Degradation of the blends of natural and synthetic copolyesters in different natural environments

The paper presents results of the biodegradation of the blends of natural and synthetic copolyesters in two different natural environments. Environmental degradation took place in compost with activated sludge at sewage farm and - for comparison - in the Baltic Sea in Gdynia Harbour. Degradation of these blends was monitored for 16 weeks in compost and for 6 weeks in sea water. The changes in macroscopic features of surface and the weight loss of the samples were measured during the performed experiment. The characteristic parameters of compost and sea water were also controlled during all incubation time and their influence on the rate of biodegradation is discussed. The results of this study revealed that the natural aliphatic copolyester i.e. 3-hydroxybutyrate-co-3-hydroxyvalerate (PHBV) and its blends with the synthetic aliphatic-aromatic copolyester of 1,4-butandiol with adipic and terephthalic acids degrade faster in compost than in sea water. The rate of the biodegradation process depends on the composition of blends and different abiotic parameters of compost and sea water.     

Influence of biodegradation on crystallization of poly (butylene adipate‐co‐terephthalate)

The biodegradation of aromatic‐aliphatic biodegradable polyester poly (butylene adipate‐co‐terephthalate) (PBAT) was studied under mesophilic (37°C) and thermophilic (55°C) anaerobic conditions. Anaerobic sludge from municipal wastewater treatment plant was utilized as an inoculum. Non‐isothermal crystallization kinetics of PBAT before and after biodegradation was explored by differential scanning calorimetry. Under mesophilic anaerobic conditions (37°C), the biodegradation after 126 days was only 2.2%, molecular weight changed from 93 000 to 25 500 g/mol, and the crystallization behavior was changed only slightly. However, biodegradation under thermophilic anaerobic conditions (55°C) caused much bigger changes: biodegradation according to biogas production reached after 126 days 8.3%, molecular weight changed from 93 000 to 9430 g/mol, and the crystallization behavior was changed significantly. While T_m increased only slightly, T_c on the other hand increased significantly for the sample after biodegradation at 55°C. Also, the crystallization rate was slower (particularly at lower cooling rates), but crystallinity was slightly higher. The diffraction pattern was observed by X‐ray diffraction.     

Synthesis and hydrolytic degradation of poly(ethylene succinate) and poly(ethylene terephthalate) copolymers

The conditions of synthesis of statistical poly(ethylene succinate-co-terephthalate) copolymers (2GTS) and high molecular weight poly(ethylene succinate) (PES) with good hydrolytic and optical parameters, designed for the production of biodegradable products and resins, are presented in this article. Copolymers were prepared by melt polycondensation of bis-(β-hydroxyethylene terephthalate) (BHET) and succinic acid (SA) with excess of ethylene glycol (2G) in the presence of a novel titanium/silicate catalyst (C-94) and catalytic grade of germanium dioxide (GeO₂) as cocatalyst. The chemical structure and physical properties of those materials were characterized by ¹H NMR, FT-IR, dynamical-mechanical thermal analyses (DMTA), differential scanning calorimetry (DSC), solution viscosity and spectroscopic methods. The hydrolytic degradation was performed in a water solution with variable pH, also in garden soil and in compost. The highest hydrolytic degradation rate was observed for pH 4 and for compost. Better hydrolytic degradation values in compost medium were observed for copolyester prepared in the presence of GeO₂ as polycondensation cocatalyst. The copolyester with 40 mol% of aliphatic units was chosen for industrial syntheses which were performed in ELANA and subsequently the processing parameters and compatibility with potato starch of this polyester were checked by BIOP Biopolymer Technologies AG.     

Reduction of pathogenic bacteria in organic compost using gamma irradiation

Organic compost is a useful fertilizer for organic farming. However, it poses a microbiological hazard to the farm products because most of the composts are originated from excremental matters of domestic animals. In this study, the radiation treatment was performed to improve microbiological safety of organic compost and the effectiveness of gamma irradiation for inactivating Salmonella Typhimurium and Escherichia coli was investigated. The total aerobic and coliform bacteria in the 16 commercial composts were ranged from 10⁵ to 10⁷ CFU/ml and 0 to 10³ CFU/ml, respectively. All coliform bacteria in the composts were eliminated by irradiation at a dose of 3 kGy, while about 10² CFU/ml of the total aerobic bacteria were survived up to 10 kGy. In the artificial inoculation test, the test organisms (inoculated at 10⁷ CFU/g) were eliminated by irradiation at 3 kGy. Approximate D₁₀ values of Salmonella Typhimurium and E. coli in the compost were 0.40 and 0.25 kGy, respectively. In the cultivation test, the test organisms of the compost had transfer a lettuce leaves. The growth pattern of lettuce was not different between irradiated and non-irradiated composts.     

Lignocellulose degradation in mushroom composts

The edible mushroomAgaricus bisporus is grown commercially on composted manure/straw mixtures. However, this proven composting procedure is wasteful of raw materials. A nonmanure compost was developed (Smith, 1980) with two main aims:

1. To conserve raw materials, while still producing a compost favoringAgaricus bisporus colonization and giving an economic yield of mushrooms.
2. To speed up composting, hence making more efficient use of labor, farm equipment, and buildings.

A “conservation compost” (wheat straw, bran, whey, urea, peat, and gypsum) is ready for inoculation with mushroom mycelium (spawning) after 7 d preparation, i.e., 2 d pre-wetting of straw, then 4–5 d composting under controlled conditions. Whereas a traditional manure/wheat straw compost is produced by composting in windrows (8–11 d) followed by a controlled pasteurization phase (5–7 d). In the preparation of a traditional mushroom compost, as much as 60% of the initial dry matter is lost by microbial degradation prior to spawning. By shortening the composting process to 7 d conservation of cellulose and hemicellulose is achieved with only some 30% loss in dry matter. Straw hemicelluloses are degraded much quicker than cellulose during composting. Hence, the measurable extracellular laminarinase and xylanase activities of the compost microflora appear much greater than their cellulase activities at this period in both composts. A peak in laminarinase and xylanase activity after 48 h in manure compost corresponds with the increase in microbial populations. A pronounced increase in thermophilic bacterial and actinomycete populations occurs in “conservation composts” as readily available soluble carbohydrates are assimilated. Initially, this results in higher uniform compost temperatures (60?C+) and leads to a reduced thermophilic fungal population (10³ viable propagules g^-1 dry wt compost), which may explain the lowered enzyme activities found in the “conservation composts” and thus the reduced degradation of lignocellulose. The compost microflora showed no laccase activity during composting, and little if any lignin was degraded. However,Agaricus bisporus does possess a moderately active lignolytic system and a strongly active cellulolytic system. Subsequent experiments have shown that increased mushroom yields may be obtained from these composts when urea is replaced by chicken manure as the nitrogen supplement (Smith, 1983); this has not affected compost “selectivity” for mushroom growth, dry matter loss, or the duration of the process. Although yield of mushrooms, based on compost weights at spawning tend to be lower than what would be expected from traditional composts, yield calculated on the basis of weight of starting materials is usually much higher.     

Degradation of aliphatic and aliphatic–aromatic co-polyesters by depolymerases from Roseateles depolymerans strain TB-87 and analysis of degradation products by LC-MS

The degradation activities of bacterium, Roseateles depolymerans TB-87 and its depolymerases Est-H and Est-L against aliphatic as well as aliphatic–aromatic co-polyesters, were investigated. Strain TB-87 and its enzymes exhibited an ability to degrade aliphatic and aliphatic–aromatic co-polyesters. Monomers produced as a result of degradation of aliphatic polyesters [poly(butylene succinate) (PBS), poly(butylene succinate-co-adipate) (PBSA)] as well as aliphatic–aromatic co-polyester [poly(butylene succinate/terephthalate/isophthalate)-co-(lactate) (PBSTIL) by depolymerases Est-H and Est-L were investigated by liquid chromatography mass-spectrometry (LC-MS). Some common monomers like succinic acid and 1,4-butanediol were detected besides adipic acid and terephthalic/isophthalic acids as degradation products from PBSA and PBSTIL, respectively, whereas lactic acid was not detected. The succinic acid monomer was detected prior to adipic acid as a result of degradation of PBSA. The enzymes depolymerized PBS also into respective monomers. The analysis of PBSTIL degradation products revealed that enzymes easily degraded aliphatic segments as compared to aromatic segments and resulted in production of succinic acid prior to terephthalic and isophthalic acid. On the basis of these results, we speculate that both the enzymes Est-H and Est-L, attacked succinic acid segments (BS) first instead of adipic acid (BA) and terephthalic/isophthalic acid (BT or BI) segments of PBSA and PBSTIL, respectively. It is concluded from the results that R. depolymerans strain TB-87 can depolymerize aliphatic as well as aliphatic–aromatic co-polyesters; therefore, its enzymes can be applied in the process of biochemical monomer recycling.     

Characterization of a mesophilic aliphatic-aromatic copolyester-degrading fungus

We isolated 5 mesophilic microorganisms that form clear zones around the colony on an opaque medium containing the aliphatic-aromatic copolyester poly(60 mol% butylene adipate-co-40 mol% butylene terephthalate) (PBAT). Among all strains, the fungal strain NKCM1712 degraded PBAT at the fastest rate (3.5 ± 0.3 μg cm⁻² h⁻¹). Genetic and morphological analyses revealed that this strain was closely related to Isaria fumosorosea (phylum Ascomycota). Mass spectroscopic analysis revealed that the degradation products were T, AB, TB, BAB, and ABT (T, terephthalic acid unit; A, adipic acid unit; B, 1,4-butanediol unit)] in the culture of the strain that used PBAT as the sole carbon source. Furthermore, the PBAT degradation ability of this strain in terms of BOD suggested that it could utilize the PBAT degradation products as growth substrates. This is the first report of a mesophilic strain that can mineralize an aliphatic-aromatic polyester into carbon dioxide on its own.     

The morphological effects upon enzymatic degradation of poly(butylene succinate-co-butylene terephthalate)s (PBST)

In this work, the enzymatic degradation of poly(butylene succinate-co-butylene terephthalate) (PBST) copolyesters was studied using the lipase from Pseudomonas (Lipase PS^®). The biodegradation behavior was found to strongly depend on the overall impacts of several important factors as the BT comonomer structure and molar content, thermal characteristics, morphology, the enzyme-substrate, and so forth. Further, the biodegraded residual film samples were allowed to be analyzed by means of gel permeation chromatography (GPC), proton nuclear magnetic resonance (¹H NMR), differential scanning calorimeter (DSC), small angle X-ray scattering (SAXS), and scanning electron microscope (SEM). On the experimental evidences, an exo-type mechanism of enzymatic chain hydrolysis preferentially occurring in the amorphous region was suggested for the PBST film samples.     

Microstructure elucidation of poly(epichlorohydrin) modified with thiol compounds using one- and two-dimensional NMR spectroscopy

Poly(epichlorohydrin) has been modified chemically using aromatic and aliphatic thiol compounds. The NMR results show that using both aromatic and aliphatic thiols, one achieves degrees of modification of up to 90% without any elimination side reaction. As a consequence no degradative chain-scission takes place. A microstructural analysis of the modified polymers has been carried out by ¹³C NMR, ¹H NMR and ¹³C DEPT spectroscopy. Additionally, 2D heteronuclear correlated spectroscopy (HMQC and HMBC) were used in order to determine the chemical shifts of quaternary carbons.     

Formulation selection of aliphatic aromatic biodegradable polyester film exposed to UV/solar radiation

Aliphatic aromatic copolyester films, poly(butylene adipate-co-terephthalate) or PBAT, are susceptible to photodegradation, leading to main chain scission and crosslinking. The presence of crosslinked structures not only decreased the mechanical properties of the film due to embrittlement, but also hindered the biodegradation process by limiting access of water and microorganisms to the polymer chains. This has limited the use of PBAT for outdoor applications, such as mulch films. In this study, response surface methodology (RSM) was used to determine the optimal concentrations of carbon black (CB) and the chain breaking antioxidant butylated hydroxytoluene (BHT) for the design of mulch films that can prevent the formation of crosslinked structures from recombination of free radicals. An overlaid contour plot of suitable concentrations of CB and BHT for the formulation of mulch film for crop production in Michigan or regions with similar solar radiation was established using selection criteria of light transmission of less than 20%, final tensile strength of at least 6.35 MPa, maximum gel fraction of 0.30, and positive number average molecular weight reduction sensitivity in the early stage of degradation.     

Biodegradation behavior of poly(butylene adipate-co-terephthalate) (PBAT), poly(lactic acid) (PLA), and their blend under soil conditions

Poly(lactic acid) (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) were mixed at a ratio of 40:60, extruded to form granules and cast into film; then, the PLA, PBAT, and PBAT/PLA film samples were buried in real soil environments. The residual degraded samples were taken regularly from the soil and analyzed by SEM, DSC, TGA, IR spectroscopy and elemental analysis. The analyses showed that PBAT and PLA had different biodegradation mechanisms. Further, the melting temperature and the melting point change of the various components in the PBAT/PLA blend before and after the biodegradation essentially followed the process of the changes in the respective single polymers. After biodegradation, the carbon atom content in the molecular structure of the PBAT, PLA, and PBAT/PLA samples decreased, while the oxygen atom content increased, indicating that the samples indeed degraded. The biodegradation rates of PBAT and PLA in the PBAT/PLA blend were not the same as those for the single materials.     

Effect of montmorillonite and chain extender on rheological,morphological and biodegradation behavior of PLA/PBAT blends

The effect of montmorillonite clay (MMT) and/or chain extender (CE) on rheological, morphological and biodegradation properties of PLA/PBAT blend was investigated. The biodegradation behavior was evaluated by CO₂ evolution in soil burial. CE incorporation resulted in an increase in the complex viscosity of PLA/PBAT blends, an increase in PLA crystallinity and a decrease in the dispersed phase diameter. MMT incorporation resulted in an increase in the complex viscosity, more pronounced shear-thinning behavior and a decrease in the dispersed phase diameter. CE incorporation resulted in a slight effect in the rheological properties of PLA/PBAT blend in the presence of MMT. Unfilled PLA/PBAT blend presented the highest amount of evolved CO₂, and the micrographs indicated that degradation tends to occur on the surface. MMT delayed biodegradation of PLA/PBAT blends even although their surfaces presented some cracks and holes in a few localized regions. PLA/PBAT + CE blend presented the lowest amount of evolved CO₂.     

A novel aromatic–aliphatic copolyester consisting of poly(1,4‐dioxan‐2‐one) and poly(ethylene‐co‐1,6‐hexene terephthalate): Preparation,thermal, and mechanical properties

A novel multiblock aromatic–aliphatic copolyester poly(ethylene‐co‐1,6‐hexene terephthalate)‐copoly(1,4‐dioxan‐2‐one) (PEHT‐PPDO) was successfully synthesized via the chain‐extension reaction of dihydroxyl teminated poly(ethylene‐co‐hexane terephthalate) (PEHT‐OH) with dihydroxyl teminated poly(1,4‐dioxan‐2‐one) (PPDO‐OH) prepolymers, using toluene‐2,4‐diisocyanate as a chain extender. To produce PEHT‐OH prepolymer with an appropriate melting point which can match the reaction temperature of PEHT‐OH prepolymer with PPDO‐OH prepolymer, 1,6‐hexanediol was used to disturb the regularity of poly(ethylene terephthalate) segments. The chemical structures and molecular weights of PEHT‐PPDO copolymers were characterized by ¹H NMR, FTIR, and GPC. The DSC data showed that PPDO‐OH segments were miscible well with PEHT‐OH segments in amorphous state and that the crystallization of copolyester was predominantly contributed by PPDO segments. The TGA results indicated that the thermal stability of PEHT‐PPDO was improved comparing with PPDO homopolymer. The novel aromatic–aliphatic copolyesters have good mechanical properties and could find applications in the field of biodegradable polymer materials. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2828–2837, 2010     

Effect of isocyanate structure on deblocking and cure reaction of N-methylaniline-blocked diisocyanates and polyisocyanates

Two series of N-methylaniline-blocked isocyanates based on monomeric diisocyanates such as 4,4′-methylene bis(phenyl isocyanate), toluene-2,4-diisocyanate, isophorone diisocyanate and 1,6-diisocyanato hexane and their NCO terminated polyurethane prepolymer (polyisocyanates) were prepared and characterized thoroughly by FTIR, ¹H NMR, ¹³C NMR and EI-Mass spectroscopic methods. The blocking reaction of N-methylaniline with aromatic isocyanates and aromatic polyisocyanates occur faster when compared to the aliphatic isocyanates. The deblocking reactions of blocked isocyanates were carried out under dynamic and isothermal conditions using hot-stage FTIR spectrophotometer. The dynamic method was used to determine the deblocking temperature, and the isothermal method was used to calculate kinetics and thermodynamics parameters. Cure reactions of blocked isocyanates with hydroxyl-terminated polybutadiene were also followed to establish the structure-property relationship of the N-methylaniline-blocked isocyanates. The deblocking studies of blocked isocyanates reveal that the aromatic isocyanates undergo deblocking easily compared to aliphatic isocyanates. The rate of deblocking reaction of N-methylaniline-blocked aromatic polyisocyanates was found to be higher compared to N-methylaniline-blocked aromatic monomeric diisocyanate adducts. On the other hand, this trend was just reverse in the cure-reaction studies. The dissolution behavior of N-methylaniline-blocked isocyanates in Terathane-2000, polypropylene glycol-2000, polycaprolactone diol-2000 and hydroxyl-terminated polybutadiene-2500 was also studied and found that all adducts are soluble in these polyols.     

Effect of copolymerized butylene terephthalate chains on polymorphism and enzymatic degradation of poly(butylene adipate)

The introduction of aromatic butylene terephthalate (BT) units into the backbone chains of aliphatic poly(butylene adipate) (PBA) not only changes the mechanical performance of the resultant P(BA-co-BT) copolymers but also affects their biodegradability. Because of the polymorphism of PBA homopolymer, the copolymerized BT units may also influence the polymorphic crystal structure as well as the biodegradation behavior. In this work, three P(BA-co-BT) copolymers with BT contents as 10, 20, and 25 mol% were chosen to study their polymorphic crystal structure, thermal properties and enzymatic degradation by means of wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC) and gravimetric methods. The results reveal that the P(BA-co-BT) copolymers with BT contents below 25 mol% can form polymorphic crystal structures after melt-crystallization at different temperatures. However, the recrystallization and transformation of polymorphic crystals are strongly affected by the rigid BT units. The enzymatic degradation rates of P(BA-co-BT) copolymers decrease with increasing the BT contents. The influences of the BT units on the polymorphism and enzymatic degradation are discussed in terms of the motion of PBA chains that copolymerized with BT units. It has been concluded from the examination of solid-state microstructure that the influence of the aromatic BT units on the motion of biodegradable PBA chains heavily influences the biodegradability.     

Biodegradable aliphatic polyesters. Part I. Properties and biodegradation of poly(butylene succinate-co-butylene adipate)

A series of aliphatic homopolyesters and copolyesters was prepared from 1,4 butanediol and dimethylesters of succinic and adipic acids through a two-step process of transesterification and polycondensation. The synthesized polyesters were characterized by means of nuclear magnetic resonance spectroscopy (NMR), gel permeation chromatography (GPC), viscosity measurements, differential scanning calorimetry (DSC), X-ray diffraction (XRD), and mechanical property measurements. The homopolymer poly(butylene succinate) exhibited the highest tensile strength, which decreased with increasing adipate unit content, passed through a minimum at copolyester composition close to equimolarity and then increased towards the value of poly(butylene adipate). It is interesting to note that in contrast to tensile strength, the elongation at break increased for adipate unit content of 20-40 mol%. The biodegradation of the polymers was investigated by soil burial and enzymatic hydrolysis using three enzymes, Candida cylindracea lipase, Rhizopus delemar lipase, and Pseudomonas fluorescens cholesterol esterase. It appears that the key factor affecting material degradation was its crystallinity.     

Degradation mechanism of green biopolyester nanocomposites with various cellulose nanocrystal based nanohybrids

Oceans and soils have been contaminated with traditional plastic due to its lack of degradability. Therefore, green biopolymer composites reinforced with cellulose nanocrystal-zinc oxide hybrids (ZnO hybrids) with good biodegradation ability provided a positive impact on reducing environmental challenges. In this work, the effect of various morphologies of ZnO hybrids on the biodegradation ability of poly(butylene adipate-co-terephthalate), PBAT) under seawater, soil burial, and UV aging conditions were investigated. Sheet-like ZnO hybrids (s-ZnO hybrid) efficiently enhanced the mechanical, UV-blocking properties and biodegradation ability of PBAT nanocomposite films. Compared to neat PBAT, the best tensile strength of PBAT nanocomposite with 2 wt% s-ZnO hybrid was increased by 15.1%, meanwhile this nanocomposite films showed the highest biodegradation rate after 80 days of soil degradation and 90 days of seawater degradation. Besides, three possible biodegradation mechanisms of green PBAT nanocomposite films were presented, hinting that such PBAT nanocomposite have great promising packaging applications.

Graphic abstract

     

TRANSESTERIFICATION OF POLY（BISPHENOL A CARBONATE） WITH AROMATIC AND ALIPHATIC SEGMENTS IN BUTYLENE TEREPHTHALATE-CAPROLACTONE COPOLYESTER

In this article, the transesterification of poly(bisphenol A carbonate) (PC) with butylene terephthalate-caprolactone copolyester at a weight ratio 50/50 (BCL(21)) was thoroughly investigated by proton nuclear magnetic resonance spectroscopy (^1H-NMR), in conjunction with a model compound. The ^1H-NMR results of the annealed blend PC/BCL(21) show that the formation of bisphenol A-terephthalate ester units is the same as in the annealed blend of PC with PBT, and the transesterification actually occurs between PC and butylene terephthalate (BT) segments in BCL(21). By comparison with the model compound bisphenol A dibutyrate, the new signal appearing at δ=2.56 in the ^1H-NMR spectrum confirms the existence of bisphenol A caprolactone ester units resulting from the exchange reaction of PC with caprolactone (CL) segments. ^1H-NMR analysis of the transesterification rates reveals that the reaction of PC with aromatic and aliphatic segments in BCL(21) proceeds in a random manner. The miscibility of the blend PC/BCL(21) copolyester is favorable for the transesterification of PC with BT segments and CL segments.     

A multiple approach in determination of interfacial tension of biodegradable melt-mixed PBAT/EVOH blends: Correlation of morphology,rheology and mechanical properties

The interfacial tension of biodegradable melt-mixed blends of poly(butylene adipate-co-terephthalate), PBAT, and poly(ethylene-co-vinyl alcohol), (EVOH), was measured by breaking thread (BT), imbedded fiber retraction (IFR), and rheological methods. The PBAT-rich blends were prepared under different melt mixing conditions in order to investigate the effect of mixing conditions and possibility of reactive mixing between the blend components on the blend morphology, rheology, mechanical properties and interfacial tension values. The conditions were varied based on a Taguchi design of experiment using four factors namely EVOH content (0–30 wt%), mixing time (2–15 min), rotor speed (50–90 rpm), and mixing temperature (185–200 °C), each varying at three levels. The average size of EVOH droplets in PBAT matrix was determined for each blend by a field emission-scanning electron microscopy technique. The values of interfacial tension of PBAT/EVOH were found to be 2.57 ± 0.22 and 2.73 ± 0.30 mN m⁻¹ by the BT and IFR methods, respectively. The Palierne, Gramespacher, and Bousmina models were fitted to the rheological data to verify the interfacial tension of the blends. The continuous relaxation spectrum of the blends was determined in order to obtain the relaxation time of the EVOH droplets in the PBAT matrix. The Taguchi analysis revealed that the most effective factor is the EVOH content, and other factors do not play a significant role in the ultimate properties of the blends. Finally, based on the obtained mechanical properties, the possibility of reactive mixing under the applied mixing conditions was ruled out by means of repeated differential scanning calorimetry (DSC) and rheological measurements.     

Selective nucleophilic substitution reactions on poly(epichlorohydrin) using aromatic and aliphatic thiol compounds

Poly(epichlorohydrin) has been modified chemically using aromatic and aliphatic thiol compounds. The reactivity and kinetics of these modifiers with respect to substitution and elimination was studied. Therefore, the chemical structure of the reaction products was analysed using ¹³C NMR, ¹H NMR and ¹³C-DEPT spectroscopies. It is shown that both, aromatic as well as aliphatic thiols, are highly selective with respect to nucleophilic substitution as reaction conditions can be found which allow one to achieve degrees of modification of up to 90% without any elimination side-reaction. As a consequence no degradative chain-scission takes place what has been confirmed by GPC analysis.A comparison between both types of thiol modifiers shows that aromatic ones react faster and that higher degrees of modification are reached than with their aliphatic homologues.