Biodegradable water-soluble polycarboxylic acid design: Biodegradability and builder performance in detergent formulation of partially dicarboxylated polyuronide containing sugar residues in the backbone

Partially dicarboxylated polyuronide having a variable amount of unreacted sugar blocks as an enzymatically cleavable segment was prepared by the controlled oxidation of pectic acid and alginic acid. It was found that partially dicarboxylated polyuronides containing uronide blocks showed better biodegradability than those having no uronide block in the polycarboxylate chain. The rate of biodegradation varies according to the degree of dicarboxylation. It was confirmed that dicarboxy polyuronides containing more than 70% unreacted uronide residues tended to biodegrade quickly. The biodegradability obtained by the BOD test and the enzymatic degradability are well correlated, suggesting that these polymers are first cleaved at the sugar blocks by carbohydrase with subsequent assimilation of the resultant oligomeric fractions. Detergency was dependent on the content of the carboxylate groups in the polymer. The polymers with high carboxylate contents showed better builder performance. The detergency of dicarboxy pectic acid was better than that of dicarboxy alginic acid when compared on the basis of an equal degree of dicarboxylation.     

New biodegradable polyester-copolymers from commodity chemicals with favorable use properties

Copolyesters composed of aliphatic and aromatic compounds were synthesized by the polycondensation of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, sebacic acid, adipic acid, and terephthalic acid. By applying an appropriate ratio of aliphatic to aromatic acids, the synthesized materials proved to be biodegradable, as was verified by several degradation test methods such as aqueous polymer suspension inoculated by a soil eluate (Sturm test), a soil burial test (at ambient temperature), and a composting simulation test at 60°C. The degradability of the polyester-copolymers (measured as weight loss) was investigated with respect to the aliphatic monomer components and the fraction of terephthalic acid. Excellent biodegradability was observed even for copolymers with a content of terephthalic acid up to 56 mol% (of the acid fraction) and melting points in the range up to 140°C. Degradation by chemical hydrolysis of the polyesters was determined independently and was found to facilitate microbial attack significantly only at higher temperatures. The findings demonstrate that biodegradable polymers with advantageous usage properties can easily be manufactured by conventional techniques from commodity chemicals (adipic acid, terephthalic acid, and ethylene glycol or 1,4-butanediol).Dedicated to Prof. J. Klein's 60th birthday.     

Evaluation of the biodegradability of copolyesters containing aromatic compounds by investigations of model oligomers

Model oligo esters of terephthalic acid with 1,2-ethanediol, 1,3-propanediol, and 1,4-butanediol have been investigated with regard to their biodegradability in different biological environments. Well-characterized oligomers with weight-average molar masses of from 600 to 2600 g/mol exhibit biodegradation in aqueous systems, soil, and compost at 60°C. SEC investigations showed a fast biological degradation of the oligomer fraction consisting of 1 or 2 repeating units, independent of the diol component used for polycondensation, while polyester oligomers with degrees of polymerization higher than 2 were stable against microbial attack at room temperature in a time frame of 2 months. At 60°C in a compost environment chemical hydrolysis also degrades chains longer than two repeating units, resulting in enhanced degradability of the oligomers. Metabolization of the monomers and the dimers as well by the microorganisms could be confirmed by comparing SEC measurements and carbon balances in a Sturm test experiment. Based on these results degradation characteristics of potential oligomer intermediates resulting from a primary chain scission from copolyesters consisting of aromatic and aliphatic dicarbonic acids can be predicted depending on their composition. These results will have an evident influence on the evaluation of the biodegradability of commercially interesting copolyesters and lead to new ways of tailor-made designing of new biodegradable materials as well.     

Hydrolytic and enzymatic degradation of poly(γ-glutamic acid) hydrogels and their application in slow-release systems for proteins

The hydrolytic and enzymatic degradation of newly developed hydrogels, produced by cross-linking purified poly(-glutamic acid) (PGA) with dihaloalkane compounds, was studied and is reported in this paper. Analysis of hydrolysis of the hydrogel as a function of pH indicated that the hydrolysis occurred slowly at neutral pH, but fast in both acidic and alkaline solutions, while the polymer could be hydrolyzed rapidly only in acidic solutions. The ester bonds were more sensitive to hydrolysis than peptide bonds. The biodegradability of the hydrogel and polymer was further confirmed when enzymatic degradation was studied by three enzymes (cathepsin B, pronase E, and trypsin), which were able to cleave both ester and peptide bonds gradually. A slow-release system for porcine somatotropin (pST) formed by using the hydrogel as matrix to entrap the hormone was evaluatedin vitro andin vivo. Results demonstrated that the hydrogel was able to release the hormone for a period of 20–30 days and indicated its potential application in slow-release systems for bioactive materials, especially macromolecules, such as peptides and proteins.     

Thermal Properties and Biodegradability Studies of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

For investigating the relationship between thermal properties and biodegradability of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), several films of PHBV containing different polyhydroxyvalerate (HV) fractions were subjected to degradation in different conditions for up to 49 days. Differential scanning calorimetry (DSC), thermogravimetry (TG), specimen weight loss and scanning electron microscopy (SEM) were performed to characterize the thermal properties and enzymatic biodegradability of PHBV. The experimental results suggest that the degradation rates of PHBV films increase with decreasing crystallinity; the degradability of PHBV occurring from the surface is very significant under enzymatic hydrolysis; the crystallinity of PHBV decreased with the increase of HV fraction in PHBV; and no decrease in molecular weight was observed in the partially-degraded polymer.     

Thermal Degradation and Kinetics of Alginate Polyurethane Hybrid Material Prepared from Alginic Acid as a Polyol

Alginate polyurethane hybrid materials are prepared by varying mole ratio of 2, 4-TDI as a di-isocyanate and alginic acid as a polyol in presence of dimethyl sulfoxide (DMSO) as a solvent. FT-IR and ¹³C one-dimensional (1D) solid state NMR (SSNMR) spectroscopy indicates that alginic acid is converted into alginate-polyurethane hybrid material via urethane linkage. Surface morphology of alginate-polyurethane hybrids changes by varying alginic acid: TDI ratio. The peak at near 221 °C in DSC thermogram of alginic acid (Alg) is shifted to higher temperature in alginate-polyurethane hybrid (Algpu1 and Algpu2). TGA study shows that alginate-polyurethane hybrid prepared using alginic acid: TDI = 1:1 (Algpu2) is more stable than alginic acid: TDI = 1:0.5 (Algpu1) at 300 °C. Kinetic analysis was performed to fit with TGA data, where the entire degradation process has been considered as three consecutive 1st order reactions. This study shows that thermal stability of alginate-polyurethane hybrid material was increased by adjusting mole ratio of 2, 4-TDI and alginic acid.     

Evaluation of the Biodegradability of Polyvinyl Alcohol/Starch Blends: A Methodological Comparison of Environmentally Friendly Materials

Polyvinyl alcohol (PVA) and starch are both biodegradable polymers. These two polymers can be prepared as biodegradable plastics that are emerging as one of the environmental friendly materials available now. In this study, after reacting with sodium trimetaphosphate (STMP), modified corn starch was blended with PVA in different ratios by a barbender. Test samples were prepared for mechanical and thermal properties measurements. The surface roughness and morphology of fractured surface of the samples were observed by an atomic force microscopy (AFM) and scanning electron microscope (SEM) measurements. Aqueous degradation by enzyme, water absorption and biodegradability behavior were evaluated for the degradability. The biodegradability of these materials was followed by bio-reactivity kinetics models. Results showed that the addition of modified starch could enhance its water uptake. With an addition of 20 wt% of modified starch, the blend had a maximum weight loss during enzymatic degradation. It was found that the degradability was enhanced with the addition of the starch. Analyzing the results of the biodegradability based on the kinetic models, the growth rate of the microorganism was found to be increasing with the increase of the content of starch in the PVA/starch blends in the first order reaction fashion. In our biodegradability analysis, i.e., based on the China national standards (CNS) 14432 regulations, we estimated the decomposition behavior based on the mentioned first order reaction. We found that the PVA/starch blends would take 32.47, 16.20 and 12.47 years to degrade by 70% as their starch content 0, 20 and 40 wt%, respectively.     

Comparison of the weight-loss degradability of various biodegradable plastics under laboratory composting conditions

Eight kinds of biodegradable plastics were compared for their degradability in controlled laboratory composting conditions. A thin film of each plastic was mixed into the composting material, and weight-loss degradability was calculated from the weight changes of the film during composting. It was found that weight-loss degradability strongly depended on the specific kind of biodegradable plastic; two were very high, four moderate, and the remaining two very slight. The most easily degradable plastic degraded by as much as 81.4% over 8 days of composting. By comparing the weight-loss degradability with ultimate degradability, which is defined as a molar ratio of carbon loss as CO₂ to the carbon contained in the biodegradable plastic, the order of the ease of degradation of the biodegradable plastics differed. Received: February 7, 2000 / Accepted April 14, 2000     

Environmental Degradation of Blends of Atactic Poly[(R,S)-3-hydroxybutyrate] with Natural PHBV in Baltic Sea Water and Compost with Activated Sludge

Degradation of atactic poly[(R,S)-3-hydroxybutyrate] (a-PHB) binary blends with natural poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV, 12 mol% of 3HV units), has been investigated and compared with plain PHBV in the compost containing activated sludge and under marine exposure conditions in the dynamic water of the Baltic Sea. Characteristic parameters of compost and the Baltic Sea water were monitored during the incubation period (6 weeks) and their influence on the degree of biodegradation is discussed. After specified degradation times of the experiments the weight loss of the samples, surface changes, changes in molecular weight and polydispersity as well as changes of the composition and thermo-mechanical properties of the blends have been evaluated. Macroscopic observations of the samples were accompanied by investigations using optical microscopy, size-exclusion chromatography (SEC), nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC) and tensile testing. The degree of degradation of blends of a-PHB with PHBV depends on the blend composition and environmental conditions. In both environments studied the weight loss of plain PHBV was more significant than changes the molecular weight. In both environments only enzymatic degradation of the blends, which proceeds via surface erosion mechanisms, was observed during the incubation period.     

Degradation of Cellulose Acetate-Based Materials: A Review

Cellulose acetate polymer is used to make a variety of consumer products including textiles, plastic films, and cigarette filters. A review of degradation mechanisms, and the possible approaches to diminish the environmental persistence of these materials, will clarify the current and potential degradation rates of these products after disposal. Various studies have been conducted on the biodegradability of cellulose acetate, but no review has been compiled which includes biological, chemical, and photo chemical degradation mechanisms. Cellulose acetate is prepared by acetylating cellulose, the most abundant natural polymer. Cellulose is readily biodegraded by organisms that utilize cellulase enzymes, but due to the additional acetyl groups cellulose acetate requires the presence of esterases for the first step in biodegradation. Once partial deacetylation has been accomplished either by enzymes, or by partial chemical hydrolysis, the polymer’s cellulose backbone is readily biodegraded. Cellulose acetate is photo chemically degraded by UV wavelengths shorter than 280 nm, but has limited photo degradability in sunlight due to the lack of chromophores for absorbing ultraviolet light. Photo degradability can be significantly enhanced by the addition of titanium dioxide, which is used as a whitening agent in many consumer products. Photo degradation with TiO₂ causes surface pitting, thus increasing a material’s surface area which enhances biodegradation. The combination of both photo and biodegradation allows a synergy that enhances the overall degradation rate. The physical design of a consumer product can also facilitate enhanced degradation rate, since rates are highly influenced by the exposure to environmental conditions. The patent literature contains an abundance of ideas for designing consumer products that are less persistent in the outdoors environment, and this review will include insights into enhanced degradability designs.     

Comparative Biodegradation Study of Starch- and Polylactic Acid-Based Materials

The degradation of starch- and polylactic acid-based plastic films by microorganisms extracted from compost was studied in a liquid medium. The various degradation products produced were measured throughout the duration of the experiment, and total carbon balances were estimated. For an easily biodegradable material, the evolution of the way carbon repartitioned between different degradation products was quite similar whatever the experimental condition or the type of substrate. On the other hand, for a resistant material exposed to these microorganisms, the nature of the biodegradation depended strongly on the experimental conditions. In the latter case, a differential scanning calorimetry analysis confirmed the importance of the applied norm on the state of the residual material. The consequences for improved methods of estimation of biodegradability of these materials are discussed.     

TiO2纳米管光电催化降解酸性橙染料

采用电化学阳极氧化法在金属钛表面制备锐钛矿型TiO2纳米管,并以TiO2纳米管薄膜为阳极,考察溶液pH、外加偏压以及NaC1浓度对酸性橙的光电催化降解反应的影响.实验结果表明:在溶液pH为3.0、外加偏压为2.5V、NaCl浓度为0.05 mol/L的最佳实验条件下反应30 min,酸性橙降解率可达99.99％;TiO2纳米管重复使用25次,酸性橙降解率仍可达94.57％.     

Environmental Relevance of CL-20: Preliminary Findings

CL-20 is a recently synthesized component of energetic propellant formulations. Although energetic aspects of CL-20 have attracted considerable attention, its environmental behavior is unknown. A multi-disciplinary study covering a variety of fate, transport, and toxicity issues of CL-20 is currently under way in the Center for Environmental Engineering at Stevens Institute of Technology. Preliminary results on water solubility, biodegradability, hydrolytic reactivity, thermal decomposition and soil microbial and plant toxicity are reported in this article.     

Effects of higher-order structure of poly(3-hydroxybutyrate) on its biodegradation. II. Effects of crystal structure on microbial degradation

As one of a series of studies concerning the relationship between the higher-order structure and the biodegradability of a biodegradable plastic, the effects of the crystal structure of the plastic on microbial degradation were investigated. Bacterial poly(d-(–)-3-hydroxybutyrate) (PHB) films which had a wide range of crystallinity were prepared by the melt-quenching method. Results of the microbial degradation indicated that the development of crystallinity evidently depressed the microbial degradability. From scanning electron microscopy (SEM) observations, it is suggested that the microbial degradation proceeded in at least two manners. One was preferential degradation of the amorphous region leaving the crystalline lamellae intact, which was considered to be a homogeneous enzymatic degradation over the surface. The other was nonpreferential spherical degradation on the surface. The SEMs indicate that the spherical holes were the result of colonization by degrading bacteria. The holes varied in size and number with the change of crystal structure. Therefore, it is considered that the crystal structure of PHB also influenced the physiological behavior of the degrading bacteria on the PHB surface.     

新兴污染物BP-3和BP-4的好氧生物降解性能

采用欧洲经济合作与发展组织（OECD）的生物降解测试标准方法——301F测压呼吸计量法，考察了2-羟基-4-甲氧基二苯甲酮（BP-3）和2-羟基-4-甲氧基二苯甲酮-5-磺酸（BP-4）的好氧生物降解性能，并研究了降解动力学及共代谢现象。实验结果表明：BP-3和BP-4的可生物降解率分别为68.36%和41.34%;根据OECD快速降解性判定标准，BP-3划归为易快速降解物质，而BP-4为不易快速降解物质;两种物质的生物降解可用一级动力学描述，半衰期分别为1.986 d和2.806 d;根据欧盟法规《化学品的注册、评估、授权和限制》（REACH法规），BP-3和BP-4均非持久性物质;与苯甲酸钠共存时，BP-3和BP-4的降解过程均表现出共代谢现象。     

Biodegradability of Banana and Plantain Cellulose Microfibrils Films in Anaerobic Conditions

Currently, cellulose microfibrils are being investigated as nanofillers for polymers to increase their biodegradability. However, until now there has been no report on their degradability by microorganisms. In this work the anaerobic degradation of cellulose microfibril films extracted from banana and plantain plant rachis residues has been studied. Samples were exposed to burial tests in nature compost during 14?days. Changes due to the degradation process were investigated by techniques as optical microscopy, tensile tests, viscosity measurements, ATR-FTIR spectroscopy, X-ray diffraction and thermogravimetric analysis. Biodegradability was higher for cellulose microfibril films extracted from banana (BCMF) than plantain films (PCMF). Growth of microorganism colonies on BCMF films and just yellowing on PCMF films was observed by microscopic analysis. New bands characteristic of aldehyde functional groups due to the breaking of ??-(1,4)-glycosidic bonds were observed in infrared spectra. This breakage was also responsible for the fall-down of mechanical properties and polymerization degree. X-ray diffraction and thermogravimetric analysis showed that BCMF films were at the first stage of degradation for the used burial test times because the microorganisms only attacked the amorphous cellulose leading to a slight increase in crystallinity. In the case of PCMF films this variation remained practically invariant.     

Oxygen Permeability and Biodegradability of Polyuronic Acids Prepared from Polysaccharides by TEMPO-Mediated Oxidation

Polyuronic acids, i.e., amylouronic acid, cellouronic acid and chitouronic acid, were prepared from starch, cellulose and chitin, respectively, by the 2,2,6,6-tetramethylpiperidine-1-oxy radical (TEMPO)-mediated oxidation, and their gas-barrier properties and biodegradability were studied in consideration to use the polyuronic acids as flexible packaging films or coating materials. Cellouronic acid and amylouronic acid had excellent oxygen-barrier properties similar to that of poly(vinyl alcohol) (PVA), while chitouronic acid did not. The regular chemical structures of the former two polyuronic acids with no bulky substituents or adducts may have brought about such high oxygen-barrier levels. An oxidized product prepared form fine microcrystalline cellulose by the TEMPO-mediated oxidation was not completely dissolved in water, but became a paste. However, this paste also formed sufficiently smooth films by coating, and had good gas-barrier property. All polyuronic acids prepared were biodegradable; cellouronic acid and chitouronic acid had high degrees of biodegradability, while amylouronic acid had quite low value. These various characteristics are significant for end use of these new polyuronic acids as gas-barrier materials for biodegradable packaging.     

Novel malonate-type copolymers containing vinyl alcohol blocks as biodegradable segments and their builder performance in detergent formulations

Poly[(disodium methylene malonate)-co-(vinyl alcohol)] [P(DSMM-VA)] and poly[(disodium ethoxymethylene malonate)-co-(vinyl alcohol)] [P(DSEMM-VA)] containing a poly(vinyl alcohol) (PVA) block as a biodegradable segment were prepared and their biodegradability and functionality were evaluated and compared with those of the corresponding fumarate and maleate copolymers. It was found that the 1,1-dicarboxylate-type copolymers, P(DSMM-VA) and P(DSEMM-VA), showed better biodegradability than the corresponding 1,2-dicarboxylate-type copolymers, P(DSF-VA) and P(DSM-VA). This improved biodegradability of P(DSMM-VA) and P(DSEMM-VA) is probably attributable to their more expanded polymer chain in aqueous solution, which will be more accessible to the degrading enzymes. The minimum chain length of the PVA-block, which acts as a biodegradable segment in the polymer chain, is estimated to be 2–3 and 3–4 monomer units for P(DSMM-VA) and P(DSEMM-VA), respectively. On the other hand, the minimum PVA block is about 5 and 7 monomer units for the fumarate and maleate copolymers, respectively. It was confirmed that P(DSMM-VA) showed excellent builder performance compared to the corresponding fumarate copolymer.Paper presented at the Bio/Environmentally Degradable Polymer Society—Second National Meeting, August 19–21, 1993, Chicago, Illinois.     

蒽醌修饰石墨毡电极预处理头孢合成废水

以钛涂钌电极为阳极、自制蒽醌修饰石墨毡电极为阴极,对头孢合成废水(COD=25 000~30 000 mg/L、ρ(NH3-N)=850~1 300 mg/L、色度为2 300~2 680度)进行了电化学氧化预处理,优化了电解条件,并对电化学体系的动力学和稳定性进行了分析。实验结果表明:蒽醌的存在可改善电化学氧化降解效果;在电解时间50 min、电流密度0.14 A/cm2、Na2SO4浓度0.1 mol/L、极板间距2 cm、初始废水p H 7.0的条件下,废水的COD、色度、NH3-N的去除率分别可达45.3%,66.9%,33.6%;BOD5/COD由处理前的0.27增至0.40,可生化性得到改善;COD、色度、NH3-N的电化学氧化降解过程均近似符合一级动力学方程;且该电化学体系的应用稳定性良好。