Investigations into the characterization, degradation, and applications of biodegradable polymers by mass spectrometry.

Biodegradable polymers have been getting more and more attention because of their contribution to the plastic pollution environmental issues and to move towards a circular economy. Nevertheless, biodegradable materials still exhibit various disadvantages restraining a widespread use in the market. Therefore, additional research efforts are required to improve their performance. Mass spectrometry (MS) affords a relevant contribution to optimize biodegradable polymer synthesis, to confirm macromolecular structures, to examine along the time the progress of degradation processes and highlight advantages and drawbacks in the extensive applications. This review aims to provide an overview of the MS investigations carried out to support the synthesis of biodegradable polymers, with helpful information on undesirable products or polymerization mechanism, to understand deterioration pathways by the structure of degradation products and to follow drug release and pharmacokinetic. Additionally, it summarizes MS studies addressed on environmental and health issues related to the extensive use of plastic materials, that is, potential migration of additives or microplastics identification and quantification. The paper is focused on the most significant studies relating to synthetic and microbial biodegradable polymers published in the last 15 years, not including agro-polymers such as proteins and polysaccharides.

Matrix-Assisted Laser Desorption and Electrospray Ionization Tandem Mass Spectrometry of Microbial and Synthetic Biodegradable Polymers.

The in-depth structural and compositional investigation of biodegradable polymeric materials, neat or partly degraded, is crucial for their successful applications. Obviously, an exhaustive structural analysis of all synthetic macromolecules is essential in polymer chemistry to confirm the accomplishment of a preparation procedure, identify degradation products originating from side reactions, and monitor chemical-physical properties. Advanced mass spectrometry (MS) techniques have been increasingly applied in biodegradable polymer studies with a relevant role in their further development, valuation, and extension of application fields. However, single-stage MS is not always sufficient to identify unambiguously the polymer structure. Thus, tandem mass spectrometry (MS/MS) has more recently been employed for detailed structure characterization and in degradation and drug release monitoring of polymeric samples, among which are biodegradable polymers. This review aims to run through the investigations carried out by the soft ionization technique matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) and electrospray ionization mass spectrometry (ESI-MS) MS/MS in biodegradable polymers and present the resulting information.

Calix[4]arene Derivative for Iodine Capture and Effect on Leaching of Iodine through Packaging.

A hydrophobic calix[4]arene derivative was investigated for its iodine (I2) capture efficiency from gaseous and liquid phase. The iodine uptake was followed by UV-vis spectroscopy. Additionally, the influence of the calix[4]arene derivative-polyolefin system on the leaching of iodine through packaging from a povidone-iodine-based (PVP-I) formulation was evaluated. In fact, iodine is a low-cost, multi-target, and broad-spectrum antiseptic. However, it is volatile, and the extended storage of I2-based formulations is challenging in plastic packaging. Here, we investigated the possibility of reducing the loss of I2 from an iodophor formulation by incorporating 4-tert-butylcalix [4]arene-tetraacetic acid tetraethyl ester (CX) and its iodine complex in high-density polyethylene (HDPE) or polypropylene (PP) via a swelling procedure. Surface and bulk changes were monitored by contact angle, thermogravimetric analysis (TGA), and UV-vis diffuse reflectance spectra. The barrier effect of the different polymeric systems (embedded with CX, iodine-CX complex, or I2) was evaluated by monitoring the I2 retention in a buffered PVP-I solution by UV-vis spectroscopy. Overall, experimental data showed the capability of the calix[4]arene derivative to complex iodine in solution and the solid state and a significant reduction in the iodine leaching by the PP-CX systems.

Synthesis, Characterization, and Soil Burial Degradation of Biobased Polyurethanes.

There is an urgent need for developing degradable polymeric systems based on bio-derived and sustainable materials. In recent years, polyurethanes derived from castor oil have emerged due to the large availability and sustainable characteristics of castor oil. However, these polymers are normally prepared through tedious and/or energy-intensive procedures or using high volatile and/or toxic reagents such as volatile isocyanates or epoxides. Furthermore, poor investigation has been carried out to design castor oil derived polyurethanes with degradable characteristics or thorough specifically sustainable synthetic procedures. Herein, castor oil-derived polyurethane with more than 90% biomass-derived carbon content and enhanced degradable features was prepared through a simple, eco-friendly (E-factor: 0.2), and scalable procedure, employing a recently developed commercially available biomass-derived (61% bio-based carbon content) low-volatile polymeric isocyanate. The novel material was compared with a castor oil derived-polyurethane prepared with a commercially available fossil-based isocyanate counterpart. The different castor oil-derived polyurethanes were investigated by means of water uptake, soil burial degradation, and disintegration tests in compost. Characterization analyses, including thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and scanning electron microscopy (SEM), were carried out both prior to and after degradation tests. The results suggest potential applications of the degradable castor oil-derived polyurethane in different fields, such as mulch films for agricultural purposes.

Influence of Calcium Carbonate Nanoparticles on the Soil Burial Degradation of Polybutyleneadipate-Co-Butylenetherephthalate Films.

A polybutyleneadipate-co-butylenetherephthalate (PBAT) sample, commercially known as Ecoflex®, was processed via melt extrusion with CaCO3 nanoparticles coated with a hydrophobic coating. Blown films of PBAT and two composites with nanofiller (2% and 5%wt) were prepared and degradation tests in soil at 30 °C up to 180 days were carried out with weight loss measurements. Furthermore, biodegradation test according to ISO 14851 was carried out at 30 °C. The effect of CaCO3 on soil burial degradation was assessed by surface wettability and SEM. ATR-FTIR and XPS analyses highlighted chemical modifications induced by soil degradation. CaCO3 nanoparticles decreased surface wettability and discouraged the disintegration in soil. Interestingly, SEM images after soil degradation highlighted in the nanocomposite films selective zones of disintegration. XPS showed an increasing peak area C 1s ratio of C-O to C=O with degradation time. Moreover, after the soil burial test, carbonyl index determined by ATR-FTIR increased in both nanocomposites. In fact, the addition of CaCO3 leads to a rise in the carbonyl zone due to the presence of the carbonate group. Remarkably, FTIR data after soil degradation showed an enrichment of the aromatic content, a preferential cleavage and erosion of the aliphatic moiety in PBAT films, amplified by the presence of the CaCO3 nanofiller.

Sequencing Biodegradable and Potentially Biobased Polyesteramide of Sebacic Acid and 3-Amino-1-propanol by MALDI TOF-TOF Tandem Mass Spectrometry.

Biodegradable and potentially biobased polyesteramide oligomers (PEA-Pro), obtained from melt condensation of sebacic acid and 3-amino-1-propanol, were characterized by nuclear magnetic resonance (NMR), matrix assisted laser desorption/ionization-time of flight/time of flight-mass spectrometry/mass spectrometry (MALDI-TOF/TOF-MS/MS), thermogravimetric analysis (TGA), and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). NMR analysis showed the presence of hydroxyl and amino terminal groups as well as carboxylic groups of the sebacate moiety. Hydroxyl and carboxyl termination had the same abundance, while the amine termination was 2.7-times less frequent. Information regarding the fragmentation pathways and ester/amide bond sequences was obtained by MALDI-TOF/TOF-MS/MS analysis performed on sodiated adducts of cyclic species and linear oligomers. Different end groups did not influence the observed fragmentation. Three fragmentation pathways were recognized. The ß-hydrogen-transfer rearrangement, which leads to the selective scission of the -O-CH2- bonds, was the main mechanism. Abundant product ions originating from -CH2-CH2- (ß-γ) bond cleavage in the sebacate moiety and less abundant ions formed by -O-CO- cleavages were also detected. TGA showed a major weight loss (74%) at 381 °C and a second degradation step (22% weight loss) at 447 °C. Py-GC/MS performed in the temperature range of 350-400 °C displayed partial similarity between the degradation products and the main fragments detected in the MALDI-TOF/TOF-MS/MS experiments. Degradation products derived from amide bonds were related to the formation of CN groups, in agreement with the literature.

Compostable Polylactide and Cellulose Based Packaging for Fresh-Cut Cherry Tomatoes: Performance Evaluation and Influence of Sterilization Treatment.

For food packaging, plastic materials display large appeal, mostly due to their versatility, mechanical, optical and barrier properties. However, they play an important role in environmental concerns and waste management issue. Compostable bioplastics represent alternative materials designed for a lower environmental impact. In this work, a biobased compostable packaging, constituted by polylactide (PLA) trays and NatureFlex™ film, was evaluated for fresh-cut cherry tomato. A comparative analysis was accomplished using traditional packaging materials, that is, polyethylene terephtalate (PET) trays and polypropylene (PP Coex) film. Structural stability under food contact conditions, mechanical and physical-chemical properties were investigated. Tensile mechanical properties, puncture resistance, contact angle (CA) and attenuated total reflection Fourier-transform infrared spectroscopy (ATR-FTIR), before and after UV or radiofrequency (RF) sterilization treatment, were evaluated. UV irradiation method resulted the less invasive one. Therefore, oxygen and water vapor transmission rate (OTR and WVTR), overall chemical migration test, biodegradation assessment by biochemical oxygen demand (BOD) according to ISO 14851 and disintegration test by ISO 20200 were carried out to establish the further influence of UV sterilization on the packaging. Overall, data showed that the biobased compostable packaging for a prolonged shelf-life of fresh-cut cherry tomato has better properties that were surprisingly enhanced by the UV treatment.

Comparative Investigation on the Soil Burial Degradation Behaviour of Polymer Films for Agriculture before and after Photo-Oxidation.

Polymer films based on biodegradable polymers, polyethylene (PE) and modified PE with oxo-degradable additive were prepared by film blowing. Carbon black (1%) was added to all the films. Commercial biodegradable Ecovio® and Mater-Bi® samples were used. Mechanical properties, soil burial degradation and surface wettability were investigated, before and after UV irradiation. Chemical modifications induced by UV and soil degradation, or a synergic effect, were highlighted by Attenuated Total Reflection-Fourier Transform Infra-Red (ATR-FTIR). Photo-oxidized film samples with an elongation at break equal to 50% and 0.5 the initial value were selected for the soil burial degradation test at 30 °C. Weight loss measurements were used to follow biodegradation in soil. Predictably, the degradation in soil was higher for biodegradable polymer-based films than for the PE-based ones. UV irradiation increased surface wettability and encouraged the disintegration in soil of all the samples. In fact, photo-oxidation produced a molar mass reduction and hydrophilic end groups, thus increasing surface erosion and weight loss. This paper not only supplies new criteria to evaluate the performance of biodegradable films in agriculture, before and after lifetime, but also provides a comparative analysis on the soil burial degradation behaviour with traditional ones.

Mass spectrometry in bioresorbable polymer development, degradation and drug-release tracking.

A detailed characterization of polymeric matrices and appropriate degradation monitoring techniques are required to sustain the development of new materials as well as to enlarge the applications of the old ones. In fact, polymer analysis is essential for the clarification of the intrinsic relationship between structure and properties that ascertains the industrial applications in diverse fields. In bioresorbable and biodegradable polymers, the role of analytical methods is dual since it is pointed both at the polymeric matrices and at degradation tracking. The structural architectures, the mechanical and morphological properties, and the degradation rate, are of outstanding importance for a specific application. In some cases, the complexity of the polymer structure, the processes of decomposition or the low concentration of the degradation products need the concurrent use of different complementary analytical techniques to give detailed information of the reactions taking place. Several analytical methods are used in bioresorbable polymer development and degradation tracking. Among them, mass spectrometry (MS) plays an essential role and it is used to refine polymer syntheses, for its high sensitivity, to highlight degradation mechanism by detecting compounds present in trace amounts, or to track the degradation product profile and to study drug release. In fact, elucidation of reaction mechanisms and polymer structure, attesting to the purity and detecting defects as well as residual catalysts, in biodegradable and bioresorbable polymers, requires sensitive analytical characterization methods that are essential in providing an assurance of safety, efficacy and quality. This review aims to provide an overview of the MS strategies used to support research and development of resorbable polymers as well as to investigate their degradation mechanisms. It is focused on the most significant studies concerning synthetic bioresorbable matrices (polylactide, polyglycolide and their copolymers, polyhydroxybutyrate, etc.), published in the last ten years.

Photo-Oxidative and Soil Burial Degradation of Irrigation Tubes Based on Biodegradable Polymer Blends.

Irrigation tubes based on biodegradable polymers were prepared via an extrusion-drawing process by Irritec and compared to conventional pipes made of high-density polyethylene (HDPE). A commercial polylactide/poly (butyleneadipate-co-butyleneterephthalate) (PLA/PBAT) blend (Bio-Flex®) and Mater-Bi® were used. The polymers were characterized from rheological and mechanical points of view. Irrigation pipes were subjected to photoaging with continued exposure to UV radiation up to 22 days. The degradability in the soil of irrigation tube samples was studied. The influence of temperature and UV irradiation on soil burial degradation was investigated. A soil burial degradation test was carried out at 30 °C and 50 °C for up to 70 days. The degree of degradation was evaluated from the weight loss percentage. The degradation rate of irrigation tube samples based on Mater-Bi® was higher at 30 °C and was stimulated after 14 days of UV irradiation. Higher temperatures or UV aging encouraged the disintegration in soil of Bio-Flex®-based irrigation tubes. Furthermore, tube samples, before and after UV and soil burial degradation, were analyzed by Attenuated Total Reflection-Fourier Transform Infra-Red (ATR-FTIR) spectroscopy.

Modern mass spectrometry in the characterization and degradation of biodegradable polymers.

In the last decades, the solid-waste management related to the extensively growing production of plastic materials, in concert with their durability, have stimulated increasing interest in biodegradable polymers. At present, a variety of biodegradable polymers has already been introduced onto the market and can now be competitive with non biodegradable thermoplastics in different fields (packaging, biomedical, textile, etc.). However, a significant economical effort is still directed in tailoring structural properties in order to further broaden the range of applications without impairing biodegradation. Improving the performance of biodegradable materials requires a good characterization of both physico-chemical and mechanical parameters. Polymer analysis can involve many different features including detailed characterization of chemical structures and compositions as well as average molecular mass determination. It is of outstanding importance in troubleshooting of a polymer manufacturing process and for quality control, especially in biomedical applications. This review describes recent trends in the structural characterization of biodegradable materials by modern mass spectrometry (MS). It provides an overview of the analytical tools used to evaluate their degradation. Several successful applications of MALDI-TOF MS (matrix assisted laser desorption ionization time of flight) and ESI MS (electrospray mass spectrometry) for the determination of the structural architecture of biodegradable macromolecules, including their topology, composition, chemical structure of the end groups have been reported. However, MS methodologies have been recently applied to evaluate the biodegradation of polymeric materials. ESI MS represents the most useful technique for characterizing water-soluble polymers possessing different end group structures, with the advantage of being easily interfaced with solution-based separation techniques such as high-performance liquid chromatography (HPLC).

Matrix-assisted laser desorption ionization time-of-flight/time-of-flight tandem mass spectra of biodegradable polybutylenesuccinate.

RATIONALE: Matrix-Assisted Laser Desorption/Ionization Time-Of-Flight/Time-Of-Flight Tandem Mass Spectrometry (MALDI-TOF MS/MS) was employed to analyze five poly(butylene succinate) (PBSu) oligomers and to investigate their fragmentation pathways. METHODS: MALDI-TOF MS/MS analysis was performed on cyclic and linear oligomers terminated by dicarboxyl groups, carboxyl and hydroxyl groups, hydroxyl and olefin groups, and dihydroxyl groups. The sodium adduct ions of these oligomers were selected as precursor ions. Experiments were carried out with and without argon as the collision gas. RESULTS: A ß-hydrogen transfer rearrangement, leading to the selective cleavage of the -O-CH2- bonds, and cleavage of the -CH2-CO- bonds, the ester bonds, and the -CH2-CH2- bonds in the diol moiety were observed. Two fragmentation mechanisms, correlated to the end-group structure of the precursor ions, were also proposed. The detection of cyclic anhydrides was related to the presence of succinic acid terminal groups. The formation of microcyclic oligoesters probably occurred via an intramolecular transesterification mechanism involving a hydroxyl end group. CONCLUSIONS: A ß-hydrogen transfer rearrangement has been proposed as the main fragmentation mechanism occurring in PBSu without using the collision gas. Cleavages of almost all types of bonds take place in the MALDI CID experiments. According to the structures of the most abundant product ions, six fragmentation pathways have been proposed when using argon as the collision gas. Two fragmentation mechanisms were suggested as being correlated to the end-group structure of the precursor ions.

Direct electrospray ionization mass spectrometry quantitative analysis of sebacic and terephthalic acids in biodegradable polymers.

A direct, rapid, and easy electrospray ionization mass spectrometry (ESI-MS) method to determine concentrations of sebacic acid (SA) and terephthalic acid (TA) residues in biodegradable copolymers was developed. Copolyester samples were synthesized from 1,4-butanediol and sebacic and terephthalic acids by melt polymerization. Extraction of monomers was performed in methanol. Their concentrations were determined by direct infusion ESI-MS, without chromatographic separation, using 1,12-dodecanedioic acid (DDA) as an internal standard. Calibration curves were obtained by plotting the ratio of the areas of the peaks relative to monomers and DDA standard as a function of their concentration ratio. We validated the method by determining the concentration of TA residue using both the ESI-MS protocol and high-performance liquid chromatography (HPLC) analysis with UV detection. The linearity range and the detection limit of this assay were 0.1-5.0 and 0.01 ppm for SA and 0.1-6.0 and 0.03 ppm for TA. This assay represents a useful alternative to conventional methods currently employed for acid quantification, resulting advantageous for its speed and high sensitivity.

Structural characterization of synthetic poly(ester amide) from sebacic acid and 4-amino-1-butanol by matrix-assisted laser desorption ionization time-of-flight/time-of-flight tandem mass spectrometry.

Matrix-assisted laser desorption/ionization time-of-flight/time-of-flight tandem mass spectrometry (MALDI-TOF/TOF-MS/MS) was employed to analyze a poly(ester amide) sample (PEA-Bu) from the melt condensation of sebacic acid and 4-amino-1-butanol. In particular, we investigated the fragmentation pathways, the ester/amide bond sequences and the structure of species derived from side reactions during the synthesis. MALDI-TOF/TOF-MS/MS analysis was performed on cyclic species and linear oligomers terminated by dicarboxyl groups, carboxyl and hydroxyl groups and diamino alcohol groups. The sodium adducts of these oligomers were selected as precursor ions. Different end groups do not influence the fragmentation of sodiated poly(ester amide) oligomers and similar series of product ions were observed in the MALDI-TOF/TOF-MS/MS spectra. According to the structures of the most abundant product ions identified, the main cleavages proceed through a beta-hydrogen-transfer rearrangement, leading to the selective scission of the --O--CH2-- bonds. Abundant product ions originating from --CH2--CH2-- (beta-gamma) bond cleavage in the sebacate moiety were also detected. Their formation should be promoted by the presence of an alpha,beta-unsaturated ester or amide end group. MALDI-TOF/TOF-MS/MS provided structural information concerning the ester/amide sequences in the polymer chains. In the MALDI-TOF/TOF-MS/MS spectra acquired, using argon as the collision gas, of cyclic species and linear oligomers terminated by diamino alcohol groups, product ions in the low-mass range, undetected in the mass spectra acquired using air as the collision gas, proved to be diagnostic and made it possible to establish the presence of random sequences of ester and amide bonds in the poly(ester amide) sample. Furthermore, MALDI-TOF/TOF-MS/MS provided useful information to clarify the structures of precursor ions derived from side reactions during the synthesis.

Matrix-assisted laser desorption/ionization time-of-flight/time-of-flight tandem mass spectra of poly(butylene adipate).

Matrix-assisted laser desorption/ionization time-of-flight/time-of-flight tandem mass spectrometry (MALDI-TOF/TOF-MS/MS) was employed to analyze four poly(butylene adipate) (PBAd) oligomers and to investigate their fragmentation pathways as a continuation of our work on the MALDI-TOF/TOF-MS/MS study of synthetic polymers. MALDI-TOF/TOF-MS/MS analysis was performed on oligomers terminated by carboxyl and hydroxyl groups, methyl adipate and hydroxyl groups, dihydroxyl groups, and dicarboxyl groups. The sodium adducts of these oligomers were selected as precursor ions. Different end groups do not influence the fragmentation of sodiated polyester oligomers and similar series of product ions were observed in all the MALDI-TOF/TOF-MS/MS spectra. According to the structures of the most abundant product ions identified in the present work, three fragmentation pathways have been proposed to occur most frequently in PBAd: beta-hydrogen-transfer rearrangement, leading to the selective cleavage of the --O--CH(2)-- bonds; --CH(2)--CH(2)-- (beta--beta) bond cleavage in the adipate moiety; and ester bond scission.

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry with size-exclusion chromatographic fractionation for structural characterization of synthetic aliphatic copolyesters.

We report matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) and off-line coupling of size-exclusion chromatography with MALDI-TOFMS analysis (SEC/MALDI-TOFMS) methods for the detailed characterization of poly[(R,S)-3-hydroxybutyrate-co-L-lactic acid], P[(R,S)-3HB-co-LA], and poly[(R,S)-3-hydroxybutyrate-co-epsilon-caprolactone], P[(R,S)-3HB-co-CL], copolymer samples which are expected to be used in special medical application as scaffolds for cartilage and soft tissue engineering. The novel copolyesters contained randomly distributed (R,S)-3-hydroxybutyrate structural units, were synthesized by transesterification of the corresponding homopolymers, i.e. atactic poly[(R,S)-3-hydroxybutyrate], a-PHB, and poly(L-Lactide) (PLLA) or poly(epsilon-caprolactone) (PCL), respectively. The MS methods used for the characterization of the resulting polydisperse copolyester samples were supported by classical methods (NMR, SEC). The structures of individual copolyester macromolecules, including end-group chemical structures, were established using initially MALDI-TOFMS and then SEC/MALDI-TOFMS. The compositions of the copolyesters were determined by two methods, namely based on 1H NMR and MALDI-TOF spectra. The two sets of values showed good agreement. The sequence distribution was determined using the signal intensities of individual copolyester macromolecules, which appeared in MALDI-TOF mass spectra. Furthermore, sequence analysis gave information about the degree of transesterification. The copolyesters synthesized, with only one exception, were demonstrated to be almost random, which implies that the ester-ester exchange was close to completion.

Sequence determination in aliphatic poly(ester amide)s by matrix-assisted laser desorption/ionization time-of-flight and time-of-flight/time-of-flight tandem mass spectrometry.

Poly(ester amide)s from dimethyl sebacate or sebacic acid and 2-aminoethanol or 4-amino-1-butanol were characterized by post-source decay matrix-assisted laser desorption/ionization time-of-flight (PSD-MALDI-TOF) and time-of-flight/time-of-flight tandem mass spectrometry (MALDI-TOF/TOF-MS/MS). Sodiated oligomers were selected as precursor ions for dissociation studies. PSD analysis was performed on dimethyl sebacate, dicarboxylic, carboxylic and amino alcohol, and diamino alcohol terminated oligomers. PSD-MALDI-TOF mass spectra yielded information on the fragmentation mechanisms of the poly(ester amide) chains, showing that the main cleavages proceed through a beta-hydrogen transfer rearrangement. MALDI-TOF/TOF-MS/MS provided structural information concerning ester/amide sequences in the polymer chains. As expected, together with the ions appearing in the PSD-MALDI mass spectrum, several new abundant fragment ions in the low-mass range are present in MALDI-TOF/TOF-MS/MS spectra. These new product ions proved to be diagnostic and made it possible to establish the presence of random sequences of ester and amide bonds in the poly(ester amide)s samples.

Evidence for selective hydrolysis of aliphatic copolyesters induced by lipase catalysis.

High molar mass random poly(butylene succinate-co-butylene sebacate), P(BS-co-BSe), and poly(butylene succinate-co-butylene adipate), P(BS-co-BA), with different composition, were synthesized and subjected to enzymatic hydrolysis by Lipase from Mucor miehei or from Rhizopus arrhizus. The enzymatic hydrolysis of P(BS-co-BSe)s and P(BS-co-BA)s films produced a mixture of water-soluble monomers and co-oligomers that were separated and identified by on-line high performance liquid chromatography/electrospray ionization mass spectrometry (HPLC/ESI-MS). Optimization of the HPLC analysis allowed the separation of isobar co-oligomers, differing only for the co-monomers sequence. Oligomers with the same monomer composition and molar mass but different sequence were identified by HPLC/ESI-MS-MS on-line analysis. The results obtained show a preferential hydrolytic cleavage induced by the lipases used. In particular, these enzymes prefer cleaving sebacic ester bonds in P(BS-co-BSe) copolymers, whereas succinic ester bonds appear to be hydrolyzed faster than adipic ester bonds in P(BS-co-BA) copolyesters. 1H NMR analysis further substantiates these findings. The primary products generated by lipase hydrolysis of polyester films underwent further degradation at longer reaction times. The HPLC/ESI-MS analysis of these mixtures at various times provided the first evidence that lipase catalysis is active also in water solution, a hydrophobic effect induced by the aliphatic units of these polyesters.