Photochromism in p-methylbenzoylthioacetone and related β-thioxoketones

Irradiation of p-methylbenzoylthioacetone with UV or visible light brings about spectral changes characteristic for the photochromic behavior of β-thioxoketones. The nature of the initial species and of the photochromic product can be assigned based on spectral studies of the electronic and IR spectra in rare gas matrices combined with quantum chemical calculations. Additional arguments for the vibrational assignments are provided by using polarized light to induce the phototransformation, and by subsequent measurements of linear dichroism on partially aligned samples. Comparison with the results previously obtained for three related molecules: thioacetylacetone, p-methyl(thiobenzoyl)acetone, and monothiodibenzoylmethane reveals a common pattern of the photochromic reaction. In all four molecules, the initial species corresponds to an intramolecularly hydrogen-bonded enolic molecular structure, and the main photochromic product to an “open”, nonchelated enethiolic counterpart. On the basis of a computational TD-DFT study of ground and excited electronic states, possible mechanisms of the photochromic transformation are discussed.     

Thermodynamically consistent nonlocal theory of ductile damage

In this paper a thermodynamically consistent, weakly nonlocal theory of ductile damage is presented. The theory is based on the classical dynamical balance laws of forces and couples in the physical space and dynamical balance laws of material forces on evolving defects and on the first and second law of thermodynamics formulated for physical and material space. Assuming general constitutive equations their frame-invariant and thermodynamically admissible form is determined. It is shown that physical and material forces and stresses consist of two parts, a nondissipative part derivable from a free energy potential, and a dissipative part, which can be obtained from a dissipation pseudo-potential, if such a pseudo-potential exists.The theory can be considered as a framework with gradient elastoplasticity, isotropic and anisotropic brittle and ductile gradient damage at finite strain as special cases.     

Verweilzeituntersuchungen an Hochdruckhydrieranlagen

Es wird über Untersuchungen des Verweilzeitverhaltens der flüssigen Phase in Hochdruckhydrieranlagen berichlet. Durch Auswahl eines geeigneten Leitisotops und der Markierungssubstanz war es möglich, die Untersuchungen bei Betriebsbedingungen durchzuführen. Als Tracer diente ^l4C-markiertes Octadecanol-1. Die Meβmethode wird beschrieben, und die erhaltenen Verweilzeitkurven werden diskutiert.     

Synthesis and properties of titanomagnetite (Fe3−xTixO4) nanoparticles: A tunable solid-state Fe(II/III) redox system

Titanomagnetite (Fe_3−xTi_xO₄) nanoparticles were synthesized by room temperature aqueous precipitation, in which Ti(IV) replaces Fe(III) and is charge compensated by conversion of Fe(III) to Fe(II) in the unit cell. A comprehensive suite of tools was used to probe composition, structure, and magnetic properties down to site-occupancy level, emphasizing distribution and accessibility of Fe(II) as a function of x. Synthesis of nanoparticles in the range 0 ? x ? 0.6 was attempted; Ti, total Fe and Fe(II) content were verified by chemical analysis. TEM indicated homogeneous spherical 9-12 nm particles. μ-XRD and Mössbauer spectroscopy on anoxic aqueous suspensions verified the inverse spinel structure and Ti(IV) incorporation in the unit cell up to x ? 0.38, based on Fe(II)/Fe(III) ratio deduced from the unit cell edge and Mössbauer spectra. Nanoparticles with a higher value of x possessed a minor amorphous secondary Fe(II)/Ti(IV) phase. XANES/EXAFS indicated Ti(IV) incorporation in the octahedral sublattice (B-site) and proportional increases in Fe(II)/Fe(III) ratio. XA/XMCD indicated that increases arise from increasing B-site Fe(II), and that these charge-balancing equivalents segregate to those B-sites near particle surfaces. Dissolution studies showed that this segregation persists after release of Fe(II) into solution, in amounts systematically proportional to x and thus the Fe(II)/Fe(III) ratio. A mechanistic reaction model was developed entailing mobile B-site Fe(II) supplying a highly interactive surface phase that undergoes interfacial electron transfer with oxidants in solution, sustained by outward Fe(II) migration from particle interiors and concurrent inward migration of charge-balancing cationic vacancies in a ratio of 3:1.     

Three-layer poly(methyl methacrylate) microsystem for analysis of lysosomal enzymes for diagnostic purposes

Lysosomal storage diseases are chronic, progressive and typically have a devastating impact on the patient and the family. The diagnosis of these diseases is still a challenge, however, even for trained specialists. Accurate diagnostic methods and high-throughput tools that could be readily incorporated into existing screening laboratories are urgently required.     

On the redox states of ruthenium porphyrin oxidation catalysts

Tetraarylporphyrin ruthenium complexes [Ru(L)(aryl(4)Por)] (L = CO or PF(3); aryl = mesityl or 10-R'-bis-methano-octahydroanthracene-9-yl with R' = H, CF(3), OCH(3) or CH(3)) show a rich electrochemistry with at least five different stable oxidation states (including the parent state). The overall character of the redox behaviour is porphyrin-centred. However detailed spectroelectrochemical investigations using IR, UV/Vis/NIR and EPR spectroscopy (X- and K band) gave clear indication for ruthenium contributions.     

A biogenetically-inspired synthesis of a ring-D model of kinamycin F: insights into the conformation of ring D

An efficient three-step construction of the highly oxygenated D-ring of the kinamycin antibiotics is reported for a simple model system. A comparison of the spectroscopic characteristics of the synthetic models with those of natural kinamycin F, which is suspected to be the bioactive form of the kinamycins, leads to the conclusion that the favored D-ring conformation of kinamycin F differs from that of the other partially or fully acylated variants.     

Behavior of neptunium in the separation process of actinides from irradiated targets

Radiochemical separations of trace amounts of actinides produced in heavy ion reactions with actinide targets are described. The neptunium behavior in the separation process using extraction chromatography with HDEHP is investigated. To select the optimal separation conditions for Np from the other actinides and from each other, their extraction by HDEHP has been studied in such solutions as HCl, NHO₃, HClO₄, HF, H₂C₂O₄ and H₃PO₄. A two-step separation procedure yields fractions of individual actinide elements.     

Near Infrared Phosphorescent,Non‐oxidizable Palladium and Platinum Perfluoro‐phthalocyanines

New Pd^II and Pt^II complexes with a highly electron‐deficient ligand (H₂PcF₆₄) were conveniently prepared in a three‐step synthesis. This is the first time that the phosphorescence of phthalocyanines with a H₂PcF₆₄ framework has been measured. Based on these measurements, the triplet‐state energies (E_T) were directly determined. Transient absorption experiments revealed broad T₁→T_n absorption spanning from ca. 350 to ca. 1000 nm and allowed determination of the triplet‐state lifetimes. Removal of the Pd or Pt from the perfluoro‐phthalocyanine resulted in a significant increase of the triplet lifetime for H₂PcF₆₄. The very efficient intersystem crossing observed for both PdPcF₆₄ and PtPcF₆₄ leads to residual fluorescence and suppresses the fluorescence lifetimes to less than 50 ps. The absence of Pd and Pt in the perfluoro‐phthalocyanine ligand, viz. H₂PcF₆₄, led to a recovery of fluorescence. Cyclic voltamperometry studies pointed to complete resistance of PdPcF₆₄ and PtPcF₆₄ to oxidation and very strong electron affinity, which rendered these materials very good electron acceptors (n‐type materials). The presence of d‐orbital metals such as Pd^II and Pt^II in the phthalocyanine ring stabilizes their reduced forms, as indicated by the spectroelectrochemical experiments. PdPcF₆₄ and PtPcF₆₄ easily sensitize singlet oxygen production with very high quantum yields. Both phthalocyanines presented resistance to photodegradation in the solid state under aerobic conditions and under intense irradiation.     

Characterization of a new external neutron beam facility at the Ohio State University

A thermal neutron beam facility has been designed and implemented at the Ohio State University Research Reactor. A project is underway to construct a large vacuum chamber such that the facility could have neutron depth profiling and neutron radiography capabilities as intended. The neutron beam is extracted from the reactor through a neutron collimator emplaced in Beam Port #2. The neutron spectrum entering the neutron collimator was unfolded from foil activation analysis results and also simulated with a full reactor core model in the MCNP Monte Carlo code. The neutron collimator uses polycrystalline bismuth as a gamma ray filter and single-crystal sapphire as a fast neutron filter. The beam is defined by multiple 3.0 cm diameter apertures made of borated aluminum. Characterization of the beam was performed using foil activation to find the flux and a low-budget neutron imaging apparatus to see the beam profile. The modulation transfer function was calculated to offer insight into the resolution of the imaging system and the collimation of the beam. The neutron collimator delivers the filtered thermal neutron beam with a ~4 cm diameter and a thermal equivalent flux of (1.27 ± 0.03) × 10⁷ n/(cm²s) at 450 kW power at the end of the collimator.