Density Functional Theory Calculations on Rhodamine B and Pinacyanol Chloride. Optimized Ground State,Dipole Moment,Vertical Ionization Potential,Adiabatic Electron Affinity and Lowest Excited Triplet State

The ground state configuration of the gas phase cationic dyes pinacyanol chloride and rhodamine B are optimized with HF/6–311 + G(2d,2p) method and basis set. B3PW91/6–311 + G(2df,2p) functional and basis set is used to calculate the Mulliken atom charge distribution, total molecular energy, the dipole moment, the vertical ionization potential, the adiabatic electron affinity and the lowest excited triplet state, the last three as an energy difference between separately calculated open shell and ground states. The triplet and extra electron states are optimized to find the relaxation energy. In the ground state optimization of both dyes the chloride anion migrates to a position near the center of the chromophore. For rhodamine B the benzoidal group turns perpendicular to the chromophore plane. For both dyes, the LUMO is mostly of π character associated with the aromatic part of the molecule containing the chromophore. The highest occupied MOs consist of three almost degenerate eigenvectors involving the chloride anion coordinated with σ electrons in the molecular framework. The fourth highest MO is of π character. For both molecules in the gas phase ionization process the chloride anion loses the significant fraction of electric charge. In electron capture, the excess charge goes mainly on the dye cation.     

Learning Robot Force/Position Control for Repetitive High Speed Applications with Unknown Non–Linear Contact Stiffness

This paper proposes a learning robot force/position control for high speed force trajectory following. Following high speed force trajectories in different repetitve robotic applications is a challenging field in robot force control. If the end–effector should provide a contact force while following a position trajectory in the non–force controlled direction a parallel force / position control is suitable. However, when it comes to high speed tasks this force control method reaches its limit. The problem can be solved by using an iterative learning control method in combination with the parallel force/position control. In this paper the learning force control method is introduced and experimental results are presented. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Radical Reactivity of the Biradical [⋅P(μ-NTer)2P⋅] and Isolation of a Persistent Phosphorus-Cantered Monoradical [⋅P(μ-NTer)2P-Et]

The activation of C−Br bonds in various bromoalkanes by the biradical [⋅P(μ-NTer)₂P⋅] ( 1 ) (Ter=2,6-bis-(2,4,6-trimethylphenyl)-phenyl) is reported, yielding trans-addition products of the type [Br−P(μ-NTer)₂P−R] ( 2 ), so-called 1,3-substituted cyclo-1,3-diphospha-2,4-diazanes. This addition reaction, which represents a new easy approach to asymmetrically substituted cyclo-1,3-diphospha-2,4-diazanes, was investigated mechanistically by different spectroscopic methods (NMR, EPR, IR, Raman); the results suggested a stepwise radical reaction mechanism, as evidenced by the in-situ detection of the phosphorus-centered monoradical [⋅P(μ-NTer)₂P-R].< To provide further evidence for the radical mechanism, [⋅P(μ-NTer)₂P-Et] ( 3Et ⋅) was synthesized directly by reduction of the bromoethane addition product [Br-P(μ-NTer)₂P-Et] ( 2 a ) with magnesium, resulting in the formation of the persistent phosphorus-centered monoradical [⋅P(μ-NTer)₂P-Et], which could be isolated and fully characterized, including single-crystal X-ray diffraction. Comparison of the EPR spectrum of the radical intermediate in the addition reaction with that of the synthesized new [⋅P(μ-NTer)₂P-Et] radical clearly proves the existence of radicals over the course of the reaction of biradical [⋅P(μ-NTer)₂P⋅] ( 1 ) with bromoethane. Extensive DFT and coupled cluster calculations corroborate the experimental data for a radical mechanism in the reaction of biradical [⋅P(μ-NTer)₂P⋅] with EtBr. In the field of hetero-cyclobutane-1,3-diyls, the demonstration of a stepwise radical reaction represents a new aspect and closes the gap between P-centered biradicals and P-centered monoradicals in terms of radical reactivity.     

Solid-Phase Synthesis of an Insect Pyrokinin Analog Incorporating an Imidazoline Ring as Isosteric Replacement of a trans Peptide Bond

A facile solid-phase synthetic method for incorporating the imidazoline ring motif, a surrogate for a trans peptide bond, into bioactive peptides is reported. The example described is the synthesis of an imidazoline peptidomimetic analog of an insect pyrokinin neuropeptide via a cyclization reaction of an iminium salt generated from the preceding amino acid and 2,4-diaminopropanoic acid (Dap).     

Integration of quantitative DCE-MRI and ADC mapping to monitor treatment response in human breast cancer: initial results

PURPOSE: The objective of this study was to assess changes in the water apparent diffusion coefficient (ADC) and in pharmacokinetic parameters obtained from the fast-exchange regime (FXR) modeling of dynamic contrast-enhanced magnetic resonance imaging (DCE-MRI) during neoadjuvant chemotherapy in breast cancer. MATERIALS AND METHODS: Eleven patients with locally advanced breast cancer underwent MRI examination prior to and after chemotherapy but prior to surgery. A 1.5-T scanner was used to obtain T1, ADC and DCE-MRI data. DCE-MRI data were analyzed by the FXR model returning estimates of K(trans) (volume transfer constant), v(e) (extravascular extracellular volume fraction) and tau(i) (average intracellular water lifetime). Histogram and correlation analyses assessed parameter changes post-treatment. RESULTS: Significant (P < .05) changes or trends towards significance (P < .10) were seen in all parameters except tau(i), although there was qualitative reduction in tau(i) values post-treatment. In particular, there was reduction (P < .035) in voxels with K(trans) values in the range 0.2-0.5 min(-1) and a decrease (P < .05) in voxels with ADC values in the range 0.99 x 10(-3) to 1.35 x 10(-3) mm2/s. ADC and v(e) were negatively correlated (r = -.60, P < .02). Parameters sensitive to water distribution and geometry (T(1), v(e), tau(i) and ADC) correlated with a multivariable linear regression model. CONCLUSION: The analysis presented here is sensitive to longitudinal changes in breast tumor status; K(trans) and ADC are most sensitive to these changes. Relationships between parameters provide information on water distribution and geometry in the tumor environment.     

Nearest neighbor and hard sphere models in continuum percolation

Consider a Poisson process X in R ^d with density 1. We connect each point of X to its k nearest neighbors by undirected edges. The number k is the parameter in this model. We show that, for k = 1, no percolation occurs in any dimension, while, for k = 2, percolation occurs when the dimension is sufficiently large. We also show that if percolation occurs, then there is exactly one infinite cluster. Another percolation model is obtained by putting balls of radius zero around each point of X and let the radii grow linearly in time until they hit another ball. We show that this model exists and that there is no percolation in the limiting configuration. Finally we discuss some general properties of percolation models where balls placed at Poisson points are not allowed to overlap (but are allowed to be tangent). © 1996 John Wiley & Sons, Inc.     

Nonequilibrium Time Reversibility with Maps and Walks

Time-reversible dynamical simulations of nonequilibrium systems exemplify both Loschmidt’s and Zermélo’s paradoxes. That is, computational time-reversible simulations invariably produce solutions consistent with the irreversible Second Law of Thermodynamics (Loschmidt’s) as well as periodic in the time (Zermélo’s, illustrating Poincaré recurrence). Understanding these paradoxical aspects of time-reversible systems is enhanced here by studying the simplest pair of such model systems. The first is time-reversible, but nevertheless dissipative and periodic, the piecewise-linear compressible Baker Map. The fractal properties of that two-dimensional map are mirrored by an even simpler example, the one-dimensional random walk, confined to the unit interval. As a further puzzle the two models yield ambiguities in determining the fractals’ information dimensions. These puzzles, including the classical paradoxes, are reviewed and explored here.     

Three-component Heck–Diels–Alder cascade processes involving alkylallenes, aryl iodides and dienophiles

A wide variety of aryl/heteroaryl iodides undergo an intermolecular Heck reaction with alkylallenes to furnish 1,3-dienes. These subsequently react in situ with various dienophiles to give Diels–Alder adducts. The chemistry has been extended to incorporate cyclisation-anion capture methodology and the stereochemistry of the products has been determined.