Comparison of the hydrolytic degradation and deformation properties of a PLLA-lauric acid based family of biomaterials

Addition of lauric acid to PLLA results in a significantly increased rate of hydrolytic degradation, with the time-to-loss of tensile strength directly related to the concentration of lauric acid. In this study, the hydrolytic degradation profiles of four materials were studied: amorphous PLLA, amorphous PLLA containing 1.8 wt % lauric acid, amorphous PLLA containing 4.5 wt % lauric acid, and pre-crystallized PLLA containing 1.8 wt % lauric acid. Hydrolytic degradation was monitored through mass profiles, molecular weight profiles, crystallinity and the development of mechanical properties and deformation mechanisms (through simultaneous small-angle X-ray scattering and tensile testing), and a "phase diagram" of properties suggested. The key factor in determining the development of properties was found to be the time at which crystallization occurred in relation to the loss of molecular weight, with the two factors most affecting this being the lauric acid content and the pre-degradation annealing treatment.     

Folate-functionalized unimolecular micelles based on a degradable amphiphilic dendrimer-like star polymer for cancer cell-targeted drug delivery

A folate-functionalized degradable amphiphilic dendrimer-like star polymer (FA-DLSP) with a well-defined poly(L-lactide) (PLLA) star polymer core and six hydrophilic polyester dendrons based on 2,2-bis(hydroxymethyl) propionic acid was successfully synthesized to be used as a nanoscale carrier for cancer cell-targeted drug delivery. This FA-DLSP hybrid formed unimolecular micelles in the aqueous solution with a mean particle size of ca. 15 nm as determined by dynamic light scattering and transmission electron microscopy. To study the feasibility of FA-DLSP micelles as a potential nanocarrier for targeted drug delivery, we encapsulated a hydrophobic anticancer drug, doxorubicin (DOX), in the hydrophobic core, and the loading content was determined by UV-vis analysis to be 4 wt %. The DOX-loaded FA-DLSP micelles demonstrated a sustained release of DOX due to the hydrophobic interaction between the polymer core and the drug molecules. The hydrolytic degradation in vitro was monitored by weight loss and proton nuclear magnetic resonance spectroscopy to gain insight into the degradation mechanism of the FA-DLSP micelles. It was found that the degradation was pH-dependent and started from the hydrophilic shell gradually to the hydrophobic core. Flow cytometry and confocal microscope studies revealed that the cellular binding of the FA-DLSP hybrid against human KB cells with overexpressed folate-receptors was about twice that of the neat DLSP (without FA). The in vitro cellular cytotoxicity indicated that the FA-DLSP micelles (without DOX) had good biocompatibility with KB cells, whereas DOX-loaded micelles exhibited a similar degree of cytotoxicity against KB cells as that of free DOX. These results clearly showed that the FA-DLSP unimolecular micelles could be a promising nanosize anticancer drug carrier with excellent targeting property.     

Tuning the polylactide hydrolysis rate by plasticizer architecture and hydrophilicity without introducing new migrants

The possibility to tune the hydrolytic degradation rate of polylactide by plasticizer architecture and hydrophilicity without introduction of new degradation products was investigated by subjecting polylactide with cyclic oligolactide and linear oligolactic acid additives to hydrolytic degradation at 37 and 60 °C for up to 39 weeks. The more hydrophilic oligolactic acid plasticizer led to larger water uptake and rapid migration of plasticizer from the films into the aging water. This resulted in a porous material more susceptible to further hydrolysis. During hydrolysis at 37 °C the mass loss was generally 10-20% higher for the material containing linear oligolactic acid plasticizers. The hydrolysis accelerating effect of the linear oligolactic acid is probably counteracted by the higher degree of crystallinity in the films containing oligolactic acid additives. The degradation process was monitored by measurements of mass loss, water uptake, molar mass changes, material composition changes, surface changes, and thermal properties. The water-soluble degradation products were analyzed by following pH changes and identified by electrospray ionization-mass spectrometry (ESI-MS). The time frame for formation of water-soluble products was influenced by the architecture and hydrophilicity of the plasticizer. Furthermore, the advantage with oligolactide and oligolactic acid plasticizers was clearly demonstrated as they do not introduce any new migrants into the degradation product patterns.     

Enzymatic, alkaline, and autocatalytic degradation of poly(L-lactic acid): effects of biaxial orientation

The hydrolytic degradation of biaxially oriented and de-oriented (melt-crystallized) poly(l-lactic acid) (PLLA) films was investigated in Tris-HCl-buffered solution (pH 8.6) with proteinase K, alkaline solution, and phosphate-buffered solution (pH 7.4) by the use of gravimetry, gel permeation chromatography, differential scanning calorimetry, and scanning electron microscopy. Biaxial orientation disturbed the proteinase K-catalyzed enzymatic degradation of PLLA films and the effects of biaxial orientation overcame those of crystallinity. The former may be due to the fact the enzyme cannot attach to the extended (strained) chains in the amorphous regions of the biaxially oriented PLLA film or cannot catalyze the cleavage of the strained chains. Another probable cause is that the enzyme can act only at the film surface of the biaxially oriented PLLA film, in marked contrast with the case of the de-oriented PLLA films where enzymatic degradation can proceed beneath the spherulitic crystalline residues. The effects of biaxial orientation on the alkaline and autocatalytic degradation of the PLLA films were insignificant for the periods studied here. The crystallinity rather than the biaxial orientation seems to determine the alkaline and autocatalytic degradation rates of the PLLA films. The accumulation of crystalline residues formed as a result of selective cleavage and removal of the amorphous chains was observed for the de-oriented PLLA films, but not for the biaxially oriented PLLA film, when degraded in the presence of proteinase K. This means the facile release of formed crystalline residues from the surface of the biaxially oriented PLLA film during enzymatic degradation, due to the fact that the crystalline regions of the biaxially oriented PLLA film were oriented with their c axis parallel to the film surface.     

Degradation of polyaminophosphazenes: effects of hydrolytic environment and polymer processing

Polyphosphazenes with amino acid ester side groups show potential as hydrolytically degradable materials for biomedical applications. This study focuses on practical aspects of their use as biodegradable materials, such as effects of the hydrolytic environment and sample processing. Poly[di(ethyl glycinato)phosphazene], PEGP, and poly[di(ethyl alaninato)phosphazene], PEAP, were prepared by macromolecular substitution reaction, ensuring the absence of the residual chlorine atoms to avoid their influence on the hydrolysis. The kinetics of polymer degradation was studied by simultaneously measuring polymer mass loss, molecular weight decrease, and the release of phosphates and ammonia. The effect of pH, buffer composition, temperature, casting solvents, and film thickness were investigated.     

Biodegradable nanogel formation of polylactide-grafted dextran copolymer in dilute aqueous solution and enhancement of its stability by stereocomplexation

Monodisperse stereocomplex nanogels were obtained through the self-assembly of an equimolar mixture of dextran-graft-poly(L-lactide) (Dex-g-PLLA) and dextran-graft-poly(D-lactide) (Dex-g-PDLA) amphiphilic copolymers with well-defined composition in a dilute aqueous solution. The stereocomplex nanogel possessed partially crystallized cores of hydrophobic polylactide (PLA) and the hydrophilic dextran skeleton by intra- and/or intermolecular self-assembly between PLLA and PDLA chains. The stereocomplex nanogels exhibited significantly lower critical aggregation concentration (CAC) value as well as stronger thermodynamic stability compared with those of the corresponding L- or D-isomer nanogels. The mean diameter of the stereocomplex nanogels was 70 nm with narrow size distribution, implying they were well-defined and presumably nanogels. Furthermore, stereocomplex nanogel exhibited strong kinetic stability. The tunable degradation properties of Dex-g-PLA nanogels were achieved by varying the number of grafted PLA chains as well as applying stereocomplexation. This study demonstrates the advantage of stereocomplexation in the design of biodegradable nanogels with enhanced stability.     

Indicator products: a new tool for lifetime prediction of polymeric materials

The possible correlation between the degree of degradation in the polymer matrix and the release of indicator products was investigated. The degree of degradation was measured by following the molar mass changes by size exclusion chromatography, while indicator products were analyzed by gas chromatography-mass spectrometry. The degree of degradation in polyethylene and polyethylene vinyl acetate matrix after thermooxidation was found to be in correlation with the amount of dicarboxylic acids and lactones formed during aging, while the degree of degradation in photooxidized polyethylene could be predicted from the amount of dicarboxylic acids. The relative amount of lactones compared to the relative amount of dicarboxylic acids increased if the oxidation temperature was increased. However, the total amount of indicator products was in correlation with the remaining number average molar mass and the number of chain scissions caused by oxidation. The amount of butanedioic acid and butyrolactone correlated well with the total amount of dicarboxylic acids and lactones, respectively. Thus, instead of the whole compound classes, butanedioic acid or butyrolactone alone could be used as indicators of oxidation. The detected correlation offers a novel tool for making lifetime predictions and studying the long-term properties of polymeric materials.     

Porosity and pore size regulate the degradation product profile of polylactide

Porosity and pore size regulated the degradation rate and the release of low molar mass degradation products from porous polylactide (PLA) scaffolds. PLA scaffolds with porosities above 90% and different pore size ranges were subjected to hydrolytic degradation and compared to their solid analog. The solid film degraded fastest and the degradation rate of the porous structures decreased with decreasing pore size. Degradation products were detected earlier from the solid films compared to the porous structures as a result of the additional migration path within the porous structures. An intermediate degradation rate profile was observed when the pore size range was broadened. The morphology of the scaffolds changed during hydrolysis where the larger pore size scaffolds showed sharp pore edges and cavities on the scaffold surface. In the scaffolds with smaller pores, the pore size decreased during degradation and a solid surface was formed on the top of the scaffold. Porosity and pore size, thus, influenced the degradation and the release of degradation products that should be taken into consideration when designing porous scaffolds for tissue engineering.     

Drug release from and hydrolytic degradation of a poly(ethylene glycol) grafted poly(3-hydroxyoctanoate)

Monoacrylate-poly(ethylene glycol)-grafted poly(3-hydroxyoctanoate) (PEGMA-g-PHO) copolymers were synthesized to develop a swelling-controlled release delivery system for ibuprofen as a model drug. The in vitro hydrolytic degradation of and the drug release from a film made of the PEGMA-g-PHO copolymer were carried out in a phosphate buffer saline (pH 7.4) medium. The hydrolytic degradation of the copolymer was strongly dependent on the degree of grafting (DG) of the PEGMA group. The degradation rate of the copolymer films in vitro increased with increasing DG of the PEGMA group on the PHO chain. The copolymer films showed a controlled delivery of ibuprofen to the medium in periods of time that depend on the composition, hydrophilic/hydrophobic characteristics, initial drug loading amount and film thickness of the graft copolymer support. The drug release rate from the grafted copolymer films was faster than the rate of weight loss of the films themselves. In particular, a combination of the low DG of the PEGMA group in the PHO chains with the low ibuprofen solubility in water led to long-term constant release from these matrices in vitro.     

In-situ formation of biodegradable hydrogels by stereocomplexation of PEG-(PLLA)8 and PEG-(PDLA)8 star block copolymers

Eight-arm poly(ethylene glycol)-poly(L-lactide), PEG-(PLLA)(8), and poly(ethylene glycol)-poly(D-lactide), PEG-(PDLA)(8), star block copolymers were synthesized by ring-opening polymerization of either L-lactide or D-lactide at room temperature in the presence of a single-site ethylzinc complex and 8-arm PEG (M(n) = 21.8 x 10(3) or 43.5 x 10(3)) as a catalyst and initiator, respectively. High lactide conversions (>95%) and well-defined copolymers with PLLA or PDLA blocks of the desired molecular weights were obtained. Star block copolymers were water-soluble when the number of lactyl units per poly(lactide) (PLA) block did not exceed 14 and 17 for PEG21800-(PLA)(8) and PEG43500-(PLA)(8), respectively. PEG-(PLA)(8) stereocomplexed hydrogels were prepared by mixing aqueous solutions with equimolar amounts of PEG-(PLLA)(8) and PEG-(PDLA)(8) in a polymer concentration range of 5-25 w/v % for PEG21800-(PLA)(8) star block copolymers and of 6-8 w/v % for PEG43500-(PLA)(8) star block copolymers. The gelation is driven by stereocomplexation of the PLLA and PDLA blocks, as confirmed by wide-angle X-ray scattering experiments. The stereocomplexed hydrogels were stable in a range from 10 to 70 degrees C, depending on their aqueous concentration and the PLA block length. Stereocomplexed hydrogels at 10 w/v % polymer concentration showed larger hydrophilic and hydrophobic domains as compared to 10 w/v % single enantiomer solutions, as determined by cryo-TEM. Correspondingly, dynamic light scattering showed that 1 w/v % solutions containing both PEG-(PLLA)(8) and PEG-(PDLA)(8) have larger "micelles" as compared to 1 w/v % single enantiomer solutions. With increasing polymer concentration and PLLA and PDLA block length, the storage modulus of the stereocomplexed hydrogels increases and the gelation time decreases. Stereocomplexed hydrogels with high storage moduli (up to 14 kPa) could be obtained at 37 degrees C in PBS. These stereocomplexed hydrogels are promising for use in biomedical applications, including drug delivery and tissue engineering, because they are biodegradable and the in-situ formation allows for easy immobilization of drugs and cells.     

Environmental degradation of polyester blends containing atactic poly(3-hydroxybutyrate). Biodegradation in soil and ecotoxicological impact

The degradation of poly[(R,S)-3-hydroxybutyrate], a-PHB, binary blends with natural PHB (n-PHB) and poly(L-lactic acid), PLLA, respectively, has been investigated in soil. In such a natural environment, a-PHB blend component was found to biodegrade. The degradation of a-PHB-containing blends proceeded faster than that of respective plain n-PHB and PLLA. The molecular weight decrease of the n-PHB component was higher, while the same rate of bioerosion of both components was observed for the a-PHB/n-PHB binary blend. For the a-PHB blend with PLLA, the weight loss was accompanied by blend composition changes and the decrease of a-PHB content. However, the PLLA molecular weight decrease was lower in the blend in comparison with the plain PLLA sample. The increase of the number of microorganisms particularly observed for the soil where binary blends were incubated indicates that microbial degradation of a-PHB takes place. The terrestrial plant growth test (cress and barley) demonstrates no environmental toxicity of the materials studied.     

Investigation of PLLA/PCL Blends and Paclitaxel Release Profiles

Blends of poly (l-lactide) (PLLA) and poly (ε-caprolactone) (PCL) with and without paclitaxel were prepared via solution casting. DSC analysis as well as SEM analysis of the PLLA/PCL blend solution cast films showed that these blends are all phase separated.%PLLA crystallinity was found to increase with increasing PCL content (up till 15 wt.%). The PCL phase is found to homogeneously disperse in the PLLA matrix as spherical domains where the pore diameters of the PCL domains significantly increased with increasing PCL content. The degradation profiles matched with the slower degrading component PCL rather than PLLA and also increasing PCL content of the blends increased the degradation rate relatively. The increased crystallinity of the PLLA phase with increasing PCL contents confirmed that the degradation occurred through PCL phase. Cell proliferation on PLLA/PCL blends showed that all these blends were suitable for the support of cellular growth. Apoptosis assay with the paclitaxel-loaded PLLA/PCL blends showed an increase in cell death throughout 7 days of incubation where the cell death was increased with increasing PCL contents. This was attributed to the faster release of paclitaxel which was at least partially affected by the faster degradation rate at increasing PCL contents. The paclitaxel release was shown to be degradation controlled in the initial stages followed by a faster diffusion-controlled release in the later stages. These polymer blends were found to be very suitable paclitaxel release agents for which the paclitaxel release times can be altered with the composition of the blend and the film thickness.     

Study on the enzymatic degradation of PBS and its alcohol acid modified copolymer

Enzymatic hydrolytic degradation of polybutylene succinate (PBS), poly(polybutylenesuccinate-co-1,4-cyclohexane dimethanol) (PBS/CHDM) and poly(polybutylene succinate-co-diglycolic acid) (PBS/DGA) in mixed solvent of tetrahydrofuran (THF) and toluene was examined. Lipase was used as catalyst to degrade polymers with molecular weight of more than 100,000, and the molecular weight of products ranged from hundreds to thousands. Thermal decomposition temperatures of all products were below 250°C. The degradation products of both PBS/CHDM and PBS/DGA showed two melting points at about 85 and 99°C. Mass spectrometry (MS) was employed to obtain the molecular weight of oligomers extracted from the products, which proved to be low-polyesters with the molecular weight of less 1,000. The butanediol (BDO) monomer was found in PBS/CHDM degradation product for the first time.     

Preparation of cellodextrins and isolation of oligomeric side components and their characterization

Cellodextrin (beta-1,4-glucose oligomer) mixtures are prepared by precipitation of oligomers with 1-propanol and ethanol after partial hydrolysis of cellulose with hydrochloric acid or by acetolysis of cellulose. Cellooligomers (DP3-DP8) can be isolated by high-resolution size-exclusion chromatography on Bio-Gel P 4 using water as eluent. Recycle operation of the columns allows the separation of oligomers up to a degree of polymerization of 12. However, ion-exchange chromatography of their borate complexes demonstrates the heterogeneity of cellodextrins, homogeneous according to size-exclusion chromatography. At least four secondary oligomeric components are observed in the different samples. By preparative affinity chromatography on phenyl-boronate-agarose two of these components could be purified and subsequently characterized. In one series of oligosaccharides the glucose unit at the reducing end of the beta-1,4-glucose oligomers is derivatized to fructose. This enolization reaction occurs during size-exclusion chromatography. The precipitation step with alkanols during preparation of oligomer mixtures generates oligomeric glycosides. Additionally, the formation of amines from respective beta-1,4-glucose oligomers is observed with the ammonium carbonate eluent used in affinity chromatography. Analysis methods combined to assess for the homogeneity of cellodextrins include enzyme- and acid-catalyzed (partial) hydrolysis of the different oligomers and subsequent analysis of degradation products by sugar borate chromatography; 13C and 1H NMR spectroscopy; and fast atom bombardment mass spectroscopy.     

Novel preparation method for poly(L-lactide)-based block copolymers: extended chain crystallites as a solid-state macro-coinitiator

A novel synthetic method for poly(L-lactide) (PLLA)-based diblock copolymers was developed by the use of PLLA extended chain crystallites (or crystalline residues) as a solid-state macro-coinitiator. In this study, we showed one example, i.e., a synthesis of diblock copolymer composed of a crystalline PLLA chain and an amorphous poly(DL-lactide) chain by ring-opening polymerization of DL-lactide initiated with stannous octoate (i.e., tin(II) 2-ethylhexanoate) in the presence of PLLA extended chain crystallites. The PLLA extended chain crystallites were prepared by hydrolytic degradation of crystallized PLLA films at 97 degrees C for 70 h. The chains inside the extended chain crystallites are expected to be protected from transesterfication reaction. Gel permeation chromatography, polarimetry, 1H NMR spectroscopy, wide-angle X-ray scattering, and differential scanning calorimetry revealed that the diblock copolymer poly(L-lactide-block-DL-lactide) was successfully prepared without significant transesterification.     

Thermal degradation processes of end-capped poly(L-lactide)s in the presence and absence of residual zinc catalyst

Thermal degradation processes of end-capped poly(L-lactide)s (PLLAs) were investigated by means of several thermoanalytical techniques under both isothermal and nonisothermal conditions. Based on the thermogravimetric analysis, it was found that two distinct processes at temperatures below and above 330 degrees C were existed in the nonisothermal degradation for PLLA samples depending on the amounts of residual zinc compounds from synthesis process. Isothermal degradation experiments at different temperature regions showed that the sample weight of PLLA decreased linearly with time in both cases, whereas the changes in molecular weight revealed different tendency for the temperature. On the basis of characterization of the residual PLLA molecules after isothermal degradation at 330 degrees C, it was confirmed that the omega chain end of the residual molecules was an acrylic ester unit. Majority of volatile products during thermal degradation of PLLA was the lactide regardless of the degradation temperature. From these results, it is concluded that, during the thermal degradation of PLLA samples in the presence of large amounts of residual zinc compounds, the zinc compounds catalyze both the intermolecular transesterification generating PLLA with low molecular weights and the selective unzipping depolymerization of PLLA with low molecular weights at temperatures below 330 degrees C. In contrast, the primary reaction of thermal degradation for PLLA in the absence of residual zinc compounds above 330 degrees C is a competition between the random chain scission via a cis-elimination reaction and the cyclic rupture via intramolecular transesterification of PLLA molecules. In addition, it was evidenced that the racemization of lactic acid units in the main chain of PLLA molecules occurred at temperatures above 330 degrees C.     

Depolymerisation and biodegradation of a synthetic tanning agent by activated sludges, the bacteria Arthrobacter globiformis and Comamonas testosteroni, and the fungus Cunninghamella polymorpha

Degradation of a synthetic tanning agent CNSF (a condensation product of 2-naphthalenesulfonic acid (2-NSA) and formaldehyde) by four activated sludges, two previously characterised bacterial strains, Arthrobacter sp. 2AC and Comamonas sp. 4BC, and the fungus Cunninghamella polymorpha, was studied in batch culture at 25°C by determining the changes in the concentrations of CNSF and its component monomers and oligomers (n2–n11). The loss of individual oligomers was correlated with the length of the NSA-CH₂ chain. Approximately 25% of the total CNSF was degraded (i.e. mineralised) by the microbes contained in the four activated sludges and by the two bacterial isolates but with different lag phases and at different overall rates. The decline in CNSF concentration was due almost entirely to the biodegradation of the monomers (34.3% of CNSF) and, in particular, 2-NSA (27% of CNSF). There was no change in the n2–n11 components. The growth of C. polymorpha, on the other hand, arose from extracellular depolymerisation of CNSF oligomers and the biodegradation of the lower molecular mass products. Between 38% and 42% of total CNSF was degraded by C. polymorpha at 25°C. The order of oligomer degradation was inversely related to degree of polymerisation. Eighty percent and 90% of the n4 and n5 and 100% oligomers n6–n11 were degraded after 120h. At a higher temperature (37°C) oligomers n4–n11 were degraded completely after 120h. A combination of biodegradation (75%) and sorption to fungal biomass (25%) accounted for the measured loss of all oligomers from the solution phase. The CNSF degradation rates and the volume of fungal biomass produced (and therefore the extent of biosorption) were dependent on the presence of a second carbon source (both optimum at glucose 5g/l). This is the first report that identifies and distinguishes between depolymerisation, sorption and biodegradation processes in the removal of CNSF and its component oligomers. The use of combinations of the depolymerising fungus C.polymorpha, and the monomer-degrading bacteria, Arthrobacter sp. 2AC and Comamonas sp. 4BC, have potential for wastewater treatment.     

In vivo study on the histocompatibility and degradation behavior of biodegradable poly(trimethylene carbonate-co-D,L-lactide)

The aim of this study was to explore the in vivo behavior and histocompatibility of poly(trimethylene carbonate-co-D,L-lactide) (PDLLA/TMC) and its feasibility of manufacturing cardiovascular stents. Copolymers with 50/50 molar ratio were synthesized by ring-opening polymerization with TMC and D, L-LA, or TMC and L-LA. Poly(L-lactide) (PLLA) was synthesized as a control. The films of the three polymers were implanted into 144 Wistar rats. At different time points of implantation, polymer films were explanted for the evaluation of degradation characteristics and histocompatibility using size exclusion chromatography , nuclear magnetic resonance , environmental scanning electron microscope , and optical microscope. Results showed that there were differences in the percentage of mass loss, molecular weight, shape and appearance changes, and inflammation cell counts between different polymers. With the time extended, the film's superficial structure transformed variously, which was rather obvious in the polymer of PDLLA/TMC. In addition, there were relatively lower inflammation cell counts in the PDLLA/TMC and poly(trimethylene carbonate-co-L-lactide) (PLLA/TMC) groups at different time points in comparison with those in the PLLA group. The differences were of statistical significance (P< 0.05) in the group of PDLLA/TMC vs. PLLA, and the group of PLLA/TMC vs. PLLA, but not within the PDLLA/TMC and PLLA/TMC groups (P> 0.05). These results suggested that the polymer of PDLLA/TMC (50/50) with favorable degradation performance and histocompatibility is fully biodegradable and suitable for manufacturing implanted cardiovascular stents.     

Characteristic chain-end racemization behavior during photolysis of poly(L-lactic acid)

Photolysis of poly(L-lactic acid) (PLLA) has many unclear points, such as the degradation mechanism, kinetics, products, and racemization mechanism. To clarify these features of PLLA photolysis, we examined the relationship between photolysis and racemization. The hexad stereosequential analysis of photodegraded PLLA was investigated to specify the racemized positions within a chain in comparison with hydrolysis and thermal degradation. Results from (13)C NMR spectra of UV-irradiated PLLA samples indicated that the samples have racemized d-lactate units at chain ends. From the comparison of racemization behavior among photolysis, hydrolysis, and thermal degradation, it was confirmed that the preferential racemization behavior of each of these three degradation processes is characteristic and distinct, being identified as chain-end racemization, poor racemization, or internal-unit racemization, respectively. The characteristic chain-end racemization behavior of photolysis was first confirmed in this study.     

Hydrolytic degradation of ricinoleic-sebacic-ester-anhydride copolymers

The degradation process of poly(ricinoleic-co-sebacic-ester-anhydride)s in buffer solution was investigated by following the composition of the degradation products released into the degradation medium and the degraded polymer. The first week of degradation was characterized by the hydrolysis of the anhydride bonds and significant release of sebacic acid (SA). The remaining oligoesters of SA and ricinoleic acid (RA) degraded into shorter oligoesters composed of RA ester dimers, trimers, and tetramers as well as dimers of RA-SA. To confirm and determine the hydrolytic behavior of the degradation products, short oligoesters of sebacic and ricinoleic acid were synthesized and degraded. It was established that during the hydrolysis under physiological conditions the degradation products have a composition and water absorption similar to those of the synthesized oligoesters.