Plutonium Activity Ratios in Plankton: New Evidence of Hold-Up Time in Irish Sea Sediments

The determination of activity ratios for radioisotopes of different half-lives can be used to estimate transit times from a point source to locations further away. For conservative elements, this time is approximately equivalent to the net hydrological transport. However, for non-conservative elements such as plutonium, the additional influence of biogeochemical processes decreases the net transport time. In this study, ²⁴¹Pu and ^239,240Pu concentrations in Irish Sea plankton samples, collected in May 1994, were determined and the ²⁴¹Pu/^239,240Pu ratios calculated. Plutonium-239,240 was measured using a standard method by ion exchange chromatography and alpha counting, and ²⁴¹Pu was determined by liquid scintillation counting using the disk-supported technique. The latter showed some methodological problems, which are briefly discussed. The ²⁴¹Pu/^239,240Pu ratios gave an estimate of the "transit time" from Sellafield to the different sampling points. In fact, this time represents the age of plutonium in plankton, i.e., the time lag between release from Sellafield and detection at the different sampling stations. The mean plutonium age was 17±2 years (n = 10) and 18.6±0.8 years (n = 13) in phytoplankton and zooplankton, respectively. The spatial distribution was reasonably homogeneous over the Irish Sea. The assimilation-elimination processes of plutonium in plankton are rather rapid. Therefore, it may be assumed that, in this time scale, the plutonium concentrations were in equilibrium with surrounding waters. Thus, it is concluded that plutonium was rather old because resuspension-sedimentation processes had occurred that delayed its transport within the Irish Sea. Therefore, the age of plutonium in plankton represented the hold-up time of plutonium in the sediments from the Irish Sea.     

Weak intramolecular proton-hydride and proton-fluoride interactions: experimental (NMR, X-ray) and DFT studies of the bis(NBH(3)) and bis(NBF(3)) adducts of 1,3-dimethyl-1,3-diazolidine

Bis(NBH(3)), bis(NBF(3)), and NBF(3)/NBH(3) adducts 1-3 were prepared from 1,3-dimethyl-1,3-diazolidine and characterized by the (1)H, (13)C, (11)B, (19)F, 2D (1)H(-13)C HETCOR and NOESY NMR spectra. The structures and conformations of the adducts were established by the variable-temperature (1)H NMR spectra, the X-ray diffraction method (adduct 2A), and density functional calculations at different theoretical levels. The experimental and theoretical data have revealed that bis adducts 1-3 prefer trans orientations of the borane groups (1A, 2A, 3A) in solution, the solid state, and the gas phase. The studies have shown that the energetic preference of trans adducts with respect to cis compounds, decreasing as 2A (2.9 kcal/mol) > 3A (2.7 kcal/mol) > 1A (1.4 kcal/mol), is dictated by spatially repulsive interactions between the CH(3), BH(3), and BF(3) groups. The results of DFT calculations agree well with an experimental trans/cis isomeric ratio of 9:1 determined in solutions of adduct 1. The calculated geometry and energy, as well as the topological analysis of electronic densities, show that trans adducts 1-3 should exist in gas phase as twist conformations T-2 stabilized by the intramolecular C-H(delta+)...(-delta)H-B or C-H(delta+)...(-delta)F-B interactions. These interactions are characterized as closed-shell. The energy of one proton-hydride and proton-fluoride intramolecular contact, estimated as 1.9 (1A-T-2) and 0.7 (2A-T-2) kcal/mol, respectively, classifies the "elongated" intramolecular interactions CH(delta+)...(-delta)HB and CH(delta+)...(-delta)FB as weak ones. It has been established that, on going from gas phase to a condensed phase (solution and solid), the twist-conformations T-2 transform to conformations T-1, probably by intermolecular dipole-dipole interactions. The data presented in this work show that despite a weakness of the "elongated" proton-hydride and proton-fluoride interactions, they can play a significant role in the stabilization of conformational molecular states, especially when cooperativity is in action.     

Supramolecular systems-based extraction-separation techniques coupled to mass spectrometry

The combination of supramolecular chemistry and MS has not only been fruitful in the field of gas-phase fundamental studies of host-guest complexes and supramolecular assemblies. Mass spectrometric analysis has also benefited from the ability of supramolecular systems to behave as pseudophases in which solutes partition from the bulk solvent phase. Supramolecular systems-based extraction and concentration schemes and separation techniques have been widely used in different fields of analytical chemistry and are ideally suited for coupling with MS. This review describes the present status of the application of supramolecular chemistry in mass spectrometric analysis and includes topics such as the use of coacervative liquid-liquid extraction and hemimicelle/admicelle-based SPE of organic compounds prior to chromatography and electrophoresis. It also discusses the recent advances in enantioselective analysis using CD in electrophoresis- and chromatography-MS. The potential and analytical challenges of these approaches in environmental and bioanalytical chemistry, where one can expect significant developments in the future, are outlined.     

Synthesis of donor-acceptor alkynylcyclopropanes by diastereoselective cyclopropanation of electron-deficient alkenes with alkoxyalkynyl Fischer carbene complexes

The reaction of electron-deficient alkenes with alkoxyalkynyl Fischer carbene complexes (FCCs) represents a straightforward route to a new type of captodative (donor-acceptor) alkynylcyclopropanes, which have been prepared in moderate to high yields and in a diastereoselective manner. Some studies regarding the employment of additives to facilitate the recovery of the metal moiety after the reaction are also described. Finally, the first example of a cyclopropanation reaction through employing Fischer carbene complexes under microwave irradiation is presented; this method proved to be an advantageous alternative to the thermal reaction.     

On-line filtration system for determining total chromium and chromium in the soluble fraction of industrial effluents by flow injection flame atomic absorption spectrometry

Two manifolds were assessed for the purpose of determining both the total chromium content and that present as a soluble form in industrial effluents by flow injection flame atomic absorption spectrometry (FI-FAAS). To determine the chromium content in the soluble fraction the samples were used without additional treatment, a 0.45 microm filter being included in the FI system. To determine the total chromium content, the samples were acidified with nitric acid 20% (v/v) and heated for 30 s in a microwave oven (temperatures of about 70 degrees C were reached). The problem posed by the very different concentration range in which total and soluble chromium are present was overcome by using programmed flow rate methodology and by only partially emptying the sample loop. A personal computer controlled both the rotation speed of a peristaltic pump and the volume of sample injected into the system, thus obtaining the dispersion degree required. Using the manifold proposed, the chromium content in the soluble fraction can be determined in the 0.5-20 microg mL(-1) range using a 10 microg mL(-1) single standard for calibration. To determine the total chromium content, a calibration line in the 20-200 microg mL(-1) range was obtained using a single 50 microg mL(-1) chromium standard solution. The reliability of the semi-automatic devices was verified by comparing the results obtained with those found by treating the samples and using both FAAS in a conventional way and a spectrophotometric method using diphenylcarbazide at the 95% confidence level (ANOVA test). The proposed procedures showed a RSD lower than +/-3%.     

Tailoring the cavities of hydrogen-bonded amphidynamic crystals using weak contacts: towards faster molecular machines

This work describes the use of C–H⋯F–C contacts in the solid-state from the stator towards the rotator to fine-tune their internal motion, by constructing a set of interactions that generate close-fitting cavities in three supramolecular rotors 1–3I. The crystal structures of these rotors, determined by synchrotron radiation experiments at different temperatures, show the presence of such C–H⋯F–C contacts between extended carbazole stators featuring fluorinated phenyl rings and the 1,4-diazabicyclo[2.2.2]octane (DABCO) rotator. According to the ²H NMR results, using deuterated samples, and periodic density functional theory computations, the rotators experience fast angular displacements (preferentially 120° jumps) due to their low rotational activation energies (E_a = 0.8–2.0 kcal mol⁻¹). The higher rotational barrier for 1 (2.0 kcal mol⁻¹) is associated with a larger number of weak C–H⋯F–C contacts generated by the stators. This strategy offers the possibility to explore the correlation among weak intermolecular forces, cavity shape, and internal dynamics, which has strong implications in the design of future fine-tuned amphidynamic crystals.

This work describes the use of C–H⋯F–C contacts in the solid-state from the stator towards the rotator to fine-tune their internal motion, by constructing a set of interactions that generate close-fitting cavities in three supramolecular rotors 1–3I.     

A DFT study on the 1,3-dipolar cycloaddition reactions of C-(methoxycarbonyl)-N-methyl nitrone with methyl acrylate and vinyl acetate

In the 1,3-dipolar cycloaddition of glyoxylic nitrones with electron-poor and electron-rich alkenes, the configurational instability of the nitrone leads to parallel models when regio- and stereoselectivities are rationalized. The energetics of the cycloaddition reactions have been investigated through molecular orbital calculations at the B3LYP/6-31-G(d) theory level. By studying different reaction channels and reagent conformations, leading to a total of sixteen transition structures for each dipolarophile, the regio- and stereochemical preferences of the reaction are discussed.     

Nitrones in Organic Synthesis. Synthesis of Secondary Allyl Amines

Nitrones 1 undergo addition of vinyl organomagnesium bromide to give the allyl hydroxylamines 3 which are easily reduced to the corresponding N-benzyl allyl amines 2.