Study of Electrochemical Oxidation of Xanthohumol by Ultra-Performance Liquid Chromatography Coupled to High Resolution Tandem Mass Spectrometry and Ion Mobility Mass Spectrometry

Electrochemically assisted oxidation off-line combined with UPLC/ESI–MS and ion mobility mass spectrometry enabled us to gain insight into the oxidation mechanisms of xanthohumol. Several types of monomeric oxidation products were identified, i.e., monohydroxylated and dehydrogenated derivatives and related quinones. Besides, high contents of dimers were observed. The structures of four main oxidative condensation products of two xanthohumol molecules were proposed based on combination of retention time, exact mass measurement, fragmentation pattern, data from on-line ion mobility mass spectrometric experiments and with the support of independent electrochemical experiments. To the best of our knowledge, this is the first evidence on formation of xanthohumol dimers. The effect of the pH on the generation of oxidation products was further investigated. The monomeric and dimeric oxidation products are favored at pH of 5.5 and 4.5, respectively.

     

Homopolar dihydrogen bonding in alkali-metal amidoboranes and its implications for hydrogen storage

The solid-state structures of LiNH(2)BH(3) and NaNH(2)BH(3) have been shown recently to exhibit intricate M(δ+)···(δ-)H-B and N-H(δ+)···(δ-)H-B interactions. However, closer inspection of these structures reveals additional homopolar H···H interactions, viz., B-H(δ-)···(δ-)H-B and N-H(δ+)···(δ+)H-N, which contribute to the relative stability of the extended structures of these crystalline materials. In addition, an NMR study of the isotopomer LiND(2)BH(3) shows that a significant quantity of H(2) is desorbed thermally along with HD, which can only arise from hydride-hydride interactions, either directly from B-H(δ-)···(δ-)H-B moieties or indirectly through the participation of Li-H intermediates.     

Characterization of silver nanoparticles using flow-field flow fractionation interfaced to inductively coupled plasma mass spectrometry

The ability to detect and identify the physiochemical form of contaminants in the environment is important for degradation, fate and transport, and toxicity studies. This is particularly true of nanomaterials that exist as discrete particles rather than dissolved or sorbed contaminant molecules in the environment. Nanoparticles will tend to agglomerate or dissolve, based on solution chemistry, which will drastically affect their environmental properties. The current study investigates the use of field flow fractionation (FFF) interfaced to inductively coupled plasma-mass spectrometry (ICP-MS) as a sensitive and selective method for detection and characterization of silver nanoparticles. Transmission electron microscopy (TEM) is used to verify the morphology and primary particle size and size distribution of precisely engineered silver nanoparticles. Subsequently, the hydrodynamic size measurements by FFF are compared to dynamic light scattering (DLS) to verify the accuracy of the size determination. Additionally, the sensitivity of the ICP-MS detector is demonstrated by fractionation of μg/L concentrations of mixed silver nanoparticle standards. The technique has been applied to nanoparticle suspensions prior to use in toxicity studies, and post-exposure biological tissue analysis. Silver nanoparticles extracted from tissues of the sediment-dwelling, freshwater oligochaete Lumbriculus variegatus increased in size from approximately 31-46nm, indicating a significant change in the nanoparticle characteristics during exposure.     

Transient entanglements and clusters in dilute polymer solutions

A convenient method to monitor polymer dissolution is to measure the pressure drop created by passing a polymer solution through a capillary constriction rheometer. In this work, we studied the dissolution of polyethylene oxide (PEO) and cationic starch (C‐starch). We found that for freshly dissolved and entangled PEO, the main contribution to the overall pressure drop is due to the contraction and expansion of PEO entanglements at the entrance and exit of the capillary, and that the friction in the capillary plays a minor role. On the other hand, for well‐dissolved PEO, because of the absence of PEO entanglements, the loss of pressure is mainly due to friction. At high velocities the contraction and expansion coefficient for freshly dissolved PEO was more than 20 times higher than for well‐dissolved PEO, resulting in a three times higher overall pressure drop. C‐starch consists of amylopectin (～ 85%) and amylose and is known to contain clusters when freshly dissolved, likely formed from the globular amylopectin molecules. For C‐starch, the main contribution to the overall pressure drop is due to friction. Entrance and exit effects contribute only 10% to the overall pressure drop, which might be due to the linear amylose molecules in C‐starch. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 253–262, 2008     

Facial characterization of simplexes

After providing a survey of the pertinent known literature, this paper defines the notion of a face of class B of a compact convex set and provides necessary and sufficient conditions on the class of all such faces in order that the given convex set be a Choquet simplex.     

Search for doubly charged Higgs bosons with lepton-flavor-violating decays involving tau leptons

We search for pair production of doubly charged Higgs particles (H+/- +/-) followed by decays into electron-tau (etau) and muon-tau (mutau) pairs using data (350 pb(-1) collected from [over]pp collisions at sqrt[s]=1.96 TeV by the CDF II experiment. We search separately for cases where three or four final-state leptons are detected, and combine results for exclusive decays to left-handed etau (mutau) pairs. We set an H+/- +/- lower mass limit of 114(112) GeV/c(2) at the 95% confidence level.