HPLC Determination of Ascorbic Acid Using Luminol-Cu(Ⅱ) Chemiluminescence-Application to the Analysis of Juice Beverage

The chemiluminescence (CL) of luminol-Cu(Ⅱ) was applied to HPLC determination of ascorbic acid, which was separated by a C18 reverse-phase column with a mobile phase of 0.25 mol/L HAc. The eluted ascorbic acid was mixed with 0.3 mmol/L luminol and 0.05 mol/L CuSO4. The light emission from the reaction of Cu(Ⅱ) oxidized ascorbic acid and luminol was detected by a modified luminometer. The detection limit was 3.6×10-6 mol/L for ascorbic acid at a S/N ratio of 3, and the linear calibration range was 2×10-4- 2×10-3 mol/L. The relative standard deviation for 5 replicate injections of 1×10-3 mol/L ascorbic acid was calculated as 4.3 %. The method was successfully applied to determination of ascorbic acid in juice beverage.     

Preconcentration of Vanadium(Ⅴ) on Crosslinked Chitosan and Determination by Graphite Furnace Atomic Absorption Spectrometry

A new method is proposed for the preconcentration of vanadium(Ⅴ) with crosslinked chitosan (CCTS) and determination by graphite furnace atomic absorption spectrometry (GFAAS). The adsorption rate of vanadium(Ⅴ) by CCTS was 97% at pH 4.0, and vanadium(Ⅴ) was eluted from crosslinked chitosan with 2 mL 2.0 mol*L-1 chlorhydric acid and determined by GFAAS. The detection limit (3σ,n=7) for vanadium(Ⅴ) was 4.8×1 0-12g and the relative standard deviation (R.S.D) at concentration level of 2.6 μg*L-1 is less than 3.6%. The method shows a good selectivity and high sensitivity, and it was applied to determination of vanadium(Ⅴ) in oyster and water samples. The analytic recoveries are (97±5)%.     

Extraction of catechins and caffeine from different tealeaves and comparison with micellar electrokinetic chromatography

This work describes the simultaneous determination of catechins and caffeine in green, black tealeaves and canned tea-drink using micellar electrokinetic chromatography. The catechins analyzed include ( )-catechin, (-)-epicatechin, (-)-epigallocatechin, (-)-epieatechin gallate and (-)-epigallocatechin gallate. Using UV absorption method at 280 nan, the limits of detections of catechins and caffeine are 10^-6mol/L, which is suitable for the real sample determination. Using this analytical method, the extraction of these compounds from the tealeaves with hot water is compared under different temperatures. The effects of temperature on the amount of eatechins and caffeine extracted are evident,showing that (-)-epigallocatechin gallate is the most easiest to be extracted at 100℃. The stability of eatechins and caffeine in stocking solution of tea-drink at 4℃ is also compared on five consecutive days. The contents of catechins and caffeine in green and black teas are discussed and the difference of the content between different tealeaves can provide a reference for the assessment of tea quality.     

Dissolution behavior and dissolution mechanism of palygorskite in HCl solution

The 1 mol/L, 3 mol/L and 5 mol/L HCl solutions were employed to leach two palygorskites with different trioctahedral contents in their crystal structure for different period of time. The results of the dissolution experiments show that the dissolution process could be divided into three steps, and that this dissolution behavior can be attributed to its higher Mg2+ content, and is restricted by the extraction behavior of Si4+. The preferential extraction for Mg2+ promotes the extraction behavior of Si4+ from Si-O framework. Because the Si4+ in the form of amorphous SiO2 is adsorbed onto the surface of palygorskite fibre, the reaction between palygorskite and acid is obstructed. With the elapsing of time, or the increasing of the acid concentration, the amorphous SiO2 flocculates, and then the channels of chemical reaction are reopened. The ratio value of Mg2+/(Fe3++Al3+) in leaching solution tends to a fixed value, showing that the acid attacks not only the surface but also the structural channels. There are no obvious three steps observed during the acid attack on the palygorskite with a lower trioctahedral content. The differential behavior for two palygorskites is discussed.     

High sensitive detection of <Emphasis Type="Italic">presenilin-1</Emphasis> point mutation based on electrochemiluminescence

Electrochemiluminescence (ECL) is a highsensitive detection method with broad biological applications.Ruthenium (Ⅱ) tris (bipyridyl) (Ru(bpy)3^2 ) and tripropylamine (TPA) are most commomly used combination of the reactive species in ECL. The redox of Ru(bpy)3^2 with excess TPA at the surface of an electrode produces a highly efficient and stable light emission due to a rapid cycle of the reactions. This rapid, highly sensitive and accurate method has been applied to gene quantification. In this work, an ECL detection system is designed and applied in detection of presenilin-1 (PS-1) gene mutation. The results show that given the same polymerase chain reaction (PCR) cycle number, the ECL intensities from the digested and the undigested wild-type samples are nearly identical, but the difference in ECL intensities between the digested and the undigested mutant samples is distinctive. This detection technology connects PCR with ECL and allows a reliable discrimination between the wild-type and the mutant genes.     

Oscillating chemiluminescence in rhodamine B-induced Belousov-Zhabotinsky reaction catalyzed by Ce（IV）

It was found that rhodamine B could induce oscillating chemiluminescence （OCL） from the Ce4＋-catalyzed Belousov-Zhabotinsky reaction. This new OCL system, i.e., rhodamine B-malonic acid-bromate- Ce（IV）-sulfuric acid, exhibited two clearly distinguished emission peaks in each oscillation period. The initial concentrations of the reactants strongly influenced the oscillation pattern. For the study of the CL mechanism, a platform for a versatile and simultaneous potential and CL measurement was estab- lished to compare the potential oscillation with the CL oscillation behavior of this system. The CL spectra, UV-visible absorption spectra and time-resolved fluorescence spectra of this OCL system were studied. A possible, simplified mechanism for the OCL is proposed. It is suggested that the generation of the two CL peaks is likely due to the oxidation of the intermediate of rhodamine B by Ce（IV） and Br2, respectively. This work provided a new method and platform to research the complex chemical oscilla- tions.     

Enzymatic Method for Rapid Determination of Oxalic Acid in Bleaching Filtrates from the Pulp and Paper Industry

Bleaching with oxygen-containing agents and recirculation of process streams in the pulp and paper industry has increased the accumulation of oxalic acid and danger for precipitation of calcium oxalate encrusts, scaling. Analysis and control of oxalic acid in bleaching filtrates is therefore becoming increasingly important in the pulp and paper industry. Chromatographic methods, such as IC and HPLC, are generally more time-consuming but are valuable as standard methods for determination of oxalic acid. However, the instrumentation needed is expensive and stationary. In this study, an enzymatic method based on oxalate oxidase and peroxidase was developed to determine oxalic acid in authentic bleaching filtrates using a spectrophotometer. The results showed that bleaching filtrates contain some compounds interfering with the enzymatic method. Pretreatment of the samples with activated charcoal was a successful approach for decreasing problems with interference. By using dilution followed by charcoal treatment, the results obtained from five bleaching filtrates with the colorimetric method correlated very well with those obtained using IC. This study offers a selective, fast and mobile analysis method to determine oxalic acid in bleaching filtrates from the pulp and paper industry. The convenient enzyme-based method improves the possibilities for control of critical oxalic acid concentrations in closed-loop bleaching streams.     

THE TRANSFER BEHAVIOUR OF SOME CATIONS AT WATER／NITROBENZENE INTERFACE BY SEMIDIFFERENTIAL CYCLIC VOLTAMMETRY

The transfer of Sr~(2+) and Ba~(2+) ion, facilitated by 18-Crown-6 present in the aqueous phase, and of succinylcholine ion at w/nb interface were investigated by semi-differential cyclic voltammetry. A good polarographic curve of succinylcholine ion dissolved in water was obtained in the system of 0.01 mol/l LiCl (w)——0.01 mol/l TBATPB (nb). The peak current is directly proportional to the concentration of SC~(2+) ion. It can be used for the determination of SC and the detection limit is 1.05×10~(-5) mol/l.The apparent D~w and D~(nb) have been estimated. The transfer of Sr~(2+) and of Ba~(2+) at the interface are facilitated by 18-Crown-6 present in the aqueous phase and the peak current is directly proportional to the concentration of 18-Crown-6 in water. This method can be used for the determination of the complexing agent and for the stability constant of the complex formed in the aqueous phase.All the experimental results are in keeping with the theoretical.     

Near-infrared absorption imaging and processing technologies based on gold nanorods

Noble metal nanoparticles with localized surface plasmon resonance (LSPR) properties are widely used as optical sensors in biochemical detection and medical diagnosis. In this paper, we propose an effective determination method to measure the LSPR absorption intensity of gold nanorods (GNRs). A near-infrared (NIR) imaging system is established, and an NIR absorption image of the multiple samples of the colloidal GNRs is captured. Then, the LSPR absorption intensities of these samples are obtained by calculating the average grayscale of the target areas based on the NIR image processing technology. By using this method, the LSPR absorption intensities of the multiple samples are determined all at once, and their accuracy is as high as that obtained by using spectrophotometry. These results suggest that this method is an efficient multi-channel determination technique with high-throughput sensing applications.     

Trace determination of zirconium using anodic adsorptive voltammetry at a carbon paste electrode modified with multi-walled carbon nanotubes

A carbon paste electrode modified with multi-walled carbon nanotubes （MWCNT） was prepared and the determination of ultra trace amount of zirconium based on the anodic adsorptive voltammetry of the zirconium-calcium-alizarin red S mix-polynuclear complex is described in this paper for the first time. The results showed that the sensitivity and the selectivity of the method are excellent. The second derivative linear scan voltammograms of the complex were recorded by polarographic analyzer from 200 to 1200 mV （vs. SCE） and it was found that the complex can be adsorbed on the surface of the electrode, yielding a peak at about 840 mV, corresponding to the oxidation of ARS in the complex. The peak current increases linearly with Zr （IV） concentration in the range of 6.0×10^-12--6.0×10^-11 mol. L^-1 （accumulation time 120 s）, 6.0×10^-11--2.0×10^-9 mol. L-1 （accumulation time 90 s） and 2.0×10^-9--1.0×10^-7 mol. L^-1 （accumulation time 60 s） and the detection limit （S/N = 3） is 2.0×10^-12 mol. L^-1 （accumulation time 180 s）. The procedure has been successfully applied to the determination of zirconium in the ore samples.     

Determination of sulfonamides with fluorescent inclusion complex of carbonic anhydrase and dansylamide

A new fluorimetric method for determination of sulfonamides was described based on the formation of a fluorescent inclusion complex of carbonic anhydrase(CA) with dansylamide(DNSA). The binding of DNSA to CA resulted in an enhancement in the fluorescence emission at 460 nm with excitation at 280 nm. Dissociation constants were determined for the carbonic anhydrase sulfonamide complexes. Linear calibration graphs of sulfonamides were obtained within a concentration range of 0- 0.058 μg/mL for DNSA; 0-0.344 μg/mL for sulfanilamide (SAN) and 0-0.286 μg/mL for P toluenesulfonamide (PTSN). The relative standard deviations were within 1.8%-4.2%. Limits of detection for DNSA, SAN and PTSN were 0.84, 19.5 and 6.1 ng/mL, respectively. The method was applied to the determination of sulfonamides in cow milk at ng/mL level.     

铂与NPTSQ的新显色反应的研究及其分析应用(英文)

A simple,rapid,sensitive spectrophotometric method has been developedfor the determination of platimum in solution.The chromogenic reagent,5-(4-nitrophenylazo)-8-(ptoluenesulfonamido)quinoline(NPTSQ),reacts with plat-imum(Ⅱ)almost instantaneously in basic medium to form a violet-red:2 complexwith an absorption maximum at 640 nm.The complexation is complete within lmin.Beer's law is obeyed over the concentration range of 0～25μg/25ml ofplatinum.The molar absorptivity is 1.37×10~5 l.mol~(-1).cm~(-1)and Sandell sensitivity is0.0014 μg.cm~(-2).The effects of pH,surfactant,concentration of the reagent,order ofaddition of reagents,and the interferences form various ions are investigated.The methodhas een used for the determination of microamount platinum in catalyst andoxidizing-residuum.     

DIFFERENTIAL PULSE VOLTAMMETRIC DETERMINATION OF 3,3＇ 5,5＇-TETRAMETHYLBENZIDINE AND ITS ANALOGUES WITH A GLASSY CARBON ELECTRODE

The differential pulse voltarametric ( DPV ) method with a glassy carbon electrode was used for the determination of 3,3‘ 5,5‘-tetramethy lbenzidine ( TMB ) , o-tolidine and benzidine in the acidic media. The pulse amplitude, interval time and scan rate of DPV are optimized to be 50 mV, 0.5 s and 10 mV/s, respectively, The peak current is proportional to the concentration of TMB and its analogues, the linear range is from 10^-8mol/l to 10^-4 mal/l, The electrochemical behaviour of the compounds is discussed, The chemical poisons can be determined directly, or indirectly by the extraction in the waste water of chemical industry and laboratory,     

Detection of TNT by a molecularly imprinted polymer film-based surface plasmon resonance sensor

A surface plasmon resonance(SPR) sensor using a molecularly imprinted polymer(MIP) film as a recognition element for detection of 2,4,6-trinitrotoluene(TNT) was developed.The TNT-imprinted polymer film was prepared by thermo initiated polymerization on the bare Au surface of an SPR sensor chip.Template TNT molecules were quickly removed with an organic solution of acetonitrile/acetic acid(9:1,v/v),causing a shift of 0.7° in SPR angle.The limit of detection for TNT was demonstrated to be as low as 1×10-8 mol/L.In the concentration range of 1×10-8-1×10-5 mol/L,the change of SPR angle was linear with the negative logarithm of TNT concentration,Selectivity studies showed that the SPR sensor had no response to TNT analogues 2,4,5-trinitrotoluene and 1,3,5-trinitrohexahydro-1,3,5-triazine at a concentration of 1×10-4 mol/L.The results suggest that the SPR sensor combined with a MIP film has the advantages of high sensitivity and selectivity,and long-term stability toward the analyte TNT.     

A simple spectroscopic method for the quantification of gold nanoparticle number concentration in water and fetal bovine serum solutions

In this work,we developed a facile and low-cost method with sufficient sensitivity for the quantitative determination of gold nanoparticles(GNPs)number concentration in water and fetal bovine serum solutions.The Au(III)digested from GNPs was reduced to Au(I)presumably by the thiol group of 2-mercaptobenzimidazole,then the Au(I)–thiolate complex was formed,the concentration of which is determined by absorbance at 300 nm.The number concentration of GNPs can be converted using microscopic images and simple calculations.The interference of serum can be avoided in this method.The limit of detection(LOD)of GNPs was calculated as 2.1 910-12mol/L in water solution and 1.3 9 10-11mol/L in fetal bovine serum(FBS)solution.This method provides a simple and fast way to determine the concentration of GNPs,which can be in carried out in the routine laboratory practice.     

The Mechanism of Cumene Peroxidation Catalyzed by Cobalt(Ⅱ)-Chelated Copolymer

1Introduction The functionalised polymers, especially for chelating polymer, have been employed to considerable effects in organic synthesis for several decades. The use of polymer groups as ligands permits the ligand surroundings to be varied and regulation of the catalytic properties of the complexes because of the flexibility of the polymer chains, their ability to adopt various conformations, and the possibility of creating various spatial distributions of metal centers immobilized on the polymer chains[1,2]. In our recently studies[3-5], the chelating copolymer with imino-diacetic acid chelating group in the polymer side chain was manufactured, and which can increase effectively amount of the chelating group within the polymer. Meanwhile, the high catalysis performance in organic synthesis had also been proved via benzaldehyde and cumene peroxidation. For cumene peroxidation,it is hardly to find such a simple catalyst with high conversion and selectivity due to hydroperoxide decomposition by a radical mechanism. The cumene peroxidation by catalyst system and its reaction mechanism as well as the kinetic study are popularly investigated object for many researchers[6-9]. However, the reaction mechanism still does not clear owing to the by-products will be produced following the different catalysts used.     

Alkylation of toluene with 1,3-pentadiene over silica supported aluminum chloride catalyst in an extracting-distilling reactor

The alkylation of toluene with 1,3-pentadiene to produce pentyltoluene is designed to obtain 2,6-dimethylnaphalene for the monomer production of 2,6-naphthalene dicarboxylic acid. The possibility of the reaction is examined by the thermodynamics of the alkylation reaction using Thinh’s group contributions method, and tested over silica supported aluminum chloride catalyst in a newly developed extracting?distilling reactor. The thermodynamics calculation results show that the alkylation reaction is exothermic and can proceed at 298?350 K under normal pressure with an equilibrium constant higher than 106. Based on the thermodynamic calculation and the properties of the reactants and product, the extracting-distilling reactor was designed to allow 1,3-pentadiene to react with toluene at much lower temperature than the boiling point of toluene at the catalyst site. The alkylation product, which has a higher boiling point than that of toluene, is transferred from the catalytic site into the toluene bath and collected. The experimental results show that the reactor functions as designed and promotes the selectivity of the alkylation reaction close to 100%. The effect of raw material ratio of toluene to 1,3-pentadiene and reaction time are discussed in this paper. The suitable catalytic reaction conditions are as follows: at reaction temperature of 338 K and ambient pressure, the reactant ratio of toluene to 1,3-pentadiene is 5:1 for a six-hour reaction.     

Development of a new method for analyzing free aluminum ions （Al3＋） in seafood using HPLC-ICP-MS

This paper presents a novel method for simultaneous online examination of free aluminum ions （Al3＋） in seafood, using solid- phase extraction and high-performance liquid chromatography online with inductively coupled plasma mass spectrometry （SPE- HPLC-ICP-MS）, without post-column reaction. The optimum conditions for chromatographic separation of Al3＋ were achieved using an IonPac CS5A analytical column with an IonPac CG5A guard column. The mobile phase consisted of 0.040 mol/L LiOH, 0.0060 mol/L 2,6-pyridinedicarboxylic acid, and 0.090 mol/L CH3COOH （pH 4.7）. The free Al3＋ ions in seafood were extracted by shaking with the mobile phase at 70℃ for 2 h. SPE was conducted using an Oasis MCX, 3cc/60 mg, 30 μm column, which was activated and equilibrated with 2 mL of methanol and 4 mL of deionized water before use. HCl （0.075 mol/L, 2 mL） was used to wash inorganic Al from the SPE column. The standard recoveries of Al3＋ were all above 89% and the relative standard deviations were all below 5%. The proposed method was successfully used for the examination of Al3＋ in seafood samples, and the results were similar to those obtained using the static equilibrium method.     

Optical Properties of Ru（bipy）2 （dppx）^2＋ in Different Environments

The emission spectra of Ru（bipy）2 （dppx）^2＋ in different environments has been studied. It was found that the solvent polarity and the ability of donating and transferring proton are the important factors in predicting luminescence intensity in different systems. The increasing content of water in the organic solutions of Ru（bipy）2 （dppx）^2＋ leads to de crease in emission intensity that follows the Perrin sphere of quenching model. The effect of base content of DNA on the fluorescence spectra of Ru （bipy）2 （dppx）^2＋ has also been studied.     

氯化亚锡作为还原剂在废旧锂离子电池有价金属浸出回收中的应用研究

The reductant is a critical factor in the hydrometallurgical recycling of valuable metals from spent lithium-ion batteries (LIBs). There is limited information regarding the use of SnCl₂ as a reductant with organic acid (maleic acid) for recovering valuable metals from spent LiCoO₂ material. In this study, the leaching efficiencies of Li and Co with 1 mol·L?1 of maleic acid and 0.3 mol·L?1 of SnCl₂ were found to be 98.67% and 97.5%, respectively, at 60°C and a reaction time of 40 min. We investigated the kinetics and thermodynamics of the leaching process in this study to better understand the mechanism of the leaching process. Based on a comparison with H₂O₂ with respect to leaching efficiency, the optimal leaching parameters, and the activation energy, we determined that it is feasible to replace H₂O₂ with SnCl₂ as a leaching reductant in the leaching process. In addition, when SnCl₂ is used in the acid-leaching process, Sn residue in the leachate may have a positive effect on the re-synthesis of nickel-rich cathode materials. Therefore, the results of this study provide a potential direction for the selection of reductants in the hydrometallurgical recovery of valuable metals from spent LIBs.