A General N-Alkylation Procedure for Ethyl Pyroglutamate

Despite several reported procedures for coupling alkyl halides and 5-oxoproline esters (pyroglutamate derivatives), no general method has been described. The reaction of pyroglutamate with sodium hydride, in anhydrous THF in the presence of the halide, provides this general and practical alkylation method. Alkylation under phase transfer conditions is a useful, but less general, alternative.     

Synthetic Approaches to 2-Pyrrolidinone-5-carboxaldehyde

We have examined routes for the preparation of 2-pyrrolidinone-5S-carboxaldehyde which include oxidation of 5-hydroxymethyl-2-pyrrolidinone and reduction of 5-oxoproline ethyl ester. Only the oxidation route proved satisfactory. Moffatt oxidation was most efficient but PCC oxidation gave modest yields of the desired aldehyde.     

On the Integrability of the Abel and of the Extended Liénard Equations

Acta Mathematicae Applicatae Sinica, English Series - We present some exact integrability cases of the extended Liénard equation y″ + f(y)(y′)n + k(y)(y′)m + g(y)y′ +...     

Interatomic Coulombic decay in mixed NeKr clusters

We report the occurrence of interatomic Coulombic decay (ICD) in mixed NeKr clusters. A well-defined feature ranging from 9 to 12 eV in kinetic energy is observed in coincidence with the Ne 2s photoelectrons. It derives from an ICD process, in which an initial Ne 2s vacancy is filled by a Ne 2p electron and an electron is emitted from a 4p level on a neighboring Kr atom. We have studied the dependence of the effect on photon energy, cluster composition, and cluster size. Interestingly, the ICD electron energy increases slightly and grows a shoulder on going from 2% to 5% Kr in the coexpansion process, which we interpret in terms of surface versus bulk effects.     

Validation of the Tessier scheme for speciation of metals in soil using the Bland and Altman test

The Tessier extraction method was used for speciation of Cu, Pb, Zn, As, Fe and Mn in a large concentration range in contaminated soil with various mineralogical compositions. The results were compared by X-ray fluorescence spectrometry (XRF) as a reference method using the Bland and Altman test. A sum of five fractions (exchangeable, bound to carbonates, Fe-Mn oxides, organic matter and residual forms) was compared with the total content determined on solid matrix by the reference method. A good agreement between the methods in the whole concentration range was found for Cu, Zn, As, and Fe. For Mn and Pb, XRF was found suitable to verify the sequential extraction only for concentrations above 250 mg kg⁻¹. This was a consequence of a poorer reproducibility of Pb extraction using the Tessier scheme due to a great difference in the mineralogical composition and the diversity of the Pb species identified in soil. The poorer result of Mn was attributed to the spectral interference of Fe in XRF. Presented at the 34th International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 21–25 May 2007.     

Preliminary investigation of a medium power argon radiofrequency capacitively coupled plasma as atomization cell in atomic fluorescence spectrometry of cadmium

The single ring electrode radiofrequency capacitively coupled plasma torch (SRTr.f.CCP) operated at 275W, 27.12 MHz and Ar flow rate below 0.7 lmin(-1) was investigated for the first time as atomization cell in atomic fluorescence spectrometry (AFS) using electrodeless discharge lamps (EDL) as primary radiation source and charged coupled devices as detector. The signal to background ratio (SBR) and limit of detection for Cd determination by EDL-SRTr.f.CCP-AFS were compared to those obtained in atomic emission spectrometry using the same plasma torch. The detection limit in fluorescence was 4.3 ngml(-1) Cd compared to 65 ngml(-1) and 40 ngml(-1) reported in r.f.CCP-atomic emission (AES) equipped with single or double ring electrode. The lower detection limit in EDL-SRTr.f.CCP-AFS is due to a much better SBR in fluorescence. The limit of detection was also compared to those in atomic fluorescence with inductively coupled plasma (0.4 ngml(-1)), microwave plasma torch (0.25 ngml(-1)) and air-acetylene flame (8 ngml(-1)). The influence of light-scattering through the plasma and the secondary reflection of the primary radiation on the wall of the quartz tube on the analytical performance are discussed. The non-spectral matrix effects of Ca, Mg and easily ionized elements are much lower in EDL-SRTr.f.CCP-AFS compared to SRTr.f.CCP-AES. The new technique was applied in the determination of Cd in contaminated soils, industrial hazardous waste (0.4-370 mgkg(-1)) and water (113 microgl(-1)) with repeatability of 4-8% and reproducibility in the range of 5-12%, similar to those in ICP-AES. The results were checked by the analysis of a soil and water CRM with a recovery degree of 97+/-9% and 98+/-4%, for a confidence limit of 95%. The present EDL-SRTr.f.CCP-AFS is a promising technique for Cd determination in environmental samples.     

Autoionization mediated by electron transfer

Electron-electron coincidence spectra of Ar-Kr clusters after photoionization have been measured. An electron with the kinetic energy range from 0 to approximately 1 eV is found in coincidence with the Ar 3s cluster photoelectron. The low kinetic energy electron can be attributed to an Ar + Kr+ + Kr+ final state which forms after electron transfer mediated decay. This autoionization mechanism results from a concerted transition involving three different atoms in a van der Waals cluster; it was predicted theoretically, but hitherto not observed.     

Some applications of the condensation of the singularities of families of nonnegative functions

RecentlyPrus-Wi?niowski [14] has proved that the continuous functions of Λ-bounded variation on [0, 1] form a set of the first category in the Banach space C[0, 1] and also in each Banach space CΓBV[0, 1] of continuous functions of Γ-bounded variation on [0, 1] provided that the sequence Γ is adequate. In the present paper these results are extended and completed by using a principle of the condensation of the singularities of a family of nonnegative functions that follows from the theorems given byBreckner [3]. It is shown that Baire category properties similar to those stated in [14] are valid for two very large classes of real-valued functions called functions of bounded λ-variation of orderp and functions of boundedmth variation of orderp, respectively. The benefit of considering these classes is that they comprise several classes of functions of bounded variation type which have occurred so far in Fourier analysis or real analysis; in particular, the functions investigated in [14]. Thus, by specializing the results derived in the present paper, they give at once Baire category information concerning a number of well-known sets of real-valued functions.