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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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).     

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.     

The influence of air inflow on CH4 composition ratio in landfill gas

When landfill gas is collected, air inflow into the landfill can reduce CH₄ productivity. The decline of CH₄ content in landfill gas (LFG) negatively affects energy projects. We studied air inflow rates and LFG characteristics from 699 vertical collection facilities (VCFs) in the 2nd landfill at the Sudokwon Landfill in South Korea. We first determined whether or not N₂ was an effective indicator of air inflow at this site using argon assays. The results of this analysis showed that the denitrification processes could be disregarded and that N₂ was an effective indicator of air inflow. Using the composition of N₂ in LFG samples, we found that air inflow occurred at 73.6 % of the VCFs, and 25.6 % of samples from these facilities showed more than 80 vol% of air inflow. In addition, we observed that the O₂ consumption rate was more than 70 % of the volume in all samples. $ R_{{{\text{CH}}_{ 4} }} $ , which is the ratio of CH₄ to the sum of CH₄ and CO₂, decreased with increasing air inflow. Finally, we found that, as air inflow increased, the variation in $ R_{{{\text{CH}}_{ 4} }} $ values for samples with equal air inflow ratios also increased due to differences in air inflow routes.     

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.     

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.     

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.     

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.     

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.     

Kinetic Analysis of the Temperature Effect on Polyhydroxyalkanoate Production by <Emphasis Type="Italic">Haloferax mediterranei</Emphasis> in Synthetic Molasses Wastewater

Haloferax mediterranei is an extremely halophilic archaeon that is able to synthesize polyhydroxyalkanoate (PHA) in high salt environment with low sterility demand. In this study, a mathematical model was validated and calibrated for describing the kinetic behavior of H. mediterranei at 15, 20, 25, and 35 °C in synthetic molasses wastewater. Results showed that the production of PHA by H. mediterranei, ranging from 390 to 620 mg h^?1 L^?1, was strongly dependent on the temperature. The specific growth rate (µ _max), specific substrate utilization rate (q _max), and specific decay rate (k _d) of H. mediterranei increased with temperature following Arrhenius equation prediction. The estimated activation energy was 58.31, 25.59, and 22.38 kJ mol^?1 for the process of cell growth, substrate utilization, and cell decay of H. mediterranei, respectively. The high temperature triggered the increased PHA storage even without nitrogen limitation. Thus, working at high temperatures seems a good strategy for improving the PHA productivity of H. mediterranei.     

Magnetic Cr(VI) Ion Imprinted Polymer for the Fast Selective Adsorption of Cr(VI) from Aqueous Solution

In this study, a novel magnetic Cr(VI) ion imprinted polymer (Cr(VI)-MIIP) was successfully synthesized and used as a selective sorbent for the adsorption of Cr(VI) ions from aqueous solution. It can be synthesized through the combination of an imprinting polymer and magnetic nanoparticles. The high selectivity achieved using MIIP is due to the specific recognition cavities for Cr(VI) ions created in Cr(VI)-MIIP. Also, the magnetic properties that could be obtained using magnetic nanoparticles, helps to separate adsorbent with an external magnetic field without either additional centrifugation or filtration procedures. The magnetic Fe₃O₄ nanoparticles (MNPs) were synthesized using an improved co-precipitation method and modified with tetraethylorthosilicate (TEOS) before imprinting. The magnetic Cr(VI) ion imprinted polymer was prepared through precipitation copolymerization of 4-vinylpyridine as the complexing monomer, 2-hydroxyethyl methacrylate as a co-monomer, the Cr⁶⁺ anion as a template, and ethylene glycol dimethacrylate (EGDMA) as a cross-linker in the presence of modified magnetite nanoparticles. This novel synthesized sorbent was characterized using different techniques. Batch adsorption experiments were performed to evaluate the adsorption conditions, selectivity, and reusability. The results showed that the maximum adsorption capacity was 39.3 mg g^?1, which was observed at pH 3 and at 25?°C. The equilibrium time was 20 min, and the amount of adsorbent which gave the maximum adsorption capacity was 1.7 g L^?1. Isotherm studies showed that the adsorption equilibrium data were fitted well with the Langmuir adsorption isotherm model and the theoretical maximum adsorption capacity was 44.86 mg g^?1. The selectivity studies indicated that the synthesized sorbent had a high single selectivity sorption for the Cr(VI) ions in the presence of competing ions. Thermodynamic studies revealed that the adsorption process was exothermic (\(\Delta H\)?<?0) and spontaneous (\(\Delta G\)?<?0). In addition, the spent MIIP can be regenerated up to five cycles without a significant decrease in adsorption capacity.