The physical properties of linear chain systems. I. The optical spectra of [(CH3)4N]NiCl3, Cs(Mg,Ni)Cl3, CsNiCl3, RbNiCl3 and CsNiBr3

The single crystal spectra of pure CsNiCl₃, CsNiBr₃, RbNiCl₃, and [(CH₃)₄]NiCl₃, and the single crystal spectrum of CsNiCl₃ diluted in CsMgCl₃ have been measured to 5°K. The spectra of the magnetically concentrated materials show a number of anomalously intense maxima. These are interpreted in terms of cooperative interactions.     

Structure and growth kinetics of the oxidation process of Fe(001) whisker surfaces over a 10-decade pressure range

Fe(001) surfaces of whiskers of good crystalline quality were oxidized in a pressure range from 10^? 7 mbar to 1 bar at different temperatures. Epitaxial Fe₃O₄ and FeO thin films with negligible strain were grown depending on the oxidation temperatures. The kinetics of the oxide thickness growth was measured and compared with the predictions of the Fromhold–Cook theory for oxidation of metals. Some discrepancies were found and a possible explanation is presented.     

Resolution and quantification of arginine,monomethylarginine, asymmetric dimethylarginine,and symmetric dimethylarginine in plasma using HPLC with internal calibration

N^G,N^G‐dimethyl‐l ‐arginine (asymmetric dimethylarginine, ADMA),N^G‐monomethyl‐l ‐arginine (l ‐NMMA) and N^G,N^G’‐dimethyl‐l ‐arginine (symmetric dimethylarginine, SDMA) are released during hydrolysis of proteins containing methylated arginine residues. ADMA and l ‐NMMA inhibit nitric oxide synthase by competing with l ‐arginine substrate. All three methylarginine derivatives also inhibit arginine transport. To enable investigation of methylarginines in diseases involving impaired nitric oxide synthesis, we developed a high‐performance liquid chromatography (HPLC) assay to simultaneously quantify arginine, ADMA, l ‐NMMA and SDMA. Our assay requires 12 μL of plasma and is ideal for applications where sample availability is limited. We extracted arginine and methylarginines with mixed‐mode cation‐exchange columns, using synthetic monoethyl‐l ‐arginine as an internal standard. Metabolites were derivatized with ortho‐phthaldialdeyhde and 3‐mercaptopropionic acid, separated by reverse‐phase HPLC and quantified with fluorescence detection. Standard curve linearity was ≥0.9995 for all metabolites. Inter‐day coefficient of variation (CV) values were ≤5% for arginine, ADMA and SDMA in human plasma and for arginine and ADMA in mouse plasma. The CV value for l ‐NMMA was higher in human (10.4%) and mouse (15.8%) plasma because concentrations were substantially lower than ADMA and SDMA. This assay provides unique advantages of small sample volume requirements, excellent separation of target metabolites from contaminants and validation for both human and mouse plasma samples. © 2015 The Authors Biomedical Chromatography published by John Wiley & Sons, Ltd.     

Structural and spectral characterization of two 1-phenyl-1,2-propanedione bis{N(4)-alkylthiosemicarbazones}

1-phenyl-1,2-propanedione bis{N(4)-methyl- and {N(4)-ethylthiosemicarbazone}, H₂Pm4M and H₂Pm4E, respectively, have been prepared, studied spectroscopically (¹H NMR, ultraviolet and infrared) and their crystal structures solved. Intermoiety hydrogen bonding does not occur in H₂Pm4M and H₂Pm4E, in contrast to the analogous bis{N(4)-thiosemicarbazones} prepared from 1-phenylglyoxal. The two thiosemicarbazone moieties are on the opposite side of the carbon–carbon backbone, but the N(4)Hs intramolecularly hydrogen bond to the imine nitrogen for each moiety.     

Effects of permeable boundaries on the diffusion-attenuated MR signal: insights from a one-dimensional model

The local magnetization distribution M(x,t) and the net MR signal S arising from a one-dimensional periodic structure with permeable barriers in a Tanner-Stejskal pulsed-field gradient experiment are considered. In the framework of the narrow pulse approximation, the general expressions for M(x,t) and S as functions of diffusion time and the bipolar field gradient strength are obtained and analyzed. In contrast to a system with impermeable boundaries, the signal S as a function of the b-value is modeled well as a bi-exponential decay not only in the short-time regime but also in the long-time regime. At short diffusion times, the local magnetization M(x,t) is strongly spatially inhomogeneous and the two exponential components describing S have a clear physical interpretation as two "population fractions" of the slow- and fast-diffusing quasi-compartments (pools). In the long-diffusion time regime, the two exponential components do not have clear physical meaning but rather serve to approximate a more complex functional signal form. The average diffusion propagator, obtained by means of standard q-space analysis procedures in the long-diffusion time regime is explored; its structure creates the deceiving appearance of a system with multiple compartments of different sizes, while in reality, it reflects the permeable nature of boundaries in a system with multiple compartments all of the same size.     

Structural, spectral and thermal studies of N-2-(4-picolyl)- and N-2-(6-picolyl)-N′-(2-chlorophenyl)thioureas and N-2-(6-picolyl)-N′-(2-bromophenyl)thiourea

N-2-(4-picolyl)-N′-2-chlorophenylthiourea, 4PicTu2Cl, monoclinic, P2₁/c, a=10.068(5), b=11.715(2), β=96.88(4)°, and Z=4; N-2-(6-picolyl)-N′-2-chlorophenylthiourea, 6PicTu2Cl, triclinic, P-1, a=7.4250(8), b=7.5690(16), c=12.664(3) Å, =105.706(17), β=103.181(13), γ=90.063(13)°, V=665.6(2) ų and Z=2 and N-2-(6-picolyl)-N′-2-bromophenylthiourea, 6PicTu2Br, triclinic, P-1, a=7.512(4), b=7.535(6), c=12.575(4) Å, a=103.14(3), β=105.67(3), γ=90.28(4)°, V=665.7(2) ų and Z=2. The intramolecular hydrogen bonding between N′H and the pyridine nitrogen and intermolecular hydrogen bonding involving the thione sulfur and the NH hydrogen, as well as the planarity of the molecules, are affected by the position of the methyl substituent on the pyridine ring. The enthalpies of fusion and melting points of these thioureas are also affected. ¹H NMR studies in CDCl₃ show the NH′ hydrogen resonance considerably downfield from other resonances in their spectra.     

Practical aspects involved in the design and set up of a 0.15 T, 6-coil resistive magnet, whole body NMR imaging facility

Many technical and logistical questions must be addressed when planning the installation of an NMR imaging system. These considerations become particularly significant when the facility is being established within an existing medical center complex. This paper presents a report on the practical aspects and experience obtained in siting a 6-coil 0.15 T resistive magnet system. The topics discussed include: floor loading; ferromagnetic environment; the effect of iron on the magnet field strength and homogeneity characteristics; shimming procedures; temperature stability requirements; rf shielding; and effects of the magnetic field on common medical instrumentation and magnetic media. It was found that the field shift as a function of the distance of a steel mass from the center of the magnet exhibited an (1/r)^5.2±0.5 to (1/r)^4.2±0.3 dependence for axial and radial positions respectively which, as expected, is somewhat weaker than the (1/r)⁶ dependence expected by point dipole approximations. Field distortions caused by the presence of ferromagnetic material in radial positions may be essentially fully compensated with first order transverse shim coils (most conveniently, the x and y imaging gradient coils could be used). Axially distributed material requires, in addition to first order z-gradient correction, higher order axial shim compensation. The temperature stability of the magnet system over the scan period must be better than 0.2°C to insure that temperature-induced field fluctuations are less than the intrinsic static inhomogeneity: and, ideally, below 0.01°C to reduce these fluctuations to less than those caused by power supply instability.