Validated, non-destructive and environmentally friendly determination of cocaine in euro bank notes

A non-destructive, fast and environmentally friendly procedure has been developed for cocaine determination in euro bank notes. Cocaine was extracted with 15 ml methanol by vortex agitation during 5 min. The extract was evaporated and reconstituted in 0.5 ml methanol. GC-MS-MS analysis was performed using as precursor ion m/z 182.2, with an excitation energy voltage of 1.60 eV, being the product ions measured m/z 150.2 and 82.0. A limit of detection of 0.15 ng per note and a repeatability of 6%, established from the relative standard deviation, of a 1 ng ml(-1) level, were achieved. Recoveries of 101+/-2 and 98+/-3% were obtained for samples spiked with 100 and 10 microg respectively. Results show that all the euro bank notes measured (16 samples) were contaminated with cocaine in the range between 1.25 and 889 microg. Two different contamination levels, high level (150-889 microg) and low one (1.25-77 microg) were found and it could be related with the direct or indirect contact with the drug.     

The Radical Cations of 4,5,7,13,15,16-Hexamethyl- and 4,5,7,8,12,13,15,16-Octamethyl [2.2]paracyclophane

4,5,7,13,15,16-Hexamethyl- (3) and 4,5,7,8,12,13,15,16-octamethyl[2.2]paracyclophane (4) have been oxidized to their radical cations in solution under relatively mild conditions. Substantial hyperfine splittings in the ESR. spectra of 3⊕. and 4⊕. arise from the methyl protons, whereas those from methylene protons are very small. This result indicates that the ethano bridges, unlike the methyl substituents, are rather ineffective in delocalizing the positive charge in 3⊕. and 4⊕. It is in line with the interpretation proposed previously to rationalize the gas-phase ionization potentials of multiply bridged [2_N]cyclophanes and methyl derivatives of [2.2]paracyclophane. The π-spin distributions in 3⊕. and 4⊕. are discussed in terms of a simple model in which the singly occupied orbitals are represented as the antibonding combinations of two benzene HOMO's.     

Effect of the parent ligand on the photophysical properties of closely-coupled, binuclear ruthenium(II) tris(2,2'-bipyridine) complexes

The photophysical properties of closely-coupled, binuclear complexes formed by connecting two ruthenium(II) tris(2,2'-bipyridine) complexes via an alkynylene group differ significantly from those of the relevant mononuclear complex. In particular, the energy of the first triplet excited state is lowered relative to the parent complex, because of the presence of the alkynylene substituent, while the triplet lifetime is prolonged, in part, because of extended electron delocalization. We now report that the triplet lifetime is also affected by the nature of the spectator 2,2'-bipyridyl ligands. Thus, replacing the parent 2,2'-bipyridine ligands with the corresponding 4,4'-dinitro-substituted ligands serves to decrease the luminescence yield and lifetime. With the corresponding carboxylate ester, the luminescence yield and lifetime are increased. Perdeuteration of the parent 2,2'-bipyridine ligands also leads to a modest increase in the luminescence yield. Such observations are indicative of electronic coupling between the various metal-to-ligand, charge-transfer excited triplet states. Temperature dependence studies confirm that these excited states are closely spaced and thermally accessible at ambient temperature. For some of the binuclear complexes, the quantum yield for formation of the lowest-energy triplet state is significantly less than unity.     

Accurate intermolecular ground state potential of the Ne-N2 van der Waals complex

Ab initio ground state potential energy surfaces are obtained from interaction energies calculated with the coupled cluster singles and doubles model including connected triples corrections [CCSD(T)] and the aug-cc-pVXZ (X=5,Q,T,D) basis sets augmented with two different sets of midbond functions (denoted 33221 and 33211). The aug-cc-pV5Z-33221 surface is characterized by a T-shaped 49.5 cm(-1) minimum at Re=3.38 Angstroms and a linear saddle point at 3.95 Angstroms with De=36.6 cm(-1). These results agree well with the values provided by the accurate semiempirical potentials available. The rovibronic spectroscopic properties are determined and compared to the available experimental data and previous theoretical results. We study the basis set convergence of the intermolecular potentials and the rotational frequencies. The aug-cc-pVTZ basis sets provide reasonable binding parameters, but seem not to be converged enough for the evaluation of the microwave spectra. The aug-cc-pVQZ basis sets considerably improve the triple zeta results. The differences between the results obtained with the aug-cc-pVTZ-33221 basis set surface and those with the aug-cc-pVQZ-33221 are smaller than those of the corresponding bases with the set of 33211 midbond functions. The aug-cc-pVQZ surfaces are close to the aug-cc-pV5Z, that are expected to be close to convergence. With our best surfaces the errors in the frequencies with respect to the accurate experimental results go down to 0.6%.     

Stereocontrolled synthesis of iminocyclitols with an ether bridge

Nor-tropane related bicyclic (6+5) iminocyclitols with an ether bridge and different substituents (hydroxymethyl, aminomethyl, and aminoethyl) on C-1 are prepared starting from a β-d-psicofuranosyl cyanide. The method involves an internal nucleophilic attack of a stabilized amide ion on a 5-mesyloxy derivative. The intermediate N-acetyl O-protected iminocyclitols present atropoisomerism due to restricted rotation of the N-CO amido bond. Conformational aspects of the prepared compounds are discussed.     

Cyclodextrin effects on physical–chemical properties of novocaine

The UV-vis absorption and the fluorescence emission spectra of novocaine were analysed in aqueous cyclodextrin (CD) solutions. Either the absorbance read at λ_max 290 nm or the fluorescence emission intensity at λ_ems 346 nm increase in the presence of both α- and β-CD due to the formation of 1:1 inclusion complexes. The lower polarity of the CD-cavity sensed by the included drug enhances the emitted fluorescence; in fact, the same effect was observed in aqueous mixtures of acetonitrile, dioxane, or dimethylsulfoxide. The inclusion complex formation between the monocation of novocaine and CDs diminishes the electrical conductance of aqueous solutions of novocaine hydrochloride (NoHCl). Both the nitrosation reaction in aqueous acid medium and the ester hydrolysis in alkaline medium are retarded in the presence of CDs. The strongest effect was observed with β-CD as a consequence of the higher stability inclusion complex.     

Role of the tautomerism of 2-azaadenine and 2-azahypoxanthine in substrate recognition by xanthine oxidase

The tautomerism of 2-azaadenine and 2-hypoxanthine has been examined in the gas phase and in aqueous solution. The tautomerism in the gas phase has been studied by means of semiempirical and ab initio quantum-mechanical computations, as well as density-functional calculations. The influence of the aqueous solvent on the relative stability between tautomers has been estimated from self-consistent reaction field calculations performed with different high-level continuum models. The results provide a detailed picture of the tautomeric preference for these purine bases. The importance of tautomerism in the substrate recognition by xanthine oxidase is discussed. Finally, the rate of oxidation of 2-azaadenine and 2- hypoxanthine by xanthine oxidase is discussed in terms of the recognition model at the enzyme active site.     

Simultaneous determination of arsenic, antimony and selenium by gas-phase diode array molecular absorption spectrometry, after preconcentration in a cryogenic trap

This paper describes a method for the simultaneous determination of As(III), Sb(III) and Se(IV) by combining hydride generation and gas phase molecular absorption spectrometry. A system for continuous hydride generation has been designed and developed, based on the use of a double process of gas-liquid separation, and optimal compromise operation conditions for the three compounds have been found. After generation, the hydrides are collected in a liquid nitrogen cryogenic trap, and then evaporated and driven to the flow cell of a diode array spectrophotometer, in which the transient signals over the 190–250 nm wavelength interval are measured. Under the recommended conditions (sample flow: 35 ml min⁻¹, 0.5 M HCl; reductor flow: 4 ml min⁻¹ of 4% NaBH₄, solution) linear response ranges above 50 μg 1⁻¹ for As(III), 30 μg 1⁻¹ for Sb(III) and 200 μg 1⁻¹ for Se(IV) are obtained with detection limits of 22 μg 1⁻¹, 15 μg 1⁻¹ and 65 μg 1⁻¹, respectively. Multiwavelength linear regression equations were used for the simultaneous determination of the three elements in different synthetic samples, with good precision and accuracy and to study simultaneously the interference from different chemical species for the three compounds. Results were similar to those obtained by other techniques using hydride generation.     

Towards the synthesis of [15]-membered stevastelins through the 2,3-epoxy analogues

A synthetic approach to the [15]-membered stevastelins, a novel class of immunosuppressant agents, is reported based on a macrolactamization route to the 2,3-epoxy derivative 6. The synthesis of this compound was achieved via a stereoselective epoxidation of the allylic alcohol 13, followed by a coupling reaction with a variety of peptide derivatives to give the epoxy peptides 7-10. After an extensive study of cyclizations with these precursors, the best result was achieved with the macrolactamization of 8 in the presence of DEPC, to obtain the epoxy cyclic depsipeptide 6 in 42% yield. From this product, an epoxy analogue of stevastelin B, compound 27, was prepared. Finally, the synthesis of the natural product was attempted through the opening of the oxirane ring contained in 6 and 26, with a variety of methyl cuprate reagents, but without success.     

On-line preconcentration and determination of mercury in biological samples by flow injection vapour generation inductively coupled plasma atomic emission spectrometry

An FI-ICP-AES method for the determination of trace levels of mercury in biological samples has been described, which is based on the extraction of the mercury complex with 1,5-bis (di-2-pyridyl)methylene thiocarbonohydrazide (DPTH) on-line into isobuthyl-methyl ketone (IBMK). The organic phase (containing the complex) has been mixed on-line with SnCl₂ in N,N-dimethylformamide. Thus, mercury vapour can be generated directly from the organic phase and separated in a gas-liquid separation device. The detection limit for mercury is 4 ng/ml and the calibration curve is linear at least from 10 to 2500 ng/ml. The relative standard deviation for 10 replicate measurements is ±1% for 100 ng/ml of Hg(II). Results from the analysis of some certified biological reference materials are given.