Anacardic acid (AA) and its derivatives are wellknown for their therapeutic applications ranging from antitumor, antibacterial, antioxidant, anticancer, and so forth. However, their poor pharmacokinetic and safety properties create significant hurdles in the formulation of the final drug molecule. As a part of our endeavor to enhance the potential and exploration of the anticancer activities, a detailed study on the properties of selected AA derivatives was performed in this work. A comprehensive analysis of the drug-like properties of 100 naturally occurring AA derivatives was performed, and the results were compared with certain marketed anticancer drugs. The work focused on the understanding of the interplay among eight physicochemical properties. The relationships between the physicochemical properties, absorption, distribution, metabolism, and excretion attributes, and the in silico toxicity profile for the set of AA derivatives were established. The ligand efficacy of the finally scrutinized 17 AA derivatives on the basis of pharmacokinetic properties and toxicity parameters was further subjected to dock against the potential anticancer target cyclin-dependent kinase 2 (PDB ID: 1W98). In the docked complex, the ligand molecules (AA derivatives) selectively bind with the target residues, and a high binding affinity of the ligand molecules was ensured by the full fitness score using the SwissDock Web server. The BOILED-Egg model shows that out of 17 scrutinized molecules, 3 molecules exhibit gastrointestinal absorption capability and 14 molecules exhibit permeability through the blood−brain barrier penetration. The analysis can also provide some useful insights to chemists to modify the existing natural scaffolds in designing new anacardic anticancer drugs. The increased probability of success may lead to the identification of drug-like candidates with favorable safety profiles after further clinical evaluation.

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Spectroscopy of vibrational optical activity has been established as a powerful tool to study molecular structures and interactions. In most cases, only fundamental molecular transitions are analyzed. In the present study, we analyze a broader range of vibrational frequencies (40−4000 cm −1 ), which could be measured on a new Raman optical activity (ROA) instrument. An unexpectedly strong vibrational Raman optical activity of 2-chloropropionitrile has been observed within the low-frequency region (40−150 cm −1 ). On the basis of combined molecular dynamics and density functional theory simulations, it could be assigned to intermolecular vibrations. A detailed analysis also revealed connection between spectral shapes and molecular structure and flexibility, such as bending of the CCN group. At the other edge of the scale, within ∼1500−4000 cm −1 , for the first time, many combination and overtone ROA bands have been observed for 2-chloropropionitrile and α-pinene. These were also partially assigned, using quantumchemical computations. The band assignment was confirmed by a comparison with Raman, absorption, and vibrational circular dichroism spectra. The measurement in the broader vibrational range thus significantly extends the information that can be obtained by optical spectroscopy, including intermolecular interactions of chiral molecules and liquids.

Phosphorus nitride (PN) is the simplest molecule formed solely by phosphorus and nitrogen. It represents an interesting model for materials, where phosphorus is directly attached to nitrogen. Nevertheless, both theoretical and experimental studies often provide an incomplete picture on the structural, electronic, and spectral properties of PN. Theoretical predictions often suffer from insufficient level of theory, incomplete basis set, or from neglecting several effects, for example, zero‐point vibrational correction (ZPVC). Therefore, we performed an extensive benchmark study on structural, electronic, and spectral properties of PN at the Hartree‐Fock, density functional theory (DFT), or even the coupled‐cluster levels. We paid special attention to the basis set effect. We tested three variants of Dunning's aug‐cc‐pVXZ basis sets with the size from double‐ζ to sextuple‐ζ, as well as Jensen's aug‐pc‐n, aug‐pcJ‐n, and aug‐pcSseg‐n basis sets, where n = 1‐4. Obtained energetics, PN distance, dipole moment, vibrational frequencies, and nuclear magnetic resonance (NMR) parameters were extrapolated to the complete basis set limit (CBS) using three‐ or two‐parameter formulas. The 31P NMR shieldings estimated with the aug‐cc‐pVXZ and aug‐cc‐pV(X + d)Z basis sets strongly depend on the basis set size providing scattered convergence patterns toward CBS. The Hartree‐Fock self‐consistent field (HF‐SCF) NMR parameters evinced similar behavior as the coupled‐cluster data. The only smooth convergence was achieved using the aug‐cc‐pCVXZ basis sets that include core‐valence effects. The KT3 functional underestimated the phosphorus CBS shieldings by about 12 ppm compared to coupled cluster with singles and doubles (CCSD) (T). Nevertheless, KT3 unambiguously surpasses the HF‐SCF and CCSD levels that provide 31P shieldings that are lower by about 150 ppm and 24 ppm compared to CCSD(T). The convergence of nitrogen shieldings was regular for all basis set hierarchies and all theoretical methods. Relativistic and vibrational effects on selected properties were also discussed.

Determination of electrophilic and nucleophilic sites of a molecule is the primary task to find the active sites of the lead molecule. In the present study, the active sites of busulfan have been predicted by molecular electrostatic potential surface and Fukui function analysis with the help of dispersion corrected density functional theory. Similarly, the identification of active binding sites of the proteins against lead compound plays a vital role in the field of drug discovery. Rigid and flexible molecular docking approaches are used for this purpose. For rigid docking, Hex 8.0.0 software employing fast Fourier transform (FFT) algorithm has been used. The partial flexible blind docking simulations have been performed with AutoDock 4.2 software; where a Lamarckian genetic algorithm is employed. The results showed that the most electrophilic atoms of busulfan bind with the targets. It is clear from the docking studies that busulfan has inhibition capability toward the targets 12CA and 1BZM. Graphical Abstract Docking of ligand and protein.

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In this study, an innovative nanocomposite of multiwalled carbon nanotubes (MWCNTs), copper oxide nanoparticles (CuONPs) and lignin (LGN) polymer were successfully synthesized and used to modify the glassy carbon electrode for the determination of chlorogenic acid (CGA). Cyclic voltammetry (CV) emphasised a quasi-reversible, adsorption controlled and pH dependent electrode procedure. In cyclic voltammetry a pair of well distinct redox peaks of CGA were observed at the LGN-MWCNTs-CuONPs-GCE in 0.1 M phosphate buffer solution (PBS), at pH 2. The synthesized nanoparticles and nanocomposites were characterized by Fourier transformation infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and x-ray diffraction (XRD) analyses. Differential pulse voltammetry (DPV) was applied to the anodic peak and used for the quantitative detection of CGA. Under optimal conditions, the proposed sensor showed linear responses from 5 μM to 50 μM, the linear regression equation I pa (μA) = 2.6074 C-5.1027 (R 2 = 0.995), whilst the limit of detection (LOD) and limit of quantifications (LOQ) were found to be 0.0125 μM and 0.2631 μM respectively. The LGN-MWCNTs-CuONPs-GCE were applied to detect the CGA in real coffee samples with the recovery ranging from 97 to 106 %. The developed sensor was successfully applied for the analysis of CGA content in the coffee samples. In addition, electrophilic, nucleophilic reactions and chlorogenic acid docking studies were carried out to better understand the redox mechanisms and were supported by density functional theory calculations.

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