Chemiluminometric determination of carvedilol in a multi-pumping flow system

In this work a simple, fast, sensitive and selective flow-based procedure for the chemiluminometric determination of carvedilol, a recent non-cardioselective β-blocker with noteworthy antioxidant activity, is proposed. The developed methodology takes advantage of the antioxidant capacity of carvedilol to inhibit the chemiluminescence response resulting from the oxidation of luminol by hypochlorite, by acting as a hypochlorite scavenger. The analytical process was implemented in a multi-pumping flow system that employs multiple solenoid actuated micro-pumps as the only active components. These acted as solution insertion, propelling and commuting units assuring an easily controlled, low cost, compact and reliable analytical system.A linear working range for carvedilol concentrations ranging from 1.2 × 10⁻⁷ to 3.0 × 10⁻⁶ mol l⁻¹ (r > 0.999, n = 6), was obtained, with a detection limit of 8.7 × 10⁻⁹ mol l⁻¹. The system handles about 65 samples per hour yielding precise results (R.S.D. < 1.3%, n = 10). Recoveries within 95 and 104% were obtained.     

Neutron induced radiography in the determination of boron in drinking water

Neutron induced radiography has been applied to the determination of boron concentrations in drinking water, collected from natural springs of Reshian and Muzaffarabad areas of Azad Kashmir, Pakistan, using CR-39 etched track detectors. The technique is based upon the simultaneous irradiation with thermal neutrons of a sample of unknown concentration and a standard of known boron concentration, fixed on a track detector. The subsequent counting of alpha and ⁷Li tracks in the detector resulting from the ¹⁰B(n,)⁷Li nuclear reaction is done after chemical etching. Boron concentration in the sample is determined by comparing ⁷Li and alpha-particle track density with that of a standard of known boron concentration. Boron concentrations in drinking water samples from Muzaffarabad and Reshian area of Azad Kashmir have been found to vary from (0.054±0.001) mg/l to (0.250±0.004) mg/l with an average of (0.16±0.002) mg/l. The observed concentration of boron in drinking water has been found to be less than the provisional Maximum Acceptable Concentration level (0.4 mg//l) of WHO. The drinking water from the reported area has been found to be within safe limits as far as boron related health hazards are concerned.This revised version was published online in November 2005 with corrections to the Cover Date.     

Penicillamin-Komplexe des Nickels,Chroms und Molybdäns — Strukturelle Besonderheiten und biologische/medizinische Relevanz

Penicillamine Complexes of Nickel, Chromium, and Molybdenum — Structural Particularity and Biological/Medical Relevance The compounds Tl₂[Ni^II(H₂O)₆][Ni^II(D-pen)(L-pen)]₂[Ni^II(SCN)₂(H₂O)₄] 1 , Tl[Ni^II(D-pen)₂H] · H₂O 2 , Tl[Cr^III(D-pen)₂] 3 , and Na₂[MoO₄(pen)₂] · 3 CH₃OH · 3 H₂O 4 have been prepared by the reaction of nickel nitrate (for 1 ), nickel acetate (for 2 ), potassium chromate (for 3 ), and sodium molybdate (for 4 ) with D- and D, L-penicillamine, respectively. They were characterized by single-crystal X-ray structure analysis and other physical methods. Whereas penicillamine acts as a bidentate (N, S)-ligand in 1 and 2 , Cr^III (in 3 ), and Mo^V (in 4 ) are coordinated to the three ligand atoms N, O, and S. The presence of three different types of Ni^II-complexes a cationic, a neutral, and an anionic one in 1 is remarkable. For crystal data see Inhaltsübersicht.     

Enrichment of hydrophobic proteins via Triton X-114 phase partitioning and hydroxyapatite column chromatography for mass spectrometry

Membrane proteins are the starting point of several signal transduction pathways. Therefore, the separation and identification of these proteins are of great interest in proteome analysis. However, the specific properties of membrane proteins seriously impede their analysis. We present an effective and highly reproducible method for the two-dimensional separation of extremely hydrophobic proteins and demonstrate the advantages of special preseparation procedures for the identification of proteins which have very similar Mr and p/. Using the example of the integral membrane protein very low density lipoprotein (VLDL) receptor (NCBI Acc. # 1730111) and the soluble heat shock protein (HSP) 90 (NCBI Acc. # 386786) we present the applicability of a phase-separation system with Triton X-114. Using matrix assisted laser desorption/ionization-time of flight-mass spectrometry (MALDI-TOF-MS) of the protein spots after 2-D separation of the hydrophilic and the strongly hydrophobic protein fraction of human endothelial cells (ECV cell line), we were able to distinguish both proteins.     

Reatarding effect of nitrogen ylide for the polymerization of N-vinyl pyrrolidone

-Picolinium-p-chlorophenacylide (-PCFY) acts as a retarder for polymerization of N-vinyl pyrrolidone. The polymerization runs were carried out at 60°C using benzene as an inert solvent. The kinetic equation for the present system may be written asR _p [-PCPY]^–1.0 [AIBN]^0.66[N-VP]^1.0. The value of overall energy of activation for polymerization in presence and absence of-PCPY was computed as 44.0 and 42.3 kJ mol^–1, respectively. The inverse relationship ofR _p and¯M _v with-PCPY suggests that-PCPY acts as a polymerization retarder. The retarding effect is also evidenced by higher initiator exponent value and higher value of energy of activation in presence of ylide. A mechanism is also proposed in which polymer propagating chain combines with one ylide component to give resonance stabilized radical.     

Photodissociation of dimethylnitrosamine

Photodissociation of (CH₃)₂N-NO following S₁(nπ^*) ← S₀ excitation yields (CH₃)₂N^? and NO with a quantum yield of 1.03 ± 0.10. These fragments recombine leaving no stable photopioducts. A fraction of NO produced by photolysis is vibrationally excited. The rate of the NO(v = 1) relaxation in collision with (CH₃)₂N-NO, measured by IR fluorescence, is (1.47 ± 0.03) × 10⁴ s^?1 Torr^?1.     

Manganese pentacarbonyl bromide as candidate for a molecular qubit system operated in the infrared regime

Our concept for a quantum computational system is based on qubits encoded in vibrational normal modes of polyatomic molecules. The quantum gates are implemented by shaped femtosecond laser pulses. We adopt this concept to the new species manganese pentacarbonyl bromide [MnBr(CO)5] and show that it is a promising candidate in the mid-infrared (IR) frequency range to connect theory and experiment. As direct reference for the ab initio calculations we evaluated experimentally the absorption bands of MnBr(CO)5 in the mid-IR as well as the related transition dipole moments. The two-dimensional potential-energy surface spanned by the two strongest IR active modes and the dipole vector surfaces are calculated with density-functional theory. The vibrational eigenstates representing the qubit system are determined. Laser pulses are optimized by multitarget optimal control theory to form a set of global quantum gates: NOT, CNOT, Pi, and Hadamard. For all of them simply structured pulses with low pulse energies around 1 microJ could be obtained. Exemplarily for the CNOT gate we investigated the possible transfer to experimental shaping, based on the mask function for pulse shaping in the frequency regime as well as decomposition into a train of subpulses.     

Kinetics of oxidation of ethyldigol by vanadium(V) in aqueous acidic medium

The kinetics of oxidation of ethyldigol by vanadium(V) in aqueous acidic medium has been carried out. The reaction is first order with respect to vanadium(V) and the substrate and is acid catalysed.Hammett acidity function (H ₀) andBunnett hypothesis have been applied. The formation of free radicals during the course of the reaction has been indicated. A probable reaction mechanism is proposed.

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Die Kinetik der Oxidation von Ethyldigol mit Vanadium(V) in wäßrigem saurem Medium

Zusammenfassung Es wurde die Kinetik der Oxidation von Ethyldigol mittels Vanadium(V) in wäßriger saurer Lösung untersucht. Die Reaktion ist erster Ordnung bezüglich Vanadium(V) und Substrat und ist säurekatalysiert. Es wurden dieHammett-Aciditätsfunktion (H ₀) und dieBunnett-Hypothese angewandt. Die Bildung von freien Radikalen während der Reaktion konnte bestätigt werden. Es wird ein Reaktionsmechanismus vorgeschlagen.

     

Hyperfine structure in the configuration 4f 115d6s 2 of Er I

Hyperfine constants of low lying levels of the configuration 4f ¹¹5d6s ² in Er I have been measured for the only stable odd isotope,¹⁶⁷Er, using high resolution laseratomic-beam spectroscopy. Hyperfine parameters were evaluated from the experimental data using the effective tensor operator formalism. For this purpose eigenfunctions have been determined from an analysis of the fine structure energies of Er I as well as from ab initio multiconfiguration Dirac-Fock calculations. With the latter method also ab initio hyperfine constants for the levels investigated were evaluated. A comparison of calculated fine structure energies, Landég _J -factors and hyperfine constants with the experimental data allowed a test of the reliability of the fine structure and multiconfiguration Dirac-Fock wavefunctions. Effective nuclear electric quadrupole moments for¹⁶⁷Er have been determined from the experimental hyperfine constants using both calculated relativistic electronic radial integrals and hyperfine parameters for the 4f and 5d electrons in the configuration 4f ¹¹5d6s ² in Er I. From a comparison with the nuclear quadrupole moment measured in the mesic atom Sternheimer shielding factors are calculated. Configuration-interaction contributions to the radial integrals 〈r ^?3〉 _nl ⁰¹ of the 4f and 5d electrons have been determined.