Structural Effects on the Adhesive Properties of Butadiene/Styrene Radial Teleblock Copolymers

The effects of butadiene/styrene ratio, monomer distribution, and molecular weight distribution and branching on the pressure sensitive adhesive properties of butadiene/ styrene radial teleblock copolymers are reported. Styrene content of polymers with varying structures shows a close relation with tack response, and styrene content and structure affect solution viscosity and shear adhesion. When part of the styrene is incorporated into the polybutadiene segment to yield a block progressively enriched in styrene (tapered block), solution viscosity and shear adhesion are reduced. When the butadiene segment is replaced by a block of randomly copolymerized butadiene and styrene, the polymers provide lower solution viscosities and shear adhesion but unchanged tack.

The molecular weight distribution of the radial teleblock polymers can vary from broad, highly branched compositions to narrow molecular weight distributions of almost Iinear polymers. The latter have relatively high solution viscosity and low shear adhesion, whereas the former polymers produce moderate solution viscosity but high shear adhesion. Tack is generally unaffected.     

Ultramicroscopy of association colloids formed from block copolymers

Ultramicroscopy studies have been made of micelle formation by two poly(styrene)-poly(isoprene) block copolymers in organic solvents (N,N-dimethylacetamide and n-decane respectively) and a poly(l-glutamic acid)-poly(l-leucine) block copolymer in an aqueous solution of 0.2M NaCl at pH = 4.0. The technique provides a method of determining the number-average translational diffusion coefficient) $\text{D}\text{?}{}_{\mathrm{n}}$, of association colloids and leads, via the Stokes-Einstein relation, to a measure of the number-average of the reciprocal hydrodynamic radius $\text{(R}{}_{\mathrm{<mtext>D</mtext><mtext>?</mtext>}}{}^1\text{)}{}_{\mathrm{n}}$ for spherical particles. Particles having a radius less than approximately 30 nm were too small to be detected by the technique.The ultramicroscopy results were compared with data obtained by laser light scattering photon correlation spectroscopy which provides a measure of the z-average translational diffusion coefficient. $\text{D}\text{?}{}_{\mathrm{z}}$. An additional comparison was made by carrying out measurements on two well-characterized poly(styrene/divinyl benzene) latices.     

The chicken beta-globin gene promoter forms a novel "cinched" tetrahelical structure

We have previously shown that the G-rich sequence G16CG(GGT)2GG in the promoter region of the chicken beta-globin gene poses a formidable barrier to DNA synthesis in vitro (Woodford et al., 1994, J. Biol. Chem. 269, 27029-27035). The K+ requirement, template-strand specificity, template concentration independence, and involvement of Hoogsteen bonding suggested that the underlying basis of this new type of DNA synthesis arrest site might be an intrastrand tetrahelical structure. However, the arrest site lacks the four G-rich repeats that are a hallmark of previously described intramolecular tetraplexes and contains a number of noncanonical bases that would be expected to greatly destabilize such a structure. Here we report evidence for an unusual K+-dependent intrastrand "cinched" tetraplex. This structure has several unique features including the incorporation of bases other than guanine into the stem of the tetraplex, interaction between loop bases and bases in the flanking region, and base pairing between bases 3 and 5 of the tetrahelix-forming region to form a molecular "cinch." This finding extends the range of sequences capable of tetraplex formation as well as our appreciation of the conformational complexity of the chicken beta-globin promoter.     

Supramalleolar osteotomy for ankle valgus in myelomeningocele

Oral fibroblasts stimulated invasion of oral-carcinoma cells into the collagen matrix. The mechanisms of the fibroblast-induced stimulation of invasiveness was further investigated by examining cell motility and proteolytic activity of tumor cells, using mainly an adenoid-cystic-carcinoma cell line (ACCS) and normal fibroblasts from gingival tissues. Conditioned medium from the fibroblasts grown in serum-free medium was fractionated on a Superdex 200 pg column, and Peak 1 eluted at 200 to 300 kDa and Peak 2 eluted at 50 to 100 kDa were found to contain different specific activity. Treatment of ACCS cells with Peak 1 resulted in an increase in the production of proteolytic enzymes. Peak 2 stimulated both chemotaxis and chemokinesis of ACCS cells. A chemotactic factor was purified from the heparin-unbound fraction of Peak 2 by anion exchange and hydrophobic chromatography, and was named "fibroblast-derived motility factor (FDMF)". At 1 microg/ml, FDMF stimulated chemotaxis of ACCS cells by 4-fold compared with unstimulated controls. Characterization of the physicochemical properties of FDMF suggested that it might be different from any known motility factors. Exposure of ACCS cells to FDMF resulted in reduced amounts of actin stress fiber in the cytoplasm and induction of tyrosine phosphorylation of several cellular proteins detectable 30 to 60 min after treatment. These FDMF-induced changes were blocked by pre-treatment either with genistein or with pertussis toxin. These findings suggest that FDMF may be a novel protein which stimulates cell motility via a signaling pathway mediated by a pertussis-toxin-sensitive G protein and tyrosine phosphorylation.     

Analogues of capsaicin with agonist activity as novel analgesic agents; structure-activity studies. 3. The hydrophobic side-chain "C-region"

Structural variants of the hydrophobic side chain ("C region") of the capsaicin molecule have been incorporated into a series of vanillylamides and vanillylthioureas. These compounds have been tested in an in vitro assay for agonism (45Ca2+ influx into dorsal root ganglia neurones), previously shown to be predictive of analgesic activity. The results of this study have established the requirement for a hydrophobic substituent of limited size (molar refractivity, MR, < 55) in order to obtain high potency. Combination of the information gained here about the "C-region" of the capsaicin molecule with the studies described in the preceding two papers provides a rational basis for the design of compounds of increased potency.     

An investigation of the different TLM configurations used in the modelling of diffusion problems

The commonly used transmission-line modelling (TLM) network of one-dimensional diffusion problems often results in unwanted oscillations. Two different TLM configurations (line boundary (LB) and resistance boundary (RB)), are investigated with some techniques necessary to reduce the oscillations. Comparisons between the various LB and RB models addressed in this paper, indicate that, in general, two-dimensional TLM models produce consistently more accurate results.