Immobilization of glucose oxidase with the blend of regenerated silk fibroin and poly(vinyl alcohol) and its application to a 1,1′- dimethylferrocene-mediating glucose sensor

The structure and properties of the blend of regenerated silk fibroin (RSF) and poly(vinyl alcohol) (PVA) were investigated. The two polymers in the blend are in the state of phase segregation. Infrared (IR) spectra indicate that the RSF in the blend maintains its intrinsic properties, thus, ethanol treatment can transfer silk I structure of RSF to silk II structure. The water absorption property and mechanical property of the blend are improved in comparison with those of RSF. The blend maintains the major merit of RSF, that is, it can immobilize glucose oxidase on the basis of the conformational transition from silk I structure to silk II structure. The properties of the immobilized enzyme are examined. Moreover, the second generation of glucose sensor based on the immobilized enzyme is fabricated and it has a variety of advantages including easy maintenance of enzyme, simplicity of construction, fast response time and high stability.     

BODIPY-based Fluorescent Probe for Fast Detection of Hydrogen Sulfide and Lysosome-targeting Applications in Living Cells

Hydrogen sulfide (H₂S) is recognized as an endogenous gaseous signaling agent in many biological activities. Lysosomes are the main metabolic site and play a pivotal role in cells. Herein, we designed and synthesized two new fluorescent probes BDP-DNBS and BDP-DNP with a BODIPY core to distinguish H₂S. The sensing mechanism is based on the inhibition-recovery of the photo-induced electron transfer (PET) process. Through comparing the responsive behaviors of the two probes toward H₂S, BDP-DNBS showed a fast response time (60 s), low limit of detection (LOD, 51 nM), high sensitivity and selectivity. Moreover, the reaction mechanism was demonstrated by mass spectrometry and fluorescence off-on mechanism was proved by density functional theory (DFT). Significantly, confocal fluorescence imaging indicated that BDP-DNBS was successfully used to visualize H₂S in lysosomes in living HeLa cells.     

Strategies for Improving the Catalytic Performance of 2D Covalent Organic Frameworks for Hydrogen Evolution and Oxygen Evolution Reactions

Hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) have been deemed as clean and sustainable strategies to solve the energy crisis and environmental problems. Various catalysts have been developed to promote the process of HER and OER. Among them, two-dimensional covalent organic frameworks (2D COFs) have received great attention due to their diverse and designable structure. In this minireview, we mainly summarize the diverse linkages of 2D COFs and strategies for enhancing the catalytic performance of 2D COFs for HER and OER, such as introducing active building blocks, metal ions and tailored linkages. Furthermore, a brief outlook for the development directions of COFs in the field of HER and OER is provided, expecting to stimulate new opportunities in future research.     

Polymer Electrolytes – New Opportunities for the Development of Multivalent Ion Batteries

Batteries, as highly concerned energy conversion system, have a great development prospect in various fields, especially in the field of energy powered vehicles. Multivalent ion batteries are getting more attention due to their low cost, high abundance in earth crust, high capacity and safety compared with Lithium batteries. Despite above advantages, several problems still need to be solved before multivalent ion batteries achieve large-scale application, such as interfacial parasitic reaction, anode passivation, and dendrites. The replacement of liquid electrolytes with gel polymer electrolytes (GPEs) which pose high safety, high mechanical strength and simplified battery system, is an effective strategy to inhibit dendrite growth and improve electrochemical performance. This review mainly discusses the advantages and challenges of multivalent ion batteries including zinc, magnesium, calcium and aluminum batteries. Meanwhile, the major targets of this review are introducing the recent developments and making a summary of the future trends of GPEs in the multivalent ion batteries.     

A Novel Fluorescence Probe for the Reversible Detection of Bisulfite and Hydrogen Peroxide Pair in Vitro and in Vivo

The detection of changes in the reactive oxygen species (ROS)/reactive sulfur species (RSS) couple is important for studying the cellular redox state. Herein, we developed a 1,8-naphthalimide-based fluorescence probe ( NI ) for the reversible detection of bisulfite (HSO₃⁻) and hydrogen peroxide (H₂O₂) in vitro and in vivo. NI has been designed with a reactive ethylene unit which specifically reacts with HSO₃⁻ by a Michael addition reaction mechanism, resulting in the quenching of yellow fluorescence at 580 nm and the appearing of green fluorescence at 510 nm upon excitation at 500 nm and 430 nm, respectively. The addition product ( NI−HSO₃ ) could be specifically oxidized to form the original C=C bond of NI , recovering the fluorescence emission and color. The detection limits of NI for HSO₃⁻ and NI−HSO₃ for H₂O₂ were calculated to be 2.05 μM and 4.23 μM, respectively. The reversible fluorescence response of NI towards HSO₃⁻/H₂O₂ couple can be repeated for at least five times. NI is reliable at a broad pH range (pH 3.0–11.5) and features outstanding selectivity, which enabled its practical applications in biological and food samples. Monitoring the reversible and dynamic inter-conversion between HSO₃⁻ and H₂O₂ in vitro and in vivo has been verified by fluorescence imaging in live HeLa cells, adult zebrafish and nude mice. Moreover, NI has been successfully applied to detect of HSO₃⁻ levels in food samples.     

A Tri-state Fluorescent Switch with “Gated” Solid-state Photochromism Induced by an External Force

Mr. Chen Qian, Dr. Zhimin Ma, Mr. Jianwei Liu, Mrs. Xue Zhang, Prof. Shitao Wang and Prof. Zhiyong Ma. In this article, we report a newly designed molecule composed of a dihydroazulene (DHA) group and a phenothiazine (PTZ) moiety, which achieves aggregation-induced emission enhancement (AIEE), mechanochromism and “gated” solid-state photochromism upon stimulation by an external force. Grinding loosens intermolecular interactions in the crystal and causes a red-shift of fluorescence from 570 nm to 600 nm. Meanwhile, the ring-opening reaction of DHA unit is activated by grinding and a remarkable photochromism could be observed from the grinded powder. The reddish emission of the grinded powder peaked at 600 nm weakened gradually and finally became dark, and a new absorption band at 470 nm emerged in the absorption spectra. Time-dependent density functional theory (TD-DFT) calculation results reveal that the intramolecular intramolecular charge-transfer (ICT) process is replaced by a locally excited (LE) emission on the DHA group, which leads to the quenching of fluorescence. Its impressive photochromic property inspired us to a simple but effective way to develop an encryption system which can let the correct information be displayed upon external stimulation.     

Advances in Electrochemical Decarboxylative Transformation Reactions

Owing to their non-toxic, stable, inexpensive properties, carboxylic acids are considered as environmentally benign alternatives as coupling partners in various organic transformations. Electrochemical mediated decarboxylation of carboxylic acid has emerged as a new and efficient methodology for the construction of carbon-carbon or carbon-heteroatom bonds. Compared with transition-metal catalysis and photoredox catalysis, electro-organic decarboxylative transformations are considered as a green and sustainable protocol due to the absence of chemical oxidants and strong bases. Further, it exhibits good tolerance with various functional groups. In this Minireview, we summarize the recent advances and discoveries on the electrochemical decarboxylative transformations on C−C and C−heteroatoms bond formations.     

Cooperatively assembled liquid crystals enable temperature-controlled Förster resonance energy transfer

Balancing the rigidity of a π-conjugated structure for strong emission and the flexibility of liquid crystals for self-assembly is the key to realizing highly emissive liquid crystals (HELCs). Here we show that (1) integrating organization-induced emission into dual molecular cooperatively-assembled liquid crystals, (2) amplifying mesogens, and (3) elongating the spacer linking the emitter and the mesogen create advanced materials with desired thermal–optical properties. Impressively, assembling the fluorescent acceptor Nile red into its host donor designed according to the aforementioned strategies results in a temperature-controlled Förster resonance energy transfer (FRET) system. Indeed, FRET exhibits strong S-curve dependence as temperature sweeps through the liquid crystal phase transformation. Such thermochromic materials, suitable for dynamic thermo-optical sensing and modulation, are anticipated to unlock new and smart approaches for controlling and directing light in stimuli-responsive devices.

A temperature-sensitive Förster resonance energy transfer system was constructed using a highly emissive liquid crystal co-assembled with Nile red, enabling thermo-optical modulation for controlling and directing light in stimuli-responsive devices.     

Streamlined construction of peptide macrocycles via palladium-catalyzed intramolecular S-arylation in solution and on DNA

A highly efficient and versatile method for construction of peptide macrocycles via palladium-catalyzed intramolecular S-arylation of alkyl and aryl thiols with aryl iodides under mild conditions is developed. The method exhibits a broad substrate scope for thiols, aryl iodides and amino acid units. Peptide macrocycles of a wide range of size and composition can be readily assembled in high yield from various easily accessible building blocks. This method has been successfully employed to prepare an 8-million-membered tetrameric cyclic peptide DNA-encoded library (DEL). Preliminary screening of the DEL library against protein p300 identified compounds with single digit micromolar inhibition activity.

A highly efficient and versatile method for construction of peptide macrocycles via palladium-catalyzed intramolecular S-arylation of alkyl and aryl thiols with aryl iodides under mild conditions is developed.     

A Small-Molecule Diketopyrrolopyrrole-Based Dye for in vivo NIR-IIa Fluorescence Bioimaging

Organic small-molecule fluorophores with near-infrared IIa (NIR-IIa) emission have great potential in pre-clinical detection and inoperative imaging due to the high-spatial resolution and deep penetration. However, developments of the NIR-IIa fluorophores are still facing considerable challenges. In this work, a series of diketopyrrolopyrrole (DPP)-based fluorophores were designed and synthesized. Subsequently, nanomaterial T25@F127 with significant NIR-IIa emission properties was rationally prepared by encapsulating DPP-based fluorophore T25 , and was selected for fluorescence angiography and cerebral vascular microscopic imaging with nearly 800 μm penetrating depth and excellent signal-background ratio of 4.07 and 2.26 (at 250 and 400 μm), respectively. Furthermore, the nanomaterial T25@cRGD with tumor targeting ability can image tiny metastatic tumor on intestine with a small size of 0.3 mm×1.0 mm and high-spatial resolution (SBR=3.84). This study demonstrates that the nanomaterials which encapsulated T25 behave as excellent NIR-IIa fluorescence imaging agents and have a great potential for in vivo biological application.