Covalent

While there are myriad ways to construct metal-organic framework (MOF) based catalysts, the introduction of catalytic functionality via covalent post-synthesis functionalization (PSM) offers multiple advantages: (i) a wide range of different catalyst types are generated from a handful of well-known parent MOFs, (ii) MOF catalyst properties can be systematically tuned while changing few variables, and (iii) catalytically active functional groups that would otherwise interfere with MOF assembly can be introduced facilely...

Due to their maximum atomic use of metal sites, single-atom catalysts (SACs) exhibit excellent catalytic activity in a variety of reactions. Although many techniques have been reported for the production of SACs, the construction of single atoms through a convenient strategy is still challenging. Here, we provide a facile method to prepare nickel SACs by utilizing the inherent confined space between the template and silica walls in template-occupied mesoporous silica KIT-6 (TOK). After the introduction of nickel-containing precursors into the inherent confined space of the TOK by solid-phase grinding, Ni SACs can be produced promptly during calcination...

The confinement effect of catalytic nanoreactors containing metal catalysts within nanometer-sized volumes has attracted significant attention for their potential to enhance reaction rate and selectivity. Nevertheless, unregulated catalyst loading, aggregation, leaching, and limited reusability remain obstacles to achieving an efficient nanoreactor. A robust and durable catalytic membrane nanoreactor prepared by incorporating palladium nanocatalysts within a 3D-continuous nanoporous covalent framework membrane is presented...

Carbon nanoallotropes have attracted significant attention in the field of materials science due to their unique combination of physicochemical and biological properties, with numerous applications. One-dimensional (1D) and two-dimensional (2D) sp2 -carbon nanoallotropes, such as carbon nanohorns (CNHs), carbon nanotubes (CNTs), and graphene, have emerged as prominent candidates for a variety of technological advancements. To fully exploit their exceptional characteristics, the covalent functionalization of these nanostructures may alleviate the problems with the processing and final performance...

Scandium oxide (Sc2 O3 ) has a wide range of applications in metallurgy, chemical industry, electronics and many other high-tech fields. However, most Sc2 O3 materials exist in the powder or bulk form, while nanostructured Sc2 O3 has rarely been reported as there is a lack of a common method to control its dimensionality, hindering the understanding of new properties and potential applications of nano-Sc2 O3 materials. In this paper, we establish a procedure to synthesize a two-dimensional (2D) Sc2 O3 -covalent organic framework (COF) composite film where the crystal size of Sc2 O3 domains is as small as ∼3 nm...

Inhibition of hypoxanthine-guanine-xanthine phosphoribosyltransferase activity decreases the pool of 6-oxo and 6-amino purine nucleoside monophosphates required for DNA and RNA synthesis, resulting in a reduction in cell growth. Therefore, inhibitors of this enzyme have potential to control infections, caused by Plasmodium falciparum and Plasmodium vivax , Trypanosoma brucei , Mycobacterium tuberculosis , and Helicobacter pylori . Five compounds synthesized here that contain a purine base covalently linked by a prolinol group to one or two phosphonate groups have K i values ranging from 3 nM to >10 μM, depending on the structure of the inhibitor and the biological origin of the enzyme...

Energetic hydrogen-bonded organic frameworks (E-HOFs), as a type of energetic material, spark fresh vitality to the creation of high energy density materials (HEDMs). However, E-HOFs containing cations and anions face challenges such as reduced energy density due to the inclusion of crystal water. In this work, the modification of amino groups in N-rich organic units could form a smart building block of hydrogen-bonded frameworks capable of changing the volume of the void space in the molecule through adaptive deformation of E-MOF blocks, thus enabling the replacement of water...

During their biosynthesis, Sonic hedgehog (Shh) morphogens are covalently modified by cholesterol at the C-terminus and palmitate at the N-terminus. Although both lipids initially anchor Shh to the plasma membrane of producing cells, it later translocates to the extracellular compartment to direct developmental fates in cells expressing the Patched (Ptch) receptor. Possible release mechanisms for dually lipidated Hh/Shh into the extracellular compartment are currently under intense debate. In this paper, we describe the serum-dependent conversion of the dually lipidated cellular precursor into a soluble cholesteroylated variant (ShhC ) during its release...

Covalent organic frameworks (COFs), which have layered stacking structures, extended π-conjugation, and periodic frameworks have become a promising class of materials for a wide range of applications. However, their synthetic pathways frequently need high temperatures, enclosed systems under high pressures, an inert atmosphere, and extended reaction time, which restrict their practicality in real-world applications. Herein, the use of gamma irradiation is presented to synthesize highly crystalline COFs at room temperature under an open-air condition within a short time...

Covalent organic frameworks (COFs) have attracted growing interests as new material platform for a range of applications. In this study, a triazine-carbazole-based covalent organic framework (COF-TCZ) was designed as highly porous material with conjugated donor-acceptor networks, and  feasibley synthesized by the Schiff condensation of 4,4',4''-(1,3,5-triazine-2,4,6-triyl)trianiline (TAPB) and 9-(4-formylphenyl)-9H-carbazole-3,6-dicarbaldehyde (CZTA) under the solvothermal condition. Considering the effect of linkage, the imine-linked COF-TCZ was further oxidized to obtain an amide-linked covalent organic framework (COF-TCZ-O)...

Ferroptosis is an emerging form of regulated cell death in an oxidative stress- and iron-dependent manner, primarily induced by the over-production of reactive oxygen species (ROS). Manipulation of ferroptosis has been considered a promising therapeutic approach to inhibit liver tumor growth. Nevertheless, the development of resistance to ferroptosis in liver cancer poses a significant challenge in cancer treatment. Post-translational modifications (PTMs) are crucial enzymatic catalytic reactions that covalently regulate protein conformation, stability and cellular activities...

Solid-state nuclear magnetic resonance spectroscopy is routinely used in the field of covalent organic frameworks to elucidate or confirm the structure of the synthesized samples and to understand dynamic phenomena. Typically this involves the interpretation and simulation of the spectra through the assumption of symmetry elements of the building units, hinging on the correct assignment of each line shape. To avoid misinterpretation resulting from library-based assignment without a theoretical basis incorporating the impact of the framework, this work proposes a first-principles computational protocol for the assignment of experimental spectra, which exploits the symmetry of the underlying building blocks for computational feasibility...

Two chiral covalent organic frameworks (CCOFs) core-shell microspheres based on achiral organic precursors by chiral-induced synthesis strategy for HPLC enantioseparation are reported for the first time. Using n-hexane/isopropanol as mobile phase, various kinds of racemates were selected as analytes and separated on the CCOF-TpPa-1@SiO2 and CCOF-TpBD@SiO2 -packed columns with a low column backpressure (3 ~ 9 bar). The fabricated two CCOFs@SiO2 chiral columns exhibited good separation performance towards various racemates with high column efficiency (e...

This study focused on the efficacy of a calcined layered double hydroxide (CLDH) clay in adsorbing two antiretroviral drugs (ARVDs), namely efavirenz (EFV) and nevirapine (NVP), from wastewater. The clay was synthesized using the co-precipitation method, followed by subsequent calcination in a muffle furnace at 500 °C for 4 h. The neat and calcined clay samples were subjected to various characterization techniques to elucidate their physical and chemical properties. Response surface modelling (RSM) was used to evaluate the interactions between the solution's initial pH, adsorbent loading, reaction temperature, and initial pollutant concentration...

Molecular knots and entanglements form randomly and spontaneously in both biological and synthetic polymer chains. It is known that macroscopic materials, such as ropes, are substantially weakened by the presence of knots, but until now it has been unclear whether similar behaviour occurs on a molecular level. Here we show that the presence of a well-defined overhand knot in a polymer chain substantially increases the rate of scission of the polymer under tension (≥2.6× faster) in solution, because deformation of the polymer backbone induced by the tightening knot activates otherwise unreactive covalent bonds...

Structure-function relationships are key to understanding enzyme mechanisms, controlling enzyme activities, and designing biocatalysts. Here, we investigate the functions of arginine residues in the active sites of pyridoxal-5'-phosphate (PLP)-dependent non-canonical D-amino acid transaminases, focusing on the analysis of a transaminase from Haliscomenobacter hydrossis. Our results show that the tandem of arginine residues R28* and R90, which form the conserved R-[RK] motif in non-canonical D-amino acid transaminases, not only facilitates effective substrate binding but also regulates the catalytic properties of PLP...

With a number of outstanding properties, gelatin is an ideal candidate for assembling nanoplatforms in biomedical applications. Generally, gelatin nanocarriers are cross-linked by aldehydes to improve their stability in water solution. However, aldehydes could cause multiple toxicities and their cross-linking products are uncontrollable. Here, we first used a self-immolative cross-linker to assemble gelatin nanocarriers for the controlled release of drugs and targeted cancer therapy. The cross-linker contains a disulphide bridge and two symmetrical succinimidyl-esters, endowing it with multiple functions: 1) to cross-link the gelatin nanocarriers and thus improve their stability in water; 2) to conjugate the drug and tumor-targeting ligands with nanocarriers through covalent linkage; 3) to redox-responsively degrade the nanocarriers through hydrolysis of disulphide bridge; and 4) to produce traceless drug molecules through self-immolative reaction...

The widespread application of engineered nanoparticles (NPs) in environmental remediation has raised public concerns about their toxicity to aquatic organisms. Although appropriate surface modification can mitigate the ecotoxicity of NPs, the lack of polymer coating to inhibit toxicity completely and the insufficient knowledge about charge effect hinder the development of safe nanomaterials. Herein, we explored the potential of polyglycerol (PG) functionalization in alleviating the environmental risks of NPs...

Glutathione S-transferases (GSTs) belong to the superfamily of multifunctional detoxification isoenzymes with an important role in cellular signaling. They can prevent reactive electrophilic compounds from harming the body by covalently binding identical type of moleculs to each other. GSTs can be used alone or in combination for cancer detection or diagnosis, in addition to therapeutic interventions. In recent years, indoles have become important due to their structural properties and biological activities such as antitubercular, antiulcer, anti-oxidant, and antidiabetic, as well as for the development of new anticancer agents...

Ionic liquids (ILs) are organic salts with a low melting point. This is due to the fact that their alkyl side chains, which are covalently connected to the ion, hinder the crystallization of ILs. The low melting point of ILs has led to their widespread use as relatively harmless solvents. However, ILs do have toxic properties, the mechanism of which is largely unknown, so identifying the cellular targets of ILs is of practical importance. In our work, we showed that imidazolium ILs are not able to penetrate model membranes without damaging them...