Synthesis and Characterisation of Unsymmetrical Porphyrazines Containing Bis(hydroxyethylthio) Substituents

Summary. Unsymmetrical porphyrazines bearing a single peripheral bis(hydroxyethylthio) moiety were synthesised by mixed condensation of bis(2-hydroxyethylthio)maleonitrile and phthalonitrile. Complexation of the thioether groups of metal-free porphyrazine with PdCl₂ further lowered the intensity of the Q-band absorption of the porphyrazine core. The new compounds were characterised by elemental analyses, IR, ¹H NMR, UV-Vis, and mass spectra.     

Crystal structures and magnetic properties of two low-dimensional materials constructed from [Mn(III)(salen)H2O]+ and [M(CN)8](3-/4-) (M = Mo or W) precursors

The syntheses, X-ray structures, and magnetic behaviors of two new cyano-bridged assemblies, the molecular [Mn(III)(salen)H2O]3[W(V)(CN)8].H2O (1) and one-dimensional [Mn(salen)(H2O)2]2[[Mn(salen)(H2O)][Mn(salen)]2[Mo(CN)(8)]].0.5ClO4.0.5OH.4.5H2O (2), are presented. Compound 1 crystallizes in the monoclinic system, has space group P2(1)/c, and has unit cell constants a = 13.7210(2) A, b = 20.6840(4) A, c = 20.6370(2) A, and Z = 4. Compound 2 crystallizes in the triclinic system, has space group P, and has unit cell dimensions a = 18.428(4) A, b = 18.521(3) A, c = 18.567(4) A, and Z = 2. The structure of 1 consists of the asymmetric V-shaped Mn-NC-W-NC-Mn-O(phenolate)-Mn molecules, where W(V) coordinates with [Mn(salen)H2O] and singly phenolate-bridged [Mn(salen)H2O]2 moieties through the neighboring cyano bridges. The [W(V)(CN)8]3- ion displays distorted square-antiprism geometry. The structure of 2 consists of the cyano-bridged [Mn3(III)Mo(IV)]n- repeating units linked by double phenolate bridges into one-dimensional zigzag chains. The Mn(III) centers are bound to Mo(IV) of square-antiprism geometry through the neighboring cyano bridges. The magnetic studies of 1 reveal the antiferromagnetic intramolecular interactions through the CN and phenolate bridges and the relatively weak intermolecular interactions. Compound 1 becomes antiferromagnetically ordered below TN = 4.6 K. The presence of the magnetic anisotropy is documented with the MH measurements carried out for both polycrystalline and single-crystal samples. At T = 1.9 K, the spin-flop transition is observed in the field of 18 kOe applied parallel to the bc plane, which is the easy plane of magnetization. Field dependence of magnetization of 1 shows field-induced metamagnetic behavior from the antiferromagnetic ground state of ST = 3/2 to the state of ST = 5/2. The magnetic properties of 2 indicate a weak antiferromagnetic interaction between Mn(III) centers in double-phenolate-bridged [Mn(III)(salen)]2 dinuclear subunits and a very weak ferromagnetic interaction between them through the diamagnetic [Mo(IV)(CN)8]4- spacer.     

Mass spectrometric analysis of androstan-17β-ol-3-one and androstadiene-17β-ol-3-one isomers

Mass spectrometric identification and characterization of steroids using electrospray ionization and tandem mass spectrometry has advantages in drug testing and doping control analysis attributable to limitations of gas chromatography followed by electron ionization mass spectrometry. Steroids with an androstadiene-17beta-ol-3-one nucleus and double bonds located either at C-1 and C-4, C-4 and C-9, or C-4 and C-6 were used to determine characteristic fragmentation pathways. Diagnostic dissociation routes are proposed using deuterium labeling, MS3 experiments, and analyses of structurally closely related compounds. Steroids such as boldenone (androst-1,4-diene-17beta-ol-3-one) produced characteristic product ions at m/z 121, 135, and 147. Compounds with double bonds at C-4 and C-9 generated abundant product ions at m/z 145 and 147. Conjugated double bonds at C-4 and C-6 gave rise to an intense and characteristic signal at m/z 133. Stereochemical differentiation between 5alpha- and 5beta-isomers of androstan-17beta-ol-3-ones was possible because of significant differences in relative abundance of product ions generated by elimination of acetone from alpha,beta-saturated 3-keto steroids.     

Polyaniline-coated silica gel

Silica gel microspheres 7 and 15 μm in diameter were coated with an overlayer of polyaniline camphorsulfonate or hydrochloride during the oxidative polymerization of aniline. Coated silica gel and polyaniline precipitate were separated using a difference in sedimentation rate. In an alternative approach, the microspheres were modified with polyaniline in the presence of 35 nm colloidal silica. This technique prevented the macroscopic precipitation of polyaniline. Coatings of neat, 3-aminopropyl- and octadecyl-modified silica gel with polyaniline hydrochloride were compared. The surface composition of coated microspheres was characterized by X-ray photoelectron spectroscopy. Potential applications of particles in electrorheology, organic catalysis, and in modeling of conductivity behavior in composites are demonstrated.     

Potentiodynamic deposition of Prussian blue from a solution containing single component of ferricyanide and its mechanism investigation

Potentiodynamic techniques were used for the direct electrodeposition of Prussian blue nano-clusters from an acidic solution of ferricyanide. Electrochemical, EQCM, IR, AFM, and UV/vis measurements were carried out to characterize deposited nano-sized Prussian blue and to explore the formation mechanism. Results showed that ferricyanide could partially dissociate to free ferric and cyanide ions. The driving force of this dissociation is the formation of PB and the evolution of HCN. The optimal potential window for the potentiodynamic formation of PB from an acidic solution (pH 1.6) is between –0.5 V and 0.4 V. In addition, the influence of surface adsorption of CN^- ions on the formation of PB was discussed.Dedicated to Professor W. Vielstich on the occasion of his 80th birthday.     

Measurements by microdialysis of free tissue concentrations of propranolol.

To determine the free concentration of a drug (propranolol) in the interstitial space in humans in vivo, seven male students were investigated by microdialysis of the periumbilical subcutaneous tissue. The microdialysis catheters were calibrated in vivo and the propranolol concentration was determined by high-performance liquid chromatography. Ten hours after intake of 80 mg of propranolol, the total plasma and free interstitial propranolol concentrations were 80 +/- 43 and 7 +/- 2 nM, respectively. After a second dose, maximum concentration was reached after 80 +/- 10 min and 98 +/- 12 min, in plasma, and the concentrations in the interstitial water were 594 +/- 138 and 27 +/- 7 nM, respectively. In a second study, microdialysis was performed on the left ventricular wall in six pigs receiving an intravenous injection of 5 mg of propranolol followed by a constant propranolol infusion for 40 min (5 mg propranolol per h). The maximum concentrations of propranolol were 97 +/- 29 and 6 +/- 2 nM in plasma and in interstitial water, respectively. The data suggest that microdialysis is a useful tool for recording the free concentrations of a drug in the interstitial space.     

Simple <Emphasis Type="Italic">b</Emphasis> ions have cyclic oxazolone structures. A neutralization-reionization mass spectrometric and computational study of oxazolone radicals

The 2-methyloxazol-5-on-2-yl radical (3) and its deuterium labeled analogs were generated in the gas-phase by femtosecond electron-transfer and studied by neutralization-reionization mass spectrometry and quantum chemical calculations. Radical 3 undergoes fast dissociation by ring opening and elimination of CO and CH(3)CO. Loss of hydrogen is less abundant and involves hydrogen atoms from both the ring and side-chain positions. The experimental results are corroborated by the analysis of the potential energy surface of the ground electronic state in 3 using density functional, perturbational, and coupled-cluster theories up to CCSD(T) and extrapolated to the 6-311 ++ G(3df,2p) basis set. RRKM calculations of radical dissociations gave branching ratios for loss of CO and H that were k(CO)/k(H) > 10 over an 80-300 kJ mol(-1) range of internal energies. The driving force for the dissociations of 3 is provided by large Franck-Condon effects on vertical neutralization and possibly from involvement of excited electronic states. Calculations also provided the adiabatic ionization energy of 3, IE(adiab) = 5.48 eV and vertical recombination energy of cation 3(+), RE(vert) = 4.70 eV. The present results strongly indicate that oxazolone structures can explain fragmentations of b-type peptide ions upon electron capture, contrary to previous speculations.     

Quantification of free and total salicylic acid in plants by solid-phase extraction and isocratic high-performance anion-exchange chromatography

Salicylic acid (SA) is an important signaling compound in plants and is involved in various defense responses. Here we report a new method for quantification of free and total soluble SA in Arabidopsis thaliana with 5-fluorosalicylic acid (5-FSA) as internal standard. The SA was isolated from leaf extracts by solid-phase extraction with phenyl-phase cartridges and selectively eluted as the cationic iron(III)-complex. Recoveries of SA and 5-FSA were equal and exceeded 90%. Free SA was subsequently released from the iron(III)-complex by addition of 2,2-bipyridyl and high-performance anion-exchange chromatography was performed on an NH₂ column. The SA appeared as last peak with a retention time of 15 min, baseline-separated from other substances. On-line detection was performed fluorimetrically for both SA and 5-FSA at an excitation wavelength of 300 nm and an emission wavelength of 410 nm, because both substances give similar fluorescence spectra. The detection limit for SA was 5 ng g^–1 FW for a sample size of 100 mg. Thus the main advantages of the method are highly selective sample preparation, increased sensitivity, reduced analysis time compared with reversed-phase HPLC, and use of a novel internal standard detectable under the same conditions as SA. The techniques described are applicable to other plant materials.     

Simultaneous determination of radionuclides separable into natural decay series by use of time-interval analysis

A delayed coincidence method, time-interval analysis (TIA), has been applied to successive – decay events on the millisecond time-scale. Such decay events are part of the ²²⁰Rn²¹⁶Po (T_1/2 145 ms) (Th-series) and ²¹⁹Rn²¹⁵Po (T_1/2 1.78 ms) (Ac-series). By using TIA in addition to measurement of ²²⁶Ra (U-series) from -spectrometry by liquid scintillation counting (LSC), two natural decay series could be identified and separated. The TIA detection efficiency was improved by using the pulse-shape discrimination technique (PSD) to reject -pulses, by solvent extraction of Ra combined with simple chemical separation, and by purging the scintillation solution with dry N₂ gas. The U- and Th-series together with the Ac-series were determined, respectively, from alpha spectra and TIA carried out immediately after Ra-extraction. Using the ²²¹Fr²¹⁷At (T_1/2 32.3 ms) decay process as a tracer, overall yields were estimated from application of TIA to the ²²⁵Ra (Np-decay series) at the time of maximum growth. The present method has proven useful for simultaneous determination of three radioactive decay series in environmental samples.     

Polymer-protected palladium nanoparticles. Morphologies and catalytic selectivities

Colloidal palladium nanocatalysts prepared by in situ reductions of palladium chloride were immobilized and protected by either of two water-soluble polymers. The particle sizes and size distributions of the palladium colloids were determined by transmission electron microscopy. Their selectivities as catalysts were determined by comparing the extents of hydrogenation of carefully chosen pairs of small-molecule olefins. There was found to be high hydrogenation selectivity with regard to cyclic vs. noncyclic olefins. Selectivity was relatively low, however, among olefins that differed only in size (such as hexene vs. octene), or olefins differing only with regard to the positions of the double bonds (such as 1-octene vs. 3-octene). Selectivity could be improved by careful choice of the immobilizing polymer, and by its use at relatively high concentrations.