Chemical characterization of black poplar (Populus nigra L.) sawdust hemicelluloses esterified with acyl chlorides

Yıl 2021, Cilt: 22 Sayı: 4, 426 - 431, 30.12.2021

Samim Yaşar , Gürcan Güler

https://doi.org/10.18182/tjf.980457

Öz

In the present study, hemicelluloses were isolated from black poplar (Populus nigra L.) sawdust, which is generated by the wood industry in large quantities as lignocellulosic waste. The monosaccharide composition of hemicelluloses was determined by gas chromatography. Xylose was the predominant monosaccharide unit, at 81.13%. Isolated hemicelluloses were then esterified with octanoyl, decanoyl, and lauroyl chloride, and the produced derivatives were characterized in terms of percent yield, degree of substitution (DS), solubility, Fourier-transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA). Hemicellulose derivatives had DS values ranging from 0.83 to 0.97, and percent yields ranging from 61.54% to 62.31%. FTIR analysis confirmed esterification. TGA indicated that the hemicellulose derivatives offered lower thermal stabilities than native hemicelluloses. Solubility analysis indicated that esterification increased the hydrophobic capacity of hemicelluloses. Generally, the hemicellulose derivatives obtained could be used to make biodegradable and environmentally friendly plastics, resins, films, and coatings for industrial utilization.

Anahtar Kelimeler

Degree of substitution, Esterification, Hemicelluloses, Percent yield, Solubility, Thermal stability

Açil klorürler ile esterlenmiş karakavak (Populus nigra L.) talaşına ait hemiselülozların kimyasal karakterizasyonu

Öz

Bu çalışmada, orman ürünleri endüstrisinde büyük miktarlarda lignoselülozik atık olarak açığa çıkan karakavak (Populus nigra L.) talaşından hemiselülozlar izole edilmiştir. Hemiselülozların monosakkarit bileşimi gaz kromatografisi ile belirlenmiştir. Ksiloz, %81.13 ile baskın monosakkarit birimi olarak tespit edilmiştir. İzole edilmiş hemiselülozlar daha sonra oktanoil, dekanoil ve lauroil klorür ile esterlenmiş ve elde edilen türevler yüzde verim, sübstitüsyon derecesi (DS), çözünürlük, Fourier dönüşümlü kızılötesi spektroskopisi (FTIR) ve termogravimetrik analiz (TGA) ile karakterize edilmiştir. Hemiselüloz türevlerinin DS değerleri 0.83 ile 0.97 arasında değişirken, yüzde verimleri %61.54 ile %62.31 arasında yer almıştır. FTIR analizi esterlenmeyi destekleyen sonuçlar sunmuştur. TGA, hemiselüloz türevlerinin, doğal hemiselülozlardan daha düşük termal stabiliteye sahip olduklarını göstermiştir. Çözünürlük analizi, esterlenmenin hemiselülozların hidrofobik kapasitesini geliştirdiğini ortaya koymuştur. Genel olarak çalışma, elde edilen hemiselüloz türevlerinin, endüstriyel kullanıma yönelik biyolojik olarak bozunabilir ve çevre dostu plastik, reçine, film ve kaplama ürünlerinin elde edilmesinde kullanılabileceğini göstermiştir.

Anahtar Kelimeler

Sübstitüsyon derecesi, Esterlenme, Hemiselülozlar, Yüzde verim, Çözünürlük, Termal stabilite

Kaynakça

• ASTM D1103, 1980. Standard test method for alpha-cellulose in wood. ASTM International, West Conshohocken, USA.
• Cao, B., Tschirner, U., Ramaswamy, S., Webb, A., 1997. A rapid modified gas chromatographic method for carbohydrate analysis of wood pulps. TAPPI Journal, 80(9): 193-197.
• Fan, X.R., Feng, Z.H., 1987. Effects of carboxymethyl-modified hemicellulose on the activity of T lymphocytes and the amount of immunocytes. Zhongguo yao li xue bao: Acta pharmacologica Sinica, 8(2): 169-173.
• Fang, J.M., Sun, R., Fowler, P., Tomkinson, J., Hill, C.A.S., 1999. Esterification of wheat straw hemicelluloses in the N, N‐dimethylformamide/lithium chloride homogeneous system. Journal of Applied Polymer Science, 74(9): 2301-2311.
• Fengel, D., Wegener, G., 1984. Wood Chemistry, Ultrastructure, Reactions. Walter de Gruyter Verlag, Berlin, Germany.
• Gaudet, M., Jorge, V., Paolucci, I., Beritognolo, I., Mugnozza, G.S., Sabatti, M., 2008. Genetic linkage maps of Populus nigra L. including AFLPs, SSRs, SNPs, and sex trait. Tree Genetics & Genomes, 4(1): 25-36.
• Gupta, S., Madan, R.N., Bansal, M.C., 1987. Chemical composition of Pinus caribaea hemicellulose. Tappi Journal, 70(8): 113-116.
• Joly, N., Martin, P., Lienard, L., Rutot, D., Stassin, F., Granet, R., 2006. Effect of degree of substitution on the mechanical and thermomechanical properties of lauroyl cellulose ester film. E- Polymers, 6(1): 1-9.
• Kahraman, T., Kahraman, F.K., Karakaya, S., Karahan, A., Ünsal, G., Karatay, H., Toplu, F., 2011. Türkiye’de Karakavakta (Populus nigra L.) Islah Çalışmaları ‘Fidanlık Aşaması Sonuçları’. Teknik Bülten No: 210, T.C. Orman ve Su İşleri Bakanlığı Kavak ve Hızlı Gelişen Orman Ağaçları Araştırma Enstitüsü Müdürlüğü, İzmit, Türkiye.
• Lepeniotis, S., Feuer, B.I., 1997. Synthesis of starch acetate: Statistical designed experiments to optimize the reaction conditions. Chemometrics and Intelligent Laboratory Systems, 36(2): 229-243.
• OGM, 2016. Oduna Dayalı Orman Ürünlerinin Üretim ve Pazarlama Faaliyetleri. Ankara, Türkiye.
• Pettersen, R.C., Schwandt, V.H., Effland, M.J., 1984. An analysis of the wood sugar assay using HPLC: a comparison with paper chromatography. Journal of Chromatographic Science, 22(11): 478-484.
• Rahn, K., Diamantoglou, M., Klemm, D., Berghmans, H., Heinze, T., 1996. Homogeneous synthesis of cellulose p-toluenesulfonates in N,N-dimethylacetamide/LiCl solvent system. Die Angewandte Makromolekulare Chemie: Applied Macromolecular Chemistry and Physics, 238(1): 143-163.
• Rathmacher, G., Niggemann, M., Köhnen, M., Ziegenhagen, B., Bialozyt, R., 2010. Short-distance gene flow in Populus nigra L. accounts for small-scale spatial genetic structures: Implications for in situ conservation measures. Conservation Genetics, 11(4): 1327-1338.
• Ren, J., Xu, F., Sun, R.C., Peng, B., Sun, J., 2008. Studies of the Lauroylation of Wheat Straw Hemicelluloses under Heating. Journal of Agricultural and Food Chemistry, 56(4): 1251–1258.
• Saikia, C.N., Ali, F., Goswami, T., Ghosh, A.C., 1995. Esterification of high a-cellulose extracted from Hibiscus cannabinus L. Industrial Crops and Products, 4(4): 233-239.
• Stettler, R., Bradshaw, T., Heilman, P., Hinckley, T., 1996. Biology of Populus and its Implications for Management and Conservation. NRC Research Press, Ottawa, Canada.
• Sun, R.C., Fang, J.M., Tomkinson, J., 2000. Characterization and esterification of hemicelluloses from rye straw. Journal Agricultural Food Chemistry, 48(4): 1247-1252.
• Sun, R.C., Fang, J.M., Tomkinson, J., Hill, C.A.S., 1999. Esterification of Hemicelluloses from Poplar Chips in Homogenous Solution of N,N-Dimethylformamide/Lithium Chloride. Journal of Wood Chemistry and Technology, 19(4): 287-306.
• Tanrıverdi, H., 2011. Haşhaş sapı (Papaver somniferum L.) hemiselülozlarının N,N-dimetilformamit/lityum klorür homojen sisteminde esterifikasyonu. Doktora Tezi, Süleyman Demirel Üniversitesi, Fen Bilimleri Enstitüsü, Isparta.
• Thompson, R.C., Moore, C.J., Vom Saal, F.S., Swan, S.H., 2009. Plastics, the environment and human health: current consensus and future trends. Philosophical transactions of the royal society B: Biological sciences, 364(1526): 2153-2166.
• Wang, H.T., Yuan, T.Q., Meng, L.J., She, D., Geng, Z.C., Sun, R.C., 2012. Structural and thermal characterization of lauroylated hemicelluloses synthesized in an ionic liquid. Polymer degradation and stability, 97(11): 2323-2330.
• Williamson, S.L., McCormick, C.L., 1998. Cellulose derivatives synthesized via isocyanate and activated ester pathways in homogeneous solutions of lithium chloride/N, N-dimethylacetamide. Journal of Macromolecular Science, Part A: Pure and Applied Chemistry, A35(12): 1915-1927.
• Wise, E.L., Karl, H.L., 1962. Cellulose and Hemicellulose in Pulp and Paper Science and Technology. Libby, C.E. (Ed.), Vol:1, Mc Graw Hill Book Co., New York, USA.
• Wu, J.H., Hsieh, T.Y., Lin, H.Y., Shiau, I.L., Chang, S.T., 2004. Properties of wood plasticization with octanoyl chloride in a solvent-free system. Wood Science and Technology, 37(5): 363-372.
• Xu, F., Jiang, J.X., Sun, R.C., She, D., Peng, B., Sun, J.X., Kennedy, J.F., 2008. Rapid esterification of wheat straw hemicelluloses induced by microwave irradiation. Carbohydrate Polymers, 73(4): 612-620.
• Yang, C.Q., Wang, X., 1996. Formation of cyclic anhydride intermediates and esterification of cotton cellulose by multifunctional carboxylic acids: An infrared spectroscopy study. Textile Research Journal, 66(9): 595-603. Yaşar, S., 2018. Ilgın (Tamarix parviflora) hemiselülozlarının oktanoil, dekanoil ve lauroil klorür ile esterlenmesi. Mehmet Akif Ersoy Üniversitesi Fen Bilimleri Enstitüsü Dergisi, 9(1): 91-97.