Adsorption of Adipic acid in Al/B-N/P nanocages: DFT investigations

Drug delivery clusters based on nanocages recently have been the most capable to study. Adipic acid (ADPA) interaction mechanism over nanocages of X(Al/B)12Y(N/P)12 was investigated. We analyzed various electronic, chemical and spectroscopic properties with nanocages of the adsorbed ADPA molecule. Adsorption energies were calculated to study the adsorption of ADPA with nanocages. Raman enhanced surface scattering is used to track the drug as an effective approach to vibrational spectroscopy. Detection of the drug has been investigated using the SERS properties of nanocages. Title drug acts as a donor of electrons and adsorbs at the electrophilic site of nanocages. Variations in chemical descriptors to recognize the sensing property of ADPA-nanocages are also noted. Analysis of various properties explains enhancement which makes it possible to detect the drug in other products.

Definition of the chalcogen bond (IUPAC Recommendations 2019)

This recommendation proposes a definition for the term “chalcogen bond”; it is recommended the term is used to designate the specific subset of inter- and intramolecular interactions formed by chalcogen atoms wherein the Group 16 element is the electrophilic site.

Identification of the Tetrel Bonds between Halide Anions and Carbon Atom of Methyl Groups Using Electronic Criterion

The consideration of the disposition of minima of electron density and electrostatic potential along the line between non-covalently bound atoms in systems with Hal−···CH3–Y (Hal− = Cl, Br; Y = N, O) fragments allowed to prove that the carbon atom in methyl group serves as an electrophilic site provider. These interactions between halide anion and carbon in methyl group can be categorized as the typical tetrel bonds. Statistics of geometrical parameters for such tetrel bonds in CSD is analyzed. It is established that the binding energy in molecular complexes with tetrel bonds correlate with the potential acting on an electron in molecule (PAEM). The PAEM barriers for tetrel bonds show a similar behavior for both sets of complexes with Br− and Cl− electron donors.

Electronic criterion for categorizing the chalcogen and halogen bonds: sulfur–iodine interactions in crystals

Diversity of mutual orientations of Y–S and I–X and covalent bonds in molecular crystals complicate categorizing noncovalent chalcogen and halogen bonds. Here, the different types of S...I interactions with short interatomic distances are analysed. The selection of S...I interactions for the categorization of the chalcogen and halogen bonds has been made using angles that determine the mutual orientation of electron lone pairs and σ-holes interacted S and I atoms. In complicated cases of noncovalent interactions with `hole-to-hole' of S and I orientations, distinguishing the chalcogen and halogen bonds is only possible if the atom is uniquely determined, which also provides the electrophilic site. The electronic criterion for chalcogen/halogen bonds categorizing that is based on analysis of dispositions of electron density and electrostatic potential minima along the interatomic lines has been suggested and its effectiveness has been demonstrated.

Prediction of the Regioselectivity of 1,3-Dipolar Cycloaddition Reactions of Nitrile Oxides with 2(5H)-Furanones Using Recent Theoretical Reactivity Indices

The regioselectivity of a series of 16 1,3-dipolar cycloaddition reactions of nitrile oxides with 2(5 H)-furanones has been analysed by means of global and local electrophilic and nucleophilic reactivity indices using density functional theory at the B3LYP level together with the 6-31G(d) basis set. The local electrophilicity and nucleophilicity indices, based on Fukui and Parr functions, have been calculated for the terminal sites, namely the C1 and O3 atoms of the 1,3-dipole and the C4 and C5 atoms of the dipolarophile. These local indices were calculated using both Mulliken and natural charges and spin densities. The results obtained show that the C5 atom of the 2(5 H)-furanones is the most electrophilic site whereas the O3 atom of the nitrile oxides is the most nucleophilic centre. It turns out that the experimental regioselectivity is correctly reproduced, indicating that both Fukui- and Parr-based indices are efficient tools for the prediction of the regiochemistry of the studied reactions and could be used for the prediction of new designed reactions of the same kind.

Silver ion binding to the organophosphorus pesticide diazinon and hydrolytic pathways revealed by mass spectrometric and NMR studies

This paper describes the first study of the interactions of Ag+ with the organophosphorus (OP) insecticide diazinon, 1. Electrospray ionization mass spectrometry (ESI-MS) with corroborative collision-induced dissociation-mass spectrometry (CID-MS) demonstrates that 1 forms a bidentate chelate with Ag+. The hydrolysis products of 1, the pyrimidinol (PY) and O,O-diethylphosphorothioic acid (PA), are also found to bind to Ag+ via N (PY) and S (PA) Lewis base sites, respectively. 31P and 1H nuclear magnetic resonance (NMR) spectra in solution, followed over time with varying ratios of Ag+ to 1, confirm the MS evidence and show Ag+ catalysis of hydrolysis (e.g., complete hydrolysis of 1 in ∼5 min (first-order half-life = 3 × 10−4 d; kobs = 2 × 103 d−1)) with equimolar Ag+; this represents an approximate 150 000-fold enhancement in hydrolysis with Ag+ as compared to its absence. A mechanism for the enhanced hydrolysis is proposed in which bidentate binding of Ag+ to S of the P=S electrophilic site in tandem with binding to N of the leaving group stabilizes the SN2(P) transition state relative to the ground state; this effect is described by qualitative energy profiles.