A bio-mechanical model for coupling cell contractility with focal adhesion formation

Focal adhesions (FAs) are large, multi-protein complexes that provide a mechanical link between the cytoskeletal contractile machinery and the extracellular matrix. They exhibit mechanosensitive properties; they self-assemble upon application of pulling forces and dissociate when these forces are decreased. We rationalize this mechano-sensitivity from thermodynamic considerations and develop a continuum framework in which the cytoskeletal contractile forces generated by stress fibers drive the assembly of the FA multi-protein complexes. The FA model has three essential features: (i) the low and high affinity integrins co-exist in thermodynamic equilibrium, (ii) the low affinity integrins within the plasma membrane are mobile, and (iii) the contractile forces generated by the stress fibers are in mechanical equilibrium and change the free energies of the integrins. A general two-dimensional framework is presented and the essential features of the model illustrated using one-dimensional examples. Consistent with observations, the coupled stress fiber and FA model predict that (a) the FAs concentrate around the periphery of the cell; (b) the fraction of the cell covered by FAs increases with decreasing cell size while the total FA intensity increases with increasing cell size; and (c) the FA intensity decreases substantially when cell contractility is curtailed.     

Free-radical polymerization of methyl methacrylate in presence of the Cr(C5H7O2)3–Al(i-C4H9)3 catalyst system

Polymerization of methyl methacrylate has been studied with the chromium acetylacetonate–triisobutyl aluminum catalyst system in benzene medium at 40°C. These studies have been carried out at an Al/Cr ratio of 12 to compare the behavior with the previously studied chromium acetyl acetonate–triethyl aluminum catalyst system. The enhanced yield and gelling of polymer suggests a free-radical mechanism of polymerization. Further, the kinetics of polymerization and the heterotactic structure of polymer as determined by NMR examination have led to confirmation of the freeradical mechanism of polymerization of methyl methacrylate by an excess of triisobutylaluminum in the presence of catalyst complex.     

Kinetics and mechanism of polymerization yielding stereoblock poly(methyl methacrylate) with VCl4-Al(C2H5)3 catalyst system

Methyl methacrylate was polymerized at 40°C with the VCl₄–AlEt₃ catalyst system in n-hexane. The rate of polymerization was proportional to the catalyst and monomer concentration at Al/V ratio of 2, indicating a coordinate anionic mechanism of polymerization. NMR spectra were further used to confirm the mechanism of polymerization and stability of active sites responsible for isotacticity.     

Polymerization of acrylonitrile with VCl4–Al(C2H5)3 catalyst system in presence of acetonitrile

The polymerization of acrylonitrile with the homogeneous catalyst system of VCl₄–AlEt₃ in acetonitrile at 40°C has been investigated. The rate of polymerization is found to be first-order with respect to monomer and inversely proportional to the catalyst concentration. The overall activation energy for this catalyst system is 10.97 kcal/mole. The inverse proportionality of rate of polymerization with the catalyst concentration is attributed to the permanent complex formation between the catalyst complex and acrylonitrile, and a reaction scheme is proposed.     

Donor–acceptor complexes in copolymerization. XLIX. Cationic polymerization of donor monomers in presence of polar solvents and acrylic monomers. A revised mechanism for polymerization of comonomer complexes

α-Methylstyrene (MS) and isobutyl vinyl ether (VE) readily polymerize, styrene (S) polymerizes to a small extent, and isobutylene (IB), butadiene (BD), and isoprene (IP) fail to polymerize in the presence of catalytic amounts of AlCl₃ when propionitrile, ethyl propionate, and methyl isobutyrate are used as reaction media. MS polymerizes readily and S polymerizes with difficulty in the presence of AlCl₃ to yield homopolymers when acrylonitrile (AN) is present and copolymers with ethyl acrylate (EA) and methyl methacrylate (MMA). VE readily homopolymerizes, while IB, BD, and IP fail to polymerize in the presence of AlCl₃ and the acrylic monomers. VE readily homopolymerizes, S and MS polymerize to a very small extent, and IB, BD, and IP do not polymerize in the presence of ethylaluminum sesquichloride (EASC) in polar solvents. VE readily homopolymerizes in the presence of EASC and the acrylic monomers. MS polymerizes to a small extent in the presence of EASC and the acrylic monomers to yield equimolar copolymers with EA and MMA and a mixture of cationic homopolymer and equimolar copolymer with AN. S yields equimolar copolymers in low yield in the presence of EASC and the acrylic monomers. IB, BD, and IP in the presence of EASC do not polymerize to any significant extent when EA is present, form AN-rich copolymers and yield poly(methyl methacrylate) in the presence of MMA. A revised mechanism is presented for the formation of cationic, radical, random, and alternating copolymers as well as alternating copolymer graft copolymers in the copolymerization of donor and acceptor monomers.     

Polymerization of styrene with chromium acetylacetonate and triethylaluminum and diethylaluminum bromide

Kinetics of the polymerization of styrene in the presence of benzene at 30°C., with chromium acetylacetonate in combination with triethylaluminum and also in combination with diethylaluminum bromide as catalyst, have been studied. Chromium acetylacetonate forms a homogeneous system with triethylaluminum, and chromium acetylacetonate with diethylaluminum bromide behaves as a heterogeneous system. This homogeneous catalyst system, though reported inactive in the polymerization of α-olefins, has been found effective with styrene. Depending on the homogeneity and heterogeneity of the system, the rate of polymerization is proportional to half order and first order of catalyst concentration. A probable reason for the effect of homogeneity on the order of reaction has been discussed. A study of the effect of diethylzinc as a chain-transfer agent has helped to confirm the mechanism of polymerization.     

An automated laboratory EXAFS spectrometer of Johansson type: indigenous development and testing

An automated linear laboratory EXAFS spectrometer of the Johansson type has been indigenously developed. Only two translational motions are required to achieve the necessary Rowland circle configuration for the (fixed) X-ray source, the dispersing and focusing bent crystal and the receiving slit. With the available crystals the spectral region from 5 to 25 keV can be scanned. The linear motions of the crystal and receiving slit including the detector assembly are achieved by employing software-controlled DC motors and utilizing optical encoders for position sensing. The appropriate rotation of the crystal is achieved by the geometry of the instrument. There is a facility to place the sample alternately in the path of the X-ray beam and out of the path to record both the incident X-ray intensityI ₀ and the transmitted intensityI employing the scintillation detector. An arrangement with a two-window proportional detector before the sample to measureI ₀ and the scintillation detector to recordI is also developed; in this case it is not necessary to oscillate the sample. Fast electronic circuits are employed to minimize counting errors. The instrument is user-friendly and it is operated through a menu-driven IBM compatible PC. EXAFS spectra of high resolution have been recorded using the spectrometer and employing the Si(111) reflecting planes; the X-ray source being a Rigaku 12 kW rotating anode with Cu target. We describe the spectrometer and discuss its performance with a few representative spectra.