Coating nano-hemalite on (Y,Gd)BO3 : Eu3+ phosphors by a facile method

(Y, Gd) BO3:Eu3+ particles coated with nano-hematite were prepared by a facile method I for example (humid) solid phase reaction at room temperature. The resulted hematite-coated (Y, Gd)BO3:Eu3+ particles were characterized by scanning electron microscopy (SEM), energy dispersive spectrometer (EDS) analysis, X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), and photoluminescence spectra (PL). The SEM and EDS analyses indicate that the particles are coated with a very thin layer of iron oxide. XPS results further confirmed that the coating was hematite, and the coating thickness was in nanometer range. XRD patterns showed that either the hematite coating was too thin or the content of hematite was too small, so that the XRD cannot detect it. The emission spectra illustrate that the peak near 580 nm disappears due to the coating of iron oxide, and when the coating is very thin, the ratio of D-5(0)-> F-7(2) to D-5(2)-> F-7(1) of coated particles is higher than that of uncoated ones, which indicates that the color purity of the phosphor is increased by coating nano-hematite.

Simultaneous determination of tramadol and lidocaine in urine by end-column capillary electrophoresis with electrochemiluminescence detection

Tramadol and lidocaine, used as analgesic and local anesthetic in surgery, are partly excreted by kidney. For the first time, we developed a simple and sensitive method, based on capillary electrophoresis with electrochemiluminescence (ECL) detection by end column mode without joint to monitor tramadol and lidocaine in urine. To eliminate the influence of ionic strength of urine sample, analytes were extracted by ether. Tripropylamine (TPA) was used as internal standard. ne recoveries of tramadol and lidocaine were between 94% and 97% at different levels. The method exhibited the linear range for the tramadol and lidocaine from 1.0 X 10(-7) to 1.0 X 10(-4) mol/L with correlation efficient of 0.998. The relative standard deviation (RSD) was 2.9% and 2.7% (n = 8) for tramadol and lidocaine, respectively. The limit of detection (LOD) was 6.0 x 10(-8) mol/L and 4.5 x 10(-8), mol/L (S/N = 3) for tramadol and lidocaine, respectively. The application for detecting tramadol and lidocaine in urine of patients showed that the method was valuable in clinical and biochemical laboratories for detecting tramadol, lidocaine and other tertiary amine pharmaceuticals for various purpose, such as metabolism investigation.

High-sensitivity molecular mass determination of lysozyme prior to MALDI-MS

Sodium dodecyl sulfate(SDS) is a powerful solubilizing detergent which is often used during the separation of highly complex protein mixtures by one- or two-dimensional (2D) gel electrophoresis. Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) is a widely used technique for mass spectrometric analysis of some protein molecules compared to other techniques. But the presence of SDS or some salts usually leads to signal deterioration when using MALDI-MS. A method for using nitrocellulose membrane as the solid-phase carrier combined with n-octyl-beta-D-glucopyranoside in the matrix highly enhances the sensitivity of the molecular mass determination of lysozyme. This technique has the advantage that the signal-to-noise of the molecular weight profile is improved compared with the mass spectrum and the profile is relatively easy to interpret.

Synthesis and characterization of a time-resolved fluorescence analysis chelate reagent-BCPDA

In this paper, we report on a solid phase time-resolved fluorescence immunoassay chelate reagent-4,7-bis(chlorosulfophenyl)1, 10-phenanthroline-2,9-dicarboxylic acid (BCPDA), which is suitable as a fluorescent labeling agent. The five step synthesis product of BCPDA was presented for improving the purity of the product based on the three step synthesis product. The approach involves chlorization, hydrolyzing the ester, preparing disodium, carboxylate to diacid, sulfonation. The yield of five step product is 99 %, 45 %, 94 %, 95 %, 80 % respectively. The structure and purity of product was characterized by the melting point, IR,H-1 NMR, UV spectrum, element analysis, and proved to be consistent with the structure predictal.

Laser-time-resolved fluorescence spectroscopy in immunoassays

This paper described a laser-excited time-resolved fluoroimmunoassay set. It made lanthanide ion to couple the anhydrde of diethylenetriaminepentaacetic acid (DTPAA) for labeling antibodies. The experiment used polystyrene tap coated with HCV antigen as the solid phase and a chelate of the rare earth metal europium as fluorescent label. A nitrogen laser beam was used to excite the Eu3+ chelates and after 60 ys delay time,the emission fluorescence was measured. Background fluorescence of short lifetimes caused by serum components and Raman scattering can be eliminated by set the delay rime. In the system condition, fluorescent spectra and fluorescent lifetimes of Eu3+ beta-naphthoyltrifluroacetone (NTA) chelates were measured. The fluorescent lifetime value is 650 mu s. The maximum emssion wavelength is 613 nm. The linear range of europium ion concentration is 1 x 10(-7)- 1 x 10(-11) g.mL(-1) and the detection limit is 1 x 10(-13) g.mL(-1). The relative standard deviation of determination ( n = 12) for samples at 0.01 ng.mL(-1) magnitude is 6.4%. Laser-TRFIA was also found to be suitable for diagnosis of HCV. The sensitvity and specificity were comparable to enzyme immunoassay. The result was obtained with laser-TRFIA for 29 human correlated well with enzyme immunoassay.

THE VALENCY AND SPECTRA OF SAMARIUM IONS IN MF(2)-MGF2 (M=CA, SR, BA)

The phosphors MMgF(4)(M = Ca, Sr, Ba) doped with samarium ions are synthesized in different atmospheres using solid phase reaction at high temperature. Samarium has been first stabilized in the divalent state in SrMgF4 and BaMgF4 matrices. Effects of matrices on the valent state of samarium ions are briefly discussed.

THERMAL ANALYSIS AND INFRARED SPECTRA OF DIALKYLAMMONIUM TETRAC HLOROCUPRATE

The thermal stability and the solid solid phase transitions in Ills compounds with n = 7-12 have been studied by DSC and TG methods. Comparision with CnZn compounds want made. The nature of three phases of CnCu has been discussed in terms of infrared spectroscopy and the assignment of the phase transitions has been given. The thermal stability of CnCu is lower than that of CnZn and presents an obvious odd even effect. All of these compounds exhibit two solid solid phase transitions in the temperature range of 248-337 K. The peak tempe nature of phase transitions changes regularly. The peak temperature or the main phase transition increases with the chain length. The total transition enthalpies and entropies increase with increasing chain length. When n <= 9, the high temperature phase exists in a partial disorder state. When n >= 10, the high temperature phase exists in a conformational disorder state. The main phase transition and the phase transition at 307.7 K of CnCu may mainly are from the change of the packing structure and the change of the partial conformational order-disorder of alkyl chain, respectively.

Analysis for Flavonoids in Bee Pollens by Capillary Electrophoresis

A capillary electrophoresis (CE) method has been developed for the determination of six bioactive flavonoids that are commonly found in health foods: hesperidin, hyperin, isorhamnetin, kaempferol, quercetin and rutin. The effects of several parameters, such as pH, buffer concentration, separation voltage and UV detector wavelength, were investigated to find the optimal conditions. Using a HbBCh-NaiB-iO? buffer (pH 9.2), the analytes can be separated within 8 min. The relative standard deviations of migration times in eight injections were between 0.77% and 0.93%, and those of the peak areas ranged from 3.8% to 8.6%. A high reproducibility and excellent linearity was observed over two orders of magnitude, with detection limits (S/N = 3) ranging from 0.34ug ml to 2.9ug ml for all the six analytes. Recoveries ranged from 80.4 % to 113.9 %. The new method is simple, reproducible and sensitive. No solid phase extraction for sample pretreatment is necessary. Analysis results are accurate in application to bee pollens.

Mass spectrometric identification of multihydroxy phenolic compounds in Tibetan herbal medicines

A highly selective and accurate method based on derivatization with dansyl chloride coupled with liquid chromatography-mass spectrometry has been developed for identification of natural pharmacologically active phenolic compounds in extracts of Lomatogonium rotatum plants (Tibetan herbal medicine) obtained by solid-phase extraction. The number of hydroxyl groups on the dansylated phenols was estimated by LC-MS-MS analysis in positive-ion mode. Dansyl derivatization of the compounds introduced basic secondary nitrogen into the phenolic core structures and this was readily ionized when acidic HPLC mobile phases were used. MS fragmentation of the derivatives generated intense protonated molecular ions of m/z [MH](+) (phenol aglycones were transformed into the corresponding free phenols by cleavage of an aglycone bond). Collision-induced dissociation of the protonated molecule generated characteristic product ions of m/z 234 and 171 corresponding to the protonated 5-(dimethylamino)naphthalene sulfoxide and 5 -(dimethylamino) naphthalene moieties, respectively. Selected reaction monitoring based on the m/z [MH](+) to 234 and 171 transitions was highly specific for these phenolic compounds. Characteristic ions with m/z values of [MH - 234](+), [MH 2 x 234](+), and [MH - 3 x 234](+) were of great importance for estimation of the presence of multihydroxyl groups on the phenolic backbone.

黄东海及朝鲜海峡冰后期陆架沉积物的环境磁学研究

There are four chapters in this dissertation. The first chapter briefly synthesizes the basic theories, methods and present-day applying situation of environmental magnetism. The second chapter probes into the magnetic mineral diagenesis in the post-glacial muddy sediments from the southeastern South Yellow Sea and its response to marine environmental changes, using the muddy sediment of Core YSDP103 formed in the shelf since about 13 ka BP. The third chapter illustrates the high-resolution early diagenetic processes by investigating the rapidly deposited muddy sediments during the last 6 ka in Cores SSDP-102 and SSDP-103 from the near-shore shelf of Korea Strait. The fourth chapter presents the results of detailed rock magnetic investigation of the surface sediments from the fine-grained depositional area on the outer shelf of the East China Sea in an attempt to provide environmental magnetic evidence for the provenance of the fine-grained deposit. Core YSDP103 was retrieved in the muddy deposit under the cold eddy of the southeastern South Yellow Sea, and the uppermost 29.79 m core represents the muddy sediments formed in the shelf since about 13 ka BP. The lower part from 29.79 to 13.35 m, called Unit A2, was deposited during the period from the post-glacial transgression to the middle Holocene (at about 6 ~(14)C ka BP) when the rising sea level reached its maximum, while the upper part above 13.35 m (called Unit Al) was deposited in a cold eddy associated with the formation of the Yellow Sea Warm Current just after the peak of post-glacial sea level rise. For the the uppermost 29.79 m core, detailed investigation of rock-magnetic properties and analyses of grain sizes and geochemistry were made. The experimental results indicate that the magnetic mineralogy of the core is dominated by magnetite, maghemite and hematite and that, except for the uppermost 2.35 m, the magnetic minerals were subject to reductive diagenesis leading to significant decline of magnetic mineral content and the proportion of low-coercivity component. More importantly, ferrimagnetic iron sulphide (greigite) is found in Unit A2 but absent in Unit Al, suggesting the control of marine environmental conditions on the magnetic mineral diagenesis. Magnetic parameters show abrupt changes across the boundary between the Unit Al and A2, which reflects a co-effect of environmental conditions and primary magnetic components of the sediments on the diagenesis. Alternating zones of high and low magnetic parameters are observed in Unit A2 of Core YSDP103, which is presumably due to periodic changes of the concentration and/or grain size of magnetic minerals carried into the study area. Cores SSDP-102 and SSDP-103, two studied sediment cores from the Korea Strait contain mud sequences (14 m and 32.62 m in thickness) that were deposited during the last 6,000 years. Analyses of grain sizes and geochemistry of the cores have demonstrated that the sediments have uniform lithology and geochemical properties, however, marked down-core changes in magnetic properties suggest that diagenesis has significantly impacted the magnetic properties. An expanded view of early diagenetic reactions that affect magnetic mineral assemblages is evident in these rapidly deposited continental shelf sediments compared to deep-sea sediments. The studied sediments can be divided into four descending intervals, based on magnetic property variations. Interval 1 is least affected by diagenesis and has the highest concentrations of detrital magnetite and hematite, and the lowest solid-phase sulfur contents. Interval 2 is characterized by the presence of paramagnetic pyrite and sharply decreasing magnetite and hematite concentrations, which suggest active reductive dissolution of detrital magnetic minerals, the absolute minimum abundance of magnetite is reached at the end of this interval. Interval 3 is marked by a progressive loss of hematite with depth, and at the base of this interval, 82% to 88% of the hematite component was depleted and the bulk magnetic mineral concentration was reduced to the lowest value in the entire studied mud section. Interval 4 has an increasing down-core enhancement of authigenic greigite, which is interpreted to have formed due to arrested pyritization resulting from consumption of pore water sulfate with depth. This is the first clear demonstration from an active depositional environment for a delay of thousands of years for acquisition of a magnetization carried by greigite. This detailed view of diagenetic processes in continental shelf sediments suggests that studies of geomagnetic field behavior from such sediments should be conducted with care. Paleoceanographic and paleoclimatic studies based on the magnetic properties of shelf sediments with high sedimentation rates like those in the Korea Strait are also unlikely to provide a meaningful signature associated with syn-depositional environmental processes. The rock magnetic properties of the surface sediments from the fine-grained depositional area on the outer shelf of the East China Sea, an area surrounded by sands, are investigated with a view to providing information on the sediment provenance. Multiple magnetic parameters such as magnetic susceptibility (%), anhysteretic remanent magnetization (ARM), saturation rernanent magnetization (SIRM), coercivities of SIRM (Her), and S ratios (relative abundance of low-coercivity magnetic minerals) are measured for all 179 surface samples, and partial representative samples are examined for their magnetic hysteresis parameters, temperature-dependence of magnetic susceptibility and x-ray diffraction spectra. Our research indicates that the magnetic mineralogy is dominated by magnetite with a small amount of hematite and is primarily of pseudo-single domain (PSD) to multidomain (MD) nature with a detrital origin. In the surface sediments, the granulometry of magnetic fractions is basically independent of grain sizes of the sediment containing the magnetic grains, and the composition of magnetic minerals remains almost homogeneous, that is, with a relatively constant ratio of low to high coercivity fraction throughout the area. The magnetic concentration in the study area generally decreases to the east or southeast accompanied by magnetic-particle fining to the east or to the northeast. The geographic pattern of magnetic properties is most reasonably explained by a major source of sediment jointly from the erosion of the old Huanghe River deposit and the discharge of the Changjiang River. The rock magnetic data facilitate understanding of the transport mechanism of fine-grained sediments in the outer shelf of the East China Sea.

Heat capacity and thermochemical study of trifluoroacetamide (C2H2F3NO)

The low-temperature heat capacities of trifluoroacetamide were precisely determined with a small sample precision automated adiabatic calorimeter over the temperature range from 78 to 404 K. A solid-to-solid phase transition, a fusion and a phase transition from a liquid crystalline phase to fully liquid phase have been observed at the temperatures of 336.911+/-0.102, 347.622+/-0.094 and 388.896+/-0.160 K, respectively. The molar enthalpies of these phase transitions as well as the chemical purity of the substance were determined to be 5.576+/-0.004, 11.496+/-0.007, 1.340+/-0.005 kJ mol(-1) and 99.30 mol%, respectively, on the basis of the heat capacity measurements. The molar entropies of the three phase transitions were calculated to be 16.550+/-0.012, 33.071+/-0.029 and 3.447+/-0.027 J mol(-1) K-1, respectively. Further researches of the thermochemical properties for this compound have been carried out by means of TG and DSC techniques. (C) 2000 Elsevier Science B.V. All rights reserved.

Homogeneous time-resolved fluoroimmunoassay of bensulfuron-methyl by using terbium fluorescence energy transfer

A sensitive homogenous time-resolved fluoroimmunoassay (TR-FIA) method for bensulfuron-methyl (BSM) based on fluorescence resonance energy transfer (FRET) from a Tb3+ fluorescent chelate with N,N,N',N'-[2,6-bis(3'-aminomethyl-1'-pyrazoly)-4-phenylpyridine] tetrakis(acetic acid) (BPTA-Tb3+) to organic dye, Cy3 or Cy3.5 has been developed. New method combined the use of BPTA-Tb3+ labeled streptavidin, Cy3 or Cy3.5 labeled anti-BSM monoclonal antibody and biotinylated BSM-BSA conjugate (BSA is bovine serum albumin) for competitive-type immunoassay. After BPTA-Tb3+ labeled streptavidin was reacted with a competitive immune reaction solution containing biotinylated BSM-BSA, BSM sample and Cy3 or Cy3.5 labeled anti-BSM monoclonal antibody, the sensitized and long-lived emission of Cy3 or Cy3.5 derived from FRET was measured, and thus the concentration of BSM in sample was calculated. The present method has the advantages of rapidity, simplicity and high sensitivity since the B/F (bound reagent/free reagent) separation steps and the solid-phase carrier are not necessary. The method gives the detection limit of 2.10 ng ml(-1). The coefficient variations of the method are less than 1.5% and the recoveries are in the range of 95-105% for BSM water sample measurement. (C) 2001 Elsevier Science B.V. All rights reserved.

UV Raman spectroscopic study on the synthesis mechanism of zeolite X

The synthesis of zeolite X is characterized by UV Raman spectroscopy, NMR spectroscopy, and X-ray diffraction. UV Raman spectra of the liquid phase of the synthesis system indicate that AI(OH); species are incorporated into silicate species, and the polymeric silicate species are depolymerized into monomeric silicate species during the early stage of zeolite formation. An. intermediate species possessing Raman bands at 307, 503, 858 and 1020 cm(-1) is detected during the crystallization ill the solid phase transformation. The intermediate species is attributed to the beta cage, the secondary building unit of zeolite X. A model for the formation of zeolite X is proposed, which involves four-membered rings connecting to each other via six-membered ring to form beta cages, then the beta cages interconnect via double six-membered rings to form the framework of zeolite X. (C) 2001 Elsevier Science B.V. All rights reserved.

Heat capacity and thermodynamic properties of N-(2-cyanoethyl) aniline (C9H10N2)

The low temperature heat capacities of N-(2-cyanoethyl)aniline were measured with an automated adiabatic calorimeter over the temperature range from 83 to 353 K. The temperature corresponding to the maximum value of the apparent heat capacity in the fusion interval, molar enthalpy and entropy of fusion of this compound were determined to be 323.33 +/- 0.13 K, 19.4 +/- 0.1 kJ mol(-1) and 60.1 +/- 0.1 J K-1 mol(-1), respectively. Using the fractional melting technique, the purity of the sample was determined to be 99.0 mol% and the melting temperature for the tested sample and the absolutely pure compound were determined to be 323.50 and 323.99 K, respectively. A solid-to-solid phase transition occurred at 310.63 +/- 0.15 K. The molar enthalpy and molar entropy of the transition were determined to be 980 +/- 5 J mol(-1) and 3.16 +/- 0.02 J K-1 mol(-1), respectively. The thermodynamic functions of the compound [H-T - H-298.15] and [S-T - S-298.(15)] were calculated based on the heat capacity measurements in the temperature range of 83-353 K with an interval of 5 K. (c) 2004 Elsevier B.V. All rights reserved.

Determination of organophosphorus pesticides in cucumber and potato by stir bar sorptive extraction

Organophosphorus pesticides (OPPs) in vegetables were determined by stir bar sorptive extraction (SBSE) and capillary gas chromatography with thermionic specific detection (TSD). Hydroxy-terminated polydimethylsioxane (PDMS) prepared by sol-gel method was used as extraction phase. The effects of extraction temperature, salting out, extraction time on extraction efficiency were studied. The detection limits of OPPs in water were <= 1.2 ng/l. This method was also applied to the analysis of OPPs in vegetable samples and matrix effect was studied. Linear ranges of OPPs in vegetable samples were 0.05-50 ng/g with detection limits <= 0. 15 ng/g and the repeatability of the method was less than 20% relative standard deviation. (c) 2005 Elsevier B.V. All rights reserved.