Kinetic Studies on the Catalytic Degradation of Rhodamine B by Hydrogen Peroxide: Effect of Surfactant Coated and Non-Coated Iron (III) Oxide Nanoparticles.

Iron (III) oxide (Fe3O4) and sodium dodecyl sulfate (SDS) coated iron (III) oxide (SDS@Fe3O4) nanoparticles (NPs) were synthesized by the co-precipitation method for application in the catalytic degradation of Rhodamine B (RB) dye. The synthesized NPs were characterized using X-ray diffractometer (XRD), vibrating sample magnetometer (VSM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Fourier transform infra-red (FT-IR) spectroscopy techniques and tested in the removal of RB. A kinetic study on RB degradation by hydrogen peroxide (H2O2) was carried out and the influence of Fe3O4 and SDS@Fe3O4 magnetic NPs on the degradation rate was assessed. The activity of magnetic NPs, viz. Fe3O4 and SDS@Fe3O4, in the degradation of RB was spectrophotometrically studied and found effective in the removal of RB dye from water. The rate of RB degradation was found linearly dependent upon H2O2 concentration and within 5.0 × 10-2 to 4.0 × 10-1 M H2O2, the observed pseudo-first-order kinetic rates (kobs, s-1) for the degradation of RB (10 mg L-1) at pH 3 and temperature 25 ± 2 °C were between 0.4 and 1.7 × 104 s-1, while in presence of 0.1% w/v Fe3O4 or SDS@Fe3O4 NPs, kobs were between 1.3 and 2.8 × 104 s-1 and between 2.6 and 4.8 × 104 s-1, respectively. Furthermore, in presence of Fe3O4 or SDS@Fe3O4, kobs increased with NPs dosage and showed a peaked pH behavior with a maximum at pH 3. The magnitude of thermodynamic parameters Ea and ΔH for RB degradation in presence of SDS@Fe3O4 were 15.63 kJ mol-1 and 13.01 kJ mol-1, respectively, lowest among the used catalysts, confirming its effectiveness during degradation. Furthermore, SDS in the presence of Fe3O4 NPs and H2O2 remarkably enhanced the rate of RB degradation.

A rapid and sensitive evaluation of nitrite content in Saudi Arabian processed meat and poultry using a novel ultra performance liquid chromatography-mass spectrometry method.

Quantitative assessment of nitrite (NO2-) anion was performed using a newly developed high throughput ultra performance liquid chromatography-mass spectrometric (UPLC-MS) method. The nitrite determination with the proposed method using micellar mobile phase was unknown. Selected ion reaction mode using negative electrospray ionization was adopted for the identification and quantitative analysis of nitrite. The chromatographic separation was performed using BEH C-18 column and a micellar mobile phase consisted of sodium dodecyl sulphate and acetonitrile in ratio 30:70 was used. The elution of nitrite anion was accomplished in less than 1 min. Under the optimal analysis conditions, the linearity of the developed method was checked in the concentration range of 0.5-20 mg kg-1 NO2- with an excellent correlation coefficient of 0.996. The precisions of the method with relative standard deviation <2% was observed when standard at concentration of 1 mg kg-1 was used. The limit of detection and limit of quantitation of the developed mass spectrometric method was found to be 0.114 and 0.346 mg kg-1, respectively. The developed UPLC/MS method was applied to quantify this anion in processed meats and poultries from various super market of Saudi Arabia (Riyadh region). The recoveries of the nitrite in the various samples were found in the range of 100.03-103.5%.

Rapid and sensitive method for analysis of nitrate in meat samples using ultra performance liquid chromatography-mass spectrometry.

A sensitive and selective ultra performance liquid chromatography-mass spectrometric method has been developed for the quantitative analysis of nitrate in meat samples. Selected ion reaction (SIR) mode was adopted to identify and quantify the nitrate. Chromatographic analyses were performed on a BEH C-18 column with a mobile phase consisting of a surfactant (Cetylpyridinium chloride) and acetonitrile in equal ratio (50/50, v/v) at a flow rate of 0.4 mL min(-1). The limit of detection and limit of quantitation of the developed method was found to be 0.0599 and 0.1817 mg kg(-1), respectively. The linearity of the proposed method was checked in the concentration range of 0.5-10 mg kg(-1) with an excellent correlation coefficient (r) of 0.997. The recovery of the nitrate in the meat samples were in the range of 98.02-98.99%.

Synthesis of silver nanoparticle: a new analytical approach for the quantitative assessment of adrenaline.

Silver nanoparticle (AgNP) has been synthesized using adrenaline. Adrenaline readily undergoes an autoxidation reaction in an alkaline medium with the dissolved oxygen to form adrenochrome, thus behaving as a mild reducing agent for the dissolved oxygen. This reducing behavior of adrenaline when employed to reduce Ag(+) ions yielded a large enhancement in the intensity of absorbance in the visible region. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) studies have been performed to confirm the surface morphology of AgNPs. Further, the metallic nanoparticles with size greater than 2 nm caused a strong and broad absorption band in the UV-visible spectrum called surface plasmon band or Mie resonance. The formation of AgNPs caused the large enhancement in the absorbance values with λmax at 436 nm through the excitation of the surface plasmon band. The formation of AgNPs was adopted to for the quantitative assessment of adrenaline using spectrophotometry with lower detection limit and higher precision values.

Spectroscopic studies on the interaction between novel polyvinylthiol-functionalized silver nanoparticles with lysozyme.

Silver nanoparticles were functionalized with polyvinylthiol (Ag-PVT) and their effect on the conformation of hen-egg white lysozyme was seen by means of spectroscopic techniques, viz., UV visible, fluorescence (intrinsic and synchronous), resonance Rayleigh scattering and circular dichroism. UV absorption spectra of lysozyme show a hyperchromic shift on the addition of Ag-PVT nanoparticles indicating the complex formation between the two. The interaction between lysozyme and Ag-PVT nanoparticles was takes place via static quenching with 1:1 binding ratio as revealed by the analysis of fluorescence measurements. Circular dichroism spectroscopic data show a decrease in α-helical content of lysozyme on interaction with Ag-PVT nanoparticles which was due to the partial unfolding of the protein. Synchronous fluorescence spectroscopy disclosed that the microenvironments of both tryptophan and tyrosine residues were perturbed in the presence of Ag-PVT nanoparticles and perturbation in the tryptophan environment was more prominent. Rayleigh scattering (RRS) intensity increases on increasing the Ag-PVT nanoparticles concentration till it reaches to the saturation. The RRS intensity increases four times as compared to the native protein indicating the possibility of protein aggregation at higher concentrations of nanoparticles.

Synthesis, characterization and kinetics of formation of silver nanoparticles by reduction with adrenaline in the micellar media.

The present paper describes about the easy, simple and convenient procedure for the synthesis of silver nanoparticles (Ag-NPs) in aqueous solutions by the reduction of silver nitrate with adrenaline. The surfactant molecules of cetyltrimethylammonium bromide (CTABr) and sodium dodecyl ate (SDS) behaved differently during the reduction of Ag(+) ions by adrenaline. The obtained data suggest that the variation of [CTABr] gave a maxima-like curve for rate constant versus [CTABr], while, the values of rate constant decreased with the increase in [SDS]. The addition of surfactant molecules stabilized the Ag-NPs. The UV-Visible spectra were analyzed to deduce the particle size. The calculated sizes of the nanoparticles were further compared by the TEM images. The XRD spectrum confirmed the crystalline nature of silver nanoparticles having the face-centered cubic crystal structure. The edge length of unit cell was found 4.076 Å. The kinetics of formation of Ag-NPs was performed at different concentrations of adrenaline, AgNO3, NaOH and [surfactant]. The values of rate constant were independent on [adrenaline] and [AgNO3]. The increase in [NaOH] increased the rate of agglomeration of silver particles to form Ag-NPs. A linear relationship was obtained for the plot of rate constant versus [NaOH].

Spectrophotometric investigation on the kinetics of oxidation of adrenaline by dioxygen of µ-dioxytetrakis(histidinato)-dicobalt(II) complex.

The cobalt(II)histidine complex binds molecular oxygen reversibly to form an oxygen adduct complex, µ-dioxytetrakis-(histidinato)dicobalt(II). The molecular oxygen can be released from the oxygenated complex by heating it or by passing N2, He or Ar gas through its solution. µ-Dioxytetrakis-(histidinato)dicobalt(II) complex oxidizes adrenaline into leucoadrenochrome at 25°C while at higher temperature (>40°C) adrenochrome with λmax at 490nm is formed. The rate of formation of leucoadrenochrome was found to be independent of [bis(histidinato)cobalt(II)]. The rate of reaction for the formation of leucoadrenochrome and adrenochrome increased with the increase in [adrenaline] at its lower concentration but become independent at higher concentration. Similarly, the rate of formation of both leucoadrenochrome and adrenochrome was linearly dependent upon [NaOH]. The values of activation parameters i.e. ΔEa, ΔH(‡) and ΔS(‡) for the formation of leucoadrenochrome are reported.