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Synthesis and self-association behavior of biodegradable amphiphilic poly[bis(ethyl glycinat-N-yl)phosphazene]- poly(ethylene oxide) block copolymers.

Amphiphilic diblock copolymers with varying compositions of hydrophilic poly(ethylene oxide) (PEO) and hydrophobic poly[bis(ethyl glycinat-N-yl)phosphazene] (PNgly) were synthesized via the controlled cationic-induced polymerization of a phosphoranimine (Cl(3)P=NSiMe(3)) at ambient temperature using a PEO-phosphoranimine macroinitiator. The aqueous-phase transition behavior of PEO-PNgly-3 (M(n) = 10,000) and micelle formation of both PEO-PNgly-3 and PEO-PNgly-4 (M(n) = 8,500) were investigated using fluorescence techniques and dynamic light scattering. The critical micelle concentrations (cmc's) of PEO-PNgly-3 and PEO-PNgly-4 were determined to be 3 and 12 mg/L with the mean diameters of micelles being 120 and 130 nm, respectively. The hydrolytic degradation of these diblock copolymers was also studied in solution. These studies coupled with the biodegradability of the poly[bis(ethyl glycinat-N-yl)phosphazene] block to give benign products make PEO-PNgly copolymers well-suited for a wide variety of biomedical applications including novel biodegradable drug-delivery systems.

Biocompatible Materials↗

Melting and crystallization behaviors of biodegradable polymers enzymatically coalesced from their cyclodextrin inclusion complexes.

Inclusion complexed (IC) and coalesced biodegradable poly(epsilon-caprolactone) (PCL), poly(L-lactic acid) (PLLA), and their diblock copolymer (PCL-b-PLLA) were achieved by forming ICs between host alpha-cyclodextrin(alpha-CD) and guest PCL, PLLA, and PCL-b-PLLA, followed by removing the alpha-CD host with an amylase enzyme. FTIR spectra of the coalesced polymers reveal that the host alpha-CD can be completely removed, without polymer degradation, by treatment with an amylase enzyme. The melting and crystallization behavior of these CD-IC treated polymers, which are crystallizable, biodegradable, and bioabsorbable, are investigated by differential scanning calorimetry (DSC) and polarized optical microscopy. Results show that coalescence increased the crystallinities of the homopolymers but decreased that of the diblock copolymer. The Avrami exponent (n), derived from both isothermal and nonisothermal crystallization models for homo-PCL and -PLLA and the PCL and PLLA blocks in the diblock copolymer samples coalesced from their ICs, is close to 4, indicating homogeneous crystallization, whereas crystallization of the blocks in the as-synthesized diblock copolymer yields an Avrami exponent around 3, indicating heterogeneous crystallization. All of these results demonstrate that the PCL and PLLA homopolymers and blocks in the IC-coalesced samples are more readily and homogeneously crystallized than those in the as-synthesized samples or their physical blend, even though the level of crystallinity in the IC-coalesced diblock copolymer is significantly lower. Moreover, unlike the as-synthesized diblock copolymer, the crystallization of PCL and PLLA blocks in the IC-coalesced diblock copolymer are not influenced by their covalent connection.

Biodegradation, Environmental↗

Syntheses and physical characterization of new aliphatic triblock poly(L-lactide-b-butylene succinate-b-L-lactide)s bearing soft and hard biodegradable building blocks.

This study presents chemical syntheses and physical characterization of a new aliphatic poly(L-lactide-b-butylene succinate-b-L-lactide) triblock copolyester with soft and hard biodegradable building blocks. First, poly(butylene succinate) (PBS) prepolymers terminated with hydroxyl functional groups were synthesized through melt polycondensation from succinic acid and 1,4-butanediol. Further, a series of new PLLA-b-PBS-b-PLLA triblock copolyesters bearing various average PLLA block lengths were prepared via ring opening polymerization of L-lactide with the synthesized hydroxyl capped PBS prepolymer (Mn = 4.9 KDa) and stannous octanoate as the macroinitiator and catalyst, respectively. By means of GPC, NMR, FTIR, DSC, TGA, and wide-angle X-ray diffractometer (WAXD), the macromolecular structures and physical properties were intensively studied for these synthesized PBS prepolymer and PLLA-b-PBS-b-PLLA triblock copolyesters. 13C NMR and GPC experimental results confirmed the formation of sequential block structures without any detectable transesterification under the present experimental conditions, and the molecular weights of triblock copolyesters could be readily regulated by adjusting the feeding molar ratio of L-lactide monomer to the PBS macroinitiator. DSC measurements showed all single glass transitions, and their glass transition temperatures were found to be between those of PLLA and PBS, depending on the lengths of PLLA blocks. It was noteworthy that the segmental flexibilities of the hard PLLA blocks were found to be remarkably enhanced by the more flexible PBS block partner, and the PBS and PLLA building blocks were well mixed in the amorphous regions. Results of TGA analyses indicated that thermal degradation and stabilities of the PLLA blocks strongly depended on the average PLLA block lengths of triblock copolyesters. In addition, FTIR and WAXD results showed the coexistence of the assembled PLLA and PBS crystal structures when the average PLLA block length became larger than 7.8. These results may be beneficial for this new biodegradable aliphatic triblock copolyester to be applied as a potential biomaterial.

Biocompatible Materials↗

Accelerated biodegradation of poly(vinyl alcohol) by glycosidations of the hydroxyl groups or addition of sugars.

Biodegradabilities of N-acetyl-d-glucosamine (GlcNAc)- (1) and chitobiose-substituted (2) poly(vinyl alcohol)s (PVA)s in a soil suspension (pH 6.5) were investigated at 25 degrees C for 40 days. Biochemical oxygen demand of 1 with a degree of substitution of 0.2-0.3 (DP = 430-480) was higher than that of PVA under the degradation condition. Size exclusion chromatography, (1)H NMR, and Fourier-transform infrared measurements of the recovered sample indicated that biodegradation of the PVA main chain was accelerated by partial glycosidation of hydroxyl groups in PVA. Similar acceleration was observed in a PVA/GlcNAc (50:50, w/w) mixture. Microbes which relate with degradation of the glycosidated polymers were grown in a culture medium including the soil suspension and the polymer as the carbon source. Polyacrylamide gel electrophoresis (SDS-PAGE) and IR measurements indicated that a cell-free extract derived from GlcNAc-substituted PVA was different from that in the PVA/GlcNAc mixture. The results suggested that the PVA main chain in GlcNAc-substituted PVA was cleaved by a different microorganism or via a mechanism different from that in the mixture. Chitobiose-substituted PVA 2 showed more enhanced acceleration, indicating that the sugar length influenced the degradability.

Biodegradation, Environmental↗

Synthesis and characterization of biodegradable amphiphilic triblock copolymers containing L-glutamic acid units.

A novel biodegradable amphiphilic triblock copolymer bearing pendant carboxyl groups PLGG-PEG-PLGG was successfully prepared by ring-opening copolymerization of l-lactide (LA) with (3s)-benzoxylcarbonylethyl-morpholine-2, 5-dione (BEMD) in the presence of dihydroxyl poly(ethylene glycol) (PEG) as a macroinitiator in bulk at 130 degrees C using SnOct(2) as catalyst and by subsequent catalytic hydrogenation. The copolymer could form micelles in aqueous solution with the cmc dependent on the composition of the copolymer. The micelles exhibited a homogeneous spherical morphology and a unimodal size distribution. Their degradation rate in the presence of proteinase K was faster than that of PLA, and they showed a low degree of cytotoxicity to the articular cartilage cells. This biodegradable amphiphilic block copolymer with pendant carboxyl groups is capable of further modification and is expected to facilitate a variety of potential biomedical applications, such as drug carriers, tissue engineering, etc.

Biodegradation, Environmental↗

Bacterial polyesters: biosynthesis, biodegradable plastics and biotechnology.

The discovery and chemical identification, in the 1920s, of the aliphatic polyester: poly(3-hydroxybutyrate), PHB, as a granular component in bacterial cells proceeded without any of the controversies which marked the recognition of macromolecules by Staudinger. Some thirty years after its discovery, PHB was recognized as the prototypical biodegradable thermoplastic to solve the waste disposal challenge. The development effort led by Imperial Chemical Industries Ltd., encouraged interdisciplinary research from genetic engineering and biotechnology to the study of enzymes involved in biosynthesis and biodegradation. From the simple PHB homopolyester discovered by Maurice Lemoigne in the mid-twenties, a family of over 100 different aliphatic polyesters of the same general structure has been discovered. Depending on bacterial species and substrates, these high molecular weight stereoregular polyesters have emerged as a new family of natural polymers ranking with nucleic acids, polyamides, polyisoprenoids, polyphenols, polyphosphates, and polysaccharides. In this historical review, the chemical, biochemical and microbial highlights are linked to personalities and locations involved with the events covering a discovery timespan of 75 years.

3-Hydroxybutyric Acid↗

Novel biodegradable polyphosphate cross-linker for making biocompatible hydrogel.

To obtain a novel biodegradable cross-linker, polymerizable polyphosphate (PIOP) was synthesized by ring-opening polymerization of 2-i-propyl-2-oxo-1,3,2-dioxaphospholane with 2-(2-oxo-1,3,2-dioxaphosphoroyloxyethyl methacrylate) (OPEMA). The number averaged molecular weight of the PIOP was 1.2 x 10(4), and the number of OPEMA units in one PIOP molecule was 2.2. Nonenzymatic degradation of the PIOP was evaluated in various pH aqueous media. The degree of hydrolysis was dependent on the pH; that is, it increased with an increase in the pH of the medium. At pH 11.0, the PIOP completely degraded in only 6 days. The poly[2-methacryloyloxyethyl phosphorylcholine (MPC)] cross-linked with the PIOP was prepared by radical polymerization. This polymer could form hydrogel, and the free water fraction in the hydrogel was high. The enzymatic activity of trypsin in contact with the hydrogel was similar to that in buffer solution. There is no adverse effect caused by the hydrogel to reduce the function of the trypsin. The cytotoxicity of poly(MPC) and degraded PIOP was evaluated using v79 cells, and it was not observed in either case. In conclusion, PIOP is a hydrolyzable polymer, which can be used as a cross-linker, and novel hydrogels having biodegradability and biocompatibility were prepared from poly(MPC) cross-linked with the PIOP.

Animals↗

Naphthalene biodegradation from non-aqueous-phase liquids in batch and column systems: comparison of biokinetic rate coefficients.

The kinetics of microbial degradation of naphthalene from a two-component non-aqueous-phase liquid (NAPL) coated onto uniformly sized nonporous particles were evaluated in a completely mixed batch reactor (CMBR) system and in flow-through column systems to examine the differences in the biodegradation kinetic coefficients, micro(max), the maximum specific growth rate coefficient, and K(s), the half saturation constant in the two systems. The values of these coefficients were estimated by nonlinear least-squares regression of the naphthalene mineralization profiles obtained from both CMBR and column biodegradation experiments. The results show that the range of values for micro(max) and K(s) obtained from column systems are very similar to the range of values obtained from CMBR systems. This suggests that coefficients estimated from CMBR or column systems are equally applicable for modeling studies. The presence of microorganisms and the development of biofilms at the NAPL-water interface reduced the mass transfer rates of naphthalene from the NAPL by 60% in CMBR and by 70% in column systems. If such changes in mass transfer coefficients are not accounted for, significantly erroneous values of biokinetic coefficients may be obtained.

Biodegradation, Environmental↗

Modeling the temperature kinetics of aerobic solid-state biodegradation.

This study evaluated three models of microbial temperature kinetics using CO2 respiration data from aerobic solid-state biodegradation experiments. The models included those of Andrews and Kambhu/Haug, Ratkowsky et al., and the Cardinal Temperature Model with Inflection (CTMI) of Rosso et al. A parameter estimation routine implemented the Complex-Box search method for each model on 48 data sets collected during the composting of synthetic food waste or sewage-sludge (biosolids) mixed with maple wood chips at different oxygen concentrations and extents of decomposition. Each of the three nonlinear temperature kinetic functions proved capable of modeling a wide range of experimental data sets. However, the models differed widely in the consistency of their parameters. Parameters in the CTMI model were more stable over the course of the degradation process, and that variability which did arise was directly related to changes in the microbial process. Additional benefits of the CTMI model include the ease of parameter determinations, which can be approximated directly from laboratory experiments or full-scale system analysis, and the direct value of its parameters in engineering design and process control under a wide range of biodegradation conditions.

Bacteria, Aerobic↗

Simultaneous biodegradation of benzene, toluene, and p-xylene in a two-phase partitioning bioreactor: concept demonstration and practical application.

In this work, a mixture of benzene, toluene, and p-xylene was simultaneously biodegraded by Pseudomonas sp. ATCC 55595 in a two-phase partitioning bioreactor. This bioreactor consisted of a 1-L cell-containing aqueous medium phase and a 500-mL immiscible organic phase. The organic solvent systematically selected for use in the bioreactor was Adol 85 NF, an industrial-grade, biocompatible solvent. In the first of three experiments, the organic phase was loaded with 2.0 g of benzene, 10.15 g of toluene, and 2.1 g of p-xylene, which partitioned into the aqueous phase at concentrations of 25, 50, and 8 mg/L, respectively. The system ultimately biodegraded all of the substrates within 144 h. During the rapid growth phase of this fermentation, the cells were oxygen-limited. This fermentation was therefore repeated using an enriched air supply to remove the oxygen limitation. The use of enriched air ultimately reduced the length of the fermentation to 108 h, thereby improving the overall volumetric consumption rates. Finally, 500 mL of Adol were used to recover 2.0 g of benzene, 10.15 g of toluene, and 2.1 g of p-xylene from silica sand that was contaminated as part of a simulated soil "spill". The solvent washing procedure was able to recover greater than 99% of each compound from the contaminated soil. The Adol was then transferred to the two-phase bioreactor to permit biological treatment of the BTX contaminants. This process was repeated when the initial BTX load had been consumed almost to exhaustion, and the solvent was able to recover the contaminants at greater than 99% efficiency once again. The system was ultimately able to degrade 4.0 g of benzene, 20.2 g of toluene, and 4.2 g of p-xylene within 144 h. These results represent an unprecedented level of BTX degradation and illustrate a potential practical application for this novel biotechnology.

Benzene↗

Methyl tert-butyl ether biodegradation by indigenous aquifer microorganisms under natural and artificial oxic conditions.

Microbial communities indigenous to a shallow groundwater system near Beaufort, SC, degraded milligram per liter concentrations of methyl tert-butyl ether (MTBE) under natural and artificial oxic conditions. Significant MTBE biodegradation was observed where anoxic, MTBE-contaminated groundwater discharged to a concrete-lined ditch. In the anoxic groundwater adjacent to the ditch, concentrations of MTBE were > 1 mg/L. Where groundwater discharge occurs, dissolved oxygen (DO) concentrations beneath the ditch exceeded 1.0 mg/Lto a depth of 1.5 m, and MTBE concentrations decreased to <1 microg/L prior to discharge. MTBE mass flux calculations indicate that 96% of MTBE mass loss occurs in the relatively small oxic zone prior to discharge. Samples of a natural microbial biofilm present in the oxic zone beneath the ditch completely degraded [U-14C]MTBE to [14C]CO2 in laboratory liquid culture studies, with no accumulation of intermediate compounds. Upgradient of the ditch in the anoxic, MTBE- and BTEX-contaminated aquifer, addition of a soluble oxygen release compound resulted in oxic conditions and rapid MTBE biodegradation by indigenous microorganisms. In an observation well located closest to the oxygen addition area, DO concentrations increased from 0.4 to 12 mg/L in <60 days and MTBE concentrations decreased from 20 to 3 mg/L. In the same time period at a downgradient observation well, DO increased from <0.2 to 2 mg/L and MTBE concentrations decreased from 30 to <5 mg/L. These results indicate that microorganisms indigenous to the groundwater system at this site can degrade milligram per liter concentrations of MTBE under natural and artificial oxic conditions.

Bacteria, Anaerobic↗

Variability in carbon isotopic fractionation during biodegradation of chlorinated ethenes: implications for field applications.

Stable carbon isotopic analysis has the potential to assess biodegradation of chlorinated ethenes. Significant isotopic shifts, which can be described by Rayleigh enrichment factors, have been observed for the biodegradation of trichloroethlyene (TCE), cis-dichloroethylene (cDCE), and vinyl chloride (VC). However, until this time, no systematic investigation of isotopic fractionation during perchloroethylene (PCE) degradation has been undertaken. In addition, there has been no comparison of isotopic fractionation by different microbial consortia, nor has there been a comparison of isotopic fractionation by consortia generated from the same source, but growing under different conditions. This study characterized carbon isotopic fractionation during reductive dechlorination of the chlorinated ethenes, PCE in particular, for microbial consortia from two different sources growing under different environmental conditions in order to assess the extent to which different microbial consortia result in different fractionation factors. Rayleigh enrichment factors of -13.8@1000, -20.4@1000, and -22.4@1000 were observed for TCE, cDCE, and VC, respectively, for dechlorination by the KB-1 consortium. In contrast, isotopic fractionation during reductive dechlorination of perchloroethylene (PCE) could not always be approximated by a Rayleigh model. Dechlorination by one consortium followed Rayleigh behavior (epsilon = -5.2), while a systematic change in the enrichment factor was observed over the course of PCE degradation by two other consortia. Comparison of all reported enrichment factors for reductive dechlorination of the chlorinated ethenes shows significant variation between experiments. Despite this variability, these results demonstrate that carbon isotopic analysis can provide qualitative evidence of the occurrence and relative extent of microbial reductive dechlorination of the chlorinated ethenes.

Biodegradation, Environmental↗

Effect of redox conditions on MTBE biodegradation in surface water sediments.

Microbial degradation of methyl tert-butyl ether (MTBE) was observed in surface water-sediment microcosms under anaerobic conditions. The efficiency and products of anaerobic MTBE biodegradation were dependent on the predominant terminal electron-accepting conditions. In the presence of substantial methanogenic activity, MTBE biodegradation was nominal and involved reduction of MTBE to the toxic product, tert-butyl alcohol (TBA). In the absence of significant methanogenic activity, accumulation of [14C]TBA generally decreased, and mineralization of [U-14C]MTBE to 14CO2 generally increased as the oxidative potential of the predominant terminal electron acceptor increased in the order of SO4, Fe(III), Mn(IV) < NO3 < O2. Microbial mineralization of MTBE to CO2 under Mn(IV)-or SO4-reducing conditions has not been reported previously. The results of this study indicate that microorganisms inhabiting the sediments of streams and lakes can degrade MTBE effectively under a range of anaerobic terminal electron-accepting conditions. Thus, anaerobic bed sediment microbial processes may provide a significant environmental sink for MTBE in surface water systems throughout the United States.

Bacteria, Anaerobic↗

TBA biodegradation in surface-water sediments under aerobic and anaerobic conditions.

The potential for [U-14C] TBA biodegradation was examined in laboratory microcosms under a range of terminal electron accepting conditions. TBA mineralization to CO2 was substantial in surface-water sediments under oxic, denitrifying, or Mn(IV)-reducing conditions and statistically significant but low under SO4-reducing conditions. Thus, anaerobic TBA biodegradation may be a significant natural attenuation mechanism for TBA in the environment, and stimulation of in situ TBA bioremediation by addition of suitable terminal electron acceptors may be feasible. No degradation of [U-14C] TBA was observed under methanogenic or Fe(III)-reducing conditions.

Bacteria, Aerobic↗

Induced phytoextraction/soil washing of lead using biodegradable chelate and permeable barriers.

Chelate-induced remediation has been proposed as an effective tool for the extraction of lead (Pb) from contaminated soils by plants. However, side-effects, mainly mobilization and leaching of Pb, raise environmental concerns. Biodegradable, synthetic organic chelate ethylenediaminedisuccinic acid (EDDS), and commonly used ethylenedimanetetraacetic acid (EDTA) were used for induced phytoextraction with a test plant Brassica rapa and in situ washing of soil contaminated with 1350 mg/kg of Pb. Horizontal permeable barriers were placed 20 cm deep in soil columns and tested for their ability to prevent leaching of Pb. The reactive materials in the barriers were nutrient enriched vermiculite, peat or agricultural hydrogel, and apatite. EDTA and EDDS addition increased Pb concentrations in the test plant by 158 and 89 times compared to the control, to 817 and 464 mg/kg, respectively. In EDTA treatments, approximately 25% or more of total initial soil Pb was leached in single cycle of chelate addition. In EDDS treatments, 20% of the initial Pb was leached from columns with no barrier, while barriers with vermiculite or hydrogel and apatite decreased leaching by more than 60 times, to 0.35%. 11.6% of total initial Pb was washed from the soil above the barrier with vermiculite and apatite, where almost all leached Pb was accumulated. Results indicate that use of biodegradable chelate EDDS and permeable barriers may lead to environmentally safe induced Pb phytoextraction and in situ washing of Pb.

Aluminum Silicates↗

Aerobic biodegradation of two commercial naphthenic acids preparations.

Naphthenic acids (NAs) have a variety of commercial uses including as emulsifiers and wood preservatives. They have been identified as being the main component responsible for the acute toxicity in produced waters in the oil sands operations in northeastern Alberta, Canada. NAs comprise a complex mixture of alkyl-substituted acyclic and cycloaliphatic carboxylic acids, with the general chemical formula CnH(2n+Z)O2, where n indicates the carbon number and Z specifies hydrogen deficiency from ring formation. In this study, commercial preparations of NAs were shown to be degraded in aerobic cultures from oil sands process-affected waters. High-performance liquid chromatography and gas chromatography-mass spectrometry (GC-MS) were used to monitor the concentrations and composition of the NA mixtures during biodegradation. Within 10 days of incubation, the NAs concentrations dropped from about 100 to <10 mg/L. This was accompanied by the release of about 60% of carbon from the NAs as CO2 and the reduction of toxicity of the culture supernatant, as measured by the Microtox assay. GC-MS results demonstrated that biodegradation changes the composition of the complex mixture of these NAs and that the lower molecular weight acids (with n = 5-13) were degraded more readily than the high molecular weight acids.

Bacteria, Aerobic↗

Isotopic and geochemical assessment of in situ biodegradation of chlorinated hydrocarbons.

Currently there is no in situ method to detect and quantify complete mineralization of chlorinated hydrocarbons (CHCs) to CO2. Combined isotopic measurements in conjunction with traditional chemical techniques were used to assess in situ biodegradation of trichloroethylene (TCE) and carbon tetrachloride (CT). Vadose zone CHC, ethene, ethane, methane, O2, and CO2 concentrations were analyzed using gas chromatography over 114 days at the Savannah River Site. delta13C of CHC and delta13C and 14C of vadose zone CO2, sediment organic matter, and groundwater dissolved inorganic carbon (DIC)were measured. Intermediate metabolites of TCE and CT accounted for < or = 10% of total CHCs. Delta13C of cis-1,2-dichloroethylene (DCE) was always heavier than TCE indicating substantial DCE biodegradation. 14C-CO2 values ranged from 84 to 128 percent modern carbon (pMC), suggesting that plant root-respired CO2 was dominant. 14C-CO2 values decreased over time (up to 12 pMC), and contaminated groundwater 14C-DIC (76 pMC) was substantially depleted relative to the control (121 pMC). 14C provided a direct measure of complete CHC mineralization in vadose zone and groundwater in situ and may improve remediation strategies.

Biodegradation, Environmental↗

Biodegradation of linear alkylbenzene sulfonates and their degradation intermediates in seawater.

A study has been made of the aerobic biodegradation of linear alkylbenzene sulfonates (C12 and C11 homologues) and sulfophenylcarboxylic acids (C5 and C11 homologues) in seawater at concentrations of the same order as those detected ones in coastal waters influenced by wastewater effluents, at different temperatures, and both with and without the addition of an inoculum adapted to the presence of linear alkylbenzene sulfonate (LAS). The biodegradation of C12LAS, C11LAS, C5SPC, and C11SPC exceeds 99% in all tests performed and can be satisfactorily fitted to a second-degree polynomial without an independent term. The kinetic of degradation of LAS presents a clear seasonal component, since the process is considerably inhibited at lower temperatures; it is also kinetically enhanced by the presence of the inoculum. The intermediates detected for all the cases are sulfophenylcarboxylic acids (SPCs), the most abundant being those intermediates produced by the omega- and beta-oxidations of the parent compound, although intermediates produced by the alpha-oxidation have also been detected. The kinetic of the SPCs generated can be described using a model composed of two terms that represent the formation and the degradation of these intermediates. The total disappearance of the SPCs in all cases indicates that the degradation of LAS in seawater at the tested concentrations in aerobic conditions is complete.

Alkanesulfonic Acids↗