Stability-indicating methods for determination of pyritinol dihydrochloride in the presence of its precursor and degradation product by derivative spectrophotometry

A first-derivative spectrophotometric (1D) method and a derivative-ratio zero-crossing spectrophotometric (1DD) method were used to determine pyritinol dihydrochloride (I) in the presence of its precursor (II) and its degradation product (III) with 0.1N hydrochloric acid as a solvent. Linear relationships were obtained in the ranges of 6-22 microg/mL for the (1D) method and 6-20 microg/mL for the (1DD) method. By applying the proposed methods, it was possible to determine pyritinol dihydrochloride in its pure powdered form with an accuracy of 100.36 +/- 1.497% (n = 9) for the (1D) method and an accuracy of 99.92 +/- 1.172% (n = 8) for the (1DD) method. Laboratory-prepared mixtures containing different ratios of (I), (II), and (III) were analyzed, and the proposed methods were valid for concentrations of < or = 10% (II) and < or = 50% (III). The proposed methods were validated and found to be suitable as stability-indicating assay methods for pyritinol in pharmaceutical formulations.     

A new approach to the facile synthesis of mono- and disubstituted quinazolin-4(3H)-ones under solvent-free conditions

Quinazolin-4(3H)-one derivatives were synthesized successfully via a one-pot, three component reaction of isatoic anhydride and an orthoester with ammonium acetate or a primary amine catalyzed by silica sulfuric acid under solvent-free conditions. This is the first report on the synthesis of 2-substituted quinazolin-4(3H)-ones by this procedure.     

Characterization of the new Bi∼6.2Cu∼6.2O8(PO4)5 oxyphosphate; a disordered compound containing 2- and 3-O(Bi, Cu)4 tetrahedra—wide polycationic ribbons

The present work is dedicated to the XRD, ED and HREM characterization of a new bismuth copper oxyphosphate Bi_∼6.2Cu_∼6.2O₈(PO₄)₅ (a=11.599(2)Å, , c=37.541(5)Å, R₁=0.0755, Rw₂₌0.174, G.S Pn2₁a). The relatively long size of its c parameter is due to the arrangement along this direction of two kinds of ribbon-like polycations formed by edge sharing O(Bi, Cu)₄ tetrahedra. The existence of such cations is characterized by the b∼5.2 Å value intrinsic to the ribbons structure and commonly found in bismuth oxyphosphate materials. In the title compound, 2-tetrahedra wide [Bi_∼2.4Cu_∼3.6O₄]^6.4+ and 3-tetrahedra wide [Bi_∼5Cu_∼3O₆]⁹⁺ ribbons are isolated by phosphate groups and alternate along c. The interstitial site created between two different sizes ribbons is occupied by Cu²⁺ cations disordered over several close crystallographic sites. The mixed Bi³⁺/Cu²⁺ nature of certain edge-of-ribbons positions induces a disorder over several configurations of the phosphate groups. The concerned oxygen atoms form the environment of the disordered interstitial Cu²⁺ cations which occupy tunnels formed by the phosphate anions. The high-resolution electron microscope study enables a precise correlation between the observed images and the refined crystal structure, evidencing the polycations visualization. Furthermore, this material being the second example of partially disordered compound similar chemical system, some topological rules can be deduced. The b-axis doubling was observed by ED and HREM and is assigned to the ordering of interstitial Cu²⁺ within tunnels cations. A partial intra-tunnel ordering was also observed.     

Platinum complexes of diazo ligands. Studies of regioselective aromatic ring amination, oxidative halogen addition and reductive halogen elimination reactions

2-(Arylazo)pyridine ligands, L1a-1c react with the salt K2[PtCl4] to give the mononuclear complexes [PtCl2(L1)](1), which readily react with ArNH2 to yield the monochloro complexes of type [PtCl(L2)](HL2= 2-[(2-(arylamino)phenyl)azo]pyridine)(2) via regioselective ortho-amine fusion at the pendent aryl ring of coordinated L1. Oxidative addition of the electrophiles Y2(Y = Cl, Br, I) to the square-planar platinum(II) complex, has led to syntheses of the corresponding octahedral platinum(IV) complexes, [PtY3(L2)](3) in high yields. Ascorbate ion reductions of the platinum(IV) complexes, , resulted in reductive halogen elimination to revert to the platinum(II) complexes almost quantitatively. Isolation of products and X-ray structure determination of the representative complexes followed all these chemical reactions. In crystal packing, the compound [PtCl2(L1c)](1c) forms dimeric units with a Pt...Pt distance of 3.699(1) A. In contrast, the crystal packing of 2b revealed that the molecules are arranged in an antiparallel fashion to form a noncovalent 1D chain to accommodate pi(aryl)-pi(pyridyl) and Pt-pi(aryl) interactions. Notably, the oxidation of [Pt(II)Cl(L2a)](2a) by I2 produced a mixed halide complex [Pt(IV)ClI2(L2a)](5), which, in turn, is reduced by ascorbate ion to produce [Pt(II)I(L2a)] with the elimination of ClI. All the platinum(II) complexes are brown, the platinum(IV) complexes, on the other hand, are green. Low-energy visible range transitions in the complexes of the extended ligand [L2]- are ascribed to ligand basedpi-pi* transitions. Cyclic voltammetric behaviour of the complexes is reported.     

Gold nanoparticles: catalyst for the oxidation of NADH to NAD(+)

Nicotinamide adenine dinucleotide is an important coenzyme involved in the production of ATP, the fuel of energy, in every cell. It alternates between the oxidized form NAD(+) and the reduced form dihydronicotinamide adenine dinucleotide (NADH) and serves as a hydrogen and electron carrier in the cellular respiratory processes. In the present work, the catalytic effect of gold nanoparticles on the oxidization of NADH to NAD(+) was investigated. The addition of gold nanoparticles was found to quench the NADH fluorescence intensities but had no effect on the fluorescence lifetime. This suggested that the fluorescence quenching was not due to coupling with the excited state, but due to changing the ground state of NADH. The intensity of the 340 nm absorption band of NADH was found to decrease while that of the 260 nm band of NAD(+) was found to increase as the concentration of gold nanoparticles increased. This conversion reaction was further supported by nuclear magnetic resonance and mass spectroscopy. The effect of the addition of NADH was found to slightly red shift and increase the intensity of the surface plasmon absorption band of gold nanoparticles at 520 nm. This gives a strong support that the conversion of NADH to NAD(+) is occurring on the surface of the gold nanoparticles, i.e. NADH is surface catalyzed by the gold nanoparticles. The catalytic property of this important reaction might have important future applications in biological and medical fields.     

Development and characterization of ion selective electrode for the assay of antimony

The construction and general performance characteristics of two novel potentiometric carbon paste electrodes (CPE) responsive to antimony are described. These sensors are based on the use of the ion associate complexes of tetraiodoantimonate (TIA) anion with cetylpyridinium (CP) and triphenyl tetrazolium (TPT) counter cations as ion exchange site in a carbon paste matrix. The two sensors exhibits fast, stable and near-Nernstian for the mono charged TIA anion over the concentration range 1 × 10⁻³ to 10⁻⁶ M at 25 °C in the pH range 4-10 with anionic slope of 58.0 ± 0.5 and 55.0 ± 0.7 per concentration decade for TIA-CP and TIA-TPT, respectively. The lower detection limits are 4 and 5 × 10⁻⁶ M and response time are 20 and 30 s in the same order of both electrodes. Selectivity coefficients for antimony relative to a number of different cations and anions were investigated. There is negligible interference from many inorganic cation and anion except for Hg²⁺, Cd²⁺, and Bi³⁺; however, their effect were eliminated by EDTA. The determination of 1.0-120.0 μg/ml of antimony in aqueous solutions shows an average recovery of 99.0 and 97.5% with relative standard deviation of 2.0% for both electrodes at 40 μg/ml. The determination of antimony in wastewater and some antibilharzial compounds using the proposed electrodes gave results that compare favorably with those obtained by the atomic absorption spectrometric method. Precipitation titrations involving cetylpyridinium chloride as titrant are monitored with both electrodes with inflection point of 180 and 100 mV for TIA-CP and TIA-TPT, respectively.     

Rotenoid and isoflavone metabolites from an antioxidant seed extract of Dalbergia lanceolaria subsp. paniculata (roxb.) thoth

Abstract

A new rotenoid named 12-O-methylrotenolol along with five known rotenoid and isoflavone metabolites were isolated from the seeds of Dalbergia lanceolaria subsp. paniculata, collected from Egypt. The structures of these compounds were identified by physical and spectroscopic data measurements ([α]_D, UV, 1D- and 2D-NMR and MS). The methanol extract of the seeds exhibited strong antioxidant activity with IC₅₀ value 0.7?µg/µl against DPPH radical, in respect to quercetin as antioxidant reference (IC₅₀ 1.5?μM), while the tested compounds from this extract showed weak activities with IC₅₀ values ranged from 19.6 to 33.0?µM.     

Sodium Borohydride – Ammonium Carbonate: An Effective Reducing System for Aldehydes and Ketones

Summary. Reduction of aldehydes and ketones to the corresponding alcohols was achieved in a simple procedure using the system sodium borohydride and ammonium carbonate. This system needs lower excesses of reducing agent and leads to significantly shortened reaction times.     

Density functional theory study on structural isomers and bonding of model complexes M(CO)5(BH3 · PH3) (M = Cr, Mo, W) and W(CO)5(BH3 · AH3) (A = N, P, As, Sb)

The influence of group 15 various substituents and effect of metal centers on metal-borane interactions and structural isomers of transition metal-borane complexes W(CO)₅(BH₃ · AH₃) and M(CO)₅(BH₃ · PH₃) (A = N, P, As, and Sb; M = Cr, Mo, and W), were investigated by pure density functional theory at BP86 level. The following results were observed: (a) the ground state is monodentate, η¹, with C₁ point group; (b) in all complexes, the η¹ isomer with C_S symmetry on potential energy surface is the transition state for oscillating borane; (c) the η² isomer is the transition state for the hydrogens interchange mechanism; (d) in W(CO)₅(BH₃ · AH₃), the degree of pyramidalization at boron, interaction energy as well as charge transfer between metal and boron moieties, energy barrier for interchanging hydrogens, and diffuseness of A increase along the series A = Sb < As < P < N; (e) in M(CO)₅(BH₃ · PH₃), interaction energy is ordered as M = W > Cr > Mo, while energy barrier for interchanging hydrogens decreases in the order of M = Cr > W > Mo.     

The quenching of CdSe quantum dots photoluminescence by gold nanoparticles in solution

The photoluminescence (PL) of CdSe quantum dots (QD) in aqueous media has been studied in the presence of gold nanoparticles (NP) with different shapes. The steady state PL intensity of CdSe QD (1.5-2 nm in size) is quenched in the presence of gold NP. Picosecond bleach recovery and nanosecond time-resolved luminescence measurements show a faster bleach recovery and decrease in the lifetime of the emitting states of CdSe QD in the presence of quenchers. Surfactant-capped gold nanorods (NR) with aspect ratio of 3 and surfactant-capped and citrate-capped nanospheres (NS) of 12 nm diameter were used as quenchers in order to study the effect of shape and surface charge on the quenching rates. The Stern-Volmer kinetics model is used to examine the observed quenching behavior as a function of the quencher concentration. It was found that the quenching rate of NR is more than 1000 times stronger than that of NS with the same capping material. We also found that the quenching rate decreases as the length of the NR decreases, although the overlap between the CdSe emission and the NR absorption increases. This suggests that the quenching is a result of electron transfer rather than long-range (Forster-type) energy transfer processes. The quenching was attributed to the transfer of electron with energies below the Fermi level of gold to the trap holes of CdSe QD. The observed large difference between NR and NS quenching efficiencies was attributed to the presence of the [110] facets only in the NR, which have higher surface energy.