Evidence for an anomalous redox ionic pair between Ru and Mn in SrRu0.5Mn0.5O3: an X-ray absorption spectroscopy approach

X-ray absorption spectroscopy studies of the polycrystalline SrRu0.5Mn0.5O3 have been performed at Ru, Mn-L2,3 edges. The 2p-->t2g related peak at the Ru-L2 edge is more intense than the Ru-L3 edge and a shift of the 2p-->eg related peak by approximately 0.8 eV to higher energy than that of the Ru(IV) compound, SrRuO3 is observed. In combination with a crystal field multiplet calculation approach, a possible anomalous change in the spectral features is explained based on the existence of a redox ionic pair involving Ru(IV)/Ru(v)<-->Mn(III)/Mn(IV).     

Tuning rate of the bergman cyclization of benzannelated enediynes with ortho substituents

[reaction: see text] The Bergman cyclization of benzannelated enediynes is highly sensitive to ortho substitution. This finding opens possibilities for the rational design of conformer-specific and pH-dependent DNA-cleaving agents.     

Enhanced aromaticity of the transition structures for the diels-alder reactions of quinodimethanes: evidence from ab initio and DFT computations

The Diels-Alder reactions of various quinodimethanes with ethylene are studied by means of ab initio molecular orbital and density functional theory (DFT) to show the effect of aromaticity on the reaction path. The calculations reveal that these reactions are both kinetically and thermodynamically much more favored than the prototype butadiene-ethylene Diels-Alder reaction due to the aromatization process in the transition state (TS) and product. A progressive aromaticity gain is noticed during the reaction, and hence the partial pi-delocalized peripheral diene ring function is coupled with the six-electron sigma,pi-delocalized cyclic unit resulting in an enhanced aromaticity of the TS. The magnetic criteria such as magnetic susceptibility exaltation and nucleus independent chemical shift provide definitive evidence for and fully support the aromatization process and the aromaticity of the TS. The extent of sigma-pi delocalization and the bond make-break at the TS are consistent with each other, and this is strongly influenced by the adjacent pi-aromatization process. Moreover, the aromaticity trends in the resulting TSs and products parallel the activation and reaction energies; the extent of aromatization increases with increasing reaction rate and exothermicity. This confirms that aromaticity is the driving factor governing cycloadditions involving quinodimethanes.     

Site-specific cross-linking of nucleic acids using the abasic site

[formula: see text] An efficient site-specific cross-linking reaction between two carbohydrate residues present in two complementary DNA sequences is described. One oligodeoxynucleotide, 5'd(GGCTGA*CTGCG)3', carries an amino nucleophile tethered to the 2'-hydroxyl of an adenosine residue (A*). The target electrophile is an abasic site generated in the complementary sequence, 5'd(CGCAGDCAGCC)3' (D represents the deoxyribose). The cross-linking reaction was carried out by a reductive amination reaction in > 95% yield.     

2'-O-[2-(guanidinium)ethyl]-modified oligonucleotides: stabilizing effect on duplex and triplex structures

[structure: see text] Oligonucleotides with a novel 2'-O-[2-(guanidinium)ethyl] (2'-O-GE) modification have been synthesized using a novel protecting group strategy for the guanidinium group. This modification enhances the binding affinity of oligonucleotides to RNA as well as duplex DNA (DeltaT(m) 3.2 degrees C per modification). The 2'-O-GE modified oligonucleotides exhibited exceptional resistance to nuclease degradation. The crystal structure of a palindromic duplex formed by a DNA oligonucleotide with a single 2'-O-GE modification was solved at 1.16 A resolution.     

Scattering theory of Kondo mirages and observation of single Kondo atom phase shift

We explain the origin of the Kondo mirage seen in recent quantum corral scanning tunneling microscope experiments with a scattering theory of electrons on the surfaces of metals. Our theory, combined with experimental data, provides a direct observation of a single Kondo atom phase shift. The Kondo mirage observed at the empty focus of an elliptical quantum corral is shown to arise from multiple electron bounces off the corral wall adatoms. We demonstrate our theory with direct quantitive comparison to experimental data.     

Lefschetz fixed point theory on fibrations

For a fibre preserving map ϕ: E → E on a fibration (E, π, B), we construct a grading preserving map T(ϕ, π) between H*(E) and H*(B) that generalizes the Lefschetz number. If T(ϕ, π) is an isomorphism between H ⁰(E) and H ⁰(B), then π restricts to a surjective local diffeomorphism on each connected component of the fixed point set of ϕ under a transversality condition. This yields a characterization for the bundle H → G → G/H to be trivial when π ₁ (G/H) = 0.     

Non-nucleoside building blocks for copper-assisted and copper-free click chemistry for the efficient synthesis of RNA conjugates

Novel non-nucleoside alkyne monomers compatible with oligonucleotide synthesis were designed, synthesized, and efficiently incorporated into RNA and RNA analogues during solid-phase synthesis. These modifications allowed site-specific conjugation of ligands to the RNA oligonucleotides through copper-assisted (CuAAC) and copper-free strain-promoted azide-alkyne cycloaddition (SPAAC) reactions. The SPAAC click reactions of cyclooctyne-oligonucleotides with various classes of azido-functionalized ligands in solution phase and on solid phase were efficient and quantitative and occurred under mild reaction conditions. The SPAAC reaction provides a method for the synthesis of oligonucleotide-ligand conjugates uncontaminated with copper ions.     

Altered condylar morphology associated with disc displacement in TMJ dysfunction: observations by MRI

Magnetic resonance images of 276 TM joints in 138 symptomatic patients were analyzed in a retrospective study to determine the condylar shape and size and to correlate it with internal derangement. Internal derangement by MRI was noted in 66% of the TM joints. Our study demonstrates that the regressive condylar changes in TM joints with internal derangement were more common (61%) than proliferative bony changes (39%). On the converse, none of the TM joints with regressive condyles revealed normal disc. The altered bony morphology also correlated with the severity of internal derangement, i.e. bony changes in TM joints with anterior closed lock were noted in 64% compared to 45% with reducible disc. The cause and effect relationship of the regressive condylar remodeling and disc abnormality is not clear and needs further study.