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LINEAR POLYMERIZATION OF A GASTROPOD HEMOCYANIN.

The decreased solubility of a gastropod hemocyanin in the region of the isoelectric point has been correlated with a sharp increase in light scattering produced by the protein in solution. Electron microscopic observations on negatively stained spray preparations in the isoelectric region demonstrated that the formation of linear polymers of the molecule underlies both the increase in light scattering as well as the decreased solubility of the protein. While the linear polymerization produces chains of varying length with no evidence of interaction between chains, the polymerization proceeds with a high degree of ordering of individual molecules. On either side of the isoelectric region of this hemocyanin two forms of molecules are present, rectangular and circular. The rectangular molecules polymerize in an end-to-end fashion in the isoelectric region. The rectangular molecules which participate in the polymerization appear to be divided perpendicularly to their length into three major segments.

Animals↗

STEREOSPECIFIC POLYMERIZATION. A REVOLUTION IN POLYMER SYNTHESIS HAS OCCURRED IN THE LAST DECADE.

The great flurry of activity which followed the announcement of Ziegler and Natta's initial results has led to the discovery of an enormous number of catalyst systems which are effective in stereospecific polymerization. However, there is little more understanding now than in 1955 of how most of these systems work. Now that the initial excitement has cooled, a larger amount of thoughtful work on the mechanisms of these reactions should appear. As a basis for understanding both the heterogeneous and homogeneous systems, more mechanism studies in organometallic chemistry are urgently needed. More specifically for the heterogeneous catalysts, continued attempts should be made to find better models for the active sites, and new analytical methods should be sought to provide more information concerning the active site itself. In homogeneous systems, greater understanding of the ion pairs, the structure of which is so critical, could be obtained by the preparation and study of nonpolymeric analogues. In addition to understanding better the catalysts that we already have, we may see in the future the development of new kinds of catalysts. Some of these may be capable of producing polymers in which the units have a more complex code than in those produced by simple stereospecific catalysts. Such catalysts already exist in nature. For example, we now know that the RNA molecule functions as a multifunctional catalyst in peptide syntheses, each sequence of three bases along the backbone corresponding to a particular amino acid. The molecule consequently acts as a catalytic template which defines the order in which these amino acids polymerize into the final peptide (32). Synthetic RNA's have also been prepared containing only one base such as uracil along the chain (33). Since three uracil units correspond to phenylalanine, the polyuracil acts as a template for the formation of a peptide containing only this amino acid. There seems no reason why, ultimately, we should not be able to synthesize polymeric catalysts of this type which can act as templates for the polymerization of specific monomers other than those found in living systems. If a number of systems such as this can be found, we will be on the road to producing catalysts which can not only control the stereochemistry of a polymer chain but also the order in which a group of different monomers can enter into it.

Catalysis↗

Response of associated oral soft tissues when exposed to Argon laser during polymerization of dental resins.

BACKGROUND AND OBJECTIVE: Polymerization of dental resins with Argon laser produces restorations with improved physical properties when compared to conventional visible-light polymerization techniques. However, the possibility of damaging adjacent soft tissues has not been addressed. STUDY DESIGN/MATERIALS AND METHODS: In this study, Argon laser (488/514 nm) was used for the polymerization of composite resins to determine effects on the parakeratinized gingiva adjacent to both restored and unrestored teeth in six dogs, using 10-, 20-, and 30-second polymerization exposures. RESULTS: Gingival tissues removed at 24 hours, 72 hours, or 5 days revealed desiccated, disrupted, hyalinized connective tissue. Tissues exposed for 10 seconds showed minimal change. This minimal degree of change was most evident at 72 hours and returned to normal limits at 5 days. The 20-second exposure produced alterations evident through all time periods. Tissues exposed for 30 seconds exhibited necrosis, severe disruption, and vessiculation, which was still unresolved at 5 days. CONCLUSION: This study demonstrates that clinically relevant Argon laser exposure (10 seconds) of parakeratinized gingiva adjacent to teeth undergoing restoration does not cause lasting damage.

Animals↗

Conformational and functional studies of three gelsolin subdomain-1 synthetic peptides and their implication in actin polymerization.

Gelsolin, a calcium and inositol phospholipid-sensitive protein, regulates actin filament length. Its activity is complex (capping, severing, etc.) and is supported by several functional domains. The N-terminal domain alone (S1), in particular, is able to impede actin polymerization. Our investigations were attempted to precise this inhibitory process by using synthetic peptides as models mimicking gelsolin S1 activity. Three peptides issued from S1 and located in gelsolin-actin interfaces were synthesized. The peptides (15-28, 42-55, and 96-114 sequences) were tested for their conformational and actin binding properties. Although the three peptides interact well with actin, only peptide 42-55 affects actin polymerization. A detailed kinetic study shows that the latter peptide essentially inhibits the nucleation step during actin polymerization. In conclusion, the present work shows that the binding of a synthetic peptide to a small sequence located outside the actin-actin interface is essential in the actin polymerization process.

Actins↗

Study of polymerization of acrylic bone cement: effect of HEMA and EGDMA.

The polymerization reaction of standard surgical Simplex-P radiopaque bone cement was investigated by differential scanning calorimetry to determine the influence of hydroxyethyl methacrylate (HEMA) and ethylene glycol dimethacrylate (EGDMA) on the polymerization reaction. From the kinetic analysis, the polymerization reaction of the modified acrylic bone cement was found to be approximately a first-order reaction. The reaction rate constants (k) were determined. It was found that the effects of HEMA and EGDMA contents on the rate and the heat of polymerization can be explained by the frequency factor and the activation energy. An increase in HEMA content tends to result in an increase in the values of both frequency factor and activation energy, whereas an increase in EGDMA content tends to induce a decrease in the frequency factor and activation energy.

Bone Cements↗

Effect of polymerization reaction inhibitor on mechanical properties and surface reactivity of bioactive bone cement.

We introduced an inhibitor to the polymerization reaction of bioactive bone cement (AWC) consisting of MgO-CaO-SiO2-P2O5-CaF2 apatite and wollastonite containing glass-ceramic powder and bisphenol-alpha-glycidyl methacrylate based resin, together with an increased amount of accelerator but without any prolongation of its setting time in order to improve the degree of polymerization and decrease the amount of incompletely polymerized monomers on the cement surface. A comparison was made between the AWC containing the inhibitor [AWC(I+)] and the AWC without it [AWC(I-)] with regard to setting parameters, mechanical properties, and surface reactivity in vitro and in vivo. The proportion of glass-ceramic powder added to the AWC was 70% (w/w). The total amount of heat generation and the peak temperature of the AWC(I+) during polymerization were slightly greater than those of the AWC(I-). The mechanical strength of AWC(I+) was higher than that of the AWC(I-) under wet conditions. In simulated body fluid, the width of the Ca-P rich layer on the surface of the AWC(I+) was less than that on the AWC(I-) after 28 days of immersion, although the rate of apatite formation on the top surface of the AWC(I+) was almost identical to that on the AWC(I-) surface. Histological examination using rat tibiae up to 26 weeks revealed that the bioactivity of the AWC(I+) was equivalent to that of the AWC(I-). Scanning electron microscopy and energy-dispersive X-ray microanalysis demonstrated that the Ca-P rich layer in the AWC(I+) was significantly narrower than that in the AWC(I-) at the same time points. These results indicate that introduction of the inhibitor improved the mechanical properties of the AWC and made the Ca-P rich layer narrower, but it had no adverse effect on bioactivity.

Animals↗

Local drug delivery of argatroban from a polymeric-metallic composite stent reduces platelet deposition in a swine coronary model.

Thrombus formation after intracoronary stent implantation provides a stimulus for neointimal hyperplasia and if excessive can result in stent thrombosis. We tested the hypothesis that local delivery of an antithrombin drug from a polymeric-metallic stent inhibits platelet thrombus formation. An uncoated metal slotted tube, a jellyroll slotted metal stent with an Argatroban-loaded polymeric sleeve, and a jellyroll slotted metal stent with a drug-leached polymeric sleeve were randomly deployed into the coronary arteries of eight juvenile farm swine. Platelet deposition in the stented segments was determined at 2 hr using autologous 111Indium oxime-labeled platelets. Platelet deposition was significantly less in the Argatroban-loaded stents compared to the Argatroban-leached stents (1.40 x 10(8) platelets/cm2 vs. 26.8 x 10(8) platelets/cm2; P=0.005). When corrected for differences in the metal surface area exposed to blood, platelet deposition was significantly lower in the Argatroban-loaded stent (1.74+/-1.95 x 10(8)/cm2) compared to the Argatroban-leached stent (33.5+/-39.1 x 10(8)/cm2; P=0.005) and the uncoated metal stent (36.2+/-73.3 x 10(8)/cm2; P=0.006). In this coronary stent thrombosis model Argatroban has local antithrombotic properties when delivered with a polymer-metallic stent. Improved polymeric designs may reduce risk of thrombus deposition at the site of stent implantation.

Animals↗

Mechanical and rheological improvement of a calcium phosphate cement by the addition of a polymeric drug.

A polymeric acrylic system supporting a derivative of the aminosalicylic acid was incorporated in a calcium phosphate cement, with the aim not only to achieve some pharmacological effects but to obtain an improvement of its mechanical and rheological properties. It is known that, besides the analgesic and anti-inflammatory properties, the salicylic group presents a calcium complexation ability. The inorganic phase of the cement consisted of alpha-tricalcium phosphate [alpha-Ca(3)(PO(4))(2)] and precipitated hydroxyapatite added as a seed. The liquid phase was an aqueous solution of Na(2)HPO(4). The polymeric drug increased the injectability of the cement. The hydrolysis of the alpha-tricalcium phosphate into calcium-deficient hydroxyapatite proceeded at a lower rate because of the addition of the polymeric drug. As a consequence, the cement hardening was slightly slower, although the final compressive strength was 25% higher. The bending strength increased from 5 to 9 MPa with the addition of the polymeric drug. The strengthening of the structure was related to the reduction of porosity and the lower size of the precipitated crystals, as observed by scanning electron microscopy.

Biocompatible Materials↗

Polybenzimidazole-supported [Rh(cod)Cl]2 complex: effective catalyst for the polymerization of substituted acetylenes.

The first heterogeneous catalyst which affords polymerization of substituted acetylenes into readily available high molecular weight polymers is reported. The catalyst (Rh/PBI) has been prepared by supporting di-mu-chloro-bis(eta4-cycloocta-1,5-diene)dirhodium(I), [Rh(cod)Cl]2, on commercial polybenzimidazole (PBI) porous beads by means of a simple quantitative adsorption from THF solution, and tested in polymerization of phenylacetylene, 4-fluorophenylacetylene, and 4-pentylphenylacetylene. The polymer molecules formed were found to be released from the Rh/PBI to surrounding solution during the polymerization performed in THF. Formation of high molecular weight ((M)w values up to 325,000) polymers in prevailing cis-transoid configuration has been observed with all monomers. In a comparison with free [Rh(cod)Cl]2 used as the homogeneous catalyst, the Rh/PBI can be used repeatedly, exhibits somewhat lower polymerization activity but almost no oligomerization activity, and provides polymers of higher molecular weight.

Journal Article↗

Neodymium alkoxides: synthesis, characterization and their combinations with dialkylmagnesiums as unique systems for polymerization and block copolymerization of ethylene and methyl methacrylate.

The synthesis and characterization (NMR and X-ray) of a variety of neodymium alkoxides derived from simple and functionalized tertiary monoalcohols, and their application as inorganic precursors in combination with dialkylmagnesium reagents for ethylene and methyl methacrylate (MMA) (co)polymerization have been investigated. Salt metathesis reactions between NdCl(3) and sodium alkoxides in THF led to the formation of trinuclear complexes [Nd(3)(mu(3)-OR)(2)(mu(2)-OR)(3)(OR)(4)(thf)(2)] with R=tBu (1), tAm (2), while aggregate structure [Nd(12)(OtAm)(26)(HOtAm)(2)Cl(11)Na].(OEt(2))(2) (3) was obtained when the synthesis was performed in Et(2)O. [Nd(3)(mu(3)-OtBu)(2)(mu(2)-OtBu)(3)(OtBu)(4)(HOtBu)(2)] (4), prepared by aminolysis of Nd[N(SiMe(3))(2)](3) in hexane, slowly decomposed in toluene into oxo complex [Nd(5)(mu(5)-O)(mu(3)-OtBu)(4)(mu(2)-OtBu)(4)(OtBu)(5)] (5). Finally, the dimer [Nd(2)(mu(2),eta(2)-OR)(2)(eta(2)-OR)(2)(eta(1)-OR)(2)] (OR=OCMe(2)CH(2)CH(2)OMe) (6) was synthesised by aminolysis reaction from the corresponding gamma-donor-functionalized alcohol. Some of these neodymium alkoxides, in particular homoleptic complex 1, when associated in situ to one equivalent of a dialkylmagnesium, allow the formation of an active catalyst for ethylene polymerization. Under mild conditions (0 degrees C, 1 bar), the latter catalyst system exhibited a moderate activity (5-10 kg mol(-1) h(-1) bar(-1)). Effective transfer reactions were observed in the presence of H(2) or PhSiH(3) and renewal/improvement of activity occurred upon extra addition of dialkylmagnesium. The most outstanding feature of this catalytic system lies in the precipitation of the active "Nd-polyethylenyl" species during the ethylene polymerization course as solid S which could be isolated. This heterogeneity was turned to good account, enabling to achieve heterogeneous solid-gas ethylene polymerization and to prepare diblock PE-PMMA copolymers with high diblock efficiency and high molecular weights (M(n) > 200 000). A catalytic cycle for this unique system is proposed based on the isolation of a transmetallation product (7) from a neodymium alkoxide/dialkylmagnesium combination and NMR studies of the latter.

Journal Article↗

The nature of the monomer insertion step in the allylnickel(II)-catalyzed 1,4-polymerization of 1,3-butadiene: sigma-allyl-insertion mechanism versus pi-allyl-insertion mechanism.

We present a theoretical investigation on the nature of the monomer insertion step in the allylnickel(II)-catalyzed 1,4-polymerization of 1,3-butadiene that employed a gradient-corrected DFT method. We have explored critical elementary steps of the whole polymerization cycle for the trans-1,4 regulating cationic allylnickel(II) [RC3H4NiII(C4H6)L]+ catalyst. These steps are i) cis-butadiene insertion into either the eta 1-sigma-butenyl-NiII bond (sigma-allyl insertion mechanism) or the eta 3-pi-butenyl-NiII bond (pi-allyl insertion mechanism) along with competing pathways for generation of trans-1,4 and cis-1,4 polymer units, and ii) anti-syn isomerization. Based on the analysis of geometric and electronic structures of key species involved and the energetics, we present a detailed insight into the different nature of the monomer insertion step according to the two mechanistic alternatives. An understanding of why the pi-allyl insertion mechanism is favored over the sigma-allyl insertion mechanism is provided. eta 1-sigma-butenyl-NiII Species are predicted to be sparsely populated and also distinctly less reactive than eta 3-pi-butenyl-NiII species. Although they are commonly believed to be reactive intermediates, eta 1-sigma-butenyl-NiII species are, therefore, not likely to be involved along viable pathways for cis-butadiene insertion into the butenyl-NiII bond. The present investigation corroborates our previous conclusion that the pi-allyl insertion mechanism represents the preferred mechanism for the monomer insertion step in the allylnickel(II)-catalyzed 1,4-polymerization of 1,3-butadiene. On the other hand, the suggested alternative sigma-allyl insertion mechanism has to be considered to be not operative, for both thermodynamic and kinetic reasons. Furthermore, the sigma-allyl insertion mechanism would neither provide a rationalization of cis-trans selectivity nor of chemoselectivity in the allylnickel(II)-catalyzed 1,4-polymerization of 1,3-butadiene.

Journal Article↗

Polymeric and polymer-supported pseudostationary phases in micellar electrokinetic chromatography: performance and selectivity.

Several types of synthetic ionic polymers have been employed as pseudostationary phases in electrokinetic chromatography. The polymers have been shown to have some significant advantages and different chemical selectivity relative to conventional surfactant micelles. Polymeric phases are effective for the separation and analysis of hydrophobic and chiral compounds, and may be useful for the application of mass spectrometric detection. Additionally, the polymeric phases often demonstrate unique selectivity relative to micellar phases, and can be designed and synthesized to provide desired selectivity. This review covers efforts to develop and characterize the performance, characteristics, and selectivity of synthetic polymeric pseudostationary phases since their introduction in 1992. Some ideas for the future development of polymeric pseudostationary phases and the role they may play in electrokinetic separations are presented.

Chromatography, Micellar Electrokinetic Capillary↗

Chiral separation of polychlorinated biphenyls using a combination of hydroxypropyl-gamma-cyclodextrin and a polymeric chiral surfactant.

Chiral separation of moderately to highly hydrophobic polychlorinated biphenyls (PCBs) using a conventional chiral micelle or a polymeric chiral surfactant, as the single chiral selector is very difficult since the hydrophobic interactions between the chiral PCB and the monomeric or polymeric surfactant is very strong. Combined use of a polymeric chiral surfactant, polysodium N-undecanoyl-D-valinate (poly-D-SUV) with hydroxypropyl-gamma-cyclodextrin (HP-gamma-CD) was successful in cyclodextrin modified electrokinetic chromatography (CD-EKC) enantioseparation of PCB congeners. Addition of HP-gamma-CD to the background electrolyte containing poly-D-SUV functioned to improved chiral resolution for the PCBs and reduce the analysis time for these congeners. In addition, concentration of methanol, concentration of 2-(N-cyclohexylamino) ethanesulfonic acid (CHES) buffer and separation voltage was also varied to optimize multicomponent separation of five chiral PCBs. Simultaneous separation and enantioseparation of all five PCBs was possible in less than 50 min under optimized conditions that requires a 5 mM CHES solution buffered at about pH 10 with 1.5% w/v (ca. 60 mM) poly-D-SUV and 16 mM HP-gamma-CD. In addition, 1 M urea and 20% v/v methanol should be added as organic modifier and the capillary temperature maintained at 45 degrees C. As expected the polymeric surfactant showed improved chiral resolution of PCBs over conventional micelles of SUV. Under optimized conditions, when CD-EKC of chiral PCBs using poly-D-SUV was compared to sodium dodecyl sulfate (SDS), better resolution, higher efficiency and shorter analysis time was achieved with poly-D-SUV.

2-Hydroxypropyl-beta-cyclodextrin↗

Effects of divalent cations on the conversion of fibrinogen to fibrin and fibrin polymerization.

Effects of divalent cations on fibrinogen and its reaction with thrombin were re-examined and correlated to improve definition of mechanisms underlying the acceleration of clot formation by the ions. The rate of release of fibrinopeptides from fibrinogen was not affected by any of the specific ions studied, but increased rates of fibrin monomer polymerization were obtained with all but magnesium ions. Maximal acceleration of monomer polymerization was observed with the divalent ions at concentration of 2.5-5 mM, and no added specific ion effects were observed with much higher levels. The acceleratory ions were found to have a corresponding effect on the solubility of fibrinogen, as judged from acceleration of its precipitation at low temperature. Although magnesium ions had no effect on fibrin monomer polymerization, they did have a low ranking effect on cryoprecipitation. These data confirm that the principal effect of divalent cations in the fibrinogen-fibrin transformation is to accelerate fibrin monomer polymerization, and suggest that the acceleration is associated with effects on the solubility of fibrinogen.

Blood Coagulation Tests↗

Band 3 peptides inhibit deoxy S polymerization: viscosity studies.

We have previously obtained evidence that N-terminal band 3 peptides inhibited deoxyhemoglobin S (deoxy S) polymerization as determined by equilibrium solubility assays. An N:1-15AA fragment binds to the 2,3-diphosphoglycerate (2,3-DPG) receptor locus of deoxy S with five to seven amino acids (AA) extending internally, while ten to eight AA remained external to deoxy S and inhibited polymerization by steric hindrance. A true mirror-image peptide, corresponding to two N:1-8AA + lysine (K) linked by coupler, binds to the 2,3-DPG loci of two deoxy S molecules, tethering them together to form "binary complexes" incapable of entering the polymer chains. The reduction in the concentration of deoxy S available for extended chain formation decreased polymerization. We now report time:viscosity profiles of the sol-gel transformation of purified solutions of deoxy S with and without peptides and studies of the gel solidity at equilibrium. Samples with peptides had longer lag times than controls of similar deoxy S concentrations. The mirror-image peptide was a more effective inhibitor than the N:1-15AA peptide. When the mirror-image peptide was present in peptide:hemoglobin molar ratios of 0.25-1:1, the increases in lag time were equivalent to decreasing the deoxy S concentrations by 15-25%, comparable to projected major therapeutic effects. Gel solidity, determined by yield temperature, was less in the sample with mirror-image peptide compared to control. These results support the proposed mechanisms of inhibition of deoxy S polymerization by band 3 peptides.

Amino Acid Sequence↗

Polymeric sensor materials: toward an alliance of combinatorial and rational design tools?

Increased selectivity, response speed, and sensitivity in the chemical and biological determinations of gases and liquids are of great interest. Particular attention is paid to polymeric sensor materials, which are applicable to sensors exploiting various energy transduction principles, such as radiant, electrical, mechanical, and thermal energy. Ideally, numerous functional parameters of sensor materials can be tailored to meet specific needs using rational design approaches. However, increasing the structural and functional complexity of polymeric sensor materials makes it more difficult to predict the desired properties. Combinatorial and high-throughput methods have had an impact on all areas of research on polymer-based sensor materials including homo- and copolymers, formulated materials, polymeric structures with engineered morphology, and molecular shape-recognition materials. Herein we report on the state-of-the-art, the development trends, and the remaining knowledge gaps in the area of combinatorial polymeric sensor materials design.

Journal Article↗

Unprecedented living olefin polymerization derived from an attractive interaction between a ligand and a growing polymer chain.

Ti complexes incorporating fluorine-containing phenoxy-imine chelate ligands (fluorinated Ti-FI catalysts) have been demonstrated to induce an unprecedented living polymerization effect with both ethylene and propylene, through an attractive interaction between the fluorine atom in the ligand and a beta-hydrogen atom on the growing polymer chain. With the aid of this attractive interaction, highly controlled living ethylene polymerization, highly-syndiospecific living propylene polymerization, the synthesis of unique block copolymers from ethylene and propylene, and the catalytic production of monodisperse polyethylene and Zn-terminated polyethylene have been realized. The attractive interaction provides a conceptually new strategy for the achievement of controlled living olefin polymerization.

Journal Article↗

Towards a universal polymer backbone: design and synthesis of polymeric scaffolds containing terminal hydrogen-bonding recognition motifs at each repeating unit.

Polymers containing terminal hydrogen-bonding recognition motifs based on diaminotriazine and diaminopyridine groups in their side chains for the self-assembly of appropriate receptors have been prepared by ring-opening metathesis polymerization (ROMP) of norbornenes. A new synthetic method for the preparation of norbornene monomers based on pure alkyl spacers is introduced. These monomers show unprecedented high reactivity using ROMP. To suppress self-association of diaminotriazine-based polymers, polymerizations were run in presence of N-butylthymine. The butylthymine acts as a protecting group via self-assembly onto the hydrogen-bonding sites of the polymeric scaffold, thereby solubilizing the polymer. Diaminopyridine monomers do not require the presence of a protecting group due to their low propensity to dimerize. In addition, they exhibit a high affinity for hydrogen-bonded receptors on both monomeric and polymeric level. These polymers present our first building blocks towards the design and synthesis of a "universal polymer scaffold".

Chemical Phenomena↗