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DMAP-catalyzed phthalylation of cellulose with with phthalic anhydride in [bmim]Cl
Li, W., Wu, L., Di, C., Liu, C., and Sun, R. (2011). "DMAP-catalyzed phthalylation of cellulose with with phthalic anhydride in [bmim]Cl," BioRes. 6(3), 2375-2385.
It has been generally accepted that some ionic liquids are good media for homogeneous functionalization of cellulose. However, phthalylated cellulosic derivatives prepared in ionic liquids without any catalyst have lower DS as compared to the acetylated ones. In order to prepare the phthalylated cellulosic derivatives with higher DS, chemical modification of sugarcane bagasse cellulose with phthalic anhydride using ionic liquid 1-butyl-3-methylimidazolium chloride ([bmim]Cl) as a solvent and 4-dimethylaminopyridine (DMAP) as a catalyst has been examined. The results indicated that DMAP could enhance the reaction efficiency. The native cellulose and cellulose phthalates were characterized by FT-IR, solid-state CP/MAS 13C NMR, and thermogravimetric analysis. The results from FT-IR and solid-state CP/MAS 13C NMR analyses indicated that the phthalylation between cellulose and phthalic anhydride was successfully achieved. In addition, it was found that the thermal stability of the cellulose phthalates decreased upon chemical modification.
DMAP-CATALYZED PHTHALYLATION OF CELLULOSE WITH PHTHALIC ANHYDRIDE IN [bmim]Cl
Weiying Li,a Lan Wu,a Di Chen,a Chuanfu Liu,a,* and Runcang Suna,b,*
Keywords: Cellulose; Ionic liquid; Phthalylation; DMAP
Contact information: a: State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640, China; b: College of Material Science and Technology, Beijing Forest University, Beijing, 100083, People's Republic of China; *Corresponding authors: chfliu@scut.edu.cn, rcsun3@bjfu.edu.cn
In recent years, utilization and development of cellulose has drawn much attention around all over the world because of its excellent properties such as sustainability as a feedstock, non-toxicity, biodegradability, and functionality (Pandey et al. 2000; Focher et al. 2001; Richardson et al. 2003; Liu et al. 2007a). However, the full potential of cellulose has not been exploited (Zhu et al. 2006). One of the reasons is due to its insolubility in water or common organic solvents, a factor that is mainly responsible for its limited application.
Since Swatloski et al. (2002) found that ionic liquids including 1-butyl-3-methylimidazolium chloride ([bmim]Cl) could be used as a non-derivatizing solvent for cellulose, the research on ionic liquids as solvents for cellulose has been blooming. Now, some ionic liquids such as [bmim]Cl have been used as solvent for cellulose dissolution (Swatloski et al. 2002; Zhang et al. 2005; Heinze et al. 2005; Fukaya et al. 2008) and reaction media for cellulose modification (Liu et al. 2007a; Wu et al. 2004; Liu et al. 2006; Barthel et al. 2006; Schlufter et al 2006; Erdmenger et al. 2007; Liu et al. 2007b; Fidale et al. 2009; Mormann et al. 2009; Zhang et al. 2009; Gericke et al. 2009). As reaction media for cellulose functionalization, ionic liquids provide a homogeneous phase for cellulose, which results in uniform and stable products (El Seoud et al. 2000; Liu et al. 2009). At present, most researchers in the area of chemical modification of cellulose focus on the acetylation of cellulose in ionic liquids because of easier reaction of cellulose with acetic anhydride or acetyl chloride. Both Wu et al. (2004) and Fidale et al. (2009) successfully prepared the acetylated cellulose with higher DS (DS>2) in ionic liquid 1-allyl-3-methylimidazolium chloride ([amim]Cl) and [bmim]Cl under mild reaction conditions without any catalyst. The order of reactivity of hydroxyl groups in cellulose was found to be C6-OH>C3-OH>C2-OH (Wu et al. 2004; Schlufter et al. 2006). Barthel et al. (2006) prepared the fully substituted cellulose derivatives in [bmim]Cl with the presence of the pyridine. Moreover, ionic liquids can also be used as homogeneous reaction media for cellulose tritylation (Zhang et al. 2009), carbanilation (Barthel et al. 2006; Schlufter et al 2006), and phthalylation (Liu et al. 2007b). Compared with cellulose acetylation, other homogeneous modifications of cellulose in ionic liquids only result in cellulose derivatives with low DS.
The monoester products of cellulose with cyclic anhydrides such as phthalic anhydride have been widely used in various applications such as water-absorbents for soil in agriculture, natural absorbents for the removal of heavy metal ions in waste water treatment, medicine for drug delivery systems, and thermoplastic materials (Hadano et al., 2003; Yoshimura et al., 2006). More importantly, they are key precursors to prepare derivatives by regioselective and quantitative chemical modification (Kurita et al. 2000; Liu et al. 2004). They provide a reactive site upon which further modification (Motawie and Sadek 1999; Nagaveni et al. 2005) for other potential utilizations such as in pharmaceutical industries is possible. In our lab, homogeneous phthalylation of cellulose were achieved without any catalyst (Liu et al. 2007b). However, cellulose phthalylation was more difficult than acetylation in ionic liquid, and the products with low DS were obtained under mild reaction conditions. Pyridine and 4-dimethylaminopyridine (DMAP) are outstanding nucleophilic basic catalyst for the acetylation of alcohols, amines, phenols and enolates (Höfle et al. 1978; Scriven 1983; Hill et al. 2000; Grondal 2003; Sakakura et al. 2007). Compared with pyridine, DMAP shows higher stability and stronger basicity. Connors and Albert (1973) found that DMAP had a specific catalytic activity about 104 times greater than that of pyridine. Because of the same function group (hydroxyl group) in alcohols and cellulose, we wonder whether DMAP is also a good catalyst for modification of cellulose. In this study, we have prepared cellulose phthalates with phthalic anhydride in ionic liquid [bmim]Cl in the presence of DMAP as a catalyst under various conditions. The modified celluloses were then characterized by DS, FT-IR, solid-state CP/MAS 13C NMR, and thermogravimetric analysis.
Sugarcane bagasse (SCB) was provided by a local factory (Guangzhou, China). It was dried in sunlight and then cut into piece to prepare 20-40 mesh size particles (450-900 μm). The cut SCB was further dried in an oven at 50 oC for 16 h before use. [bmim]Cl was obtained from the Chemer Chemical Co., Ltd., Hangzhou, China, and used as received. All of other chemicals were of analytical-reagent grade and received from Guangzhou Chemical Reagent Factory, China.
Extraction of Cellulose from Sugarcane Bagasse
The dried SCB powder was first dewaxed with toluene-ethanol (2:1 v/v) in a Soxhlet apparatus for 6 h. Then the dewaxed SCB (100 g) was extracted with 2 L distilled water at 80 oC for 2 h. After filtration and drying, the insoluble residue was delignified with 100 g sodium chlorite in acidic solution (pH 4.0, adjusted by 10% acetic acid) at 75 oC for 1 h, and then 50 g sodium chlorite was added to further delignify for another 1 h. The residue (holocellulose) was subsequently washed with distilled water and ethanol, and then dried in oven. The holocellulose was further extracted with 10% KOH at 25oC for 10 h to remove the hemicelluloses. After extraction, the residue (cellulose) was obtained by filtration, washed thoroughly with distilled water until the filtrate was neutral, then washed with 95% ethanol and dried in an oven at 50 oC for 16 h.
Preparation of Cellulose Phthalates in [bmim]Cl using DMAP as a Catalyst
For each trial, 0.2 g dried cellulose was added to 10 g [bmim]Cl in a three-necked flask. The mixture of cellulose/[bmim]Cl was purged with N2 and stirred at 100 oC up to 10 h to guarantee the complete dissolution of cellulose. Then phthalic anhydride with or without DMAP was added to cellulose solution to synthesize the cellulose phthalate at the selected temperature for a specific period under N2 atmosphere. After the required time, the mixture was slowly poured into isopropanol with stirring to stop the reaction. The solid was filtered out, washed thoroughly with isopropanol to remove contaminants such as ionic liquid, un-reacted anhydride, DMAP and by-products, and then dried in vacuum at 50 oC for 16 h.
Determination of the Degree of Substitution
The DS of cellulose phthalates was determined by the back-titration method (Stojanović et al. 2002). A certain weight of the sample was dispersed in 10 mL of NaOH by stirring at 50 oC for 30 min. Then 0.025 M HCl was used to back-titrate the excess of NaOH using phenolphthalein as the indicator. The titration was repeated at least three times, and the average value of the HCl volume was used for the calculations. The DS was obtained by using the following equation,
where 162 g/mol and 148 g/mol are the molar mass of an AGU and the net increase in the mass of an AGU for each phthaloyl substituted, respectively, m represents the weight of sample analyzed, and nCOOH is the amount of COOH calculated from the obtained value of the equivalent volume of known molarity HCl according to the following equation:
nCOOH=(VNaOH×CNaOH–VHCl×CHCl)/2 (2)
Characterization of the Native and Cellulose Phthalates
The FT-IR spectra of cellulose and cellulose phthalates were recorded on an FT-IR spectrophotometer (Nicolet 510) from finely ground sample (1%) in KBr pellets in the range 4000-400cm-1 with a resolution of 2 cm-1 in the transmission mode.
The solid-state CP/MAS 13C-NMR spectra of unmodified cellulose and phthalyl-ated cellulosic preparations were recorded on a Bruker DRX-400 spectrometer at the frequency of 100 MHz with 5 mm MAS BBO probe. Acquisition time was 0.034 s. The delay time was 2 s, and the proton 90o pulse time 4.85 μs. Each spectrum was obtained with an accumulation of 5000 scans.
Thermal stability of cellulose and cellulose phthalates were performed using thermogravimetric analysis (TGA) and differential thermal analysis (DTA) on a simulta-neous thermal analyzer (SDT Q600, TA Instrument). The sample weighed between 8 and 12 mg. The scans were run from room temperature to 550 oC at a rate of 10 oC per minute under nitrogen flow.
Modification and the Degree of Substitution
Scheme 1 shows the reaction of phthalic anhydride with cellulose. In our previous work, phthalylation of cellulose was carried out in ionic liquid, which resulted in a much lower degree of substitution under mild reaction conditions (Liu et al. 2007b). Therefore, a suitable solvent or catalyst should be added to the reaction system to reduce the activation energy or enhance the accessibility of the reactive hydroxyl groups of cellulose to the reactants (Khalil et al. 1995). Pyridine and DMAP are common effective nucleophilic basic catalyst for the esterification of hydroxyl (Hill et al. 2000; Sakakura et al. 2007). Compared with pyridine, DMAP shows higher stability, stronger basicity and greater catalytic ability. Therefore, DMAP is chosen as a basic catalyst for cellulose. In the present study, we studied the phthalylation reaction of cellulose with phthalic anhydride in ionic liquid using DMAP as a catalyst to improve modification efficiency. Table 1 shows the various conditions of the phthalylation of cellulose.
Scheme 1. The reaction of phthalic anhydride with cellulose
Table 1. The Degree of Substitution (DS) of Cellulose Phthalate
The effect of DMAP dosage on DS of cellulose derivatives is given in samples 1-6 in Table 1. The reaction was conducted at 80 oC for 60 min with 2.0% cellulose and a molar ratio of phthalic anhydride/AGU 4:1. As shown in Table 1, the DS of cellulose phthalate obtained without any catalyst was only 0.28. However, with the increase of DMAP dosage (based on phthalic anhydride) from 0 to 1%, 3% and 5% led to a significant increment of the DS of products from 0.28 to 0.88, 1.11 and 1.31, respect-tively. Obviously, a certain dosage of DMAP is one of the most important factors for the reaction, which has great effect on the DS of cellulose phthalates. However, further increase in the DMAP dosage from 5% to 15% led to a decrement in DS from 1.13 to 0.69. This result indicated that 5% was the optimum dosage for catalyzed phthalylation under the conditions used.
The possible reaction of the DMAP-catalyzed esterification of cellulose with phthalic anhydride is shown in Scheme 2. The mechanism of cellulose phthalylation with DMAP as a catalyst is considered to be a nucleophilic substitution reaction (Bhandari et al. 2002). In the substitution reaction, phthalic anhydride reacts with DMAP to form phthaloyl pyridinium intermediate. This intermediate can attack hydroxyl groups of cellulose more easily than phthalic anhydride. Because of the tendency of hydroxyl oxygen of cellulose to link with carboxyl group, DMAP is eliminated for the next cycle of catalyzation.
The reaction time and temperature also have important effects on the DS of products, as shown in samples 4 and 7-14 in Table 1. The DS of cellulose derivatives increased as the reaction time was raised from 30 to 60 min. It reached 0.77 within 30 min, 0.97 within 45 min, and 1.31 within 60 min. The reason for this increment of phthalylation by prolonging the reaction time was due to the favorable effect of time on absorption of the reactants between the phthalic anhydride and cellulose (Hill et al. 1998). However, as the reaction time further increased from 60 to 120 min, the DS of products decreased from 1.31 to 0.44, which indicated that a sufficient time did not result in further increase in the phthalylation. The reason may be due to the cleavage of the ester bond with phthalic acid, by-product yielded during the reaction (Jayakumar et al. 2000). These results were in accordance with our previous study (Liu et al. 2007a). Therefore, 60 min was considered as optimum reaction time under the reaction conditions given.
Scheme 2. Proposed mechanism for the phthalylation of cellulose with phthalic anhydride in the presence of DMAP
The DS of cellulose phthalates increased from 0.69 to 1.31 with the increase of reaction temperature from 70 to 80 oC. This affect indicates that a higher temperature had a positive effect on the molecule motion and collisions of phthalic anhydride with hydroxyl, which led to the increase of cellulose macroradicals and thus enhanced the reaction rate (Yoshimura et al. 2006). However, further increase in the reaction temperature from 80 oC to 110 oC led to a decrease in the DS from 1.31 to 0.36, which probably was due to the formation of by-product and degradation of cellulose and cellulose derivatives at a relatively higher reaction temperature. This was a satisfactory result due to less energy cost and less degradation of cellulose derivatives under relatively lower temperature.
FT-IR Spectra
FT-IR spectroscopy is one of the most used technologies to prove the esterfication of cellulose. The FT-IR spectra of unmodified cellulose (spectrum a) and cellulose phthalate sample 3 (spectrum b) are given in Fig. 1. Compared to spectrum a, the presence of the peaks at 1719, 1579, and 747 cm-1 in spectrum b provided evidence of the phthalylation. The band at 1719 cm-1 is due to the absorption of carbonyl group in carbonyl and ester (Gu et al. 1998). The peak at 1579 cm-1 is attributed to the antisymmetric stretching of carboxylic anions (Chang and Chang 2001). The absorption at 747 cm-1 corresponds to out-of-plane C-H bending of the ortho disubstituted benzene. Moreover, the intensity of the absorption band at 1289 cm-1 for C-O symmetric stretching in ester and carboxyl also increased. These changes indicated that carboxylic groups and phthaloyl groups were introduced into the cellulosic molecules and esterification reaction occurred. In addition, the absence of peaks at 1850 and 1780 cm-1 in spectrum of cellulose phthalate confirmed that the product was free of the un-reacted phthalic anhydride (Gu et al. 1998).
Solid-State CP/MAS 13C-NMR Spectra
To verify the chemical changes in the structure of the polymer, both native cellulose (spectrum a) and cellulose phthalate sample 4 (spectrum b) were further characterized by CP/MAS 13C-NMR spectroscopy, and their spectra are illustrated in Fig. 2. The carbons of carbohydrate moiety are mainly shown in the region between 50 and 110 ppm. The signals at 101.9 (C-1), 85.9 (C-4 of crystalline cellulose), 80.3 (C-4 of amorphous cellulose), 71.9 (C-5), 68.6 (C-2 and C-3), 61.8 ppm (C-6 of crystalline cellulose) and 59.5 (C-6 of amorphous cellulose) are all observed in spectrum a (Fringant et al. 1996). Compared to spectrum a, the presence of the signals at 129.5 ppm for benzene ring and 170.6 ppm for carboxylic in spectrum b directly proved the evidence of phthalylation (Jeon et al. 1999). In addition, the absence of the signal at 85.9 ppm for C-4 of crystalline cellulose and the shift of the signal for C-6 from 61.8 ppm to 60.8 ppm in spectrum b indicated that the crystalline structure of the cellulose was disrupted during dissolution and modification.
Fig. 1. FT-IR spectra of unmodified cellulose (spectrum a) and cellulose phthalate sample 3 (spectrum b)
Generally, the three free hydroxyl groups at C-6, C-2, and C-3 position are the main reactive sites in cellulose. As shown in Fig. 2, the intensity of the signals at 61.8 ppm for C-6 and 68.6 ppm for C-2 and C-3 decreased after phthalylation, which indicated that phthalylation reaction occurred at C-6, C-2, and C-3 positions.
Fig. 2. Solid state CP/MAS 13C-NMR spectra of unmodified cellulose (spectrum a) and cellulose phthalate sample 4 with DMAP as a catalyst (spectrum b)
Thermogravimetry is one of the common techniques to characterize the thermal stability of polymers such as cellulose. The TGA and DTA thermograms of unmodified cellulose (a) and cellulose phthalate sample 6 (b) are given in Figure 3. Usually, the TGA curves are used to determine the weight loss of the products as it is heated, cooled or held isothermally. As shown in Fig. 3, unmodified cellulose and cellulose phthalate sample 6 started to decompose at 240 oC and 204 oC, respectively.
Fig. 3. Thermograms and their 1st derivatives of native cellulose (spectrum a) and cellulose phthalate sample 6 (spectrum b)
Beyond these temperatures, there was a sharp weight loss. Similarly, at 50% weight loss, the decomposition temperature occurred at 328 oC for native cellulose and 310 oC for cellulose phthalate sample 6, respectively. These data implied that the thermal stability of cellulose phthalate decreased after dissolution and modification in ionic liquid. Similar result has been reported by Swatloski et al. (2002) and Liu et al. (2007a) during the dissolution and modification of cellulose in the ionic liquid. However, cellulose phthalate can still be used as novel and biodegradable absorbents for metal ions from waste water due to the thermal stability at 200 oC.
DMAP is an effective catalyst for cellulose phthalylation in the ionic liquid 1-butyl-3-methylimidazolium chloride. The DS of cellulose phthalates increased from 0.28 without any catalysts to the range of 0.36-1.31 under the catalytic conditions given.
Under the conditions given, the optimum reaction time, reaction temperature, and DMAP dosage (based on phthalic anhydride) is 60 min, 80 oC, and 5%, respectively.
The possible mechanism of DMAP-catalyzed phthalylation in ionic liquid is proposed as the formation of intermediate complex of phthalic anhydride with DMAP.
The FT-IR and solid-state CP/MAS 13C NMR spectra confirmed that phthalylation of hydroxyl groups in cellulose occurred at the C-6, C-3, and C-2 position. The thermal stability of cellulose phthalate decreased upon chemical modification.
We wish to express our gratitude for the financial support of this research from the National Natural Science Foundation of China (Nos.30871994, 30972325 and 30930073), the Fundamental Research Funds for the Central Universities (2009ZZ0024), and National Basic Research Program of China (2010CB732201).
Barthel, S., and Heinze, T. (2006). "Acylation and carbanilation of cellulose in ionic liquids," Green Chem. 8, 301-306.
Bhandari, P. N., and Singhal, R. S. (2002). "Studies on the optimisation of preparation of succinate derivatives from corn and amaranth starches," Carboh. Polym. 47, 277-283.
Chang, S. T., and Chang, H. T. (2001). "Comparisons of the photostability of esterified wood," Polym. Degrad. Stabil. 71, 261-266.
Connors, K. A., and Albert, K. S. (1973). "Determination of hydroxy compounds by 4-dimethylaminopyridine-catalyzed acetylation," J. Pharm. Sci. 62, 845-846.
El Seoud, O. A., Koschella, A., Fidale, L. C., Dorn, S., and Heinze, T. (2007). "Applications of ionic liquids in carbohydrate chemistry: a window of opportunities," Biomacromolecules 8, 2629-2647.
Erdmenger, T., Haensch, C., Hoogenboom, R., and Schubert, U. S. (2007). "Homogeneous tritylation of cellulose in 1-butyl-3-methylimidazolium chloride," Macromol. Biosci. 7, 440-445.
Fidale, L. C., Possidonio, S., and El Seoud, O. A. (2009). "Application of 1-allyl-3-(1-butyl) imidazolium chloride in the synthesis of cellulose esters: Properties of the ionic liquid, and comparison with other solvents," Macromol. Biosci. 9, 813-821.
Focher, B., Palma, M. T., Canetti, M., Torri, G., Cosentino, C., and Gastaldi, G. (2001). "Structural differences between non-wood plant celluloses: evidence from solid state NMR, vibrational spectroscopy and X-ray diffractometry," Industrial Crops and Products 13, 193-208.
Fringant, C., Desbrieres, J., and Rinaudo, M. (1996). "Physical properties of acetylated starch-based materials: Relation with their molecular characteristics," Polymer 37, 2663-2673.
Fukaya, Y., Hayashi, K., Wada, M., and Ohno, H. (2008). "Cellulose dissolution with polar ionic liquids under mild conditions: required factors for anions," Green Chem. 10, 44-46.
Gericke, M., Liebert, T., and Heinze, T. (2009). "Polyelectrolyte synthesis and in situ complex formation in ionic liquids," J. Am. Chem. Soc. 131, 13220-13221.
Grondal, C. (2003). "4-Dimethylamino-pyridine (DMAP)," Synlett 10, 1568-1569.
Gu, X., and Yang, C. Q. (1998). "FT-IR and FT-Raman spectroscopy study of the cyclic anhydride intermediates for esterification of cellulose: I. Formation of anhydrides without a catalyst," Res. Chem. Intermediate. 24, 979-996.
Hadano, S., Onimura, K., Tsutsumi, H., Yamasaki, H., and Oishi, T. (2003). "Syntheses of chemical-modified cellulose obtained from waste pulp," J. Appl. Polym. Sci. 90, 2059-2065.
Heinze, T., Schwikal, K., and Barthel, S. (2005). "Ionic liquids as reaction medium in cellulose functionalization," Macromol. Biosci. 5, 520-525.
Hill, C. A. S., Jones, D., Strickland, G., and Cetin, N. S. (1998). "Kinetic and mechanistic aspects of the acetylation of wood with acetic anhydride," Holzforschung 52, 623-629
Höfle, G., Steglich, W., and Vorbruggen, H. (1978). "4-Dialkylaminopyridines as highly active acylation catalysts," Angew. Chem. Int. Ed. Engl. 17, 569-583.
Jayakumar, R., Balaji, R., and Nanjundan, S. (2000). "Studies on copolymers of 2-(N-phthalimido) ethyl methacrylate with methyl methacrylate," Eur. Polym. J. 36, 1659-1666.
Jeon, Y. S., Lowell, A., and Gross, R. A. (1999). "Studies of starch esterification: Reactions with alkenylsuccinates in aqueous slurry systems," Starch/Stärke 51, 90-93.
Khalil, M. I., Hashem, A., and Hebeish, A. (1995). "Preparation and characterization of starch acetate," Starch/Stärke 47, 394-398.
Kurita, K., Kojima, T., Nishiyama, Y., and Shimojoh, M. (2000). "Synthesis and some properties of nonnatural amino polysaccharides: Branched chitin and chitosan," Macromolecules 33, 4711-4716.
Liu, C. F., Sun, R. C., Zhang, A. P., Ren, J. L., and Geng, Z. C. (2006). "Structural and thermal characterization of sugarcane bagasse cellulose succinates prepared in ionic liquid," Polym. Degrad. Stabil. 91, 3040-3047.
Liu, C. F., Sun, R. C., Zhang, A. P., Ren, J. L., Wang, X. A., Qin, M. H., Chao, Z. N., and Luo, W. (2007a). "Homogeneous modification of sugarcane bagasse cellulose with succinic anhydride using an ionic liquid as reaction medium," Carbohydr. Res. 342, 919-926.
Liu, C. F., Sun, R. C., Zhang, A. P., and Ren, J. L. (2007b). "Preparation of sugarcane bagasse cellulosic phthalate using an ionic liquid as reaction medium," Carbohydr. Polym. 68, 17-25.
Liu, C. F., Zhang, A. P., Li, W. Y., Yue, F. X., and Sun, R. C. (2009). "Homogeneous modification of cellulose in ionic liquid with succinic anhydride using n-bromosuccinimide as a catalyst," J. Agric. Food Chem. 57, 1814-1820.
Liu, L., Li, Y. P., Li, Y., Fang ,Y. E. (2004). "Rapid n-phthaloylation of chitosan by microwave irradiation," Carbohyd. Polym. 57, 97-100.
Mormann, W., and Wezstein, M. (2009). "Trimethylsilylation of cellulose in ionic liquids," Macromol. Biosci. 9, 369-375.
Motawie, A. M., and Sadek, E. M. (1999). "Adhesives and coatings based on phenolic epoxy resins," Polym. Advan. Technol. 10, 223-228.
Nagaveni, H. C., Vijayalakshmi, G., and Chauhan, S. S. (2005). "Decay resistance of esterified and oligoesterified rubberwood (hevea brasiliensis)," J. Trop. For. Sci. 17, 588-595.
Pandey, A., Soccol, C. R., Nigam, P., and Soccol, V. T. (2000). "Biotechnological poten-tial of agro-industrial residues. I: Sugarcane bagasse," Bioresour. Technol. 74, 69-80.
Richardson, S., and Gorton, L. (2003). "Characterisation of the substituent distribution in starch and cellulose derivatives," Anal. Chim. Acta 497, 27-65.
Schlufter, K., Schmauder, H., Dorn, S., and Heinze, T. (2006). "Efficient homogeneous chemical modification of bacterial cellulose in the ionic liquid 1-N-butyl-3-methylimidazolium chloride," Macromol. Rapid Commun. 27, 1670-1676.
Scriven, E. F. V. (1983). "4-dialkylaminopyridines: super acylation and alkylation catalysts," Chem. Soc. Rev. 12, 129-161.
Stojanović, Ž., Jeremić , K., Jovanović, S., and Lechner, M. D. (2005). "A comparison of some methods for the determination of the degree of substitution of carboxymethyl starch," Starch/Stärke 57, 79-83.
Swatloski, R. P., Spear, S. K., Holbrey, J. D., and Rogers, R. D. (2002). "Dissolution of cellose with ionic liquids," J. Am. Chem. Soc. 124, 4974-4975.
Wu, J., Zhang, J., Zhang, H., He, J. S., Ren, Q., and Guo, M. (2004). "Homogeneous acetylation of cellulose in a new ionic liquid," Biomacromolecules 5, 266-268.
Yoshimura, T., Matsuo, K., and Fujioka, R. (2006). "Novel biodegradable superabsorbent hydrogels derived from cotton cellulose and succinic anhydride: Synthesis and characterization," J. Appl. Polym. Sci. 99, 3251-3256.
Zhang, H., Wu, J., Zhang, J., and He, J. S. (2005). "1-Allyl-3-methylimidazolium chloride room temperature ionic liquid: A new and powerful nonderivatizing solvent for cellulose," Macromolecules 38, 8272-8277.
Zhang, J. M., Wu, J., Cao, Y., Sang, S. M., and He, J. S. (2009). "Synthesis of cellulose benzoates under homogeneous conditions in an ionic liquid," Cellulose 16, 299-308.
Zhu, S. D., Wu, Y. X., Chen, Q. M, Yu, Z. N., Wang, C. W., Jin, S. W., Ding, Y. G, and Wu, G. (2006). "Dissolution of cellulose with ionic liquids and its application: A mini-review," Green Chem. 8, 325-327.
Article submitted: February 19, 2011; Peer review completed: March 11, 2011; Revised version accepted: April 30, 2011; Published: May 6, 2011.


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Sugar Witch is an Adventure, Puzzle, Match-3, Single-player and Multiplayer video game developed and published by Cubeflux for Android and iOS as well as Facebook. The game takes you on an epic adventure with small Witch to locate the best sweet in the world. During the gameplay, you'll experience interesting and new modes and levels that are more thrilling. It offers you a chance to show off your matching skills in the game to impress your fellows. The game contains over 1100 levels with increasing difficulties and uses the new mechanics, enabling you to match blocks with more strategic options. Find ghosts hidden in the sweets is the new mode in the game with improved graphics. You have to gather as many gingerbread men as possible to progress through the game. The game looks easy but hard to master. Polish your match-3 skills and combine three same colored sweets to smash and make a space for more. The more you play, the more you engage in puzzle experience. Sugar Witch offers prominent features such as 1100 Levels, New Mechanics, Enhanced Graphics, Daily Bonus, Friendly Competition, and more. Try it out, and it'll entertain you.
#4 Dodo Pop
Dodo Pop is an Action-Adventure, Puzzle, Match-3, and Single-player video game developed and published by Disney. The game takes place on the tropical Islands full of colorful gumballs. The game story revolves around the dodo bird who lost the way of his home. You can help the bird to find the way using your matching skills. In the game, you must match and gather gumballs your way through island and assist the bird fly his home way. During the gameplay, you have to match same colored gumballs and smash them to crash. There are multiple power-ups such as Rainbow Splash and Strike One. The game rewards you with three stars if you complete the objectives within time limit. You must help the bird to fly and move to the next level with increasing difficulty. Dodo Pop offers prominent features such as Match and Pop Bunches, Explore 140 Levels, Power-ups, Earn 3-Stars, Tough Obstacles, and more. Try it out, and you'll love it.
#5 Jewels of the Amazon
Jewels of the Amazon is a Traditional Match-3, Puzzle and Single-player video game developed by MindJolt for iOS and Facebook. The game puts you in the role of the adventurer and lets you a chance to unearth the ancient relic and collect treasures. It comprises up to seventy puzzle levels with temples, jungles, waterfalls, etc. themes and lets you explore each level, match three or more jewels your way to score the points and progress through the game. Seventy levels are divided into eight stages, and you need to gather up to 186 stars to become the winner. During the gameplay, you can unlock up to thirty-six achievement badges and collect boosters, power-ups to increase your abilities. As you proceed, the game becomes tough to master. The game lets you explore the Amazon, follows the saga of Sarah, discover and collect relics, power boosters, and more. Jewels of the Amazon includes exciting features such as 36 Achievements, Multiplier, Collect 186 Stars, Multiple Modes, and more.
#6 7 Wonders 2
7 Wonders 2 is a Puzzle, Match-3, and Single-player video game developed and published by MumboJumbo for multiple platforms. The game takes you back in time when magnificent structures were being constructed in far away lands. It takes place in the beautiful world, offering seven new locations and it comes with new hundreds of treasure to collect. It offers easy to learn but hard to master. Your ultimate task is to match three or more same items to offer the resources to your workers to build the unbelievable sights from the Taj Mahal to Stonehenge. It offers incredible bonuses and power-ups assist you in discovering the secret route and hidden maps, leading you to the most wondrous sight. As the game advances, it becomes challenging to play. 7 Wonders 2 offers core features such as Seven New Locations, New Power-ups, Enhanced Gameplay and Graphics, and more. Try it out, and you'll like it.
#7 Fish Mania
Fish Mania is a Puzzle, Match-3, Fish Raising, and Single-player video game developed and published by TaoGames Limited for Android and iOS as well as Facebook. The game takes place in the sea environment full of beautiful fish, and it lets you engage yourself in a sea of Match-3 Puzzles gameplay experience. In the game, your objective is to gather all types of distinctive fish that will keep you company while you are struggling to feed them, use tons of decoration to build an aquatic world for your fish. Dive into the sea world where you have to score as many points as possible by matching three or more similar items of the same colour. The game has more than hundreds of levels with increasing difficulty, and the player needs to complete the requirement of each level to move to the next one. During the gameplay, you can gather a dozen of decorations and can use them to make the aquariums beautiful. Fish Mania includes core features such as Distinctive Gameplay, Collect Decorations, Boosters, Unlock Unique Aquariums, Dozens of Fish, and more. Try it out, and you'll love it.
#8 Sweet Road
Sweet Road is an Action-Adventure, Match-3, and Single-player Puzzle video game developed and published by CookApps for Android and iOS as well as Facebook. The game follows the traditional Match-3 gameplay and lets the player save the Gingerbread George in the way possible. There are a variety of levels, and each level is full of candies, puzzles, and challenges. Your ultimate task is to smash candies by forming chain consists of three or more candies while rescuing cookies. Prepare the sweet desserts including chocolate, candies, lollipops, and gummy jellies. Each level is full of desserts and candies. As the game advances, it becomes difficult to master. Unlock additional content, power-ups, and boosters while playing the game for fastest progress. Sweet Road includes core features such as Gingerbread Cookies, Beautiful Graphics, Offline Play, Variety of Tasty Sweets, Different Modes, Exciting Challenges, and more. Try it out, and you'll love it.
#9 Smoothie Swipe
Smoothie Swipe is a Match-3, Puzzle, and Single-player video game developed and published by Hapti.co, Limited for Android and iOS. It offers the juicy gameplay and offers dozens of levels full of tasty fruits. The player needs to connect similar fruits to smash and earn points. It has more than four-hundred levels with increasing difficulty. In the game, the player can compete against friends on leaderboards and assist each other with extra lives. He can embark on an epic adventure as the player moves from the tropical island to island. Each island offers a unique mechanic to the gameplay. The game offers boosters and power-ups to destroy smash lots of fruits in your way. It supports both Single-player and Multiplayer modes. The player can challenge his friend in multiplayer mode to watch who will top the leaderboards. Smoothie Swipe offers core features such as over 400 Levels, Touch Controls, Cool Boosters, Difficult Levels, and more. Check it out, and have fun.
#10 Sir Match-A-Lot
Sir Match-A-Lot is a Puzzle-based, Match-3, and Single-player video game developed by Big Fish Games for multiple platforms. The game offers addictive gameplay comes with challenging layouts and exciting boosts. During the gameplay, the player needs to solve the magical and fun puzzles in the quests to rescue the kingdom. The player needs to pop, squish, and blast his way through beautiful jewel-toned items to form a chain of powerful matches. The player needs to crush bosses by accomplishing special puzzle levels. It has a series of levels with increasing difficulty and the game unlock additional content to become the master. The player has to match treats his way through over dozen of lands. Sir Match-A-Lot includes core features such as Match-3 Boosts, Heroic Matching, Limited Moves, Play against Bosses, Gather Keys, Sweet Rewards, and more. With addictive gameplay, superb mechanics, smooth controls, Sir Match-A-Lot is the best game compared to other Puzzle games.
#11 Deep Voyage
Deep Voyage is a Puzzle, Match-3, and Single-player video game by Notus Games Ltd for Microsoft Windows, Mac, and mobile platforms. The game takes place in the underwater kingdom and offers an addictive story, revolving around the female protagonist, who dreams of becoming a gardener and winning the design competition. In the game, the player needs to match same colored three or more items to win the tokens for power-ups in the sea garden to advance through the game. There are over 200 eye-popping levels. As the game advances, it becomes difficult to master. The game rewards the player with points for each completed levels and the player can use these points to become the master. To complete each level, the player has limited moves in which the player must clear the screen filled with items of different colors. Deep Voyage offers core features such as immersive Gameplay, Level Difficulty, and more. Try it out, and you'll like it.
#12 Mystery Match
Mystery Match developed by Outplay Entertainment Ltd is a Puzzle, Match-3, and Single-player video game for Android and iOS. The game mixes the puzzle-solving and matching with a challenging mystery elements. During the gameplay, the player experience an enchanting setting with aristocracy as the player embarks on an epic adventure through international locals. The player must effort to match jewels his way through multiple levels to find hidden objects and clues as he follow the trail of shadow of the legendary inventor. Along the journey, the player will encounter fascinating characters, unearth hidden worlds, discover surprising secrets, and more. The game has five unique modes and each mode offers challenging gameplay. Fruit Fever World offers prominent features such as Jewel-matching Gameplay, Five Modes, Unleash your Detective Skills, Find Hidden Objects, and more. With touch controls, relaxing soundtracks, mystery-based gameplay, and brilliant mechanics, Fruit Fever World is the best game to play and enjoy.
#13 Angry Birds Blast
Angry Birds Blast is a Tilt-Matching, Puzzle and Single-player video game published by Rovio Entertainment and developed by Mybo. The gameplay needs to smash two or more balloons of the same color to free the captured birds. It takes place in the beautiful world consists of dozens of levels with increasing difficulty. The game rewards the player with booster by forming more balloons which can be used to clear the single color balloons from the screen in a single row or column. Other levels will be unlocked as the player advances through the game or acquired the required points. The game introduces the map level selection similar to the Angry Birds Pop. It has multiple modes and each mode offers unique and challenging gameplay. There are different types of objectives such as Pop the Pigs, Pop the required of Balloons, Gather Baskets, and more. It has two main currencies using in the game such as Silver and Gold. With impressive gameplay, touch controls, and thrilling graphics, Angry Birds Blast is the best game to play.
#14 Wonderland Epic
Wonderland Epic is a Puzzle-based, Match-3, and Single-player video game by App-O-Rama for Android and iOS. It brings a fantastic story, in which it puts you in the role of the hero and enable you to battle against the evil king to save the land by block-busting puzzle gameplay. You can play hundreds of challenging levels full of fun, obstacles, and more. It offers simple to play, but hard to master gameplay. Step into the world of wonderland where you have to face an evil king and must struggle to take down his unholy plans to become the master. It has up to 200 levels with increasing levels, and each level is full of colourful items. The primary job is to match three or more items your way through plenty of levels to score the best points. You can set your record of high scores and can share your progress on Facebook. It supports both online and offline modes. Wonderland Epic brings addictive gameplay for those who love playing match-3 games.
#15 Wicked Snow White
Wicked Snow White is an Arcade, Match-3, and Single-player Puzzle video game developed by Cogoo Inc. for Android and iOS. The game takes you on an epic adventure to the enchanted forest consists of more than 900 levels where you have to rescue the Seven Dwarves from the evil Wicked Princess. It has multiple modes such as Magic Mirror Stage, Dwarves Stage, Snow White Stage and Wicked Stage. Each stage offers challenging gameplay with a set of the objective to accomplish at any cost to progress through the game. In the game, you must swipe and match four or more apples to make charms. During the play, you can drag and drop charms to use magic spells and can struggle to save the frozen Dwarves and minions from the evil princess. The game rewards you with points which can be used to unlock mysterious magic forest. You can match four or more apples to smash and create the chain to score the best points. To complete each level, you have limited moves in which you must achieve the objectives by clearing the screen from items. Wicked Snow White includes core features such as Star-based Rewards System, Multiple Modes, New Updates, 900 Levels, Leaderboards, and more. Try it out, if you love playing Match-3 games.
#16 Piyo Blocks 2
Piyo Blocks 2 is a Match-3, Puzzle and Single-player video game serves as the sequel to Piyo Blocks. The game offers retina graphics and comes with new modes, online battles and more. There are dozens of levels with increasing difficulty. In each level, the player has to match same colored blocks to remove them and struggle to score the points before the time runs out to level up. During the gameplay, you can use combos and unique power-ups to assist match as many blocks as possible. It has six amazing Single-player modes such as Piyo Mode, Hyaku Mode, Time Attack, three Second Mode, Disco Mode and Endless Mode. In Piyo mode, the player has to capture the specific number to level. The player can collect 99 or more types of Piyo to move to the next level. The player has 1, 2 or four minute to capture as many blocks as he can in Time Attack mode. The game also offers online Multiplayer mode, where the player can compete against other player and can show off his matching skills by completing the stage. Piyo Blocks 2 includes core features such as Achievements, Online Multiplayer Battles, Hd Graphics, Single-player Modes, and more.
#17 Donut Dazzle
Donut Dazzle is an addictive, Fast-paced Puzzle and Match-4 video game developed and published by Cloud5Labs for Android and iOS. It offers a simple gameplay where you have to match four or more donuts of the same king to earn points. There are a variety of levels with increasing difficulty and you must tap the screen to rotate the donuts and match to clear the playfield to move to the next level. During the gameplay, you can make combos to progress faster through the game. The game offers you a speed bump every 10 levels, which you can use to boost your speed. You can play through your way, match different donuts to unlock unique power-ups to earn donuts and coffee, and use them to unlock items and power-ups. You must make sure that the playfield doesn't fill up with donuts to avoid death. Donut Dazzle includes key features such as Unlockable Themes, Hundreds of Stage Goals, Unlock Items, Leaderboards, Compete against Friends, and more. Try it out, and you'll love it.
#18 Empires and Puzzles: RPG Quest
Empires and Puzzles: RPG Quest offers the blend of Traditional Match-3 and Role-playing genres developed and published by Small Giant Games for Mobile devices. The game features legendary heroes with unique abilities, skills and personalities. It supports both Single-player and Multiplayer modes and enables you to collect powerful heroes while engaging in matching gameplay experience with your friends with a turn-based battle twist. There are lots of exciting locations where the game takes place and lets you explore each one in your style and battle against rivals to raise up your level. During the gameplay, you can fight, gather, build, raid, upgrade and team up with other players from across the globe and can involve in PvP battles to show off your abilities. It uses amazing graphics and offers a variety of levels with increasing difficulty. Empires and Puzzles RPG Quest includes key features such as Send your Troops to Attach, Rebuild a War Fortress, Fight in PvP, Level your Heroes, and more.
#19 Cradle of Empires
Cradle of Empires is a Puzzle-based Match-3 and Single-player video game created and published by Awem Games Limited for Android and iOS. The game takes place in the stunning world and takes you on an epic adventure where you must help the ancient empire rise from the ruins using traditional match-3 mechanics with a rich storyline consists of captivating characters and thrilling quests. The game offers a breathtaking environment and challenges your collecting, building and matching skills. With the assist from Egyptian and Nimiru settlers, you can break the curse of Amrun and can restore the peace and the ancient civilization to its former glory. It has multiple modes with unique gameplay focuses on traditional match-3 mechanics. In the game, you have to match three or more items in vertical or horizontal position. The items will be disappeared from the screen as you matched them. Cradle of Empires includes core features such as Ancient Cities, Regular Updates, Mega-sized Adventure, Different Modes, and more.
#20 Simon's Cat: Crunch Time
Simon's Cat: Crunch Time is a Puzzle, Match-3, and Single-player video game created by Strawdog Publishing. The game takes you on an adventure in a beautiful world where the devilish crows have swipe the tasty treats of the Simon's Cats. You can help the cats to find their treats. In the game, you must match three or more delicious items your way through multiple levels of increasing difficulty to progress through the game. As you match three similar items of same coloured, they will disappear and create a space for oncoming items. The game looks easy but hard to master. The game offers amazing power-ups that you can use to increase your abilities and a bomb which you can use to smash the treats in the playfield. To complete each level, you have limited moves, and you must defeat the devilish crow to restore the treats of the cats. Simon's Cat: Crunch Time offers core features such as Connect Treats to Win, New Levels, Takedown Angry Villains, Star-based System, and more. Check it out, and have fun.
#21 Clockmaker: Amazing Match 3
Clockmaker: Amazing Match 3 is an Adventure, Puzzle, and Single-player video game focuses on Traditional Match-3 elements developed and published by Belka Games for Android and iOS. The game puts you on an epic adventure to solve a series of challenging quests and save the town from an evil curse of the old clock master. It takes place in the intense mystical environment and offers more than 550 quests to solve. During the gameplay, you must match three or more gems to score the points and save the villagers to become the hero. You have an opportunity to explore the mythical world while engaging in match-3 gameplay experience. It has hundreds of fun-filled levels, most of them are locked. Each level is full of different colored gems and your task is to make a chain three or more gems and struggle to clear the screen within limited moves. You can access boosters and power-ups to blast your way and complete levels within few moves. Clockmaker: Amazing Match 3 offers prominent features such as 550 Levels, Achievements, Rewards, Mystical Atmosphere, and more.
#22 Collision Effect
Collision Effect is an addictive Cosmic Puzzle and Single-player video game developed and published by Vishindo for iOS. The game lets you experience the fast-paced fun and thoughtful gameplay that you have seen before. It is the brilliant blend of puzzle and action elements, you must guide the cosmic zybbles, toward one another of the same colored, but don't let them collide each other. The ultimate task is to bring the orbs of the same color to earn points. To combine same colored orbs, you must plan your path to avoid crashing into a different color orbs. The game will end, if two different color orbs collide together. It has four modes such as Collide, Classic, Life Force and Puzzle. In classic mode, the game offers endless gameplay with three level difficulty settings and the player can easily overcome Easy and Normal modes, but feel difficult to play fast-paced gameplay in Hard mode. Collision Effect offers exciting gameplay, superb mechanics, and touch controls, Collision Effect is the exciting gameplay to experience both puzzle and action genres.
#23 Dungeon Gems
Dungeon Gems is a Fast-paced Puzzle video game with an emphasis on Strategic Role-playing elements developed and published by Gameloft. The game offers an opportunity to the player to join the thousands of players from across the globe in an epic quest to take down the dragon. It provides easy to learn but hard to win gameplay and lets the player drag his finger using the touch screen over elemental runes to connect them and then trigger to attack. The player must connect same coloured tunes to release the focused attacks or connect different colored runes to launch the devastating attack, but beware and it will cost the player action points. There are more than 220 mighty warriors available each with its unique skills and abilities. In the game, the player must select the warrior wisely, because each can release a different elemental attack. The player must power up his character, then evolve it into a new legendary form. The game has numerous levels, and each level offers challenging gameplay with the unique difficulty setting. With addictive gameplay, superb graphics, and stunning controls, Dungeon Gems is the best game to play.
#24 Monster Busters: Ice Slide
Monster Busters: Ice Slide focuses on Traditional Match-3 elements and available to play on mobile devices such as Android and iOS. The game supports Single-player mode and it is developed and published by Playdog. It allows the players to connect monsters through hexagonal blocks and struggle to rescue the gingerbreads to become the hero of Ice Tower. The game comes with new missions and introduces the variety of features to explore. During the gameplay, the player will join the exciting adventure of adorable kids including Namu, Bruce, Boo, and effort to complete the variety of levels to the Top of the Ice Tower, where innocent gingerbread friends are stuck. The player must save them from vicious monsters. In the game, the player can try his best to clear the level by making a match linking three or more monsters of the same color in six directions on the board. As the game advances, it becomes difficult to play, and further levels and power-ups will be unlocked to enjoy. Monster Busters: Ice Slide includes core features such as Little Helpers, Unique Rules, Advanced Boss Fights, Multiplayer Mode, and more. Try it out, and you'll like it.
#25 The Secret Life of Pets: Unleashed
The Secret Life of Pets: Unleashed offers the Falling Block Puzzle and Tilt-matching gameplay for mobile devices, developed by EA Salt Lake. The game mainly revolves around the Match-3 elements to offers the superb gameplay based on the film The Secret Life of Pets. It introduces several characters from the movie including Max, Gidget, Leonard, Norman, and Chloe. The game is set on the board and offers the swapping mechanics similar to Bejeweled video game series. The player can switch the positions of two toys using the swipes, either vertically or horizontally. The main goal of the player is to match three or more gems to earn points and the connected gems disappear from the screen. There are many levels and each level is full of gems of different colors which the player must connect to create the chain of similar color to advance through the game. During the gameplay, the player can use several power-ups and boosters to increase the speed of the game. The Secret Life of Pets: Unleashed includes core features such as Increasing Difficulty, Several Levels, and more. Check it out, and have fun.
More About Magical Drop
Magical Drop is a series of Puzzle video games developed and published by Data East. The series of fantastic gameplay, revolving around bubble shooter elements and mixes the Tilt-Matching, Puzzle, Anime-based, and Side-view elements. In the series, a stack of different coloured bubbles descends from the top of the screen, and you are defeated when the stack of bubbles hits the screen's bottom. During the gameplay, the bubbles can be dropped and picked up by the clown of you at the bottom and smashed when three or more same coloured bubbles are put together. There are more than twenty-four levels with increasing difficulty available, and you have to complete each one to become the master. To score the best points and achieve the level, you have to form a chain of three or more bubbles to smash and earn points for each destroyed bubble. The game becomes difficult to play as you advance through it. The series comes with several games such as Magical Drop, Magical Drop 2, Magical Drop 3, Magical Drop V and more. Try it out, and you'll love it.
2D Match-3 Single-Player

redpajama_set_name: RedPajamaCommonCrawl


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How to stop the fracking boom: Why it's not working
A natural gas industry that has been booming in Australia for more than a decade has now become a major industry in its own right.
In Queensland, the gas and power sector has become the largest employer in the state.
The mining sector has also gained ground, with the state's coal and iron ore mines accounting for the largest share of total mining activity.
In New South Wales, the oil and gas sector has expanded rapidly, becoming one of the biggest in the country.
And in Victoria, the dairy sector has now overtaken the beef industry as the largest in the nation.
All of these sectors are making massive gains in the years to come, driven in large part by the fracking revolution.
But while the growth of the natural gas and oil and natural gas sector is unprecedented, the growth in mining and mining services has also been remarkable.
The growth in both sectors has been driven by the boom in the number of fracking operations.
This growth has been particularly fast in New South Welsh and Victoria, where fracking has been banned in recent years.
The New Southwales region has seen the growth rates of both mining and natural water services increase more than tenfold.
But what is it about these sectors that has driven these growth rates?
The natural gas boom The natural growth in the natural water and natural resource sectors has come at a price.
New South Wales is a boomtown, with its population of over 15,000 people, but the growth has also resulted in significant environmental damage and social disruption.
"It is the first boomtown to have gone through a fracking boom," said Dr Mark Tarnopolsky, a water expert from the University of Sydney's School of Public Policy.
And while the fracking industry has been widely welcomed by the local communities and government, it has also drawn criticism from many environmental groups. "
So it's a real issue that is a big concern for the community, for the water table, and for the environment."
And while the fracking industry has been widely welcomed by the local communities and government, it has also drawn criticism from many environmental groups.
The boom has caused massive amounts of wastewater to be released into the environment, including hundreds of millions of litres of untreated waste, and some scientists have claimed the release has had an adverse effect on the environment.
"The gas industry is responsible for almost a third of the emissions that are being released into our environment from natural gas development," Dr Tarnosky told the ABC.
"And it is a very significant environmental issue."
Dr Ternopolsker said the environmental impact of the boom had been overblown.
"Some of the data that is out there that was collected by the Natural Resource Action Centre, for example, it was really not looking at the impact on water, and it was just focusing on the environmental impacts," he said.
"But there are many other impacts, from climate change, to health issues, to water quality, to air quality, all of which are not included in those figures."
Dr Peter Lewis, a former member of the NSW Environmental Protection Authority, said the boom was a big issue for many of the communities in the region.
"These communities are really impacted by the pollution of the gas industry, they are suffering economically from it, they have lost jobs because of it, and the community is really suffering," he told the Sydney Morning Herald.
"This is not sustainable.
It is going to create enormous challenges for them, particularly for their water and wastewater systems."
As well as environmental issues, there have also been social problems.
The booming natural gas industries are now driving a large population to the region, with many of those people living in poverty.
The influx of people has caused a huge increase in unemployment, particularly in remote communities.
"They are not only taking advantage of the opportunity to make money, but they are also putting their own wellbeing at risk," said Tarnopsky.
"I have seen people in the community being taken out of work and sent to a housing estate."
And as a result, there are significant pressures on services for people with disabilities.
"For example, if you are a disabled person with learning disabilities or dementia, you can expect to live in isolation, with limited access to services," Dr Lewis said.
In addition, the boom has brought about a significant decline in services for those with mental health issues.
The number of people in crisis accommodation has dropped by almost 50 per cent since the boom began, while the number for the mental health sector has dropped over 70 per cent.
"People are very concerned about the quality of services that they are receiving," Dr Mark Paine, the founder and CEO of the New Southwyne Mental Health and Development Society, told the Herald.
"[Fracking] is the latest manifestation of the failure of governments and the Australian community to deal with mental illness."
What's happening in New Zealand?
Despite the economic and environmental benefits, New Zealand is a different story.
While the boom is being driven by gas, the country is also
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'It's Not My Job' – We'll Help You Out With Your Online Purchase
Which natural gas fields are ripe for a new gas boom?


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Ricky Martin's twins' Las Vegas playdates could include Jennifer Lopez, Celine Dion and Britney Spears' kids
February 22, 2017	 by HOLA! USA
Ricky Martin has a host of playdate options when he and his two sons begin to call Las Vegas their home in April. During an appearance on the Dr. Oz Show airing February 22, the Living La Vida Loca singer shared about the prospects of meeting up with Britney Spears, Celine Dion or Jennifer Lopez while in Sin City. "I haven't but I will," the 45-year-old said about reaching out to the crooners before asking, "How do you do it?"
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Ricky and his family are moving to Las Vegas Photo: Instagram/@ricky_martin
GALLERY: CELEBRITIES AND ROYALS WHO ARE PARENTS TO TWINS
Dr. Oz suggested setting up playdates with their children. Ricky, who is a dad to eight-year-old twins Valentino and Matteo, could have double the fun especially with Jennifer and Celine's sets of twins once he kicks off his concerts at the Park Theater in the Monte Carlo Casino and Resort. His boys will be front and center as they watch their dad take the stage along with his fiancé Jwan Yosef though he has said his kids are his biggest critics. "You don't know the level of criticism I get from my kids," he told People magazine. "Wow. It's as raw and honest as you can receive from an 8-year-old. They go, 'Dad, that movement I don't like. Dad, that song, you gotta change it,' and they bring good points. I tell them, 'Son, that's something that I will consider.'"
Ricky said he would want his sons to hangout with Jennifer Lopez, Celine Dion and Britney Spears' kids Photo: Jason LaVeris/FilmMagic
MORE: Jennifer Lopez on why her twins' eighth birthday was hard
One thing that is certain is that Ricky considers a lot more than just their stage critiques. "Everything that I do, every decision that I make is based on them - is based on their well-being," he shared with Dr. Oz. "That was a commitment that I made when I decided to become a father. And they are a little bit like my religion because, they don't know it, but they're like my little life-savers. Because once again, when I have to make a decision, whatever that decision is, I think of them and it turns out to be the right decision."
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GDPR – The monster under the bed or an opportunity to enhance security?
The new EU regulation of the Privacy world (the GDPR) is frequently portrayed as a scary and formidable piece of legislation that's going to rock the online & off-line world. This webinar will explore what the implications really are. How much will change from the present regime? How difficult will it be to comply? Also is there an opportunity hidden in the challenge? And where will security and security professionals fit in the new picture?
Title: GDPR – The monster under the bed or an opportunity to enhance security?


Anfibio Packrafting Store is operated by Schellin & Kreinacker GbR. The company is the legal entity of our person. The partnership was founded in 2011.
We consider ourselves independent around the concept of packrafting as a way of amphibious travel. This means, Anfibio Packrafting Store aims to promote the sport and drive new developments in the field of hiking with boats, thus develop the market as such. We are in contact with manufacturers of different accessories alike. We have our own opinion on the specific needs of packrafting and like to share it with customers. Therefore like to have a great contact to the community from expeditions to leisure adventures.
Our main goal currently is to make the right selection and have packrafts conveniently available in Europe: straightforward, reliable and quick. Hence we share a good relation with current suppliers. In the long run we like to broaden equipment needed for land-water use and have producers considered the specific needs of packrafting.
Our personal, private initiative around the topic of packrafting we run on packrafting.de, a blog and community site with tips, tricks and trips of packrafting, geographically focusing on Europe. There you can also find information to our person.


Majestic Realty Co. adds Michael Kapoor to assist with growing Commercenter portfolio in Aurora • News • Majestic Realty Co.
AURORA, CO – Majestic Realty Co. today announced the addition of Michael Kapoor to its development team at the Majestic Commercenter. An attorney with experience across commercial real estate business and legal elements, Kapoor will serve as an ownership representative and help manage and grow the company's portfolio at the 1,500-acre industrial park located at the intersection of I-70 and Tower Road in Aurora.
Kapoor joins Majestic from the Brownstein Hyatt Farber Schreck law firm. He will provide oversight on all aspects of the park's development from proposals and lease agreements to entitlements and future development opportunities within what has been the City of Aurora's largest industrial development over the past two decades.
The Majestic Commercenter is home to 50 companies and more than 3,000 employees. Since purchasing the park in 1995, Majestic Realty has invested more than a quarter of a billion dollars in the Aurora market through its buildings and land acquisitions, including its 2015 acquisition of an additional 500 acres directly adjacent to the original Commercenter park.
Most recently, Majestic completed construction of a 701,900-square-foot speculative building, nicknamed the "Big Bomber" which is immediately available and divisible to 150,000 square feet.


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Serie C Group A
Novara - Albinoleffe
Novara vs Albinoleffe Summary
Novara 8 34 25 32 28 654% 545% 416% 220% 880%
Albinoleffe 12 31 25 29 29 342% 457% 1040% 450% 450%
Novara vs Albinoleffe Head 2 Head
Albinoleffe
CGrA
21 Mar 14:00 14:00, 21 Mar fin
Serie C Group A League Table. Season 2022/2023
1 Pordenone 12 6 4 2 19 9 22 12 6 4 2 20 10 22 24 12 8 4 39 19 44 20 1.60
2 Feralpisalo 12 6 1 5 13 11 19 12 6 5 1 9 3 23 24 12 6 6 22 14 42 8 0.90
3 L. R. Vicenza 12 7 3 2 28 9 24 12 5 2 5 15 17 17 24 12 5 7 43 26 41 17 1.80
4 Pro Sesto 12 5 4 3 16 15 19 12 6 3 3 16 19 21 24 11 7 6 32 34 40 -2 1.30
5 Lecco 11 8 1 2 18 6 25 13 3 5 5 13 24 14 24 11 6 7 31 30 39 1 1.30
6 Renate 12 6 3 3 15 11 21 12 4 5 3 17 16 17 24 10 8 6 32 27 38 5 1.30
7 Pro Patria 12 6 3 3 15 11 21 12 4 3 5 10 14 15 24 10 6 8 25 25 36 0 1.00
8 Novara 12 6 4 2 20 8 22 12 4 0 8 10 19 12 24 10 4 10 30 27 34 3 1.30
9 Arzignano Valchiampo 12 3 6 3 11 10 15 12 5 4 3 14 14 19 24 8 10 6 25 24 34 1 1.00
10 Pro Vercelli 12 5 3 4 16 14 18 12 4 3 5 15 16 15 24 9 6 9 31 30 33 1 1.30
11 Padova 13 4 7 2 17 13 19 11 4 2 5 11 14 14 24 8 9 7 28 27 33 1 1.20
12 Albinoleffe 13 3 6 4 14 14 15 11 4 4 3 14 13 16 24 7 10 7 28 27 31 1 1.20
13 Juventus (U23) 13 7 3 3 18 13 24 11 1 4 6 12 18 7 24 8 7 9 30 31 31 -1 1.30
14 Mantova 12 6 3 3 17 12 21 12 2 3 7 12 25 9 24 8 6 10 29 37 30 -8 1.20
15 Trento 11 3 3 5 13 15 12 13 5 2 6 15 16 17 24 8 5 11 28 31 29 -3 1.20
16 Virtus Verona 11 1 3 7 8 15 6 13 5 6 2 14 6 21 24 6 9 9 22 21 27 1 0.90
17 Pergolettese 12 7 1 4 22 17 22 12 0 4 8 4 16 4 24 7 5 12 26 33 26 -7 1.10
18 San Giuliano City 12 5 2 5 14 13 17 12 2 1 9 11 20 7 24 7 3 14 25 33 24 -8 1.00
19 Piacenza 11 2 4 5 15 19 10 13 3 4 6 13 21 13 24 5 8 11 28 40 23 -12 1.20
20 Triestina 13 4 3 6 11 17 15 11 0 3 8 7 19 3 24 4 6 14 18 36 18 -18 0.80
Novara Last Matches
+ + - - - + + 0 0 + + - - - + + - + - 0 - + - 0 - + - + - +
01 Feb 17:00 17:00, 01 Feb fin
L. R. Vicenza
Novara 1
Pro Vercelli 1
Virtus Verona
Feralpisalo
Albinoleffe Last Matches
0 - 0 + - - 0 - 0 0 0 + + - 0 0 + 0 0 - + - + 0 - + + - 0 -
Pro Sesto
Novara Results
Albinoleffe Results
Novara Goals
Albinoleffe Goals
Novara Strength
Albinoleffe Strength
Novara Early Birds (Last 30 games)
Albinoleffe Early Birds (Last 30 games)
Novara Top Scorers
Mattia Bortolussi 0/0 0/0 0/0 0/0 0/0 3/0 0/0 0/0 0/0 0/0 3/0
Omar Khailoti 0/0 1/0 0/0 0/0 0/0 1/0 0/0 0/0 0/0 0/0 2/0
Pablo Andres Gonzalez 0/0 1/0 0/0 0/0 0/0 1/0 0/0 0/0 0/0 0/0 2/0
Patrizio Masini 0/0 0/0 0/0 0/0 0/0 0/0 0/0 0/0 0/0 1/0 1/0
Michele Rocca 0/0 0/0 0/0 0/0 0/0 0/0 0/0 0/0 0/0 1/0 1/0
Yohan Benalouane 0/0 0/0 0/0 0/0 0/0 0/0 0/0 1/0 0/0 0/0 1/0
Iulius Marginean 0/0 0/0 0/0 1/0 0/0 0/0 0/0 0/0 0/0 0/0 1/0
Francesco Galuppini 0/0 1/0 0/0 0/0 0/0 0/0 0/0 0/0 0/0 0/0 1/0
Albinoleffe Top Scorers
Andrea Cocco 1/0 0/0 0/0 0/0 0/0 2/0 1/0 0/0 0/0 1/0 5/0
Jacopo Manconi 0/0 0/0 1/0 0/0 0/0 1/0 1/0 0/0 0/0 0/0 3/0
Stefano Marchetti 0/0 0/0 0/0 0/0 0/0 0/0 0/0 0/0 1/0 0/0 1/0
Diego Borghini 0/0 0/0 0/0 1/0 0/0 0/0 0/0 0/0 0/0 0/0 1/0
Novara Bad Boys
Simone Ciancio - - - - - - - - 1/0 - 1/0 1 1.0/0.0
Davide Bertoncini - - - - 1/0 - - - - - 1/0 1 1.0/0.0
Novara 1.84 1.17 1.64 1.16 1
Albinoleffe 0.5 1.17 0.59 1.43 1
Novara vs Albinoleffe
The last meeting of these teams took place more than a month ago (9 October 2022) and ended with the victory of Albinoleffe with a score 3-1.
Novara takes the 8th position in the league table with 34 points. This is the 24th of 38 team game in the tournament.
The difference with the nearest team on top is 2 points (Novara can score 42 points). In addition, the distance from the TOP-4 is 6 points (42 points are possible). The nearest pursuer has the same number of points with Novara and can score 42 points. The goal difference is 30:27.
Albinoleffe takes the 12th position in the league table with 31 points. This is the 24th of 38 team game in the tournament.
The difference with the nearest team on top is 2 points (Albinoleffe can score 42 points). The distance from the bottom league record is 13 points. The nearest pursuer has the same number of points with Albinoleffe and can score 42 points. The goal difference is 28:27.
Novara Stats
The team scored 18 points оn its own field in 10 last matches, with the following results 5 wins, 3 draws and 2 losses. The difference between scored and conceded goals is 16-6. The average number of goals is 1.6. The average number of cards in 10 last matches is 0.2.
Albinoleffe Stats
30 April 2021 mirror.co.uk Bruno Fernandes has become the vital cog in the Manchester United wheel since his January arrival last year, but Juventus and AC Milan are reportedly eyeing a move for the playmaker 26 August 2020 sportsmole.co.uk Cristiano Giaretta has been appointed as Watford 's new sporting director, the Sky Bet Championship club have announced. 12 April 2020 marca.com Bruno Fernandes had been taking the Premier League by storm until COVID-19 interrupted the season. Manchester United plucked him from Sporting CP in January for 55 million euros and the Portuguese was proving his worth in his early days in England. 29 January 2020 talksport.com Manchester United have finally agreed a deal to sign Bruno Fernandes from Sporting Lisbon. 21 January 2020 talksport.com Over the course of the last three transfer windows, there are few, if any, players to have been discussed more often than the 25-year-old Portuguese international Bruno Fernandes. 13 January 2020 talksport.com Manchester United are looking to land Portugal ace Bruno Fernandes this month with reports a £65million deal is close to completion.