Diassociative algebras and Milnor's invariants for tangles

We extend Milnor's mu-invariants of link homotopy to ordered (classical or virtual) tangles. Simple combinatorial formulas for mu-invariants are given in terms of counting trees in Gauss diagrams. Invariance under Reidemeister moves corresponds to axioms of Loday's diassociative algebra. The relation of tangles to diassociative algebras is formulated in terms of a morphism of corresponding operads.Comment: 17 pages, many figures; v2: several typos correcte

Finite Type Invariants of Classical and Virtual Knots

We observe that any knot invariant extends to virtual knots. The isotopy classification problem for virtual knots is reduced to an algebraic problem formulated in terms of an algebra of arrow diagrams. We introduce a new notion of finite type invariant and show that the restriction of any such invariant of degree n to classical knots is an invariant of degree at most n in the classical sense. A universal invariant of degree at most n is defined via a Gauss diagram formula. This machinery is used to obtain explicit formulas for invariants of low degrees. The same technique is also used to prove that any finite type invariant of classical knots is given by a Gauss diagram formula. We introduce the notion of n-equivalence of Gauss diagrams and announce virtual counter-parts of results concerning classical n-equivalence.Comment: 22 pages, many figure

On homotopies with triple points of classical knots

We consider a knot homotopy as a cylinder in 4-space. An ordinary triple point $p$ of the cylinder is called {\em coherent} if all three branches intersect at $p$ pairwise with the same index. A {\em triple unknotting} of a classical knot $K$ is a homotopy which connects $K$ with the trivial knot and which has as singularities only coherent triple points. We give a new formula for the first Vassiliev invariant $v_2(K)$ by using triple unknottings. As a corollary we obtain a very simple proof of the fact that passing a coherent triple point always changes the knot type. As another corollary we show that there are triple unknottings which are not homotopic as triple unknottings even if we allow more complicated singularities to appear in the homotopy of the homotopy.Comment: 10 pages, 13 figures, bugs in figures correcte

A New Type of Stereoselectivity in Baeyer–Villiger Reactions: Access to E- and Z-Olefins

A new concept for accessing configurationally defined trisubstituted olefins has been developed. Starting from a common ketone precursor of the type 4-ethylidenecyclohexanone, Baeyer–Villiger monooxygenases are employed as catalysts in diastereoselective Baeyer–Villiger reactions leading to the corresponding E- or Z-configurated lactones. Wild-type cyclohexanone monooxygenase (CHMO) as catalyst delivers the E-isomers and a directed evolution mutant the opposite Z-isomers. Subsequent transition metal-catalyzed chemical transformations of a key product containing a vinyl bromide moiety provide a variety of different trisubstituted E- or Z-olefins. A model based on QM/MM sheds light on the origin of this unusual type of diastereoselectivity. In contrast to this biocatalytic approach, traditional Baeyer–Villiger reagents such as m-CPBA fail to show any selectivity, 1:1 mixtures of E- and Z-olefins being formed

Charge migration engineered by localisation: electron-nuclear dynamics in polyenes and glycine

We demonstrate that charge migration can be ‘engineered’ in arbitrary molecular systems if a single localised orbital – that diabatically follows nuclear displacements – is ionised. Specifically, we describe the use of natural bonding orbitals in Complete Active Space Configuration Interaction (CASCI) calculations to form cationic states with localised charge, providing consistently well-defined initial conditions across a zero point energy vibrational ensemble of molecular geometries. In Ehrenfest dynamics simulations following localised ionisation of -electrons in model polyenes (hexatriene and decapentaene) and -electrons in glycine, oscillatory charge migration can be observed for several femtoseconds before dephasing. Including nuclear motion leads to slower dephasing compared to fixed-geometry electron-only dynamics results. For future work, we discuss the possibility of designing laser pulses that would lead to charge migration that is experimentally observable, based on the proposed diabatic orbital approach

Graph complexes in deformation quantization

Kontsevich's formality theorem and the consequent star-product formula rely on the construction of an $L_\infty$-morphism between the DGLA of polyvector fields and the DGLA of polydifferential operators. This construction uses a version of graphical calculus. In this article we present the details of this graphical calculus with emphasis on its algebraic features. It is a morphism of differential graded Lie algebras between the Kontsevich DGLA of admissible graphs and the Chevalley-Eilenberg DGLA of linear homomorphisms between polyvector fields and polydifferential operators. Kontsevich's proof of the formality morphism is reexamined in this light and an algebraic framework for discussing the tree-level reduction of Kontsevich's star-product is described.Comment: 39 pages; 3 eps figures; uses Xy-pic. Final version. Details added, mainly concerning the tree-level approximation. Typos corrected. An abridged version will appear in Lett. Math. Phy

Sums over Graphs and Integration over Discrete Groupoids

We show that sums over graphs such as appear in the theory of Feynman diagrams can be seen as integrals over discrete groupoids. From this point of view, basic combinatorial formulas of the theory of Feynman diagrams can be interpreted as pull-back or push-forward formulas for integrals over suitable groupoids.Comment: 27 pages, 4 eps figures; LaTeX2e; uses Xy-Pic. Some ambiguities fixed, and several proofs simplifie

Multiple effects of silymarin on the hepatitis C virus lifecycle

Silymarin, an extract from milk thistle (Silybum marianum), and its purified flavonolignans have been recently shown to inhibit hepatitis C virus (HCV) infection, both in vitro and in vivo. In the current study, we further characterized silymarin's antiviral actions. Silymarin had antiviral effects against hepatitis C virus cell culture (HCVcc) infection that included inhibition of virus entry, RNA and protein expression, and infectious virus production. Silymarin did not block HCVcc binding to cells but inhibited the entry of several viral pseudoparticles (pp), and fusion of HCVpp with liposomes. Silymarin but not silibinin inhibited genotype 2a NS5B RNA-dependent RNA polymerase (RdRp) activity at concentrations 5 to 10 times higher than required for anti-HCVcc effects. Furthermore, silymarin had inefficient activity on the genotype 1b BK and four 1b RDRPs derived from HCV-infected patients. Moreover, silymarin did not inhibit HCV replication in five independent genotype 1a, 1b, and 2a replicon cell lines that did not produce infectious virus. Silymarin inhibited microsomal triglyceride transfer protein activity, apolipoprotein B secretion, and infectious virion production into culture supernatants. Silymarin also blocked cell-to-cell spread of virus. CONCLUSION: Although inhibition of in vitro NS5B polymerase activity is demonstrable, the mechanisms of silymarin's antiviral action appear to include blocking of virus entry and transmission, possibly by targeting the host cell