Tests for liquid chromatographs

Summary The paper describes tests for liquid chromatographs to assess the autosampler and pump flow rate precision; suitability of the instrument for normal phase chromatography; UV detector performance; and external band broadening characteristics. Tests for mixing and proportioning characteristics of solvent pumps and performance of diode array detectors are also considered. These tests are designed to evaluate the performance of both newly released liquid chromatography equipment and equipment already in operation. Data from evaluations carried out by instrument manufacturer’s and suppliers is reported and discussed. This data offers specifications to a common format for initial selection of instruments prior to purchase.     

A reinvestigation of o-phenylenemercurials : IV. Adducts of perfluorotribenzo[b,e,b][1,4,7]trimercuronin and the crystal and molecular structure of its 1 : 1 4-phenylpyridine solvate

Perfluorotribenzo[b,e,h][1,4,7]trimercuronin forms adducts of 1 : 1, 1 : 2 and 1 : 3 stoicheiometry with a variety of polar organic molecules. The structure of the 1 : 1 adduct with 4-phenylpyridine was solved by X-ray methods to an R factor of 7.4% for 3528 observed reflections.     

A solution for the lateral stability of beams using an electrical analog

This paper shows how an electrical-resistance analog based on the “conjugate-beam” concept and developed to simulate the elastic behavior of beams in the plane of loading may be used to examine the lateral buckling behavior of beams.     

Minimization of convex functionals over frame operators

We present results about minimization of convex functionals defined over a finite set of vectors in a finite-dimensional Hilbert space, that extend several known results for the Benedetto-Fickus frame potential. Our approach depends on majorization techniques. We also consider some perturbation problems, where a positive perturbation of the frame operator of a set of vectors is realized as the frame operator of a set of vectors which is close to the original one.     

The crystal and molecular structures of bis (pentafluorophenyl)disulphide and bis(pentafluorophenyl)diselenide

The structures of (C₆F₅)₂S₂ and (C₆F₅)₂Se₂ have been determined by single crystal, X-ray diffraction techniques. The compounds are isostructural although the molecules are packed differently in the crystal in comparison with their phenyl analogues. Important bond lengths and angles are: SS, 2.059(4)Å; SeSe, 2.319(4)Å; SC, 1.770Å; SeC, 1.910(15)Å; SSC, 101.3(3)°; SeSeC, 98.8(1)°.     

Identification of a major new involatile N-nitroso compound in smoked bacon

The new N-nitroso compound identified in smoked bacon is 2-(hydroxymethyl)-3-nitrosothiazolidine-4-carboxylic acid. Identification was based on comparison of data from liquid chromatography, capillary gas chromatography and mass spectrometry with those for the authentic compound, the synthesis of which is described.     

Low-energy electrons and X-ray irradiation effects on plasma-polymerized allylamine bioactive coatings for stents

Radiation used in biomedical applications causes chemical changes to biomedical materials. This work is an ex situ simulation of the influence of low-energy electron (LEE) impact and X-ray irradiation on the chemical properties of plasma-polymerized allylamine (PPA) bioactive and biocompatible stent coatings. Preliminary X-ray photoelectron spectroscopy (XPS) results show that PPA coatings oxidize in contact with ambient air by the detection of C-O and CO bonds which are typical of polymer oxidation. Chemical changes after LEE and X-ray irradiation are mainly a loss of oxygen, assuming a surface deoxidizing and not a complete destruction of the surface. XPS survey analyses show that the amine groups remain stable during irradiation. LEE impact measurements by TOF mass spectrometry show that the main ionic losses are H⁻ ions. It appears that CN groups are stable under irradiation and we observe a loss of hydrogen and oxygen as the main chemical modifications. In conclusion, these results suggest that PPA coatings are stable under biomedical radiation, and they can therefore be used for bioactive and biocompatible stent coatings.     

Towards a fluorescent molecular switch for nucleic acid biosensing

A novel fluorescent molecular switch for the detection of nucleic acid hybridization has been explored in relation to the development of a structure that would be amenable for operation when immobilized for solid-phase analyses. The structure was prepared by self-assembly, and used Neutravidin as the central multivalent docking molecule, a newly synthesized biotinylated long-chain linker for intercalating dye that was modified with thiazole orange (TO) at one end, and a biotinylated probe oligonucleotide. Self-assembly of the biotinylated components on adjacent Neutravidin binding sites allowed for physical placement of an oligonucleotide probe molecule next to tethered TO. The TO located at the end of the flexible linker chain was available to intercalate, and could report if a duplex structure was formed by a probe–target interaction by means of fluorescence intensity. Subsequently, regeneration of the single-stranded probe was possible without loss of the intercalator to solution. The switch constructs were assembled in solution and subsequently immobilized onto biotin functionalized optical fibers to complete the sensor design. Solution-phase fluorescence lifetime data showed a biexponential behavior for switch constructs, suggesting intercalation as well as a significant secondary binding mode for the immobilized TO. It was found that the secondary binding mechanism for the dye to DNA could be decreased, thus shifting the dye to intercalative binding modes, by adjusting the solution conditions to a pH below the pI of Neutravidin, and by increasing the ionic strength of the buffer. Preliminary work demonstrated that it was possible to achieve up to a fivefold increase in fluorescence intensity on hybridization to the target.