Sodium (Na) metal is a promising alternative to lithium metal as an anode material for the next-generation energy storage systems due to its high theoretical capacity, low cost, and natural abundance. However, dendritic/mossy Na growth caused by uncontrollable plating/stripping results in serious safe concerns and rapid electrode degradation. This study presents Sn 2+ pillared Ti 3 C 2 MXene serving as a stable matrix for high-performance dendrite-free Na metal anode. The intercalated Sn 2+ between Ti 3 C 2 layers not only induces Na to nucleate and grow within Ti 3 C 2 interlayers, but also endows the Ti 3 C 2 with larger interlayer space to accommodate the deposited Na by taking advantage of the "pillar effect," contributing to uniform Na deposition. As a result, the pillar-structured MXene-based Na metal electrode could enable high current density (up to 10 mA cm −2 ) along with high areal capacity (up to 5 mAh cm −2 ) over long-term cycling (up to 500 cycles). The full cell using MXene-based Na metal anode exhibits superior electrochemical performance than that using host-less commercial Na. It is believed that the well-controlled MXene-based Na anode not only extends the application scope of MXene, but also provides guidance in designing high-performance Na metal batteries.

Sodium metal is an attractive anode for next-generation energy storage systems owing to its high specific capacity, low cost, and high abundance. Nevertheless, uncontrolled Na dendrite growth caused by the formation of unstable solid electrolyte interphase (SEI) leads to poor cycling performance and severe safety concerns. Sodium polysulfide (Na S ) alone is revealed to serve as a positive additive or pre-passivation agent in ether electrolyte to improve the long-term stability and reversibility of the Na anode, while Na S -NaNO as co-additive has an adverse effect, contrary to the prior findings in the lithium anode system. A superior cycling behavior of Na anode is first demonstrated at a current density up to 10 mA cm and a capacity up to 5 mAh cm over 100 cycles. As a proof of concept, a high-capacity Na-S battery was prepared by pre-passivating the Na anode with Na S . This study gives insights into understanding the differences between Li and Na systems.

Mechanistic proposals for nickel-catalyzed coupling reactions often invoke five-coordinate alkyl- or aryl-bound Ni(II) and/or high-valent nickel(III) species, but because of their reactive nature, they have been difficult to study and fingerprint. In this work, we invoked the stabilizing properties of fluoroalkyl ligands to access such nickel species bearing ligands that are commonplace in organic coupling reactions. We show that five-coordinate Ni(II) complexes containing nickel-carbon bonds can readily be prepared given the appropriate precursor, and we also present evidence for the formation of Ni(III) species upon chemical and electrochemical oxidation of the five-coordinate complexes.

Heterocyclic compounds play an important role as the main sources of lead molecules of agrochemicals. Synthesis and biological activity of thiadiazole-containing 1,2,4-triazolo[3,4-b][1,3,4]-thiadiazoles were seldom reported. To find novel lead compounds with various biological activities, a series of 6-substituted-3-(4-methyl-1,2,3-thiadiazolyl)[1,2,4]triazolo[3,4-b][1,3,4]thiadizoles were rationally designed and synthesized according to the principle of combinations of bioactive substructures by the condensation of 3-(4-methyl-1,2,3-thiadiazolyl)-4-amino-1,2,4-triazole-5-thione with various carboxylic acids and phosphorus oxychloride. All newly synthesized compounds were identified by proton nuclear magnetic resonance ((1)H NMR), infrared spectroscopy (IR), electroionization mass spectrometry (EI/MS), and elementary analysis. The crystal structure of 3-(4-methyl-1,2,3-thiadiazolyl)-6-(4-methylphenyl)[1,2,4]triazolo[3,4-b][1,3,4]thiadizole was determined by X-ray diffraction crystallography. In this crystal, two intermolecular hydrogen bonds (N2...H-C12 and N3...H-C13), a weak intermolecular interaction (S...S), and the weak ppi-ppi intermolecular interaction were observed. Fungicide screening indicated that all of the target compounds showed certain extent of growth inhibition against fungi tested. 3-(4-Methyl-1,2,3-thiadiazolyl)-6-n-propyl[1,2,4]triazolo[3,4-b][1,3,4]thiadizole and 3-(4-methyl-1,2,3-thiadiazolyl)-6-trichloromethyl[1,2,4]triazolo[3,4-b][1,3,4]thiadizole were found to have potential wide spectrum of fungicide activity. The median effective concentrations (EC(50)) detected for 3-(4-methyl-1,2,3-thiadiazolyl)-6-trichloromethyl[1,2,4]triazolo[3,4-b][1,3,4]thiadizole to six fungi were from 7.28 micromol/L against Pellicularia sasakii (Shirai) to 42.49 micromol/L against Alternaria solani . The results indicated that thiadiazole-containing 1,2,4-triazolo[3,4-b][1,3,4]-thiadiazoles were potential fungicide lead compounds.

Traditional single-molecule methods do not report whole-molecule kinetic conformations, and their adaptive shape changes during the process of self-assembly. Here, using graphene liquid-cell electron microscopy with electrons of low energy at low dose, we show that this approach resolves the time dependence of conformational adaptations of macromolecules for times up to minutes, the resolution determined by motion blurring, with DNA as the test case. Single-stranded DNA molecules are observed in real time as they hybridize near the solid surface to form double-stranded helices; we contrast molecules the same length but differing in base-pair microstructure (random, blocky, and palindromic hairpin) whose key difference is that random sequences possess only one stable final state, but the others offer metastable intermediate structures. Hybridization is observed to couple with enhanced translational mobility and torsion-induced rotation of the molecule. Prevalent transient loops are observed in error-correction processes. Transient melting and other failed encounters are observed in the competitive binding of multiple single-stranded molecules. Among the intermediate states reported here, some were predicted but not observed previously, and the high incidence of looping and enhanced mobility come as surprises. The error-producing mechanisms, failed encounters, and transient intermediate states would not be easily resolved by traditional single-molecule methods. The methods generalize to visualize motions and interactions of other organic macromolecules.

With the merits of a naturally abundant sodium (Na) resource with similar electrochemical characteristics to that of lithium-ion batteries, Na-based batteries have been widely studied as the next-generation economical and practical energy storage choices. Particularly, the Na metal anode possesses a high theoretical specific capacity of 1166 mAh/g and low electrochemical potential of −2.71 V (vs standard hydrogen electrode), and it is therefore considered as the ultimate anode material for Na-based batteries. Nevertheless, the commercialization of the Na metal anode is still largely hindered by several long-lasting challenges, namely, metallic Na dendrite growth and unstable solid electrolyte interphase (SEI) formation. In this review, we first go over the fundamental mechanisms associated with these challenges. Then, we provide an in-depth discussion on the recent key advancements from the perspectives of liquid electrolyte optimization, artificial SEI fabrication, and solid-state electrolyte implementation. Lastly, we highlight the promising aspects from each strategy for the future development of Na-based batteries.

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Complexes of Fe3+ engage in rich aqueous solution speciation chemistry in which discrete molecules can react with solvent water to form multinuclear μ-oxo and μ-hydroxide bridged species. Here we demonstrate how pH- and concentration-dependent equilibration between monomeric and μ-oxo-bridged dimeric Fe3+ complexes can be controlled through judicious ligand design. We purposed this chemistry to develop a first-in-class Fe3+-based MR imaging probe, Fe-PyCy2AI, that undergoes relaxivity change via pH-mediated control of monomer vs dimer speciation. The monomeric complex exists in a S = 5/2 configuration capable of inducing efficient T 1-relaxation, whereas the antiferromagnetically coupled dimeric complex is a much weaker relaxation agent. The mechanisms underpinning the pH dependence on relaxivity were interrogated by using a combination of pH potentiometry, 1H and 17O relaxometry, electronic absorption spectroscopy, bulk magnetic susceptibility, electron paramagnetic resonance spectroscopy, and X-ray crystallography measurements. Taken together, the data demonstrate that PyCy2AI forms a ternary complex with high-spin Fe3+ and a rapidly exchanging water coligand, [Fe­(PyCy2AI)­(H2O)]+ (ML), which can deprotonate to form the high-spin complex [Fe­(PyCy2AI)­(OH)] (ML­(OH)). Under titration conditions of 7 mM Fe complex, water coligand deprotonation occurs with an apparent pK a 6.46. Complex ML­(OH) dimerizes to form the antiferromagnetically coupled dimeric complex [(Fe­(PyCy2AI))2O] ((ML) 2 O) with an association constant (K a) of 5.3 ± 2.2 mM–1. The relaxivity of the monomeric complexes are between 7- and 18-fold greater than the antiferromagnetically coupled dimer at applied field strengths ranging between 1.4 and 11.7 T. ML­(OH) and (ML) 2 O interconvert rapidly within the pH 6.0–7.4 range that is relevant to human pathophysiology, resulting in substantial observed relaxivity change. Controlling Fe3+ μ-oxo bridging interactions through rational ligand design and in response to local chemical environment offers a robust mechanism for biochemically responsive MR signal modulation.