Hamdy S. El-Sheshtawy

Halogen vs hydrogen bonding in thiazoline-2-thione stabilization with σ- and π-electron acceptors adducts: theoretical and experimental study.

Molecular charge-transfer complexes (CT) between thiazoline-2-thione (THZ) and different σ- (I2) and π-acceptors (Tetracyanoethylene (TCNE), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), and 2,3,5,6-tetrachloro-1,4-benzoquinone (CHL)) were investigated. UV-Vis absorption spectroscopy and theoretical calculations using both MP2/aug-cc-pVDZ-PP and B3LYP/6-311++G(d,p) level of theory were corroborated to study the nature of the stabilizing forces for THZ-I2, THZ-DDQ, THZ-TCNE, and THZ-CHL. Halogen bonding (XB) was the stabilizing attractive force in THZ-I2 and THZ-CHL whereas; hydrogen bonding (HB) was dominated in both THZ-TCNE, and THZ-DDQ complexes. Formation constant (K), extinction coefficient (ɛ), thermodynamic parameters such as enthalpy change (ΔH), entropy (ΔS), and Gibbs free energy (ΔG) were measured in different solvents.

Synthesis, characterization and medical efficacy (hepatoprotective and antioxidative) of albendazole-based copper(II) complexes – an experimental and theoretical approach

A series of albendazole-based copper(II) complexes with different counter anions, [Cu(Albz)(H2O)2](ClO4)2 (1), [Cu(Albz)2(Cl)]Cl·2H2O (2), [Cu(Albz)2(NO3)](NO3) (3), and [Cu2(Albz)2(μ-SO4)2(H2O)2] (4) (Albz = albendazole), have been synthesized and characterized. Their structures and properties were characterized by elemental analysis, thermal analysis (TGA, DTG and DTA), IR, UV–vis and ESR spectroscopies, cyclic voltammetry, electrical molar conductivity, and magnetic moment measurements. A square-planar geometry is proposed for 1, whereas the five-coordinate copper(II) complexes 2, 3, and 4 have a square pyramidal geometry. Theoretical calculations (DFT) using B3LYP/6–311 + G(d,p) level of theory corroborated the experimental results to investigate both the drug Albz and its copper(II) complex, 1. The hepatoprotective and antioxidative efficacy of Albz and 1–4 were evaluated against carbon tetrachloride-induced acute hepatotoxicity in rats. Hepatotoxicity in experimental rats was evidenced by significant decrease in the antioxidant enzyme activities (SOD, GSH-S-transfers, and GSH-Rd levels). The results have strong impact for designing anticancer drugs, combined with their potential cytotoxic and antioxidant activities, which can be targeted selectively against cancer cells and increase their therapeutic index and advantages over other anticancer drugs. The DNA cleavage studies of Albz and its copper(II) complexes using genomic DNA indicated that Albz has no role in cleavage of DNA, and only 1 played a marked role in the DNA cleavage without any external additives.

Orthogonal hydrogen/halogen bonding in 1-(2-methoxyphenyl)-1H-imidazole-2(3H)-thione-I2 adduct: An experimental and theoretical study

The molecular complex between 1-(2-methoxyphenyl)-1H-imidazole-2(3H)-thione (Hmim(OMe)) and iodine (I2) was investigated. Single crystal of [(Hmim(OMe))I2] adduct was grown by slow evaporation technique from chloroform at room temperature. Spectroscopic techniques such as FT-IR and Raman techniques, as well as elemental and thermal analysis were used to characterize the complex. The crystal structure shows that the formed adduct stabilized by two noncovalent interactions, namely, hydrogen bond (HB) and halogen bond (XB). Orthogonal HB/XB associated with iodine atom (I) was observed and fully characterized. The ability of iodine to behave as hydrogen bond acceptor and halogen bond donor was held responsible for the orthogonal HB/XB presence. In addition, the structure of Hmim(OMe)I2 was investigated theoretically using MP2/aug-cc-pVDZ level of theory. Natural bond orbital analysis (NBO) was used to investigate the molecular orbitals interactions and orbitals stabilization energies.

Synthesis, Structural, and Theoretical Studies of Quinazoline-2,4-dione Derivatives

ABSTRACT New quinazolin-2,4-dione derivatives have been synthesized and fully characterized. The new derivatives were synthesized using 3-(2-imino-4-oxo-3H,4H,5H-thiazolidin-3-yl)-1H-quinazolin-2,4-dione by nucleophilic addition mechanism. DFT calculations using B3LYP/6–311++G(d,p) level of the theory were used to investigate the molecular structures and the relative stabilities of the anticipated isomers (E and Z). Both experimental and theoretical calculations confirmed the higher stability of the Z-isomers compared to the E-isomers. The former is stabilized by two intramolecular hydrogen bonds compared to only one in the latter isomer. The frontier orbital calculations (HOMO and LUMO), and the energy gap confirmed the stability of the molecules.

Five-Component Self-Assembly of Cucurbituril-Based Hetero-pseudorotaxanes

Abstract [5]Pseudorotaxanes can be obtained by self‐sorting using heteroditopic guests and various cucurbituril homologues as hosts. The assembly and chemically induced disassembly of the pseudorotaxanes can be monitored by measuring the fluorescence of the anthracene guest in solution. Mass spectral evidence for the supramolecular assemblies is obtained in the gas phase. The disassembly in the gas phase can be achieved by collision‐induced dissociation leading to the corresponding [2]‐ and [3]pseudorotaxanes.

Synthesis, Structural Characterization, Spectroscopic Properties, and Theoretical Investigations of Aminoacridine Derivatives

ABSTRACT Synthesis of four N-(heterocyclic)-9-aminoacridine derivatives was investigated. The synthesized compounds, N-thiazolyl-9-aminoacridine (AC1), N-(1,3,4-thiadiazolyl)-9-aminoacridine (AC2), N-(5-methyl-1,3,4-thiadiazolyl)-9-aminoacridine (AC3), and N-(5-phenyl-1,3,4-thiadiazolyl)-9-aminoacridine (AC4) were characterized by FT-IR, 1H NMR, mass-spectral, and elemental analysis. Amine-imine tautomerism was suggested by density functional theory (DFT) calculations. The optimized structures were obtained using B3LYP/6–311++G(d,p) level of theory. The UV–Vis absorption spectra were measured in various organic solvents. The synthesized compounds AC1–AC4 exhibit absorption spectra characteristic of typical donor–acceptor compounds. The highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) analysis have been used to explain the internal charge transfer (ICT) phenomena within the molecules. Also, simulated UV spectra were calculated using TD-DFT (B3LYP/6–311++G(d,p) and the results were compared with the experimental values.

Halogen bond triggered aggregation induced emission in an iodinated cyanine dye for ultra sensitive detection of Ag nanoparticles in tap water and agricultural wastewater

Aggregation induced emission (AIE) has emerged as a powerful method for sensing applications. Based on AIE triggered by halogen bond (XB) formation, an ultrasensitive and selective sensor for picomolar detection of Ag nanoparticles (Ag NPs) is reported. The dye (CyI) has an iodine atom in its skeleton which functions as a halogen bond acceptor, and aggregates on the Ag NP plasmonic surfaces as a halogen bond donor or forms halogen bonds with the vacant π orbitals of silver ions (Ag+). Formation of XB leads to fluorescence enhancement, which forms the basis of the Ag NPs or Ag+ sensor. The sensor response is linearly dependent on the Ag NP concentration over the range 1.0–8.2 pM with an LOD of 6.21 pM (σ = 3), while for Ag+ it was linear over the 1.0–10 μM range (LOD = 2.36 μM). The sensor shows a remarkable sensitivity for Ag NPs (pM), compared to that for Ag+ (μM). The sensor did not show any interference from different metal ions with 10-fold higher concentrations. This result indicates that the proposed sensor is inexpensive, simple, sensitive, and selective for the detection of Ag NPs in both tap and wastewater samples.

Fenton-like nanocatalyst for photodegradation of methylene blue under visible light activated by hybrid green DNSA@Chitosan@MnFe 2 O 4

High efficient 3,5-Dinitrosalicylic acid/Chitosan/MnFe2O4 (DNSA@CS@MnFe2O4) nano photocatalyst was prepared to enrich both adsorption and photodecomposition under visible light. This paper focused on the importance of DNSA@CS as an excellent connector between methylene blue (MB) and MnFe2O4 for accelerating photodegradation with the encouragement of photo-Fenton catalytic reagent hydrogen peroxide (H2O2). The optimum conditions were: contact time, 30 min, H2O2 concentration, 0.16 M, pH factor 9 and dosage 0.06 g/l at R.T, allowing excellent catalytic achievements 98.9% degree of decolorization in 30 min. More interestingly, the hybrid DNSA@CS@MnFe2O4 mechanism explained on the basis of coexistence of Mn2+/Mn3+ and Fe3+/Fe2+ redox couples during the reaction. The photocatalytic decolorization experimentally affirmed the suitability of DNSA@CS@MnFe2O4 obeying Langmuir-Hinshelwood model. Also, the nano-catalytic system was stable even after five runs. The prepared nanostructured catalyst provides simple fabrication to promote deep understand criteria for the mechanistic role of MnFe2O4 catalyst for degradation of MB molecules.