Synthesis and SAM formation of water soluble functional carboxymethylcelluloses: thiosulfates and thioethers
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Functional thiomethyl and thiosulfate derivatives of carboxymethylcellulose (CMC, DS = 0.9) were synthesized by nucleophilic displacement reactions. Alkylation of CMC by allyl glycidyl ether took mainly place at the primary positions of the cellulose backbone and yielded a 6-O-(3′-allyloxy-2′-hydroxypropyl)-CMC 1 with a partial DS of 3′-allyloxy-2′-hydroxypropyl substituents DSallyl of up to 0.43. Addition of tetrathionate to the allyl groups gave rise to 6-O-(2′′,3′′-bis(thiosulfato)propoxy-2′-hydroxypropyl)-CMC 2. As the addition of tetrathionate was sluggish and incomplete, alternatively bromine was added and the resulting dibromide was substituted by thiosulfate. A 40% conversion of the allyl groups was achieved by this two-step procedure. On the other hand, the addition of bromine to 1 in aqueous solution almost quantitatively yielded the bromohydrin derivative which was converted by displacement reaction with thiosulfate to 6-O-(2′′-hydroxy-3′′-thiosulfatopropoxy-2′-hydroxypropyl)-CMC 4. 6-Thiomethyl-6-deoxy-CMC 6 was synthesized by displacement reaction of 6-O-tosylcellulose with sodium methylsulfide and subsequent carboxymethylation of the cellulose backbone. A partial DS of thiomethyl substituents DSThM=0.65 exclusively at the primary positions was obtained. All functional CMC derivatives, 2, 4, and 6 were readily available in gram quantities, rather stable and highly water soluble for pH > 3. On gold surfaces they form self-assembled monolayers (SAMs) with thicknesses of 1.2 to 2.4 nm as determined by surface plasmon resonance (SPR).
- Axen R.E.A.V., Porath J.O. and Carlsson P.J.E. 1975. Thiopolymers and derivatives. Patent DE 2523793, Exploaterings AB T.B.F. Chem. Abstr. 84, 151744.
- Baker A.A., Helbert W., Sugiyama J. and Miles M.J. 2000. New insight into cellulose structure by atomic force microscopy shows the Iα crystal phase at near-atomic resolution. Biophys. J. 79: 1139-1145.
- Beulen M.W.J., Huisman B.-H., van der Heijden P.A., van Veggel F.C.J.M., Simons M.G., Biemond E.M.E.F., de Lange P.J. and Reinhoudt D.N. 1996. Evidence for nondestructive adsorption of dialkyl sul des on gold. Langmuir 12: 6170-6172.
- Choi S., Lauer H., Wenz G., Bruns M. and Petri D.F.S. 2000. Formation of dense cellulose monolayers on silver surfaces. J. Braz. Chem. Soc. 11: 11-15.
- Distler H. 1967. The chemistry of bunte salts. Angew. Chem., Int. Ed. Engl. 6: 544-553.
- Heuser E., Heath M. and Shochley W.H. 1950. The rate of esterication of primary and secondary hydroxyls of cellulose with p-toluenesulfonyl (tosyl)chloride. J. Am. Chem. Soc. 72: 670-674.
- Ho F.F.L. and Klosiewicz D.W. 1980. Proton nmr spectrometry for determination of substituents and their distribution in carboxymethylcellulose. Anal.Chem. 52: 913-916.
- Itoh T., Tsujii Y., Suzuki H., Fukuda T. and Miyamoto T. 1992. Mono-and multilayer Langmuir-Blodgett films of cellulose tri-n-alkyl esters study by transmission electron microscopy. Polym. J. 24: 641-652.
- Jaehne E., Kowalik T., Adler H.-J., Plagge A. and Stratmann M. 2002. Ultra-thin layers of phosphorylated cellulose derivatives on metal surfaces. Macromol. Symp. 177: 97-109.
- Kamide K. and Saito M. 1983. Persistence length of cellulose and cellulose derivatives in solution. Macromol. Chem. Rapid Commun. 4: 33-39.
- Kawaguchi T., Nakahara H. and Fukuda K. 1985. Mono-and multilayers of amphiphilic cellulose esters and some novel comblike polymers. J. Colloid Interface Sci. 104: 290-293.
- Khan A.R., Barton L. and T. D'Souza V. 1996. Epoxides of the secondary side of cyclodextrins. J. Am. Chem. Soc. 61: 8301-8303.
- Klemm D., Heinze T., Philipp B. and Wagenknecht W. 1997. New approaches to advanced polymers by selective cellulose functionalization. Acta Polym. 48: 277-297.
- Kowalik T., Adler H.-J., Plagge A. and Stratmann M. 2000. Ultrathin layers of phosphorylated cellulose derivatives on aluminium surfaces. Macromol. Chem. Phys. 15: 2064-2069.
- Kulicke W.-M., Kull A.H., Kull W., Thielking H., Engelhardt J. and Pannek J.-B. 1996. Characterization of aqueous carboxymethylcellulose solutions in terms of their molecular structure and its influence on rheological behaviour. Polymer 37: 2723-2731.
- Lehr B., Seufert M., Wenz G. and Decher G. 1996. Fabrication of poly(p-phenylene vinylene) (ppv) nano-heterocomposite films via layer-by-layer adsorption. Supramol. Sci. 2: 199-207.
- Lynch D.W. and Hunter W.R. 1985. Optical constants of metals. In: Palik E.D. (ed.), Handbook of Optical Constants of Solids. Academic Press, San Diego, CA, pp. 286-295.
- Mays J.W. 1988. Solution properties and chain stiffness of (cyanoethyl) (hydroxypropyl)cellulose. Macromolecules 21: 3179-3183.
- Michielsen S. 1999. Specific refractive index of polymers in dilute solution/c. Refractometric calibration data. Brandrup J., Immergut E.H. and Grulke E.A., Polymer Handbook. J. Wiley & Sons, New York, pp. VII/500.
- Rahn K., Diamantoglou M., Klemm D., Berghmans H. and Heinze T. 1996. Homogeneous synthesis of cellulose p-to-luenesulfonates in N,N-dimethylacetamide/LiCl solvent system. Angew. Makromol. Chem. 238: 143-163.
- Schaub M., Mathauer K., Schwiegk S., Albouy P.A., Wenz G. and Wegner G. 1992. Investigation of molecular superstructures of hairy rodlike polymers by X-ray reflection. Thin Solid Films 210: 397-400.
- Schaub M., Wenz G., Wegner G., Stein A. and Klemm D. 1993. Ultrathin fllms of cellulose on silicon wafers. Adv. Mater. 12: 919-921.
- Takahashi S.I., Fujimoto T., Barua B.M. and Miyamoto T. 1986. 13-C-nmr spectral studies on the distribution of substituents in some cellulose derivatives. J. Polym. Sci., Part A: Polym. Chem. Ed. 24: 2981-2993.
- Wenz G., Choi S., Bruns M., Schimmel T., Beyer H. and Siqueira Petri D.F. 1999. Synthesis of a cellulose thiosulfate and its immobilization on gold surfaces. Polymer 40: 1593-1601.
- Wenz G., Petri D.F. and Choi S.W. 2001. Polymer thiosulfates for coating of metals. Patent US 6,245,579 B1 Universität Karlsruhe, Chem.Abstr. 130, 183895.
- Zynio S.A., Samoylov A.V., Surovtseva E.R., Mirsky V.M. and Shirshov Y.M. 2002. Bimetallic layers increase sensitivity of affinity sensors based on surface plasmon resonance. Sensors 2: 62-70.
- Synthesis and SAM formation of water soluble functional carboxymethylcelluloses: thiosulfates and thioethers
Volume 12, Issue 1 , pp 85-96
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- Carboxymethylcellulose (CMC)
- CMC allylhydroxypropylether
- CMC thiosulfate
- Self-assembled monolayer (SAM)
- Thiomethyl CMC
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