Detection, quantification, and identification of dermorphin in equine plasma and urine by LC–MS/MS for doping control

Dermorphin is a unique opioid peptide that is 30–40 times more potent than morphine. It was misused and went undetected in horse racing until 2011 when intelligence obtained from a few North American race tracks suggested its use. To prevent such misuse, a reliable analytical method became necessary for detection and identification of dermorphin in post-race horse samples. This paper describes the first liquid chromatography–tandem mass spectrometry (LC–MS/MS) method for such a purpose. Equine plasma and urine samples were pre-treated with ethylenediamine tetra-acetic acid and urea prior to solid-phase extraction (SPE) on Oasis MCX cartridges. Resulting eluates were dried under vacuum and analyzed by LC–MS/MS for dermorphin. The matrix effect, SPE efficiency, intra-day and inter-day accuracy and precision, and stability of the analyte were assessed. The limit of detection was 10 pg/mL in plasma and 20 pg/mL in urine, and the limit of confirmation was 20 pg/mL in plasma and 50 pg/mL in urine. Dermorphin in plasma is stable at ambient temperature, but its diastereomer is unstable. With isotopically labeled dermorphin as an internal standard, the quantification range was 20–10,000 pg/mL in plasma and 50–20,000 pg/mL in urine. The intra-day and inter-day accuracy was from 91 % to 100 % for the low, intermediate, and high concentrations. The intra-day and inter-day coefficients of variation were less than 12 %. The method differentiates dermorphin from its diastereomer. This method is very specific for identification of dermorphin in equine plasma and urine, as assessed by BLAST search and targeted SEQUEST search, and by MS/MS spectrum library search. The method has been successfully applied to analysis of samples collected following dermorphin administration to research horses and of official post-race samples.

Regioselective Synthesis of Benzofuran‐Annulated Six‐Membered Sulfur Heterocycles by Aryl Radical Cyclization

The tin hydride–mediated cyclization of a number of sulfides and sulfones under mild and neutral conditions has been investigated. The sulfides were in turn derived from 3(2H) benzothiofuranone and 2‐bromobenzyl bromides by phase‐transfer‐catalyzed reaction, and the corresponding sulfones were prepared by treatment of the corresponding sulfides with m‐CPBA at room temperature. The sulfides and sulfones were then reacted with ⁿ Bu₃SnH‐AIBN to afford regioselectively benzofuran‐annulated six‐membered sulfur heterocycles.     

Search of truncation of (N−1) electron basis containing full connected triple excitations in computing main and satellite ionization potentials via Fock‐space coupled cluster approach

A valence‐universal multireference coupled cluster (VUMRCC) theory, realized via the eigenvalue independent partitioning (EIP) route, has been implemented with full inclusion of triples excitations for computing and analyzing the entire main and several satellite peaks in the ionization potential spectra of several molecules. The EIP‐VUMRCC method, unlike the traditional VUMRCC theory, allows divergence‐free homing‐in to satellite roots which would otherwise have been plagued by intruders, and is thus numerically more robust to obtain more efficient and dependable computational schemes allowing more extensive use of the approach. The computed ionization potentials (IPs) as a result of truncation of the (N−1) electron basis manifold involving virtual functions such as 2h‐p and 3h‐2p by different energy thresholds varying from 5 to 15 a.u. with 1 a.u. intervals as well as thresholds such as 20, 25, and 30 a.u. have been carefully looked into. Cutoff at around 25 a.u. turns out to be an optimal threshold. Molecules such as C₂H₄ and C₂H₂ (X = D,T), and N₂ and CO (X = D,T,Q) with Dunning's cc‐pVXZ bases have been investigated to determine all main and 2h‐p shake‐up and 3h‐2p double shake‐up satellite IPs. We believe that the present work will pave the way to a wider application of the method by providing main and satellite IPs for some problematic N‐electron closed shell systems. © 2013 Wiley Periodicals, Inc.     

Control of molecular architecture by hydrogen bonding: mononuclear versus dinuclear copper(II) complexes with tridentate N2O donor Schiff base isomers

Two isomeric Schiff bases, HL ¹  = 1-[(2-dimethylamino-ethylimino)-methyl]-naphthalen-2-ol and HL ²  = 1-[(2-ethylamino-ethylimino)-methyl]-naphthalen-2-ol, have been used to prepare copper(II) complexes in presence of thiocyanate. HL ¹ forms a mononuclear complex [Cu(L ¹ )NCS] with terminal thiocyanate, whereas the isomeric Schiff base HL ² , which is capable of hydrogen bonding, gives a dimeric complex, [Cu₂ (L ² ) ₂(NCS)₂], with double μ-1,1-NCS bridges. Both complexes are characterized by physico-chemical and spectroscopic methods as well as by single crystal X-ray diffraction studies.     

Radioanalytical separation and size-dependent ion exchange property of micelle-directed titanium phosphate nanocomposites

Nanocomposite titanium-phosphate (TiP) of different sizes was synthesized using Triton X-100 (polyethylene glycol-p-isooctylphenyl ether) surfactant. The materials were characterized by FTIR and powdered X-ray diffraction (XRD). The structural and morphological details of the material were obtained by scanning electron microscopy (SEM) and transmission electron microscopy. The SEM study was followed by energy dispersive spectroscopic analysis for elemental analysis of the sample. The important peaks of the XRD spectra were analyzed to determine the probable composition of the material. The average size distribution of the particles was determined by dynamic light scattering method. Ion exchange capacity was measured for different metal ions with sizes of the TiP nanocomposite and size-dependent ion exchange property of the material was investigated thoroughly. The nanomaterial of the smallest size of around 43 nm was employed to separate carrier-free ^137mBa from ¹³⁷Cs in column chromatographic technique using 1.0 M HNO₃ as eluting agent at pH 5.     

Fabrication and Characterization of Zinc Oxide Nanowire Based Two-electrode Capacitive Biosensors on Flexible Substrates for Estimating Glucose Content in a Sample

The present work deals with fabrication and characterization of the zinc oxide (ZnO) nanowire based novel two-electrode capacitive biosensors on flexible Polyethylene terephthalate (PET) substrates for accurate estimation of glucose by analyzing the fundamental dielectric nature of the relevant sample. The morphology and crystalline quality of grown nanowires are analyzed by using field-emission scanning electron microscope (FESEM) and X-ray diffractometer (XRD), respectively. Current and capacitance values of the device have been studied for ten different glucose concentrations relevant to the physiological standards. The analytical performance of the devices in terms of enzyme activity, reliability and flexibility has also been evaluated.     

Partonic Flow and phi-Meson production in Au+Au collisions at sqrt radical sNN = 200 GeV

We present first measurements of the phi-meson elliptic flow (v2(pT)) and high-statistics pT distributions for different centralities from radical sNN=200 GeV Au+Au collisions at RHIC. In minimum bias collisions the v2 of the phi meson is consistent with the trend observed for mesons. The ratio of the yields of the Omega to those of the phi as a function of transverse momentum is consistent with a model based on the recombination of thermal s quarks up to pT approximately 4 GeV/c, but disagrees at higher momenta. The nuclear modification factor (R CP) of phi follows the trend observed in the K S 0 mesons rather than in Lambda baryons, supporting baryon-meson scaling. These data are consistent with phi mesons in central Au+Au collisions being created via coalescence of thermalized s quarks and the formation of a hot and dense matter with partonic collectivity at RHIC.     

The Roles of Composition and Mesostructure of Cobalt-Based Spinel Catalysts in Oxygen Evolution Reactions

By using the crystalline precursor decomposition approach and direct co-precipitation the composition and mesostructure of cobalt-based spinels can be controlled. A systematic substitution of cobalt with redox-active iron and redox-inactive magnesium and aluminum in a cobalt spinel with anisotropic particle morphology with a preferred 111 surface termination is presented, resulting in a substitution series including Co₃O₄, MgCo₂O₄, Co₂FeO₄, Co₂AlO₄ and CoFe₂O₄. The role of redox pairs in the spinels is investigated in chemical water oxidation by using ceric ammonium nitrate (CAN test), electrochemical oxygen evolution reaction (OER) and H₂O₂ decomposition. Studying the effect of dominant surface termination, isotropic Co₃O₄ and CoFe₂O₄ catalysts with more or less spherical particles are compared to their anisotropic analogues. For CAN-test and OER, Co³⁺ plays the major role for high activity. In H₂O₂ decomposition, Co²⁺ reveals itself to be of major importance. Redox active cations in the structure enhance the catalytic activity in all reactions. A benefit of a predominant 111 surface termination depends on the cobalt oxidation state in the as-prepared catalysts and the investigated reaction.     

Self‐Assembly of DNA–Oligo(p‐phenylene‐ethynylene) Hybrid Amphiphiles into Surface‐Engineered Vesicles with Enhanced Emission

Surface‐addressable nanostructures of linearly π‐conjugated molecules play a crucial role in the emerging field of nanoelectronics. Herein, by using DNA as the hydrophilic segment, we demonstrate a solid‐phase “click” chemistry approach for the synthesis of a series of DNA–chromophore hybrid amphiphiles and report their reversible self‐assembly into surface‐engineered vesicles with enhanced emission. DNA‐directed surface addressability of the vesicles was demonstrated through the integration of gold nanoparticles onto the surface of the vesicles by sequence‐specific DNA hybridization. This system could be converted to a supramolecular light‐harvesting antenna by integrating suitable FRET acceptors onto the surface of the nanostructures. The general nature of the synthesis, surface addressability, and biocompatibility of the resulting nanostructures offer great promises for nanoelectronics, energy, and biomedical applications.     

Rules of Boron–Nitrogen Doping in Defect Graphene Sheets: A First‐Principles Investigation of Band‐Gap Tuning and Oxygen Reduction Reaction Catalysis Capabilities

Introduction of defects and nitrogen doping are two of the most pursued methods to tailor the properties of graphene for better suitability to applications such as catalysis and energy conversion. Doping nitrogen atoms at defect sites of graphene and codoping them along with boron atoms can further increase the efficiency of such systems due to better stability of nitrogen at defect sites and stabilization provided by B?N bonding. Systematic exploration of the possible doping/codoping configurations reflecting defect regions of graphene presents a prevalent doping site for nitrogen‐rich BN clusters and they are also highly suitable for modulating (0.2–0.9 eV) the band gap of defect graphene. Such codoped systems perform significantly better than the platinum surface, undoped defect graphene, and the single nitrogen or boron atom doped defect graphene system for dioxygen adsorption. Significant stretching of the O?O bond indicates a lowering of the bond breakage barrier, which is advantageous for applications in the oxygen reduction reaction.