Electronic structure of some adenosine receptor antagonists: I. Equilibrium geometries,charge density distributions,and substituent effects

Ab initio molecular orbital calculations were implemented to investigate the variation of the electronic structure of a series of different xanthine derivatives. MP2(full)/6‐31G calculations have been carried out and used to investigate the geometric features of the studied compounds. Alkyl xanthines studied in the present work are highly polarized with the σ and π frameworks polarized in opposite directions. This polarization is sensitive to substitution. The trend observed for the variation of dipole moment with substitution is interesting. Thus, electron‐withdrawing substituents lower the magnitude of the dipole moment, which reaches its smallest value in the case of ? CF₃ substituent. The ? NO₂ group not only reduces the dipole moment but it also inverts its direction as well. The effect of the basis set on these geometric features has been investigated through implementation of polarization function in MP2(full)/6‐31G/6‐311G** calculations, where it was found that inclusion of the polarization function led to a noticeable redistribution of the charge density. Thus, charge density that was originally accumulated on the atomic centers is redistributed into the bonding regions and this is the reason for the smaller net charges and the larger bond orders predicted at the 6‐311G** level. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002     

Mössbauer and electrical conduction investigations of LiFe(BaTi)(PO<Subscript>4</Subscript>) NASICON nano composite

NASICON glass sample with a composition of Li _1.3Fe _0.3(BaTi) _1.7(PO ₄) ₃ was prepared using the conventional melt-quenching technique at 1300 ^°C for one hour after two stages of calcination process at 300 ^°C and 600 ^°C respectively. DTA was used to determine (T _g) and (T _c) of the as-quenched glass sample. XRD was used to confirm the glassy state of the prepared sample. The as-quenched glass sample was heat treated near its onset crystallization temperature for different times 1, 2, 3, 4, and 5 hours. The gradual precipitation of the crystalline nano-particles with NASICON type structure was also confirmed using XRD. The as-prepared sample and the five heat treated (HT) samples were investigated using Mössbauer spectroscopy, DC and AC conductivities and dielectric permittivity. FTIR, density, and TEM measurements were also performed. After HT, XRD and FTIR measurements conformed the formation of NASICON phase. The results of the dielectric permittivity showed no maximum peak in the studied temperature and frequency ranges, which indicates the absence of ferroelectric behavior of the HT glass sample. Mössbauer data showed that the iron in the glass and its HT samples include two ionic states, Fe ³⁺ (O _h) and Fe ²⁺ (O _h) ions. It is observed that the DC conductivity of the HT glass for 5 h was almost two orders of magnitude higher than that of the parent glass.     

Molecular dynamics and conduction mechanism of poly(vinyl chloride-co-vinyl acetate-co-2-hydroxypropyl acrylate) terpolymer containing ionic liquid

Dielectric spectroscopy (DS) measurements were performed to probe the segmental dynamics and ion mobility of poly(vinyl chloride-co-vinyl acetate-co-2-hydroxypropyl acrylate) terpolymer dopped with different amounts of tetrabutylammonium tetrafluoroborate ([TBA] [BF₄]) ionic liquid (IL). Differential scanning calorimetry (DSC) was also employed to trace the change in the glass transition temperature (T_g) at different loads of IL. The DSC measurements revealed a remarkable reduction in the PVVH T_g from 344 to 310 K just by adding 20 wt% of IL. The DS measurements revealed three relaxation processes named α, β₁, and β₂. The α-process is related to the segmental motion of PVVH while the β₁ and β₂ are due to the restricted local dynamics of side chains. The segmental relaxation times (α-relaxation) speed up with increasing the concentration of IL due to the plasticization effect of IL on polymer chains. The temperature dependence of α-relaxation follows the Vogel-Fulcher-Tammann (VFT) relation with dynamic glass transition between 323 and 294 K in agreement with the DSC measurements. The β₁ and β₂-relaxations have an Arrhenius temperature dependence. The temperature dependence of ionic conductivity obeys the VFT behavior indicating the coupling between the segmental motion of PVVH chains and ion transport. Polaronic tunneling is the predominant conduction mechanism in PVVH and its composites. The specific capacitance increases with increasing both the temperature and IL concentration.     

Synthesis and Antioxidant Evaluation of Some Nicotinonitriles

One‐pot condensation of malononitrile 1 , furan‐2‐carbaldehyde 2 , butan‐2‐one 3 , and ammonium acetate in ethanol, followed by cyanoacetylation of the formed nicotinonitrile 4 with 3‐(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)‐3‐oxopropanenitrile 5 afforded the cyanoacetamide 6 . Compound 6 was used as a key intermediate for synthesis of nicotinonitriles via reaction with different reagents.     

Synergistic effect between surfactants and polyacrylates-maleicanhydride copolymers to improve the flow properties of waxy crude oil

Four copolymers were prepared by copolymerization of octadecyl acrylate with maleic anhydride abbreviated as [ODM], the resulted copolymer was reacted with octadecylalcohol [ODMSA], hexadecylamine [ODMCA], benzyl alcohol [ODMBA] and aniline [ODMAn]. Three oil-soluble surfactants were also prepared by esterification of mono, di and tri ethanolamine with oleic acid, abbreviated as [MEAO, DEAO and TEAO]. These compounds were purified and characterized by FTIR, ¹H-NMR and GPC. The prepared copolymers were evaluated individually and mixed with the oil-soluble surfactants and evaluated as flow improvers and pour point depressants for waxy crude oil. It was found that, the polymer with aromatic side chain [ODMBA] exhibited the maximum pour point depression ΔPP?=?24°C at concentration 1000?ppm, while the minimum pour point depression was obtained by [ODMCA] which pronounced ΔPP?=?15°C at 1000?ppm. Furthermore, the blend [B4] between [ODMBA] and oil-soluble surfactant [TEAO] achieved extra depression of pour point (ΔPP?=?30°C). The rheological properties of the treated and untreated crude oil with the polymeric additives were also investigated and it was found that Bingham yield value (τ_B) was decreased from 1.63?Pa at 32°C to 0.3?Pa at the same temperature and 500?ppm concentration of [ODMBA].     

Overview of the synthetic routes to tadalafil and its analogues

The biological and medicinal properties of tadalafil and its analogues have prompted enormous research aimed at developing synthetic routes to these heterocyclic analogues. This review focuses on the chemical properties associated with this system.     

Electrocatalytic Nitrite Determination Using Iron Phthalocyanine Modified Gold Nanoparticles

Electrochemical detection of nitrite was achieved via electrodeposition of gold nanoparticles (AuNPs) onto glassy carbon electrodes, followed by 3‐mercaptopropionic acid (MPA) self‐assembly, enabling attachment of an iron(III) monoamino‐phthalocyanine (FeMAPc) catalyst via amide bond formation. The use of scanning electron microscopy, energy dispersive X‐ray spectroscopy and ultraviolet‐visible spectroscopy realised surface characterisation while cyclic voltammetry and electrochemical impedance spectroscopy techniques were applied for electrochemical interrogation. The electrochemical behaviour of nitrite at the bare (GCE), AuNPs/GCE, FeMAPc/GCE and FeMAPc‐MPA/AuNPs/GCE was further scrutinised using differential pulse voltammetry in phosphate buffer solution (0.1 M PBS, pH 5.8). Overall the FeMAPc‐MPA/AuNPs/GCE resulted in sensitivity 14.5 nA/µM, which was double that of AuNPs/GCE, 2.4 times FeMAPc/GCE and 3.5 times the response at a bare GCE, with linear range 1.9 µM–2.04 mM (PBS, pH 5.8) and LOD 0.21 µM. An interference study revealed that the proposed sensor (FeMAPc‐MPA/AuNPs/GCE) exhibited a selective response in the presence of interfering anions and the analytical capability of the sensor was demonstrated via nitrite ion determination in real water samples.     

New cytotoxic bio-transformed sesquiterpene by Rhizopus oryzae fungus

Due to the rapidly increasing number of pathogenic bacteria, viruses, and tumor cells that possess resistance toward established therapies, lead structures for the development of new drugs are in high demand. The plant material of Tanacetum sinaicum is considered a prolific source of the potent biologically active sesquiterpene Tanacetolide A ( 1 ). In our research, we focused on the structural transformation of the substrate Tanacetolide A (compound 1 ) by suspended culture of the novel locally isolated terrestrial fungus Rhizopus oryzae KX685359. The fungal transformation resulted in the formation of 1β,3α-dihydroxy-6α-hydroperoxy-eudsm-4(15)-ene 12-oic acid ( 2 ) with higher antiproliferative activity against colon cancer cell line (Caco-2) than that of the parent compound ( 1 ).     

Design and synthesis of D-π-A fluorescent dyes based on nicotinonitrile and azobenzene derivatives

Study the synthesis and fluorescent properties of a new series of D-π-A fluorescent dyes based on nicotinonitrile and azobenzene is the main objective for this work. Reduction with Zn/HCl, diazotization with HCl/NaNO₂, and coupling using catalytic NaOH or AcONa are simple applied methods. Where, nicotinonitrile 3 was synthesized via reduction of nitro derivative 1 followed by diazotization with HCl/NaNO₂ in acetic acid. The formed benzene diazonium chloride was coupled with several activated phenols, aniline, and α-CH acids to yield the respective azo dyes 4-11 in moderate to good yield. Dyes 11a-d subjected to intermolecular cyclization with hydrazine hydrate resulted in pyrazole dyes 12-15 in moderate yield. Dyes containing pyrazole moiety or electron-withdrawing groups at the sixth position of pyridine nucleus exhibit stronger blue-green emission (λ_fl.max = 503, 507, 500, 501, 502, 493, and 514 nm) than that of the rest of compounds.     

Spectroscopic Studies of Proton Transfer Equilibria In Hydrogen Bonded Complexes

Abstract

Recent studies on proton transfer equilibria for many hydrogen bonded complexes are discussed. These studies employ various spectroscopic techniques as infrared, ultraviolet, ¹H NMR, ¹³C NMR, ¹⁵N NMR and nuclear quadrupole resonance (NQR) spectroscopy. Special attention has been paid to Fourier transform infrared (FTIR), and it forms the main focus of this review, in particular for the study of proton transfer equilibria in proton sponges hydrogen bonded complexes. The influence of proton transfer equilibria on the physical, chemical and biological properties of hydrogen bonded complexes is shown. Some applications of proton transfer equilibria are also discussed.