Gas Chromatographic Determination of Guanidino Compounds Using Hexafluoroacetylacetone and Ethyl Chloroformate as Derivatizing Reagents

Guanidino compounds guanidine, methylguanidine, guanidinoacetic acid, guanidinobutyric acid, guanidinopropionic acid, and guanidinosuccinic acid after derivatization with hexafluoroacetylacetone and ethyl chloroformate at pH 9 in aqueous phase, eluted, and separated from gas chromatographic column HP-5 (30 m × 0.32 mm id) with film thickness of 0.25 μm at an initial column temperature 90 °C for 2 min, followed by heating rate of 10 °C min^?1 up to 220 °C with nitrogen flow rate of 1 mL min^?1. The detection was by flame ionization detector. The linear calibration ranges of each of guanidino compounds were obtained within 1–10 μg mL^?1, and the limit of detection was within 0.014–0.19 μg mL^?1. The derivatization and gas chromatography elution and separation were repeatable in terms of retention time and peak height/peak area with relative standard deviation (RSD) (n = 4) within 1.7–2.9 % and 1.4–2.8 %, respectively. The method was applied for the determination of guanidino compounds from deproteinized serum of uremic patients and healthy volunteers, and was found in the range below the limit of quantitation (BLOQ) to 1.25 μg mL^?1 with RSD within 1.4–3.6 %, and BLOQ to 0.4 μg mL^?1 with RSD 1.3–3.4 %, respectively. A number of pharmaceutical additives did not effect the determination with RSD within ±3.1 %.     

Thermal degradation pathways of nickel(II) bipyridine complexes to size-controlled nickel nanoparticles

Tris(bipyridine)nickel(II) chloride (1) and bis(bipyridine)nickel(II) chloride (2) pyrolize at heating rate of 50 °C/min to a maximum of 450 °C for 24 h under an inert atmosphere of flowing argon gas, to yield size-controlled nickel nanoparticles. Thermogravimetric studies of the complexes (1) and (2) and GC–MS analysis of the trapped volatile matter evolved during thermal degradation of the complexes indicate their clean decomposition pathway to zero-valent nickel. Both heating rate and argon gas flow rate affect purity, particle size, and shape of the particles. X-ray powder diffractometry and atomic force microscopy showed the formation of face-centered cubic (fcc) structured nickel particles having particle size in the range of 3.5–5.0 nm. Magnetic susceptibility measurements suggest nickel nanoparticles to be ferromagnetic in nature characterized by particle size–dependent Curie temperature and high coercivity that is comparable to the bulk iron.     

Study of cesium phospho(vanado)molybdates active in the oxidative dehydrogenation of cyclohexane

Cs₂.₅M_0.08H_0.26PMo₁₂O₄₀and Cs₂.₅M_0.08H_1.26PMo₁₁VO₄₀(M: Ni, Fe) heteopolyanions were selectively prepared, characterized by IR, Raman, ³¹P NMR, XPS and XRD and tested in the ODH of cyclohexane. The salt structure, and reaction mechanism and kinetics are discussed. This revised version was published online in June 2006 with corrections to the Cover Date.     

Electrochemical Investigation of Metal-Free and Nickel-Containing Porphyrazines Carrying Eight Tosylaminoethylthia Groups

 In this study, the electrochemical properties of metal-free and nickel-containing porphyrazines with eight tosylaminoethylthia groups were investigated using cyclic voltammetry, double potential step chronoamperometry, double potential step chronocoulometry, and controlled potential coulometry. Cyclic voltammetry measurements showed that both compounds exhibit two quasi-reversible and an irreversible reduction waves. The first electron transfer reaction was followed by an irreversible chemical reaction, the second one by a reversible chemical reaction for both species. The electrode processes of metal-free and nickel-containing porphyrazines are diffusion controlled, but the double potential step chronocoulometry measurements indicated that the nickel porphyrazine is adsorbed at the electrode. However, a small adsorption current has no significant effect on the mass transport mechanism of the system. Diffusion coefficients of both compounds were determined by both cyclic voltammetric and chronocoulometric measurements. The diffusion coefficients of the reduced forms of the porphyrazines were found to be smaller than those of the neutral forms.     

Voltammetric determination of antibacterial drug gemifloxacin in solubilized systems at multi-walled carbon nanotubes modified glassy carbon electrode

A sensitive electroanalytical method for determination of gemifloxacin in pharmaceutical formulation has been investigated on the basis of the enhanced electrochemical response at multi-walled carbon nanotubes modified glassy carbon electrode in the presence of CTAB. Solubilized system of different surfactants including SDS, Tween-20 and CTAB were taken for the study of electrochemical behaviour of gemifloxacin at modified electrode. The reduction peak current increases in the presence of CTAB while other surfactants show opposite effect. The modified electrode exhibits catalytic activity, high sensitivity, stability and is applicable over wide range of concentration for the determination of gemifloxacin. The mechanism of electrochemical reduction of gemifloxacin has been proposed on the basis of CV, SWV, DPV and coulometeric techniques. The proposed squarewave voltammetric method shows linearity over the concentration range 2.47-15.5 μg/mL. The achieved limits of detection (LOD) and quantification (LOQ) are 0.90 ng/mL and 3.0 ng/mL respectively.     

ESR and TL studies of irradiated Anatolian laurel leaf (Laurus nobilis L.)

Laurel leaf (Laurus nobilis L.) samples that originated from Turkey were analyzed by electron spin resonance (ESR) and thermoluminescence (TL) techniques before and after γ-irradiation. Unirradiated (control) laurel leaf samples exhibit a weak ESR singlet centered at g=2.0020. Besides this central signal were two weak satellite signals situated about 3 mT left and right to it in radiation-induced spectra. The dose–response curve of the radiation-induced ESR signal at g=2.0187 (the left satellite signal) was found to be described well by a power function. Variation of the left satellite ESR signal intensity of irradiated samples at room temperature with time in a long term showed that cellulosic free radicals responsible for the ESR spectrum of laurel leaves were not stable but detectable even after 100 days. Annealing studies at four different temperatures were used to determine the kinetic behavior and activation energy of the radiation-induced cellulosic free radicals responsible from the left satellite signal (g=2.0187) in laurel leaves. TL measurements of the polymineral dust isolated from the laurel leaf samples allowed distinguishing between irradiated and unirradiated samples.     

Absolute optimal solution for a compact and convex game

This paper investigates the existence of absolute optimal solutions for a partition P in continuous and quasiconcave games. We show that the P-consistency property introduced in the paper, together with the quasiconcavity and continuity of payoffs, permits the existence of P-absolute optimal solutions in games with compact and convex strategy spaces. The P-consistency property is a general condition that cannot be dispensed with for the existence of P-absolute optimal solutions. We also characterize the existence of P-absolute optimal solutions by providing necessary and sufficient conditions. Moreover, we suggest an algorithm for efficiently computing P-absolute optimal solutions.     

Thermodynamics of New Modified Chaplygin Gas in Magnetic FRW Universe

We study the generalized second law of thermodynamics in the presence of non-interacting magnetic field and new modified Chaplygin gas with FRW universe. In this scenario, we investigate the validity of this law on Hubble, apparent, particle and event horizons. It is found that this law is respected on all horizons for specific values of the model parameters except on the event horizon where it does not hold for short time but remains valid otherwise. Finally, we explore the statefinders and Om diagnostic to check the viability of the present cosmological model.     

Synthesis of New Naphthyl Aceto Hydrazone-Based Metal Complexes: Micellar Interactions,DNA Binding,Antimicrobial, and Cancer Inhibition Studies

In the present study, naphthyl acetohydrazide (HL) ligand was prepared and used for the synthesis of new six amorphous transition metal (Co(II), Ni(II), Cu(II), Zn(II), Pb(II), Cd(II)) complexes. All the compounds were characterized by elemental analysis, UV-vis, FT-IR, ¹H- and ¹³C-NMR, and Matrix-Assisted Laser Desorption Ionization (MALDI). The solubilization study was carried out by estimating the interaction between the metal complexes with surfactants viz. sodium stearate (SS) and Cetyltrimethylammonium bromide (CTAB). UV-Visible spectroscopy was employed to determine partitioning and binding parameters, whereas electrical conductivity measurements were employed to estimate critical micellar concentration (CMC), the extent of dissociation, and free energy of micellization. The CT-DNA interaction of synthesized compounds with DNA represents the major groove binding. The synthesized ligand and metal complexes were also tested against bacterial and fungal strains and it has been observed that Cu(II) complex is active against all the strains except Candida albicans, while Cd(II) complex is active against all bacterial and fungal strains except Pseudomonas. Among all compounds, only the Pd(II) complex shows reasonable activity against cervical cancer HeLa cell lines, representing 97% inhibition.