caa a22 4500 467952159 CHVBK 20180405193743.0 cr unu---uuuuu 170328e20050201xx s 000 0 eng 10.1007/s10570-004-0199-7 doi (NATIONALLICENCE)springer-10.1007/s10570-004-0199-7 (NATIONALLICENCE)springer-10.1023/B:CELL.0000049406.09515.83 Synthesis and SAM formation of water soluble functional carboxymethylcelluloses: thiosulfates and thioethers [Elektronische Daten] [Gerhard Wenz, Petra Liepold, Nico Bordeanu] 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 2.4nm as determined by surface plasmon resonance (SPR). Springer, 2005 c : weight concentration nationallicence CMC : carboxymethylcellulose nationallicence d : days nationallicence DMAc : N,N-dimethylacetamide nationallicence DMSO : dimethylsulfoxide nationallicence DP : degree of polymerization nationallicence DS : degree of substitution nationallicence EA : elemental analysis nationallicence h : hours nationallicence m : mol/l nationallicence MALLS : multi angle laser light scattering nationallicence min : minutes nationallicence mdeg : millidegrees nationallicence MW : weight average molecular weight nationallicence n : refractive index nationallicence r.t. : room temperature nationallicence s : seconds nationallicence SAM : self-assembled monolayer nationallicence SPR : surface plasmon resonance nationallicence λ : wavelength nationallicence Carboxymethylcellulose (CMC) nationallicence CMC allylhydroxypropylether nationallicence CMC thiosulfate nationallicence Self-assembled monolayer (SAM) nationallicence Thiomethyl CMC nationallicence Wenz Gerhard Organische Makromolekulare Chemie, Universität des Saarlandes, Postfach 151150, D-66041, Saarbrücken, Germany aut Liepold Petra FRIZ Biochem, München, Germany aut Bordeanu Nico Organische Makromolekulare Chemie, Universität des Saarlandes, Postfach 151150, D-66041, Saarbrücken, Germany aut Cellulose Kluwer Academic Publishers 12/1(2005-02-01), 85-96 0969-0239 12:1<85 2005 12 10570 https://doi.org/10.1007/s10570-004-0199-7 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/s10570-004-0199-7 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Wenz Gerhard Organische Makromolekulare Chemie, Universität des Saarlandes, Postfach 151150, D-66041, Saarbrücken, Germany aut NATIONALLICENCE 700 1- Liepold Petra FRIZ Biochem, München, Germany aut NATIONALLICENCE 700 1- Bordeanu Nico Organische Makromolekulare Chemie, Universität des Saarlandes, Postfach 151150, D-66041, Saarbrücken, Germany aut NATIONALLICENCE 773 0- Cellulose Kluwer Academic Publishers 12/1(2005-02-01), 85-96 0969-0239 12:1<85 2005 12 10570 NATIONALLICENCE 856 40 https://doi.org/10.1023/B:CELL.0000049406.09515.83 text/html Onlinezugriff via DOI Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE NATIONALLICENCE NL-springer