New Insight into the Electronic Effect for Cu Porphyrin Catalysts in Electrocatalytic of CO2 into CH4.

Perturbation of the copper (Cu) active site by electron manipulation is a crucial factor in determining the activity and selectivity of electrochemical carbon dioxide (CO2 ) reduction reaction (e-CO2 RR) in Cu-based molecular catalysts. However, much ambiguity is present concerning their electronic structure-function relationships. Here, three molecular Cu-based porphyrin catalysts with different electron densities at the Cu active site, Cu tetrakis(4-methoxyphenyl)porphyrin (Cu─T(OMe)PP), Cu tetraphenylporphyrin (Cu─THPP), and Cu tetrakis(4-bromophenyl)porphyrin (Cu─TBrPP), are prepared. Although all three catalysts exhibit e-CO2 RR activity and the same reaction pathway, their performance is significantly affected by the electronic structure of the Cu site. Theoretical and experimental investigations verify that the conjugated effect of ─OCH3 and ─Br groups lowers the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbitals (LUMO) gap of Cu─T(OMe)PP and Cu─TBrPP, promoting faster electron transfer between Cu and CO2 , thereby improving their e-CO2 RR activity. Moreover, the high inductive effect of ─Br group reduces the electron density of Cu active site of Cu─TBrPP, facilitating the hydrolysis of the bound H2 O and thus creating a preferable local microenvironment, further enhancing the catalytic performance. This work provides new insights into the relationships between the substituent group characteristics with e-CO2 RR performance and is highly instructive for the design of efficient Cu-based e-CO2 RR electrocatalysts.

Construction of Low-Coordination Cu-C2 Single-Atoms Electrocatalyst Facilitating the Efficient Electrochemical CO2 Reduction to Methane.

Constructing Cu single-atoms (SAs) catalysts is considered as one of the most effective strategies to enhance the performance of electrochemical reduction of CO2 (e-CO2 RR) towards CH4 , however there are challenges with activity, selectivity, and a cumbersome fabrication process. Herein, by virtue of the meta-position structure of alkynyl in 1,3,5-triethynylbenzene and the interaction between Cu and -C≡C-, a Cu SAs electrocatalyst (Cu-SAs/HGDY), containing low-coordination Cu-C2 active sites, was synthesized through a simple and efficient one-step method. Notably, this represents the first achievement of preparing Cu SAs catalysts with Cu-C2 coordination structure, which exhibited high CO2 -to-CH4 selectivity (72.1 %) with a high CH4 partial current density of 230.7 mA cm-2 , and a turnover frequency as high as 2756 h-1 , dramatically outperforming currently reported catalysts. Comprehensive experiments and calculations verified the low-coordination Cu-C2 structure not only endowed the Cu SAs center more positive electricity but also promoted the formation of H•, which contributed to the outstanding e-CO2 RR to CH4 electrocatalytic performance of Cu-SAs/HGDY. Our work provides a novel H⋅-transferring mechanism for e-CO2 RR to CH4 and offers a protocol for the preparation of two-coordinated Cu SAs catalysts.

Ceria Nanoenzyme-Based Hydrogel with Antiglycative and Antioxidative Performance for Infected Diabetic Wound Healing.

Diabetic wound healing still faces a dilemma because of the hostile hyperglycemic, oxidative, and easily-infected wound microenvironment. In addition, advanced glycation end products (AGEs) further impede wound repair by altering the immunological balance. Herein, ceria nanorods with distinctive antiglycative and excellent antioxidative capacities are innovatively introduced into a self-healing and erasable hydrogel, which could reshape the wound microenvironment by expediting hemostasis, inhibiting infection, reducing AGEs, and continuously depleting reactive oxygen species. The remitted oxidative stress and glycosylation synergistically regulate inflammatory responses, and promote revascularization and extracellular matrix deposition, resulting in accelerated diabetic wound repair. This study provides a highly efficient strategy for constructing nanoenzyme-reinforced antiglycative hydrogel that regulates every wound healing stage for diabetic wound management.

Construction of Synergistic Ni3 S2 -MoS2 Nanoheterojunctions on Ni Foam as Bifunctional Electrocatalyst for Hydrogen Evolution Integrated with Biomass Valorization.

The intrinsic sluggish kinetics of the oxygen evolution reaction (OER) limit the improvement of hydrogen evolution reaction (HER) performance, and substituting the anodic oxidation of biomass materials is an alternative approach, given its lower oxidation potential and higher added value compared to those of OER. In this study, a Ni3 S2 -MoS2 nanoheterojunction catalyst with strong electronic interactions is prepared. It exhibits high efficiency for both the HER and the electrooxidation of 5-hydroxymethylfurfural (HMF). In a two-electrode cell with Ni3 S2 -MoS2 serving as both the anode and cathode, the potential is only 1.44 V at a current density of 10 mA cm-2 , which is much lower than that of pure water splitting. Density functional theory calculations confirm that the strong chemisorption of H and HMF at the interface leads to outstanding electrocatalytic activity. The findings not only provide a strategy for developing efficient electrocatalysts, but also provide an approach for the continuous production of high value-added products and H2 .

Correction to "Structure Based Design of Non-Natural Peptidic Macrocyclic Mcl-1 Inhibitors".

[This corrects the article DOI: 10.1021/acsmedchemlett.6b00464.].

Structure Based Design of Non-Natural Peptidic Macrocyclic Mcl-1 Inhibitors.

Mcl-1 is a pro-apoptotic BH3 protein family member similar to Bcl-2 and Bcl-xL. Overexpression of Mcl-1 is often seen in various tumors and allows cancer cells to evade apoptosis. Here we report the discovery and optimization of a series of non-natural peptide Mcl-1 inhibitors. Screening of DNA-encoded libraries resulted in hit compound 1, a 1.5 µM Mcl-1 inhibitor. A subsequent crystal structure demonstrated that compound 1 bound to Mcl-1 in a ß-turn conformation, such that the two ends of the peptide were close together. This proximity allowed for the linking of the two ends of the peptide to form a macrocycle. Macrocyclization resulted in an approximately 10-fold improvement in binding potency. Further exploration of a key hydrophobic interaction with Mcl-1 protein and also with the moiety that engages Arg256 led to additional potency improvements. The use of protein-ligand crystal structures and binding kinetics contributed to the design and understanding of the potency gains. Optimized compound 26 is a <3 nM Mcl-1 inhibitor, while inhibiting Bcl-2 at only 5 µM and Bcl-xL at >99 µM, and induces cleaved caspase-3 in MV4-11 cells with an IC50 of 3 µM after 6 h.

[3-D endocardial surface modelling based on the convex hull algorithm].

In this paper, a method based on the convex hull algorithm is presented for extracting modelling data from the locations of catheter electrodes within a cardiac chamber, so as to create a 3-D model of the heart chamber during diastole and to obtain a good result in the 3-D reconstruction of the chamber based on VTK.

[Fluoroscopic image capturing and DICOM storage application in the cardio-catheter room].

This paper analyses the data structure of DICOM standard by the applications in the Non-DICOM format fluoroscopic images converted into the DICOM format images. It puts forward a solution to integrate the Multi-Channel Electrophysiology Recorder System with the X -ray system in the cardio-catheter room.