Theoretical investigation into coordination and selectivity of uranyl-unilateral benzotriazole salophens (X = O/S) for R/S-triadimefons

The design of new uranyl-ligands (uranyl-Ls) is of great significance for the separation and utilization of uranium. In this paper, the triazole group was introduced into uranyl-salophen (uranyl-S) to form new asymmetric uranyl-unilateral benzotriazole salophen (uranyl-UBS); we further replaced two oxygen atoms of uranyl-UBS with two sulfur atoms to generate uranyl-unilateral benzotriazole thio-salophen (uranyl-UBTS) as a new receptor. Then, we comprehensively explored coordination models of uranyl-UBS and uranyl-UBTS with R/S-triadimefons (R/S-TDFs) enantiomers as the guests using density functional theory calculations at the B3LYP//RECP/6-311G** level; we then investigated enantioselectivity recognition of the new receptors to the guests R/S-TDFs. The results indicated that the uranium atoms of the receptors uranyl-S, uranyl-UBS and uranyl-UBTS could coordinate with the carbonyl oxygens in guests R/S-TDFs to form complexes of guest-receptors R/S-TDFs-uranyl-Ls that exhibited two stable V-shaped structures with quite different properties. It was found that the coordination ability to the guests R/S-TDFs is uranyl-UBTS > uranyl-UBS > uranyl-S, while the enantioselectivity for the guests is uranyl-UBTS > uranyl-S > uranyl-UBS and, when the receptor is the same, R-TDF has stronger coordination ability than S-TDF. These results provide information and theoretical supports for the experiments of asymmetric uranyl-UBS with R/S-TDFs, and produce a reference for further exploring the coordination characteristics of asymmetric uranyl-salophen with the triazole derivatives.     

Lithium–Lanthanide Bimetallic Metal–Organic Frameworks towards Negative Electrode Materials for Lithium-Ion Batteries

Novel lithium–lanthanide (Ln: cerium and praseodymium) bimetallic coordination polymers with formulas C₁₀H₂LnLiO₈ (Ln: Ce (CeLipma) and Pr (PrLipma)) and C₁₀H₃CeO₈ (Cepma) were prepared through a simple hydrothermal method. The three compounds were characterized by means of FTIR spectroscopy, X-ray diffraction, single-crystal X-ray diffraction, SEM, TEM, and X-ray photoelectron spectroscopy. The results of structural refinement show that they belong to triclinic symmetry and P space group with cerium (or praseodymium) and lithium cations, forming coordination bonds to oxygen atoms from different pyromellitic acid molecules, and leading to the construction of 3D structures. It is interesting to note that the frameworks exclude any coordination water and lattice water. As an electrode material for lithium-ion batteries, CeLipma exhibits a maximum capacity of 800.5 mAh g⁻¹ and a retention of 91.4 % after 50 cycles at a current density of 100 mA g⁻¹. The favorable electrochemical properties of the lanthanide coordination polymers show potential application prospects in the field of electrode materials.     

In Vitro Antifungal Activity and Mechanism of Ag3PW12O40 Composites against Candida Species

Fungal infections pose a serious threat to human health. Polyoxometalates (POMs) are metal–oxygen clusters with potential application in the control of microbial infections. Herein, the Ag₃PW₁₂O₄₀ composites have been synthesized and verified by Fourier transform infrared (FT-IR) spectrum, transmission electron microscopy (TEM), scanning electron microscope (SEM), elemental analysis, and X-ray diffraction (XRD). The antifungal activities of Ag₃PW₁₂O₄₀ were screened in 19 Candida species strains through the determination of minimum inhibitory concentration (MIC) by the microdilution checkerboard technique. The minimum inhibitory concentration (MIC₅₀) values of Ag₃PW₁₂O₄₀ are 2~32 μg/mL to the Candida species. The MIC₈₀ value of Ag₃PW₁₂O₄₀ to resistant clinical isolates C. albicans HL963 is 8 μg/mL, which is lower than the positive control, fluconazole (FLC). The mechanism against C. albicans HL963 results show that Ag₃PW₁₂O₄₀ can decrease the ergosterol content. The expressions of ERG1, ERG7, and ERG11, which impact on the synthesis of ergosterol, are all prominently upregulated by Ag₃PW₁₂O₄₀. It indicates that Ag₃PW₁₂O₄₀ is a candidate in the development of new antifungal agents.     

Ultrathin Mn Doped Ni-MOF Nanosheet Array for Highly Capacitive and Stable Asymmetric Supercapacitor

In this study, we demonstrate that an Mn-doped ultrathin Ni-MOF nanosheet array on nickel foam (Mn_0.1-Ni-MOF/NF) serves as a highly capacitive and stable supercapacitor positive electrode. The Mn_0.1-Ni-MOF/NF shows an areal capacity of 6.48 C cm⁻² (specific capacity C: 1178 C g⁻¹) at 2 mA cm⁻² in 6.0 m KOH, outperforming most reported MOF-based materials. More importantly, it possesses excellent cycle stability to maintain 80.6 % capacity after 5000 cycles. An asymmetric supercapacitor device utilizing Mn_0.1-Ni-MOF/NF as the positive electrode and activated carbon as the negative electrode attains a high energy density of 39.6 Wh kg⁻¹ at 143.8 Wkg⁻¹ power density with a capacitance retention of 83.6 % after 5000 cycles.     

Cycloaddition Reactions of an Active Cyclic Phosphane/Borane Pair with Alkenes,Alkynes, and Carbon Dioxide

The active six-membered cyclo-FLP 6 undergoes a rapid P/B addition reaction to carbon dioxide. At elevated temperature, the resulting heterobicyclo[2.2.2]octane derived product 7 undergoes ring opening and equilibrates with the cyclotetramer (7)₄ . In the large macrocyclic structure, four monomeric six-membered cyclo-FLP units are connected by four CO₂ molecules to form the supramolecular ring system. The P/B cyclo-FLP 6 undergoes a variety of additional cycloaddition reactions.     

Construction of ZIF-8/AuNPs/PVP–rGO/GCE Electrochemical Sensor and Its Sensitive Determination of Salbutamol

Russian Journal of Electrochemistry - An excellent electrochemical sensor based on glassy carbon electrode (GCE) modified in order with polyvinyl pyrrolidone-dispersed reduced graphene oxide...     

Decomposable super‐simple NRBIBDs with block size 4 and index 6

Necessary conditions for the existence of a super‐simple, decomposable, near‐resolvable ‐balanced incomplete block design (BIBD) whose 2‐component subdesigns are both near‐resolvable ‐BIBDs are (mod ) and . In this paper, we show that these necessary conditions are sufficient. Using these designs, we also establish that the necessary conditions for the existence of a super‐simple near‐resolvable ‐RBIBD, namely (mod ) and , are sufficient. A few new pairwise balanced designs are also given.     

In-situ cation exchange enhances room temperature phosphorescence of a family of metal-organic frameworks

The rational designability and chemical tunability of metal-organic frameworks(MOFs)are enabling tributes to efficaciously enhance their room temperature phosphorescence(RTP)performance.A family of stable anionic MOFs,[Zn₂(4,5-ImDC)₂]M₂(NKU-132,M=(CH₃)₂NH₂or(CH₂CH₃)₂NH₂),featuring significant RTP have been synthesized.By rational cation selection and in-situ replacement from dimethylammonium to diethylammonium,the phosphorescence lifetime is increased from 30.88 to126.3 ms,along with less sensitivity to air.This work provides an anti-quenching and lifetime tuning example for RTP-MOFmaterials via facile host-guest chemistry.     

Multi-emissive 1D Cd(II) polymers with a biphenyl bridged bisazamacrocycle for ratiometric discrimination of nitroaromatics and selective visual detection of picric acid

Three one-dimensional ladder-like coordination polymers consisting of Cd₆ metalloring as the building unit, {[Cd₄LCl₄]·3H₂O}_n ( 1 ), {[Cd₃L(ClO₄)(H₂O)]ClO₄·3H₂O}_n ( 2 ), and {[Cd₆(L)₂(NO₃)₂(CH₃OH)(H₂O)](NO₃)₂·2CH₃OH·5H₂O}_n ( 3 ), were solvothermally constructed from a carboxylic functionalized bisazamacrocyclic ligand 4,4′-bis((4,7-bis(2-carboxyethyl)-1,4,7-triazacyclonon-1-yl)methyl)-1,1′-biphenyl (H₄L). These compounds dispersed in ethanol show the multiple emissions originating from the monomeric and intramolecularly overlapping biphenyl moieties which could be sensitively quenched by picric acid (PA) and 4-nitrophenol (4-NP) through the effective fluorescence resonance energy transfer process. The differential fluorescent responses of each compound on exposure to PA and 4-NP individually make the convenient ratiometric discrimination of two analytes based on the fluorescent intensity ratio (I₃₂₀/I₃₆₀) attainable, and 1 and 2 as ratiometric chemosensors for PA present a broad linear detection range from 4 to 300 μM with detection limits of 0.84 and 0.93 μM, respectively. Furthermore, the blue light emission of 1 under an ultraviolet lamp could be selectively quenched by PA even in the presence of all other interfering nitroaromatic pollutants, which empowers the fast visual detection of PA by naked eye.