Stabilizing Lithium Metal Batteries by Synergistic Effect of High Ionic Transfer Separator and Lithium-Boron Composite Material Anode.

The development of lithium (Li) metal batteries (LMBs) has been limited by problems, such as severe dendrite growth, drastic interfacial reactions, and large volume change. Herein, an LMB (8AP@LiB) combining agraphene oxide-poly(ethylene oxide) (PEO) functionalized polypropylene separator (8AP) with a lithium-boron (LiB) anode is designed to overcome these problems. Raman results demonstrate that the PEO chain on 8AP can influence the Li solvation structure in the electrolyte, resulting in Li homogeneous diffusion and Li deposition barrier reduction.

Functional Polymers as Artificial Solid Electrolyte Interfaces for Stabilizing Lithium Metal Anode.

The practical implementation of the lithium metal anode (LMA) has long been pursued due to its extremely high specific capacity and low electrochemical equilibrium potential. However, the unstable interfaces resulting from lithium ultrahigh reactivity have significantly hindered the use of LMA. This instability directly leads to dendrite growth behavior, dead lithium, low Coulombic efficiency, and even safety concerns.

Reactive Polymer as Artificial Solid Electrolyte Interface for Stable Lithium Metal Batteries.

Lithium (Li) metal anodes have the highest theoretical capacity and lowest electrochemical potential making them ideal for Li metal batteries (LMBs). However, Li dendrite formation on the anode impedes the proper discharge capacity and practical cycle life of LMBs, particularly in carbonate electrolytes. Herein, we developed a reactive alternative polymer named P(St-MaI) containing carboxylic acid and cyclic ether moieties which would in situ form artificial polymeric solid electrolyte interface (SEI) with Li.

Building Sustainable Saturated Fatty Acid-Zinc Interfacial Layer toward Ultra-Stable Zinc Metal Anodes.

The commercialization pace of aqueous zinc batteries (AZBs) is seriously limited due to the uncontrolled dendrite growth and severe corrosion reaction of the zinc anode. Herein, a universal and extendable saturated fatty acid-zinc interfacial layer strategy for modulating the interfacial redox process of zinc toward ultrastable Zn metal anodes is proposed. The in situ complexing of saturated fatty acid-zinc interphases could construct an extremely thin zinc compound layer with continuously constructed zincophilic sites which kinetically regulates Zn nucleation and deposition behaviors.

Supramolecular Engineering Strategy to Construct BODIPY-Based White Light Emission Materials.

Two kinds of 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) dyads BDP-OH containing 4-hydroxystyrene groups and BDP-PY bearing pyridinyl units were prepared. In addition, a naphthalene derivative NAP-PY modified by pyridinyl moieties substituent was made. The above three dyads could be used to construct white-light emission (WLE) material by a supramolecular engineering strategy due to their three primary colors of blue, green and red.

Chemical anchoring of SeS on a fluoro-substituted covalent organic framework as a high-performance cathode material.

In this work, a high-performance cathode material was achieved by using SeS2 post-functionalization of a fluorinated covalent organic framework (COF) through SNAr chemistry. The chemical and physical confinement of polysulfides and polyselenides combined with enhanced conductivity boosted its electrochemical performance as a cathode material for lithium-sulfur batteries (LSBs). COF-F-SeS2 delivered a discharge capacity of 1633 mA h g-1 at 0.

BODIPY-Based Conjugated Porous Polymer and Its Derived Porous Carbon for Lithium-Ion Storage.

Conjugated porous polymers (CPPs) possess great potential in the energy storage aspect. In this work, a boron-dipyrromethene (BODIPY)-conjugated porous polymer (CPP-1) is achieved by a traditional organic synthesis route. Following this, a carbonization process is employed to obtain the carbonized porous material (CPP-1-C).

Morphologies Transformation of BODIPY-Based Main Chain Supramolecular Polymers Amphiphiles: From Helical Nanowires to Nanosheets.

The aggregate morphologies of 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) main chain supramolecular polymer amphiphiles (SPA) are tunable by a fine balance of different non-covalent interactions. When the BODIPY segments and sodium cholate are mixed in aqueous solution, they form SPA by electrostatic attraction and hydrogen-bonds. This SPA displays helical nanowires' morphology.

Highly Fluoro-Substituted Covalent Organic Framework and Its Application in Lithium-Sulfur Batteries.

We report the preparation of a highly fluoro-substituted crystalline covalent organic framework (COF) and its application as a cathode material in lithium-sulfur batteries (LSBs) upon sulfur confinement. A sulfur-functionalized COF with high sulfur content (60 wt %) was obtained through physisorption of elemental sulfur and subsequent SAr reaction of sulfur with aromatic fluorides on the COF backbone. After such physical and chemical confinement of sulfur through a postfunctionalization approach, the COF material still shows some structural order, allowing us to investigate the structure-property relationship of such COF materials in LSB application.

Photoresponsive, Water-Soluble Supramolecular Dendronized Polymer with Specific Lysosome-Targetable Bioimaging Application in Living Cells.

A novel photoresponsive, water-soluble supramolecular dendronized polymer (SDP) is prepared through a γ -cyclodextrin (γ -CD)-coumarin host-guest interaction. The supramolecular formation, photoresponsive process, and fluorescence properties are investigated by nuclear magnetic resonance (NMR) techniques and spectrometric measurements. Upon different-wavelength light irradiation, this supramolecular polymer undergoes noncovalent polymer and covalent polymer conversion due to coumarin cycloaddition and cleavage reactions.

Synthesis and Morphology Evolution of Ultrahigh Content Nitrogen-Doped, Micropore-Dominated Carbon Materials as High-Performance Supercapacitors.

Nitrogen-doped carbon-based materials including nanocarbons, graphene, and conductive polymers are impressive as supercapacitor electrodes. However, ultrahigh nitrogen contents, micropore dominated, and morphology evolving carbonaceous electrodes have not achieved until now which are crucial for supercapacitor. Herein, we prepare a novel fumaronitrile (FUM) derived covalent triazine framework (FUM-CTF) and activated it by using KOH at different temperatures to obtain the corresponding carbon materials, which were used as supercapacitor electrode materials.

BODIPY-based Carbonaceous Materials for High Performance Electrical Capacitive Energy Storage.

Incorporation of heteroatoms into carbon materials is crucial to tailor carbon materials' donor-acceptor properties and consequently tune their chemical and electrical performance. However, doping carbon materials with multi-heteroatoms (three or more, especially the light elements) has been rarely payed attention until now. In this work, we develop a porous organic polymer containing boron, nitrogen, fluorine elements and realize its corresponding carbonaceous materials by subsequent carbonation or KOH activation process.

Near-Infrared-Emissive Amphiphilic BODIPY Assemblies Manipulated by Charge-Transfer Interaction: From Nanofibers to Nanorods and Nanodisks.

A novel near-infrared (NIR)-emissive amphiphilic BODIPY derivative, BBDP, was successfully prepared and thoroughly characterized. The photophysical properties in various organic solvents and THF/H O mixtures with different fractions of water were investigated. BBDP self-assembled into nanofibers in a water environment owing to its amphiphilic properties.

Cucurbit[8]uril-Based Water-Soluble Supramolecular Dendronized Polymer: Evidence from Single Polymer Chain Morphology and Force Spectroscopy.

A novel water-soluble supramolecular dendronized polymer (SDP) was prepared through cucurbit[8]uril (CB[8])-naphthalene host-guest interaction. The composition ratio between BDP and CB[8] of as-prepared luminescent supramolecular polymer was confirmed by H NMR technique and mass spectrometry. In addition, atomic force microscopy (AFM) images showing the polymer chain length up to 150 nm and height up to 1.

Amphiphilic BODIPY derivatives: the solvophobic effect on their photophysical properties and bioimaging in living cells.

Three novel amphiphilic BODIPY derivatives were prepared and their photophysical properties in THF/water mixtures with varying fractions of water were investigated. BDP-1 could self-assemble into different vesicle architectures in aqueous solution, while BDP-2 and BDP-3 with more hydrophilic abilities formed spherical and worm-like micelles. The BODIPY derivatives could be absorbed by HeLa cells and showed no apparent toxicity during the course of the test.

A ferrocene-azobenzene derivative showing unprecedented phase transition and better solubility upon UV irradiation.

The ferrocene-aspartic acid-azobenzene derivative 1 showing an unprecedented photoinduced crystal-liquid phase transition at an elevated temperature and better solubility in organic solvents has been successfully reported.

BODIPY-based fluorescent thermometer as a lysosome-targetable probe: how the oligo(ethylene glycols) compete photoinduced electron transfer.

A novel BODIPY-based fluorescent thermometer, which shows a lysosome-targeting property, was successfully prepared. Due to the electron-donating ability of the oligo(ethylene glycols), the photoinduced electron-transfer pathway from morpholine to BODIPY dye is blocked. The fluorescence of the thermometer quenched by intramolecular rotation at room temperature was progressively enhanced during heating due to the increased microviscosity around the fluorophore.

BODIPY-based oligo(ethylene glycol) dendrons as fluorescence thermometers: when thermoresponsiveness meets intramolecular electron/charge transfer.

The temperature-dependent photophysical properties of a series of 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) derivatives with different oligo(ethylene glycol) (OEG) dendrons were investigated. Weak fluorescence emission was observed for these BODIPY derivatives in dilute solution with low viscosity. BDP-G0 and BDP-G1-TEG exhibit a high quantum yield in viscous glycerol solutions, contrary to the moderate and little fluorescence enhancement for BDP-G1 and BDP-G2 under the same conditions.

Chemoselective sequential "click" ligation using unsymmetrical bisazides.

Unsymmetrical bisazides containing chelating and nonchelating azido groups undergo chemoselective three-component copper(I)-catalyzed azide-alkyne conjugation reactions with two different alkyne molecules. In conjunction with the reactivity gap between aromatic and aliphatic alkynes, a bistriazole molecule can be generated with excellent regioselectivity by mixing two alkynes and a bisazide in a single reaction container. This method is applicable in aqueous solutions at neutral pH, which may lend utilities in bioconjugation applications.

Balance between fluorescence enhancement and association affinity in fluorescent heteroditopic indicators for imaging zinc ion in living cells.

A fluorescent heteroditopic indicator for the zinc(II) ion possesses two different zinc(II) binding sites. The sequential coordination of zinc(II) at the two sites can be transmitted into distinct fluorescence changes. In the heteroditopic ligand system that our group developed, the formations of mono- and dizinc(II) complexes along an increasing gradient of zinc(II) concentration lead to fluorescence enhancement and an emission bathochromic shift, respectively.

Experimental investigation on the mechanism of chelation-assisted, copper(II) acetate-accelerated azide-alkyne cycloaddition.

A mechanistic model is formulated to account for the high reactivity of chelating azides (organic azides capable of chelation-assisted metal coordination at the alkylated azido nitrogen position) and copper(II) acetate (Cu(OAc)(2)) in copper(II)-mediated azide-alkyne cycloaddition (AAC) reactions. Fluorescence and (1)H NMR assays are developed for monitoring the reaction progress in two different solvents, methanol and acetonitrile. Solvent kinetic isotopic effect and premixing experiments give credence to the proposed different induction reactions for converting copper(II) to catalytic copper(I) species in methanol (methanol oxidation) and acetonitrile (alkyne oxidative homocoupling), respectively.

Polymorphism of amino acid-based dendrons: from organogels to microcrystals.

There is a delicate balance for a low-weight molecule to behave as a gelator or crystal. The synthesis of two novel amino acid-based naphthalene-dendrons, Nap-G1 and Nap-G2 is described. Both dendrons display polymorphic properties in organic solvents.

Chelation-assisted, copper(II)-acetate-accelerated azide-alkyne cycloaddition.

We described in a previous communication a variant of the popular Cu(I)-catalyzed azide-alkyne cycloaddition (AAC) process where 5 mol % of Cu(OAc)(2) in the absence of any added reducing agent is sufficient to enable the reaction. 2-Picolylazide (1) and 2-azidomethylquinoline (2) were found to be by far the most reactive carbon azide substrates that convert to 1,2,3-triazoles in as short as a few minutes under the discovered conditions. We hypothesized that the abilities of 1 and 2 to chelate Cu(II) contribute significantly to the observed high reaction rates.

A fluorescent heteroditopic ligand responding to free zinc ion over six orders of magnitude concentration range.

A fluorescent heteroditopic ligand useful in live-cell imaging studies responds to free zinc ion concentration over a range of six orders of magnitude in a buffered aqueous solution via dual-channel fluorescence.