Oligomers as initiators of free radical polymerization

Methyl methacrylate, benzyl methacrylate, butyl methacrylate, and methacrylic acid can be polymerized by 1, 2, 2-tetraphenyl-1, 2-diphenoxyethane (TPPA), 1, 1, 2, 2-tetraphenyl-1, 2-bis-(trimethylsiloxy) ethane (TPSA), and 1, 1, 2, 2-tetraphenyl-1, 2-dicyanoethane (TPCA) (1–3). The polymerization with these initiators is characterized by three steps; in the first period oligomers from MMA and initiator radicals are formed by primary radical termination.     

Kinetic energy and angular distributions of instantaneous fission fragments in a classical model

The process of instantaneous fission in deep inelastic collisions is investigated in a classical model. Kinetic energies and angular distributions of the fragments are calculated for the proposed reaction Pb+U atE _cm ^inc =750 MeV; an experimental setup for the separation of the fragments originating from instantaneous fission from the fragments of thermal fission is explained. We also discuss fusion following instantaneous fission as a mechanism for the production of superheavy elements and arrive at rather promising estimates.     

The contraction number of a multigrid method for solving the Poisson equation

Summary The treatment of a multigrid method in the framework of numerical analysis elucidates that regularity of the solution is not necessary for the convergence of the multigrid algorithm but only for fast convergence. For the linear equations which arise from the discretization of the Poisson equation, a convergence factor 0,5 is established independent of the shape of the domain and of the regularity of the solution.Dedicated to Professor Dr.Dr.h.c. Lothar Collatz on the occasion of his 70 th birthday     

Coherent electromagnetic radiation from the fragments of nuclear fission

The electromagnetic radiation from two vibrating fission fragments is classically treated. The rotational and translational motion of the fragments during emission and the interference of the radiation from the two individual fragments are taken into account. It is shown that the angular distribution of the radiation contains valuable information on the fission process and that the spectral distribution depends sensitively on the damping of the shape vibration.Dedicated to Professor P. Armbruster and P. Kienle on the occasion of their 60th birthday     

Ultrafast ring-closure reaction of photochromic indolylfulgimides studied with UV-pump-IR-probe spectroscopy

The ring-opening and ring-closure reactions of a photochromic indolylfulgimide are investigated with femtosecond vibrational spectroscopy. Spectral signatures due to excited-state decay and vibrational cooling are seen in the mid-IR region. For the ring-opening reaction triggered with visible pulses, a lifetime of the excited electronic state of 4 ps was obtained in polar solution. In a nonpolar solvent, this time constant is reduced to 2 ps. The ring-closure reaction induced with UV pulses displays an excited-state lifetime and thus a building of the photoproduct of roughly 0.5 ps. For all processes, the subsequent cooling occurs on a 15-ps time scale lasting up to approximately 50 ps. The time-resolved IR measurements do not support the existence of any long-living intermediate states.     

P-hydrogen-substituted 1,3,2-diazaphospholenes: molecular hydrides

P-Hydrogen-substituted 1,3,2-diazaphospholenes 1 were prepared by an improved procedure from diazadienes and were characterized by spectroscopy and in one case by X-ray diffraction. A unique hydride-type reactivity of the P-H bonds was documented by extensive reactivity studies. Aldehydes and ketones were readily reduced to diazaphospholene derivatives of the corresponding alcohols, with alkyl-substituted ketones being converted at much lower rates than aldehydes or diaryl ketones. Reactions with the tetrachlorides of group 14 elements proceeded via hydride/chloride metathesis to give either partially chlorinated derivatives EH(n)Cl(4-n) (n = 0-3 for E = C, Si) or HCl and phosphenium salts 16c[ECl3] (for E = Ge, Sn) which were characterized by spectroscopic and X-ray diffraction studies. Tin dichloride was readily reduced to the element. Reactions of 1c with the P-chloro-diazaphospholene 3c and the salt 16c[OTf] allowed the first experimental detection of intermolecular exchange of a hydride, rather than a proton, between phosphine derivatives. Computational studies indicated that the hydride transfer between 1c and the cation 16c involves a transient H-bridged species with bonding properties similar to those of B2H7-. The preference for the formation of these bridged intermediates over P-P bonded phosphenium-phosphine adducts is attributed to the low electrophilicity of the diazaphospholenium cations and characterizes a novel reaction mode for phosphenium ions.     

Phase behavior of colloidal suspensions with critical solvents in terms of effective interactions

We study the phase behavior of colloidal suspensions the solvents of which are considered to be binary liquid mixtures undergoing phase segregation. We focus on the thermodynamic region close to the critical point of the accompanying miscibility gap. There, due to the colloidal particles acting as cavities in the critical medium, the spatial confinements of the critical fluctuations of the corresponding order parameter result in the effective, so-called critical Casimir forces between the colloids. Employing an approach in terms of effective, one-component colloidal systems, we explore the possibility of phase coexistence between two phases of colloidal suspensions, one being rich and the other being poor in colloidal particles. The reliability of this effective approach is discussed.     

Epothilone Analogues with Benzimidazole and Quinoline Side Chains: Chemical Synthesis,Antiproliferative Activity,and Interactions with Tubulin

A series of epothilone B and D analogues bearing isomeric quinoline or functionalized benzimidazole side chains has been prepared by chemical synthesis in a highly convergent manner. All analogues have been found to interact with the tubulin/microtubule system and to inhibit human cancer cell proliferation in vitro, albeit with different potencies (IC₅₀ values between 1 and 150 nM ). The affinity of quinoline‐based epothilone B and D analogues for stabilized microtubules clearly depends on the position of the N‐atom in the quinoline system, while the induction of tubulin polymerization in vitro appears to be less sensitive to N‐positioning. The potent inhibition of human cancer cell growth by epothilone analogues bearing functionalized benzimidazole side chains suggests that these systems might be conjugated with tumor‐targeting moieties to form tumor‐targeted prodrugs.     

Screening Dyrk1A inhibitors by MALDI-QqQ mass spectrometry: systematic comparison to established radiometric,luminescence, and LC–UV–MS assays

Enzyme-catalyzed reactions play key roles in disease pathology, thus making them relevant subjects of therapeutic inhibitor screening experiments. Matrix-assisted laser desorption/ionization (MALDI) assays have been demonstrated to be able to replace established screening approaches. They offer increased sample throughput, but care must be taken to avoid instrumental bias from differences in ionization efficiencies. We compared a MALDI-triple-quadrupole (QqQ) method for the Dyrk1A peptide substrate woodtide to LC–MS, liquid chromatography with ultraviolet detection (LC–UV), luminescence, and radiometric assays. MALDI measurements were performed on a MALDI-QqQ instrument in the multiple-reaction monitoring mode. Different MALDI conditions were investigated to address whether matrix type, sample support, and MRM- or SIM-based detection conditions can be used to accommodate the molar responses of substrate peptide and its phosphorylated form. UV detection served as a reference method. The impact of MALDI matrix on IC₅₀ values was small, even considering that matrix preparations were used that are known to alleviate response differences. IC₅₀ values determined by MALDI were ca. 2-fold lower than those determined by LC–UV. Although MALDI generated lower ion yields for the phosphorylated peptide than for the peptide substrate, we found that a correction of compound potencies was readily possible using correction factors based on unbiased LC–UV results. A thorough method development delivered a robust assay with excellent performance (Z′ > 0.91) that was close to that seen for LC–UV.