthermore, the sensor was utilized to detect the content of BHb in real urine with a recovery of 98.6-100.5%. The CD@SiO2@MIP sensors present a high potential for applications in the detection of BHb in biological systems. Graphical abstract.

Metal-Free Dehydrogenative Double C-H Sulfuration To Access Thieno[2,3-b]indoles Using Elemental Sulfur.

We report a base-promoted metal-free approach for the synthesis of thieno[2,3-b]indole derivatives. This method combined four C-H σ-bond cleavage reactions of two different kinds of C-H bonds and two C-S σ-bond formation processes. A series of thieno[2,3-b]indoles were obtained starting from 3-benzylindole derivatives with good yields and high regioselectivity, with the elemental sulfur serving as a cheap and readily available sulfur source. Good efficiency could be maintained even when the reaction was performed on a gram scale. A plausible mechanism was proposed on the basis of mechanistic studies.

Fluorescent probe based on carbon dots/silica/molecularly imprinted polymer for lysozyme detection and cell imaging.

The abnormal concentration of lysozyme in body fluids and tissues is a potential indicator for diseases such as leukemia and meningitis. In this work, by combining the excellent optical properties of carbon dots (CDs) with the favorable selectivity of molecularly imprinted polymer (MIP), a novel fluorescent probe for lysozyme detection and cell imaging was constructed, where silanized CDs with low cytotoxicity (CDs/SiO2) were used as the fluorescence signal reporter and N-isopropylacrylamide (NIPAM) was used as the temperature-sensitive monomer. The as-prepared CDs/SiO2/MIP showed a thermo-sensitive property for the response to lysozyme. Moreover, this probe could be used for quantitative detection of lysozyme, with a wider detection range (0.001~0.01 mg/mL), a low detection limit (0.55 µg/mL), and a high selectivity. Importantly, the MTT assay testified that the fluorescent CDs/SiO2/MIP probe had low cytotoxicity. In addition, human hepatoma carcinoma cells (HepG-2 cells) could be stained by the CDs/SiO2/MIP, and showed a bright intracellular green fluorescence, indicating that the imaging of live cells was possible. This study provides a new way to detect lysozyme in vitro and an attractive perspective to probe intracellular lysozyme in vivo.

Nitrogen-Doped Highly Photoluminescent Carbon Dots Derived from Citric Acid and Guanidine Carbonate.

A facile one-pot hydrothermal method for fabricating nitrogen-doped carbon dots (N-CDs) was developed by using citric acid as a carbon source and guanidine carbonate as a nitrogen and carbon source. X-ray diffraction, X-ray photoelectron spectroscopy, and Fourier transform infrared spectra indicated that the N-CDs were rich in elemental nitrogen. They had excellent stability in the presence of various salt concentrations and under UV irradiation. The N-CDs exhibited high quantum yields (52%), as well as down-conversion and up-conversion photoluminescence. The N-CD photoluminescence was quenched in the presence of Hg2+, while nearly no intensity changes were observed when in the presence of Na+, Mg2+, Mn2+, Zn2+, Ni2+, Cu2+, Ba2+, Cd2+ or Ca2+. The binding constant (KSV) and detection limit were also determined.

Cationic gemini surfactant as a dual linker for a cholic acid-modified polysaccharide in aqueous solution: thermodynamics of interaction and phase behavior.

Understanding the thermodynamics of formation of biocompatible aggregates is a key factor in the bottom up approach to the development of novel types of drug carriers and their structural tuning using small amphiphilic molecules. We chose an anionic amphiphilic and biocompatible polymer that consists of a dextran and grafted cholic acid pendants, randomly distributed along the dextran backbone, with a degree of substitution (DS) of 15 mol% (designated Dex-15CACOONa). The thermodynamics of interaction and phase behavior of mixtures of this polyelectrolyte and a cationic gemini surfactant hexanediyl-α,ω-bis(dodecyldimethylammonium bromide) (C12C6C12Br2) or its monomer surfactant dodecyltrimethylammonium bromide (DTAB) in aqueous solution were characterized by isothermal titration calorimetry (ITC) and turbidity, together with cryogenic transmission electron microscopy (Cryo-TEM). The various critical concentrations and the enthalpy changes of the corresponding phase transitions for the oppositely charged system were obtained from the plots of the observed enthalpy change (ΔHobs) and turbidity measurements as a function of gemini concentration. The morphologies of the aggregates in various phases were observed by Cryo-TEM. Altogether these results suggest the critical role of gemini as a dual linker. At the concentrations where the crosslink between the pendant aggregates happens, the free gemini concentration is proximately zero and the aggregate retains its negative charge. The analysis of various factors involved in the interaction allowed a rationalization of the driving forces for mixed aggregate formation, which will contribute to a subsequent rational design of drug delivery systems based on this polymer/surfactant system.

Chloroacetate-promoted selective oxidation of heterobenzylic methylenes under copper catalysis.

The efficient selective oxidation and functionalization of C-H bonds with molecular oxygen and a copper catalyst to prepare the corresponding ketones was achieved with ethyl chloroacetate as a promoter. In this transformation, various substituted N-heterocyclic compounds were well tolerated. Preliminary mechanistic investigations indicated that organic radical species were involved in the overall process. The N-heterocyclic compounds and ethyl chloroacetate work synergistically to activate C-H bonds in the methylene group, which results in the easy generation of free radical intermediates, thus leading to the corresponding ketones in good yields.

Dynamically Favorable Ion Channels Enabled by a Hybrid Ionic-Electronic Conducting Film toward Highly Reversible Zinc Metal Anodes.

Aqueous zinc ion batteries show great promise for future applications due to their high safety and ecofriendliness. However, nonuniform dendrite growth and parasitic reactions on the Zn anode have severely impeded their use. Herein, a hybrid ionic-electronic conducting ink composed of graphene-like carbon nitride (g-C3N4) and conductive polymers (CP) of poly(3,4ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) is introduced to Zn anode using a scalable spray-coating strategy. Notably, the g-C3N4 promotes a screening effect, disrupting the coulombic interaction between the PEDOT+ segments and PSS- chains within CP, thereby reducing interfacial resistance and homogenizing the surface electric field distribution of the Zn anode. Furthermore, the abundant N-containing species and ─SO3 - groups in g-C3N4/CP exhibit strong zincophilicity, which accelerates the diffusion of Zn2+ and disrupts the solvation structure of Zn(H2O)6 2+, thus improving the Zn2+ transfer capability. Consequently, the g-C3N4/CP can powerfully stabilize the Zn2+ flux and thus enable a high coulombic efficiency of 99.47% for 1500 cycles and smooth Zn plating/stripping behaviors more than 3000 h at a typical current density of 1 mA cm-2. These findings shed new light on the Zn electrodeposition process under the mediation of g-C3N4/CP and offer sustainability considerations in designing more stable Zn-metal anodes with enhanced reversibility.

Intelligent Coatings with Controlled Wettability for Oil-Water Separation.

Intelligent surfaces with controlled wettability have caught much attention in industrial oily wastewater treatment. In this study, a hygro-responsive superhydrophilic/underwater superoleophobic coating was fabricated by the liquid-phase deposition of SiO2 grafted with perfluorooctanoic acid. The wettability of the surface could realize the transformation from superhydrophilicity/underwater superoleophobicity (SHI/USOB) to superhydrophobicity/superoleophilicity (SHB/SOI), both of which exhibited excellent separation performance towards different types of oil-water mixtures with the separation efficiency higher than 99%. Furthermore, the long-chain perfluoroakyl substances on the surface could be decomposed by mixing SiO2 with TiO2 nanoparticles under UV irradiation, which could reduce the pollution to human beings and environment. It is anticipated that the prepared coating with controlled wettability could provide a feasible solution for oil-water separation.

Fabrication of Durable Superhydrophobic Surface for Versatile Oil/Water Separation Based on HDTMS Modified PPy/ZnO.

Superhydrophobic materials have been widely applied in rapid removal and collection of oils from oil/water mixtures for increasing damage to environment and human beings caused by oil-contaminated wastewater and oil spills. Herein, superhydrophobic materials were fabricated by a novel polypyrrole (PPy)/ZnO coating followed by hexadecyltrimethoxysilane (HDTMS) modification for versatile oil/water separation with high environmental and excellent reusability. The prepared superhydrophobic surfaces exhibited water contact angle (WCA) greater than 150° and SA less than 5°. The superhydrophobic fabric could be applied for separation of heavy oil or light oil/water mixtures and emulsions with the separation efficiencies above 98%. The coated fabric also realized highly efficient separation with harsh environmental solutions, such as acid, alkali, salt, and hot water. The superhydrophobic fabric still remained, even after 80 cycles of separation and 12 months of storage in air, proving excellent durability. These novel superhydrophobic materials have indicated great development potentials for oil/water separation in practical applications.

Ionic Liquid Mixture Electrolyte Matching Porous Carbon Electrodes for Supercapacitors.

Ionic liquids (ILs), with their wide electrochemical stable potential window, are promising electrolytes for supercapacitors (SCs). The suitable matching of the ion size and shape of the ILs to the pore size and structure of porous carbon (PC) electrode materials can realize the enhanced capacitive performance of the SCs. Here we report an interesting result: The capacitance of PC-based SCs shows a quasi-sinusoidal relationship with the composition (mass fraction) of the binary IL mixture as the electrolyte. This relationship is also interpreted based on the matching between the pore sizes of the PC materials and the size/shape of various ions of the IL mixture electrolyte. This can provide a new strategy to improve the performance of SCs by formulating a suitable mixture of different ILs to match the carbon-based electrode materials with a special pore size distribution.

An azobenzene-modified redox-active ionic liquid electrolyte for supercapacitors.

A new redox-active ionic liquid (2-(4-(phenyldiazenyl)phenoxy)ethyl)-1-methyl-imidazolium tetrafluoroborate ([ABEMIM][BF4]) is demonstrated. It is incorporated into another ionic liquid ([EMIM][BF4]) to form a mixed IL electrolyte, which can markedly improve the capacitance performance of carbon-based supercapacitors via extra pseudocapacitance contribution. It opens up a new path to develop high-energy supercapacitors through introducing a redox-active ionic liquid to electrolytes.

Correction: An azobenzene-modified redox-active ionic liquid electrolyte for supercapacitors.

Correction for 'An azobenzene-modified redox-active ionic liquid electrolyte for supercapacitors' by Yuhua Zhao et al., Chem. Commun., 2022, https://doi.org/10.1039/d2cc04081f.

Interactions of 1-butyl-3-methylimidazolium carboxylate ionic liquids with glucose in water: a study of volumetric properties, viscosity, conductivity and NMR.

Extensive applications of ionic liquids (ILs) may result in their accumulation in the ecological environment and organisms. Although ILs are popularly called "green solvents", their toxicity, in fact, has been exhibited. Therefore the interaction of ILs with biomolecules is a cutting-edge research subject. Herein, the interactions of 1-butyl-3-methylimidazolium carboxylate ionic liquids ([C(4)mim][HCOO], [C(4)mim][CH(3)COO] and [C(4)mim][CH(3)CH(2)COO]) with glucose in water were studied for their volumetric properties, viscosity, conductivity and NMR spectra. Limiting apparent molar volumes (V(Φ, IL)(0)), viscosity B-coefficients, limiting molar conductivities (Λ(0)) and Walden products (Λ(0)η(0)) were evaluated for the ILs in glucose + water solutions. Volumetric interaction parameters were also obtained from the transfer volumes of the ionic liquids. The contributions of the solvent properties (B(1)) and the ionic liquid-solvent interactions (B(2)) to the B-coefficient were extracted, together with molar activation energies (Δµ(IL)(0≠)) of the ionic liquids for viscous flow of the aqueous glucose + IL solution. In addition, the (13)C and (1)H NMR spectra of methyl ß-D-glucopyranoside and ILs in ß-D-glucopyranoside + IL + D(2)O were studied. The NMR results show that no special and strong interactions were observed between glucopyranoside and the ILs. However, it was confirmed that the H2 on the imidazolium ring has more activity (acidity) than atoms H4 and H5. The macro-properties and their changes were also discussed in terms of the size, structure and solvation of the ILs and glucose.

3D hierarchical porous carbon matching ionic liquid with ultrahigh specific surface area and appropriate porous distribution for supercapacitors.

Supercapacitors, as one of the most promising energy storage devices, have high power density but low energy density. An appropriate collocation of porous carbon electrodes and ionic liquid electrolytes can improve notably the performance of supercapacitors. Herein, we report a pre-assembly strategy to prepare three-dimensional (3D) hierarchical porous carbons (HPCs) as the electrode materials for supercapacitors. Three long-chain hydrophilic polymers polyacrylamide (PAM)/gelatin/F127 in water form 3D frameworks by pre-assembly and further form a hydrogel. Then the hydrogel is freeze-dried, carbonized, and etched to form 3D hierarchical porous carbons. The effects of pore volume, pore size, and ratio of mesopores to micropores on the performance of ionic liquid-based supercapacitors are investigated. The porous structure of the prepared HPCs can well match EMIMBF4. Therefore, HPCs as electrode materials for supercapacitors exhibit an excellent specific capacity of 216.5 F g-1 at 1 A g-1, and the as-assembled symmetric supercapacitor delivers a superior energy density of 108.6 W h kg-1 at a power density of 961.1 W kg-1. Meanwhile, the symmetric supercapacitor maintains 84.4% of its initial capacitance after 10 000 cycles at 3 A g-1. This work provides a guide for developing new porous carbon materials for supercapacitors with a high energy density.

Controllable enzymatic superactivity of α-chymotrypsin activated by the electrostatic interaction with cationic gemini surfactants.

Surfactant plays a critical role in enzymatic multi-functionalization processes. However, a deep understanding of surfactant-enzyme interactions has been lacking up until now due to the extreme complexity of the mixed system. This work reported the effect of cationic gemini surfactants, alkanediyl-α,ω-bis(dimethyldodecylammonium bromide) (C12C S C12Br2, S = 2, 6, and 10) on the enzymatic activity and conformation of α-chymotrypsin (α-CT) in phosphate buffer solution (PBS, pH 7.3). The enzymatic activity was assessed by the rate of 2-naphthyl acetate (2-NA) hydrolysis measured by UV-vis absorption. The superactivity of α-CT in the presence of C12C S C12Br2 appears in the concentration region below the critical micelle concentration (cmc) of the surfactant, and its maximum superactivity is correlated to the spacer length of C12C S C12Br2. Subtle regulation of the charge density of headgroups of the cationic surfactant can be achieved through partial charge neutralization of cationic headgroups by introducing inorganic counterions or oppositely charged surfactant, demonstrating that the electrostatic interaction plays the crucial role for emergence of the superactivity. The interaction between C12C S C12Br2 (S = 2,6, and 10) and α-CT was characterized by isothermal titration calorimetry (ITC), and the obtained endothermic enthalpy change indicates that the interaction induces the change in conformation and enzymatic superactivity. The methodologies of fluorescence spectroscopy, circular dichroism (CD), and differential scanning calorimetry (DSC) show that the gemini surfactants with different spacer lengths induct and regulate the secondary, tertiary and even fourth structures of the protein. The present work is significant to get deeper insight into the mechanism of the activation and denaturation of enzymes.