An ultrasensitive fluorescence sensor for determination of trace levels of copper in blood samples

A novel SBA-15-based fluorescent sensor, SBA-PI: mesoporous SBA-15 structure modified with iminostilbene groups, was designed, synthesized, and characterized by Fourier transform-infrared spectroscopy (FT-IR), ultraviolet–visible spectroscopy, field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), thermogravimetric analysis (TGA), low-angle X-ray diffraction techniques (low-angle XRD), and N₂ adsorption–desorption techniques. The SBA-PI as a sensor with a selective behavior for detection of Cu²⁺ comprises iminostilbene carbonyl as the fluorophore group. The SBA-PI sensor displays an excellent fluorescence response in aqueous solutions and the fluorescence intensity quenches remarkably upon addition of Cu²⁺. Other common interfering ions even at high concentration ratio showed either no or very small changes in the fluorescence intensity of SBA-PI in the absence of Cu²⁺. A limit of detection of 8.7 × 10⁻⁹ M for Cu²⁺ indicated that this fluorescence sensor has a high sensitivity and selectivity toward the target copper (II) ion. The fabricated Cu²⁺ sensor was successfully applied for the determination of the Cu²⁺ in human blood samples without any significant interference. With the selective analysis of Cu²⁺ ions down to 0.9 nM in blood, the sensor is a promising and a novel detection candidate for Cu²⁺ and can be applied in the clinical laboratory. A reversibility and accuracy in the fluorescence behavior of the sensor was found in the presence of I^¯ that was described as a masking agent for Cu²⁺.

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Simultaneous Spectrophotometric Determination of Group B Vitamins Using Parallel Factor Analysis: PARAFAC

In this work, a simple and rapid analytical procedure was applied for simultaneous determination of folic acid (vitamin B₀), thiamin (vitamin B₁), riboflavin (vitamin B₂) and pyridoxal (vitamin B₆) based on the absorbance data in the pH range 2.0‐12.0 at 25 °C using parallel factor analysis (PARAFAC). The effect of the pH as the most important factor on the sensitivity of the determination was studied. The spectral data were recorded in 400‐650 nm intervals and a 2‐12 pH range for all four vitamins. The calibration set was constructed in the concentration ranges of 4‐22, 1‐20, 6‐26, and 4‐20 μg mL^?;1 for B₆,B₂,B₁ and B₀, respectively. The root mean squares errors of prediction for the prediction set, (RMSEP), are 0.65, 0.63, 1.13 and 0.34 for B₀,B₁,B₂ and B₆, respectively. The recovery percent for the validation set are in the range of 90.6 to 107.0%. The effect of the experimental conditions and diverse species were discussed. The optimum values of these factors were searched according to the relative standard deviation of the prediction set of mixtures solutions.     

KINETIC MODELING OF ESTERIFICATION OF EPOXY RESIN IN THE PRESENCE OF TRIPHENYLPHOSPHINE FOR PRODUCING VINYL ESTER RESIN: MECHANISTIC RATE EQUATION

Due to its mechanical properties and ease of use, vinyl ester resin is enjoying increasing consideration. This resin normally is produced by reaction between epoxy resin and unsaturated carboxylic acid. In the present study, bis-phenol A based epoxy resin and methacrylic acid was used to produce vinyl ester resin. The reaction was conducted under both stoichiometric and non-stoichiometric conditions in the presence of triphenylphosphine as catalyst. The stoichiometric and non-stoichiometric experiments were conducted at 95, 100, 105 and 110℃and at 90 and 95℃, respectively. The first order rate equation and mechanism based rate equation were examined. Parameters are evaluated by least square method. A comparison of mechanism based rate equation and experimental data show an excellent agreement. Finally, Arrhenius equation and activation energy were presented.     

Iranian natural clinoptilolite and its synthetic zeolite P for removal of cerium and thorium from nuclear wastewaters

The ion-exchange behaviors of an Iranian natural clinoptilolite and its modified forms as well as a relevant synthetic zeolite P were investigated toward cerium and thorium from nuclear wastewaters. Column experiments were performed on different exchangers in various conditions and the effect of parameters such as particle size, pH, temperature, and time were considered. The distribution coefficient, cation exchange capacity and some thermodynamic parameters were calculated. Ion-exchange isotherms and break-through curves were plotted. As a result, the selectivity of synthetic zeolite P from Iranian natural clinoptilolite toward cerium and thorium was compared with that of natural and cationic forms of clinoptilolite     

Quantitative determination of Malathion in pesticide by modified attenuated total reflectance-Fourier transform infrared spectrometry applying genetic algorithm wavelength selection method

A simple and environment friendly method was developed for determination of Malathion content of analytical and commercial insecticide samples with no special preparation. Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectra were characterized and 1000-2000 cm⁻¹ region was selected for quantitative analysis utilizing partial least square (PLS) and two wavelength selection methods: (a) principal component regression (PCR) and (b) genetic algorithm (GA). Relative error of prediction (REP) was calculated in PLS, PCR-PLS and GA-PLS methods and was 3.536, 1.656 and 0.188, respectively. Proposed method is successfully applicable for quantification of Malathion in commercial grade samples and reliable results in comparison with known methods, confirms this idea.     

The effect of vicinyl olefinic halogens on cross-coupling reactions using Pd(0) catalysis

(trans) 1-Chloro-2-iodoethylene (3), (trans) 1-bromo-2-iodoethylene (4), (trans) 1,2-diiodoethylene (5) and (cis and trans) 1,2-dibromoethylene (11) were reacted under Suzuki, Sonogashira and Negishi cross-coupling conditions using Pd catalysis to obtain mono coupled products. Only olefin template 3 provided the desired coupling products reliably under all reaction conditions. Compound 5 did not provide cross coupled products under any of the reaction conditions used. The Negishi reaction was the only one that worked for templates 4 and 11. Studies indicate that oxidative addition of the most reactive carbon-halogen bond to Pd(0) is followed by elimination of the second halide, when the second halide is a bromide or an iodide. This happens to a much lesser degree when the second halogen is a chloride.     

Thermodynamic characterization of the dimerization equilibrium of an asymmetric dye by spectral titration and chemometric analysis

The monomer-dimer equilibrium of an asymmetric cyanine dye has been investigated by means of UV-Vis spectroscopy. The data have been processed by a recently developed chemometric method for quantitative analysis of undefined mixtures, that is based on simultaneous resolution of the overlapping bands in the whole set of absorption. In this work the dimerization constant of 1-carboxydecyl-4-{3-[3-methyl-3H-benzothiazol-2-ylidene]-propenyl}-quinolinium (TO-3) has been determined by studying the dependence of absorption spectrum on temperature in the range 25-72.5 °C at different total concentrations of dye (8.5×10⁻⁶ to 2.87×10⁻⁵ M). Utilizing the van’t Hoff relation, which describes the dependence of the equilibrium constant on temperature, as constraint we determine the spectral responses of the monomer and dimer species as well as the enthalpy and entropy of the dimerization equilibrium.     

Spectrophotometric Determination of Acidity Constants of 4‐(2‐Pyridylazo) Resorcinol in Various Micellar Media Solutions

Dissociation equilibria of 4‐(2‐pyridylazo) resorcinol (PAR) in aqueous micellar solutions were determined spectrophotometrically at 25 °C and at the constant ionic strength I = 0.1 M KNO₃. For this purpose, the effect of nonionic (Brij‐35, Triton X‐100, Triton X‐114, Triton X‐405), and anionic (SDS) surfactants on the absorption spectra of PAR at different pH values was studied. Results show that the pK_a values and pure spectra of each species of PAR are influenced by percentages of a neutral and an anionic surfactant such as Brij‐35, Triton X‐100, Triton X‐114, Triton X‐405 and SDS, respectively, added to the solution of this reagent.     

Liquid-liquid-liquid phase microextraction of aromatic amines in water using crown ethers by high-performance liquid chromatography with monolithic column

Liquid-liquid-liquid phase microextraction (LLLME) coupled with high-performance liquid chromatography (HPLC) for the analysis of some aromatic amines is described. These compounds were extracted from 4.0 mL aqueous sample that adjusted to pH 13 with, NaOH-NaCl buffer solution (donor phase, P₁) into an organic phase (P₂) 150 μl benzyl alcohol and ethyl acetate (2:1) and then back extracted into a microdrop of aqueous acceptor phase (P₃), adjusted at pH 2, with Na₂HPO₄-H₃PO₄ buffer solution. The extraction time, T₁ (from P₁ to P₂) was 20 min and T₂ (from P₂ to P₃) was 1 min. Different crown ethers as complexing agents for amines were added to the acceptor phase to improve the extraction time. Factors such as organic solvents, extraction times, and addition of crown ethers to acceptor phase and stirring rate were optimised. The method was applied for determination of aromatic amines in wastewater samples. Enrichment factors ranged from 184.5 to 389.7. The linearity range was from 3 to 1000 ng/ml and the detection limits varied from 0.8 to 1.80 ng/ml. Relative standard deviations (%, n = 5) were found (at S/N 3) in the range of 1.9 to 10.1. All experiments were carried out at room temperature, 22 ± 0.5 °C.     

Transformation optics and infrared metamaterials for optical devices

The coordinate transformation approach is applied for the design of an optical mode adaptor between two different width waveguides in the near IR telecom optical domain. The control of the mode profile in the adaptor is achieved by considering a composite waveguide consisting of a thin metamaterial (MM) layer intercalated between 2???m thick SU8 photoresist slab and a glass substrate. We demonstrate that intercalated metafilm enables the realization of a space coordinate transformation and allows a precise control of the light propagation in the composite waveguide. Numerical simulations and experimental realizations of the metamaterial layer are performed in order to validate the device concept and realization feasibility.