Tuning Local Coordination Environments of Manganese Single-Atom Nanozymes with Multi-Enzyme Properties for Selective Colorimetric Biosensing.

Single-atom nanozymes (SAzymes) are promising in next-generation nanozymes, nevertheless, how to rationally modulate the microenvironment of SAzymes with controllable multi-enzyme properties is still challenging. Herein, we systematically investigate the relationship between atomic configuration and multi-enzymatic performances. The constructed MnSA -N3 -coordinated SAzymes (MnSA -N3 -C) exhibits much more remarkable oxidase-, peroxidase-, and glutathione oxidase-like activities than that of MnSA -N4 -C. Based on experimental and theoretical results, these multi-enzyme-like behaviors are highly dependent on the coordination number of single atomic Mn sites by local charge polarization. As a consequence, a series of colorimetric biosensing platforms based on MnSA -N3 -C SAzymes is successfully built for specific recognition of biological molecules. These findings provide atomic-level insight into the microenvironment of nanozymes, promoting rational design of other demanding biocatalysts.

Abiotic synthesis of purine and pyrimidine ribonucleosides in aqueous microdroplets.

Aqueous microdroplets (<1.3 µm in diameter on average) containing 15 mM d-ribose, 15 mM phosphoric acid, and 5 mM of a nucleobase (uracil, adenine, cytosine, or hypoxanthine) are electrosprayed from a capillary at +5 kV into a mass spectrometer at room temperature and 1 atm pressure with 3 mM divalent magnesium ion (Mg2+) as a catalyst. Mass spectra show the formation of ribonucleosides that comprise a four-letter alphabet of RNA with a yield of 2.5% of uridine (U), 2.5% of adenosine (A), 0.7% of cytidine (C), and 1.7% of inosine (I) during the flight time of ∼50 µs. In the case of uridine, no catalyst is required. An aqueous solution containing guanine cannot be generated under the same conditions given the extreme insolubility of guanine in water. However, inosine can base pair with cytidine and thus substitute for guanosine. Thus, a full set of ribonucleosides to generate the purine-pyrimidine base pairs A-U and I-C are spontaneously generated in aqueous microdroplets under similar mild conditions.

Abiotic production of sugar phosphates and uridine ribonucleoside in aqueous microdroplets.

Phosphorylation is an essential chemical reaction for life. This reaction generates fundamental cell components, including building blocks for RNA and DNA, phospholipids for cell walls, and adenosine triphosphate (ATP) for energy storage. However, phosphorylation reactions are thermodynamically unfavorable in solution. Consequently, a long-standing question in prebiotic chemistry is how abiotic phosphorylation occurs in biological compounds. We find that the phosphorylation of various sugars to form sugar-1-phosphates can proceed spontaneously in aqueous microdroplets containing a simple mixture of sugars and phosphoric acid. The yield for d-ribose-1-phosphate reached over 6% at room temperature, giving a ΔG value of -1.1 kcal/mol, much lower than the +5.4 kcal/mol for the reaction in bulk solution. The temperature dependence of the product yield for the phosphorylation in microdroplets revealed a negative enthalpy change (ΔH = -0.9 kcal/mol) and a negligible change of entropy (ΔS = 0.0007 kcal/mol·K). Thus, the spontaneous phosphorylation reaction in microdroplets occurred by overcoming the entropic hurdle of the reaction encountered in bulk solution. Moreover, uridine, a pyrimidine ribonucleoside, is generated in aqueous microdroplets containing d-ribose, phosphoric acid, and uracil, which suggests the possibility that microdroplets could serve as a prebiotic synthetic pathway for ribonucleosides.

Correction: Observation of crystalline changes of titanium dioxide during lithium insertion by visible spectrum analysis.

Correction for 'Observation of crystalline changes of titanium dioxide during lithium insertion by visible spectrum analysis' by Inho Nam et al., Phys. Chem. Chem. Phys., 2017, 19, 13140-13146.

Observation of crystalline changes of titanium dioxide during lithium insertion by visible spectrum analysis.

Real-time analysis of changes in the atomic environment of materials is a cutting edge technology that is being used to explain reaction dynamics in many fields of science. Previously, this kind of analysis was only possible using heavy nucleonic equipment such as XANES and EXAFS, or Raman spectroscopy on a moderate scale. Here, a new methodology is described that can be used to track changes in crystalline developments during complex Li insertion reactions via the observation of structural color. To be specific, the changes in atomic crystalline and nanostructure are shown during Li insertion in a complex TiO2 polymorph. Structural color corresponds to the refractive indices of materials originating from their atomic bonding nature and precise wave interferences in accordance with their nanostructure. Therefore, this new analysis simultaneously reveals changes in the nanostructure as well as changes in the atomic bonding nature of materials.

Sponge-Like Li4Ti5O12 Constructed on Graphene for High Li Electroactivities.

A sponge-like Li(4)Ti(5)O(12)/graphene composite was prepared via sequential hydrothermal process and solid-state heat treatment process for the application to high-power lithium ion batteries. The as-prepared electrode showed outstanding Li electroactivities with a rapid and reversible Li insertion/ extraction of up to 10 C-rate (1.75 A/g). It delivered a discharge capacity of 174 mAh/g at 0.5 C, near the theoretical capacity of Li(4)Ti(5)O(12), with good rate capability and cyclic stability. First-principles calculations revealed the intimate interaction of the Li(4)Ti(5)O(12) and graphene, which implies that graphene functions as an 'electron tunnel.' Electrochemical impedance spectroscopy also proved that the graphene-hybridization and the unique structure of the Li(4)Ti(5)O(12) material significantly reduce the resistive behavior of electrodes. The 3D structured Li(4)Ti(5)O(12)/graphene hybrid reported herein could be a promising candidate for a safe, low-cost, high-power anode for lithium ion batteries, and our seeding-growth-sintering method for decorating graphene with active material will offer an effective upgrade on highly insulating Li(4)Ti(5)O(12) materials.

Unveiling the Role of DMAP for the Se-Catalyzed Oxidative Carbonylation of Alcohols: A Mechanism Study.

Considering the remarkable catalytic activity (160 times higher) of Se/DMAP for the oxidative carbonylation of alcohols, unveiling the role of DMAP in catalysis is highly required. We investigated DFT calculations, and the proposed intermediates were verified with in situ ATR-FTIR analysis. DFT showed that the formation of [DMAP···HSe]δ-[DMAP(CO)OR]δ+ (IV) via nucleophilic substitution of DMAP at the carbonyl group of DMAP···HSe(CO)OR is the most energetically favorable. DMAP acts as both a nucleophile and a hydrogen bond acceptor, which is responsible for its remarkable activity.

One-pot synthesis of silicon nanoparticles trapped in ordered mesoporous carbon for use as an anode material in lithium-ion batteries.

Silicon nanoparticles trapped in an ordered mesoporous carbon composite were prepared by a one-step self-assembly with solvent evaporation using the triblock copolymer Pluronic F127 and a resorcinol-formaldehyde polymer as the templating agent and carbon precursor respectively. Such a one-pot synthesis of Si/ordered mesoporous carbon nanocomposite is suitable for large-scale synthesis. Characterization confirmed that the Si nanoparticles were trapped in the ordered mesoporous carbon, as evidenced by transmission electron microscopy, x-ray diffraction analysis and nitrogen sorption isotherms. The composite showed a high reversible capacity above 700 mA h g(-1) during 50 cycles at 2 A g(-1). The improved electrochemical performance of the composite can be ascribed to the buffering effect of spaces formed in the ordered pore channels during the volume expansion of silicon and the rapid movement of lithium ions through the uniform cylindrical pore structure of the mesopores.

Preparation via an electrochemical method of graphene films coated on both sides with NiO nanoparticles for use as high-performance lithium ion anodes.

We report on a simple strategy for the direct synthesis of a thin film comprising interconnected NiO nanoparticles deposited on both sides of a graphene sheet via cathodic deposition. For the co-electrodeposition, graphene oxide (GO) is treated with water-soluble cationic poly(ethyleneimine) (PEI) which acts as a stabilizer and trapping agent to form complexes of GO and Ni2+. The positively charged complexes migrate toward the stainless steel substrate, resulting in the electrochemical deposition of PEI-modified GO/Ni(OH)2 at the electrode surface under an applied electric field. The as-synthesized film is then converted to graphene/NiO after annealing at 350 ° C. The interconnected NiO nanoparticles are uniformly deposited on both sides of the graphene surface, as evidenced by field emission scanning electron microscopy, transmission electron microscopy and energy dispersive spectrometry. This graphene/NiO structure shows enhanced electrochemical performance with a large reversible capacity, good cyclic performance and improved electronic conductivity as an anode material for lithium ion batteries. A reversible capacity is retained above 586 mA h g−1 after 50 cycles. The findings reported herein suggest that this strategy can be effectively used to overcome a bottleneck problem associated with the electrochemical production of graphene/metal oxide films for lithium ion battery anodes.

Amorphous Mn oxide-ordered mesoporous carbon hybrids as a high performance electrode material for supercapacitors.

A supercapacitor has the advantages of both the conventional capacitors and the rechargeable batteries. Mn oxide is generally recognized one of the potential materials that can be used for a supercapacitor, but its low conductivity is a limiting factor for electrode materials. In this study, a hybrid of amorphous Mn oxide (AMO) and ordered mesoporous carbon (OMC) was prepared and characterized using X-ray diffraction, transmission electron microscopy, N2/77 K sorption techniques, and electrochemical analyses. The findings indicate that the electrochemical activities of Mn oxide were facilitated when it was in the hybrid state because OMC acted as a pathway for both the electrolyte ions and the electrons due to the characteristics of the ordered mesoporous structure. The ordered mesoporous structure of OMC was well maintained even after hybridization with amorphous Mn oxide. The electrochemical-activity tests revealed that the AMO/OMC hybrid had a higher specific capacitance and conductivity than pure Mn oxide. In the case where the Mn/C weight ratio was 0.75, the composite showed a high capacitance of 153 F/g, which was much higher than that for pure Mn oxide, due to the structural effects of OMC.

Agarose Gel-Templating Synthesis of a 3D Wrinkled Graphene Architecture for Enhanced Supercapacitor Performance.

The increasing use of rapidly fluctuating renewable energy sources, such as sunlight, has necessitated the use of supercapacitors, which are a type of energy storage system with high power. Chemically exfoliated graphene oxide (GO) is a representative starting material in the fabrication of supercapacitor electrodes based on reduced GO (rGO). However, the restacking of rGO sheets driven by π-π stacking interactions leads to a significant decrease in the electrochemically active surface area, leading to a loss of energy density. Here, to effectively inhibit restacking and construct a three-dimensional wrinkled structure of rGO (3DWG), we propose an agarose gel-templating method that uses agarose gel as a soft and removable template. The 3DWG, prepared via the sequential steps of gelation, freeze-drying, and calcination, exhibits a macroporous 3D structure and 5.5-fold higher specific capacitance than that of rGO restacked without the agarose template. Further, we demonstrate a "gel-stamping" method to fabricate thin-line patterned 3DWG, which involves the gelation of the GO-agarose gel within micrometer-sized channels of a customized polydimethylsiloxane (PDMS) mold. As an easy and low-cost manufacturing process, the proposed agarose gel templating method could provide a promising strategy for the 3D structuring of rGO.

Evaluating the Electrochemical Properties of Supercapacitors using the Three-Electrode System.

The three-electrode system is a basic and general analytical platform for investigating the electrochemical performance and characteristics of energy storage systems at the material level. Supercapacitors are one of the most important emergent energy storage systems developed in the past decade. Here, the electrochemical performance of a supercapacitor was evaluated using a three-electrode system with a potentiostat device. The three-electrode system consisted of a working electrode (WE), reference electrode (RE), and counter electrode (CE). The WE is the electrode where the potential is controlled and the current is measured, and it is the target of research. The RE acts as a reference for measuring and controlling the potential of the system, and the CE is used to complete the closed circuit to enable electrochemical measurements. This system provides accurate analytical results for evaluating electrochemical parameters such as the specific capacitance, stability, and impedance through cyclic voltammetry (CV), galvanostatic charge-discharge (GCD), and electrochemical impedance spectroscopy (EIS). Several experimental design protocols are proposed by controlling the parameter values of the sequence when using a three-electrode system with a potentiostat device to evaluate the electrochemical performance of supercapacitors. Through these protocols, the researcher can set up a three-electrode system to obtain reasonable electrochemical results for assessing the performance of supercapacitors.

Exploring the Effect of Cation Vacancies in TiO2: Lithiation Behavior of n-Type and p-Type TiO2.

TiO2 offers several advantages over graphite as an anode material for Li-ion batteries (LIBs) but suffers from low electrical conductivity and Li-diffusion issues. Control over defect chemistry has proven to be an effective strategy to overcome these issues. However, defect engineering has primarily been focused on oxygen vacancies (VO). The role of another intrinsic TiO2 vacancy [i.e., titanium vacancies (VTi)] with regard to the Li+ storage behavior of TiO2 has largely evaded attention. Hence, a comparison of VO- and VTi-defective TiO2 can provide valuable insight into how these two types of defects affect Li+ storage behavior. To eliminate other factors that may also affect the Li+ storage behavior of TiO2, we carefully devised synthesis protocols to prepare TiO2 with either VO (n-TiO2) or VTi (p-TiO2). Both TiO2 materials were verified to have a very similar morphology, surface area, and crystal structure. Although VO provided additional sites that improved the capacity at low C-rates, the benefit obtained from over-lithiation turned out to be detrimental to cycling stability. Unlike VO, VTi could not serve as an additional lithium reservoir but could significantly improve the rate performance of TiO2. More importantly, the presence of VTi prevented over-lithiation, significantly improving the cycling stability of TiO2. We believe that these new insights could help guide the development of high-performance TiO2 for LIB applications.

Synthesizing a Gel Polymer Electrolyte for Supercapacitors, Assembling a Supercapacitor Using a Coin Cell, and Measuring Gel Electrolyte Performance.

Supercapacitors (SC) have attracted attention as energy storage devices due to their high density and long cycle performance. SCs used in devices operating in stretchable systems require stretchable electrolytes. Gel polymer electrolytes (GPEs) are an ideal replacement for liquid electrolytes. Polyvinyl alcohol (PVA) and polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP) have been widely applied as a polymer-matrix-based electrolytes for supercapacitors because of their low cost, chemically stable, wide operating temperature range, and high ionic conductivities. Herein, we describe the procedures for (1) synthesizing a gel polymer electrolyte with PVA and PVDF-HFP, (2) measuring the electrochemical stability of the gel polymer electrolytes by cyclic voltammetry (CV), (3) measuring the ionic conductivity of the gel polymer electrolytes by electrochemical impedance spectroscopy (EIS), (4) assembling symmetric coin cells using activated carbon (AC) electrodes with the PVA- and PVDF-HFP-based gel polymer electrolytes, and (5) evaluating the electrochemical performance using galvanostatic charge-discharge analysis (GCD) and CV at 25 °C. Additionally, we describe the challenges and insights gained from these experiments.

Low-Crystalline AuCuIn Catalyst for Gaseous CO2 Electrolyzer.

Despite its importance for the establishment of a carbon-neutral society, the electrochemical reduction of CO2  to value-added products has not been commercialized yet because of its sluggish kinetics and low selectivity. The present work reports the fabrication of a low-crystalline trimetallic (AuCuIn) CO2  electroreduction catalyst and demonstrates its high performance in a gaseous CO2  electrolyzer. The high Faradaic efficiency (FE) of CO formation observed at a low overpotential in a half-cell test is ascribed to the controlled crystallinity and composition of this catalyst as well as to its faster charge transfer, downshifted d-band center, and low oxophilicity. The gaseous CO2  electrolyzer with the optimal catalyst as the cathode exhibits superior cell performance with a high CO FE and production rate, outperforming state-of-the-art analogs. Thus, the obtained results pave the way to the commercialization of CO2  electrolyzers and promote the establishment of a greener society.

Selective CO2 adsorption and bathochromic shift in a phosphocholine-based lipid and conjugated polymer assembly.

We assemble a film of a phosphocholine-based lipid and a crystalline conjugated polymer using hydrophobic interactions between the alkyl tails of the lipid and alkyl side chains of the polymer, and demonstrated its selective gas adsorption properties and the polymer's improved light absorption properties. We show that a strong attractive interaction between the polar lipid heads and CO2 was responsible for 6 times more CO2 being adsorbed onto the assembly than N2, and that with repeated CO2 adsorption and vacuuming procedures, the assembly structures of the lipid-polymer assembly were irreversibly changed, as demonstrated by in situ grazing-incidence X-ray diffraction during the gas adsorption and desorption. Despite the disruption of the lipid structure caused by adsorbed polar gas molecules on polar head groups, gas adsorption could promote orderly alkyl chain packing by inducing compressive strain, resulting in enhanced electron delocalization of conjugated backbones and bathochromic light absorption. The findings suggest that merging the structures of the crystalline functional polymer and lipid bilayer is a viable option for solar energy-converting systems that use conjugated polymers as a light harvester and the polar heads as CO2-capturing sites.

Recycling Black Tea Waste Biomass as Activated Porous Carbon for Long Life Cycle Supercapacitor Electrodes.

Value creation through waste recycling is important for a sustainable society and future. In particular, biomass, which is based on crops, is a great recyclable resource that can be converted into useful materials. Black tea is one of the most cultivated agricultural products in the world and is mostly discarded after brewing. Herein, we report the application of black tea waste biomass as electrode material for supercapacitors through the activation of biomass hydrochar under various conditions. Raw black tea was converted into hydrochar via a hydrothermal carbonization process and then activated with potassium hydroxide (KOH) to provide a large surface area and porous structure. The activation temperature and ratio of KOH were controlled to synthesize the optimal black tea carbon (BTC) with a large surface area and porosity suitable for use as electrode material. This method suggests a direction in which the enormous amount of biomass, which is simply discarded, can be utilized in the energy storage system. The synthesized optimal BTC has a large surface area of 1062 m2 and specific capacitance up to 200 F∙g-1 at 1 mV∙s-1. Moreover, it has 98.8% retention of charge-discharge capacitance after 2000 cycles at the current density of 5 A∙g-1.

Printable Gel Polymer Electrolytes for Solid-State Printed Supercapacitors.

Supercapacitors prepared by printing allow a simple manufacturing process, easy customization, high material efficiency and wide substrate compatibility. While printable active layers have been widely studied, printable electrolytes have not been thoroughly investigated despite their importance. A printable electrolyte should not only have high ionic conductivity, but also proper viscosity, small particle size and chemical stability. Here, gel-polymer electrolytes (GPE) that are compatible with printing were developed and their electrochemical performance was analyzed. Five GPE formulations based on various polymer-conductive substance combinations were investigated. Among them, GPE made of polyvinylidene difluoride (PVDF) polymer matrix and LiClO4 conductive substance exhibited the best electrochemical performance, with a gravimetric capacitance of 176.4 F/g and areal capacitance of 152.7 mF/cm2 at a potential scan rate of 10 mV/s. The in-depth study of the in-plane solid-state supercapacitors based on various printed GPEs suggests that printable electrolytes provide desirable attributes for high-performance printed energy devices such as supercapacitors, batteries, fuel cells and dye-sensitized solar cells.

Elaborate Control of Inkjet Printer for Fabrication of Chip-based Supercapacitors.

There are tremendous efforts in various fields to apply the inkjet printing method for the fabrication of wearable devices, displays, and energy storage devices. To get high-quality products, however, sophisticated operation skills are required depending on the physical properties of the ink materials. In this regard, optimizing the inkjet printing parameters is as important as developing the physical properties of the ink materials. In this study, optimization of the inkjet printing software parameters is presented for fabricating a supercapacitor. Supercapacitors are attractive energy storage systems because of their high power density, long lifespan, and various applications as power sources. Supercapacitors can be used in the Internet of Things (IoT), smartphones, wearable devices, electrical vehicles (EVs), large energy storage systems, etc. The wide range of applications demands a new method that can fabricate devices in various scales. The inkjet printing method can break through the conventional fixed-size fabrication method.

Methodologies for Fabricating Flexible Supercapacitors.

The spread of wearable and flexible electronics devices has been accelerating in recent years for a wide range of applications. Development of an appropriate flexible power source to operate these flexible devices is a key challenge. Supercapacitors are attractive for powering portable lightweight consumer devices due to their long cycle stability, fast charge-discharge cycle, outstanding power density, wide operating temperatures and safety. Much effort has been devoted to ensure high mechanical and electrochemical stability upon bending, folding or stretching and to develop flexible electrodes, substrates and overall geometrically-flexible structures. Supercapacitors have attracted considerable attention and shown many applications on various scales. In this review, we focus on flexible structural design under six categories: paper-like, textile-like, wire-like, origami, biomimetics based design and micro-supercapacitors. Finally, we present our perspective of flexible supercapacitors and emphasize current technical difficulties to stimulate further research.