Flow injection determination of metoclopramide based on KMnO4—HCHO chemiluminescence in a micellar medium

A novel flow injection chemiluminescence (CL) analysis method for the determination of metoclopramide in the presence of sodium dodecyl sulfonate (SDS) surfactant micelles is described. This method is based on the luminescent properties of the KMnO₄-HCHO-metoclopramide in acid medium sensitized by SDS. The optimized experimental conditions were evaluated and the possible mechanism was discussed. The CL increase is linearly related to the concentration of metoclopramide in the range 0-80.0 μg/ml with a detection limit of 31.3 ng/mL (S/N=3).The relative standard deviation for 20.0 μg/ml samples was 2.6% (n=11). The proposed method has been successfully applied to the determination of metoclopramide in tablets.     

Peroxyoxalate-chemiluminescence of Tinopal CBS as a commercially important optical brightener: Mechanistic study and quantification

The peroxyoxalate-chemiluminescence arising from reaction of bis(2,4,6-trichlorophenyl)oxalate with hydrogen peroxide in the presence of a brightener Tinopal CBS (2,2′-((1,1′-biphenyl)-4,4′-diyldi-2.1-ethenediyl)bisbenzene sulfonic acid, disodium salt) has been studied. The relationship between the chemiluminescence intensity and concentrations of bis(2,4,6-trichlorophenyl)oxalate, sodium salicylate (as catalyst), hydrogen peroxide and Tinopal CBS is reported. The chemiluminescence parameters including intensity at maximum chemiluminescence, time at maximum intensity, total light yield, theoretical maximum level of intensity and pseudo-first-order rate constants for the rise and fall of the chemiluminescence burst (k_r and k_f) were evaluated from computer fitting of the resulting intensity-time plots. The activation parameters E_a, ΔH^‡, ΔS^‡ and ΔG^‡ for the rise and fall steps were evaluated from the temperature dependence of k_r and k_f values. The results were discussed in terms of chemically initiated electron transfer between a reactive intermediate and Tinopal CBS as fluorescence activator. A possible mechanism involving dioxetanone derivatives as intermediates is proposed. Since there is a linear relationship between reciprocal of chemiluminescence intensity and reciprocal of fluorescer concentration, an analytical method based on partial least squares (PLS) regression was proposed for quantitative determination of Tinopal CBS. Satisfactory results were obtained with percent relative prediction error (RPE%) of 2.52 and detection limit of 2.7×10⁻⁵ M.     

Chemiluminescence of curcumin and quenching effect of dimethyl sulfoxide on its peroxyoxalate system

The chemiluminescence behavior of the reaction between bis(2,4,6-trichlorophenyl)oxalate (TCPO) and hydrogen peroxide, in the presence of curcumin as fluorophore, has been investigated. Experimental factors such as TCPO, sodium salicylate (SS), hydrogen peroxide and curcumin concentration were optimized. The chemiluminescence signal showed a linear decay while dimethyl sulfoxide (DMSO) was added to the peroxyoxalate (PO-CL) system. The reaction resulted in a Stern-Volmer plot with a K_q value of 7.3×10⁴. The evaluated lower and upper detection limits of measurable concentrations of DMSO are 3.50×10⁻⁵ and 1.53×10⁻⁴ M, respectively. The PO-CL parameters were estimated by computer fitting of the experimental CL intensity to proper models.     

Dye-sensitized phototransformation of chlorophenols and their subsequent chemiluminescence reactions

A novel chemiluminescence (CL) reaction of chlorophenols (CPs), including 2-chlorophenol (2-CP), 4-CP, 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP) and pentachlorophenol (PCP) was reported, which was based on the oxidation of the phototransformed CPs by N-bromosuccinimide (NBS). It was found that the dye-sensitized phototransformation is a prerequisite for the subsequent CL reaction, and the presence of 1.9×10^-2 mol L⁻¹ Triton X-100 or 3.7×10^-3 mol L⁻¹ CTAB can greatly enhance the CL intensity. A neutral sample solution with the presence of 2×10^-5 mol L⁻¹ fluorescein (FL) was found to be optimum for the phototransformation of 2-CP, 4-CP, 2,4-DCP and PCP, but a lower pH of 5.3 was more suitable for 2,4,6-TCP. Based on the CL reaction, detection limits of 8.6×10⁻⁸, 1.1×10⁻⁷, 1.5×10^-7, 4.6×10^-8 and 3.0×10⁻⁵ mol L⁻¹ were achieved, respectively, for 2-CP, 4-CP, 2,4-DCP, 2,4,6-TCP and PCP with the optimized conditions in the flow system. The mechanism of the phototransformation and the subsequent CL reaction were preliminarily studied and it was suggested that the singlet oxygen formed in the dye-sensitization process was responsible for the conversion of CPs into light-emitting precursors. These intermediate products were suggested to be peroxide compounds after testing by a luminal-based post-column CL detection experiment.     

Ultrasonic flexural vibration assisted chemical mechanical polishing for sapphire substrate

The sapphire substrates are polished by traditional chemical mechanical polishing (CMP) and ultrasonic flexural vibration (UFV) assisted CMP (UFV-CMP) respectively with different pressures. UFV-CMP combines the functions of traditional CMP and ultrasonic machining (USM) and has special characteristics, which is that ultrasonic vibrations of the rotating polishing head are in both horizontal and vertical directions. The material removal rates (MRRs) and the polished surface morphology of CMP and UFV-CMP are compared. The MRR of UFV-CMP is two times larger than that of traditional CMP. The surface roughness (root mean square, RMS) of the polished sapphire substrate of UFV-CMP is 0.83 Å measured by the atomic force microscopy (AFM), which is much better than 2.12 Å obtained using the traditional CMP. And the surface flatness of UFV-CMP is 0.12 μm, which is also better than 0.23 μm of the traditional CMP. The results show that UFV-CMP is able to improve the MRR and finished surface quality of the sapphire substrates greatly. The material removal and surface polishing mechanisms of sapphire in UFV-CMP are discussed too.     

A Batch Chemiluminescence Determination of Enoxacin Using a Tris-(1,10-phenanthroline)ruthenium(II)–Cerium(IV) System

A batch type chemiluminescence (CL) determination of enoxacin is described. In this work, it was observed that enoxacin could enhance the chemiluminescence (CL) emission Ru(phen)₃ ²⁺–Ce(IV) system and this enhancement effect was dependent on the concentration of enoxacin, based on which, CL system was established for the determination of enoxacin. Under the optimum experimental conditions, the linear range and detection limit are 0.6406–64.06 μg/ml and 0.0210 μg/ml, respectively. The R.S.D. is 1.75%. (n=10). The proposed method has been applied to detect the content of enoxacin in pharmaceutical formulation and human serum with satisfactory results. The possible mechanism of the CL reaction was discussed.     

Electron beam induced green luminescence and degradation study of CaS:Ce nanocrystalline phosphors for FED applications

Green luminescence and degradation of Ce³⁺ doped CaS nanocrystalline phosphors were studied with a 2 keV, 10 μA electron beam in an O₂ environment. The nanophosphors were synthesized by the co-precipitation method. The samples were characterized using X-ray diffraction, Transmission electron microscopy, Scanning electron microscopy/electron dispersive X-ray spectroscopy and Photoluminescence (PL) spectroscopy. Cubic CaS with an average particle size of 42 ± 2 nm was obtained. PL emission was observed at 507 nm and a shoulder at 560 nm with an excitation wavelength of 460 nm. Auger electron spectroscopy and Cathodoluminescence (CL) were used to monitor the changes in the surface composition of the CaS:Ce³⁺ nanocrystalline phosphors during electron bombardment in an O₂ environment. The effect of different oxygen pressures ranging from 1 × 10⁻⁸ to 1 × 10⁻⁶ Torr on the CL intensity was also investigated. A CaSO₄ layer was observed on the surface after the electron beam degradation. The CL intensity was found to decrease up to 30% of its original intensity at 1 × 10⁻⁶ Torr oxygen pressure after an electron dose of 50 C/cm². The formation of oxygen defects during electron bombardment may also be responsible for the decrease in CL intensity.     

异丙醇-ClO——H2O2化学发光新体系研究

本文首次报道异丙醇-ClO--H2O2新体系的化学发光,对影响该化学发光反应的因素进行了研究,并探讨了该发光新体系的分析应用和反应机理。     

Solution synthesis and optimization of ZnO nanowindmills

In this work, novel windmill-like ZnO structures were fabricated through a solution route at low reaction temperature. The as-synthesized ZnO nanowindmill has a central trunk of nanorod and six symmetrical nanorods grown epitaxially on the surface of the ZnO trunk along [0 0 0 1] direction. Each nanorod forming the windmill with a smooth top is about 6 μm in length and about 700 nm in diameter. Several control experiments were conducted to study the formation of the nanowindmills of ZnO in detail. Cathodoluminescence (CL) property of the as-obtained product was investigated, which shows there are three emission peaks centered at 384, 616 and 753 nm in CL spectrum.     

Determination of norfloxacin using gold nanoparticles catalyzed cerium(IV)-sodium sulfite chemiluminescence

A rapid flow-injection chemiluminescence (CL) method is proposed for the determination of norfloxacin (NFLX). The method is based on the fact that the weak CL from the redox reaction of Ce(IV)-Na₂SO₃ can be greatly strengthened by gold nanoparticles (NPs). UV-visible spectra, fluorescence spectra and transmission electron microscopy (TEM) studies are carried out before and after the CL reactions to investigate the CL reinforcing mechanism. The mechanism is supposed to originate from the reinforcer of gold NPs, which facilitates the radical generations and electron-transfer processes taking place on the surface of the gold NPs. Under the selected experimental conditions, a linear relationship was obtained between the CL intensity and the concentrations of NFLX in the range 7.9×10⁻⁷ to 1.9×10⁻⁵ M and the detection limit was 8.2×10⁻⁸ M. This method is successfully applied to the determination of NFLX in human urine.     

Hologram multiplexing in acrylamide hydrophilic photopolymers

Unslanted diffraction gratings are recorded in a 900 μm thick acrylamide photopolymer by means of peristrophic multiplexing. A solid state Nd:YAG (λ = 532 nm) laser is used as the recording beam, with a total incident intensity of 5 mW/cm², and a He-Ne laser as the reconstruction beam. The dye concentration in the photopolymer is optimized so that it does not limit the dynamic range. Nine holograms are recorded using constant exposure time scheduling and variable exposure time scheduling. From the results obtained it may be deduced that optimization of the dye allows us to work in the linear response region of the photopolymer and at the same time obtain high values of diffraction efficiency for each hologram. An exponential increase in exposure time as the number of holograms increases enables the values of diffraction efficiency to be homogenized with regard to the case of constant exposure scheduling. In this way, better use is made of the dynamic range of acrylamide hydrophilic photopolymer.     

Nitrogen binding behavior in ZnO films with time-resolved cathodoluminescence

ZnO film with (1 0 0) orientation was produced on silicon substrate and doped with nitrogen using plasma immersion ion implantation. The effects due to N doping were investigated using cathodoluminescence (CL). In the heavily nitrogen-doped ZnO film, the intensity of ultraviolet (UV) band decreases and that of the visible band increases as a function of the electron bombardment cycle i.e. time. Based on the X-ray photoelectron spectroscopy (XPS) analysis, the unstable ZnN bond is responsible for the CL behavior and the experimental results agree well with the first-principle calculation. Our work is helpful to our understanding of the role of p-type dopants in ZnO.     

化学发光法测定尿液中8羟-基脱氧鸟苷

利用8-羟基脱氧鸟苷（8-OHdG）在酸性邻菲咯啉（Phen）-Cu化学发光体系中发光信号强的特点,建立了一种测定尿样中8-OHdG含量的方法。本方法的线性范围为1.67—333.33μg/L,检出限（S/N=3）为0.83μg/L。对167.00μg/L的8-OHdG平行测定11次,其相对标准偏差为1.2%。该法用于尿液中8-OHdG的测定,方法简便、灵敏、快速,分析结果令人满意。     

丙酮敏化光泽精氧化发光反应的研究及应用

本文研究了H2O2-ClO-氧化光泽精发光的特性及丙酮的敏化作用,对发光和敏化机理进行了探讨,同时还研究了丙酮敏化光泽精氧化发光反应的分析应用.     

Magnetic and structural properties of iron phosphate-phenolic soft magnetic composites

This work focuses on the effect of phosphate modification on the magnetic and surface properties of iron-phenolic soft magnetic composite materials. Fourier transform infrared (FTIR) spectra, EDX analysis, distribution maps, X-ray diffraction pattern and density measurements show that the particles surface layer contains a thin layer of nanocrystalline/amorphous phosphate with high coverage of powders surface. Magnetic measurements show that phosphating treatment decreases the loss factor, imaginary part of permeability, increases the electrical resistivity and operating frequencies by decreasing the effective particle size. The operating frequency increases from 200 kHz for uncoated-powders samples to 1 MHz for phosphated-powders samples at optimum concentration. Phosphated iron powders that are covered by 0.7 wt% of phenolic resin exhibits lower magnetic loss and higher frequency stability. The minimum loss factor and maximum permeability at each frequency can be obtained for 0.01 g/ml orthophosphoric acid concentration in comparison with other concentrations including 0.005 and 0.04 g/ml.     

Determination of calf thymus DNA using resonance light-scattering quenching method based on the terbium (Ш) (Tb)/europium (Ш) (Eu)-quercetin system

It is found that at pH 7.5 Tris-HCl buffer solution, calf thymus DNA (ctDNA) can quench the resonance light-scattering (RLS) of terbium (Ш) (Tb³⁺)/europium (Ш) (Eu³⁺)-quercetin system. Based on this, a sensitive method for the determination of ctDNA is proposed. The characteristics of RLS spectra, the effective factors and optimal experimental conditions were investigated. Under the optimal conditions, the quenched RLS intensity is in proportion to the concentration of ctDNA. For Tb³⁺-quercetin-ctDNA system, the linear concentration ranges for determining ctDNA are 0.03-0.2 and 0.5-4 μg/ml, respectively, while for Eu³⁺-quercetin-ctDNA system, the linear concentration range is 0.05-2.5 μg/ml.     

丙酮化学发光反应中卤素离子敏化效应的研究

本文报导了丙酮化学发光反应中卤素离子的敏化效应,对其敏化机理进行了探讨,并研究卤素离子敏化效应的分析应用。     

Hypericin from St. John’s Wort (hypericum perforatum) as a novel natural fluorophore for chemiluminescence reaction of bis (2,4,6-trichlorophenyl) oxalate–H2O2–imidazole and quenching effect of some natural lipophilic hydrogen peroxide scavengers

Hypericin (HYP) molecule is a natural photoactive pigment, which plays a role as an effective photoreceptor in some plants of the Hypericum species (the most common of which is Saint John’s Wort) and some insect species. The present work deals with the first attempt to the study of peroxyoxalate chemiluminescence (POCL) system in the presense of HYP as a natural fluorophore. Reaction of bis (2,4,6-trichlorophenyl) oxalate(TCPO)–H₂O₂–imidazole can transfer energy to a HYP via formation of dioxetane through the chemically initiated electron exchange luminescence (CIEEL) mechanism and can emits a very intense red light. The effects of HYP, hydrogen peroxide, TCPO and imidazole concentrations on kinetic chemiluminescence parameters were also studied. These parameters including rise and fall rate constant for the chemiluminescence burst, theoretical and experimental maximum intensity, theoretical and experimental time to reach maximum intensity and total light yield emission were evaluated by using a pooled intermediate model for a non-linear least-squares curve fitting program, KINFIT. Moreover, quenching effect of two lipophilic natural antioxidant, Quercetin and β-carotene on it system was also investigated. The measurable concentration range of 7×10^?6 M to 7.5×10^?5 M of antioxidants were evaluated from the proper Stern–Volmer plots with satisfactory RSD% and corresponding detection limits of 2.2×10^?6 and 3.7×10^?6 for β-carotene and quercetin respectively.     

The effect of different gas atmospheres on luminescent properties of pulsed laser ablated SrAl2O4:Eu,Dy thinfilms

SrAl₂O₄:Eu²⁺,Dy³⁺ thin films were grown on Si (1 0 0) substrates using the pulsed laser deposition (PLD) technique to investigate the effect of vacuum, oxygen (O₂) and argon (Ar) deposition atmospheres on the structural, morphological, photoluminescence (PL) and cathodoluminescence (CL) properties of the films. The films were ablated using a 248 nm KrF excimer laser. Atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS) and fluorescence spectrophotometry were used to characterize the thin films. Auger electron spectroscopy (AES) combined with CL spectroscopy were employed for the surface characterization and electron-beam induced degradation of the films. Better PL intensities were obtained from the unannealed films prepared in Ar and O₂ atmospheres with respect to those prepared in vacuum. A stable green emission peak at 515 nm, attributed to 4f⁶5d¹→4f⁷ Eu²⁺ transitions were obtained with less intense peaks at 619 nm, which were attributed to transitions in Eu³⁺. After annealing the films prepared in vacuum at 800 °C for 2 h, the intensity of the green emission (520 nm) of the thin film increased considerably. The amorphous thin film was crystalline after the annealing process. The CL intensity increased under prolonged electron bombardment during the removal of C due to electron stimulated surface chemical reactions (ESSCRs) on the surface of the SrAl₂O₄:Eu²⁺, Dy³⁺ thin films. The CL stabilized and stayed constant thereafter.     

Sonodegradation of 17α-ethynylestradiol in environmentally relevant matrices: laboratory-scale kinetic studies

The sonochemical degradation of 17α-ethynylestradiol (EE2) in secondary treated effluents was investigated. Ultrasound irradiation was provided by a horn-type sonicator operating at 80 kHz. The effect of various operating conditions such as estrogen concentration (25-160 μg/L), power density (18-46 W/L), liquid bulk temperature (15-60 °C), gas sparging (air, oxygen, and helium), solution pH (3 and 7.8), as well as the addition of radical promoters (hydrogen peroxide) or catalysts (TiO₂ and Fe²⁺) on degradation kinetics was evaluated. Changes in estrogen concentration were followed by high performance liquid chromatography and the yeast estrogen screening (YES) assay. EE2 degradation in the range 25-110 μg/L follows first order kinetics in regard to its concentration, while lower order kinetics occur at higher concentrations. The reaction rate increases linearly with applied power and decreases exponentially with temperature at the conditions in question. Continuous sparging of air or oxygen has little effect on the kinetics relative to air-equilibrated conditions, while helium has a marginally positive effect. The inorganic and organic contents of the wastewater matrix appear to promote degradation at inherent conditions in comparison to experiments in ultrapure water. Nevertheless, the addition of H₂O₂ (8.6 and 86 mg/L), Fe²⁺ (2.5-25 mg/L) or TiO₂ (50-2000 mg/L) has no or, in some cases, adverse effect on kinetics.