Use of U-shaped donor-bridge-acceptor molecules to study electron tunneling through nonbonded contacts

A systematic determination of electronic coupling matrix elements in U-shaped molecules is demonstrated. The unique architecture of these systems allows for the determination of the electronic coupling through a pendant molecular moiety that resides between the donor and acceptor groups; this moiety quantifies the efficiency of electron tunneling through nonbonded contacts. Experimental electron-transfer rate constants and reaction free energies are used to calibrate a molecular-based model that describes the solvation energy. This approach makes it possible to experimentally determine electronic couplings and compare them with computational values.     

Macrophage-targeting oligopeptides from Mortierella alpina

The realm of natural products of early diverging fungi such as Mortierella species is largely unexplored. Herein, the nonribosomal peptide synthetase (NRPS) MalA catalysing the biosynthesis of the surface-active biosurfactants, malpinins, has been identified and biochemically characterised. The investigation of the substrate specificity of respective adenylation (A) domains indicated a substrate-tolerant enzyme with an unusual, inactive C-terminal NRPS module. Specificity-based precursor-directed biosynthesis yielded 20 new congeners produced by a single enzyme. Moreover, MalA incorporates artificial, click-functionalised amino acids which allowed postbiosynthetic coupling to a fluorophore. The fluorescent malpinin conjugate penetrates mammalian cell membranes via an phagocytosis-mediated mechanism, suggesting Mortierella oligopeptides as carrier peptides for directed cell targeting. The current study demonstrates substrate-specificity testing as a powerful tool to identify flexible NRPS modules and highlights basal fungi as reservoir for chemically tractable compounds in pharmaceutical applications.

Specificity profiling of a nonribosomal peptide synthetase of an early diverging fungus revealed high substrate flexibility. Feeding studies with click-functionalised amino acids enabled the production of fluorescent peptides targeting macrophages.     

Multivalency as a Chemical Organization and Action Principle

Multivalent interactions can be applied universally for a targeted strengthening of an interaction between different interfaces or molecules. The binding partners form cooperative, multiple receptor–ligand interactions that are based on individually weak, noncovalent bonds and are thus generally reversible. Hence, multi‐ and polyvalent interactions play a decisive role in biological systems for recognition, adhesion, and signal processes. The scientific and practical realization of this principle will be demonstrated by the development of simple artificial and theoretical models, from natural systems to functional, application‐oriented systems. In a systematic review of scaffold architectures, the underlying effects and control options will be demonstrated, and suggestions will be given for designing effective multivalent binding systems, as well as for polyvalent therapeutics.     

Contribution of the triangle graphs to the neutron electric dipole moment

In the Kobayashi-Maskawa model we compute a new contribution to the neutron electric dipole moment induced byCP violating flavour-changing transitions of the typess→d+gluon+γ through heavy quark loops. This contribution, essentially given by the triangle anomaly graph, is by itself gauge invariant. We obtain from this mechanismD _n /e=3.10^?32 cm, one order of magnitude below our previous estimate from usual penguin diagram contributions.     

Invariants for E0-Semigroups on II1 Factors

We introduce four new cocycle conjugacy invariants for E ₀-semigroups on II ₁ factors: a coupling index, a dimension for the gauge group, a super product system and a C*-semiflow. Using noncommutative Itô integrals we show that the dimension of the gauge group can be computed from the structure of the additive cocycles. We do this for the Clifford flows and even Clifford flows on the hyperfinite II ₁ factor, and for the free flows on the free group factor ${L(F_\infty)}$ L ( F ∞ ) . In all cases the index is 0, which implies they have trivial gauge groups. We compute the super product systems for these families and, using this, we show they have trivial coupling index. Finally, using the C*-semiflow and the boundary representation of Powers and Alevras, we show that the families of Clifford flows and even Clifford flows contain infinitely many mutually non-cocycle-conjugate E ₀-semigroups.     

Femtosecond holography in lithium niobate crystals

Spatial gratings are recorded holographically by two femtosecond pump pulses at 388 nm in lithium niobate (LiNbO3) crystals and read out by a Bragg-matched, temporally delayed probe pulse at 776 nm. We claim, to our knowledge, the first holographic pump-probe experiments with subpicosecond temporal resolution for LiNbO3. An instantaneous grating that is due mostly to the Kerr effect as well as a long-lasting grating that results mainly from the absorption caused by photoexcited carriers was observed. The Kerr coefficient of LiNbO3 for our experimental conditions, i.e., pumped and probed at different wavelengths, was approximately 1.0 x 10(-5) cm2/GW.