Biodegradation of Poly-ε-caprolactones and Poly-<Emphasis Type="SmallCaps">l</Emphasis>-lactides by Fungi

This work assessed biodegradation, by Aspergillus, Fusarium, Penicillium and Parengyodontium fungi, of four samples of poly-ε-caprolactone (PCL), three samples of poly-l-lactide (PLA) and one sample of poly-d,l-lactide (DL-PLA) produced by ring-opening polymerization initiated by aluminium complexes of corresponding lactones. Mesophilic fungal strains actively biodegrading PCL (F. solani) and PLA (Parengyodontium album and A. calidoustus) were selected. The rate of degradation by the selected fungi was found to depend on the physicochemical and mechanical properties of the polymers (molecular weight, polydispersity, crystallinity). The most degradable poly-ε-caprolactone sample was shown to have the lowest molecular weight; the most biodegradable polylactide DL-PLA had the lowest crystallinity. Mass spectral analysis of biodegraded polymer residues showed PCL to be degraded more intensively than PLA. It is established that in the case of Parengyodontium album the colonization of the films of polypropylene composites with DL-PLA is observed, which will undoubtedly contribute to their further destruction under the influence of abiotic factors in the environment.     

Biodegradable Compatibilized Poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactide)/Thermoplastic Polyurethane Blends: Design,Preparation and Property Testing

Biodegradable blends of poly(l-lactide) (PLL) toughened with a polycaprolactone-based thermoplastic polyurethane (TPU) elastomer and compatibilized with a purpose-designed poly(l-lactide-co-caprolactone) (PLLCL) copolymer were prepared. Both 2-component (PLL/TPU) and 3-component (PLL/TPU/PLLCL) blends of various compositions were prepared by melt mixing, hot-pressed into thin films and their properties tested. The results showed that, although the TPU could toughen the PLL, the blends were immiscible leading to phase separation with the TPU domains distributed in the PLL matrix. However, addition of the PLLCL copolymer could partially compatibilize the blend by improving the interfacial adhesion between the two phases. Biodegradability testing showed that the blends were biodegradable and that the PLLCL copolymer could increase the rate of biodegradation under controlled composting conditions. The 3-component blend of composition PLL/TPU/PLLCL?=?90/10/10 parts by weight was found to exhibit the best all-round properties.     

Non-sterile simultaneous saccharification and fermentation of corn leaves and stalks to <Emphasis Type="SmallCaps">l</Emphasis>-lactic acid without external nutrient addition

Fermentation of lignocellulosic biomass requires auxiliary materials, including nutrients, to ensure the proliferation of microorganisms. Nutrients are usually inexpensive, but their contribution to the cost is considerable because of the very low prices of fermentation products, such as bio-ethanol. Using substances present in native lignocellulosic biomass as nutrients for fermentation was proposed and demonstrated. Leaves and stalks of corn plants were used as biomass, and nutrients were recovered as a nutrient solution by soaking them in water before alkaline peroxide pretreatment. Pretreated biomass and the nutrient solution derived from the same lot were used for non-sterile simultaneous enzymatic saccharification and thermophilic l-lactic acid fermentation (SSF). Using the nutrient solution in the saccharification step did not impact sugar recovery, and instead improved sugar yields because of the presence of eluted sugars in the solution. The l-lactic acid yield of 0.33 g g^?1 based on native biomass weight indicated that the nutrient solution functioned as a source of nutrients and sugars, especially as a source of essential phosphorus. Comparatively, autoclaved SSF yielded less or no l-lactic acid, indicating an apparent inhibitive effect derived from the nutrient solution on bacterial growth.     

Investigation of pH-Sensitive Swelling and Curcumin Release Behavior of Chitglc Hydrogel

Hydrogels are in use for encapsulation of curcumin for possible use in wound healing. Encapsulation helps in targeted delivery and enhanced activity of curcumin. We report here a pH sensitive hydrogel developed from chitosan. The hydrogel was prepared by reaction of chitosan and d-glucose, facilitated by the reducing agent Na-cyanoborohydride. The maximum yield of the hydrogel was obtained at pH 4.5 with the amount of chitosan, d-glucose and Na-cyanoborohydride as 0.3, 2.0 and 2.0 g respectively. A maximum curcumin loading efficiency of 74% was observed with curcumin amount in the feed at 0.15 g. The release study revealed a sustained release pattern over a period of 80 h with an initial burst release. Curcumin loaded hydrogel showed mild antibacterial activity against Proteus mirabilis and Enterobacter aerogenes.     

Optimization of Microwave-Assisted and Conventional Heating Comparative Synthesis of Poly(lactic acid) by Direct Melt Polycondensation from Agroindustrial Banana (Musa AAA Cavendish) and Pineapple (Ananas comosus) Fermented Wastes

In Costa Rica, a lot of pineapple (Ananas comosus) and banana (Musa AAA) agroindustrial residues are generated each year. These residues can be used to obtain l-lactic acid by fermentation, ultrafiltration and electrodialysis. Poly(l-lactic acid) (PLLA) is a biodegradable and renewable polyester with many industrial and biomedical applications. There is a growing interest to improve the energetic efficiency of the synthesis of PLLA, because the main issue to produce this polymer is the high productive cost compared with petrochemical traditional commodities. In this research, the synthesis of PLLA through two different techniques was compared: microwave-assisted and conventional heating. On microwave synthesis the best results were obtained using lower temperatures and lower reaction times than the conventional heated synthesis. The reaction time was reduced from 15 h by conventional heating to 4.5 h using microwave-assisted synthesis.     

Application of ameliorated wood pulp to recover Cd(II), Pb(II), and Ni(II) from e-waste

In this study, dl-malic acid and hydrogen peroxide were used as leaching agents to remove metals from e-waste (printed-circuit boards) and itaconic acid-grafted poly(vinyl alcohol)-encapsulated wood pulp (IA-g-PVA-en-WP) to uptake metals from leachate with high proficiency [11.63 mg g^?1; 93.03 % for Cd(II), 11.90 mg g^?1; 95.18 % for Pb(II), and 12.14 mg g^?1; 97.08 % for Ni(II)]. Metals were recovered from the loaded biosorbent by desorption studies. The standard analytical techniques, such as elemental analysis, Fourier-transform-infrared spectroscopy, scanning electron microscopy, atomic force microscopy, and thermogravimetric analysis, were used to characterize the recovering agent (biosorbent). At equilibrium, the metal uptake data were fitted to Langmuir and D–R isotherms (R ² > 0.99) significantly, revealing, the homogeneous distribution of active sites on biosorbent’s backbone. The possible mechanism appeared to be ion exchanges of metal ions with H⁺ together with binding over functionalities (COO^?). Dimensionless equilibrium parameter (R _L) showed the favourability of metal uptake at lower concentration, while mean adsorption energy (E) certified the physical binding of metal on functionalities which was further confirmed by sticking probability and activation energy parameters. Reusability studies were also conducted to state the performance of biosorbent.     

Green Synthesis of Silver Nanoparticles and Study of Their Antimicrobial Properties

One of the major disadvantages of polymers when used in food-contact applications is that they are very susceptible to microbial attack. On the other hand, silver nanoparticles have received increased attention as novel antimicrobial agents. Therefore, the introduction of silver nanoparticles into conventional polymers results in new materials with improved properties. In this investigation, colloidal silver nanoparticles using an environmentally friendly procedure were synthesized. An aqueous solution of AgNO₃ was used as a silver precursor with ‘green’ reducing agents either different types of honey, or β-d-glucose. In the first case, different pH values, as well as the addition of poly(ethylene glycol), PEG were studied, while in the latter, the effect of reduction time in the presence of PEG with various average molecular weights was examined. Properties of the nanoparticles were measured using X-Ray diffraction, UV–Vis and FTIR spectroscopy. Using honey it seems that spherical particles are produced with the smaller average particle size obtained at pH 8.5. Use of honey has the advantage of being a natural product, although its main drawback is that its composition varies and it cannot be predefined to result in reproducible results. Use of β-d-glucose results in stable silver nanoparticles with small average particle size after 24 h reduction. The addition of low molecular weight PEG seems to be beneficial in the production of stable nanoparticles. Finally, the antimicrobial activity of the nanoparticles produced was investigated at different concentrations on both Gram positive and negative bacteria, such as Bacillus cereus, Bacillus subtilis, Escherichia coli and Staphylococcus aureus.     

Novel Glycopolymers Based on d-Mannose and Methacrylates: Synthesis, Thermal Stability and Biodegradability Testing

This paper presents the synthesis, thermal stability and biodegradability of new d-mannose glycopolymers. These glycopolymers have been obtained by free radical bulk copolymerization of d-mannose based glycomonomer, 1-O-(2′-hydroxy-3′-methacryloyloxypropyl)-2,3:5,6-di-O-isopropylidene-d-mannofuranose (Mm), and respectively d-mannose derived oligomer (Mo) with methyl methacrylate and respectively 2-hydroxypropyl methacrylate. The chemical structures of Mm and Mo have been confirmed via FTIR, ¹H-NMR and HPLC–MS spectroscopy. The copolymerization process has been investigated using differential scanning calorimetry, which allowed calculating the activation energies by applying Kissinger–Akahira–Sunose method. The glycopolymers are thermally stable, fact assessed by TG analysis; their glass transition temperature exceeds 50 °C, so they are part of the glassy class of polymers. The biodegradability of these glycopolymers has been investigated in vitro, using pure cultures of Zymomonas mobilis and Trichoderma reesei. The glycopolymers lose up to 55 % weight in just 14 days of incubation as their surface and composition is altered by colonies of microorganisms that grow on/into them, fact demonstrated using SEM/EDX.     

Characterization of dried sewage sludge for co-firing in coal power plant by using thermal gravimetric analysis

This research studied the characteristics of dried sewage sludge using TGA to co-fire dried sewage sludge with coal in power plants. The sewage sludges that were discharged from Daejeon, Korea were dried and examined fundamental properties to use them as a fuel. Also, the properties of bituminous coal and wood pellet, which are used in domestic coal power plants, were analyzed and compared with them of sewage sludges and non-isothermal analyses of dried sewage sludges were performed at the heating rates of 5, 10, 20, and 30C /min using TG analyzer to investigate the basic combustion characteristics. As a results of these TGA/DTG analyses, sewage sludges showed its primary peak at the temperature of 250–500?°C, which overlapped with main peak of wood and secondary peak at around 500–600?°C, which overlapped with main peak of coals. Also for the interpretation by Friedman method, the activation energies in the section of highest weight loss were 525.16 kJ/mole for dried digested sewage sludge, 544.88 kJ/mole for dried excess sewage sludge, 203.86 kJ/mole for wood pellet and 146.4585 kJ/mole for bituminous coal. The reaction orders for dried digested excess sewage sludge, dried excess sewage sludge, wood pellet and bituminous coal were 28.775, 24.319, 18.398 and 9.1005, respectively, and the frequency factors were 5.89?\(\times \hspace{0.17em}\)10²⁸, 1.65?\(\times \hspace{0.17em}\)10^24,, 9.59?\(\times \hspace{0.17em}\)10¹⁶ and 1.77?\(\times \hspace{0.17em}\)10⁸ for each, respectively.     

Modelling and Optimization of Uranium (VI) Ions Adsorption Onto Nano-ZnO/Chitosan Bio-composite Beads with Response Surface Methodology (RSM)

Nano-ZnO-chitosan bio-composite beads were prepared for the sorption of \({\text{UO}}_{2}^{{2+}}\) from aqueous media. The resulting nano-ZnO/CTS bio-composite beads were characterized by TEM, XRD etc. The sorption of \({\text{UO}}_{2}^{{2+}}\) by bio-composite beads was optimized using RSM. The correlation between four variables was modelled and studied. According to RSM data, correlation coefficients (R²?=?0.99) and probability F-values (F?=?2.24?×?10^??10) show that the model fits the experimental data well. Adsorption capacity for nano-ZnO/CTS bio-composite beads was obtained at 148.7 mg/g under optimum conditions. The results indicate that nano-ZnO/CTS bio-composite beads are appropriate for the adsorption of \({\text{UO}}_{2}^{{2+}}\) ions from aqueous media. Also, the suitability of adsorption values to adsorption isotherms was researched and thermodynamic data were calculated.     

Characteristic Properties of Novel Organosolv Lignin/Polylactide/Delta-Valerolactone Terpolymers

Compostable terpolymers of l-lactide (LLA), delta-valerolactone (DVL), and switchgrass organosolv lignin (OSL) were synthesized via ring-opening polymerization to improve on polylactide homopolymer properties for commercial applications. OSL has properties that improve some of the deficiencies of polylactide, including polylactide’s limitations for use in food, beverage and medical applications due to its high water permeability and low ultraviolet light (UV) blocking capabilities. DVL was incorporated into these polymers to add flexibility. The addition of DVL to the polymer had a positive effect on the tensile strain properties of the resultant terpolymer, resulting in a more flexible polymer with a reduced Young’s modulus. Water vapor transmission rate calculations confirmed that water vapor was transported more slowly through terpolymer films than through the PLLA homopolymer under varying hygrostatic conditions. While the addition of DVL increased UV permeability, the addition of even a small amount of lignin can effectively counteract this effect.     

Synthesis and Properties of Poly(d,l-lactide-co-p-dioxanone) Random and Segmented Copolymers

Two different polymerization routes, one-step and two-step bulk ring-opening polymerizations of d,l-lactide (LA) and p-dioxanone (PDO) monermers using stannous octoate [Sn(Oct)₂]/n-dodecanol as the initiating system, were employed to synthesize poly(d,l-lactide-co-p-dioxanone) P(LA-co-PDO) random and segmented copolymers with different compositions and chain microstructure. For the two-step copolymers, the average sequence lengths of the lactidyl (L_LA) and dioxanyl (L_PDO) units calculated from the ¹H-NMR spectra were much longer than those values for the one-step copolymers with the same LA/PDO feed ratio. Corresponding to this difference in microstructure, the two-step copolymers were semi-crystalline even when the PDO content was as low as 14.5 mol%, while the one-step copolymers were completely amorphous with PDO content below 60.6 mol%. However, irrespective of polymerization route, both types of copolymers displayed a single glass transition temperature that was in a linear relation with composition. The decrease of maximum decomposition temperature of the copolymers was in accordance with the decrease of L_PDO value. The mechanical and degradation properties of the copolymers were significantly affected by both the polymerization route and the chemical composition as well. In conclusion, the properties of P(LA-co-PDO) copolymers could be adjusted conveniently to meet specific applications by changing the composition and microstructure of the copolymers via different polymerization routes.     

Effects of heating rate and temperature on product distribution of poly-lactic acid and poly-3-hydroxybutyrate-co-3-hydroxyhexanoate

In this study, poly-lactic acid (PLA) and poly-3-hydroxybutyrate-co-3-hydroxyhexanoate (PHBH) were pyrolyzed at various temperatures (300, 350, 400, 500, 600, and 700 °C) and heating rates (5, 10, 20, 30, and 40 °C min⁻¹) using a pyrolysis–gas chromatograph/mass spectrometer (Py–GC/MS). The results revealed that the main pyrolysis products of PLA were acetaldehyde, lactide (including meso-lactide and d-, l-lactide), and oligomers. Crotonic acid and its oligomers accounted for most of the PHBH pyrolyzates. The pyrolysis temperature significantly correlated with the product distribution, but the heating rate had a small effect on the product distribution. Lactide and crotonic acid were two kinds of high-value chemicals, and their highest yields were obtained at 400 and 600 °C with 29.7 and 72.6 area %, respectively. Secondary reactions could not be neglected at 700 °C, and acetaldehyde and crotonic acid decreased to 65.0 and 69.6 area %, respectively. These results imply that pyrolyzate selectivity can be controlled by temperature management during pyrolysis.

     

Effect of Hexadecyl Lactate as Plasticizer on the Properties of Poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactide) Films for Food Packaging Applications

In this study, poly(l-lactide) (PLA) films were fabricated by melt processing and the plasticizing effect of hexadecyl lactate (HL) (0, 5, 7.5, 10, and 12.5 wt% on PLA were investigated by scanning electron microscopy (SEM), differential scanning calorimetry, thermogravimetric analysis, tensile, transparency, and water vapor permeability tests. The SEM analysis revealed that PLA with 10 wt% HL appeared uniform with extra small bumps, confirmed the interaction between PLA and HL. The thermal analysis revealed a glass transition temperature of 57.4 °C for neat PLA film, but the addition of HL elicited a decrease in the temperature of the peak (43.8 °C). The incorporation of plasticizer into PLA resulted in the increase of elongation at break, as well as the decrease of tensile strength and tensile modulus. Even though a decrease in transparency was recorded, the PLA/HL blend films appeared transparent by visually observation. The water vapor permeability of PLA/HL blend films increased with the increase of HL. The PLA/HL blend films could effectively extend the shelf-life of fresh-cut pears as the commercial low density polyethylene films. The results indicated that the properties of PLA films can be modified with the addition of HL and PLA/HL blend films could serve as an alternative as food packaging materials to reduce environmental problems associated with synthetic packaging films.     

Optimization of Poly(<Emphasis Type="SmallCaps">dl</Emphasis>-Lactic Acid) Degradation and Evaluation of Biological Re-polymerization

Poly(dl-lactic acid) or PLA is a biodegradable polymer. It has received much attention since it plays an important role in resolving the global warming problem. The protease produced by Actinomadura keratinilytica strain T16-1 was previously reported as having PLA depolymerase potential and being applicable to PLA biodegradation, which was used in this work. Therefore, this research demonstrates the important basic knowledge on the biological degradation process by the crude PLA-degrading enzyme from strain T16-1. Its re-polymerization was evaluated. The optimization of PLA degradation by statistical methods based on central composite design was determined. Approximately 6700 mg/l PLA powder was degraded by the crude enzyme under optimized conditions: an initial enzyme activity of 200 U/ml, incubated at 60 °C for 24 h released 6843 mg/l lactic acid with 82% conversion, which was similar to the commercial enzyme proteinase K (81%). The degradable products were re-polymerized repeatedly by using commercial lipase as a catalyst under a nitrogen atmosphere for 6 h. A PLA oligomer was achieved with a molecular weight of 378 Da (n = 5). This is the first report to demonstrate the high efficiency of the enzyme to degrade 100% of PLA powder and to show the biological recycling process of PLA, which is promising for the treatment and utilization of biodegradable plastic wastes in the future.     

Production of Poly(l-Lactide)-Degrading Enzyme by Amycolatopsis orientalis ssp. orientalis and Its Catalytic Ability in Biological Recycling of Poly(l-Lactide)

The fermentation conditions for poly(l-lactide) (PLA)-degrading enzyme production by Amycolatopsis orientalis ssp. orientalis were statistically optimized by response surface methodology. The optimal value of the most important factors was 0.39 % PLA and 0.34 % gelatin for 2.81 days of cultivation. Under these conditions, the model predicted a PLA-degrading activity of 155.30 U/l. The verification showed the production amount of 154.2 U/l. The crude enzyme from A. orientalis ssp. orientalis showed potent PLA-degrading ability, which is efficient for the biological recycling of PLA. Up to 4,000 mg/l of PLA granule was completely degraded within 5 days at 45 °C by the crude enzyme. l-lactic acid (600 mg/l) was obtained as a degradation product of PLA after only 2 h of incubation. The results indicated that the crude PLA-degrading enzyme from A. orientalis ssp. orientalis has the potential to degrade PLA to lactic acid for the recycling of PLA industry and waste disposal.     

Dynamic studies on lead volatilization from CaO–SiO2–Al2O3 molten slag under N2–CO–CO2, N2–HCl and N2–H2S gas atmospheres

Dynamic studies on the volatilization of lead from CaO–SiO₂–Al₂O₃ molten slags were conducted in a lab-scale melting furnace from 1623 to 1773 K under different mixed gas atmospheres of CO 0.05–0.3 atm to CO₂ 0–0.3 atm to N₂ (balance), HCl 1.7 × 10^?3–6.7 × 10^?3 atm to N₂ (balance), and H₂S 3.0 × 10^?4 to 1.7 × 10^?3 atm to N₂ (balance). The slag samples consisted of the mixed powders of 20–50 wt% CaO, 30–60 wt% SiO₂, and 10–40 wt% Al₂O₃, containing 2000 ppm PbO.Results showed that the rates of volatilization of lead from the CaO–SiO₂–Al₂O₃ molten slags under the N₂–CO–CO₂, N₂–HCl, and N₂–H₂S gas atmospheres were higher than those under the simulated air (N₂–O₂), which increased with CO, HCl, and H₂S partial pressures. At \(p_{{HCl}}\)  =  \(p_{H_{2}S}\)  = 1.7 × 10^?3 atm, the apparent rate constants for the volatilization of lead under the N₂–H₂S and N₂–HCl gas atmospheres were nearly equal, which increased with a rise in temperature. Results also showed that the rate of volatilization of lead from the molten slag decreased drastically with the increasing viscosity of the molten slag, in the viscosity range lower than 3 Pa s. Consequently, the volatilization of lead from the CaO–SiO₂–Al₂O₃ molten slag was significantly influenced by CO, HCl, and H₂S partial pressures and by the viscosity of the molten slag.     

Enzyme-Assisted Extraction and Pb<Superscript>2+</Superscript> Biosorption of Polysaccharide from <Emphasis Type="Italic">Cordyceps militaris</Emphasis>

The enzyme assisted extraction conditions of polysaccharide from Cordyceps militaris mycelia were firstly investigated by kinetics analysis and the optimal operating was found to be: extraction temperature 40 °C; solid-solvent ratio 1:20; extraction pH 4.0; cellulase concentration 2.0%. The polysaccharide extraction yield was 5.99% under these optimized conditions. Furthermore, a fundamental investigation of the biosorption of Pb²⁺ from aqueous solution by the C. militaris polysaccharide was performed under batch conditions. The suitable pH (5.0), polysaccharide concentration (0.20 g L^?1), initial Pb²⁺ concentration (300 mg L^?1) and contact time (40 min) were outlined to enhance Pb²⁺ biosorption from aqueous medium. The Langmuir isotherm model and pseudo first order kinetic model fitted well to the data of Pb²⁺ biosorption, suggesting the biosorption of Pb²⁺ onto C. militaris polysaccharide was monolayer biosorption and physical adsorption might be the rate-limiting step that controlled the adsorption process. FTIR analysis showed that the main functional groups of C. militaris polysaccharide involved in adsorption process were carbonyl, carboxyl, and hydroxyl groups.