A chromatographic determination of nitrate with amperometric detection at a copperized cadmium electrode

A copperized cadmium flow-through electrode is applied for cathodic detection of nitrate in the effluent stream of a liquid chromatograph. The nitrate is separated from dissolved oxygen in a small (10 cm) column of strong-base, anion-exchange resin (Dowex 1-X8) with 5 mM perchloric acid as the eluent. The effluent stream is buffered to pH 8 by mixing with a stream of buffer prior to detection. A large excess of chloride added to the sample dramatically improves the separation of nitrate from dissolved oxygen in the sample.     

Photochemically modulated endothelial cell thrombogenicity via the thrombomodulin-tissue factor pathways

Photodynamic therapy (PDT) is based on a photochemical reaction using a photosensitizer and light to produce reactive oxygen species that have biological effects. Although its application in some fields is largely based on thrombosis, in the vascular setting thrombosis must be prevented. In this study we examined the effects of PDT on the changes in activity of thrombomodulin (TM) and tissue factor (TF) as important regulators of the coagulation process of endothelial cells. Human umbilical vein endothelial cells were treated with PDT (chloro-aluminum-sulfonated phthalocyanine, lambda = 630 nm) at different light-energy doses, and TM and TF levels were measured using fluorescence spectroscopy. Microparticles (MP) were analyzed using flow cytometry analysis. PDT alters the thrombogenic state of endothelial cells by causing decreased expression of TM and increased expression of functional TF in a light-energy dose-dependent way. PDT-treated endothelial cells shed large numbers of MP containing high levels of TF. TF functionality of PDT-treated cells, measured by a Factor Xa-generating assay, was high. TF was located mostly intracellularly and in MP. The disturbed anticoagulant balance described in this study may explain the occurrence of thrombosis induced by PDT and, if not contained, dispute the suitability of PDT as an adjuvant modality to treat vascular restenosis.     

Aldol reactions of a cyclobutanone enolate

Addition of an aldehyde and zinc chloride to a cyclobutanone enolate, prepared by the reaction of an α-chlorocyclobutanone with dimethylcopperlithium, gave an aldol adduct in good yield.     

Determination of interferon-gamma in Chinese hamster ovary cell culture supernatant by coupled-column liquid chromatography

A robust tandem HPLC method coupling size-exclusion (Shodex Asahipak GS-320HQ) and reversed phase (Vydac 218TP54) columns with ultraviolet detection was developed for quantitative determination of interferon-gamma (IFN-gamma) in Chinese hamster ovary cell culture supernatant. The 2D-HPLC system was linked up by a 6-port 2-position low hold-up volume switch valve. Compared to a commercial ELISA kit for IFN-gamma, the coupled column LC approach was able to detect and quantify soluble IFN-gamma, regardless of the glycoprotein's molecular/conformational variability and sample background. Each LC-LC analysis took 90 minutes inclusive of column regeneration. The relative standard deviation of measurements (n = 5) was less than 3%. The limit of detection (LOD) was determined to be 0.35 microg IFN-gamma.     

Regioselective synthesis of antiparallel loops on a macrocyclic scaffold constrained by oxazoles and thiazoles

The regioselective syntheses and structures are reported for two tris-macrocylic compounds, each possessing two antiparallel loops on a macrocyclic scaffold constrained by two oxazoles and two thiazoles. NMR solution structures show the loops projecting from the same face of the macrocycle. Such molecules are shown to be prototypes for mimicking multiple loops of proteins.[structure: see text]     

Fourier multipliers of Lipschitz spaces

Let G denote an infinite, compact, metrizable, 0-dimensional, Abelian group. The following are characterized: (i) the multipliers from one Lipschitz space Lip(α, p; G) to another Lipschitz space Lip(β, q; G) for 0 < α < β < ∞ and 1 ? p, q ? ∞; and (ii) the multipliers from Lip(α, p; G) to Lip(β, q; G) for 0 < β ? α < ∞ and 1 < q ? 2 ? p < ∞. Two special cases of (i), namely the case q = ∞ and the case p = 1, were obtained by the authors in an earlier publication (1981). A. Zygmund (J. Math. Mech.8 (1959), 889–895) and T. Mizuhara (Tôhoku Math. J.24 (1972), 263–268) have characterized the multipliers of certain Lipschitz spaces defined on the circle group.     

A diatropic ring current in a fluorofullerene trannulene

Ipsocentric current-density maps for a fluorofullerene derivative, C60F15H3, modelling the addition pattern of the experimentally characterised C60F15[CBr(CO2Et)2]3 which contains an [18]trans-annulene system, reveal a diamagnetic ring current dominated by the contribution of the four HOMO electrons, as in a classical (4n + 2) aromatic annulene.     

Terphenyl ligand systems in lanthanide chemistry: use of the 2,6-di(1-naphthyl)phenyl ligand for the synthesis of kinetically stabilized complexes of trivalent ytterbium, thulium, and yttrium

The molecular structures of terphenyl derivatives of trivalent ytterbium, thulium, and yttrium of general composition DnpLnCl(2)(THF)(2) [Dnp = 2,6-di(1-naphthyl)phenyl] are reported. The complexes (Ln = Yb: 1; Ln = Tm: 2; Ln = Y: 3) are synthesized by reaction of 1 equiv of DnpLi with 1 equiv of LnCl(3) (Ln = Yb, Tm, or Y) in tetrahydrofuran at room temperature in 50% yield. Attempts to prepare a Dnp scandium compound gave heterobimetallic [(THF)(3)Sc(2)OCl(5)Li(THF)](2) (4) in low yield. 1 crystallizes in the monoclinic space group C2/c. Crystal data for 1 at 203 K: a = 14.333(3) A, b = 16.353(3) A, c = 12.427(2) A, beta = 91.021(4) degrees, Z = 4, D(calcd) = 1.637 g cm(-3), R(1) = 4.44%. 2 crystallizes in the monoclinic space group C2/c. Crystal data for 2 at 203 K: a = 14.333(1) A, b = 16.374(2) A, c = 12.404(1) A, beta = 90.934(2) degrees, Z = 4, D(calcd) = 1.628 g cm(-3), R(1) = 3.00%. 3 crystallizes in the monoclinic space group C2/c. Crystal data for 3 at 203 K: a = 14.348(3) A, b = 16.476(3) A, c = 12.356(2) A, beta = 90.987(4) degrees, Z = 4, D(calcd) = 1.441 g cm(-3), R(1) = 5.62%. 4 crystallizes in the monoclinic space group P2(1)/n. Crystal data for 4 at 203 K: a = 11.0975(9) A, b = 11.0976(9) A, c = 21.3305(18) A, beta = 94.718(2) degrees, Z = 2, D(calcd) = 1.051 g cm(-3), R(1) = 3.45%. Complexes 1-3 represent examples of novel chiral (racemic) organometallic complexes of the lanthanide elements ytterbium and thulium and the group 3 element yttrium, respectively. The molecular structures of monomeric 1-3 exhibit distorted trigonal-bipyramidal coordination environments at the metal center, with the two oxygen atoms of the tetrahydrofuran ligands occupying the axial positions of a trigonal-bipyramidal coordination polyeder. The molecular structure of the scandium compound 4 shows a complex polynuclear heterobimetallic arrangement.     

An evaporation-based microfluidic sample concentration method

We present a method for sample concentration within microfluidic devices using evaporation-induced flow. Evaporation-induced flow is easy to incorporate into microfluidic designs and can be used to concentrate a wide variety of molecules. The practicality of this method was demonstrated with 0.2 microm fluorescent spheres and FITC-labeled BSA. Thirty two percent of the 0.6 microL fluorescent sphere suspension was concentrated into a well within a microfluidic device. In the same amount of time, 93% of the 0.6 microL FITC-labeled BSA solution was concentrated.     

Factorization of Lipschitz functions and absolute convergence of Vilenkin-Fourier series

LetG be a Vilenkin group (i.e., an infinite, compact, metrizable, zero-dimensional Abelian group). Our main result is a factorization theorem for functions in the Lipschitz spaces \(\mathfrak{L}\mathfrak{i}\mathfrak{p}\) (α,p; G). As colloraries of this theorem, we obtain (i) an extension of a factorization theorem ofY. Uno; (ii) a convolution formula which says that \(\mathfrak{L}\mathfrak{i}\mathfrak{p} (\alpha , r; G) = \mathfrak{L}\mathfrak{i}\mathfrak{p} (\beta , l; G)*\mathfrak{L}\mathfrak{i}\mathfrak{p} (\alpha - \beta , r; G)\) for 0<β<α<∞ and 1≤r≤∞; and (iii) an analogue, valid for allG, of a classical theorem ofHardy andLittlewood. We also present several results on absolute convergence of Fourier series defined onG, extending a theorem ofC. W. Onneweer and four results ofN. Ja. Vilenkin andA. I. Rubinshtein. The fourVilenkin-Rubinshtein results are analogues of classical theorems due, respectively, toO. Szász, S. B. Bernshtein, A. Zygmund, andG. G. Lorentz.