ABSTRACT
Tellurates have attracted the attention of researchers over the past decade due to their properties and as less toxic forms of tellurium derivatives. However, the speciation of Te(VI) in aqueous solutions has not been comprehensively studied. We present a study of the equilibrium speciation of tellurates in aqueous solutions at a wide pH range, 2.5-15 by 17O, 123Te, and 125Te NMR spectroscopy. The coexistence of monomeric, dimeric, and trimeric oxidotellurate species in chemical equilibrium at a wide pH range has been shown. NMR spectroscopy, DFT computations, and single-crystal X-ray diffraction studies confirmed the formation and coexistence of trimeric tellurate anions with linear and triangular structures. Two cesium tellurates, Cs2[Te4O8(OH)10] and Cs2[Te2O4(OH)6], were isolated from the solution at pH 5.5 and 9.2, respectively, and studied by single-crystal X-ray diffractometry, revealing dimeric and tetrameric tellurate anions in corresponding crystal structures.
Subject(s)
Tellurium , Water , Tellurium/chemistry , Anions , Magnetic Resonance SpectroscopyABSTRACT
In this work, the solution conformations of seventeen 3,7-diacyl bispidines were studied by means of NMR spectroscopy including VT NMR experiments. The acyl groups included alkyl, alkenyl, aryl, hetaryl, and ferrocene moieties. The presence of syn/anti-isomers and their ratios were estimated, and some reasons explaining experimental facts were formulated. In particular, all aliphatic and heterocyclic units in the acylic R(CO) fragments led to an increased content of the syn-form in DMSO-d6 solutions. In contrast, only the anti-form was detected in DMSO-d6 and CDCl3 in the case when R = Ph, ferrocenyl, (R)-myrtenyl. In the case of a chiral compound derived from the natural terpene myrtene, a new dynamic process was found in addition to the expected inversion around the amide N-C(O) bond. Here, rotation around the CO-C=C bond in the acylic R fragment was detected, and its energy was estimated. For this compound, ΔG for amide N-C(O) inversion was found to be equal to 15.0 ± 0.2 kcal/mol, and for the rotation around the N(CO)-C2' bond, it was equal to 15.6 ± 0.3 kcal/mol. NMR analysis of the chiral bispidine-based bis-amide was conducted for the first time. Two X-ray structures are reported. For the first time, the unique syn-form was found in the crystal of an acyclic bispidine-based bis-amide. Quantum chemical calculations revealed the unexpected mechanism for amide bond inversion. It was found that the reaction does not proceed as direct N-C(O) bond inversion in the double-chair (CC) conformation but rather requires the conformational transformation into the chair-boat (CB) form first. The amide bond inversion in the latter requires less energy than in the CC form.
ABSTRACT
For the first time, derivatives of 3,7-diazabicyclo[3.3.1]nonane (bispidine) were proposed as potential inhibitors of the SARS-CoV-2 main viral protease (3-chymotrypsin-like, 3CLpro). Based on the created pharmacophore model of the active site of the protease, a group of compounds were modeled and tested for activity against 3CLpro. The 3CLpro activity was measured using the fluorogenic substrate Dabcyl-VNSTLQSGLRK(FAM)MA; the efficiency of the proposed approach was confirmed by comparison with literature data for ebselen and disulfiram. The results of the experiments performed with bispidine compounds showed that 14 compounds exhibited activity in the concentration range 1-10 µM, and 3 samples exhibited submicromolar activity. The structure-activity relationship studies showed that the molecules containing a carbonyl group in the ninth position of the bicycle exhibited the maximum activity. Based on the experimental and theoretical results obtained, further directions for the development of this topic were proposed.
ABSTRACT
Sodium peroxostannate nanoparticles with graded composition were produced from aqueous hydrogen peroxide-sodium hydroxostannate solution. The uniform particles were converted to composition graded sodium stannate by mild thermal treatment for peroxide decomposition and yielded yolk-shell tin dioxide particles by dilute acid treatment. The mechanism of formation of the graded sodium concentration is explained in view of the solubility of peroxostannate in H2O2-H2O solution and based on 119Sn NMR, XRD, dynamic light scattering (DLS) and electron microscopy studies. Initial studies illuminating sensitive hydrogen sensing by yolk-shell tin oxide particles are presented.
