Analysis of estrogens in environmental waters using polymer monolith in-polyether ether ketone tube solid-phase microextraction combined with high-performance liquid chromatography

A simple, rapid and sensitive on-line method for simultaneous determination of four endocrine disruptors (17 beta-estradiol, estriol, bisphenol A and 17 alpha-ethinylestradiol) in environmental waters was developed by coupling in-tube solid-phase microextraction (SPME) to high-performance liquid chromatography (HPLC) with fluorescence detection (FLD). A poly(acrylamide-vinylpyridine-NAP-methylene bisacrylamide) monolith, synthesized inside a polyether ether ketone (PEEK) tube, was selected as the extraction medium. To achieve optimum extraction performance, several parameters were investigated, including extraction flow-rate, extraction time, and pH value, inorganic salt and organic solvent content of the sample matrix. By simply filtered with nylon membrane filter and adjusting the pH of samples to 6.0 with phosphoric acid, the sample solution then could be directly injected into the device for extraction. Low detection limits (S/N = 3) and quantification limits (S/N = 10) of the proposed method were achieved in the range of 0.006-0.10 ng/mL and 0.02-0.35 ng/mL from spiked lake waters, respectively. The calibration curves of four endocrine disruptors showed good linearity ranging from quantification limits to 50 ng/mL with a linear coefficient R-2 value above 0.9913. Good method reproducibility was also found by intra- and inter-day precisions, yielding the RSDs less than 12 and 9.8%, respectively. Finally, the proposed method was successfully applied to the determination of these compounds in several environmental waters. (c) 2006 Elsevier B.V. All rights reserved.

Shallow gas in the muddy sediments of Eckernförde Bay, Germany

The seafloor of central Eckernförde Bay is characterised by soft muddy sediments that contain free methane gas. Bubbles of free gas cause acoustic turbidity which is observed with acoustic remote sensing systems. Repeated surveys with subbottom profiler and side scan sonar revealed an annual period both of depth of the acoustic turbidity and backscatter strength. The effects are delayed by 3–4 months relative to the atmospheric temperature cycle. In addition, prominent pockmarks, partly related to gas seepage, were detected with the acoustic systems. In a direct approach gas concentrations were measured from cores using the gas chromatography technique. From different tests it is concluded that subsampling of a core should start at its base and should be completed as soon as possible, at least within 35 min after core recovery. Comparison of methane concentrations of summer and winter cores revealed no significant seasonal variation. Thus, it is concluded that the temperature and pressure influences upon solubility control the depth variability of acoustic turbidity which is observed with acoustic remote sensing systems. The delay relative to the atmospheric temperature cycle is caused by slow heat transfer through the water column. The atmospheric temperature cycle as ‘exiting function’ for variable gas solubility offers an opportunity for modelling and predicting the depth of the acoustic turbidity. In practice, however, small-scale variations of, e.g., salinity, or gas concentration profile in the sediment impose limits to predictions. In addition, oceanographic influences as mixing in the water column, variable water inflow, etc. are further complications that reduce the reliability of predictions.

Analysis of high wheat yields in Northwest China

Grain yields of over 14 Mg ha(-1) were reported in 1978 for spring wheat (Triticum aestivum L.) grown in Northwest China. Understanding the circumstances under which this record yield was achieved may be useful in defining the key factors that lead to high grain yields and in determining the limits to wheat yield. A relatively simple, mechanistic model was used in an effort to simulate the record yield. The model was used as a framework in which various crop traits could be adjusted to match the observed crop growth. The weather that was characterized by cool temperatures and high levels of solar radiation, proved to be especially important in allowing a full-season crop to achieve record yields. Variables defining plant development in the model also had to be set to describe the high yielding cultivar grown in China. Leaf development was defined by the length of a phyllochron, which was set equal to 78 TU (thermal units, base temperature equal to 0 degrees C) based on independent data. The description of grain fill had to be defined to match simulation results with the observations. Two variables, length of the grain-fill period and the grain growth rate, were set in response to the unique traits of this cultivar and the low temperatures during grain development. These simulations led to important suggestions for examining the interaction between cool temperature regimes and developmental traits of wheat cultivars. (C) 1997 Published by Elsevier Science Ltd.

白垩纪超静磁带地球磁场古强度测定

The long-term variations in the strength of the geomagnetic field provide important constraints on the chemical-physical processes of the Earth’s interior. Especially, the intensity of the geomagnetic field during the Cretaceous normal superchron (CNS) is crucial to understand the geodynamo. But a paucity of paleointensity further limits to obtain essential knowledge interior process in the deep earth. In order to improve the experimental efficiency, this study tried to apply two new rock magnetic methods (FORC diagram and low-temperature demagnetization technique) to determine the paleointensity. First, some problems in the theory and technique in paleointensity experiments were introduced. A combined palaeomagnetic and geochronologic study was further conducted on a basaltic lava sequence at Jianchang in Liaoning Province, northeastern China. Radiometric 40Ar/39Ar dating indicates that the volcanism occurred at about 119 Ma within the marine anomaly C34n in Cretaceous normal superchron (CNS). Rock magnetic investigations show that pseudo-single domain (PSD) titanium-poor titanomagnetite is dominant in the studied lava flows. Both stepwise thermal and alternating field demagnetizations isolate the well-defined normal characteristic remanent magnetization (ChRM) in three independent lava flows with a mean direction of D/I = 6.0/51.9 degree(a95 = 12.3degree). Palaeointensity was determined using the modified Thellier method with systematic partial thermoremanent magnetization (pTRM) checks on total 72 samples, but only 10 samples exhibit ideal linear behavior on the Arai-plot in the temperature interval of 300-560 C and yield an average paleointensity of (25.8+/-1.4)uT. In addition, slopes of the line defined by the initial and the final points on the Arai-plot for the other 18 samples with characteristic PSD features give an average paleointensity estimation value of (24.8+/-1.9)uT. The consistency of these two approaches confidently demonstrates the fidelity of our results. The overall mean field strength determined using both approaches are thus estimated to be (25.2+/-0.7 )uT. This value corresponds to the virtual dipole magnetic moments (VDM) of (4.5+/-0.1)E22 Am^2, which is about half of the value of present field. This finding suggests that palaeointensity just at the onset of the CNS is characterized by a weak magnetic field.

Self-similarity limits of genomic signatures

It is shown that metric representation of DNA sequences is one-to-one. By using the metric representation method, suppression of nucleotide strings in the DNA sequences is determined. For a DNA sequence, an optimal string length to display genomic signature in chaos game representation is obtained by eliminating effects of the finite sequence. The optimal string length is further shown as a self-similarity limit in computing information dimension. By using the method, self-similarity limits of bacteria complete genomic signatures are further determined.

Investigation on mechanism of critical cavitating flow in liquid jet pumps under operating limits

The critical cavitating flow in liquid jet pumps under operating limits is investigated in this paper. Measurements on the axial pressure distribution along the wall of jet pumps indicate that two-phase critical flow occurs in the throat pipe under operating limits. The entrained flow rate and the distribution of the wall pressure upstream lowest pressure section does not change when the outlet pressure is lower than a critical value. A liquid-vapor mixing shockwave is also observed under operating limits. The wave front moves back and forth in low frequency around the position of the lowest pressure. With the measured axial wall pressures, the Mach number of the two-phase cavitating flow is calculated. It's found that the maximum Mach number is very close to I under operating limits. Further analysis infers a cross-section where Mach number approaches to I near the wave front. Thus, the liquid-vapor mixture velocity should reach the local sound velocity and resulting in the occurrence of operating limits.

Experimentally Determined Flame Properties near Flammability Limits Under Gravity and Microgravity Conditions

Flammability limits for flames propagating in a rich propane/air mixture under gravity conditions appeared to be 6.3% C3H8 for downward propagation and 9.2% C3H8 for upward propagation. Different limits might be explained by the action of preferential diffusion of the deficient reactant (Le < 1) on the limit flames, which are in different states of instability. In one of the previous studies, the flammability limits under microgtravity conditions were found to be between the upward and downward limits obtained in a standard flammability tube under normal gravity conditions. It was found in those experiments that there are two limits under microgravity conditions: one indicated by visible flame propagation and another indicated by an increase of pressure without observed flame propagation. These limits were found to be far behind the limit for downward-propagating flame at 1 g (6.3% C3H8) and close to the limit for upward-propagating flame at 1 g (9.2% C3H8). It was decided in the present work to apply a special schlieren system and instant temperature measuring system for drop tower experiments to observe combustion development during propagation of the flame front. A small cubic closed vessel (inner side, 9 cm 9 cm 9 cm) with schlieren quality glass windows were used to study limit flames under gravity and microgravity conditions. Flame development in rich limit mixtures, not visible in previous experiments under microgravity conditions for strait photography, was identified with the use of the schlieren method and instant temperature measuring system. It was found in experiments in a small vessel that there is practically no difference in flammability limits under gravity and microgravity conditions. In this paper, the mechanism of flame propagation under these different conditions is systematically studied and compared and limit burning velocity is estimated.

Polaronic correction to the first excited electronic energy level in an anisotropic semiconductor quantum dot

Within the framework of second-order Rayleigh-Schrodinger perturbation theory, the polaronic correction to the first excited state energy of an electron in an quantum dot with anisotropic parabolic confinements is presented. Compared with isotropic confinements, anisotropic confinements will make the degeneracy of the excited states to be totally or partly lifted. On the basis of a three-dimensional Frohlich's Hamiltonian with anisotropic confinements, the first excited state properties in two-dimensional quantum dots as well as quantum wells and wires can also be easily obtained by taking special limits. Calculations show that the first excited polaronic effect can be considerable in small quantum dots.

Comparative cytogenetics of bats (Chiroptera): The prevalence of Robertsonian translocations limits the power of chromosomal characters in resolving interfamily phylogenetic relationships

Although the monophyly of Chiroptera is well supported by many independent studies, higher-level systematics, e.g. the monophyly of microbats, remains disputed by morphological and molecular studies. Chromosomal rearrangements, as one type of rare genomic changes, have become increasingly popular in phylogenetic studies as alternatives to molecular and other morphological characters. Here, the representatives of families Megadermatidae and Emballonuridae are studied by comparative chromosome painting for the first time. The results have been integrated into published comparative maps, providing an opportunity to assess genome-wide chromosomal homologies between the representatives of eight bat families. Our results further substantiate the wide occurrence of Robertsonian translocations in bats, with the possible involvement of whole-arm reciprocal translocations (WARTs). In order to search for valid cytogenetic signature(s) for each family and superfamily, evolutionary chromosomal rearrangements identified by chromosomal painting and/or banding comparison are subjected to two independent analyses: (1) a cladistic analysis using parsimony and (2) the mapping of these chromosomal changes onto the molecularly defined phylogenetic tree available fromthe literature. Both analyses clearly indicate the prevalence of homoplasic events that reduce the reliability of chromosomal characters for resolving interfamily relationships in bats.

Experimental study of the U-238(S-36,3-5n)(269-271)Hs reaction leading to the observation of (270)Hs

The deformed doubly magic nucleus (270)Hs has so far only been observed as the four-neutron (4n) evaporation residue of the reaction Mg-26+Cm-248, where a maximum cross section of 3 pb was measured. Theoretical studies on the formation of (270)Hs in the 4n evaporation channel of fusion reactions with different entrance channel asymmetry in the framework of a two-parameter Smoluchowski equation predict that the reactions Ca-48+Ra-226 and S-36+U-238 result in higher cross sections due to lower reaction Q values, in contrast to simple arguments based on the reaction asymmetry, which predict opposite trends. Calculations using HIVAP predict cross sections for the reaction S-36+U-238 that are similar to those of the Mg-26+Cm-248 reaction. Here, we report on the first measurement of evaporation residues formed in the complete nuclear fusion reaction S-36+U-238 and the observation of (270)Hs, which is produced in the 4n evaporation channel, with a measured cross section of 0.8(-0.7)(+2.6) pb at 51-MeV excitation energy. The one-event cross-section limits (68% confidence level) for the 3n, 4n, and 5n evaporation channels at 39-MeV excitation energy are 2.9 pb, while the cross-section limits of the 3n and 5n channel at 51 MeV are 1.5 pb. This is significantly lower than the 5n cross section of the Mg-26+Cm-248 reaction at similar excitation energy.

Anodic Stripping Voltammetry at Bismuth-Coated and Uncoated Carbon Microdisk Electrodes:Application to Trace Metals Analysis in Flood Samples

This article reports on the performance of a bismuth-coated carbon microdisk electrode (BiFμE) for the determination of trace heavy metals by anodic stripping voltammetry (ASV). The BiFμE was prepared by electrodeposition of a metallic bismuth film onto the microdisk, by applying an in-situ electroplating procedure. To test the performance of the BiFμE, ASV measurements were performed on synthetic solutions containing Cd2+, Pb2+, and Cu2+ as target ions. The results indicated that cadmium and lead gave well-defined ASV peaks with no interference, and their quantitative determination could be carried out straightforwardly. In particular, linear calibration curves over the range 5.0 x 10-8-1.0 x 10-6M for both ions, and detection limits of 7.8 and 2.9 nM, for cadmium and lead, respectively, after applying a 60 sec preconcentration step, were obtained. The reproducibility was also satisfactory, the relative standard deviation (RSD) being within 2.5% for both ions. Copper, instead, gave an ASV response that. in most experimental conditions, overlapped with that of bismuth. This circumstance made the determination of copper at the BiFμE difficult. Since the latter element could be detected reliably at the uncoated carbon microdisk electrode (CμE), both BiFμE and CμE were employed, respectively, for the determination of lead and copper ions in drinking water, wine, and tomato sauce.

Field-amplified sample stacking capillary electrophoresis with electrochemiluminescence applied to the determination of illicit drugs on banknotes

Capillary electrophoresis (CE) with Ru(bpy)(3)(2+) electrochemiluminescence. (ECL) detection system was established to the determination of contamination of banknotes with controlled drugs and a high efficiency on-column field-amplified sample stacking (FASS) technique was also optimized to increase the ECL intensity. The method was illustrated using heroin and cocaine, which are two typical and popular illicit drugs. Highest sample stacking was obtained when 0.01 mM acetic acid was chosen for sample dissolution with electrokinetical injection for 6 s at 17 kV. Under the optimized conditions: ECL detection at 1.2 V, separation voltage 10.0 kV, 20 mM phosphate-acetate (pH 7.2) as running buffer, 5 mM Ru(bpy)(3)(2+) with 50 mM phosphate-acetate (pH 7.2) in the detection cell, the standard curves were linear in the range of 7.50 x 10(-8) to 1.00 x 10(-5) M for heroin and 2.50 x 10(-7) to 1.00 x 10(-4) M for cocaine and detection limits of 50 nM for heroin and 60 nM for cocaine were achieved (S/N = 3), respectively. Relative standard derivations of the ECL intensity and the migration time were 3.50 and 0.51% for heroin and 4.44 and 0.12% for cocaine, respectively.The developed method was successfully applied to the determination of heroin and cocaine on illicit drug contaminated banknotes without any damage of the paper currency.

Study of a new derivatizing reagent that improves the analysis of amino acids by HPLC with fluorescence detection: application to hydrolyzed rape bee pollen

A simple and sensitive method for evaluating the chemical compositions of protein amino acids, including cystine (Cys)(2) and tryptophane (Try) has been developed, based on the use of a sensitive labeling reagent 2-(11H-benzo[alpha]-carbazol-11-yl) ethyl chloroformate (BCEC-Cl) along with fluorescence detection. The chromophore of the 1,2-benzo-3,4-dihydrocarbazole-ethyl chloroformate (BCEOC-Cl) molecule was replaced with the 2-(11H-benzo[alpha]-carbazol-11-yl) ethyl functional group, yielding the sensitive fluorescence molecule BCEC-Cl. The new reagent BCEC-Cl could then be substituted for labeling reagents commonly used in amino acid derivatization. The BCEC-amino acid derivatives exhibited very high detection sensitivities, particularly in the cases of (Cys)(2) and Try, which cannot be determined using traditional labeling reagents such as 9-fluorenyl methylchloroformate (FMOC-Cl) and ortho-phthaldialdehyde (OPA). The fluorescence detection intensities for the BCEC derivatives were compared to those obtained when using FMOC-Cl and BCEOC-Cl as labeling reagents. The ratios I (BCEC)/I (BCEOC) = 1.17-3.57, I (BCEC)/I (FMOC) = 1.13-8.21, and UVBCEC/UVBCEOC = 1.67-4.90 (where I is the fluorescence intensity and UV is the ultraviolet absorbance). Derivative separation was optimized on a Hypersil BDS C-18 column. The detection limits calculated from 1.0 pmol injections, at a signal-to-noise ratio of 3, ranged from 7.2 fmol for Try to 8.4 fmol for (Cys)(2). Excellent linear responses were observed, with coefficients of > 0.9994. When coupled with high-performance liquid chromatography, the method established here allowed the development of a highly sensitive and specific method for the quantitative analysis of trace levels of amino acids including (Cys)(2) and Try from bee-collected pollen (bee pollen) samples.

Synthesis of a terbium fluorescent chelate and its application to time-resolved fluoroimmunoassay

A new nonadentate ligand, N, N, N-1, N-1-[2,6-bis(3'-aminomethyl-1 1'-pyrazolyl)-4-phenylpyridine]tetrakis(acetic acid) (BPTA) for a Tb3+ fluorescent complex was synthesized. The Tb3+ complex is strongly fluorescent, having a large fluorescence quantum yield of 1.00 and very long fluorescence lifetime of 2.681 ms in 0.05 M berate buffer of pH 9.1. Streptavidin (SA) was labeled with SPTA by using its succinimidyl monoester, and the BPTA-Tb3+-labeled SA was used in sandwich-type time-resolved fluoroimmunoassay (TR-FIA) of alpha -fetoprotein (AFP) and carcinoembryonic antigen (CEA) in human sera. The Tb3+-labeled SA was also used in competitive type TR-FIA of bensulfuron- methyl (BSM) in water. The detection limits of these assays are 42 pg/mL for AFP, 70 pg/mL for CEA, and 0.4 ng/mL for BSM. In addition, a new simultaneous measurement method for AFP and CEA in a human serum sample was developed by using 4,4'-bis(1 " ,1 " ,1 " ,2 " ,2 " ,3 " ,3 " -heptafluoro-4 " ,6 " -hexanedion-6 " -yl)chlorosulfo-o-terphenyl ((BHHCT)-Eu3+-labeled anti-AFP antibody, biotinylated anti-CEA antibody, and BPTA-Tb3+-labeled SA. The concentrations of AFP and CEA in 39 human serum samples were determined, and the results were compared with those of the independently determined AFP and CEA by TR-FIA with a single-label method. A good correlation was obtained with the correlation coefficients of 0.991 for AFP and 0.994 for CEA.