Pentacyanoiron(II) as an electron donor group for nonlinear optics: medium-responsive properties and comparisons with related pentaammineruthenium(II) complexes

In this article, we describe a series of complex salts in which electron-rich {Fe(II)(CN)(5)}(3)(-) centers are coordinated to pyridyl ligands with electron-accepting N-methyl/aryl-pyridinium substituents. These compounds have been characterized by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. Molecular quadratic nonlinear optical (NLO) responses have been determined by using hyper-Rayleigh scattering (HRS) at 1064 nm, and also via Stark (electroabsorption) spectroscopic studies on the intense, visible d --> pi* metal-to-ligand charge-transfer (MLCT) bands. The relatively large static first hyperpolarizabilities, beta(0), increase markedly on moving from aqueous to methanol solutions, accompanied by large red-shifts in the MLCT transitions. Acidification of aqueous solutions allows reversible switching of the linear and NLO properties, as shown via both HRS and Stark experiments. Time-dependent density functional theory and finite field calculations using a polarizable continuum model yield relatively good agreement with the experimental results and confirm the large decrease in beta(0) on protonation. The Stark-derived beta(0) values are generally larger for related {Ru(II)(NH(3))(5)}(2+) complexes than for their {Fe(II)(CN)(5)}(3)(-) analogues, consistent with the HRS data in water. However, the HRS data in methanol show that the stronger solvatochromism of the Fe(II) complexes causes their NLO responses to surpass those of their Ru(II) counterparts upon changing the solvent medium.     

Extended dipolar nonlinear optical chromophores based on trans-bis[1,2-phenylenebis(dimethylarsine)]chlororuthenium(II) centers

Four new complex salts trans[RuIICl(pdma)2LA][PF6]n [pdma = 1,2-phenylenebis(dimethylarsine); LA = 1,4-bis[E-2-(4-pyridyl)ethenyl]benzene (bpvb), n = 1, 1; LA = N-methyl-1,4-bis(E-2-(4-pyridyl)ethenyl)benzene (Mebpvb+), n = 2, 2; LA = N-phenyl-1,4-bis(E-2-(4-pyridyl)ethenyl)benzene (Phbpvb+), n = 2, 3; LA = N-(2-pyrimidyl)-1,4-bis(E-2-(4-pyridyl)ethenyl)benzene (Pymbpvb+), n = 2, 4] have been prepared. The electronic absorption spectra of 1-4 display intense, visible metal-to-ligand charge-transfer (MLCT) bands, with lambda(max) values in the range 432-474 nm in acetonitrile. Intense intraligand charge-transfer (ILCT) bands due to LA are also observed, with lambda(max) values in the range 350-416 nm. Cyclic voltammetric studies in acetonitrile reveal reversible RuIII/II waves with E(1/2) values of ca. 1.05 V vs Ag/AgCl, together with LA-based reduction processes that are irreversible with the exception of 1. Salts 1-4 have been investigated by using Stark (electroabsorption) spectroscopy in butyronitrile glasses at 77 K. These studies have afforded dipole moment changes, Deltamu12, for the MLCT and ILCT transitions which have been used to calculate molecular static first hyperpolarizabilities, Beta0, according to the two-state equation Beta0 = 3Deltamu12(mu12)2/(Emax)2 (mu12 = transition dipole moment, Emax = MLCT/ILCT energy). In contrast with related RuII ammine complexes, replacement of a central E-ethylene bond with a 1,4-phenylene unit does not appear to be an especially effective strategy for combating the NLO transparency-efficiency tradeoff in these pdma complexes. Single-crystal X-ray studies with the complex salts 2 and 3 and also with the pro-ligand salt [Phbpvb+] PF6.0.5HPF6 show that these materials all adopt centrosymmetric packing structures.     

A new synthesis of imidazolidin-2-ones via Pd-catalyzed carboamination of N-allylureas

A new strategy for the preparation of substituted imidazolidin-2-ones in two steps from readily available N-allylamines is described. Addition of the amine starting materials to isocyanates affords N-allylureas, which are converted to imidazolidin-2-one products with generation of two bonds and up to two stereocenters when treated with aryl bromides and catalytic amounts of Pd2(dba)3/Xantphos in the presence of NaO(t)Bu. [reaction: see text]     

Palladium-catalyzed alkene carboamination reactions for the synthesis of substituted piperazines

A strategy for the stereoselective preparation of enantiomerically enriched cis-2,6-disubstituted piperazines from amino acid precursors is described. The target compounds are generated in 95-99% ee with good to excellent levels of diastereoselectivity (usually 14:1 to >20:1) using Pd-catalyzed carboamination reactions between aryl or alkenyl halides and substituted ethylenediamine derivatives to form the heterocyclic rings. The synthesis requires only 4-5 steps from commercially available amino acids, and allows for the modular construction of piperazines bearing different substituents at N¹, N⁴, C², and C⁶. The use of this strategy for the construction of 2,3-disubstituted piperazines, fused bicyclic piperazines, and tetrahydroquinoxalines is also reported. In addition, the mechanism of the key carboamination reactions is discussed, and new models that predict and explain the stereochemical outcome of these transformations are presented.     

Contribution of constitutively proliferating precursor cell subtypes to dentate neurogenesis after cortical infarcts

Background  

It is well known that focal ischemia increases neurogenesis in the adult dentate gyrus of the hippocampal formation but the cellular mechanisms underlying this proliferative response are only poorly understood. We here investigated whether precursor cells which constitutively proliferate before the ischemic infarct contribute to post-ischemic neurogenesis. To this purpose, transgenic mice expressing green fluorescent protein (GFP) under the control of the nestin promoter received repetitive injections of the proliferation marker bromodeoxyuridine (BrdU) prior to induction of cortical infarcts. We then immunocytochemically analyzed the fate of these BrdU-positive precursor cell subtypes from day 4 to day 28 after the lesion.     

The method of images for regularized Stokeslets

The image system for the method of regularized Stokeslets is developed and implemented. The method uses smooth localized functions to approximate a delta distribution in the derivation of the fluid flow due to a concentrated force. In order to satisfy zero-flow boundary conditions at a plane wall, the method of images derived for a standard (singular) Stokeslet is extended to give exact cancellation of the regularized flow at the wall. As the regularization parameter vanishes, the expressions reduce to the known images for singular Stokeslets. The advantage of the regularized method is that it gives bounded velocity fields even for isolated forces or for distributions of forces along curves. These are useful in the simulation of ciliary beats, flagellar motion, and particle suspensions. The expression relating force and velocity can be inverted to find the forces that generate a given velocity boundary condition. The latter is exemplified by modeling a cilium as a filament moving in a three-dimensional flow. The cilium velocity at various times is constructed from known data and used to determine the force field along the filament. Those forces can then reproduce the flow everywhere. The validity of the method is evaluated by computing the drag on a sphere moving near a wall. Comparisons with known expressions for the drag show that the method gives accurate results for spheres even within a distance from the wall equal to the surface discretization size.     

Autoimmune hemolytic anemia: magnetic resonance findings

Idiopathic autoimmune hemolytic anemia (AIHA) is a rare hematological disease typically characterized by extracellular hemolysis. An unusual case of AIHA with interesting magnetic resonance imaging (MRI) appearances is presented. Possible explanations for the MRI findings are discussed.     

Interfacial pH at an isolated silica-water surface

Tethering a pH-sensitive dye to a silica surface enables the interfacial pH to be measured optically and is found to be 2 pH units lower than that of the bulk. The positive H+ ions are attracted by the surface potential and have an enhanced concentration consistent with the previously determined surface potential of order -120 mV, with respect to zero in the bulk. A stable near-surface charged layer once formed is not disrupted by the bulk pH.