Assay of cholinesterase in an electrode system with an immobilized substrate

A rapid, simple method for the measurement of cholinesterase based on an immobilized acetylcholine substrate is described. Each assay requires only 3 min and the immobilized substrate can be used for 10 assays with excellent results; the substrate can then be renewed easily and quickly. The precision obtained (2.5 %) is the same as that possible with the soluble substrate system.     

Fluorescence Lifetimes: Effect of Precision of Relaxation Times from Fluorescence Depolarization Data

Abstract

The fluorescence lifetime τ enters into the Perrin-Weber equation used to determine rotational relaxation times of proteins by the steady-state depolarization method. If is either too short or too long, the relaxation time cannot be measured with precision. With reasonable assumptions as to photometric precision, it has been possible to compute the precision of relaxation time assays for different lifetime:relaxation time ratios, thus also determining the “optimum” lifetimes for different systems. These results provide a basis for designing experiments requiring optimal conditions, and also provide insight into the amount of allowable deviation from optimal conditions. The short lifetimes of intrinsic protein fluorescence can often be used to determine the global relaxation rate of the macromolecule with acceptable precision.     

Purity of potassium hydrogen phthalate, determination with precision coulometric and volumetric titration--a comparison

The mass fraction of potassium hydrogen phthalate (KHP) from a specific batch was certified as an acidimetric standard. Two different analytical methods on a metrological level were used to carry out certification analysis: precision constant current coulometric and volumetric titration with NaOH. It could be shown that with a commercial automatic titration system in combination with a reliable software for the end-point detection it is possible to produce equivalent results with the same accuracy in comparison to a definite method handled by a fundamental apparatus for traceable precision coulometry. Prerequisite for titrations are that a high number of single measurement are applied which are calibrated with a high precision certified reference material.     

Comparative sampling trials with dioxin samplers

Conclusions Dioxin sampling is a complicated operation which needs to be carried out carefully with suitable specified equipment in a correct manner.The intra-laboratory precision can be within 10%. However the interlaboratory precision is very poor.There is an urgent need for certified analytical standards and reference materials to be made available for dioxin analysis at both high and low levels.Samplers without flexible links should be used whereever possible. No new sampling positions on plant with dioxin emission limits should be designed which require the use of flexible links.Regular dioxin measurement is a significant cost on small businesses where absoulte annual emissions are low but the concentrations may be above 0.1 ng TEO m^–3.     

Flie?injektionsanalyse in der Bodenuntersuchung und Pflanzenanalyse

Summary It could be shown that the flow injection technique can be well introduced in labs which need a high sample throughput without any loss of precision. For normal labs with agrochemical tasks it is possible to adapt the proposed flow injection methods for nitrogen and phosphorus. For the determination of ammonia in juices and musts flow injection is better in precision and faster than the conventional methods. The determination of nitrate in plant extracts can be performed without any clean-up of the crude extract by introducing a dialysis cell in the normal flow injection system. For the determination of proline and arginine methods were developed for flow injection. Both are selective with a high precision and crude plant extracts can be injected for determination. Flow diagrams and equipment parameters are described.     

Potentiometric titration of fluoride,sulfate, chromate,molybdate, tungstate,oxalate, phosphate,pyrophosphate and hexacyanoferrate(II) ions with lead(II) solutions and a fluoride-selective electrode

A semi-automatic potentiometric method is described for the direct titration of fluoride with lead(II) solutions in the presence of added chloride. Sulfate, chromate, molybdate, tungstate, oxalate, phosphate, pyrophosphate, and hexacyanoferrate(II) are titrated similarly in the presence of added chloride and fluoride. A fluoride-selective electrode is used to detect the end-points. Fluoride in the range 0.57–5.7 mg can be determined with a precision of about 0.3%. The other ions can be determined in the range 0.025–0.30 mmol with a precision of 0.5–1%.     

Gamma ray spectroscopy with ultra-high precision

The energy of gamma rays emitted after thermal neutron capture can nowadays be measured with parts-per-million precision. This precision allows one to measure tiny Doppler effects caused by recoil due to the preceding emission of gamma rays or neutrinos. The study of the Doppler profiles of gamma rays has given rise to new applications in nuclear and solid state physics     

The determination of low d5-phenylalanine enrichment (0.002-0.09 atom percent excess), after conversion to phenylethylamine, in relation to protein turnover studies by gas chromatography/electron ionization mass spectrometry.

A gas chromatography/mass spectrometry (GC/MS) method for measuring very low levels of enrichment of d5-phenylalanine (0.002-0.09 atom percent excess) is described. This method makes it possible to determine the enrichment of amino acid incorporated into tissue protein during studies of protein synthesis in man. Phenylalanine is enzymatically converted to phenylethylamine and the d5-enrichment is measured in the heptafluorobutyryl derivative by selective-ion recording under electron ionization conditions. The coefficients of variation for muscle-protein hydrolysate samples enriched with d5-phenylalanine at the 0.005 and 0.05 atom percent excess levels were 6.0 and 1.2%, respectively. This precision at low enrichment and the small amount of protein needed (about 1 mg) provide real advantages for clinical studies of tissue protein synthesis. Moreover, in contrast to the conventional approach which uses GC/MS for plasma amino acids (typically 2-20 atom percent excess) but gas isotope-ratio mass spectrometry for protein-bound amino acids, the enrichment of both plasma-free and protein-bound d5-phenylalanine can be measured with a single instrument.     

Comparative study on the precision of potentiometric techniques applied with ion-selective electrodes: Part 1. Direct techniques

The measurement techniques used with ion-selective electrodes, e.g. standard edition, double known addition, known subtraction, etc., are summarized. In each case, the error in the unknown concentration measured (c_x) can be characterized by the term [σ(C_x)/C_x]/σ(E) where σ(E) is the standard deviation of the potential measurement. The formulae developed make it possible to calculate the expected error for any strategy of standard addition or subtraction and to optimize precision by proper selection of the concentration and volumes of standard solutions.     

Direct computation of general chemical energy differences: Application to ionization potentials, excitation, and bond energies

Chemists are mainly interested in energy differences. In contrast, most quantum chemical methods yield the total energy which is a large number compared to the difference and has therefore to be computed to a higher relative precision than would be necessary for the difference alone. Hence, it is desirable to compute energy differences directly, thereby avoiding the precision problem. Whenever it is possible to find a parameter which transforms smoothly from an initial to a final state, the energy difference can be obtained by integrating the energy derivative with respect to that parameter (cf. thermodynamic integration or adiabatic connection methods). If the dependence on the parameter is predominantly linear, accurate results can be obtained by single-point integration. In density functional theory and Hartree-Fock, we applied the formalism to ionization potentials, excitation energies, and chemical bond breaking. Example calculations for ionization potentials and excitation energies showed that accurate results could be obtained with a linear estimate. For breaking bonds, we introduce a nongeometrical parameter which gradually turns the interaction between two fragments of a molecule on. The interaction changes the potentials used to determine the orbitals as well as the constraint on the orbitals to be orthogonal.     

Direct determination of molybdenum in mineral waters by atomic absorption spectrometry with electrothermal atomization

A new method for the direct determination of molybdenum by ETA-AAS in mineral waters without prior separation or concentration is proposed. With careful control of the graphite furnace conditions selective volatilization of the salt matrix is successfully attained. The possible spectroscopic interference due to common metals as well as the reproducibility, precision and repeatability of the method has been studied and the molybdenum content of 21 mineral waters measured.     

Utilization of flow injection with hydrazine reduction and photometric detection for the determination of nitrate in rain-water

The hydrazine reduction method for determination of nitrate at the parts per million level is adapted to flow injection sample processing of rain-water. Reagent composition and physical variables were evaluated and optimized. Forty samples per hour can be processed. A precision of better than 3% is possible in the range of 1.0–10.0 ppm nitrate. Results for nitrate obtained from 9 rain-water samples agreed favorably with those determined by ion chromatography.     

Spectroscopy of growing and evaporating water droplets: exploring the variation in equilibrium droplet size with relative humidity

We demonstrate that the thermodynamic properties of a single liquid aerosol droplet can be explored through the combination of a single-beam gradient force optical trap with Raman spectroscopy. A single aqueous droplet, 2-6 microm in radius, can be trapped in air indefinitely and the response of the particle to variations in relative humidity investigated. The Raman spectrum provides a unique fingerprint of droplet composition, temperature, and size. Spontaneous Raman scattering is shown to be consistent with that from a bulk phase sample, with the shape of the OH stretching band dependent on the concentration of sodium chloride in the aqueous phase and on the polarization of the scattered light. Stimulated Raman scattering at wavelengths commensurate with whispering gallery modes is demonstrated to provide a method for determining the size of the trapped droplet with nanometer precision and with a time resolution of 1 s. The polarization dependence of the stimulated scatter is consistent with the dependence observed for the spontaneous scatter from the droplet. By characterizing the spontaneous and stimulated Raman scattering from the droplet, we demonstrate that it is possible to measure the equilibrium size and composition of an aqueous droplet with variation in relative humidity. For this benchmark study we investigate the variation in equilibrium size with relative humidity for a simple binary sodium chloride/aqueous aerosol, a typical representative inorganic/aqueous aerosol that has been studied extensively in the literature. The measured equilibrium sizes are shown to be in excellent agreement with the predictions of K?hler theory. We suggest that this approach could provide an important new strategy for characterizing the thermodynamic properties and kinetics of transformation of aerosol particles.     

Direct measurement of homovanillic, vanillylmandelic and 5-hydroxyindoleacetic acids in urine by capillary electrophoresis

Separation conditions in CE, with a neutral coated capillary and reversed polarity, have been optimised to make direct measurement of vanillylmandelic acid, homovanillic acid and 5-hydroxyindoleacetic acid possible in urine samples without pre-treatment. The method developed has been validated, presenting adequate parameters for linearity, accuracy and precision. Detection limits range from 0.03 to 2.5 microM. Finally the method has been applied to urine samples taken from patients, both adults and children, in hospital. Some of them were also measured by immunoassay and HPLC-electrochemical detection and results have been compared.     

Mass-spectrometric multielement analysis of copper and copper-base alloys, with electrical detection

Relative sensitivity coefficients have been determined for 21 elements in copper and its alloys, with iron as an internal standard, by spark-source mass-spectrometry with electrical detection and magnetic peak-switching. Twenty calibration standards ranging from pure copper to 60%-copper alloys were used. The sensitivity coefficients measured appear to be independent of the elemental concentration and are obtained with a mean precision of 15%.     

巯基棉富集分离分光光度法测定尿硒含量

为探索用巯基棉富集分离分光光度法测定尿硒含量的最佳实验条件,在表面活性剂吐温-80溶液存在下,改变酸度、温度、显色剂用量测定了尿样硒含量。结果表明,该法准确度、精密度高,用于尿硒、血硒含量测定,均能收到满意效果。     

An inductively coupled plasma-time-of-flight mass spectrometer for elemental analysis. Part III: Analytical performance

A time-of-flight mass spectrometer (TOFMS) was evaluated as a mass analyzer for inductively coupled plasma mass spectrometry (ICP-MS). The long-term drift of signals was in the range of 7–8% relative standard deviation, whereas the short-term precision was between 5 and 20%, somewhat worse than is typically reported for commercial ICP-MS instruments (5%). However, precision can be improved considerably in the TOFMS by ratioing isotopic peaks or through internal standardization, a consequence of its ability to extract all measured ions simultaneously from the inductively coupled plasma. This feature was demonstrated by monitoring the ²⁰⁶Pb/²⁰⁸Pb ratio with boxcar averagers. In this ratioing mode, precision was improved to approximately 0. 5%. Detection limits were measured with two alternative signal processing systems: (1) discriminator-gated integration and (2) integration of digitized spectra. Both methods improved the signal-to-noise ratio by a factor of from 10 to 100, although detection limits were still 1–2 orders of magnitude poorer for most elements than from the best commercial ICP-MS instruments. The dynamic range of the discriminator-gated integration system is over 4 orders of magnitude, but can be extended to 10⁶ with planned increases in primary ion-beam current, which is currently 10–100 times lower than is found in other instruments. Virtually simultaneous multielement and multiisotope analysis is possible for masses from ⁷Li to ²⁰⁹Bi with minimal mass bias and detection limits on the 0. 4–2-ppb level.     

催化裂解-金汞齐富集-冷原子吸收光谱仪测定土壤样品中总汞含量

为避免汞消解过程中产生的蒸发损失及前处理过程中产生器具与样品污染,通过配制汞总量为0～2、0～15和25～1 023 ng的三种不同汞浓度系列的标准工作曲线,选取9个土壤样品、3种国家土壤有证标准物质,同一样品分别进行6组平行测定,并抽取3个土壤样品进行3种不同浓度加标回收实验,以对其方法精密度和准确度进行论证,建立了催化裂解-金汞齐富集-冷原子吸收光谱法即直接测汞仪测定土壤样品中汞含量的方法。结果显示,仪器信号值与Hg总量之间均呈良好的线性关系。根据仪器多次测定空白数据结果,按照称样量0.1 g计算,方法检出为0.09 ng/g;平行测定结果相对标准偏差均小于10%,土壤标准物质测定值与参考值均相符,不同浓度的加标回收率范围为69.0%～97.0%。方法可用于批量土壤样品中汞含量的快速测定,精密度和准确度可满足测定要求,且实验过程中无需前处理消解,操作方便、快速高效。     

Determination of photopeak energy in instrumental neutron activation analysis

The precision and accuracy of the peak energy allocation in γ-ray spectrometry govern the subsequent computer processing of the data. By applying the main procedures for peak energy determination to a well-defined case, it is possible to define the minimal statistical uncertainties to be expected. The systematic bias of the energies obtained is caused mainly by changes in the total count rate. A correction can be applied based on the pulser peak. From the precision and the accuracy of the peak energy determination, the scanning width for automatic peak indexing follows.     

The determination of cadmium,copper, lead and thallium in human liver and kidney tissue by flame atomic absorption spectrometry after enzymatic digestion

Digestion of human liver and kidney tissue by the proteolytic enzyme subtilisin provides suitable solutions for direct determinations of Cd, Cu, Pb and Tl. Good precision and accuracy are demonstrated. Normal concentrations of Cd and Cu can be determined in these tissues; the poorer sensitivity for Pb and Tl precludes determinations of normal levels but typical concentrations found in acute poisoning can be measured. The metal concentrations in tissue digest solutions are stable for at least one month at 5°C.