Sequence and Structure of Peptoid Oligomers Can Tune the Photoluminescence of an Embedded Ruthenium Dye

The understanding of structure–function relationships within synthetic biomimetic systems is a fundamental challenge in chemistry. Herein we report the direct correlation between the structure of short peptoid ligands—N-substituted glycine oligomers incorporating 2,2′-bipyridine groups—varied in their monomer sequence, and the photoluminescence of Ru^II centers coordinated by these ligands. Based on circular dichroism and fluorescence spectroscopy we demonstrate that while helical peptoids do not affect the fluorescence of the embedded Ru^II chromophore, unstructured peptoids lead to its significant decay. Transmittance electron microscopy (TEM) revealed significant differences in the arrangements of metal-bound helical versus unstructured peptoids, suggesting that only the latter can have through-space interactions with the ruthenium dye leading to its quenching. High-resolution TEM enabled the remarkable direct imaging of singular ruthenium-bound peptoids and bundles, supporting our explanation for structure-depended quenching. Moreover, this correlation allowed us to fine-tune the luminescence properties of the complexes simply by modifying the sequence of their peptoid ligands. Finally, we also describe the chiral properties of these Ru–peptoids and demonstrate that remote chiral induction from the peptoids backbone to the ruthenium center is only possible when the peptoids are both chiral and helical.     

Generation and EPR Spectroscopy of the First Silenyl Radicals,R2C=Si.−R: Experiment and Theory

The first two persistent silenyl radicals (R₂C=Si^.?R), with a half‐life (t_1/2) of about 30 min, were generated and characterized by electron paramagnetic resonance (EPR) spectroscopy. The large hyperfine coupling constants (hfccs) (a(²⁹Si_α)=137.5–148.0 G) indicate that the unpaired electron has substantial s character. DFT calculations, which are in good agreement with the experimentally observed hfccs, predict a strongly bent structure (?C=Si?R=134.7–140.7°). In contrast, the analogous vinyl radical, R₂C=C^.?R (t_1/2≈3 h), exhibits a small hfcc (a(¹³C_α)=26.6 G) and has a nearly linear geometry (?C=C?R=168.7°).     

Mechanism of the Thermal Z⇌E Isomerization of a Stable Silene; Experiment and Theory

The E and Z geometric isomers of a stable silene (tBu₂MeSi)(tBuMe₂Si)Si=CH(1‐Ad) ( 1 ) were synthesized and characterized spectroscopically. The thermal Z to E isomerization of 1 was studied both experimentally and computationally using DFT methods. The measured activation parameters for the 1Z ? 1E isomerization are: E_a=24.4 kcal mol^?1, ΔH^≠=23.7 kcal mol^?1, ΔS^≠=?13.2 e.u. Based on comparison of the experimental and DFT calculated (at BP86‐D3BJ/def2‐TZVP(‐f)//BP86‐D3BJ/def2‐TZVP(‐f)) activation parameters, the Z?E isomerization of 1 proceeds through an unusual (unprecedented for alkenes) migration–rotation–migration mechanism (via a silylene intermediate), rather than through the classic rotation mechanism common for alkenes.     

Energy scan in heavy-ion collisions and search for a critical point

Experimental data on inclusive spectra measured in heavy-ion collisions at RHIC and SPS over a wide range of the energy $\sqrt {s_{NN} } = 9 - 200$ GeV are analyzed in the framework of z scaling. A microscopic scenario of constituent interactions in the framework of this approach is discussed. Dependence of the energy loss on the momentum of the produced hadron, energy, and centrality of the collision, is studied. Self-similarity of the constituent interactions in terms of momentum fractions is used to characterize the nuclear medium by ??specific heat?? and colliding nuclei by fractal dimensions. Preferable kinematical regions for search for signatures of the phase transition of the nuclearmatter produced inHIC are discussed. Discontinuity of ??specific heat?? is assumed to be a signature of the phase transition and the Critical Point.     

Sensitivity of cross section andT 20 to secondary interactions in the reaction indp → ppn at medium energies

Secondary effects in deuteron breakup reactions are reexamined for the process¹ H(d, p) pn with a proton detected at 0° and for the process¹ H (d, pp)n with two fast forward moving protons fixed at the beam line. Sensitivity of the cross section and the tensor asymmetryT ₂₀ to the double-scattering and final-state-interaction corrections is demonstrated. The nonrelativistic method used here incorporates both the energy-conserving and the principal-value part of the free nucleon propagator. The calculations are compared with the inclusive experimental data¹ H(d, p)X at the 1.25 and 2.1 GeV deuteron kinetic energy.The author would like to express his thanks to Prof. B. Tecoult for valuable ideas stimulating this work and Yu.Panebratsev and A. Litvinenko for many helpful discussions. For ideas and advice concerning Sect. 4, I thank to G. Lykasov and S. Shimansky.     

Improvement of the antimicrobial potency,pharmacokinetic and pharmacodynamic properties of albicidin by incorporation of nitrogen atoms

The worrisome development and spread of multidrug-resistant bacteria demands new antibacterial agents with strong bioactivities particularly against Gram-negative bacteria. Albicidins were recently structurally characterized as highly active antibacterial natural products from the bacterium Xanthomonas albilineans. Albicidin, which effectively targets the bacterial DNA-gyrase, is a lipophilic hexapeptide mostly consisting of para amino benzoic acid units and only one α-amino acid. In this study, we report on the design and synthesis of new albicidins, containing N-atoms on each of the 5 different phenyl rings. We systematically introduced N-atoms into the aromatic backbone to monitor intramolecular H-bonds and for one derivative correlated them with a significant enhancement of the antibacterial activity and activity spectrum, particularly also towards Gram-positive bacteria. In parallel we conducted DFT calculations to find the most stable conformation of each derivative. A drastic angle-change was observed for the lead compound and shows a preferred planarity through H-bonding with the introduced N-atom at the D-fragment of albicidin. Finally, we went to the next level and conducted the first in vivo experiments with an albicidin analogue. Our lead compound was evaluated in two different mouse experiments: In the first we show a promising PK profile and the absence of toxicity and in the second very good efficiency and reduction of the bacterial titre in an E. coli infection model with FQ-resistant clinically relevant strains. These results qualify albicidins as active antibacterial substances with the potential to be developed as a drug for treatment of infections caused by Gram-negative and Gram-positive bacteria.

A systematic pyridine-scan of the albicidin molecule provides a new lead structure with improved antimicrobial properties.     

Self-similarity of high <Emphasis Type="Italic">p</Emphasis><Subscript><Emphasis Type="Italic">T</Emphasis></Subscript> hadron production in cumulative processes and violation of discrete symmetries at small scales (suggestion for experiment)

The hypothesis of the self-similarity of hadron production in relativistic heavy-ion collisions to search for the phase transition in nuclear matter is discussed. Using the established features of z-scaling is suggested to reveal the signatures of new physics in the cumulative region. It is noted that selecting events on centrality in the cumulative region could help localize the position of a critical point. The change in the parameters of the theory (a specific heat and fractal dimensions) near the critical point is considered a signature of new physics. The relationship between the power asymptotic of Ψ(z) at high values of the similarity parameter z, the anisotropy of momentum space due to spontaneous symmetry breaking, and discrete (C, P, T) symmetries is emphasized.     

Generalized z-scaling for charged hadrons and jets

Generalization of z-scaling observed in the inclusive high-p _T-charged hadron and jet production is proposed. Scaling function ψ(z) describing both charged hadrons and jets produced in proton-(anti)proton colisions for various multiplicity densities and collision energies is constructed. Anomalous fractal dimensions and parameters characterizing an associated medium for both classes of events are established. The basic features of the scaling established in minimum bias events are shown to be preserved up to the highest multiplicity densities measured in the experiments UA1, E735, CDF, and STAR. The obtained results are of interest for use of z-scaling as a tool for searching for new physics phenomena of particle production at a high transverse momentum and in the high-multiplicity region at U70, Tevatron, RHIC, and LHC. The text was submitted by the authors in English.     

Evolution of clans in multiparticle production

An alternative interpretation of the development of the clan structure arising formally from the natural decomposition of the negative binomial multiplicity distribution is presented here. Our approach is based on stochastico-physical ideas of multiple production on the parton level. Specific differential-difference evolution equations have been proposed which besides the elementary processes involving the ingredients of QCD branching describe collective phenomena of clan's collapsing and clan's coherent disintegration.