Calculated Dipole Moments Research Articles

Visible Opacities of S-type Stars: The d 3Φ–a 3Δ Band System of ZrO

ZrO is a well-studied metal monoxide because of its astrophysical importance in characterizing S stars. The bands of the d 3Φ–a3Δ system (γ system) with v′≤4 and v″ ≤ 5 are rotationally analyzed using the PGOPHER program to provide spectroscopic constants. The high-resolution ZrO emission spectrum was recorded with a Fourier transform spectrometer using a high-temperature carbon furnace source. New ab initio calculations of the transition dipole moment were carried out in order to determine the vibronic band strengths. The spectroscopic constants, along with the band strengths, are used to calculate a line list for the γ system. This line list can be used to determine Zr abundances in S stars. We also correct the line strengths for the B 1Π–A 1Δ transition calculated in our previous work.

The analysis of sarcosine phosphate single crystal based on polarized IR and Raman spectra

For the first time, the room temperature polarized IR reflection and Raman spectra of sarcosine phosphate (sar)·H3PO4, in the form of an oriented single crystal have been measured. The polarized spectra are discussed with respect to the crystal structure (X-ray diffraction) data and the literature data on the normal coordinate analysis of the zwitterionic and cationic forms of the sarcosine molecule. Based on the analysis of the spectra and transition dipole moment calculations for each internal mode with respect to the experimental X(a), Y(b) and Z(c) axes, we have been able to determine the directionality and strength of the complicated hydrogen bonds network in the crystal. The A-B-C band structure of the OH stretching vibrations in the strongest hydrogen bonds (HBs) has been assigned. Independent interactions of each HB with light are confirmed based on their polarization properties. The differences within the band of carboxyl group components are ascribed to a rather strong Davydov-type interaction between the carboxyl groups in the title crystal, they may also be caused by participation of the carboxyl-oxygen atom in the medium-strong HB with phosphate-oxygen. These studies are interesting from the point of view of designing strategy for the molecular engineering of new compounds with strong hydrogen bonds, new phase-change materials, as well as crystals with improved optical, magnetic and nonlinear optical properties.

Space and laboratory discovery of iminopentadienylidene, HNC5

We report the discovery of HNC$_5$ in TMC-1. Six lines have been found in harmonic relation, with quantum numbers $J$=12-11 up to $J$=17-16. The lines can be reproduced with the standard frequency relation for linear molecules with $B$=1361.75034pm 0.00033 MHz and $D$=32.2pm 0.7 Hz. The assignment of the carrier to iminopentadienylidene was achieved through examining the possible candidates at a high level of theoretical ab initio calculations. Motivated by the good agreement between the observed $B$ and the calculated value for HNC$_5$, we searched for it in the laboratory and observed the transitions $J$=5-4 to 7-6. The derived rotational and distortion constants are 1361.74998pm 0.00040 MHz and 26.5pm 5.5 Hz, respectively. Hence, we solidly conclude that the carrier of the lines found in TMC-1 is HNC$_5$. The calculated dipole moment for this species is 7.7\,D and the derived column density is (1.3pm 0.2)times 1010 $. We used the new QUIJOTE data to improve previous observations of HC$_4$NC and found that the abundance ratio HC$_4$NC/HNC$_5$ is 10pm 2. The abundance ratio of HC$_5$N and its two isomers HC$_4$NC and HNC$_5$ is 500pm 80 and 5100pm 800, respectively. These abundance ratios are higher by a factor of sim 10 than those of the equivalent isomers of HC$_3$N. Chemical models reproduce the observed abundances reasonably well when a chemistry similar to that of the smaller species C$_3$HN isomers is adopted. The formation of HNC$_5$ and HC$_4$NC arises from the dissociative recombination with electrons of the cations HC$_5$NH$^+$ and HC$_4$NCH$^+$.

Theoretical evaluation of C24 nanocage functionalization with protons for enhanced sulfacetamide drug delivery: A DFT study with non-covalent interaction analyses

In the realm of drug design, achieving precise and effective drug delivery poses a significant challenge. In this computational study, we explore the capacity of pristine C24 nanocages and those modified with 1H+ and 2H+ ions to serve as carriers for the sulfacetamide (SA) drug, employing density functional theory (DFT) calculations. Geometry optimizations of the SA&C24, SA&H+C24, and SA&2H+C24 complexes were conducted at the cam-B3LYP/6–31+G (d, p) level of theory. The optimized structures of all complexes exhibit local minima on the potential energy surface, indicated by the absence of imaginary frequencies, which confirms their thermodynamic stability. The negative values of adsorption energy (Eads) denote an exothermic and favorable adsorption process, with H+ ion functionalization enhancing the drug's binding affinity to the nanocages. Further analysis of the structural properties of the complexes was conducted through natural bond orbital (NBO) charge distribution, dipole moment calculations, and frontier molecular orbital analysis. Additionally, Atoms in Molecules (AIM), reduced density gradient (RDG), and electron localization function (ELF) analyses were employed to elucidate the nature of intermolecular interactions governing the drug-nanocage binding. UV-visible and nonlinear optical (NLO) response calculations reveal the potential of both pristine and functionalized C24 nanocages as optical sensors for SA drug detection. Our findings suggest that these nanocages hold promise for the development of sensitive drug delivery vehicles and targeted therapeutic agents.

Theoretical investigation of the electronic structure of the Rhodium Halides molecules RhF and RhCl with dipole moment calculation

The current study involves an ab initio exploration of the ground and low-lying excited electronic states of the rhodium halide molecules RhF and RhCl using the complete active space self-consistent field (CASSCF) with multireference configuration interaction (MRCI+Q) method including single and double excitations and with Davidson corrections. We investigated the potential energy curves, the transition and permanent electric dipole moments, the electronic energy relative to the ground state Te, the harmonic frequency ωe, the internuclear distance Re, and the rotational constant Be corresponding to each of the bounded states. Our findings demonstrate good agreement with the available experimental data. Notably, this work represents the inaugural theoretical investigation of the excited states of RhF and RhCl molecules, identifying the ground state of both to be X3Π, as observed in the sole two experimental investigations.

Molecular self-assembled helix peptide nanotubes based on some amino acid molecules and their dipeptides: molecular modeling studies.

The paper considers the features of the structure and dipole moments of several amino acids and their dipeptides which play an important role in the formation of the peptide nanotubes based on them. The influence of the features of their chirality (left L and right D) and the alpha-helix conformations of amino acids are taken into account. In particular, amino acids with aromatic rings, such as phenylalanine (Phe/F), and branched-chain amino acids (BCAAs)-leucine (Leu/L) and isoleucine (Ile/I)-as well as corresponding dipeptides (diphenylalanine (FF), dileucine (LL), and diisoleucine (II)) are considered. The main features and properties of these dipeptide structures and peptide nanotubes (PNTs), based on them, are investigated using computational molecular modeling and quantum-chemical semi-empirical calculations. Their polar, piezoelectric, and photoelectronic properties and features are studied in detail. The results of calculations of dipole moments and polarization, as well as piezoelectric coefficients and band gap width, for different types of helical peptide nanotubes are presented. The calculated values of the chirality indices of various nanotubes are given, depending on the chirality of the initial dipeptides-the results obtained are consistent with the law of changes in the type of chirality as the hierarchy of molecular structures becomes more complex. The influence of water molecules in the internal cavity of nanotubes on their physical properties is estimated. A comparison of the results of these calculations by various computational methods with the available experimental data is presented and discussed. The main tool for molecular modeling of all studied nanostructures in this work was the HyperChem 8.01 software package. The main approach used here is the Hartree-Fock (HF) self-consistent field (SCF) with various quantum-chemical semi-empirical methods (AM1, PM3, RM1) in the restricted Hartree-Fock (RHF) and in the unrestricted Hartree-Fock (UHF) approximations. Optimization of molecular systems and the search for their optimal geometry is carried out in this work using the Polak-Ribeire algorithm (conjugate gradient method), which determines the optimized geometry at the point of their minimum total energy. For such optimized structures, dipole moments D and electronic energy levels (such as EHOMO and ELUMO), as well as the band gap Eg = ELUMO - EHOMO, were then calculated. For each optimized molecular structure, the volume was calculated using the QSAR program implemented also in the HyperChem software package.

Molecules in Cool Stars: The A2Π − X2Σ+ and the B2Σ+ − X2Σ+ Band Systems of CaCl

Cool red giant stars exhibit absorption bands of calcium monochloride (CaCl) in the optical region. In this work, the bands of CaCl corresponding to the A2Π − X2Σ+ transition with v′≤ 4 and v″ ≤ 4, and B2Σ+ − X2Σ+ transition with v′≤ 2 and v″ ≤ 2 are rotationally analyzed with PGOPHER, a multipurpose program for simulating and fitting molecular spectra. All bands were analyzed using high-resolution absorption spectra collected at the National Solar Observatory in 1985, calibrated with atomic lines from a high-resolution emission spectrum obtained in a separate hollow cathode experiment. The results are compared with previous laser-induced fluorescence measurements. Overall, the accuracy of spectroscopic constants for the A2Π and B2Σ+ states is improved. Scaled transition dipole moment calculations were used to obtain line strengths. Line lists are provided with Einstein A coefficients and oscillator strengths, which can be used to determine CaCl stellar abundances. Additionally, isotope splittings allowed us to estimate band origins for the 40Ca37Cl isotopologue based on band-head positions.

SLIMP 2.0: A new version of strong laser interaction model package for atoms and molecules, now with molecular orbital tomography based on high-order harmonic spectra

A new version of strong laser interaction model package for atoms and molecules is presented. Its capacities are enhanced by incorporating modules related to molecular orbital tomography (MOT) in length and velocity forms based on high-order harmonic spectra (HHS). This advanced package enables two-dimensional and three-dimensional MOT of both symmetric and asymmetric molecules using HHS, providing an efficient means for both experimental and theoretical investigations of molecular orbital structures. In addition, it can calculate the precise theoretical orbitals corresponding to those reconstructed by MOT. Furthermore, the package can calculate the transition dipole moment (TDM) in the plane wave approximation and allow for reference MOT based on TDM. It can evaluate the quality of reconstructed orbitals based on HHS and reveal the physical and numerical effects on MOT. This package is suitable for MOT under conditions of driving laser at different intensities and wavelengths, and can be applied to different molecules with various structures. It is designed to facilitate easy expansion for additional capabilities. Program summaryProgram Title: SLIMP, version 2.0CPC Library link to program files:https://doi.org/10.17632/jgcb7m7wwv.1Licensing provisions: GPLv3Programming language: Fortran 90Journal reference of previous version: Comput. Phys. Commun. 192 (2015) 330-341.Does the new version supersede the previous version?: Yes.Reasons for the new version: Molecular orbital tomography (MOT) [1] based on high-order harmonic spectra (HHS) [2] is an important research topic in the field of strong-field physics. It provides an efficient way to probe molecular orbital structures experimentally, which was not considered in the former version of SLIMP [3] and is now included in SLIMP 2.0. The new version package allows performing two-dimensional (2D) and three-dimensional (3D) MOT [4] based on HHS obtained from experiments or simulations, providing reliable detections for many orbitals of interest, either symmetric or asymmetric molecules.Summary of revisions: Extending capacities focus on enabling performing 2D and 3D MOT on symmetric and asymmetric molecules based on HHS, and together the relevantly precise theoretical orbital output, calculation of transition dipole moment (TDM) and reference MOT based on TDM. For 2D MOT, MOT in both length and velocity forms are implemented.Nature of problem: To perform MOT based on HHS, the user needs general reconstruction programs, taking symmetric and asymmetric molecules, 2D and 3D orbitals, and MOT in length and velocity forms into account. In addition, evaluation of imaging quality is required, which can reveal the physical and numerical effects on reconstructions.Solution method: The 2D symmetric and asymmetric, length- and velocity-form, and 3D reconstruction algorithms are implemented based on Fortran 90. Furthermore, this package provides a reference MOT based on directly calculated TDM, served as a comparable result to the reconstructed orbital based on HHS. The comparison between reconstructions based on HHS and TDM can reveal the effects on MOT in physical and numerical aspects.Additional comments including restrictions and unusual features: This package does not include MOT of asymmetric molecules in velocity form. For the 2D MOT based on HHS, the reconstructed 2D projection of gerade, ungerade orbital or the gerade and ungerade components of asymmetric orbital must have the axial symmetry about the x- and z-axis. For the 3D MOT, the reconstructed 3D orbital has to be cylindrically symmetric.

Theoretical investigation of the silver chalcogenide molecules AgSe and AgTe electronic structure with dipole moment calculation

The spectroscopic constants (Re, Te, ωe, Be) are determined for 46 doublet and quartet low-lying states of the molecules AgTe and AgSe using CASSCF/MRCI (single and double excitations plus Davidson correction) calculations. The equilibrium bond length Re, and the vibrational frequency ωe of the ground state of both molecules have also been investigated using the density functional theory (DFT) incorporating eight different functionals along with different basis sets. The potential energy and permanent dipole moment curves of 23 states of each molecule have been investigated and depicted. This study represents the first theoretical investigation of the molecules AgSe and AgTe.

Diamond two-phonon infrared absorption spectrum calculated from first principles using the finite displacement method

We calculate the two-phonon contribution to the dielectric susceptibility of diamond at room and elevated temperatures, utilizing a general ab initio model that can be extended to higher n phonon processes. We calculate the second-order dipole moments using a finite displacement method to calculate the derivatives of the Born effective charge tensor. Specifically, we use results obtained from density-functional theory and density-functional perturbation theory in this finite displacement method to calculate the dipole moments of diamond in the two-phonon case. We use the calculated dipole moment to determine the contribution of two-phonon processes to the dielectric susceptibility. We then calculate the absorption curve as a function of wave-number at room or elevated temperatures. Our results indicate that the calculated absorption is in good agreement with previous calculations, and that it increases in magnitude with temperature while maintaining a consistent shape.

Resolving the Anisotropic Dynamical Evolution of Wide Bandgap GeSe2 Under Polarized Photoexcitation

AbstractGermanium diselenide (GeSe2) has recently emerged as a promising material for high‐performance optoelectronic devices due to its high absorption coefficient, wide direct bandgap, and anisotropic electronic properties. For the future applications, it is necessary to understand the dynamic evolution of carriers with ultrafast response. In this work, the transient absorption spectroscopy measurements are performed to study the anisotropic dynamic evolution of GeSe2 under the polarized photoexcitation. It is find that the dynamics exhibit linear dichroism and show a significant Auger recombination process when the photoexcitation is perpendicular to the b‐axis of GeSe2. Using first‐principle and transition dipole moment calculations, it is confirmed that the more carrier localization at Γ point along the Γ‐X (perpendicular to the b‐axis) and increase the Auger recombination. In addition, the Auger recombination coefficient ≈ 1.1×10−31 cm6 s−1 is determined and demonstrated that the defect‐assisted indirect Auger recombination plays a key role in the carrier relaxation process. Through time‐resolved transient absorption spectra, it is further revealed that the ultrafast dynamical evolution of excited state absorption peaks under polarized photoexcitation. These results have implications for improving the quantum efficiency of high‐field polarization‐sensitive optoelectronics.

Mitochondria Play Essential Roles in Intracellular Protection against Oxidative Stress-Which Molecules among the ROS Generated in the Mitochondria Can Escape the Mitochondria and Contribute to Signal Activation in Cytosol?

Questions about which reactive oxygen species (ROS) or reactive nitrogen species (RNS) can escape from the mitochondria and activate signals must be addressed. In this study, two parameters, the calculated dipole moment (debye, D) and permeability coefficient (Pm) (cm s-1), are listed for hydrogen peroxide (H2O2), hydroxyl radical (•OH), superoxide (O2•-), hydroperoxyl radical (HO2•), nitric oxide (•NO), nitrogen dioxide (•NO2), peroxynitrite (ONOO-), and peroxynitrous acid (ONOOH) in comparison to those for water (H2O). O2•- is generated from the mitochondrial electron transport chain (ETC), and several other ROS and RNS can be generated subsequently. The candidates which pass through the mitochondrial membrane include ROS with a small number of dipoles, i.e., H2O2, HO2•, ONOOH, •OH, and •NO. The results show that the dipole moment of •NO2 is 0.35 D, indicating permeability; however, •NO2 can be eliminated quickly. The dipole moments of •OH (1.67 D) and ONOOH (1.77 D) indicate that they might be permeable. This study also suggests that the mitochondria play a central role in protecting against further oxidative stress in cells. The amounts, the long half-life, the diffusion distance, the Pm, the one-electron reduction potential, the pKa, and the rate constants for the reaction with ascorbate and glutathione are listed for various ROS/RNS, •OH, singlet oxygen (1O2), H2O2, O2•-, HO2•, •NO, •NO2, ONOO-, and ONOOH, and compared with those for H2O and oxygen (O2). Molecules with negative electrical charges cannot directly diffuse through the phospholipid bilayer of the mitochondrial membranes. Short-lived molecules, such as •OH, would be difficult to contribute to intracellular signaling. Finally, HO2• and ONOOH were selected as candidates for the ROS/RNS that pass through the mitochondrial membrane.

Conditions for the efficiency of optical limiting based on experiment and quantum chemical calculations.

The development of suitable protection against laser radiation has proven challenging due to the lack of predictive models. The purpose of this article is to exclude the existing drawback by creating a universal strategy based on correlations between experimental and theoretical data characterizing the nonlinear optical properties of absorbers, for which a series of low-symmetry penta(chloro)cyclotriphosphazene-substituted monophthalocyanines was chosen. To search for correlations on a small series of dyes, we used the advanced algorithm CORRELATO, which has been proven to construct even the most unusual relationships demonstrated in our previous works. Due to the reducing symmetry of molecules, large values of the nonlinear absorption coefficient (more than 3000 cm GW-1) and, as a result, wide dynamic ranges (up to 630) with a high degree of attenuation of nanosecond laser radiation (10-20 times) were achieved. The use of the finite-field DFT method has allowed the calculation of dipole moments, polarizabilities and hyperpolarizabilities. The numerical data obtained during the calculations were used in correlations of theory vs. experiment to derive mathematical expressions (inequalities) to assess the effectiveness of absorbers in limiting the power of laser radiation.

Opacities of S-type Stars: The Singlet B 1Π–X 1Σ+, B 1Π–A 1△, and C 1Σ+–X 1Σ+ Band Systems of ZrO

The ZrO B 1Π–X 1Σ+, B 1Π–A 1Δ, and C 1Σ+–X 1Σ+ band systems are important opacity sources in the near-infrared and optical spectra of S-type stars. A total of 21 rovibronic bands with v″ ≤ 7 and were observed and fit for the B 1Π–X 1Σ+ transition, five bands for the 90ZrO B 1Π–A 1Δ transition and one band for the 90ZrO C 1Σ+–X 1Σ+ transition. All band systems were analyzed using high-temperature, high-resolution emission spectra collected at the National Solar Observatory (Kitt Peak). A modern spectroscopic analysis was performed using the PGOPHER program to provide updated spectroscopic constants. In general, we improve the accuracy of the line positions reported in the literature and slightly extend the vibrational analysis. Equilibrium molecular constants were then derived and combined with new ab initio calculations of transition dipole moment functions to produce line lists with line strengths.

Noncentrosymmetric Na6Pb3P4S16 and Centrosymmetric K2MIIP2S6 (MII = Mg and Zn) Displaying Multiple Membered-Ring Configurations and Strong Optical Anisotropy.

Three thiophosphates including noncentrosymmetric Na6Pb3P4S16 and centrosymmetric K2MIIP2S6 (MII = Mg and Zn) were successfully synthesized in vacuum-sealed silica tubes. Note that interesting multiple six membered-rings (6-MRs) including 6-NaS6-MRs and 6-KSn-MRs (n = 6 and 7) formed by A+-centered polyhedra were discovered in the structures of title thiophosphates and these MR-composed three-dimensional (3D) tunnels show great possibility to facilitate the filling of various structural blocks (such as zero-dimensional (0D) Pb3S10 trimers or one-dimensional (1D) (MIISn)n chains). Na6Pb3P4S16 exhibits the strongest nonlinear optical (NLO) response (5.4 × AgGaS2) with phase-matching (PM) behavior among the known Pb-based PM NLO sulfides, which is much larger than that of Pb3P2S8 (3.5 × AgGaS2); it was verified that such large second harmonic generation (SHG) response in Na6Pb3P4S16 can be attributed to the huge contribution of stereochemically active PbS4 units based on the SHG-density and dipole-moment calculations. Moreover, title thiophosphates show large birefringences (Δn = 0.102-0.21), which indicates that incorporation of [P2S6] dimers or polarized PbS4 units into structures provides positive benefits for the onset of strong optical anisotropy.

One-loop matching of the CP-odd three-gluon operator to the gradient flow

The calculation of the neutron electric dipole moment within effective field theories for physics beyond the Standard Model requires non-perturbative hadronic matrix elements of effective operators composed of quark and gluon fields. In order to use input from lattice computations, these matrix elements must be translated from a scheme suitable for lattice QCD to the minimal-subtraction scheme used in the effective-field-theory framework. The accuracy goal in the context of the neutron electric dipole moment necessitates at least a one-loop matching calculation. Here, we provide the one-loop matching coefficients for the CP-odd three-gluon operator between two different minimally subtracted 't Hooft–Veltman schemes and the gradient flow. This completes our program to obtain the one-loop gradient-flow matching coefficients for all CP-violating and flavor-conserving operators in the low-energy effective field theory up to dimension six.

Accurate ab initio calculations of adiabatic energy and dipole moment: Prospects for the formation of cold Alkaline-Earth-Francium molecular ions ALKE-Fr+ (ALKE = Be, Mg, Ca, and Sr)

Alkaline-earth and alkali-metal mixtures have an electronic structure that is perfect for laser cooling. This makes them highly attractive for trapping and laser cooling experiments, allowing the formation of cold molecules. For this object, potential-energy curves and relevant spectroscopic parameters of the low-lying electronic excited states of 1,3Σ+, 1,3Π, and 1,3Δ symmetries of molecular-ion systems composed of alkaline-earth-ion and Francium alkali-metal-atom: ALKE-Fr+ (ALKE = Be, Mg, Ca and Sr), are determined using advanced theoretical technique in quantum chemistry, including a non-empirical pseudopotential, core-valence correlation, large Gaussian basis sets and Full Configuration Interaction (FCI). In order to obtain a more accurate understanding of the electronic structure of these systems, we also determined transition and permanent dipole moments and vibrational properties. Thereafter, the spontaneous and the black-body stimulated transition rates were determined and were employed to calculate lifetimes for all vibrational states of the ground electronic states 11Σ+ of molecular-ions under consideration. For the first and the second excited states, radiative lifetimes were investigated via the Franck–Condon approximation including bound-bound and bound-free transitions. High diagonal structure and large Franck Condon Factor (FCF) values f 00 = 0.987, f 11 = 0.959 and f 22 = 0.919 were obtained for the 11Π (v′ = 0, 1, 2)→ 11Σ+ (v = 0, 1, 2) transition making the BeFr+ system a good candidate for laser cooling. Furthermore, the current results could be used to investigate elastic scattering properties in cold-ion-atom collisions for the first excited states and may help the experimentalists for possible formation, spectroscopy, and photoassociation of cold ion-atom mixtures.

Magnetic/optical assessments of RFeO3 (R=La, Pr, Nd, and Sm) ceramics: An experimental and theoretical discernment

Experimental and Density Functional Theory (DFT) studies on the structural, magnetic and optical properties of rare-earth orthoferrites RFeO3 (R = La, Pr, Nd, and Sm) were performed. The synthesis was carried out via the Ethylenediaminetetraacetic acid (EDTA)-citrate method. All these perovskites exhibited orthorhombic crystal structures with a space group Pbnm, and their lattice parameters and unit cell volumes decreased as a function of the rare earth ionic radius, as it was expected. The microstructural analysis indicates that all the perovskites share similar textural properties. The magnetic characterization revealed a weak ferromagnetic behavior attributed to the canted antiferromagnetic Fe3+ sublattices, with the dominant magnetic configuration identified as the G-type. Super-exchange interactions between Fe3+-O-Fe3+, R3+-O-Fe3+, and R3+-O-R3+ couplings facilitated a long-range magnetic ordering. The optical characterization indicated d-d electronic transitions, and the perovskites were confirmed as semiconductors with a bandgap of approximately 2.1 eV. The calculation of the transition dipole moment demonstrates two significant aspects: the electronic transition is direct and allowed, and its enhancement is evident in the Sm sample. Overall, this study provides valuable insights into the crystal structure, magnetic properties and optical behavior of RFeO3 perovskites, synthesized via the EDTA-citrate method.

Synthesis, biological evaluations and in silico studies on pyrimidine-appended fused pyrazolones as anticancer and antimicrobial agents

A series of twenty-two new pyrimidine appended fused pyrazolones 6a‒k and 7a‒k has been efficiently synthesized in good yields. Their structural characterization was achieved by physical and spectral analysis data (FTIR, NMR (1H & 13C), 2D NMR and HRMS) and single-crystal X-ray crystallography. All compounds were assayed for their in vitro anticancer activity against three human cancer cell lines viz. (i) human colorectal carcinoma (HCT116), (ii) human breast carcinoma (MCF7), and (iii) human prostate cancer (PC3) employing sulphorhodamine B assay by taking Camptothecin as a standard reference drug, and were also evaluated for their in vitro antimicrobial activities against two Gram-positive bacterial strains viz. E. faecalis (MTCC 439) and S. aureus (NDRI 110), two Gram-negative bacterial strains viz. E. coli (MTCC 723) and S. Typhi (MTCC 3224), and one fungal strain R. oryzae (MTCC 262) employing a quantitative micro-spectrophotometric assay by taking Tetracycline and Fluconazole as standard reference drugs for the antibacterial and antifungal testing, respectively. Amongst all the newly synthesized pyrazolones, 6e and 6j were found to exhibit maximal inhibitory activity against all the tested cancer cell lines, however, these are well active in comparison to the standard drug Camptothecin. The antimicrobial activity evaluation results revealed that compound 6k showed the highest potency against all the bacterial and fungal strains under study in comparison to the respective standard drugs Tetracycline and Fluconazole. Furthermore, in vitro anticancer activity was supported by docking studies performed on the derivatives 6e and 6j with their binding scores ‒65.842 and ‒64.555, respectively whereas the binding score of co-crystallized Topotecan was ‒65.675. Using X-ray crystal structure of compound 6e, DFT analysis gave energies of HOMO and LUMO as ‒0.2268 a.u.and ‒0.0872 a.u., respectively while the calculated dipole moment was 9.202833 D. The HOMO is mainly concentrated on chlorophenyl and indenopyrazolone nucleus while LUMO showed larger coefficient on dimethylpyrimidine ring which is in accord with binding interaction results of docking studies.

Controlling Extraction of Rare Earth Elements Using Functionalized Aryl-vinyl Phosphonic Acid Esters.

Ligands that can discriminate between individual rare earth elements are important for production of these critical elements. A set of aryl-vinyl phosphonic acid ligands for extracting rare earth elements were designed and synthesized under the hypothesis that the strength of the rare earth-ligand interactions could be tuned by changing the dipole moment of the ligand. The ligands were synthesized via a two-step reaction procedure using a Heck coupling reaction to functionalize vinyl phosphonic acid, followed by Steglich esterification to obtain high-purity styryl phosphonic acid monoesters with varying dipole moments along the P-C bond. The metal binding strength and composition of the rare earth complexes formed with these styryl phosphonic acid monoesters were experimentally studied by liquid-liquid extraction techniques, while DFT calculations were performed to determine the dipole moments of the free and complexed ligands and the electronic structure of the complexes formed. All three prepared ligands were much stronger extracting agents for europium(III) than the dialkylphosphonic acids usually used for this separation. However, the order of increasing extraction strength was found to match the order of the decreasing calculated dipole moment along the P-C bond of the three styryl-based ligands, rather than correlating with increasing ligand basicity, as reflected by the pKa of the ligands. These findings suggest that this approach can be used to systematically alter the extraction strength of aromatic phosphonic monoesters for rare earth element purification.