Push-pull complexes

The processes of meiosis and mitosis involve many motile events, from the separation of the daughter chromosomes to the final act of cell separation at cytokinesis (Wadsworth, 1993). DNA replication itself may be considered as a motile event, because the polymerase complex moves along the linear DNA. One of the most obvious motile events is the separation of the chromosomes along the mitotic spindle at anaphase. Details of the structure and polarity of microtubules in the spindle apparatus in meiosis and mitosis are known through electron and light microscopy, but it is not yet clear whether the chromosomes are pushed, pulled or... 

Why is the complex OsHCl(CO)(P Pr3)2 stable, when it is unsaturated It has been argued that lone pairs on the alpha atom of a ligand M—X (M is a transition metal) can have a major influence on reactivity and structure. If M has empty orbitals of appropriate symmetry, X M tt donation creates an M—X multiple bond, with consequent transfer of electron density to M decreasing its Lewis acidity.23 The presence of a carbonyl ligand in OsHCl(CO)(P Pr3)2) increases the n-donor capacity of chloro by means of the push-pull effect making this molecule not a truly 16-valence electron species. 

Marc Van Regenmortel I think the synthesis that is relevant is a nonlinear synthesis. Linear synthesis and push-pull causality have been given up, because complexity cannot be analysed using linear mathematical tools. 

Spectral Tuning in Push-Pull Type Complexes 728... 

In Sect. 5.2, the strong 7r-donor ability of methoxide and fluoride has been elaborated. These two ligands effect a push-pull effect on the nitrosonium ion bound in Os(OEP)NO(OMe) [31c] and Os(OEP)NO(F) [3Id], as indicated by the low NO-stretching frequencies of the NO ion as compared with the dinitrosyl Os(OEP)(NO)2 [31e] and the perchlorato complex, 0s(0EP)N0(0C103) ([3If], Table 11). Thus, the a/7r-donor balance for the coordinated anions decreases in the series OMe > F > NO > OClOf. [31c] and [3Id] can be vaporized at 200°C/10-6 Torr in a mass spectrometer, while the dinitrosyl [31e] decomposes above 100 °C. This demonstrates the push-pull effect also in a chemical sense. 

The nature of the bonding in Zeise s anion and other r -olefin complexes is illustrated in Fig. 18.2. Without the push-pull mechanism, the 7r electrons of the olefin would have little or no tendency to allow themselves... 

Carbon acids activated by strong ji-acceptors that also contain a jt-donor capable of interacting with the ji-acceptor in a push-pull fashion pose an interesting problem. Fischer carbene complexes such as 20,94 23,97 36,96 37,96 38,98 and 3998 fall into this category. Thermodynamic... 

The insertion of a photosensitive group or of a redox active unit into the push-pull system 1 yields switchable molecular wires and push-pull molecules that contain a photo-switch or a redox switch S, as represented in 4. Compounds of such type containing for instance electroactive ferrocene groups and photosensitive metal complexes, have been synthesized. Some of them are shown in series 5 (Marczinke, B. Przibilla, K.J. Lehn, J.-M., unpublished data). 

In enzymes, the active site may possess acid and base groups intimately associated with the conjugate base and acid functions, respectively, of the complexed substrate the push-pull mechanism is possible but might not be a driving force. The halogenation of acetone in the presence of aqueous solutions of carboxylic acid buffers exhibits the rate law of Equation 11.2 where the third-order term, although small, has been shown to be significant and due to bifunctional concerted acid-base catalysis (Scheme 11.13) ... 

Fig. 6. Proposed push-pull model for nematode sperm locomotion. Assembly and bundling of MSP filaments into fiber complexes (dark band spanning the lamellipo-dium) pushes the membrane at the leading edge forward. At the same time a second force, associated with disassembly of the fiber complexes at the base of the lamellipo-dium, pulls the cell body forward. In this model, attachments where the cytoskeleton is linked to the membrane and the membrane anchored to the substratum establish traction and separate mechanically the forces produced at opposite ends of the fiber complexes. Thus, rather than canceling each other, these forces can be exerted independently against the substratum. Reproduced from The Journal of Cell Biology, 2000, vol. 149, pp. 7-12 by copyright permission of the Rockefeller University Press.

The principles of the push-pull model probably apply generally to amoeboid cell motility. Indeed, a consensus is developing that in both sperm and actin-based crawling cells the force for protrusion is derived from localized cytoskeletal assembly (reviewed by Pollard and Borisy, 2003). However, as applied to nematode sperm locomotion, the model envisions that lamellipod extension and cell body retraction are linked reciprocally to the polymerization state of the cytoskeleton. The lack of structural polarity of MSP filaments, the precise localization of cytoskeletal polymerization and depolymerization at opposite ends of the fiber complexes, and insights gained from reconstitution of cytoskeletal dynamics and motility in vitro and in vivo all support the conclusion that nematode sperm move without using motor proteins and that, instead, they rely on... 

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