DNA-binding of semirigid binuclear ruthenium complex delta,delta-[mu-(11,11'-bidppz)(phen)(4)ru(2)](4+): extremely slow intercalation kinetics

We here report a remarkably slow rearrangement of binding modes for a binuclear ruthenium(II) complex upon interaction with DNA. It has been previously shown that Delta,Delta-[mu-(11,11'-bidppz)(phen)4Ru2]4+ binds to DNA in one of the grooves. However, we find that this is only an initial, metastable, binding mode, which is extremely slowly reorganized into an intercalative binding geometry. The slow rearrangement and dissociation, revealed by flow linear dichroism and fluorescence spectroscopy, are concluded to be a result from the complex being threaded through the DNA, with one of the bridging aromatic dppz ligands intercalated between the base pairs of the DNA, placing one metal center in the minor groove and one in the major groove. A negative LD, a high luminescence quantum yield, and long luminescence lifetimes, similar to the intercalating complex Delta-[Ru(phen)2dppz]2+, indicate intercalation of the bidppz moiety. The unique slow dissociation of the complex in its final DNA-binding mode suggests that this class of threading, partially intercalated binuclear complexes may be interesting in the context of cancer therapy. Also, their unique optical and photophysical properties could make such complexes, either alone or scaffolded by DNA structures, of interest for the development of nanometer-sized molecular optoelectronic devices.     

HEAT TRANSFER AND PRESSURE DROP FROM LOUVERED SURFACES IN AUTOMOTIVE HEAT EXCHANGERS

An investigation of heat transfer and pressure drop from some louvered surfaces is presented. The test rig and the measuring as well as the data evaluating procedures are described. The measured data are transferred and presented in a nondimenswnal form. The heal transfer data are provided mainly as Stanton numbers versus Reynolds number, and the pressure drop is given as Darcy friction factors versus Reynolds number. For comparing the performance of the various louvered surfaces, the flow area goodness factors and the so-called volume goodness factors are presented. All the louvered surfaces have been found to be more efficient than the corresponding smooth surface. The standard multilouvered fin surfaces were found to be most efficient, but one of the new surfaces also performed very well.     

What Is a Quantum-Mechanical “Weak Value” the Value of?

A so called “weak value” of an observable in quantum mechanics (QM) may be obtained in a weak measurement + post-selection procedure on the QM system under study. Applied to number operators, it has been invoked in revisiting some QM paradoxes (e.g., the so called Three-Box Paradox and Hardy’s Paradox). This requires the weak value to be interpreted as a bona fide property of the system considered, a par with entities like operator mean values and eigenvalues. I question such an interpretation; it has no support in the basic axioms of quantum mechanics and it leads to unreasonable results in concrete situations.     

Absorption Statistics in Linear Dichroism

Attention is called to an artifact in linear dichroism (LD), so called absorption statistics, which leads to reduced LD intensity in regions of high absorption. The reduction factor is larger than that governing the corresponding reduction in absorption, when LD is measured by using a Legrand-Grosjean circular dichroism spectrophotometer. In the case of infinite fibres at perfect order it coincides with the absorption statistical reduction factor of optical activity. The artifact was observed for β-carothene solubilized in lecithin liposomes oriented at flow.     

Effects of the type of crosslink on viscoelastic properties of natural rubber

The viscoelastic properties of various crosslinked natural rubbers, NR, were investigated by mechanical spectroscopy. The glass transition temperature, T_g, was found to be dependent on both the crosslink density and the crosslink type. Higher values of T_g were obtained for sulfur-crosslinked NR than for peroxide-crosslinked NR at the same crosslink density. The greater influence of the sulfur content on T_g may be attributed to polysulfidic crosslinks and cyclic sulfide structures favored at high sulfur contents. Sulfur-vulcanized NRs with monosulfidic crosslinks, favored at relatively high accelerator/sulfur ratios, have properties more similar to the peroxide-cured NR with simple carbon(SINGLE BOND)carbon crosslinks covalent bonds, resulting in only small shifts in T_g. A qualitative analysis of monosulfidic crosslinks and polysulfidic structures was performed with ¹³C solid-state NMR spectroscopy. The storage modulus, E′, in the rubbery plateau region increased with increasing crosslink density. However, the crosslink type did not influence the moduli values as much as it influenced the T_g values. Different methods of detecting the crosslink density were also discussed. © 1996 John Wiley & Sons, Inc.     

Amino acid catalyzed neogenesis of carbohydrates: a plausible ancient transformation

Hexose sugars play a fundamental role in vital biochemical processes and their biosynthesis is achieved through enzyme-catalyzed pathways. Herein we disclose the ability of amino acids to catalyze the asymmetric neogenesis of carbohydrates by sequential cross-aldol reactions. The amino acids mediate the asymmetric de novo synthesis of natural L- and D-hexoses and their analogues with excellent stereoselectivity in organic solvents. In some cases, the four new stereocenters are assembled with almost absolute stereocontrol. The unique feature of these results is that, when an amino acid is employed as the catalyst, a single reaction sequence can convert a protected glycol aldehyde into a hexose in one step. For example, proline and its derivatives catalyze the asymmetric neogenesis of allose with >99 % ee in one chemical manipulation. Furthermore, all amino acids tested catalyzed the asymmetric formation of natural sugars under prebiotic conditions, with alanine being the smallest catalyst. The inherent simplicity of this catalytic process suggests that a catalytic prebiotic "gluconeogenesis" may occur, in which amino acids transfer their stereochemical information to sugars. In addition, the amino acid catalyzed stereoselective sequential cross-aldol reactions were performed as a two-step procedure with different aldehydes as acceptors and nucleophiles. The employment of two different amino acids as catalysts for the iterative direct aldol reactions enabled the asymmetric synthesis of deoxysugars with >99 % ee. In addition, the direct amino acid catalyzed C(2)+C(2)+C(2) methodology is a new entry for the short, highly enantioselective de novo synthesis of carbohydrate derivatives, isotope-labeled sugars, and polyketide natural products. The one-pot asymmetric de novo syntheses of deoxy and polyketide carbohydrates involved a novel dynamic kinetic asymmetric transformation (DYKAT) mediated by an amino acid.     

Brownian Approximation and Monte Carlo Simulation of the Non-Cutoff Kac Equation

The non-cutoff Boltzmann equation can be simulated using the DSMC method, by a truncation of the collision term. However, even for computing stationary solutions this may be very time consuming, in particular in situations far from equilibrium. By adding an appropriate diffusion, to the DSMC-method, the rate of convergence when the truncation is removed, may be greatly improved. We illustrate the technique on a toy model, the Kac equation, as well as on the full Boltzmann equation in a special case.