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Das, Udita; Das, Ankita; Das, Asim K.
doi: 10.1039/d5dt00001gpmid: 40183367
Molybdenum and tungsten, being congeners of the 6th group of d-block elements, are similar in many respects in terms of their properties. In fact, both participate in similar types of oxotransferase activity in their enzymes. Molybdenum is regarded as the heaviest essential trace metal in all forms of life; however, its next heavier congener, tungsten, as the heaviest metal, is found only in some prokaryotic organisms. Tungstoenzymes are generally selected by nature for carrying out low-potential redox activities under anaerobic conditions in prokaryotic organisms. This nature's molybdenum vs. tungsten selectivity for their biological functions under different working conditions (surrounding temperature and aerobic/anaerobic environment) is determined mainly by the relativistic effect, which is experienced to different extents by these two congeners. Understanding the mechanistic aspects of the relativistic effect-controlled enzymatic activities of tungstoenzymes is of immense biotechnological interest to develop eco-friendly and cost-effective methods for the commercial synthesis of acetaldehyde through the hydration of acetylene and commercial production of hydrogen (H2, a green fuel) by producing tungsten-incorporated nitrogenase (W–N2-ase) in CA6 (mutant strain) and to develop a biomimetic method to replace the hazardous Birch reduction in organic synthesis.
Zhao, Shujuan; Han, Yue; Lian, Shixun; Zhang, Jilin
doi: 10.1039/d4dt02968bpmid: 40227890
Luminescent materials have played a vital role in human society, with phosphor-converted light-emitting diodes (pc-LEDs) representing the cutting-edge in lighting solutions. As societal demands for improved material quality continue to rise, the quest for materials with enhanced performance has become paramount. Eu2+/Ce3+-activated inorganic luminescent materials have garnered significant attention due to their high luminescence efficiency and tunable properties. Recent research has focused on developing Eu2+/Ce3+-activated inorganic luminescent materials with anti-/zero thermal quenching behavior, leveraging the benefits of host structures and activator ions. To facilitate their commercial viability, a comprehensive understanding of their properties, mechanisms, and current status is essential. This study delves into the luminescence mechanisms of Eu2+/Ce3+ activator ions, provides a detailed analysis of the typical thermal behaviors of Eu2+/Ce3+-activated inorganic phosphors, outlines strategies for enhancing thermal stability from both intrinsic and extrinsic perspectives, and categorizes the reported instances of anti-/zero thermal quenching in Eu2+/Ce3+-activated phosphors. Lastly, drawing on the present landscape, this paper offers insights into the future development and prospects of similar phosphors, aiming to serve as a valuable reference for the advancement of Eu2+/Ce3+-activated inorganic luminescent materials.
Jiang, Xianren; Ding, Chang-Hua; Qiu, Zaozao; Xie, Zuowei
doi: 10.1039/d5dt00981bpmid: 40377369
A Pd-catalyzed one-pot regioselective difunctionalization of 3-iodo-o-carborane has been achieved for the synthesis of a wide variety of 3-alkyl-4-Nu-o-carboranes (Nu = aryl, alkyl, amino, or thio groups) in moderate to excellent yields. This protocol combines the sequential activation of cage B(3)–I and B(4)–H bonds via Pd 1,4-migration.
doi: 10.1039/d5dt00984gpmid: 40396583
The synthesis of transition-metal complexes bearing a macrocyclic tetradentate phosphine ligand is relatively undeveloped. Herein, an open-chain tetradentate phosphine ligand with two P-containing rings was synthesized and coordinated to a Mo-oxo template. After deprotonation and cyclization with suitable alkyl chains, a series of planar macrocyclic tetradentate phosphine–Mo complexes was obtained without stereoisomers.
Peng, Yi-Mei; Guan, Yu-Ming; Bai, Qixia; Chen, Gang; Lin, Wei-Quan; Pang, Jing-Xian; Xu, Wen-Bo; Wang, Pingshan; Xie, Ting-Zheng
doi: 10.1039/d5dt00041fpmid: 40391589
The use of fluorescent probes for heavy metal ions is an efficient, low-cost, on-site operable detection method, and has been widely applied in both environmental and biomedical monitoring. Herein, we present a single-molecule anti AIE fluorescent sensor for the detection of heavy metal ions based on the fold/unfold conformational transition of AIE molecular modules in a single molecule triggered by the coordination of heavy metal ions. The fluorescent probe is able to detect a range of heavy metal ions at concentrations well below the “Hygienic Standard for Drinking Water”, and is expected to be used as a fluorescent probe with a new detection mechanism for heavy metal ions for environmental detection or bio-monitoring applications.
Wu, Lei; Huang, Hongyu; Wang, Jialong; Jing, Qun; Huang, Yi; Yu, Xue; Chen, Zhaohui
doi: 10.1039/d5dt00810gpmid: 40391765
Na3Cd4(PO4)(P2O7)2 and Na4Mg3(PO4)2(P2O7) were synthesized via a high-temperature solution. Their structures altered from disorder to order, and symmetry shifts were also documented. They exhibited the shortest cutoff edges (<190 nm) among mixed P–O anionic phosphates. Na4Mg3(PO4)2(P2O7) exhibited moderate second harmonic generation (SHG) efficiency (∼0.5 × KH2PO4 (KDP)) with phase-matching capability.
Belova, Svetlana A.; Belov, Alexander S.; Bugaenko, Margarita G.; Danshina, Anastasia A.; Dmitriev, Alexey I.; Zhidkov, Mikhail V.; Korchagin, Denis V.; Voloshin, Yan Z.
doi: 10.1039/d5dt00649jpmid: 40396788
The titled compound was prepared by carrying out template condensation of chelating and capping ligand synthons on cobalt(ii) ion as a matrix. Its three-dimensional molecule has a trigonal-prismatic geometry favorable for appearance of slow magnetic relaxation. Magnetism measurements, supported by ab initio calculations, revealed its strong uniaxial magnetic anisotropy and zero-field SIM behaviour.
Ramasubramanian, Ramamoorthy; Anandababu, Karunanithi; Kumar, Mukesh; Mayilmurugan, Ramasamy
doi: 10.1039/d4dt02079kpmid: 40326617
A novel copper(i) complex, [CuI(L)(CH3CN)]CF3SO3 (1) (L = 1,1,2-tri(pyridin-2-yl)propan-1-ol), has been synthesized, characterized, and investigated as a bioinspired model for copper monooxygenases. Under aerobic conditions in CH3CN, complex 1 undergoes conversion to a dicopper complex, [(CuIIL)(CuIIL H)(SO3CF3)2]·CF3SO3·H2O (2), whose molecular structure reveals a Cu–Cu distance of 2.96 Å. A dicopper(ii) complex, [(LCuII)2(SO3CF3)2] (3), has been synthesized for comparison, which exhibits a similar Cu–Cu distance of 2.97 Å. EPR spectroscopy has ascertained the solution-state geometries of complexes 2 and 3, which displayed g∥ > g⊥ values, indicative of distorted square pyramidal geometries consistent with their solid-state structures. Complex 1 selectively hydroxylates benzene in the presence of O2 and Et3N, affording 7% phenol based on the substrate, without any side products. However, the use of H2O2 as the oxygen source under identical conditions significantly increases the phenol yield to 19%. The catalytically active intermediates generated by the reaction of complex 1 with dioxygen showed an O (π*σ) → Cu ligand-to-metal charge transfer (LMCT) transition at 360 nm and a d–d transition at 650 nm. These spectral features are more pronounced with H2O2, showing a new LMCT transition at 360 nm and a very weak d–d transition at 689 nm. This is supported by solution FT-IR spectroscopy, which showed an O–O stretching frequency at 890 cm−1 (DFT spectra at 829 cm−1), corresponding to a Cu–OOH intermediate. The structure of the [(L)CuII–OOH]+ species was optimized by DFT calculations. Kinetic isotope effect (KIE) studies using C6H6/C6D6 (1 : 1) (kH/kD = 1.03) and isotopic labeling experiments using H218O2 support our proposed mechanism of benzene hydroxylation. In contrast, dinuclear complexes 2 and 3 exhibited poor benzene hydroxylation activity even with H2O2 and yielded only 4% and 6% phenol, respectively, along with by-products such as biphenyl and quinone under identical conditions.
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