Structure and bonding in a cyclobutyl tris(pyrazolyl)boratoniobium complex and the variation in agostic behaviour with ring size in the series Tp(Me2)NbCl(c-C(n)H(2n-1))(MeC[triple bond]CMe), n = 3-6

The synthesis and characterisation of the cyclobutyl complex Tp(Me2)NbCl(c-C4H7)(MeC[triple bond]CMe) completes the family of cycloalkyl complexes Tp(Me2)NbCl(c-C(n)H(2n-1)), n = 3-6. The properties of the cyclobutyl complex are qualitatively similar to those of its cyclopentyl and cyclohexyl analogues, and dramatically different from those of the cyclopropyl derivative. Most conspicuously, the cyclobutyl system has an alpha-C-H agostic interaction in the dominant isomer, with no evidence for the alpha-C-C agostic character found for the smaller ring. C-C agostic character therefore seems to be unique to the cyclopropyl complex, where the acute C-C-C angles destabilise the C-C bonding orbitals.     

Acoustic rotational manipulation using orbital angular momentum transfer

We report on the first quantitative test of acoustic orbital angular momentum transfer to a sound absorbing object immersed in a viscous liquid. This is done by realizing an original experiment that is to spin a millimeter-size target disk using an ultrasonic vortex beam. We demonstrate the balance between the acoustic radiation torque calculated from the Brillouin stress tensor and the viscous torque evaluated from the steady state spinning frequency. Moreover, we unveil a rotational acoustic streaming phenomenon that results from the acoustic angular momentum transfer to the host fluid. We show that it lowers the viscous torque, thereby restoring the torque balance.     

Electrochemical approaches for the fabrication and/or characterization of pure and hybrid templated mesoporous oxide thin films: a review

Electrochemistry can be used for fabrication and characterization of mesoporous oxide films. First, this review provides insight into the methods used to prepare templated mesoporous thin films on an electrode surface, i.e., evaporation-induced self-assembly (EISA) and electrochemically assisted self-assembly (EASA). Electrochemical characterization of mass transport processes in pure and organically functionalized mesoporous oxide films is then discussed. The electrochemical response can be basically restricted by the electron/mass transfer reaction at the electrode–film interface and diffusion through mesopore channels. The contributions of cyclic voltammetry, hydrodynamic voltammetry, electrochemical impedance spectroscopy, and scanning electrochemical microscopy to the characterization of films with distinct mesostructures are finally described, with special emphasis on identification of conditions that can affect the electrochemical response recorded with such modified electrodes.

External Approximation of Nonlinear Operator Equations

Based on an external approximation scheme for the underlying Banach space, a nonlinear operator equation is approximated by a sequence of coercive problems. The equation is supposed to be governed by the sum of two nonlinear operators acting between a reflexive Banach space and its dual. Under suitable stability assumptions and if the underlying operators can be approximated consistently, weak convergence of a subsequence of approximate solutions is shown. This also proves existence of solutions to the original equation.     

Effect of substitution on the intramolecular 1,3-dipolar cycloaddition of alkene tethered münchnones

A sequence of chemoselective activation of N-acylaminoacids, münchnone generation, intramolecular 1,3-dipolar cycloaddition, and ring opening efficiently generated functionalized polycyclic structures such as cyclopenta[b]pyrroles or zwitterionic bicyclo[4.3.0]nonane or bicyclo[3.3.0]octanes in one operation is given. These zwitterionic species were isolated for the first time and were subsequently reduced to bicyclic aminoalcohols. The effect of the substitution of both the dipolarophile and the münchnone on the intramolecular cycloaddition outcome was examined. It was found that either nonactivated or electron-poor alkenes can react with the münchnone if these alkenes are tethered at position 4 on the münchnone (2, R2 = alkene tether), whereas only an electron-poor alkene at position 2 (2, R3 = alkene tether) could undergo successful cycloaddition. Also, münchnones substituted at position 2 with a phenyl (2, R3 = Ph) showed a dramatic increase in reactivity, whereas a phenyl at position 4 (2, R2 = Ph) had a very limited effect.     

Hierarchy of effective modes for the dynamics through conical intersections in macrosystems

An extension of the effective-mode theory for the short-time dynamics through conical intersections in macrosystems [L. S. Cederbaum et al., Phys. Rev. Lett. 94, 113003 (2005)] is proposed. The macrosystem, containing a vast number of nuclear degrees of freedom (modes), is decomposed into a system part and an environment part. Only three effective modes are needed-together with the system's modes-to accurately calculate low resolution spectra and the short-time dynamics of the entire macrosystem. Here, the authors propose an iterative scheme to construct a hierarchy of additional triplets of effective modes. This naturally extends the effective-mode formulation. By taking into account more and more triplets, the dynamics are accurately predicted for longer and longer times, and more resolved spectra can be calculated. Numerical examples are presented, computed using various numbers of additional effective modes.     

Reduction of symmetric semidefinite programs using the regular \ast-representation

We consider semidefinite programming problems on which a permutation group is acting. We describe a general technique to reduce the size of such problems, exploiting the symmetry. The technique is based on a low-order matrix $*$ -representation of the commutant (centralizer ring) of the matrix algebra generated by the permutation matrices. We apply it to extending a method of de Klerk et al. that gives a semidefinite programming lower bound to the crossing number of complete bipartite graphs. It implies that cr(K _8,n ) ≥ 2.9299n ² ? 6n, cr(K _9,n ) ≥ 3.8676n ² ? 8n, and (for any m ≥ 9) $$\lim_{n\to\infty}\frac{{\rm cr}(K_{m,n})}{Z(m,n)}\geq 0.8594\frac{m}{m-1},$$ where Z(m,n) is the Zarankiewicz number $\lfloor\frac{1}{4}(m-1)^2\rfloor\lfloor\frac{1}{4}(n-1)^2\rfloor$ , which is the conjectured value of cr(K _m,n ). Here the best factor previously known was 0.8303 instead of 0.8594.     

Direct measurement of hydrophobic forces on cell surfaces using AFM

Although hydrophobic forces are of great relevance in biological systems, quantifying these forces on complex biosurfaces such as cell surfaces has been difficult owing to the lack of appropriate, ultrasensitive force probes. Here, chemical force microscopy (CFM) with hydrophobic tips was used to measure local hydrophobic forces on organic surfaces and on live bacteria. On organic surfaces, we found an excellent correlation between nanoscale CFM and macroscale wettability measurements, demonstrating the sensitivity of the method toward hydrophobicity and providing novel insight into the nature of hydrophobic forces. Then, we measured hydrophobic forces associated with mycolic acids on the surface of mycobacteria, supporting the notion that these hydrophobic compounds represent an important permeation barrier to drugs.     

Evidence of superparamagnetic co clusters in pulsed laser deposition-grown Zn0.9Co0.1O thin films using atom probe tomography

Nanosized Co clusters (of about 3 nm size) were unambiguously identified in Co-doped ZnO thin films by atom probe tomography. These clusters are directly correlated to the superparamagnetic relaxation observed by ZFC/FC magnetization measurements. These analyses provide strong evidence that the room-temperature ferromagnetism observed in the magnetization curves cannot be attributed to the observed Co clusters. Because there is no experimental evidence of the presence of other secondary phases, our results reinforce the assumption of a defect-induced ferromagnetism in Co-doped ZnO diluted magnetic semiconductors.