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Construction and Band Gap-Regulation of Ordered Macro-Microporous Single Crystals of an Amine-Linked Covalent Organic Framework.

ACS Appl Mater Interfaces

January 2025

State Key Laboratory of Bioinspired Interfacial Materials Science, Institute of Functional Nano & Soft Materials (FUNSOM), Soochow University, Suzhou 215123, China.

Heterogeneity engineering provides an effective route to manipulate the chemical and physical properties of covalent organic frameworks (COFs) but is still under development for their single-crystal form. Here, we report the strategy based on a combination of the template-assisted modulated synthesis with a one-pot crystallization-reduction method to directly construct ordered macro-microporous single crystals of an amine-linked three-dimensional (3D) COF (OM-COF-300-SR). In this strategy, the colloidal crystal-templating synthesis not only assists the formation of ordered macropores but also greatly facilitates the in situ conversion of linkages (from imine to amine) in the COF-300 single crystals.

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We report on the synthesis and characterization of an imine-type nickel complex produced the complexation of an generated 2-(iminomethyl)phenol ligand with Ni ion. The use of this complex as an electrocatalyst for H evolution in a DMF solution, with acetic acid as the proton source, was investigated in detail, employing both experimental analyses (electrochemical analysis, spectroscopy analysis) and theoretical analysis (plateau current analysis). The overpotential required for H evolution is about 590 mV with a faradaic efficiency of 49% after 3 hours bulk electrolysis, competing with the two-electron reduction of free-imine groups in the ligand.

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Small interfering RNA (siRNA) therapy in acute myeloid leukemia (AML) is a promising strategy as the siRNA molecule can specifically target proteins involved in abnormal cell proliferation. The development of a clinically applicable method for delivering siRNA molecules is imperative due to the challenges involved in effectively delivering the siRNA into cells. We investigated the delivery of siRNA to AML MOLM-13 cells with the use of two lipid-substituted polyethyleneimines (PEIs), a commercially available reagent (Prime-Fect) and a recently reported reagent with improved lipid substitution (PEI1.

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Identifying facile strategies for hierarchically structuring crystalline porous materials is critical for realizing diffusion length scales suitable for broad applications. Here, we elucidate synthesis-structure-function relations governing how room temperature catalytic conditions can be exploited to tune covalent organic framework (COF) growth and thereby access unique hierarchical morphologies without the need to introduce secondary templates or structure directing molecules. Specifically, we demonstrate how scandium triflate, an efficient catalyst involved in the synthesis of imine-based COFs, can be exploited as an effective growth modifier capable of selectively titrating terminal amines on 2D COF layers to facilitate anisotropic crystal growth.

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Photocatalytic Three-Component Reductive Coupling Synthesis of -Difluorohomoallyl Secondary Amines.

J Org Chem

January 2025

Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Sciences, Zhejiang Normal University, 688 Yingbin Road, Jinhua 321004, P. R. China.

-Difluorohomoallyl amines, an important class of -difluoroalkenes, are prevalent moieties in many bioactive compounds. However, limited methods are suitable for the synthesis of this type of compound containing secondary amines. Here, we display a photocatalytic multicomponent protocol for the synthesis of -difluoroalkenes containing secondary amines, which makes use of readily available materials: arylamines, alkyl aldehydes, and α-trifluoromethyl alkenes.

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