Tetrahedral Pegs in Square Holes: Stereochemistry of Diboron Porphyrazines and Phthalocyanines

The first examples of diboron complexes of the tetrapyrroles octaethylporphyrazine (OEPz) and 2,9,16,23‐tetra‐t‐butyl‐phthalocyanine (Pc) are reported, counterpoints to the better known monoboron tripyrroles, subporphyrazine and subphthalocyanine. Two stereochemical possibilities are observed, with cisoid‐B₂OF₂(OEPz), both cisoid‐B₂OPh₂(OEPz) and transoid‐B₂OPh₂(OEPz), transoid‐B₂OF₂(Pc) and cisoid‐B₂OPh₂(Pc) having been isolated and characterised, including structure determinations for the OEPz complexes. This variation in stereochemistry, which can be extended to include the previously reported transoid‐B₂OF₂(porphyrin), cisoid‐[B₂OF₂(corrole)]^?, and both transoid‐ and cisoid‐B₂OF₂(calixphyrin), prompted a wider DFT study to elucidate the factors influencing the stereochemical preferences. This shows that the cisoid/transoid preference is correlated to the ease with which the macrocycle accommodates a rectangularly distorted N₄ cavity.     

Proton-detected separated local field spectroscopy

PISEMO, a separated local field experiment that can be performed with either direct (15)N (or (13)C) detection or indirect (1)H detection, is demonstrated on a single crystal of a model peptide. The (1)H signals modulated by (1)H-(15)N heteronuclear dipole-dipole couplings are observed stroboscopically in the windows of the multiple-pulse sequence used to attenuate (1)H-(1)H homonuclear dipole-dipole couplings. (1)H-detection yields spectra with about 2.5 times the signal to noise ratio observed with (15)N-detection under equivalent conditions. Resolution in both the (15)N chemical shift and (1)H-(15)N heteronuclear dipole-dipole coupling dimensions is similar to that observed with PISEMA, however, since only on-resonance pulses are utilized, the bandwidth is better.     

On Large-Scale Friction Control in Turbulent Wall Flow in Low Reynolds Number Channels

The present study reconsiders the control scheme proposed by Schoppa & Hussain (Phys. Fluids 10, 1049–1051 1998), using a new set of numerical simulations. The computations are performed in a turbulent channel at friction Reynolds numbers of 104 (the value employed in the original study) and 180. In particular, the aim is to better characterise the physics of the control as well as to investigate the optimal parameters. The former purpose lead to a re-design of the control strategy: moving from a numerical imposition of the mean flow to the application of a volume force. A comparison between the two is presented. Results show that the original method only gave rise to transient drag reduction. The forcing method, on the other hand, leads to sustained drag reduction, and thus shows the superiority of the forcing approach for all wavelengths investigated. A clear maximum efficiency in drag reduction is reached for the case with a viscous-scaled spanwise wavelength of the vortices of 1200, which yields a drag reduction of 18 %, as compared to the smaller wavelength of 400 suggested as the most efficient vortex in Schoppa & Hussain. Various turbulence statistics are considered, in an effort to elucidate the causes of the drag-reducing effect. For instance, a region of negative production was found, which is quite unusual for developed turbulent channel flow.     

Furylhydroquinones and miscellaneous compounds from the roots of Lithospermum erythrorhizon and their anti-inflammatory effect in HaCaT cells

One new furylhydroquinone derivative (1) and seven known compounds (2–8) were isolated from the roots of Lithospermum erythrorhizon Sieb. et Zucc (Boraginaceae). The structure of 1 was elucidated by extensive spectroscopic methods using NMR and MS. The absolute configuration of shikonofuran J (1) was unambiguously determined by aid of comparison experimental ECD with predicted ECD spectra. All the isolates were tested for their inhibitory activities against IL-6 production in HaCaT cells stimulated by tumor necrosis factor (TNF)-α. It was found that gracicleistanthoside (5) and uridine (7) remarkably down-regulated the TNF-α-induced synthesis of interleukin-6 (IL-6), a pro-inflammatory cytokine associated with cutaneous inflammation, in HaCaT cells.     

The formation of dinuclear trichloro-bridged and mononuclear ruthenium complexes from the reactions of dichlorotris(p-tolylphosphine)ruthenium(II) with diazabutadiene ligands

Transition Metal Chemistry - Ru(II) complexes with diazabutadiene (R-DAB) ligands have been prepared. The reaction of RuCl3·nH2O with P(p-tolyl)3 gave a [RuCl2{P(p-tolyl)3}] precursor, whose...     

Binding Sites,Vibrations and Spin-Lattice Relaxation Times in Europium(II)-Based Metallofullerene Spin Qubits

To design molecular spin qubits with enhanced quantum coherence, a control of the coupling between the local vibrations and the spin states is crucial, which could be realized in principle by engineering molecular structures via coordination chemistry. To this end, understanding the underlying structural factors that govern the spin relaxation is a central topic. Here, we report the investigation of the spin dynamics in a series of chemically designed europium(II)-based endohedral metallofullerenes (EMFs). By introducing a unique structural difference, i. e. metal-cage binding site, while keeping other molecular parameters constant between different complexes, these manifest the key role of the three low-energy metal-displacing vibrations in mediating the spin-lattice relaxation times (T₁). The temperature dependence of T₁ can thus be normalized by the frequencies of these low energy vibrations to show an unprecedentedly universal behavior for EMFs in frozen CS₂ solution. Our theoretical analysis indicates that this structural difference determines not only the vibrational rigidity but also spin-vibration coupling in these EMF-based qubit candidates.     

Acoustic Properties of Micro-Perforated Panels Made from Oil Palm Empty Fruit Bunch Fiber Reinforced Polylactic Acid

This paper presents the development and performance of micro-perforated panels (MPP) from natural fiber reinforced composites. The MPP is made of Polylactic Acid (PLA) reinforced with Oil Palm Empty Fruit Bunch Fiber (OPEFBF). The investigation was made by varying the fiber density, air gap, and perforation ratio to observe the effect on the Sound Absorption Coefficient (SAC) through the experiment in an impedance tube. It is found that the peak level of SAC is not affected, but the peak frequency shifts to lower frequency when the fiber density is increased. This phenomenon might be due to the presence of porosity in the inner wall of the holes. Increasing or decreasing the air gap and perforation ratio shifts the peaks of acoustic absorption either way.