氧化再生纖維素 (Oxidized regenerated cellulose) 具有生物體內降解性及止血功能，因此，氧化再生纖維素已被廣泛應用於外科手術之生醫材料上。傳統之纖維素氧化法是以NO2 氣體或含有NaNO2 之硝酸與磷酸混合液來進行氧化，但此兩種方式所使用的溶劑為強酸對環境會造成汙染。TEMPO是一種高效率、且對於纖維素結構中C6上之羥基具有專一性氧化的催化劑。故本研究選用TEMPO當作催化劑來製備氧化再生纖維素，並探討其生物降解性及止血功能。
再生纖維素嫘縈絲 (rayon) 經NaOH絲光化 (mercerization) 處理後，以TEMPO為觸媒在pH10 ，NaClO之反應液中進行氧化反應。反應一小時後，可得羧基含量為19.06% 之氧化再生纖維素。經氧化過後，嫘縈絲纖維素之聚合度由218下降為36，結晶度不受氧化反應所影響。置於37℃，pH=7.4 磷酸緩衝溶液中，12小時內所製備之氧化再生纖維素質量損失高達90% 。氧化再生纖維素需要有鈣離子的存在才有活化血漿及加速血漿凝血的效果。此外因為TEMPO價格昂貴，所以本論文欲進一步將TEMPO接枝於水溶性之聚乙二醇上，以利 TEMPO回收再重複使用，所得 mPEG- TEMPO的氧化效率較 TEMPO 低約50%，但仍然保有催化氧化反應的效果。

Oxidized regenerated cellulose (ORC) containing rich carboxyl groups is an important class of bioabsorbable and hemostatic polymer. ORC can be used as biomaterials to stop bleeding during surgery and prevent the formation of post-surgical adhesions. Commercially, OC is produced by oxidizing regenerated cellulose with nitrogen dioxide(NO2) or HNO3/H3PO4-NaNO2. Recently, TEMPO (2,2,6,6 – Tetramethyl piperidine-1-oxyl radical), water-soluble and stable nitroxyl radicals, has been extensively utilized in catalytic oxidation for selective and effective conversion of alcoholic hydroxyls to carboxyl under aqueous condition.
In this study rayon as regenerated cellulose was oxidized by NaClO and catalytic amount of NaBr in the presence of TEMPO with pH controlled at 10. Mercerization of rayon with 2 N NaOH before TEMPO mediated oxidation can generate ORC containing 19.06% carboxyl group and the degrees of polymerization was decreased from 218 to 36 after 1 h reaction. More than 90% weight loss of carboxyl-rich ORC was observed when incubated in PBS buffer for 12 h. The as-prepared ORC also demonstrated its capability to enhance the coagulation of serum in the presence of calcium ions.

Abaev I, Kaputskiĭ V, Adarchenko A, Sobeshchukh O. 1986. Mechanism of the antibacterial action of monocarboxycellulose and other ion-exchange derivatives of cellulose. Antibiotikii Meditsinskala Bioteknologiia 31:624-8
Abuchowski A, McCoy JR, Palczuk NC. 1977. Effect of covalent attachment of polyethylene glycol on immunogenicity and circulating life of bovine liver catalase. Journal of Biological Chemistry 252:3582-6
Alinovskaya VA, Yurkshtovich TL, Kaputskii FN. 1989. Effect of the type of an ionic group in the composition of cellulose on immobilization of trypsin. Vestsi Akademiia Navuk BSSR Serial Khimiko Navuk:27-31
Ashton WH. 1968. Oxidized cellulose product and method for preparing the same. United States Patent 3,364,200
Beatty KE, Xie F, Wang Q, Tirrell DA. 2005. Selective dye-labeling of newly synthesized proteins in bacterial cells. Journal of the American Chemical Society 127:14150-1
Bertocchi C, Konowicz P, Zanetti F, Signore S, Flaibani A, et al. 1995. Synthesis and characterisation of polyglucuronan. carbohydrate Polymers 27:295-7
Binder WH, Sachsenhofer R. 2007. 'Click' chemistry in polymer and materials science. Macromolecular Rapid Communications 28:15-54
Binder WH, Sachsenhofer R, Straif CJ, Zirbs R. 2007. Surface-modified nanoparticles via thermal and Cu(i)-mediated "click" chemistry: Generation of luminescent CdSe nanoparticles with polar ligands guiding supramolecular recognition. Journal of Materials Chemistry 17:2125-32
Blume G, Cevc G. 1993. Molecular mechanism of the lipid vesicle longevity in vivo. Biochimica et Biophysica Acta - Biomembranes 1146:157-68
Bock VD, Hiemstra H, Van Maarseveen JH. 2006. CuI-catalyzed alkyne-azide "click" cycloadditions from a mechanistic and synthetic perspective. European Journal of Organic Chemistry:51-68
Bragd PL, Besemer AC, van Bekkum H. 2000. Bromide-free TEMPO-mediated oxidation of primary alcohol groups in starch and methyl [alpha]-d-glucopyranoside. Carbohydrate Research 328:355-63
Chang KP, Hao SP, Lin SY, Ueng SH, Pai PC, et al. 2006. The 30-bp deletion of Epstein-Barr virus latent membrane protein-1 gene has no effect in nasopharyngeal carcinoma. Laryngoscope 116:541-6
Chanzy HD, Roche EJ. 1975. Fibrous mercerization of Valonia cellulose. Journal of Polymer Science: Polymer Physics Edition 13:1859-62
Chen G, Tao L, Mantovani G, Ladmiral V, Burt DP, et al. 2007. Synthesis of azide/alkyne-terminal polymers and application for surface functionalisation through a [2 + 3] Huisgen cycloaddition process, "click chemistry". Soft Matter 3:732-9
Chen Y, Kang ET, Neoh KG, Wang P, Tan KL. 2000. Surface modification of polyaniline film by grafting of poly(ethylene glycol) for reduction in protein adsorption and platelet adhesion. Synthetic Metals 110:47-55
Diaz DD, Punna S, Holzer P, McPherson AK, Sharpless KB, et al. 2004. Click chemistry in materials synthesis. 1. Adhesive polymers from copper-catalyzed azide-alkyne cycloaddition. Journal of Polymer Science, Part A: Polymer Chemistry 42:4392-403
de Nooy AEJ, Besemer AC, van Bekkum H. 1995. Highly selective nitroxyl radical-mediated oxidation of primary alcohol groups in water-soluble glucans. Carbohydrate Research 269:89-98
Dol'berg EB, Shuteeva LN, Yasnitskii BG, Obolentseva GV, Khadzhai YI, Furmanov YA. 1974. Certain aspects of interaction of oxidized cellulose with pharmaceutical compounds. Pharmaceutical Chemistry Journal 8:414-7
Fadeeva J, Shmukler L, Safonova L. 2003. Investigation of the phosphoric acid -N,N-dimethylformamide system as potential solvent for cellulose. Journal of Molecular Liquids.103:339-47
Fan X, Lin L, Messersmith PB. 2006. Cell fouling resistance of polymer brushes grafted from Ti substrates by surface-initiated polymerization: Effect of ethylene glycol side chain length. Biomacromolecules 7:2443-8
Fee CJ, Van Alstine JM. 2006. PEG-proteins: Reaction engineering and separation issues. Chemical Engineering Science 61:934-9
Fichter KM, Zhang L, Kiick KL, Reineke TM. 2008. Peptide- functionalized poly(ethylene glycol) star polymers: DNA delivery vehicles with multivalent molecular architecture. Bioconjugate Chemistry 19:76-88
Fujisawa S, Isogai T, Isogai A. 2010. Temperature and pH stability of cellouronic acid. Cellulose 17:607-615
Fukuzumi H, Saito T, Iwata T, Kumamoto Y, Isogai A. 2008. Transparent and High Gas Barrier Films of Cellulose Nanofibers Prepared by TEMPO-Mediated Oxidation. Biomacromolecules 10:162-5
Gheorghe A, Matsuno A, Reiser O. 2006. Expedient Immobilization of TEMPO by Copper-Catalyzed Azide-Alkyne [3+2]-Cycloaddition onto Polystyrene Resin. Advanced Synthesis & Catalysis 348:1016-20
Gierlich J, Burley GA, Gramlich PME, Hammond DM, Carell T. 2006. Click chemistry as a reliable method for the high-density postsynthetic functionalization of alkyne-modified DNA. Organic Letters 8:3639-42
Harris JM. 1997. Introduction to biomedical and biotechnical applications of polyethylene glycol. American Chemical Society, Polymer Preprints, Division of Polymer Chemistry 38:520-1
Helms B, Mynar JL, Hawker CJ, Frechet JMJ. 2004. Dendronized linear polymers via "click chemistry". Journal of the American Chemical Society 126:15020-1
Hirota M, Tamura N, Saito T, Isogai A. 2009. Oxidation of regenerated cellulose with NaClO2 catalyzed by TEMPO and NaClO under acid-neutral conditions. Carbohydrate Polymers 78:330-5
Isogai A, Kato Y. 1998. Preparation of Polyuronic Acid from Cellulose by TEMPO-mediated Oxidation. Cellulose 5:153-64
Isogai A, Saito T, Fukuzumi H. 2011a. TEMPO-oxidized cellulose nanofibers. Nanoscale 3:71-85
Isogai T, Saito T, Isogai A. 2010. TEMPO Electromediated Oxidation of Some Polysaccharides Including Regenerated Cellulose Fiber. Biomacromolecules 11:1593-9
Isogai T, Saito T, Isogai A. 2011b. Wood cellulose nanofibrils prepared by TEMPO electro-mediated oxidation. Cellulose 18:421-31
Johnson, Care JP, Inc. 1989. Surgicel AbsorbableHemostate. PC-0506:08901-2023
Khil MS, Kim HY, Kang YS, Bang HJ, Lee DR. 2005. preparation of electrospun oxidized cellulose mats and their in vitro degradation behavior Macromolecular Research 13:62-7
Kim HW, Chung CW, Rhee YH. 2005. UV-induced graft copolymerization of monoacrylate-poly(ethylene glycol) onto poly(3-hydroxyoctanoate) to reduce protein adsorption and platelet adhesion. International Journal of Biological Macromolecules 35:47-53
Kolpak FJ, Blackwell J. 1978. Mercerization of cellulose: 2. The morphology of Mercerized cotton cellulose. Polymer 19:132-5
Krizova P, Mašova L, Suttnar J, Salaj P, Dyr JE, et al. 2007. The influence of intrinsic coagulation pathway on blood platelets activation by oxidized cellulose.Journal of Biomedical Materials Research - Part A 82:274-80
Kumar V, Deshpande GS. 2001. Noncovalent immobilization of bovine serum albumin on oxidized cellulose. Artificial Cells, Blood Substitutes, and Immobilization Biotechnology 29:203-12
Kumar V, Yang T. 2002. HNO3/H3PO4-NANO2 mediated oxidation of cellulose -- preparation and characterization of bioabsorbable oxidized celluloses in high yields and with different levels of oxidation. carbohydrate Polymers 48:403-12
Larson PO. 1988. Topical hemostatic agents for dermatologic surgery. Journal of Dermatologic Surgery and Oncology 14:623-32
LaVan DA, Lynn DM, Langer R. 2002. Moving smaller in drug discovery and delivery. Nat Rev Drug Discov 1:77-84
Li H, Cheng F, Duft AM, Adronov A. 2005. Functionalization of single-walled carbon nanotubes with well-defined polystyrene by "click" coupling. Journal of the American Chemical Society 127:14518-24
Lutz JF. 2007. 1,3-Dipolar cycloadditions of azides and alkynes: A universal ligation tool in polymer and materials science. Angewandte Chemie - International Edition 46:1018-25
Moxley G, Zhu Z, Zhang YHP. 2008. Efficient sugar release by the cellulose solvent-based lignocellulose fractionation technology and enzymatic cellulose hydrolysis. Journal of Agricultural and Food Chemistry 56:7885-90
Nandivada H, Jiang X, Lahann J. 2007. Click chemistry: Versatility and control in the hands of materials scientists. Advanced Materials 19:2197-208
Nie FQ, Xu ZK, Ye P, Wu J, Seta P. 2004. Acrylonitrile-based copolymer membranes containing reactive groups: Effects of surface-immobilized poly(ethylene glycol)s on anti-fouling properties and blood compatibility. Polymer 45:399-407
Nelson, M.L., O'Connor, R.T., 1964b. Relation of certain infrared 1bands to cellulose crystallinity and crystal lattice type. Part II. A 1new infrared ratio for estimation of crystallinity in cellulose I and II. 1Journal of Applied Polymer Science.. 8: 1325-1341.
O'Reilly RK, Joralemon MJ, Hawker CJ, Wooley KL. 2007. Preparation of orthogonally-functionalized core Click cross-linked nanoparticles. New Journal of Chemistry 31:718-24
Ossipov DA, Hilborn J. 2006. Poly(vinyl alcohol)-based hydrogels formed by "click chemistry". Macromolecules 39:1709-18
Pahimanolis N, Vesterinen AH, Rich J, Seppala J. 2010. Modification of dextran using click-chemistry approach in aqueous media. Carbohydrate Polymers
Parpot P, Servat K, Bettencourt AP, Huser H, Kokoh KB. 2010. TEMPO mediated oxidation of carbohydrates using electrochemical methods. Cellulose 17:815-24
Peer D, Karp JM, Hong S, Farokhzad OC, Margalit R, Langer R. 2007. Nanocarriers as an emerging platform for cancer therapy. Nat Nanotechnol 2:751-60
Pimenta M, Carvalho A, Vilaseca F, Girones J, Lopez J, et al. 2008. Soda-Treated Sisal/Polypropylene Composites. Journal of Polymers and the Environment 16:35-9
Pozzi G, Cavazzini M, Quici S, Benaglia M, Dell'Anna G. 2004. Poly(ethylene glycol)-Supported TEMPO: An Efficient, Recoverable Metal-Free Catalyst for the Selective Oxidation of Alcohols. Organic Letters 6:441-3
Praskalo J, Kostic M, Potthast A, Popov G, Pejic B, Skundric P. 2009. Sorption properties of TEMPO-oxidized natural and man-made cellulose fibers. carbohydrate Polymers 77:791-8
Queiroz JA, Garcia FAP, Cabral JMS. 1996. Hydrophobic interaction chromatography of Chromobacterium viscosum lipase on polyethylene glycol immobilized on Sepharose. Journal of Chromatography A 734:213-9
Rattaz A, Mishra SP, Chabot B, Daneault C. 2011. Cellulose nanofibres by sonocatalysed-TEMPO-oxidation. Cellulose 18:585-93
Saito T, Isogai A. 2004. TEMPO-Mediated Oxidation of Native Cellulose. The Effect of Oxidation Conditions on Chemical and Crystal Structures of the Water-Insoluble Fractions. Biomacromolecules 5:1983-9
Saito T, Kimura S, Nishiyama Y, Isogai A. 2007. Cellulose Nanofibers Prepared by TEMPO-Mediated Oxidation of Native Cellulose. Biomacromolecules 8:2485-91
Saito T, Okita Y, Nge TT, Sugiyama J, Isogai A. 2006. TEMPO- mediated oxidation of native cellulose: Microscopic analysis of fibrous fractions in the oxidized products. Carbohydrate Polymers 65:435-40
Schatz A, Grass RN, Stark WJ, Reiser O. 2008. TEMPO supported on magnetic C/Co-nanoparticles: A highly active and recyclable organocatalyst. Chemistry - A European Journal 14:8262-6
Sharma JB, Malhotra M. 2006. Successful management of uterine incision hemorrhage in caesarean section with topical oxidized regenerated cellulose (Surgicel Nu Knit): A case report. Archives of Gynecology and Obstetrics 274:115-6
Sinha TJM, Vasudevan P. 1984. Blood-Cellulosics Interactions. Artificial Cells, Blood Substitutes and Biotechnology 12:273-87
Son WK, Youk JH, Park WH. 2003. Preparation of Ultrafine Oxidized Cellulose Mats via Electrospinning. Biomacromolecules 5:197-201
Swatloski RP, Spear SK, Holbrey JD, Rogers RD. 2002. Dissolution of cellose with ionic liquids. Journal of the American Chemical Society 124:4974-5
Tokunaga Y, Kojima T, Naruse T. 1998. Antitumor effect of oxycellulose as a hemostatic during operation. Cancer Biotherapy and Radiopharmaceuticals 13:437-45
Zalipsky S. 1995a. Chemistry of polyethylene glycol conjugates with biologically. Advanced Drug Delivery Reviews 16:157-82
Zalipsky S. 1995b. Functionalized poly(ethylene glycol) for preparation of biologically relevant conjugates. Bioconjugate Chemistry 6:150-65
Zhang M, Desai T, Ferrari M. 1998. Proteins and cells on PEG immobilized silicon surfaces. Biomaterials 19:953-60
Zhang YHP, Ding SY, Mielenz JR, Cui JB, Elander RT, et al. 2007. Fractionating recalcitrant lignocellulose at modest reaction conditions. Biotechnology and Bioengineering 97:214-23
Zhang YHP, Lynd LR. 2004. Toward an aggregated understanding of enzymatic hydrolysis of cellulose: Noncomplexed cellulase systems. Biotechnology and Bioengineering 88:797-824
Zhao MM, Li J, Mano E, Song ZJ, Tschaen DM. 2005. Oxidation of primary alcohols to carboxylic acids with sodium chlorite catalyzed by tempo and bleach: 4-methoxyphenylacetic acid. In Organic Syntheses 81: 195
洪世榮, 張珮珮. 2005四甲基哌啶氧化物之合成研究. 2005年化工學會年會論文集
陳建誠. 2009. 經聚乙二醇雙性高分子修飾之胰凝乳蛋白脢的熱穩定性. 台灣科技大學碩士論文
蕭昌福, 張明宗, 侯志賢. 1992. 不同絲光劑於定張力下絲光處理時對棉樹脂加工布架橋構造與物性影響之研究. 中國文化大學紡織工程學系第四屆:341