Tuning the push–pull configuration for efficient second-order nonlinear optical properties in some chalcone derivatives

Using the density functional theory methods, we effectively tune the second-order nonlinear optical (NLO) properties in some chalcone derivatives. Various unique push–pull configurations are used to efficiently enhance the intramolecular charge transfer process over the designed derivatives, which result in significantly larger amplitudes of the first hyperpolarizability as compared to their parent molecule. The ground state molecular geometries have been optimized using B3LYP/6-311G** level of theory. A variety of methods including B3LYP, CAM-B3LYP, PBE0, M06, BHandHLYP and MP2 are tested with 6-311G** basis set to calculate the first hyperpolarizability of parent system 1. The results of M06 are found closer to highly correlated MP2 method, which has been selected to calculate static and frequency dependent first hyperpolarizability amplitudes of all selected systems. At M06/6-311G** level of theory, the permanent electronic dipole moment (μ_tot), polarizability (α₀) and static first hyperpolarizability (β_tot) amplitudes for parent system 1 are found to be 5.139 Debye, 274 a. u. and 24.22 × 10⁻³⁰ esu, respectively. These amplitudes have been significantly enhanced in designed derivatives 2 and 3. More importantly, the (β_tot) amplitudes of systems 2 and 3 mount to 75.78 × 10⁻³⁰ and 128.51 × 10⁻³⁰ esu, respectively, which are about 3 times and 5 times larger than that of their parent system 1. Additionally, we have extended the structure-NLO property relationship to several newly synthesized chalcone derivatives. Interestingly, the amplitudes of dynamic frequency dependent hyperpolarizability μβ_ω (SHG) are also significantly larger having values of 366.72 × 10⁻⁴⁸, 856.32 × 10⁻⁴⁸ and 1913.46 × 10⁻⁴⁸ esu for systems 1–3, respectively, at 1400 nm of incident laser wavelength. The dispersion behavior over a wide range of change in wavelength has also been studied adopting a range of wavelength from 1907 to 544 nm. Thus, the present work realizes the potential of designed derivatives as efficient NLO-phores for modern NLO applications.     

Tautomerism in pyridazin-3(2H)-one: A theoretical study using implicit/explicit solvation models

The tautomeric conversion of pyridazin-3(2H)-one 1 into pyridazin-3-ol 2 has been theoretically studied using density functional theory (DFT) methods at the B3LYP/6-311++G** level. Two mechanisms have been considered for this process: (i) one in which the hydrogen is directly transferred through TS12; and (ii) another one in which a double hydrogen transfer takes place via TS1122 upon formation of the corresponding dimer. The former requires a very high activation energy of 42.64 kcal/mol as a consequence of the strain associated with the formation of the four-membered TS12, while the latter requires a much lower activation energy, 14.66 kcal/mol. Implicit, explicit, and a combination of both implicit and explicit solvation models, using both protic and aprotic polar solvents, have been considered for the first mechanism. This study allows the establishment of the requirement to use protic polar solvents in order to reduce the high activation energy associated with TS12.     

Stereoelectronic interaction effects on the conformational properties of hydrogen peroxide and its analogues containing S and Se atoms: An ab initio,hybrid-DFT study and NBO analysis

Ab initio molecular orbital (MP2/6-311+G**//MP2/6-31G+G**) and hybrid-density functional theory (B3LYP/6-311+G**//MP2/6-311+G**) methods and NBO analysis were used to study the stereoelectronic interaction effects on the conformational properties of hydrogen peroxide (1), hydrogen disulfide (2) and hydrogen diselenide (3). The results showed that the Gibbs free energy difference (G_T − G_S) values at 298.15 K and 1 atm between the skew (S) and trans (T) conformations (ΔG_T–S) increase from compound 1 to compound 2 but decrease from compound 2 to compound 3. The C conformations of compounds 1–3 are less stable than their S and T conformations. Based on these results, the racemization processes of the axial symmetrical (C₂ symmetry) conformations of compounds 1–3 take place via their T conformations. Based on the optimized ground state geometries using the MP2/6-311+G** level of theory, the NBO analysis of donor–acceptor (bond–antibond) interactions revealed that the stabilization (resonance) energy associated with LP₂M2 → σ*_M3-H4 electronic delocalization for the S conformations of compounds 1–3 are 1.35, 5.94 and 4.68 kcal mol⁻¹, respectively. There is excellent agreement between the variations of the calculated ΔG_T–S and stabilization (resonance) energies associated with LP₂M2→σ*_M3-H4 electronic delocalization for the S conformations of compounds 1–3. The correlations between resonance energies, orbital integrals, dipole moments, bond orders, structural parameters and conformational behaviors of compounds 1–3 have been investigated. Test were made of complete basis set methods (CBS-QB3, CBS-4 and CBS-Q), the first two gave results essentially indistinguishable from those we used, but the CBS-Q results were in disagreement with experimental and other theoretical results.     

Vibrational analysis and formation mechanism of typical deep eutectic solvents: An experimental and theoretical study

Deep eutectic solvents (DESs), as ionic liquid analogues for green solvents, have gained increasing attentions in chemistry. In this work, three typical kinds of DESs (ChCl/Gly, ChCl/AcOH and ChCl/Urea) were successfully synthesized and characterized by Fourier transform infrared spectroscopy (FTIR) and Raman. Then comprehensive and systematical analyses were performed by the methods of density functional theory (DFT). Two methods (B3LYP/6-311 + +G(2d,p) and dispersion-corrected B3LYP-D3/6-311 + +G(2d,p)) were employed to investigate the structures, vibrational frequencies and assign their ownership of vibrational modes for the DESs, respectively. Nearly all the experimental characteristic peaks of IR and Raman were identified according to the calculated results. By linear fitting of the combined calculated vs experimental vibration frequencies, it can be found that both of the two methods are excellent to reproduce the experimental results. Besides, hydrogen bonds were proved to exist in DESs by IR spectrum, structure analysis and RDG analysis. This work was aimed at predicting and understanding the vibrational spectra of the three typical DESs based on DFT methods. Moreover, by comparing experimental and theoretical results, it provides us a deep understanding of the formation mechanisms of DESs.     

Conformational study of the structure of 18-thiacrown-6

Conformational analysis was performed for 18-thiacrown-6 (18t6) using the CONFLEX method and the MMFF94s force field. Computations were performed for some of the low energy conformations at the HF, B3LYP, CAM-B3LYP, M06, M06L, M062x, M06HF and MP2 levels. The computations were also performed using the DFT-D3 method along with the TPSS and PBE functionals. The study predicted a new C₂ conformation as the ground state conformation of 18t6. This new C₂ conformation is more stable than the experimentally known solid state conformation by 4.7 kcal/mol at the MP2/6-311G** level. This conformation has all of the SCCS dihedral angles adopt exodentate structure. However, the experimentally known conformation of the solid phase has two of the SCCS dihedral angles violating this exodentate rule. It was concluded that for 18t6 stability a linear dihedral SCCS angle requirement is more important than a gauche CSCC dihedral angle requirement.     

A DFT study on the physical adsorption of cyclophosphamide derivatives on the surface of fullerene C60 nanocage

The physical sorption of a series of cyclophosphamide drug derivatives with formula

where x = 2, X = F (2), Cl (3), Br (4); x = 3, X = F (5), Cl (6), Br (7) and x = 4, X = F (8), Cl (9), Br (10) on the surface of fullerene C₆₀ was studied using density functional theory (DFT) at B3LYP and B3PW91 levels. The most negative binding energies obtained using the B3LYP approach and corrected for geometrical BSSE and dispersion energies (gCP-D3-ΔE_binding) were measured for compounds 8 (among isolated drugs) and 13 (among complexes). The dipole moments of isolated drugs were obtained close to those of their complexes with C₆₀ (∼4.0–5.5 Debye) indicating their hydrophililic nature that is an appropriate property appealing for drug delivery in biological media. The adsorption of all drugs on the surface of fullerene was endergonic with all of the ΔG_adsorption > 0. The ΔH_adsorption values at B3PW91 level were only negative for complexes 14–16 indicating their exothermic adsorption nature. The HOMO–LUMO band gaps of complexes 11–19 were about 2.7 eV and are comparable with the gap in C₆₀ but are much smaller than the gaps in isolated drugs 2–10 (6.5–8.0 eV) reflecting the increase in electrical conductivities upon complexation. The QTAIM data supported the covalent character of the C–O, C–N and N–H bonds, the intermediate character of PO, P–O and P–N bonds while the electrostatic nature of PO…C(fullerene) interactions. According to the gCP-D3-ΔE_binding binding energies and ΔH_adsorption values at B3LYP level, it seems that the complexes 12 and 13 can be the most promising prodrug + carrier delivery systems.

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Designing of potential inhibitors against Staphylococcus aureus sortase A: Combined analogue and structure based approach with in vitro validation

Staphylococcus aureus sortase A is an attractive target of Gram-positive bacteria that plays a crucial role in anchoring of surface proteins to peptidoglycan present in bacterial cell wall. Inhibiting sortase A is an elementary and essential effort in preventing the pathogenesis. In this context, in silico virtual screening of in-house database was performed using ligand based pharmacophore model as a filter. The developed pharmacophore model AAHR 11 consists of two acceptors, one hydrophobic and one ring aromatic feature. Top ranked molecule KKR1 was docked into the active site of the target. After profound analysis, it was analyzed and optimized based on the observations from its binding pose orientation. Upgraded version of KKR1 was KKR2 and has improved docking score, binding interactions and best fit in the binding pocket. KKR1 along with KKR2 were further validated using 100 ns molecular dynamic studies. Both KKR1 and KKR2 contain Indole-thiazolidine moiety and were synthesized. The disk diffusion assay has good initial results (ZI of KKR1, KKR2 were 24, 38 mm at 10 μg/mL and ZI of Ampicillin was 22 at 10 μg/mL) and calculated MICs of the molecules (KKR1 5.56 ± 0.28 μg/mL, KKR2 1.32 ± 0.12 μg/mL, Ampicillin 8 ± 1.1 μg/mL) were in good agreement with standard drug Ampicillin. KKR1 has shown IC₅₀ of 1.23 ± 0.14 μM whereas the optimized lead molecule KKR2 show IC₅₀ of 0.008 ± 0.07 μM. Results from in silico were validated by in vitro studies and proved that indole-thiazolidine molecules would be useful for future development as lead molecules against S. aureus sortase A.     

Insight into the interaction between DNA bases and defective graphenes: Covalent or non-covalent

Although some metal clusters and molecules were found to more significantly bind to defective graphenes than to pristine graphenes, exhibiting chemisorptions on defective graphenes, the present investigation shows that the adsorption of DNA bases on mono- and di-vacant defective graphenes does not show much difference from that on pristine graphene, and is still dominantly driven by noncovalent interactions. In the present study the adsorptions of the nucleobases, adenine (A), cytosine (C), guanine, (G), and thymine (T) on pristine and defective graphenes, are fully optimized using a hybrid-meta GGA density functional theory (DFT), M06-2X/6-31G*, and the adsorption energies are then refined with both M06-2X and B97-D/6-311++G**. Graphene is modeled as nano-clusters of C₇₂H₂₄, C₇₁H₂₄, and C₇₀H₂₄ for pristine, mono- and di-vacant defective graphenes, respectively, supplemented by a few larger ones. The result shows that guanine has the maximum adsorption energy in all of the three adsorption systems; and the sequence of the adsorption strength is G > A > T > C on the pristine and di-vacant graphene and G > T > A > C on the mono-vacant graphene. In addition, the binding energies of the DNA bases with the pristine graphene are less than the corresponding ones with di-vacant defective graphene; however, they are greater than those of mono-vacant graphene with guanine and adenine, while it is dramatic that the binding energies of mono-vacant graphene with thymine and cytosine appear larger than those of pristine graphene.     

Tautomeric transformation of temozolomide,their proton affinities and chemical reactivities: A theoretical approach

The gas-phase geometry optimizations of bare, mono- and dihydrated complexes of temozolomide isomers were carried out using density functional calculation at the M06 − 2X/6 − 31 + G(d,p) level of the theory. The structures and protonation energies of protonated species of temozolomide are reported. Chemical indices of all isomers and protonated species are also reported. Energies, thermodynamic quantities, rate constants and equilibrium constants of tautomeric and rotameric transformations of all isomers I1 ↔ TZM ↔ HIa ↔ HIb ↔ I2 ↔ I3 in bare and hydrated systems were obtained.     

DFT study on X−·(H2O)n=1-10 (X = OH,NO2, NO3, CO3) anionic water cluster

A theoretical study to understand the interaction between anion and the water molecules through the hydration (X⁻·(H₂O)_n (X = OH, NO₂, NO₃, CO₃), where n = 1–10), using the density functional theory method with B3LYP functional and 6-311++G(d,p) basis set has been carried out systematically. In these hydrated clusters we notice three different cases of bond arrangements, namely, symmetrical double hydrogen bond, single hydrogen bond and inter-water hydrogen bond. All the complexes are dominated by the OH⋯O hydrogen bond, in which the anion act as a proton acceptor, while the water molecule act as a proton donor. A linear correlation is obtained between the solvent stabilization energy and the size (n) of the hydrated cluster for all the anions. The weighted average interaction energy values, shows that the water molecules strongly bind with the OH⁻ anion. Besides, the solvation of the OH⁻ anion requires less number of water molecules when compared with the other anions. Energy decomposition analysis (EDA) shows the strong dominance of the electrostatic energy component within the interaction energy. The total NPA charges on the anions indicate an increase in the solvation due to hydration. From AIM analysis, excellent linear inverse correlation is observed for both the electron density and Laplacian of the electron density with respect to the hydrogen bond length. Natural bonding orbital analysis (NBO) predicts large charge transfer between the OH⁻ anion and the water molecules.     

Blue electroluminescent materials based on phenylanthracene-substituted fluorene derivatives for organic light-emitting diodes

Two phenylanthracene-substituted fluorene derivatives, 10-(9,9′-dimethyl-2-(10-phenylanthracen-9-yl)-9H-fluoren-7-yl)-phenylanthracene (1) and 2′,7′-di-(10-phenylanthracen-9-yl)-9,9′-spirobi[9H-fluorene] (2) have been designed, synthesized, and characterized. A device using compound 1 as an emitting material exhibited luminous efficiency, power efficiency, external quantum efficiency and CIE coordinates of 3.37 cd/A, 1.50 lm/W, 1.87% at 20 mA/cm² and (0.18, 0.25) at 7 V, respectively. Furthermore, by exploiting this efficient blue fluorescent material as a blue emitting material with the combination of red phosphorescent bis(2-phenylquinoline)acetylacetonate [(pq)₂Ir(acac)], an efficient white OLED (WOLED) with a external quantum efficiency of 1.70%, luminous efficiency of 1.38 cd/A, power efficiency of 0.94 lm/W at 20 mA/cm² and the color coordinates of (0.33, 0.36) at 14 V is demonstrated.     

Small molecules with pyridine backbone modified with carbazole,fluorine and bromine for white light-emitting diode applications

Seven compounds with pyridine as the backbone modified by carbazole moiety, bromine atom and fluorine atom were synthesized. Compounds 1, 2, 3 with bromo substitution at the 2-position and carbazole modification at the 5-position of pyridine emit not only a sharp blue singlet fluorescence but also a wide banded excimer-based orange emission. The two colors coming from a single molecule can be used to fabricate a simplified white light emitting device. The electroluminescence based on 1 and 2 exhibits white-light emission with CIE coordinates of x = 0.25 and y = 0.30 for 1 and x = 0.33 and y = 0.37 for 2 at high current densities, very close to pure white emission. In addition, the role of bromo-substitution at pyridine is concluded to be essential to generate molecular interaction thus an excimer emission.     

Computing Modular Invariants of p-groups

Let V be a finite dimensional representation of a p -group, G, over a field,k , of characteristic p. We show that there exists a choice of basis and monomial order for which the ring of invariants, k [ V ]^G, has a finite SAGBI basis. We describe two algorithms for constructing a generating set for k [ V ] G. We use these methods to analyse k [2V₃ ]^U₃where U₃is the p -Sylow subgroup ofGL₃ (F_p) and 2 V₃is the sum of two copies of the canonical representation. We give a generating set for k [2 V₃]^U₃forp =  3 and prove that the invariants fail to be Cohen–Macaulay forp >  2. We also give a minimal generating set for k [mV₂ ]^Z / pwere V₂is the two-dimensional indecomposable representation of the cyclic group Z / p.     

On decidability of monadic logic of order over the naturals extended by monadic predicates

A fundamental result of Büchi states that the set of monadic second-order formulas true in the structure (Nat,  <) is decidable. A natural question is: what monadic predicates (sets) can be added to (Nat,  <) while preserving decidability? Elgot and Rabin found many interesting predicates P for which the monadic theory of 〈Nat, <,  P〉 is decidable. The Elgot and Rabin automata theoretical method has been generalized and sharpened over the years and their results were extended to a variety of unary predicates. We give a sufficient and necessary model-theoretical condition for the decidability of the monadic theory of (Nat, <, P₁, … , P_n).We reformulate this condition in an algebraic framework and show that a sufficient condition proposed previously by O. Carton and W.Thomas is actually necessary. A crucial argument in the proof is that monadic second-order logic has the selection and the uniformization properties over the extensions of (Nat, <) by monadic predicates. We provide a self-contained proof of this result.     

DFT studies on armchair (5, 5) SWCNT functionalization. Modification of selected structural and spectroscopic parameters upon two-atom molecule attachment

Density functional theory (DFT) studies on adsorption of several gaseous homo- and hetero-diatomic molecules (AB) including H₂, O₂, N₂, NO and CO on external surface of H-capped pristine armchair (5, 5) single-walled carbon nanotube (SWCNT) were conducted. Structures of C₇₀H₁₀ and the corresponding C₇₀H₁₀–AB adducts were fully optimized at the B3LYP/6-311G* level of theory. Calculated HOMO/LUMO energy gaps (E_g), ¹³C NMR chemical shifts and IR/Raman parameters were analyzed and critically compared with available experimental data. Significant changes of carbon NMR atom chemical shifts (up to −100 ppm) and shielding anisotropies (up to −180 ppm) at sites of addition were observed. Functionalized SWCNTs produced IR and Raman spectra different from the pristine nanotube model. The selective changes in vibrational spectra will help in assigning the topology of functionalization at the nanotube wall.     

Modal analysis and modified cascade neural networks in identification of geometrical parameters of circular arches

A hybrid computational system, composed of the finite element method (FEM) and cascade neural network system (CNNs), is applied to the identification of three geometrical parameters of elastic arches, i.e. span l, height f and cross-sectional thickness h. FEM is used in the direct (forward) analysis, which corresponds to the mapping α = {l, f, h} → {ω_j}, where: α – vector of control parameters, ω_j – arch eigenfrequencies. The reverse analysis is related to the identification procedure in which the reverse mapping is performed {ω_j} → {α_i}. For the identification purposes a recurrent, three level CNNs of structure (D^k-H^k-1)_s was formulated, where: k – recurrence step, s = I, II, III-levels of cascade system. The Semi-Bayesian approach is introduced for the design of CNNs applying the MML Maximum Marginal Likelihood) criterion. The computation of hyperparameters is performed by means of the Bayesian procedure evidence. The numerical analysis proves a great numerical efficiency of the proposed hybrid approach for both the perfect (noiseless) values of eigenfrequencies and noisy ones simulated by an added artificial noise.     

Arylhydrazone derivatives of naproxen as new analgesic and anti-inflammatory agents: Design,synthesis and molecular docking studies

A series of new arylidenehydrazone derivatives of naproxen were synthesized and evaluated for their analgesic and anti-inflammatory activities. Some of the synthesized analogues showed comparable activities when compared against naproxen for their analgesic and anti-inflammatory properties. 2-(6-methoxy-2-naphthyl)-N′-[(pyridine-4-yl)methylene]propanoic acid hydrazide 4j was found to be the most active analgesic agent. 2-(6-methoxy-2-naphthyl)-N′-[4-nitrobenzylidene]propanoic acid hydrazide 4g showed highest anti-inflammatory activity in comparison to the naproxen. Molecular modeling study of the synthesized compounds suggested that the designed molecules were well located and bound to the COX-1 and COX-2 active sites. Compound 4g showed the highest selectivity for COX-2 (R_{COX-2/COX-1 =} 1.94) and higher affinity rather than naproxen in COX-2 active site (R_{COX-2/naproxen =} 1.28). Moreover, the structural analyses confirmed that the E-ap rotamer is the preferred structure for the arylidenehydrazone derivatives.     

Evolution of structure,stability, and nonlinear optical properties of the heterodinuclear CNLin (n = 1–10) clusters

The lowest-energy structures and stabilities of the heterodinuclear clusters, CNLi_n (n = 1–10) and relevant CNLi_n⁺ (n = 1–10) cations, are studied using the density functional theory with the 6-311 + G(3df) basis set. The CNLi₆ and CNLi₅⁺ clusters are the first three-dimensional ones in the CNLi_n^0/+ series, respectively, and the CN group always caps the Li_n^0/+ moiety in the CNLi_n^0/+ (n = 1–9) configurations. The CN triple bond is found to be completely cleaved in the CNLi₁₀^0/+ clusters where the C and N atoms are bridged by two Li atoms. The CNLi_n (n = 2–10) clusters are hyperlithiated molecules with delocalized valence electrons and consequently possess low VIP values of 3.780–5.674 eV. Especially, the CNLi₈ and CNLi₁₀ molecules exhibit lower VIPs than that of Cs atom and can be regarded as heterobinuclear superalkali species. Furthermore, these two superalkali clusters show extraordinarily large first hyperpolarizabilities of 19,423 and 42,658 au, respectively. For the CNLi_n⁺ cationic species, the evolution of the energetic and electronic properties with the cluster size shows a special stability for CNLi₂⁺.