Thermal and spectroscopic investigation of europium and samarium sulphates hydrates by TG-FTIR and ICP-MS techniques

The investigation of europium(III) sulphate hydrate and samarium(III) sulphate hydrate was performed by thermal analysis (TG-DTG) and simultaneous infrared evolved gas analysis-Fourier transformed infrared (EGA-FTIR) spectroscopy. The TG, DTG and DTA curves were recorded at the 25–1400 °C in the dynamic air atmosphere by TG/DTA analyser. The infrared evolved gas analysis was obtained on the FTIR spectrometer. Eu₂(SO₄)₃·nH₂O (n = 3.97) and Sm₂(SO₄)₃·nH₂O (n = 8.11) were analysed, the dehydration and decomposition steps were investigated and the water content was calculated. The formation of different oxysulphates was studied.

The trace rare earth elements in Eu and Sm sulphates were determined by ICP-MS. The concentration of trace Eu, Sm, La, Gd, Y and Ce ranged from 3.9 × 10⁻⁶ to 1.5 × 10⁻⁴% (m/m).     

Ultraviolet B Irradiation Modulates the Immune System of Fish (Rutilus rutilus, Cyprinidae). I. Phagocytes

Roach ( Rutilus rutilus ) were irradiated with a single dose of ultraviolet B (UVB) radiation (0.4 J/cm²) in order to study the effects of UVB on the nonspecific immune defense mechanisms of fish. Neutrophils and macrophages were isolated from the head kidney of fish on days 1–14 postirradiation. Both random and directed migration of neutrophils, studied by migration under agarose assay, were suppressed on day 1 after UVB irradiation. The respiratory burst of phorbol 12-myristate 13-acetatestimulated neutrophils and macrophages was also suppressed at days 1 and 2 after UVB irradiation. The suppression of migration and respiratory burst were restored or the responses were even enhanced later, but on the other hand spontaneous cytotoxicity of neutrophils toward ⁵¹chromium-labeled K562 target cells stayed suppressed throughout the 14 day follow-up. This study indicates that UVB radiation has the potential to suppress the functioning of phagocytes and to compromise the immune system of fish.     

Mechanisms for the solvolytic decompositions of nucleoside analogues—I: Acidic hydrolysis of 2-substituted 1-(1-ethoxyethyl)benzimidazoles

A few 2-substituted 1-(1-ethoxyethyl)benzimidazoles have been prepared and the rate constants for their hydrolysis measured at various temperatures and oxonium ion concentrations. The formal kinetics followed and the effect of varying the 2-substitution on the hydrolysis rate suggest that the acid-catalyzed cleavage of these compounds involves a rapid initial protonation of the benzimidazole ring and a subsequent rate-limiting heterolysis of the protonated substrate to form a free nitrogen base and an ocarbenium ion derived from the ethoxyethyl group. The values obtained for the entropy of activation are consistent with the assumed unimolecular nature of the rate-limiting step. The effects of 2-substituents on the acidities of the protonated substrates and their heterolysis rates have been compared. The latter partial reaction has been suggested to be the subject of steric acceleration.     

Mass spectra of halogenated esters. 7. Methyl esters of 2-chloro C2?C20 n-alkanoic acids

The mass spectral fragmentation of a homologous series of methyl esters of 2-chloro n-alkanoic acids ranging from acetic (C₂) to eicosanoic (C₂₀) acid on electron impact has been investigated. The fragmentation pathways were elucidated with the aid of the first field-free region metastable ions, the results being presented with one compound, i.e. with ionized methyl 2-chloro-octauoate. Owing to the Cl/H exchanges and to the formation of the non-chlorinated parent esters prior to the fragmentations the spectra show the peak pairs with and without the chlorine atom. The effects become more evident with increasing chain length; shown most visually by the abundance ratios of the McLafferty rearrangement ions atm/z108/110 and 74, and fragments at m/z121/123 and 87.     

Novel Thiazole-Containing Complexing Agents and Luminescence of Their Europum(III) and Terbium(III) Chelates

The synthesis of novel thiazole-containing complexing agents and their luminescence properties with Eu^III and Tb^III ions are reported. One of these terpyridine analogues was also tested as an Eu^III labelling reagent, and its luminescence properties as an antibody conjugate were studied.     

Novel selectfluor and deoxo-fluor-mediated rearrangements. New 5(6)-methyl and phenyl methanopyrrolidine alcohols and fluorides

Stereoselective syntheses of novel 5,6-difunctionalized-2-azabicyclo[2.1.1]hexanes containing 5-anti-fluoro or hydroxyl in one methano bridge and a variety of syn- or anti-chloro, fluoro, hydroxy, methyl, or phenyl substituents in the other methano bridge have been effected. Rearrangements of iodides to alcohols were initiated using Selectfluor. Rearrangement of alcohols to fluorides was initiated using Deoxo-Fluor. Ring opening of 2-azabicyclo[2.2.0]hex-5-ene exo-epoxide with organocopper reagents is regioselective at C(5).     

Expanding the Scope of the Cleavable N-(Methoxy)oxazolidine Linker for the Synthesis of Oligonucleotide Conjugates

Oligonucleotides modified by a 2′-deoxy-2′-(N-methoxyamino) ribonucleotide react readily with aldehydes in slightly acidic conditions to yield the corresponding N-(methoxy)oxazolidine-linked oligonucleotide-conjugates. The reaction is reversible and dynamic in slightly acidic conditions, while the products are virtually stable above pH 7, where the reaction is in a ‘‘switched off-state’’. Small molecular examinations have demonstrated that aldehyde constituents affect the cleavage rate of the N-(methoxy)oxazolidine-linkage. This can be utilized to adjust the stability of this pH-responsive cleavable linker for drug delivery applications. In the present study, Fmoc-β-Ala-H was immobilized to a serine-modified ChemMatrix resin and used for the automated assembly of two peptidealdehydes and one aldehyde-modified peptide nucleic acid (PNA). In addition, a triantennary N-acetyl-d-galactosamine-cluster with a β-Ala-H unit has been synthesized. These aldehydes were conjugated via N-(methoxy)oxazolidine-linkage to therapeutically relevant oligonucleotide phosphorothioates and one DNA-aptamer in 19–47% isolated yields. The cleavage rates of the conjugates were studied in slightly acidic conditions. In addition to the diverse set of conjugates synthesized, these experiments and a comparison to published data demonstrate that the simple conversion of Gly-H to β-Ala-H residue resulted in a faster cleavage of the N-(methoxy)oxazolidine-linker at pH 5, being comparable (T_0.5 ca 7 h) to hydrazone-based structures.