Microanalysis of “biometallic” compounds using nuclear and atomic activation

A novel method for the characterization of metal containing biological compounds has been developed which utilizes both nuclear activation [e.g.,¹²C(³He, α)¹¹C] and atomic activations (X-ray emission) induced by 8 MeV³He bombardment. Detection limits for carbon (≈1 μg), oxygen (≈1μg), and metals (1 to 10 ng for elements between P and Zn) were obtained under routine experimental conditions. The metal stoichiometry of six different compounds (alkaline phosphatase, amylase, carbonic anhydrase, diamine oxidase, my oglobin, vitamin B₁₂) were determined with typical relative precisions of ±25% for a 40 μg sample. A comparison of these ratios with carbon and metal measurements obtained by other methods showed a relative accuracy of 1 to 20%.     

The design and development of a multichannel atomic absorption spectrometer for the simultaneous determination of trace metals in hair

A multichannel atomic absorption spectrometer capable of analysing up to nine elements simultaneously in human hair has been designed. Light from an array of hollow-cathode lamps is passed through an electrically heated graphite tube into a direct reading spectrometer. The photomultiplier output is fed into a novel transient signalprocessing device which separates the absorption pulse from the continuous background and increases linear range and sensitivity. Solutions containing Ni, Co, Si, Mn, Al, Cu, Ag, Cr and Fe in nanogram and sub-nanogram amounts can be determined with reasonable precision.     

Possibilities for the simultaneous preconcentration and flame atomic absorption spectrometric determination of Cr(III) and Cr(VI) using a C18 column and sorption loop

The sorption loop as a preconcentration unit used so far in the low-pressure flow injection (FI) system was combined with the hydraulic high-pressure nebulizer (HHPN) and a high-pressure liquid chromatographic (HPLC) column. Thus, the sorption preconcentration of Cr(VI) can be coupled to a powerful sample introduction method or preconcentration techniques of Cr(III). The subsequent determination of the Cr(VI) content of the samples was carried out by flame atomic absorption (FAAS).     

A new neutron activation technique for simultaneous determination of inorganic and total mercury contents in human hair

A simple method for simultaneous determination of inorganic and total mercury contents in human hair by neutron activation analysis (NAA) has been developed. The method is based on the selective extraction of methylmercury from hair by hydrochloric acid. Thus, the residual phase containing inorganic mercury can be determined by NAA. Further, the methylmercury contents in hair samples are easily calculated by subtracting the inorganic mercury contribution from the total Hg simultaneously given by INAA. Several reference materials of human hair, including IAEA hair RM 085 and 086, Chinese hair RMs GBW 09101 and 07601, were analyzed by this method. Our results show that the method is reliable.     

A semi-automatic system for activation analysis using the WWR nuclear reactor

A semi-automatic pneumatic transport system for nuclear reactors is described. The sealed polyethylene capsules containing the sample are placed into transport containers. Ten such containers are placed manually into a feeding device. All subsequent operations (irradiation, removal of the capsule from the container, and transport of the capsule to the laboratory for activity measurement) are automated. Total time from the completion of irradiation to the beginning of measurement is 10–20 sec.     

Thermal characterization of hair using TG-MS combined thermoanalytical technique

Four amino acids and four different hair samples were studied in order to get information about the decomposition of human hair, using combined (TG-MS) and DSC techniques. The thermal stability of the investigated amino acid samples was different. Since they contain identical functional groups (-NH₂, -COOH) some common mass/charge units were identified. However, due to their different chemical composition remarkable differences have also been obtained. The results of the investigation of the amino acids were helpful to study the thermal fragmentation of the hair samples. In our experiments, the effect of the heating rates was also studied. This revised version was published online in July 2006 with corrections to the Cover Date.     

Frequency-modulated simultaneous multielement atomic absorption spectrometry using electrothermal atomizer and deuterium background correction

Characteristic data of the frequency-modulated simultaneous multielement atomic absorption spectrometry (FREMSAAS) using electrothermal atomizer with deuterium background correction, have been determined. The data obtained have been processed by using several statistical tests recommended for quality control purposes. The instrumentation has been presented as well as procedures of separating elements into measure groups and fixing of variable conditions. Detection limits, characteristic masses and working ranges have been given for the eleven elements examined. The data have been in good agreement to results obtained with conventional one-channel AAS instruments. The eleven elements have been simultaneously determined in a standard reference material (SRM) and all results are compatible with a 95% certainty with the certified values. FREMSAAS has been applied to a real sample.Dedicated to Professor Dr. Dieter-Klockow on the occasion of his 60th birthday     

Low power capacitively coupled plasma microtorch for simultaneous multielemental determination by atomic emission using microspectrometers

A new, low power capacitively coupled plasma microtorch (30 W, 13.56 MHz, 0.5 L min^?1 Ar) was investigated in conjunction with commercially available microspectrometers for the simultaneous multielemental analysis by atomic emission spectrometry of liquid samples without desolvation. Emission spectrum is simpler than in ICP-AES, the resonance lines are the most intense, so that a microspectrometer with FWHM of at least 1.5 nm is satisfactory for the record. The deviation from the Boltzmann distribution for Fe I has demonstrated the departure from the LTE in plasma. The non-spectral matrix effects of Li, Na, K, Ca and Mg on analytes emission are depressive and depend on matrix volatility, ionization potential of the interferent and analyte excitation energy. The detection limits (μg mL^?1) are in the range 0.003 (Li) and 1.5 (Mn). The use of the standard additions method allowed the simultaneous determination of elements in environmental certified reference materials with overall recovery of 95 ± 10% and relative standard deviation of 1.7–8.2%. Compared to the traditional ICP, the microtorch has a simple construction, runs at low argon flow and can be integrated in a portable system suitable for in-situ simultaneous determination of elements.     

Possibilities for separation and simultaneous determination of N-unsubstituted- and N-substituted nitroimidazoles and criteria for their identification

The N-unsubstituted nitroimidazoles have an imino hydrogen atom in contrast to the N-substituted derivatives, and react with hydroxide to give the yellow nitroimidazole anions. The difficulty of reducing the nitro-group in these anions, together with the shift of the absorption maximum to longer wavelengths makes it possible to analyse polarographically or spectrophotometrically a mixture of N-unsubstituted nitroimidazole with N-substituted derivatives. The presence of the N-unsubstituted nitroimidazole and the N-substituted derivatives is first established by chromatography. Other criteria are also proposed for distinguishing between these substances.     

Possibilities of simultaneous determination of lead and thallium in environmental and biological samples by microtron photon activation analysis with radiochemical separation

A method for simultaneous determination of lead and thallium by photon activation analysis with radiochemical separation using irradiation with bremsstrahlung produced by a 20 MeV microtron is described. The detection limits for 500-mg samples of 0.9 g·g^-1 and 0.15 g·g^-1 for lead and thallium, respectively, were achieved that are sufficiently low for the reliable determination of both elements at levels commonly occurring in environmental samples and at elevated levels in biological materials. The accuracy of the procedure developed was proved by analyses of a number of environmental and biological reference materials. Possibilities of detection limit improvements are also discussed.     

Determination of rare-earth elements by the simultaneous gamma-neutron activation analyses using a microtron

The combination of photon and neutron activation provides an effective method of analysis of rare earths and other elements. A mixed -neutron field is obtained with electron-to-gamma /e/ and gamma-to-neutron /n/ converters combined with a lucite moderator. The samples are activated simultaneously. The sensitivities of this method have been compared with neutron activation in a graphite moderator cube using the same microtron. The advantages and shortcomings of the method are discussed.Dedicated to Prof. V.D. Nefedov on the occasion of his 70th birthday     

Structural characterization of self-assembled monolayers of neoglycoconjugates using atomic force microscopy

Thiolated self-assembled monolayers of carbohydrates may serve as useful polyvalent tools to mimic the organized presentation of such molecules at the cell surface. SAMs presenting the disaccharide maltose as a neoglycoconjugate were produced, and the structure was studied by high resolution atomic force microscopy. The molecules form highly ordered structures on a gold (111) surface, with lattice parameters determined by the linker moiety rather than the headgroup.     

Neutron activation analysis of human hair for environmental purposes

The possibility of using human hair as a monitor for the pollution of the environment with metals is discussed. Analyzed are 15 cases by means of Instrumental Neutron Activation Analysis. Elements Se, Cu, Ca, Na, Mn and S in Bulgarian hair are compared with those from other countries. Analyzed cases are divided into two groups: metal burdened and nonburdened. A difference in Na, Ca and Mn content in hair of both groups is observed. A value of Mn is outlined which indicates with a high probability the metal burden of a person.     

Aerosol characterization and apportionment using cascade impactors and activation analysis

The use of particle-size distribution measurements and techniques for aerosol physical characterization, together with composition data for 30 elements, has led to useful deductions about the sources of airborne particulates. Collections with cascade impactors operated at three locations in Toronto, Canada, were analyzed by INAA and photonuclear activation (IPAA). The efficiency and reliability of impactors for aerosol size-distribution characterization was studied by scanning electron microscopy and calculating equivalent aerodynamic diameters; values obtained in this way were in close agreement with predicted values. Toronto aerosols exhibited both expected and unusual particle-size distribution patterns with many elements exhibiting either size distributions biased toward large (e.g. Al, Sc, Ti, Fe) or small particles (e.g. Br, Cl, Cu). Other elements (viz. Pb, Zn, As, Sb) exhibited different and unusual size distributions, presumably from different sources. Factor analysis and chemical mass balance (CMB) applied to data for a suburban site allowed emission source identification and aeorosol apportionment with a fair degree of certainty, and, preliminary results using factor analysis for size-fractionated samples, indicate a potential for relatively accurate source apportionment in more complex airsheds.     

The simultaneous determination of 235U and 239Pu using delayed neutron activation analysis

Delayed neutron activation analysis (DNAA) remains one of the most sensitive methods of nondestructively determining fissile materials in a variety of sample matrices, provided that the samples contain only a single fissile component. This has historically been the limiting factor in many applications of DNAA, and often chemically destructive methods of analysis have needed to be utilized for many real-world samples. This work seeks to develop a method that will allow for DNAA to be utilized on samples containing multiple fissile components. Initial efforts, presented here, show that using a multivariate linear regression model to describe the delayed neutron emission profile of an irradiated sample allows for the concurrent determination of fissile nuclides in samples containing both ²³⁵U and ²³⁹Pu, without chemical separations and using only a single counting step.     

Determination of aluminium and manganese in human scalp hair by electrothermal atomic absorption spectrometry using slurry sampling

Methods for the determination of aluminium and manganese in human scalp hair samples by electrothermal atomic absorption spectrometry using the slurry sampling technique were developed. Palladium and magnesium nitrate were used as chemical modifiers. Hair samples were pulverized using a zirconia vibrational mill ball, and were prepared as aqueous slurries. Determinations can be performed in the linear ranges of 1.9–150 μg l⁻¹ Al³⁺ and 0.03–10.0 μg l⁻¹ Mn²⁺. Limits of detection of 0.9 mg kg⁻¹ and 27.6 μg kg⁻¹ were obtained for aluminium and manganese, respectively. The analytical recoveries were between 99.6 and 101.8% for aluminium and in the 98.3–101.3% range for manganese. The repeatability of the methods (n=11), slurry preparation procedure and ETAAS measurement, was 16.0 and 7.9% for aluminium and manganese, respectively. The methods were finally applied to the aluminium and manganese determination in 25 scalp hair samples from healthy adults. The levels for aluminium were between 8.21 and 74.08 mg kg⁻¹, while concentrations between 0.03 and 1.20 mg kg⁻¹ were found for manganese.     

Copper ion-induced activation and asymmetric benzoylation of 1,2-diols: kinetic chiral molecular recognition

New catalytic ability of copper(II) ion has been exploited for monobenzoylation of 1,2-diols. The catalyst can be readily modified by ligation to acquire higher stereoselectivity. Highly effective kinetic resolution of dl-1,2-diols was achieved. The enantiodiscrimination process was clearly shown to be controlled by the kinetics of acylation of dl-1,2-diols. The catalytic method was successfully applied to asymmetric desymmetrization of meso-hydrobenzoin.     

Neutron activation for precise nuclear data

Techniques for extracting neutron flux parameters pertaining to the irradiation positions and nuclear data pertaining to the isotopes concemed from measured reaction rates have been developed. An adjustment procedure based on the generalized least squares method with incorporates the, evaluated literature nuclear data, estimates of flux parameters and the experimentally measured reaction rates using high resolution -ray spectrometry is applied. More precise values of the nuclear data, i.e., thermal neutron cross sections, resonance integrals and -ray emission probabilities are thus generated. The irradiation of a multi-element standard (MES) containing 24 elements is carried out in six diffieret positions in two diverse types of reactor in the UK and Russia. It is shown that the improvement in nuclear data is revelaed in moire than 90% of the cases.