CHEMICAL COMMUNICATIONS

Mass-tagged aminated probes for rapid discovery of azaphilic natural products in fungal crude extracts
Flon V, Pavesi C, Oger S, Leleu S, Retailleau P, Jennings LK, Prado S and Franck X
Reactivity-based screening (RBS) was used to screen fungal crude extracts for the presence of new azaphilic natural products. A probe composed of a nucleophilic primary amine and an isotopic mass tag was designed for its reactivity towards azaphilic compounds. Addition of the probe to crude extracts of fungal complexes, together with analytical tools for dereplication such as haloseeker and molecular networking, allowed easy detection of azaphilic compounds. The exploitation of this RBS protocol led to the isolation and structural characterization of new azaphilones.
Machine learning directed discovery and optimisation of a platinum-catalysed amide reduction
Casillo E, Maliszewski BP, Urbina-Blanco CA, Scattolin T, Cazin CSJ and Nolan SP
The discovery and optimisation of reaction conditions leading to the reduction of amides, a fundamental large-scale industrial reaction, is achieved using a machine learning (ML) platform and a platinum catalyst. The optimisation leads to the discovery of a new platinum-based catalytic system that displays unexpectedly high performance. The approach enables rapid and high conversions at ppm-level catalyst loadings.
Unveiling the effect of codoping in strontium ferrite for oxygen evolution in alkaline media
Zhu S, Wang M, Mao Y, Wang J, Ding J, Liu G and Zhang W
Co and Ni codoped strontium ferrite particles were prepared by a solid-state strategy and employed as catalysts for the OER. They exhibited a Tafel slope of 55 mV dec and required an overpotential of 334 mV to afford a current density of 10 mA cm, which is lower than that of Co and Ni separately doped samples. The DFT calculations reveal the redistribution of local charge around Fe atoms, decrease of energy barriers, and increase of conductivity by doping. This work unveils the effect of codoping on the activities of Fe-based perovskite oxide for the OER, providing a strategy to engineer other perovskite-based materials for catalysis.
Efficient CO photoreduction using a water-soluble conjugated polyelectrolyte grafted imidazolium-functionalized side chain
Chen M, Li W, Zhang T, Xu T, Wang B, Zeng C, Li F and Dai C
Herein, we reported the development of a water-soluble conjugated polyelectrolyte (CPE) for efficient CO photoreduction under visible light ( > 420 nm). Bearing a fluorene-benzothiadiazole backbone and imidazolium-functionalized side chains, PFBT-Im exhibits remarkable photocatalytic activity with nearly 100% selectivity and a CO yield of 453.16 μmol g within 4 h, which is 8.6 and 2.5 times larger than those of conjugated polymers grafted with octyl and trimethylammonium side chains, respectively.
Fabrication of gelatin hydrogels using pre-coordinated lanthanide complexes imine crosslinking
Yu CC, Hsu YY, Su YC, Yang YC, Wang TY and Yeh YC
Pre-coordinated lanthanide-containing complexes are used to crosslink polyethyleneimine-modified gelatin to form gelatin hydrogel through imine bond formation.
The effects of fluorinated metal-organic frameworks as additives in polymer-based electrolytes for all-solid-state lithium batteries
He L, Di Z, Li J, Wang S, Kong W, Li R, Proskurin A, Lv C and Wei T
In this study, solid composite electrolytes (SCEs) comprising UIO-66-F(Zr) were obtained by using a simple solution casting method. By introducing fluorinated groups, the interaction between the MOF and the polymer was significantly improved, which not only stabilizes the SEI layer but also improves the ionic conductivity of the SCEs, thus advancing the practical application of solid composite electrolytes in lithium metal batteries.
Recent advances in the synthesis of N-heterocycles from α-amino acids mediated by iodine
Yang DS, Xiang JC and Wu AX
The synthesis of N-heterocycles has received extensive attention from scientists considering their important role in organic synthesis, pharmaceuticals, and materials chemistry. α-Amino acids (α-AAs), both natural and non-natural, are structurally diverse, containing basic amino groups, acidic carboxyl groups, and various side-chain R groups in a single molecule. Given their structural properties and wide range of sources, they have undoubtedly become suitable synthetic building blocks for organic synthesis. However, conventional transformations of amino acids (AAs) focus on the amino and carboxyl groups independently. Conversions for these two prominent functional groups generally do not affect both their alpha positions and their branched chains. Over the past decade, with the application of iodine (I) in the field of heterocyclic synthesis, the use of α-AAs for diverse construction of complex N-heterocyclic structures has gained increasing attention. This synthetic strategy relies on the I-mediated Strecker degradation, which introduces α-AAs as electrophilic carbon species into the domino reaction sequence decarboxylation and deamination processes. In this review, we have summarized recent advances in this emerging area.
RAFT solution polymerisation of bio-based γ-methyl-α-methylene-γ-butyrolactone monomer in DMSO and Cyrene
Harris OJ, Larder RR, Jordan B, Prior I, El-Khoury R, Sebakhy KO and Hatton FL
Reversible addition fragmentation chain transfer (RAFT) solution polymerisation of the bio-based lactone monomer γ-methyl-α-methylene-γ-butyrolactone (γMeMBL) has been demonstrated in DMSO and Cyrene. RAFT control was evidenced by control over molecular weights, low disperisites, and kinetic evaluation. Purified P(γMeMBL) homopolymers exhibited high glass transition temperatures (206-221 °C) and excellent thermal stabilities. This work demonstrates the first RAFT solution polymerisation of γMeMBL and the first example of RAFT polymerisation in Cyrene.
Synthesis of aryl fluorocyclopropanes from aryl fluorodiazirines and alkenes in continuous flow
To HM, Mirakhorli S and Ollevier T
Photochemically induced generation of aryl fluorocarbenes from aryl fluorodiazirines and their subsequent [2+1] cycloaddition with alkenes was developed in continuous flow. The generated electrophilic aryl fluorocarbene reacted with a range of alkenes enabling the synthesis of the corresponding 3-fluoro-3-aryl-cyclopropanes in a 5-minute residence time under 380-nm LED irradiation in continuous flow (20 examples). The scaled-up reaction of 3-fluoro-3-(4-chlorophenyl)-3-diazirine with styrene under irradiation at 380 nm led to the fluorocyclopropane with a 77% yield, providing a throughput yield of 0.945 g h.
Effects of dissolved 3d-block metal ions on PEM water electrolysis performance
Kong S, Fushimi K, Li A and Nakamura R
The influence of water impurities caused by 3d-block metal ion dissolution on proton exchange membrane (PEM) water electrolysis was investigated. While Co and Ni significantly decreased membrane conductivity, MnO anions exhibited a negligible effect. As MnO had low affinity for perfluorosulfonic acid in the PEM, Mn oxides materials have promising potential for use in PEM water electrolyzers.
Boosting the electrochemical performance of the Ni-rich LiNiCoMnO cathode by high-valence Zr/Mo dual-doping
Cao H, Zhang Y, Zhou X, Yu J, Chen X and Li L
Ni-rich oxides are attractive high-energy cathodes for lithium-ion batteries but suffer from inherent instability. Herein, we employed an ectopic Zr/Mo dual-doping strategy to reinforce the layered structure through robust M-O bonds and the pillar effect. This strategy mitigates lattice distortion during cycling and inhibits the interface side reactions.
Sulfinfinitenes: infinitenes of fused thiophene rings
Karadakov PB and Cummings E
Sulfinfinitenes, analogues of infinitene constructed from thiophene rings and assembled by applying a "cut-twist-restitch" sequence to two sulflowers, are explored through DFT calculations. The sulfinfinitene with 16 thiophene rings is only slightly more strained than the [8]sulflower, which has been synthesized, and can be considered as a promising synthetic target.
Sustainable production of aromatic chemicals from lignin using enzymes and engineered microbes
Sodré V and Bugg TDH
Lignin is an aromatic biopolymer found in plant cell walls and is the most abundant source of renewable aromatic carbon in the biosphere. Hence there is considerable interest in the conversion of lignin, either derived from agricultural waste or produced as a byproduct of pulp/paper manufacture, into high-value chemicals. Although lignin is rather inert, due to the presence of ether C-O and C-C linkages, several microbes are able to degrade lignin. This review will introduce these microbes and the enzymes that they use to degrade lignin and will describe recent studies on metabolic engineering that can generate high-value chemicals from lignin bioconversion. Catabolic pathways for degradation of lignin fragments will be introduced, and case studies where these pathways have been engineered by gene knockout/insertion to generate bioproducts that are of interest as monomers for bioplastic synthesis or aroma chemicals will be described. Life cycle analysis of lignin bioconversion processes is discussed.
Spatially confined FeF cathodes in N-doped carbon nanotubes for lithium storage
Li J, Li X, Li M, Jiang Q, Liu J, Duan R, Cao G, Wang J and Li W
Herein, a N-doped carbon nanotube encapsulated FeF nanoparticle (FeF@N-CNTs) composite was developed pyrolysis and gas-phase fluorination strategies. The 3D carbon constrained scaffold enhances conversion reaction kinetics and effectively suppresses significant volume changes in the FeF cathode during cycling. Consequently, FeF@N-CNTs exhibits excellent rate capability and maintains a high discharge capacity of 110.6 mA h g after 5000 cycles at 2 A g. It is believed that this study presents an innovative strategy for the development of long-cycling conversion-type cathode materials.
Palladium-catalyzed cascade cyclization of isocyanides with di-(-iodophenyl)sulfonylguanidines: access to heterocyclic fused quinazolines
Ge S, Zhu YM, Xu XP, Zi Y and Ji SJ
A palladium-catalyzed cascade cyclization reaction of di--iodophenyl sulfonylguanidines with isocyanides for the efficient and selective synthesis of 5- or 6-membered heterocyclic fused quinazolines has been developed. Diverse functional groups are well tolerated, and this method has been successfully applied to a larger scale synthesis.
Hydrazone-linked covalent organic frameworks for fluorescence detection of Hg
Wang X, Yang Z, Meng L, Li X, Wei H, Ning J, Wang S, Cao D and Hao L
A hydrazone-linked COF (DvDf-C3XJ-COF) with hydrogen-bond reinforcement and abundant coordination sites was synthesized, exhibiting strong fluorescence and high sensitivity/selectivity for Hg detection, with a detection limit of 1.65 × 10 M. The fluorescence quenching for Hg is attributed to coordination interactions, which occur through a dynamic quenching process.
Amorphous Fe-O-P electro(pre)catalysts for energy-efficient H production coupled with ethylene glycol oxidation
Yuan F, Chen X, Yang W, Wu W, Zheng M, Xu J, Yu N and Chen L
This study presents the synthesis and electrocatalytic performance of amorphous Fe-O-P nanocages derived from Fe-MOFs for water and ethylene glycol (EG) oxidation. Despite structural and compositional changes, the electrocatalyst in an electrolytic cell with Pt/C shows high activity and reduced cell voltage, efficiently generating H and formic acid in a KOH-EG mixed electrolyte.
Positional effects of electron-donating and withdrawing groups on the photophysical properties of single benzene fluorophores
Kim D, Kim JY, Kim H, Jeong E, Lee M, Kim D, Kim J, Park MH and Kim M
We investigated how the positional arrangement of electron-donating (amino) and electron-withdrawing (ester) groups in single benzene-based fluorophores influences their emission properties. By synthesizing 26 regioisomeric fluorophores, we achieved wavelength modulation from 322 to 539 nm, revealing key correlations between functional group positioning and photophysical behavior.
Tunable electronic structure and excellent catalytic properties of transition-metal-doped BeN monolayer
Zhao WH, Sun DY, Deng ZQ, Liu SY, Cao LM, Deng XH, Yin WJ and Tang ZK
The electronic properties and OER catalytic activity of pristine BeN monolayers and single-transition-metal-doped BeN monolayers (TM@BeN) were systematically investigated using density functional theory. Among all the types of TM@BeN analyzed, Fe@BeN was determined to exhibit the best OER activity, with an overpotential of 0.33 V, and to display excellent metallic conductivity. Besides, the OER catalytic activity of Fe@BeN can be further enhanced by applying biaxial strain and designing X-Fe@BeN (X = B, C, O, P, S) catalysts.
C-H/F bond activation and borylation with iron
Zars E, Pick L, Kankanamge A, Gau MR, Meyer K and Mindiola DJ
Reduction of [K{(pyrrpyr)Fe}(μ-N)] (1) with two equiv. of KC in the presence of crown-ether 18-C-6 yields the N adduct [{K(18-C-6)}(pyrrpyr)Fe(N)] (2). Complex 2 heterolytically splits the C-H bond of benzene to form [{K(18-C-6)}(pyrrpyr)Fe(CH)] (3), whereby usage of a diboron Bpin promotes hydride elimination to form the salt [K(18-C-6)HBPin] (4). Similarly, 3 can also be formed by cleavage of the C-F bond of fluorobenzene. Reaction of 3 with ClBcat yields [K(18-C-6)(thf)][(pyrrpyr)FeCl] (5) and PhBcat and the former can be reduced to 2 to complete a synthetic cycle for heterolytic benzene C-H activation and borylation.
Varied CO photoreduction activities of UiO-66-NH MOFs with different aggregation morphologies
Zhang SR, Zou YH, Wang HN, Xu GJ, Xie W, Xu N, Xu YH and Lan YQ
Several kinds of UiO-66-NH with different aggregation morphologies were prepared to verify that the morphology of the photocatalyst could influence charge transfer. That showing poor aggregation exhibits superior CO photoreduction performance, attributed to the small particle size related to the poor aggregation and to the resulting high efficiency of separation of photogenerated electrons and holes.