Pull-push model

VII. A Push-Pull Model for Nematode Sperm Amoeboid Motility... 

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... 

K. J. Duff, H. L. Gray, R. J. Gray, and C. C. Bahler, Chiral stationary phases in concert with homologous chiral mobile phases additives Push/pull model. Chirality 5 (1993), 201... 

Flynn et al." applied a finite element based numerical model to solve the problem of a push-pull flow with cross-drafts and demonstrate that the results show good agreement with experimental data. They note, however, that the numerical method is time consuming and therefore computationally expensive. 

Sutherland RL, Brant MC, Heinrichs J, Rogers JE, Slagle JE, McLean DG, Fleitz PA (2005) Excited-state characterization and effective three-photon absorption model of two-photon-induced excited-state absorption in organic push-pull charge-transfer chromophores. J Opt... 

The STRAIN AND DISTORTION model for catalysis involves pushing, pulling, or twisting a bond that is to be made or broken during the reaction. Parts of the substrate not involved directly in the chemical reaction are required to hold the substrate on the enzyme in the distorted form. The distortion and strain make it easier to reach the transition state. 

For the cylindrical coordinates of the fiber push-out model shown in Fig. 4.36 where the external (compressive) stress is conveniently regarded as positive, the basic governing equations and the equilibrium equations are essentially the same as the fiber pull-out test. The only exceptions are the equilibrium condition of Eq. (4.15) and the relation between the IFSS and the resultant interfacial radial stress given by Eq. (4.29), which are now replaced by ... 

Fig. 4.41. Schematic drawings of loading and unloading processes measuring the relative displacements 5 and 6, in (a) fiber pull-out and (b) fiber push-out models under cyclic loading. After Zhou et al. (1993).

Scheme 6.141 Mechanistic proposal for the 121-catalyzed asymmetric intramolecular Michael addition exemplified for the model substrates ( )-4-hydroxy-l-phenyl-2-buten-l-one (n = 0) and ( )-5-hydroxy-l-phenyl-2-buten-l-one (n = 1) 121 functions as push/pull-type bifunctional catalyst inducing the cyclization of boronic acid hemiester (1) to form intermediate (2) release ofdiol product (3) by oxidation.

In the in-line push-pull mechanisms of Rabin and Roberts, the highest energy transition state may be either the pentacovalent intermediate or the alkoxide (hydroxide) state with 02 or 05" deprotonated but not bonded to P. Incipient deprotonation of 02 in an activated state is equivalent. Protonation of X or Y or nearby positive charge could stabilize the pentacovalent intermediate. Removal of either could facilitate formation of the alkoxide in the breakdown of the intermediate. Restoration of the initial state of the enzyme is required in this mechanism and could be rate limiting. In the adjacent (pseudorotation) models of Witzel, Hammes, Usher, or Wang protonation of X or Y would be required to allow one of the two pseudomers to exist. In step 1 this requirement (and thus perhaps a rate limiting process) applies to the attack by 02. Deprotonation would force or facilitate reversal or pseudorotation to... 

This opens up the possibility of a systematic investigation of pericyclic reactions not only for model cases of parent unsubstituted systems, but for inclusion if zwitterionic contributions also enable the analysis of the eventual mechanistic changes induced by the polar substitution. As an example, the push-pull substituted Diels-Alder system will be analysed, in which the diene component is substituted in position 1 by a donor, and dienophilic component in position 6 by an acceptor substitution. In order to avoid the problems with the relative wieght of individual limiting structures of the intermediate (Eq. 30), the coulombic integrals modelling the substitution in the HMO wave function were arbitrarily set to a = 3/ and a = — 3) so that there is sufficient polarity in the system to secure the approximation of the intermediate by pure zwitterionic structure Z,. 

In homogeneous model systems, this mechanism is scarcely realized because of proton exchange simplicity between the donor and the acceptor. It proceeds without substrate and, therefore, the efficiency of the push-pull mechanism in solution is reduced. Moreover, both the donor and the acceptor of protons are usually located far from the places required for proton transfer in solutions. This hinders the required alignment of reacting molecules being achieved. 

Organometallic systems such as porphyrines have been investigated because of the possibility to fine tune their response by functionalization[105-107]. Systems of increased the dimensionality have been of particular interest [108-111], Concomitant to the large effort to establish useful structure-to-properties relationships, considerable effort has now been put to investigate the environmental effects on TPA[112-114], For example, the solvent effect has been studied for a small linear push-pull chromophore using a self-consistent reaction field (homogeneous solvation) method employing a spherical cavity and an internal force field (IFF) method[l 12] in another study the polarizable continuum model has been employed to calculate the relevant quantities to obtain the TPA cross-section in the limit of a two-state model[113] Woo et al. made a critical study of experimental comparison of TPA cross-sections in different solvents[114]. 

Specific Interactions in Solid State Dimers of Push-Pull Molecules Motivations and Model... 

Since the vibrational spectra obtained for these two structures (iii) are very similar, we will describe in detail only the results obtained for the stacking geometry (Figure 4.17). This architecture seems to be a better model mimicking the arrangement of strongly interacting dimers as observed in crystals of similar push-pull polyenes [2],... 

The conductor-like continuum solvation model, modified for ab initio in the quantum-chemistry program GAMESS, implemented at the Meller-Plesset order 2 (MP2) level of theory, has been applied to a group of push-pull thiophene systems to illustrate the effects of donor/acceptor and solvation on the stability and energetics of such systems. The most accurate theoretical gas- and solution-phase data to date have been presented for the parent thiophene-2-carbaldehyde system <2000JCP(113)7519>. 

The simplest model consists of two centres, one donor (D) and one acceptor (A), separated by a distance I and contains two electrons. Here we consider this simple system to illustrate some general relations between charge transfer, transition intensities and linear as well as non-linear optical polarizabilities. We will show below that the electro-optic parameters and the molecular polarizabilities may be described in terms of a single parameter, c, that is a measure of the extent of coupling between donor and acceptor. Conceptually, this approach is related to early computations on the behaviour of inorganic intervalence complexes (Robin and Day, 1967 Denning, 1995), Mulliken s model for molecular CT complexes (Mulliken and Pearson, 1969) and a two-form/two-state analysis of push-pull molecules (Blanchard-Desce and Barzoukas, 1998). 

---