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1.
The deliberate poisoning of A. Litvinenko in London in late 2006 with 210Po, attracted attention to the difficulties in identifying internal contamination with alpha emitting radionuclides and to the limited knowledge available on the cycling of many naturally occurring radioisotopes in the body and their baseline concentration values in humans. To cope with the emergency caused by the spread of high 210Po activity, which contaminated several people and places in London, we were called upon to analyze urine samples in potentially contaminated people. A reference group of adult humans was also selected for determination of baseline 210Po values to be used for comparative purposes. Concentrations of 210Po in urine samples from three Portuguese citizens that have been at contaminated places, in London, ranged from 2.3 to 4.1 mBq·L−1 while in the reference group 210Po concentrations ranged from 0.5 to 4.8 mBq·L−1. Analytical quality of results was ensured through participation in an international inter laboratory comparison exercise on 210Po determination in aqueous samples. Results indicated that people potentially exposed to 210Po in London were not internally contaminated with the radionuclide used as a poisoning agent, and the levels of this radionuclide measured in the urine were similar to the naturally occurring levels in the reference group. Polonium levels in urine and in man are discussed in the light of 210Po levels in the human diet.  相似文献   

2.
The activity concentration of beryllium-7 (7Be), a naturally occurring cosmogenic radionuclide produced in the upper atmosphere, was measured in plants on the Loess plateau of China during the growing season of 2005. The 7Be mass activity concentration on July 27 ranged from 34.8 to 147.1 Bq kg−1 in herbaceous plants, from 47.6 to 116.1 Bq kg−1 in subshrubs, and from 15.7 to 56.8 Bq kg−1 in crop plants. The 7Be mass and areal activity concentrations of a mixture of herbaceous plants increased from 66.8 to 288.7 Bq kg−1 and from 0.7 to 46.5 Bq m−2, respectively, during the growing season. On an areal basis, the fraction of 7Be in plants in the soil–plant system increased from 0.4 to 8.4% during the growing season. Positive linear correlations were found between the increases of 7Be mass and areal activity concentrations in the inter-sampling intervals and the amount of precipitation.  相似文献   

3.
Abstract

Recent measurements of the heat capacity at constant pressure Cp for lead from 300 to 850°K have shown that Cp for liquid lead decreases continuously from the melting point to 850°K. Using data in the literature of density and velocity of sound, the dilation correction has been applied to Cp to obtain the heat capacity at constant volume Cv for liquid lead. Application of the dilation correction to solid lead gives a Cv curve which uncreases only about one joule/gm-atom-°K from 300 to 600°K, whereas the Cv curve for liquid lead decreases almost 5 joules/gm-atom-°K from 600 to 850°K. A careful assessment of the uncertainty in the quantities used in the dilation correction leads to an uncertainty in Cv of ± 2.5% (about one joule/gm-atom-°K), and thus the decrease in Cv for liquid lead is quite real.  相似文献   

4.
Antimony (Sb) contamination has become a growing concern in recent years. Strategies for reducing Sb contamination and its related health risks are urgently desired. This study was conducted to explore the possibility of selenium (Se) detoxification on Sb toxicity in paddy rice in order to find a feasible method to reduce the health risk of Sb pollution. Seedlings of paddy rice were exposed to 5 mg L1 Sb (KSbC4H4 O7·1/2H2O), in the presence of Se (Na2SeO3) at 0.1, 1, 5 mg L1 in culture solution, with no Sb and Se addition as the control. Paddy rice took up Sb greatly and the highest Sb contents measured among all treatments in this experiment in the leaves, stems and roots were 65.5, 298.5 and 195.7 mg kg1, respectively. Without Sb addition in the solution, single exposure to 0.1 mg L1 Se remarkably reduced the malondialdehyde (MDA) formation in paddy rice,demonstrating the beneficial effect of Se at low dosages. The addition of 5 mg L1 Sb was found to generate toxicity to paddy rice, showing as decreased biomass and increased leaf MDA content in paddy rice, while addition of 1 mg L1 Se mitigated the toxicity of Sb, as seen with the decreased leaf MDA content and increased biomass, indicating antidotal role of Se to Sb. In addition, the presence of 0.1, 1, 5 mg L1 Se generally decreased the accumulation of Sb in the leaves, stems and roots in paddy rice. Toxicity was also seen when paddy rice was exposed to single Se at 1 and 5 mg L1 levels, however, 5 mg L1 Sb addition was found to decrease the contents of Se in the leaves/stems whereas increased them in roots, accompanied with decreased MDA contents and increased biomass in paddy rice, indicating a possible detoxification role of Sb to Se too. Therefore, Sb, although toxic, could also be an antitoxin to Se in paddy rice at certain condition. Our results showed that Se could alleviate Sb toxicity efficiently in paddy rice through two effects as antagonism and antioxidation.  相似文献   

5.
The densities of anthracene, tetracyanoethylene, maleic anhydride, N-phenylmaleineimide, trans, trans-1,4-diphenylbuta-1,3-diene, and their Diels-Alder adducts were measured in the solid state and in solution at 25 °C. The reaction volumes in the solid state were calculated from the difference in molar volumes. They turned out to be low, close to each other (–4 to –11 cm3 mol–1), and slightly different from the reaction volumes (–8±1 cm3 mol–1) calculated from the van der Waals radii. The reaction volumes in solutions (–15 to –32 cm3 mol–1) were found from the difference in partial molar volumes of the reactants in dioxane, acetonitrile, and 1,2-dichloroethane, The experimental Diels-Alder reaction volumes in solution are determined not only by the formation of new bonds in an adduct: a considerably higher contribution (to 75%) is made by a change in the volume of intermolecular empty spaces in solution on going from reactants to adducts.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2386–2390, November, 2004.  相似文献   

6.
Transplantation of pancreatic islets is efficient in improving the metabolic control and quality of life and in preventing severe hypoglycemia in patients with brittle type 1 diabetes mellitus. More accurate methods to assess islet viability would be extremely useful in designing target interventions for islet cytoprotection and in reducing the number of islets required to achieve insulin independence. Here we report on an application of calorimetry to evaluate the metabolic response of pancreatic islets to glucose stimulation. A significant increase in metabolic heat was produced by islet samples when consecutively subjected to 2.8 and 16.3 mmol L−1 glucose. Under these glucose concentrations, 1000 islets released average heat values of 9.16 ± 0.71 mJ and 14.90 ± 1.21 mJ over 50 min, respectively. Additionally, the glucose stimulation indexes were 1.67 ± 0.30 for insulin, 1.72 ± 0.13 for heat and 2.91 ± 0.50 for lactate, raising the important possibility of substituting the secreted insulin index/ratio by the index/ratio of the heat released in the evaluation of Langerhans islets viability for transplantation. Altogether, our results demonstrate the applicability of calorimetry to assess the quality of isolated pancreatic islets and to study vital islet functions.  相似文献   

7.
Prion proteins that have transformed from their normal cellular counterparts (PrPc) into infectious form (PrPres) are responsible for causing progressive neurodegenerative diseases in numerous species, such as bovine spongiform encephalopathy (BSE) in cattle (also known as mad cow disease), scrapie in sheep, and Creutzfeldt-Jakob disease (CJD) in humans. Due to a possible link between BSE and CJD it is highly desirable to develop non-invasive and ante mortem tests for the detection of prion proteins in bovine samples. Such ante mortem tests of all cows prior to slaughter will help to prevent the introduction of PrPres into the human food supply. Furthermore, detection of PrPres in donated blood will also help to prevent the transmission of CJD among humans through blood transfusion. In this study, we have continued development of a micromechanical resonator array that is capable of detecting PrPc in bovine blood serum. The sensitivity of the resonators for the detection of PrPc is further enhanced by the use of secondary mass labels. A pair of antibodies is used in a sandwich immunoassay format to immobilize PrPc on the surface of resonators and attach nanoparticles as secondary mass labels to PrPc. Secondary mass labeling is optimized in terms of incubation time to maximize the frequency shifts that correspond to the presence of PrPc on the surface of resonators. Our results show that a minimum of 200 pg mL−1 of PrPc in blood serum can be detected using micromechanical resonator arrays.  相似文献   

8.
A systematic study was carried out to understand the effect of structural modification of Cnmim+ moiety of CnmimBr (n = 6, 8 or 10) on the electrochemical behavior of uranium. The cyclic voltammetric study of the above room-temperature ionic liquids (RTIL) media revealed that with increase in the chain length the electrochemical window extended more towards the negative potential. This resulted in the possibility of conversion of U(VI) to U(III) or even possibly to, U metal via U(IV) (as UO2) when n ≥ 10. The diffusion coefficient of U(VI) was found to decrease from n = 6 to 8 to 10 due to the increasing order of viscosity of the RTIL. As a consequence, the activation energy was found to follow reverse order i.e. E act(C6mimBr) < E act(C8mimBr) < E act(C10mimBr). The conversion of UO2 2+ to UO2 was found to be quasi reversible and also exothermic while the entropy was found to decrease due to the reduction reaction. An UV–Vis spectroscopic study was also carried out to understand the local environment around uranium in aqueous and RTIL media. Among several cationic and anionic species, the predominance of UO2Cl4 2? in 7 M HCl with D4h coordination symmetry was observed. The decrease in symmetric stretching frequency of UO2 2+ in RTILs in comparison with aqueous system indicates that the bond strength of UO2 2+ in aqueous is less than that of UO2 2+ in RTILs.  相似文献   

9.
The present plutonium levels in the Pacific Ocean are summarized. The 239,240Pu concentrations in surface seawaters in the early 2000s were in the range of 1.5 to 9.2 mBq·m−3 in the North Pacific and 0.8 to 4.1 mBq·m−3 in the South Pacific. There is no marked difference of surface 239,240Pu distributions between the North and South Pacific subtropical gyres. The vertical profile of 239,240Pu in the South Pacific was the similar pattern to that in the North Pacific, which is controlled by biogeochemical processes. The 239,240Pu inventories (down to 2300 m) in the North Pacific are generally greater than that in the South Pacific, which reflects the geographical distribution of global fallout and effect of close-in fallout in the Marshall Islands.  相似文献   

10.
The conversion of low-priced glycerol to higher value products has been proposed as a way to improve the economic viability of the biofuels industry. In a previous study, the conversion of glycerol to ethanol in a metabolically engineered strain of Saccharomyces cerevisiae was accomplished by minimizing the synthesis of glycerol, the main by-product in ethanol fermentation processing. To further improve ethanol production, overexpression of the native genes involved in conversion of pyruvate to ethanol in S. cerevisiae was successfully accomplished. The overexpression of an alcohol dehydrogenase (adh1) and a pyruvate decarboxylase (pdc1) caused an increase in growth rate and glycerol consumption under fermentative conditions, which led to a slight increase of the final ethanol yield. The overall expression of the adh1 and pdc1 genes in the modified strains, combined with the lack of the fps1 and gpd2 genes, resulted in a 1.4-fold increase (about 5.4 g/L ethanol produced) in fps1Δgpd2Δ (pGcyaDak, pGupCas) (about 4.0 g/L ethanol produced). In summary, it is possible to improve the ethanol yield by overexpression of the genes involved in the conversion of pyruvate to ethanol in engineered S. cerevisiae using glycerol as substrate.  相似文献   

11.
α,β-Unsaturated aldehyde acetals add :CCl2 (obtained in accordance with Makosza procedure) to form gem-dichlorocyclopropanecarboxaldehyde acetals (1) in high yields when the ratio of reactants is no less than 1:4. The addition of :CCl2 to polyunsaturated aldehyde acetals in the above conditions proceeds regioselectively at double bonds enriched by electrons. Compounds 1 are reduced by sodium in liquid ammonia to give cyclopropanecarboxaldehyde acetals (2). Both 1 and 2 are hydrolized by dilute H3P04 to the corresponding aldehydes and are added to vinyl ethers in the presence of BF3·Et2O to produce only 1:1 adducts which are hydrolyzed by a mixture of AcOH-AcONa-H2O to give β-formylcyclopropanes which were previously unknown.  相似文献   

12.
This paper investigates the interface between philosophy and biochemistry. While it is problematic to justify the application of a particular philosophical model to biochemistry, it seems to be even more difficult to develop a special “Philosophy for Biochemistry”. Alternatively, philosophy can be used in biochemistry based on an alternative approach that involves an interdependent iteration process at a philosophical and (bio)chemical level (“Exeter Method”). This useful iteration method supplements more abstract approaches at the interface between philosophy and natural sciences, and serves the biochemical community to systematically locate logical inconsistencies that arise from more theoretical aspects of the scientific process. Initial cycles of this iteration process identify the in vitro–in vivo problem as a central epistemological difficulty in biochemical research. While previous attempts have generated ad hoc rules to mend the gap between chemistry, biochemistry and biology in order to justify in vitro experimentation, this paper concludes that in vitro experimentation is heavily based on chemistry and cannot derive definite statements about biological processes. It can, however, generate results that will influence the direction of future biological research. The consequence is that the relationship between in vitro and in vivo experimentation is more of a psychological or social one than of a logical nature. Apart from highlighting these inconsistencies in biochemical thinking (“problem awareness”), the Exeter Method demands an improvement of biochemical terminology that contains separate and unequivocally defined terms for in vitro and in vivo systems. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   

13.
The present study is conducted, in order to contribute to a future waste management policy related to the presence of technologically enhanced natural occurring radioactive material (TENORM) in Iran petroleum industry. Samples were collected from offshore oil company for analysis of 238U, 235U, and 232Th series in produced waters. The activities of samples were determined by high-purity germanium detector, well for lowlevel activity γ-spectrometry. The results have shown that, 226Ra concentration ranges from 5.26 Bq/L to 27.93 Bq/L. Also the total activity in produced water is in the range of 16–840 Bq/L were mainly due to enhanced levels of dissolved 226Ra, 214Pb, 214Bi ions. Also, enhanced dissolution of elements such as radium by increasing of salinity, result in higher concentration of NORM in old oil region. Measured values are above EPA regulation (40 CFR 141055) & aqueous Derived Release Limit (DRL) of Canadian guideline for the management of (NORM). Therefore produced water has to dispose in pits which have to design for decrease the environmental effects. Also according to this study, re-injection of produced water in to abandon well of Iran Offshore Oil Company in Persian Gulf, have preference over discharging to the pits.  相似文献   

14.
The infrared spectra of ethylmethylfluorosilane (CH3SiHFCH2CH3) have been recorded as a vapour, liquid and solid at 78 K in the 4000–50 cm−1 range and isolated in an argon matrix at ca. 5 K. Infrared spectra of two different solid phases were obtained after annealing to temperatures of 120 and 130 K, and recooling to 78 K. Although the IR spectra were quite similar in the MIR region, certain differences were noted in the FIR region below 400 cm−1. The most stable conformer MeMe was present after annealing to 130 K, but three bands belonging to MeH were detected after annealing to 120 K. Various infrared bands changed intensity when the argon matrix was annealed to temperatures between 20 and 35 K, and some of these were related to changes in the conformational abundance.Raman spectra of the liquid were recorded at room temperature and at various temperatures between 295 and 153 K. Spectra of an amorphous and annealed solid were recorded at 78 K. In the variable temperature Raman spectra, various bands changed in intensity and were interpreted in terms of conformational equilibria between the three possible conformers. Complete assignments were made for all the bands of the most stable conformer MeMe. From various bands assigned to the three conformers, the conformational enthalpy difference ΔH from MeMe to the intermediate energy conformer MeH was found to be 0.5 kJ mol−1 and to the highest conformer MeF was 0.7 kJ mol−1. At ambient temperature this leads to 39% MeMe, 32% MeH and 29% of the MeF conformer in the liquid.Ab initio calculations in the RHF, MP2, DFT approximations and very accurate G2 calculations were carried out. With one exception, the MeMe conformer had the lowest enthalpy in all these calculations, the MeH had the intermediate and the MeF the highest enthalpy, and the calculations were in good agreement with the measurements.  相似文献   

15.
N. Rodríguez  L.A. Sarabia 《Talanta》2009,77(3):1129-782
In this work, a four-way tensor is used to model the quenching effect in fluorescent measurements. By means of the analysis of excitation-emission matrices obtained in the determination of tetracycline in tea, which acts as quencher, it is shown as the impossibility to use a calibration, or an addition standard based on a three-way model. It is analysed the quencher multiplicative effect made on the tetracycline signal by means of an ANOVA. However, by arranging the experimental data in a four-way tensor, it is viable to perform a calibration based on the parallel factor analysis, PARAFAC, decomposition and a four-way partial least squares, 4-PLS, regression to quantify the tetracycline in the presence of the matrix quencher effect. 4-PLS calibration provides better results. In the range from 40 to 220 μg L−1 gives an average of relative errors in absolute value equal to 8.02% in prediction (3.40% in calibration). The repeatability as standard deviation in this range is 5.08 μg L−1 and the method is accurate, slope and intercept being statistically equal to 1 and 0, respectively when a regression calculated versus true concentration is performed. Moreover, it has a decision limit (CCα) of 13.87 μg L−1 for a probability of false positive, α, equal to 0.05 and a capability of detection (CCβ) of 26.63 μg L−1 (for probabilities of false positive, α, false negative, β, equals to 0.05).  相似文献   

16.
The effects of temperature on the stability of a soil humic acid were studied in the present work. Solid samples of Gohy-573 humic acid (HA) and dissolved ones in aqueous solution (pH 6.0, 0.1 mol L−1 NaClO4) were investigated in order to understand the impact of temperature on the chemical properties of the material. The methods applied to solid samples in the present investigation were thermogravimetric analysis (TGA), temperature-programmed desorption coupled with mass spectrometry (TPD-MS), and in situ diffuse reflectance infrared Fourier transformed spectroscopy (in situ DRIFTS). Humic acid samples were studied in the 25-800 °C range, with focus on thermal/chemical processes up to 250 °C. The reversibility of the changes observed was investigated by cyclic changes to specified temperature ranges (40-110 °C). All measurements were conducted under inert-gas atmosphere in order to avoid samples combustion at increased temperatures. Aqueous solutions were analyzed by UV-vis absorption spectroscopy after storage at temperatures up to 95 °C, and storage times up to 1 week. For temperatures below 100 °C experiments on solid and aqueous samples have shown results which were consistent to each other. The amount of water desorbed is temperature dependent and up to 70 °C this process was totally reversible. Above 70 °C an irreversible loss of water was also observed, which according to UV-vis spectroscopy corresponds to water produced by condensation leading to more condensed polyaromatic structures. The water released up to 110 °C was about 7 wt% of the total mass of the dried humic acid, where less than 50% corresponded to reversibly adsorbed water. At higher temperatures (>110 °C), gradual decomposition resulting in the formation of carbon dioxide (110-240 °C), and carbon monoxide (140-240 °C) takes place. Hence, thermal treatment of Gohy-573 humic acid above 70 °C results in irreversible structural changes, that could affect chemical properties (e.g., complex formation) of the material.  相似文献   

17.
The effects of 16O → 18O substitution on the vibrational frequencies of N,N-dimethylformamide have been studied. To understand these and the effects of previously measured shift data due to 13C, 2H and 15N ab initio calculations of frequencies and intensities have been carried out at the 3-21G level. Accord between theory and experiment is generally good. A surprising result is the prediction of a weak band near 2000 cm−1 in DMF due to in-plane interaction between the methyl umbrella modes and the anti-symmetric CN stretch. This abnormally high frequency is explained as arising due to the planar trigonal C3N entity. Previous problems in reproducing isotope shifts are shown to be due to this mode being previously assigned near 1500 cm−1. The effects of suppressing reference to one of a set of internal valence angles involved in a redundancy are explored. It is shown that the principal effect is to add the diagonal quadratic constant for that coordinate to all other quadratic terms involving pairs of the angles involved in the redundancy. This results in large, almost equal, interaction constants amongst this set. Such effects are seen in the present work. The ab initio field is shown to be compatible with ab initio fields of mono N-methyl amides extant in the literature.  相似文献   

18.
Ion-beam irradiation effects on polyimide, Kapton™, were studied with respect to optical and electronic properties. Stack films of Kapton™ (12.5 μm thick) were irradiated to various ion beams in air or vacuo at room temperature and subjected to ultraviolet–visible (UV–vis) spectroscopy, and change in absorbance and energy gap is discussed. The UV–vis absorption spectrum, which is assigned to the transition of electrons in benzene rings from π to π* orbital, upon He2+ (6 MeV/u) irradiation in air, shifted towards longer wavelength direction for all cases, and the shift was more obvious for higher linear energy transfer (LET) ion beams. The energy gap of the transition was estimated, and the H+ and He2+ ion beams caused little change in the transition energy gap Eg, while the heavier ions such as C6+ and Si14+ caused more significant decrease. This decrease is assumed to the structural changes around benzene rings, and the infrared spectroscopy revealed breakage in imide groups next to benzene ring in the repeating unit of polyimide.  相似文献   

19.
The values of pseudo first‐order rate constants (kobs) for the cleavage of N‐(2‐hydroxyphenyl)phthalamic acid ( 7 ), obtained at 4.9 × 10?2 M HCl, 35°C, and within CH3CN content range 2–80% (v/v) in mixed aqueous solvent are smaller than kobs for the cleavage of N‐(2‐methoxyphenyl)phthalamic acid ( 8 ), obtained under almost similar experimental conditions, by nearly 1.5‐ to 2‐fold. These observations show the absence of expected intramolecular general acid catalysis due to 2‐OH group in 7 . The values of kobs for the cleavage of 7 and 8 decrease by more than 20‐fold with the increase in the content of CH3CN from 2 to 80–82% (v/v) in mixed aqueous solvent. The kinetic data reveal that in acidic aqueous cleavage of 7 , N‐cyclization (leading to the formation of imide) and O‐cyclization (leading to the formation of phthalic anhydride) vary from ~10 to 15% and ~90 to 85%, respectively, with the increase in CH3CN content from 2 to 80% (v/v). Similar increase in CH3CN content causes increase in N‐cyclization from ~0 to 5% and decrease in O‐cyclization from ~100 to 95% in the acidic aqueous cleavage of 8 . Some speculative, yet conceivable, reasons for nearly 10 and 0% N‐cyclization in the cleavage of respective 7 and 8 at low content of CH3CN have been described. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 746–758, 2006  相似文献   

20.
The diffusion-limited binding kinetics of antigen in solution to antibody immobilized on a biosensor surface is analyzed within a fractal framework. Changes in the fractal dimension, Df observed are in the same and in the reverse directions as the forward binding rate coefficientk. For example, an increase in the concentration of the isoenzyme human creatine kinase isoenzyme MB form (CK-MB) (antigen) solution from 0.1 to 50 ng/mL and bound to anti-CK-MB antibody immobilized on fused silica fiber rods leads to increases in the fractal dimension Df from 0.294 to 0.5080, and in the forward binding rate coefficientk from 0.1194 to 9.716, respectively. The error in the fractal dimension Df decreases with an increase in the CK-MB isoenzyme concentration in solution. An increase in the concentration of human chorionic gonadotrophin (hCG) in solution from 4000 to 6000 mIU/mL hCG and bound to anti-hCG antibody immobilized on a fluorescence capillary fill device leads to a decrease in the fractal dimension Df from 2.6806 to 2.6164, and to an increase in the forward binding rate coefficientk from 3.571 to 4.033, respectively. The different examples analyzed and presented together indicate one means by which the forward binding rate coefficientk may be controlled, that is by changing the fractal dimension or the ‘disorder’ on the surface. The analysis should assist in helping to improve the stability, the sensitivity, and the response time of biosensors.  相似文献   

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