Transition Metal Complexes with Bidentate Ligands Spanning trans-Positions. VIII. The reactions of the nucleophile trans-[RuCl(NO)(1)] (1 = 2,11-bis(diphenylphosphinomethyl)benzo[c]-phenanthrene) with carbon monoxide and the phosphite ligand (2) (2 = 1-ethyl-3,5,8-trioxa-4-phosphabicyclo (2.2.2)octane)

The preparation of the nucleophile trans-[RuCl(NO)( 1 )], where 1 is the bidentate ligand Ph₂PCH₂C₁₈CH₂PPh₂, and of the five-coordinate species [RuCl(CO)(NO)( 1 )], [RuCl(CO)(NO)(Ph₂PCH₂Ph)₂] and [RuCl(NO)( 2 )( 1 )] are reported. The crystal structure of [RuCl(CO)(NO)( 1 )] shows that the coordination around the metal atom is distorted trigonal bipyramidal with the phosphorus atoms in axial positions. The Ru? N? O bond angle is 142.8°. ¹H- and ³¹P-NMR. and \documentclass{article}\pagestyle{empty}\begin{document}$ \tilde \nu $\end{document}_NO IR.-data for the above complexes are reported and related to the coordination geometry.     

Automorphisms of (B)-geometries

(B)-Geometries are incidence structures arising from permutation sets. The present paper studies the automorphism groups of (B)-Geometries. In certain cases these automorphisms yield examples of inversive planes and of subplanes which are embedded in Minkowski planes (chapter 2). In chapter 3 we describe the automorphism groups of the (B)-Geometries arising from the groups PL(2, pⁿ) and AL(1, pⁿ) in their natural representations on the points of the projective and affine line.Dedicated to Prof.Dr. Walter Benz on his 60th birthdayWork done within the activity of G.N.S.A.G.A. of C.N.R. and supported by the 40% grants of M.U.R.S.T.     

The conformation of rifamycin S in solution by 1H NMR spectroscopy

The ¹H NMR spectra of rifamycin S in different solvents and at different temperatures strongly suggest the existence of a dominant conformer. The nine dihedral angles of the ansa chain from C-28 to C-19, considered conformationally flexible, were obtained from the vicinal interproton coupling constants by the Karplus equation and the proper alternative for each of them compares well with the corresponding values given by X-ray analysis in solid state.All the possible conformations derivable from the intrinsic alternatives of the NMR method were calculated for the ansa chain between C-28 and C-19 and, by applying geometrical considerations, such as closure of the polygonal path of the ansa and the steric incompatibility between the various atoms of the ansa and of the chromophore, only two of them appeared real. Thus, NMR spectroscopy can be used for studying the conformation of the ansa chain of rifamycins in solution.     

Gear effect—10 : Conformational aspects of the positive or negative buttressing effects of methyl groups: polymethylpyridines

The effect of the shape of a methyl group on reactivity, which cannot be accounted for by considering a methyl group as a spherical substituent with the appropriate van der Waals radius, was considered in kinetics of alkylalion of substituted pyridines and barriers to rotation and ground state conformations of an isopropyl group attached to a planar framework. The perturbation of a methyl group by an o-methyl group is accounted for by a unique conformational explanation which involves the polyhedral shape of the methyl group.     

Temperature dependence of the time-resolved emissions of CsI:Tl

Abstract

Time-resolved emissions of Csl:T1 are investigated. The system is laser-excited in the A-band at 308 nm and the emissions are observed in the range 370–650 nm, from 30 K to 300 K. Their analysis by means of a deconvolution permits the valuation of decay-times down to 1 ns. At every temperature many bands are observed and some of them show slow and fast components. The decay-times of the fast components are in the range 1–10 ns while the slow ones are even longer than 1 μs. In many cases intermediate decay-times of the order of 100 ns exist. The competition among the bands interests the application of this system as active material for tunable solid-state laser.     

Ionic electroactive polymer metal composites: Fabricating,modeling, and applications of postsilicon smart devices

Smart systems adapt to the surrounding environments in a number of ways. They are capable to scavenge energy from available sources, sense and elaborate external stimuli and adequately react. Electro Active Polymers are playing a main role in the realization of smart systems for applications if fields such as bio inspired and autonomous robotics, medicine, and aerospace. This paper focus on the possibility to use Ionic Polymer Metal Composites as a class of materials relevant to the realization of post silicon smart systems. The three main aspects of this new technology, i.e., fabrication methods, modeling, and applications are described with emphasis to most recent results. Attention is given to main challenges and shortcomings to be solved for technology, modelling, and control of IPMC based devices that need to be solved before this new technology can be fully exploited in real world applications. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013     

Recent Progress on Manganese-Based Nanostructures as Responsive MRI Contrast Agents

Manganese-based nanostructured contrast agents (CAs) entered the field of medical diagnosis through magnetic resonance imaging (MRI) some years ago. Although some of these Mn-based CAs behave as classic T₁ contrast enhancers in the same way as clinical Gd-based molecules do, a new type of Mn nanomaterials have been developed to improve MRI sensitivity and potentially gather new functional information from tissues by using traditional T₁ contrast enhanced MRI. These nanomaterials have been designed to respond to biological environments, mainly to pH and redox potential variations. In many cases, the differences in signal generation in these responsive Mn-based nanostructures come from intrinsic changes in the magnetic properties of Mn cations depending on their oxidation state. In other cases, no changes in the nature of Mn take place, but rather the nanomaterial as a whole responds to the change in the environment through different mechanisms, including changes in integrity and hydration state. This review focusses on the chemistry and MR performance of these responsive Mn-based nanomaterials.     

Design,Synthesis, and Biochemical Evaluation of Alpha-Amanitin Derivatives Containing Analogs of the trans-Hydroxyproline Residue for Potential Use in Antibody-Drug Conjugates

Alpha-amanitin, an extremely toxic bicyclic octapeptide extracted from the death-cap mushroom, Amanita phalloides, is a highly selective allosteric inhibitor of RNA polymerase II. Following on growing interest in using this toxin as a payload in antibody-drug conjugates, herein we report the synthesis and biochemical evaluation of several new derivatives of this toxin to probe the role of the trans-hydroxyproline (Hyp), which is known to be critical for toxicity. This structure activity relationship (SAR) study represents the first of its kind to use various Hyp-analogs to alter the conformational and H-bonding properties of Hyp in amanitin.