The Effect of Auxiliary Nitrogenated Linkers on the Design of New Cadmium-Based Coordination Polymers as Sensors for the Detection of Explosive Materials

Three new cadmium-based coordination polymers, denoted [Cd(hfipbb)(4,4’-bipy)] ( CdPF-1 ), [Cd(hfipbb)(2,2’-bipy)] ( CdPF-2 ), and [Cd(hfipbb)(1,10-phen)] ( CdPF-3 ), have been hydrothermally synthesized by using the well-known V-shaped organic linker 4,4’-(hexafluoroisopropylidene)bis(benzoic acid) (H₂hfipbb), together with different nitrogenated auxiliary linkers. Considering the d¹⁰ configuration of the transition metal selected, the luminescent properties for these CdPF-n materials were explored, finding that materials CdPF-2 and CdPF-3 act as excellent sensors in the detection of explosive nitro aromatic compounds. The photoluminescence properties of CdPF-2 and CdPF-3 revealed that significant and sensitive fluorescence quenching was observed toward NP (nitrophenol) for CdPF-2 and PA (picric acid) for CdPF-3 in MeOH suspensions.     

Synthesis and Biological Activity of Ferrocenyl and Ruthenocenyl Analogues of Etoposide: Discovery of a Novel Dual Inhibitor of Topoisomerase II Activity and Tubulin Polymerization

Two series of the ferrocenyl and ruthenocenyl analogues of etoposide bearing 1,2,3-triazolyl or aminoalkyl linker were synthesized and evaluated for their cytotoxic properties, influence on the cell cycle, ability to induce tubulin polymerization, and inhibition of topoisomerase II activity. We found that the replacement of the etoposide carbohydrate moiety with a metallocenyl group led to organometallic conjugates exhibiting differentiated antiproliferative activity. Biological studies demonstrated that two ferrocenylalkylamino conjugates were notably more active than etoposide, with submicromolar or low-micromolar IC₅₀ values towards SW620, etoposide-resistant SW620E, and methotrexate-resistant SW620M cancer cell lines. Moreover, the simplest ferrocenylmethylamino conjugate exerted dual inhibitory action against tubulin polymerization and topoisomerase II activity while other studied compounds affected only topoisomerase II activity.     

Filling the Charge–Discharge Voltage Gap in Flexible Hybrid Zinc-Based Batteries by Utilizing a Pseudocapacitive Material

The high charge–discharge voltage gap is one of the main bottlenecks of zinc–air batteries (ZABs) because of the kinetically sluggish oxygen reduction/evolution reactions (ORR/OER) on the oxygen electrode side. Thus, an efficient bifunctional catalyst for ORR and OER is highly desired. Herein, honeycomb-like MnCo₂O_4.5 spheres were used as an efficient bifunctional electrocatalyst. It was demonstrated that both ORR and OER catalytic activity are promoted by Mn^IV-induced oxygen vacancy defects and multiple active sites. Importantly, the multivalent ions present in the material and its defect structure endow stable pseudocapacitance within the inactive region of ORR and OER; as a result, a low charge–discharge voltage gap (0.43 V at 10 mA cm⁻²) was achieved when it was employed in a flexible hybrid Zn-based battery. This mechanism provides unprecedented and valuable insights for the development of next-generation metal–air batteries.     

Electrochemical Tri- and Difluoromethylation-Triggered Cyclization Accompanied by the Oxidative Cleavage of Indole Derivatives

Considering their unique roles in organic synthesis, and pharmaceutical and agrochemical applications, the development of fluoroalkylation, cyclization, and indole oxidative cleavage are important topics. Herein, an unprecedented electrochemical tri- and difluoromethylation/cyclization/indole oxidative cleavage process occurring in an undivided cell is presented. The protocol employs a readily prepared Langlois reagent as the fluoroalkyl source, affording a series of tri- or difluoromethylated 2-(2-acetylphenyl)isoquinoline-1,3-diones in good yields with excellent stereoselectivity. It is worth noting that this new methodology merges the fluoroalkylation/cyclization of N-substituted acrylamide alkenes with the oxidative cleavage of an indole C(2)=C(3) bond under external oxidant-free conditions.     

Novel WS2/Fe0.95S1.05 Hierarchical Nanosphere as a Highly Efficient Electrocatalyst for Hydrogen Evolution Reaction

Fe_0.95S_1.05 with high reactivity and stability was incorporated into WS₂ nanosheets via a one-step solvothermal method for the first time. The resulted hybrid catalyst has much higher catalytic activity than WS₂ and Fe_0.95S_1.05 alone, and the optimal WS₂/Fe_0.95S_1.05 hybrid catalyst was found by adjusting the feed ratio. The addition of Fe_0.95S_1.05 was proven to be able to enhance the hydrogen evolution reaction (HER) activity of WS₂, and vice versa. At the same time, it was found that the catalytic effect of the hybrid catalyst was the best when the feed ratio was W : Fe=2 : 1. In other words, we confirmed that there is a synergistic effect between W- and Fe-based sulfide hybrid catalysts, and validated that the reason for the improved HER performance is the strong interaction between the two in the middle sulfur. WS₂/Fe_0.95S_1.05-2 hybrid catalyst leads to enhanced HER activity, which shows a low overpotential of ∼0.172 V at 10 mA cm⁻², low Tafel slope of ∼53.47 mV/decade. This study supplies innovative synthesis of a highly active WS₂/Fe_0.95S_1.05 hybrid catalyst for HER.     

A Novel Reactivity of Phosphanylalumane (>P−Al<): Reversible Addition of a Saturated Interelement Bond to Olefins

The reversible addition of olefins to a phosphanylalumane, P−Al single-bond species, was investigated. The P−Al bond added to ethylene and relatively small terminal alkenes (propylene and hex-1-ene) at room temperature to give the corresponding alkene adducts. Heating the terminal alkene adducts released the corresponding alkenes and regenerated the P−Al bond, but no release of ethylene was observed even under vacuum conditions. The reactivity of ethylene adduct as a new saturated C₂ vicinal P/Al-based FLP was also investigated. The ethylene adduct was found to undergo complexation with nitriles to give the corresponding nitrile adducts to the Al center, which retained the ethylene tether as in the case of the corresponding P/B-based FLP. However, the reactivity of ethylene toward CO₂ and benzaldehyde differed from that of the P/B system giving the corresponding adducts.     

Forever Young: Structural Stability of Telomeric Guanine Quadruplexes in the Presence of Oxidative DNA Lesions**

Human telomeric DNA, in G-quadruplex (G4) conformation, is characterized by a remarkable structural stability that confers it the capacity to resist to oxidative stress producing one or even clustered 8-oxoguanine (8oxoG) lesions. We present a combined experimental/computational investigation, by using circular dichroism in aqueous solutions, cellular immunofluorescence assays and molecular dynamics simulations, that identifies the crucial role of the stability of G4s to oxidative lesions, related also to their biological role as inhibitors of telomerase, an enzyme overexpressed in most cancers associated to oxidative stress.     

RNA Ligation for Mono and Dually Labeled RNAs

Labeled RNAs are invaluable probes for investigation of RNA function and localization. However, mRNA labeling remains challenging. Here, we developed an improved method for 3′-end labeling of in vitro transcribed RNAs. We synthesized novel adenosine 3′,5′-bisphosphate analogues modified at the N6 or C2 position of adenosine with an azide-containing linker, fluorescent label, or biotin and assessed these constructs as substrates for RNA labeling directly by T4 ligase or via postenzymatic strain-promoted alkyne-azide cycloaddition (SPAAC). All analogues were substrates for T4 RNA ligase. Analogues containing bulky fluorescent labels or biotin showed better overall labeling yields than postenzymatic SPAAC. We successfully labeled uncapped RNAs, NAD-capped RNAs, and 5′-fluorescently labeled m⁷Gp₃A_m-capped mRNAs. The obtained highly homogenous dually labeled mRNA was translationally active and enabled fluorescence-based monitoring of decapping. This method will facilitate the use of various functionalized mRNA-based probes.     

A Porphyrin-Based Covalent Organic Framework for Metal-Free Photocatalytic Aerobic Oxidative Coupling of Amines

Imines are important intermediates in drug synthesis. Photocatalytic aerobic oxidative coupling of amines has been considered as a clean and promising way to produce imines and has attracted great attention. Herein, we designed and synthesized a novel two-dimensional porphyrin-based covalent organic framework (Por-BC-COF) which adopts an AA stacking mode with excellent crystallinity, high Brunauer–Emmett–Teller surface areas (1200 m² g⁻¹), wide light absorption range (200–1300 nm) and good stability in a variety of organic solvents. Por-BC-COF can be used as a metal-free heterogeneous photocatalyst for the photocatalytic oxidation of amines to imines under visible light and red light with a high yield (97 %). This work presents a novel and efficient COF photocatalyst in the application of light-driven organic synthesis.