Dynamic kinetic resolution of transient hemiketals: a strategy for the desymmetrisation of prochiral oxetanols

Identification of an electron poor trifluoroacetophenone allows the formation of uniquely stable hemiketals from prochiral oxetanols. When exposed to a cobalt(ii) catalyst, efficient ring-opening to densely functionalized dioxolanes is observed. Mechanistic studies suggest an unprecedented redox process between the cobalt(ii) catalyst and the hemiketal that initiates the oxetane-opening. Based on this observation, a dynamic kinetic resolution of the transient hemiketals is explored that uses a Katsuki-type ligand for stereoinduction (up to 99 : 1 dr and 96 : 4 er) and allows a variety of 1,3-dioxolanes to be accessed (20 examples up to 98% yield).

Desymmetrization of prochiral oxetanols via an electron-deficient hemiketal intermediate is achieved. Key to this process is the catalyst''s chiral recognition of one of the two hemiketal enantiomers enabling an efficient dynamic kinetic resolution.     

Facile synthesis of pH‐responsive glycopolypeptides with adjustable sugar density

Well‐defined pH‐responsive glycopolypeptides were prepared by polymer‐analogous aqueous amide coupling of d ‐glucosamine to poly(α,l ‐glutamic acid) (PGA) using the coupling agent 4‐(4,6‐dimethoxy‐1,3,5‐triazin‐2‐yl)‐4‐methylmorpholinium chloride (DMT‐MM) without any organic solvents, additives, or buffers. Degrees of substitution (DS) up to 80% can be achieved, and the DS is adjustable by the molar ratio of DMT‐MM to PGA repeating units. Successful glycosylation of both low MW and high MW PGA was confirmed by ¹H NMR and FTIR spectroscopy as well as by an enhanced solubility at low pH. CD spectroscopy revealed that glycosylated PGAs with a DS up to 0.63 are able to undergo a pH‐responsive and reversible helix‐coil transition. However, for polymers with higher DS no transition occurs. A comparison with PGAs functionalized with monoethanolamine showed that the low helicity at high DS is not a steric effect due to the bulky sugar moieties, but a solvation effect. Preliminary turbidimetric tests with the lectin Concanavalin A indicate a biological activity of these glycosylated polypeptides. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3925–3931     

Rückbezüge des Mathematikunterrichts und der Methodik des Mathematikunterrichts in der DDR auf historische Vorausentwicklungen

The author discusses at some examples exemplarily, how the pedagogy of mathematics education in the GDR from curricular and educational/psychological knowledge from the time before 1945 has developed scientifically.     

Large electron polarization of H-like20Ne-ions traversing gd foils at very high velocities

It is shown that transient magnetic fields in Gd-host for²⁰Ne ions at a mean velocity of 12.5v₀(v₀=c/137), considerably beyond the Bohr velocity of 1s electrons of Ne ions (v_1s=10v₀), are dominated by the Fermi contact field of these electrons. The first excited 2⁺-state of²Ne was used as probe. The derived value for the mean degree of polarization p_1s=0.32(13), is surprisingly large, though still consistent with values obtained at lower velocities. Present calculations of spin exchange cross sections severely underestimate the observed polarization at this high velocity.The authors are grateful to the operating staff of the UNILAC for providing excellent beam conditions. They also thank Dr. P. Maier-Komor for preparing the delicate targets. Support by the BMFT is acknowledged.     

Search for delayed fission products from superheavy nuclei in the reaction136Xe+208Pb

The production of superheavy elements in binary reactions of the type²⁰⁸Pb (¹³⁶Xe, X) Y was investigated atE _c.m.=470 MeV. The experiment was designed to search for delayed fission products from elements withZ between 108 and 116 and fission lifetimes ofΤ?10^?12 s. No fission events were observed the upper limit for the formation cross section being 1.2 Μbarn.     

Charge and mass transfer in the reaction136Xe+208Pb at energies close to the coulomb barrier

Mass and charge transfer was investigated for the system¹³⁶Xe+²⁰⁸Pb at 5.9 MeV/nucleon incident energy with aΔE —E-time of flight telescope. The angle and energy integrated cross section for the strongly damped events was found to be 510 mb, very close to the total reaction cross section. The width of the mass distribution as function of the total kinetic energy loss was measured and is compared to the width of the corresponding charge distribution. An upper limit of 1 μb has been found for processes with very large mass transfer.     

Excitation-energy sharing in uranium induced dissipative collisions

Strongly damped collisions were studied in uranium induced reactions on¹¹⁰Pd and¹²⁴Sn target nuclei near the barrier. The excitation-energy splitting was deduced from binary reaction yields and those in which the heavy fragment undergoes sequential fission. For systems with 87≦Z≦95 for the heavy fragment, the excitation energy is concentrated in the lighter nucleus, at best shared equally. The results indicate a non-equilibrated energy dissipation, and support nucleon exchange based on average single-particle strength functions as the underlying dissipation mechanism at the barrier.     

Bias and temperature dependence of the noise in a single electron transistor

Models generalizing the su (2) XX spin-chain were recently introduced. These XXC models also have an underlying su (2) structure. Their construction method is shown to generalize to the chains based on the fundamental representations of the A_m Lie algebras. Integrability of the new models is shown in the context of the quantum inverse scattering method. Their R-matrix is found and shown to yield a representation of the Hecke algebra. The diagonalization of the transfer matrices is carried out using the algebraic Bethe Ansatz. I comment on eventual generalizations and possible links to reaction-diffusion processes. Received: 24 June 1998 / Received in final form: 8 September 1998 / Accepted: 10 September 1998     

The extended finite element method for two-phase and free-surface flows: A systematic study

In immiscible two-phase flows, jumps or kinks are present in the velocity and pressure fields across the interfaces of the two fluids. The extended finite element method (XFEM) is able to reproduce such discontinuities within elements. Robust and accurate interface capturing schemes with no restrictions on the interface topology are thereby enabled. This paper investigates different enrichment schemes and time-integration schemes within the XFEM. Test cases with and without surface tension on moving or stationary meshes are studied and compared to interface tracking results when possible. A particularly useful setting is extracted which is recommended for two-phase flows. An extension of this formulation for the simulation of free-surface flows and of floating objects is proposed.