Reaction intermediates of quinol oxidation in a photoactivatable system that mimics electron transfer in the cytochrome bc1 complex

Current competing models for the two-electron oxidation of quinol (QH2) at the cytochrome bc1 complex and related complexes impose distinct requirements for the reaction intermediate. At present, the intermediate species of the enzymatic oxidation process have not been observed or characterized, probably due to their transient nature. Here, we use a biomimetic oxidant, excited-state Ru(bpy)2(pbim)+ (bpy=2,2'-dipyridyl, pbim=2-(2-pyridyl)benzimidazolate) in an aprotic medium to probe the oxidation of the ubiquinol analogue, 2,3-dimethoxy-5-methyl-1,4-benzoquinol (UQH2-0), and the plastoquinol analogue, trimethyl-1,4-benzoquinol (TMQH2-0), using time-resolved and steady-state spectroscopic techniques. Despite its simplicity, this system qualitatively reproduces key features observed during ubiquinol oxidation by the mitochondrial cytochrome bc1 complex. Comparison of isotope-dependent activation properties in the native and synthetic systems as well as analysis of the time-resolved direct-detection electron paramagnetic resonance signals in the synthetic system allows us to conclude that (1) the initial and rate-limiting step in quinol oxidation, both in the biological and biomimetic systems, involves electron and proton transfer, probably via a proton-coupled electron-transfer mechanism, (2) a neutral semiquinone intermediate is formed in the biomimetic system, and (3) oxidation of the QH*/QH2 couple for UQH2-0, but not TMQH2-0, exhibits an unusual and unexpected primary deuterium kinetic isotope effect on its Arrhenius activation energy (DeltaGTS), where DeltaGTS for the protiated form is larger than that for the deuterated form. The same behavior is observed during steady-state turnover of the cyt bc1 complex using ubiquinol, but not plastoquinol, as a substrate, leading to the conclusion that similar chemical pathways are involved in both systems. The synthetic system is an unambiguous n=1 electron acceptor, and it is thus inferred that sequential oxidation of ubiquinol (by two sequential n=1 processes) is more rapid than a truly concerted (n=2) oxidation in the cyt bc1 complex.     

Gamma and Alpha decay from the 2.1-msec isomer213mRa

The isomer^213mRa was produced by the reaction²⁰⁹Bi(¹⁰B, 6n), as well as by bombardments of¹²C on Pb isotopes,¹⁴N on Bi, and¹⁶O on natural Hg, with projectile energies in the range 60–100 MeV. The isomer decays with a halflife of 2.1 ms both via gamma internal transitions and via alpha branching to levels in²⁰⁹Rn. A level scheme is proposed in which the isomeric state is assigned as either 17/2^– or 13/2⁺ with shell-model configurations either of theh _9/2 protons coupled to ap _1/2 neutron hole, or of an uncoupledi _13/2 neutron hole. On the basis of alpha decay rate predictions from the new Fliessbach theory, the 17/2^– isomeric assignment is to be preferred.Phys. Abstracts classifications 4.200–4.375     

An SCF-state interaction method for coupled oscillator systems

A computational method is presented for the treatment of coupled systems of oscillators by a SCF-like formalism. Extensions to state interaction (analogous to configuration interaction) are presented and explored numerically for the Henon—Heiles system. The formalism is presented for an MCSCF-like approach to such problems.     

High temperature determination of the rate coefficient for the reaction H2O + CN → HCN + OH

The rate coefficient, k, of the reaction has been determined in the temperature range 2460–2840 K using a shock tube technique. C₂N₂? H₂O? Ar mixtures were heated behind incident shock waves and the CN and OH concentration time histories were monitored simultaneously using broad-band absorption near 388 nm (CN) and narrow-line laser absorption at 306.67 nm (OH). The rate coefficient expression providing the best fit to the data was with uncertainty limits of about ±45% in the temperature range 2460–2840 K. The rate coefficient of the reverse reaction was calculated using detailed balancing, and its extrapolation to lower temperatures was compared with previously published results.     

Mitotic and amitotic cell replication in malignant melanoma: the role of subdivisional cell replication

It is widely assumed that significant mitotic activity is typical of malignant melanoma and many believe that significant mitotic activity is essential for this diagnosis. We have studied mitotic activity in 205 malignant melanomas and have found that mitotic activity is often minimal or absent, even in malignant melanomas which have recurred or metastasized. Based on our previous work suggesting that new cells can form from nucleoli via nucleolar stalks, we also studied nucleolar stalks in our cases. These were present in greater numbers than mitoses and help explain the anomaly of infrequent mitoses in a highly malignant neoplasm.     

Phase behaviour and electro-optic characteristics of a polymer stabilized ferroelectric liquid crystal

The effects of adding a diacrylate monomer or its polymerized network to a ferroelectric liquid crystal have been characterized. The monomer lowers the temperatures of transition to the more ordered phases, whereas the polymer network phase separates into polymer rich and LC rich phases and has little effect on the LC phase behaviour. Ferroelectric polarization decreases comparably in both monomer and networked systems. As the network concentration increases, the size of LC domains decreases considerably. With low concentrations of polymer and, thus large LC domains, optical response and tilt angle remain fairly independent of polymer concentration, but as the polymer concentration increases, switching speed and tilt angle decrease dramatically. Polymerization rate maxima increase with monomer concentration until saturation of monomer in the liquid crystal is reached. The rate maxima then decrease as monomer must diffuse from monomer rich droplets. Double bond conversion during the polymerization is comparable for all monomer concentrations below 50 per cent.     

New insights on reaction dynamics from formaldehyde photodissociation

We review the photodissociation dynamics of formaldehyde with an emphasis on recent calculations that make use of a global ab initio-based potential energy surface for the S(0) state. These calculations together with recent experiments reveal striking departures from conventional transition state theory for the formation of the molecular products H(2) + CO. The evidence for this departure is reviewed in detail by examining properties of the new potential surface and results of quasiclassical trajectory dynamics calculations using this surface. We also review very recent work on the dynamics governing the formation of radical products, H + HCO. These products can be formed on the T(1) surface as well as the S(0) one, and we present some results contrasting the dynamics on these two surfaces. This work makes use of a new semi-global ab initio-based T(1) potential energy surface.     

Vibrational analysis of the H5O2+ infrared spectrum using molecular and driven molecular dynamics

Standard molecular and driven molecular dynamics are used to analyze prominent spectral features in the H5O2+ infrared spectrum. In the driven method, the molecular Hamiltonian is augmented with a time-dependent term, mu x epsilon(0) sin(omegat), where mu is the dipole moment of H5O2+, epsilon0 is the electric field, and omega is the frequency. The magnitude of the electric field determines whether the driving is mild (the harmonic limit) or strong (anharmonic motion and mode coupling). We analyze the spectrum in the wavenumber range from 600 to 1900 cm(-1), where recent experimental measurements are available for H5O2+. On the basis of the simulations, we have assigned the broad feature around 1000 cm(-1) to the proton transfer coupled with the torsion motion. Intense absorption near 1780 cm(-1) is assigned to the H2O monomer bend coupled with proton transfer.