Determination of 99Tc in bentonite clay samples using inductively coupled plasma mass spectrometry

A method was developed for the determination of ⁹⁹Tc at low concentrations in clay samples. The chemical treatment of the samples prior to chemical separation and analysis comprised leaching with sulphuric acid/ sodium bromate. After leaching, pertechnetate was extracted with Alamine-336/chloroform and then back-extracted into nitric acid. Detection was carried out using inductively coupled plasma mass spectrometry, ICP-MS. The instrumental detection limit was 0.45 pg/mL, which corresponds to 0.28 mBq/mL. With the use of a desolvating nebuliser, the detection limit was lowered by about a factor of five. The results were compared with a method using radiometric detection. Received: 16 April 1998 / Revised: 12 June 1998 / Accepted: 16 June 1998     

On the structure and dynamics of the hydrated sulfite ion in aqueous solution--an ab initio QMCF MD simulation and large angle X-ray scattering study

Theoretical ab initio quantum mechanical charge field molecular dynamics (QMCF MD) formalism has been applied in conjunction to experimental large angle X-ray scattering to study the structure and dynamics of the hydrated sulfite ion in aqueous solution. The results show that there is a considerable effect of the lone electron-pair on sulfur concerning structure and dynamics in comparison with the sulfate ion with higher oxidation number and symmetry of the hydration shell. The S-O bond distance in the hydrated sulfite ion has been determined to 1.53(1) ? by both methods. The hydrogen bonds between the three water molecules bound to each sulfite oxygen are only slightly stronger than those in bulk water. The sulfite ion can therefore be regarded as a weak structure maker. The water exchange rate is somewhat slower for the sulfite ion than for the sulfate ion, τ(0.5) = 3.2 and 2.6 ps, respectively. An even more striking observation in the angular radial distribution (ARD) functions is that the for sulfite ion the water exchange takes place in close vicinity of the lone electron-pair directed at its sides, while in principle no water exchange did take place of the water molecules hydrogen bound to sulfite oxygens during the simulation time. This is also confirmed when detailed pathway analysis is conducted. The simulation showed that the water molecules hydrogen bound to the sulfite oxygens can move inside the hydration shell to the area outside the lone electron-pair and there be exchanged. On the other hand, for the hydrated sulfate ion in aqueous solution one can clearly see from the ARD that the distribution of exchange events is symmetrical around the entire hydration sphere.     

Debundling and dissolution of single-walled carbon nanotubes in amide solvents

Wet chemical methods involving ultrasound and amide solvents were used to purify and separate large bundles of single-walled carbon nanotubes (SWNTs) into individual nanotubes that could then be transported to silicon or mica substrates. The SWNTs studied were produced by the arc-discharge process. Dry oxidation was used in an initial step to remove amorphous carbon. Subsequently, two acid purification schemes were investigated (HCl- and HNO(3)-reflux) to remove the metal growth catalyst (Ni-Y). Finally, ultrasonic dispersion of isolated tubes into either N,N-dimethylformamide (DMF) or N-methyl-2-pyrrolidone (NMP) was carried out. Raman scattering, atomic force microscopy (AFM), and electron microscopy were used to study the evolution of the products. Raman scattering was used to probe possible wall damage during the chemical processing. We found that both HCl and HNO(3) could be used to successfully remove the Ni-Y below approximately 1 wt %. However, the HNO(3)-reflux produced significant wall damage (that could be reversed by vacuum annealing at 1000 degrees C). In the dispersion step, both amide solvents (DMF and NMP) produced a high degree of isolated tubes in the final product, and no damage during this dispersion step was observed. HNO(3)-refluxed tubes were found to disperse the best into the amide solvents, perhaps because of significant wall functionalization. AFM was used to study the filament diameter and length distributions in the final product, and interesting differences in these distributions were observed, depending on the chemical processing route.     

O-acetyl galactoglucomannan esters for barrier coatings

A major enhancement of grease and water vapor barrier properties was accomplished with a 1–10 g/m² coating of O-acetyl galactoglucomannan (GGM) ester or with GGM coatings applied as water dispersions on cartonboard. GGMs were esterified with phthalic and benzoic anhydrides, respectively. The novel phthalic esters of GGM (GGM-Ph) were characterized with HPLC, NMR, and matrix-assisted laser desorption/ionization with mass spectrometry (MALDI-TOF-MS). The degree of substitution of GGM-Ph was obtained by ¹H NMR, ¹³C NMR, and HPLC. The GGM esters and GGM were coated onto cartonboard, and they demonstrated good moisture and very good grease resistance even with thin 1–3 g/m² coatings. The time for penetration of 0.1 % rapeseed oil was 54 h with the 2.4 g/m² coating thickness. The lowest water vapor transmission value was 39 g/m²/24 h with 9.7 g/m² coating. The GGM esters had clearly higher water resistance and slightly higher grease barrier values than native GGM. High-molar-mass-based GGM (50 kg/mol) and GGM-Ph rendered better water vapor and grease barrier properties than low-molar-mass GGM (9 kg/mol) and GGM-Ph. The GGM-based coatings can be safely used on an industrial scale as water was used as a solvent. As obtained from non-food-based side-stream wood-based resources, GGM and GGM esters project a sustainable and modern conception for barrier purposes in food packaging.     

Purification and partial characterization by matrix-assisted laser desorption ionization time-of-flight mass spectrometry of the recombinant transposase,TniA

This work deals with zone electrophoresis (ZE) separations of proteins on a poly(methyl methacrylate) chip with integrated conductivity detection. Experiments were performed in the cationic mode of the separation (pH 2.9) with a hydrodynamically closed separation compartment and suppressed electroosmotic flow. The test proteins reached the detector in less than 10 min under these working conditions and their migration times characterized excellent repeatabilities (0.1–0.6% RSD values). The chip-to-chip agreements of the migration times, evaluated from the ZE runs performed on three chips, were within 1.5%. The conductivity detection provided for protein, loaded on the chip at 10–1000 μg/ml concentrations, detection responses were characterized by 1–5% RSD values of their peak areas. Such migration and detection performances made a frame for reproducible baseline separations of a five-constituent mixture (cytochrome c, avidin, conalbumin, human hemoglobin and trypsin inhibitor). On the other hand, a high sample injection channel/separation compartment volume ratio of the chip (500 nl/8500 nl) restricted the resolution of proteins of very close effective mobilities in spite of the fact that in the initial phase of the separation an electric field stacking was applied. A maximum macroconstituent/trace constituent ratio attainable for proteins on the chip was assessed for cytochrome c (quantifiable when its concentration in the loaded sample was 10 μg/ml) and apo-transferrin (containing a trace constituent migrating in the position of cytochrome c detectable when the load of apo-transferrin was 2000 μg/ml). This assessment indicated that a ratio of 1000:1 is attainable with the aid of conductivity detection on the present chip.     

Synthesis of R-(-)-imperanene from the natural lignan hydroxymatairesinol

A convenient and high yielding method for the synthesis of R-(-)-imperanene, starting from the readily available natural lignan hydroxymatairesinol from Norway spruce, was developed. Hydroxymatairesinol was degraded in strongly basic aqueous conditions to (E)-4-(4-hydroxy-3-methoxyphenyl)-2-(4-hydroxy-3-methoxyphenylmethyl)but-3-enoic acid, which was esterified and then reduced by LiAlH(4) to afford R-(-)-imperanene. The configuration at the crucial stereocenter was preserved in the synthesis, and the obtained product was identified by optical rotation measurements and chiral HPLC analyses as the R-(-)-enantiomer (ee 86-92%).     

An acoustooptic method of measuring the noise equivalent power of optical heterodyne systems

The noise equivalent power of optical heterodyne detection at 10.6 m has been measured with a method based on Raman-Nath diffraction of a CO₂ laser beam. One of the frequency shifted first order diffracted beams is used as the signal radiation. The local oscillator radiation is obtained by splitting off a part of the laser beam incident upon the device used for the acoustooptic diffraction. The signal power can be varied over a large dynamic range by changing the acoustic input power. A study of the probable errors shows that the total error in the NEP measurement is less than 30%.     

Large-scale purification of single-wall carbon nanotubes: process, product, and characterization

Received: 13 February 1998