The potential of serially coupled alkyl-bonded silica monolithic columns for high resolution separations of pharmaceutical compounds in biological fluids

Summary In this paper we investigate the potential of alkyl-bonded silica monolithic columns for the isolation and identification of drug-related components in biological fluids. Up to 6 columns have been connected in series to produce a chromatographic system with up to 40,000 plates. This high-resolution chromatography system has been coupled to both MS and NMR to enable efficient detection and characterisation of drug-related components in biological fluids. The use of six coupled columns has been shown to give enhanced resolution over a high quality silica particulate column packed with 3 μm material which exhibits the same back pressure. The effect of volume and mass load on the performance of monolithic columns for semi-preparative chromatography of biological fluids has also been investigated. In these studies it was possible to inject up to 100 mL of neat urine with no loss of chromatographic performance. Furthermore, upon re-testing, the columns showed similar chromatographic performance. Again several columns were serially connected, producing enhanced resolution in the semi-preparative mode.     

Synthesis and spectroscopic studies of methoxy-substituted phenylthienylnicotinamidines

Abstract

Five thienylnicotinamidine derivatives 5a–e were prepared from their corresponding nicotinonitriles 3a–e on treatment with lithium trimethylsilylamide [LiN(TMS)₂] followed by hydrolysis using ethanolic/HCl (gas). The nicotinonitriles 3a–e were prepared via Suzuki coupling reaction of bromothienyl derivative 1 with the appropriate phenylboronic acids 2a–e. The DFT calculation was used to optimize the geometric structure of the newly synthesized nicotinamidines. The comparison of DFT/B3LYP calculated spectral data (¹H-NMR and ¹³C-NMR) with the experimental data showed acceptable agreement. Mass fragmentation patterns of 3,4-dimethoxyphenyl, 3,5-dimethoxyphenyl, and 3,4,5-trimethoxyphenyl thienylnicotinamidine derivatives were investigated.     

Intramolecular energy-transfer in a europium(III) chelate with salicylidene-valinate schiff base

Summary An intense fluorescence,⁵D⁷F, of the europium(III) ion was observed at room temperature in DMSO and DMF solutions of the europium(III) chelate with salicylidene-valinate Schiff base, as a result of an intramolecular energy-transfer from the ligand to the metal ion. The metal chelate has been characterized and appears to possess an octahedral configuration. These results offer an interesting opportunity to probe the active sites of pyridoxal enzymes.     

The anionic alkylation of easily reducible arenes. A photochemical route to nucleophilic aromatic substitution of anthracene by organolithiums

High yield nucleophilic addition ensues upon mixing tetrahydrofuran solutions of benzyllithium or cyclooctadienyllithium and anthracene at low temperatures At least part of this addition proceeds by a single electron transfer pathway. Photolysis of the resulting adducts leads to the elimination of lithium hydride, giving net nucleophilic substitution in approximately 50% yield. The analogous reaction fails with naphthalene, where photolysis of the organolithium/ arene mixture leads to dimeric products derived from the organolithium.     

Th,U and trace elements determination in Egyiptian Lake sediments by INAA and laser fluorimetry

A study was undertaken to determine element concentrations in Aswan High Dam Lake sediments. Sediment samples were collected from 40 to 500 km upstream of the dam to follow the sedimentation process and the distribution of Th, U and the trace elements in the lake. INAA was applied for the determination of Sm, Ce, Lu, Th, Cr, Yb, Au, Hf, Ba, Nd, Cs, Tb, Sc, Rb, Fe, Zn, Co, Eu, and Sb, while Laser Fluorimetry was applied for U determination. The accuracy and the reproducibility of the techniques were tested with IAEA standard materials (SL, Soil-7). The U values ranged from 4 ppm to 18 ppm, Th values were between 2 and 10 ppm, and showed a very good correlation with the rare earth elements and Fe. The distribution of most of the elements in the lake follows the same trend as the distribution of the clays in the sediments. Ba showed a negative correlation with most of the elements under investigation.Paper presented at the 3th International Conf. on Nuclear and Radiochemistry (NRC-3), Vienna, 1992.     

Analysis of tungsten-containing mixtures and some alloy steels by potentiometric titration methods

Reliable potentiometric titration methods are adopted for the analysis of tungsten mixtures analogous to some industrially important alloys such as low alloy tap steel, tungsten chisel, and high speed steels. Tungsten is separated as Hg₂WO₄ and unreacted Hg(I) is titrated with KBr. The techniques of oxidation with I₂ or reduction with KI and use of the selective arsenite reduction of Cr(VI) and/or Mn(IV) in the presence of V(V) or Fe(III) make it possible to determine alloy components without tedious separations. In all titrations the potential break is sharp enough for the precise establishment of the end point.     

The effect of intramolecular‐hydrogen bonds in the synthesis of novel imidates from a 13‐membered dioxadithia crown ether diester

The synthesis and structural properties of three novel imidates, 11,13‐bis‐(2‐amino‐ethylimino)‐1,10‐dioxa‐4,7‐dithiacyclotridecane ( 2 ), 11,13‐bis‐(3‐aminopropylimino)‐1,10‐dioxa‐4,7‐dithiacyclotridecane, ( 3 ) and 2,11‐dioxa‐5,8‐dithia‐13,16,19,22‐tetraazabicyclo[10.10.1]tricosa‐1(22),12‐diene, ( 4 ) have been described. These compounds were synthesized by treating 1,10‐dioxa‐4,7‐dithiacyclotridecane‐11,13‐diester ( 1 ) with the appropriate diamine under N₂ and their structures have been characterised by elemental analyses, ¹H‐ and ¹³C‐nmr, ir, and mass spectral studies. Elemental analyses and spectroscopic data support the proposed imidate structures. In addition, total energy and heat of formation (Figure 2) calculated for imidates 2a‐4a and 2b‐4b by the semiempirical AM1 calculations have shown that imidates 2b‐4b having intramolecular hydrogen bonds are more stable (5‐10 kcal/mol) than compounds 2a‐4a .     

Über Halogenphenylester der Phosphorsäure

A simple method for preparing halogenphenylesters of phosphoric, phenylphosphonic and phosphorous acid from the respective acid chlorides and phenols in the presence of various nitrogen-containing catalysts is described. Contrary to other methods, these reactions give high yields, despite of steric hindrance.