99mTc-labelled human serum albumin: Chemical and electrochemical labelling methods

The labelling of human serum albumin /HSA/ with^99mTc has been investigated using a chemical method /stannous citrate/ and electrolytically generated tin/II/ ions. A comparative study of various chemical parameters and current intensities has been carried out in order to find the optimal conditions for labelling. The labelling yield was over 95%, for the chemical and electrolytical methods.     

A 45 ns 8+ isomer in the doubly odd150Eu nucleus

In the doubly odd ₆₃ ¹⁵⁰ Eu⁸⁷ nucleus a 45 ns 8⁺ isomer at 589 keV excitation has been identified through (p, 3n) in beamγ ande ^? measurements. The low lying negative parity levels populated in its decay show great similarity to analogous states in the lighter odd-odd Eu neighbours suggesting a spherical shape for¹⁵⁰Eu. A spherical shape is also proposed for the isomer which is assigned as (πh _11/2 vf ₇ ^2/?3 )8⁺ state analogous to the 9⁺ isomers known in¹⁴⁸Eu and¹⁴⁶Eu. The spin change is attributed to the crossing of the half-filledf _7/2 neutron shell atN=86.     

Direct determination of the complete set of iron normal modes in a porphyrin-imidazole model for carbonmonoxy-heme proteins: [Fe(TPP)(CO)(1-MeIm)

Detailed Fe vibrational spectra have been obtained for the heme model complex [Fe(TPP)(CO)(1-MeIm)] using a new, highly selective and quantitative technique, Nuclear Resonance Vibrational Spectroscopy (NRVS). This spectroscopy measures the complete vibrational density of states for iron atoms, from which normal modes can be calculated via refinement of the force constants. These data and mode assignments can reveal previously undetected vibrations and are useful for validating predictions based on optical spectroscopies and density functional theory, for example. Vibrational modes of the iron porphyrin-imidazole compound [Fe(TPP)(CO)(1-MeIm)] have been determined by refining normal mode calculations to NRVS data obtained at an X-ray synchrotron source. Iron dynamics of this compound, which serves as a useful model for the active site in the six-coordinate heme protein, carbonmonoxy-myoglobin, are discussed in relation to recently determined dynamics of a five-coordinate deoxy-myoglobin model, [Fe(TPP)(2-MeHIm)]. For the first time in a six-coordinate heme system, the iron-imidazole stretch mode has been observed, at 226 cm(-)(1). The heme in-plane modes with large contributions from the nu(42), nu(49), nu(50), and nu(53) modes of the core porphyrin are identified. In general, the iron modes can be attributed to coupling with the porphyrin core, the CO ligand, the imidazole ring, and/or the phenyl rings. Other significant findings are the observation that the porphyrin ring peripheral substituents are strongly coupled to the iron doming mode and that the Fe-C-O tilting and bending modes are related by a negative interaction force constant.     

Optimization of heat transfer and pressure drop in a tube with loose-fit perforated twisted tapes by Taguchi method and grey relational analysis

Journal of Thermal Analysis and Calorimetry - This work introduces the determination of the optimum values of the design parameters in a tube with loose-fit perforated twisted tapes. The effects of...     

A nonnormal look at polychoric correlations: modeling the change in correlations before and after discretization

Two algorithms for establishing a connection between correlations before and after ordinalization under a wide spectrum of nonnormal underlying bivariate distributions are developed by extending the iteratively found normal-based results via the power polynomials. These algorithms are designed to compute the polychoric correlation when the ordinal correlation is specified, and vice versa, along with the distributional properties of latent, continuous variables that are subsequently ordinalized through thresholds dictated by the marginal proportions. The method has broad applicability in the simulation and random number generation world where modeling the relationships between these correlation types is of interest.     

In situ electrochemical solid-phase extraction of anions and cations using polypyrrole and overoxidized sulfonated polypyrrole

A new method for the extraction of both anions and cations is proposed using electro-synthesized polypyrrole (PPy) and overoxidized sulfonated polypyrrole film (OSPPy). In situ anion (chloride, nitrate, sulfate) and cation (calcium, magnesium) uptake and release were examined under controlled potential conditions for prospective applications in electrochemically controlled solid-phase extraction (EC-SPE). The PPy film was used as an anode (anion-exchanger) and OSPPy film was used as a cathode (cation-exchanger) material and reverse order of the electrodes were investigated in EC-SPE. This new cell arrangement containing two ion exchanger polymer electrodes was developed to provide in situ removal of both anions and cations from aqueous solution. Simple preparation of the film coatings on a platinum plate was possible using a constant potential method. Applied positive and negative potentials facilitated the in situ extraction and desorption of ions, respectively. Both anions and cations were desorbed into sample aliquot and were determined by ion chromatography (IC). The method was validated using a standard reference material and tested for the determination of the ions in real water samples.     

How nitrogenase shakes--initial information about P-cluster and FeMo-cofactor normal modes from nuclear resonance vibrational spectroscopy (NRVS)

Nitrogenase catalyzes a reaction critical for life, the reduction of N(2) to 2NH(3), yet we still know relatively little about its catalytic mechanism. We have used the synchrotron technique of (57)Fe nuclear resonance vibrational spectroscopy (NRVS) to study the dynamics of the Fe-S clusters in this enzyme. The catalytic site FeMo-cofactor exhibits a strong signal near 190 cm(-)(1), where conventional Fe-S clusters have weak NRVS. This intensity is ascribed to cluster breathing modes whose frequency is raised by an interstitial atom. A variety of Fe-S stretching modes are also observed between 250 and 400 cm(-)(1). This work is the first spectroscopic information about the vibrational modes of the intact nitrogenase FeMo-cofactor and P-cluster.     

Nuclear resonance vibrational spectra of five-coordinate imidazole-ligated iron(II) porphyrinates

Nuclear resonance vibrational spectra have been obtained for six five-coordinate imidazole-ligated iron(II) porphyrinates, [Fe(Por)(L)] (Por = tetraphenylporphyrinate, octaethylporphyrinate, tetratolylporphyrinate, or protoporphyrinate IX and L = 2-methylimidazole or 1,2-dimethylimidazole). Measurements have been made on both powder and oriented crystal samples. The spectra are dominated by strong signals around 200-300 cm(-1). Although the in-plane and out-of-plane vibrations are seriously overlapped, oriented crystal spectra allow their deconvolution. Thus, oriented crystal experimental data, along with density functional theory (DFT) calculations, enable the assignment of key vibrations in the spectra. Molecular dynamics are also discussed. The nature of the Fe-N(Im) vibrations has been elaborated further than was possible from resonance Raman studies. Our study suggests that the Fe motions are coupled with the porphyrin core and peripheral groups motions. Both peripheral groups and their conformations have significant influence on the vibrational spectra (position and shape).     

161Dy Time‐Domain Synchrotron Mössbauer Spectroscopy for Investigating Single‐Molecule Magnets Incorporating Dy Ions

Time‐domain synchrotron Mössbauer spectroscopy (SMS) based on the Mössbauer effect of ¹⁶¹Dy has been used to investigate the magnetic properties of a Dy^III‐based single‐molecule magnet (SMM). The magnetic hyperfine field of [Dy(Cy₃PO)₂(H₂O)₅]Br₃?2 (Cy₃PO)?2 H₂O?2 EtOH is with B₀=582.3(5) T significantly larger than that of the free‐ion Dy^III with a ⁶H_15/2 ground state. This difference is attributed to the influence of the coordinating ligands on the Fermi contact interaction between the s and 4f electrons of the Dy^III ion. This study demonstrates that ¹⁶¹Dy SMS is an effective local probe of the influence of the coordinating ligands on the magnetic structure of Dy‐containing compounds.