Straightforward access to new vinca-alkaloids via selective reduction of a nitrile containing anhydrovinblastine derivative

A procedure to exclusively obtain 3′S-cyanoanhydrovinblastine 12 from two naturally occurring vinca-alkaloids (catharanthine and vindoline) in one step with good yield is described. Stereoselective reductions of 12, providing straightforward access to three new vinca-alkaloids, including two diastereomers 3′S-cyano-(4′R,5′-dihydro)-anhydrovinblastine and 3′S-cyano-(4′S,5′-dihydro)-anhydrovinblastine as well as (3′S-aminomethyl)-(4′S,5′-dihydro)-anhydrovinblastine in good yields is also reported.     

Remote entanglement between a single atom and a Bose-Einstein condensate

Entanglement between stationary systems at remote locations is a key resource for quantum networks. We report on the experimental generation of remote entanglement between a single atom inside an optical cavity and a Bose-Einstein condensate (BEC). To produce this, a single photon is created in the atom-cavity system, thereby generating atom-photon entanglement. The photon is transported to the BEC and converted into a collective excitation in the BEC, thus establishing matter-matter entanglement. After a variable delay, this entanglement is converted into photon-photon entanglement. The matter-matter entanglement lifetime of 100 μs exceeds the photon duration by 2 orders of magnitude. The total fidelity of all concatenated operations is 95%. This hybrid system opens up promising perspectives in the field of quantum information.     

Atomic mechanism of the heating-induced phase transitions of the simple monatomic glasses

Atomic mechanism of the heating-induced phase transitions of the monatomic Lennard-Jones (LJ) glass has been studied via molecular dynamics (MD) simulations. Monatomic LJ glass was heated up at two different heating rates, crystallization occurs at the lowest one and further heating leads to the melting of LJ crystal. Thermodynamics of the phase transitions and corresponding evolution of structural properties upon heating have been analyzed in details. Atomic mechanism of a crystallization of the glassy state was monitored via spatio-temporal arrangements of the atoms involved in the 1421 bond-pair of the fcc crystalline structure. The 1421 bond-pair was detected via the Honeycutt-Andersen analysis [J.D. Honeycutt, H.C. Andersen, J. Phys. Chem. 91 (1987) 4950]. We found that crystallization of the monatomic LJ glass occurs via homogeneous local rearrangements of atoms in the glassy matrix and we found an important role of the liquid-like atoms (existed in the glassy state) in crystallization of the system. In addition, spatio-temporal arrangements of the liquid-like atoms in the system upon further heating were shown in order to clarify the atomic mechanism of a melting of the obtained LJ crystal. Liquid-like atoms were defined by the Lindemann melting criterion. Our results provide previously un-reported data and give deeper understanding of the heating-induced phase transitions in the less stable metallic glasses, which have been observed in practice.     

Monotonicity of the reflected Bessel transition density on the diagonal

For α∈R$\alpha \in \mathbb{R}$, let p^R(t,x,x)$p^R(t,x,x)$ denote the diagonal of the transition density of the α$\alpha$-Bessel process in (0,1]$(0,1]$, killed at 0 and reflected at 1. As a function of x$x$, if either α≥3$\alpha \ge 3$ or α=1$\alpha =1$, then for t>0$t>0$, the diagonal is nondecreasing. This monotonicity property fails if 1≠α<3$1\ne \alpha <3$.     

Stimulus‐responsive polymers based on 2‐hydroxypropyl acrylate prepared by RAFT polymerization

Homopolymerization and diblock copolymerization of 2‐hydroxypropyl acrylate (HPA) has been conducted using reversible addition fragmentation chain transfer (RAFT) chemistry in tert‐butanol at 80 °C. PHPA homopolymers were obtained with high conversions and narrow molecular weight distributions over a wide range of target degrees of polymerization. Like its poly(2‐hydroxyethyl methacrylate) isomer, PHPA homopolymer exhibits inverse temperature solubility in dilute aqueous solution, with cloud points increasing systematically on lowering the mean chain length. The nature of the end groups is shown to significantly affect the cloud point, whereas no effect of concentration was observed over the PHPA concentration range investigated. Various thermoresponsive PHPA‐based diblock copolymers were prepared via one‐pot syntheses in which the second block was either permanently hydrophilic or pH‐responsive. Preliminary studies confirmed that poly(ethylene oxide)‐poly(2‐hydroxypropyl acrylate) (PEO₄₅‐PHPA₄₈) and poly(2‐hydroxypropyl acrylate)‐ poly(2‐hydroxyethyl acrylate) (PHPA₄₉‐PHEA₆₈)diblock copolymers formed well‐defined PHPA‐core micelles in 10 mM sodium nitrate solution at 40 °C and 70 °C with mean hydrodynamic diameters of 20 nm and 35 nm, respectively. In contrast, most other PHPA‐based diblock copolymers investigated formed larger colloidal aggregates in 10 mM NaNO₃ solution at elevated temperatures. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2032–2043, 2010     

Thin-Film Zinc/Manganese Dioxide Electrodes

Summary.  Thin-film electrodes allow the manufacturing of flat batteries of variable design. Their electric performance is better than that of customary cells because of a larger contact area between anode and cathode and better utilization of the electrochemically active materials. Bipolar thin-film electrodes for the rechargeable alkaline zinc/manganese dioxide system were assembled using graphite-filled plastics (high-density polyethylene and polyisobutylene). In a different approach, extremely thin electrodes were obtained using 25 μm thick foils made of non-conductive micro-porous polypropylene. The electroactive materials were electrolytically deposited into the pores of the previously metallized foil, providing the required conductive connection through the plastic matrix by themselves. Cycle behavior, cumulated capacities, and energies of batteries with up to two bipolar units were measured. At this early stage of development, batteries based on graphite-filled polymer foils showed better results with regard to storage capacity per unit area and to cycle life. Prototypes based on micro-porous polypropylene suffered from the relatively small fraction of pore volume available for the deposition of active material (about 38%) and from current collector corrosion. Received May 30, 2000. Accepted December 18, 2000     

Specific features in the vibronic fluorescence spectra of analogues of 1,4-bis(5-phenyl-2-oxazolyl)benzene with oxadiazole and furan rings

The fine-structure fluorescence and fluorescence excitation spectra of conjugated chain compounds, namely, 2,5-bis(5-phenyl-1,3,4-oxadiazol-2-yl)furan (PDFDP) and 2,5-bis[5-(2,4-dimethylphenyl)-1,3,4-oxadiazol-2-yl]furan (XDFDX), were obtained by the Shpolskii method in an n-octane matrix at a temperature of 4.2 K. These spectra were simulated by representing the band of each of the vibronic transitions as the sum of a zero-phonon line and a phonon wing with the corresponding parameters, such as the half-widths of the spectral lines and the Debye-Waller factors. The results obtained made it possible to estimate the relative intensities of the vibronic transitions between the S ₀ and S*₁ states. The anharmonicity revealed in the conjugate spectra of fluorescence and fluorescence excitation of the PDFDP and XDFDX compounds was explained in terms of the interference of the Franck-Condon and Herzberg-Teller interactions occurring in the molecules under investigation. The influence of the substitution of the furan heterocycle (F) for the central benzene ring (P) in 1,4-bis-(5-phenyl-2-oxadiazolyl)benzene (PDPDP) on the parameters of the intramolecular interactions responsible for the formation of the vibronic spectra was considered.