Determination of ethane,pentane and isoprene in exhaled air using a multi-bed adsorbent and end-cut gas-solid chromatography

A method for the determination of exhaled ethane, pentane and isoprene was developed and validated. The method was based on pre-concentration of the analytes on a multi-bed solid adsorbent tube containing Tenax TA, Carboxen 569 and Carboxen 1000, thermal desorption and gas chromatography (GC) with flame ionisation detection (FID). A pre-column in an end-cut GC system was used to avoid problems with water and strongly retained substances. The detection limits were 5, 2 and 6 pmol per sample for ethane, pentane and isoprene, respectively, using a sample volume of 500 ml. The linearity was good for all analytes with correlation coefficients exceeding 0.999. The repeatability for exhaled air samples was 7, 10 and 12% for ethane, pentane and isoprene, respectively. Analysis of a certified reference material of ethane and pentane did not differ significantly from the certified values. Ethane and pentane levels were stable up to six days of storage in sample tubes. Isoprene levels were not stable during storage in the sample tubes used here, but using Carbopack X instead of Carboxen 569, levels were stable up to two days. The levels of exhaled ethane, pentane and isoprene in healthy subjects (n = 4) were 8.1+/-5.8 pmol l(-1), 11+/-5.8 pmol l(-1) and 2.4+/-0.90 mnol l(-1), respectively. The method could, with minor modifications, be used to determine other low-molecular hydrocarbons in exhaled air as well.     

Ionization energies of the nucleotides

The vertical ionization energies of the four nucleotides have been computed. Geometries have been chosen to mimic orientations as they appear in B-DNA. The negative charge on the phosphate was neutralized by protonation, and also by the inclusion of counterions. Calculations have been performed with electron propagator methods (P3), M?ller-Plesset second-order perturbation theory, and density functional theory to determine the nature of the orbitals associated with the highest lying ionization energies. Calculations at the MP2/6-311G(d,p)//P3/6-311G(d,p) level of theory yield vertical ionization energies for 5'-dTMP 9.05 eV, for 5'-dCMP 8.40 eV, for 5'-dAMP 8.16 eV and for 5'-dGMP 7.96 eV. In all cases the highest occupied molecular orbital resides on the base moieties.     

Biochemical and biomedical application of monodisperse polymer particles

Macroporous particles with large pores are used for size exclusion chromatography of carbohydrates with very high molecular weights. Macroporous particles of different sizes are used for multiple immunofluorometric analysis by flow cytometry. Porous magnetic particles with protein A coupled to the surface of the pores combine a high capacity in binding of IgG with easy handling of the particles. Magnetic beads with boronic acid coupled to the surface are applied for selective isolation of subclasses of cells. The beads are detached from the cells by addition of sorbitol, leaving free, pure cell fractions in good yield. The use of magnetic particles in molecular biology is described.     

Exploiting the Aromatic Chameleon Character of Fulvenes for Computational Design of Baird‐Aromatic Triplet Ground State Compounds

Due to the reversal in electron counts for aromaticity and antiaromaticity in the closed‐shell singlet state (normally ground state, S₀) and lowest ππ* triplet state (T₁ or T₀), as given by Hückel's and Baird's rules, respectively, fulvenes are influenced by their substituents in the opposite manner in the T₁ and S₀ states. This effect is caused by a reversal in the dipole moment when going from S₀ to T₁ as fulvenes adapt to the difference in electron counts for aromaticity in various states; they are aromatic chameleons. Thus, a substituent pattern that enhances (reduces) fulvene aromaticity in S₀ reduces (enhances) aromaticity in T₁, allowing for rationalizations of the triplet state energies (E_T) of substituted fulvenes. Through quantum chemical calculations, we now assess which substituents and which positions on the pentafulvene core are the most powerful for designing compounds with low or inverted E_T. As a means to increase the π‐electron withdrawing capacity of cyano groups, we found that protonation at the cyano N atoms of 6,6‐dicyanopentafulvenes can be a route to on‐demand formation of a fulvenium dication with a triplet ground state (T₀). The five‐membered ring of this species is markedly Baird‐aromatic, although less than the cyclopentadienyl cation known to have a Baird‐aromatic T₀ state.     

Design of novel bilayer compounds of the CPO-8 type containing 1D channels

The reaction between Zn(NO3)2.6H2O and 5-aminoisophthalic acid (aip) in a mixture of diethylformamide (DEF) and ethanol resulted in [Zn(C8H5NO4)(C5H11NO)]n (CPO-8-DEF). This compound is composed of infinite 2D layers with tetrahedral Zn atoms and aip ligands in a triangular topology. The DEF molecules are bonded to Zn, and within each layer, the DEF molecules are oriented in the same direction, while in the subsequent layer, the DEF molecules are oriented in the opposite direction. By introduction of the pillaring ligands 4,4-bipyridine (BPY), 1,2-di-4-pyridylethylene (DPE), 1,2-di-4-pyridylethane (DPA), and 1,3-di-4-pyridylpropane (DPP) into mixtures of N,N'-dimethylformamide and water with Zn(NO3)2 and aip, we have successfully synthesized a series of related pillared bilayer compounds with the same common triangular Zn(aip) layer structural motif as that observed in CPO-8-DEF. The compounds are denoted as CPO-8-BPY ([Zn(C8H5NO4)(C10H8N2)(0.5)]n.3nH2O), CPO-8-DPE ([Zn(C8H5NO4)(C12H10N2)(0.5)]n.2.5nH2O), CPO-8-DPA ([Zn(C8H5NO4)(C12H12N2)(0.5)]n.2.5nH2O), and CPO-8-DPP ([Zn(C8H5NO4)(C13H14N2)(0.5)]n.3nH2O). In all cases, the pillars create spaces inside the bilayers that result in 1D channels running along the [010] directions with dimensions of 3.5 x 6.7 A(2). These channels contain water molecules that can be removed on heating to 150 degrees C, resulting in porous structures. The crystal structures of these porous high-temperature variants have been determined on the basis of powder X-ray diffraction data. All of the compounds show preferential adsorption of H2 over N2 at 77 K.     

A revisit to the bending problem of a thin elliptic aelotropic plate with simply supported edge and uniform lateral load

The complex solution method of Okubo for the deflection of a thin circular aelotropic plate with simply supported edge and uniform lateral load was extended to an elliptic plate by Ohasi. In his work however several inconsistencies appear, of which at least one disqualifies a central part. From a revisit to the works of Okubo and Ohasi a new solution for the deflection of a thin elliptic aelotropic plate with simply supported edge and uniform lateral load emerged. The solution is a generalisation of Okubo’s solution and is valid for any angle between material and geometric principal axes. Previously known solutions, including those for circular plates, are reproduced as special cases of the new solution and results of numerical calculations in new situations appear reasonable.     

Rank estimates in a class of semiparametric two-sample models

We consider a two-sample semiparametric model involving a real parameter and a nuisance parameter F which is a distribution function. This model includes the proportional hazard, proportional odds, linear transformation and Harrington-Fleming models (1982, Biometrika, 69, 533–546). We propose two types of estimates based on ranks. The first is a rank approximation to Huber's M-estimates (1981, Robust Statistics, Wiley) and the second is a Hodges-Lehmann type rank inversion estimate (1963, Ann. Math. Statist., 34, 598–611). We obtain asymptotic normality and efficiency results. The estimates are consistent and asymptotically normal generally but fully efficient only for special cases.Research partially supported by National Science Foundation Grant DMS-86-02083 and National Institute of General Medical Sciences Grant SSS-Y1RO1GM35416-01     

Third Rank Killing Tensors in General Relativity. The (1 + 1)-dimensional Case

Third rank Killing tensors in (1 +1)-dimensional geometries are investigated andclassified. It is found that a necessary and sufficientcondition for such a geometry to admit a third rankKilling tensor can always be formulated as a quadratic PDE, oforder three or lower, in a Kahler type potential for themetric. This is in contrast to the case of first andsecond rank Killing tensors for which the integrability condition is a linear PDE. The motivation for studying higher rank Killing tensors in (1 +1)-geometries, is the fact that exact solutions of theEinstein equations are often associated with a first orsecond rank Killing tensor symmetry in the geodesicflow formulation of the dynamics. This is in particulartrue for the many models of interest for which thisformulation is (1 + 1)-dimensional, where just one additional constant of motion suffices forcomplete integrability. We show that new exact solutionscan be found by classifying geometries admitting higherrank Killing tensors.     

Mass spectrometry of onium compounds—IV: Diazonium salts

The zwitterions of diazotized ortho and para aminophenol are very volatile and give strong peaks in the mass spectra corresponding to the molecular ion. The m-isomer, which cannot be stabilized through a simple quinonoid structure, gives rise to a complex spectrum through decomposition and coupling reactions. The zwitterions of diazotized anthranilic and sulphanilic acids did not give the molecular ion peak.     

Photochemistry of the anthracene chromophore: novel isomerization of 1-(9-anthryl)-2-benzoylethylenes

Photoexcited cis-1-(9-anthryl)2-benzoylethylenes undergo a novel type of isomerization by skeletal rearrangement to give furano-annelated 5H-dibenzo[a,d]cycloheptenes.