Complicity of degradable polymers in health-care applications

Polymeric biomaterials have revolutionized biomedical technology and related fields as biomaterials for health-care applications. Recent trend in polymeric medical technology has adapted a tendency to substitute degradable polymers instead of non-degradable synthetic polymers for the advancement of various health-care modalities. They have got considerable attention for their potential in various interdisciplinary arenas, which implies tissue engineering scaffolds, sustainable drug release, delivery agents, regenerative medicine, and development of life-saving devices, implants, dental products as well as in food technology. Various types of degradable polymers are been developed to date having stringent features applicable for various aspects in modern science. Thus, being the most renovative field of biomedicine and biomedical technology degradable polymers has gained substantial acceptance and appreciation recent times. This review critically underlines various degradative polymers and their subtypes, potential applications, types of degradation, and their possible effects in the biological system. Assessment of possible toxicological risks behind is an important criterion to be focused before validating any biomaterial safe for biomedical applications. Therefore various toxicological assessment strategies and their impact in biomedicine and technology were also included. In addition, the risk versus benefit assessment is also critically summarized.     

On the product distribution in the iodination of phenol

The product distribution in the iodination of phenol with I₂, in water solution is buffer and pH dependent with the ortho product increasing at low pH and low buffer concentration. This effect is attributed to different rates of proton transfer from the 4-iodo-2,5-; and 2-iodo-3,5-cyclohexadienone intermediate.     

Polylactides - degradable polymers for fibres and films

Modification of a poly(L-lactide) (PLLA) base resin, by treatment with peroxides and compounding with plasticisers, yield resins which can be processed by conventional techniques and equipment to thin blown films, fibres and nonwoven fabrics having properties comparable to those of corresponding PP and PE samples. Film samples have tensile strength between 30 and 50 MPa, elongation at break around 250%, and puncture resistance, measured as dart drop values, of 12 g/μm. Fibres can be spun to filaments or directly to nonvowen fabrics by spun-bond techniques. These fabrics have mechanical properties comparable to polypropylene materials. The polymer products are readily degraded in a compost to carbon dioxide, water and biomass.     

Functionalized and degradable polymers of malic acid stimulate bone repair

A water soluble and hydrolysable polyester derived from malic acid has been synthesized by copolymerization of three different malolactonic acid esters. Functional pendant groups have been selected to interact with and protect heparin binding growth factors (HBGF). Three β-substituted β-lactones have been synthesized by using aspartic acid as a chiral precursor and benzyl, allyl and butyl alcohols in the formation of the ester pendant groups. The terpolymer has been subjected to three consecutive different chemical modifications. This modified terpolymer, able to induce new bone formation in an in vivo model, has the same property as carboxymethyl benzylamide sulfonate dextrans (CMDBS). Consequently, the distribution of the lateral functional groups is more essential than the glucidic nature of the backbone to acquire biological efficiency.     

A simple method suitable to test the ultimate biodegradability of environmentally degradable polymers

A straightforward experimental set-up derived from the Biometer Flask previously utilized for experiments of pesticides biodegradation, has been adopted for testing the ultimate biodegradability of natural, synthetic and semi-synthetic polymeric materials on solid substrates such as soil and mature compost. The use of these whole substrates as incubation media in respirometric experiments, may negatively affect the accuracy of the test due to the large amount of carbon dioxide developed from the blanks, especially in the presence of specimen degrading at low or moderate rates. In the present test procedure soil and compost samples are diluted with perlite, a naturally occurring inert aluminum silicate widely utilized in horticultural applications, in order to ensure optimal conditions for the microbial growth while reducing the carbon dioxide emissions from the blanks. The results so far reported clearly indicate that the adopted procedure is extremely valuable and versatile for the appreciation of even subtle differences in the biodegradation rate of different polymeric materials, as well as for long-term degradation experiments.     

Geminal poly(silyl ester)s: Highly labile degradable polymers

Geminal silyl ester linkages were used for the backbone construction of linear polymers, which exhibit rapid cleavage in the presence of atmospheric water. A series of poly(gem-silyl ester)s with two ester groups flanking each silicon atom were synthesized, in order to probe the effects of different silyl-substituted side-chain groups upon the physical and chemical properties. The transsilylation condensation reaction of bis(trimethylsilyl) terephthalate with dichlorodiisopropylsilane, dichlorodicyclohexylsilane, dichloromethyl-n-octadecylsilane, and dichloromethyl-4-methylphenethylsilane gave the four poly(gem-silyl ester)s with two isopropyl, two cyclohexyl, one methyl plus one octadecyl, and one methyl plus one 4-methyl-phenethyl side-chain groups per silicon, respectively. The polymers were characterized by NMR (¹H, ¹³C, and ²⁹Si), infrared spectroscopy (IR), size-exclusion chromatography (SEC), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). Hydrolytic degradation studies of the polymers solvated in tetrahydrofuran and as bulk samples in the solid state were performed in the presence of atmospheric water as the nucleophilic cleavage agent, and the molecular weight loss was monitored by SEC. Poly(diisopropylsilyl terephthalate) (1a) and poly(dicyclohexylsilyl terephthalate) (1b) were found to be more stable towards nucleophilic degradation in comparison to poly(methyl-n-octadecylsilyl terephthalate) (1c) and poly(methyl-4-methylphenethylsilyl terephthalate) (1d), due to the presence of sterically bulky isopropyl or cyclohexyl groups attached to the silicon atoms. All of the polymers degraded into small molecules upon hydrolysis, with the exception that the degradation products of 1c and 1d self-condensed in the solid state to form the respective polysiloxanes. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3606–3613, 1999     

Metal free thiol-maleimide 'Click' reaction as a mild functionalisation strategy for degradable polymers

The stoichiometric reaction between thiols and maleimide-functional poly(ester)s is demonstrated to be a quantitative, tolerant, mild and efficient method for polymer modification.     

Preparation and functionalization of linear and reductively degradable highly branched cyanoacrylate‐based polymers

Ethyl cyanoacrylate (ECA) was polymerized radically in the presence of small amounts of trifluoroacetic acid as effective inhibitor of incidental anionic polymerization. Methyl methacrylate and other functional vinyl monomers (e.g., 2‐chloroethyl and 2‐bromoethyl methacrylate) were copolymerized with ECA, yielding linear ECA‐rich copolymers, which could readily undergo further modifications, for instance nucleophilic substitution with azide. In the presence of a disulfide‐containing dimethacrylate crosslinker and a chain transfer agent (CBr₄) during the free radical copolymerizations of ECA with methacrylates, highly branched ECA‐based polymers containing disulfide groups at the branching points were obtained prior to gelation. The polymers degraded upon addition of reducing agents. The prepared polymers, which contained peripheral (chain end) alkyl bromide groups as well as pendant alkyl chloride or bromide groups were then reacted with sodium azide, affording azide‐containing polymers that were reacted with functional alkynes under copper‐catalyzed “click” chemistry conditions. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3683–3693     

On the flexibility of cyclochain polymers

Conformational parameters for a wide variety of aromatic cyclochain polymers have been computed assuming free rotation about virtual bonds. The flexibility with free rotation is shown to be determined by the geometry of the repeat unit and can vary over a wide range (15–1500 Å). Experimental values of the Kuhn segment length A are calculated from literature data on the hydrodynamic behavior of polymeric macromolecules of this class in solution. For most polymers A_fr for free rotation is equal to the experimental A_exp, and hindered rotation is mainly due to bulky substituents. © 1993 John Wiley & Sons, Inc.     

Molecular weight distribution in branched polymers

The distribution of molecular weights in realistic free-radical polymerizations with branching was analyzed theoretically. Series solutions were obtained for the fraction of molecules with r repeating units and the number of branch points contained in molecules with r repeating units. Branching by transfer processes was found to increase the proportion of both high and low molecular weight components in the system. The apportioning of branch points among r-mer molecules was shown to be somewhat narrower than a Poisson distribution. The major difference between the calculated distributions and previous model distributions for branched systems was the absence of discontinuities in the moments at all levels of branching.     

Photochemically degradable polymers containing metal-metal bonds along their backbones: the effect of stress on the rates of photochemical degradation

The syntheses of polymers that have metal-metal bonds along their backbones are described. The polymers are photodegradable because the metal-metal bonds homolyze when irradiated with visible light. The photochemical reactions of the polymers in solution are identical to the photochemical reactions of the discrete metal-metal bonded dimers. Typical reactions include metal-metal bond disproportionation and metal radical capture, for example, by chlorine atom abstraction from carbon tetrachloride. The polymers are also photochemically degradable in the solid state; thin films of the polymers degrade when irradiated with visible light in the presence of oxygen or in the absence of oxygen if the polymer backbone has a built-in radical trap. The origin of tensile stress-induced rate enhancements in the photodegradation of polymers was studied using the polymers with metal-metal bonds along their backbones and with built-in radical traps. By eliminating the need for external oxygen to act as a radical trap, the experimentally challenging problem of diffusion-controlled oxidation kinetics was avoided. Analysis of plots of quantum yields for degradation vs. stress reveals that stress increases the separation of the radical fragments produced by photolysis. An increased separation leads to less radical-radical recombination, which increases the efficiency of degradation. Quantitative knowledge of the factors that control polymer degradation rates will eventually allow synthesis of an ideal photodegradable polymer - one that has a tunable onset of degradation and that degrades quickly once degradation has started.     

CO product distribution in the unimolecular dissociation of HCO

The unimolecular dissociation of HCO ground state was investigated with the time-dependent full-quantum symplectic propagation based on the newest potential energy surface of the system. Calculated energy and widths of HCO resonance states agree well with those in the literature. CO product distribution was systematically investigated. A simple model was presented to interpret the rovibrational distributions in HCO dissociation.     

On the inhomogeneous deformation of rubber-elastic polymers

Measurements in a gas dilatometer on carbon-black filled rubber cross-linked with sulfur show a large pressure drop in the specimen chamber, which to a large extent cannot be explained by a volume change of the specimen. The extension ratio at which the pressure starts to fall depends on the carbon-black content. Comparative measurements in a deformation calorimeter show that crystallisation always begins first at higher strains. It is assumed that the investigated specimens are inhomogeneously deformed even at small strains, depending on the carbon-black content, and that internal voids are formed, onto the surfaces of which gas molecules are deposited. This gas adsorption causes the pressure drop measured in the dilatometer; it is dependent on the nature of the gas. Argon shows no interaction with internal surfaces in the specimen; for measurements in an argon atmosphere, volume increases and strain-induced crystallisation can be properly determined. It is presumed that strain-induced crystallisation sets in earlier for specimens with larger carbonblack content, corresponding to the more inhomogeneous character of the deformation.Dedicated to Prof. Dr. R. Bonart on the occasion of his 60th birthday     

NMR study of the tie-chain length distribution in oriented polymers

Wide-line NMR has been used in an investigation of noncrystalline (amorphous) regions in oriented semicrystalline polymers. Nylon 6 was chosen as a model material. The tie-chain length distribution function, the fraction of tie chains in the total number of chains in the crystallite cross section, and the relative number of taut tie chains have been determined. The data on the tie-chain length distribution are used in discussing specific features of vitrification of the amorphous regions in oriented polymers and in prediction macroscopic mechanical properties.     

Synthesis of degradable poly(methyl methacrylate) star polymers via RAFT copolymerization with cyclic ketene acetals

Copolymerization of the cyclic ketene acetal 5,6‐benzo‐2‐methylene‐1,3‐dioxepane (BMDO) with methyl methacrylate (MMA) is studied with respect to its copolymerization parameters and the suitability to control BMDO/MMA copolymerizations via the reversible addition‐fragmentation chain transfer (RAFT) technique to obtain linear and 4‐arm star polymers. BMDO shows disparate copolymerization behavior with MMA and r₁ = 0.33 ± 0.06 and r₂ = 6.0 ± 0.8 have been determined for polymerization at 110 °C in anisole from fitting copolymer composition vs. comonomer feed data to the Lewis–Mayo equation. Copolymerization of the two monomers is successful in RAFT polymerization employing a trithiocarbonate control agent. As desired, polymers contain only little amount of polyester units stemming from BMDO units and preliminary degradation experiment show that the polymer degrades slowly, but steadily in aqueous 1 M NaOH dispersion. Within ten days, the polymers are broken down to low molecular weight segments from an initial molecular weight of M_n = 6000 g mol^?1. Star (co)polymerization with an erythritol‐based tetra‐functional RAFT agent following the Z‐group approach proceeds efficiently and polymers with a number‐average molecular weight of 10,000 g mol^?1 are readily obtained that degrade in similar manner as the linear copolymer counterparts. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1633–1641