Biodegradable polymers as drug delivery systems.

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Biodegradable polymers as drug delivery systems

DUE TO COPYRIGHT RESTRICTIONS ONLY AVAILABLE FOR CONSULTATION AT ASTON UNIVERSITY LIBRARY AND INFORMATION SERVICES WITH PRIOR ARRANGEMENT

The synthesis and avaluation of Friedel-Crafts polymers

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Dynamics of anchored polymers under an oscillating force

We study the dynamics of a polymer of varying stiffness, pinned or grafted at both ends and subjected to an oscillatory forcing at an intermediate point. Via stochastic simulations, we find a crossover from a periodic limit cycle to an aperiodic dynamics as the polymer gets "stiffer." An analytical argument valid in the 2D grafted case shows that in such a case this aperiodic dynamics has some chaotic signatures. © 2007 The American Physical Society.

Oxidative degradation and stabilisation of polymers

The aim of this review is to present a coherent treatment of the fundamental aspects of the science that underpins current technological practices, and future advances, in the stabilisation of synthetic organic polymers. Aspects of polymer oxidation are introduced first before discussing the role of antioxidants, with numerous examples, to illustrate their basic mechanisms of action. The state of the art is discussed with particular emphasis on recent development and progress.

Dynamics of linear polymers in random media

We study phenomenological scaling theories of the polymer dynamics in random media, employing the existing scaling theories of polymer chains and the percolation statistics. We investigate both the Rouse and the Zimm model for Brownian dynamics and estimate the diffusion constant of the center-of-mass of the chain in such disordered media. For internal dynamics of the chain, we estimate the dynamic exponents. We propose similar scaling theory for the reptation dynamics of the chain in the framework of Flory theory for the disordered medium. The modifications in the case of correlated disorders are also discussed. .

Metallocene ethylene-1-octene copolymers:effect of extrusion conditions on thermal oxidation of polymers with different comonomer content

Metallocene ethylene-1-octene copolymers having different densities and comonomer content ranging from 11 to 36 wt% (m-LLDPE), and a Ziegler copolymer (z-LLDPE) containing the same level of short-chain branching (SCB) corresponding to one of the m-LLDPE polymers, were subjected to extrusion. The effects of temperature (210-285 °C) and multi-pass extrusions (up to five passes) on the rheological and structural characteristics of these polymers were investigated using melt index and capillary rheometry, along with spectroscopic characterisation of the evolution of various products by FTIR, C-NMR and colour measurements. The aim is to develop a better understanding of the effects of processing variables on the structure and thermal degradation of these polymers. Results from rheology show that both extrusion temperature and the amount of comonomer have a significant influence on the polymer melt thermo-oxidative behaviour. At low to intermediate processing temperatures, all m-LLDPE polymers exhibited similar behaviour with crosslinking reactions dominating their thermal oxidation. By contrast, at higher processing temperatures, the behaviour of the metallocene polymers changed depending on the level of comonomer content: higher SCB gave rise to predominantly chain scission reactions whereas polymers with lower level of SCB continued to be dominated by crosslinking. This temperature dependence was attributed to changes in the different evolution of carbonyl and unsaturated compounds including vinyl, vinylidene and trans-vinylene. © 2007 Elsevier Ltd. All rights reserved.

Reactive processing of polymers:functionalisation of ethylene-propylene diene terpolymer (EPDM) in the presence and absence of a co-agent and effect of functionalised EPDM on compatibilisation of poly(ethylene terephthalate)/EPDM blends

Ethylene-propylene diene terpolymer (EPDM) was functionalized with glycidyl methacrylate (GMA) during melt processing by free radical grafting with peroxide initiation in the presence and absence of a reactive comonomer trimethylolpropane triacrylate (Tris). Increasing the peroxide concentration resulted in an increase in the GMA grafting yield, albeit the overall grafting level was low and was accompanied by higher degree of crosslinking of EPDM which was found to be the major competing reaction. The presence of Tris in the grafting system gave rise to higher grafting yield produced at a much lower peroxide concentration though the crosslinking reactions remained high but without the formation of GMA-homopolymer in either of the two systems. The use of these functionalized EPDM (f-EPDM) samples with PET as compatibilisers in binary and ternary blends of PET/EPDM/f-EPDM was evaluated. The influence of the different functionalisation routes of the rubber phase (in presence and absence of Tris) and the effect of the level of functionality and microstructure of the resultant f-EPDM on the extent of the interfacial reaction, morphology and mechanical properties was also investigated. It is suggested that the mechanical properties of the blends are strongly influenced by the performance of the graft copolymer, which is in turn, determined by the level of functionality, molecular structure of the functionalized rubber and the interfacial concentration of the graft copolymer across the interface. The cumulative evidence obtained from torque rheometry, scanning electron microscopy, SEM, dynamic mechanical analysis (DMA), tensile mechanical tests and Fourier transform infrared (FTIR) supports this. It was shown that binary and ternary blends prepared with f-EPDM in the absence of Tris and containing lower levels of g-GMA effected a significant improvement in mechanical properties. This increase, particularly in elongation to break, could be accounted for by the occurrence of a reaction between the epoxy groups of GMA and the hydroxyl/carboxyl end groups of PET that would result in a graft copolymer which could, most probably, preferentially locate at the interface, thereby acting as an 'emulsifier' responsible for decreasing the interfacial tension between the otherwise two immiscible phases. This is supported by results from FTIR analysis of the fractionated PET phase of these blends which confirm the formation of an interfacial reaction, DMA results which show a clear shift in the T s of the blend components and SEM results which reveal very fine morphology, suggesting effective compatibilisation that is concomitant with the improvement observed in their tensile properties. Although Tris has given rise to highest amount of g-GMA, it resulted in lower mechanical properties than the optimized blends produced in the absence of Tris. This was attributed to the difference in the microstructure of the graft and the level of functionality in these samples resulting in less favourable structure responsible for the coarser dispersion of the rubber phase observed by SEM, the lower extent of T shift of the PET phase (DMA), the lower height of the torque curve during reactive blending and FTIR analysis of the separated PET phase that has indicated a lower extent of the interfacial chemical reaction between the phases in this Tris-containing blend sample. © 2005 Elsevier Ltd. All rights reserved.

Reactive processing of polymers:effect of in situ compatibilisation on characteristics of blends of polyethylene terephthalate and ethylene-propylene rubber

Ethylene-propylene rubber (EPR) functionalised with glycidyl methacrylate (GMA) (f-EPR) during melt processing in the presence of a co-monomer, such as trimethylolpropane triacrylate (Tris), was used to promote compatibilisation in blends of polyethylene terephthalate (PET) and f-EPR, and their characteristics were compared with those of PET/f-EPR reactive blends in which the f-EPR was functionalised with GMA via a conventional free radical melt reaction (in the absence of a co-monomer). Binary blends of PETand f-EPR (with two types of f-EPR prepared either in presence or absence of the co-monomer) with various compositions (80/20, 60/40 and 50/50 w/w%) were prepared in an internal mixer. The blends were evaluated by their rheology (from changes in torque during melt processing and blending reflecting melt viscosity, and their melt flow rate), morphology scanning electron microscopy (SEM), dynamic mechanical properties (DMA), Fourier transform infrared (FTIR) analysis, and solubility (Molau) test. The reactive blends (PET/f-EPR) showed a marked increase in their melt viscosities in comparison with the corresponding physical (PET/EPR) blends (higher torque during melt blending), the extent of which depended on the amount of homopolymerised GMA (poly-GMA) present and the level of GMA grafting in the f-EPR. This increase was accounted for by, most probably, the occurrence of a reaction between the epoxy groups of GMA and the hydroxyl/carboxyl end groups of PET. Morphological examination by SEM showed a large improvement of phase dispersion, indicating reduced interfacial tension and compatibilisation, in both reactive blends, but with the Tris-GMA-based blends showing an even finer morphology (these blends are characterised by absence of poly-GMA and presence of higher level of grafted GMA in its f-EPR component by comparison to the conventional GMA-based blends). Examination of the DMA for the reactive blends at different compositions showed that in both cases there was a smaller separation between the glass transition temperatures compared to their position in the corresponding physical blends, which pointed to some interaction or chemical reaction between f-EPR and PET. The DMA results also showed that the shifts in the Tgs of the Tris-GMA-based blends were slightly higher than for the conventional GMA-blends. However, the overall tendency of the Tgs to approach each other in each case was found not to be significantly different (e.g. in a 60/40 ratio the former blend shifted by up to 4.5 °C in each direction whereas in the latter blend the shifts were about 3 °C). These results would suggest that in these blends the SEM and DMA analyses are probing uncorrelatable morphological details. The evidence for the formation of in situ graft copolymer between the f-EPR and PET during reactive blending was clearly illustrated from analysis by FTIR of the separated phases from the Tris-GMA-based reactive blends, and the positive Molau test pointed out to graft copolymerisation in the interface. A mechanism for the formation of the interfacial reaction during the reactive blending process is proposed.

Spin transition of 1D, 2D and 3D iron(II) complex polymers - the tug-of-war between elastic interaction and a shock-absorber effect

The structures of linear chain Fe(II) spin-crossover compounds of α,β- and α,ω-bis (tetrazol-1-yl)alkane type ligands are described in relation to their magnetic properties. The first threefold interlocked 3-D catenane Fe(II) spin-transition system, [μ-tris(1,4-bis(tetrazol-1-yl)butane-N1,N1′) iron(II)] bis(perchlorate), will be discussed. An analysis is made among the structures and the cooperativity of the spin-crossover behaviour of polynuclear Fe(II) spin-transition materials.

Learning from mother nature:exploiting a biological antioxidant for the melt stabilisation of polymers

An overview of the antioxidant role of the biologically active form of vitamin E, α-tocopherol, in polyolefins is discussed. The effect of the vitamin antioxidant on the melt and colour stability of polyethylene (PE) and polypropylene (PP) is highlighted. It is shown that tocopherol is a highly effective antioxidant that results in superior melt stabilisation of polyolefins particularly when used at much lower concentration than that needed for conventional synthetic hindered phenol processing stabilisers. As with other hindered phenols,α-tocopherol imparts also some colour to the polymer but this is shown to be reduced drastically in the presence of other antioxidants, such as phosphites, or other additives, such as polyhydric alcohols.

Reactive processing of polymers:melt grafting of glycidyl methacrylate on ethylene propylene copolymer in the presence of a coagent

Glycidyl methacrylate (GMA) was grafted on ethylene-propylene copolymer during melt processing with peroxide initiation in the presence and absence of a more reactive comonomer (coagent), trimethylolpropane triacrylate (Tris). The characteristics of the grafting systems in terms of the grafting reaction yield and the nature and extent of the competing side reactions were examined. The homopolymers of GMA (Poly-GMA) and Tris (Poly-Tris) and the GMA-Tris copolymer (GMA-co-Tris) were synthesized and characterized. In the absence of the coagent, high levels of poly-GMA, which constituted the major competing reaction, was formed, giving rise to low GMA grafting levels. Further, this grafting system resulted in a high extent of gel formation and polymer crosslinking due to the high levels of peroxide needed to achieve optimum GMA grafting and a consequent large drop in the melt index (increased viscosity) of the polymer. In the presence of the coagent, however, the grafting system required much lower peroxide concentration, by almost an order of magnitude, to achieve the optimum grafting yield. The coagent-containing GMA-grafting system has also resulted in a drastic reduction in the extent of all competing reactions, and in particular, the GMA homopolymerization, leading to improved GMA grafting efficiency with no detectable gel or crosslinking. The mechanisms of the grafting reactions, in the presence and absence of Tris, are proposed.

Responsive hydrophobically associating polymers:a review of structure and properties

Responsive hydrophobically associating polymers can in many ways be considered to be analogous to proteins in their ability to form compact molecules with a defined secondary structure, and hence, functionality. These molecules are characterized by the presence of alternating charged and hydrophobic groups. The balance between charge repulsion and hydrophobic interactions is sensitive to environmental pH and therefore changes in pH produce controllable conformational changes. The change from a charged extended chain to a collapsed uncharged coil structure is sometimes referred to as hypercoiling behaviour and enables the polymer to act as a simple switch between an 'on' and 'off' state. The purpose of this review is to illustrate the structure and behaviour of polymers that exhibit hypercoiling behaviour and to highlight their potential pharmaceutical applications, which in terms of drug delivery is likely to be related to their surface behaviour and solubilizing activity. © 2001 Elsevier Science B.V. All rights reserved.

Polymerisable octahedral rhenium cluster complexes as precursors for photo/electroluminescent polymers

New polymerisable photoluminescent octahedral rhenium cluster complexes trans-[{Re6Q8}(TBP)4(VB)2] (Q = S or Se; TBP-p-tert-butylpyridine; VB-vinyl benzoate) have been synthesised, characterised and used to construct rhenium cluster-organic polymer hybrid materials. These novel polymer systems are solution-processable and the rhenium clusters retain their photoluminescent properties within the polymer environment. Notably, when the rhenium cluster complexes are incorporated into the matrix of the electroluminescent polymer poly(N-vinylcarbazole), the resultant cluster polymer hybrid combined properties of both components and was used successfully in the construction of a polymer light emitting diode (PLED). These prototype devices are the first PLEDs to incorporate octahedral rhenium clusters and provide the first direct evidence of the electroluminescent properties of rhenium clusters and indeed, to the best of our knowledge, of any member of the family of 24-electron hexanuclear cluster complexes of molybdenum, tungsten or rhenium.

Pseudoperiodic "Living" and/or controlled cationic ring-opening copolymerization of oxetane with tetrahydropyran:microstructure of polymers vs kinetics of chain growth

The "living" and/or controlled cationic ring-opening bulk copolymerization of oxetane (Ox) with tetrahydropyran (THP) (cyclic ether with no homopolymerizability) at 35°C was examined using ethoxymethyl-1 -oxoniacyclohexane hexafluoroantimonate (EMOA) and (BF3 · CH3OH)THP as fast and slow initiator, respectively, yielding living and nonliving polymers with pseudoperiodic sequences (i.e., each pentamethylene oxide fragment inserted into the polymer is flanked by two trimethylene oxide fragments). Good control over number-average molecular weight (Mn up to 150000 g mol-1) with molecular weight distribution (MWD ∼ 1.4-1, 5) broader than predicted by the Poison distribution (MWDs > 1 +1/DPn) was attained using EMOA as initiating system, i.e., C 2H5OCH2Cl with 1.1 equiv of AgSbF6 as a stable catalyst and 1.1 equiv of 2,6-di-tert-butylpyridine used as a non-nucleophilic proton trap. With (BF3 · CH 3OH)THP, a drift of the linear dependence M n(GPC) vs Mn(theory) to lower molecular weight was observed together with the production of cyclic oligomers, ∼3-5% of the Ox consumed in THP against ∼30% in dichloromethane. Structural and kinetics studies highlighted a mechanism of chains growth where the rate of mutual conversion between "strain ACE species" (chain terminated by a tertiary 1-oxoniacyclobutane ion, Al) and "strain-free ACE species" (chain terminated by a tertiary 1-oxoniacyclohexane ion, Tl) depends on the rate at which Ox converts the stable species T1 (kind of "dormant" species) into a living "propagating" center A1 (i.e., k aapp[Ox]). The role of the THP solvent associated with the suspension of irreversible and reversible transfer reactions to polymer, when the polymerization is initiated with EMOA, was predicted by our kinetic considerations. The activation -deactivation pseudoequilibrium coefficient (Qt) was then calculated in a pure theoretical basis. From the measured apparent rate constant of Ox (kOxapp) and THP (kTHPapp = ka(endo)app) consumption, Qt and reactivity ratio (kp/kd, k a(endo)/ka(exo), and ks/ka(endo) were calculated, which then allow the determination of the transition rate constant of elementary step reactions that governs the increase of Mu with conversion. © 2009 American Chemical Society.