Dalton Transactions

doi: 10.1039/D2DT90132Cpmid: N/A

doi: 10.1039/D2DT90133Apmid: N/A

Das, Bindusagar; Makol, Abhishek; Kundu, Subrata

doi: 10.1039/d2dt01499hpmid: 35920252

The synthesis and characterization of isolable radicals of main-group elements have been a long-pursued quest. Although there has been considerable progress in this area, particularly in isolating carbon radicals, the isolation of radicals comprising heavier p-block elements is still scarce. Among heavier p-block elements, the radical chemistry involving silicon and phosphorus is explored considerably. This review focuses on isolable phosphorus-centered radicals. Most of the compounds described here have been characterized by single-crystal X-ray analysis and EPR spectroscopy. The cyclic voltammetry study revealed interesting redox chemistry for many of these compounds. Here, we described the synthesis and properties of the radicals and radical ions comprising the phosphorus center.

Polyzou, Christina D.; Gkolfi, Patroula; Chasapis, Christos T.; Bekiari, Vlasoula; Zianna, Ariadni; Psomas, George; Ondrej, Malina; Tangoulis, Vassilis

doi: 10.1039/d2dt01509apmid: 35920617

Aminated silica hybrid, spin-crossover (SCO) nanoparticles (AmNPs) coupled with (S)-naproxen (NAP) were proposed for potential drug nanocarriers through drug release experiments at various pH values. DNA- and albumin-binding studies were also carried out using diverse techniques in order to investigate the interaction of the nanoparticles with calf-thymus DNA and serum albumins and to determine the corresponding binding constants.

Jiang, Wenjun; Wang, Jinjin; Chen, Yilin; Chen, Zhikang; Li, Jiancheng; Jiang, Liuyin; Peng, Yanbo; Zhu, Hongping

doi: 10.1039/d2dt01018fpmid: 35943027

Cuproussiloxane (1) was prepared from the reaction of silanediol R(Me)Si(OH)2 (R = N(SiMe3)(2,6-iPr2C6H3)) and (CuMes)4 (Mes = 2,4,6-Me3C6H2). The prepared compound crystalizes into two self-assemblies: Cu24O24Si12Me12R12 ([(CuO)2Si(Me)R]12, 1a) and Cu20O20Si10Me10R10 ([(CuO)2Si(Me)R]10, 1b). 1a and 1b feature dodecagonal and decagonal prism X-ray structures, respectively. 1 was found to exhibit good to excellent activity for catalyzing the aerobic CP cross-coupling reaction of terminal alkynes with H-phosphonates to form alkynylphosphonates (7099% yields).

Klika, Karel D.; Alsalim, Rana; Eftekhari, Mohammad; Makarem, Ata

doi: 10.1039/d2dt01702dpmid: 35943556

The HBED chelator is used to stabilize small and hard metal ions such as Fe3+, Ti4+, Ga3+ and Al3+ in both medicine and industry. While the coordination of hexadentate HBED4− is known in the case of Fe3+, Ti4+ and Ga3+, it is unknown in the case of the small Al3+ ion since its corresponding complex has never been fully characterized. Thus, in this work the coordination pattern in a newly synthesized aluminum HBED-based complex ([Al–HBED–NN]−Na+) was determined using 2D NMR in conjunction with DFT calculations.

Noda, Daichi; Yamada, Iori; Shinozaki, Kenji; Tagaya, Motohiro

doi: 10.1039/d2dt01488bpmid: 35946403

The phase transition of Ca-deficient hydroxyapatite (CDHA) with citric acid (Cit) coordination was investigated. Cit promoted the substitution of K+ ions into CDHA to generate the HA phase. The K+-doping increased the phase transition temperature of CDHA, providing the transition to - and -tricalcium phosphates at higher temperatures. These results suggest controllable phase transition via Cit addition.

Paul, Navendu; Sarkar, Rudra; Sarkar, Sabyasachi

doi: 10.1039/d2dt01863bpmid: 35946479

Oxo-molybdenum (dithiolene) complexes covalently linked individually to iron and zinc porphyrin have been synthesized to show an electron transfer between the two metal centres in relevance to electron transfer from Mo-cofactor to cytochrome b5 domains in the oxidative half of the catalytic cycle of native sulfite oxidase. This association has been investigated by electrochemical, EPR measurement and X-ray absorbance spectroscopy techniques.

Das, Athulya; Mohammed, Thasnim P.; Kumar, Rajesh; Bhunia, Sarmistha; Sankaralingam, Muniyandi

doi: 10.1039/d2dt00555gpmid: 35730410

A carbazolyl appended trans-pyridyl porphyrin (1) was synthesized and its dicationic form 2 was obtained by methylation of the pyridyl group. Copper and zinc complexes of porphyrin 2 (Cu(ii), 3; Zn(ii), 4) were isolated and characterized by various modern spectroscopic techniques. The DNA binding properties of 2, 3, and 4 have been explored against calf thymus-DNA (CT-DNA). DNA binding was quantized using the intrinsic binding constant (Kb) that was calculated by UV-visible absorption spectroscopy, and the value Kb = 1.6 106 M1 for compound 2 reveals a better interaction of 2 towards CT-DNA than those of 3 (3.1 105 M1) and 4 (3.4 105 M1), which follows the order 2 > 4 > 3. The fluorescence quenching efficiency and ethidium bromide quenching assay also indicated a good binding affinity of all the compounds towards CT-DNA. Furthermore, the spectroscopic data suggest that the possible mode of interaction is intercalation. The docking studies were in accordance with the experimental results. Notably, DNA cleavage studies reveal that 2 shows better damage than 3 and 4 which is in accordance with the binding affinity order 2 > 4 > 3. The observed quantum yield (2: 0.65, 3: 0.33, and 4: 0.97) and no change in DNA cleavage in the presence of NaN3 reveal the involvement of singlet oxygen. The singlet excited state lifetimes were in the range of 6.31.2 ns. Furthermore, these porphyrins can be investigated as interesting photosensitizers in photodynamic therapy and photochemotherapy.

Pramanik, Atin; Manche, Alexis G.; Clulow, Rebecca; Lightfoot, Philip; Armstrong, A. Robert

doi: 10.1039/d2dt01447epmid: 35899863

The fundamental understanding of electrochemical reaction kinetics for lithium/sodium-ion batteries (LIBs & NIBs) is a significant criterion for advancing new-generation electrode materials. Herein, we demonstrate a novel lithium-rich perovskite oxalate KLi3Fe(C2O4)3 (KLFC) cathode with the combination of cation and anion redox delivering discharge capacities of 86 and 99 mA h g−1 after 100 cycles for a LIB and NIB, respectively, with good cyclability. Experimental Raman spectroscopy analysis combined with DFT calculations of charged/discharged samples illustrate the oxalate anion redox activity. Further, first-principles calculations of the partial density of states and Bader charges analysis have also characterised the redox behaviour and charge transfer during the potassium extraction processes.