Near‐field laser ablation inductively coupled plasma mass spectrometry: a novel elemental analytical technique at the nanometer scale

An analytical technique utilizing a near‐field effect (to enhance the incident light energy on the thin tip of an Ag needle) in a laser ablation inductively coupled plasma mass spectrometry (NF‐LA‐ICP‐MS) procedure was developed. To produce the thin needles with a tip diameter in the hundreds of nm range a robust needle etching procedure was established. The ‘sample‐to‐tip’ distance was controlled via the measurement of a tunnel current between the needle and sample surface. The NF‐LA‐ICP‐MS technique thus developed was applied for the analysis of copper isotopic standard reference material NIST SRM 976 and tungsten‐molybdenum alloy NIST SRM 480 in the nm resolution range. The observed craters ranged from 200 nm to about 2 µm in diameter and were dependent on the needle used as well as on the ‘sample‐to‐tip’ distance. The mass spectrometric measurements of ⁶³Cu⁺ ion intensity on NIST SRM 976 showed that using near‐field enhancement in laser ablation allowed a roughly 6‐fold increase in the ion intensity of the analyte when the needle was about 100 nm (and below) from the surface, in contrast to when it was far away (e.g. 10 µm) from the sample. The relative standard deviation (RSD) of the ⁶⁵Cu⁺/⁶³Cu⁺ isotopic ratio measurements by NF‐LA‐ICP‐MS was 3.9% (n = 9). The detection efficiencies obtained for the compared LA‐ICP‐MS and NF‐LA‐ICP‐MS methods were found to be 4.6 * 10^?3 counts per second (cps)/ablated atom and 2.7 * 10^?5 cps/ablated atom, respectively. Copyright © 2008 John Wiley & Sons, Ltd.     

Topologically novel multiple rotaxanes and catenanes based on tetraurea calix[4]arenes

Calix[4]arenes bearing at their wide rim four urea residues easily form hydrogen bonded dimeric capsules. This has been used to preorganise alkenyl functions attached to these urea groups for their controlled connection via metathesis reaction. Multimacrocyclic tetraurea derivatives are thus obtained in excellent yields via heterodimers which are formed exclusively with tetratosylurea derivatives. Heterodimerisation of such bis- and tetraloop tetraureas leads analogously to multicatenanes, or to rotaxanes by stoppering. Huge macrocycles are detached from tetraloop derivatives by cleavage of the urea function.     

Heterogeneity and hierarchy of clinoptilolite porosity

The porous structure of the raw and the modified clinoptilolite has been investigated by nitrogen adsorption method, polarized light, scanning electron and atomic force microscopy as well as by thermogravimetric analysis. The relative moisture, specific gravity, bulk density and inter-particle porosity have been tested using thermostatic, pycnometric and hydrostatic weighing methods. The geometric method has been used to calculate the external surface area of the clinoptilolite crystallites in the clinoptilolite rock and to evaluate the volume of the clinoptilolite framework channels. Generally two types of porosities such as primary porosity and secondary one are observed. The primary porosity may be defined as microporosity presented by nanotube system of the clinoptilolite 3-dimensional aluminosilicate framework. The secondary porosity is formed by meso- and macropores, where the first ones are presented by slot pores determined mainly by cleavability of the zeolite crystallites. Total volume of the zeolite channels equals 0.332 cm³/g which has been obtained using a geometric method. Micropores volumes of the raw and the acid-treated samples are 0.0031 and 0.0342 cm³/g by nitrogen adsorption, respectively. According to thermogravimetric analysis the structural water lost at 150-750 °C placed the pore volume 0.087 cm³/g with the surface area 360 m²/g.     

Rational synthesis of multicyclic bis[2]catenanes

Bis-loop tetraurea calix[4]arene 6 has been prepared by acylation of the wide-rim calix[4]arene tetraamine 1 with the activated bis(urethane) 8 under dilution conditions. Similarly the bis(Boc-protected) tetraamine 2 is converted into the mono-loop derivative 3 which after deprotection and acylation gives the bisalkenyl derivative 5. In apolar solvents this tetraurea calix[4]arene 5 forms regioselectively a single hydrogen-bonded homodimer, from which the bis[2]catenane 10a is formed in 49% by a metathesis reaction followed by hydrogenation. Bis-loop derivative 6 forms no homodimers for steric reasons, but a stoichiometric mixture with the open-chain tetraalkenyl derivative 7a contains exclusively the heterodimer. Metathesis and subsequent hydrogenation now yields 65 % of the pure bis[2]catenane 10a which could not be isolated from the complex reaction mixture obtained from the homodimer 7a.7a. The chirality of 10a (D(2) symmetry) has been verified by optical resolution using HPLC on a chiral stationary phase.     

Development of a relatively cheap and simple automated separation system for a routine separation procedure based on extraction chromatography

A robust analytical method has been developed in our laboratory for the separation of radionuclides by means of extraction chromatography using an automated separation system. The proposed method is both cheap and simple and provides the advantageous, rapid and accurate separation of the element of interest. The automated separation system enables a shorter separation time by maintaining a constant flow rate of solution and by avoiding clogging or bubbling in the chromatographic column. The present separation method was tested with two types of samples (water and urine) using UTEVA-, TRU- and Sr-specific resins for the separation of U, Th, Am, Pu and Sr. The total separation time for one radionuclide ranged from 60 to 100 min with the separation yield ranging from 68 to 98% depending on the elements separated. We used ICP-QMS, multi-low-level counter and alpha spectroscopy to measure the corresponding elements.     

Structural features of natural and acids modified chrysotile nanotubes

The structural features of the natural chrysotile have been studied by transmission electron microscopy, scanning electron microscopy, energy-dispersive X-ray spectrometry, thermogravimetric and low-temperature nitrogen adsorption techniques. The chrysotile fibers are present as nanotubes of cylindrical morphology of various forms (rectilinear cylinders, cylinders with cup-like ends, tube twins, cylinder-in-cylinder and cone-in-cone tubes) with the outer diameters of 15-30 nm and the inner ones of 2-6 nm. The surface areas of the raw and the acid leached chrysotile samples obtained by nitrogen adsorption are 15.3 and 63.6 m²/g with the average pore diameter 9.8 and 3.9 nm, respectively. The inner and the outer surfaces of the chrysotile nanotubes are evaluated by the geometric method as 16 and 80 m²/g. The thermogravimetric analysis reveals two main phases of mass loss associated with dehydration and dehydroxylation (with two overlaying steps) processes. The first phase is attributed to the dehydration reaction at low temperature range 293-450 K with activation energy in the range 22-32 kJ/mol. The second phase occurs between 798 and 985 K with activation energy 249-298 kJ/mol for the raw sample and 130-146 kJ/mole for the acid treated one.