Photodegradation of Poly(lactic acid) Stereocomplex by UV-Irradiation

Neat poly(l-lactic acid) (PLLA) and poly(d-lactic acid) (PDLA) films and PLLA/PDLA blend films were prepared by solution casting, and their photodegradation by UV-irradiation was investigated using wide-angle X-ray scattering (WAXS), gel permeation chromatography, differential scanning calorimetry, tensile testing, and polarized optical microscopy. The PLLA/PDLA blend film was more photodegradation-resistant than the neat PLLA and PDLA films when photodegradation was monitored by molecular weight, melting temperature, and WAXS crystalline peak positions. This indicates that the chains in both amorphous and crystalline regions of the PLLA/PDLA blend film were photo-cleavage-resistant compared to those of the neat PLLA and PDLA films. The changes in melting temperature and WAXS crystalline peak positions before and after photodegradation respectively indicated the increased crystalline lattice disorder and the decreased crystalline lattice sizes of the neat PLLA and PDLA films, whereas these changes were insignificant for the blend films. Photodegradation caused no significant change in tensile properties, with the exception of significant decreases in the tensile strength and elongation at break of PLLA/PDLA blend film. However, the tensile strength and elongation at break of the PLLA/PDLA blend film retained higher values compared to those of the neat PLLA and PDLA films during photodegradation. In spite of the slower photodegradation of the PLLA/PDLA blend film traced by M _n, T _m, and WAXS crystalline peak positions than that of neat PLLA and PDLA films, the rapid decrease in tensile strength and elongation at break of the former than that of the latter should be due to the highly-ordered structural difference between them, i.e., the three dimensional dry gel of the former and the spherulites of the latter.     

Crystallization Behavior and Dynamic Mechanical Properties of Poly(l-Lactic Acid) with Poly(Ethylene Glycol) Terminated by Benzoate

Effect of the addition of poly(ethylene glycol) terminated by benzoate (PEG-BA) on the crystallization behavior and dynamic mechanical properties of poly(l-lactic acid) PLLA is studied as compared with poly(ethylene glycol) (PEG-OH). It is found that PEG-BA is miscible with PLLA and shows good plasticizing effect. Because PEG-OH having the same degree of polymerization is immiscible with PLLA, the end group in PEG-BA, i.e., benzoate, plays an important role in the miscibility. Furthermore, PEG-BA does not induce the PLLA degradation at melt-processing, whereas PEG-OH leads to the hydrolysis degradation. Finally, the addition of PEG-BA pronounces the crystallization rate of PLLA at low crystallization temperatures and thus enhances the degree of crystallinity at conventional processing. Consequently, the temperature dependence of dynamic mechanical properties are similar to that for isotactic polypropylene.     

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.     

Effects of washing with water on enzymatic saccharification and d-lactic acid production from steam-exploded sugarcane bagasse

This study investigated the production of d-lactic acid from unutilized sugarcane bagasse using steam explosion pretreatment. The optimal steam pressure for a steaming time of 5?min was determined. The steam-exploded sugarcane bagasse was hydrolyzed using cellulase (Meicelase) and then the hydrolyzate was subjected to fermentation substrate. By enzymatic saccharification using Meicelase, the highest recovery of glucose from raw bagasse, 73.7?%, was obtained at a steam pressure of 20?atm. For extracted residue with water after steam explosion, the glucose recovery increased up to 94.9?% at a steam pressure of 20?atm. These results showed that washing with water is effective in removing enzymatic reaction inhibitors. After steam pretreatment (steam pressure of 20?atm), d-lactic acid was produced by Lactobacillus delbrueckii NBRC 3534 from the enzymatic hydrolyzate of steam-exploded bagasse and washed residue. The conversion rate of d-lactic acid obtained from the glucose concentration was 66.6?% for the hydrolyzate of steam-exploded bagasse without washing with water and 90.0?% for that derived from the extracted residue with water after steam explosion. These results also demonstrated that the hydrolyzate of steam-exploded bagasse (without washing with water) contains fermentation inhibitors and washing with water can remove them.     

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.     

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.     

Bioethanol production from enzymatically saccharified lawn clippings from a golf course

The utilization of bioethanol is being focused on as a fuel alternative to oil and or natural gas. Bioethanol production from cellulosic plant residues is one of the solutions proposed for the problems caused by usage of food crops that are also vital for human consumption, such as sugar cane and corn, as a source of bioethanol. However, to utilize these new sources for bioethanol production, conditions for saccharification in each different material have not been optimized. In this study, we reported some optimum conditions for the saccharification of Korean lawn grass (KL) and bent grass (BG) using acremonium cellulase and endoglucanase as saccharifying enzymes for ethanol fermentation. With respect to saccharification of KL and BG, 0.19 and 0.18 g of d-glucose per g-substrate at maximum were produced, respectively. Comminution with a ball mill was found to be effective in the saccharification of KL, while ball-milled BG showed no significant improvement in saccharification. Being incorporated with 99 % of d-glucose consumption, saccharified KL was incubated for 3 days with Saccharomyces cerevisiae and Zymomonas mobilis, respectively, and each mixture fermented to ethanol yielding approximately 100 % of theoretical values from d-glucose consumption, respectively.     

Poly(Lactic Acid)-co-Aspartic Acid Copolymers: Possible Utilization in Drug Delivery Systems

The synthesis and characterization of poly(lactic acid)-co-aspartic acid copolymers (PLA-co-Asp) were presented. Subsequently, the synthesized PLA-co-Asp copolymers were tested as biodegradable carriers in drug delivery systems. PLA-co-Asp copolymers were synthesized by solution polycondensation procedure, using different molar ratios PLA/l-aspartic acid (2.33/1, 1/1, 1/2.33), manganese acetate and phosphoric acid as catalysts and N,N′-dimethyl formamide (DMF)/toluene as solvent mixture. The copolymers were characterized by FT-IR and ¹H-NMR spectroscopy, gel permeation chromatography (GPC), DSC and TG-DTG analyses. Diclofenac sodium, a non steroidal anti-inflammatory drug was subsequently loaded into PLA-co-Asp copolymers. The in vitro drug release experiments were done by dialysis of the copolymer/drug systems, in phosphate buffer solution (pH = 7.4, at 37 °C) and monitored by UV spectroscopy.     

Fungal Degradation of Poly(l-lactide) in Soil and in Compost

The biodegradability of polymers by microorganisms is generally studied in a real environment that contains a natural mixture of fungi and bacteria. The present research mainly focused on the purely fungal degradation of poly(l-lactide), PLLA, to enclose the part of fungi in a real process of biodegradation and to understand the kinetics of biodegradation. Respirometric tests were realized in soil at 30?°C, and in compost at 30?and 58?°C. Results indicated that temperature is the predominant parameter governing the fungal degradation of PLLA. Moreover, in real compost, the biodegradation kinetics of the PLLA revealed a synergy between bacteria and fungi. The curves of PLLA and cellulose biodegradation were modeled by Hill sigmo?d. Fungal degradation was completed by investigating the physical and the chemical properties of the polymer during the process of degradation using several analytical methods such as matrix assisted laser desorption ionization-time of fly spectroscopy, infrared spectroscopy, size exclusion chromatography, and differential scanning calorimetry. These experiments led to a better understanding of the various stages of fungal degradation of PLLA: hydrolysis as well as mineralization. Furthermore, metabolizing products (by-products) of PLLA was investigated also.     

Production of 2-Pyrrolidone from Biobased Glutamate by Using Escherichia coli

We have developed a simple and highly efficient process for the production of 2-pyrrolidone (2-PRN) from biobased l-glutamic acid (Glu). First, we produced γ-aminobutyric acid (GABA) from Glu obtained by fermentation of biomass using Escherichia coli, which is known to possess GABA producing activity. The reaction solution contained only the substrate Glu, bacterial cells, and water, and did not require buffers or coenzymes, pyridoxal-5′-phosphate (PLP). Every 24 h, cells were removed by centrifugation, and GABA containing supernatant was obtained. This reaction can be repeated 14 times by adding water and Glu, without any decrease in activity. Finally, 303.7 g of GABA was produced from 560 g (40 g × 14 times) of Glu with a yield of 77.4 %. The concentration of this solution was almost 40 %. The GABA was then converted to biobased 2-PRN by heating and distillation under reduced pressure without pretreatment. The yield obtained with this chemical process was 95.8 %. These results showed that biobased 2-PRN could be produced from biomass-derived Glu. Biobased 2-PRN has great potential as a raw material to change other petroleum-based materials to biobased materials.     

Effect of Nucleation of Tricalcium Phosphate and Isothermal Annealing on the Crystallization of Poly(l-lactide-co-glycolide)

We investigated the effect of nucleation and isothermal annealing on the crystallization behavior of a random copolymer, poly(l-lactide-co-glycolide) (PLLGA), with monomer molar ratios of 85/15 (PLLGA85/15) by scanning electron microscopy, polarizing optical microscopy, differential scanning calorimetry, and X-ray diffraction, and examination of the tensile properties of the resultant product. The effect of heterogeneous nucleation was assessed by the addition of tricalcium phosphate (TCP) as a nucleating agent. Nucleation and isothermal annealing of PLLGA at 130 °C were conducted to improve the degree of crystallinity of the copolymer. The fracture surfaces of the TCP/PLLGA85/15 composite bar showed a considerable number of spherulites with TCP as their nucleus. Addition of TCP and subsequent annealing improved the degree of crystallinity. After annealing, the TCP/PLLGA85/15 composite samples gained nearly the same strength that the pure PLLGA85/15 samples possessed. It is believed that this method will enhance the practical application of this nucleating agent in the processing of polymers.     

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.     

Hydrolytic Degradation of PPDO/PDLLA Blends Containing the Compatibilizer PLADO

The poly(para-dioxanone) (PPDO)/poly poly (dl-lactide) (PDLLA) blends containing various contents of compatibilizer (0, 1, 3, 5, 10 %) were prepared by solution co-precipitation, which were dissolved in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) to form 10 % wt/vol solutions. Then in vitro hydrolytic degradation of PPDO/PDLLA blends containing poly (dl-lactide-co-para-dioxanone) (PLADO) as the compatibilizer was studied by the changes of weight loss, water absorption, thermal properties, surface morphology and mechanical properties of samples in phosphate buffered saline (pH 7.44) at 37 °C for 8 weeks. During the degradation, the weight loss and water absorption increased significantly for all blends, whereas hydrolysis rate of blends varied with the blend composition. The samples’ glass transition temperature decreased notably, while the degrees of crystallinity increased. Compared with uncompatibilized PPDO/PDLLA blends, PPDO/PDLLA blends with compatibilizer exhibited higher hydrolysis rate. The results suggested that the compatibilizer (PLADO) accelerated the hydrolysis rate of PPDO/PDLLA blends during the degradation.     

Longitudinal Dispersion Characteristics of Rivers and Natural Streams in Greece

An optimized parameterization of the non-dimensional longitudinal dispersion coefficients in Greek rivers, $K_{x_a } $ , is described in terms of parameters derived from cross-section river geometry and longitudinal velocity data. Optimization is accomplished, using various combinations of the selected parameters, either for subsets of $K_{x_a } $ values, according to the cross-section aspect ratio range, or for the entire $K_{x_a } $ population. The use of shape factors associated with the river cross-section transverse profiles of depth-mean longitudinal velocities and the normalized intensities of longitudinal velocity variations from the overall mean cross-sectional velocity improves the parameterization. The statistical behavior of $K_{x_a } $ in terms of skewness, flatness and other shape coefficients is also examined. $K_{x_a } $ histograms show that these coefficients have a log-normal distribution. An empirical expression for $K_{x_a } $ is also proposed that takes into account both contributions from the transverse velocity profile and from the vertical profile of longitudinal velocities, at each cross-section, in shaping the value of dispersion coefficients when the aspect ratio of the cross-section is of O(1) and/or when $K_{x_a } $ is of O(1).     

Crystal and Thermal Properties of PLLA/PDLA Blends Synthesized by Direct Melt Polycondensation

We herein report the effects of the component ratio and method of blending on the synthesis of stereocomplex poly(lactic acid) (SC-PLA) based on poly(l-lactic acid) (PLLA) and poly(d-lactic acid) (PDLA) prepolymers. PLLA and PDLA were prepared by direct melt polycondensation of lactic acid (DMP). Combined with the dual catalyst system, PLA prepolymers with M_w more than 20,000 were prepared by DMP. PLLA was mixed by powder blending or melt blended with PDLA. It is revealed that melt-point and spherulite growth rate of SC-PLA is strongly dependent on the perfection of SC structure. The melt point of PLA can be increased by nearly 50 °C because of the particular strong intermolecular interaction between PLLA and PDLA chains. Solid-state polycondensation (SSP) is an efficient method to increase the molecular weight of SC-PLA, but it can have a negative effect on the regularity of linear chains of SC-PLA. Thermogravimetry analyzer (TGA) results show that SC structure cannot cause the delay reaction on the thermal degradation of PLA.     

Chelating Ability and Microbial Stability of an <Emphasis Type="SmallCaps">l</Emphasis>-Arginine-Modified Chitosan-Based Environmental Remediation Material

To improve the heavy metal ion chelating ability and the microbiological stability of chitosan (CS), l-arginine (l-Arg) was grafted on CS polymer in the presence of the condensing agent 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (EDC) and the coupling reagent N-hydroxysuccinimide (NHS) to prepare a natural polymer-based environmental rehabilitation material: l-arginine-grafted chitosan (CA). The graft mechanism is discussed, and the reaction conditions were optimized. The product was characterized using elemental analysis, infrared spectroscopy (FT-IR) and ¹³C-NMR spectroscopy (¹³C-NMR). The optimal reaction conditions were a reactant molar ratio nCS:nArg:nEDC:nNHS of 3:3:3:1, a reaction time of 12 h, and a reaction system pH?=?5. Under these conditions, the grafting ratio (GR) was 16.85%, while the product yield (PY) was 90.48%. The results of the adsorption experiments showed that the CA (GR?=?16.85%) had a better removal capacity for highly concentrated Cu²⁺ and Ni²⁺ ions than CS. The antibacterial activity of the CA was also enhanced. When the GR reached 16.85%, the CA almost completely inhibited the growth of colibacillus and Staphylococcus aureus. Due to its high chelating ability and microbiological stability, this novel metal-ion adsorption material, CA, can be considered to have broad application potential in heavy metal ion-polluted water and soil remediation.     

Microwave Assisted Short-Time Alkaline Extraction of Birch Xylan

Efficacy of microwave energy for the extraction of xylan from birch wood as an alternative to conventional method of extraction was investigated. Effect of irradiation time and microwave power input on the solubilization of wood and yield of extracted xylan was studied. The maximum yield of xylan obtained at the higher power level was significantly lesser compared to the lower power level indicating the molecular degradation of the polymer. The highest yield of xylan (60 % of the original xylan) was obtained at the lowest power level studied, 110 W, for an irradiation time of 10 min. Comparison with conventional extraction showed that 10 min of microwave extraction provided a similar wood dissolution to that at 90 °C for 1.5 h, but with a higher yield of xylan. Characterization of the precipitated xylan indicated that the extracted xylan contained 68–88 % of xylose with the major chemical structure consisting of a linear backbone of (1-4) β-d-xylopyransoyl residues. Molecular mass of the extracted xylan indicated that the xylan extracted using microwave contained 60–70 % of high molecular weight fraction, and about 30–40 % of low molecular weight fraction, whereas xylan extracted using conventional method showed a reverse trend. Molecular mass of non-aggregated xylan was reported to be 6,000 Da (in terms of dextran equivalents). Crystallinity of wood fibers increased irrespective of the method of extraction indicating no degradation of the strength of the fibers occurred during the extraction.     

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.     

Synthesis and Properties of Biodegradable Poly(vinyl alcohol)/Organo-nanoclay Bionanocomposites

Biodegradable nanocomposites comprising of biodegradable polymers and bioactive organically modified layered silicates commonly reveal extremely enhanced mechanical and various other properties when compared to those of virgin polymers. This work was undertaken with a view to preparation of polymer bionanocomposites consisting of biodegradable poly(vinyl alcohol) (PVA) and organo-nanoclay. Cloisite Na⁺ and ammonium salt of l-isoleucine amino acid was used for the preparation of the novel chiral organo-nanoclay via an intercalation reaction in an aqueous solution. PVA/organo-nanoclay bionanocomposites of various compositions were created through the solution intercalation method by ultrasound-assisted technique. The resulting novel materials were characterized by X-ray diffraction and Fourier transform infrared spectroscopy techniques. Thermogravimetric analysis (TGA) and UV/vis spectroscopy were applied to test the properties of PVA bionanocomposites. TGA indicate that the thermal stability is enhanced distinctly, without a sacrifice in optical clarity. The improvement of thermal properties was attributed to the homogeneous and good dispersion of organo-nanoclay in polymeric matrix and the strong hydrogen bonding between O?CH groups of PVA and the oxygen atoms of silicate layers or carbonyl group as well as OH group of intercalated amino acid. The morphology of the organo-nanoclay and PVA bionanocomposites was examined by scanning electron microscopy and transmission electron microscopy techniques. Uniform distribution of clay due to intimate interaction between clay and polymer appears to be the cause for improved properties.