Standardization of calibration procedures for quantification of gross alpha and gross beta activities using liquid scintillation counter

Simultaneous measurement of gross alpha and gross beta activities by liquid scintillation counting technique using LKB Wallac Quantulus 1220 liquid scintillation counter (LSC) equipped with Pulse Shape Analyzer (PSA) is described. Three sets of pure alpha and pure beta standards simulating the activity concentration values of real samples in terms of α/β activity ratios were used to calibrate the LSC. Calibration methodology for the Quantulus 1220 with respect to the above measurements using ²⁴¹Am and ⁹⁰Sr/⁹⁰Y standards of respective activity concentrations of ~25 dpm and ~10⁴ dpm is described in detail. Also highlighted the need to calibrate the LSC using another set of ²⁴¹Am and ⁹⁰Sr/⁹⁰Y standards of low and high activity concentrations respectively. The practicability and working performance of these calibration plots was checked by the validation trials with test samples spiked with ²⁴¹Am and ⁹⁰Sr/⁹⁰Y covering range of α/β activity ratios from 1:1 to 1:50.     

Radioactivity levels of <Superscript>238</Superscript>U and <Superscript>232</Superscript>Th,the α and β activities and associated dose rates from surface soil in Ulu Tiram,Malaysia

A survey was carried out to determine terrestrial gammaradiation dose rates, the concentration level of ²³⁸U and ²³²Th and α and β activities for the surface soil in Ulu Tiram, Malaysia A 125 measurements were performed using a NaI(T1) gamma-ray detector with crystal size of 1″ × 1″ on 15 soil samples collected from the site area about 102 km^{2 238}U and ²³²Th concentrations were determined in soils by using hyper pure germanium (HPGe) gamma-ray spectrometry. The activity of α and β from the surface soil was counted by using alpha beta counting system. The average value of ²³⁸U and ²³²Th concentrations in soil samples collected are 3.63±0.39 ppm within the range of 1.74±0.20 to 4.58±0.48 and 43.00±2.31 ppm within the range of 10.68±0.76 to 82 10±4.01 ppm, respectively. The average estimate of α and β activity in soil samples collected are 0.65±0.09 Bqg⁻¹ and 0.68±0.08 Bqg⁻¹, respectively. The average of terrestrial gamma-radiation dose rates measured in Ulu Tiram was found to be 200 nGy h⁻¹, within the range of 96 to 409 nGy h⁻¹. The population weighted outdoor annual effective dose was 1.2 mSv.     

Danube River Water Data Modelling by Multivariate Data Analysis

 A data set (48×19) consisting of Danube river water analytical data collected at Galati site, Romania, during a four-year period has been treated by principal components analysis (PCA). The PCA indicated that seven latent factors (“hardness”, “biochemical”, “waste inlets”, “turbidity”, “acidity”, “soil extracts” and “organic wastes”) are responsible for the data structure and explain over 80 % of the total variance of the system. Its complexity is further proved by the application of multiple linear regression analysis on the absolute principal components scores (APCS) where the contribution of each natural or anthropogenic sources in the factor formation is shown. The apportioning makes clear that each variable participates to a different extent to each source and, in this way, no pure natural or pure anthropogenic influence could be determined. No specific seasonality for the variables in consideration is found. Received January 24, 2001. Revision July 6, 2001.     

Fast LC analysis of the α-acid content of “fresh” and “aged” hops

Summary A quaternary mobile phase was optimized in conjunction with Fast LC techniques to separate α and β acids extracted from hops in less than 4 minutes. The method is proposed for automated analysis of large numbers of hop samples and its usefulness is demonstrated by comparing α-acid levels obtained by liquid chromatographic and conductometric techniques. Both assays provided similar values for “fresh” hops but in “aged” hops liquid chromatography showed a lower level of α-acids.     

Multivariate statistical analysis of coastal sediment data

Multivariate statistical analysis of sediment data (information matrix 123 × 16) from the Gulf of Mexico, USA shows that the data structure is defined by four latent factors conditionally called “inorganic natural”, “inorganic anthropogenic”, “bioorganic” and “organic anthropogenic” explaining 39.24%, 23.17%, 10.77% and 10.67% of the total variance of the data system, respectively. The receptor model obtained by the application of the PCR approach makes it possible to apportion the contribution of each chemical component for the latent factor formation. A separation of the contribution of each chemical parameter is achieved within the frames of “natural” and “anthropogenic” origin of the respective heavy metal or organic matter to the sediment formation process. This is a new approach as compared to the traditional “one dimensional” search with a limited number of preliminary selected tracer components. The model suggested divides natural from anthropogenic influences and allows in this way each participant in the sediment formation process to be used as marker of either natural or anthropogenic effects. Received: 20 March 1999 / Revised: 1 June 1999 / Accepted: 3 June 1999     

Multivariate statistical analysis of coastal sediment data

Multivariate statistical analysis of sediment data (information matrix 123 × 16) from the Gulf of Mexico, USA shows that the data structure is defined by four latent factors conditionally called “inorganic natural”, “inorganic anthropogenic”, “bioorganic” and “organic anthropogenic” explaining 39.24%, 23.17%, 10.77% and 10.67% of the total variance of the data system, respectively. The receptor model obtained by the application of the PCR approach makes it possible to apportion the contribution of each chemical component for the latent factor formation. A separation of the contribution of each chemical parameter is achieved within the frames of “natural” and “anthropogenic” origin of the respective heavy metal or organic matter to the sediment formation process. This is a new approach as compared to the traditional “one dimensional” search with a limited number of preliminary selected tracer components. The model suggested divides natural from anthropogenic influences and allows in this way each participant in the sediment formation process to be used as marker of either natural or anthropogenic effects. Received: 20 March 1999 / Revised: 1 June 1999 / Accepted: 3 June 1999     

Applications of ESR and CIDEP to mechanistic studies of lignin chemistry

Using time-resolved CIDEP and conventional ESR as well as optical studies much can be elucidated concerning the initial photochemical reactions of lignin model compounds such as α-guaiacoxyacetoveratrone and α-guaiacoxy-β-propioveratrone. The resulting transient radicals are models for intermediates in the processes of photoyellowing of lignin containing mechanical pulps and papers. Model solution experiments which produce evidence for the roles of free radicals in reductive bleaching of mechanical pulps and in the oxidative aging of papers are also described. The more thorough understanding of these complex processes allows the development of strategies to try to “protect” mechanical pulps and papers from light and thermally induced damage and to “repair” any damage which invevitably occurs.     

The mechanism of spin polarization in aromatic free radicals

 The spin-polarization mechanism in aromatic systems is analyzed with reference to the prototypical phenoxyl, cyclohexadienyl and benzyl radicals. In particular, a decomposition into “first-order” and “second-order” contributions is proposed, which helps to rationalize the different nature of the spin density for atoms in α or in β positions with respect to the radical center. The different weights of the two contributions are discussed on the basis of Hartree–Fock and density functional computations. Received: 17 September 1999 / Accepted: 3 February 2000 / Published online: 29 June 2000     

Radiological characterization of commercially available “radon spa sources”

Nowadays, artificial “radon spa sources” for home baths are commercially available. Although these sources could give a potential radiation exposure to the users, few studies have been reported on their radiological measurements. In the present study, five types of radon spa sources were collected and their radiological characterization was investigated. The followings were estimated for these samples: (1) radon emanation coefficients (dry and water-saturated conditions), (2) surface γ-ray dose rate, (3) surface count rates for α- and β-rays, (4) activity concentrations of ²²⁶Ra, ²³²Th and ⁴⁰K, and (5) concentrations of radon and thoron generated from the sources located in an air flow system. The activity concentrations were very high (except for one sample (named “sample B”), although radon emanation coefficient was low compared with soil. This leads to high concentrations of radon/thoron generated from the sample. The maximum surface γ-ray dose rate was observed for sample A (2.7 μGy h⁻¹). If people stay very close to the sample for a long time, the exposure might be significant.     

Determination of Testosterone Metabolites in Rat Hepatocytes with and without Cryopreservation by On-Line SPE Column-Switching LC and MS Detection

In a recently published paper development of a sensitive automated “on-line” solid-phase extraction (SPE)/RP-HPLC assay for 6β-hydroxytestosterone (6β-OHT) with corticosterone as the internal standard (IS) was reported and its potential for quantification of various testosterone metabolites in culture media reflecting metabolic activity of cultured human and animal hepatocytes demonstrated [1]. In this following contribution the technique has been extended to determination of another five testosterone metabolites in cultured rat hepatocytes using an identical “on-line” SPE/RP-HPLC procedure and detection by tandem MS-MS with an atmospheric pressure chemical ionization (APCI) source in the selected reaction monitoring (SRM) mode as that described in [1]. All six testosterone metabolites, namely 2α-OHT, 2β-OHT, 6α-OHT, 6β-OHT, 7α-OHT and 16α-OHT, could be sufficiently separated from each other and thus an unequivocal assignment to the individual structures was achieved. Validation data are presented specifying the limits of quantitation as well as the mean values of the coefficients of variation (CV) for the target analytes and the accuracy obtained at five different days. Regio- and stereoselective testosterone hydroxylation by rat hepatocytes was measured in a long-term culture system with and without exposure to rifampicin as an inducer of liver CYP 3A4 activity. In addition, testosterone hydroxylation was analyzed in cultures of cryopreserved hepatocytes that had been stored at −196 °C. The rat hepatocytes were cultured after thawing for up to 11 days and induction of testosterone hydroxylase activity could be demonstrated in cultures which underwent a new cryopreservation protocol. This paper is dedicated to Professor Hinrich Cramer on the occasion of his 75th birthday.     

New data on derivatives of 1-alkoxyaziridine-2-carboxylic acids

Esters of β-alkoxyamino-α-bromopropionic acids were obtained by reaction of α,β-dibromopropionic acid esters with alkoxyamines in the presence of triethylamine at 20°C for 1 month. When the products are refluxed in acetonitrile in the presence of triethylamine, they are converted to aziridines. Selective amidation of the alkoxyaziridines with excess dimethylamine in absolute methanol in the presence of sodium methoxide leads to enrichment with the cis isomer. The parameters of inversion of the nitrogen atom in the alkoxyaziridines were determined. Communication 20 from the series “Asymetric Unbridged Nitrogen”; see [1] for communication 19. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 212–215. February, 1980.     

Broadband dielectric spectroscopy of the inter- and intramolecular dynamics of a series of random polyester copolymers

Broadband dielectric spectroscopy (1–10⁶ Hz, 183–423 K) and differential scanning calorimetry are employed to analyze the inter- and intramolecular dynamics of a series of random copolymers based on poly(ethylene terephthalate) and poly(1,4-cyclohexylene dimethylene terephthalate). In addition to an interfacial relaxation (α*-process), three dielectric relaxation processes are observed: The α-relaxation (“dynamic glass transition”) and two secondary relaxations (β- and β*-relaxations). The α-relaxation depends sensitively on the composition of the copolymer and shows a rapid slowing down with increasing content of cyclohexylene dimethylene (CHDM) linkages. Besides the β-relaxation, attributed to local motion of the ester group, an additional process (β*-relaxation) is observed on introducing the CHDM linkages. Increasing the content of the latter reduces the strength of the β-relaxation strongly and increases its activation energy by more than 30%. This proves that owing to interactions between the cylohexylene rings and the ester group the β-relaxation no longer has local character only. Received: 28 September 2000 Accepted: 29 January 2001     

The role of different soil sample digestion methods on trace elements analysis: a comparison of ICP-MS and INAA measurement results

The measurement of trace-element concentration in soil, sediment and waste, is generally a combination of a digestion procedure for dissolution of elements and a subsequent measurement of the dissolved elements. “Partial” and “total” digestion methods can be used in environmental monitoring activities. To compare measurement results obtained by different methods, it is crucial to determine and to maintain control of the bias of the results obtained by these methods. In this paper, ICP-MS results obtained after matrix digestion with modified aqua regia (HCl+HNO₃+H₂O₂) method and two “total” digestion methods (microwave aqua regia+HF and HNO₃+HF) are compared with those obtained by instrumental neutron activation analysis, a non-destructive analytical method for the determination of the total mass concentrations of inorganic components in environmental matrices. The comparison was carried out on eight agricultural soil samples collected in one test area and measured by k₀-INAA and ICP-MS to determine As, Co, Cr, Sb and Zn mass concentration. The bias of results for As, Cd, Co, Cr, Cu, Ni, Pb, Sb and Zn of the three digestion methods were assessed using selected measurement standards. This paper highlights that the digestion procedure is an integral part of the measurement and can affect the measurement result in environmental analysis.     

Multivariate statistical assessment of polluted soils

This study deals with the application of several multivariate statistical methods (cluster analysis, principal components analysis, multiple regression on absolute principal components scores) for assessment of soil pollution by heavy metals. The sampling was performed in a heavily polluted region and the chemometric analysis revealed four latent factors, which describe 84.5 % of the total variance of the system, responsible for the data structure. These factors, whose identity was proved also by cluster analysis, were conditionally named “ore specific”, “metal industrial”, “cement industrial”, and “steel production” factors. Further, the contribution of each identified factor to the total pollution of the soil by each metal pollutant in consideration was determined.     

Size scaling behaviour in protein domains belonging to the all-α, all-β, α / β, and α?+?β folding classes

We studied the size scaling behaviour in an ensemble of 8,614 non-redundant protein domains belonging to the all-α, all-β, α / β, and α + β folding classes. We find that the most compact structural domains can be characterized by an effective exponent ν _eff  = 0.39 ± 0.01, which is larger than the value for “collapsed-polymers,” i.e., ν = 1/3. We also show that the global ν _eff -exponent is an average of the scaling regimes for short and long compact chains, where the values change from ν _eff ≈ 0.37 to ν _eff ≈ 0.45 at chain length of ca. 269. A transition from short-chain to long-chain scaling behaviour is found in all major folding classes, over a window of chain lengths between 216 and 269 residues. In addition, variations in scaling exponent with respect to folding class indicates that the smallest domains in the (all-β) and (α / β) families appear to be more compact structures than the smallest (all-α)- and (α + β)-domains.     

Production and purification of CGTase of alkalophylicBacillus isolated from Brazilian soil

Alkalophylic bacilli that produce cyclodextringlycosyltransferase (CGTase) were isolated from Brazilian soil, with a scheme of two plating steps. In the first step, the bacterial isolate forms a halo in the cultivation medium that contains γ-cyclodextrin (CD) complexing dyes. The CGTase of an isolate was purified 157-fold by biospecific affinity chromatography, with β-CD showing a mol wt of 77,580 Daltons. It produces a γ- to β-CD ratio of 0.156 and a small amount of α-CD, using maltodextrin 10% as substrate, at 50°C, pH 8.0 and 22 h reaction time, reaching 21.4% conversion of the substrate to cyclodextrins. In the second screening step, the isolates chosen give larger halos with β-CD complexing dyes, and smaller halos with β-CD complexing dyes, leading to a 30% improvement in γ-CD selectivity, although at lower total yield for cyclodextrins (11.5%).     

Epoxy derivatives of {(5-[(1-Phenylethyl)aminocarbonyl]-cyclopent-2-en-1-yl}methyl acetates

Diastereoisomeric [(1R,5S)-5-“[(1R)-1-phenylethyl]aminocarbonyl”cyclopent-2-en-1-yl]methyl acetate and [(1S,5R)-5-“[(1R)-1-phenylethyl]aminocarbonyl”cyclopent-2-en-1-yl]methyl acetate reacted with m-chloroperoxybenzoic acid to give the corresponding stereoisomeric α- and β-epoxy derivatives, which were identified on the basis of their spectral parameters.     

Stability and reproducibility of gel-suspension samples for the liquid scintillation counting of14C using N-lauroyl-L-glutamic-α,γ-dibutylamide

Stability and reproducibility of gel-suspension samples were investigated in order to evaluate the characteristic feature of the gel-suspension method for¹⁴C activity measurement. Commercially available gelling agent, N-lauroyl-L-glutamic-α,γ-dibutylamide, was used for the gelformatio of the samples. No change of the counting rate for the gel-suspension sample was observed for more than 2 years after the sample preparation. Four samples used for checking the reproducibility of the sample preparation method. The same values were obtained for the counting rate of¹⁴C activity within the counting error. No change of the counting rate was observed for the “re-gelated” sample. These results show that the gel-suspension method is appropriate for the¹⁴C activity measurement by the liquid scintillation method and is useful for a long-term preservation of the sample for repeated measurement.     

Structure of guest-host complexes of β-cyclodextrin with arenes: a quantum-chemical study

The structure of β-cyclodextrin (β-CD), as well as the structure and energetics of β-CD-naphthalene, β-CD-fluorene, β-CD-phenanthrene, β-CD-cyclohexane (1:1), and β-CD-naphthalene (2:2) inclusion complexes was studied by the semiempirical MNDO/PM3 method. Calculations of a β-CD-naphthalene-cyclohexane (1:1:1) complex were also performed. The minimum heat of formation was found for the symmetric β-CD conformation withC ₇ symmetry axis. The structure is stabilized by the ring of interunit H-bonds formed by the protons of the 2-OH groups and the O atoms of the 3′-OH groups of the glucose units. Preferableness of this orientation of interunit H-bonds was confirmed byab initio calculations of the molecule of α-(1–4)-glucobiose (maltose) in the MP2/6-31G(d,p)//6-31G(d,p) approximation. The formation of any inclusion compounds of β-CD with arenes is energetically favorable: the complexation energy varies in the range −9 to −12 kcal mol⁻¹. Among complexes with naphthalene, that of composition 2:2 is the most energetically favorable, which is in agreement with experimental data. In this complex, β-CD exists as a dimer of the “head-to-head” type, in which both partners are linked by a system of H-bonds. The structure of the “head-to-head” dimer of β-CD was simulated byab initio calculations of the H-bonded dimer of α-d-glucose in the RHF/6-31G(d,p) approximation. In the dimer, both components are linked by a pair of H-bonds formed by the protons of the 3-OH groups and the O atoms of the, 2-OH groups. The dimerization energies obtained fromab initio and semiempirical MNDO/PM3 and AM1 calculations differ by about 2.5 times (8.6vs 3.2 and 3.8 kcal mol⁻¹, respectively).     

Molecular dynamics studies of α-helix stability in fibril-forming peptides

Diseases associated with protein fibril-formation, such as the prion diseases and Alzheimer’s disease, are gaining increased attention due to their medical importance and complex origins. Using molecular dynamics (MD) simulations in an aqueous environment, we have studied the stability of the α-helix covering positions 15–25 of the amyloid β-peptide (Aβ) involved in Alzheimer’s disease. The effects of residue replacements, including the effects of Aβ disease related mutations, were also investigated. The MD simulations show a very early (2 ns) loss of α-helical structure for the Flemish (Aβ(A21G)), Italian (Aβ(E22K)), and Iowa (Aβ(D23N)) forms associated with hereditary Alzheimer’s disease. Similarly, an early (5 ns) loss of α-helical structure was observed for the Dutch (Aβ(E22Q)) variant. MD here provides a possible explanation for the structural changes. Two variants of Aβ, Aβ(K16A,L17A,F20A) and Aβ(V18A,F19A,F20A), that do not produce fibrils in vitro were also investigated. The Aβ(V18A,F19A,F20A) initially loses its helical conformation but refolds into helix several times and spends most of the simulation time in helical conformation. However, the Aβ(K16A,L17A,F20A) loses the α-helical structure after 5 ns and does not refold. For the wildtype Aβ(1–40) and Aβ(1–42), the helical conformation is lost after 5 ns or after 40 ns, respectively, while for the “familial” (Aβ(A42T)) variant, the MD simulations suggest that a C-terminal β-strand is stabilised, which could explain the fibrillation. The simulations for the Arctic (Aβ(E22G)) variant indicate that the α-helix is kept for 2 ns, but reappears 2 ns later, whereafter it disappears after 10 ns. The MD results are in several cases compatible with known experimental data, but the correlation is not perfect, indicating that multimerisation tendency and other factors might also be important for fibril formation.