Calix[6]arene-based cuprous "funnel complexes": a mimic for the substrate access channel to metalloenzyme active sites

Two calixarene-based model systems (a and b) for monocopper enzymes are compared. Both present a tris(pyridine) coordination site for Cu that mimics the imidazole-rich neutral binding site in enzymes. Upon reaction with 1 equiv of copper(I), the tridentate ligands gave rise to ill-defined unsymmetrical complexes. However, in the presence of an organonitrile RCN (R = Me, Et, Ph), tetrahedral species were obtained, with the nitrilo ligand included in the calixarene hydrophobic cone. System b presents a larger cavity than system a, with a wider opening thanks to the removal of three tBu groups from the calixarene structure. As a result, the recognition pattern for MeCN vs PhCN is inverted, and the relative affinity constants differ by 3 orders of magnitude. The mechanism of the acetonitrile exchange at the cuprous centers was studied by (1)H NMR spectroscopy. Thermodynamic and kinetic data show that it follows a dissociative pathway in both cases. The main differences between systems a and b stem from the presence of a door that entraps the guest in case a. In system b indeed, the removal of three calixarene tBu groups led to a 100-fold acceleration of the MeCN exchange rate. Hence, these supramolecular systems provide a rare and interesting model for the hydrophobic substrate channel giving access to a metalloenzyme active site.     

Selective spreading and jetting of electrically driven dielectric films

We study the electrically driven spreading of dielectric liquid films in wedge-shaped gaps across which a potential difference is applied. Our experiments are in a little-studied regime where, throughout the dynamics, the electrical relaxation time is long compared to the time for charge to be convected by the fluid motion. We observe that at a critical normal electric field the hump-shaped leading edge undergoes an instability in the form of a single Taylor cone and periodic jetting ensues, after which traveling waves occur along the trailing thin film. We propose a convection-dominated mechanism for charge transport to describe the observed dynamics and rationalize the viscosity dependence of the self-excited dynamics.     

Exotic nuclei produced by heavy-ions induced fission

About thirty nuclei in theA≈100 mass region have been produced as fission fragments following the fusion-evaporation reactions^28,30Si+¹⁷⁶Yb at 145 MeV bombarding energy. These nuclei have been individually identified from their γ-ray cascades detected with the Eurogam2 array. The level schemes of several stable or neutron-rich nuclei have been extended to higher spins. From cross coincidences between transitions in complementary fragments, γ-rays de-exciting high-spin states of new isotopes can be identified and some aspects of the fission mechanism can be analyzed.     

High-spin structures observed in the 101Tc fission fragment

High-spin states have been studied in ¹⁰¹Tc produced as a fission fragment in the reaction ¹⁷⁶Yb +²⁸Si at 145 MeV. Gamma rays were detected with the EUROGAM2 array. The level scheme of ¹⁰¹Tc has been extended up to 4.2 MeV excitation energy and several band structures are observed. Configurations are assigned to two new bands on the basis of their behaviour and of cranked Hartree-Fock-Bogolyubov calculations. Received: 4 January 1999     

Highest spin reached in the superdeformed well in the A≈190 mass region

The high efficiency of the new-generation of γ-arrays as EUROGAM or GAMMASPHERE makes reachable the fission limit in angular momentum of the nuclei populated by means of heavy ion reactions in the A ≈ 190 mass region. This is established by the strong correlation between the fissility parameters Z ²/A and the spin values of the state of highest energy observed in the yrast superdeformed bands.     

Biomimetic copper(I)--CO complexes: a structural and dynamic study of a cali

Four novel calix[6]arene-based cuprous complexes are described. They present a biomimetic tris(imidazole) coordination core associated with a hydrophobic cavity that wraps the apical binding site. Each differs from the other by the methyl or ethyl substituents present on the phenoxyl groups (OR1) and on the imidazole arms (NR2) of the calix[6]arene structure. In solution, stable CO complexes were obtained. We have investigated their geometrical and dynamic properties with respect to the steric demand. IR and NMR studies revealed that, in solution, these complexes adopted two distinct conformations. The preferred conformation was dictated only by the size of the OR1 group. When R1 was an ethyl group, the complex preferentially adopted a flattened C3-symmetrical structure. The corresponding helical enantiomers were in conformational equilibrium, which, however, was slow on the 1H NMR time scale at -80 degrees C. When R1 was a methyl group, the low-temperature NMR spectra revealed the partial inclusion of one tBu group. The complex wobbled between three dissymmetric but equivalent conformations. Hence, small differences in the steric demand of the calixarene's skeleton changed the geometry and dynamics of the system. Indeed, this supramolecular control was promoted by the strong conformational coupling between the metal center and the host structure. Interestingly, this was not only the result of a covalent preorganization, but also stemmed from weak interactions within the hydrophobic pocket. The vibrational spectra of the bound CO were revealed to be a sensitive gauge of this supramolecular behavior, similar to copper proteins in which allosteric effects are common.     

Pulse dynamics in low-Reynolds-number interfacial hydrodynamics: Experiments and theory

We analyze interaction of nonlinear pulses in active–dispersive–dissipative nonlinear media. A particular example of such media is a viscous thin film coating a vertical fibre. Experiments for this system reveal that the interface evolves into a train of droplike solitary pulses in which numerous inelastic coalescence events take place. In such events, larger pulses catch up with smaller ones and annihilate them. However, for certain flow conditions and after a certain distance from the inlet, no more coalescence is observed and the flow is described by quasi-equilibrium solitary pulses interacting continuously with each other through attractions and repulsions, and, eventually they form bound states of groups of pulses in which the pulses travel with the same velocities as a whole. This experimental study represents the first evidence of formation of bound states in low-Reynolds-number interfacial hydrodynamics. To gain theoretical insight into the interaction of the pulses and formation of bound states, we derive a weakly nonlinear model for the flow, the generalized Kuramoto–Sivashinsky (gKS) equation, that retains the fundamental mechanisms of the wave evolution, namely, dominant nonlinearity, instability, stability and dispersion. Much like in the experiments, the spatio-temporal evolution of the gKS equation is dominated by quasi-stationary solitary pulses which continuously interact with each other through coalescence events or attractions/repulsions. To understand the latter case, we utilize a weak-interaction theory for the solitary pulses of the gKS equation. The theory is based on representing the solution of the equation as a superposition of the pulses and an overlap function and leads to a coupled system of ordinary differential equations describing the evolution of the locations of the pulses, or, alternatively, the evolution of the separation distances. By analyzing the fixed points of this system, we obtain bound states of interacting pulses. For two pulses, we provide a criterion for the existence of a countable infinite or finite number of bound states, depending on the strength of the dispersive term in the equation. The interaction theory and resulting bound states are corroborated by computations of the full equation. We also find qualitative agreement between the theory and the experiments.