The hazardous production of HF poses a major chemical and societal challenge. How to incorporate fluorine (F) atoms into organic molecules, circumventing HF generation? Recently, Gouverneur and co-workers reported an innovative method to activate fluorspar (CaF2), mitigating the environmental impact of the fluorination process.
This article showcases recent breakthroughs by Scheidt and co-workers in the photoexcited structural reconstruction of carboxylic acids. By leveraging hydrogen-atom transfer and cyclization sequences, the generated diradicals facilitate the synthesis of valuable α-hydroxyl and amino phosphonates in a highly efficient and sustainable manner.
C. Wang et al. recently developed a near-infrared-activated charge transfer complex-based nanoparticle with donor- acceptor (D–A) units, which enhances photothermal conversion and generates reactive oxygen species (ROS) synergistically combines photothermal and photodynamic therapies (PTT/PDT). Preclinical experiments have shown a strong immunotherapeutic effect by integrating programmed cell death protein 1 antibody combination therapy. While the use of D–A units in nanosystems for photoimmunotherapy is still emerging, it holds great potential to revolutionize cancer treatment.
Fallon, Shende, Moore, and co-workers have identified for the first time genes encoding giant type I polyketide synthases (PKZILLA-1 & 2) in the “golden alga” Prymnesium parvum for the biosynthesis of the polyether toxin prymnesin-1, corroborating long-held biosynthetic postulates. The authors’ approach may serve as a blueprint for the future discovery of the biosynthetic machineries underlying other polyether toxins.
The Nobel Prize for Chemistry 2024 was jointly awarded to David Baker for computational protein design and to Demis Hassabis and John Jumper for protein structure prediction. This highlight showcases the impact of the Nobel prize laureates’ contributions and summarizes the history, state of the art, applications and future directions of these methods.
Davis, Koh, and co-workers disclosed a method for transforming native sugars through homolytic cleavage of an isolatable S-glycoside, in notable >95 : 5 α : β stereoselectivity. The sugar is activated by 2-chloro-1,3-dimethylimidazolinium chloride (DMC) for the installation of an S-moiety that undergoes desulfurative C−C coupling using a combination of Hantzsch ester (HE) as reductant and 1,4-diazabicyclo[2.2.2]octane (DABCO) under LED irradiation.
This paper highlights a smart sustainable Ni@TiOx catalyst, Ni encapsulated in TiOx, for propane dehydrogenation (PDH), as reported by Gong and co-workers. The catalyst demonstrates exceptional performance in PDH, achieving 94 % propylene selectivity and high stability. This design offers a cost-effective and environmentally friendly alternative to traditional noble metal-based catalysts, with potential for broader industrial applications.
In a recent study, Forse and co-workers show that structural disorder in nanoporous carbon materials significantly enhances capacitance performance, surpassing traditional factors like pore size and surface area. This discovery provides a new direction for the development of high-energy-density supercapacitors, guiding the design and synthesis of new efficient electrode materials.
A new bilayer-forming supramolecular amphiphile, reported by Elizebath et al., helps elucidate mechanisms of curvature induction in synthetic membranes. Assembly in water led initially to aggregates but, over time, membrane budding and vesicle formation were observed due to asymmetric protonation of the water-exposed terminal tertiary amines. Insights could lead to the development of new hierarchical life-like materials and artificial cells.
Kawamata, Baran, and Shenvi disclose a solitary iron-catalyzed conceptually distinct platform for constructing quaternary carbons using readily available and structurally diverse redox-active esters (RAEs) and olefins as modular coupling fragments. The heteroselective radical quaternization exhibits appreciable functional group tolerance and enables the synthesis of a palette of quaternary carbon-containing molecules under practical conditions.
A novel electrocatalyst with three finely-tuned active sites was created by doping Pd atoms to Cu2O followed by a in situ electroreduction treatment, which can speed up the complex reactions of CO2 electroreduction to C2+ products in high FE and yield of C2+ products at ampere level current density.
Xiao et al. demonstrate the use of an ionic liquid (IL) additive in zinc-iodine (Zn−I2) batteries, which serves to optimize Zn solvation and the anode interface, as well as aids in inhibiting polyiodide dissolution. The research findings reveal a capacity decay rate of 0.01 % per cycle over 18,000 cycles (4 A g−1) in a full cell. Such promising results suggest a significant advancement in the field, offering high performing Zn−I2 batteries.
Wet chemical strategies make it difficult to suppress capillary contraction and achieve orderly assembly of isotropic sheets. Cheng, Baughman, and co-workers have now used a nanoconfined water-induced alignment strategy to avoid capillary contraction, and obtained ultrastrong isotropic graphene sheets with a tensile strength of 1.87 GPa and porosity of 3.87 %.
Murai and Yamaguchi report on near-infrared emitters derived from the dithieno[2,3-b : 3′,2′-f]azepine core. Low band gaps were achieved by fusing antiaromatic azepine with thiophene rings equipped with electron-accepting moieties, which relieves the antiaromaticity of azepine through the formation of a quinoid structure. This novel approach provides dyes with fluorescence quantum yields of up to 0.02 at 878 nm.
Accessing pyridines by directly and selectively replacing a C-atom from aromatic ring systems with a nitrogen remains underexplored, while also being crucial for nitrogen scans in drug discovery processes. In this direction, a recent contribution by Levin's group involving the one-pot nitrene internalization reaction for ipso-selective C-to-N transmutation provides a direct access to pyridyl isomers.
A new PROTAC (proteolysis targeting chimera) method, reported by Zhang et al., uses self-assembling peptides as carriers of POI (protein of interest) and E3 ligase ligands. Cellular nanofibrils built upon the peptide assembly can serve as degradation centers (Nano-PROTACs) through the formation of polynary POI:Nano-PROTAC : E3 complexes. This strategy has the potential to overcome the hook effect of traditional PROTACs.
The recent findings from J. Wei et al. where they developed a catalytic system to convert mixed oxygenated aromatic plastic waste into liquid organic hydrogen carriers are highlighted herein. The catalytic system comprises a physical mixture of Ru−ReOx supported on SiO2 and zeolite HZSM-5, which work together to break apart C−O bonds in the polymers to form cycloalkanes via hydrodeoxygenation.
Tao Li and co-workers reported a material based on metal–organic framework nanocrystals which contains the largest reported permanent pores for a liquid. They described the CO2 and water adsorption, as well as the thermal switching properties of the porous liquid. This is the first example of a dual micro-macroporous liquid created using design rules of hierarchical porosity.
A new design strategy reported in Angewandte Chemie by Guo et al. involving the doping of polyaromatic hydrocarbons (PAHs) with boron and nitrogen atoms leads to an increase of the diradical character and offers potential applications in the fields of organic electronics and spintronics.
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