Ion-pair reversed-phase high-performance liquid chromatography analysis of oligonucleotides: retention prediction

An ion-pair reversed-phase HPLC method was evaluated for the separation of synthetic oligonucleotides. Mass transfer in the stationary phase was found to be a major factor contributing to peak broadening on porous C18 stationary phases. A small sorbent particle size (2.5 microm), elevated temperature and a relatively slow flow-rate were utilized to enhance mass transfer. A short 50 mm column allows for an efficient separation up to 30mer oligonucleotides. The separation strategy consists of a shallow linear gradient of organic modifier, optimal initial gradient strength, and the use of an ion-pairing buffer. The triethylammonium acetate ion-pairing mobile phases have been traditionally used for oligonucleotide separations with good result. However, the oligonucleotide retention is affected by its nucleotide composition. We developed a mathematical model for the prediction of oligonucleotide retention from sequence and length. We used the model successfully to select the optimal initial gradient strength for fast HPLC purification of synthetic oligonucleotides. We also utilized ion-pairing mobile phases comprised of triethylamine (TEA) buffered by hexafluoroisopropanol (HFIP). The TEA-HFIP aqueous buffers are useful for a highly efficient and less sequence-dependent separation of heterooligonucleotides.     

Cyclotetrasilazane als precursor für cyclotrisilazane und bis(cyclodisilazan-1-yl)silane

Di-lithiated octamethylcyclotetrasilazane (OMCTS, 1) reacts with halosilanes in different ways. Ring contraction with formation of the isomeric cyclodisilazanes 2, 3 occurs in the reaction with chloro- and fluorotrimethylsilanes. Substitution (6) and ring contraction with formation of the isomeric six-membered ring 7 occurs with chlorodimethylsilane. 2, 3, 6 and 7 are excellent precursors of silyl-bridged, SiH-functional, four-membered ring systems (4, 5, 9–11). The mechanism of the isomerization reactions are discussed.     

Synthesis,renal vasodilator and dopamine-sensitive adenylate cyclase activities of O-Methyl derivatives of 6-chloro-2,3,4,5-tetr ahydro-1-(4-hydroxyphenyl)-1H-3-benzazepin-7,8-diol (SK&F 82526)

The three possible mono-O-methyl derivatives of 6-chloro-2,3,4,5-tetrahydro-1-(4-hydroxyphenyl)-1H-3-benzazepin-7,8-diol (SK&F 82526) ( 1 ) have been synthesized to facilitate the isolation and characterization of metabolites of this compound and for biological testing. The syntheses generally involved preparation of appropriately substituted benzaldehydes, conversion of these to phenylacetic acids and use of these to N-acylate arylethanolamines. The phenylacetamides thus formed were reduced to amines and these were deprotected and cyclized to the desired final products. In one case deprotection followed cyclization. These compounds were tested as activators of dopamine-sensitive adenylate cyclase (a measure of DA-1 agonist activity) and as renal vasodilators. All three O-methyl derivatives were much less potent than 1 in cyclase activation and as renal vasodilators. Weak inhibition of adenyl cyclase was also observed for all three compounds and one showed weak renal vasoconstrictor activity. Preliminary investigation of the metabolism of 1 disclosed that two of the three monomethoxy compounds were formed in trace amounts in the rat and the dog. In a related investigation, the trimethoxy derivative of 1 was subjected to acid-catalyzed hydrolysis conditions. The relative ease of cleavage of methoxy groups was 7 > > 4′ > 8.     

Untersuchungen über ternäre Chalkogenide. XXIV. Zur Struktur des TlGaSe2

On Ternary Chalcogenides. XXIV. The Structure of TlGaSe₂ TlGaSe₂ is monoclinic with a = 10.772(3), b = 10.771(5), c = 15.636(8) Å, ß = 100.6(3)°, Z = 16, space group Cc. The refinement yielded an R value of 0.082 for 1366 unique observed reflections (MoKα). The compound crystallizes with a layer structure with two anion layers perpendicular to c* in the unit cell. The structural motive of the layers are large corner-linked Ga₄Se₁₀- tetraeder consisting of four corner-linked GaSe₄ tetrahedra. Two adjacent layers are turned relative to each other by 90°. They are kept together by Tl¹⁺ ions, which are situated on straight lines parallel to the edges of the Ga₄Se₁₀ groups. They are surrounded by six selenium atoms forming trigonal-prismatic TlSe₆ polyhedra. 4₂ screw-axes within the layers are the reason for a strongly pronounced pseudo tetragonal symmetry. Different possibilities of stacking cause a onedimensional disorder along the c* direction. The relations between the TlGaSe₂ type and the TlSe type and also the high-pressure modifications of some compounds with the TlGaSe₂ structure are discussed.     

Templated ceramic microstructures by using the breath-figure method

We describe the synthesis of two cyclobutadiene(cyclopentadienyl)cobalt-containing poly(p-phenylene ethynylene)s (PPEs) and their use as precursors for stable ceramic surface coatings. Organometallic PPEs were shaped into hexagonally ordered assemblies by using the breath-figure method. Such breath figures can be washed away with an appropriate solvent. Upon pyrolysis at 500 degrees C under either nitrogen or air, the bubble arrays persist as ceramics and are insoluble in organic solvents or water. The formed pyrolyzed bubble arrays were analyzed by optical and scanning electron microscopy, as well as energy dispersive X-ray microanalysis (EDX). The composition of the ceramic materials is discussed based on EDX and IR data.     

Nonspecific interactions of a carboxylate-substituted PPE with proteins. A cautionary tale for biosensor applications

Two carboxylate-substituted, fluorescent (Phi = 0.08), water-soluble poly(p-phenyleneethynylene)s (PPE) and a water-soluble model compound were exposed to a series of proteins and bovine serum. While the anionic PPEs do not have any specific binding sites, they form stable complexes with histone, lysozyme, myoglobin, and hemoglobin. The complex formation was evidenced by fluorescence quenching. Bovine serum albumin does not quench the fluorescence of the PPEs but enhances it, probably due to its surfactant character. These results imply that the use of charged conjugated polymers as biosensors, while an attractive proposition, has to take into account strong nonspecific interactions between conjugated polymers and the host of proteins that is found in cells and complex biological fluids.     

High performance liquid chromatographic separation of dipeptide and tripeptide enantiomers using a chiral crown ether stationary phase

A chiral stationary phase (CSP) based on (-)-(18-crown-6)-2,3,11,12-tetracarboxylic acid was evaluated for the direct resolution of the enantiomers of dipeptides and tripeptides. The type and concentration of the acid and the methanol content were optimized with regard to retention time and resolution using Ala-Phe as model peptide. A mobile phase consisting of 10 mM sulfuric acid in 70% aqueous methanol was applied to the separation of a set of 16 structurally diverse dipeptides and tripeptides. Generally, the configuration of the amino acid at the N-terminus determined the enantiomer elution order. With a few exceptions the LL- and LD-enantiomers interacted stronger with the CSP compared to the corresponding DD- or DL-enantiomers. The experimental conditions also allowed the simultaneous separation of all four stereoisomers of Ala-Phe. Addition of ammonium sulfate generally reduced retention times and enantiomer resolution. Addition of triethylamine as modifier led to an overall increase of the retention times while the resolution did not show a general trend, increasing in the case of Ala-Ala but decreasing in the case of Ala-Phe.     

Beiträge zur Chemie des Phosphors. 111. 1,2-Dichlor-1,2-di-tert-butyldiphosphan

Contributions to the Chemistry of Phosphorus. 111. 1,2-Dichloro-1,2-di-tert-butyl-diphosphane The reaction of tri-tert-butyl-cyclotriphosphane, (t-BuP)₃, with phosphorus(V) chloride (molar ratio 1:2) leads to the title compound Cl(t-Bu)P? P(t-Bu)Cl ( 1 ), which is remarkably stable against disproportionation reactions. As the first 1,2-dichloro-1,2-diorganyldiphosphane, 1 has been isolated in a pure state and was thoroughly characterized. At room temperature, 1 exists in a mixture of the d,l and meso form (about 20:80). The mutual repulsion of the negative polarized Cl atoms and their preferred gauche arrangement to the free electron pairs of neighboured P atoms leads to a gauche-conformation of the lone electron pairs in the d,l- and to a trans-conformation in the meso-configuration.     

Zur Reaktion von Hydrazinen mit Fluorsilanen und lithiierten Aminen

Lithium salts of hydrazines react with fluorosilanes under formation of fluorosilylhydrazines and LiF. Five membered rings are obtained in the reaction of bis(fluorosilyl)-hydrazines with lithiated amines. The mass,¹H-and¹⁹F-nmr spectra of the compounds are reported.

     

Mass spectrometric analysis of ceramic components for solid oxide fuel cells

For the determination of trace impurities in ceramic components of solid oxide fuel cells (SOFCs), some mass spectrometric methods have been applied such as spark source mass spectrometry (SSMS), laser ionization mass spectrometry (LIMS), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and inductively coupled plasma mass spectrometry (ICP-MS). Due to a lack of suitable standard reference materials for quantifying of analytical results on La _x Sr _y MnO₃ cathode material a matrix-matched synthetic standard-high purity initial compounds doped with trace elements-was prepared in order to determine the relative sensitivity coefficients in SSMS and LA-ICP-MS. Radiofrequency glow discharge mass spectrometry (rf-GDMS) was developed for trace analysis and depth profiling of thick non-conducting layers. Surface analytical techniques, such as secondary ion mass spectrometry (SIMS) and sputtered neutral mass spectrometry (SNMS), were used to determine the element distribution on surfaces (homogeneity) and the surface contaminants of SOFC ceramic layers.Dedicated to Professor Dr. rer. nat. Hubertus Nickel on the occasion of his 65th birthday