Solvation Dynamics of a Radical Ion Pair in Micro‐Heterogeneous Binary Solvents: A Semi‐Quantitative Study Utilizing MARY Line‐Broadening Experiments

This work aims at elucidating the mechanism of solvation of a radical ion pair (RIP) in a micro‐heterogeneous binary solvent mixture using magnetically affected reaction yield (MARY) spectroscopy. For the exciplex‐forming 9,10‐dimethylanthracene/N,N‐dimethylaniline system a comparative, composition‐dependent MARY line‐broadening study is undertaken in a heterogeneous (toluene/dimethylsulfoxide) and a quasi‐homogenous (propyl acetate/butyronitrile) solvent mixture. The half‐saturation field extrapolated to zero‐quencher concentration, B_1/2, and the self‐exchange rate constants are analyzed in the light of solvent dynamical properties of the mixtures and a dielectric continuum solvation model. The dependence of B_1/2 on the solvent composition is explained by cluster formation giving rise to shortened RIP lifetimes. The results are in qualitative agreement with the continuum solvation model suggesting that it could serve as a theoretical basis for quantitative modeling.     

Visual spatial memory is enhanced in female rats (but inhibited in males) by dietary soy phytoestrogens

Background  

In learning and memory tasks, requiring visual spatial memory (VSM), males exhibit superior performance to females (a difference attributed to the hormonal influence of estrogen). This study examined the influence of phytoestrogens (estrogen-like plant compounds) on VSM, utilizing radial arm-maze methods to examine varying aspects of memory. Additionally, brain phytoestrogen, calbindin (CALB), and cyclooxygenase-2 (COX-2) levels were determined.     

Demonstration of image-zooming capability for diffractive axicons

Diffractive axicons are optical components producing achromatic nondiffracting beams. They thus produce a focal line rather than a focal point for classical lenses. This gives the interesting property of a long focal depth. We show that this property can be used to design a simple imaging system with a linear variable zoom by using and translating a diffractive axicon as the only optical component.     

A cheap metal for a "noble" task: preparative and mechanistic aspects of cycloisomerization and cycloaddition reactions catalyzed by low-valent iron complexes

Reaction of ferrocene with lithium in the presence of either ethylene or COD allows the Fe(0)-ate complexes 1 and 4 to be prepared on a large scale, which turned out to be excellent catalysts for a variety of Alder-ene, [4+2], [5+2], and [2+2+2] cycloadditon and cycloisomerization reactions of polyunsaturated substrates. The structures of ferrates 1 and 4 in the solid-state reveal the capacity of the reduced iron center to share electron density with the ligand sphere. This feature, coupled with the kinetic lability of the bound olefins, is thought to be responsible for the ease with which different enyne or diyne substrates undergo oxidative cyclization as the triggering event of the observed skeletal reorganizations. This mechanistic proposal is corroborated by highly indicative deuterium labeling experiments. Moreover, it was possible to intercept two different products of an oxidative cyclization manifold with the aid of the Fe(+1) complex 6, which, despite its 17-electron count, also turned out to be catalytically competent in certain cases. The unusual cyclobutadiene complex 38 derived from 6 and tolane was characterized by X-ray crystallography.     

Relevance of continuously self-imaging gratings for noise robust imagery

We have designed miniaturized, simple, and robust cameras composed of a single diffractive optical element (DOE) that generates a continuously self-imaging (CSI) beam. Two different DOEs are explored: the J₀ Bessel transmittance, characterized by a continuous optical transfer function (OTF) and the CSI grating (CSIG), characterized by a sparse OTF. In this Letter, we will analyze the properties of both DOEs in terms of radiometric performances. We will demonstrate that the noise robustness is enhanced for a CSIG, thanks to the sparsity of its OTF. A camera using this DOE has been made and experimental images are presented to illustrate the noise robustness.     

On the Coherent Description of Diffusion‐Influenced Fluorescence Quenching Experiments II: Early Events

In a previous article we showed how to perform and analyze steady‐state and nanosecond time‐resolved experiments on fluorescence quenching by electron transfer in a coherent manner. Now, by making use of a superior time resolution, we explore the first stages of this kind of reaction. The novel information gained enables us to merge the results on the viscosity and the driving‐force dependencies of the reaction rate. A unique set of parameters for a single reaction channel suffices to describe all the results in the frame of differential encounter theory for diffusion‐influenced, bimolecular, remote electron‐transfer reactions. The inclusion of the solvent structure is crucial for the understanding of the reaction kinetics. To the authors’ best knowledge, this is the first time that such a comprehensive set of data has been successfully and jointly explained in the field, with physically sound parameters for electron‐transfer reactions.