Synthesis Characterization and Application of Phosphorus-Containing Derivatives of Chitosan

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1 PROGRESS IN CHEMISTRY Vol. 22 No. 5 May 2010 * / O A X Synthesis Characterization and Application of Phosphorus-Containing Derivatives of Chitosan Ma li Guo Jing Liu Pu Department of Chemistry Zhengzhou University Zhengzhou China Abstract Chitosan is a renewable and natural basic polysaccharide with a variety of excellent features. However since the dissolution of chitosan is poor it can only be dissolved in some dilute acids which restricts its further research and application. Therefore to exploit the unique properties and to realize the full potential of the versatile polysaccharides attempts are being made to chemically modify them. Phosphorylation or phosphoryl modification of chitosan is one of the methods. In this paper introducing phosphorus-containing groups into chitosan to form phosphorus-containing derivatives are reviewed. And their synthesis and purification methods characterization of the structure properties and applications are presented and discussed detailedly. Finally the opinions with respect to prospects of phosphorus-containing derivatives of chitosan are proposed. Key words chitosan phosphorus-containing derivatives characterization Contents 1 Introduction 2 Synthesis and purification of phosphorus-containing derivatives of chitosan 3 Characterization and properties of phosphoruscontaining derivatives of chitosan 3. 1 Characterization of chemical structure 3. 2 Physical properties and morphology 3. 3 Physical and anti-bacterial properties 4 Application of phosphorus-containing derivatives of chitosan 4. 1 Adsorption of metal ions and chelating capacity of phosphorus-containing derivatives of chitosan 4. 2 Application of phosphorus-containing of chitosan in drug delivery * No Corresponding author liupu@ zzu. edu. cn

2 Application of phosphorus-containing derivatives of chitosan in the field of biomedical 4. 4 Application of phosphorus-containing derivatives of chitosan in the fuel cells 5 Outlook 1 chitin β-1 4- Sakaguchi chitosan % CH 3 SO 3 H P 2 O 5 ClCH 2 CH 2 P O OH 2 ClP O OCH 2 CH 3 2 Sakaguchi 6 Nishi 7 -D- P 2 O Scheme 1 Structure of chitosan Jung h 50 6h

3 h Cardenas 19 6h 3 4h 30min 24h 6 N h 70 6h Jayakumar h C 2 -NH 2 ph N- NaOH ph carboxy-ethyl phosphonic acid 15 Lebouc 5 N C NMR EDC CH 3 2 N 70 7h % 80% 90% 100% Palma 18 C 3 C 6 KOH-CH 3 OH 22 4h 2- / 2h 12h 70 6h ph = 48h h ph h 8 Meng 23-15

4 COP 37 24h 3h 2h 70% COP COP- 25 P 2 O 5 H 3 PO 4 Et 3 PO h 1 9 Kang 24 Michael ph ph MAEP 1% NaOH ph h P 2 O 5 H 3 PO 4 Et 3 PO h 37 24h P 2 O 5 / CH 3 SO 3 H H 3 PO 4 / urea / DMF FT-IR Jayakumar 2 C 3 C 6 C 2 11 P 2 O 5 H 3 PO 4 Et 3 PO 4 1h 75 72h

5 C 3 C Ma cm - 1 / cm cm - 1 P O P O 26 X NMR H NMR 13 C NMR 31 P NMR C NMR 31 P NMR H NMR 2 1 H NMR 13 C NMR 1 H NMR DCl / D 2 O δ = H 1 δ = H 2 δ / = H 3 H 4 H 5 H 6 δ = NCOCH 3 13 C NMR DCl / D 2 O δ = C 1 δ = C 2 δ = C 3 δ = C 4 δ = C 5 δ = C 6 XRD SEM 1 H NMR 13 C NMR NaOH 1% HCl 1% 1% 1 H NMR 13 C NMR C H Wan 28 swelling index SI 31 P NMR W d W w 0 9ppm H 3 PO 4 H 3 PO SI = W w - W d / W d 100% 238ppm C 6 235ppm 224ppm

6 Ma 27 C O C Ca SEM SEM ph X XRD / XRD 32 2θ Jung % 70% % 70% ph = % F 0. 5mg / L % Wan 28

7 % 34 97% q = c 0 - c V / m q mg Ca 2 + / g V L c 0 Ca 2 + mg / L c 27 Ramos 15 N- mg / L m g q Jayakumar 34 ph ph Ni 2 + Cu 2 + Zn 2 + Nishi 35 Nishi 35 ph ph Mg 2 + Ca 2 + Sr Ba 2 + Mn 2 + Ni 2 + Cu 2 + Zn 2 + Cd % Ni 2 + Cu 2 + Zn Win ph ATP 90% ph 36 ph 7. 4 ph 1. 4 ph 7. 4 Jayakumar 20 ph 7. 4 ph 1. 4

8 Ma 27 1 P 2 O 5 Ca min 37 Ca OH 2 Ca Amaral N- Ca OH 2 NaOH / / Li / 43 N- NH N-

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